JP2008056861A - Gas barrier film, gas barrier laminate and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an excellent gas barrier laminate whose gas barrier property is little dependent on humidity and whose film is not cracked by tension. <P>SOLUTION: This gas barrier film is characterized by comprising a polymer of an unsaturated carboxylic acid multi-basic metal salt (a) containing a modified vinyl alcohol-based polymer (B). This gas barrier laminate is characterized by forming the gas barrier film on at least one side of a substrate layer. The method for producing the gas barrier laminate is characterized by coating at least one side of a substrate layer with a solution of a multiple basic metal salt of unsaturated carboxylic acid compound (a) having a polymerization degree of <20 and containing a modified vinyl alcohol-based polymer (B), and then polymerizing the compound to form the polymer (A) of the multiple basic metal salt of unsaturated carboxylic acid compound (a) containing the modified vinyl alcohol-based polymer (B). <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention is a gas barrier film having transparency, excellent gas barrier properties such as oxygen and water vapor, particularly gas barrier properties under high and low humidity, and suitable for packaging materials having a tough gas barrier layer. The present invention relates to a gas barrier laminate and a method for producing the same.

Conventionally, as a barrier material against oxygen or water vapor, etc., packaging materials using a metal foil such as aluminum, which is less affected by temperature, humidity, etc., as a gas barrier layer are generally used. There is a problem that things cannot be confirmed. Therefore, in recent years, a transparent gas barrier film in which an inorganic oxide such as silicon oxide or aluminum oxide is formed on a film substrate by vacuum deposition, sputtering, ion plating, chemical vapor deposition, or the like has attracted attention. ing. Such a transparent gas barrier film is a film obtained by depositing an inorganic oxide on a base material surface made of a biaxially stretched polyester film that is generally excellent in transparency and rigidity. When used as a packaging film, it may cause cracks in the inorganic oxide due to rubbing or elongation during post-processing printing or laminating or filling the contents, and gas barrier properties may be reduced. However, there is a problem that sufficient gas barrier properties cannot be obtained.
As a method for improving such a defect, a method of laminating a polyvinyl alcohol having gas barrier properties on a metal oxide thin film (for example, Patent Document 1), a water-soluble polymer on a vapor deposition layer surface made of an inorganic compound, and (a) one kind A laminated film coated with an aqueous solution containing at least one of the above metal alkoxides and / or their hydrolysates or (b) tin chloride or a water / alcohol mixed solution (Patent Document 2), specific A laminated film (Patent Document 3) obtained by applying a coating composition comprising an organosilane, a silyl group-containing fluoropolymer and an organopolysiloxane, and a coating agent comprising a polyvinyl alcohol resin and a metal alcoholate. Gas barrier coating film (Patent Document 4) or poly (meta) A gas barrier film is produced by a method in which a film-like product obtained by heat treatment after forming a film-like product having a composition mainly composed of crylic acid and a polyalcohol-based polymer is immersed in a medium containing metal. A method (Patent Document 5) and the like have been proposed. However, a coating film made of an alkoxide or the like is inferior in toughness, and depending on the usage of the packaging material, the film may be broken and the gas barrier property may be lowered.
In addition, a gas barrier film formed by laminating polyvinyl alcohol may have a reduced oxygen barrier property under high humidity, and a composition of poly (meth) acrylic acid and a polyalcohol polymer may have a barrier under high humidity. In order to have the property, treatment at a high temperature of 180 to 200 ° C. for at least 5 minutes is required.

JP-A-6-316025 (Claim 1) Japanese Patent No. 2790054 (Claim 1) JP-A-2000-63752 (Claims 7 and 11) JP 2002-173631 A (Claim 1, Claim 11) JP-A-10-237180 (Claim 15)

  Accordingly, an object of the present invention is to obtain a gas barrier film and a gas barrier laminate that are less dependent on the humidity of the gas barrier property and are excellent in toughness.

The present invention has been proposed to achieve the above object, and is a polymer of an unsaturated carboxylic acid compound polyvalent metal salt (a) containing a modified vinyl alcohol polymer (B), preferably a modified vinyl. Polymer of unsaturated carboxylic acid compound polyvalent metal salt (a) containing 50% by weight or less of alcohol-based polymer (B), preferably νC = carboxylic acid group near 1700 cm ⁻¹ in infrared absorption spectrum the ratio of the absorbance a, based on the νC = O absorbance a ₀ and 1520 cm ^-1 vicinity carboxylate ions based on O (a ₀ / a) is modified vinyl alcohol polymer is less than 0.25 comprising the (B) A gas barrier film comprising a polymer of a polyvalent metal salt (a) of an unsaturated carboxylic acid compound and a gas barrier laminate comprising such a gas barrier film laminated on a base material layer It is intended to provide.

  The present invention also relates to a degree of polymerization comprising the modified vinyl alcohol polymer (B), preferably 50% by weight or less of the modified vinyl alcohol polymer (B) on at least one surface of the substrate or the substrate layer (C). After applying a polyvalent metal salt solution of an unsaturated carboxylic acid compound having a molecular weight of less than 20, or a modified vinyl alcohol polymer (B), preferably 50% by weight or less of a modified vinyl alcohol polymer (B). After coating a solution containing an unsaturated carboxylic acid compound having a polymerization degree of less than 20 and a polyvalent metal compound, a polyvalent metal salt of an unsaturated carboxylic acid compound containing a modified vinyl alcohol polymer (B) (a ) Polymer (A) is formed, and a method for producing a gas barrier film or gas barrier laminate is provided.

From the polymer (A) of the unsaturated carboxylic acid compound polyvalent metal salt (a) containing the modified vinyl alcohol polymer (B) of the present invention, preferably containing 50% by weight or less of the modified vinyl alcohol polymer (B). The gas barrier film characterized by the above has transparency, is excellent in gas barrier properties such as oxygen and water vapor, especially in high and low humidity, and has flexibility.
The method for producing a gas barrier film or gas barrier laminate of the present invention comprises a polyvalent metal salt (a) of an unsaturated carboxylic acid compound having a degree of polymerization of less than 20 and a modified vinyl alcohol polymer (B), preferably 50 weights. % Of the modified vinyl alcohol-based polymer (B) is used, and the shape of the substrate is not limited to a film shape, and can be easily applied to a substrate of any shape, From the polymer (A) layer of the unsaturated carboxylic acid compound polyvalent metal salt (a) including the modified vinyl alcohol polymer (B) having a high degree of neutralization, ie, excellent gas barrier properties and flexibility. Can be easily manufactured.

Unsaturated carboxylic acid compound The unsaturated carboxylic acid compound forming the unsaturated carboxylic acid compound polyvalent metal salt (a) according to the present invention is an α-, β-ethylenically unsaturated group such as acrylic acid, methacrylic acid, maleic acid, itaconic acid. A carboxylic acid compound having a saturated group and having a polymerization degree of less than 20, preferably a monomer or a polymer having 10 or less. When a polymer (polymer compound) having a polymerization degree exceeding 20 is used, a salt with a polyvalent metal compound described later may not be formed completely. As a result, the metal salt may be modified with a modified vinyl alcohol heavy polymer. The layer obtained by copolymerization with the combined body (B) may be inferior in gas barrier properties under high humidity. These unsaturated carboxylic acid compounds may be one kind or a mixture of two or more kinds.
Among these unsaturated carboxylic acid compounds, it is easy to form a salt in which the monomer is completely neutralized with a polyvalent metal compound, and a copolymer layer obtained by copolymerizing the salt is formed on at least one surface of the base material layer. Laminated gas barrier laminates are preferred because they are particularly excellent in gas barrier properties under high humidity.

Polyvalent metal compound The polyvalent metal compound which is a component forming the unsaturated carboxylic acid compound polyvalent metal salt (a) according to the present invention is a metal belonging to Groups 2A to 7A, 1B to 3B and Group 8 of the periodic table. And, specifically, magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu) , Zinc (Zn), aluminum (Al) and other divalent or higher metals, oxides, hydroxides, halides, carbonates, phosphates, phosphites, hypophosphites, sulfuric acids of these metals Salt or sulfite. Among these metal compounds, divalent metal compounds are preferable, and magnesium oxide, calcium oxide, barium oxide, zinc oxide, magnesium hydroxide, calcium hydroxide, barium hydroxide, zinc hydroxide, and the like are particularly preferable. When these divalent metal compounds are used, the gas barrier property under high humidity of the film obtained by polymerizing the salt with the unsaturated carboxylic acid compound is particularly excellent. At least one kind of these polyvalent metal compounds is used, and only one kind may be used or two or more kinds may be used in combination. Among these polyvalent metal compounds, Mg, Ca, Zn, Ba and Al, and particularly Zn are preferable.

Unsaturated carboxylic acid compound polyvalent metal salt (a)
Polymer (A) of unsaturated carboxylic acid compound polyvalent metal salt (a) containing modified vinyl alcohol polymer (B) of the present invention (hereinafter sometimes referred to as “polymer (A)”). The unsaturated carboxylic acid compound polyvalent metal salt (a), which is one of the components constituting the gas barrier film, is a salt of the unsaturated carboxylic acid compound having a polymerization degree of less than 20 and the polyvalent metal compound. is there. These unsaturated carboxylic acid compound polyvalent metal salts (a) may be one kind or a mixture of two or more kinds. Among such unsaturated carboxylic acid compound polyvalent metal salts (a), the polymer layer from which zinc (meth) acrylate is obtained is particularly excellent in hot water resistance, which is preferable.

Vinyl alcohol polymer The vinyl alcohol polymer used as the base of the modified vinyl alcohol polymer (B) of the present invention is a polymer mainly composed of vinyl alcohol, and is usually obtained by saponifying polyvinyl acetate. It is a polymer and may contain 19 mol% or less, preferably 15 mol% or less of ethylene.
Such vinyl alcohol polymers can be used usually having a degree of polymerization of 100 to 3000, preferably 300 to 2000. Further, from the viewpoint of gas barrier properties of the polymer (A) obtained by polymerization with the unsaturated carboxylic acid compound polyvalent metal salt (a), those having a high saponification degree of 70 to 99.9% are preferably used. Or 99.9% is preferred.

