Polymerizable composition and uses of same

Abstract

[Problem] A method for improving water vapor barrier performance is still required for a composite material that uses a layered inorganic compound. [Solution] Disclosed is a polymerizable composition which comprises: (A) a layered inorganic compound which contains, as exchangeable cations, at least one kind of ions that are selected from among sodium ions and lithium ions; (B) at least one material that is selected from among a glycidyl amine-type epoxy resin, methylol melamine, a combination of a nitrogen-free epoxy resin and an amine-based compound, a combination of a nitrogen-free epoxy resin and a thiol-based compound, and a nitrogen-free epoxy resin that has an epoxy equivalent of 80-165 g / eq and a molecular weight of 180-420 g / mol; and (C) a carboxylic acid compound.

Description

Polymerizable composition and its uses

[0001] The present invention relates to a polymerizable composition containing a layered inorganic compound. More specifically, the present invention relates to a polymerizable composition having excellent moisture resistance, a film, an adhesive, a coating agent, a laminate, and methods for producing the same, and uses thereof.

[0002] Layered inorganic compounds such as layered clay minerals consist of plate-like inorganic crystal sheets such as silicate layers and interlayer ions that compensate for the charge of the inorganic crystal sheets. Many of the inorganic crystal sheets that make up layered inorganic compounds have a negative permanent charge, and to compensate for this negative permanent charge, inorganic cations, such as sodium ions and lithium ions, exist as interlayer ions (exchangeable cations) between the layers of the layered inorganic compound.

[0003] Because layered inorganic compounds have excellent gas barrier properties, films have been developed that have improved gas barrier properties by adding layered inorganic compounds to polymers as fillers to form composites. However, layered inorganic compounds have a problem in that their barrier effect (moisture resistance) against water (water vapor) is insufficient due to their high hygroscopicity.

[0004] As a method for improving such moisture resistance, for example, Patent Documents 1 and 2 propose a method of substituting cations such as sodium with lithium ions, which have a smaller ionic radius, by focusing on the fact that the moisture absorption of clay is due to the hydration force of cations present between the layers of clay crystals. Also, Patent Document 3 proposes a method for improving water vapor barrier properties by using nanosheets, which are cleavage products of specific layered inorganic compounds, in combination with amines.

[0005] JP 2008-247719 A JP 2011-51845 A JP 2011-213111 A

[0006] The method of Patent Document 1 requires high-temperature treatment, which limits its applications and also results in low yields. The method of Patent Document 2 is an ion exchange method using a column, which is extremely time-consuming. The method of Patent Document 3 requires ion exchange resin treatment, organic solvent substitution, and the like, which is extremely time-consuming and leaves room for improvement in moisture resistance at high temperatures. Therefore, there is still a need for a method to improve the water vapor barrier performance of composite materials using layered inorganic compounds.

[0007] The present inventors have found that excellent moisture-proofing properties can be obtained by blending a layered inorganic compound with a specific polymerizable compound and a carboxylic acid compound, and have thus completed the present invention. That is, the present invention is, for example, as follows.

[0008] [1] A polymerizable composition comprising: (A) a layered inorganic compound containing at least one exchangeable cation selected from sodium ions and lithium ions; (B) at least one selected from a glycidylamine-type epoxy resin, a methylol melamine, a combination of a nitrogen-free epoxy resin and an amine-based compound, a combination of a nitrogen-free epoxy resin and a thiol-based compound, and a nitrogen-free epoxy resin having an epoxy equivalent of 80 to 165 g / eq and a molecular weight of 180 to 420 g / mol; and (C) a carboxylic acid compound. [2] The composition according to [1], wherein component (C) is a carboxylic acid compound having only carboxy groups as active hydrogen groups. [3] The composition according to [1] or [2], wherein component (B) has an acid dissociation constant pKa of 3 or greater. [4] The composition according to any one of [1] to [3], wherein component (A) includes at least one selected from smectite, vermiculite, and swellable mica. [5] The composition according to any one of [1] to [4], wherein the component (C) is contained in an amount of 0.15 or more times the equivalent of the cation exchange capacity (CEC) of the component (A). [6] The composition according to any one of [1] to [5], wherein the weight ratio of the component (A) to the component (B) [(A) / (B)] is in the range of 5 / 1 to 1 / 10. [7] The composition according to any one of [1] to [6], wherein the average particle size of the component (A) is in the range of 0.1 to 30 μm. [8] The composition according to any one of [1] to [7], wherein the number of carboxy groups in the component (C) is 1 to 6. [9] The composition according to any one of [1] to [8], wherein the glycidylamine-type epoxy resin and the nitrogen-free epoxy resin each have two or more glycidyl groups.

[10] The composition according to any one of [1] to [9], wherein the component (B) is at least one selected from a glycidylamine-type epoxy resin, a methylolmelamine, a combination of a nitrogen-free epoxy resin and an amine compound, and a combination of a nitrogen-free epoxy resin and a thiol compound. [10-1] The composition according to any one of [1] to [9], wherein the component (B) is at least one selected from a glycidylamine-type epoxy resin and a methylolmelamine.

[11] The composition according to

[10] or [10-1], wherein the glycidyl amine-type epoxy resin and the nitrogen-free epoxy resin have an epoxy equivalent of 80 to 165 g / eq and a molecular weight of 180 to 420 / mol.

[0009]

[12] A cured product of the composition according to any one of [1] to

[11] .

[13] A gas barrier film comprising the cured product of the composition according to

[12] .

[14] A coating agent or adhesive comprising the composition according to any one of [1] to

[11] .

[15] A laminate comprising a substrate and a barrier layer comprising the cured product of the composition according to

[12] .

[0010] According to one embodiment of the present invention, there are provided a polymerizable composition that can exhibit excellent moisture resistance (particularly moisture resistance at high temperatures), and a film, adhesive, coating agent, and laminate using the same.

[0011] FIG. 1 is a diagram illustrating the state immediately after blending the components of a polymerizable composition according to one embodiment of the present invention. FIG. 1 is a diagram illustrating the state in which the components of a polymerizable composition according to one embodiment of the present invention are blended, the carboxylic acid compound interacts with the sodium ion of component (A), and the carboxylic acid compound becomes a trihydrate upon heating. FIG. 2 is a diagram illustrating the mechanism in which the components of a polymerizable composition according to one embodiment of the present invention are blended and further heated, causing water molecules of component (A) to be eliminated and nitrogen atoms in component (B) to interact with the sodium ion of component A. FIG. 1 is an IR chart of a gas barrier film coated with a coating liquid containing the polymerizable composition of Example 1-1 and dried. FIG. 2 is an IR chart of a gas barrier film coated with a coating liquid containing the polymerizable composition of Comparative Example 1-1 and dried. FIG. 3 is an IR chart of a gas barrier film coated with a coating liquid containing the polymerizable composition of Comparative Example 1-2 and dried. FIG. 4 is an IR chart of a gas barrier film coated with a coating liquid containing the polymerizable composition of Comparative Example 1-3 and dried.

[0012] Hereinafter, embodiments of the present invention will be described in detail. The present invention is not limited to the following embodiments and can be modified as desired without departing from the spirit and scope of the present invention. The upper and lower limits of the numerical ranges described in this specification can be combined arbitrarily. For example, when "X to Y" and "Z to W" are described, the ranges "X to W" and "Z to Y" are also included as numerical ranges within the scope of the present invention. Furthermore, unless otherwise specified, the numerical range "lower limit to upper limit" described in this specification means a range between the lower limit and the upper limit. In this specification, "moisture-proof" refers to barrier properties against gases containing water vapor and water vapor itself, and refers to low moisture permeability.

[0013] <<Polymerizable Composition>> One aspect of the present invention relates to a polymerizable composition (hereinafter also simply referred to as a "polymerizable composition") comprising: (A) a layered inorganic compound containing, as an exchangeable cation, at least one selected from sodium ions and lithium ions; (B) at least one selected from methylol melamine and an epoxy resin; and (C) a carboxylic acid compound. One embodiment of the present invention relates to a polymerizable composition comprising: (A) a layered inorganic compound containing, as an exchangeable cation, at least one selected from sodium ions and lithium ions; (B) at least one selected from a glycidylamine-type epoxy resin, methylol melamine, a combination of a nitrogen-free epoxy resin and an amine-based compound, a combination of a nitrogen-free epoxy resin and a thiol-based compound, and a nitrogen-free epoxy resin having an epoxy equivalent of 80 to 165 g / eq and a molecular weight of 180 to 420 g / mol; and (C) a carboxylic acid compound. One embodiment of the present invention relates to a polymerizable composition comprising (A) a layered inorganic compound containing, as an exchangeable cation, at least one selected from sodium ions and lithium ions; (B) at least one selected from a glycidylamine-type epoxy resin, a methylolmelamine, a combination of a nitrogen-free epoxy resin and an amine compound, and a combination of a nitrogen-free epoxy resin and a thiol compound; and (C) a carboxylic acid compound. The polymerizable composition exhibits excellent moisture resistance (particularly at high temperatures) by blending (A) a layered inorganic compound containing, as an exchangeable cation, at least one selected from a glycidylamine-type epoxy resin, a methylolmelamine, a combination of a nitrogen-free epoxy resin and an amine compound, a combination of a nitrogen-free epoxy resin and a thiol compound, and a nitrogen-free epoxy resin having an epoxy equivalent of 80 to 165 g / eq and a molecular weight of 180 to 420 g / mol; and (C) a carboxylic acid compound.

[0014] Although the details of the factors that produce such excellent moisture-proof property are unknown, the inventor presumes that the interaction between the exchangeable cations of the layered inorganic compound (A) and the carboxyl group of the component (C) causes the component (A) to be modified by the component (C) (forming carboxylate), and as a result, the hydration of the exchangeable cations is inhibited, thereby improving the moisture-proof property.In addition, the interaction (chemical adsorption or polar covalent bond) occurs between the exchangeable cations of the layered inorganic compound (A) and at least one selected from the lone electron pair of the nitrogen atom of the component (B), the lone electron pair of the sulfur atom, the lone electron pair of the oxygen atom of the ether group part of glycidyl ether, and the lone electron pair of the oxygen atom of the ester group part of glycidyl ester (hereinafter, these may be referred to as the lone electron pairs of nitrogen atom, etc.), which can further prevent the adsorption of water molecules to the exchangeable cations, and furthermore, the component (B) fills the inorganic crystal interlayer space of the component (A) from the exchangeable cations, and in this state, the polymerization or hardening of the component (B) occurs, thereby improving the moisture-proof property. Hereinafter, as component (A), swelling mica (exchangeable cation: Na ＋ ), terephthalic acid as component (C), and N,N,N',N'-tetraglycidyl-m-xylylenediamine as component (B) are used as an example, and the mechanism by which the moisture-proof property of the polymerizable composition is exhibited will be described with reference to FIGS. 1A to 1C.

[0015] Swellable mica has sodium ions (Na ions) as interlayer ions (exchangeable cations) between the silicate layers. ＋) exists. When swellable mica is dispersed in water, water molecules are coordinated or hydrated around the sodium ions (typically in the form of a tetrahydrate). Further water coordination (hydration) causes the interlayer distance between the silicate layers to expand (swell) (Figure 1A). When swellable mica is mixed with N,N,N',N'-tetraglycidyl-m-xylylenediamine and terephthalic acid in water, terephthalic acid and N,N,N',N'-tetraglycidyl-m-xylylenediamine enter between the silicate layers. When heated in this state, the water molecules coordinated to the sodium ions are released, and terephthalic acid enters between the sodium ions. The carboxyl group of terephthalic acid coordinates with the sodium ions, forming a sodium carboxylate (disodium terephthalate). This state, in which water molecules are coordinated or hydrated around the sodium ions, changes to a trihydrate state (Figure 1B). This reduces or prevents re-coordination and hydration of water molecules to the sodium ions. Further heating causes the water molecules coordinated around the sodium ions to be released, and the lone electron pair of the nitrogen atom of N,N,N',N'-tetraglycidyl-m-xylylenediamine chemically adsorbs to the sodium of disodium terephthalate, further reducing or preventing re-coordination and hydration of water molecules (Figure 1C). Then, N,N,N',N'-tetraglycidyl-m-xylylenediamine undergoes addition polymerization and polymerization starting from the exchangeable cations, resulting in the silicate layer surface being covered with a polymer bonded at multiple points via the exchangeable cations modified with carboxylic acids. It is presumed that this results in a stray effect due to the clay-resin complexation, improving moisture resistance. However, the present invention is not limited to this mechanism. Below, each component contained in the polymerizable composition will be described in order.

[0016] (A) Layered inorganic compound containing at least one exchangeable cation selected from sodium ions and lithium ions. The polymerizable composition contains a layered inorganic compound containing at least one exchangeable cation selected from sodium ions and lithium ions. The layered inorganic compound can improve gas barrier properties due to the so-called labyrinth effect. A layered inorganic compound containing at least one exchangeable cation selected from sodium ions and lithium ions is composed of an inorganic crystal layer (inorganic crystal sheet) and exchangeable cations including sodium ions and / or lithium ions. The inorganic crystal layers constituting the layered inorganic compound have a negative permanent charge, and sodium ions or lithium ions exist as exchangeable cations between the inorganic crystal layers (on the surfaces of inorganic crystal layers with insufficient charge) as interlayer ions (particularly interlayer cations) to compensate for the negative permanent charge. (Hereinafter, a layered inorganic compound containing at least one exchangeable cation selected from sodium ions and lithium ions will sometimes be simply referred to as a "layered inorganic compound.")

