JP5400825B2 - Gas barrier sheet containing layered inorganic compound - Google Patents

Description

  The present invention relates to a gas barrier sheet containing a layered inorganic compound having excellent water vapor gas barrier properties, a method for producing the same, and a method for producing a gas barrier coating liquid.

  Materials having a water vapor gas barrier property are widely used in industry. Fields of use include, for example, electronic materials such as displays, solar cell substrates and back sheets, packaging materials such as retort foods, tanks for gasoline, etc., and transport tubes. In many fields, glass, metal, or plastic is used as the material. Among them, glass and metal are often used in applications that require higher water vapor gas barrier performance. However, there is a problem with glass that it is not flexible, is easily broken, and is heavy. Moreover, since metal does not transmit light, there is a problem that the contents cannot be seen.

  On the other hand, by using layered inorganic compounds such as clay minerals typified by smectite group clay and mica group clay for gas barrier sheets, studies are being made to improve the dimensional stability, heat resistance and gas barrier properties of the material of the gas barrier sheet itself. I have been.

  By the way, the layered inorganic compound is composed of a plate-like inorganic crystal called a nanosheet as a unit structure and interlayer ions that compensate for the charge when the nanosheet has a charge. Many of the nanosheets constituting the layered inorganic compound have a negative permanent charge, and in order to compensate for the negative permanent charge, inorganic ions typified by sodium ions and lithium ions are intercalated between the nanosheet layers ( In particular, it exists as an interlayer cation) and retains electrical neutrality (see, for example, Non-Patent Document 1).

  Extensive research has been conducted on materials in which layered inorganic compounds such as clay minerals as described above are added to resins, and some gas barrier films have been put into practical use (see, for example, Non-Patent Document 2).

  However, a conventional gas barrier film using a material in which a layered inorganic compound is added to a resin has a large amount of organic ions on the surface of the nanosheet in order to improve the dispersibility of the layered inorganic compound in a hydrophobic resin and an organic solvent. A process of organic modification is required. As a result, there is a problem in that the gap between layers formed by stacking nanosheets (hereinafter referred to as interlayer distance) is widened by organic ions used for organic modification, and gas barrier properties are insufficient.

  In addition, when a layered inorganic compound having a long average length in the longitudinal direction of the nanosheet (that is, a high aspect ratio) is used, the gas barrier property is generally improved. Therefore, fluorination synthesized by natural montmorillonite or a melting method or a talc modification method. Studies have been carried out using mica or fluorinated hectorite. However, these high-aspect-ratio layered inorganic compounds have poor dispersibility in organic solvents even if their nanosheets are organically modified, so that clay minerals with an aspect ratio of about 50 are used, and gas barrier properties are insufficient. There was a problem. (For example, refer to Patent Document 1).

  In addition, layered inorganic compounds using sodium ions or lithium ions as interlayer ions usually have high water swellability and are highly dispersed only in water-based solvents, so they are combined with hydrophobic resins that are hardly soluble in water. Difficult to do. Therefore, many materials obtained using a layered inorganic compound having a high water swellability are poor in water vapor gas barrier performance because they themselves dissolve in water or swell by absorbing water.

  A method has also been proposed in which lithium ions are used as interlayer ions and heated to lower the hydrophilicity of the material. However, this method requires heat resistance of the constituent members that can be applied because heating at a high temperature of about 400 ° C. is required. Therefore, the types of additives are limited, and the gas barrier sheet formed on the resin film-like support can be heated to such an extent that the hydrophilicity of the gas barrier sheet can be lowered due to the low heat resistance of the resin film. (See, for example, Patent Documents 2 and 3).

  Due to the above problems, many conventional gas barrier films using a layered inorganic compound exhibit high gas barrier properties against dry gas containing almost no water vapor, but in an atmosphere with a high water vapor concentration. There has been a problem that the gas barrier performance and the barrier performance of water vapor itself are poor (see, for example, Non-Patent Document 3).

JP 2008-50235 A JP 2007-277078 A JP 2008-247719 A

Edited by Sudo Kodankai, “Invitation to Clay Science: Clay's Face and Charm”, Sankyo Publishing, p. 6-34 (2000) Nakasumi, edited by “Development of Polymer Nanocomposites”, Frontier Publishing, p. 25-90 (2004) “Overview of Flexible Display”, eExpress, p. 223-224 (2005)

  The present invention provides a gas barrier sheet containing a nanosheet of a layered inorganic compound having excellent water vapor gas barrier properties (that is, a gas containing water vapor and a barrier property against water vapor itself), a method for producing the same, and a method for producing the gas barrier sheet It aims at providing the manufacturing method of a coating liquid.

As a result of intensive research to solve the above problems, the present inventors use a nanosheet that is a cleavage product of a specific clay mineral, and in the presence of an amine, the organic substance that cures by reacting with the amine is cured. Thus, it was found that a gas barrier sheet having excellent water vapor gas barrier properties was obtained, and the present invention was completed. That is, the present invention is as follows.
[1] A gas barrier sheet having a gas barrier layer,
The gas barrier layer is a cured product of a nanosheet-containing composition comprising (a) a nanosheet, (b) an amine, and (c) a curable organic material,
The (a) nanosheet is a cleavage product of one or more layered inorganic compounds selected from the group consisting of a smectite group and a mica group,
The (c) curable organic substance is an organic substance that cures by reacting with an amine;
(A) the average aspect ratio of the nanosheet is 150 or more, and
The gas barrier sheet, wherein the nanosheet is laminated so that the surface direction of the (a) nanosheet is substantially parallel to the surface direction of the gas barrier layer.
[2] The gas barrier sheet according to claim 1, wherein the proportion of the (a) nanosheet in the gas barrier layer is 50% by mass or more and 99% by mass or less.
[3] The above-mentioned [1] or [2], wherein the nanosheet-containing composition has a molar ratio of (b) amine to (c) curable organic material of 10: 1 to 1: 5. Gas barrier sheet.
[4] The gas barrier sheet according to any one of [1] to [3], wherein the (b) amine has two or more amino groups.
[5] The gas barrier sheet according to any one of the above [1] to [4], wherein the (c) curable organic material has an epoxy group.
[6] The gas barrier sheet according to any one of [1] to [5], wherein in the gas barrier sheet, at least a part of the amine (b) is ionically bonded to the nanosheet (a) in a cationic state.
[7] The gas barrier sheet comprises the gas barrier layer,
The (b) amine has two or more amino groups;
(C) the curable organic material is a compound having two or more epoxy groups, and
The gas barrier sheet according to the above [6], wherein the cured body forming the gas barrier layer has a structure in which two or more molecules of (b) amine are chemically bonded to one molecule of (c) curable organic material. .
[8] The gas barrier sheet according to any one of [1] to [7], wherein the layered inorganic compound is a smectite group fluorinated smectite.
[9] The gas barrier sheet according to any one of [1] to [7], wherein the layered inorganic compound is a mica group fluorinated mica.
[10] A method for producing the gas barrier sheet according to any one of [1] to [9] above,
(1) (a) Preparation of aqueous dispersion for dispersion medium substitution, which is obtained by treating an aqueous dispersion obtained by dispersing nanosheets in water with at least one of an ion exchange resin and a semipermeable membrane to obtain an aqueous dispersion for dispersion medium substitution. Process,
(2) An organic solvent dispersion is obtained by substituting part or all of the water in the aqueous dispersion for dispersion medium substitution with an organic solvent, or by adding an organic solvent to the aqueous dispersion for dispersion medium substitution. An organic solvent dispersion preparation step;
(3) A nanosheet-containing composition containing (a) a nanosheet, (b) an amine, and (c) a curable organic substance by adding (b) an amine and (c) a curable organic substance to the organic solvent dispersion; Forming a coating liquid comprising a dispersion medium, a coating liquid forming step;
(4) After applying the coating liquid on the substrate, the dispersion medium in the coating liquid is removed, and the (b) amine and the (c) curable organic substance are reacted to form the nanosheet-containing composition. Forming a gas barrier layer, which is a cured product of the product, on the substrate; and
A method for producing a gas barrier sheet, comprising forming a gas barrier sheet having a gas barrier layer by including the steps in the order described above.
[11] A method for producing a gas barrier coating liquid used for producing the gas barrier sheet according to any one of [1] to [9],
(1) (a) Preparation of aqueous dispersion for dispersion medium substitution, which is obtained by treating an aqueous dispersion obtained by dispersing nanosheets in water with at least one of an ion exchange resin and a semipermeable membrane to obtain an aqueous dispersion for dispersion medium substitution. Process,
(2) An organic solvent dispersion is obtained by substituting part or all of the water in the aqueous dispersion for dispersion medium substitution with an organic solvent, or by adding an organic solvent to the aqueous dispersion for dispersion medium substitution. An organic solvent dispersion preparation step;
(3) A nanosheet-containing composition containing (a) a nanosheet, (b) an amine, and (c) a curable organic substance by adding (b) an amine and (c) a curable organic substance to the organic solvent dispersion; Forming a coating liquid comprising a dispersion medium, a coating liquid forming step;
The manufacturing method of the coating liquid for gas barriers including performing in order of the said description.

  ADVANTAGE OF THE INVENTION According to this invention, the coating liquid which can be used in order to manufacture the gas barrier sheet which has high water vapor | steam gas barrier property, and this gas barrier sheet can be provided.

3 is a diagram showing an X-ray diffraction spectrum of a gas barrier sheet formed in Example 1. FIG. 2 is a diagram showing a TEM photograph of a cross section of a gas barrier sheet formed in Example 1. FIG.

<Gas barrier sheet>
The present invention is a gas barrier sheet having a gas barrier layer, wherein the gas barrier layer is a cured body of a nanosheet-containing composition containing (a) a nanosheet, (b) an amine, and (c) a curable organic substance, ) The nanosheet is a cleavage product of one or more layered inorganic compounds selected from the group consisting of the smectite group and the mica group, (c) the curable organic substance is an organic substance that is cured by reacting with an amine, a) The average aspect ratio of the nanosheet is 150 or more, and in the gas barrier layer, the nanosheet is laminated so that the surface direction of the (a) nanosheet is substantially parallel to the surface direction of the gas barrier layer. A gas barrier sheet is provided. The gas barrier sheet of the present invention including the nanosheet can have an excellent water vapor gas barrier property due to the above configuration. As used herein, the term “gas barrier layer” refers to a layer that exhibits water vapor gas barrier properties (that is, a barrier property against gas containing water vapor and water vapor itself), and “gas barrier sheet” refers to at least one gas barrier layer. It refers to a sheet having a layer. That is, the gas barrier sheet includes both those composed only of the gas barrier layer and those composed of the gas barrier layer and other layers.

[(A) Nanosheet]
The (a) nanosheet, which is a cleavage product of one or more layered inorganic compounds selected from the group consisting of smectite group and mica group (hereinafter sometimes simply referred to as layered inorganic compound) used in the present invention, will be described. Smectites and mica belong to clay minerals. Clay minerals are classified into 1: 1 type and 2: 1 type according to the shape of the layer. For example, the kaolinite group is classified into the 1: 1 type, and the pyrophyllite group, smectite group, Vermiculite, mica, brittle mica, and chlorite are classified. These clay minerals have a layered inorganic compound structure, and are composed of nanosheets as minimum basic units and interlayer ions.

  In addition, regarding the term “(a) nanosheet”, unless otherwise specified, the present invention includes nanosheets including those in which a layered inorganic compound is cleaved from a unit layer (ie, one layer) to several tens of layers (particularly 10 layers). Called. (A) The nanosheet is preferably cleaved so as to be as close to the unit layer as possible. (A) The nanosheet is obtained by, for example, a method as described later, by laminating a layered inorganic compound in an aqueous dispersion or an organic solvent dispersion from a unit layer (ie, one layer) to several tens of layers, preferably as close to the unit layer as possible. Thus, it can be formed by cleaving (peeling).

  The smectite group, vermiculite group, and mica group have a characteristic that they are easily cleaved (peeled) in an organic solvent. In the present invention, from the viewpoint of transparency of the gas barrier sheet, at least one selected from the group consisting of smectite group and mica group is used. In addition, it can confirm that a layered inorganic compound exists as a nanosheet which is a cleaved substance in a dispersion liquid by a small angle X-ray-scattering measurement. In the present invention, the smectite group includes clay minerals such as montmorillonite, hectorite, and saponite, and hectorite is particularly preferable.

  From the viewpoint of easy cleavage (peeling) in an organic solvent, the cation exchange capacity of the layered inorganic compound is preferably 10 meq / 100 g or more, and more preferably 40 meq / 100 g or more. Moreover, 200 meq / 100g or less is preferable and 150 meq / 100g or less is more preferable. In addition, the said cation exchange capacity | capacitance can be calculated | required by the well-known method using ammonium acetate and sodium chloride or potassium chloride based on the Schollenberger method.

  As the layered inorganic compound for forming the nanosheet (a) used in the present invention, either natural clay or synthetic clay can be used. Natural clays generally contain iron ions in the soil and may be colored brown. In order to give the gas barrier sheet of the present invention high transparency, in particular, no coloring, it is preferable to use synthetic clay. The smectite group and mica group minerals used in the present invention are also advantageous from the viewpoint of ease of synthesis.

  From the viewpoint of water vapor gas barrier properties, a nanosheet having a large average aspect ratio is preferred. The average aspect ratio of (a) nanosheets calculated by the method described later is 150 or more, more preferably 500 or more, and most preferably 1000 or more.

  (A) The larger the average aspect ratio of the nanosheet, the higher the effect of improving the gas barrier property. However, if the average aspect ratio is too large, the cleavage / dispersibility tends to be lowered, and the solid content of the nanosheet dispersion is increased by thickening. It tends to be difficult to increase the concentration. From the above viewpoint, (a) the average aspect ratio of the nanosheet is usually preferably 30000 or less, and more preferably 10,000 or less.

