JP2006188643A - Polymer-containing composition and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polymer composition excellent in water vapor barrier property and a method for producing the same.
SOLUTION: A first step of preparing a solution (S1) containing a hydroxyl group-containing polymer (A), a compound (B) containing a silicon atom to which at least one selected from a halogen atom and an alkoxy group is bonded, and a boron atom A second step of preparing a solution (S2) containing a composition having a compound (B) / compound (C) molar ratio of 1.5 to 10,000 obtained by mixing a compound (C) containing And a third step of preparing the solution (S3) by mixing the solution (S1) and the solution (S2).
[Selection figure] None

Description

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

  Gas barrier properties, particularly oxygen barrier properties are often required for packaging materials for packaging foods and various articles. Conventionally, these food packaging materials include a packaging material having a barrier layer made of a halogen-containing polymer such as polyvinylidene chloride, a metal foil such as an aluminum foil, and a barrier layer made of a metal or a metal compound typified by an aluminum vapor deposition layer. Packaging materials having a barrier layer made of a vinyl alcohol polymer or an ethylene-vinyl alcohol copolymer are used.

In addition, as one of means for obtaining a packaging material having excellent gas barrier properties, in recent years, by using a sol-gel method, a metal alkoxide such as silicon alkoxide is polycondensed in the presence of an organic polymer. A method for preparing an organic / inorganic composite in which a metal oxide is relatively finely dispersed in an organic polymer has been proposed. As a specific method, for example, a vinyl alcohol polymer composition is produced from a solution containing a metal alkoxide and a vinyl carboxylate polymer, and the solvent is removed after adding the metal alkoxide to the solution of the composition. A method is disclosed (see Patent Document 1). Also disclosed is a gas barrier coating composition comprising (a) a polyvinyl alcohol-based resin, (b) a metal alcoholate or a derivative thereof represented by a specific general formula, and (c) a boron compound. (See Patent Document 2).
JP 2002-138109 A JP 2002-047442 A

  In recent years, the required performance of the market has further increased, and a barrier material excellent in not only gas barrier properties but also water vapor barrier properties has been demanded in the market. Specifically, not only the use of the packaging material as described above but also a barrier material having an excellent water vapor barrier property is required in the field of application as a covering material for articles. However, the barrier material obtained by the conventional technique still has room for improvement in water vapor barrier properties.

  Under such circumstances, there is a demand for a barrier material that is excellent in water vapor barrier properties and has little coloration and excellent appearance. Such a barrier material is more preferably excellent in gas barrier properties. An object of the present invention is to provide a polymer-containing composition capable of constituting a barrier material having excellent water vapor barrier properties, a method for producing the same, and a water vapor barrier material using the same.

  The inventors of the present invention diligently studied to solve the above-mentioned problems and have completed the present invention. That is, in the method of the present invention for producing a polymer-containing composition, the first step of preparing the solution (S1) containing the hydroxyl group-containing polymer (A) is combined with at least one selected from a halogen atom and an alkoxy group. A composition having a compound (B) / compound (C) molar ratio of 1.5 to 10,000, obtained by mixing a compound (B) containing a silicon atom and a compound (C) containing a boron atom. A method for producing a polymer-containing composition, comprising: a second step of preparing a solution (S2) containing; and a third step of preparing the solution (S3) by mixing the solution (S1) and the solution (S2). It is.

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

The first polymer-containing composition of the present invention is a hydrolyzed condensate of a hydroxyl group-containing polymer (A) and a compound (B) containing a silicon atom to which at least one selected from a halogen atom and an alkoxy group is bonded, A polymer-containing composition comprising a hydrolysis condensate of a compound (C) containing a boron atom, wherein the molar ratio of the compound (B) / compound (C) is in the range of 1.5 to 10,000, The water vapor transmission rate under an atmosphere of 90 ° C.-90% RH is 20 g · 2 μm / m ² · day or less.

The second polymer-containing composition of the present invention is a polymer-containing composition containing a hydroxyl group-containing polymer (A), a silicon oxide, and a boron oxide (in the silicon oxide). Silicon atom) / (boron atom in the boron oxide) is in the range of 1.5 to 10000, and the water vapor transmission rate in a 40 ° C.-90% RH atmosphere is 20 g · 2 μm / m ² · day. It is as follows.

  Moreover, the water vapor | steam barrier material of this invention contains the polymer containing composition of the said invention.

  According to the present invention, a polymer-containing composition having excellent water vapor barrier properties can be obtained. Therefore, the polymer-containing composition of the present invention is effectively used as a packaging material for foods, medicines, medical devices, machine parts, clothing, and various articles that require water vapor barrier properties.

  Hereinafter, embodiments of the present invention will be described. In the following description, specific examples are shown as compounds that express a specific function, but the present invention is not limited thereto. 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.

  Below, the method of this invention for manufacturing a polymer containing composition is demonstrated. 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, a solution (S1) containing the hydroxyl group-containing polymer (A) is prepared (first step). Thereafter, a compound (B) / a compound (C) mole obtained by mixing a compound (B) containing a silicon atom to which at least one selected from a halogen atom and an alkoxy group is bonded and a compound (C) containing a boron atom are mixed. A solution (S2) containing a composition having a ratio of 1.5 to 10000 is prepared (second step). Thereafter, the solution (S1) and the solution (S2) are mixed to prepare a solution (S3) (third step).

  A hydroxyl-containing polymer (A) is a polymer which has a monomer unit containing a hydroxyl group as a monomer unit which comprises a polymer. As a hydroxyl-containing polymer (A), it is preferable that the monomer unit containing the said hydroxyl group is contained 50 mol% or more with respect to all the monomer units which comprise (A), 60 mol% It is more preferable that it is contained above, and it is further more preferable that 70 mol% or more is contained. As such a hydroxyl group-containing polymer (A), a vinyl alcohol polymer is particularly preferable.

  The vinyl alcohol polymer used as the hydroxyl group-containing polymer (A) is a polymer obtained by saponifying a vinyl carboxylate polymer (vinyl ester polymer). 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 another monomer copolymerizable with vinyl carboxylate. It is a copolymer. In the vinyl alcohol polymer, the total content of vinyl alcohol units and vinyl carboxylate units is preferably 50 mol% or more, and 60 mol% or more based on all monomer units constituting the polymer. Is more preferably 70 mol% or more, and particularly preferably 80 mol% or more. 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.

  From the viewpoint of the water vapor barrier property of the polymer-containing composition of the present invention, the vinyl alcohol polymer used is preferably unmodified polyvinyl alcohol. On the other hand, in a preferred embodiment, the polymer-containing composition of the present invention can be used as a gas barrier material by taking advantage of its excellent oxygen barrier property. In such an embodiment, it may be preferable to use a polymer obtained by saponifying a copolymer of vinyl carboxylate and another monomer copolymerizable therewith as the vinyl alcohol polymer. . The proportion of other monomer units used for copolymerization with vinyl carboxylate is preferably 40 mol% or less, more preferably 30 mol% or less, and even more preferably 20 mol% or less. Other monomers that can be used for copolymerization 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 and the like, among which ethylene is preferable from the viewpoint of the oxygen barrier property of the polymer-containing composition. As the vinyl alcohol polymer, polyvinyl alcohol, polyvinyl alcohol partial saponification product, ethylene-vinyl alcohol copolymer, or ethylene-vinyl alcohol copolymer partial saponification product having crystallinity is preferable. Used. When ethylene is copolymerized, the suitable copolymerization ratio of ethylene is preferably 1 to 20 mol%, more preferably 2 to 18 mol%, and even more preferably 3 to 15 mol%.

  The degree of polymerization of the hydroxyl group-containing polymer (A) used in the present invention is not particularly limited. From the viewpoint of water vapor barrier properties, mechanical properties, and processability of the polymer-containing composition obtained by the production method of the present invention, the degree of polymerization is preferably 100 to 10,000, more preferably 200 to 5,000. Preferably, it is 300-3000.

  The compound (B) containing a silicon atom to which at least one selected from a halogen atom and an alkoxy group used in the present invention is bonded may be a single compound or a plurality of types of compounds. The compound (B) preferably has one silicon atom and a chemical structure in which two, three or four alkoxy groups or halogen groups are bonded to the silicon atom. Here, the number of alkoxy groups or halogen groups bonded to the silicon atom is more preferably 3 or 4, and particularly preferably 4. Among the compounds (B), the compound containing a silicon atom to which an alkoxy group is bonded is at least one component selected from silicon alkoxides and oligomers derived from silicon alkoxides.

  The silicon alkoxide preferably has one silicon atom and a chemical structure in which two, three or four alkoxy groups are bonded to the silicon atom. 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, or the like Of the aryl group and the like. Specific examples of the silicon alkoxide include tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, octyltrimethoxysilane, and phenyltrimethoxysilane, preferably tetramethoxysilane and tetraethoxysilane. is there.

  The oligomer derived from silicon alkoxide is an oligomer that can be produced by hydrolyzing and condensing silicon alkoxide by a known method. In addition, the oligomer derived from silicon alkoxide and one or more metal alkoxides other than silicon alkoxide is known by mixing one kind of metal alkoxide selected from silicon alkoxide and one or more metal alkoxides other than silicon alkoxide, It is an oligomer that can be produced by hydrolysis and condensation according to the method.

  Specific examples of oligomers derived from the above silicon alkoxide include tetramethoxysilane dimer or oligomers of trimers or higher, tetraethoxysilane dimer or oligomers of trimers or higher, oligodimethylsiloxane, and the like. Examples thereof include tetramethoxysilane dimers or oligomers of trimers or higher, tetraethoxysilane dimers or oligomers of trimers 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.

  Among the compounds (B) containing a silicon atom to which at least one selected from a halogen atom and an alkoxy group is bonded, the halogen atom in the compound containing a silicon atom to which a halogen atom is bonded includes a chlorine atom, a bromine atom, a fluorine atom, and the like. Illustrated. In addition, when the number of halogen 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, or the like Of the aryl group and the like. Specific examples of the compound containing a silicon atom to which a halogen atom is bonded include, for example, vinyltrichlorosilane, tetrachlorosilane, tetrabromosilane and the like.

