JP2012024758A - Method of manufacturing multilayer structure - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of manufacturing a multilayer structure which is excellent in adhesion of a resin layer formed by reacting a thermal reactive composition with an inorganic layered compound layer.SOLUTION: The method of manufacturing the multilayer structure includes a base material layer, the inorganic layered compound layer, and the resin layer. The method of manufacturing the multilayer structure comprises all the following steps: (1) a step of coating a base material layer surface with an inorganic layered compound dispersion containing a liquid medium and an inorganic layered compound to form a coating film, of carrying out a dry treatment under temperature conditions of 20-150°C, and of removing the liquid medium from the coating film to form the inorganic layered compound layer (I), (2) a step of forming the thermal reactive composition layer (I) on the inorganic layered compound layer (I) and of manufacturing a preliminary structure, and (3) a step of heating the preliminary structure, of narrowing an interlayer distance of the inorganic layered compounds in the inorganic layered compound layer (I), of reacting components in the thermal reactive composition layer (I), and of forming the resin layer to obtain the multilayer structure.

Description

  The present invention relates to a method for producing a multilayer structure.

Aromatic polyimide is widely used industrially because of its excellent heat resistance and mechanical properties, and its film is particularly important as a substrate for electronic parts. For example, as described in Patent Document 1, an aromatic polyimide film is obtained by applying a heat-reactive composition solution containing a solvent, a heat-reactive monomer aromatic carboxylic acid, and an aromatic diamine onto a base material layer. After the coating, it is produced by heating to cause an aromatic carboxylic acid and an aromatic diamine to undergo a polymerization reaction. Since the thus obtained aromatic polyimide film is inferior in gas barrier properties, its usage is limited, and improvement of gas barrier properties is required for further application development.
On the other hand, a multilayer structure including a layer containing an inorganic layered compound is known as a multilayer structure excellent in gas barrier properties. For example, Patent Document 2 discloses that a multilayer structure in which a layer containing an inorganic layered compound is laminated on a thermoplastic resin film is excellent in gas barrier properties.

JP2004-352912 JP 03-30944

  In order to impart gas barrier properties to an aromatic polyimide film, it is considered effective to laminate a layer containing an inorganic layered compound as disclosed in Patent Document 2 on an aromatic polyimide film. However, like an aromatic polyimide, an inorganic layered compound layer is applied to a resin layer formed by coating a heat-reactive composition solution containing a monomer on a base material layer and heating to polymerize the monomer. When the layers are laminated, the adhesion may be insufficient.

  The subject of this invention provides the manufacturing method of the multilayered structure which is excellent in the adhesiveness of the resin layer formed by making a heat-reactive composition react, and an inorganic layered compound layer.

That is, this invention is a manufacturing method of the multilayer structure containing a base material layer, an inorganic layered compound layer, and a resin layer, Comprising: It is a manufacturing method of a multilayer structure including all the following processes.
(1) An inorganic layered compound dispersion containing an inorganic layered compound and a liquid medium is applied to the surface of the base material layer to form a coating film, and then subjected to a drying treatment at a temperature of 20 to 150 ° C., Step (2) of forming the inorganic layered compound layer (I) by removing the liquid medium from the coating film, forming the thermally reactive composition layer (I) on the inorganic layered compound layer (I), Step (3) for manufacturing the structure: The preliminary structure is heated to reduce the interlayer distance of the inorganic layered compound in the inorganic layered compound layer (I), and the components in the thermally reactive composition layer (I) The step of forming a resin layer by reacting to obtain a multilayer structure Further, in another aspect, the present invention is a method for producing a multilayer structure including a base material layer, an inorganic layered compound layer, and a resin layer, comprising: A method for producing a multilayer structure including all the steps.
(1) Step of forming the heat-reactive composition layer (I) on the surface of the substrate layer (2) An inorganic layered compound dispersion containing an inorganic layered compound and a liquid medium on the heat-reactive composition layer (I) To form a coating film, followed by drying under a temperature condition of 20 to 150 ° C., removing the liquid medium from the coating film to form an inorganic layered compound layer (I), Step (3) for producing the preliminary structure: heating the preliminary structure to narrow the interlayer distance of the inorganic layered compound in the inorganic layered compound layer (I), and the components in the thermally reactive composition layer (I) In another aspect, the present invention is a method for producing a multilayer structure including a base material layer, an inorganic layered compound layer, and a resin layer. It is a manufacturing method of a multilayer structure including all the following processes.
(1) Step of forming the heat-reactive composition layer (I) on the surface of the substrate layer (2) An inorganic layered compound dispersion containing an inorganic layered compound and a liquid medium on the heat-reactive composition layer (I) To form an inorganic layered compound layer (I) by forming a coating film, followed by drying under a temperature condition of 20 to 150 ° C., removing the liquid medium from the coating film (3) A step of producing a preliminary structure by forming a heat-reactive composition layer (II) on the inorganic layered compound layer (I). (4) An inorganic layered compound layer by heating the preliminary structure. A step of obtaining a multilayer structure by narrowing the interlayer distance of the inorganic layered compound in (I) and reacting the components in the thermally reactive composition layers (I) and (II) to form a resin layer

  According to the method for producing a multilayer structure of the present invention, a multilayer structure having excellent adhesion between a resin layer formed by reacting a thermally reactive composition and an inorganic layered compound layer can be produced.

A first aspect of the present invention is a method for producing a multilayer structure including a base material layer, an inorganic layered compound layer, and a resin layer, and a method for producing a multilayer structure including all the following steps.
(1) An inorganic layered compound dispersion containing an inorganic layered compound and a liquid medium is applied to the surface of the base material layer to form a coating film, and then subjected to a drying treatment at a temperature of 20 to 150 ° C., Step (2) of forming the inorganic layered compound layer (I) by removing the liquid medium from the coating film, forming the thermally reactive composition layer (I) on the inorganic layered compound layer (I), Step (3) for manufacturing the structure: The preliminary structure is heated to reduce the interlayer distance of the inorganic layered compound in the inorganic layered compound layer (I), and the components in the thermally reactive composition layer (I) A process of forming a resin layer by reacting to obtain a multilayer structure

  As the inorganic layered compound used in the step (1) in the first embodiment, a clay mineral having a swelling property to a solvent and a cleavage property is preferably used. An inorganic layered compound refers to a product in which unit crystal layers are stacked to form a layered structure. A layered structure is a structure in which atoms that are strongly bonded by a covalent bond or the like and densely arranged are stacked almost in parallel by a weak binding force such as van der Waals. Among inorganic layered compounds, clay minerals having swelling property to a solvent are particularly preferably used.

  Clay minerals generally include (i) a type having a two-layer structure having an octahedral layer with aluminum, magnesium, etc. as a central metal above the silica tetrahedral layer, and (ii) the silica tetrahedral layer is made of aluminum. And a type having a three-layer structure in which an octahedral layer having a central metal such as magnesium is sandwiched from both sides. Examples of the two-layer structure type viscosity mineral (i) include clay minerals such as kaolinite group and antigolite group. Examples of the clay mineral of the three-layer structure type (ii) include clay minerals such as smectite group, vermiculite group, and mica group depending on the number of interlayer cations.

  These clay minerals include kaolinite, dickite, nacrite, halloysite, antigolite, chrysotile, pyrophyllite, montmorillonite, beidellite, nontronite, saponite, sauconite, stevensite, hectorite, tetrasilic mica, sodium tenio. Light, muscovite, margarite, talc, vermiculite, phlogopite, xanthophyllite, chlorite and the like. In addition, these clay minerals treated with organic substances such as ion exchange and improved dispersibility (see Asakura Shoten, “Encyclopedia of Clay”; hereinafter may be referred to as organically modified clay minerals) are also used as inorganic layered compounds. Can be used. As the organic substance for treating clay mineral, known quaternary ammonium salts such as dimethyl distearyl ammonium salt and trimethyl stearyl ammonium salt, phosphonium salts, imidazolium salts and the like can be used.

Among the clay minerals, smectite group, vermiculite group and mica group clay minerals are preferable, and smectite group is particularly preferable. Examples of the smectite group include montmorillonite, beidellite, nontronite, saponite, soconite, stevensite, and hectorite. In particular, montmorillonite is preferably used.
Two or more kinds of inorganic layered compounds may be used.