  Here, the method for calculating the average aspect ratio Z of the nanosheet (a) used in the present invention will be described in relation to the average particle diameter X.

  The average aspect ratio Z is defined as a value indicating the relationship of (a) the unit thickness d of the nanosheet and Z = X / d, where X is the average particle diameter of the (a) nanosheet used in the present invention. If the nanosheet is dispersed in the desired dispersion medium, the average particle diameter X is determined from the measurement of the dispersion by the dynamic light scattering method. The average particle diameter X can also be obtained by applying the diluted dispersion on a flat substrate (for example, cleaved surface of mica mineral), drying the solvent, and measuring with an AFM (atomic force microscope). . Here, (a) the unit thickness d of the nanosheet is the thickness of the unit layer of the layered inorganic compound. As described above, the nanosheet in the present specification includes a layered inorganic compound cleaved from a unit layer (that is, one layer) to several tens of layers. Therefore, the average aspect ratio of the nanosheet (a) when the layered inorganic compound is cleaved to two or more layers means the average aspect ratio converted per unit layer of the layered inorganic compound.

  The unit thickness d is (a) only on the nanosheet powder, or on a base material (for example, a smooth resin substrate or a silicon wafer) from which the influence of the base material can be sufficiently eliminated during measurement. It is a value obtained by a known measurement method such as an X-ray diffraction method for a thin film obtained after the dispersion liquid contained as a solid content is dropped and sufficiently dried. The unit thickness d of the nanosheet is generally known to be about 0.93 nm to 1.04 nm in smectite group and mica group clay minerals. In addition, in the smectite group clay minerals, in which the interlayer ions are exchanged from sodium ions to lithium ions and then heated at about 600 ° C. to remove moisture, the nanosheets come close to the theoretical limit. The unit thickness d obtained by the above measuring method is 0.95 nm. Therefore, in these clay minerals (a clay mineral belonging to the smectite group generally having a 2: 1 type structure and a mica group clay mineral), the unit thickness d of the nanosheet may be considered to be 0.95 nm. In this specification, unless otherwise specified, the unit thickness d of the nanosheet in the smectite group clay mineral and mica group clay mineral having a 2: 1 type structure is treated as 0.95 nm.

  (A) The average particle diameter of the nanosheet (that is, the average length in the longitudinal direction) is preferably 38 nm or more, more preferably 142.5 nm or more, particularly preferably 475 nm or more from the viewpoint of water vapor gas barrier properties. From the viewpoint of ease of dispersion, it is preferably 95000 nm or less, more preferably 28500 nm or less, and particularly preferably 9500 nm or less. (A) The average particle diameter of the nanosheet can be measured by the dynamic light scattering method or the method of measuring the length by AFM after applying the dispersion on a flat substrate as described above.

  From the viewpoint of high transparency and easy synthesis, the layered inorganic compound is preferably the smectite group fluorinated smectite, and is preferably the mica group fluorinated mica.

  Further, as a layered inorganic compound having a large average aspect ratio as described above, being easy to cleave and having high transparency, specifically, a fluorinated hectorite synthesized by a melting method (for example, NHT sol B2 or classified NHT (NHT classified sol, manufactured by Topy Industries, Ltd.), fluorinated mica synthesized by the melting method (for example, NTS-5, manufactured by Topy Industries, Ltd.), high purity talc Swellable mica obtained by heat treatment with sodium or lithium silicofluoride (for example, ME-100 or MEB-3, manufactured by Coop Chemical Co., Ltd.) and the like are most preferable. These layered inorganic compounds may be used alone or in combination of two or more.

  In addition, regarding a composition of a layered inorganic compound (namely, nanosheet and interlayer ion), it represents with the composition formula described in well-known literature. Therefore, the composition formula described in this specification shows an ideal composition, and the composition of the various layered inorganic compounds used in the present invention needs to exactly match the composition formula in the literature. Absent. The layered inorganic compound may be derived from a clay mineral containing impurities.

[(B) Amine]
The (b) amine used in the present invention will be described. In the present invention, (a) a nanosheet which is a cleavage product of one or more layered inorganic compounds selected from the group consisting of a smectite group and a mica group is used in combination with (b) an amine. (B) The amine is typically (a) by adding (b) the amine into the organic solvent dispersion in which the nanosheets are dispersed in the organic solvent and then removing the organic solvent. Combined with nanosheets. Thereby, (b) at least a part of the amine is adsorbed on the (a) nanosheet. (B) Since the amine adsorbs to the (a) nanosheet, the surface of the (a) nanosheet can be hydrophobized, so that the gas barrier sheet of the present invention exhibits excellent water vapor gas barrier properties.

  Further, in a preferred embodiment of the present invention, (b) at least a part of the amine is ionized (particularly in a cationic state), and (a) is more strongly adsorbed to the nanosheet by being ionically bonded to the nanosheet. . In this case, the water vapor gas barrier property is particularly good. (B) The presence of a state in which the amine is cationized and (a) is ionically bonded to the nanosheet is obtained by, for example, immersing the nanosheet with nitric acid or the like, and quantifying the cation species in the obtained treatment liquid. This is confirmed by a method for detecting the presence of amine ions.

  As the (b) amine, an organic amine is preferable from the viewpoint that (a) the nanosheet can be favorably hydrophobized. In addition, any of primary amines, secondary amines and tertiary amines can be used, and any of arylamines, heterocyclic amines, aliphatic polyamines, aromatic amines and the like can be used. Suitable amines include, for example, ammonia, methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, cyclohexylamine, benzylamine, dimethylamine, diethylamine, di-n-propylamine, trimethylamine, triethylamine, tri-amine. n-propylamine, aniline, N-methylaniline, N, N-dimethylaniline, p-toluidine, p-fluoroaniline, p-chloroaniline, p-bromoaniline, p-iodoaniline, p-alicydin, p-nitro Aniline, pyrrole, pyrocidine, imidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, epoxy-imidazole adduct, pyro Gin, piperidine, N, N-dimethylpiperazine, triethylenediamine, benzyldimethylamine, 2- (dimethylaminomethyl) phenol, 2,4,6-tris (dimethylaminomethyl) phenol, diethylenetriamine, 1,2-diaminocyclohexane, Triethylenetetramine, tetraethylenepentamine, dipropyleneamine, diethylaminopropylamine, AMINE248, N-aminoethylpiperazine, ramiron C-260, AralgitHY-964, mensendiamine, isophoronediamine, S Cure211, 212, Wandamine HM, 1.3 BAC, m-xylenediamine, Shoamine X, amine black, Shoamine black, Shoamine N, 1001, 1010, metaphenylenediamine , Diaminodiphenylmethane, diaminodiphenylsulfone, diazabicycloundecene, and the like. These amines may be used alone or in combination of two or more.

  (A) Since there is a charge on the surface of the nanosheet, the highly polar functional group has good adsorbability to the (a) nanosheet. From this viewpoint, it is preferable that the (b) amine used in the present invention has a highly polar functional group. As the highly polar group, for example, a carboxyl group, a ketone group, a hydroxyl group, a cyano group, an amide group, and an epoxy group are preferable.

  An amine having two or more amino groups is particularly preferable in that (a) it can be adsorbed to two or more of the same or different anions in the nanosheet and can exhibit high water vapor gas barrier properties. Examples of the amine having two or more amino groups include 1,2-phenylenediamine, cis-1,2-cyclohexanediamine, trans-1,2-cyclohexanediamine, 1,3-cyclohexanediamine, N-benzylethylenediamine, N , N′-dibenzylethylenediamine, metaxylenediamine, diethylenetriamine, triethylenediamine, imidazole, 1-methylimidazole, 1,2-dimethylimidazole, 2-hectadecylimidazole, 2-ethyl-4-methylimidazole, and the like. . These amines may be used alone or in combination of two or more.

  (B) The cationization of the amine can occur, for example, when (a) a cation present as an interlayer ion of the nanosheet reacts with the amine. For example, when the interlayer cation between layered inorganic compounds (a) nanosheets is ammonium ions, (a) the amine is deprived of the protons from the ammonium ions in the organic solvent dispersion in which the nanosheets are dispersed in the organic solvent. (B) The base dissociation constant pKb of the amine is preferably smaller than 4.74 which is the pKb of ammonia. However, in the case of using an organic solvent dispersion in which the nanosheet (a) of the layered inorganic compound containing a hydrogen ion type cation as an interlayer cation is used, the hydrogen ion type cation reacts with any amine to convert the amine into a cation. The preferred base dissociation constant of the amine is not limited to the above, because the reaction to convert the amine proceeds.

[(C) Curable organic substance]
The (c) curable organic substance used in the present invention is an organic substance that cures by reacting with an amine. Accordingly, (c) the curable organic substance has a structure (typically a functional group) having reactivity with an amine in the molecule. Examples of structures that react with amines include functional groups such as epoxy groups, acrylic groups, amide groups, carboxylic acid groups, and acid anhydride groups.

  In the present invention, typically, (b) an amine in (b) an organic solvent dispersion in which (a) a nanosheet is dispersed, which is a cleavage product of one or more layered inorganic compounds selected from the group consisting of a smectite group and a mica group In the presence of (c), (c) a curable organic substance is added, and heating or ultraviolet irradiation is performed before or after film formation, whereby (c) the curable organic substance is cured by reacting with (b) an amine. Thereby, the gas barrier layer which is a hardening body of the nanosheet containing composition containing this (a) nanosheet, this (b) amine, and this (c) curable organic substance can be obtained.

  In a preferred embodiment of the present invention, (b) a part of the amine is ionized (particularly cationized), and (a) is ionically bonded to the nanosheet and more strongly adsorbed. In this case, (c) the curable organic substance reacts with this amine, and (a) the nanosheet surface is hydrophobized without greatly increasing the interlayer distance of the nanosheet without using a large amount of organic substance. Can do. Therefore, in this case, a particularly high water vapor barrier property can be obtained.

  Moreover, it is preferable that (c) curable organic substance has two or more functional groups which react with an amine in a molecule | numerator. In this case, (a) the curable organic substance reacts so as to connect (b) amines that are ionically bonded to the nanosheet, so that the two (a) nanosheets can be connected and a higher water vapor gas barrier It is preferable at the point which can express sex.

  (C) As a curable organic substance, the compound which has 1 or more types of functional groups selected from an epoxy group, an acryl group, an amide group, a carboxylic acid group, and an acid anhydride group is preferable. (C) Preferable examples of the curable organic material include a compound having an epoxy group, a compound having an acrylic group, a compound having an amide group, a compound having a carboxylic acid group, and a compound having an acid anhydride group. For the reasons described above, compounds having two or more of these functional groups in the molecule are particularly preferred.

  In particular, from the viewpoint of adhesion of the gas barrier layer to the support, the (c) curable organic material preferably has an epoxy group, and particularly preferably has two or more epoxy groups.

  In a particularly preferred embodiment, there is provided a cured body that (b) an amine has two or more amino groups, (c) a curable organic substance is a compound having two or more epoxy groups, and forms a gas barrier layer. (C) It has a structure in which two or more molecules of (b) amine are chemically bonded to one molecule of the curable organic substance. This aspect is particularly advantageous when the gas barrier sheet is composed of a gas barrier layer, and provides the advantage that the support and the gas barrier layer are brought into close contact with each other.

  Examples of the compound having an epoxy group that is particularly preferable as the (c) curable organic substance include, for example, bisphenol A type epoxy resin; bisphenol F type epoxy resin; bisphenol AD type epoxy resin; 1,4-butanediol, 1,6 -Polyglycidyl ethers of polyhydric alcohols such as hexanediol, polyethylene glycol, polypropylene glycol, trimethylolpropane, resorcinol; polyglycidyls of polycarboxylic acids such as phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, sebacic acid and dodecanoic acid Esters; Polyepoxides of polybutadiene; Epoxy resins such as phenol novolac type and cresol novolac type; Trifunctional or higher functional epoxy compounds such as tetraglycidyl compound; Polyethylene glycol glycol And the like; Jill ether, low molecular weight epoxy resin which is a butanediol diglycidyl ether. These can be used alone or in combination of two or more.

  In particular, from the viewpoint of transparency of the gas barrier layer, the (c) curable organic material preferably has an amide group or a carboxylic acid.

  (C) As a compound having an amide group particularly preferable as a curable organic substance, for example, lactam such as ε-caprolactam, undecane lactam, lauryl lactam; formamide, N-methylformamide, N-ethylformamide, N, N-dimethyl Examples include formamide, N, N-diethylformamide, N-methylacetamide, N-ethylacetamide, N, N-dimethylacetamide, N, N-diethylacetamide, N-methylpyrrolidone and the like.

  (C) Examples of the compound having a carboxylic acid group that are particularly preferable as the curable organic substance include aromatic polyvalent carboxylic acids such as orthophthalic acid, isophthalic acid, terephthalic acid, toluene dicarboxylic acid, trimellitic acid, and hemimellitic acid; Polynuclear aromatic carboxylic acids such as naphthalene dicarboxylic acid; other active hydrogen-containing aromatic carboxylic acids such as hydroxybenzoic acid and aminobenzoic acid; and derivatives thereof; adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecane Aliphatic dicarboxylic acids such as diacids; unsaturated aliphatic dicarboxylic acids such as dimer acids and dihydromuconic acids; fats such as tetrahydrophthalic anhydride, 1,2,3-propanetricarboxylic acid and 4-methylhexahydrophthalic acid (ring ) Group polycarboxylic acid; aminovaleric acid, oxyundecanoic acid, etc. Active hydrogen-containing fats (ring) aromatic carboxylic acids; and derivatives thereof. Further, a compound having an ester group and a compound having a lactone are also particularly preferable because they are hydrolyzed to generate a carboxylic acid group. Examples of the compound having an ester group include ethyl acetate, phenyl acetate, acetic acid = 2,2,2-trifluoroethyl, diethyl methylmalonate, and ethyl cyclohexanecarboxylate. Examples of the compound having a lactone include α-acetolactone, β-propiolactone, γ-butyrolactone, δ-valerolactone, and ε-caprolactone.