[0017] The layered inorganic compound is not particularly limited, and may be any compound having sodium ions or lithium ions between the inorganic crystal layers. Examples of the layered inorganic compound include layered silicates, layered titanates, layered tungstates, layered manganates, layered cobaltates, layered vanadates, layered niobates, layered tantalates, layered titanium niobates, layered titanium tantalates, layered molybdates, and layered ruthenates that have sodium ions (Na ions) between the inorganic crystal layers. ＋ ) or lithium ion (Li ＋ ) and the like.

[0018] Among these, layered silicates are preferred because they are available industrially at relatively low cost and generally have interlayer gaps of 5 Å or more, resulting in excellent intercalation ability. Layered silicates are a type of clay mineral in which silicate layers are stacked in layers. Their crystalline structure is (Si,Al)O ４ A tetrahedron layer in which tetrahedra are bonded two-dimensionally, and M(O, OH) ６(M = Al, Mg, Fe, Ti, etc.) Octahedrons are connected in a two-dimensional network to form octahedral layers, which share some O ions to form a layered structure. The combination of these tetrahedral and octahedral layers forms basic layers (silicate layers) called 1:1 or 2:1 layers, and various types of layered silicates exist depending on the stacking pattern of these basic layers. In the present invention, layered silicates in which each silicate layer (surface) has a permanent negative charge and sodium ions and / or lithium ions are present between the silicate layers are preferably used. In such layered silicates, the lack of positive charge in the silicate layers is compensated for by sandwiching sodium ions and / or lithium ions between the silicate layers (surface).

[0019] Specific examples of layered silicates include smectite, vermiculite, and swelling mica (swelling mica). Examples of smectite include montmorillonite, bentonite, saponite, hectorite, paidellite, stevensite, and nontronite. Montmorillonite is preferred because it is relatively inexpensive and suitable for coating when forming a laminate. Vermiculite is a substance obtained by calcining and foaming mica-based vermiculite at around 800°C to expand it by 10 times or more. Layered inorganic compounds that exhibit swelling or cleavage properties in solvents are preferably used because they exhibit excellent barrier properties. In this specification, "swelling" refers to a layered inorganic compound in which the interlayer spacing increases as seen by X-ray diffraction when immersed in a large excess of solvent, and "cleavage" refers to a compound that exhibits behavior in which the peak indicating the interlayer spacing decreases or disappears when subjected to the same procedure. Specifically, such layered inorganic compounds are preferably at least one selected from montmorillonite, vermiculite, and swellable mica. More preferably, from the viewpoint of coating suitability, at least one selected from montmorillonite and swellable mica is preferred, with swellable mica being particularly preferred for the reasons described below. Hydroxyl groups derived from the octahedral structure of swellable mica are substituted with fluorine, allowing the particle size to be selected depending on the application, and those with large particle sizes can exhibit barrier properties even with the addition of a small amount. The layered inorganic compounds may be used alone or in combination of two or more. Furthermore, the layered inorganic compounds may be naturally occurring or synthetic.

[0020] The average particle size of the layered inorganic compound is preferably in the range of 0.1 to 30 μm. A particle size of 0.1 μm or greater is preferred because it can improve moisture resistance. A particle size of 30 μm or less is preferred because it can produce a laminate with good transparency. A more preferred range is 0.2 to 18 μm, and even more preferred is 0.4 to 15 μm. The average particle size (X) of the layered inorganic compound used in the present invention can be obtained by measuring a dispersion obtained by dispersing the layered inorganic compound used in the present invention in a desired dispersion medium using dynamic light scattering. An example of a measuring instrument is the Microtrac 3300 particle size distribution analyzer (manufactured by Microtrac-Bell Co., Ltd.). The average aspect ratio (Z) is defined as the value derived from the average particle size (X) and the unit thickness (d) of the nanosheet according to the relationship Z = X / d. Note that, to calculate the average aspect ratio in the present invention, the unit thickness (d) of the nanosheet is 0.95 nm (approximately 1 nm) obtained from the bottom reflection of X-ray diffraction as described in known literature and technical documents.

[0021] The aspect ratio of the layered inorganic compound is preferably in the range of 100 to 30,000, more preferably in the range of 200 to 18,000, and even more preferably in the range of 400 to 15,000. The larger the aspect ratio, the more improved the labyrinth effect, the more suppressed the permeation of water vapor, and the more moisture-proof. There is no particular upper limit to the aspect ratio, but as long as it is within the above range, it is possible to prevent the polymerizable composition from becoming too viscous when used as a coating material. The aspect ratio of the inorganic layered compound is the value obtained by dividing the average particle size of the layered inorganic compound by the thickness a of the unit crystal layer of the inorganic layered compound, which can be measured by powder X-ray diffraction.

[0022] The cation exchange capacity (CEC) of the layered inorganic compound is not particularly limited, but for example, a CEC of 25 to 200 meq / 100g is preferred, 50 to 150 meq / 100g is more preferred, and 70 to 130 meq / 100g is even more preferred. When the CEC is 25 meq / 100g or higher, the cationic substance inserted (intercalated) between the layers of the inorganic layered compound by ion exchange can make the interlayer space organophilic. On the other hand, the larger the CEC, the stronger the bonding strength between the layers of the inorganic layered compound, making it more difficult for the crystal flakes to peel off and tending to deteriorate dispersibility. However, when the CEC is 200 meq / 100g or lower, good dispersibility can be exhibited. "Cation exchange capacity (CEC)" refers to the ability to exchange one set of cations (typically inorganic ions, such as sodium, calcium, or hydrogen) with another set of cations (either inorganic or organic). The CEC was measured according to the method described in the Japan Bentonite Industry Association Standard Test Method JBAS-106-77. More specifically, the cations present between the layers were completely exchanged for ammonium ions with 1 M ammonium acetate, and then the ammonium ions were again expelled with potassium ions from a KCl (potassium chloride) solution, and the amount of potassium ions was measured using an ammonium electrode to quantify the CEC.

[0023] Commercially available layered inorganic compounds can be used, and examples of commercially available smectite layered silicates include the "Kunipia Series," "Sumecton Series" (Kunimine Industries Co., Ltd.), and "BEN-GEL Series" (Hojun Co., Ltd.). Commercially available swellable mica and smectite layered silicates include the "TN Series," "TS Series," and "NHT Series" (Topy Industries Co., Ltd.), the "Lucentite Series," "Micromica Series," and "Somasif Series" (Katakura Co-op Agri Co., Ltd.). Each of these commercially available products is available in various grades depending on their properties, such as crystal structure, cation exchange capacity, and specific surface area, and any of them can be used in the present invention.

[0024] (B) Methylolmelamine and / or Epoxy Resin The polymerizable composition includes, as component (B), at least one selected from methylolmelamine and an epoxy resin. In some embodiments, the epoxy resin has an epoxy equivalent of 80 to 165 g / eq and a molecular weight of 180 to 420 g / mol. In some embodiments, the polymerizable composition includes, as component (B), at least one selected from a glycidylamine-type epoxy resin, methylolmelamine, a combination of a nitrogen-free epoxy resin and an amine-based compound, a combination of a nitrogen-free epoxy resin and a thiol-based compound, and a nitrogen-free epoxy resin having an epoxy equivalent of 80 to 165 g / eq and a molecular weight of 180 to 420 g / mol. In some embodiments, the polymerizable composition includes, as component (B), at least one selected from a glycidylamine-type epoxy resin, methylolmelamine, a combination of a nitrogen-free epoxy resin and an amine-based compound, and a combination of a nitrogen-free epoxy resin and a thiol-based compound. In some embodiments, the polymerizable composition includes, as component (B), at least one selected from a glycidylamine-type epoxy resin and a methylol melamine. In the above embodiments, the glycidylamine-type epoxy resin and the nitrogen-free epoxy resin in component (B) have two or more glycidyl groups. Having two or more glycidyl groups is preferable in that it increases the polymerization and crosslink density during polymerization. As the number of glycidyl groups increases, the molecular weight tends to increase and the viscosity tends to increase. The number of glycidyl groups is preferably 6 or less, more preferably 4 or less. In one embodiment, the glycidylamine-type epoxy resin and the nitrogen-free epoxy resin preferably have 2 to 6, more preferably 2 to 4 glycidyl groups. Hereinafter, the glycidylamine-type epoxy resin, methylol melamine, the combination of a nitrogen-free epoxy resin and an amine-based compound, the combination of a nitrogen-free epoxy resin and a thiol-based compound, and the nitrogen-free epoxy resin having an epoxy equivalent of 80 to 165 g / eq and a molecular weight of 180 to 420 g / mol in component (B) may be referred to as the "nitrogen-containing polymerizable compound, etc."

[0025] The nitrogen-containing polymerizable compound of component (B) is a compound that can be polymerized by heating or ultraviolet irradiation, and can be polymerized and cured by heat treatment or the like (polymerization and curing conditions, for example, a temperature of 120 to 180°C), as described below. By filling the spaces between the inorganic crystalline layers of component (A) with the nitrogen-containing polymerizable compound and heating, a polymerization reaction proceeds, resulting in excellent gas barrier properties and moisture resistance. In particular, the nitrogen-containing polymerizable compound can be imparted with excellent moisture resistance by interacting (through chemical adsorption or polar covalent bonding) with the exchangeable cations of component (A) (exchangeable cations coordinated with carboxylic acids) via lone electron pairs of the highly nucleophilic nitrogen atom. When a curing agent is blended with the nitrogen-containing polymerizable compound, the nitrogen-containing polymerizable compound can be used to fill the spaces between the inorganic crystalline layers of the layered inorganic compound of component (A) and further polymerize and cure, thereby imparting even more excellent moisture resistance.

[0026] Component (B) preferably has an acid dissociation constant pKa of 3 or more. When the acid dissociation constant pKa is 3 or more, the nucleophilicity (basicity) is increased, which facilitates chemical adsorption to metal surfaces such as sodium, thereby improving moisture resistance. The acid dissociation constant pKa of component (B) is more preferably 4 or more, and even more preferably 7 or more. When a nitrogen-containing compound chemically adsorbs to a metal surface, it provides an unshared electron pair to the metal, so a compound with higher nucleophilicity (basicity) is more advantageous for chemical adsorption. The acid dissociation constant pKa refers to the pKa in an aqueous solution, as described, for example, in "Chemical Handbook: Basics (II)" (Revised 4th Edition, 1993, edited by the Chemical Society of Japan, Maruzen Co., Ltd.), and a lower value indicates a higher acid strength. Furthermore, in the case of nitrogen-containing and sulfur-containing compounds, a higher value indicates a higher nucleophilicity (basicity). Values ​​not listed in the literature can be calculated using the method described in the literature.

[0027] As described above, in some embodiments, component (B) comprises at least one of (B-1) a glycidylamine-type epoxy resin, (B-2) methylol melamine, and (B-3) a nitrogen-free epoxy resin. In some embodiments, the nitrogen-free epoxy resin (B-3) comprises at least one selected from (B-31) a nitrogen-free epoxy resin having an epoxy equivalent of 80 to 165 g / eq and a molecular weight of 180 to 420 g / mol, (B-32) a combination of a nitrogen-free epoxy resin and an amine-based compound, and (B-33) a combination of a nitrogen-free epoxy resin and a thiol-based compound. These compounds are described in detail below.

[0028] (B-1) Glycidylamine-Type Epoxy Resin In some embodiments, component (B) includes (B-1) a glycidylamine-type epoxy resin. The glycidylamine-type epoxy resin is not particularly limited as long as it is an amine-type epoxy resin having one or more glycidyl groups per molecule. Because glycidylamine-type epoxy resins have a tertiary amine in the molecule, they undergo addition polymerization (self-polymerization) upon heating. Furthermore, an epoxy resin (cured product) can be formed by an addition polymerization reaction with a curing agent (D), which will be described later. It is preferable for the epoxy resin to have two to four glycidyl groups per molecule. In this specification, glycidylamine-type epoxy resins also include those having a triazine ring or an isocyanuric ring in the molecule.

[0029] Specific examples of the glycidylamine type epoxy resin include, but are not limited to, diglycidylaniline, tetraglycidyldiaminodiphenylmethane, N,N-diglycidyl-o-toluidine, N,N-diglycidylaniline, tetraglycidylbisaminomethylcyclohexanone, N,N,N',N'-tetraglycidyl-m-xylenediamine, 1,3-bis(N,N-glycidylaminomethyl)cyclohexane, N,N-diglycidyl-4-(glycidyloxy)aniline, 1,3,5-tris(2,3-epoxypropyl)-1,3,5-triazine-2,4 ,6(1H,3H,5H)-trione, 1,3,5-tris(3,4-epoxybutyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 1,3,5-tris(5,6-epoxybutyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, tris{2,2-bis[(oxiran-2-ylmethoxy)methyl]butyl}-3,3',3''-[1,3,5-triazine-2,4,6(1H,3H,5H)-trione-1,3,5-triyl]tripanoate, triglycidyl isocyanurate, and the like. Among these, N,N,N',N'-tetraglycidyl-m-xylylenediamine, 1,3-bis(N,N-glycidylaminomethyl)cyclohexane, N,N-diglycidylaniline, N,N-diglycidyl-4-(glycidyloxy)aniline, and triglycidyl isocyanurate are preferred, with N,N,N',N'-tetraglycidyl-m-xylylenediamine and N,N-diglycidyl-4-(glycidyloxy)aniline being particularly preferred. It is believed that the reason triglycidyl isocyanurate exhibits good moisture resistance is that, first, the molecular weight of isocyanuric acid is within an appropriate range; second, the presence of three nitrogen atoms per molecule facilitates chemical adsorption of the lone electron pair of the nitrogen atom with the exchangeable cation of component (A); and third, because it has a small epoxy equivalent and is a trifunctional epoxy resin, it undergoes addition polymerization (self-polymerization) upon heating and crosslinks with a curing agent, thereby increasing the crosslink density.