  Specific examples of the compound (B) containing a silicon atom to which a halogen atom and an alkoxy group are bonded include, for example, chlorotrimethoxysilane, chlorotriethoxysilane, dichlorodimethoxysilane, dichlorodiethoxysilane, and trichloromethoxy. Examples thereof include silane and trichloroethoxysilane.

  Among the compounds (B) shown above, from the viewpoint of water vapor barrier properties of the polymer-containing composition, it is preferable to use a compound containing a silicon atom to which an alkoxy group is bonded, and is derived from silicon alkoxide and / or silicon alkoxide. It is more preferable to use the oligomer to be used.

  As the compound (C) containing a boron atom used in the present invention, a compound containing a boron atom to which at least one selected from an alkoxy group, a hydroxyl group and a hydrogen atom is bonded is preferable. Specific examples include boric acid, metal salts of boric acid, borate minerals, and organic boron compounds.

  Examples of boric acid include orthoboric acid, metaboric acid, and tetraboric acid, and orthoboric acid is preferably used.

  Examples of metal salts of boric acid include calcium borate, cobalt borate, zinc borate (zinc tetraborate, zinc metaborate, etc.), aluminum borate / potassium borate, ammonium borate (ammonium metaborate, ammonium tetraborate) , Ammonium pentaborate, ammonium octaborate, etc.), cadmium borate (cadmium orthoborate, cadmium tetraborate, etc.), potassium borate (potassium metaborate, potassium tetraborate, potassium pentaborate, potassium hexaborate) , Potassium octaborate, etc.), silver borate (silver metaborate, silver tetraborate, etc.), copper borate (cupric borate, copper metaborate, copper tetraborate, etc.), sodium borate (metaborate) Sodium, sodium diborate, sodium tetraborate, sodium pentaborate, sodium hexaborate, octaborate Thorium, etc.), lead borate (lead metaborate, lead hexaborate, etc.), nickel borate (nickel orthoborate, nickel diborate, nickel tetraborate, nickel octaborate, etc.), barium borate (orthoboric acid) Barium, barium metaborate, barium diborate, barium tetraborate, etc.), bismuth borate, magnesium borate (magnesium orthoborate, magnesium diborate, magnesium metaborate, trimagnesium tetraborate, pentamagnesium tetraborate) Etc.), manganese borate (manganese borate, manganese metaborate, manganese tetraborate, etc.), lithium borate (lithium metaborate, lithium tetraborate, lithium pentaborate, etc.).

  Examples of the borate minerals include borax, carnite, inyoite, agate stone, suian stone, and zyberite.

  Examples of the organic boron compound include borane, boroxine, phenylboric acid, diphenylboric acid, and a boric acid ester compound of boric acid and an alcohol compound or a phenol compound. Here, as the borate ester compound, for example, an aliphatic monoalcohol having 1 to 20 carbon atoms, a polyhydric alcohol (ethylene glycol, tetrabutylene glycol, glycerin, pentaerythritol, etc.), a phenol compound (phenol, catechol, resorcinol, Boric acid mono-, di-, tri- or tetraester compounds with hydroquinone, cresol, etc.) and mixtures thereof, and metal salts thereof. Among these boric acid ester compounds, ester compounds with aliphatic monoalcohols having 1 to 20 carbon atoms are preferable, and trimethoxyborane and triethoxyborane are particularly preferable.

  Among the compounds (C) containing a boron atom shown above, an organic boron compound and boric acid are preferable from the viewpoint of highly expressing the water vapor barrier property of the polymer-containing composition obtained by the production method of the present invention. Moreover, from a viewpoint that a favorable mixed state with a compound (B) is obtained, a boric acid ester compound and boric acid are more preferable.

  As described above, the production method of the present invention comprises a compound (B) obtained by mixing a compound (B) containing a silicon atom to which at least one selected from a halogen atom and an alkoxy group is bonded and a compound (C) containing a boron atom. A step (second step) of preparing a solution (S2) containing a composition having a molar ratio of B) / compound (C) of 1.5 to 10,000 is included. In the step of preparing the solution (S2), it is preferable to use the catalyst (D) from the viewpoint of smoothly progressing the step.

  Examples of the catalyst (D) used in the production method of the present invention include basic catalysts and salts thereof, and acid catalysts and salts thereof. Examples of the basic catalyst include ammonia, sodium hydroxide, potassium hydroxide, and the like. Examples of the salt of the basic catalyst include ammonium fluoride. On the other hand, various known acid catalysts can be used as the acid catalyst, such as hydrochloric acid, sulfuric acid, nitric acid, p-toluenesulfonic acid, benzoic acid, acetic acid, lactic acid, butyric acid, carbonic acid, oxalic acid, and maleic acid. Can be mentioned. Among these, it is preferable to add an acid catalyst as a catalyst from the viewpoint that the water vapor barrier property of the polymer-containing composition obtained by the production method of the present invention is good. Among the above acid catalysts, hydrochloric acid, sulfuric acid, nitric acid Acetic acid and lactic acid are particularly preferred.

  In the first step of the present invention, a solution (S1) containing the hydroxyl group-containing polymer (A) is prepared. The solvent used for the preparation of the solution (S1) is not particularly limited as long as it is a solvent that dissolves the hydroxyl group-containing polymer (A). 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. When the hydroxyl group-containing polymer (A) used is not highly soluble in water, it is preferable to use a mixed solvent of water and alcohol. On the other hand, when the hydroxyl group-containing polymer (A) to be used has sufficient solubility in water, it is preferable to use water as a solvent from the viewpoint of influence on the environment. The concentration of the hydroxyl group-containing polymer (A) in the solution (S1) is preferably in the range of 1 to 50% by weight, more preferably 3 to 30% by weight from the ease of handling of the solution, Preferably it is the range of 5-20 weight%.

  In the first step, the hydroxyl group-containing polymer (A) is obtained by adding a compound (b) containing a silicon atom to which at least one selected from a halogen atom and an alkoxy group is bonded to a solution containing a vinyl carboxylate polymer. A polymer obtained by being a vinyl alcohol polymer produced by simultaneously proceeding a saponification reaction of a vinyl carboxylate polymer and a reaction of the vinyl carboxylate polymer with the compound (b) It is preferable from the viewpoint of the water vapor barrier property of the containing composition. The vinyl carboxylate polymer described above is used as the vinyl carboxylate polymer. As the compound (b), one or more of the compounds described for the compound (B) containing a silicon atom to which at least one selected from the halogen atoms and alkoxy groups described above is bonded can be applied. Compound (B) and compound (b) may be the same or different. From the viewpoint of water vapor barrier properties of the polymer-containing composition obtained by the production method of the present invention, it is possible to use silicon alkoxide and / or an oligomer derived from silicon alkoxide as at least one component of compound (b). preferable.

  Here, the saponification reaction of the vinyl carboxylate polymer is a reaction for producing a vinyl alcohol polymer from the vinyl carboxylate polymer, and the vinyl carboxylate monomer unit in the vinyl carboxylate polymer The derived acyloxy group is converted into a hydroxyl group, and at the same time, it is selected from carboxylic acid, carboxylic acid ester and carboxylate, although it is different depending on the carboxylic acid compound (the organic solvent used, the type of catalyst, etc. One or more compounds) are by-produced. On the other hand, the reaction between the vinyl carboxylate polymer and the compound (b) causes the compound (b) to exchange with the ester group contained in the carboxylate ester polymer to bond to the polymer. In that case, the obtained vinyl alcohol polymer includes a group derived from the compound (b). In the above reaction, a reaction in which the compounds (b) are usually dehydrated and condensed also occurs.

  In obtaining a vinyl alcohol polymer by the above method, 0.01 to 75 moles of silicon atoms in the compound (b) per 100 moles of acyl groups derived from vinyl carboxylate units in the vinyl carboxylate polymer. It is preferable to use an amount of the compound (b) that falls within the range. When the said ratio is 0.01 mol or more, the water vapor | steam barrier property of the polymer-containing composition obtained becomes more favorable. Moreover, when the said ratio is 75 mol or less, the polymer containing composition obtained has small performance spots (gap of gas barrier performance accompanying storage of solution (S3)). The amount of the compound (b) used is such that the silicon atom in the compound (b) is 0.01 to 50 mol with respect to 100 mol of the acyl group derived from the vinyl carboxylate unit in the vinyl carboxylate polymer. It is more preferable to use such an amount of the compound (b), more preferably 0.1 to 20 mol, particularly preferably 0.1 to 10 mol.

  When conducting a saponification reaction of a vinyl carboxylate polymer, various known catalysts can be used in a general saponification reaction. Usable catalysts include hydrochloric acid, sulfuric acid, p-toluenesulfonic acid, benzoic acid, acetic acid, lactic acid, carbonic acid, oxalic acid, maleic acid and other acidic catalysts, and sodium hydroxide, potassium hydroxide and other alkali metal hydroxides Compounds; alkaline earth metal hydroxide compounds such as magnesium hydroxide and calcium hydroxide; basic catalysts such as amine compounds such as ammonia, triethylamine and ethylenediamine can be mentioned, and these may be used alone or in combination A combination of the above may also be used.

  From the viewpoint of improving the coating suitability (viscosity and appearance of the coating film) of the solution (S3) obtained in the production method of the present invention and the water vapor barrier performance of the polymer-containing composition, the saponification reaction of the vinyl carboxylate polymer is performed. It is preferable to use a basic catalyst. Among these, it is more preferable to use one or more compounds selected from alkali metal hydroxide compounds and alkaline earth metal hydroxide compounds. 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 catalyst used is not necessarily strictly limited, but is derived from the number of moles of halogen atoms and alkoxy groups in the compound (b) to be used and the vinyl carboxylate unit in the vinyl carboxylate polymer to be used. 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 of the total number of acyl groups (total number of mols). preferable.