  In particular, from the viewpoint of heat resistance of the gas barrier layer, the (c) curable organic material preferably has an acid anhydride group.

  (C) Examples of the compound having an acid anhydride group particularly preferable as the curable organic substance include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, and -3 -Chlorophthalic anhydride, 4-chlorophthalic anhydride, benzophenone tetracarboxylic anhydride, succinic anhydride, methyl succinic anhydride, dimethyl succinic anhydride, dichlor succinic anhydride, methyl nadic acid, dodecyl succinic acid, chlorendec anhydride, maleic anhydride Etc.

[Characteristics of nanosheet-containing composition, gas barrier layer and gas barrier sheet]
The gas barrier sheet of the present invention has a gas barrier layer that is a cured body of a nanosheet-containing composition containing (a) a nanosheet, (b) an amine, and (c) a curable organic material. The gas barrier sheet may be a gas barrier layer alone, or may be composed of a substrate and a gas barrier layer formed by laminating a gas barrier layer on a substrate by a method described later, or a gas barrier layer laminated on a substrate. A gas barrier sheet composed of a support and a gas barrier layer formed by peeling and laminating this on a new support may also be used. In addition to the gas barrier layer and the substrate and / or the support, the gas barrier sheet is used to prevent a gas barrier film made of an inorganic material, a reinforcing material made of a resin material, scratches, etc., as will be described in detail later. These layers may further include a protective layer, a smoothing layer for smoothing the surface, an anchor coat layer, and the like.

  The material of the substrate or the support when it is a constituent member of the gas barrier sheet is not particularly limited, but when the gas barrier sheet is required to be transparent, the substrate or the support preferably has a visible light transmission property. As a substrate or support having visible light transmission, among resin materials, for example, polyethylene terephthalate resin, polyethylene naphthalate resin, polyimide resin, polysulfone resin, polyethersulfone resin, polycarbonate resin, polyarylate resin, polyetherimide Examples thereof include resins, polybutylene terephthalate resins, nylon resins, polymethyl methacrylate resins, triacetyl cellulose resins, amorphous polyolefin resins, fluororesins, cycloolefin resins, and ethylene vinyl acetate resins. Polyimide resin, polyethersulfone resin and fluororesin are preferable from the viewpoint of heat resistance, and polyethylene naphthalate resin is preferable from the balance of transparency, heat resistance and solvent resistance, and polyethylene from the viewpoint of cost. A terephthalate resin is preferred. When the gas barrier layer is used while being fixed (attached) on the substrate or the support, the gas barrier layer which is a film-like material (typically a transparent material) is made difficult to peel from the substrate or the support. Therefore, an anchor coat layer may be provided on the surface of the substrate or the support. Moreover, when using only the gas barrier layer peeled from the board | substrate or the support body as a gas barrier sheet of this invention, it is good to carry out the easy peeling process on the surface of a board | substrate or a support body.

  In one embodiment of the present invention, the proportion of (b) amine in the total mass of (a) nanosheet and (b) amine in the nanosheet-containing composition is preferably 50% by mass or less, more preferably 50%. It is less than mass%, more preferably 30 mass% or less. In this case, although it depends on the cation exchange capacity of the (a) nanosheet, it is advantageous in that it is considered that the interlayer distance of the (a) nanosheet does not spread to 5.0 nm or more. Moreover, the ratio of (b) amine in the total mass of (a) nanosheet and (b) amine in the nanosheet-containing composition is 1 in that (b) amine is favorably adsorbed on (a) nanosheet. The content is preferably at least 3% by mass, more preferably at least 3% by mass.

  That is, the proportion of (a) nanosheets in the total mass of (a) nanosheets and (b) amine in the nanosheet-containing composition is preferably 50% by mass or more, more preferably more than 50% by mass, More preferably, it is 70 mass% or more, and it is preferable that it is 99 mass% or less, More preferably, it is 97 mass% or less.

  The ratio of (b) amine to (c) curable organic material in the nanosheet-containing composition is preferably 10: 1 to 1: 5 in molar ratio. The abundance of the (c) curable organic substance in the nanosheet-containing composition is preferably 1/10 or more in terms of molar ratio to (b) amine. In this case, the water vapor gas barrier property is exhibited better. The abundance is more preferably at least 1/5 times the molar ratio of (b) amine, and more preferably at least 1/2 times the molar ratio of (b) amine. Moreover, it is preferable that the existing amount of (c) curable organic substance in a nanosheet containing composition is 5 times or less by molar ratio with respect to (b) amine. In this case, (a) expansion between the layers of the nanosheet is suppressed. The abundance is more preferably 2 times or less in molar ratio to (b) amine, and further preferably 1 time or less in molar ratio to (b) amine.

  In one embodiment of the present invention, the total of (a) nanosheet, (b) amine, and (c) curable organic substance in the nanosheet-containing composition, depending on the molecular weight of (b) amine and (c) curable organic substance. The ratio of the total mass of (b) amine and (c) curable organic substance in the mass (that is, the ratio of (a) organic substance to the total mass of the nanosheet and the organic substance) is (b) amine and (c) curable. It is preferably 2% by mass or more, more preferably 5% by mass or more, and still more preferably 8% by mass or more in that the (a) hydrophobic effect on the surface of the nanosheet by the reaction product of the organic matter is favorably obtained. In addition, (a) the nanosheet interlayer distance is preferably 50% by mass or less, more preferably less than 50% by mass, even more preferably 4 in that it is considered that the interlayer distance of the nanosheet does not extend to 5.0 nm or more. Mass%, particularly preferably at most 30 mass%.

  That is, in other words, the proportion of (a) nanosheets in the total mass of (a) nanosheets, (b) amines and (c) curable organic materials is preferably 50% by mass or more, more preferably more than 50% by mass. More preferably, it is 60% by mass or more, particularly preferably 70% by mass or more, and preferably 98% by mass or less, more preferably 95% by mass or less, and further preferably 92% by mass or less. .

  In the gas barrier sheet of the present invention, the proportion of the (a) nanosheet in the gas barrier layer is preferably 50% by mass or more and 99% by mass or less. When the said ratio is 50 mass% or more, it is advantageous at the point considered that the interlayer distance of (a) nanosheet does not spread to 5.0 nm or more. Moreover, when the said ratio is 99 mass% or less, the hydrophobization effect of the (a) nanosheet surface by the reaction product of (b) amine and (c) curable organic substance is favorable. The ratio is more preferably 60% by mass or more and 97% by mass or less, still more preferably 70% by mass or more and 95% by mass or less, and particularly preferably 80% by mass or more and 93% by mass or less.

((A) Confirmation of plane orientation of nanosheet)
As a method for confirming the orientation lamination state of the nanosheet (a) in the gas barrier layer, analysis of an X-ray diffraction spectrum by an X-ray diffractometer and direct observation of the lamination state by a TEM (transmission electron microscope) are effective. Conventionally, various researches and evaluations have been conducted on the orientation and lamination state of a film formed on a support such as a glass substrate by X-ray diffraction measurement, and the state of nanosheet dispersion and peeling in a nanocomposite material containing clay. In general, the lamination state of nanosheets depends on the relative intensity and number of peaks generated in the X-ray diffraction spectrum by the first-order diffraction of the layered inorganic compound on the 001 plane, the position of the peak represented by the diffraction angle 2θ and the half-value width thereof And the distribution of interlayer distance.

  In the gas barrier sheet according to the present invention, in the gas barrier layer, (a) the nanosheet is laminated so that the surface direction of the nanosheet is substantially parallel to the surface direction of the gas barrier layer, thereby providing an excellent water vapor gas barrier property. Have. In the gas barrier layer, (a) the surface direction of the nanosheet is oriented as described above, which means that the X-ray diffraction of the gas barrier layer is a sharp peak due to the first-order diffraction of the 001 plane of the mineral crystal constituting the nanosheet (a). In addition, since only the peak showing the first order diffraction of the 00n plane (n is an integer) appears, the 001 plane of the mineral crystal of the nanosheet in the gas barrier layer is substantially the same as the plane direction of the gas barrier layer. It can be confirmed that they are lined up in parallel. (A) The above-described plane orientation of the nanosheet is achieved by (a) the (b) amine regularly adsorbed on the nanosheet, and (c) the curable organic substance reacting with the (b) amine. The

((A) Confirmation of presence of (b) amine and (c) curable organic substance adsorbed on nanosheet)
The presence of (b) amine and (c) curable organic substance adsorbed on (a) nanosheet is confirmed by the fact that the peak appearance of the X-ray diffraction spectrum of the gas barrier layer has the following characteristics.

  (A) For the oriented laminate of nanosheets obtained by removing the dispersion medium from the aqueous dispersion in which the nanosheets are dispersed in a dispersion medium (mainly water) to which no additive is added, When the X-ray diffraction measurement was performed at a temperature of 25 ° C. and a relative humidity of 50% using a wavelength of 1.54 mm which is a general copper Kα ray, (a) in the case of an oriented laminate of nanosheets obtained from an aqueous dispersion, A sharp peak due to the first-order diffraction of the 001 plane is produced in the region of 6.76 to 7.18 degrees at 2θ (1.23 to 1.30 nm in terms of interlayer distance). Therefore, when an X-ray diffraction spectrum is measured under the same conditions for a nanosheet laminate containing an additive (for example, cycloolefin copolymer) from which the dispersion medium has been sufficiently removed, it is 6.76 degrees or more at 2θ (interlayer distance) It is considered that (b) amine is not adsorbed to (a) nanosheets in the laminate in which the peak top due to the first-order diffraction of the 001 plane exists only in the diffraction region of 1.30 nm or less in terms of ().

  On the other hand, for example, as described later, after adding the appropriate (b) amine and (c) curable organic material to the organic solvent dispersion, the dispersion medium is removed and (b) the amine and (c) the curable organic material. (B) a reaction product of the amine and (c) curable organic substance (hereinafter also simply referred to as a reaction product) can be formed by reacting with (a) at least part of the structure adsorbed between the layers of the nanosheet In the case of the cured product having the above structure, a peak top due to the first-order diffraction of the 001 plane is usually generated in a diffraction region of less than 6.76 degrees at 2θ (exceeding 1.30 nm in terms of interlayer distance). The positions of the peak tops are (b) amine loading (that is, (b) amine content relative to the total mass of (a) nanosheets and (b) amine), (b) amine molecular size, (a ) Depending on various factors such as the interaction between the nanosheet and (b) amine, etc., in the present invention, when the peak top due to the first-order diffraction of the 001 plane is in the above range (ie, less than 6.76 degrees at 2θ), (B) It is determined that the gas barrier sheet has a structure in which at least part of the amine is adsorbed between (a) nanosheet layers.

  However, if the ratio of (b) amine and (c) curable organic substance to (a) nanosheets increases and the intercalation advances and the nanosheet interlayer distance is too large, generally including water vapor gas barrier properties, Gas barrier properties are reduced. Therefore, from the viewpoint of gas barrier properties, the position of the peak top due to the first-order diffraction of the 001 plane is preferably 1.75 degrees or more in terms of 2θ (5.0 nm or less in terms of interlayer distance) and more than 1.75 degrees (interlayer interlayer) More preferably, it is less than 5.0 nm in terms of distance), more preferably 2.21 degrees or more (4.0 nm or less in terms of interlayer distance), and more than 2.94 degrees (3.0 nm in terms of interlayer distance). The following is more preferable.

  In a particularly preferred embodiment of the present invention, (a) the X-ray diffraction spectrum generated by the first-order diffraction of the 001 plane of the nanosheet has a peak top in the diffraction region of 1.75 <2θ <6.76.

  It should be noted that (a) the plane-aligned laminated state of the nanosheets and whether the average interlayer distance of the (a) nanosheets in the gas barrier layer is within the predetermined range can also be confirmed by measuring the interlayer distance by TEM image observation. be able to.

(Confirmation of composition of nanosheet-containing composition and gas barrier layer)
The presence of (b) amine and (c) curable organic substance in the nanosheet-containing composition can be confirmed by IR or solid-state NMR of the transmission method. (B) When an amine is present, a peak derived from an amino group can be confirmed at a wave number of 3500 to 3200 cm ⁻¹ . Further, whether or not (b) amine and (c) curable organic substance reacted and cured in the gas barrier layer was detected by the nanosheet-containing composition in the measurement by IR or solid NMR (c) curing It can be confirmed whether or not the peak derived from the reactive group of the organic organic substance disappears in the gas barrier layer.

  In addition, as a method for evaluating the presence and abundance of the reaction product of (b) amine and (c) curable organic substance in the state where the gas barrier layer is formed, IR of permeation method and the like can be mentioned.

  The amount of (b) amine and (c) curable organic substance in the nanosheet-containing composition can be quantified by thermogravimetric analysis. When (b) amine or (c) curable organic substance is present, weight loss due to decomposition of (b) amine and (c) curable organic substance is observed between about 300 ° C. and 800 ° C. The presence or absence of the decomposition (that is, the presence of decomposition products) can be confirmed by mass analysis of the generated gas.

  The content of the nanosheet (a) in the nanosheet-containing composition and in the gas barrier layer can be quantified as the amount remaining after heating from 30 ° C. to 800 ° C. in thermogravimetric analysis.