  The aspect ratio of the inorganic layered compound is preferably 20 or more from the viewpoint of improving gas barrier properties. Moreover, it is preferable that the aspect-ratio of this inorganic layered compound is 10,000 or less from a viewpoint that it is easy to swell and cleave and gas barrier property improves. The aspect ratio of the inorganic layered compound is a value in an inorganic layered compound dispersion containing the inorganic layered compound and a liquid medium.

  The inorganic layered compound preferably has an average particle size of 10 μm or less from the viewpoint of improving gas barrier properties, transparency, and film forming properties. Particularly in applications where transparency is required, it is preferably 1 μm or less.

  In the present invention, the aspect ratio (Z) of the inorganic layered compound is defined by the formula: Z = L / a. In the formula, L is the average particle diameter of the inorganic layered compound, a is the unit thickness of the inorganic layered compound, that is, the thickness of the unit crystal layer of the inorganic layered compound, and is determined by the powder X-ray diffraction method (“instrumental analysis”). No. (a) "(1985, published by Kagaku Dojinsha, supervised by Jiro Shiokawa, p. 69).

  The average particle diameter of the inorganic layered compound is a particle diameter (volume-based median diameter) obtained by a diffraction / scattering method in a liquid medium. That is, it can be obtained by calculating the particle size distribution most consistent with the above diffraction / scattering pattern from the diffraction / scattering pattern obtained when light is passed through the dispersion of the inorganic layered compound by Mie scattering theory or the like. it can. Specifically, for example, the measurement range of the particle size distribution is divided into appropriate sections, the representative particle diameter is determined for each section, and the particle size distribution, which is originally a continuous quantity, is converted into a discrete quantity and calculated. A method is mentioned.

  Specifically, the inorganic layered compound preferably has a swelling value of 5 or more, more preferably a swelling value of 20 or more according to the following swellability test. Further, those having a cleavage value of 5 or more by cleavage test described below are preferred, and those having a cleavage value of 20 or more are more preferred.

(Swellability test)
Into a 100 ml graduated cylinder, 100 ml of liquid medium is added, and 2 g of inorganic layered compound is gradually added thereto. After standing at 23 ° C. for 24 hours, the volume (ml) of the inorganic layered compound dispersion layer is read from the scale of the interface between the inorganic layered compound dispersion layer and the supernatant in the graduated cylinder. It shows that swelling property is so high that this numerical value (swelling value) is large.

[Cleavage test]
Gradually add 30 g of inorganic layered compound into 1,500 ml of liquid medium, disperser (Asada Tekko Co., Ltd., Despa MH-L, blade diameter 52 mm, rotation speed 3,100 rpm, container volume 3 L, distance between bottom surface and blades 28 mm) at a peripheral speed of 8.5 m / min and at 23 ° C. for 90 minutes, 100 ml of this dispersion is collected in a graduated cylinder. After standing for 60 minutes, the volume (ml) of the inorganic layered compound dispersion layer is read from the scale of the interface between the layered compound dispersion layer and the supernatant in the graduated cylinder. The larger this numerical value (cleavage value), the higher the cleavage property.

  The liquid medium contained in the inorganic layered compound dispersion is not particularly limited, but it is preferable to use a liquid medium that swells and cleaves the inorganic layered compound described below.

  As a liquid medium for swelling and cleaving the inorganic layered compound, when the inorganic layered compound is a hydrophilic swelling clay mineral, water, alcohols (methanol, ethanol, propanol, isopropanol, ethylene glycol, diethylene glycol, etc.), dimethyl Examples include formamide, dimethyl sulfoxide, acetone and the like, and water, alcohol, and a water-alcohol mixture are particularly preferable.

  When the inorganic layered compound is an organically modified clay mineral, aromatic hydrocarbons such as benzene, toluene and xylene, ethers such as ethyl ether and tetrahydrofuran, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, n -Aliphatic hydrocarbons such as pentane, n-hexane, n-octane, halogenated hydrocarbons such as chlorobenzene, carbon tetrachloride, chloroform, dichloromethane, 1,2-dichloroethane, perchloroethylene, ethyl acetate, methacrylic acid Methyl, dioctyl phthalate, dimethylformamide, dimethyl sulfoxide, methyl cellosolve, silicone oil, etc. can be used as the liquid medium.

  The volume fraction of the inorganic layered compound in the inorganic layered compound layer included in the multilayer structure is preferably 90 to 100 vol%, more preferably 95 to 100 vol%, and 98 to 100 vol%. More preferred is 100 vol%.

The inorganic layered compound dispersion includes a liquid medium and an inorganic layered compound. The method for preparing the inorganic layered compound dispersion is not particularly limited, but it is preferable to gradually add and disperse the inorganic layered compound to the liquid medium using a disperser as in the above-described cleavage test.
When preparing an inorganic layered compound dispersion, it is preferable to carry out a high pressure dispersion treatment using a high pressure dispersing device from the viewpoint of dispersibility of the inorganic layered compound. Examples of the high-pressure dispersing device include an ultra-high pressure homogenizer (trade name: Microfluidizer) manufactured by Microfluidics Corporation, a nanomizer manufactured by Nanomizer, a Manton Gorin type high-pressure dispersing device, and a homogenizer manufactured by Izumi Food Machinery. The high-pressure dispersion treatment means that the inorganic layered compound dispersion is passed through a plurality of thin tubes at a high speed and then merged, and the inorganic layered compound dispersions collide with each other or the inorganic layered compound dispersion and the inner wall of the thin tube. This is a treatment method of applying high shear and / or high pressure to the inorganic layered compound dispersion. In the high-pressure dispersion treatment, it is preferable that the inorganic layered compound dispersion is passed through a thin tube having a tube diameter of about 1 μm to 1000 μm, and at this time, treatment is performed so that a maximum pressure of 100 kgf / cm ² or more is applied. Maximum pressure is more preferably at 500 kgf / cm ² or more, and particularly preferably 1000 kgf / cm ² or more. Further, when the inorganic layered compound dispersion liquid passes through the narrow tube, the maximum arrival speed of the dispersion liquid is preferably 100 m / s or more, and the heat transfer rate due to pressure loss is preferably 100 kcal / hr or more.

Inorganic layered compounds usually have cations between layers. The cation is usually a sodium ion, but the sodium ion is preferably exchanged for a lithium ion, more preferably a hydrogen ion by the method described later.
Although it does not specifically limit as a method of adjusting the cation density | concentration between the layers of an inorganic layered compound, What is necessary is just to perform a well-known ion exchange process. The ion exchange treatment is, for example, an ion exchange resin having hydrogen ions and / or lithium ions and an ion exchange resin after contacting a dispersion containing an inorganic layered compound in which the cation between layers is sodium ions and a liquid medium. And a dispersion containing an inorganic layered compound in which the cation between layers is sodium ion and a liquid medium are brought into contact with a liquid containing hydrogen ions and / or lithium ions through a semipermeable membrane, The method of ion-exchange using a pressure difference or electrodialysis is mentioned. After the ion exchange of the inorganic layered compound dispersion liquid, it can be used as it is as a coating liquid for forming the inorganic layered compound layer (I).

Thus, the cation concentration in the inorganic layered compound layer contained in the multilayer structure can be controlled by using the inorganic layered compound in which cations between layers are exchanged. The sodium ion concentration in the inorganic layered compound layer contained in the multilayer structure is preferably 400 μmol / g or less, more preferably 300 μmol / g or less, and even more preferably 100 μmol / g or less.
The total concentration of lithium ions and hydrogen ions in the inorganic layered compound layer included in the multilayer structure is preferably 400 μmol / g or more, more preferably 500 μmol / g, and 600 μmol / g. More preferably.
More preferably, the sodium ion concentration satisfies the above-described conditions, and the total concentration of lithium ions and hydrogen ions satisfies the above-described conditions.
When the inorganic layered compound layer included in the multilayer structure satisfies the requirements for the sodium ion concentration, lithium ion concentration, and hydrogen ion concentration, a multilayer structure excellent in water resistance can be obtained.

  About the qualitative and quantitative method of the cation in the inorganic layered compound layer contained in the multilayer structure, measurement is performed using an inductively coupled plasma emission spectrometer. In the present invention, the sodium concentration and the lithium concentration measured using an inductively coupled plasma optical emission spectrometer are set as a sodium ion concentration and a lithium ion concentration, respectively. The hydrogen ion concentration can be determined by measuring the sodium ion concentration of the inorganic layered compound that has not been subjected to ion exchange, and then subtracting the sodium ion concentration and lithium ion concentration of the inorganic layered compound after ion exchange.