[0030] The glycidylamine type epoxy resins may be used alone or in combination of two or more kinds.

[0031] In terms of moisture resistance, the glycidylamine-type epoxy resin preferably has an epoxy equivalent of 80 to 165 g / eq, more preferably 85 to 160 g / eq, and even more preferably 90 to 140 g / eq. In terms of moisture resistance, the glycidylamine-type epoxy resin preferably has a molecular weight of 180 to 420 g / mol, more preferably 190 to 410 g / mol, and even more preferably 200 to 380 g / mol. In such glycidylamine-type epoxy resins, the lone electron pair of the nitrogen atom in the resin is likely to form a favorable interaction with the exchangeable cation contained in the layered inorganic compound (A), which is thought to contribute to improved moisture resistance. In addition, in compounds such as N,N-diglycidyl-4-(glycidyloxy)aniline, which have both a glycidyl amine group and a glycidyl ether group, the lone electron of the ether moiety of the glycidyl ether is also thought to form a favorable interaction with the exchangeable cation contained in the layered inorganic compound (A).

[0032] (B-2) Methylolmelamine In some embodiments, component (B) includes (B-2) methylolmelamine, which forms a melamine resin (cured product) through a condensation polymerization reaction.

[0033] Methylolmelamine is a melamine compound that has three amino groups (-NH ２ ) in which one or more hydrogen atoms are methylol groups (-CH ２ Methylolmelamine is a compound obtained by condensing melamine with formaldehyde. In this specification, methylolmelamine is a compound in which three amino groups (-NH ２ ) in which one or more hydrogen atoms are alkoxymethyl groups (-CH ２ This does not include methylol melamine alkyl ethers (methylol melamine alkyl ethers) substituted with OR (R: alkyl group, cycloalkyl group). Methylol melamine has a higher acid dissociation constant than methylol melamine alkyl ethers, which makes it more likely to chemically adsorb to metal surfaces such as sodium, and is also highly reactive, making it preferable in that it polymerizes at low temperatures.

[0034] Specific examples of methylolmelamine include, but are not limited to, monomethylolmelamine, dimethylolmelamine, trimethylolmelamine (also known as cealisine), tetramethylolmelamine, pentamethylolmelamine, and hexamethylolmelamine.

[0035] Among these, from the viewpoints of water solubility, crosslinkability, self-condensation property, and low-temperature polymerizability, methylol melamines having 1 to 3 methylol groups (hydroxymethyl groups) are preferred, more preferably monomethylol melamine and dimethylol melamine, and particularly preferably dimethylol melamine.

[0036] The methylol melamine to be used may be a synthesized product or a commercially available product. Examples of commercially available products include "Nikaredin (registered trademark) S-260 (dimethylol melamine)" and "Nikaredin (registered trademark) S-176 (monomethylol melamine)" manufactured by Nippon Carbide Industries Co., Ltd. Methylol melamine may be used alone or in combination of two or more types.

[0037] (B-3) Nitrogen-Free Epoxy Resin (B-31) Nitrogen-Free Epoxy Resin Having an Epoxy Equivalent of 80 to 165 g / eq and a Molecular Weight of 180 to 420 g / mol In some embodiments, component (B) comprises (B-31) a nitrogen-free epoxy resin having an epoxy equivalent of 80 to 165 g / eq and a molecular weight of 180 to 420 g / mol. Such nitrogen-free epoxy resins are preferred in terms of improving moisture resistance. The lone electron pair possessed by the oxygen atom of the ether moiety of the glycidyl ether group in the resin, the lone electron pair possessed by the oxygen atom of the ester moiety of the glycidyl ester group, and the like, are likely to form favorable interactions with the exchangeable cations contained in the layered inorganic compound (A), which is thought to contribute to improved moisture resistance.

[0038] Examples of nitrogen-free epoxy resins include glycidyl ether type epoxy resins, glycidyl ester type epoxy resins, alicyclic epoxy resins, linear aliphatic epoxy resins, etc. Among these, glycidyl ether type epoxy resins and glycidyl ester type epoxy resins, which have a lone electron pair of an oxygen atom in the ether group or ester group moiety, are preferred in terms of moisture resistance.

[0039] The epoxy equivalent of the nitrogen-free epoxy resin is more preferably 85 to 160 g / eq, and even more preferably 90 to 140 g / eq, from the viewpoint of moisture resistance. The molecular weight of the nitrogen-free epoxy resin is more preferably 190 to 410 g / mol, and even more preferably 200 to 380 g / mol, from the viewpoint of moisture resistance.

[0040] Specific examples of such nitrogen-free epoxy resins include: - Glycidyl ether-type epoxy resins: glycidyl ether-type aliphatic epoxy resins such as propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, and pentaerythritol tetraglycidyl ether; and glycidyl ether-type aromatic epoxy resins such as resorcinol diglycidyl ether, 1,6-bis(2,3-epoxypropoxy)naphthalene, and 4,4'-bis(2,3-epoxypropoxy)biphenyl. - Glycidyl ester-based epoxy resins: aromatic glycidyl esters such as phthalic acid diglycidyl ester and terephthalic acid diglycidyl ester. Alicyclic epoxy resins such as 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methylcyclohexylcarboxylate, etc. Among these, 1,6-hexanediol diglycidyl ether and pentaerythritol tetraglycidyl ether are more preferred as nitrogen-free epoxy resins.

[0041] (B-31) Nitrogen-free epoxy resin having an epoxy equivalent of 80 to 165 g / eq and a molecular weight of 180 to 420 g / mol can be mixed with an amine compound or a thiol compound described below within a range that does not impair the effects of the present invention.

[0042] (B-32) Combination of Nitrogen-Free Epoxy Resin and Amine-Based Compound In some embodiments, component (B) includes (B-32) a nitrogen-free epoxy resin and an amine-based compound.

[0043] Examples of nitrogen-free epoxy resins include glycidyl ether-type epoxy resins, glycidyl ester-type epoxy resins, alicyclic epoxy resins, and linear aliphatic epoxy resins. Among these, glycidyl ether-type epoxy resins and glycidyl ester-type epoxy resins are preferred. The lone electron pair of the oxygen in the ether moiety of the glycidyl ether-type epoxy resin and the lone electron pair of the oxygen in the ester moiety of the glycidyl ester-type epoxy resin are nucleophilic, resulting in favorable interactions with the exchangeable cations contained in the layered inorganic compound (A). The nitrogen-free epoxy resin used in combination with the amine-based compound may have a molecular weight of less than 180 g / mol. In some embodiments, the nitrogen-free epoxy resin used in combination with the amine-based compound is a glycidyl ether-type epoxy resin having a molecular weight of 120 g / mol or more and less than 180 g / mol. In some embodiments, the nitrogen-free epoxy resin used in combination with the amine-based compound is a glycidyl ether-type epoxy resin having a molecular weight of 120 g / mol or more and less than 180 g / mol and an epoxy equivalent of 80 to 165 g / eq. In one embodiment, the nitrogen-free epoxy resin used in combination with the amine-based compound is ethylene glycol diglycidyl ether.

[0044] (Amine Compound) Examples of the amine compound include aromatic amines, aliphatic amines, alicyclic amines, and triazine ring amines. The amine compounds may be used alone or in combination of two or more. By using the amine compound in combination with a nitrogen-free epoxy resin, the nucleophilicity of the nitrogen lone pair of the amine compound compensates for the lack of nucleophilicity of the oxygen lone pair in the ether moiety of the glycidyl ether epoxy resin, thereby generating a good interaction with the exchangeable cations contained in the (A) layered inorganic compound, thereby improving moisture resistance.

[0045] Aromatic amine is a general term for compounds having an amino group directly bonded to an aromatic ring. Examples of such aromatic amines include compounds having one aromatic ring, such as aminobenzylamine and diethyltoluenediamine, and compounds having two aromatic rings, such as 3,3'-diethyl-4,4'-diaminodiphenylmethane. Aromatic amines can also be classified based on the number of amino groups, and both aromatic monoamines and aromatic polyamines can be used. Aromatic amines improve moisture resistance by condensing with component (C), described below, to form aromatic amides.

[0046] The aromatic monoamine is not particularly limited, but examples thereof include aniline, toluidine, diphenylamine, naphthylamine, etc. The aromatic monoamine may be used alone or in combination of two or more kinds.

[0047] The aromatic polyamine is not particularly limited, but is preferably one having 6 to 20 carbon atoms, and examples thereof include 1,2-, 1,3-, and 1,4-phenylenediamine, 2,4'- and 4,4'-diphenylmethanediamine, crude diphenylmethanediamine [polyphenylpolymethylenepolyamine], diaminodiphenylsulfone, benzidine, thiodianiline, bis(3,4-diaminophenyl)sulfone, 2,6-diaminopyridine, m-aminobenzylamine, triphenylmethane-4,4',4''-triamine, and naphthylenediamine. The aromatic monoamines may be used alone or in combination of two or more. Among these, 1,3-phenylenediamine (metaphenylenediamine) is preferred because of its excellent total light transmittance and moisture resistance.

[0048] The aliphatic amine may be either an aliphatic monoamine or an aliphatic diamine. Examples of the aliphatic monoamine include, but are not limited to, hexylamine, octylamine, dodecylamine, hexadecylamine, stearylamine, and oleylamine. The aliphatic monoamine may be used alone or in combination of two or more.

[0049] The aliphatic diamine is not particularly limited, and examples thereof include ethylenediamine, 1,3-diaminopropane, 1,3-diaminobutane, 1,4-diaminobutane, hexamethylenediamine, 2,5-dimethylhexamethylenediamine, trimethylhexamethylenediamine, diethylenetriamine, iminobispropylamine, bis(hexamethylene)triamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, N-hydroxyethylethylenediamine, tetra(hydroxyethyl)ethylenediamine, metaxylylenediamine, paraxylylenediamine, etc. The aliphatic diamines may be used alone or in combination of two or more.

[0050] The alicyclic amine may be either an alicyclic monoamine or an alicyclic diamine. Examples of the alicyclic monoamine include, but are not limited to, cyclohexylamine and dicyclohexylamine. The alicyclic monoamine may be used alone or in combination of two or more. Examples of the alicyclic diamine include, but are not limited to, isophorone diamine, methacenediamine, N-aminoethylpiperazine, bis(4-amino-3-methyldicyclohexyl)methane, bis(aminomethyl)cyclohexane, 3,9-bis(3-aminopropyl)-2,4,8,10-tetraoxaspiro(5,5)undecane, and norbornene diamine. The alicyclic diamine may be used alone or in combination of two or more.

[0051] Examples of triazine ring amines include melamine, acetoguanamine, benzoguanamine, acrylguanamine, 2,4-diamino-6-nonyl-1,3,5-triazine, 2,4-diamino-6-hydroxy-1,3,5-triazine, 2-amino-4,6-dihydroxy-1,3,5-triazine, 2,4-diamino-6-methoxy-1,3,5-triazine, 2,4-diamino-6-ethoxy-1,3,5-triazine, 2,4-diamino-6-propoxy-1,3,5-triazine, 2,4-diamino-6-isopropoxy-1,3,5-triazine, 2,4-diamino-6-mercapto-1,3,5-triazine, and 2-amino-4,6-dimercapto-1,3,5-triazine. The triazine ring amines may be used alone or in combination of two or more. In this specification, methylolmelamine is not included in the triazine ring amines.

[0052] (B-33) Combination of Nitrogen-Free Epoxy Resin and Thiol Compound In some embodiments, component (B) comprises a nitrogen-free epoxy resin and a thiol compound. The nitrogen-free epoxy resin may be the same as the nitrogen-free epoxy resin described in (B-32). The nitrogen-free epoxy resin used in combination with the thiol compound may have a molecular weight of less than 180 g / mol. In some embodiments, the nitrogen-free epoxy resin used in combination with the thiol compound is a glycidyl ether epoxy resin having a molecular weight of 120 g / mol or more and less than 180 g / mol. In some embodiments, the nitrogen-free epoxy resin used in combination with the thiol compound is a glycidyl ether epoxy resin having a molecular weight of 120 g / mol or more and less than 180 g / mol and an epoxy equivalent of 80 to 165 g / eq. In one embodiment, the nitrogen-free epoxy resin used in combination with the thiol compound is ethylene glycol diglycidyl ether.

[0053] (Thiol Compound) The thiol compound may be any compound having one or more thiol groups (—SH) in the molecule, but in terms of increasing the polymerization and crosslink density during polymerization, a compound having 1 to 6 (more preferably 1 to 4, and even more preferably 2 to 4) thiol groups in the molecule is preferred. In some embodiments, the thiol compound is compound 2 or 3. By using a thiol compound in combination with a nitrogen-free epoxy resin, the nucleophilicity of the lone electron pair of the nitrogen in the thiol compound is compensated for by the lack of nucleophilicity of the lone electron pair of the oxygen in the ether portion of the glycidyl ether epoxy resin, thereby generating a good interaction with the exchangeable cations contained in the layered inorganic compound (A), thereby improving moisture resistance.