  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 resulting vinyl alcohol polymer is a by-product carboxylic acid. May contain salt. 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 (S1) and the solution (S3) and the gas barrier property of the polymer-containing composition, the amount of the carboxylate is 5% by weight or less based on the dry weight of the vinyl alcohol polymer. Preferably, it is 2% by weight or less, more preferably 1% by weight or less.

  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. The vinyl alcohol polymer can be washed by a known method using, for example, alcohol or a mixed solvent of alcohol and water.

  When performing the saponification reaction of the vinyl carboxylate polymer, before starting the saponification reaction of the vinyl carboxylate polymer, by controlling the amount of water contained in the reaction solution, water vapor barrier properties, solution solubility and It is possible to obtain a polymer-containing composition having good solution stability. The amount of water contained in the reaction solution is not necessarily limited, but is preferably in the range of 300 to 200000 ppm (weight ratio), more preferably in the range of 2000 to 100000 ppm with respect to the reaction solution. , More preferably in the range of 3000 to 80000 ppm, particularly preferably in the range of 3000 to 60000 ppm.

  A solution (sol) obtained by dissolving a vinyl carboxylate polymer and a compound (b) in a solvent is used as a reaction solution for the saponification reaction of the vinyl carboxylate polymer. The solvent used at that time is not particularly limited as long as it can sufficiently dissolve both the vinyl carboxylate polymer and the compound (b), but an organic solvent is preferably used. Examples of the organic solvent include alcohols such as methanol, ethanol, propanol and butanol; amides such as dimethylformamide and dimethylacetamide; sulfoxides such as dimethyl sulfoxide and the like. These may be used alone or in combination of two or more thereof. It is preferable to use a mixture. Among these, it is particularly preferable to use methanol, ethanol, or dimethyl sulfoxide. Although the amount of the organic solvent used is not necessarily limited, from the viewpoint that the handling property during the production of the hydroxyl group-containing polymer (A) and the water vapor barrier property of the polymer-containing composition obtained by the production method of the present invention are good, The total weight of the vinyl carboxylate polymer and the compound (b) is preferably in the range of 20 to 2000 parts by weight, more preferably in the range of 100 to 1000 parts by weight. In order to reduce the residual ratio of acyl groups (acyl groups derived from vinyl carboxylate units) in the vinyl alcohol polymer, a uniform containing an organic solvent having an affinity for the vinyl alcohol polymer in a proportion of 5% by weight or more It is preferable to use an organic solvent.

  When carrying out the saponification reaction of the vinyl carboxylate polymer, 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 within the range of 0.01 to 10 hours, preferably within the range of 0.01 to 5 hours, more preferably 0.02. Within 3 hours. Further, the atmosphere of the reaction system is not necessarily limited, and conditions such as an air atmosphere and a nitrogen stream can be employed.

  In the first step, a particularly preferable method for preparing the solution (S1) is as follows. According to the above-described method, a solution containing a vinyl alcohol polymer is produced by simultaneously proceeding a saponification reaction of a vinyl carboxylate polymer and a reaction of the vinyl carboxylate polymer and the compound (b). The solvent is removed from the solution containing the obtained vinyl alcohol polymer and dried to obtain a solid content. The vinyl alcohol polymer 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 solid content is washed and dried by a known method using a solvent, if necessary. As the solvent for washing, an alcohol solvent, a mixed solvent of alcohol and water, or the like can be used. The solid content thus obtained is dissolved in a solvent to prepare a solution (S1).

  The second step in the production method of the present invention is obtained by mixing a compound (B) containing a silicon atom to which at least one selected from a halogen atom and an alkoxy group is bonded, and a compound (C) containing a boron atom. In this step, a solution (S2) containing a composition having a compound (B) / compound (C) molar ratio of 1.5 to 100,000 is prepared. In the step of preparing the solution (S2), it is preferable to use the catalyst (D) from the viewpoint of smoothly progressing the step. From the viewpoint of water vapor barrier properties of the polymer-containing composition obtained by the production method of the present invention, the lower limit of the molar ratio of compound (B) / compound (C) is preferably 2 or more, more preferably 3 or more. More preferably, it is 3.5 or more, and particularly preferably 4 or more. Similarly, the upper limit of the molar ratio of compound (B) / compound (C) is preferably 5000 or less, more preferably 1000 or less, still more preferably 100 or less, and particularly preferably 50 or less.

  Although the preparation method of solution (S2) is not specifically limited, It is preferable to mix a compound (B), a compound (C), and the catalyst (D) added as needed in a solution. In preparing the solution (S2), the compound (B) may be added alone or as a solution containing the compound (B). When the compound (B) is added as a solution, the solvent is not particularly limited, but alcohol solvents such as methanol, ethanol, isopropanol, and propanol are preferable. The concentration of the solution containing the compound (B) is not particularly limited. From the viewpoint of the productivity of the polymer-containing composition obtained by the production method of the present invention, the lower limit of the concentration of the solution containing the compound (B) is preferably 1% by weight or more, and preferably 5% by weight or more. Is more preferably 10% by weight or more, and particularly preferably 20% by weight or more. Further, the upper limit of the concentration of the solution containing the compound (B) is preferably 90% by weight or less, more preferably 80% by weight or less, further preferably 70% by weight or less, and 60% by weight or less. It is particularly preferred that

  Similarly, the compound (C) may be added alone or as a solution containing the compound (C). When compound (C) is added as a solution, the solvent is not particularly limited, but alcohol solvents such as methanol, ethanol, isopropanol, and propanol are preferable. The concentration of the solution containing the compound (C) is not particularly limited. From the viewpoint of productivity of the polymer-containing composition obtained by the production method of the present invention, the lower limit of the concentration of the solution containing the compound (C) is preferably 1% by weight or more, and preferably 5% by weight or more. Is more preferably 10% by weight or more, and particularly preferably 20% by weight or more. Further, the upper limit of the concentration of the solution containing the compound (C) is preferably 90% by weight or less, more preferably 80% by weight or less, still more preferably 70% by weight or less, and 60% by weight or less. It is particularly preferred that

  Moreover, although a catalyst (D) may be used independently and a catalyst may be used with water, it is preferable to use a catalyst with water. When using a catalyst with water, water and a catalyst may be added simultaneously, a catalyst may be added after adding water, and water may be added after adding a catalyst. Moreover, water and a catalyst may be added at once, and may be added gradually over time.

From the viewpoint of improving the water vapor barrier property of the polymer-containing composition obtained by the production method of the present invention, the method for preparing the solution (S2) recommended by the present inventors is the following (I) to (III). Is the method.
Method (I): A method of preparing the solution (S2) by adding the catalyst (D) after mixing the compound (B) and the compound (C).
Method (II): A method of preparing the solution (S2) by adding the compound (C) after adding the catalyst (D) to the compound (B).
Method (III): A method of preparing the solution (S2) by adding the catalyst (D) to the compound (B), then adding the compound (C), and further adding the catalyst (D).

The preparation methods (I) to (III) are more preferably the following methods (I ′) to (III ′).
Method (I ′): A method of preparing the solution (S2) by adding the solution containing the compound (C) to the solution containing the compound (B) and then adding the catalyst (D).
Method (II ′): A method of preparing the solution (S2) by adding the catalyst (D) to the solution containing the compound (B) and then adding the solution containing the compound (C).
Method (III ′): After adding the catalyst (D) to the solution containing the compound (B), the solution containing the compound (C) is added, and further the catalyst (D) is added to prepare the solution (S2). Method.

  Among the above-mentioned methods (I) to (III), which are methods for preparing the solution (S2), from the viewpoint of the water vapor barrier property of the polymer-containing composition obtained by the production method of the present invention, the method (II) and The method (III) is more preferred, and the method (III) is more preferred.

  Since the addition amount of the catalyst (D) varies depending on the type of catalyst used and the preparation method of the solution (S2), it is difficult to generally define the addition amount, but the silicon atom derived from the compound (B) and the compound (C ) The water vapor barrier property of the polymer-containing composition obtained by the production method of the present invention is in the range of 0.00001 to 10 mol with respect to 1 mol of the total amount of boron atoms derived from the solution (S3). It is preferable from the viewpoint of improving the solution stability, and more preferably in the range of 0.0001 to 5 mol.

  When the method for preparing the solution (S2) is the above method (I) and method (II), the catalyst is used with respect to 1 mol of the total amount of silicon atoms derived from the compound (B) and boron atoms derived from the compound (C). The amount of (D) added is preferably in the range of 0.00001 to 10 mol, more preferably in the range of 0.0001 to 2 mol, and still more preferably in the range of 0.0005 to 1 mol. .

  Furthermore, when the preparation method of solution (S2) is said preparation method (III), the addition amount of the catalyst (D) to compound (B) is set to 0. 0 with respect to 1 mol of silicon atoms derived from compound (B). The range is preferably from 00001 to 10 mol, more preferably from 0.0001 to 2 mol, and still more preferably from 0.0005 to 1 mol. After mixing the compound (B) and the compound (C), the addition amount of the catalyst (D) when the catalyst (D) is further added is the amount of silicon atoms derived from the compound (B) and boron atoms derived from the compound (C). It is preferably in the range of 0.00001 to 5 mol, more preferably in the range of 0.0001 to 2 mol, and further preferably in the range of 0.0005 to 1 mol with respect to 1 mol of the total amount. .

  In addition, in the second step of preparing the solution (S2), it is preferable to add water. However, the amount of water added when preparing the solution (S2) is determined based on the silicon atom derived from the compound (B) and the compound ( From the viewpoint that the water vapor barrier property of the polymer-containing composition obtained by the production method of the present invention is in the range of 0.1 to 10 mol with respect to 1 mol of the total amount of boron atoms derived from C). preferable. The amount of water added is more preferably in the range of 0.5 to 8 mol, and still more preferably in the range of 1 to 4.