  When an inorganic layered compound dispersion having a known solid content concentration of the inorganic layered compound is available, each ion concentration can be measured using a sample obtained by removing the liquid medium from the inorganic layered compound dispersion. If the inorganic layered compound dispersion is not available, measure the ion concentration of the entire multilayer structure described later, and subtract the cation concentration contained in the layers other than the inorganic layered compound layer to obtain the ion concentration. The way you ask can be.

  A surfactant may be added to the inorganic layered compound dispersion. By applying an inorganic layered compound dispersion containing a surfactant to form an inorganic layered compound layer, the adhesion between the layer and the adjacent layer can be improved. The content of the surfactant contained in the inorganic layered compound dispersion is 0.001% by weight or more from the viewpoint of improving adhesion when the weight of the inorganic layered compound dispersion is 100% by weight. It is preferable. Moreover, it is preferable that content of surfactant is 5 weight% or less from a viewpoint that gas-barrier property is not impaired.

  As the surfactant, a known surfactant such as an anionic surfactant, a cationic surfactant, an amphoteric surfactant, and a nonionic surfactant can be used. In particular, an alkali metal salt of a carboxylic acid having an alkyl chain of 6 to 24 carbon atoms, an ether type nonionic surfactant such as a polydimethylsiloxane-polyoxyethylene copolymer (silicone-based nonionic surfactant) ) Or a fluorine-type nonionic surfactant (fluorine-based nonionic surfactant) such as a perfluoroalkylethylene oxide compound is preferable from the viewpoint of improving adhesion.

  As a method of forming a coating film by coating an inorganic layered compound dispersion on the surface of a base material layer, a gravure method such as a direct gravure method or a reverse gravure method, a two-roll beat coat method, a bottom feed three reverses Examples thereof include a roll coating method such as a coating method, a doctor knife method, a die coating method, a bar coating method, a dipping method, a spray coating method, and a spin coating method. When the multilayer structure obtained by the production method of the present invention is a film, it is preferable to employ a gravure method, a spin coating method or a die coating method since a layer having a uniform thickness can be provided. In addition, a coating film may be formed in a part of base material layer surface, and may be formed in the whole surface.

The coating film is dried under a temperature condition of 20 to 150 ° C., the liquid medium is removed from the coating film, and the inorganic layered compound layer (I) is formed. The temperature condition is preferably 30 to 140 ° C, more preferably 40 to 130 ° C, and still more preferably 50 to 120 ° C. The drying time is usually 1 second to 24 hours. The water vapor concentration during the drying treatment is preferably 0 to 40 g / m ³ . The heat source used for the drying treatment is not particularly limited, and various methods such as hot roll contact, heat medium contact (air, etc.), infrared heating, microwave heating, etc. can be applied.

In the first embodiment, in the step (2), the heat-reactive composition layer (I) is formed on the inorganic layered compound layer (I) to produce a preliminary structure.
A heat-reactive composition is a relatively low molecular weight substance that is liquid, semi-solid or solid at room temperature and exhibits fluidity at room temperature or under heating. Is a composition capable of forming a network-like three-dimensional structure while increasing the molecular weight. The heat-reactive composition used in the present invention is soluble in a solvent when used in step (2), and the resin layer formed by heat treatment in step (3) is insoluble in the solvent. Those are preferred.

Examples of the thermally reactive composition include a composition containing two or more types of monomers that react with each other, a composition containing a monomer that is polymerized by heating to form a polymer, and a polymerization initiator. Examples of the composition containing two or more kinds of monomers that react with each other include a composition containing a monomer containing a hydroxyl group and a monomer containing a carboxyl group. Examples of the monomer that polymerizes by heating to form a polymer include epoxy compounds, (meth) acryloyl compounds, allyl compounds, and vinyl compounds.
The heat-reactive composition is preferably a composition containing an epoxy compound and a polymerization initiator, or a composition containing a monomer containing a hydroxyl group and a monomer containing a carboxyl group.

  The epoxy compound refers to a compound having at least one epoxy group. The number of epoxy groups in the epoxy compound is preferably 1 or more per molecule, and more preferably 2 or more per molecule. Here, the number of epoxy groups per molecule is obtained by dividing the total number of epoxy groups in the epoxy compound by the total number of molecules in the epoxy compound.

  As the epoxy compound, a compound having a known epoxy group can be used, for example, a bisphenol type epoxy compound, a novolac type epoxy compound, a glycidyl ester type epoxy compound, a glycidyl amine type epoxy compound, a fluorene type epoxy. Examples of the compound are epoxy compounds having an aromatic ring in the molecule. An epoxy compound having a siloxane bond in the molecule such as a silsesquioxane unit can also be used. The heat-reactive composition may contain two or more types of epoxy compounds.

  Examples of polymerization initiators for epoxy compounds include amines such as bis (4-aminocyclohexyl), methanediaminodiphenylsulfone, 1,5-azabicyclo- (4,3,0) -nonene-7, and salts thereof. Acid anhydrides such as phthalic anhydride and dodecenyl succinic anhydride; polyhydric phenols such as bisphenol F and phenol novolak; imidazoles such as 2-methylimidazole and 2-ethyl-4-methylimidazole BF3 complex compounds of amines as described above; Bronsted acid salts such as aromatic sulfonium salts, iodonium salts and phosphonium salts; organic acid hydrazides such as adipic acid dihydrazide and phthalic acid dihydrazide; dicyandiamides; adipic acid and sebacic acid , Terephthalic acid, trimellitic acid and carboxy Polycarboxylic acids such as group-containing polyester. Ionic thermal latent cations such as benzylsulfonium salt, benzylammonium salt, benzylpyridinium salt, and benzylphosphonium salt with antimony hexafluoride, phosphorous hexafluoride, and boron fluoride as counter anions from the viewpoint of reaction rate Polymerization initiator: It is preferable to use a nonionic thermal latent cationic polymerization initiator such as N-benzylphthalimide and aromatic sulfonate ester. The polymerization initiator preferably has a polyimide skeleton in the molecule. The polyimide skeleton here refers to a structure in which aromatic compounds are directly linked by an imide bond. Two or more kinds of polymerization initiators may be used.

Examples of the composition containing a monomer containing a hydroxyl group and a monomer containing a carboxyl group include a composition containing an aromatic alcohol and an aromatic carboxylic acid.
Specifically, a combination of an aromatic hydroxycarboxylic acid, an aromatic dicarboxylic acid and an aromatic diol, a plurality of types of aromatic hydroxycarboxylic acids, a combination of an aromatic dicarboxylic acid and an aromatic diol, Can be used in which a part of the aromatic hydroxycarboxylic acid is replaced with an aromatic aminocarboxylic acid, and a part of the aromatic diol is replaced with an aromatic amine and / or an aromatic diamine having a phenolic hydroxyl group. (1) aromatic hydroxycarboxylic acid, (2) aromatic dicarboxylic acid and (3) aromatic diamine, aromatic amine having a hydroxyl group or aromatic amino acid, It is preferable to contain.

Examples of the aromatic hydroxycarboxylic acid represented by the above (1) include p-hydroxybenzoic acid, 2-hydroxy-6-naphthoic acid, 4-hydroxy-4′-biphenylcarboxylic acid, and the like. It preferably contains hydroxy-6-naphthoic acid. Two or more of these may be used.
Examples of the aromatic dicarboxylic acid represented by the above (2) include terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, and the like, and preferably includes isophthalic acid. Two or more of these may be used.
Examples of the aromatic diamine represented by the above (3), the aromatic amine having a hydroxyl group or the aromatic amino acid include 3-aminophenol, 4-aminophenol, 1,4-phenylenediamine, 1,3-phenylenediamine, An aminobenzoic acid etc. are mentioned, However, It is preferable that 4-aminophenol is included. Two or more of these may be used.

  In the above (1) to (3), an ester-forming derivative may be used. Examples of ester-forming derivatives of carboxylic acids include those in which the carboxyl group is a derivative having a high reaction activity such as an acid chloride or an acid anhydride that promotes the reaction to form a polyester. And those that form esters with alcohols, ethylene glycol, or the like that form polyesters by transesterification. Examples of the ester-forming derivative of a phenolic hydroxyl group include those in which a phenolic hydroxyl group forms an ester with a carboxylic acid so that a polyester is produced by a transesterification reaction. Examples of the ester-forming derivative of an amino group include those in which an amino group forms an ester with a carboxylic acid so that a polyester is produced by a transesterification reaction.