Modified vinyl alcohol polymer (B)
The modified vinyl alcohol polymer (B), which is one of the components constituting the gas barrier film made of the polymer (A) of the present invention, is a group having various known reactivities with the vinyl alcohol polymer ( A copolymer obtained by copolymerizing a vinyl ester such as vinyl acetate and an unsaturated compound having a reactive group, by modifying the reactive group) by addition, substitution or esterification, etc. There is no particular limitation as long as the polymer has a reactive group in the molecule.
As such a modified vinyl alcohol polymer (B), those having a polymerization degree of 100 to 3000, preferably 300 to 2000 can be used. Further, from the viewpoint of gas barrier properties of the polymer (A) obtained by polymerization with the unsaturated carboxylic acid compound polyvalent metal salt (a), those having a high saponification degree of 70 to 99.9% are preferably used. Or 99.9% is preferred.
Specific examples of the reactive group that the modified vinyl alcohol polymer (B) has include, for example, a (meth) acrylate group, a (meth) acryloyl group, a (meth) acrylamide group, a vinyl group, an allyl group, and a styryl group. Thiol group, silyl group, acetoacetyl group, epoxy group and the like. The amount of the reactive group in the modified vinyl alcohol polymer (B) can be determined as appropriate. However, when the amount of the OH group of the vinyl alcohol polymer serving as the substrate decreases, the gas barrier property inherent in the vinyl alcohol polymer. In general, the amount of reactive groups is in the range of 0.001 to 50 mol% (the total of reactive groups and OH groups is 100 mol%). The modified vinyl alcohol polymer (B) is preferably soluble in water, lower alcohols, organic solvents and the like, and particularly preferably soluble in water or water-lower alcohol mixed solvents.
When the modified vinyl alcohol polymer (B) modified with such a reactive group is used as one of the components, the modified vinyl alcohol is mixed with the unsaturated carboxylic acid compound polyvalent metal salt (a) for polymerization. A gas barrier film having improved gas barrier properties under low humidity, comprising a polymer (B) and a polymer (A) in which at least a part of the unsaturated carboxylic acid compound polyvalent metal salt (a) has some bonds, is obtained. It is done.
Specific examples of such a modified vinyl alcohol polymer (B) include:
For example, a part of the OH group of the vinyl alcohol polymer used as the substrate is a carboxylic acid compound having an α or β ethylenically unsaturated group such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid or a derivative thereof. (Meth) acrylate group-modified vinyl alcohol polymer (B1) obtained by reacting and introducing a (meth) acrylate group;
Vinyl acetate and vinyl acetate having isothiuronium salt or thiolate ester are copolymerized, and the resulting polymer is decomposed with acid or base to form a thiol group. A substrate obtained by a method of introducing a reactive functional group, a method of polymerizing vinyl esters in the presence of thiolic acid, and introducing a thiol group only at the end of the molecule by saponifying the obtained polymer; A thiol group-modified vinyl alcohol polymer (B2) having a thiol group (—SH group) in a part of the OH groups of the vinyl alcohol polymer obtained;
A method of adding a silyl group by post-modification using a silylating agent such as organohalogen silane, organoacetoxy silane, organoalkoxy silane to a vinyl alcohol polymer or a vinyl acetate polymer containing a carboxyl group or a hydroxyl group, or acetic acid Saponification of copolymers of vinyl and silyl group-containing olefinically unsaturated compounds such as vinyl silane and (meth) acrylamide-alkyl silane, and silanol which is an alkoxysilyl group, an acyloxysilyl group or a hydrolyzate thereof in the molecule A trialkoxysilane group such as a trimethoxysilane group or a triethoxysilane group, a trialkyloxysilane group, A silyl group having a carbonyloxysilane group or the like Sex vinyl alcohol polymer (B3);
Disperse vinyl alcohol polymer in acetic acid solvent, add diketene to it, dissolve vinyl alcohol polymer in solvent such as dimethylformamide or dioxane in advance and add diketene to this An acetoacetyl group-modified vinyl alcohol system having an acetoacetyl group in a part of the OH group of a vinyl alcohol polymer as a substrate, obtained by a method and a method of directly contacting a diketene gas or liquid diketene with a vinyl alcohol polymer Polymer (B4);
Other monomers with reactive functional groups are copolymerized with vinyl acetate and then saponified to introduce reactive functional groups into the side chain, and reactive functional groups are introduced into the side chain of polyvinyl alcohol by polymer reaction. And (meth) acrylamide groups, allyl groups, vinyl groups, styryl groups, intramolecular doubles in the molecule by various known methods such as a method of introducing a reactive functional group at the end using a chain transfer reaction, etc. Examples thereof include a modified vinyl alcohol polymer obtained by adding other radical polymerizing groups such as a bond and a vinyl ether group, and a modified vinyl alcohol polymer obtained by adding a cationic polymer group such as an epoxy group and a glycidyl ether group.
Among these modified vinyl alcohol polymers (B), the gas barrier film made of the polymer (A) obtained using the (meth) acrylate group-modified vinyl alcohol polymer (B1) has a high humidity and a low humidity. Laminate (laminated film) that has excellent gas barrier properties (oxygen barrier properties) underneath, has no deterioration in gas barrier properties (hot water resistance) after hydrothermal treatment, has flexibility, and has such a gas barrier film formed ) Is used for a packaging material or the like, the heat seal strength is improved.

(Meth) acrylate group-modified vinyl alcohol polymer (B1)
As the (meth) acrylate group-modified vinyl alcohol polymer (B1), the amount of (meth) acryloyl group (compared with —OH group; esterification rate) is preferably 0.001 to 50%, more preferably It is in the range of 0.1 to 40%. If the esterification rate is less than 0.001%, the hot water resistance and flexibility of the resulting gas barrier film may not be improved. On the other hand, if it exceeds 50%, the hot water resistance and oxygen barrier of the resulting gas barrier film will not be improved. There is a risk that the properties and the like will not be improved.
The (meth) acrylate group-modified vinyl alcohol polymer (B1) according to the present invention includes, for example, a vinyl alcohol copolymer and (meth) acrylic acid or (meth) acrylic acid halide, (meth) acrylic anhydride. By reacting with a (meth) acrylic acid derivative such as (meth) acrylic acid ester in the presence or absence of a catalyst such as Bronsted acid, Bronsted base, Lewis acid, Lewis base, metal compound, etc. can get. Further, (meth) acrylic having a functional group in the molecule that reacts with OH group of vinyl alcohol copolymer and vinyl alcohol copolymer such as glycidyl (meth) acrylate and 2-isocyanatoethyl (meth) acrylate, for example. The (meth) acrylate group can also be indirectly introduced into the vinyl alcohol copolymer by reacting with an acid derivative.

Thiol group-modified vinyl alcohol polymer (B2)
As the thiol group-modified vinyl alcohol polymer (B2), a vinyl monomer having an isothiuronium salt or a thiolic acid ester and vinyl acetate are copolymerized, and the resulting polymer is decomposed with an acid or a base to form a thiol group. Method, a method of introducing a reactive functional group into a side chain of a polyvinyl alcohol polymer by a polymer reaction, a thiolcarboxylic acid such as thiolacetic acid, thiolpropionic acid, thiolbutyric acid, including an organic thiol acid having a —COSH group In the presence of acid, vinyl esters such as vinyl formate, vinyl acetate, vinyl propionate, vinyl versatate, vinyl laurate, and vinyl stearate are polymerized, and the resulting polymer is saponified to end the molecule. The thiol group is added to the molecule by a known method such as a method of introducing a thiol group only. In the polymer, typically, a thiol group modification ratio is in the range of 0.1 to 50 mol%.
As these thiol group-modified vinyl alcohol polymers (B2), for example, “M-115” and “M-205” are manufactured and sold by Kuraray Co., Ltd. under the trade name of Kuraray M polymer.

Silyl group-modified vinyl alcohol polymer (B3)
Examples of the silyl group-modified vinyl alcohol polymer (B3) include vinyl alcohol polymers or vinyl acetate polymers containing a carboxyl group or a hydroxyl group, trimethylchlorosilane, dimethyldichlorosilane, methyltrichlorosilane, vinyltrichlorosilane. Silyl groups by post-modification using silylating agents such as organohalogen silanes such as diphenyldichlorosilane, organoacetoxy silanes such as trimethylacetoxysilane and dimethyldiacetoxysilane, or organoalkoxysilanes such as trimethoxysilane and dimethyldimethoxysilane Or vinyl acetate and, for example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris- (β-methoxyethoxy) silane, vinyltriacetoxysilane, Riltrimethoxysilane, allyltriacetoxysilane, vinylmethyldimethoxysilane, vinyldimethylmethoxysilane, vinylmethyldiethoxysilane, vinyldimethylethoxysilane, vinylmethyldiacetoxysilane, vinyldimethylacetoxysilane, vinylisobutyldimethoxysilane, vinyltriiso Vinyloxysilanes such as propoxysilane, vinyltributoxysilane, vinyltrihexyloxysilane, vinylmethoxydihexyloxysilane, vinyldimethoxyoctyloxysilane, or 3- (meth) acrylamide-propyltrimethoxysilane, 3- (meth) acrylamide- Propyltriethoxysilane, 3- (meth) acrylamide-propyltri (β-methoxyethoxy) silane, 2- (meth) acrylamide -Methylpropyltrimethoxysilane, 2- (meth) acrylamide-2-methylethyltrimethoxysilane, N- (2- (meth) acrylamido-ethyl) -aminopropyltrimethoxysilane, 3- (meth) acrylamide-propyltri Acetoxysilane, 2- (meth) acrylamide-ethyltrimethoxysilane, 1- (meth) acrylamide-methyltrimethoxysilane, 3- (meth) acrylamide-propylmethyldimethoxysilane, 3- (meth) acrylamide-propyldimethylmethoxysilane 3- (N-methyl- (meth) acrylamide) -propyltrimethoxysilane, 3-((meth) acrylamide-methoxy) -3-hydroxypropyltrimethoxysilane, 3-((meth) acrylamide-methoxy)- In the molecule obtained by saponifying a copolymer with a silyl group-containing olefinically unsaturated compound such as (meth) acrylamide-alkylsilane such as propyltrimethoxysilane, an alkoxysilyl group, an acyloxysilyl group or these And a polymer having a silyl group such as a silanol group or a salt thereof, which is a hydrolyzate of the above. The modification amount of the silyl group is usually in the range of 0.1 to 50 mol%.
As these silyl group-modified vinyl alcohol polymers (B3), for example, “R-1130”, “R-2105” and “R-2130” are manufactured and sold under the trade name of Kuraray R polymer from Kuraray Co., Ltd. Has been.

Acetoacetyl group-modified vinyl alcohol polymer (B4)
The acetoacetyl group-modified vinyl alcohol polymer (B4) is obtained by adding and reacting a liquid or gaseous diketene to a solution, dispersion or powder of the vinyl alcohol polymer. The degree of acetylation is in the range of 1 to 10 mol%, preferably 3 to 5 mol%.
As these acetoacetyl group-modified vinyl alcohol polymers (B4), for example, from Nippon Synthetic Chemical Industry Co., Ltd. under the product names of “Gosefimer Z100”, “Z200”, “Z200H” and “Z210” Manufactured and sold.