  When a component containing water such as hydrochloric acid is used as the catalyst (D), the amount of water used should be determined in consideration of the amount of water introduced by the component.

  In the second step of preparing the solution (S2), the temperature of the reaction system is not necessarily limited, but is usually in the range of 5 to 100 ° C, preferably in the range of 10 to 60 ° C, Preferably it exists in the range of 10-50 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. Within the range of ~ 6 hours. Further, the atmosphere of the reaction system is not necessarily limited, and conditions such as an air atmosphere and a nitrogen stream can be employed.

  The third step in the production method of the present invention is a step of preparing the polymer-containing composition by preparing the solution (S3) by mixing the solution (S1) and the solution (S2). The method for mixing the solution (S1) and the solution (S2) is not particularly limited. The solution (S2) may be added to the solution (S1), the solution (S1) may be added to the solution (S2), and the solution (S1) and the solution (S2) may be added simultaneously to any container. May be mixed. Among these, from the viewpoint of the stability of the solution, it is preferable to prepare the solution (S3) by adding the solution (S2) to the solution (S1).

  In the third step of the production method of the present invention, it is preferable to adjust the pH of the solution (S3) because the storage stability of the solution is improved and also from the viewpoint of developing a high barrier property. The pH of the solution (S3) is preferably in the range of 1.0 to 7.0, more preferably in the range of 1.5 to 6.0, and in the range of 2.0 to 4.0. Is more preferable, and 2.5 to 3.5 is particularly preferable.

  A known technique can be used to adjust the pH of the solution (S3). For example, acidic compounds such as hydrochloric acid, nitric acid, acetic acid, butyric acid, ammonium sulfate, sodium hydroxide, potassium hydroxide, ammonia, trimethylamine, sodium carbonate The pH can be adjusted by adding a basic compound such as sodium acetate.

  In the third step of the production method of the present invention, the solid content concentration of the solution (S3) is not particularly limited, but is preferably in the range of 0.1 to 40% by weight, 0.5 It is more preferably within the range of ˜20% by weight, and further preferably within the range of 1 to 12% by weight. When the solid content concentration is in the range of 0.1 to 40% by weight, the water vapor barrier property of the polymer-containing composition obtained by the production method of the present invention becomes better. On the other hand, when the solid content concentration exceeds 40% by weight, the storage stability of the solution (S3) may be deteriorated. When the solid content concentration is less than 0.1% by weight, the polymer-containing composition obtained by the production method of the present invention may be used. Water vapor barrier performance spots may be easily generated. Although it does not specifically limit as a solvent used when adjusting solid content concentration, Water; Alcohols, such as methanol, ethanol, and isopropanol; Dimethyl sulfoxide etc. can be mentioned.

  The method for producing a polymer-containing composition of the present invention preferably includes a fourth step of removing the solvent from the solution (S3). In the fourth step, the method of removing the solvent from the solution (S3) is not particularly limited, but a method of removing the solvent by heating with hot air or the like is preferably applied. The temperature of the heating medium when removing the solvent 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 0.0001 to 60 hours, more preferably in the range of 0.001 to 10 hours, and further preferably in the range of 0.001 to 1 hour. preferable. Moreover, about the atmosphere at the time of removing a solvent, although not necessarily limited, conditions, such as under air atmosphere and nitrogen stream, are employable.

  When a composition produced using a sol-gel method of a metal alkoxide compound is used as a barrier material or the like, a metal alkoxide compound is subjected to hydrolysis and condensation reactions to improve the physical properties of the material. Generally, heat treatment is performed after removing the solvent of the solution made of the alkoxide compound. The polymer-containing composition obtained by the production method of the present invention can also be subjected to heat treatment at an arbitrary time as long as the solvent removal from the solution (S3) is almost completed. By performing the heat treatment at a temperature in the range, the water vapor barrier performance is remarkably improved. The temperature of the heat treatment is more preferably in the range of 140 to 240 ° C, and still more preferably in the range of 150 to 230 ° C.

  As a result of examining the heat treatment conditions in more detail by the present inventors, surprisingly, the polymer-containing composition obtained by the production method of the present invention is compared with the polymer composition obtained by the conventional technique, It has been found that excellent water vapor barrier properties and oxygen barrier properties can be obtained even with shorter heat treatment times. Specifically, as will be apparent from the description of Examples and Comparative Examples described later, the polymer-containing composition of Comparative Example 1 of the present application has a water vapor barrier property and an oxygen barrier when the heat treatment time is less than 1 minute. Sexual expression is not always sufficiently obtained. On the other hand, the polymer-containing compositions of the inventions of Examples 1 to 8 can exhibit excellent water vapor barrier properties and gas barrier properties even when the heat treatment time is within 1 minute. The ability to shorten the heat treatment time is extremely preferable from the viewpoint of product production speed, that is, productivity, and also from the viewpoint of saving utility costs such as power consumption. Furthermore, since the heat treatment time can be shortened, coloring and / or cracking of a molded article (for example, a coating film) made of the polymer-containing composition can be effectively suppressed. From this point of view, the industrial significance of the present invention is great.

  The heat treatment can be performed using a known method. Specifically, a hot air system, a thermal drum system, infrared heating, microwave heating, and the like. These methods may be performed alone or in combination of two or more.

  Further, the polymer-containing composition may be subjected to ultraviolet irradiation or electron beam irradiation. Ultraviolet irradiation and electron beam irradiation may be performed any time after the solvent removal from the solution (S3) 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 performing at least one of heat treatment, ultraviolet irradiation, and electron beam irradiation, the performance of the water vapor barrier material of the polymer-containing composition and the water vapor barrier material using the composition is improved.

  In the production method of the present invention, a metal salt, a metal complex, a crosslinking agent, a plasticizer, an antioxidant, an ultraviolet absorber, a flame retardant, and the like are added to the reaction system as necessary within a range that does not impair the effects of the present invention. Can do. Examples of metal salts or metal complexes include metal oxide fine powder produced by wet hydrolysis and polycondensation of the above metal alkoxide compounds; dry hydrolysis, polycondensation or combustion of metal alkoxide compounds. Fine powder of prepared metal oxide; fine silica powder prepared from water glass; inorganic acid metal salt such as carbonate, hydrochloride and nitrate; organic acid metal salt such as oxalate; acetylacetate such as aluminum acetylacetonate Examples thereof include metal complexes such as a nate metal complex, a cyclopentadienyl metal complex, and a cyano metal complex.

Hereinafter, the 1st and 2nd polymer containing composition of this invention is demonstrated. The first polymer-containing composition of the present invention comprises a hydroxyl group-containing polymer (A) and at least one compound (B) containing a silicon atom to which at least one characteristic group selected from a halogen atom and an alkoxy group is bonded. A polymer-containing composition comprising a hydrolyzed condensate of the above and a hydrolyzed condensate of a compound containing a boron atom (C), wherein the molar ratio of the compound (B) / compound (C) is 1.5 to The water vapor transmission rate in the range of 10,000 and 40 ° C.-90% RH is 20 g · 2 μm / m ² ·
It is a polymer-containing composition that is not more than day.

  The hydrolyzed condensate of compound (B) substantially becomes silicon oxide when the condensation polymerization reaction proceeds. In the second polymer-containing composition of the present invention, the hydrolysis condensate is a silicon oxide. In that case, “hydrolysis condensate of compound (B)” can be read as “silicon oxide” in the following description. Similarly, the hydrolysis-condensation product of compound (C) substantially becomes a boron oxide when the condensation polymerization reaction proceeds. In the second polymer-containing composition of the present invention, the hydrolysis condensate is a boron oxide. In that case, in the following description, “hydrolysis condensate of compound (C)” can be read as “boron oxide”.

  As the hydroxyl group-containing polymer (A) contained in the polymer-containing composition of the present invention, those described above can be used. The hydroxyl group-containing polymer (A) is preferably a vinyl alcohol polymer. The vinyl alcohol polymer 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 used in the production method of the present invention contains a group derived from at least one compound (b) containing a silicon atom to which at least one selected from a halogen atom and an alkoxy group is bonded. Is preferred. The compound (b) undergoes an exchange reaction with the ester group contained in the vinyl carboxylate polymer and binds to the polymer. In that case, the vinyl alcohol polymer includes a group derived from the compound (b) including a metal atom to which at least one selected from a halogen atom and an alkoxy group is bonded.

  Moreover, the above-mentioned thing can be used also about the compound (B) containing a silicon atom to which at least 1 chosen from a halogen atom and an alkoxy group couple | bonded, and the compound (C) containing a boron atom.

  The polymer-containing resin composition of the present invention comprises a hydrolyzate of a hydroxyl group-containing polymer (A) and at least one compound (B) containing a silicon atom to which at least one characteristic group selected from a halogen atom and an alkoxy group is bonded. A decomposition condensate (or silicon oxide) and a hydrolysis condensate of a compound (C) containing a boron atom are included. In a preferred embodiment, the first polymer-containing composition of the present invention comprises 0.1 to 200 parts by weight of the hydroxyl group-containing polymer (A) and 100 parts by weight of the hydrolytic condensate of the compound (B). Compound (C) 0.01 to 60 parts by weight. Similarly, in a preferred embodiment, the second polymer-containing composition of the present invention comprises 0.1 to 200 parts by weight of the hydroxyl group-containing polymer (A) and boron oxide with respect to 100 parts by weight of silicon oxide. 0.01 to 60 parts by weight. If the content of the hydroxyl group-containing polymer (A) is less than 0.1 parts by weight, the molded product made of the polymer-containing composition may become brittle and cause defects. Moreover, when content of a hydroxyl-containing polymer (A) exceeds 200 weight part, water vapor | steam barrier property may deteriorate. The content of the hydroxyl group-containing polymer (A) with respect to 100 parts by weight of the hydrolysis condensate (or silicon oxide) of the compound (B) is more preferably 1 to 180 parts by weight, still more preferably 10 to 160 parts by weight. Part, particularly preferably 40 to 150 parts by weight.