(Gas gas permeation amount and water vapor permeation amount of gas barrier sheet)
The gas gas permeation amount of the gas barrier sheet is preferably less than 0.1 cc · μm / (m ² · day · atm) as a permeation coefficient converted to a typical oxygen gas when the film thickness is 1 μm. more preferably 0.01 cc · [mu] m / less than ^{(m 2 · day · atm)} , more preferably less than ^{0.001cc · μm / (m 2 ·} day · atm), particularly preferably 0.0001cc · μm / (M ² · day · atm). The gas permeation amount is preferably equal not only in a dry environment but also in an environment containing a large amount of water vapor (for example, in an environment with a relative humidity of 90% at 40 ° C.). The gas permeation amount is a value measured according to JIS K7126.

Similarly, the water vapor permeation amount of the gas barrier sheet is 0.1 g / (as a permeation coefficient converted in the case of a film thickness of 1 μm in an environment of 40 ° C. and 90% relative humidity under an oxygen atmosphere in accordance with JIS K7126. preferably m ² · day) is less than, more preferably less than ^{0.05g / (m 2 · day)} , more preferably less than ^{0.01g / (m 2 · day)} , still more preferably 0 It is less than 0.002 g / (m ² · day), more preferably less than 0.0001 g / (m ² · day), and particularly preferably less than 0.00001 g / (m ² · day).

  The film thickness of the gas barrier layer is preferably 0.001 to 1000 μm, more preferably 0.01 to 100 μm, and still more preferably 0.1 to 10 μm. The film thickness can be measured by, for example, a stylus type surface shape measuring instrument.

<Method for producing gas barrier sheet and method for producing gas barrier coating solution>
The present invention is also a method for producing the above-described gas barrier sheet of the present invention, which is (1) a cleavage sheet of one or more layered inorganic compounds selected from the group consisting of a smectite group and a mica group. A dispersion dispersion-dispersing aqueous dispersion preparation step, in which an aqueous dispersion prepared by dispersing the dispersion in water is treated with at least one of an ion exchange resin and a semipermeable membrane to obtain a dispersion-dispersion-dispersing aqueous dispersion; Organic solvent dispersion wherein an organic solvent dispersion is obtained by substituting part or all of the water in the aqueous dispersion for dispersion medium substitution with an organic solvent, or by adding an organic solvent to the aqueous dispersion for dispersion medium substitution And (3) adding (b) amine and (c) curable organic substance to the organic solvent dispersion, thereby including (a) nanosheet, (b) amine and (c) curable organic substance. Nanosea A coating liquid forming step of forming a coating liquid comprising the containing composition and the dispersion medium, and (4) after applying the coating liquid on the substrate, removing the dispersion medium in the coating liquid and (B) A film-forming step of forming a gas barrier layer, which is a cured product of the nanosheet-containing composition, on the substrate by reacting the amine with the (c) curable organic material is performed in the order described above. By including this, the manufacturing method of the gas barrier sheet which forms the gas barrier sheet which has a gas barrier layer is provided.

  The present invention is also a method for producing a gas barrier coating solution used for producing the above-described gas barrier sheet of the present invention, wherein (1) one or more layered inorganic substances selected from the group consisting of smectite group and mica group (A) Dispersion medium replacement water obtained by treating an aqueous dispersion formed by dispersing nanosheets in water with at least one of an ion exchange resin and a semipermeable membrane to obtain a dispersion medium replacement water dispersion. A dispersion preparation step, and (2) by replacing part or all of the water in the dispersion medium replacement water dispersion with an organic solvent, or by adding an organic solvent to the dispersion medium replacement water dispersion, An organic solvent dispersion preparation step for obtaining an organic solvent dispersion; and (3) (a) a nanosheet by adding (b) an amine and (c) a curable organic substance to the organic solvent dispersion, (b) Amine And (c) a coating liquid forming step of forming a coating liquid comprising a nanosheet-containing composition containing a curable organic material and a dispersion medium, in the order described above, A manufacturing method is provided. Further, in place of (2) and (3) in the above step or in addition to the above step, the dispersion medium replacement aqueous dispersion obtained in the above step (1), an organic solvent, (b) amine and (c ) A method for producing a gas barrier coating solution including a step of mixing a mixture of a curable organic substance and the mixture.

  Hereinafter, the example of the suitable aspect of the manufacturing method of the gas barrier sheet of this invention and the manufacturing method of the coating liquid for gas barriers is demonstrated.

[Aqueous dispersion preparation process]
In this step, (a) an aqueous dispersion obtained by dispersing nanosheets in water, which is a cleavage product of one or more layered inorganic compounds selected from the group consisting of smectite group and mica group, is used for ion exchange resin and semipermeable membrane. By treating with at least one, excess ions (that is, ions not contributing to charge compensation) were removed from the aqueous dispersion obtained by dispersing the nanosheet (a) of the layered inorganic compound having exchangeable ions in water. An aqueous dispersion for dispersing medium replacement is obtained. The (a) nanosheet which is a cleavage product of one or more layered inorganic compounds selected from the group consisting of smectite group and mica group can be formed by the method described above. In the present specification, the aqueous dispersion is defined as a dispersion in which the dispersion medium is mainly water (that is, more than 50 mass% and 100 mass% or less of the entire dispersion medium is water). As a dispersion medium in the aqueous dispersion, in addition to water, for example, one or more of alcohols may be used.

  By simply mixing the dispersion medium and the layered inorganic compound nanosheet, the high dispersion state required as an aqueous dispersion may not be obtained. That is, as the average aspect ratio of the nanosheet increases, the larger the area where the nanosheets interact with each other, the higher the charge density of the layered inorganic compound, and the more the charge is present on the surface of the nanosheet, the more the nanosheet Since the bonding force between the layer surfaces of the layers is usually increased, it becomes difficult to cleave and disperse the nanosheets that are unit layers of the layered inorganic compound. In such a difficult dispersion state, when the aqueous dispersion is treated with at least one of an ion exchange resin and a semipermeable membrane, the removal rate of excess ions and the exchange rate of interlayer ions may be reduced. .

  In order to obtain a desired high dispersion state as an aqueous dispersion, a known fine dispersion device such as a shaking device, ultrasonic dispersion, bead mill, ball mill, roll mill, homomixer, ultramixer, dispermixer, penetrating high pressure The layered state is obtained by applying mechanical force to the layered inorganic compound by a dispersion device, a collision type high pressure dispersion device, a porous type high pressure dispersion device, a decoy type high pressure dispersion device, a (collision + penetration) type high pressure dispersion device, or an ultrahigh pressure homogenizer. It is preferable to further promote the peeling / cleavage of the inorganic compound in the sense that the dispersion of the layered inorganic compound is promoted to approach the dispersed state of cleaving to the nanosheet as the unit layer. Further, applying a mechanical force to the layered inorganic compound is also preferable in that the liquid crystal transition of the layered inorganic compound tends to be promoted.

  Among them, ultrasonic dispersion, homomixer, ultramixer, dispermixer, penetration type high pressure dispersion device, collision type high pressure dispersion device, porous type high pressure dispersion device, deduction type high pressure dispersion device, (collision + penetration) It is more preferable to use a mold type high pressure dispersing device, an ultra high pressure homogenizer, or the like.

Examples of the high-pressure dispersing device include an ultra-high pressure homogenizer (trade name: Microfluidizer) manufactured by Microfluidics Corporation and a nanomizer manufactured by Nanomizer. Can be mentioned. As a preferable pressure for the dispersion treatment, a high pressure, particularly a pressure of 100 kgf / cm ² or more is preferable. However, when the layered inorganic compound is cracked and refined by dispersion treatment under high pressure and the average aspect ratio is reduced, the water vapor gas barrier property of the gas barrier sheet of the present invention and the material formed by applying the present invention is lowered. When the material is made into a film, film formation characteristics and mechanical strength may be deteriorated. Therefore, it may be preferable to disperse the layered inorganic compound under a pressure of 100 kgf / cm ² or less.

  Note that the layered inorganic compound that is difficult to cleave and disperse because the average aspect ratio is too high can be obtained by utilizing the feature that the layered inorganic compound is cracked and refined by dispersing by high pressure or ultrasonic waves. By performing ultrasonic treatment or the like, the layered inorganic compound may be dispersed to an average aspect ratio that is easy to disperse and does not cause a significant decrease in water vapor gas barrier properties. In particular, since the synthesized fluorinated mica has a large average aspect ratio and a strong interlaminar bond strength, it is preferable to carry out the above-described refinement treatment in order to promote further cleavage.

  Another method for obtaining a highly dispersed state suitable as an aqueous dispersion is a method of separating and extracting a layered inorganic compound in a highly dispersed state. That is, it is preferable to separate a component having a low degree of dispersion by a separation method that applies a large gravitational acceleration, such as a centrifugal separation method, and extract and use a component having a high degree of dispersion. In this method, a liquid crystal phase may be separated / extracted from a layered inorganic compound that undergoes liquid crystal transition, and impurities derived from nature (for example, silicon oxide, calcium carbonate, etc.) or a vitreous material generated during synthesis may be extracted from the layered inorganic compound. When such impurities are contained, it is preferable that they can be settled and removed, and a material having a higher water vapor gas barrier property can be obtained.

  In order to cleave and stably disperse the layered inorganic compound, a dispersant represented by a known anionic system such as sodium polyacrylate, polyacrylic acid, or phosphoric acid having a relatively low molecular weight is used as a dispersion promoting additive. Specifically, it is suitable in the present invention to add less than 0.5% by mass, preferably about 0.15% by mass to the aqueous dispersion with respect to 100% by mass of the layered inorganic compound.

  In the present invention, instead of producing the above-mentioned aqueous dispersion, a dispersion of a layered inorganic compound that is commercially available in a state of being dispersed to some extent in water may be used. In this case, the fine dispersion treatment, separation / extraction treatment, addition of additives, and the like as described above may be further performed.

  Next, the aqueous dispersion prepared as described above or commercially available is treated with at least one of an ion exchange resin and a semipermeable membrane. When manufacturing the coating liquid for gas barrier sheet manufacture, in order to improve the dispersibility of (a) nanosheet, the process by ion exchange and / or a semipermeable membrane is an important process.

  As described above with respect to the prior art, many of the nanosheets usually have a negative permanent charge, and in order to compensate for the negative permanent charge, inorganic ions such as sodium ions and lithium ions are present between the nanosheet layers. It is known that it is present as interlayer ions and maintains electrical neutrality. However, according to the study of the present inventor, inorganic ions exceeding the amount necessary to maintain electrical neutrality exist between the layers of the nanosheets, and in addition, inorganic cations and anions Was found to exist as a counter ion. In this specification, inorganic ions exceeding the amount necessary for maintaining the above-described electrical neutrality and counter ions (that is, ions that do not contribute to charge compensation) of the cation and the anion are combined to be referred to as “surplus ions”. ". The present inventor finds that the dispersibility of the nanosheet is hindered by the presence of these surplus ions, and in order to reduce surplus ions, the ion exchange and / or treatment with a semipermeable membrane described below is important. I found it.

  Surplus ions are exchangeable ions that can be ion-exchanged by a normal ion exchange technique. Therefore, in the dispersion medium replacement aqueous dispersion preparation step in the present invention, an aqueous dispersion in which a nanosheet (usually having exchangeable ions) is dispersed in water is treated with an ion exchange resin and / or a semipermeable membrane. Excess ions in the aqueous dispersion can be reduced.

  In the ion exchange, among the exchangeable ions contained in the aqueous dispersion described above, ions that exist in excess of the amount that contributes to compensation of the charge of the layered inorganic compound (that is, the charge of the nanosheet), that is, ions that can be regarded as impurities The excess ions (both positive ions and anions present as a pair thereof) are removed to an extent as close as possible using an ion exchange resin and / or a semipermeable membrane.

  Although dispersibility of the nanosheet is improved only by performing ion exchange treatment to remove surplus ions, in the present invention, an interlayer ion itself existing in order to compensate the charge of the nanosheet in a solid state is an ammonium ion that is an inorganic ion. It has been found that the dispersibility is further improved by exchanging them.

  By using the aqueous dispersion for replacing the dispersion medium obtained in this manner, the nanosheet is dispersed in the dispersion medium in both the aqueous dispersion mainly composed of water and the dispersion mainly composed of an organic solvent. Can be dispersed well. That is, according to the present invention, it is possible to greatly improve the dispersion stability of the (a) nanosheet with respect to the dispersion medium without performing conventional organic modification with organic ions, silylation treatment, and the like.

The above-mentioned surplus ions vary depending on the type of layered inorganic compound, the production area, the purification method, and the raw material and method of synthesis when the layered inorganic compound is a synthetic product. Examples include sodium ion, lithium ion, calcium ion, magnesium ion, potassium ion, aluminum ion, ammonium ion, and iron ion. Examples of the anion include sulfate ion, hydroxide ion, fluorine ion, chlorine ion, and nitrate ion. Illustrated. In particular, sulfates having sulfate ions (SO ₄ ²⁻ ) are often contained in both natural clay minerals and synthesized clay minerals. In addition, in the synthetic fluorinated hectorite and synthetic fluorinated mica obtained by fluorinating the hydroxyl group of the octahedral layer of the nanosheet, the fluorine raw material used in the synthesis usually remains as fluorine ions.

  Most of these surplus ions can be removed by an ion exchange method using an ion exchange resin. When the surplus ions are composed of surplus anions and surplus cations, the surplus cations are exchanged for at least one of ammonium ions and hydrogen ions using a cation exchange resin, and the surplus ions are surplus using an anion exchange resin. It is preferable to exchange the anions of the above with hydroxide ions. In this case, the surplus ammonium ion or hydrogen ion generated by the cation exchange described above reacts with the surplus hydroxide ion generated by the anion exchange, and water or ammonia that can be easily removed is produced. Therefore, excessive ions are substantially removed from the aqueous dispersion without increasing the ion concentration in the dispersion.