[0054] Specific examples of thiol compounds include decanethiol, trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), trimethylolpropane tris(3-mercaptobutyrate), trimethylolethane tris(3-mercaptobutyrate), trimethylolethane tris(3-mercaptobutyrate), ethylene glycol bis(3-mercaptoglycolate), butanediol bis(3-mercaptoglycolate), trimethylolpropane tris(3-mercaptoglycolate), pentaerythritol tetrakis(3-mercaptoglycolate), tris-[(3-mercaptopropionyloxy)-ethyl]-isocyanurate, pentaerythritol tetrakis(3-mercaptopropionate), tetraethylene glycol bis(3-mercaptopropionate), and dipentaerythritol. Examples of suitable thiol compounds include hexakis(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptobutyrate), 1,4-bis(3-mercaptobutyryloxy)butane, 1,3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, thiocyanuric acid, 1,2-ethanedithiol, 1,3-propanedithiol, 1,4-butanedithiol, 2,3-butanedithiol, 1,5-pentanedithiol, and 1,6-hexanedithiol. In one embodiment, the thiol compound is at least one selected from thiocyanuric acid and 1,4-butanedithiol. These compounds are preferred because they have low-temperature, fast-curing properties.

[0055] In some embodiments, the polymerizable composition is at least one selected from a glycidylamine-type epoxy resin, methylol melamine, a combination of ethylene glycol diglycidyl ether and an amine-based compound, a combination of ethylene glycol diglycidyl ether and a thiol-based compound, and a nitrogen-free epoxy resin having an epoxy equivalent of 80 to 165 g / eq and a molecular weight of 180 to 420 g / mol. In some embodiments, the polymerizable composition is at least one selected from a glycidylamine-type epoxy resin, methylol melamine, and a nitrogen-free epoxy resin having an epoxy equivalent of 80 to 165 g / eq and a molecular weight of 180 to 420 g / mol. By including these components (B), moisture resistance is further improved.

[0056] In some embodiments, the nitrogen-free epoxy resin (B-3) does not include an amine-based compound. In some embodiments, the nitrogen-free epoxy resin (B-3) does not include a thiol-based compound. In some embodiments, the polymerizable compound does not include an amine-based compound. In some embodiments, the polymerizable compound does not include a thiol-based compound.

[0057] (C) Carboxylic Acid Compound The polymerizable composition contains a carboxylic acid compound. The number of carboxy groups contained in the carboxylic acid compound is preferably in the range of 1 to 6, more preferably 1 to 4, even more preferably 2 to 4, and most preferably 2. By incorporating the carboxylic acid compound, specific exchangeable cations contained in the layered inorganic compound (A) can interact with the carboxy groups of the carboxylic acid compound to form a carboxylate salt. This modifies the inorganic crystal layer (e.g., silicate layer) of the layered inorganic compound with component (C), thereby inhibiting adsorption (hydration) of water molecules to the exchangeable cations and improving moisture resistance. The molecular weight of the carboxylic acid compound is preferably 72 to 600, more preferably 116 to 500, and particularly preferably 116 to 400. The use of such a low-molecular-weight carboxylic acid compound is preferred because it facilitates the interaction between specific exchangeable cations contained in the layered inorganic compound and the carboxy groups of the carboxylic acid compound to form a carboxylate salt. In some embodiments, the polymerizable composition does not contain a high-molecular-weight carboxylic acid compound having a repeating unit (a polymer having a carboxy group). In some embodiments, the polymerizable composition does not contain a carboxylic acid compound with a molecular weight exceeding 600. The carboxylic acid compound is preferably hydrophobic, and the water solubility (20°C) of the carboxylic acid compound is preferably 20 g / L or less. In particular, when a glycidylamine-type epoxy resin is used as component (B), the carboxylic acid compound having this water solubility is preferred.

[0058] The carboxylic acid compound may be any of aromatic carboxylic acid compounds, aliphatic carboxylic acid compounds, and alicyclic carboxylic acid compounds, but aromatic compounds are preferred in terms of the water solubility and acid dissociation constant of the carboxylic acid compound. Examples of aromatic carboxylic acid compounds include aromatic monocarboxylic acids, aromatic dicarboxylic acids, aromatic tricarboxylic acids, aromatic tetracarboxylic acids, aromatic pentacarboxylic acids, and aromatic hexacarboxylic acids. Examples of aliphatic carboxylic acid compounds include aliphatic monocarboxylic acids, aliphatic dicarboxylic acids, aliphatic tricarboxylic acids, aliphatic tetracarboxylic acids, aliphatic pentacarboxylic acids, and aliphatic hexacarboxylic acids. Examples of alicyclic carboxylic acid compounds include alicyclic monocarboxylic acids, alicyclic dicarboxylic acids, alicyclic tricarboxylic acids, alicyclic tetracarboxylic acids, and alicyclic hexacarboxylic acids.

[0059] These carboxylic acid compounds can be classified into those having only carboxy groups as active hydrogen groups and those having both carboxy groups and other active hydrogen groups (e.g., hydroxyl groups or amino groups) as active hydrogen groups. Examples of carboxylic acid compounds having both carboxy groups and other active hydrogen groups as active hydrogen groups include aspartic acid, glutamic acid, and citric acid. Carboxylic acid compounds having only carboxy groups as active hydrogen groups are preferred because they readily coordinate with the cations of component (A). Examples of carboxylic acid compounds having only carboxy groups as active hydrogen groups include terephthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, and pyromellitic acid. In this specification, the term "carboxylic acid compound" includes not only carboxylic acids but also anhydrides that decompose to produce acids during the reaction and blocked carboxylic acids. In this specification, a "blocked carboxylic acid" refers to a compound in which the carboxy group of a carboxylic acid is made latent, and the carboxy group is protected by a protecting group (blocking agent) (e.g., vinyl ether). The blocking group of the blocked carboxylic acid dissociates upon heating to generate the carboxylic acid. Commercially available blocked carboxylic acids can be used, such as the "Nofcure series" and "Santacid series" (NOF Corporation).

[0060] Alternatively, a carboxylic acid compound may be neutralized with a basic compound (neutralizing agent) to form a carboxylate salt, which may be blended with the polymerizable compound. Neutralization can make the coating solution aqueous, and even when a carboxylic acid compound with low water solubility is used in the aqueous solution, the coating solution can be used as an aqueous solution of the carboxylate salt. That is, the polymerizable compound may contain a neutralizing agent. Alternatively, the carboxylic acid compound may be a carboxylate salt formed from a carboxylic acid and a neutralizing agent (e.g., an ammonium carboxylate salt, an inorganic carboxylate salt). Furthermore, neutralizing the carboxylic acid with a neutralizing agent inhibits the reaction with the glycidyl group. The reaction proceeds due to the evaporation of the neutralizing agent, which also has the advantage of extending the pot life of the coating solution.

[0061] The neutralizing agent is not particularly limited as long as it is a basic compound capable of neutralizing carboxylic acid, and examples thereof include ammonia, amine compounds, inorganic bases, etc. The neutralizing agents may be used alone or in combination of two or more kinds.

[0062] Examples of the amine compound include tertiary amines such as trimethylamine, triethylamine, tributylamine, dimethylethanolamine, and triethanolamine; secondary amines such as dimethylamine, diethylamine, dibutylamine, methylethanolamine, diethanolamine, and morpholine; primary amines such as methylamine, ethylamine, propylamine, and ethanolamine; and quaternary ammonium compounds such as ammonia. The amine compounds may be used alone or in combination of two or more. For example, aqueous ammonia (pKa: 9.3), methylamine (pKa: 10.63, boiling point: −6.3° C.), dimethylamine (pKa: 10.68, boiling point: 7° C.), ethylamine (pKa: 10.7, boiling point: 17° C.), and diethylamine (pKa: 11.02, boiling point: 55° C.) may be used as a neutralized solution to prepare an aqueous solution of an ammonium carboxylate salt.

[0063] Examples of inorganic bases include alkali metal hydroxides and alkaline earth metal hydroxides. These inorganic bases may be used alone or in combination of two or more. Examples of alkali metal hydroxides include potassium hydroxide and sodium hydroxide. Examples of alkaline earth metal hydroxides include calcium hydroxide and magnesium hydroxide.

[0064] Among these, the neutralizing agent is preferably a volatile base, more preferably a volatile organic base or ammonia, and even more preferably ammonia. Ammonia is preferably used in the form of an aqueous ammonia solution. The concentration of the aqueous ammonia is preferably in the range of, for example, 2 to 30% by weight. When highly volatile ammonia is used as the neutralizing agent, curing at low temperatures is favorable. Furthermore, in terms of improving the stability of the methylol melamine aqueous solution and preventing gelation due to the methylenation reaction, it is desirable to use an inorganic base or an organic base as the neutralizing agent and maintain the pH at 8 to 10. This extends the pot life.

[0065] The aromatic carboxylic acid compound is preferably one having an aromatic hydrocarbon group having 6 to 18 carbon atoms (more preferably 6 to 16 carbon atoms, even more preferably 6 to 14 carbon atoms, and particularly preferably 6 to 12 carbon atoms). Examples of aromatic monocarboxylic acids include benzoic acid, biphenyl 2-carboxylic acid, biphenyl 4-carboxylic acid, 1-naphthalenecarboxylic acid, and 2-naphthalenecarboxylic acid. Examples of aromatic dicarboxylic acids include terephthalic acid, phthalic acid, isophthalic acid, 2,3-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 2,2'biphenyldicarboxylic acid, 4,4'biphenyldicarboxylic acid, 4,4'-methylenebisbenzoic acid, 4,4'-carbonylbisbenzoic acid, and 4,4'-isopropylidenedibenzoic acid. Examples of aromatic tricarboxylic acids include 1,2,5-benzenetricarboxylic acid (trimellitic acid), 1,3,5-benzenetricarboxylic acid (trimesic acid), etc. Examples of aromatic tetracarboxylic acids include pyromellitic acid, 3,3',4,4'-biphenyltetracarboxylic acid, 2,3,3',4'-biphenyltetracarboxylic acid, 2,2',3,3'-biphenyltetracarboxylic acid, 3,3',4,4'-benzophenonetetracarboxylic acid, naphthalene-1,4,5,8-tetracarboxylic acid, and naphthalene-2,3,6,7-tetracarboxylic acid.

[0066] The aliphatic carboxylic acid compound is preferably one having a saturated or unsaturated, linear or branched aliphatic hydrocarbon group having 2 to 18 carbon atoms (more preferably 2 to 14 carbon atoms, even more preferably 3 to 12 carbon atoms, and particularly preferably 3 to 10 carbon atoms). Examples of aliphatic monocarboxylic acids include acrylic acid, methacrylic acid, and 2-ethylhexyl acid. Examples of aliphatic dicarboxylic acids include succinic acid, adipic acid, suberic acid, maleic acid, 1,6-hexanedicarboxylic acid, 1,7-heptanedicarboxylic acid, 1,8-octanedicarboxylic acid, 1,9-nonanedicarboxylic acid, 1,10-decanedicarboxylic acid, 1,11-undecanedicarboxylic acid, and 1,12-dodecanedicarboxylic acid. Examples of aliphatic tricarboxylic acids include tricarballylic acid, aconitic acid, and camphoronic acid. Examples of aliphatic tetracarboxylic acids include butanetetracarboxylic acid.

[0067] The alicyclic carboxylic acid compound preferably has a saturated or unsaturated alicyclic hydrocarbon group having 4 to 18 carbon atoms (more preferably 4 to 14 carbon atoms, even more preferably 5 to 12 carbon atoms, and particularly preferably 5 to 10 carbon atoms). Examples of alicyclic monocarboxylic acids include cyclohexane monocarboxylic acid. Examples of alicyclic dicarboxylic acids include 1,3-cyclopentane dicarboxylic acid, 1,4-cyclohexane dicarboxylic acid, and 5-norbornene-2,3-dicarboxylic acid. Examples of alicyclic tricarboxylic acids include 1,2,4-cyclohexane tricarboxylic acid and 1,3,5-cyclohexane tricarboxylic acid. Examples of alicyclic tetracarboxylic acids include cyclobutane tetracarboxylic acid, 1,2,3,4-cyclopentane tetracarboxylic acid, 3,3',4,4'-bicyclohexyl tetracarboxylic acid, and 1,2,4,5-cyclohexane tetracarboxylic acid.

[0068] Examples of the acid anhydride include the acid anhydrides of the aliphatic, aromatic, and alicyclic polycarboxylic acids listed above. Examples include aromatic acid anhydrides such as 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA), trimellitic anhydride (TMA), pyromellitic anhydride (PMDA), and benzophenonetetracarboxylic acid (BTDA), and alicyclic acid anhydrides such as hexahydrophthalic anhydride (HHPA), tetrahydrophthalic anhydride (THPA), methyltetrahydrophthalic anhydride (MTHPA), methylhexahydrophthalic anhydride (MHHPA), and methylhimic anhydride (MHACP). The carboxylic acid compounds can be used alone or in combination of two or more.

[0069] The carboxylic acid compound may be a polycarboxylic acid compound. Polycarboxylic acid compounds can form more stable salts with exchangeable cations on the surface of the inorganic crystal layer (e.g., a silicate layer), thereby preventing or reducing hydration. Among polycarboxylic acid compounds, those with a structure in which two or more carboxy groups are located at distant positions (a structure in which the carboxy groups are not adjacent to each other) are more preferred. For example, terephthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, pyromellitic acid, 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA), and the like are preferred, with terephthalic acid, 2,6-naphthalenedicarboxylic acid, and 4,4'-biphenyldicarboxylic acid being more preferred.

[0070] Furthermore, compounds in which the positions between carboxy groups of the carboxylic acid compound are located in positions that facilitate interaction with specific exchangeable cations on the surface of the inorganic crystal layer (e.g., silicate layer) are preferred. Therefore, in the case of polycarboxylic acid compounds, compounds in which the positions between multiple carboxy groups are located in positions that facilitate interaction with exchangeable cations on the surface of the inorganic crystal layer (e.g., silicate layer) are preferred. In some preferred embodiments, component (A) is swellable mica, and component (C) is terephthalic acid, 2,6-naphthalenedicarboxylic acid, or 4,4'-biphenyldicarboxylic acid. In some preferred embodiments, component (A) is montmorillonite, and component (C) is terephthalic acid.