When the heat-reactive composition is a composition containing an aromatic alcohol and an aromatic carboxylic acid, use a prepolymerized part thereof in a range soluble in the aprotic solvent shown below. It doesn't matter.
Examples of the aprotic solvent include halogen solvents such as 1-chlorobutane, chlorobenzene, 1,1-dichloroethane, 1,2-dichloroethane, chloroform, 1,1,2,2-tetrachloroethane, diethyl ether, tetrahydrofuran Ether solvents such as 1,4-dioxane, ketone solvents such as acetone and cyclohexanone, ester solvents such as ethyl acetate, lactone solvents such as γ-butyrolactone, carbonate solvents such as ethylene carbonate and propylene carbonate, triethylamine Amide solvents such as pyridine, amine solvents such as acetonitrile and succinonitrile, amide solvents such as N, N′-dimethylformamide, N, N′-dimethylacetamide, tetramethylurea and N-methylpyrrolidone Nitro solvents such as nitromethane and nitrobenzene, sulfide solvents such as dimethyl sulfoxide and sulfolane, and phosphoric acid solvents such as hexamethylphosphoric acid amide and tri-n-butylphosphoric acid.

As a method for forming the heat-reactive composition layer (I) on the inorganic layered compound layer (I), a coating liquid in which the heat-reactive composition is dissolved or dispersed in a liquid medium is used. ) To form a coating film and remove the liquid medium from the coating film. When removing the liquid medium, the liquid medium is dried at a low temperature so as to suppress the reaction of the monomer contained in the heat-reactive composition layer as much as possible. The temperature is usually 20 to 150 ° C., and the drying time is usually 0.1 seconds to 1 hour. The heat-reactive composition layer (I) in the preliminary structure obtained in the step (2) is a layer in which the reaction is not completely completed and the reaction can proceed in the step (3).
The liquid medium contained in the coating liquid used to form the heat-reactive composition layer is not particularly limited as long as it is a liquid medium in which the heat-reactive composition is dissolved or dispersed. And a liquid medium that swells and cleaves the aprotic solvent. A surfactant may be added to the coating solution from the viewpoint of improving adhesion. The content of the surfactant is usually 0.001 to 5% by weight in 100% by weight of the coating solution.
As a method for forming the heat-reactive composition layer on the inorganic layered compound layer (I), the same method as the method for forming the inorganic layered compound layer (I) on the base material layer can be used.

In the step (3) in the first embodiment, the preliminary structure is heated to reduce the interlayer distance of the inorganic layered compound in the inorganic layered compound layer (I), and the components in the thermally reactive composition layer (I) To form a resin layer to obtain a multilayer structure. In the present invention, by heating the preliminary structure, the interlayer distance of the inorganic layered compound in the inorganic layered compound layer (I) is reduced, and at the same time, the components in the thermally reactive composition layer (I) are reacted to form a resin layer. It is important to form As a result, a multilayer structure having excellent adhesion between the inorganic layered compound layer and the resin layer can be obtained.
The conditions for heating the preliminary structure in the step (3) are preferably 160 to 400 ° C, more preferably 170 to 380 ° C, and further preferably 200 to 360 ° C. The heat treatment is preferably carried out in an atmosphere having a water vapor concentration of less than 50 g / m ³ . The time for the heat treatment is usually 1 second to 24 hours. The heat source used for the heat treatment is not particularly limited, and the same method as the drying treatment in step (1) can be applied.

When the resin formed by reacting the components in the heat-reactive composition layer (I) is a heat reaction product of a composition containing an aromatic alcohol and an aromatic carboxylic acid, a structure derived from an aromatic diamine It is preferable to contain 10 to 35 mol% of a unit, a structural unit derived from an aromatic amine having a hydroxyl group, a structural unit derived from an aromatic amino acid, or two or more of the structural units. The resin includes structural units represented by the following formulas (1) to (3) as structural units, the structural unit represented by the formula (1) is 30 to 80 mol%, and the structure represented by the formula (2). The unit is preferably 35 to 10 mol%, and the structural unit represented by the formula (3) is preferably 35 to 10 mol%.
Formula (1) -O-Ar1-CO-
Formula (2) -CO-Ar2-CO-
Formula (3) -X-Ar3-Y-
Here, Ar1 represents 1,4-phenylene, 2,6-naphthalene, or 4,4′-biphenylene. Ar2 represents 1,4-phenylene, 1,3-phenylene, or 2,6-naphthalene. Ar3 represents 1,4-phenylene or 1,3-phenylene. X represents —NH—, and Y represents —O— or —NH—.

The multilayer structure obtained by the production method of the present invention has a base material layer. The material which comprises a base material layer is not specifically limited, A metal, resin, wood, ceramic, glass, etc. are mentioned. The form of the base material layer is not particularly limited, and examples thereof include paper, cloth, nonwoven fabric, and film.
Although it does not specifically limit as a metal, Copper, iron, silver, aluminum, a silica, titanium etc. are mentioned, These alloys are also included.
As the resin, a thermoplastic resin, a thermosetting resin, a photocurable resin, or the like can be used. Examples of the thermoplastic resin used include olefinic resins such as polyethylene, ethylene-α-olefin copolymer, polypropylene, polybutene-1, and poly-4-methylpentene-1; ethylene-vinyl acetate copolymer or saponified product thereof , Ethylene copolymers such as ethylene-α / β unsaturated carboxylic acid ester copolymers, ethylene-α / β unsaturated carboxylic acid copolymers; ester resins such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate Amide resins such as nylon-6 (Ny-6), nylon-6,6, metaxylenediamine-adipic acid condensation polymer, polymethylmethacrylamide, polymetaxylylene adipamide (MXD6-Ny); polyarylate Polycarbonate, polymethyl methacrylate, etc. Acrylic resin; polystyrene; styrene resin such as AS resin and ABS resin; hydrophobized cellulose resin such as cellulose triacetate and cellulose diacetate; chlorine resin such as polyvinyl chloride and polyvinylidene chloride; polyvinyl fluoride, Fluorine resins such as polyvinylidene fluoride, polytetrafluoroethylene, ethylene-tetrafluoroethylene copolymer, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer; polyvinyl alcohol, ethylene-vinyl alcohol copolymer (EVOH), cellulose Hydrogen bonding resin satisfying a ratio of hydroxyl group weight per unit weight of resin such as a derivative of 20 to 60%; carbonate resin, sulfone resin, ether sulfone resin, ether ether ketone resin, phenylene oxide resin, methyl N'okishido resins, imide resins.
Examples of the thermosetting resin include a known phenol resin, melamine resin, urea resin, and a resin made of a heat reaction product of the above-described heat-reactive composition.
Examples of the photocurable resin include known epoxy resins and acrylic resins.

When the multilayer structure obtained by the production method of the present invention is a film, the base material layer may be any of an unstretched film, a uniaxially stretched film, and a biaxially stretched film.
The base material layer may be a multilayer film such as Ny-6 / MXD6-Ny / Ny-6 or PP / EVOH / PP, or a film on which aluminum, alumina, or silica is deposited.

  In laminating the substrate layer with other layers, surface treatment such as corona treatment, ozone treatment, electron beam treatment, ion treatment, flame treatment using gas such as silane, atmospheric pressure or reduced pressure plasma treatment, etc. It may be given in advance. An anchor coat layer may be provided on the surface of the base material layer. The anchor coat layer can be formed using a known ethyleneimine-based, two-component curable urethane-based anchor coat agent or the like. In addition, when the inorganic layered compound layer (I) is laminated on the heat-reactive composition layer (I), or when the heat-reactive composition layer (I) is laminated on the inorganic layered compound layer (I), each of them is thermally reactive. The surface treatment may also be performed on the composition layer (I) and the inorganic layered compound layer (I).