Gas barrier film The gas barrier film of the present invention comprises a modified vinyl alcohol polymer (B), preferably 50% by weight or less, more preferably 40 to 0.001% by weight, particularly preferably 30 to 0.01% by weight. A gas barrier film comprising a polymer (A) of an unsaturated carboxylic acid compound polyvalent metal salt (a) containing a range of modified vinyl alcohol polymer (B).
In the present invention, it is desirable to heat-treat the gas barrier film.
The heat treatment is desirably performed at a temperature of usually 60 to 350 ° C., preferably 100 to 300 ° C., more preferably 150 to 250 ° C., and preferably in an inert gas atmosphere. The pressure is not particularly limited, and may be any of under pressure, under reduced pressure, and normal pressure. The heat treatment time is usually about 1 second to 90 minutes, with 1 minute to 70 minutes being preferred, and 5 minutes to 60 minutes being particularly preferred.
The film to be subjected to the heat treatment is usually heat-treated while being applied to the base material layer, but may be peeled off from the base material layer and heat-treated if necessary.
In the present invention, the polymerized film may be continuously heat-treated, or may be subjected to heat treatment after the film is once returned to room temperature. Usually, it is desirable in terms of production efficiency that the process of forming a film by polymerization and the process of heat treatment are continued.
It is presumed that the film subjected to the heat treatment has a film structure determined by polymerization. By further heat-treating this, it is presumed that the dehydration and the film structure become a more stabilized film by partial rearrangement, and the gas barrier property is more stable. Thereby, the gas barrier film | membrane excellent in transparency and excellent in gas barrier property can be manufactured.
The gas barrier film made of the polymer (A) of the present invention preferably has an absorbance A ₀ based on νC═O of a carboxylic acid group near 1700 cm ⁻¹ in the infrared absorption spectrum and νC = carboxylate ions near 1520 cm ^−1. The gas barrier film has a ratio (A ₀ / A) to an absorbance A based on O of less than 0.25, more preferably less than 0.20, and even more preferably less than 0.15.
Since the gas barrier film of the present invention contains the modified vinyl alcohol polymer (B), the gas barrier property under low humidity is improved, and the gas barrier property (hot water resistance) after the hot water treatment is not lowered, Toughness (elongation) is imparted to the film. When the content of the modified vinyl alcohol polymer (B) exceeds 50% by weight, the gas barrier property of the obtained film, particularly the gas barrier property (oxygen barrier property) under high humidity may be somewhat lowered. On the other hand, if the content of the modified vinyl alcohol polymer (B) is too small, the effect of improving gas barrier properties under low humidity may be insufficient.
The gas barrier film comprising the polymer (A) of the present invention comprises a carboxylate ion and a free carboxylic acid formed by ionic crosslinking of the carboxylic acid group and the polyvalent metal of the unsaturated carboxylic acid compound polymetallic salt (a). In the infrared spectrum, the absorption based on νC═O of the free carboxylic acid group is around 1700 cm ^{−1 and the} absorption based on νC═O of the carboxylate ion is around 1520 cm ⁻¹ , respectively.
In the gas barrier film according to the present invention, (A ₀ / A) being less than 0.25 indicates that there are no or few free carboxylic acid groups. Since the content of free carboxylic acid groups is large and the gas barrier resistance under high humidity may not be improved, (A ₀ / A) is preferably less than 0.25.
Ratio of absorbance A ₀ based on νC═O of a carboxylic acid group near 1700 cm ⁻¹ in the present invention to absorbance A based on νC═O of a carboxylate ion near 1520 cm ⁻¹ in an infrared absorption spectrum (A ₀ / A) Cuts out a sample for measurement of 1 cm × 3 cm from the gas barrier film, and obtains an infrared absorption spectrum of the surface [polymer (A) layer] by infrared total reflection measurement (ATR method). A ₀ and absorbance A were determined.
1700cm absorbance based νC = O ^-1 vicinity of the carboxylic acid groups A _0: a absorbance of the infrared absorption spectrum of 1660 cm ^-1 and 1760 cm ^-1 connected by a straight line (N), 1660~1760cm maximum absorbance between ^-1 ( The straight line (O) was dropped vertically from around 1700 cm ^−1, and the absorbance distance (length) between the intersection of the straight line (O) and the straight line (N) and the maximum absorbance was defined as absorbance A ₀ .
1520 cm ^-1 vicinity of carboxylate ion of νC = O based upon the absorbance A: connected by a straight line (L) and the absorbance of the infrared absorption spectrum of 1480 cm ^-1 and 1630 cm ^-1, the maximum absorbance between 1480~1630cm ^{-1 (1520cm The} straight line (M) was dropped vertically from the vicinity of ⁻¹ ), and the absorbance distance (length) between the intersection of the straight line (M) and the straight line (L) and the maximum absorbance was defined as absorbance A. The peak position of maximum absorbance (near 1520 cm ⁻¹ ) may vary depending on the metal species of the counter ion. For example, calcium is near 1520 cm ⁻¹ , zinc is near 1520 cm ⁻¹ , and magnesium is near 1540 cm ^−1. is there.
Next, the ratio (A ₀ / A) was determined from the absorbance A ₀ and absorbance A determined by the above method.
In addition, the measurement of the infrared spectrum (infrared total reflection measurement: ATR method) in the present invention uses an FT-IR350 apparatus manufactured by JASCO Corporation, and a KRS-5 (Thallium Bromide-Iodide) crystal is attached, and the incident angle is 45. Temperature, room temperature, resolution of 4 cm ⁻¹ , and accumulation of 150 times.
The thickness of the gas barrier film of the present invention can be determined according to various uses, but is usually in the range of 0.01 to 100 μm, preferably 0.05 to 50 μm, more preferably 0.1 to 10 μm.

In the gas barrier film of the present invention, natural water-soluble polymers such as starch, gum arabic, gelatin, polysaccharides, etc., in addition to the modified vinyl alcohol polymer (B), as long as the object of the present invention is not impaired. Cellulose derivatives such as methyl cellulose, ethyl cellulose and carboxymethyl cellulose; semi-synthetic water-soluble polymers such as modified starch; vinyl alcohol polymers such as polyvinyl alcohol and ethylene / vinyl alcohol copolymer; polyvinyl pyrrolidone, polyvinyl ethyl ether, polyacrylamide, Contains high molecular weight compounds (polymers) such as polyethyleneimine synthetic water-soluble polymer acrylic acid ester polymers, ethylene / acrylic acid copolymers, polyvinyl acetate, ethylene / vinyl acetate copolymers, polyester, polyurethane, etc. You may go out.
In addition, the gas barrier film of the present invention includes ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, PEG # 200 • diacrylate, PEG # 400 • within the range that does not impair the object of the present invention. Diacrylate, polyunsaturated carboxylic acid ester such as PEG # 600 / diacrylate, unsaturated carboxylic acid compound monovalent metal salt, methyl (meth) acrylate, acrylic acid ester compound such as ethyl (meth) acrylate, acetic acid Contains various additives such as vinyl ester compounds such as vinyl, olefin compounds such as ethylene, lubricants, slip agents, anti-blocking agents, antistatic agents, antifogging agents, pigments, dyes, inorganic and organic fillers, etc. Or improve wettability, adhesion, etc. with the substrate described later For it may contain various surfactants and the like.

Gas barrier laminate The gas barrier laminate of the present invention is a polymer of an unsaturated carboxylic acid compound polyvalent metal salt (a) containing the modified vinyl alcohol polymer (B) on at least one surface of a base material layer (C). A gas barrier film made of (A) is formed. By forming (laminating) such a polymer (A), it has transparency, excellent gas barrier properties (oxygen barrier properties) under high and low humidity, and gas barrier properties (hot water resistance) after hydrothermal treatment. ) And a tough laminate.
Moreover, when using the gas-barrier laminated body which used the film base material (C1) as a base material layer (C) for a packaging material etc., it has the characteristics that heat seal intensity | strength is improved.
Another aspect of the gas barrier laminate of the present invention is a base material layer in which an inorganic compound vapor deposition layer (D) described later is formed on at least one surface of the base material layer (C) as a base material layer (C) described later. It is a laminate in which the gas barrier film is formed on at least one surface of the inorganic compound vapor deposition layer (D). By using the base material layer in which the inorganic compound vapor deposition layer (D) is formed as the base material layer, a gas barrier laminate having moisture resistance can be obtained.
Another aspect of the gas barrier laminate of the present invention is a gas barrier laminate in which an inorganic compound vapor deposition layer (D) described later is formed on at least one surface of the gas barrier film forming the gas barrier laminate. By forming the inorganic compound vapor deposition layer (D) on the gas barrier film, a gas barrier laminate having moisture resistance can be obtained.
Moreover, when laminating a gas-barrier film on the base material layer (C), for example, base material layer (C) / gas barrier film / inorganic compound vapor deposition layer (D) / gas barrier film / inorganic compound vapor deposition layer (D) / The gas barrier film and the inorganic compound vapor deposition layer (D) may be laminated in layers with the gas barrier film.
Such a multi-layered gas barrier laminate can almost completely block gas such as oxygen or water vapor.
The gas barrier laminate of the present invention is a laminate having various known shapes such as a laminate film (sheet), a hollow container, a cup, and a tray, depending on the shape of the base material layer (C) described later and depending on the application. be able to.
Although the thickness of the gas barrier laminate of the present invention can be variously determined depending on the application, the thickness of the base material layer (C) is usually 5 to 1500 μm, preferably 5 to 500 μm, more preferably 9 to 100 μm. More preferably, when having an inorganic compound vapor deposition layer (D), the thickness of the vapor deposition layer (D) is 15 to 5000 mm, preferably 15 to 1000 mm, more preferably 230 to 450 mm, and the polymer (A ) The thickness of the gas barrier film comprising layers is 0.01 to 100 μm, preferably 0.05 to 50 μm, more preferably 0.1 to 10 μm, and the total thickness of the gas barrier laminate is 5 to 1600 μm, preferably It exists in the range of 5-550 micrometers, More preferably, 10-150 micrometers, More preferably, it is 10-40 micrometers.