[0071] (Other Components) The polymerizable composition may further contain other components in addition to the above-described components (A), (B), and (C), such as at least one of (D) a curing agent, (E) a curing catalyst, (F) a thickener, (G) a polar solvent, (H) a nitrogen-containing polymerizable compound other than component (B), and (I) other additives.

[0072] (D) Curing Agent The polymerizable composition may contain a (D) curing agent. The (D) curing agent is a compound that promotes the polymerization and curing of the component (B) or undergoes a polymerization and curing reaction together with the component (B), and is appropriately selected depending on the type of nitrogen-containing polymerizable compound. The curing agent may be used alone or in any combination of two or more types in any blending ratio.

[0073] When the component (B) is (B-2) methylolmelamine, the curing agent (D) is an optional component.

[0074] When the component (B) is a glycidylamine-type epoxy resin (B-1), the curing agent (D) is an optional component, but the polymerizable composition may contain a curing agent (D) for the purpose of reacting with the epoxy groups of component (B) to cure the resin. The curing agent is not particularly limited, and those generally known as curing agents for epoxy resins can be used. Specific examples include amine-based curing agents, phenolic resin-based curing agents, ketimine-based curing agents, thiol-based curing agents, imidazole-based curing agents, acid anhydride-based curing agents, and active ester-based curing agents. One type of curing agent may be used alone, or two or more types may be used in combination. When two or more types of curing agents are used in combination, they may be mixed in advance to prepare a mixed curing agent and then used, or when mixing the individual components, each component of the curing agent may be added separately and mixed simultaneously.

[0075] In particular, when component (B) is (B-1) a glycidylamine-type epoxy resin, it is preferable that (D) the curing agent contains an amine-based curing agent from the viewpoints of improving the adsorption to exchangeable cations modified with a carboxylic acid and improving the crosslink density.

[0076] When the component (B) is (B-3) a nitrogen-free epoxy resin, the curing agent (D) is an optional component. In some embodiments, when the component (B) is (B-3) a nitrogen-free epoxy resin, the polymerized composition does not contain the curing agent (D).

[0077] (E) Curing Catalyst The polymerizable composition may contain a curing catalyst. The curing catalyst is not particularly limited as long as it catalyzes the polymerization and curing reaction of the component (B), and may be appropriately selected depending on the type of component (B). Examples of the curing catalyst include diammonium imide disulfonate catalysts, ammonium chloride, imidazoles such as 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, and 2-phenyl-4-methylimidazole, phenol salts, phenol novolac salts, carbonates or formates of dialkylaminoalkylamines (dimethylaminoethylamine, dimethylaminopropylamine, diethylaminopropylamine, dibutylaminoethylamine, dimethylaminooctylamine, and dipropylaminopropylamine, etc.) or heterocyclic aminoalkylamines (2-(1-aziridinyl)ethylamine, 4-(1-piperidinyl)-2-hexylamine, etc.), organophosphines such as ethylphosphine and triphenylphosphine, p-toluenesulfonic acid, ammonium p-toluenesulfonate, and 2-amino-2-methyl-1-propanol. The curing catalysts may be used alone or in combination of two or more.

[0078] (F) Thickener The polymerizable composition may contain a thickener. The thickener is added for the purpose of adjusting the viscosity of the coating liquid containing the polymerizable composition of this embodiment to a suitable range. Examples of thickeners include polyvinylpyrrolidone, polyvinyl alcohol, methyl cellulose, hydroxypropyl methyl cellulose, and hydroxyethyl methyl cellulose. The thickeners may be used alone or in combination of two or more.

[0079] (G) Polar Solvent The polymerizable composition may contain a polar solvent. The polar solvent is used to dissolve or disperse the other components. As the polar solvent, water, alcohols, sulfoxide compounds, nitrile-based solvents, and ether-based solvents are preferred because they have excellent solubility and dispersibility for the above components (A) to (C).

[0080] Examples of water include ion-exchanged water, deionized water, and distilled water. Examples of alcohols include monoalcohols having 1 to 10 carbon atoms, such as methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, t-butyl alcohol, isobutyl alcohol, n-hexyl alcohol, and n-octyl alcohol; and alcohols having an alkoxy group, such as ethylene glycol monobutyl ether, propylene glycol monomethyl ether, and propylene glycol monoethyl ether. Examples of nitrile solvents include acetonitrile, propionitrile, butyronitrile, isobutyronitrile, and benzonitrile. Examples of ether solvents include monoglyme, diglyme, triglyme, tetraglyme, diethyl ether, diisopropyl ether, di-n-butyl ether, t-butyl methyl ether, cyclopentyl methyl ether, tetrahydrofuran (THF), tetrahydropyran, 1,4-dioxane, 1,3-dioxolane, anisole, and morpholine. Polar solvents may be used alone or in combination of two or more. Among these, water or a mixed solvent of water and a polar solvent with a boiling point lower than that of water is preferred. Examples of polar solvents with a boiling point lower than that of water include alcohols and ether-based solvents. 1,3-dioxolane is particularly preferred. By using a polar solvent with a boiling point lower than that of water in combination with water, compounds that are difficult to dissolve in water can be dissolved, and because the boiling point is lower than that of water, the solvent can be efficiently volatilized during low-temperature drying.

[0081] (H) Nitrogen-containing polymerizable compound not corresponding to component (B) The polymerizable composition may contain a nitrogen-containing polymerizable compound not corresponding to component (B) within the range that does not impair the effects of the present invention. For example,２ ) in which one or more hydrogen atoms are alkoxymethyl groups (-CH ２ Examples of methylol melamine alkyl ethers include those substituted with OR (R: alkyl group, cycloalkyl group) such as trimethoxymethylol melamine and hexamethoxymethylol melamine.

[0082] (I) Other Additives The polymerizable composition may contain additives such as organic fillers such as rubber particles, silicone powder, nylon powder, and fluororesin powder; silicone-based, fluorine-based, and polymer-based antifoaming agents or leveling agents; antioxidants (e.g., phenyl phosphites, phenols, sulfur-based antioxidants, and phosphorus-based antioxidants); heat stabilizers; light stabilizers; silane coupling agents; silylation agents; flame retardants; thermoplastic resins such as water-soluble polyester resins, water-soluble acrylic resins, water-soluble urethane resins, and water-soluble olefin resins; inorganic fillers; and flexibility-imparting and toughness-improving agents such as carboxy-terminated butadiene nitrile rubber (CTBN), epoxy-modified rubber, and acrylic pressure-sensitive adhesives, as long as the effects of the present invention are not impaired.

[0083] Examples of the silane coupling agent include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-(2-aminoethyl)aminopropyltrimethoxysilane, γ-(2-aminoethyl)aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, N-β-(N-vinylbenzylaminoethyl)-γ-aminopropylmethoxysilane hydrochloride, aminosilane, methyltrimethoxysilane, vinyltriacetoxysilane, γ-mercaptopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, hexamethyldisilazane, vinyltris(β-methoxyethoxy)silane, octadecyldimethyl[3-(trimethoxysilyl)propyl]ammonium chloride, methyltrichlorosilane, and dimethyldichlorosilane. Examples of silylating agents include N,O-bis(trimethylsilyl)trifluoroacetamide, N,O-bis(trimethylsilyl)acetamide, hexamethyldisilazane, etc. By incorporating a silane coupling agent or a silylating agent, even in component (A) that has hydroxyl groups on its crystal end faces, the hydroxyl groups on those crystal end faces can be modified, thereby further improving moisture resistance. Examples of inorganic fillers include silicates such as talc, calcined clay, uncalcined clay, mica, and glass; oxides such as titanium oxide, alumina, boehmite, silica, and fused silica; carbonates such as calcium carbonate, magnesium carbonate, and hydrotalcite; hydroxides such as aluminum hydroxide, magnesium hydroxide, and calcium hydroxide; sulfates or sulfites such as barium sulfate, calcium sulfate, and calcium sulfite; borates such as zinc borate, barium metaborate, aluminum borate, calcium borate, and sodium borate; nitrides such as aluminum nitride, boron nitride, silicon nitride, and carbon nitride; and titanates such as strontium titanate and barium titanate.

[0084] (Combination of Components) From the viewpoint of moisture resistance, the weight ratio of component (A) to component (B) [(A) / (B)] is preferably in the range of 5 / 1 to 1 / 10, more preferably 5 / 1 to 2 / 5, and even more preferably 4 / 1 to 2 / 3. When component (B) includes a combination of (B-32) a nitrogen-free epoxy resin and an amine compound or a combination of (B-33) a nitrogen-free epoxy resin and a thiol compound, the weight of component (B) refers to the total amount of the nitrogen-free epoxy resin and the amine compound and / or thiol compound. When component (B) includes a combination of (B-32) a nitrogen-free epoxy resin and an amine compound, the weight ratio of the nitrogen-free epoxy resin to the amine compound [nitrogen-free epoxy resin / amine compound] is not particularly limited, but is preferably in the range of 5 / 1 to 1 / 10, more preferably 5 / 1 to 2 / 3, and even more preferably 4 / 1 to 1 / 1. When component (B) includes a combination of (B-33) a nitrogen-free epoxy resin and a thiol compound, the weight ratio of the nitrogen-free epoxy resin to the thiol compound [nitrogen-free epoxy resin / thiol compound] is not particularly limited, but is preferably in the range of 5 / 1 to 1 / 10, more preferably 5 / 1 to 2 / 3, and even more preferably 4 / 1 to 1 / 1. Component (C) is preferably included in an amount of 0.15 equivalents or more relative to the cation exchange capacity (CEC) of component (A). By including component (C) in an amount of 0.15 equivalents or more, a certain amount of interaction is formed between the exchangeable cations of component (A) and the carboxyl groups of component (C), inhibiting the adsorption (hydration) of water molecules to the exchangeable cations, thereby improving moisture resistance. The amount of component (C) is more preferably 0.5 equivalents or more relative to the cation exchange capacity (CEC) of component (A), more preferably 0.8 equivalents or more, and particularly preferably 1 equivalent or more. The upper limit of the amount of the component (C) is not particularly limited, but from the viewpoint of moisture resistance, it is preferably 5 times or less equivalents, more preferably 4 times or less equivalents, even more preferably 3 times or less equivalents, and particularly preferably 2 times or less equivalents relative to the cation exchange capacity (CEC) of the component (A).

[0085] When the polymerizable composition contains the components (D) to (I), the amount of each component contained in the polymerizable composition is not particularly limited, but may be, for example, as follows: The content of the component (D) curing agent is preferably 1 to 250 parts by weight, more preferably 2 to 200 parts by weight, and even more preferably 3 to 100 parts by weight, relative to the total amount (100 parts by weight) of component (B) (non-volatile content) contained in the polymerizable composition. The content of the component (E) curing catalyst is preferably 0.1 to 5 parts by weight, more preferably 0.2 to 2 parts by weight, and even more preferably 0.3 to 1 part by weight, relative to the total amount (100 parts by weight) of component (B) (non-volatile content) contained in the polymerizable composition. The content of the component (G) polar solvent is preferably adjusted so that the solids concentration of the polymerizable composition is 1 to 10% by weight. The content of the nitrogen-containing polymerizable compound (H) not corresponding to component (B) is preferably in the range of 30 to 250 parts by weight, more preferably 40 to 200 parts by weight, and even more preferably 50 to 100 parts by weight, relative to the total amount (100 parts by weight) of component (B) (non-volatile content) contained in the polymerizable composition. The content of component (I) and other additives may be adjusted appropriately depending on the type of additive. For example, the content of component (I) is in the range of 30 to 250 parts by weight relative to the total amount (100 parts by weight) of component (B) (non-volatile content) contained in the polymerizable composition.

[0086] <<Preparation of Polymerizable Composition>> The method for preparing the polymerizable composition is not particularly limited. In some embodiments, the polymerizable composition is prepared by a method including the following step (i) and, if necessary, step (ii): (i) preparing a dispersion A by dispersing component (A) in a solvent and a dispersion B by dispersing or dissolving component (B) in a solvent, and mixing the dispersion A and the dispersion B; (ii) partially or completely neutralizing the carboxyl group of component (C) with a neutralizing agent to obtain a neutralized solution C, and adding the neutralized solution C to the mixture obtained in step (i) and mixing them.

[0087] In such a method, by uniformly dispersing or dissolving each of the components (A) to (C), the components (B) and (C) are filled between the inorganic crystal layers of the component (A), and stable interactions are easily formed between the exchangeable cations of the component (A) and the nitrogen atoms of the component (B) and the carboxy groups of the component (C), which can improve the moisture resistance of the cured product after the polymerization and curing reaction.

[0088] Step (i) As the dispersion medium for Dispersion A, those listed as (G) polar solvents above are preferably used. The solids concentration of Dispersion A is preferably in the range of 0.1 to 10 wt%, more preferably 1 to 8 wt%, and even more preferably 1.5 to 5 wt%. As the dispersion medium for Dispersion B, those listed as (G) polar solvents above are preferably used. The solids concentration of Dispersion B is preferably in the range of 0.1 to 10 wt%, more preferably 1 to 8 wt%, and even more preferably 1.5 to 5 wt%. The method for mixing Dispersion A and Dispersion B is not particularly limited. For example, the two may be mixed at room temperature and stirred.