The second aspect of the present invention is a method for producing a multilayer structure including a base material layer, an inorganic layered compound layer, and a resin layer, and a method for producing a multilayer structure including all the following steps.
(1) Step of forming the heat-reactive composition layer (I) on the surface of the substrate layer (2) An inorganic layered compound dispersion containing an inorganic layered compound and a liquid medium on the heat-reactive composition layer (I) To form a coating film, followed by drying under a temperature condition of 20 to 150 ° C., removing the liquid medium from the coating film to form an inorganic layered compound layer (I), Step (3) for producing the preliminary structure: heating the preliminary structure to narrow the interlayer distance of the inorganic layered compound in the inorganic layered compound layer (I), and the components in the thermally reactive composition layer (I) Is a process of forming a resin layer by reacting to obtain a multilayer structure

The heat-reactive composition layer (I) in the second embodiment uses the same material as the material used when forming the heat-reactive composition layer (I) in the step (2) of the first embodiment. It can be formed by a similar method. The thermal reactive composition layer (I) in the step (1) in the second embodiment and the thermal reactive composition layer (I) contained in the preliminary structure obtained in the step (2) both react. It is a layer that is not completely completed and in which the reaction can proceed in step (3). However, in the heat-reactive composition layer (I) in the step (2), the reaction of the monomers contained in the layer proceeds more than the heat-reactive composition layer (I) formed in the step (1). Also good.
The heat-reactive composition layer (I) may be formed on a part of the surface of the base material layer or on the entire surface.
Moreover, the inorganic layered compound layer (I) in the second embodiment can be formed by the same method using the same material as the inorganic layered compound layer (I) in the first embodiment.
In the second aspect, by heating the preliminary structure in the step (3), the interlayer distance of the inorganic layered compound in the inorganic layered compound layer (I) is reduced, and at the same time, in the thermally reactive composition layer (I) The resin layer is formed by reacting the components. As a result, a multilayer structure having excellent adhesion between the inorganic layered compound layer and the resin layer can be obtained.

The third aspect of the present invention is a method for producing a multilayer structure including a base material layer, an inorganic layered compound layer, and a resin layer, and is a method for producing a multilayer structure including all the following steps.
(1) Step of forming the heat-reactive composition layer (I) on the surface of the substrate layer (2) An inorganic layered compound dispersion containing an inorganic layered compound and a liquid medium on the heat-reactive composition layer (I) To form an inorganic layered compound layer (I) by forming a coating film, followed by drying under a temperature condition of 20 to 150 ° C., removing the liquid medium from the coating film (3) A step of producing a preliminary structure by forming a heat-reactive composition layer (II) on the inorganic layered compound layer (I). (4) An inorganic layered compound layer by heating the preliminary structure. A step of obtaining a multilayer structure by narrowing the interlayer distance of the inorganic layered compound in (I) and reacting the components in the thermally reactive composition layers (I) and (II) to form a resin layer

In the third embodiment, after the step (2) of the second embodiment, a heat-reactive composition layer (II) is formed on the inorganic layered compound layer (I) formed in the step (2), and a preliminary structure is formed. A process for producing a body. The heat-reactive composition layer (II) is formed by the same method using the same material as that used when forming the heat-reactive composition layer (I) in the step (2) of the first aspect. can do. The heat-reactive composition layer (I) and the heat-reactive composition layer (II) may have the same composition or different compositions.
In the heat-reactive composition layer (I) and the heat-reactive composition layer (II) contained in the preliminary structure obtained in the step (3) of the third embodiment, the reaction is not completely completed. In the step (4), the reaction can proceed. However, the thermally reactive composition layer (I) contained in the preliminary structure obtained in the step (3) is contained in the layer more than the thermally reactive composition layer (I) in the steps (1) and (2). The monomer reaction may proceed.
The heat-reactive composition layer (II) may be formed on a part of the surface of the inorganic layered compound layer (I) or on the entire surface.
Moreover, the inorganic layered compound layer (I) in the third embodiment can be formed by the same method using the same material as the inorganic layered compound layer (I) in the first embodiment.
In the third aspect, by heating the preliminary structure in the step (4), the interlayer distance of the inorganic layered compound in the inorganic layered compound layer (I) is reduced, and at the same time, the thermally reactive composition layers (I) and ( II) The components in are reacted to form a resin layer. As a result, a multilayer structure having excellent adhesion between the inorganic layered compound layer and the resin layer can be obtained.

When using the multilayer structure obtained by this invention, you may use it, removing a part or all part of a base material layer. As a material constituting the removable base material layer, copper, fluorine resin, and polyolefin resin are preferable. Although it does not specifically limit as a method of removing a base material layer, For example, when a base material layer is copper, the method of removing by immersing in ferric chloride aqueous solution etc. and dissolving copper is mentioned.
When removing a base material layer, you may carry out after any process included in each aspect, However, After obtaining a multilayer structure, it is preferable to remove a base material layer.

The multilayer structure obtained by the production method of the present invention may have a layer other than the inorganic layered compound layer, the resin layer, and the base material layer. Moreover, you may have multiple layers of the same composition as an inorganic layered compound layer and a resin layer, respectively. As the configuration of the multilayer structure obtained by the production method of the present invention, for example, base material layer / inorganic layered compound layer / resin layer (configuration 1),
Base layer / inorganic layered compound layer / resin layer / additional layer A (Configuration 2),
Base material layer / inorganic layered compound layer / resin layer / additional layer B / additional layer C (configuration 3),
Base layer / inorganic layered compound layer / resin layer / additional layer D / additional layer E / additional layer F (configuration 4),
Base material layer / resin layer / inorganic layered compound layer (configuration 5),
Base layer / resin layer / inorganic layered compound layer / additional layer G (configuration 5),
Base material layer / resin layer / inorganic layered compound layer / additional layer H / additional layer I (configuration 6),
Base material layer / resin layer / inorganic layered compound layer / additional layer J / additional layer K / additional layer L (Configuration 7)
Is mentioned.
Here, the additional layers A, B, D, F, I, and K may have the same composition as the inorganic layered compound layer, and the additional layers C, E, G, H, J, and L have the same composition as the resin layer. There may be.

  The thickness of each layer which comprises the multilayer structure obtained with the manufacturing method of this invention is not specifically limited. The thickness of the inorganic layered compound layer and the resin layer is usually 1 μm to 50 μm when the multilayer structure obtained in the present invention is used as a gas barrier material. From the viewpoint of bending resistance, the thickness of the inorganic layered compound layer is preferably thinner than the thickness of the resin layer. The thickness of the additional layer is usually 1 μm to 50 μm. When the anchor coat layer is provided on the base material layer, the thickness of the anchor coat layer is usually 0.01 to 5 μm.

  Each layer which comprises the multilayer structure of this invention may contain various additives, such as a ultraviolet absorber, a coloring agent, and antioxidant, as needed.

The multilayer structure obtained by the production method of the present invention includes a tire, a screw, a liquid crystal display, a flexible display substrate such as an organic EL or an optical component member such as a sealing material, a substrate such as a solar cell or a dye-sensitized solar cell, Examples thereof include an electronic component member such as a sealing material, and a vacuum heat insulating material panel.
When the multilayer structure is used, for example, as a display substrate, it can meet the demands for weight reduction and enlargement compared to a glass substrate that is heavy, easily broken, and difficult to enlarge, and has a high degree of freedom in shape. Curved surface display is possible. Furthermore, since a roll-to-roll system is possible, the productivity is better than glass and it is advantageous in terms of cost reduction. In addition, the gas barrier property of water vapor or air is higher than that of a substrate using a conventional plastic or the like. For example, the problem of deteriorating the liquid crystal in the liquid crystal cell, resulting in a display defect and degrading the display quality can be solved. .
When used as a substrate for silicon-type or dye-sensitized solar cells, if the multilayer structure obtained in the present invention is used as a back sheet or a front plate, gas such as water vapor or oxygen is transferred to electrodes, semiconductors, dyes, electrolytes. It is possible to suppress deterioration of photoelectric conversion characteristics caused by acting on the liquid crystal. Moreover, since it is excellent also in heat resistance, it can be used suitably also when forming a silicon layer etc. with a thin film. Further, when used as an electronic component member, it is suitable for use as a printed wiring board because it is excellent in heat resistance and excellent in alkali resistance and acid resistance during etching.
Further, by using the multilayer structure obtained by the production method of the present invention as a packaging material, it is possible to prevent oxygen and water vapor deterioration of the contents packaged with the packaging material. When the multilayer structure is used as a packaging material, examples of the shape include a film, a bag, a pouch, a bottle, a bottle cap, a carton container, a cup, a plate, a tray, a tank, and a tube. The contents packed by the multilayer structure obtained by the production method of the present invention include cakes, pastries such as castella, Japanese sweets such as Daifuku and mochi, snacks such as potato chips, and fishery products such as bamboo rings and rice cakes. Examples include processed products, miso, pickles, rice cakes, meatballs, hamburgers, hams and sausages, beverages such as coffee, tea and juice, dairy products such as milk and yogurt, cooked rice and curry. In addition to food products, toiletries such as detergents, baths, and cosmetics, fuels such as gasoline and hydrogen gas, pharmaceuticals and medical devices such as powders, tablets, eye drops, and infusion bags, electronic components such as hard disks and silicon wafers, It can also be used as a packaging material for electronic devices.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these. Measurement methods for various physical properties are described below.