  In the present invention, the content of the inorganic components (compound (B) and compound (C)) in the polymer-containing composition can be calculated from the weight of the raw material used when preparing the composition. That is, compound (B) and compound (C), compound (B) and compound (C) partially hydrolyzed, compound (B) and compound (C) completely hydrolyzed, compound (B ) And compound (C) partially hydrolyzed / condensed, compound (B) and compound (C) completely hydrolyzed and partially condensed, or a combination thereof It is assumed that silicon oxide and boron oxide are obtained by hydrolysis / condensation, and the weight of the silicon oxide and boron oxide is calculated.

  Moreover, in the 1st polymer containing resin composition of this invention, the molar ratio of the said compound (B) / the said compound (C) is the range of 1.5-10000. Similarly, in the second polymer-containing resin composition of the present invention, the molar ratio of (silicon atom in the silicon oxide) / (boron atom in the boron oxide) is in the range of 1.5 to 10,000. It is. When the molar ratio is less than 1.5 and when the molar ratio exceeds 10,000, sufficient water vapor barrier properties cannot be obtained. The upper limit of the molar ratio is preferably 2 or more, more preferably 3 or more, still more preferably 3.5 or more, and particularly preferably 4 or more. Further, the lower limit of the molar ratio is preferably 5000 or less, more preferably 1000 or less, still more preferably 100 or less, and particularly preferably 50 or less. The molar ratio can be determined by inductively coupled plasma atomic emission spectroscopy.

The water vapor transmission rate of the polymer-containing composition of the present invention is 20 g · 2 μm / m ² · day or less (40 ° C.-90% RH atmosphere). The upper limit of the water vapor transmission rate is preferably 15 g · 2 μm / m ² · day or less, and more preferably 12 g · 2 μm / m ² · day or less.

Moreover, it is preferable that the polymer containing composition of this invention is excellent in gas barrier property. Specifically, the oxygen permeation rate of the polymer-containing composition is preferably 2.0 cc · 2 μm / m ² · day · atm or less (20 ° C.-85% RH atmosphere). The upper limit of the oxygen transmission rate is more preferably 1.0 cc · 2 μm / m ² · day · atm or less, and further preferably 0.5 cc · 2 μm / m ² · day · atm or less.

  In the polymer-containing composition of the present invention, the water vapor barrier property can be further improved by adding the inorganic layered compound (E). Examples of the inorganic layered compound (E) include montmorillonite, saponite, hectorite, beidellite, stevensite, nontritite, and mica. These may be natural products and synthetic products. Among these, montmorillonite and mica are particularly preferable from the viewpoint of the transparency of the polymer-containing composition and the water vapor barrier property. These inorganic layered compounds (E) can be organically treated.

  In the method for producing a polymer-containing composition of the present invention, the inorganic layered compound (E) may be added to any of the solution (S1), the solution (S2), and the solution (S3). In view of the above, the solution (S1) and the solution (S3) are more preferable. In the present invention, a liquid obtained by adding the inorganic layered compound (E) to the solution (S1), the solution (S2), and the solution (S3) may also be expressed as a “solution”.

  In consideration of adverse effects on the stability of the solution (S3) and the appearance of the polymer-containing composition, the amount of the inorganic layered compound is preferably 0.1 to 50% by weight in the polymer-containing composition. 0.1 to 20% by weight is more preferable, and 0.1 to 10% by weight is more preferable.

  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 solvent exemplified in the description of the method for producing the polymer-containing composition described above can be used.

(Water vapor barrier material)
The water vapor barrier material of the present invention includes a portion comprising the polymer-containing composition of the present invention. By placing the solution (S3) in a mold having a predetermined shape, a polymer-containing composition having a predetermined shape such as a film or sheet can be produced. In addition, a fibrous polymer-containing composition can be produced by spinning the solution (S3) according to a known spinning method and, if necessary, subjecting the reaction to heat treatment or ultraviolet irradiation. . As a known spinning method, a wet spinning method or a dry wet spinning method and a method of impregnating and / or applying the solution (S3) to the fibrous structure are preferably exemplified.

  As described above, in a preferred embodiment of the present invention, since the polymer-containing composition of the present invention exhibits excellent oxygen barrier properties, it can be used as a gas barrier material. In a more preferred embodiment, it can be used as a water vapor barrier material and an oxygen barrier material.

  A typical example of the water vapor barrier material is a water vapor barrier sheet, and the portion is a layer formed 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 water vapor 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 layers (sheets) made of other materials include polyolefins such as polyethylene (hereinafter sometimes abbreviated as “PE”) and polypropylene (hereinafter sometimes abbreviated as “PP”); polycycloolefin (Hereinafter sometimes abbreviated as “PCy”); polyethylene terephthalate (hereinafter sometimes abbreviated as “PET”), polybutylene terephthalate (hereinafter sometimes abbreviated as “PBT”), polyethylene naphthalate (Hereinafter, may be abbreviated as “PEN”) and the like; nylon 6 (hereinafter, sometimes abbreviated as “Ny6”), nylon 66 (hereinafter, abbreviated as “Ny66”), and the like Polyamide; Polyvinyl chloride; Polyurethane; Polyethersulfone, Polycarbonate (hereinafter abbreviated as “PC”) And a sheet made of a metal oxide, a metal, or the like. The lamination method may be dry lamination or wet lamination, and is selected according to the material. In a preferred embodiment, the layer (sheet) made of the other material is a layer containing a thermoplastic resin. In a more preferred embodiment, the layer containing the thermoplastic resin is a thermoplastic resin film having a thickness of 10 to 1000 μm. As the thermoplastic resin, those described above are used. Moreover, it is preferable that the thickness of the layer which consists of a resin composition of this invention is 0.1-100 micrometers. From the viewpoint of the barrier properties of the obtained laminate, the thickness of the layer made of the resin composition of the present invention is more preferably 0.2 μm or more, still more preferably 0.3 μm or more, and particularly preferably 0.00. 5 μm or more. On the other hand, from the viewpoint of preventing cracking of the film, the thickness of the layer made of the resin composition of the present invention is more preferably 50 μm or less, further preferably 20 μm or less, and particularly preferably 10 μm or less.

  The sheet-like polymer-containing composition exhibits a higher level of water vapor barrier properties when laminated with a film having excellent water vapor barrier properties, such as polyolefins such as polypropylene and polyethylene, polycycloolefin (PCy), and polyethersulfone. Can be made.

  When the solution (S3) is used as a coating agent, the polymer-containing composition is formed into a fiber aggregate base by impregnating a base made of a fiber aggregate such as fabric, paper, or wood and then allowing the reaction to proceed. A composite in a form impregnated with a material can be produced. Polyolefins such as PE and PP; Polycycloolefins (PCy); Polyesters such as PET, PBT, and PEN; Polyamides such as Ny6 and Ny66; Heavy metals such as polyvinyl chloride, polyurethane, polyethersulfone, and polycarbonate (PC) Coated; Paper; Metal oxides; Laminate having a coating film composed of a polymer-containing composition by coating a base film or molded product of a predetermined shape composed of metals, etc., and then continuing the reaction while drying. The body can be manufactured. The above laminates include polyester / polymer-containing compositions, polyamide / polymer-containing compositions, polyolefin / polymer-containing compositions, polycycloolefin / polymer-containing compositions, and polyethersulfone / polymer-containing compositions. A laminate comprising at least one layer configuration selected from the composition is preferred, and from the viewpoint of the mechanical properties of the resulting laminate, from a polyester / polymer-containing composition / polyamide or a polyamide / polymer-containing composition. A laminate including the layer structure is more preferable. Specifically, as a laminate including the above layer structure, polyester / polymer-containing composition / polyolefin, polymer-containing composition / polyester / polyolefin, polyamide / polymer-containing composition / polyolefin, polyolefin / polymer-containing Composition / polyolefin, polyester / polymer-containing composition / polyamide / polyolefin, polymer-containing composition / polyester / polyester / 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, etc. Polyester / polymer-containing composition / polyolefin, polymer-containing composition / polyester / polyolefin, polyamide / polymer-containing composition / polyolefin, polyester / polymer-containing composition / polyamide / polyolefin, polymer-containing composition Polyester / Polyester / Polyolefin, Polyamide / Polymer-containing composition / Polyester / Polyolefin are preferred, Polyamide / Polymer-containing composition / Polyolefin, Polyester / Polymer-containing composition / Polyamide / Polyolefin, Polymer-containing composition / More preferred are polyester / polyester / polyolefin, polyamide / polymer-containing composition / polyester / polyolefin. 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.

  In order to form a film made of the solution (S3) 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. Similarly, a laminate of a metal surface and a metal oxide can 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 excellent barrier properties against water vapor. For this reason, it is suitably used as a water vapor barrier material. In addition, as described above, the polymer-containing composition of the present invention has an excellent gas barrier property against a gas such as oxygen in a preferred embodiment, and is used as a good water vapor barrier material and gas barrier material. Furthermore, the polymer-containing composition of the present invention can maintain a high level of barrier properties even after being exposed to high humidity conditions and bending conditions. For this reason, the polymer-containing composition of the present invention is particularly useful as a packaging material for electronic material packaging films and food packaging films. As described above, for example, a laminate such as a film having a coating film made of a polymer-containing composition produced by advancing the reaction after coating on the surface of the base film also has excellent water vapor barrier properties. Since it can be held even after being exposed to high-humidity conditions or bending conditions, it is suitably used as a packaging material such as an electronic material packaging film and a food packaging film.

  Moreover, the polymer-containing composition of the present invention can be used as a protective film for a member that deteriorates due to oxygen or water. Examples of the member include electronic parts and metals. In a preferred embodiment, after coating the base film with the polymer-containing composition of the present invention, the base film is applied to a member to be protected. In another preferred embodiment, the polymer-containing composition of the present invention is coated on the part to be protected of the member. Since the polymer-containing composition of the present invention has excellent water vapor barrier properties, the resulting member can have a long life. For this reason, the said laminated body can be used as a protective film of the member which deteriorates with oxygen or water. In particular, it is useful as a protective film for an element that is easily deteriorated by oxygen or water, such as an organic EL element.