[0089] Step (ii) The method for obtaining the neutralized solution C by neutralizing component (C) with a neutralizing agent is not particularly limited. The neutralizing agent may be any of the compounds listed above as basic compounds capable of neutralizing carboxylic acid compounds. The solvent for the neutralized solution C is not particularly limited, and those listed above as polar solvents (G) are preferably used. Water is preferred. The neutralizing agent is not limited as long as it is a basic compound capable of neutralizing the carboxy group of the carboxylic acid compound, and the compounds listed above can be used. The neutralizing agent is preferably used in the form of an aqueous solution. When used as an aqueous solution, the concentration of the neutralizing agent is preferably in the range of, for example, 2 to 30% by weight. The carboxy groups of component (C) in the neutralized solution do not need to be completely neutralized; they may be partially neutralized, but complete neutralization is preferred.

[0090] Next, the neutralization liquid C is added to the mixed solution obtained in (i) and mixed, thereby obtaining a polymer composition.

[0091] (Other Components) When other components (component (D), component (E), component (F), component (H), and component (I)) are blended into the polymerizable composition, the method of addition and mixing is not particularly limited, and may be performed according to a conventional method. For example, when a curing agent (D) and / or a thickener (F) are blended into the polymerizable composition, component (D) and / or component (F) can be added and mixed in step (i). Specifically, a dispersion D of the curing agent (D) and / or a dispersion F of the thickener (F) are prepared, and then mixed with dispersion A and dispersion B. As the dispersion medium for dispersion D, those listed above as polar solvents (G) are preferably used. The solids concentration of dispersion D is preferably in the range of 0.1 to 10 wt %. As the dispersion medium for dispersion F, those listed above as polar solvents (G) are preferably used. The solids concentration of dispersion F is preferably in the range of 0.1 to 10 wt %. For example, when a curing catalyst (E) is blended into the polymerizable composition, component (E) can be added and mixed in step (ii). Specifically, a dispersion E of the curing catalyst (E) is prepared, and this is added to the mixed liquid together with the neutralizing liquid C, and then mixed. As the dispersion medium for dispersion E, those listed above as the polar solvent (G) are preferably used. The solids concentration of dispersion E is preferably in the range of 0.1 to 10 wt %.

[0092] <<Cured Product>> Another aspect of the present invention relates to a cured product of the polymerizable composition of the present invention. The cured product is a product (cured product) obtained by thermally curing the polymerizable composition. The method for producing the cured product of the polymerizable composition is not particularly limited, but examples include a method comprising forming a coating film of the polymerizable composition on a substrate, drying it as necessary, and then heating to cure it. The curing conditions are not particularly limited as long as they are conditions under which component (B) polymerizes and cures. For example, heat treatment at a temperature of 120 to 180°C is preferred. The heat treatment time depends on the coating amount, but drying for preferably 0.5 to 180 minutes, more preferably 1 to 60 minutes, and even more preferably 1 to 30 minutes can form a cured product with excellent moisture resistance. A film-like cured product (film) can be obtained by molding the polymerizable composition into a film and curing the film-like polymerizable composition. The film-like cured product (film) has excellent moisture resistance. In some embodiments, a gas barrier film containing the cured product is provided. The conditions for polymerization and curing vary depending on the type of nitrogen-containing polymerizable compound of component (B), but it is usually preferable to heat at a temperature of 120 to 180°C.

[0093] <<Laminate>> Another aspect of the present invention relates to a laminate (hereinafter also simply referred to as "laminate") comprising a substrate and a barrier layer containing a cured product of the polymerizable composition of the present invention. The cured product of the polymerizable composition has excellent moisture resistance and can function as a barrier layer. The substrate may be appropriately selected depending on the application of the laminate, and examples include films, nonwoven fabrics, and papers made of synthetic resins such as polyethylene terephthalate (PET), polyethylene naphthalate, polyethylene, polypropylene, polycarbonate, triacetyl cellulose, aramid, polyimide, polyamide, polyphenylene sulfide, polyetherimide, polyethersulfone, aromatic polyamide, and polysulfone. Furthermore, the substrate may have its surface treated with corona, anchor coat, plasma, ozone, flame, or the like. The laminate may have one or more additional layers between the substrate and the barrier layer or on the barrier layer. Examples of the additional layer include a heat seal layer, an undercoat layer, a printing layer, a matting agent layer, a protective layer, an antistatic layer, a smoothing layer, an adhesion improving layer, a light-shielding layer, an antireflection layer, a hard coat layer, a stress relaxation layer, an antifogging layer, an antifouling layer, a printable layer, and an easy-adhesion layer.

[0094] <<Method for Producing Laminate>> The method for producing the laminate is not particularly limited, and the laminate can be produced by a conventional method. In some embodiments, the method for producing the laminate includes the following steps (I) to (III): (I) a step of applying a polymerizable composition obtained by dispersing the components (A), (B), and (C) in the component (G) onto a substrate; (II) a step of drying the composition at 50 to 100°C as needed; and (III) a step of heat treating the composition at a temperature of 120 to 180°C to form a barrier layer. According to the production method of this embodiment, a laminate having a barrier layer that excels in moisture prevention properties can be obtained under mild conditions (a temperature of 120 to 180°C) and / or using a simple production step.

[0095] Step (I) In step (I), a polymerizable composition is applied to a substrate. First, a polymerizable composition is prepared by dispersing component (A), component (B), and component (C) in component (G). Examples of a method for preparing the polymerizable composition include the methods including steps (i) to (iii) described above in the section <<Preparation of Polymerizable Composition>>.

[0096] Subsequently, the polymer composition is applied onto the substrate. As the application method, various known methods can be appropriately selected. For example, coating methods such as gravure coating, gravure reverse coating, roll coating, reverse roll coating, air knife coating, bar coating, Mayer bar coating, dip coating, die coating, spray coating, and spin coating; and casting methods can be mentioned.

[0097] The amount of coating (thickness of the coating film) is not particularly limited, but in general, the thickness after drying is preferably 0.1 to 50 μm, more preferably 0.5 to 20 μm.

[0098] Step (II) After the polymer composition is applied to the substrate, it is preferable to dry it as needed. By undergoing the drying step, the film becomes denser, and the interaction between the specific exchangeable cations of component (A) and the nitrogen atoms of component (B) and the carboxyl groups of component (C) is easily and stably formed, so that the moisture-proof property of the cured product after the polymerization and curing reaction can be improved.

[0099] The drying conditions are usually 50 to 100°C, preferably 60 to 90°C, and more preferably 70 to 80°C. The drying time is usually 30 seconds to 1 hour, and preferably 1 to 10 minutes. Examples of drying methods include hot air drying, heat roll drying, infrared irradiation, ultraviolet irradiation, and microwave irradiation.

[0100] Step (III) In step (III), a barrier layer is formed by heat treatment. Component (B) is polymerized and cured by the heat treatment, forming a barrier layer containing a cured product of the polymerizable composition. The heat treatment temperature is not particularly limited as long as it is a condition that polymerizes and cures component (B). For example, heat treatment is preferably performed at a temperature of 120 to 200°C (preferably 130 to 180°C, more preferably 140 to 160°C). The heat treatment time depends on the coating amount, but by drying for preferably 0.5 to 180 minutes, more preferably 1 to 60 minutes, and even more preferably 1 to 30 minutes, a cured product with excellent moisture resistance can be formed.

[0101] Additional optional steps: For example, when producing a film, a release film can be used, and after the above step (III), the release film can be peeled off to obtain a film consisting only of the cured product of the polymerizable composition. Examples of release films include polyolefin films such as polyethylene film, polypropylene film, polyvinyl chloride film, polymethylpentene (TPX) film, and cycloolefin polymer film; polyester films such as polyethylene terephthalate (PET) film and polyethylene naphthalate (PEN) film; films that have been subjected to a release treatment, polyimide films that have been subjected to a release treatment, polyphenylene sulfide films that have been subjected to a release treatment; and metal foils such as aluminum foil, stainless steel foil, and copper foil that have been subjected to a release treatment. Examples of release treatments include release treatments using release agents such as silicone resin-based release agents, alkyd resin-based release agents, and fluororesin-based release agents.

[0102] <<Characteristics>> The polymeric composition of the present invention preferably has the following properties in a laminate in which a barrier layer made of a cured product of the polymeric composition is formed on a PET film (thickness 25 μm) as a substrate. The total light transmittance of the laminate is preferably 75% or more, more preferably 80% or more, and particularly preferably 85% or more. A total light transmittance of 75% or more is preferable because, even when the laminate is applied to a solar cell, sunlight can be transmitted to an extent that the solar cell element can generate electricity. The total light transmittance and moisture permeability of these laminates can be measured by the methods described in the Examples below.

[0103] <<Applications>> The applications of the polymerizable composition, cured product, or laminate are not particularly limited. As described above, the polymerizable composition, cured product, or laminate of the present invention have excellent moisture resistance and can be used in various applications requiring moisture resistance. For example, a gas barrier film containing a cured product of the polymerizable composition can be suitably used as a packaging material for electronic components (hard disks, printed circuit boards, liquid crystal displays, electronic paper, solar cells, etc.), a packaging material for various foods (dried foods, liquid foods, boiled / retort foods, supplement foods, etc.), and pharmaceuticals (powders, granules, tablets, infusion bags). The polymerizable composition can also be suitably used as a sealing material, adhesive, coating agent, etc. for electronic components (hard disks, printed circuit boards, liquid crystal displays, electronic paper, solar cells, etc.). It can also be used as a molding material for synthetic decorative boards, melamine decorative boards, glass epoxy boards, etc. Furthermore, since the cured product of the polymerizable composition has excellent transparency, the cured product or laminate can be suitably used as an optical component.

[0104] The present invention will be described in more detail below based on examples, but the present invention is not limited to these examples. The amounts and contents of each component in the tables are converted to pure amounts and are expressed in "% by weight" unless otherwise specified. In this specification, "room temperature" generally refers to a temperature range of about 10°C to about 35°C. In this specification, "high temperature" refers to a temperature range of 80°C to 90°C. In this specification, the term "about" can mean ±10%.

[0105] The product names of the various components used in the examples are shown below. (Component A) Swellable mica 1: "Somasif MEB-3" manufactured by Katakura Co-op Agri Co., Ltd., average particle size: 2.5 μm, aspect ratio: 2500, CEC: 120 meq / 100 g, solid content: 8%) Swellable mica 2: "Somasif ME300B-4T" manufactured by Katakura Co-op Agri Co., Ltd., average particle size: 13 μm, aspect ratio: 13000, CEC: 80 meq / 100 g, solid content: 8%) Montmorillonite: "Kunipia F" manufactured by Kunimine Industries Co., Ltd., average particle size: 0.5 μm, aspect ratio: 500, CEC: 120 meq / 100 g

[0106] (Component B) (B-1) Glycidylamine-type epoxy resins Glycidylamine-type epoxy resin 1 (1,3-bis(N,N-glycidylaminomethyl)cyclohexane) manufactured by Mitsubishi Gas Chemical Company, Inc., "TETRAD-C", molecular weight: 366.5 g / mol, epoxy equivalent weight 100-110 g / eq, pKa=8.62 Glycidylamine-type epoxy resin 2 (N,N,N',N'-tetraglycidyl-m-xylenediamine) manufactured by Mitsubishi Gas Chemical Company, Inc., "TETRAD-X", molecular weight: 360.4 g / mol, epoxy equivalent weight 95-100 g / eq, pKa=7.77 Glycidylamine-type epoxy resin 3 (N,N-diglycidyl-o-toluidine) "GOT" manufactured by Nippon Kayaku Co., Ltd., molecular weight: 219.28 g / mol, epoxy equivalent weight 110 g / eq, pKa = 4.67. Glycidylamine type epoxy resin 4 (N,N-diglycidylaniline). "GAN" manufactured by Nippon Kayaku Co., Ltd., molecular weight: 205.25 g / mol, epoxy equivalent weight 115-135 g / eq, pKa = 4.13. Glycidylamine type epoxy resin 5 (N,N-diglycidyl-4-(glycidyloxy)aniline). "jER630" manufactured by Mitsubishi Chemical Corporation, molecular weight: 277.32 g / mol, epoxy equivalent weight 90-106 g / eq, pKa = 4.78. Glycidylamine type epoxy resin 6 (triglycidyl isocyanurate (TEPIC)). Molecular weight: 297.27 g / mol, epoxy equivalent: 100 g / eq, pKa = -2.44 (B-2) Methylolmelamine Dimethylolmelamine "Nikaredin (registered trademark) S-260" manufactured by Nippon Carbide Industries Co., Ltd., pKa = 13.2 Monomethylolmelamine "Nikaredin (registered trademark) S-176" manufactured by Nippon Carbide Industries Co., Ltd., pKa = 13.69 (B-3) Nitrogen-free epoxy resin Glycidyl ether type epoxy resin 1 (1,4-butanediol diglycidyl ether) (manufactured by Tokyo Chemical Industry Co., Ltd.) Molecular weight: 202.25 g / mol, epoxy equivalent: 101 g / eq Glycidyl ether type epoxy resin 2 (1,6-Hexanediol diglycidyl ether (Epogose HD (D) (manufactured by Yokkaichi Synthetic Co., Ltd.)) Molecular weight: 230.3 g / mol, epoxy equivalent: 110 to 130 g / eq. Glycidyl ether type epoxy resin 3 (pentaerythritol tetraglycidyl ether (Shofree PETG)) Molecular weight: 360.4 g / mol, epoxy equivalent: 90 to 100 g / eq. Glycidyl ether type epoxy resin 4 Resorcinol diglycidyl ether (Denacol EX-201 (manufactured by Nagase ChemteX Corporation)) Molecular weight: 222.24 g / mol, epoxy equivalent: 117 g / eq. Glycidyl ether type epoxy resin 5 (1,6-Hexanediol diglycidyl ether (Epogose HD (Yokkaichi Synthetic Co., Ltd.)) Molecular weight: 230.3 g / mol, epoxy equivalent: 150 to 160 g / eq. Glycidyl ether type epoxy resin 6 (ethylene glycol diglycidyl ether) (Denacol EX-810P (manufactured by Nagase ChemteX Corporation)) molecular weight: 174.196 g / mol, epoxy equivalent: 95 g / eq. Glycidyl ether type epoxy resin 7 (bisphenol A diglycidyl ether) (JER825 (manufactured by Mitsubishi Chemical Corporation)) molecular weight: 340.4 g / mol, epoxy equivalent: 170 to 180 g / eq. Alicyclic epoxy resin 8 (3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (Celloxide 2021P (manufactured by Daicel Corporation)) molecular weight: 252.31 g / mol, epoxy equivalent: 130 g / eq. Linear aliphatic epoxy resin 9 (1,7-octadiene diepoxide) (manufactured by Tokyo Chemical Industry Co., Ltd.) Molecular weight: 142.20 g / mol, epoxy equivalent: 71 g / eq (B-3') Amine compounds Metaphenylenediamine (1,3-phenylenediamine), pKa1 = 5.11 (B-3') Thiol compounds Thiocyanuric acid (1,3,5-triazine-2,4,6-trithiol), pKa = 6.35 1,4-butanedithiol, pKa = 10.07