[Thickness measurement]
The thickness of 0.5 μm or more was measured using a commercially available digital thickness gauge (contact thickness gauge, trade name: ultra-high precision deci-micro head MH-15M, manufactured by Nippon Optical Co., Ltd.). The thickness of less than 0.5 μm was determined by cross-sectional observation with a transmission electron microscope (TEM).

(Particle size measurement)
Measurement was performed using a laser diffraction / scattering particle size distribution analyzer (LA910, manufactured by Horiba, Ltd.). The coating liquids (1) to (3) described below are diluted, the average particle size of the inorganic layered compound in the diluted solution is measured with a flow cell at an optical path length of 4 mm, and the obtained average particle size is determined as the inorganic layered compound. The average particle size L was considered.
In addition, without diluting the coating liquids (1) to (3), the average particle diameter of the inorganic layered compound in the coating liquid was measured at an optical path length of 50 μm using a paste cell, When the value of the average particle diameter L obtained with the diluted solution almost coincided, it was determined that the inorganic layered compound was sufficiently swollen and cleaved in the dispersion.

[Aspect ratio calculation]
Using an X-ray diffractometer (XD-5A, manufactured by Shimadzu Corporation), the inorganic layered compound itself was subjected to diffraction measurement by a powder method. As a result, the unit thickness a of the inorganic stratiform compound was determined, and the aspect ratio Z was calculated from the equation Z = L / a using the particle size L determined by the above-described method.

[Distance between inorganic layered compounds]
Using an X-ray diffractometer (XD-5A, manufactured by Shimadzu Corporation), diffraction measurement is performed by a powder method to determine the interlayer distance of the inorganic layered compound in the inorganic layered compound layer included in the preliminary structure and the multilayer structure. Asked.
In each of the examples and comparative examples, the same heat treatment as the drying treatment and heat treatment performed until the preliminary structure is obtained is performed on the coating liquids (1) to (3) containing the inorganic layered compound, and the interlayer distance is measured by the above method. 1 was determined. The interlayer distance 1 was considered as the interlayer distance of the inorganic layered compound in the inorganic layered compound layer in the preliminary structure.
Further, in each of the examples and comparative examples, the same heat treatment as the drying treatment and heat treatment performed until the multilayer structure is obtained is performed on the coating liquids (1) to (3) containing the inorganic layered compound, and the above method is used. The interlayer distance 2 was determined. The interlayer distance 2 was regarded as the interlayer distance of the inorganic layered compound in the inorganic layered compound layer in the multilayer structure.

[Measurement of cation concentration of inorganic layered compounds]
About the below-mentioned coating liquid (1)-(3), the sodium ion and lithium ion density | concentration were measured using the inductively coupled plasma optical emission spectrometer (VISTA-PRO, Agilent Technologies). The sample preparation method is as follows. After 0.5 g of sample was collected in an evaporating dish, it was dry ashed (500 ° C.) with an electric furnace to remove organic substances. Dissolve the residue on the evaporating dish with 0.4 mL of 36% high-purity hydrochloric acid and dilute it to 10 mL with ultrapure water. It was measured. Thereafter, from the solid content concentration of the inorganic layered compound dispersed in the coating liquids (1) to (3), the inorganic layered compound layer formed using the coating liquids (1) to (3) The sodium concentration and the lithium concentration were calculated and used as the sodium ion and lithium ion concentrations. The hydrogen ion concentration in the inorganic layered compound layer formed using the coating liquid (2) is determined from the sodium ion concentration in the inorganic layered compound layer formed using the coating liquid (1). A value obtained by subtracting the sodium ion concentration and the lithium ion concentration in the inorganic layered compound layer formed using the liquid (2) was used.

[Adhesion evaluation]
On the surface of the multilayer structure that was allowed to stand for 24 hours under an atmosphere of 23 ° C. and 50% RH, a 1 mm square 100-cut grid-like cut was made so as to penetrate the film with a cutter knife, and tape (No. 2561 manufactured by Nichiban Co., Ltd.) was peeled off in the vertical direction, and the peeling between the resin layer and the inorganic layered compound layer was evaluated by the number of peeling per 100 grids.
○ ... 0-50% peeling × ... 51-100% peeling

(Water resistance evaluation)
A multilayer structure having a size of 50 mm × 50 mm was immersed in water at 23 ° C. for 1 hr. Thereafter, peeling of the coating film was visually confirmed and evaluated.
○ ・ ・ ・ No peeling × ・ ・ ・ Partial peeling or whole surface peeling

(Oxygen permeability measurement)
Based on JIS K7126, measurement was performed under conditions of 23 ° C. and 90% RH with an oxygen transmission rate measuring device (OX-TRANML, manufactured by MOCON).

(Measurement of water vapor transmission rate)
Based on JIS K7129B, it measured with 40 degreeC 90% RH conditions with the water-vapor-permeation rate measuring apparatus (PERMATRAN W 3/33).

[Preparation of coating solution]
(1) Preparation of coating liquid (1) High-purity montmorillonite was added to the stirring system under high-speed stirring (3,000 rpm, peripheral speed = 8.2 m / min) of ion-exchanged water 1000 g at room temperature with a stirrer. (Product name: Kunipia G; manufactured by Kunimine Kogyo Co., Ltd.) Gradually add 30 g, and after completion of the addition, stirring is continued at room temperature for 60 minutes to form an inorganic layered compound layer (1) Got. The cleaved montmorillonite average particle size L in the coating liquid (1) was 560 nm, the value a obtained from powder X-ray diffraction was 1.22 nm, and the aspect ratio Z was 460. Further, the sodium ion concentration in the inorganic layered compound layer formed from the coating liquid (1) was 900 μmol / g, and the lithium ion concentration was below the measurement limit.

(2) Preparation of coating liquid (2) About 1030 g of coating liquid (1), 30 g of ion exchange resin (Duolite C255LFH; manufactured by Nihon Suken Co., Ltd.) was added, and then stirred for 30 minutes to obtain a mixed liquid ( 1) was obtained. Thereafter, the mixture (1) is filtered using a filter (fluid opening 297 μm) to remove the residue of the ion exchange resin, and the coating liquid (2) used to form the inorganic layered compound layer Got. The cleaved montmorillonite average particle diameter L in the coating liquid (2) was 560 nm, the a value obtained from powder X-ray diffraction was 1.22 nm, and the aspect ratio Z was 460. In the inorganic layered compound layer formed from the coating liquid (2), the sodium ion concentration was 40 μmol / g, the lithium ion concentration was below the measurement limit, and the hydrogen ion concentration was 860 μmol / g.

(3) Preparation of coating liquid (3) 60 g of ion exchange resin (Duolite C-20LF; manufactured by Nihonsuiken Co., Ltd.) and 600 g of 10% aqueous lithium chloride solution were mixed, and then stirred at high speed for 30 minutes (3, 000 rpm, peripheral speed = 8.2 m / min), and then the ion exchange resin was recovered to produce a lithium ion exchange resin. About 1030 g of coating liquid (1), 30 g of this lithium ion exchange resin was added, and then stirred for 30 minutes to obtain a mixed liquid (2). Thereafter, the mixture (2) is filtered using a filter (fluid aperture of 297 μm) to remove the residue of the ion exchange resin, and the coating liquid (3) used to form the inorganic layered compound layer Got. The cleaved montmorillonite average particle diameter L in the coating liquid (3) was 560 nm, the a value obtained from powder X-ray diffraction was 1.22 nm, and the aspect ratio Z was 460. Further, the sodium ion concentration in the inorganic layered compound layer formed from the coating solution (3) was below the measurement limit, and the lithium ion concentration was 850 μmol / g.