The present invention will be described in more detail with reference to the following examples. However, 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 analysis of the hydroxyl group-containing polymer (A) used in Examples and Comparative Examples was performed by the following method (1
) And (2).

(1) Amount of acyl group 270 MHz ¹ H-NMR (Japan) for vinyl carboxylate polymer (polyvinyl acetate, vinyl polypropionate, ethylene-vinyl acetate copolymer, etc.) and the composition obtained by the saponification reaction The monomer composition of the polymer was determined using “JNM-GSX270” manufactured by Denshi, and the acyl group content of the polymer and the acyl group remaining rate after the saponification reaction were quantified.

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

When an alkali metal hydroxide compound or an alkaline earth metal hydroxide compound is used as a catalyst for the saponification reaction of the vinyl carboxylate polymer, the carboxylate produced as a by-product in the saponification reaction is not removed by drying. From the weight ratio of the carboxylate to the composition determined by the method, the number of moles of acyl groups derived from the carboxylate contained per unit weight of the composition is calculated, and then determined from the ¹ H-NMR. In addition, the number of moles of acyl groups derived from the carboxylate is subtracted from the number of moles of all acyl groups in the composition, and the number of acyl groups present bound to the polymer contained per unit weight of the composition. The number of moles is calculated, and from the ratio of 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 (mole) %)It was determined.

(2) Amount of carboxylate salt A small sample of the composition obtained by the saponification reaction of the vinyl carboxylate polymer was collected, placed in a platinum crucible and treated with an electric furnace (600 ° C), and then polarized Zeeman atomic absorption photometry. Using a meter (“Z-5300” manufactured by Hitachi, Ltd.), the metal atom content in the ash was quantified. Assuming that the metal atom is present in the form of a carboxylate by-produced by the saponification reaction in the composition, the weight ratio of the carboxylate to the polymer-containing composition obtained by the saponification reaction (unit:% by weight) 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.

<Synthesis Example 1>
400 parts by weight of a methanol solution containing 38% by weight of an ethylene-vinyl acetate copolymer (ethylene content 8 mol%) having a viscosity average polymerization degree of 500 was prepared. To this, 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, the amount of water contained in the system was measured, and water was added so that the amount of water contained in the system was 5000 ppm. Then, 20.9 parts by weight of a 10% sodium hydroxide / methanol solution was added, and a saponification reaction was performed at 40 ° C. The system gelled in about 10 minutes after adding the sodium hydroxide / methanol solution. Even after gelation, the mixture was allowed to stand for 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, the system temperature was adjusted to 40 ° C., and the mixture was stirred for 1 hour. After 1 hour, methanol was removed by filtration, and 1500 parts by weight of methanol was added again. The temperature of the system was adjusted to 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 adjusted to 65 ° C. In this way, a vinyl alcohol copolymer (ethylene-vinyl alcohol copolymer having an ethylene content of 8 mol%) which is the hydroxyl group-containing polymer (A-2) used in the examples and comparative examples of the present invention is obtained. Obtained. When this vinyl alcohol polymer 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 amount was 1.0. % By weight. The amount of silicon atoms bonded to the vinyl alcohol polymer was 5.0 mol of silicon atoms per 100 mol of acyl groups derived from vinyl carboxylate units.

  The types of the hydroxyl group-containing polymer (A) used in Examples and Comparative Examples of the present invention are shown in Table 1 below.

<Example 1>
As the hydroxyl group-containing polymer (A), the hydroxyl group-containing polymer (A-1) described in Table 1 is used as the compound (B) containing a silicon atom to which at least one selected from a halogen atom and an alkoxy group is bonded. Trimethoxyborane was used as the compound (C) containing boron atom and silane, respectively. A solution containing 450.0 parts by weight of distilled water to 50.0 parts by weight of the hydroxyl group-containing polymer (A-1), dissolved by heating at 90 ° C. for 1 hour, and containing a hydroxyl group-containing polymer (A) having a solid content concentration of 10% by weight. (S1-1) was prepared (first step).

  Next, after dissolving 126.6 parts by weight of tetramethoxysilane in 126.6 parts by weight of methanol, 4.2 parts by weight of distilled water and 10.4 parts by weight of 0.1N (normal) -hydrochloric acid were added to prepare a sol. . After the obtained sol was reacted at 10 ° C. for 30 minutes with stirring, 4.3 parts by weight of trimethoxyborane (manufactured by Wako Pure Chemicals, grade 1) was added to the sol. After further adding 4.2 parts by weight of distilled water and 10.4 parts by weight of 0.1N (normal) -hydrochloric acid to the sol, the mixture was reacted at 10 ° C. for 30 minutes with stirring to obtain a solution (S2-1). Was prepared (second step). The molar ratio of compound (B) / compound (C) contained in the obtained solution (S2-1) was 13.3.

After diluting the solution (S2-1) obtained by the above method with 217.6 parts by weight of distilled water, the diluted solution is quickly added to the solution (S1-1) prepared in the first step with stirring. did. Furthermore, 1N (normal) -hydrochloric acid was added to the solution so that the pH of the solution was 3.0 to prepare a solution (S3-1) (third step). The solution (S3-1) was allowed to stand for 30 minutes in an atmosphere at 25 ° C. after the preparation.
By removing the solvent of the solution (S3-1) (fourth step), the polymer-containing composition of the present invention can be obtained in a solid state. The content of the hydroxyl group-containing polymer (A) in the polymer-containing composition in this example is 49.3% by weight, the content of silicon oxide is 49.3% by weight, and the content of boron oxide The amount was 1.4% by weight.

Two-pack anchor coating agent (AC; Takelac 3210 (trade name) and Takenate A3072 (trade name) manufactured by Mitsui Takeda Chemical Co., Ltd.) on a stretched PET film (OPET; Lumirror (trade name) manufactured by Toray Industries, Inc.) A base material (AC / OPET) having an anchor coat layer of 0.2 μm was prepared by coating and drying. On the base material made of AC / OPET, the solution (S3-1) after standing was applied by a bar coater so that the thickness after drying was 1 μm. The substrate after coating was dried at 120 ° C. for 5 minutes, and then heat treated at 200 ° C. for 30 seconds. In this way, a laminate (polymer-containing composition (1 μm) / AC (0.2 μm) / OPET (12 μm)) having a colorless and transparent coating film was obtained. Using the obtained laminate, the appearance of the laminate was evaluated according to the following method, and the water vapor transmission rate and the oxygen transmission rate were measured. The appearance of the laminate in this example is good (evaluation: ◯ judgment), the water vapor transmission rate is 10 g · 2 μm / m ² · day, and the oxygen transmission rate is 0.3 cc · 2 μm / m ² · day · atm. Met.

(3) Evaluation of appearance of laminate The appearance of the laminate obtained by the above method was visually evaluated. Appearance evaluation complied with the following criteria.
A: Colorless, transparent, free of bumps and excellent in appearance.
○: Slightly opaque and / or irregularities are observed, but there is no major problem in appearance.
X: Opaque and / or bumpy and poor in appearance.

(4) Water vapor transmission rate Two samples (12 cm × 12 cm square) were prepared from the laminate obtained by the above method. Using the water vapor transmission rate measuring device ("MOCON PERMATRAN-3 / 31" manufactured by Modern Control Co., Ltd.) for the two samples, the water vapor transmission rate was measured under conditions of a temperature of 40 ° C and a humidity of 90% RH. The water vapor permeation rate (unit: g · 2 μm / m ² · day) of the polymer-containing composition was determined by converting the average value of the polymer into a thickness.

(5) Oxygen transmission rate Two samples (12 cm × 12 cm square) were produced from the laminate obtained by the above method. Using the oxygen permeation rate measuring device (“MOCON OX-TRAN 2/20” manufactured by Modern Control Co., Ltd.), the 10 samples were subjected to conditions of a temperature of 20 ° C., a humidity of 85% RH, and an oxygen pressure of 2.5 kgf / cm ² . The oxygen permeation rate was measured for each, and the average value thereof was converted into thickness to determine the oxygen permeation rate (unit: cc · 2 μm / m ² · day · atm) of the polymer-containing composition.

<Example 2>
A solution (S2-2) was prepared in the same manner as in Example 1 except that in the second step of Example 1, the amount of trimethoxyborane added was 0.086 parts by weight. The molar ratio of compound (B) / compound (C) contained in the obtained solution (S2-2) was 999.

  A solution (S3-2) was prepared in the same manner as in Example 1 except that the solution (S2-2) prepared above was used instead of the solution (S2-1) in Example 1, and the solution (S3) was prepared. -2) was used to obtain a laminate (polymer-containing composition (1 μm) / AC (0.2 μm) / OPET (12 μm)). Table 2 shows the composition of the polymer composition obtained in this example and the evaluation results of the laminate.

<Example 3>
A solution (S2-3) was prepared in the same manner as in Example 1 except that in the second step of Example 1, the addition amount of trimethoxyborane was 13.0 parts by weight. The molar ratio of compound (B) / compound (C) contained in the obtained solution (S2-3) was 5.7.

  In Example 1, a solution (S3-3) was prepared in the same manner as in Example 1 except that the prepared solution (S2-3) was used instead of the solution (S2-1), and the solution (S3) was prepared. -3) was used to obtain a laminate (polymer-containing composition (1 μm) / AC (0.2 μm) / OPET (12 μm)). Table 2 shows the composition of the polymer composition obtained in this example and the evaluation results of the laminate.