  When excess ions are removed by an ion exchange method, a method using a known ion exchange resin, which is represented by a method in which a column is filled with an ion exchange resin and a dispersion is passed, is preferable. In this case, as the order of exchange between the cation and the anion, it is usually preferable to perform the anion exchange first and then the cation exchange. In particular, in fluorinated hectorite and fluorinated mica (especially synthetic fluorinated hectorite and synthetic fluorinated mica) having an average aspect ratio of 150 or more, the cation can be exchanged after the anion is exchanged first. Very suitable. If this order is reversed or substantially simultaneously, the column may be clogged, the gelation of the dispersion may progress with time, or the gelation rate may increase.

  Surplus ions can also be removed by treating the aqueous dispersion with a semipermeable membrane. Semi-permeable membranes having an average pore size that does not permeate nanosheet particles having a size and aspect ratio that are not less than a preferred value, and permeate small ionic species, such as ultrafiltration membranes, microfiltration By performing a known membrane separation operation using a membrane or a reverse osmosis membrane, surplus ions can be separated together with the dispersion medium. In this case, since a part of the dispersion medium is usually separated together with the surplus ions, the solid content concentration of the aqueous dispersion in which the nanosheet is dispersed is increased and the viscosity is increased, and the separation of the surplus ions may not proceed. is there. In that case, it is preferable to suppress an increase in viscosity by appropriately adding a dispersion medium to the aqueous dispersion.

  As used herein, surplus ions have the meaning of including cations and anions as described above, but the preferred amount of surplus ions in the aqueous dispersion for dispersion medium replacement obtained by the above operation is dispersion. When the content of the nanosheet (a) in the aqueous dispersion for medium substitution is k mass%, the total amount of residual anionic species can be exemplified as 0.0002 × kmol / L or less, The amount is more preferably 0.00016 × kmol / L or less, more preferably 0.0001 × kmol / L or less, and particularly preferably 0.00006 × kmol / L. The amount is L or less. Among them, the content of sulfate ions is preferably 0.00001 × kmol / L or less, more preferably 0.000005 × kmol / L, and particularly preferably 0.000002 × kmol. / L or less. In addition, about the lower limit of a surplus ion, it is so preferable that there are few, and it is most preferable that it is 0 kmol / L.

The respective ion amounts of the cation species and the anion species and the sum thereof can be obtained by calculating the sum from the amount of each ion measured by the following method. Regarding the amount of ions in the dispersion, a mixed solution of 0.50 mMol / L histidine and 2.5 mMol nitric acid was measured with a TSKgel Super IC-Cation column (size 4.6 mm ID × 15 cm). As an eluent, the anion was measured with a TSKgel Super IC-AP column (size 4.6 mm ID × 15 cm) at a flow rate of 1.0 mL / min and an injection volume of 30 μL. This is a value obtained by measurement under the conditions of a flow rate of 0.8 mL / min and an injection volume of 30 μL using a mixed solution of NaHCO 3 solution and 1.8 mMol of Na ₂ CO ₃ solution as an eluent.

  Among the exchangeable ions of the (a) nanosheet of the layered inorganic compound, ammonium ions are preferably selected as the main ion species corresponding to the interlayer ions existing between the (a) nanosheet layers in the solid state.

  When the main interlayer ion is a hydrogen ion, compared to the case where the interlayer ion is an ammonium ion, there is a tendency that the layered inorganic compound itself decomposes and a problem of aggregation accompanying it tends to occur. Limited compared to ammonium ion.

  On the other hand, when the interlayer ions are ammonium ions, good dispersion stability can be obtained both in the state of the aqueous dispersion and in the state of the organic solvent dispersion, the solid content concentration of the dispersion can be easily improved, and in the organic solvent dispersion It is easy to reduce the proportion of water in the water, so it is easy to mix with highly hydrophobic additives. Furthermore, the additive tends to easily intercalate between (a) nanosheets. For the above reason, it is most preferable that the interlayer ion of the nanosheet (a) at the time when the aqueous dispersion for replacing the dispersion medium is prepared is an ammonium ion.

  By exchanging interlayer ions for ammonium ions by the above-described method, it is possible to obtain a layered inorganic compound nanosheet in which interlayer ions are exchanged for ammonium ions at the same time as the removal of excess ions by ion exchange. Is the most preferred method. That is, the removal of surplus ions and the exchange of interlayer ions to ammonium ions can be achieved simultaneously only by exchanging the cation species in the aqueous dispersion with ammonium ions and the anion species with hydroxide ions.

  When exchanging interlayer ions with ammonium ions, the remaining ammonium ions and hydroxide ions react slightly in the aqueous dispersion by heating or depressurizing the aqueous dispersion after ion exchange. It is preferable because the reaction to become water and ammonia further proceeds, and ammonium ions and hydroxide ions derived from surplus ions in the aqueous dispersion can be removed more favorably from the aqueous dispersion.

  As the exchange rate of interlayer ions to ammonium ions, it is preferable that 50% by mass or more of ionic species before exchange is exchanged for ammonium ions, more preferably 75% by mass or more, and still more preferably 85% by mass or more, More preferably, 90% by mass or more, more preferably 95% by mass or more, more preferably 97% by mass or more, and particularly preferably 99% by mass or more is exchanged with ammonium ions. The exchange rate is desirably as close to 100% by mass as possible.

  The exchange rate can be calculated from the measured value of the dispersion before and after the exchange by measuring the amount of ions in the dispersion by the method described above.

  The ion exchange rate, the ion content ratio, and the ratio of the interlayer ions to the total exchangeable ions are ammonium acetate and sodium chloride or potassium chloride based on the Schollenberger method when the interlayer ions are cations. The cation exchange capacity can be determined by a known method using and, and the concentration of the ionic species can be determined by measuring the dispersion by an ion chromatography method. The amount of charge corresponding to the cation exchange capacity (CEC) is basically associated with the amount of interlayer ions (if the effect of the charge at the end of the nanosheet is not taken into account) and exceeds that amount. Are basically associated with surplus ions.

  When there is a problem in measurement by ion chromatography (for example, when nanosheets are decomposed), the amount of exchangeable ions originally possessed by the layered inorganic compound and the amount of exchangeable ions after ion exchange And the amount of decrease in specific ions due to ion exchange may be calculated from the values before and after the exchange, and the exchange rate for ammonium ions may be calculated therefrom. For example, in many commercially available synthetic clay minerals, most of the exchangeable cations are sodium ions. In that case, the amount of sodium ions may be measured before and after the exchange to calculate the amount of decrease, and the exchange rate for ammonium ions may be calculated therefrom. Of course, when other ionic species other than sodium ions are ignored, the exchange rate is calculated after quantifying them.

  In this way, when the excess ion concentration in the aqueous dispersion is sufficiently reduced, and (a) the main interlayer ions existing between the nanosheet layers are replaced with ammonium ions in the solid state, only the aqueous dispersion is used. In addition, even in the organic solvent dispersion, the effect that the nanosheet (a) of the layered inorganic compound is highly dispersed is obtained. Therefore, a conventional hydrophilic polymer or metal alkoxide or the like can be used without modifying or modifying a part of the layered inorganic compound by treatment with an organic ion such as an organic cation or silane as in the past. Even if the hydrolyzate is not added, the effect that (a) the nanosheet is highly dispersed without causing aggregation or gelation in the organic solvent dispersion can be obtained. According to the above technique, such a high degree of dispersion is similarly developed for the (a) nanosheet of the layered inorganic compound having an average aspect ratio of 150 or more, and more than 1000.

[Organic solvent dispersion preparation process]
In this step, the organic solvent is obtained by substituting part or all of the water in the aqueous dispersion for dispersion medium replacement obtained above with an organic solvent, or by adding an organic solvent to the aqueous dispersion for dispersion medium replacement. A dispersion is obtained. According to the organic solvent dispersion preparation step, the organic solvent dispersion is obtained by substituting the organic solvent with water in the aqueous dispersion for dispersion medium replacement after the above-described step of reducing excess ions and exchanging interlayer ions with ammonium ions. Preferably, it is possible to form an organic solvent dispersion liquid in which a layered inorganic compound (a) nanosheet in which main interlayer ions are exchanged into ammonium ions is dispersed in an organic solvent. In this specification, an organic solvent dispersion is defined as a dispersion in which the dispersion medium contains an organic solvent (over 10 mass% and 100 mass% or less of the entire dispersion medium is an organic solvent). Therefore, in this step, it is sufficient to replace water with an organic solvent to such an extent that the organic solvent dispersion is obtained, and this replacement is to replace all of the water in the aqueous dispersion for dispersion medium replacement with an organic solvent. It is not limited. In the present invention, a hydrophobic additive that is hardly soluble in water can be used through this step, unlike the case of a conventional dispersion using water as a main dispersion medium. For example, before mixing the hydrophobic additive, the dispersion medium in the aqueous dispersion that has undergone ion exchange or semipermeable membrane treatment for reducing excess ions is organically dissolved to such an extent that the hydrophobic additive can be dissolved. By replacing the solvent with the main one, the hydrophobic additive can be uniformly mixed. It is preferable that more than 35% by mass and 100% by mass or less of the entire dispersion medium is an organic solvent in that a hydrophobic additive that is more hardly soluble in water can be used, and more than 40% by mass and 100% by mass of the entire dispersion medium. % Or less is more preferably an organic solvent, and most preferably more than 50% by mass and 100% by mass or less of the entire dispersion medium is an organic solvent.

  As an effective method of this step, an organic solvent having a high affinity with water (specifically, a high compatibility with water) is mixed with the dispersion medium mainly composed of water in the aqueous dispersion for replacing the dispersion medium. The method of doing can be mentioned.

  Examples of the organic solvent highly compatible with water include organic solvents having high polarity, such as methanol, ethanol, 2-methoxyethanol, 2-ethoxyethanol, 2-isopropoxyethanol, 2- (methoxyethoxy). Ethanol, 2-butoxyethanol, 1-propanol, 2-propanol, 2-butanol, t-butanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 2-methoxyethyl acetate, diacetone alcohol, free Alcohol, ethyl acetoacetate, tetrahydrofurfuryl alcohol, ethylene glycol, diethylene glycol, dipropylene glycol, diethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, diethylene glycol Monoethyl ether, dipropylene glycol monoethyl ether, triethylene glycol, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, acetone, acetonyl acetone, acetonitrile, ethylene carbonate, propylene carbonate, acetic acid, formic acid, formamide, N-methylformamide, N, N -Dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, N, N, N, N-tetramethylurea, 2-pyrrolidone, N-methylpyrrolidone, methyl carbamate, gamma butyrolactone, triacetin, isopropyl formate , Triethylamine, tetrahydrofuran, 1,2-dimethoxyethane, 1,4-dioxane, dimethyl sulfoxide, trimethyl phosphate, triethyl phosphate , Tributyl phosphate, pyridine and the like. Among these, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, γ-butyrolactone, pyridine and N-methylpyrrolidone are suitable solvents.

  Only one type of the above organic solvent may be mixed with the dispersion medium replacement water dispersion, or a plurality of different types may be mixed with the dispersion medium replacement water dispersion. When a plurality of different types of organic solvents are mixed with the dispersion medium replacement aqueous dispersion, the organic solvent may be sequentially added to the dispersion medium replacement aqueous dispersion, or the organic solvent mixed in advance at a predetermined ratio may be dispersed. It may be added to the medium-dispersing aqueous dispersion, or both methods may be used in combination. Further, the organic solvent may be added to the aqueous dispersion for dispersion medium substitution while stirring or performing the fine dispersion treatment described above.

  A preferred dispersion medium replacement method in the present invention is a mixture of a dispersion medium replacement water dispersion containing water as a main dispersion medium (the amount of water in the dispersion may be reduced) and an organic solvent, In this method, the ratio of water in the dispersion, which is the resulting mixture, is decreased to increase the ratio of the organic solvent in the dispersion medium in the dispersion. By this method, the proportion of water in the dispersion medium can be greatly reduced, and the main part of the dispersion medium (that is, more than 50% by mass), particularly the majority of the dispersion medium can be used as the organic solvent. As a method of reducing the proportion of water after mixing the dispersion medium-dispersing water dispersion and the organic solvent, for example, heating the dispersion which is a mixture of the aqueous dispersion and the organic solvent under normal pressure or reduced pressure, A method of selectively evaporating the water component can be mentioned. This method can be preferably employed when the boiling point of the organic solvent to be mixed is higher than the boiling point of water.

  Further, the amount of water in the dispersion medium may be reduced by using a water adsorbent such as molecular sieve, silica gel, activated alumina, zeolite, soda lime, magnesium sulfate, or certain ion exchange resins. Further, water may be removed by a hydrolysis reaction using a silane compound such as tetraethoxysilane or tetramethoxysilane, or magnesium ethylate. Further, a plurality of methods as described above may be used in combination. For example, after removing most of the water by heating under reduced pressure, the water may be further removed by molecular sieves or the like. Alternatively, water is removed by a filtration method using a semipermeable membrane having an average pore size corresponding to the difference in molecular size between water and an organic solvent, such as an ultrafiltration membrane, a microfiltration membrane, or a reverse osmosis membrane. May be.

  Moreover, as a suitable organic solvent dispersion medium replacement method, a method in which a relatively high concentration aqueous dispersion is prepared and an organic solvent is added thereto can be used as a major part of the dispersion medium. In this method, the boiling point of the organic solvent to be mixed with the dispersion liquid for replacing the dispersion medium is low, and when the ratio of the organic solvent is decreased in the step of reducing the ratio of water, and the boiling point of the organic solvent to be mixed is It can be more preferably employed when the boiling point is lower than the boiling point of water (for example, when pyridine, acetonitrile or the like is used).

