JP2005307042A - Polymer-containing composition and method for manufacturing the same, and gas barrier material using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polymer-containing composition for constituting a gas barrier material capable of sustaining its remarkable gas barrier property even after heat treatment and a method for manufacturing the same, and to provide a gas barrier material using the same. <P>SOLUTION: The polymer-containing composition comprises the product of hydrolytic condensation of a compound (A) including a metal atom (M) coupled with at least one selected from the group consisting of halogen atoms and alkoxy groups, a vinyl alcohol polymer (B), a carboxylic unit-containing polymer (C1), and a carboxylic unit-containing polymer (C2). The carboxylic unit-containing polymer (C1) contains at least one monomer unit selected from the group consisting of an acrylic acid unit, an acrylate unit, a methacrylic acid unit, and a methacrylate unit, with the content in total accounting for ≥30 mol% of the polymer (C1). The carboxylic acid unit-containing polymer (C2) contains at least one monomer unit selected from the group consisting of a maleic acid unit, maleic acid ester unit and a maleate acid salt unit, with the content in total accounting for ≥30 mol% of the polymer (C2). <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a polymer-containing composition, a method for producing the same, and a gas barrier material using the same.

  Gas barrier properties, particularly oxygen barrier properties are often required for packaging materials for packaging foods and various articles. This is to prevent the influence of the contents being oxidized and deteriorated by oxygen or the like. In particular, when the contents are food, there is a problem that microorganisms propagate due to the presence of oxygen, and the contents decay. For this reason, in the conventional packaging material, the gas barrier layer which prevents permeation | transmission of oxygen etc. is provided.

  As one kind of the gas barrier layer, a metal foil or a metal or metal compound vapor deposition layer is used, and generally an aluminum foil or an aluminum vapor deposition layer is used. However, these metals have the disadvantage that the contents cannot be seen and that they are difficult to dispose of.

  As the gas barrier layer, a vinyl alcohol polymer such as polyvinyl alcohol or an ethylene-vinyl alcohol copolymer may be used. These vinyl alcohol-based polymers have excellent gas barrier properties, are transparent, and have the advantage of being easy to discard, so that their uses are becoming widespread.

  However, since the package for retort food is sterilized with hot water or steam after filling the retort food, the vinyl alcohol polymer absorbs water during sterilization and gas barrier properties are reduced. . Furthermore, the sterilization treatment with hot water or steam deteriorates the mechanical properties of the gas barrier layer, which causes a problem that the packaging package causes delamination or easily breaks.

  In recent years, there has been proposed a method for producing an organic / inorganic composite in which a minute metal oxide is dispersed in a polymer by polycondensation of a metal alkoxide in the presence of the polymer. For example, a method of polycondensing a mixture containing polyvinyl alcohol or ethylene-vinyl alcohol copolymer, a silane coupling agent, and alkoxysilane by a sol-gel method is disclosed (see Patent Documents 1 and 2).

  Also disclosed is a method of hydrolyzing and polycondensing tetraethoxysilane in the presence of a silyl-modified vinyl alcohol polymer (see Patent Document 3).

  Also disclosed is a method of saponifying a copolymer of a polymerizable silane compound (such as vinyltrimethoxysilane) and a vinyl carboxylate compound (such as vinyl acetate) with hydrochloric acid (see Patent Document 4).

Also disclosed is a method of producing a vinyl alcohol polymer composition from a solution containing a metal alkoxide and a vinyl carboxylate polymer, removing the solvent after adding the metal alkoxide to the solution of the composition ( (See Patent Document 5).
Japanese Patent Laid-Open No. 04-345841 Japanese Patent Application Laid-Open No. 08-099390 JP 09-278968 A Japanese Patent Laid-Open No. 10-001515 JP 2002-138109 A

  However, any of the above methods using the sol-gel method has a large variation in gas barrier properties. One reason for this is considered to be large variation in the mixed state of the organic polymer and the metal oxide and poor reproducibility. Furthermore, when these organic / inorganic composites are used as a retort food package, the mechanical properties of the organic / inorganic composite layer are reduced by sterilization with hot water, steam, etc. However, there were problems that caused delamination and made it easier to break the bag.

  Under such circumstances, there is a demand for a gas barrier material that is excellent in gas barrier properties, particularly gas barrier properties after being treated with hot water or steam. Therefore, an object of the present invention is to provide a polymer-containing composition that can constitute such a gas barrier material, a method for producing the same, and a gas barrier sheet using the same.

  The present inventors have intensively studied to achieve the above object, and have completed the present invention. That is, the first polymer-containing composition of the present invention includes a hydrolysis condensate of a compound (A) containing a metal atom (M) to which at least one selected from a halogen atom and an alkoxy group is bonded, and a vinyl alcohol polymer. (B), a carboxylic acid unit-containing polymer (C1) and a carboxylic acid unit-containing polymer (C2), wherein the carboxylic acid unit-containing polymer (C1) is an acrylic acid unit, an acrylate unit, or a methacrylic acid unit. And at least one monomer unit selected from methacrylate units in a proportion of 30 mol% or more in total, and the carboxylic acid unit-containing polymer (C2) comprises a maleic acid unit, a maleic ester unit and a maleic acid At least one monomer unit selected from acid salt units is contained in a proportion of 30 mol% or more in total.

  In addition, the second polymer-containing composition of the present invention comprises a metal oxide containing a metal atom (M), a vinyl alcohol polymer (B), a carboxylic acid unit-containing polymer (C1), and a carboxylic acid unit-containing weight. The carboxylic acid unit-containing polymer (C1) contains a combination (C2), and the polymer (C1) contains at least one monomer unit selected from acrylic acid units, acrylate units, methacrylic acid units, and methacrylate units in total 30 The carboxylic acid unit-containing polymer (C2) is contained in a proportion of not less than mol%, and the polymer (C2) contains at least one monomer unit selected from maleic acid units, maleic acid ester units and maleate units in total 30 mol%. It contains in the above ratio.

  Further, the method of the present invention for producing a polymer-containing composition includes a compound (a1) containing a metal atom (m1) to which at least one selected from a halogen atom and an alkoxy group is bonded, a vinyl carboxylate polymer, In a solution (S) containing a saponification reaction of the vinyl carboxylate polymer and a reaction of the compound (a1) and the vinyl carboxylate polymer, a vinyl alcohol polymer (b At least one selected from a compound (a2) containing a metal atom (m2) to which at least one selected from a halogen atom and an alkoxy group is bonded, and an oligomer derived from the compound (a2) Compound, vinyl alcohol polymer (b), carboxylic acid unit-containing polymer (c1), carboxylic acid unit-containing polymer a second step of preparing a solution (T) containing c2) and a solvent, wherein the carboxylic acid unit-containing polymer (c1) is composed of an acrylic acid unit, an acrylate unit, a methacrylic acid unit and a methacrylate unit. It contains at least one monomer unit selected in a proportion of 30 mol% or more in total, and the carboxylic acid unit-containing polymer (c2) is selected from maleic acid units, maleic acid ester units and maleate units. At least one monomer unit is contained in a proportion of 30 mol% or more in total.

  The polymer-containing composition produced by the above production method constitutes another aspect of the polymer-containing composition of the present invention.

  Moreover, the gas barrier material of this invention contains the part which consists of a polymer containing composition of the said invention.

  According to the present invention, a polymer-containing composition having excellent gas barrier properties, in particular, gas barrier properties and mechanical strength after being treated with hot water or steam can be obtained. The gas barrier material of the present invention including a layer comprising this polymer-containing composition has a high gas barrier property after heat treatment. Therefore, the gas barrier material of the present invention is suitably used as a food packaging material, particularly as a packaging material for retort food that requires sterilization treatment with hot water or steam.

  Hereinafter, embodiments of the present invention will be described. In the following description, specific compounds are exemplified as compounds that exhibit a specific function, but the present invention is not limited to these. Further, the exemplified materials may be used alone or in combination unless otherwise specified. Unless otherwise specified, the “polymer-containing composition” means a solid polymer-containing composition.

(Polymer-containing composition)
Below, the 1st and 2nd polymer containing composition of this invention is demonstrated. The first polymer-containing composition of the present invention comprises a hydrolysis condensate of a compound (A) containing a metal atom (M) to which at least one selected from a halogen atom and an alkoxy group is bonded, a vinyl alcohol polymer (B ), A carboxylic acid unit-containing polymer (C1) and a carboxylic acid unit-containing polymer (C2). The carboxylic acid unit-containing polymer (C1) is a total of at least one monomer unit selected from an acrylic acid unit, an acrylate unit, a methacrylic acid unit, and a methacrylate unit (at least 30 mol% (total monomers)). (In units). The carboxylic acid unit-containing polymer (C2) comprises at least one monomer unit selected from a maleic acid unit, a maleic ester unit and a maleate unit in a total amount of 30 mol% or more (in all monomer units). Contains in proportions.

  The hydrolysis condensate of compound (A) becomes a metal oxide substantially when the condensation polymerization reaction proceeds. In the second polymer-containing composition of the present invention, the hydrolysis condensate is a metal oxide containing a metal atom (M). In that case, “hydrolysis condensate of compound (A)” can be read as “metal oxide” in the following description.

  Compound (A) may be a single compound or may include a plurality of types of compounds. The metal atom (M) contained in the compound (A) is a divalent or higher, more preferably a trivalent or tetravalent metal atom. For example, at least one selected from the group consisting of silicon, titanium, aluminum and zirconium It is a metal atom. Silicon may be classified as a similar metal element, but in this specification, it will be described as a metal element. The number of metal atoms (M) contained in one molecule of the compound (A) as a starting material is usually one, but may be plural.