<Example 4>
In the second step of Example 1, 126.6 parts by weight of tetramethoxysilane was dissolved in 126.6 parts by weight of methanol, and then 4.3 parts by weight of trimethoxyborane (manufactured by Wako Pure Chemical Industries, Ltd., first grade) was added. After further adding 8.4 parts by weight of distilled water and 20.8 parts by weight of 0.1N (normal) -hydrochloric acid to the sol, the mixture was reacted at 10 ° C. for 60 minutes with stirring to obtain a solution (S2-4) Was prepared. The molar ratio of compound (B) / compound (C) contained in the obtained solution (S2-4) was 13.3.

  A solution (S3-4) was prepared in the same manner as in Example 1 except that the solution (S2-4) prepared above was used instead of the solution (S2-1) in Example 1, and the solution (S3) was prepared. -4) was used to obtain a laminate (polymer-containing composition (1 μm) / AC (0.2 μm) / OPET (12 μm)). Table 2 shows the composition of the polymer composition obtained in this example and the evaluation results of the laminate.

<Example 5>
In the second step of Example 1, 126.6 parts by weight of tetramethoxysilane was dissolved in 126.6 parts by weight of methanol, and then 8.4 parts by weight of distilled water and 20.8 parts by weight of 0.1N (normal) -hydrochloric acid. Then, the mixture was reacted at 10 ° C. for 60 minutes with stirring. To the obtained sol, 4.1 parts by weight of trimethoxyborane (manufactured by Wako Pure Chemicals, grade 1) was added to prepare a solution (S2-5). The molar ratio of compound (B) / compound (C) contained in the obtained solution (S2-5) was 13.3.

  In Example 1, except that the solution (S2-5) prepared above was used instead of the solution (S2-1), a solution (S3-5) was prepared in the same manner as in Example 1, and the solution (S3 -5) was used to obtain a laminate (polymer-containing composition (1 μm) / AC (0.2 μm) / OPET (12 μm)). Table 2 shows the composition of the polymer composition obtained in this example and the evaluation results of the laminate.

<Example 6>
As the hydroxyl group-containing polymer (A), (A-1) described in Table 1 above was used. (A-1) 360.0 parts by weight of distilled water was added to 40.0 parts by weight and dissolved by heating to prepare a solution (S1-6) containing a hydroxyl group-containing polymer (A) having a solid content concentration of 10% by weight (S1-6). First step).

  Next, after dissolving 151.9 parts by weight of tetramethoxysilane in 151.9 parts by weight of methanol, 5.0 parts by weight of distilled water and 12.0 parts by weight of 0.1N (normal) -hydrochloric acid were added to prepare a sol. . After the obtained sol was reacted at 10 ° C. for 30 minutes with stirring, 5.2 parts by weight of trimethoxyborane (manufactured by Wako Pure Chemicals, grade 1) was added. After further adding 5.0 parts by weight of distilled water and 12.0 parts by weight of 0.1N (normal) -hydrochloric acid to the sol, the mixture was reacted at 10 ° C. for 30 minutes with stirring to obtain a solution (S2-6) Was prepared (second step). The molar ratio of compound (B) / compound (C) contained in the obtained solution (S2-1) was 13.3.

  After diluting the solution (S2-6) obtained by the above method with 261.2 parts by weight of distilled water, the diluted solution is quickly added to the solution (S1-6) prepared in the first step with stirring. did. Furthermore, 1N (normal) -hydrochloric acid was added to the solution so that the pH of the solution was 3.0 to prepare a solution (S3-6) (third step).

  In Example 1, a laminate (polymer-containing composition (1 μm) / AC) was obtained in the same manner as in Example 1 except that the solution (S3-6) prepared above was used instead of the solution (S3-1). (0.2 μm) / OPET (12 μm)) was obtained. Table 2 shows the composition of the polymer composition obtained in this example and the evaluation results of the laminate.

<Example 7>
As the hydroxyl group-containing polymer (A), (A-2) prepared in Synthesis Example 1 was used. (A-2) 517.4 parts by weight of distilled water was added to 57.5 parts by weight and dissolved by heating at 90 ° C. for 1 hour, and a solution containing a hydroxyl group-containing polymer (A) having a solid concentration of 10% by weight (S1-7) ) Was prepared (first step).

  Next, 119.1 parts by weight of tetramethoxysilane was dissolved in 119.1 parts by weight of methanol, and then 3.9 parts by weight of distilled water and 9.8 parts by weight of 0.1N (normal) -hydrochloric acid were added to prepare a sol. . After the obtained sol was reacted at 10 ° C. for 30 minutes with stirring, 4.1 parts by weight of trimethoxyborane (manufactured by Wako Pure Chemicals, grade 1) was added to the sol. Further, 3.9 parts by weight of distilled water and 9.8 parts by weight of 0.1N (normal) -hydrochloric acid were added to the sol to prepare a sol, which was then reacted at 10 ° C. for 30 minutes with stirring to obtain a solution. (S2-7) was prepared (second step). The molar ratio of compound (B) / compound (C) contained in the obtained solution (S2-7) was 13.3.

  After diluting the solution (S2-7) obtained by the above method with 204.8 parts by weight of distilled water, the diluted solution is quickly added to the solution (S1-7) prepared in the first step with stirring. did. Furthermore, 1N (normal) -hydrochloric acid was added to the solution so that the pH of the solution was 3.0 to prepare a solution (S3-7) (third step).

  In Example 1, a laminate (polymer-containing composition (1 μm) / AC) was obtained in the same manner as in Example 1 except that the prepared solution (S3-7) was used instead of the solution (S3-1). (0.2 μm) / OPET (12 μm)) was obtained. Table 2 shows the composition of the polymer composition obtained in this example and the evaluation results of the laminate.

<Example 8>
As the hydroxyl group-containing polymer (A), 517.4 parts by weight of distilled water was added to 57.5 parts by weight of the hydroxyl group-containing polymer (A-2) produced in Synthesis Example 1 and dissolved by heating. A solution containing A-2) was prepared. Further, 10 parts by weight of mica (trade name “ME-100”, manufactured by Coop Chemical Co., Ltd.) and 90 parts by weight of distilled water as the inorganic layered compound (E) were mixed at 13,000 rpm using a mixer (manufactured by NAVIC, spindle EL-64). The mixture was stirred for 1 hour to prepare a dispersion of the inorganic layered compound (E). After adding the dispersion of the inorganic layered compound (E) to the solution containing (A-2) produced above, the mixture is stirred for 1 hour at 13,000 rpm using a mixer (made by NAVIC, spindle EL-64). Then, a solution (S1-8) containing (A-2) having a solid content concentration of 10% by weight and the inorganic layered compound (E) was prepared (first step).

  A solution (S3-8) was prepared in the same manner as in Example 1 except that the solution (S1-8) prepared above was used instead of the solution (S1-1) in Example 1, and the solution (S3 -8) was used to obtain a laminate (polymer-containing composition (1 μm) / AC (0.2 μm) / OPET (12 μm)). Table 2 shows the composition of the polymer composition obtained in this example and the evaluation results of the laminate.

<Example 9>
In Example 8, a laminate (polymer-containing composition (1 μm) /) was used in the same manner as in Example 8 except that the solution (S3-9) in which the pH of the solution (S3-8) was adjusted to 2.4 was used. AC (0.2 μm) / OPET (12 μm)) was obtained. Table 2 shows the composition of the polymer composition obtained in this example and the evaluation results of the laminate.

<Example 10>
In Example 8, a laminate (polymer-containing composition (1 μm) /) was used in the same manner as in Example 8 except that the solution (S3-10) in which the pH of the solution (S3-8) was adjusted to 3.6 was used. AC (0.2 μm) / OPET (12 μm)) was obtained. Table 2 shows the composition of the polymer composition obtained in this example and the evaluation results of the laminate.

<Example 11>
In the second step of Example 1, a solution (S2-11) was prepared in the same manner as in Example 1 except that 2.6 parts by weight of orthoboric acid was added instead of trimethoxyborane. The molar ratio of compound (B) / compound (C) contained in the obtained solution (S2-11) was 13.3.

  A solution (S3-11) was prepared in the same manner as in Example 1 except that the solution (S2-11) prepared above was used instead of the solution (S2-1) in Example 1, and the solution (S3) was prepared. -11) was used to obtain a laminate (polymer-containing composition (1 μm) / AC (0.2 μm) / OPET (12 μm)). Table 2 shows the composition of the polymer composition obtained in this example and the evaluation results of the laminate.

<Example 12>
As the hydroxyl group-containing polymer (A), 517.4 parts by weight of distilled water was added to 57.5 parts by weight of the hydroxyl group-containing polymer (A-2) produced in Synthesis Example 1 and dissolved by heating. A solution containing A-2) was prepared. Furthermore, as an inorganic layered compound (E), 10 parts by weight of montmorillonite (trade name “Kunipia F”, manufactured by Kunimine Chemical Co., Ltd.) and 90 parts by weight of distilled water were mixed at 13,000 rpm using a mixer (manufactured by NAVIC, spindle EL-64). The mixture was stirred for 1 hour to prepare a dispersion of the inorganic layered compound (E). After adding the dispersion of the inorganic layered compound (E) to the solution containing (A-2) produced above, the mixture is stirred for 1 hour at 13,000 rpm using a mixer (made by NAVIC, spindle EL-64). Then, a solution (S1-12) containing (A-2) having a solid content concentration of 10% by weight and the inorganic layered compound (E) was prepared (first step).

  A solution (S3-11) was prepared in the same manner as in Example 1 except that the solution (S1-12) prepared above was used instead of the solution (S1-1) in Example 1, and the solution (S3 -12) was used to obtain a laminate (polymer-containing composition (1 μm) / AC (0.2 μm) / OPET (12 μm)). Table 2 shows the composition of the polymer composition obtained in this example and the evaluation results of the laminate.

<Comparative Example 1>
In the second step of Example 1, a solution (S2-C1) was prepared in the same manner as in Example 1 except that trimethoxyborane was not added at the time of preparing the solution (S2).