  In the present invention, when the proportion of water in the dispersion medium in the mixture of the dispersion medium-dispersing water dispersion and the organic solvent is reduced, the proportion of water in the dispersion medium of the mixture is 35% by mass or less of the entire dispersion medium. Is preferably reduced to 25 mass% or less. In particular, when a hydrophobic additive hardly soluble in water is added to the prepared organic solvent dispersion, it is preferable to further reduce the ratio of water. In such a case, although depending on the type of the additive, the proportion of water is generally preferably reduced to 15% by mass or less, more preferably 10% by mass or less. On the other hand, if the layered inorganic compound is reduced to the bound water bound between the layers of the (a) nanosheet, the dispersion of the (a) nanosheet into the organic solvent may not proceed. Therefore, the proportion of water in the dispersion medium of the mixture is preferably 0.1% by mass or more, and more preferably 0.5% by mass or more of the entire dispersion medium.

  In the present invention, according to the aspect in which the excess ions are reduced and the main interlayer ions are replaced with ammonium ions, the conventional organic ions or silanes can be obtained even if the water content in the dispersion medium is sufficiently reduced in this way. The effect is obtained that the layered inorganic compound can be highly dispersed in the dispersion medium without organic modification by treatment.

  In addition, the dispersion stability of the (a) nanosheet in the dispersion liquid which uses the organic solvent as the main dispersion medium obtained by this step varies greatly depending on the residual amount of surplus ions. In the present invention, surplus ions are sufficiently removed by treatment with an ion exchange resin and / or a semipermeable membrane, so that a better (a) nanosheet dispersion state can be obtained in an organic solvent, and the solid state of the organic solvent dispersion can be obtained. The partial concentration can be improved.

  An organic solvent dispersion can be obtained as described above. This organic solvent dispersion is preferably an organic solvent dispersion in which the main interlayer ions of the (a) nanosheet of the layered inorganic compound are exchanged with ammonium ions.

[Coating liquid formation process]
In this step, by adding (b) amine to the organic solvent dispersion prepared by the above-described method, a dispersion in which (b) amine is adsorbed on (a) nanosheet can be obtained. The amine may be added while subjecting the organic solvent dispersion to stirring or fine dispersion treatment. (B) The amine may be added after diluting with an organic solvent. Specific embodiments of (b) amine that can be used are as described above in the section of [(b) amine].

  (B) The amount of amine added to the organic solvent dispersion is equal to or more than the amount of the cation calculated from the cation exchange capacity of the layered inorganic compound (for example, the amount of ammonium ion when the interlayer ion is ammonium ion). It is preferable.

  Further, the proportion of (b) amine in the total mass of (a) nanosheet and (b) amine is preferably 1% by mass or more, more preferably 3% by mass or more, and preferably in the coating liquid. Is 50% by mass or less, more preferably less than 50% by mass, further preferably 30% by mass or less, and particularly preferably less than 30% by mass.

  However, when an amine having a boiling point below the drying temperature or having a vapor pressure below the drying temperature is selected in the following film forming step, excess amine is volatilized in the drying step, and only the necessary amount is adsorbed by the amine. This is preferable because a gas barrier layer obtained can be obtained.

  In this step, (c) a curable organic substance is further added to the organic solvent dispersion. (C) The curable organic substance may be added after (b) addition of the amine, or may be added before (b) addition of the amine. Moreover, you may add (b) amine and (c) curable organic substance simultaneously. (C) A curable organic substance may also be added while subjecting the organic solvent dispersion to stirring or fine dispersion treatment in the same manner as (b) amine. (C) The curable organic material may be diluted with an organic solvent.

  (C) It is preferable that the addition amount of the curable organic substance to the organic solvent dispersion is 1/10 or more in terms of a molar ratio with respect to (b) amine in terms of good water vapor gas barrier properties. Further, it is preferable that the addition amount is 5 times or less in terms of molar ratio with respect to (b) amine in that the mass of organic matter is hardly formed in the gas barrier layer, and the surface of the gas barrier sheet becomes smooth. The addition amount is more preferably 2 times or less in molar ratio to (b) amine, and further preferably 1 time or less in molar ratio to (b) amine. As described above, a coating liquid comprising the nanosheet-containing composition containing (a) nanosheet, (b) amine, and (c) curable organic substance and the dispersion medium can be formed.

[Film forming process]
In this step, after applying the coating liquid formed above onto the substrate, the dispersion medium in the coating liquid is removed, for example, by drying, and (b) amine and (c) curable organic substance are reacted. (C) The curable organic material is cured. Thereby, the gas barrier layer which is a hardening body of this nanosheet containing composition is formed on a board | substrate. Either the removal of the dispersion medium or curing may be performed first, or both may be performed simultaneously. When the (c) curable organic material that is cured by heating is used, the dispersion medium can be removed and cured by drying or the like at the same time.

The coating liquid applied on the substrate may be as it is formed in the coating liquid forming step, or may be pre-cured by heating or the like to a certain extent that can be applied on the substrate. It may be a thing. Examples of the pre-curing condition include heating the coating solution at 50 ° C. for 1 hour on a water bath.

  The solid content concentration of the coating liquid is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, further preferably 1.0% by mass or more, and further preferably 2.0% by mass or more. A mass% or more is particularly preferred. If it is the said solid content density | concentration, the drying time for dispersion medium removal can be shortened more, or a drying temperature can be lowered | hung. The solid content concentration of the dispersion liquid may be a concentration that allows mixing, defoaming, and the like, and the coating liquid may be a paste with a very high viscosity. As a method for removing the dispersion medium from the coating liquid, centrifugation, filtration, vacuum drying, freeze vacuum drying, standing in an inert gas atmosphere, and heating evaporation are preferable. Or you may combine two or more among these methods.

  In addition, when a gas component is mixed in the coating liquid by performing the above-described stirring or fine dispersion treatment, the gas component is degassed by a treatment such as vacuum defoaming, ultrasonic irradiation, or centrifugation. It is preferable to do. These treatments may be performed after the aforementioned stirring or fine dispersion treatment, or may be carried out simultaneously during these treatments. Bubbles derived from gas components mixed in the coating liquid cause voids in the gas barrier layer formed by using the coating liquid, and cause a decrease in water vapor gas barrier properties and transparency. It is important to perform sufficient deaeration before removing the dispersion medium from the liquid.

  The curing reaction between (b) amine and (c) curable organic material can be carried out by light irradiation and / or heating.

  Examples of the light source used for light irradiation include a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, a xenon lamp, a fluorescent lamp, a tungsten lamp, an argon laser, and a helium cadmium laser. Among these, a high pressure mercury lamp and an ultra high pressure mercury lamp are preferable.

  Heating can be performed by an oven, a hot plate, or the like. As a specific example of heating, for example, in a forced air oven or the like, the temperature is 30 ° C. or higher and 250 ° C. or lower, preferably 40 ° C. or higher and 200 ° C. or lower, more preferably 50 ° C. or higher and 150 ° C. or lower. Examples include a method of drying the dispersion for a period of time, preferably 1 minute to 10 hours, more preferably 3 minutes to 6 hours, and even more preferably 5 minutes to 3 hours. As described above, a desired gas barrier layer can be formed. However, the optimum drying time greatly depends on the shape of the material formed using the coating liquid, the solid content concentration of the coating liquid, the dispersion medium used, the heat-resistant temperature of the substrate, the amount of the coating liquid, and the like.

  The four steps of (1) dispersion medium replacement aqueous dispersion preparation step, (2) organic solvent dispersion preparation step, (3) coating solution forming step, and (4) film forming step are performed in the order described above. Or as an alternative to (2) and (3) of the above step, or in addition to the above step, an aqueous dispersion for replacing the dispersion medium obtained in the step (1), an organic solvent, an amine, and a curable organic substance. The gas barrier layer can be formed on the substrate by the step of mixing with the mixture. In the case of producing a gas barrier sheet comprising a substrate and a gas barrier layer, other steps are not essential. However, in the case of producing a gas barrier sheet further comprising other layers, the steps (1) to (4) are performed. Steps for forming other layers can optionally be added at least before or after any. Moreover, after peeling a gas barrier layer from the said board | substrate, the process etc. which again laminate | stack this gas barrier layer on another support body can also be included. By the above procedure, a gas barrier sheet having a gas barrier layer can be produced.

  In the present invention, additives as described later, other optional additives, and the like may be mixed in a dispersion liquid at an arbitrary timing until an organic solvent dispersion liquid is obtained. In any case, a gas barrier layer containing these additives can be formed by removing the dispersion medium by heat drying or the like in the film forming step.

  In the organic solvent dispersion liquid, a hydrophobic organic substance that is hardly soluble in water, which cannot be easily mixed uniformly by precipitation or the like when there is a large amount of water, can be uniformly combined as an additive.

  The additive is not particularly limited as long as it is uniformly dissolved or finely dispersed in the dispersion medium of the dispersion liquid in any step in the present invention, and any known additive can be used. The above additives can be combined with the dispersion of any step in the present invention by itself or in the form of a solution or dispersion obtained by dissolving or dispersing in an appropriate solvent.

  Since the gas barrier sheet according to the present invention is excellent in water vapor gas barrier properties, it can be used in various fields. Some specific examples are described below.

  In the gas barrier sheet according to the present invention, when interlayer ions are exchanged for ammonium ions, a gas barrier layer containing almost no sodium is obtained. Such a gas barrier layer is considered to be suitable for applications that dislike alkali metals, such as substrates and sealing films for electronic devices, packaging materials, and optical films.

  Moreover, when using the gas barrier sheet of this invention for an electronic device use, it is suitable to use the gas barrier sheet formed in the film | membrane or the film form for the substrate and gas barrier film of a liquid crystal display, an organic EL display, and electronic paper. It is also preferable to use the organic EL element for illumination. The gas barrier layer formed in the present invention can be selected not only with high water vapor gas barrier properties but also with high heat resistance, low linear expansion, high transparency, high flexibility, etc. by selecting the type and ratio of the layered inorganic compound and additives. It is possible to simultaneously satisfy a plurality of required physical properties essential for display applications. Therefore, for example, an active matrix drive circuit serving as a backplane can be directly formed at a high temperature on a gas barrier sheet formed into a film or film.

  Since the drive circuit can be directly formed on the film or film-like gas barrier sheet, it is necessary to use a conventional method such as forming the drive circuit on a heat-resistant support such as a glass substrate and then transferring the drive circuit to a resin film. This eliminates the manufacturing process of the display. Thereby, not only is it suitable for the production of the next-generation flexible display material, but also the advantage that it is superior in terms of weight and cost can be obtained. Unlike batch production of display materials using glass substrates, a gas barrier sheet having a gas barrier layer containing nanosheets of layered inorganic compounds is formed as a roll-like film formed into a film, and this is used as it is. Roll-to-roll production is also possible in which display materials are produced continuously.

  These drive circuits may be configured by conventional silicon-based semiconductor technology, but organic semiconductors or amorphous inorganic semiconductors typified by pentacene and thiophenes may be used. In that case, a photolithography method may be used for circuit formation, or a printing method such as an inkjet method or a nanoimprint method may be used.

  In addition, in the use of the organic EL display and the backplane of electronic paper, that is, in the direction opposite to the light extraction direction, transparency is generally unnecessary, but the layered inorganic compound nanosheet formed by applying the present invention is used. When the gas barrier sheet to be included is transparent, it is preferable to use the gas barrier sheet on the viewing side of the display and the light extraction side of the organic EL illumination.

  The liquid crystal display system to which the gas barrier sheet of the present invention can be applied includes TN, STN, VA, IPS, and the like. By using a birefringence control agent, birefringence in the film thickness direction can be freely set. Since it can be adjusted, the above method is not particularly limited. The gas barrier sheet can be used as a retardation plate by adjusting the birefringence by the thickness and the birefringence control agent.

  Moreover, also in an organic EL display and organic EL illumination, the gas barrier sheet of the present invention can be applied to both a top emission type and a bottom emission type. Further, the gas barrier sheet can be used as electronic paper without being particularly limited by, for example, an electrophoretic drive method, an electronic powder fluid method, a method using liquid crystal, or the like.

  The gas barrier sheet can be used for both the passive matrix system and the active matrix system as a circuit for driving the display. As a utilization form, any of a substrate for forming a circuit and a gas barrier layer for blocking oxygen and water vapor from the outside is possible.

  In addition, a film-like gas barrier sheet can also be used widely as a flexible substrate for an electric circuit by taking advantage of the characteristic that the gas barrier sheet of the present invention can be made insulating. When the gas barrier sheet is used as a substrate for an electric circuit, image processing is often used for alignment when mounting an electronic component. In that case, the substrate is required to be transparent, and thus a transparent film. A gas barrier sheet in a shape is suitable. In particular, in a flexible printed circuit board in which a conductive portion on a substrate is formed by applying or printing conductive ink, the conductive ink is baked at a higher temperature by taking advantage of the heat resistance and low linear expansion coefficient of the film-like gas barrier sheet. Therefore, it is possible to lower the resistivity of the conductor portion formed by coating or printing. Suitable applications of such flexible substrates and flexible printed substrates include RFID tag substrates and copper clad laminates.

  Furthermore, the gas barrier sheet of the present invention can also be applied to solar cells that require light to pass through and that require gas barrier properties. Since the substrate for a solar cell, the protective layer, and the back sheet are also required to have a high gas barrier property, the gas barrier sheet processed into a film is suitable for solar cell applications. Examples of applicable solar cells include crystalline silicon-based, thin-film silicon-based, CIGS-based compounds, dye-sensitized solar cells, organic thin-film solar cells, and the like, and organic thin films that require particularly high gas barrier properties. Suitable for solar cells.

  Further, the gas barrier sheet is promising as a protective film for protecting the information recording portion of a recording medium such as CD-R and DVD from oxygen or the like.

  Further, by using the gas barrier sheet for a packaging material or container for packing food, pharmaceuticals, electronic parts, etc., the gas barrier sheet can be formed so that it can be transparent and visible, and the gas barrier of the packaging material and container is used. Can be improved.