  Of the compound (A) containing a metal atom (M) to which at least one selected from a halogen atom and an alkoxy group is bonded, the compound containing a metal atom (M) to which an alkoxy group is bonded is a metal other than silicon alkoxide and silicon alkoxide. It is at least one compound selected from alkoxides and oligomers derived from silicon alkoxides and / or metal alkoxides other than silicon alkoxides. A representative example of such a compound is silicon alkoxide. When the compound (A) used in the present invention contains silicon alkoxide, a composition having a high gas barrier property under high humidity can be obtained.

  The silicon alkoxide is preferably a silicon alkoxide containing one silicon atom and 2, 3 or 4 alkoxy groups bonded thereto. Here, the number of alkoxy groups bonded to the silicon atom is more preferably 3 or 4, and particularly preferably 4. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, and a butoxy group. In addition, when the number of alkoxy groups bonded to the silicon atom is 2 or 3, the silicon atom further includes an alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, or a butyl group; a phenyl group, a naphthyl group An aryl group such as, for example, an atomic group such as a halogen atom such as a chlorine atom or a fluorine atom is bonded. Specific examples of the silicon alkoxide include, for example, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, octyltrimethoxysilane, phenyltrimethoxysilane, and chlorotrimethoxysilane, preferably tetramethoxysilane. Silane or tetraethoxysilane.

  Examples of metal alkoxides other than silicon alkoxide include metal alkoxides containing one polyvalent metal atom (preferably trivalent or tetravalent) such as titanium, aluminum, and zirconium, and one or more alkoxy groups bonded thereto. preferable. The number of alkoxy groups bonded to the polyvalent metal atom is preferably 2 or more, more preferably 3 or more. Specific examples of the alkoxy group bonded to the polyvalent metal atom and the substituent other than the alkoxy group include the same atomic groups as those exemplified for the silicon alkoxide. Examples of the metal alkoxide include alkoxytitanium compounds such as tetramethoxytitanium, tetraethoxytitanium, tetraisopropoxytitanium, and methyltriisopropoxytitanium; trimethoxyaluminum, triethoxyaluminum, triisopropoxyaluminum, methyldiisopropoxyaluminum, Examples include alkoxyaluminum compounds such as tributoxyaluminum and diethoxyaluminum chloride; alkoxyzirconium compounds such as tetraethoxyzirconium, tetraisopropoxyzirconium and methyltriisopropoxyzirconium.

  Of the compounds (A) containing a metal atom (M) to which at least one selected from a halogen atom and an alkoxy group is bonded, the compound containing a metal atom (M) to which a halogen atom is bonded is a metal halide or an oligomer thereof. . Examples of the metal halide include those obtained by replacing the alkoxy group of the above-described silicon alkoxide or metal alkoxide with a halogen atom. Examples of the halogen atom include a chlorine atom and a bromine atom. Typical examples of the compound containing a halogen atom include chlorotrimethoxysilane, chlorotriethoxysilane, dichlorodimethoxysilane, dichlorodiethoxysilane, bromotrimethoxysilane, and bromotriethoxysilane.

  The vinyl alcohol polymer (B) contained in the composition of the present invention is a polymer obtained by saponifying a vinyl carboxylate polymer (vinyl ester polymer). The polymer-containing composition of the present invention is preferably produced by the production method of the present invention. At this time, the vinyl alcohol polymer (b) used in the production method of the present invention contains a group derived from the compound (a1) containing a metal atom to which at least one selected from a halogen atom and an alkoxy group is bonded. preferable. The compound (a1) undergoes an exchange reaction with the ester group contained in the vinyl carboxylate polymer and is bonded to the polymer. In that case, the vinyl alcohol polymer (B) includes a group derived from the compound (a1) including a metal atom to which at least one selected from a halogen atom and an alkoxy group is bonded. The compound described for the compound (A) can be applied to the compound (a1), but the compound (A) and the compound (a1) may be the same or different.

  The vinyl carboxylate polymer is a polymer having a vinyl carboxylate unit (vinyl ester unit), and is a polymer of vinyl carboxylate alone and / or a copolymer of vinyl carboxylate and other monomers. It is. The vinyl carboxylate unit is saponified and converted into a vinyl alcohol unit, but the conversion rate (saponification degree) is preferably 80 mol% or more. When the saponification degree is less than 80 mol%, the gas barrier property of the polymer-containing composition may be lowered. In order to obtain a high gas barrier property, the saponification degree of the vinyl alcohol polymer is preferably 90 mol% or more, and more preferably 95 mol% or more. Some of the vinyl carboxylate units may not be saponified, in which case the vinyl carboxylate units remain. Examples of the vinyl carboxylate to be polymerized include vinyl acetate, vinyl propionate, vinyl 2-methylpropionate and the like, preferably vinyl acetate.

  Other monomers copolymerizable with vinyl carboxylate include α-olefins such as ethylene, propylene and 1-butene; vinyl ethers such as methyl vinyl ether, ethyl vinyl ether and t-butyl vinyl ether; allyl alcohol; vinyl trimethylsilane. Among them, ethylene is preferable. The proportion of monomer units other than vinyl carboxylate units contained in the vinyl carboxylate polymer is preferably 40 mol% or less, more preferably 30 mol% or less, and even more preferably 20 mol% or less. As the vinyl alcohol polymer, polyvinyl alcohol, polyvinyl alcohol partial saponified product, ethylene-vinyl alcohol copolymer, or ethylene-vinyl alcohol copolymer partial saponified product having crystallinity is preferable. Used. When copolymerizing ethylene, considering the oxygen barrier property after retorting and the oxygen barrier property under high humidity, the preferred copolymerization ratio of ethylene is preferably 1 to 20 mol%, and 2 to 18 mol%. More preferably, 3-15 mol% is further more preferable.

  The carboxylic acid unit-containing polymer (C1) is a total of at least one monomer unit selected from an acrylic acid unit, an acrylate unit, a methacrylic acid unit, and a methacrylate unit, in a proportion of 30 mol% or more (total In monomer units). That is, the carboxylic acid unit-containing polymer (C1) is a polymer in which at least one monomer selected from acrylic acid, acrylate, methacrylic acid and methacrylate is copolymerized at a ratio of 30 mol% or more. is there.

  When the ratio of the monomer unit contained in the carboxylic acid unit-containing polymer (C1) is less than 30 mol%, the gas barrier property of the polymer-containing composition is inferior, and sterilized with hot water, steam, or the like. Gas barrier properties and mechanical properties after treatment (hereinafter sometimes referred to as retort treatment) are poor. The content of the monomer units contained in the carboxylic acid unit-containing polymer (C1) is preferably 50 mol% or more, and more preferably 70 mol% or more.

  As the carboxylic acid unit-containing polymer (C1), polyacrylic acid, polymethacrylic acid, or a copolymer of acrylic acid and methacrylic acid, and a part of the carboxyl groups in these polymers are salts. A polymer etc. can be used. In addition, a copolymer of acrylic acid and / or methacrylic acid and one or more vinyl compounds, and a polymer in which a part of the carboxyl groups in these polymers is a salt can also be used. Examples of vinyl compounds to be copolymerized include (meth) acrylic acid esters such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, and butyl methacrylate; vinyl formate and vinyl acetate One or more vinyl compounds selected from olefins such as styrene, p-styrene sulfonic acid, propylene, and isobutylene can be used. Among these, it is preferable to use at least one selected from polyacrylic acid and a partially neutralized product of polyacrylic acid as the carboxylic acid unit-containing polymer (C1).

  In addition, the carboxylic acid unit-containing polymer (C2) is a total of at least one monomer unit selected from a maleic acid unit, a maleic acid ester unit, and a maleate unit, and a ratio of 30 mol% or more (total single amount). In body units). That is, the carboxylic acid unit-containing polymer (C2) is a polymer in which at least one monomer selected from maleic acid, maleic acid ester and maleate is copolymerized in a proportion of 30 mol% or more in total. . Maleic anhydride may be copolymerized instead of maleic acid. In this case, maleic anhydride becomes maleic acid in the process of forming the composition. Accordingly, in this specification, maleic anhydride units are described as being included in maleic acid units and maleate units.

  When the proportion of the monomer units contained in the carboxylic acid unit-containing polymer (C2) is less than 30 mol%, the gas barrier property of the polymer-containing composition is inferior and is sterilized with hot water, steam, or the like. Gas barrier properties and mechanical properties after treatment (hereinafter sometimes referred to as retort treatment) are poor. The content of the monomer units contained in the carboxylic acid unit-containing polymer (C2) is preferably 50 mol% or more, and more preferably 70 mol% or more.

  As the carboxylic acid unit-containing polymer (C2), maleic acid and / or a copolymer of maleic acid ester and one or more vinyl compounds, and a part of the carboxyl groups in these polymers are converted into salts. Can be used. Examples of the vinyl compound to be copolymerized include olefins such as ethylene, propylene, isobutylene, styrene, and p-styrenesulfonic acid; methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate And (meth) acrylic acid esters such as butyl methacrylate; vinyl esters such as vinyl formate and vinyl acetate. Among these, as the carboxylic acid unit-containing polymer (C2), it is preferable to use at least one selected from an isobutylene-maleic acid copolymer and a partially neutralized product of an isobutylene-maleic acid copolymer.

  In the composition of the present invention, the content of the metal oxide (or hydrolysis condensate of compound (A)) at the time of drying, that is, the content in the components other than the solvent is in the range of 10 to 65% by weight. It is preferable. When the content is less than 10% by weight, the gas barrier property of the polymer-containing composition, particularly the oxygen barrier property in a high humidity atmosphere may be deteriorated. Further, when the content exceeds 65% by weight, the gas barrier property of the polymer-containing composition is lowered, and the mechanical properties may be lowered. The content is more preferably in the range of 20 to 55% by weight, still more preferably in the range of 25 to 45% by weight.