Base material layer (C)
The base material layer (C) forming the gas barrier laminate of the present invention is usually a film-like material such as a sheet or film made of a thermosetting resin or a thermoplastic resin, or a container-like material such as a tray, a cup or a hollow body. It consists of what has a shape, film-like things, such as paper or aluminum foil, or those composites. Such a base material layer (C) may be a single layer or a multilayer body of the same or different resins.
Examples of the thermosetting resin include various known thermosetting resins such as epoxy resins, unsaturated polyester resins, phenol resins, urea / melamine resins, polyurethane resins, silicone resins, and polyimides.
As the thermoplastic resin, various known thermoplastic resins such as polyolefin (polyethylene, polypropylene, poly-4-methyl / 1-pentene, polybutene, etc.), polyester (polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, etc.), polyamide (Nylon-6, nylon-66, polymetaxylene adipamide, etc.), polyvinyl chloride, polyimide, ethylene / vinyl acetate copolymer or saponified product thereof, polyvinyl alcohol, polyacrylonitrile, polycarbonate, polystyrene, ionomer, or these And the like. Biodegradable plastics such as aliphatic polyesters such as polylactic acid can also be used. Of these, thermoplastic resins having good stretchability and transparency, such as polypropylene, polyethylene terephthalate, and polyamide, are preferable.
Moreover, when using a film base material (C1) as a base material layer (C), the uniaxial or biaxially stretched film base material may be sufficient. When a biaxially stretched film substrate is used as the film substrate (C1), a laminate excellent in transparency, heat resistance, rigidity, and the like can be obtained.
Moreover, the inorganic compound vapor deposition layer (D) may be formed in the surface of a base material layer (C).
The inorganic compound deposited on the surface of the base material layer (C) or the gas barrier film is not particularly limited as long as it is an inorganic compound that can be deposited. Specifically, for example, chromium (Cr), zinc Examples thereof include metals such as (Zn), cobalt (Co), aluminum (Al), tin (Sn), and silicon (Si), and oxides, nitrides, sulfides, and phosphides of these metals. Among these inorganic compounds, oxides, particularly oxides such as aluminum oxide, zinc oxide, and silica (silicon oxide) are preferable because of excellent transparency.
As a method of forming the vapor deposition layer (D) of these inorganic compounds on the surface of the base material layer (C) or the surface of the gas barrier film, chemical vapor deposition such as chemical vapor deposition (CVD), low pressure CVD and plasma CVD, or vacuum vapor deposition Examples thereof include physical vapor deposition methods (PVD) such as (reactive vacuum deposition), sputtering (reactive sputtering) and ion plating (reacted ion plating), and plasma spray methods such as low-pressure plasma spray and plasma spray.
The surface of the base material layer (C) may be coated with polyvinylidene chloride, polyvinyl alcohol, ethylene / vinyl alcohol copolymer, acrylic resin, urethane resin, or the like.
These base material layers (C) have a surface activation treatment such as corona treatment, flame treatment, plasma treatment, undercoat treatment, primer coat treatment, etc., in order to improve adhesion to the gas barrier film. You may keep going.

Method for Producing Gas Barrier Film and Gas Barrier Laminate Film The method for producing a gas barrier film and a gas barrier laminate of the present invention (hereinafter also referred to as a method for producing a gas barrier film or the like) is a modified vinyl alcohol type on at least one side of a substrate. The above-mentioned polymerization comprising the polymer (B), preferably 50% by weight or less, more preferably 40 to 0.001% by weight, particularly preferably 30 to 0.01% by weight of the modified vinyl alcohol polymer (B). A gas barrier laminate comprising polymerizing the unsaturated carboxylic acid compound polyvalent metal salt (a) after coating a solution of the unsaturated carboxylic acid compound polyvalent metal salt (a) having a degree of less than 20 It is a manufacturing method.
In the method for producing a gas barrier film or the like of the present invention, when the substrate layer (C) is used as a substrate, a gas barrier laminate in which the gas barrier film is laminated on at least one surface of the present invention can be obtained. In addition, the base layer (C), an inorganic substance such as glass, ceramic, metal, or other materials, or other materials, and a heavy weight obtained by polymerizing the unsaturated carboxylic acid compound polyvalent metal salt (a), etc. If the combined body (A) is peeled from the substrate, a single-layer gas barrier film of the present invention can be obtained.
As a method of forming a gas barrier film on at least one surface of the base material layer (C), for example, a modified vinyl alcohol polymer (B) and an unsaturated carboxylic acid compound polyvalent metal having a polymerization degree of less than 20 are preferable. The salt (a) is dissolved in a solvent such as water in a desired amount, and then a solution of the mixture is applied. The solution of the modified vinyl alcohol polymer (B) and the degree of polymerization are less than 20 individually. After preparing a solution of the saturated carboxylic acid compound polyvalent metal salt (a), a solution of the modified vinyl alcohol polymer (B) and a solution of the unsaturated carboxylic acid compound polyvalent metal salt (a) having a polymerization degree of less than 20 Or an unsaturated carboxylic acid compound having a polymerization degree of less than 20 or a polyvalent metal compound added to the solution to obtain an unsaturated carboxylic acid compound polyvalent metal salt ( a) formed However, the method is not limited to such a method, and the main point is that the coating is applied to the base material layer, but the modified vinyl alcohol polymer (B) or the solution thereof is mixed in a desired amount. The unsaturated carboxylic acid compound polyvalent metal salt (a) mixture formed from an unsaturated carboxylic acid compound having a degree of polymerization of less than 20 containing the modified vinyl alcohol polymer (B) is formed. Just do it.
Moreover, as a method of applying the solution of the mixture to at least one surface of the substrate layer (C), etc., a method of applying the solution to the substrate layer (C) with a brush, a coater, or the like, a substrate to the solution of the mixture Various known coating methods can be adopted depending on the shape of the substrate layer (C), such as a method of immersing the layer (C), a method of spraying a solution of the mixture on the surface of the substrate layer (C), etc. .

When the unsaturated carboxylic acid compound having a polymerization degree of less than 20 and the polyvalent metal compound are directly dissolved in a solvent as a method for producing a gas barrier film or the like of the present invention, that is, the unsaturated carboxylic acid having a polymerization degree of less than 20 When a solution containing a compound and the polyvalent metal compound is used, the polyvalent metal compound in an amount exceeding 0.3 chemical equivalent may be added to the unsaturated carboxylic acid compound having a polymerization degree of less than 20. preferable. When a mixed solution having a polyvalent metal compound addition amount of 0.3 chemical equivalent or less is used, a laminate having a large content of free carboxylic acid groups may be formed, resulting in a laminate having a low gas barrier property. is there. Moreover, although the upper limit of the addition amount of the polyvalent metal compound is not particularly limited, since the amount of the unreacted polyvalent metal compound increases when the addition amount of the polyvalent metal compound exceeds 1 chemical equivalent, it is usually 5 chemical equivalents or less. Preferably, 2 chemical equivalents or less are sufficient.
In addition, when using a solution in which an unsaturated carboxylic acid compound having a polymerization degree of less than 20 and a polyvalent metal compound are used, a saturated carboxylic acid compound having a polymerization degree of less than 20 and a polyvalent metal compound are usually dissolved in a solvent. While the unsaturated carboxylic acid compound polyvalent metal salt (a) is formed, it is preferable to mix for 1 minute or more in order to ensure the formation of the polyvalent metal salt.

The solvent used in the solution of the unsaturated carboxylic acid compound polyvalent metal salt (a) and / or the modified vinyl alcohol polymer (B) having a polymerization degree of less than 20 is a lower solvent such as water, methyl alcohol, ethyl alcohol, isopropyl alcohol, etc. Although organic solvents, such as alcohol or acetone, methyl ethyl ketone, or those mixed solvents are mentioned, Water is the most preferable.
As a method of applying a solution of an unsaturated carboxylic acid compound polyvalent metal salt (a) having a degree of polymerization of less than 20 containing the modified vinyl alcohol polymer (B) on at least one side of the substrate layer (C) and the like, In addition to the method of immersing the base material layer (C) in the solution, the method of spraying the solution on the surface of the base material layer (C), etc., for example, air knife coater, direct gravure coater, gravure offset, arc gravure Reverse roll coaters such as coaters, gravure reverse and jet nozzle type gravure coaters, top feed reverse coaters, bottom feed reverse coaters and nozzle feed reverse coaters, 5-roll coaters, lip coaters, bar coaters, bar reverse coaters, die coaters The degree of polymerization is 20 using various known coating machines. Usually an amount in the mixed solution (solid content) of the fully unsaturated carboxylic acid compound polyvalent metal salt (a) and modified vinyl alcohol polymer and ^{(B), 0.05~10g / m 2} , preferably 0 It may be applied so as to be 1 to 5 g / m ² .

When the unsaturated carboxylic acid compound polyvalent metal salt (a) and / or the modified vinyl alcohol polymer (B) is dissolved or when the unsaturated carboxylic acid compound and the polyvalent metal compound are dissolved, as described above. As long as the object of the present invention is not impaired, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, PEG # 200 diacrylate, PEG # 400 diacrylate, PEG # 600 diacrylate, etc. Polyunsaturated carboxylic acid ester, unsaturated carboxylic acid compound monovalent metal salt, methyl (meth) acrylate, acrylic acid ester compound such as ethyl (meth) acrylate, vinyl ester compound such as vinyl acetate, ethylene, etc. Monomers such as olefin compounds or low molecular weight Natural water-soluble polymers such as natural products, starch, gum arabic, gelatin, polysaccharides, cellulose derivatives such as methylcellulose, ethylcellulose and carboxymethylcellulose, semi-synthetic water-soluble polymers such as modified starch, polyvinyl alcohol and ethylene / vinyl alcohol Vinyl alcohol polymers such as polymers, synthetic water-soluble polymer acrylate polymers such as polyvinyl pyrrolidone, polyvinyl ethyl ether, polyacrylamide, and polyethyleneimine, ethylene / acrylic acid copolymers, polyvinyl acetate, ethylene / acetic acid A high molecular weight compound (polymer) such as a vinyl copolymer, polyester, or polyurethane may be added.
Further, when the unsaturated carboxylic acid compound polyvalent metal salt (a) and / or the modified vinyl alcohol polymer (B) is dissolved, or when the unsaturated carboxylic acid compound and the polyvalent metal compound are dissolved, Various additives such as a lubricant, a slip agent, an anti-blocking agent, an antistatic agent, an antifogging agent, a pigment, a dye, an inorganic or organic filler may be added as long as the object of the invention is not impaired. In order to improve the wettability with the base material layer, various surfactants and the like may be added.