(4) Preparation of coating liquid (4) In a glass container, 941 g (5.0 mol) of 2-hydroxy-6-naphthoic acid, 273 g (2.5 mol) of 4-aminophenol, 415.3 g of isophthalic acid ( 2.5 mol) and 1123 g (11 mol) of acetic anhydride. After sufficiently replacing the inside of the container with nitrogen gas, the temperature was raised to 150 ° C. over 15 minutes under a nitrogen gas stream while stirring, and the mixture was refluxed for 3 hours while maintaining the temperature. Thereafter, the temperature was raised to 320 ° C. over 170 minutes while distilling off by-product acetic acid and unreacted acetic anhydride, and the contents were taken out. 0.5 g of the content was added to 9.5 g of N, N′-dimethylacetamide and completely dissolved to obtain a coating liquid (4) used for forming a heat-reactive composition layer.

(5) Preparation of coating liquid (5) Dispersion kettle (trade name: Despa MH-L, manufactured by Asada Tekko Co., Ltd.), cyclohexanone 206 g and cresol novolac epoxy compound (Unidic V8000C1 DIC Co., Ltd.) ) 25.8 g and 100 g of polyimide skeleton-containing compound (Unidic V8000 DIC Co., Ltd.) are mixed, stirred at high speed (3000 rpm, peripheral speed = 8.2 m / min), and dissolved by stirring at room temperature for 30 minutes. The coating liquid (5) used for forming a heat-reactive composition layer was obtained.

[Example 1]
A copper foil having a thickness of 18 μm (3EL-VLP, manufactured by Mitsui Mining & Smelting Co., Ltd .; hereinafter referred to as Cu) was used as a base material layer. The above-described coating liquid (4) is applied to the MIII-treated surface of the base material layer with an applicator (clearance 150 μm), dried (80 ° C., 20 minutes), and a thermally reactive composition is formed on the base material layer. A physical layer (I) was formed. Thereafter, on the thermally reactive composition layer (I), in the same manner as described above, the coating liquid (2) is coated with an applicator (clearance 150 μm) and dried (80 ° C., 20 minutes). The inorganic layered compound layer (I) was formed to obtain a preliminary structure (1). The preliminary structure (1) was heat-treated at 290 ° C. for 3 hours in a nitrogen atmosphere to obtain a multilayer structure (1) composed of a base material layer, a resin layer, and an inorganic layered compound layer. The resin layer had a thickness of 5 μm, and the inorganic layered compound layer had a thickness of 2 μm. Thereafter, the multilayer structure (1) was evaluated. The results are shown in Table 1.

[Example 2]
A polyimide film having a thickness of 50 μm (Kapton 200H / V, manufactured by Toray DuPont Co., Ltd .: PI) was used for the base material layer. The substrate layer is subjected to corona treatment, and the above-mentioned coating liquid (5) is applied to the corona-treated surface with an applicator (clearance 150 μm) and dried (80 ° C., 20 minutes), and the substrate layer A heat-reactive composition layer (I) was formed thereon. Thereafter, on the thermally reactive composition layer (I), in the same manner as described above, the coating liquid (2) is coated with an applicator (clearance 150 μm) and dried (80 ° C., 20 minutes). The inorganic layered compound layer (I) was formed to obtain a preliminary structure (2). The preliminary structure (2) was heat-treated at 200 ° C. for 1 hour in an air atmosphere to obtain a multilayer structure (2) composed of a base material layer, a resin layer, and an inorganic layered compound layer. The resin layer had a thickness of 5 μm, and the inorganic layered compound layer had a thickness of 2 μm. Thereafter, the multilayer structure (2) was evaluated. The results are shown in Table 1.

[Comparative Example 1]
Using a copper foil having a thickness of 18 μm as a base material layer, the above-mentioned coating liquid (4) was applied to the MIII-treated surface of the base material layer with an applicator (clearance 150 μm), and dried (80 ° C., 20 And the thermally reactive composition layer (I) was formed on the base material layer. Thereafter, heat treatment was performed at 290 ° C. for 3 hours to form a laminate composed of a base material layer and a resin layer. On the resin layer, the coating liquid (2) is applied with an applicator (clearance 150 μm) using the coating liquid (2) in the same manner as described above, and then dried (80 ° C., 20 minutes). The inorganic layered compound layer (I) was formed to obtain a preliminary structure (3). The preliminary structure (3) was heat-treated at 290 ° C. for 3 hours in a nitrogen atmosphere to obtain a multilayer structure (3) composed of a base material layer, a resin layer, and an inorganic layered compound layer. The resin layer had a thickness of 5 μm, and the inorganic layered compound layer had a thickness of 2 μm. Thereafter, the multilayer structure (3) was evaluated. The results are shown in Table 1.

[Comparative Example 2]
Using a polyimide film having a thickness of 50 μm as a base material layer, the base material layer is subjected to corona treatment, and the above-mentioned coating solution (5) is applied to the corona-treated surface with an applicator (clearance 150 μm) and dried. It processed (80 degreeC, 20 minutes), and formed the heat-reactive composition layer (I) on the base material layer. Thereafter, a heat treatment was performed at 200 ° C. for 1 hour to form a laminate composed of a base material layer and a resin layer. On the resin layer, the coating liquid (2) is applied with an applicator (clearance 150 μm) using the coating liquid (2) in the same manner as described above, and then dried (80 ° C., 20 minutes). The inorganic layered compound layer (I) was formed to obtain a preliminary structure (4). The preliminary structure (4) was heat-treated at 200 ° C. for 1 hour in an air atmosphere to obtain a multilayer structure (4) composed of a base material layer, a resin layer, and an inorganic layered compound layer. The resin layer had a thickness of 5 μm, and the inorganic layered compound layer had a thickness of 2 μm. Thereafter, the multilayer structure (4) was evaluated. The results are shown in Table 2.

[Example 3]
On the inorganic layered compound layer (I) of the preliminary structure (1) of Example 1, the coating liquid (4) was further coated with an applicator in the same manner as the thermally reactive composition layer (I) (clearance). 150 μm), followed by drying (80 ° C., 20 minutes) to form a heat-reactive composition layer (II) to obtain a preliminary structure (5). The preliminary structure (5) was heat-treated at 290 ° C. for 3 hours in a nitrogen atmosphere to obtain a multilayer structure (5) composed of a base material layer, a resin layer, an inorganic layered compound layer, and a resin layer. The thickness of each resin layer was 5 μm, and the thickness of the inorganic layered compound layer was 2 μm. Thereafter, the multilayer structure (5) was evaluated. The results are shown in Tables 2 and 3.

[Comparative Example 3]
On the inorganic layered compound layer of the multilayer structure (3) of Comparative Example 1, the coating liquid (4) was further coated with an applicator in the same manner as the thermally reactive composition layer (I) (clearance 150 μm). Thereafter, drying treatment (80 ° C., 20 minutes) was performed to form a heat-reactive composition layer (II) to obtain a preliminary structure (6). The preliminary structure (6) was heat-treated at 290 ° C. for 3 hours in a nitrogen atmosphere to obtain a multilayer structure (6) composed of a base material layer, a resin layer, an inorganic layered compound layer, and a resin layer. . The thickness of each resin layer was 5 μm, and the thickness of the inorganic layered compound layer was 2 μm. Thereafter, the multilayer structure (6) was evaluated. The results are shown in Tables 2 and 3.

[Example 4]
In the same manner as in Example 1 except that the coating liquid (2) was used in place of the coating liquid (4) and the coating liquid (4) was used in place of the coating liquid (2), the preliminary structure (7 ) The preliminary structure (7) was heat-treated at 290 ° C. for 3 hours in a nitrogen atmosphere to obtain a multilayer structure (7) composed of a base material layer, an inorganic layered compound layer, and a resin layer. The inorganic layered compound layer had a thickness of 2 μm, and the resin layer had a thickness of 5 μm. Thereafter, the multilayer structure (7) was evaluated. The results are shown in Table 4.

[Comparative Example 4]
The preliminary structure (8) was prepared in the same manner as in Comparative Example 1 except that the coating liquid (2) was used instead of the coating liquid (4), and the coating liquid (4) was used instead of the coating liquid (2). ) The preliminary structure (8) was heat-treated at 290 ° C. for 3 hours in a nitrogen atmosphere to obtain a multilayer structure (8) composed of a base material layer, an inorganic layered compound layer, and a resin layer. The inorganic layered compound layer had a thickness of 2 μm, and the resin layer had a thickness of 5 μm. Thereafter, the multilayer structure (8) was evaluated. The results are shown in Table 4.