  In the present invention, the content of the metal oxide (or hydrolysis condensate of compound (A)) in the composition is obtained after the organic components of the composition are thermally decomposed and removed, as shown in Examples described later. It is determined from the weight of the metal oxide obtained and the weight of the composition before pyrolysis.

  In the composition of the present invention, the total content of the vinyl alcohol polymer (B), the carboxylic acid unit-containing polymers (C1) and (C2) at the time of drying is in the range of 45 wt% to 80 wt%. It is preferable that it is in the range of 55% by weight to 75% by weight.

  In the composition of the present invention, the weight ratio of [carboxylic acid unit-containing polymer (C1)] / [carboxylic acid unit-containing polymer (C2)] is preferably in the range of 99/1 to 10/90. A polymer-containing composition having a weight ratio in this range is excellent in gas barrier properties, and particularly excellent in gas barrier properties and mechanical properties after retorting. The weight ratio of [carboxylic acid unit-containing polymer (C1)] / [carboxylic acid unit-containing polymer (C2)] is more preferably in the range of 95/5 to 20/80, and still more preferably 90/10 to 10/10. The range is 30/70.

  In the composition of the present invention, the weight ratio of [vinyl alcohol polymer (B)] / [total of carboxylic acid unit-containing polymers (C1) and (C2)] is 99.5 / 0.5 to 70 / A range of 30 is preferred. In order to suppress a decrease in gas barrier properties and mechanical properties caused by retort treatment, it is important that the polymer-containing composition contains carboxylic acid unit-containing polymers (C1) and (C2). When the said weight ratio becomes higher than 99.5 / 0.5, the mechanical physical property of a polymer containing composition may fall by retort processing. Moreover, when the said weight ratio becomes lower than 70/30, the gas-barrier property of a polymer containing composition may deteriorate before and after a retort process. The weight ratio is preferably in the range of 99/1 to 80/20, more preferably in the range of 98/2 to 90/10.

  Furthermore, the present inventors have found that the carboxylic acid unit-containing polymer (C1) is at least one selected from polyacrylic acid and a partially neutralized product of polyacrylic acid, and the carboxylic acid unit-containing polymer (C2). Has been found to be preferably at least one selected from isobutylene-maleic acid copolymers and partially neutralized products of isobutylene-maleic acid copolymers. According to this combination, the gas barrier properties and mechanical properties of the polymer-containing composition are particularly excellent after retorting. When this combination is used, the weight ratio of [carboxylic acid unit-containing polymer (C1)] / [carboxylic acid unit-containing polymer (C2)] is preferably in the range of 90/10 to 30/70. When it exists in this range, the balance of the gas barrier property of a polymer containing composition and the gas barrier property after a retort process is excellent. For the same reason, when the above combination is used, the weight ratio of [vinyl alcohol polymer (B)] / [total of carboxylic acid unit-containing polymers (C1) and (C2)] is 98/2 to It is preferable to be in the range of 90/10.

  The polymer-containing composition of the present invention may be a liquid obtained by dispersing the above-described polymer-containing composition in a solvent such as an organic solvent. Such a composition can be used as a coating agent (coating composition) or a raw material for a film. The amount of solvent is determined depending on the use of the composition. As the solvent, the solvents exemplified below in the description of the method for producing the polymer-containing composition can be used.

(Method for producing polymer-containing composition)
Below, the method of this invention for manufacturing a polymer containing composition is demonstrated. In addition, description may be abbreviate | omitted about the part which overlaps with the description mentioned above. According to this production method, the polymer-containing composition of the present invention described above can be easily produced. The polymer-containing composition produced by this production method constitutes another aspect of the polymer-containing composition of the present invention.

  In the production method of the present invention, in the solution (S) containing a compound (a1) containing a metal atom (m1) to which at least one selected from a halogen atom and an alkoxy group is bonded, and a vinyl carboxylate polymer, A vinyl alcohol polymer (b) is produced by performing a saponification reaction of an acid vinyl polymer and a reaction between the compound (a1) and the vinyl carboxylate polymer (first step). Thereafter, at least one compound selected from a compound (a2) containing a metal atom (m2) to which at least one selected from a halogen atom and an alkoxy group is bonded, and an oligomer derived from the compound (a2), a vinyl alcohol polymer A solution (T) containing (b), a carboxylic acid unit-containing polymer (c1), a carboxylic acid unit-containing polymer (c2), and a solvent is prepared (second step). The carboxylic acid unit-containing polymer (c1) contains at least one monomer unit selected from an acrylic acid unit, an acrylate unit, a methacrylic acid unit, and a methacrylate unit in a proportion of 30 mol% or more in total. . The carboxylic acid unit-containing polymer (c2) contains at least one monomer unit selected from maleic acid units and maleate units in a proportion of 30 mol% or more in total.

  The weight ratio of [vinyl alcohol polymer (b)] / [total of carboxylic acid unit-containing polymers (c1) and (c2)] in the solution (T) is 99.5 / 0.5 to 70/30. A range is preferable. As described above, the weight ratio of [carboxylic acid unit-containing polymer (c1)] / [carboxylic acid unit-containing polymer (c2)] is preferably in the range of 99/1 to 10/90.

  For the metal atoms (m1) and (m2), the metal atom described for the metal atom (M) can be applied independently, and for example, at least one selected from silicon, titanium, aluminum and zirconium.

  As the compounds (a1) and (a2), one kind or two or more kinds of compounds exemplified for the compound (A) can be applied independently. In addition, one type or two or more types of polymers exemplified for the vinyl carboxylate polymer described above can be applied to the vinyl carboxylate polymer. Compound (a1) and / or compound (a2) becomes compound (A). The number of metal atoms (m1) contained in one molecule of the compound (a1) as a starting material is usually one, but may be plural. The compound (a1) and the compound (a2) may be the same as or different from each other. When the compound (a1) contains silicon alkoxide, a solution (S) and a solution (T) with high storage properties are obtained, and a composition with high gas barrier properties under high humidity is obtained.

  The oligomer derived from the compound (a2) may be a hydrolysis condensate of the compound (a2). Hydrolytic condensation can be performed by a known method. For example, it can be obtained by hydrolysis / condensation of a metal alkoxide or metal halide by a known method such as a method used in a sol-gel method.

  Specific examples of oligomers derived from silicon alkoxide include tetramethoxysilane dimer or trimer oligomer, tetraethoxysilane dimer or trimer oligomer, oligodimethylsiloxane, and the like. . Among these, tetramethoxysilane dimer or oligomer of trimer or higher, tetraethoxysilane dimer or oligomer of trimer or higher are preferably used. The degree of polymerization is not necessarily limited, but is preferably in the range of 2 to 25, and more preferably in the range of 2 to 10.

  An oligomer derived from an alkoxide containing a metal alkoxide other than silicon alkoxide is obtained by hydrolyzing and condensing one or more metal alkoxides (including at least a metal alkoxide other than silicon alkoxide) according to a known method. . Preferable specific examples include, for example, tetraisopropoxytitanium dimer or oligomer of trimer or higher. The degree of polymerization is not necessarily limited, but is preferably in the range of 2 to 25, and more preferably in the range of 2 to 10.

  Furthermore, when the metal atom (m1) contained in the compound (a1) is different from the metal atom (m2) contained in the compound (a2) and the oligomer derived therefrom, the molar ratio thereof, [metal atom (m1) ) / Metal atom (m2)] is preferably in the range of 0.01 to 18000. By setting the molar ratio within this range, the mixed state of the organic component (vinyl alcohol polymer (b) and carboxylic acid unit-containing polymers (c1) and (c2)) and the metal oxide is made better. A composition having particularly good gas barrier properties can be obtained before and after the retort treatment. The molar ratio is more preferably in the range of 0.1 to 5000, further preferably in the range of 1 to 1000, and particularly preferably in the range of 1 to 500.

  In the first step of the present invention, a vinyl alcohol polymer is obtained by performing a saponification reaction of the vinyl carboxylate polymer and a reaction of the compound (a1) and the vinyl carboxylate polymer in the solution (S). (B) is obtained.

  The saponification reaction of a vinyl carboxylate polymer is a reaction that forms a vinyl alcohol polymer. In this reaction, the acyloxy group derived from the vinyl carboxylate unit in the vinyl carboxylate polymer is converted to a hydroxyl group, and at the same time, it varies depending on the carboxylate compound (the organic solvent used, the type of catalyst, etc.). Usually, one or more compounds selected from carboxylic acids, carboxylic acid esters and carboxylates are by-produced.

  On the other hand, the reaction between the compound (a1) and the vinyl carboxylate polymer is a reaction in which the functional group contained in the compound (a1) is dehydrated and condensed. In the first step, a reaction in which the compounds (a1) are usually dehydrated and condensed also occurs.

  By allowing the vinyl carboxylate polymer saponification reaction and the reaction of the compound (a1) and the vinyl carboxylate polymer to proceed in parallel in the same system, the gas barrier property under high humidity is good. A coalescence-containing composition can be obtained.

  In the first step, the metal atom (m1) in the compound (a1) is in the range of 0.01 to 75 mol per 100 mol of the acyl group derived from the vinyl carboxylate unit in the vinyl carboxylate polymer before saponification. It is preferred to use such an amount of compound (a1). When the said ratio is 0.01 mol or more, the gas barrier property under the high humidity of the polymer containing composition obtained becomes favorable. Moreover, when the said ratio is 75 mol or less, the polymer containing composition obtained has a small performance spot (gap in the gas barrier performance accompanying storage of a solution (T)). In this case, the gas barrier property can be maintained at a high level even after being exposed to bending conditions. In consideration of gas barrier properties under high humidity, performance irregularities, and gas barrier properties after being exposed to bending conditions, with respect to 100 mol of acyl groups derived from vinyl carboxylate units in the vinyl carboxylate polymer before saponification The amount of the compound in which the metal atom (m1) in the compound (a1) is in the range of 0.01 to 50 mol (more preferably 0.1 to 20 mol, particularly preferably 0.1 to 10 mol). It is preferable to use (a1).