Polymerize a solution (coating layer) of an unsaturated carboxylic acid compound polyvalent metal salt (a) containing a modified vinyl alcohol polymer (B) formed (coated) on at least one side of the base material layer (C), etc. In order to achieve this, there are various known methods, specifically, for example, a method by irradiation with ionizing radiation or heating.
When ionizing radiation is used, it is not particularly limited as long as the wavelength region is an energy ray in the range of 0.0001 to 800 nm. Examples of such energy rays include α rays, β rays, γ rays, X rays, and visible rays. , Ultraviolet rays, electron beams and the like. Among these ionizing radiations, visible light in the wavelength range of 400 to 800 nm, ultraviolet light in the range of 50 to 400 nm, and electron beam in the range of 0.01 to 0.002 nm are easy to handle and the devices are widespread. Therefore, it is preferable.
In the present invention, the polymerized film may be continuously irradiated with ionizing radiation, or may be irradiated after the film is once returned to room temperature. Usually, it is desirable in terms of production efficiency that the process of forming a film by polymerization and the process of heat treatment are continued. When ionizing radiation is irradiated again, the film performance is improved.
The electron beam (electron beam; EB) applied to the solution of the unsaturated carboxylic acid compound polyvalent metal salt is not particularly limited as long as the unsaturated carboxylic acid compound polyvalent metal salt is polymerized. It is preferable to use an electron beam having an acceleration voltage of 30 kV to 300 kV and a dose of 10 to 300 kilogray (kGy). If the acceleration voltage is increased too much, the penetration depth of the electron beam becomes deep, and the base material layer may be deteriorated. On the other hand, if the acceleration voltage is reduced too much, the penetration depth of the electron beam becomes shallow, which is not good. The polymerization of the saturated carboxylic acid compound polyvalent metal salt may be insufficient. In addition, if the dose is increased too much, the line speed may be slowed and productivity may be reduced. If the dose is decreased too much, polymerization of the unsaturated carboxylic acid compound polyvalent metal salt may be insufficient. is there.
When using visible light and ultraviolet light as ionizing radiation, it is necessary to add a photopolymerization initiator to the solution of the unsaturated carboxylic acid compound polyvalent metal salt (a) containing the modified vinyl alcohol polymer (B). Become. As the photopolymerization initiator, known ones can be used. For example, 2-hydroxy-2methyl-1-phenyl-propan-1-one (trade name; Darocur 1173, manufactured by Ciba Specialty Chemicals), 1-Hydroxy-cyclohexyl ruphenyl ketone (Ciba Specialty Chemicals product name; Irgacure 184), Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (Ciba Specialty Chemicals product name) Irgacure 819), 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one (trade name; Irgacure 2959, manufactured by Ciba Specialty Chemicals) ), Α-hydroxy ketone, acylphosphine oxa , A mixture of 4-methylbenzophenone and 2,4,6-trimethylbenzophenone (trade name; Essaure KT046 manufactured by Lamberti Chemical Specialty), Esacure KT55 (Lamberti Chemical Specialty), 2,4,6- The radical polymerization initiator manufactured and sold by brand names, such as a trimethyl benzoyl diphenyl phosphine oxide (Ramson Fire Chemical company brand name; Speed Cure TPO), can be mentioned. Furthermore, a polymerization accelerator can be added to improve the polymerization degree or polymerization rate, and examples thereof include N, N-dimethylamino-ethyl- (meth) acrylate, N- (meth) acryloyl-morpholine, and the like. .
Moreover, in order to advance superposition | polymerization, it is desirable to perform irradiation of these ionizing radiations several times. For example, it is desirable to irradiate ultraviolet rays having an illuminance of 200 mW / cm ² or more in a wavelength range of 280 to 320 nm a plurality of times, for example, twice using an electrodeless or electrode type ultraviolet lamp.

When the unsaturated carboxylic acid compound polyvalent metal salt (a) containing the modified vinyl alcohol polymer (B) is polymerized, the solution may be polymerized in a state containing a solvent such as water or partially dried. However, if the solution is polymerized immediately after coating, the resulting polymer (A) layer may be whitened because of the evaporation of the solvent when the metal salt (a) is polymerized. There is a case. On the other hand, as the solvent (moisture) decreases, the unsaturated carboxylic acid compound polyvalent metal salt (a) may be precipitated as crystals, and formation of the polymer (A) layer obtained by polymerization in such a state may occur. There is a possibility that the gas barrier property may not be stable because the polymer (A) layer is whitened due to insufficient. Therefore, when the coated unsaturated carboxylic acid compound polyvalent metal salt (a) is polymerized, it is preferably polymerized in a state containing appropriate moisture.
Further, when the unsaturated carboxylic acid compound polyvalent metal salt (a) containing the modified vinyl alcohol polymer (B) is polymerized, it may be polymerized by irradiating with ionizing radiation at once, or twice or more. The polymerization may be carried out separately or continuously. Moreover, when irradiating twice or more, for example, the first eye may be weakened, the second time or more may be strongly irradiated, and the irradiation intensity may be changed the same or continuously.

If the laminate is a laminate film, the gas barrier laminate of the present invention is a laminate film suitable as a heat-sealable packaging film by laminating (bonding) a heat-sealing layer on at least one surface thereof ( A multilayer film). Such a heat-fusible layer is usually a homo- or copolymer of 痾 -olefin such as ethylene, propylene, butene-1, hexene-1, 4-methylpentene-1, octene-1 and the like known as a heat-fusible layer. , High pressure method low density polyethylene, linear low density polyethylene (so-called LLDPE), high density polyethylene, polypropylene, polypropylene random copolymer, polybutene, poly-4-methyl pentene-1, low crystalline or amorphous ethylene Propylene random copolymer, ethylene / butene-1 random copolymer, composition containing polyolefin such as propylene / butene-1 random copolymer alone or in combination of two or more, ethylene / vinyl acetate copolymer (EVA), ethylene・ (Meth) acrylic acid copolymer or its metal salt, EVA and polyolefin A layer obtained from adult or the like.
Among these, a heat-sealing layer obtained from an ethylene-based polymer such as high-pressure method low-density polyethylene, linear low-density polyethylene (so-called LLDPE), or high-density polyethylene is preferable because it has excellent low-temperature heat sealability and heat seal strength.
In the gas barrier laminate of the present invention, the base material layer (C) is laminated on the gas barrier film surface of the gas barrier laminate or the surface on which the gas barrier film is not formed, depending on various applications. Also good.

  EXAMPLES Next, although an Example demonstrates this invention further more concretely, this invention is not limited at all by these Examples.

The physical property values and the like in Examples and Comparative Examples were obtained by the following evaluation methods.

<Evaluation method>
(1) Polymerization rate (%): The polymerization rate (%) of the unsaturated carboxylic acid compound polyvalent metal salt in the present invention was determined by the following measuring method.
Polymerization rate (%) = [1- (B ₁ / B) after UV / (B ₁ / B) monomer] × 100
* (B ₁ / B) after UV: after UV irradiation of (polymer) (B ₁ / B)
* (B ₁ / B) Monomer: Monomer (before polymerization) of (B ₁ / B)
* Monomer: unsaturated carboxylic acid compound polyvalent metal salt (a)
(B ₁ / B) was defined as described below.
Ratio of absorbance B ₁ based on νC—H of hydrogen bonded to a vinyl group near 830 cm ⁻¹ to absorbance B based on νC═O of carboxylate ion near 1520 cm ⁻¹ in the infrared absorption spectrum (B ₁ / B) Cut out a measurement sample of 1 cm × 3 cm from the polymerized film, and obtained an infrared absorption spectrum of the surface (polymer (A) layer surface) by infrared total reflection measurement (ATR method). Absorbance B ₁ and absorbance B are determined.
830 cm ^-1 vicinity absorbance based .delta.C-H of hydrogen binding to vinyl groups B _1: bear and the absorbance of the infrared absorption spectrum of 800 cm ^-1 and 850 cm ^-1 in a straight line (P), between 800～850Cm ^-1 A straight line (Q) is dropped vertically from the maximum absorbance (near 830 cm ⁻¹ ), and the distance (length) of absorbance between the intersection of the straight line (Q) and the straight line (P) and the maximum absorbance is defined as absorbance B ₁ .
1520 cm ^-1 absorbance based νC = O of carboxylate ions in the vicinity of B: the absorbance of the infrared absorption spectrum of 1480 cm ^-1 and 1630 cm ^-1 connected by a straight line (L), 1480~1630cm maximum absorbance between ^-1 (1520 cm ^The straight line (M) was dropped vertically from ( ^-1 vicinity), and the absorbance distance (length) between the intersection of the straight line (M) and the straight line (L) and the maximum absorbance was defined as absorbance B. The maximum absorbance (1520 cm around ^-1), there is the peak position by counter-ions of the metal species is changed, for example, around 1520 cm ^-1 in calcium, near 1520 cm ^-1 in zinc, around 1540 cm ^-1 in the magnesium is there.
Next, the ratio (B ₁ / B) is determined from the absorbance B ₁ and absorbance B determined by the above method. The rate of polymerization as described above formulas, the absorbance ratio of the unsaturated carboxylic acid compound polyvalent metal salt (a) (monomer) of (B ₁ / B) monomer and polymer after UV irradiation (A) (B ₁ / B) Measure after UV.
In addition, the measurement of the infrared spectrum (infrared total reflection measurement: ATR method) in the present invention uses an FT-IR350 apparatus manufactured by JASCO Corporation, and a KRS-5 (Thallium Bromide-Iodide) crystal is attached, and the incident angle is 45. Temperature, room temperature, resolution of 4 cm ⁻¹ , and integration 150 times.
(2) Absorbance ratio (A ₀ / A): measured by the method described above.
(3) Oxygen permeability [ml / (m ² · day · MPa)]: A multilayer film obtained by laminating a gas barrier laminate film or a linear low density polyethylene film described later, OX-TRAN 2/21 ML manufactured by Mocon In accordance with JIS K 7126 (isobaric method), it was measured after adjusting for 3 hours under conditions of a temperature of 20 ° C. and a humidity of 90% RH. Further, using OX-TRAN 2/20 SM manufactured by Mocon, the measurement was carried out after adjusting for 3 hours under conditions of a temperature of 20 ° C. and a humidity of 0% RH in accordance with JIS K 7126 (isobaric method).
(4) Production of multilayer film: 50 μm thick linear low density polyethylene film (trade name: TUX FCS manufactured by Tosero Co., Ltd.) on one side with urethane adhesive [polyurethane adhesive (Mitsui Takeda Chemical Product name: Takelac A310): 12 parts by weight, isocyanate curing agent (trade name: Takenate A3 manufactured by Mitsui Takeda Chemical Co., Ltd .: 1 part by weight) and ethyl acetate (manufactured by Kanto Chemical Co., Ltd .: 7 parts by weight) After the construction and drying, the surfaces of the gas barrier laminate films obtained in Examples and Reference Examples were bonded together (dry laminated) with the Zn acrylate polymer layer (unsaturated carboxylic acid compound polyvalent metal salt polymer layer) surface. ) A multilayer film was prepared.
(5) Boil treatment: The multilayer film obtained by the above method was treated in 95 ° C. hot water for 30 minutes.
(6) Heat seal strength (HS strength; N / 15 mm): Using the multilayer film obtained by the above method, the linear low density polyethylene film surfaces of the multilayer film are heated at 130 ° C. for 1 second at 2 kg / cm ² . After sealing, the sample was sampled to a width of 15 mm, and under the conditions of temperature: 23 ° C., humidity: 50% RH, using a tensile tester (manufactured by Orientec; Tensilon Universal Tester RTC-1225) at a speed of 300 mm / min. The heat seal strength was measured.
(7) Moisture content [% by weight] of coating liquid (coating film): A 120 × 297 mm measurement sample was cut out from a gas barrier laminated film coated with an unsaturated carboxylic acid compound polyvalent metal salt solution and its weight ( After measuring Wg), it is dried for 10 minutes in a hot air drier at a temperature of 130 ° C. and its weight (W dry g) is measured. Separately, a sample for measurement of 120 × 297 mm is cut out from a substrate film (film to which an unsaturated carboxylic acid compound polyvalent metal salt solution is applied), and the weight (W substrate g) is measured. And the moisture content in a coating film was calculated | required with the following formula | equation using the weight of each said film.
Water content (% by weight) = [{(W-W substrate)-(W dry-W substrate)} / (WW substrate)] × 100

<Preparation of solution (X)>
Zinc acrylate (Zn salt of acrylic acid) aqueous solution (manufactured by Asada Chemical Co., Ltd., concentration 30 wt% (acrylic acid component: 20 wt%, Zn component 10 wt%)) and photopolymerization diluted to 25 wt% with methyl alcohol Initiator [1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one (trade name; Irgacure 2959, manufactured by Ciba Specialty Chemicals)] and Surfactant (trade name; manufactured by Kao Corporation; Emulgen 120) is mixed so as to be 98.5%, 1.2%, and 0.3% in terms of mol fraction, respectively, to produce a Zn acrylate solution (X). did.