[Example 5]
A preliminary structure (9) was prepared in the same manner as in Example 2 except that the coating liquid (2) was used instead of the coating liquid (5), and the coating liquid (5) was used instead of the coating liquid (2). ) The preliminary structure (9) was heat-treated at 250 ° C. for 1 hour in an air atmosphere to obtain a multilayer structure (9) composed of a base material layer, an inorganic layered compound layer, and a resin layer. The inorganic layered compound layer had a thickness of 2 μm, and the resin layer had a thickness of 5 μm. Thereafter, the multilayer structure (9) was evaluated. The results are shown in Tables 5 and 6.

[Example 6]
A preliminary structure (10) was obtained in the same manner as in Example 5 except that the coating liquid (3) was used instead of the coating liquid (2). The preliminary structure (10) was heat-treated at 250 ° C. for 1 hour in an air atmosphere to obtain a multilayer structure (10) composed of a base material layer, an inorganic layered compound layer, and a resin layer. The inorganic layered compound layer had a thickness of 2 μm, and the resin layer had a thickness of 5 μm. Thereafter, the multilayer structure (10) was evaluated. The results are shown in Tables 5 and 6.

[Example 7]
In the same manner as in Example 5, a preliminary structure (11) was obtained. The preliminary structure (11) was heat-treated at 200 ° C. for 1 hour in an air atmosphere to obtain a multilayer structure (11) composed of a base material layer, an inorganic layered compound layer, and a resin layer. The inorganic layered compound layer had a thickness of 2 μm, and the resin layer had a thickness of 5 μm. Thereafter, the multilayer structure (11) was evaluated. The results are shown in Tables 5 and 6.

[Comparative Example 5]
A preliminary structure (12) was obtained in the same manner as in Example 5 except that the coating liquid (1) was used instead of the coating liquid (2). The preliminary structure (12) was heat-treated at 250 ° C. for 1 hour in an air atmosphere to obtain a multilayer structure (12) composed of a base material layer, an inorganic layered compound layer, and a resin layer. The inorganic layered compound layer had a thickness of 2 μm, and the resin layer had a thickness of 5 μm. Thereafter, the multilayer structure (12) was evaluated. The results are shown in Tables 5 and 6.

[Comparative Example 6]
Using a polyimide film having a thickness of 50 μm as a base material layer, the base material layer is subjected to corona treatment, and the above-mentioned coating solution (2) is applied to the corona-treated surface with an applicator (clearance of 150 μm) and dried. It processed (80 degreeC, 20 minutes), and formed the inorganic layered compound layer (I) on the base material layer. Thereafter, a heat treatment was performed at 250 ° C. for 1 hour to form a laminate composed of a base material layer and an inorganic layered compound layer. On the inorganic layered compound layer, the coating liquid (5) is coated with an applicator (clearance: 150 μm) using the coating liquid (5) in the same manner as described above, and then dried (80 ° C., 20 minutes). The heat-reactive composition layer (I) was formed to obtain a preliminary structure (14). The preliminary structure (14) was heat-treated at 250 ° C. for 1 hour in an air atmosphere to obtain a multilayer structure (14) composed of a base material layer, an inorganic layered compound layer, and a resin layer. The inorganic layered compound layer had a thickness of 2 μm, and the resin layer had a thickness of 5 μm. Thereafter, the multilayer structure (14) was evaluated. The results are shown in Tables 5 and 6.

[Comparative Example 7]
A preliminary structure (15) was obtained in the same manner as in Comparative Example 7 except that the coating liquid (3) was used instead of the coating liquid (2). The preliminary structure (15) was heat-treated at 250 ° C. for 1 hour in an air atmosphere to obtain a multilayer structure (15) composed of a base material layer, an inorganic layered compound layer, and a resin layer. The inorganic layered compound layer had a thickness of 2 μm, and the resin layer had a thickness of 5 μm. Thereafter, the multilayer structure (15) was evaluated. The results are shown in Tables 5 and 6.

[Example 8]
In the same manner as in Example 5, a preliminary structure (11) was obtained. The preliminary structure (11) was heat-treated at 350 ° C. for 1 hour in an air atmosphere to obtain a multilayer structure (18) composed of a base material layer, an inorganic layered compound layer, and a resin layer. The inorganic layered compound layer had a thickness of 2 μm, and the resin layer had a thickness of 5 μm. Thereafter, the multilayer structure (18) was evaluated. The results are shown in Tables 7 and 8.

[Reference Example 1]
A multilayer structure comprising a base material layer, an inorganic layered compound layer, and a resin layer in the same manner as in Example 5 except that the coating was performed with a spin coater (rotation speed 1000 rpm, 10 seconds) instead of coating with an applicator. Body (16) was obtained. The inorganic layered compound layer had a thickness of 0.05 μm, and the resin layer had a thickness of 1 μm. Thereafter, the oxygen transmission rate of the multilayer structure (16) was measured and found to be 10 cc / m ² · day · atm.

[Reference Example 2]
A multilayer structure comprising a base material layer, an inorganic layered compound layer and a resin layer in the same manner as in Comparative Example 5 except that the coating was performed by a spin coater (rotation speed 1000 rpm, 10 seconds) instead of coating by an applicator. Body (17) was obtained. The inorganic layered compound layer had a thickness of 0.05 μm, and the resin layer had a thickness of 1 μm. Thereafter, the oxygen transmission rate of the multilayer structure (17) was measured and found to be 50 cc / m ² · day · atm.

Claims (8)

A method for producing a multilayer structure including a base material layer, an inorganic layered compound layer, and a resin layer, the method comprising producing all of the following steps.
(1) An inorganic layered compound dispersion containing an inorganic layered compound and a liquid medium is applied to the surface of the base material layer to form a coating film, and then subjected to a drying treatment at a temperature of 20 to 150 ° C., Step (2) of forming the inorganic layered compound layer (I) by removing the liquid medium from the coating film, forming the thermally reactive composition layer (I) on the inorganic layered compound layer (I), Step (3) for manufacturing the structure: The preliminary structure is heated to reduce the interlayer distance of the inorganic layered compound in the inorganic layered compound layer (I), and the components in the thermally reactive composition layer (I) A process of forming a resin layer by reacting to obtain a multilayer structure A method for producing a multilayer structure including a base material layer, an inorganic layered compound layer, and a resin layer, the method comprising producing all of the following steps.
(1) Step of forming the heat-reactive composition layer (I) on the surface of the substrate layer (2) An inorganic layered compound dispersion containing an inorganic layered compound and a liquid medium on the heat-reactive composition layer (I) To form a coating film, followed by drying under a temperature condition of 20 to 150 ° C., removing the liquid medium from the coating film to form an inorganic layered compound layer (I), Step (3) for producing the preliminary structure: heating the preliminary structure to narrow the interlayer distance of the inorganic layered compound in the inorganic layered compound layer (I), and the components in the thermally reactive composition layer (I) Is a process of forming a resin layer by reacting to obtain a multilayer structure A method for producing a multilayer structure including a base material layer, an inorganic layered compound layer, and a resin layer, the method comprising producing all of the following steps.
(1) Step of forming the heat-reactive composition layer (I) on the surface of the substrate layer (2) An inorganic layered compound dispersion containing an inorganic layered compound and a liquid medium on the heat-reactive composition layer (I) To form an inorganic layered compound layer (I) by forming a coating film, followed by drying under a temperature condition of 20 to 150 ° C., removing the liquid medium from the coating film (3) A step of producing a preliminary structure by forming a heat-reactive composition layer (II) on the inorganic layered compound layer (I). (4) An inorganic layered compound layer by heating the preliminary structure. A step of obtaining a multilayer structure by narrowing the interlayer distance of the inorganic layered compound in (I) and reacting the components in the thermally reactive composition layers (I) and (II) to form a resin layer The method for producing a multilayer structure according to any one of claims 1 to 3, wherein the aspect ratio of the inorganic layered compound in the inorganic layered compound dispersion is 20 to 10,000. The method for producing a multilayer structure according to any one of claims 1 to 4, wherein a volume fraction of the inorganic layered compound in the inorganic layered compound layer contained in the multilayer structure is 90 to 100 vol%. The method for producing a multilayer structure according to any one of claims 1 to 5, wherein a sodium ion concentration in the inorganic layered compound layer contained in the multilayer structure is 400 µmol / g or less. The method for producing a multilayer structure according to any one of claims 1 to 6, wherein the total concentration of lithium ions and hydrogen ions in the inorganic layered compound layer contained in the multilayer structure is 400 µmol / g or more. A method for producing a laminate by removing a base material layer from the multilayer structure according to claim 1.