  In the first step, a known catalyst used in a general saponification reaction can be used. Examples of the catalyst include acidic catalysts such as hydrochloric acid, sulfuric acid, p-toluenesulfonic acid, benzoic acid, acetic acid, lactic acid, carbonic acid, oxalic acid and maleic acid; alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; water Basic catalysts such as alkaline earth metal hydroxides such as magnesium oxide and calcium hydroxide; amine compounds such as ammonia, triethylamine and ethylenediamine can be used. These can be used alone or in combination of two or more.

  In order to obtain a solution (T) having high coating suitability (viscosity and appearance of the coating film) and to obtain a polymer-containing composition having high gas barrier performance, a basic catalyst is generally used in the first step. Among these, it is more preferable to use one or more compounds selected from alkali metal hydroxides and alkaline earth metal hydroxides. Specifically, one or more compounds selected from sodium hydroxide, potassium hydroxide, calcium hydroxide, and magnesium hydroxide are preferably used as the catalyst. The amount of the catalyst used is not necessarily strictly limited, but the number of moles of halogen atoms and alkoxy groups in the compound (a1) used and the number of acyl groups derived from the vinyl carboxylate unit in the vinyl carboxylate polymer used. It is preferably in the range of 0.001 to 0.1 mol, more preferably in the range of 0.01 to 0.08 mol, per mol of the sum with the number (total number of moles).

  When an alkali metal compound (for example, alkali metal hydroxide) and / or an alkaline earth metal compound (for example, alkaline earth metal hydroxide) is used as a catalyst, the vinyl alcohol polymer (b) obtained in the first step is It may contain a carboxylate that is a by-product. The carboxylate is, for example, an alkali metal salt and / or an alkaline earth metal salt of a carboxylic acid represented by sodium acetate, potassium acetate, sodium propionate, and potassium propionate. Considering the storage stability of the solution (S) and the solution (T) and the gas barrier property of the polymer-containing composition, the amount of the carboxylate is 5 with respect to the dry weight of the vinyl alcohol polymer (b). It is preferably no more than wt%, more preferably no more than 2 wt%, and even more preferably no more than 1 wt%. The vinyl alcohol polymer (b) can be dried by a known method for drying the vinyl alcohol polymer. Drying may be performed at room temperature or under heating, and may be performed under normal pressure or under reduced pressure.

  The content of the carboxylate can be adjusted, for example, by the amount of the catalyst used in the first step or by washing the vinyl alcohol polymer (b). The vinyl alcohol polymer (b) can be washed by a known method using, for example, alcohol or a mixed solvent of alcohol and water.

  In the first step, it is possible to obtain a polymer-containing composition having good gas barrier properties, solution solubility, and solution stability by managing the amount of water contained in the solution (S). The amount of water contained in the solution (S) is not necessarily limited, but is preferably in the range of 300 to 200,000 ppm (weight ratio) with respect to the solution (S), and in the range of 2000 to 100,000 ppm. Is more preferable, it is more preferable to be in the range of 3000 to 80000 ppm, and it is particularly preferable to be in the range of 3000 to 60000 ppm.

  As the solution (S), a solution (sol) obtained by dissolving a vinyl carboxylate polymer and the compound (a1) in a solvent can be used. The solvent to be used is not particularly limited as long as it can sufficiently dissolve both the vinyl carboxylate polymer and the compound (a1), but an organic solvent is preferably used. Examples of the organic solvent include solvents such as alcohols such as methanol, ethanol, propanol, and butanol; amides such as dimethylformamide and dimethylacetamide; and sulfoxides such as dimethyl sulfoxide. be able to. Among these, methanol, ethanol, dimethyl sulfoxide and the like are particularly preferable. The amount of the organic solvent used is not necessarily limited, but is preferably in the range of 20 to 2000 parts by weight with respect to 100 parts by weight of the total weight of the vinyl carboxylate polymer and the compound (a1), and is 100 to 1000 parts by weight. More preferably, it is in the range of parts. In order to reduce the residual ratio of acyl groups (acyl groups derived from vinyl carboxylate units) in the vinyl alcohol polymer (b), 5% by weight of an organic solvent having an affinity for the vinyl alcohol polymer (b) is used. It is preferable to use a uniform organic solvent contained in the above proportion.

  In the first step, the temperature of the reaction system is not necessarily limited, but is usually in the range of 20 to 100 ° C, preferably in the range of 30 to 60 ° C. The reaction time varies depending on the reaction conditions such as the amount and type of the catalyst, but is usually in the range of 0.01 to 10 hours, preferably in the range of 0.01 to 5 hours, and more preferably 0.8. The range is 02 to 3 hours. The atmosphere of the reaction system is not necessarily limited, and for example, an atmosphere such as an air atmosphere or a nitrogen stream can be employed.

  After the first step, at least one compound selected from the compound (a2) and an oligomer derived from the compound (a2), the vinyl alcohol polymer (b) obtained in the first step, the carboxylic acid unit-containing weight A solution (T) containing the union (c1), the carboxylic acid unit-containing polymer (c2) and the solvent is prepared (second step). Hereinafter, the oligomer derived from the compound (a2) and the compound (a2) may be collectively referred to as a component (a2).

  The second step includes, for example, a step of preparing a solution (t) containing a vinyl alcohol polymer (b), a carboxylic acid unit-containing polymer (c1), and a carboxylic acid unit-containing polymer (c2), and the solution A step of preparing the solution (T) by adding the above-mentioned at least one compound (compound (a2) component) to (t) may be included. The component (a2) may be added alone or in the form of a solution containing it.

  The solution (t) can be prepared, for example, by the following method. First, the solvent is removed from the reaction solution after completion of the reaction in the first step to obtain a solid content. The solid content is washed and dried by a known method using a solvent, if necessary. As the solvent, an alcohol solvent, a mixed solvent of alcohol and water, or the like can be used. Thereafter, the washed solid and the carboxylic acid unit-containing polymer are dissolved in a solvent. As the solvent, for example, water or a mixed solvent of water and alcohol can be used. Examples of the alcohol used for the mixed solvent include methanol, ethanol, 1-propanol, 2-propanol, and ethylene glycol. A solution (t) is thus obtained.

  The solution (T) may contain only an oligomer derived from the compound (a2) as the component (a2). According to this configuration, a composition having a high gas barrier property can be obtained. The oligomer of the compound (a2) is an oligomer obtained by hydrolysis and condensation of the compound (a2) in a reaction system (R) containing the compound (a2), an acid catalyst, water, and if necessary, an organic solvent. It is preferable.

  Hereinafter, a method for producing an oligomer from the compound (a2) will be described. This method can be similarly applied to the method for producing the compound (a1) when the compound (a1) is an oligomer derived from a metal alkoxide or a metal halide.

  As the acid catalyst used for the production of the oligomer, a known acid catalyst can be used, for example, hydrochloric acid, sulfuric acid, nitric acid, p-toluenesulfonic acid, benzoic acid, acetic acid, lactic acid, butyric acid, carbonic acid, oxalic acid, maleic acid, etc. Can be used. Of these, hydrochloric acid, sulfuric acid, nitric acid, acetic acid, lactic acid and butyric acid are particularly preferred. Although the preferable addition amount of an acid catalyst changes with kinds of catalyst to be used, it is preferable that it is the range of 0.00001-10 mol per 1 mol of metal atoms (m2) contained in a compound (a2) component. The range of 0001 to 5 mol is more preferable, and the range of 0.0005 to 1 mol is more preferable. When the catalyst addition amount is within this range, the gas barrier properties of the polymer-containing composition, and the stability of the solution (t) and the solution (T) are particularly excellent.

  Moreover, although the quantity of the water added to reaction system (R) changes with kinds of compound (a2) component, it is 0.1-10 mol per 1 mol of metal atoms (m2) contained in a compound (a2) component. It is preferable that it is the range of 1-4, It is more preferable that it is the range of 1-4 mol, It is more preferable that it is the range of 1.5-3 mol. When the amount of water added is in this range, the gas barrier properties of the polymer-containing composition and the stability of the solution (t) and the solution (T) are particularly excellent. When a component containing water (for example, hydrochloric acid) is used, the amount of water used is determined in consideration of the amount of water introduced by the component.

  An organic solvent may be added to the reaction system (R) as necessary. The organic solvent to be added is not particularly limited as long as the compound (a2) component can be dissolved, but alcohols such as methanol, ethanol, isopropanol, and propanol are preferably used, and the alkoxy contained in the compound (a2) component. Alcohols having the same type of alkoxy component as the group are more preferably used. Specifically, methanol is preferred for tetramethoxysilane and ethanol is preferred for tetraethoxysilane. The amount of the organic solvent used is not particularly limited, but the concentration of the component (a2) component is in the range of 1 to 90% by weight (more preferably 10 to 80% by weight, still more preferably 20 to 70% by weight). It is preferable that the amount is small.

  The temperature of the reaction system (R) when producing the oligomer of the compound (a2) is not necessarily limited, but is usually in the range of 0 to 100 ° C, preferably in the range of 5 to 60 ° C, and more preferably 10 It is the range of -50 degreeC. The reaction time varies depending on the reaction conditions such as the amount and type of the catalyst, but is usually in the range of 0.01 to 60 hours, preferably in the range of 0.1 to 12 hours, more preferably 0.1. It is in the range of ~ 6 hours. Moreover, the atmosphere of reaction system (R) is not necessarily limited, For example, atmospheres, such as under air atmosphere and nitrogen stream, are employable.

  As the solution (T), for example, a solution containing the vinyl alcohol polymer (b), the carboxylic acid unit-containing polymers (c1) and (c2), and the reaction system (R) in which the reaction has ended are mixed. Can be prepared. The solvent contained in the solution (T) is, for example, the solvent of the solution (t) described above or the solvent of the reaction system (R).