A solution (S3-C1) was prepared in the same manner as in Example 1, except that the solution (S2-C1) prepared above was used instead of the solution (S2-1). Using the solution (S3-C1), in the same manner as in Example 1, on the substrate made of AC / OPET, the solution (S3-1) after standing was dried to have a thickness of 1 μm. It was coated with a bar coater. The substrate after coating was dried at 120 ° C. for 5 minutes and then heat-treated at 200 ° C. for 30 seconds to obtain a laminate (polymer-containing composition (1 μm) / AC (0. 2 μm) / OPET (12 μm)). The resulting laminate had a water vapor transmission rate of 50 g · 2 μm / m ² · day, and an oxygen transmission rate of 1.5 cc · 2 μm / m ² · day · atm. On the other hand, the laminate before drying and heat treatment prepared according to the above method was dried at 120 ° C. for 5 minutes, and then further subjected to heat treatment at 200 ° C. for 5 minutes to have a colorless transparent coating film (polymer-containing composition) Product (1 μm) / AC (0.2 μm) / OPET (12 μm)). The resulting laminate had a water vapor transmission rate of 30 g · 2 μm / m ² · day, and an oxygen transmission rate of 0.5 cc · 2 μm / m ² · day · atm. Table 2 shows the composition of the polymer composition obtained in this comparative example and the evaluation results of the laminate.

<Comparative example 2>
A solution (S2-C2) was prepared in the same manner as in Example 1 except that in the second step of Example 1, the amount of trimethoxyborane added was 43.2 parts by weight. The molar ratio of compound (B) / compound (C) contained in the obtained solution (S2-C2) was 1.

  A solution (S3-C2) was prepared in the same manner as in Example 1 except that the solution (S2-C2) prepared above was used instead of the solution (S2-1) in Example 1. Since a gel-like precipitate was formed, the solution could not be used as a coating agent.

<Comparative Example 3>
As the hydroxyl group-containing polymer (A), (A-1) described in Table 1 above was used. (A-1) 450.0 parts by weight of distilled water was added to 50.0 parts by weight and dissolved by heating to prepare a solution (S1-C3) containing a hydroxyl group-containing polymer (A) having a solid content concentration of 10% by weight. When 4.3 parts by weight of trimethoxyborane (manufactured by Wako Pure Chemical Co., Ltd., first grade) was added to the solution (S1-C3), a gel-like precipitate was formed in the solution. Therefore, the solution should be used as a coating agent. I could not.

<Comparative example 4>
As the hydroxyl group-containing polymer (A), (A-1) described in Table 1 above was used. (A-1) A solution (S1-C4) containing a hydroxyl group-containing polymer (A) having a solid content concentration of 10% by weight and a solid content concentration of 10% by weight by adding 450 parts by weight of distilled water to 50 parts by weight. Prepared.

  Next, after dissolving 126.6 parts by weight of tetramethoxysilane in 126.6 parts by weight of methanol, 4.2 parts by weight of distilled water and 10.4 parts by weight of 0.1N (normal) -hydrochloric acid were added to prepare a sol. . The obtained sol was reacted at 10 ° C. for 60 minutes with stirring to obtain a solution (S2-C4).

  After the solution (S2-C4) obtained by the above method was diluted with 204.8 parts by weight of distilled water, the prepared solution (S1-C4) was quickly added to the diluted solution with stirring. When 4.3 parts by weight of trimethoxyborane (manufactured by Wako Pure Chemical Co., Ltd., first grade) was further added to the resulting solution, a gel-like precipitate was formed in the solution, so that the solution could be used as a coating agent. There wasn't.

<Comparative Example 5>
As the hydroxyl group-containing polymer (A), (A-1) described in Table 1 above was used. (A-1) A solution (S1-C5) containing a hydroxyl group-containing polymer (A) having a solid content concentration of 10% by weight and a solid content concentration of 10% by weight by adding 450 parts by weight of distilled water to 50 parts by weight. Prepared.

  After adding 126.6 parts by weight of tetramethoxysilane and 10.4 parts by weight of 0.1N (normal) -hydrochloric acid to the prepared solution (S1-C5), trimethoxyborane (manufactured by Wako Pure Chemicals, grade 1) When 3 parts by weight were added, a gel-like precipitate was formed in the solution, and thus the solution could not be used as a coating agent.

<Comparative Example 6>
As the hydroxyl group-containing polymer (A), (A-1) described in Table 1 above was used. (A-1) A solution (S1-C6) containing a hydroxyl group-containing polymer (A) having a solid content concentration of 10% by weight and a solid content concentration of 10% by weight by adding 450 parts by weight of distilled water to 50 parts by weight. Prepared.

  Next, after adding 177.5 parts by weight of tetra-i-propoxytitanium to 124.3 parts by weight of acetylacetone to synthesize a titanium chelate compound, 4.2 parts by weight of distilled water and 0.1N (normal) -hydrochloric acid 10. 4 parts by weight was added to prepare a sol. After the obtained sol was reacted at 10 ° C. for 30 minutes with stirring, 4.3 parts by weight of trimethoxyborane (manufactured by Wako Pure Chemicals, grade 1) was added to the sol. Further, 4.2 parts by weight of distilled water and 10.4 parts by weight of 0.1N (normal) -hydrochloric acid were added to the sol, followed by reaction at 10 ° C. for 30 minutes with stirring to obtain a solution (S2-C6). Was prepared (second step).

  When the solution (S2-C6) obtained by the above method was diluted with 217.6 parts by weight of distilled water, the solution became cloudy and then gelled, so that the solution could not be used as a coating agent.

  The laminates of Examples 1 to 12 were excellent in appearance and excellent in both water vapor barrier properties and oxygen barrier properties.

  Unlike the laminated body of Examples 1-8, when the heat processing time was less than 1 minute, the laminated body of Comparative Example 1 was inferior in water vapor | steam barrier property and oxygen barrier property. Moreover, the laminated body of the comparative example 1 was inferior in the water vapor | steam barrier property compared with the laminated body of Examples 1-8, when sufficient heat processing time was spent.

  In Comparative Examples 2 to 5 in which the polymer-containing composition was prepared by a method different from the production method of the present invention, a gel-like precipitate was generated in the solution in any of them and could not be used as a coating agent. .

In Comparative Example 6 where a polymer-containing composition was prepared using tetra-i-propoxytitanium instead of the compound (B) containing a silicon atom to which at least one selected from a halogen atom and an alkoxy group was bonded, In either case, a gel-like precipitate was formed in the solution and could not be used as a coating agent.

Claims (20)

A first step of preparing a solution (S1) containing a hydroxyl group-containing polymer (A);
Compound (B) / Compound (C) mole obtained by mixing a compound (B) containing a silicon atom to which at least one selected from a halogen atom and an alkoxy group is bonded, and a compound (C) containing a boron atom A second step of preparing a solution (S2) comprising a composition having a ratio of 1.5 to 10,000;
A third step of preparing the solution (S3) by mixing the solution (S1) and the solution (S2), and a method for producing a polymer-containing composition. The method for producing a polymer-containing composition according to claim 1, wherein in the second step, the solution (S2) is prepared by adding the catalyst (D) after mixing the compound (B) and the compound (C). The method for producing a polymer-containing composition according to claim 1, wherein in the second step, after adding the catalyst (D) to the compound (B), the compound (C) is added to prepare the solution (S2). In the second step, after adding the catalyst (D) to the compound (B), the compound (C) is added, and then the catalyst (D) is further added to prepare the solution (S2). The manufacturing method of the polymer containing composition of description. The manufacturing method of the polymer containing composition of any one of Claims 1-4 including the 4th process of removing a solvent from the said solution (S3) after a 3rd process. The method for producing a polymer-containing composition according to any one of claims 1 to 5, wherein the hydroxyl group-containing polymer (A) is a vinyl alcohol polymer. The manufacturing method of the polymer containing composition of any one of Claims 1-6 which is an object for water vapor | steam barrier materials. Hydrolysis condensate of hydroxyl group-containing polymer (A), compound (B) containing a silicon atom to which at least one selected from halogen atoms and alkoxy groups is bonded, and hydrolysis condensate of compound (C) containing a boron atom A polymer-containing composition comprising:
The compound (B) / compound (C) molar ratio is in the range of 1.5 to 10,000,
A polymer-containing composition having a water vapor transmission rate of 20 g · 2 μm / m ² · day or less in a 40 ° C.-90% RH atmosphere. A polymer-containing composition comprising a hydroxyl group-containing polymer (A), a silicon oxide, and a boron oxide,
The molar ratio of (silicon atom in the silicon oxide) / (boron atom in the boron oxide) is in the range of 1.5 to 10,000.
A polymer-containing composition having a water vapor transmission rate of 20 g · 2 μm / m ² · day or less in a 40 ° C.-90% RH atmosphere. 10. The polymer-containing composition according to claim 8, wherein an oxygen permeation rate under an atmosphere of 20 ° C.-85% RH is 2.0 cc · 2 μm / m ² · day · atm or less. The polymer-containing composition according to any one of claims 8 to 10, wherein the hydroxyl group-containing polymer (A) is a vinyl alcohol polymer. The polymer containing composition of Claims 8-11 containing 0.1 to 50 weight% of inorganic layered compounds (E). The polymer containing composition by which the polymer containing composition of any one of Claims 8-12 is disperse | distributed to the solvent. The water vapor | steam barrier material containing the part containing the polymer containing composition of any one of Claims 8-13. The water vapor barrier material according to claim 14, wherein the portion is a layer containing the polymer-containing composition. The water vapor barrier material according to claim 15, wherein a layer containing a thermoplastic polymer is laminated on the layer. The water vapor barrier material according to claim 16, wherein the layer containing the thermoplastic polymer is at least one layer selected from a polyester layer, a polyamide layer, and a polyolefin layer. The water vapor barrier material according to claim 16, wherein the layer containing the thermoplastic polymer is at least one layer selected from a polycycloolefin layer and a polyether sulfone layer. A display formed by laminating the water vapor barrier material according to any one of claims 14 to 18 on at least one surface of a display element. The display according to claim 19, wherein the display element of the display is an organic EL element.