<Modified vinyl alcohol polymer (B); Modified PVA>
<< Acrylate group-modified vinyl alcohol polymer (B1)
(1) 19% acrylated polyvinyl alcohol (B1-1)
Put 10.0 g (0.23 mol) of polyvinyl alcohol-1 (Wako Pure Chemical Industries, polymerization degree 500, saponification degree 98.5 mol%, trade name; PVA500) into a 500 mL round bottom three-necked flask, and purge the flask with nitrogen did. 300 mL of 1-methyl-2-pyrrolidinone (hereinafter abbreviated as NMP) was added to the flask. The temperature was raised to 100 ° C. and stirred for 2 hours to obtain a uniform solution. After cooling the homogeneous solution to 25 ° C., 10.2 g (0.113 mol) of acryloyl chloride was dropped into the flask and reacted. After 90 minutes, the reaction mixture was dropped into 1800 mL of tetrahydrofuran (hereinafter abbreviated as THF) to precipitate acrylated polyvinyl alcohol. The supernatant was removed by decantation, and the resulting precipitate was dissolved in 100 mL of water / methanol (1/1 vol). The obtained solution was dropped into 800 mL of THF to precipitate acrylated polyvinyl alcohol. The supernatant was removed by decantation. The reprecipitation operation was further repeated twice to purify the acrylated polyvinyl alcohol. A portion of the purified acrylated polyvinyl alcohol (about 50 mg) was dissolved in 1 mL of deuterated dimethyl sulfoxide (hereinafter abbreviated as DMSO-d ₆ ) and subjected to 1H-NMR measurement. The substitution rate of the acryloyl group Was 19 mol%. The purified acrylated polyvinyl alcohol was dissolved in 100 mL of water / methanol (1/1 vol) to obtain a solution of 19% acrylated polyvinyl alcohol (B1-1) having a solid content concentration of 8.9% by weight. .
(2) 14% acrylated polyvinyl alcohol (B1-2)
Reaction and post-treatment were performed in the same manner as in B1-1 except that water / methanol (1/1 vol), which is a good solvent in the reprecipitation operation, was replaced with water (100 mL) for 45 minutes. It was. The substitution rate of acryloyl group was 14 mol%. By dissolving the purified acrylated polyvinyl alcohol in 100 mL of water, an aqueous solution of 14% acrylated polyvinyl alcohol (B1-2) having a solid content concentration of 9.5% by weight was obtained.
(3) 11% acrylated polyvinyl alcohol-1 (B1-3)
Except that polyvinyl alcohol-1 was 12.0 g (0.27 mol), acryloyl chloride was 5.2 g (57.5 mmol), the reaction time was 28 hours, and the good solvent during the reprecipitation operation was replaced with water (100 mL). The reaction and post-treatment were performed in the same manner as in B1-1. The substitution rate of the acryloyl group was 11 mol%. The purified acrylated polyvinyl alcohol was dissolved in 100 mL of water to obtain an aqueous solution of 11% acrylated polyvinyl alcohol (B1-3) having a solid content concentration of 9.0% by weight.
(4) 7.9% acrylated polyvinyl alcohol-1 (B1-4)
Except that polyvinyl alcohol-1 was 12.0 g (0.27 mol), acryloyl chloride was 4.2 g (46.4 mmol), the reaction time was 7 hours, and the good solvent during the reprecipitation operation was replaced with water (100 mL). The reaction and post-treatment were performed in the same manner as in B1-1. The substitution rate of the acryloyl group was 7.9 mol%. The purified acrylated polyvinyl alcohol was dissolved in 100 mL of water to obtain an aqueous solution of 7.9% acrylated polyvinyl alcohol (B1-4) having a solid content concentration of 8.9% by weight.
(5) 3.4% acrylated polyvinyl alcohol (B1-5)
Except that 12.0 g (0.27 mol) of polyvinyl alcohol-1 and 2.45 g (27.1 mmol) of acryloyl chloride, the reaction time was 18 hours, and the good solvent during the reprecipitation operation was replaced with water (100 mL). The reaction and post-treatment were performed in the same manner as in B1-1. The substitution rate of the acryloyl group was 3.4 mol%. By dissolving the purified acrylated polyvinyl alcohol in 100 mL of water, an aqueous solution of 3.4% acrylated polyvinyl alcohol (B1-5) having a solid content concentration of 10.7% by weight was obtained.
(6) 7.5% acrylated polyvinyl alcohol (B1-6)
12.0 g (0.27 mol) of polyvinyl alcohol-2 (polymerization degree 1000, saponification degree 98.5%, manufactured by Kuraray Co., Ltd., trade name: PVA110), 4.98 g (55.0 mmol) of acryloyl chloride, reaction time For 21 hours, the reaction was carried out in the same manner as in the preparation method of B1-1, except that the good solvent during the reprecipitation operation was changed to water (100 mL) and the amount of THF used as the poor solvent during the reprecipitation operation was changed to 1750 mL. Processed. The substitution rate of acryloyl group was 7.5 mol%. The purified acrylated polyvinyl alcohol was dissolved in 100 mL of water to obtain an aqueous solution of 7.5% acrylated polyvinyl alcohol (B1-6) having a solid content concentration of 8.4% by weight.
(7) 3.5% acrylated polyvinyl alcohol (B1-7)
12.0 g (0.27 mol) of polyvinyl alcohol-3 (polymerization degree 1700, saponification degree 98.5%, manufactured by Kuraray Co., Ltd., trade name: PVA117) was placed in a 500 mL round bottom three-necked flask, and the atmosphere in the flask was replaced with nitrogen. . NMP (300 mL) was added to the flask. The temperature was raised to 120 ° C. and stirred for 1 hour to obtain a uniform solution. After cooling the homogeneous solution to 25 ° C., 3.52 g (38.9 mmol) of acryloyl chloride was dropped into the flask to cause reaction. After 18 hours, the reaction mixture was dropped into 1600 mL of THF / isopropanol (hereinafter abbreviated as IPA) (1/1 vol) to precipitate acrylated polyvinyl alcohol. The supernatant was removed by decantation, and the resulting precipitate was dissolved in 150 mL of water. The resulting solution was dropped into 1200 mL of IPA to precipitate acrylated polyvinyl alcohol. The supernatant was removed by decantation. The reprecipitation operation was further repeated twice to purify the acrylated polyvinyl alcohol. A part (about 50 mg) of the purified acrylated polyvinyl alcohol was dissolved in 1 mL of DMSO-d ₆ and subjected to 1H-NMR measurement. As a result, the substitution rate of the acryloyl group was 3.5 mol%. The purified acrylated polyvinyl alcohol was dissolved in 150 mL of water to obtain a solution of 3.5% acrylated polyvinyl alcohol (B1-7) having a solid content concentration of 4.8% by weight.
<< thiol group-modified vinyl alcohol polymer (B2) >>
(8) Thiol group-modified polyvinyl alcohol: polymerization degree 1500, saponification degree 97.5%, manufactured by Kuraray Co., Ltd., trade name: M-115 (B2-1)
<< Silyl group-modified vinyl alcohol polymer (B3) >>
(9) Silyl group-modified vinyl alcohol polymer; polymerization degree 1700, saponification degree 98.5%, manufactured by Kuraray Co., Ltd., trade name: R-1130 (B3-1)
<< Acetoacetyl group-modified vinyl alcohol polymer (B4) >>
(10) Acetacetyl group-modified polyvinyl alcohol: polymerization degree 1200, saponification degree 99.5%, manufactured by Nippon Synthetic Chemical Co., Ltd., trade name: Z-200 (B4-1)
In preparing the coating solution using the modified vinyl alcohol polymer, a 10% by weight aqueous solution of the modified vinyl alcohol polymer was prepared and used in advance.

<Vinyl alcohol polymer (C); PVA>
(11) Polyvinyl alcohol: polymerization degree 500, saponification degree 98.5%, manufactured by Wako Pure Chemical Industries, Ltd., trade name: PVA500 (C)

Examples 1 and 2
Zinc acrylate and 19% acrylated polyvinyl alcohol (B1-1) in an aqueous solution of Zn acrylate solution (X) and 19% acrylated polyvinyl alcohol (B1-1) in the weight ratio (solid content) described in Table 1, respectively. Then, the solid content concentration of the solution was adjusted to 16% by weight to prepare a coating solution. Next, the coating solution was applied to a corona-treated surface of a substrate film made of a biaxially stretched polyester film having a thickness of 12 μm (trade name; Emblet PET12, manufactured by Unitika Co., Ltd.), and a solid content of 1.6 g / m with a Mayer bar. It applied so that it might become ² , and it dried using the hot air dryer. Thereafter, the coated surface is quickly fixed on the stainless steel plate, and UV intensity: 180 mW / cm ² , integrated light quantity: 180 mJ / cm ² using a UV irradiation device (EYE GRANDAGE model ECS 301G1 manufactured by Eye Graphic). Polymerization was performed by irradiating ultraviolet rays under the conditions described above to obtain a gas barrier laminate film. The obtained gas barrier laminate film was evaluated by the method described above.
In addition, the moisture content of the coating film just before UV irradiation of Example 1 calculated | required by said method was 43 weight%.

Examples 3-5
Example except that 14% acrylated polyvinyl alcohol (B1-2) was used instead of 19% acrylated polyvinyl alcohol (B1-1) used in Example 1, and each was mixed at a weight ratio shown in Table 1. 1 was performed to obtain a gas barrier laminate film. The obtained gas barrier laminate film was evaluated by the method described above.
The evaluation results are shown in Table 1.