  In the production method of the present invention, when preparing the solution (S) by adding the compound (a1) to a solvent, and when preparing the solution (T) by adding the component (a2) to the solvent, The total amount to be added may be added at once, or the total amount to be added may be added in multiple portions.

  In order to produce a polymer-containing composition having better gas barrier performance, the pH of the solution (T) is preferably in the range of 1.0 to 8.0, and in the range of 1.0 to 6.0. More preferably, it is more preferably in the range of 1.5 to 4.0.

  A known method can be used to adjust the pH of the solution (T). For example, the pH can be adjusted by adding acidic compounds such as hydrochloric acid, nitric acid, acetic acid, butyric acid, ammonium sulfate, and basic compounds such as sodium hydroxide, potassium hydroxide, ammonia, trimethylamine, sodium carbonate, sodium acetate. .

  The production method of the present invention may include a step of removing the solvent from the solution (T). By removing the solvent, a solid polymer-containing composition is obtained. In the process of removing the solvent, the reaction proceeds in the components contained in the solution (T). For example, a reaction such as a hydrolysis reaction or a condensation reaction proceeds within and / or between the components of the vinyl alcohol polymer (b), the carboxylic acid unit-containing polymer, and the compound (a2). When the hydrolysis condensation reaction of the component (a2) proceeds, a metal oxide is formed. In addition, it can also use as a coating agent or a film raw material, without removing a solvent.

  A method for removing the solvent is not particularly limited, but a method of removing the solvent by heating with hot air or the like is preferably applied. The heating temperature is usually preferably in the range of 30 to 200 ° C, more preferably in the range of 50 to 150 ° C. The drying time is usually preferably in the range of 0.001 to 60 hours, more preferably in the range of 0.002 to 10 hours, and further preferably in the range of 0.002 to 1 hour. Moreover, there is no limitation in particular in the atmosphere at the time of removing a solvent, For example, atmosphere, such as under an air atmosphere or nitrogen stream, is employable.

  You may heat-process a polymer containing composition. The heat treatment may be performed at any time after the solvent removal from the solution (T) is almost completed. The heat treatment temperature is preferably in the range of 50 to 250 ° C, more preferably in the range of 60 to 230 ° C.

  Further, the polymer-containing composition may be subjected to ultraviolet irradiation or electron beam irradiation. Ultraviolet irradiation and electron beam irradiation may be performed anytime after the solvent removal from the solution (T) is almost completed. The method is not particularly limited, and a known method can be applied.

  Heat treatment, ultraviolet irradiation, and electron beam irradiation may be performed individually or in combination. By applying at least one of heat treatment, ultraviolet irradiation, and electron beam irradiation, the gas barrier performance of the polymer-containing composition and the gas barrier sheet using the same and the mechanical properties after retorting are improved.

(Gas barrier material)
The gas barrier material of the present invention includes a portion comprising the polymer-containing composition of the present invention. A typical example of the gas barrier material is a gas barrier sheet, and the portion is a layer made of the polymer-containing composition of the present invention. In this specification, “sheet” includes a thin sheet (film) in addition to a plate-like sheet. The gas barrier sheet may be formed of only a layer made of the polymer-containing composition of the present invention, or may contain other layers. The polymer-containing composition of the present invention can be processed into a sheet by a known method. Furthermore, the laminated body which has various characteristics is obtained by laminating | stacking the layer (sheet) which consists of a polymer containing composition of this invention, and the layer (sheet) which consists of another material. Examples of the layer (sheet) made of other materials include polyolefins such as polyethylene (hereinafter sometimes abbreviated as “PE”) and polypropylene (hereinafter sometimes abbreviated as “PP”); polyethylene terephthalate ( Hereinafter, polyesters such as “PET”, polybutylene terephthalate (hereinafter sometimes abbreviated as “PBT”), polyethylene naphthalate (hereinafter sometimes abbreviated as “PEN”), and the like; Polyamide such as nylon 6 (hereinafter sometimes abbreviated as “Ny6”), nylon 66 (hereinafter sometimes abbreviated as “Ny66”); polyvinyl chloride; polymer such as polyurethane; paper; metal oxide A sheet made of metal or the like. The lamination method may be dry lamination or wet lamination, and is selected according to the material.

  The solution (T) can be used as a coating agent. For example, after impregnating a substrate made of a fiber assembly such as fabric, paper, wood, etc. with the solution (T), the solvent is removed from the solution (T) to advance the reaction, whereby the fiber assembly (substrate ) In the form of a polymer-containing composition filled in the gap. This composite has gas barrier properties.

  Moreover, the coating film which consists of a polymer containing composition can be formed by advancing reaction, after coating a solution (T) on a predetermined base material. A sheet-like base material or a molded product can be applied to the base material. By using a sheet-like base material, a laminate including a layer made of the polymer-containing composition of the present invention is obtained. Examples of the base material include polyolefins such as PE and PP; polyesters such as PET, PBT and PEN; polyamides such as Ny6 and Ny66; polymers such as polyvinyl chloride and polyurethane; and paper; metal oxides; metals Etc.

  The laminate preferably includes at least one layer selected from a polyester layer, a polyamide layer, and a polyolefin layer. For example, when the polymer-containing composition of the present invention is expressed as “polymer-containing composition”, polyester / polymer-containing composition, polyamide / polymer-containing composition of the present invention, and polyolefin / polymer-containing composition. A laminate including one or more layer configurations selected from layer configurations such as a product is preferable. Furthermore, a laminate including a layer structure of polyester / polymer-containing composition / polyamide or polyamide / polymer-containing composition is more preferable.

  Specific examples of the structure of the laminate including the above layer structure include polyester / polymer-containing composition / polyolefin, polyamide / polymer-containing composition / polyolefin, polyolefin / polymer-containing composition / polyolefin, polyester / heavy Composition-containing composition / polyamide / polyolefin, polyester / polymer-containing composition / polyester / polyolefin, polyamide / polymer-containing composition / polyester / polyolefin, polymer-containing composition / polyester / polyamide / polyolefin, polyolefin / paper / polyolefin / Polymer-containing composition / polyolefin, polymer-containing composition / polyvinyl chloride / paper, and the like. Among them, polyester / polymer-containing composition / polyolefin, polyamide / polymer-containing composition / polyolefin, polyester / polymer-containing composition / polyamide / polyolefin, polyester / polymer-containing composition / polyester / polyolefin, polyamide / heavy Polymer-containing composition / polyester / polyolefin is preferred, and a layer structure of polyamide / polymer-containing composition / polyolefin, polyester / polymer-containing composition / polyamide / polyolefin, polyamide / polymer-containing composition / polyester / polyolefin is more preferred. . Further, from the viewpoint of the mechanical properties of the obtained laminate, it is preferable to use PET as the polyester, and Ny6 as the polyamide.

  As a method for forming a film made of the solution (T) on the substrate, a known method such as a casting method, a dipping method, a roll coating method, a spray method, or a screen printing method can be employed. According to this method, a laminate of metal or metal oxide can also be obtained. Furthermore, you may use the well-known undercoating agent or adhesive agent generally used according to the kind of base material when laminating | stacking each layer.

  The polymer-containing composition obtained by the production method of the present invention has an excellent barrier property against gases such as oxygen, water vapor, carbon dioxide gas, and nitrogen, and the excellent barrier property even under high humidity conditions. Even after bending, it can be kept highly. Furthermore, this composition exhibits excellent gas barrier properties even after being subjected to heat treatment with hot water or steam. Thus, the polymer-containing composition of the present invention has a good gas barrier property that is not affected by environmental conditions such as humidity, maintains a good gas barrier property even after being exposed to bending conditions, and is sterilized by heating. Is also possible. For this reason, the polymer-containing composition of the present invention is suitable for packaging materials such as foods, and is particularly suitable as a packaging material for retort foods that is sterilized by hot water or steam.

  The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. In the following examples, “%” and “part” mean “% by weight” and “part by weight” unless otherwise specified.

  The vinyl alcohol polymers used in the examples and comparative examples were analyzed by the following methods (1) and (2).

(1) Amount of acyl group 270 MHz ¹ H-NMR (“JNM-GSX270” manufactured by JEOL Ltd.) of a vinyl carboxylate polymer (ethylene-vinyl acetate copolymer) and a composition obtained by saponification thereof The composition of the monomer units of the polymer was determined. Then, the acyl group content of the polymer and the acyl group residual ratio of the composition were quantified.

Regarding the composition obtained by the saponification reaction, a small amount of the composition was collected and dried to remove low-boiling components such as a solvent and then weighed. Next, the dried composition was dissolved in deuterated dimethyl sulfoxide and analyzed using 270 MHz ¹ H-NMR in the presence of a reference substance (tetramethoxysilane) having a known abundance (number of moles). . Among the monomer units contained in the polymer after the saponification reaction, monomer units derived from vinyl carboxylate units include unreacted vinyl carboxylate units, vinyl alcohol units, and vinyl alcohol units and compounds ( There are monomer units and the like having a structure in which a1) is chemically bonded (hereinafter, these monomer units are collectively referred to as “monomer units derived from vinyl carboxylate”). The number of moles of all acyl groups (acetyl group, propionyl group, etc.) contained per unit weight of the composition, and the number of moles of monomer units derived from vinyl carboxylate contained per unit weight of the composition The acyl group residual ratio (mol%) after the saponification reaction was determined from the ratio between the two.