  In addition, since the gas barrier sheet of the present invention can be formed by applying a coating liquid that is a dispersion, it can be used as a coating material for protecting the surface of an object from oxygen and water vapor. At this time, the shape of the surface on which the dispersion is applied (coating) does not need to be flat, and may be uneven in three dimensions. By such a coating, it is possible to suppress deterioration of the surface and the inside of the object due to oxidation or the like. For example, instead of the back sheet of the solar cell, it is also possible to apply the dispersion directly on the surface of the solar cell to impart gas barrier properties.

  Further, by applying the dispersion liquid to the bonded portion of the object using the above-described coating characteristics, it is possible to suppress the ingress of gas from the bonded surface.

  The gas barrier sheet of the present invention is also preferably used by coating a tube for transporting liquid and gas, a tank for storage and the like in addition to the use of the electronic device as described above. In this case, the gas barrier sheet can be three-dimensionally coated on the inner and outer surfaces of the tube and tank by applying the dispersion liquid. Moreover, a gas barrier sheet is also suitably used as the constituent material itself of a hydrogen tank and a transport hose of a fuel cell, and a gasoline hose and tank that require gas barrier properties. The gas barrier sheet is also suitable for use as a vacuum holding material for a vacuum heat insulating material, taking advantage of high gas barrier properties and low thermal conductivity compared to metals.

  In each of the above applications, a gas barrier sheet using (a) fluorinated hectorite or fluorinated mica (in particular, synthetic fluorinated hectorite or synthetic fluorinated mica) having an average aspect ratio of the nanosheet of 150 or more is particularly suitable. is there.

  It should be noted that the above-described display, flexible substrate, flexible printed substrate, solar cell, electronic device having an organic semiconductor or an amorphous inorganic semiconductor, etc., packaging materials, containers, tubes and tanks, surface coatings, etc. Alternatively, when a film-like gas barrier sheet is applied, the gas barrier sheet may be applied as it is, or a formed body having another function as necessary (for example, a gas barrier film mainly composed of an inorganic material, a resin material, or the like). A reinforcing material, a protective layer for preventing scratches, a smoothing layer for smoothing the surface, and the like may be provided. In particular, in order to further improve the gas barrier properties, it is effective to laminate a known inorganic thin film, the above film-like or film-like gas barrier sheet, and a film mainly composed of a resin material that protects them.

  For example, on the gas barrier sheet of the present invention formed in a film shape on an arbitrary resin film, and further composed of a resin or an inorganic material, for example, one layer or two or more layers in any combination of film materials You may laminate by a multilayer. Further, the laminated multilayer film may be peeled off from the resin film. For example, a combination such as resin film-anchor coat layer- {film gas barrier sheet in the present invention-film made of resin or inorganic material-} smoothing layer-protective layer is suitable. The laminated portion of the film-like gas barrier sheet and the film made of resin or inorganic material shown in parentheses may be laminated one by one or in multiple layers in any combination. Further, a film made of a resin or an inorganic material, an anchor coat layer, a smoothing layer, and a protective layer may or may not be provided, and each layer may be a single layer or a plurality of layers.

  In the case of laminating the films made of the above inorganic materials, the films include silicon oxide, aluminum, zinc tin, and lead oxide, carbide, nitride, oxycarbide, oxynitride, carbonitride, and oxycarbonitride. Among them, any thin film layer known as a gas barrier material made of one kind or a mixture of two or more kinds is suitable.

  Furthermore, laminating a film having water swellability (hygroscopicity) as disclosed in Japanese Patent Application Laid-Open No. 2007-63118 with the film-like gas barrier sheet of the present invention having a high water vapor gas barrier property is disclosed in This is suitable for improving gas barrier properties including water vapor gas barrier properties disclosed in 22075. The film having water swellability is not particularly limited, but the effect of the present invention is more remarkable when the film contains a layered inorganic compound mainly containing inorganic ions as interlayer ions. The gas barrier film in which the film-like gas barrier sheet of the present invention and the film having water swellability are combined can maintain high gas barrier properties even in an environment where there is a lot of water vapor, and is a product sealed with the gas barrier film For example, moisture generated from an organic EL element or the like disclosed in Japanese Patent Application Laid-Open No. 2007-42616 can also be adsorbed. The above-mentioned gas barrier film is an organic EL element that requires very high barrier properties against oxygen and water vapor, particularly a top emission type organic EL element that cannot use a colored desiccant, and it is difficult to contain a desiccant. It is particularly suitable for a perfect solid organic EL element.

  In addition, since the gas barrier coating liquid according to the present invention can be easily applied to materials requiring heat resistance and materials requiring hydrophobicity, a surface for forming a gas barrier sheet on the surface of these materials. Suitable as a coating agent.

  Hereinafter, the present invention will be described more specifically with reference to examples. The physical properties of the dispersions and gas barrier sheets in the following examples and comparative examples were evaluated by the following methods.

(1) Presence ratio of ions in the dispersion liquid It was evaluated by ion chromatography analysis. For cations, a TSKgel Super IC-Cation column (size 4.6 mm ID × 15 cm) was used with a mixed solution of 0.50 mMol / L histidine and 2.5 mMol nitric acid as the eluent. Measurement was carried out under conditions of 0 mL / min and an injection volume of 30 μL to quantify. Regarding the anion, a mixed solution of 1.7 mMol NaHCO ₃ solution and 1.8 mMol Na ₂ CO ₃ solution was used as an eluent through a TSKgel Super IC-AP column (size 4.6 mm ID × 15 cm). Measured and quantified under the conditions of a flow rate of 0.8 mL / min and an injection volume of 30 μL.

(2) Average particle size of (a) nanosheet in dispersion The average particle size was determined by a dynamic light scattering method. As the apparatus, a solid content concentration of the dispersion liquid is used in the range of about 0.005 mass% to 0.5 mass% at a liquid temperature of 25 ° C. using a zeta potential / particle size measurement system ELSZ-2 manufactured by Otsuka Electronics Co. The range in which the dependence of the zeta potential on the concentration was not observed was determined. Further, a concentration having high scattering intensity is arbitrarily determined within the range, and measurement is performed three times at the concentration, and the average value of the average particle diameter based on the cumulant analysis result is calculated as the average of (a) nanosheets in the dispersion The particle diameter was taken.

(3) Film thickness of gas barrier layer of gas barrier sheet Using a stylus type surface shape measuring instrument (DEKTAK 6M (manufactured by ULVAC, Inc.)), scan length 2000 μm, time 13 seconds, stylus force 3 mg, stylus diameter 12. Measurement was performed at 5 μm.

(4) X-ray diffraction analysis (XRD) of gas barrier sheet
The measurement was carried out by an X-ray diffractometer “RINT-2500” manufactured by Rigaku Corporation. As the X-ray wavelength, 1.54056 mm of Cu / Kα was used. The measurement environment was an air temperature of 25 ° C. and a relative humidity of 50%.

(5) IR Measurement of Gas Barrier Sheet The measurement was performed with a Varian IR measurement device “FTS-575C / UMA500”. The measurement method was a transmission method. The sample plate was made of Ge crystal and the number of integration was 100 times. The measurement environment was an air temperature of 25 ° C. and a relative humidity of 50%.

(6) Quantitative measurement of (a) nanosheet in gas barrier layer It was performed by a thermogravimetric analyzer “TGA-50” manufactured by Shimadzu Corporation. 5 mg of the gas barrier layer separated by a spatula scraping method from the gas barrier sheet produced in each example and comparative example was placed on a platinum cell, and nitrogen gas was flowed at 50 ml / min, from 30 ° C. to 800 ° C. at 10 ° C./min. The temperature was raised. The weight loss between 300 ° C. and 800 ° C. was defined as the amount of (b) amine and (c) curable organic material, and the remaining ratio was defined as the amount of (a) nanosheet.

(7) Cross-sectional TEM observation of gas barrier sheet The cross section of the obtained gas barrier sheet was processed by FIB to produce a thin piece, and observed at 200 kV with a TEM “HF-2000” of Hitachi, Ltd.

(8) Water vapor gas barrier property of gas barrier sheet Using a differential pressure method, a gas / water vapor permeability measuring device GTR-30XAAS manufactured by GTR Tech Co., Ltd. conforming to JIS K7126, a permeation area of 50.24 cm ² , a differential pressure of 1 atm, The measurement was performed for 5 minutes at 40 ° C. and 90% relative humidity using oxygen gas as a carrier gas.

[Example 1]
A dispersion of fluorinated hectorite (trade name: classified NHT, manufactured by Topy Industries, Ltd.) synthesized by a melting method in which interlayer ions are mainly sodium ions was used. 400 g of a classified NHT dispersion with a solid content concentration of 2% by mass diluted with pure water, using a centrifugal separator himac CR20 (manufactured by Hitachi, Ltd.), using a rotor number 13, 500 ml centrifuge tube, and 8000 rpm for 10 minutes. Centrifugation was performed under the conditions described above to separate and remove the sediment. The weight of the aqueous dispersion obtained by discarding 260 g of the supernatant was 90 g, and the solid content concentration was 2.4% by mass. The proportion of sodium ions to the solid content in the dispersion was 4.2% by mass, fluorine ions were 0.28% by mass, and sulfate ions were 0.11% by mass. The average particle size of the solid content measured by the dynamic scattering method was 3000 nm.

  40 ml of an anion exchange resin (Amberlite IRA400, manufactured by Organo Corporation), which was sufficiently adjusted to a hydroxide ion type with 1N potassium hydroxide and thoroughly washed with pure water, was packed in a glass column. 200 ml of the aqueous dispersion diluted to 2% by mass with distilled water is passed through the column filled with the anion exchange resin at a rate of about 1 drop every second to perform anion exchange into hydroxide ions. It was. About 40 ml of a cation exchange resin (Amberlite IR120B, manufactured by Organo Corp.) sufficiently adjusted to an ammonium ion type with a 1N ammonium chloride aqueous solution was packed in a glass column, and the dispersion subjected to the anion exchange described above was prepared. The cation exchange into ammonium ions was carried out at a rate of about 1 drop per second through a column packed with the above cation exchange resin. The obtained dispersion was further centrifuged under the same centrifuge at 8000 rpm for 10 minutes to separate and remove the slightly generated sediment. The solid concentration of the obtained dispersion after ion exchange was 1.07% by mass. The ratio of sodium ions to the solid content in the dispersion is 0.04% by mass, ammonium ions are 3.2% by mass, fluorine ions are 0.014% by mass, and sulfate ions are 0.002% by mass. there were. That is, 99.0% of sodium ions were removed by the ion exchange.

  50 g of this dispersion after ion exchange (as a dispersion for replacing the dispersion medium) and 30 g of N, N-dimethylformamide (DMF) are mixed and heated under reduced pressure on a rotary evaporator at about 30 to 120 hPa at 55 ° C. Then, the dispersion medium was removed, and about 19 g of a transparent dispersion liquid (as an organic solvent dispersion liquid) having a solid content concentration of about 2.8% by mass using DMF as a main dispersion medium was obtained. The water content in the dispersion analyzed by gas chromatography was about 4% by mass.

  After taking out one drop of this organic solvent dispersion, it was fully diluted with DMF, applied to the cleaved surface of fresh mica, and when the thickness of the nanosheet (a) was measured with AFM, the average particle size was several μm. Almost all, including a high aspect ratio (a) nanosheet, was about 1 nm, suggesting that (a) the nanosheet was peeled and dispersed into a single layer in an organic solvent.

  (±) -trans-1,2-diaminocyclohexane (manufactured by Tokyo Chemical Industry Co., Ltd.) (as (b) amine) 27.0 mg dissolved in 0.41 g of DMF was added to 6 g of the organic solvent dispersion. After stirring at room temperature for 1 hour, 26.1 mg of resorcinol diglycidyl ether (manufactured by Aldrich Corporation) was added and stirred at room temperature for 1 hour to obtain a transparent coating solution. After depressurizing and depressurizing with a diaphragm pump while stirring the coating solution, a 100 micron thick PEN film (manufactured by Teijin DuPont Films Co., Ltd.) is set on an automatic film applicator (manufactured by BYK-Gardner). A 2 mil bar film applicator (manufactured by BYK-Gardner) was placed on top, and this coating solution was poured in front of about 3 ml bar film applicator and applied at a coating speed of 50 mm / s. Thereafter, it was put into a safety oven SPHH-201 (manufactured by ESPEC), dried at 50 ° C. for 10 minutes, then heated to 180 ° C. under the condition of 1.08 ° C./min, and then held at 180 ° C. for 2 hours. Thus, a gas barrier sheet in which a gas barrier layer was formed on the PEN film was obtained.

  It was 0.8 micrometer when the film thickness of the gas barrier layer of this gas barrier sheet was measured. Moreover, the ratio of the (a) nanosheet in a gas barrier layer was 78.2 mass% by thermogravimetric analysis measurement. The average aspect ratio of the a) nanosheet obtained by dividing the average particle diameter of 3000 nm by the unit thickness d of 0.95 nm was 3200.

  1 is a diagram showing an X-ray diffraction spectrum of a gas barrier sheet formed in Example 1. FIG. The peak corresponding to the first-order diffraction of the strongest 001 plane was present at 2θ = 5.24 °, and was (a) 1.69 nm in terms of the interlayer distance of the nanosheet.

Further, from the IR spectrum of the gas barrier sheet, a peak derived from an amino group was confirmed at 3271 cm ⁻¹ . From the results of XRD and IR, it was confirmed that (b) amine had a structure adsorbed on (a) nanosheet. Moreover, the peak of the benzene ring derived from an epoxy has been confirmed at 1604 cm ⁻¹ and 1496 cm ⁻¹ . Moreover, since the peak of the glycidyl group disappeared at 905 cm ⁻¹ , it was confirmed that the epoxy had reacted with (b) amine.