[0107] (Component B') Phenol novolac epoxy resin "jER152" manufactured by Mitsubishi Chemical Corporation, weight average molecular weight: 416 g / mol, epoxy equivalent: 172 to 178 g / eq

[0108] (Component C) (1) Aromatic dicarboxylic acids: terephthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid (2) Aromatic monocarboxylic acids: benzoic acid, biphenyl-4-carboxylic acid (3) Aromatic tetracarboxylic acids: pyromellitic acid, 1,4,5,8-naphthalenetetracarboxylic acid (4) Aromatic acid anhydrides: 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) (5) Aliphatic dicarboxylic acids: succinic acid, adipic acid, suberic acid (6) Alicyclic monocarboxylic acids: 5-norbornene-2-carboxylic acid (7) Aliphatic monocarboxylic acids: acrylic acid, methacrylic acid (8) Aliphatic tetracarboxylic acids: butanetetracarboxylic acid (9) Alicyclic acid anhydrides: methyl hydric anhydride (MHACP) (10) Others (carboxylic acid compounds having an active hydrogen group other than a carboxy group): citric acid Aspartic acid

[0109] (Component D) Diethyltoluenediamine (DETDA) pKa = 4.6 4,4'-diaminodiphenylmethane (MDA) pKa = 5.32 "WANAMINE MDA-100" manufactured by Mitsui Chemicals Fine Co., Ltd.

[0110] (Component E) Diammonium imide disulfonate catalyst "Catanit" manufactured by MRC Unitech Co., Ltd.

[0111] (Component H) Trimethoxymethylolmelamine (Nicalac MX-035, manufactured by Nippon Carbide Industries Co., Ltd.) pKa=4.99 Hexamethoxymethylolmelamine (Nicalac MW-30, manufactured by Nippon Carbide Industries Co., Ltd.) pKa=2.20

[0112] (Component I) Water-soluble polyester resin (Plascoat Z-687, manufactured by GOO Chemical Industry Co., Ltd., acid value less than 5 mmgKOH / g)

[0113] 1. Preparation of Moisture-Proof Coating (Coating Liquid) [Example 1-1] As component A, deionized water and 1,3-dioxolane were added to swellable mica 1 so that the weight ratio of deionized water / 1,3-dioxolane was 8 / 2, and the mixture was thoroughly stirred to obtain an aqueous dispersion of component A with a concentration of 3 wt %.

[0114] As component B, glycidylamine-type epoxy resin 1 was dissolved in 1,3-dioxolane, and then deionized water was added thereto so that the weight ratio of deionized water / 1,3-dioxolane was 8 / 2. The mixture was thoroughly stirred to obtain an aqueous solution of component B with a concentration of 3% by weight.

[0115] As component C, deionized water and 1,3-dioxolane were added to terephthalic acid so that the weight ratio of deionized water to 1,3-dioxolane was 8 / 2, and the mixture was neutralized with aqueous ammonia (28%) (manufactured by Tokyo Chemical Industry Co., Ltd.) and thoroughly stirred to obtain an aqueous solution of component C with a concentration of 3 wt %.

[0116] 4 parts of the aqueous dispersion of Component A were mixed with 2 parts of an aqueous solution of Component B and stirred thoroughly. Next, 0.4 parts of an aqueous solution of Component C was added and further stirred to obtain a coating solution with sufficient dispersibility and a solids concentration of approximately 3 wt%. The solids content (weight ratio) of Component A, Component B, and Component C is as shown in Table 1.

[0117] Examples 1-2 to 1-14 Coating fluids were prepared in the same manner as in Example 1-1, except that the type and / or amount of component B was changed to the composition shown in Table 1, the amount of component (C) was changed to the composition shown in Table 1, and in Examples 1-11 to 1-13, component D was added. Component D was added in the form of an aqueous solution of component D with a concentration of 3% by weight, which was prepared by dissolving component D in 1,3-dioxolane, adding deionized water to achieve a deionized water / 1,3-dioxolane ratio of 8 / 2 (weight ratio), and thoroughly stirring the mixture.

[0118] Comparative Examples 1-1 to 1-5 A coating solution was obtained in the same manner as in Example 1-1, except that the types and / or amounts of Components B to C were changed to the compositions shown in Table 1, and in Comparative Examples 1-4 and 1-5, Component D was added in the same manner as in Example 1-11.

[0119] Examples 2-1 to 2-15 The types and / or amounts of Components B and C were changed to the compositions shown in Table 2, and coating fluids were obtained in the same manner as in Example 1-1.

[0120] [Examples 3-1 to 3-6] The types and / or amounts of Components A to C were changed to the compositions shown in Table 3, and in Examples 3-4 to 3-6, Component D was blended in the same manner as in Example 1-11, and a coating solution was obtained in the same manner as in Example 1-1. In Examples 3-5 and 3-6, the solid content concentration was adjusted to about 8 wt % to obtain a coating solution.

[0121] Examples 4-1 to 4-13 Coating fluids were prepared in the same manner as in Example 1-1, except that component E was added, the types and / or amounts of components B and C were changed to those shown in Table 4, component H was added in Examples 4-7 to 4-10, component D was blended in Examples 4-11 and 4-12 in the same manner as in Example 1-11, and component I was added in Example 4-13. The curing catalyst for component E was an imidedisulfonic acid diammonium catalyst (Catanit, manufactured by MRC Unitech Co., Ltd.) that was added in a 0.5 wt% aqueous solution by adding deionized water and thoroughly stirring. The nitrogen-containing polymerizable compound not corresponding to component (B) of component H was added in the form of a 3 wt% aqueous solution of component H by diluting component H with deionized water, adding 1,3-dioxolane to the diluent so that the weight ratio of deionized water to 1,3-dioxolane was 8:2, and thoroughly stirring. The water-soluble polyester resin of Component I was prepared by diluting Component I with deionized water, then adding 1,3-dioxolane to the mixture so that the weight ratio of deionized water to 1,3-dioxolane was 8:2, and thoroughly stirring the mixture to obtain an aqueous solution of Component I with a concentration of 3% by weight.

[0122] [Examples 4-14] For Component A, deionized water was added to swellable mica 1 and the mixture was thoroughly stirred to obtain an aqueous dispersion of Component A with a concentration of 3 wt%. For Component B, dimethylol melamine was added to deionized water and the mixture was thoroughly stirred to obtain an aqueous solution of Component B with a concentration of 3 wt%. For Component C, deionized water was added to terephthalic acid, the mixture was neutralized with aqueous ammonia (28%) (Tokyo Chemical Industry Co., Ltd.), and the mixture was thoroughly stirred to obtain an aqueous solution of Component C with a concentration of 3 wt%. Four parts of the aqueous dispersion of Component A were mixed with three parts of an aqueous solution of Component B and the mixture was thoroughly stirred. Next, 0.4 parts of an aqueous solution of Component C was added and the mixture was further stirred to obtain a coating liquid with sufficient dispersibility and a solids concentration of approximately 3 wt%.

[0123] Comparative Examples 4-1 to 4-4 A coating solution was obtained in the same manner as in Example 4-1, except that the types and / or amounts of Components B to C were changed to the compositions shown in Table 4, and in Comparative Examples 4-3 and 4-4, Component H was added in the same manner as in Example 4-7.

[0124] Examples 5-1 to 5-17 Except for changing the type and / or amount of Component C to the compositions shown in Table 5, coating fluids were obtained in the same manner as in Example 4-1.

[0125] [Examples 6-1 to 6-11] Coating solutions were obtained in the same manner as in Example 4-1, except that the types and / or amounts of Components A to C were changed to the compositions shown in Table 6. In Examples 6-6 to 6-8, the solid content concentration was adjusted to about 8 wt % to obtain coating solutions.

[0126] Examples 7-1 to 7-18, Comparative Examples 7-1 to 7-5 Except for changing the types and / or amounts of Components A to C to the compositions shown in Table 7, coating fluids were obtained in the same manner as in Example 1-1.

[0127] (Equivalent ratio of component C to CEC of component A) The silicate layers of swellable mica and montmorillonite have a lack of positive charge due to atomic deficiency and isomorphous atomic substitution. The interlayer cation of swellable mica 1 (Somasif MEB-3) is Na. ＋ The CEC (cation exchange capacity) is approximately 120 meq / 100 g. The Na content in 4 g of dried Somasif MEB-3 (solid) ＋The carboxyl group of component C is Na. ＋ Assuming that the component C coordinates with the ion to form a sodium carboxylate, when component C is terephthalic acid (molecular weight: 166.13 g / mol, bifunctional), the equivalent weight is 0.4 g. When 2,6-naphthalenedicarboxylic acid (molecular weight: 216.19 g / mol, bifunctional) is used with 4 parts of expandable mica 1, the equivalent weight is 0.52 parts.

[0128] (Na in the silicate layer of component A ＋ Ion distribution) The true specific gravity of swelling mica 1 (Somasif MEB-3) (solid) is 2.6 g / cm ３ Therefore, Somasif MEB-3, 1.54 cm ３ Na contained in (4g) ＋ The silicate layer (silicate layer) has a unit crystal thickness of about 1 nm. When resin is inserted between the layers of the swelling mica and the silicate layer becomes a single layer, Na is introduced to both sides of the silicate layer according to the charge deficiency of the silicate layer. ＋ Ions are distributed. If we assume that the plate is 1 nm thick, Na ＋ It is calculated that the ions are distributed on both sides of the silicate layer at intervals of about 1 nm. The interval of about 1 nm is almost the same as the size of terephthalic acid. When the same calculation is performed for the swelling mica 2 (Somasif ME300B-4T), Na ＋ The calculation shows that ions are distributed on both sides of the silicate layer at intervals of about 1.3 nm. ＋ It is calculated that the ions are distributed on both sides of the silicate layer at intervals of about 1 nm.

[0129] 2. Preparation of Laminates A 25 μm thick polyethylene terephthalate film (manufactured by Toray Industries, Inc., trade name "Lumirror T60", one side corona treated) was used as a substrate, and each of the coating solutions obtained in 1. above was applied to the corona treated surface of the substrate using a wire bar so that the film thickness after drying would be 1 μm. The coating was then dried in an oven at 75° C. for 7 minutes and then further dried in an oven at 160° C. for 7 minutes to obtain a laminate (moisture-proof coated film) in which a moisture-proof coating layer was formed on the substrate. The thickness of the moisture-proof coating layer was calculated by measuring the total thickness of the laminate and subtracting the thickness of the polyethylene terephthalate film from the obtained measurement.

[0130] 3. Evaluation of Properties The moisture-proof coated films obtained in 2 above were used to evaluate total light transmittance and moisture-proof property by the following methods.

[0131] (1) Total Light Transmittance The total light transmittance (%) of the moisture-proof coated film was measured in accordance with JIS K7136:2000 using a turbidity meter (manufactured by Nippon Denshoku Industries Co., Ltd., trade name "NDH 4000").

[0132] (2) Moisture Proof (Moisture Permeability) Using a moisture permeability test cup (manufactured by Intec Co., Ltd.), the moisture permeability (g / m) of the moisture-proof coated film was measured in accordance with JIS Z0208:2021. ２ / 24h) was measured by the cup method in an atmosphere of 85°C and 85% RH. The moisture-proof coated film was placed so that the moisture-proof coating layer was on the outer surface (high humidity side) of the moisture-permeable cup, and the measurement was performed. The evaluation criteria are as follows: ◎: 30 or less; ◯: More than 30 and 60 or less; △: More than 60 and 100 or less; ×: More than 100

[0133] (3) FT-IR Using an FT-IR spectrophotometer (FT / IR-4000) manufactured by JASCO Corporation, the moisture-proof coating film was measured by the ATR method (attenuated total reflection method).

[0134] The results are shown in Tables 1 to 7 and Figures 2 to 5.

[0135]

[0136]

[0137]

[0138]

[0139]

[0140]

[0141]

[0142] [Discussion] (FT-IR spectrum) Figure 3 shows the results of FT-IR measurement (ATR method) of the surface of the moisture-proof coating layer of the laminate obtained in Comparative Example 1-1. As shown in Figure 3, the carboxylic acid C=O stretching of terephthalic acid is 1689 cm －１ So, 1551 cm －１ The shift to Na in the silicate interlayer ＋ It is suggested that Na salts are formed between the ions and the carboxyl groups of the carboxylic acid compounds. ＋ It is presumed that carboxylate ions are coordinated to the silicate ions, and sodium carboxylate salts are formed in the areas of the silicate layer where there is a lack of positive charge.