When an alkali metal hydroxide or an alkaline earth metal hydroxide is used as a catalyst for the saponification reaction of a vinyl carboxylate polymer, the carboxylate produced as a by-product in the saponification reaction is not removed by drying. The residual ratio of acyl group was determined by removing the influence of. Specifically, first, the weight proportion of the carboxylate contained in the composition is determined by the method described later, and the carboxyl group-derived acyl group derived from the weight proportion per unit weight of the composition is determined. The number of moles was calculated. Next, a polymer contained in the composition per unit weight by subtracting the number of moles of acyl groups derived from carboxylate from the number of moles of all acyl groups in the composition determined by ¹ H-NMR. The number of moles of the acyl group bonded to was calculated. Then, from the ratio of the calculated number of moles of acyl groups and the number of moles of monomer units derived from vinyl carboxylate contained per unit weight of the composition, the residual ratio of acyl groups after saponification reaction (mol%) It was determined.

(2) Amount of carboxylate salt A small sample was taken from the composition obtained by the saponification reaction of the vinyl carboxylate polymer, placed in a platinum crucible, and heat-treated in an electric furnace (600 ° C). Next, the metal atom content in the ash obtained by the heat treatment was quantified using a polarized Zeeman atomic absorption photometer (“Z-5300” manufactured by Hitachi, Ltd.). The metal atom was regarded as being present in the form of a carboxylate by-produced by the saponification reaction, and the ratio of the carboxylate to the polymer-containing composition obtained by the saponification reaction (unit: wt%) was calculated. The weight of the polymer-containing composition was measured in a dry state in which the solvent was removed by vacuum drying the composition at 65 ° C. for 24 hours.

<Example 1>
A methanol solution containing an ethylene-vinyl acetate copolymer having a polymerization degree of 500 (ethylene modification rate of 8 mol%) at a content of 38% by weight was prepared. To 400 parts by weight of this methanol solution, 13.3 parts by weight of tetramethoxysilane and 84.1 parts by weight of methanol were added and stirred for about 10 minutes so that the solution was uniform. Thereafter, the solution was sampled, and the amount of water contained in the solution was measured. And water was added so that the moisture content contained in a solution might be 5000 ppm.

  20.9 parts by weight of a sodium hydroxide methanol solution (sodium hydroxide 10%) was added to the resulting solution (S), and a saponification reaction was performed at 40 ° C. The solution gelled about 10 minutes after the addition of the sodium hydroxide methanol solution. Even after gelation, the product was allowed to stand for an additional 20 minutes at a temperature of 40 ° C. to proceed the saponification reaction. After the saponification reaction, the obtained gel was pulverized, 1500 parts by weight of methanol was added thereto, and the system temperature was kept at 40 ° C. and stirred for 1 hour. After stirring, methanol was removed by filtration, and 1500 parts by weight of methanol was added again. Next, the temperature of the system was kept at 40 ° C. and stirred for 1 hour. Then, methanol was removed from the product by filtration, and the product was dried in a hot air dryer adjusted to 65 ° C. for 20 hours. In this way, a vinyl alcohol polymer (b) was obtained. When this vinyl alcohol polymer (b) and its composition were analyzed, the residual ratio of acyl groups derived from vinyl carboxylate units in the ethylene-vinyl acetate copolymer was 1.0 mol%, and the residual sodium acetate The amount was 1.0% by weight. The amount of Si atoms bonded to the vinyl alcohol polymer (b) was 5.0 mol with respect to 100 mol of the acyl group derived from the vinyl carboxylate unit before saponification.

  50.0 parts by weight of this vinyl alcohol polymer (b) was dissolved in distilled water to prepare an aqueous solution having a solid content concentration of 10% by weight. Separately, an aqueous solution of polyacrylic acid (manufactured by Nippon Shokubai Co., Ltd. PSA-HL415, number average molecular weight 10,000) was prepared so that the solid content concentration was 10% by weight. Further, isobutylene-maleic anhydride alternating copolymer (Isoban 600 manufactured by Kuraray Co., Ltd .: maleic anhydride unit content: 50 mol%) contains 0.75 moles of ammonia with respect to the carboxyl group of maleic anhydride. It was made to melt | dissolve in ammonia water and the aqueous solution of the isobutylene-maleic acid alternating copolymer salt was obtained. At this time, it was dissolved in aqueous ammonia so that the concentration of the isobutylene-maleic acid alternating copolymer salt was 10% by weight.

  500.0 parts by weight of the aqueous solution of the vinyl alcohol polymer (b), 16.0 parts by weight of the aqueous solution of polyacrylic acid, and 16.0 parts by weight of the aqueous solution of the isobutylene-maleic acid alternating copolymer salt are mixed, A solution in which the weight ratio of vinyl alcohol polymer (b) (ethylene-modified PVA) / polyacrylic acid (PAA) / isobutylene-maleic acid alternating copolymer salt (P (MA / IB)) is 94/3/3 (T) was prepared.

  Next, after dissolving 72.3 parts by weight of tetramethoxysilane in 72.3 parts by weight of methanol, 4.8 parts by weight of distilled water and 11.9 parts by weight of 0.1N (0.1 N) -hydrochloric acid were added. A sol was prepared by reacting at 40 ° C. for 1 hour with stirring. The obtained sol was diluted with 124.3 parts by weight of distilled water, and the solution (t) was quickly added while stirring the solution to prepare a solution (T). The solution (T) was allowed to stand for 1 hour in an atmosphere at 25 ° C. after its preparation.

  On the other hand, an anchor coating agent (two-pack type, Takelac A3210 and Takenate A3072, manufactured by Mitsui Takeda Chemical Co., Ltd., may be described as “AC”) is drawn PET film (Toray Lumirror, thickness 12 μm, described as “OPET”. The substrate was dried and a substrate was prepared. On this base material, the solution (T) was coated with a bar coater so that the thickness after drying was 1 μm, dried at 80 ° C. for 5 minutes, and further heat-treated at 200 ° C. for 5 minutes. In this way, a laminate (polymer-containing composition (1 μm) / AC / OPET (12 μm)) having a transparent and colorless coating film having a good appearance was obtained. Using the laminate, the content of the metal oxide in the polymer-containing composition was measured according to the following method. The content of the metal oxide in the polymer-containing composition in this example was 40% by weight.

(3) Metal oxide content The polymer-containing composition layer is coated by the above-described method on a laminate composed of an anchor coat layer / OPET layer (12 μm) whose weight has been measured in advance. A laminate (size: 10 cm × 10 cm) composed of (1 μm) / anchor coat layer / OPET layer (12 μm) was produced. The prepared laminate was placed in a vacuum dryer at 60 ° C. for 24 hours, and then water adhering to the laminate was removed. The weight of the anchor coat layer / OPET layer measured in advance was subtracted from the weight of the laminated body after drying to obtain the weight of the polymer-containing composition in the laminated body. Next, the laminate is put into an electric furnace, and while supplying air, the temperature of the electric furnace is raised from room temperature to 600 ° C., and further maintained at 600 ° C. for 5 hours to completely thermally decompose the organic components. Removed. And the weight of the white inorganic compound obtained by this heat processing was measured. The content of the metal oxide in the polymer-containing composition was calculated from the weight of the polymer-containing composition before pyrolysis and the weight obtained after pyrolysis.

  Next, stretched nylon 6 film (Unitika emblem, thickness 15 μm, hereinafter may be referred to as ONy), and polypropylene film (Tosero RXC-18, thickness 50 μm, hereinafter referred to as “PP” may be described. ) Were coated with an adhesive (AD-385, A-50, manufactured by Toyo Morton), and dried. These two types of films and the above laminate (polymer-containing composition / AC / OPET) are laminated, and a laminate having a structure of PP / adhesive / OPET / AC / polymer-containing composition / adhesive / ONy. Got the body. A sample for retort treatment was prepared using the laminate, and the oxygen permeability before retort treatment was measured. In addition, the oxygen permeability after retort treatment and appearance evaluation were performed using the sample. Moreover, the peel strength after the hot water treatment was measured using this laminate.

(4) Measurement of oxygen permeability before retort treatment A 12 cm × 12 cm square laminate (PP / adhesive / OPET / AC / polymer-containing composition / adhesive / ONy) was prepared, and an oxygen permeability measurement device. (Modern Control “MOCON OX-TRAN 2/20”) was used to transmit oxygen under the conditions of temperature 20 ° C., humidity 95% RH and oxygen pressure 24.5 N / cm ² (2.5 kgf / cm ² ). The degree (unit: cc / m ² · 24 hr · atm) was measured.

(5) Measurement of oxygen permeability after retorting and evaluation of sample appearance Two 12 cm × 12 cm square laminates (PP / adhesive / OPET / AC / polymer-containing composition / adhesive / ONy) Two pieces were laminated so that the PP surfaces of the respective laminates were inside. Then, the three sides of the two superimposed squares were heat-sealed with a width of 5 mm from the end, and then 80 g of distilled water was added. Subsequently, the remaining one side was heat-sealed while venting air so that no air remained inside.

  Next, the obtained bag was retorted by the following method. First, the bag was placed in an autoclave, and water was poured into the autoclave to completely immerse the bag. Next, after raising the temperature of the autoclave to 120 ° C., the autoclave was held at 120 ° C. for 30 minutes. Thereafter, the internal temperature of the autoclave was lowered to 60 ° C. in 10 minutes. When the temperature reached 60 ° C., the bag was taken out of the autoclave, the water adhering to the surface of the bag was wiped off, and left in a constant temperature and humidity room set at 20 ° C. and 65% RH for 1 hour. Thus, the retort process was performed.

After the retort treatment, the appearance of the bag was observed. Next, the heat seal portion of the bag was cut, and one laminate was taken out, and the laminate was set in an oxygen permeability measuring device. “MOCON OX-TRAN 2/20” manufactured by Modern Control Co., Ltd. was used as the oxygen permeability measuring device. The Ny6 surface was disposed on the oxygen supply side, and the PP surface was disposed on the side through which oxygen passes. The humidity on the oxygen supply side was 65% RH, and the humidity on the side through which oxygen permeated was 100% RH. The temperature was 20 ° C., and the oxygen pressure was 24.5 N / cm ² (2.5 kgf / cm ² ). Under such conditions, the oxygen permeability (unit: cc / m ² · 24 hr · atm) was measured.