  2 is a cross-sectional TEM photograph of the gas barrier sheet formed in Example 1. FIG. The TEM photograph showed a cross section in the thickness direction, and (a) a structure in which the nanosheets were oriented and laminated so that the plane direction of the nanosheet was substantially parallel to the plane direction of the gas barrier layer could be confirmed.

The permeation amount of water vapor of this material measured by the differential pressure method was below the detection limit of the device after 54 hours (0.002 g / m ² · day or less).

[Example 2]
Instead of the fluorinated hectorite dispersion (trade name: Classified NHT, manufactured by Topy Industries, Ltd.) synthesized by the melting method in which interlayer ions are mainly sodium ions in Example 1, interlayer ions are mainly sodium ions. A dispersion of fluorinated mica synthesized by the talc modification method (trade name: MEB3, manufactured by Corp Chemical Co., Ltd.) was used. A dispersion of 400 g of MEB3 diluted with pure water to a solid content concentration of 2% by mass was centrifuged at 2000 rpm for 10 minutes using the same centrifuge as in Example 1, and the precipitate was separated and removed. Got. The resulting aqueous dispersion had a solid content concentration of 1.29% by mass. The ratio of sodium ions to the solid content in the dispersion was 3.3% by mass, fluorine ions were 0.26% by mass, and sulfate ions were 0.024% by mass.

  This aqueous dispersion was subjected to removal of surplus ions and ion exchange of interlayer ions with ammonium ions in the same manner as in Example 1 to obtain a dispersion after ion exchange having a solid content concentration of 1.06% by mass. The ratio of sodium ions to the solid content in the dispersion is 0.060% by mass, ammonium ions are 2.4% by mass, fluorine ions are 0.042% by mass, and sulfate ions are 0.010% by mass. there were. That is, 98.2% of sodium ions were removed by the ion exchange.

  25.0 g of the dispersion after ion exchange (as an aqueous dispersion for replacing the dispersion medium) and 25.0 g of DMF are mixed, and the dispersion medium is removed by heating under reduced pressure at about 30 to 120 hPa and 55 ° C. with a rotary evaporator. 21. A transparent dispersion (as an organic solvent dispersion) having a solid content concentration of about 1.17% by mass, using DMF whose residual water content is reduced to about 6.5% by mass as a main dispersion medium. 6 g was obtained.

  (±) -trans-1,2-diaminocyclohexane (manufactured by Tokyo Chemical Industry Co., Ltd.) (as (b) amine) 25.0 mg dissolved in 0.41 g of DMF was added with 6 g of the organic solvent dispersion. After stirring for 1 hour at room temperature, 24.2 mg of resorcinol diglycidyl ether (manufactured by Aldrich Corporation) was added to obtain a transparent coating solution. Thereafter, a gas barrier sheet was obtained in the same manner as in Example 1.

  When the film thickness of the gas barrier layer of this gas barrier sheet was measured by the same method as in Example 1, it was 0.8 μm. Moreover, the ratio of the (a) nanosheet in a gas barrier layer was 75.4 mass% by thermogravimetric analysis measurement. (A) The average aspect ratio of the nanosheet was 3200.

  When X-ray diffraction of this gas barrier sheet was measured, a clear peak due to first-order diffraction on the 001 plane was observed at 2θ = 5.24.

The amount of water vapor permeated through the gas barrier sheet measured by the differential pressure method was below the device detection limit (0.002 g / m ² · day or less) after 54 hours.

[Comparative Example 1]
Pure water 995g was added to 5.0g of smecton SA (Kunimine Kogyo Co., Ltd.), which is a smectite group, and shaken to obtain a 0.50 wt% aqueous dispersion. The particle diameter measured by the dynamic scattering method was 50 nm.

  This aqueous dispersion was subjected to removal of excess ions and ion exchange of interlayer ions to ammonium ions in the same manner as in Example 1 to obtain an ion exchange dispersion having a solid content concentration of 0.46% by mass.

  100.0 g of ion exchange dispersion and 25.0 g of DMF are mixed and heated under reduced pressure on a rotary evaporator under conditions of about 30 to 120 hPa and 55 ° C. to remove the dispersion medium, and the solid content concentration is about 1.01% by mass. 15.0 g of a transparent dispersion was obtained.

  27.0 mg of 2,2-bis (4-glycidyloxyphenyl) propane having an epoxy group (manufactured by Wako Pure Chemical Industries, Ltd.) and 27.0 mg of dicyandiamide (manufactured by Wako Pure Chemical Industries, Ltd.) which is solid at room temperature The mixture was added and stirred at room temperature for 1 hour to obtain a transparent dispersion.

  Thereafter, a gas barrier sheet was obtained in the same manner as in Example 1.

  When the film thickness of the gas barrier layer of this gas barrier sheet was measured by the same method as in Example 1, it was 0.8 μm. Moreover, the ratio of the (a) nanosheet in a gas barrier layer was 79.4 mass% by thermogravimetric analysis measurement. (A) The average aspect ratio of the nanosheet was 53.

  When X-ray diffraction of this material was measured, a clear peak due to first-order diffraction on the 001 plane was observed at 2θ = 5.24.

The water vapor transmission rate of the gas barrier sheet measured by the differential pressure method was 1.02 g / m ² · day after 54 hours.

[Example 3]
KAYARAD ZFA-266H (Nipponization), which is an acrylic monomer having a bisphenol A skeleton, was added to 6.0 g of a transparent dispersion having a solid content concentration of about 2.8% by mass, using DMF of Example 1 as a main dispersion medium. 1.00 g of 131 mg, manufactured by Yakuhin Co., Ltd., 34 mg of N- [3- (dimethylamino) propyl] acrylamide (manufactured by Tokyo Chemical Industry Co., Ltd.), and 4 mg of photo radical initiator Irgacure OXE-01 (manufactured by Ciba Japan Co., Ltd.) A solution dissolved in DMF was mixed, and a coating liquid was obtained by the procedure described in [Coating liquid forming step].

Then, after coating as in Example 1, it was dried at 50 ° C. Thereafter, an energy amount of 500 mJ / cm ² was exposed in the atmosphere with an i-line intensity of 25 mW / cm ² with a high-pressure mercury lamp. Subsequently, the temperature was raised from 50 ° C. to 180 ° C. in an oven over 2 hours, and a heat treatment was performed for 2 hours at 180 ° C. to obtain a gas barrier sheet.

  When the film thickness of the gas barrier layer of this gas barrier sheet was measured by the same method as in Example 1, it was 0.8 μm. Moreover, the ratio of the (a) nanosheet in a gas barrier layer was 75.4 mass% by thermogravimetric analysis measurement. (A) The average aspect ratio of the nanosheet was 3200.

  When X-ray diffraction of this material was measured, a clear peak due to first-order diffraction on the 001 plane was observed at 2θ = 5.05.

The permeation amount of water vapor of this gas barrier sheet measured by the differential pressure method was 0.7 g / m ² · day.

[Example 4]
To ± 6.0 g of a transparent dispersion having a solid content concentration of about 2.8% by mass using DMF of Example 1 as a main dispersion medium, (±) -trans-1,2-diaminocyclohexane (Tokyo Chemical Industry Co., Ltd.) 18.9 mg of the above dispersion was added to 6 g of the above dispersion and stirred for 1 hour at room temperature, then 9.0 mg of ε-caprolactam (manufactured by Wako Pure Chemical Industries, Ltd.) dissolved in 0.3 g of DMF was added, The mixture was stirred at room temperature for 1 hour to obtain a transparent dispersion. Thereafter, a gas barrier sheet was obtained in the same manner as in Example 1.

  When the film thickness of the gas barrier layer of this gas barrier sheet was measured by the same method as in Example 1, it was 0.7 μm. Moreover, the ratio of the (a) nanosheet in a gas barrier layer was 85.3 mass% by thermogravimetric analysis measurement. (A) The average aspect ratio of the nanosheet was 3200.

  When X-ray diffraction of this material was measured, a clear peak due to first-order diffraction on the 001 plane was observed at 2θ = 6.38.

The amount of water vapor permeated through the gas barrier sheet measured by the differential pressure method was below the device detection limit (0.002 g / m ² · day or less) after 54 hours.

[Example 5]
The dispersion after ion exchange in Example 1 (as a dispersion for replacing the dispersion medium) was heated under reduced pressure on a rotary evaporator under conditions of about 45 to 120 hPa and 55 ° C. to evaporate the water and concentrate to obtain a solid content concentration. A transparent aqueous dispersion having a mass of about 3.33% by mass was obtained.

  To 5.50 g of DMF, 6.00 g of the aqueous dispersion was added little by little with stirring, and stirred for 3 hours to obtain an organic solvent dispersion. To this organic solvent dispersion, 0.240 g of a solution of N, N′-dibenzylethylenediamine (manufactured by Tokyo Chemical Industry Co., Ltd.) dissolved in 20% by mass DMF was added, stirred for 30 minutes, and resorcinol diglycidyl ether (Aldrich). 0.244 g of a solution prepared by dissolving 20% by mass in DMF was added and stirred at room temperature for 1 hour to obtain a transparent coating solution.

  Then, the gas barrier sheet was able to be obtained by using the same procedure as Example 1. When the film thickness of the gas barrier layer of this gas barrier sheet was measured by the same method as in Example 1, it was 0.3 μm. It is considered that a good water vapor gas barrier property can be obtained also by this gas barrier sheet.

[Example 6]
An organic solvent dispersion was obtained by adding 6.01 g of an aqueous dispersion obtained in the same manner as in Example 5 to 5.52 g of γ-butyrolactone (manufactured by Wako Pure Chemical Industries, Ltd.) and stirring for 3 hours. To this organic solvent dispersion, 0.240 g of a solution obtained by dissolving N, N′-dibenzylethylenediamine (manufactured by Tokyo Chemical Industry Co., Ltd.) in 20% by mass γ-butyrolactone was added and stirred for 30 minutes, and then resorcinol diglycidyl ether. A 0.244 g solution of 20% by mass γ-butyrolactone (manufactured by Aldrich Co., Ltd.) was added and stirred at room temperature for 1 hour to obtain a transparent coating solution.

  Then, the gas barrier sheet was able to be obtained by using the same procedure as Example 1. When the film thickness of the gas barrier layer of this gas barrier sheet was measured by the same method as in Example 1, it was 0.3 μm. It is considered that a good water vapor gas barrier property can be obtained also by this gas barrier sheet.

Claims (9)

A gas barrier sheet having a gas barrier layer,
The gas barrier layer is a cured product of a nanosheet-containing composition comprising (a) a nanosheet, (b) an amine, and (c) a curable organic material,
The (a) nanosheet is a cleavage product of one or more layered inorganic compounds selected from the group consisting of a smectite group and a mica group,
(B) The base dissociation constant pKb of the amine is less than 4.74, and at least a part of the amine is cationized by ion exchange with ammonium ions as interlayer cations between the nanosheets of the layered inorganic compound. Exists in an ionic bond with
The (c) curable organic substance is an organic substance that cures by reacting with an amine;
(A) the average aspect ratio of the nanosheet is 150 or more, and
The gas barrier sheet, wherein the nanosheet is laminated so that the surface direction of the (a) nanosheet is substantially parallel to the surface direction of the gas barrier layer.   The gas barrier sheet according to claim 1, wherein the proportion of the (a) nanosheet in the gas barrier layer is 50 mass% or more and 99 mass% or less.   The gas barrier sheet according to claim 1 or 2, wherein a ratio of (b) amine and (c) curable organic substance in the nanosheet-containing composition is 10: 1 to 1: 5 in molar ratio.   The gas barrier sheet according to any one of claims 1 to 3, wherein the (b) amine has two or more amino groups.   The gas barrier sheet according to any one of claims 1 to 4, wherein the (c) curable organic substance has an epoxy group. The gas barrier sheet comprises the gas barrier layer;
The (b) amine has two or more amino groups;
(C) the curable organic material is a compound having two or more epoxy groups, and
The gas barrier layer cured embodying forming a has a structure in which two or more molecules of (b) an amine is chemically bound to one molecule of (c) a curable organic material, any of claims 1 to 5 1 The gas barrier sheet according to item . The gas barrier sheet according to any one of claims 1 to 6 , wherein the layered inorganic compound is a smectite group fluorinated smectite. The gas barrier sheet according to any one of claims 1 to 6, wherein the layered inorganic compound is a mica group fluorinated mica. A method for producing the gas barrier sheet according to any one of claims 1 to 8 ,
(1) A cleavage product of one or more layered inorganic compounds selected from the group consisting of a smectite group and a mica group (a) An aqueous dispersion obtained by dispersing nanosheets in water is used as an ion exchange resin and a semipermeable membrane. A dispersion medium replacement water dispersion preparation step of obtaining a dispersion medium replacement water dispersion by treating with either
(2) An organic solvent dispersion is obtained by substituting part or all of the water in the aqueous dispersion for dispersion medium substitution with an organic solvent, or by adding an organic solvent to the aqueous dispersion for dispersion medium substitution. An organic solvent dispersion preparation step;
(3) A nanosheet-containing composition containing (a) a nanosheet, (b) an amine, and (c) a curable organic substance by adding (b) an amine and (c) a curable organic substance to the organic solvent dispersion; Forming a coating liquid comprising a dispersion medium, a coating liquid forming step;
(4) After applying the coating liquid on the substrate, the dispersion medium in the coating liquid is removed, and the (b) amine and the (c) curable organic substance are reacted to form the nanosheet-containing composition. Forming a gas barrier layer, which is a cured product of the product, on the substrate; and
A method for producing a gas barrier sheet, comprising forming a gas barrier sheet having a gas barrier layer by including the steps in the order described above.