Examples 6-8
Example 11 except that 11% acrylated polyvinyl alcohol (B1-3) was used instead of 19% acrylated polyvinyl alcohol (B1-1) used in Example 1, and each was mixed at a weight ratio shown in Table 1. 1 was performed to obtain a gas barrier laminate film. The obtained gas barrier laminate film was evaluated by the method described above.
The evaluation results are shown in Table 1.

Examples 9-11
Instead of 19% acrylated polyvinyl alcohol (B1-1) used in Example 1, 7.9% acrylated polyvinyl alcohol (B1-4) was used, except that they were mixed at a weight ratio shown in Table 1, respectively. In the same manner as in Example 1, a gas barrier laminate film was obtained. The obtained gas barrier laminate film was evaluated by the method described above.
The evaluation results are shown in Table 1.

Examples 12 and 13
The procedure was carried out except that 3.4% acrylated polyvinyl alcohol (B1-6) was used instead of 19% acrylated polyvinyl alcohol (B1-1) used in Example 1, and mixing was carried out at a weight ratio shown in Table 1. In the same manner as in Example 1, a gas barrier laminate film was obtained. The obtained gas barrier laminate film was evaluated by the method described above.
The evaluation results are shown in Table 1.

Example 14
Instead of 19% acrylated polyvinyl alcohol (B1-1) used in Example 1, 7.5% acrylated polyvinyl alcohol (B1-6) was used, except that mixing was carried out at a weight ratio shown in Table 1. In the same manner as in Example 1, a gas barrier laminate film was obtained. The obtained gas barrier laminate film was evaluated by the method described above.
The evaluation results are shown in Table 1.

Example 15
Instead of 19% acrylated polyvinyl alcohol (B1-1) used in Example 1, 3.5% acrylated polyvinyl alcohol (B1-7) was used, except that mixing was carried out at a weight ratio shown in Table 1. In the same manner as in Example 1, a gas barrier laminate film was obtained. The obtained gas barrier laminate film was evaluated by the method described above.
The evaluation results are shown in Table 1.

Example 16
Instead of 19% acrylated polyvinyl alcohol (B1-1) used in Example 1, thiol group-modified polyvinyl alcohol (B2-1) was used, and the mixture was mixed at the weight ratio shown in Table 1, and was the same as Example 1. To obtain a gas barrier laminate film. The obtained gas barrier laminate film was evaluated by the method described above.
The evaluation results are shown in Table 1.

Examples 17 and 18
Instead of the 19% acrylated polyvinyl alcohol (B1-1) used in Example 1, a silyl group-modified vinyl alcohol polymer (B3-1) was used, except that each was mixed at a weight ratio shown in Table 1. In the same manner as in Example 1, a gas barrier laminate film was obtained. The obtained gas barrier laminate film was evaluated by the method described above.
The evaluation results are shown in Table 1.

Examples 19-21
Example 1 except that acetoacetyl group-modified polyvinyl alcohol (B4-1) was used in place of 19% acrylated polyvinyl alcohol (B1-1) used in Example 1, and each was mixed at a weight ratio shown in Table 1. In the same manner as above, a gas barrier laminate film was obtained. The obtained gas barrier laminate film was evaluated by the method described above.
The evaluation results are shown in Table 1.

Reference example 1
In place of the coating solution used in Example 1, except that the coating solution was used by adjusting the Zn acrylate solution (X) to a solid content concentration of 16% by weight with water. 1 was performed to obtain a gas barrier laminate film. The obtained gas barrier laminate film was evaluated by the method described above.
The evaluation results are shown in Table 1.

Reference examples 2 and 3
It replaces with 19% acrylated polyvinyl alcohol (B1-1) used in Example 1, and uses a vinyl alcohol polymer (C), and is the same as Example 1 except mixing in the weight ratio of Table 1, respectively. To obtain a gas barrier laminate film. The obtained gas barrier laminate film was evaluated by the method described above.
The evaluation results are shown in Table 1.

Example 22
The base film used in Example 5 was formed from a 12 μm-thick biaxially stretched polyester film (trade name, manufactured by Unitika Ltd .; Emblet PET12), and a 12 μm thick aluminum oxide-deposited biaxially stretched polyethylene terephthalate film (deposited PET: Tohsero) A gas barrier laminate film was obtained in the same manner as in Example 5 except that the product name was changed to TL-PET H). Next, the obtained gas barrier laminate film was laminated with a linear low density polyethylene film by the method described above to obtain a multilayer film. The obtained multilayer film was evaluated by the method described above.
The evaluation results are shown in Table 2.

Example 23
The base film used in Example 5 was converted from a biaxially stretched polyester film (trade name, manufactured by Unitika Ltd .; Emblet PET12) having a thickness of 12 μm to a biaxially stretched polypropylene film (OPP: trade name, manufactured by Tosero). A gas barrier laminate film was obtained in the same manner as in Example 5 except that OP HE-1) was used. Next, the obtained gas barrier laminate film was laminated with a linear low density polyethylene film by the method described above to obtain a multilayer film. The obtained multilayer film was evaluated by the method described above.
The evaluation results are shown in Table 2.

Example 24
The base film used in Example 5 was a biaxially stretched polyester film (ONY: product name manufactured by Unitika Co., Ltd.) having a thickness of 15 μm from a biaxially stretched polyester film (product name; manufactured by Unitika Corp .; Emblet PET12) having a thickness of 12 μm; A gas barrier laminate film was obtained in the same manner as in Example 5 except that the emblem ON15) was used. Next, the obtained gas barrier laminate film was laminated with a linear low density polyethylene film by the method described above to obtain a multilayer film. The obtained multilayer film was evaluated by the method described above.
The evaluation results are shown in Table 2.

Example 25
The base film used in Example 18 is a 12 μm thick biaxially stretched polyester film (trade name; Emblet PET12, manufactured by Unitika Ltd.) and a 12 μm thick aluminum oxide-deposited biaxially stretched polyethylene terephthalate film (deposited PET: East Cello). A gas barrier laminate film was obtained in the same manner as in Example 18 except that the product name was changed to TL-PET H). Next, the obtained gas barrier laminate film was laminated with a linear low density polyethylene film by the method described above to obtain a multilayer film. The obtained multilayer film was evaluated by the method described above.
The evaluation results are shown in Table 2.

Example 26
The base film used in Example 19 is a 12 μm thick biaxially stretched polyester film (trade name; Emblet PET12, manufactured by Unitika Ltd.) and a 12 μm thick aluminum oxide-deposited biaxially stretched polyethylene terephthalate film (deposited PET: East Cello). A gas barrier laminate film was obtained in the same manner as in Example 19 except that the product name was changed to TL-PET H). Next, the obtained gas barrier laminate film was laminated with a linear low density polyethylene film by the method described above to obtain a multilayer film. The obtained multilayer film was evaluated by the method described above.
The evaluation results are shown in Table 2.

Reference example 4
The base film used in Reference Example 1 is a 12 μm thick biaxially stretched polyester film (trade name; Emblet PET12, manufactured by Unitika Ltd.), and a 12 μm thick aluminum oxide vapor deposited biaxially stretched polyethylene terephthalate film (deposited PET: East Cello). A gas barrier laminate film was obtained in the same manner as in Reference Example 1 except that the product name was changed to TL-PET H). Next, the obtained gas barrier laminate film was laminated with a linear low density polyethylene film by the method described above to obtain a multilayer film. The obtained multilayer film was evaluated by the method described above.
The evaluation results are shown in Table 2.

Reference Example 5
The base film used in Reference Example 3 is a 12 μm-thick biaxially stretched polyester film (trade name; Emblet PET12, manufactured by Unitika Ltd.) and a 12 μm thick aluminum oxide-deposited biaxially stretched polyethylene terephthalate film (deposited PET: East Cello). A gas barrier laminate film was obtained in the same manner as in Reference Example 3 except that the product name was changed to TL-PET H). Next, the obtained gas barrier laminate film was laminated with a linear low density polyethylene film by the method described above to obtain a multilayer film. The obtained multilayer film was evaluated by the method described above.
The evaluation results are shown in Table 2.

Examples of heat treatment are shown below. The permeability (water vapor permeability) was determined by the following method.
Water vapor permeability [g / (m ² · day)]: Fold the multilayer film and heat-seal the two sides (linear low-density polyethylene film surface) to form a bag, and then add calcium chloride as the contents. One side was heat-sealed to make a bag with a surface area of 0.01 m ² , and the bag was made 40 ° C., 90% H. The water vapor permeability was measured by the difference in weight.

<Preparation of solution (X)>
Zinc acrylate (Zn salt of acrylic acid) aqueous solution (manufactured by Asada Chemical Co., Ltd., concentration 30 wt% (acrylic acid component: 20 wt%, Zn component 10 wt%)) and photopolymerization diluted to 25 wt% with methyl alcohol Initiator [1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one (trade name; Irgacure 2959, manufactured by Ciba Specialty Chemicals)] and A surfactant (trade name; Emulgen 120, manufactured by Kao Corporation) was mixed so that the molar fractions were 98.5%, 1.2%, and 0.3%, respectively, and consisted of a Zn acrylate solution (X). An unsaturated carboxylic acid compound polyvalent metal salt solution was prepared.

Example 27
The base film used in Example 13 was formed from a 12 μm-thick biaxially stretched polyester film (trade name; Emblet PET12, manufactured by Unitika Ltd.) and a 12 μm-thick aluminum oxide-deposited biaxially stretched polyethylene terephthalate film (deposited PET: East Cello). A gas barrier laminate film was obtained in the same manner as in Example 13 except that the product name was changed to TL-PET H). Next, the obtained gas barrier laminate film was laminated with a linear low density polyethylene film by the method described above to obtain a multilayer film. The obtained multilayer film was evaluated by the method described above.
The evaluation results are shown in Table 3.

Example 28
The base film used in Example 17 was formed from a 12 μm-thick biaxially stretched polyester film (trade name; Emblet PET12, manufactured by Unitika Co., Ltd.) and a 12 μm thick aluminum oxide-deposited biaxially stretched polyethylene terephthalate film (deposited PET: East Cello). A gas barrier laminate film was obtained in the same manner as in Example 13 except that the product name was changed to TL-PET H). Next, the obtained gas barrier laminate film was laminated with a linear low density polyethylene film by the method described above to obtain a multilayer film. The obtained multilayer film was evaluated by the method described above.
The evaluation results are shown in Table 3.

Example 29
The gas barrier laminated film obtained in Example 27 was further subjected to heat treatment at 120 ° C. for 10 minutes to obtain a heat treated gas barrier laminated film. Next, the obtained heat-treated gas barrier laminate film was laminated with a linear low density polyethylene film by the method described above to obtain a multilayer film. The obtained multilayer film was evaluated by the method described above.
The evaluation results are shown in Table 3.