The appearance after the retort treatment was evaluated according to the following criteria.
○: No change in appearance compared to before retort treatment.
(Triangle | delta): There exists a part which has peeled slightly in the edge part etc. of a bag. Or the surface is somewhat rough.
X: There exists big peeling. Or the surface is greatly rough.

(6) Peel strength of laminate after retorting treatment A rectangular laminate (PP / adhesive / OPET / AC / polymer-containing composition / adhesive / ONy) having a size of 2.5 cm × 15.5 cm is prepared and autoclaved. Put in. Subsequently, water was poured into the autoclave so that the rectangular laminate was completely immersed. And after heating up an autoclave to 120 degreeC, it hold | maintained at 120 degreeC for 30 minutes. Thereafter, the internal temperature of the autoclave was lowered to 60 ° C. in 10 minutes. When the temperature reached 60 ° C., the laminate was taken out from the autoclave and immersed in water at 20 ° C. The immersed state was maintained for 60 minutes. After taking out from water, it cut | disconnected rapidly to 1.5 cm width, the interface between a polymer containing composition and an adhesive agent was exposed, and it set to the peeling strength measuring apparatus. And T-peel strength was measured. The time from removal from water to the start of peel strength measurement was 4 minutes. The measurement was performed using Shimadzu Corporation AUTOGRAPH AG-5000B.

In the sample of this example, the oxygen permeability before retorting was 0.9 cc / m ² · 24 hr · atm, and the oxygen permeability after retorting was 0.9 cc / m ² · 24 hr · atm. Moreover, when the external appearance of the sample after a retort process was evaluated, there was no change of an external appearance compared with the pre-retort process. And the peeling strength of the laminated body after a retort process was 640 g / 1.5cm.

<Example 2>
First, an aqueous solution of vinyl alcohol polymer (b), an aqueous solution of polyacrylic acid, and an aqueous solution of alternating isobutylene-maleic acid copolymer salt were prepared in the same manner as in Example 1. Then, 500.0 parts by weight of the aqueous solution of the vinyl alcohol polymer (b), 15.6 parts by weight of the aqueous solution of polyacrylic acid, and 5.2 parts by weight of the aqueous solution of the isobutylene-maleic acid alternating copolymer salt are mixed. A solution (t) having a weight ratio of vinyl alcohol polymer (b) / polyacrylic acid / isobutylene-maleic acid alternating copolymer salt of 96/3/1 was prepared.

  Next, after dissolving 70.4 parts by weight of tetramethoxysilane in 70.4 parts by weight of methanol, 4.7 parts by weight of distilled water and 11.6 parts by weight of 0.1N hydrochloric acid were added. A sol was prepared by reacting at 40 ° C. for 1 hour with stirring. After the obtained sol was diluted with 121.0 parts by weight of distilled water, the solution (b) was rapidly added while stirring the solution to prepare a solution (T). The prepared solution (T) was left under an atmosphere of 25 ° C. for 1 hour.

  A sample for evaluation was prepared in the same manner as in Example 1 except that the solution (T) prepared by the above method was used instead of the solution (T) prepared in Example 1. The evaluation was performed in the same way.

<Example 3>
First, an aqueous solution of vinyl alcohol polymer (b), an aqueous solution of polyacrylic acid, and an aqueous solution of alternating isobutylene-maleic acid copolymer salt were prepared in the same manner as in Example 1. Then, 500.0 parts by weight of the aqueous solution of the vinyl alcohol polymer (b), 2.5 parts by weight of the aqueous solution of the polyacrylic acid, and 2.5 parts by weight of the aqueous solution of the alternating copolymer of isobutylene-maleic acid are mixed. Then, a solution (t) in which the weight ratio of the vinyl alcohol polymer (b) / polyacrylic acid / isobutylene-maleic acid alternating copolymer salt was 99 / 0.5 / 0.5 was prepared.

  Next, after dissolving 67.7 parts by weight of tetramethoxysilane in 67.7 parts by weight of methanol, 4.5 parts by weight of distilled water and 11.1 parts by weight of 0.1N hydrochloric acid were added, and the resulting solution was added. A sol was prepared by reacting at 40 ° C. for 1 hour with stirring. The obtained sol was diluted with 116.5 parts by weight of distilled water, and the solution (t) was quickly added while stirring the solution to prepare a solution (T). The prepared solution (T) was left under an atmosphere of 25 ° C. for 1 hour.

  A sample for evaluation was prepared in the same manner as in Example 1 except that the solution (T) prepared in the above method was used instead of the solution (T) prepared in Example 1, and the same method as in Example 1 was used. The evaluation was done.

<Comparative Example 1>
50.0 parts by weight of the vinyl alcohol polymer (b) prepared in the same manner as in Example 1 was dissolved in distilled water to prepare a solution (t-c1) having a solid content concentration of 10% by weight.

  Next, after dissolving 66.9 parts by weight of tetramethoxysilane in 66.9 parts by weight of methanol, 4.4 parts by weight of distilled water and 11.0 parts by weight of 0.1N-hydrochloric acid were added, and this was stirred. The reaction was performed at 40 ° C. for 1 hour to prepare a sol. After diluting the obtained sol with 115.0 parts by weight of distilled water, 500.0 parts by weight of the above solution (t-c1) was rapidly added while stirring this to prepare a solution (T-c1). . The prepared solution (T-c1) was allowed to stand for 1 hour in an atmosphere at 25 ° C.

  A sample for evaluation was prepared in the same manner as in Example 1 except that the solution (T-c1) prepared by the above method was used instead of the solution (T) prepared in Example 1, and The evaluation was performed in the same way.

<Comparative example 2>
50.0 parts by weight of the vinyl alcohol polymer (b) prepared in the same manner as in Example 1 was dissolved in distilled water to prepare an aqueous solution having a solid content concentration of 10% by weight. Separately, an aqueous solution of polyacrylic acid (manufactured by Nippon Shokubai Co., Ltd., PSA-HL415, number average molecular weight 10,000) was prepared so that the solid content concentration was 10% by weight. 500.0 parts by weight of the aqueous solution of the vinyl alcohol polymer (b) and 55.6 parts by weight of the aqueous solution of the polyacrylic acid were mixed, and the weight ratio of the vinyl alcohol polymer (b) / polyacrylic acid was 90. A solution (tc2) that is / 10 was prepared.

  Next, after dissolving 76.3 parts by weight of tetramethoxysilane in 76.3 parts by weight of methanol, 5.1 parts by weight of distilled water and 12.5 parts by weight of 0.1N hydrochloric acid were added, and this was stirred. The reaction was performed at 40 ° C. for 1 hour to prepare a sol. The obtained sol was diluted with 131.1 parts by weight of distilled water, and the solution (t-c2) was quickly added while stirring the solution to prepare a solution (T-c2). The prepared solution (T-c2) was allowed to stand for 1 hour in an atmosphere at 25 ° C.

  A sample for evaluation was prepared in the same manner as in Example 1 except that the solution (T-c2) prepared in the above method was used instead of the solution (T) prepared in Example 1. The evaluation was performed in the same way.

<Comparative Example 3>
50.0 parts by weight of a vinyl alcohol polymer (b) produced by the same method as in Example 1 was dissolved in distilled water to prepare an aqueous solution having a solid content concentration of 10% by weight.

  Separately, isobutylene-maleic anhydride alternating copolymer (Isoban 600 manufactured by Kuraray Co., Ltd.) was dissolved in ammonia water containing 0.75 times mole of ammonia with respect to the carboxyl group of maleic anhydride, and isobutylene-maleic acid alternating An aqueous solution of copolymer salt was obtained. At this time, it was dissolved in ammonia water so that the concentration of the isobutylene-maleic acid alternating copolymer salt was 10% by weight.

  Next, 500.0 parts by weight of the aqueous solution of the vinyl alcohol polymer (b) and 55.6 parts by weight of an aqueous solution of isobutylene-maleic acid alternating copolymer salt are mixed, and the vinyl alcohol polymer (b) is mixed. A solution (tc3) in which the weight ratio of / isobutylene-maleic acid alternating copolymer salt was 90/10 was prepared.

  Next, after dissolving 76.3 parts by weight of tetramethoxysilane in 76.3 parts by weight of methanol, 5.1 parts by weight of distilled water and 12.5 parts by weight of 0.1N (normal) -hydrochloric acid were added. A sol was prepared by reacting at 40 ° C. for 1 hour with stirring. The obtained sol was diluted with 131.1 parts by weight of distilled water, and then the above solution (t-c3) was rapidly added while stirring the solution to prepare a solution (BC3). The prepared solution (T-c3) was allowed to stand for 1 hour in an atmosphere at 25 ° C.

  A sample for evaluation was prepared in the same manner as in Example 1 except that the solution (T-c3) prepared in the above method was used instead of the solution (T) prepared in Example 1. The evaluation was performed in the same way.