[0143] 4 shows the results of FT-IR measurement (ATR method) of the surface of the moisture-proof coating layer of the laminate obtained in Comparative Example 1-2. As shown in FIG. 4, it can be seen that no distinctive absorption was observed.

[0144] 2 shows the results of FT-IR measurement (ATR method) of the surface of the moisture-proof coating layer of the laminate obtained in Example 1-1. As shown in FIG. 2, the carboxylic acid C═O stretching of terephthalic acid is 1556 cm －１ It is assumed that Na and terephthalic acid in the interlayer space of the swellable mica form a disodium salt. In this case, the absorption of the carboxylic acid C=O stretching was smaller in Example 1-1 (Fig. 2) compared to Comparative Example 1-1 (Fig. 3). In addition, in Example 1-1 (Fig. 2), there was a peak at 1062 cm －１ This absorption is believed to be due to the coordination of the nitrogen atom of glycidylamine, which has a higher acid dissociation constant, with the sodium of disodium terephthalate.

[0145] (Examples Using Glycidylamine-Type Epoxy Resin) As shown in Tables 1 to 3, the examples in which (A) a layered inorganic compound having exchangeable cations, (B) a glycidylamine-type epoxy resin, and (C) a carboxylic acid compound were blended were confirmed to have low moisture permeability and excellent moisture resistance. In contrast, Comparative Examples 1-2, 1-4, and 1-5, which did not contain the (C) carboxylic acid compound, had high moisture permeability and poor moisture resistance. Furthermore, Comparative Example 1-1, which did not contain the (B) glycidylamine-type epoxy resin, had high moisture permeability and poor moisture resistance. Comparative Example 1-3 (FIG. 5), which used a phenol novolac-type epoxy resin instead of the (B) glycidylamine-type epoxy resin and did not use a curing agent, had high moisture permeability and poor moisture resistance.

[0146] By applying a moisture-proof coating layer and drying it by heating, the hydrated Na between the clay layers is removed. ＋ Carboxylic acid is coordinated to the ion, forming a sodium carboxylate salt in the area where the positive charge of the silicate layer is lacking. Next, the nitrogen atoms of the nitrogen-containing polymerizable compound, such as glycidyl amine, methylol melamine, or aromatic amine, chemically adsorb to the sodium of the sodium carboxylate, thereby reducing the amount of water molecules coordinated to the sodium. The nitrogen-containing polymerizable compound then polymerizes starting from the exchangeable cations, covering the silicate layer surface with a polymer bonded at multiple points via the exchangeable cations modified with carboxylic acid. It is believed that this results in a stray effect due to the clay-resin complex, improving moisture resistance.

[0147] In particular, when swelling mica 1 (Somasif MEB-3) was used as component A and terephthalic acid was used as component C, Na ＋It is estimated that the ions are distributed on both sides of the silicate layer at intervals of about 1 nm, and that this interval is almost the same as the molecular size of terephthalic acid, so that the formation of disodium terephthalate salt is promoted using two of the missing positive charges in the silicate layer as scaffolds, resulting in further improvement in moisture resistance.In addition, the combination of Swellable Mica 2 (Somasif ME300B-4T) with 2,6-naphthalenedicarboxylic acid and the combination of Swellable Mica 2 (Somasif ME300B-4T) with 4,4-biphenyldicarboxylic acid also showed a similar effect to the Na ＋ It is presumed that the formation of sodium carboxylate salts is promoted because the size of the ionic spacing is close to the molecular size of the carboxylic acid compound (the arrangement of the carboxyl groups), further improving moisture resistance.

[0148] The influence of differences in the structure of glycidylamine-type epoxy resins on moisture resistance was confirmed in Examples 1-1, 1-3, 1-10, and 1-14. Aromatic glycidylamine-type epoxy resin 2 (Example 1-3) and glycidylamine-type epoxy resin 5 (Example 1-10) tend to have better moisture resistance than alicyclic glycidylamine-type epoxy resin 1 (Example 1-1, Example 1-14).

[0149] Examples 1-2 to 1-5 and 1-7 to 1-9 are examples in which the amount of terephthalic acid added was changed, and it can be seen that when the equivalent ratio of component (C) to CEC of component (A) is 1 or more, extremely excellent moisture-proof properties are exhibited.

[0150] In Examples 1-11 to 1-13, a portion of the glycidylamine-type epoxy resin was replaced with an aromatic amine as component D (curing agent), and all of them showed improved moisture resistance. It is presumed that the improved moisture resistance was due to the improved crosslink density resulting from the addition polymerization of the glycidylamine-type epoxy resin and the ester synthesis (addition polymerization) of the glycidylamine-type epoxy resin and a carboxylic acid compound, as well as the addition polymerization of the glycidylamine-type epoxy resin and the aromatic amine.

[0151] Improvement in moisture resistance was confirmed for various (C) carboxylic acid compounds (Table 2). It can be seen that aromatic carboxylic acids have higher moisture resistance than aliphatic carboxylic acids and alicyclic carboxylic acids. It is speculated that this is because aromatic carboxylic acids have lower solubility in water, and form stable sodium salts in the areas of the silicate layer that lack positive charges, making them less susceptible to the effects of water molecules. Even highly hydrophobic monocarboxylic acids showed high moisture resistance. It can also be seen that dicarboxylic acids exhibit the highest moisture resistance.

[0152] Examples 2-1 to 2-6 are examples in which the amount of carboxylic acid added was changed. In all cases, the moisture-proofing properties were excellent when the equivalent ratio was 0.5 to 4.2, the moisture-proofing properties were further improved when the equivalent ratio was in the range of 1 to 3.5, and the moisture-proofing properties were extremely excellent when the equivalent ratio was in the range of 1.5 to 2.

[0153] In Examples 3-1, 3-2, and 3-3, the component (A) in Examples 1-3, 2-7, and 2-8 was changed from Swellable Mica 1 to Swellable Mica 2, respectively, and it was found that all of them exhibited good moisture-proof properties.

[0154] When Swellable Mica 2 was used, 2,6-naphthalenedicarboxylic acid and 4,4-biphenyldicarboxylic acid showed higher moisture-proof properties than terephthalic acid. ＋ It is presumed that the above results were obtained because the ions were distributed on both sides of the silicate layer at intervals of about 1.3 nm.

[0155] (Examples Using Methylol Melamine) As shown in Tables 4 to 6, the examples in which (A) a layered inorganic compound having exchangeable cations, (B) methylol melamine, and (C) a carboxylic acid compound were blended were confirmed to have low moisture permeability and excellent moisture proof properties. In contrast, Comparative Example 4-2, which did not contain (C) a carboxylic acid compound, had high moisture permeability and poor moisture proof properties. Furthermore, Comparative Example 4-1, which did not contain (B) methylol melamine, had high moisture permeability and poor moisture proof properties. Furthermore, Comparative Examples 4-3 and 4-4, which did not contain (B) methylol melamine and used a compound (component H) in which the methylol group was methoxylated, had high moisture permeability and poor moisture proof properties. In these comparative examples, the methoxylation of the methylol groups increased hydrophobicity and decreased the acid dissociation constant. As a result, it became difficult for the nitrogen atom of methoxymethylolmelamine to coordinate with the sodium of the disodium carboxylate formed by coordination of the sodium ion of component (A) with the carboxylic acid of component (C), and it is presumed that this resulted in a decrease in moisture resistance.

[0156] Examples 4-7 to 4-10 are examples in which part of (B) methylolmelamine was replaced with a nitrogen-containing polymerizable compound (component H) that does not fall under component (B), but it can be seen that they exhibit moisture resistance at a level that does not pose any practical problems.

[0157] Examples 4-11 and 4-12 are examples in which part of the methylol melamine (B) was replaced with an aromatic amine (component D), and it can be seen that all of them exhibited high moisture resistance.

[0158] Example 4-13 is an example in which a polyester resin (component I) having a low acid value is blended with Example 4-6, and it is clear that the total light transmittance is improved while the moisture resistance remains good.

[0159] In Example 4-14, dioxolane was not used as a dilution solvent, and the solution was dissolved, diluted, and mixed only with ion-exchanged water, without the use of a curing catalyst. The coating solution was slightly cloudy, but stable and presented no practical problems. It was clear that a completely aqueous coating solution was obtained. It was also clear that the moisture resistance was extremely excellent.

[0160] Improvement in moisture resistance was confirmed for various carboxylic acid compounds (C) (Table 5). It is also clear that polycarboxylic acids have better moisture resistance than monocarboxylic acids.

[0161] Examples 4-1 to 4-4 are examples in which the amount of carboxylic acid added was changed, but all of them were excellent in moisture resistance, and it was found that when the equivalent ratio was 0.5 or more, the moisture resistance was extremely excellent.

[0162] When comparing Examples 5-6 and 5-8 in which the only active hydrogen group in the carboxylic acid was a carboxy group with Examples 5-6 and 5-8 in which active hydrogen groups other than the carboxy group were present in the carboxylic acid, the Examples in which the only active hydrogen group was a carboxy group had better moisture resistance.

[0163] From the results of Examples 6-5 to 6-7, it can be seen that even when the content ratio of component (A) is small, the moisture-proof property is excellent.

[0164] It was confirmed that excellent moisture-proof properties were achieved when layered inorganic compounds (swellable mica 1, 2, montmorillonite) having an average particle size of 0.1 μm or more were used as component A (Table 6).

[0165] (Examples Using Nitrogen-Free Epoxy Resins) As shown in Table 7, examples (Examples 7-1 to 7-13, 7-17, and 7-18) incorporating (A) a layered inorganic compound having exchangeable cations, (C) a carboxylic acid compound, and (B) a nitrogen-free epoxy resin having an epoxy equivalent of 80 to 165 g / eq and a molecular weight of 180 to 420 g / mol were confirmed to have low moisture permeability and excellent moisture resistance. Also, as shown in Table 7, examples (Examples 7-14, 7-17, and 7-18) incorporating (A) a layered inorganic compound having exchangeable cations, (C) a carboxylic acid compound, and (B) a combination of a nitrogen-free epoxy resin and an amine-based compound were confirmed to have low moisture permeability and excellent moisture resistance. Furthermore, examples (Examples 7-15 and 7-16) incorporating a combination of a nitrogen-free epoxy resin and a thiol-based compound were confirmed to have low moisture permeability and excellent moisture resistance. In contrast, Comparative Examples 7-1 and 7-2, which contained only a nitrogen-free epoxy resin with a molecular weight outside the range of 180 to 420 g / mol, exhibited high moisture permeability and poor moisture resistance. On the other hand, it was found that combining a nitrogen-free epoxy resin with a molecular weight of less than 180 g / mol with an amine compound or a thiol compound reduced moisture permeability and achieved excellent moisture resistance (Examples 7-14 to 7-16). Comparative Example 7-3, which contained a nitrogen-free epoxy resin with an epoxy equivalent outside the range of 80 to 165 g / eq, exhibited high moisture permeability and poor moisture resistance. Comparative Examples 7-4 and 7-5, which did not contain a (C) carboxylic acid compound, exhibited high moisture permeability and poor moisture resistance.

Claims

1. A polymerizable composition comprising: (A) a layered inorganic compound containing at least one exchangeable cation selected from sodium ions and lithium ions; (B) at least one selected from a glycidylamine epoxy resin, a methylol melamine, a combination of a nitrogen-free epoxy resin and an amine compound, a combination of a nitrogen-free epoxy resin and a thiol compound, and a nitrogen-free epoxy resin having an epoxy equivalent of 80 to 165 g / eq and a molecular weight of 180 to 420 g / mol; and (C) a carboxylic acid compound.

2. The composition according to claim 1, wherein component (C) is a carboxylic acid compound having only carboxy groups as active hydrogen groups.

3. The composition according to claim 1, wherein component (B) has an acid dissociation constant pKa of 3 or more.

4. The composition of claim 1, wherein component (A) comprises at least one selected from smectite, vermiculite, and swellable mica.

5. The composition according to claim 1, wherein the component (C) is contained in an amount equivalent to or greater than 0.15 times the cation exchange capacity (CEC) of the component (A).

6. The composition according to claim 1, wherein the weight ratio of component (A) to component (B) [(A) / (B)] is in the range of 5 / 1 to 1 / 10.

7. The composition according to claim 1, wherein the average particle size of component (A) is in the range of 0.1 to 30 μm.

8. The composition according to claim 1, wherein the number of carboxy groups in component (C) is 1 to 6.

9. The composition according to claim 1, wherein the glycidylamine-type epoxy resin and the nitrogen-free epoxy resin have two or more glycidyl groups.

10. The composition according to claim 1, wherein component (B) is at least one selected from the group consisting of glycidylamine-type epoxy resins, methylol melamine, combinations of nitrogen-free epoxy resins and amine-based compounds, and combinations of nitrogen-free epoxy resins and thiol-based compounds.

11. The composition of claim 10, wherein the glycidyl amine type epoxy resin and the nitrogen-free type epoxy resin have an epoxy equivalent weight of 80 to 165 g / eq and a molecular weight of 180 to 420 g / mol.

12. A cured product of the composition according to any one of claims 1 to 11.

13. A gas barrier film comprising a cured product of the composition according to claim 12.

14. A coating or adhesive comprising the composition of any one of claims 1 to 11.

15. A laminate comprising a substrate and a barrier layer comprising the cured composition of claim 12.

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