Example 30
The gas barrier laminated film obtained in Example 27 was further heat-treated at 150 ° C. for 10 minutes to obtain a heat-treated gas barrier laminated film. Next, the obtained heat-treated gas barrier laminate film was laminated with a linear low density polyethylene film by the method described above to obtain a multilayer film. The obtained multilayer film was evaluated by the method described above.
The evaluation results are shown in Table 3.

Example 31
The gas barrier laminated film obtained in Example 27 was further heat-treated at 200 ° C. for 60 minutes to obtain a heat-treated gas barrier laminated film. Next, the obtained heat-treated gas barrier laminate film was laminated with a linear low density polyethylene film by the method described above to obtain a multilayer film. The obtained multilayer film was evaluated by the method described above.
The evaluation results are shown in Table 3.

Example 32
The gas barrier laminate film obtained in Example 28 was further heat-treated at 200 ° C. for 60 minutes to obtain a heat-treated gas barrier laminate film. Next, the obtained heat-treated gas barrier laminate film was laminated with a linear low density polyethylene film by the method described above to obtain a multilayer film. The obtained multilayer film was evaluated by the method described above. The evaluation results are shown in Table 3.

Example 33
The base film used in Example 13 was formed from a 12 μm-thick biaxially stretched polyester film (trade name; Emblet PET12, manufactured by Unitika Ltd.) and a 12 μm-thick aluminum oxide-deposited biaxially stretched polyethylene terephthalate film (deposited PET: East Cello). In place of the product name: TL-PET H), an electrodeless ultraviolet irradiation device (Fusion Co., Ltd. model: CV-110Q-G, type F600V-10) was used as the UV ultraviolet irradiation device, and the illuminance: 1760 mW / cm 2 And light quantity: 300 mJ / cm <2> ultraviolet rays were irradiated and superposed | polymerized, and the gas barrier laminated film which laminated | stacked the gas barrier film was obtained. Next, the obtained gas barrier laminate film was laminated with a linear low density polyethylene film by the method described above to obtain a multilayer film. The obtained multilayer film was evaluated by the method described above. The evaluation results are shown in Table 3.

Example 34
The gas barrier laminate film obtained in Example 33 was further irradiated with ultraviolet rays using an electrodeless ultraviolet irradiation device to obtain a UV-treated gas barrier laminate film. Next, the obtained UV-treated gas barrier laminate film was laminated with a linear low density polyethylene film by the method described above to obtain a multilayer film. The obtained multilayer film was evaluated by the method described above. The evaluation results are shown in Table 3.

尚、表３における注１及び注２は以下の通りである。
＊注１ 紫外線照射装置（アイグラフィック社製 ＥＹＥ ＧＲＡＮＤＡＧＥ 型式ＥＣ Ｓ ３０１Ｇ１）を用いて、紫外線を照射して重合した。
＊注２ 紫外線照射装置に（フージョン社製 型式：ＣＶ−１１０Ｑ−Ｇ、種類 Ｆ６０ ０Ｖ−１０）を用いて、紫外線を照射して重合した。

Note 1 and 2 in Table 3 are as follows.
* Note 1 Polymerization was performed by irradiating ultraviolet rays using an ultraviolet irradiation device (EYE GRANDAGE model EC S 301G1 manufactured by Eye Graphic).
* Note 2 Polymerization was performed by irradiating with ultraviolet rays using an ultraviolet ray irradiation apparatus (model: CV-110Q-G, type F60 0V-10, manufactured by Fusion Company).

As is clear from Table 1, in the system to which the modified vinyl alcohol polymer was added, the oxygen barrier property under low humidity was improved, and further, delamination did not occur due to the boil treatment, and the hot water resistance was also improved. On the other hand (Examples 1 to 21), in the additive-free system (Reference Example 1), the oxygen barrier property at 90% RH and the hot water resistance are excellent, but the oxygen barrier property at low humidity decreases. Moreover, in the system to which polyvinyl alcohol is added (Reference Examples 2 and 3), the barrier property under low humidity is improved as compared with the case where no addition is made, but delamination occurs due to the boil treatment, and the hot water resistance is lowered.
Further, as apparent from Table 2, by forming the polymer (A) on the aluminum oxide transparent deposited layer, a film having excellent oxygen barrier properties at both high humidity and low humidity and excellent in hot water resistance can be obtained. Obtained (Examples 22, 25, 26). Furthermore, it was confirmed that the same physical properties as those of the biaxially stretched PET film were obtained even when the base film was a biaxially stretched polypropylene film (Example 23) and a biaxially stretched polyamide film (Example 24).
Further, as apparent from Table 3, the moisture resistance is improved by the heat treatment.

A gas barrier film made of a polymer of an unsaturated carboxylic acid compound polyvalent metal salt containing the modified vinyl alcohol polymer of the present invention, and a gas barrier laminate formed by forming such a gas barrier film have a high humidity and a low humidity. Because of its excellent oxygen permeation resistance (gas barrier properties), it is necessary to take advantage of these characteristics to provide packaging materials for dried foods, water, boiled / retort foods, supplement foods, and especially high gas barrier properties. Packaging materials, packaging materials for toiletries such as shampoos, detergents, bathing agents, fragrances, etc., pharmaceuticals such as powders, granules, tablets, liquid medicines including infusion bags, medical instruments For medical use such as packaging bags and packaging containers, hard disk, wiring board, electronic parts packaging materials such as printed board, liquid crystal display, plasma display Various materials such as inorganic / organic EL displays, barrier materials for flat panel displays such as electronic paper, electronic materials such as barrier members for solar cells, barrier materials for vacuum insulation materials, packaging materials for industrial products such as ink cartridges, etc. It can also be suitably used as a protective material for packaging materials, electronic materials, precision parts, pharmaceuticals, etc., and materials that dislike oxygen gas permeation and moisture.

Claims (26)

  A gas barrier film comprising a polymer (A) of an unsaturated carboxylic acid compound polyvalent metal salt (a) containing a modified vinyl alcohol polymer (B).   The gas barrier film according to claim 1, wherein the content of the modified vinyl alcohol polymer (B) is 50% by weight or less. The ratio of the absorbance A ₀ based on νC═O of the carboxylic acid group near 1700 cm ⁻¹ and the absorbance A based on νC═O of the carboxylate ion near 1520 cm ⁻¹ in the infrared absorption spectrum (A ₀ / The gas barrier film according to claim 1 or 2, wherein A) is less than 0.25.   The modified vinyl alcohol polymer (B) is a (meth) acrylate group modified vinyl alcohol polymer (B1), a thiol group modified vinyl alcohol polymer (B2), a silyl group modified vinyl alcohol polymer (B3), and The gas barrier film according to claim 1 or 2, which is at least one selected from acetoacetyl group-modified vinyl alcohol polymers (B4).   The gas barrier film according to claim 1, wherein the polyvalent metal of the unsaturated carboxylic acid compound polyvalent metal salt (a) is at least one selected from Mg, Ca, Zn, Ba and Al.   The gas barrier film according to claim 1, wherein the unsaturated carboxylic acid compound polyvalent metal salt (a) is a polyvalent metal salt obtained from an unsaturated carboxylic acid compound having a degree of polymerization of less than 20.   The gas barrier film according to claim 1, wherein the unsaturated carboxylic acid compound polyvalent metal salt (a) is a polyvalent metal salt obtained from (meth) acrylic acid.   The gas barrier film according to any one of claims 1 to 7, wherein the gas barrier film is processed by heat treatment or irradiation with ionizing radiation a plurality of times.   A gas barrier laminate in which the gas barrier film according to any one of claims 1 to 8 is formed on at least one surface of the base material layer (C). The gas barrier laminate according to claim 9, wherein the substrate layer (C) is a film substrate (C1).   The gas barrier laminate according to claim 9, wherein the base material layer (C) is a base material layer in which the inorganic compound vapor deposition layer (D) is formed.   The gas barrier laminate according to claim 9, wherein the inorganic compound vapor deposition layer (D) is laminated on at least one of the gas barrier films formed on at least one surface of the base material layer (C).   The gas barrier laminate according to claim 9, wherein the base material layer (C) is a hollow body (C2).   After applying a solution of a polyvalent metal salt of an unsaturated carboxylic acid compound having a polymerization degree of less than 20 containing the modified vinyl alcohol polymer (B) on at least one surface of the substrate or substrate layer (C), A method for producing a gas barrier film or a gas barrier laminate, comprising forming a polymer (A) of a polyvalent metal salt (a) of an unsaturated carboxylic acid compound containing a modified vinyl alcohol polymer (B).   After coating a solution containing a modified vinyl alcohol polymer (B), an unsaturated carboxylic acid compound having a polymerization degree of less than 20 and a polyvalent metal compound on at least one surface of the substrate or the substrate layer (C), the modification A method for producing a gas barrier film or a gas barrier laminate, comprising forming a polymer (A) of a polyvalent metal salt (a) of an unsaturated carboxylic acid compound containing a vinyl alcohol polymer (B).   The method for producing a gas barrier film or gas barrier laminate according to claim 14, wherein the content of the modified vinyl alcohol polymer (B) is 50% by weight or less.   The gas barrier film or gas barrier laminate according to claim 15, wherein the content of the modified vinyl alcohol polymer (B) is 50% by weight or less (the total amount of unsaturated carboxylic acid and polyvalent metal compound is 50% by weight or more). Body manufacturing method.   The modified vinyl alcohol polymer (B) is a (meth) acrylate group modified vinyl alcohol polymer (B1), a thiol group modified vinyl alcohol polymer (B2), a silyl group modified vinyl alcohol polymer (B3), and The method for producing a gas barrier film or gas barrier laminate according to any one of claims 14 to 17, which is at least one selected from acetoacetyl group-modified vinyl alcohol polymers (B4).   The method for producing a gas barrier film or gas barrier laminate according to claim 14 or 15, wherein the unsaturated carboxylic acid compound is an unsaturated carboxylic acid monomer or a polymer having a polymerization degree of 10 or less.   The method for producing a gas barrier film or gas barrier laminate according to any one of claims 14 to 19, wherein the unsaturated carboxylic acid compound is (meth) acrylic acid.   The method for producing a gas barrier film or gas barrier laminate according to claim 14 or 15, wherein the solution is an aqueous solution.   The method for producing a gas barrier film or gas barrier laminate according to claim 14 or 15, wherein the polyvalent metal salt of the unsaturated carboxylic acid compound is polymerized in the presence of moisture.   The method for producing a gas barrier laminate according to claim 14 or 15, wherein the substrate layer (C) is a film substrate (C1).   The method for producing a gas barrier laminate according to claim 14 or 15, wherein the base material layer (C) is a base material layer formed by forming an inorganic compound vapor deposition layer (D).   The method for producing a gas barrier laminate according to claim 14 or 15, wherein the substrate layer (C) is a hollow body (C2). A gas barrier film or a gas barrier laminate obtainable by the production method according to any one of claims 14 to 25.