<Comparative example 4>
400 parts by weight of a methanol solution containing an ethylene-vinyl acetate copolymer having a polymerization degree of 500 (ethylene modification rate of 8 mol%) at a content of 38% by weight was prepared. To this, 85.6 parts by weight of methanol was added and stirred for about 10 minutes so that the solution became homogeneous. Thereafter, 20.9 parts by weight of a sodium hydroxide methanol solution (sodium hydroxide 10%) was added, and a saponification reaction was carried out at 40 ° C. The system gelled about 10 minutes after adding the sodium hydroxide methanol solution. Even after gelation, the product was allowed to stand for an additional 20 minutes at a temperature of 40 ° C. to proceed the saponification reaction. After the saponification reaction, the obtained gel was pulverized, 1500 parts by weight of methanol was added thereto, and the system temperature was kept at 40 ° C. and stirred for 1 hour. After stirring, methanol was removed by filtration, and 1500 parts by weight of methanol was added again. Next, the temperature of the system was kept at 40 ° C. and stirred for 1 hour. Thereafter, methanol was removed by filtration, and drying was carried out for 20 hours in a hot air drier maintained at 65 ° C. In this way, a vinyl alcohol polymer was obtained. The vinyl alcohol polymer had a residual ratio of acyl groups derived from vinyl carboxylate units in the ethylene-vinyl acetate copolymer of 0.8 mol% and a residual sodium acetate content of 0.6% by weight. .

  50.0 parts by weight of this vinyl alcohol polymer was dissolved in distilled water to prepare an aqueous solution having a solid content concentration of 10% by weight. Separately, an aqueous solution of polyacrylic acid (manufactured by Nippon Shokubai Co., Ltd., PSA-HL415, number average molecular weight 10,000) was prepared so that the solid content concentration was 10% by weight. Furthermore, an isobutylene-maleic anhydride alternating copolymer (Isoban 600 manufactured by Kuraray Co., Ltd., number average molecular weight 6000) is dissolved in ammonia water containing 0.75 times mole of ammonia with respect to the carboxyl group of maleic anhydride, An aqueous solution of alternating isobutylene-maleic acid copolymer salt was obtained. At this time, it was dissolved in aqueous ammonia so that the concentration of the isobutylene-maleic acid alternating copolymer salt was 10% by weight.

  500.0 parts by weight of the aqueous solution of the vinyl alcohol polymer, 16.0 parts by weight of the aqueous solution of polyacrylic acid, and 16.0 parts by weight of the aqueous solution of the alternating copolymer of isobutylene-maleic acid are mixed, A solution (tc4) in which the weight ratio of the copolymer / polyacrylic acid / isobutylene-maleic acid alternating copolymer salt was 94/3/3 was prepared.

Next, 177.3 parts by weight of water is added to 177.3 parts by weight of a colloidal silica solution (manufactured by Nissan Chemical Industries, Snowtex ST-XS, average particle size 4-6 nm, SiO ₂ concentration 20%) and diluted. And 354.6 parts by weight of a mixed solution (SiO ₂ concentration: 10%) were prepared. While stirring this mixed solution, the above solution (t-c4) was added to prepare a solution (T-c4). The prepared solution (T-c4) was left in an atmosphere at 25 ° C. for 1 hour.

  A sample for evaluation was prepared in the same manner as in Example 1 except that the solution (T-c4) prepared by the above method was used in place of the solution (T) prepared in Example 1. The evaluation was performed in the same way.

  Table 1 shows the manufacturing conditions of the laminate and the evaluation results of the laminate for Examples 1 to 3 and Comparative Examples 1 to 4.

  The laminates of Examples 1, 2, and 3 had high peel strength after the hot water treatment, and the oxygen barrier property was good before and after the retort treatment.

  The laminate of Comparative Example 1 had good oxygen barrier properties before retorting. However, in this laminate, the layer of the polymer-containing composition was peeled off by retort treatment. For this reason, it was not possible to measure the peel strength and oxygen permeability after retort. The laminates of Comparative Examples 2 and 3 had high peel strength after the hot water treatment. However, the laminates of Comparative Examples 2 and 3 had low oxygen barrier properties before and after the retort treatment. In the laminate of Comparative Example 4, the coating film had already been whitened before the retort treatment, and the appearance was poor. And by performing the retort process, the coating film was further whitened and the appearance was further deteriorated. Furthermore, this laminate had a relatively high peel strength after the hot water treatment, but the oxygen permeability before and after the retort treatment was considerably high.

  The present invention can be applied to a polymer-containing composition that can be used as a packaging material and a method for producing the same. According to the present invention, a polymer-containing composition having excellent gas barrier properties, in particular, gas barrier properties and mechanical strength after being treated with hot water or steam can be obtained. This composition is suitably used as a food packaging material, particularly a retort food packaging material that requires sterilization with hot water or steam.

Claims (22)

Hydrolysis condensate of compound (A) containing a metal atom (M) to which at least one selected from a halogen atom and an alkoxy group is bonded, a vinyl alcohol polymer (B), a carboxylic acid unit-containing polymer (C1), and a carboxyl An acid unit-containing polymer (C2),
The carboxylic acid unit-containing polymer (C1) contains at least one monomer unit selected from an acrylic acid unit, an acrylate unit, a methacrylic acid unit and a methacrylate unit in a proportion of 30 mol% or more in total. And
The polymer containing the carboxylic acid unit-containing polymer (C2) containing at least one monomer unit selected from maleic acid units, maleic acid ester units and maleate units in a proportion of 30 mol% or more in total. Composition.   The polymer-containing composition according to claim 1, wherein the content of the hydrolysis-condensation product is in the range of 10 to 65% by weight. A metal oxide containing a metal atom (M), a vinyl alcohol polymer (B), a carboxylic acid unit-containing polymer (C1) and a carboxylic acid unit-containing polymer (C2),
The carboxylic acid unit-containing polymer (C1) contains at least one monomer unit selected from an acrylic acid unit, an acrylate unit, a methacrylic acid unit and a methacrylate unit in a proportion of 30 mol% or more in total. And
The polymer containing the carboxylic acid unit-containing polymer (C2) containing at least one monomer unit selected from maleic acid units, maleic acid ester units and maleate units in a proportion of 30 mol% or more in total. Composition.   The polymer-containing composition according to claim 3, wherein the content of the metal oxide is in the range of 10 to 65% by weight.   The weight ratio of [the vinyl alcohol polymer (B)] / [total of the carboxylic acid unit-containing polymers (C1) and (C2)] is in the range of 99.5 / 0.5 to 70/30. The polymer-containing composition according to any one of claims 1 to 4.   The weight ratio of [the carboxylic acid unit-containing polymer (C1)] / [the carboxylic acid unit-containing polymer (C2)] is in the range of 99/1 to 10/90. The polymer-containing composition according to item.   The polymer-containing composition according to any one of claims 1 to 4, wherein the metal atom (M) is at least one selected from the group consisting of silicon, titanium, aluminum, and zirconium.   The polymer according to any one of claims 1 to 7, wherein the vinyl alcohol polymer (B) includes a group derived from a compound containing a metal atom to which at least one selected from a halogen atom and an alkoxy group is bonded. Containing composition.   The polymer-containing composition according to any one of claims 1 to 8, wherein the carboxylic acid unit-containing polymer (C1) is at least one selected from polyacrylic acid and a partially neutralized product of polyacrylic acid. .   The carboxylic acid unit-containing polymer (C2) is at least one selected from an isobutylene-maleic acid copolymer and a partially neutralized product of an isobutylene-maleic acid copolymer. The polymer-containing composition described in 1.   The polymer containing composition by which the polymer containing composition of any one of Claims 1-10 is disperse | distributed to the solvent. Saponification of the vinyl carboxylate polymer in a solution (S) containing a compound (a1) containing a metal atom (m1) to which at least one selected from a halogen atom and an alkoxy group is bonded and a vinyl carboxylate polymer A first step of producing a vinyl alcohol polymer (b) by performing a reaction and a reaction between the compound (a1) and the vinyl carboxylate polymer;
At least one compound selected from a compound (a2) containing a metal atom (m2) to which at least one selected from a halogen atom and an alkoxy group is bonded, and an oligomer derived from the compound (a2), the vinyl alcohol polymer ( b), a second step of preparing a solution (T) containing a carboxylic acid unit-containing polymer (c1), a carboxylic acid unit-containing polymer (c2), and a solvent,
The carboxylic acid unit-containing polymer (c1) contains at least one monomer unit selected from an acrylic acid unit, an acrylate unit, a methacrylic acid unit and a methacrylate unit in a proportion of 30 mol% or more in total. And
The polymer in which the carboxylic acid unit-containing polymer (c2) contains at least one monomer unit selected from a maleic acid unit, a maleic acid ester unit and a maleate unit in a proportion of 30 mol% or more in total. The manufacturing method of a containing composition.   The second step is a step of preparing a solution (t) containing the vinyl alcohol polymer (b), the carboxylic acid unit-containing polymer (c1), and the carboxylic acid unit-containing polymer (c2); The method for producing a polymer-containing composition according to claim 12, comprising the step of adding the at least one compound to the solution (t) to prepare the solution (T).   The polymer-containing composition according to claim 12 or 13, wherein the metal atoms (m1) and (m2) are each independently at least one selected from the group consisting of silicon, titanium, aluminum and zirconium. Method.   The weight ratio of [the vinyl alcohol polymer (b)] / [total of the carboxylic acid unit-containing polymers (c1) and (c2)] in the solution (T) is 99.5 / 0.5 to 70. It is the range of / 30, The manufacturing method of the polymer containing composition of any one of Claims 12-14.   The weight ratio of [the carboxylic acid unit-containing polymer (c1)] / [the carboxylic acid unit-containing polymer (c2)] is in the range of 99/1 to 10/90. The manufacturing method of a polymer containing composition as described in an item.   The method for producing a polymer-containing composition according to any one of claims 12 to 16, further comprising a step of removing the solvent from the solution (T).   The polymer containing composition manufactured with the manufacturing method of any one of Claims 12-17.   The gas barrier material containing the part which consists of a polymer containing composition of any one of Claims 1-10 and 18.   The gas barrier material according to claim 19, wherein the portion is a layer made of the polymer-containing composition.   The gas barrier material according to claim 20, wherein at least one layer selected from a polyester layer, a polyamide layer, and a polyolefin layer is laminated on the layer.   The gas barrier material according to claim 20 or 21, which is a packaging material for retort food.