Hydroxyl group-containing polyamide resin composition, laminate, packaging material, and gas barrier material

Abstract

To provide a resin composition that has high gas barrier properties and can be applied as a coating agent. [Solution] A hydroxyl group-containing polyamide resin composition comprising a hydroxyl group-containing polyamide resin (A) that satisfies the following (1) and (2), and a compound (B) having a metalloxane bond. (1) The amount of hydroxyl groups is 500 to 6000 eq / t (2) When the total amount of all dicarboxylic acid components and all diamine components constituting the hydroxyl group-containing polyamide resin (A) is set to 100 mol%, it contains 1 mol% or more of the diamine (a1) of the following formula. JPEG2026068032000009.jpg56170 (In the formula, X and Y represent direct bonds or alkylene groups, and R1 to R4 represent H or organic groups.)

Description

[Technical Field]

[0001] The present invention relates to a hydroxyl group-containing polyamide resin composition, and laminates, packaging materials, and gas barrier materials using the same. [Background technology]

[0002] Traditionally, packaging materials used for food, medical products, and other items have been required to prevent or suppress deterioration of their contents. This requires preventing gases that can alter the contents (e.g., oxygen) from passing through the packaging material and coming into contact with the contents. Therefore, packaging materials are required to possess gas barrier properties that block these gases, and the required performance is increasing year by year.

[0003] Patent Document 1 discloses a gas barrier laminate having a gas barrier thin film made of a metal compound formed by physical vapor deposition and a polyamide film formed by vapor deposition synthesis on a resin film substrate. Patent Document 2 discloses polyamide resin and a resin composition compounded with polyamide resin and glass fibers as gas barrier materials. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2002-254552 [Patent Document 2] Japanese Patent Application Publication No. 2-4831 [Overview of the project] [Problems that the invention aims to solve]

[0005] The method described in Patent Document 1 required specialized equipment to form a film by vapor deposition. In the method described in Patent Document 2, polyamide resin or resin composition was processed into a film or molded body by press molding, making it difficult to apply to applications requiring thinner films, such as coating films.

[0006] This invention was made against the backdrop of the problems of the prior art. Specifically, the problem that this invention aims to solve is to provide a resin composition that has high gas barrier properties and can be applied as a coating agent. [Means for solving the problem]

[0007] As a result of diligent research, the present inventors have discovered that a resin composition containing a polyamide resin having a specific amount of hydroxyl groups and a compound having metalloxane bonds exhibits high gas barrier properties due to the interaction between the polyamide resin and the metalloxane bonds, while also exhibiting excellent solvent solubility, thus leading to the present invention. That is, the present invention consists of the following configuration.

[0008] [1] A hydroxyl group-containing polyamide resin composition comprising a hydroxyl group-containing polyamide resin (A) that satisfies the following (1) and (2), and a compound (B) having a metalloxane bond. (1) The hydroxyl group content is 500-6000 eq / t. (2) When the total amount of all dicarboxylic acid components and all diamine components constituting the hydroxyl group-containing polyamide resin (A) is set to 100 mol%, it contains 1 mol% or more of an aromatic diamine (c) in which two amino groups are located on substituents that are at the meta position of the aromatic ring. [2] The hydroxyl group-containing polyamide resin composition according to [1], wherein the compound (B) having a metalloxane bond contains at least one metal element selected from silicon, titanium, aluminum, and zirconium. [3] The hydroxyl group-containing polyamide resin composition according to [1] or [2], wherein the compound (B) having a metalloxane bond is a compound derived from at least one of a trifunctional metal alkoxy compound and a tetrafunctional metal alkoxy compound. [4] The hydroxyl group-containing polyamide resin composition according to any one of [1] to [3], wherein the aromatic diamine (c) in which the two amino groups constituting the hydroxyl group-containing polyamide resin (A) are located on substituents that are each located at the meta position of the aromatic ring is metaxylylenediamine. [5] A hydroxyl group-containing polyamide resin composition according to any one of the above [1] to [4], further containing an organic solvent. [6] A hydroxyl group-containing polyamide resin composition according to any one of the above [1] to [5], further comprising a curing agent. [7] A hydroxyl group-containing polyamide resin composition according to any one of [1] to [6], further containing a layered inorganic material. [8] A laminate having a layer made of a hydroxyl group-containing polyamide resin composition according to any one of [1] to [7] above, and one or more layers selected from the group consisting of film, sheet, metal vapor deposition layer, woven fabric, nonwoven fabric, and paper. [9] A packaging material having the laminate described in [8] above as a component.

[10] A gas barrier material having a layer made of a hydroxyl group-containing polyamide resin composition according to any one of [1] to [7] above. [Effects of the Invention]

[0009] The hydroxyl group-containing polyamide resin composition of the present invention overcomes a conventional challenge for polyamide resins: high gas barrier properties under high humidity, providing remarkable industrial value. Furthermore, due to its excellent solvent solubility, it can be widely used as a laminate applied to various film substrates as a coating layer. Moreover, the presence of hydroxyl groups improves compatibility with metalloxane components and dispersibility of layered inorganic materials, further enhancing gas barrier properties. [Modes for carrying out the invention]

[0010] One embodiment of the present invention will be described in detail below. However, the present invention is not limited thereto, and can be implemented in various modified forms within the scope described.

[0011] <Properties of the Hydroxyl-Containing Polyamide Resin (A)> The hydroxyl-containing polyamide resin (A) used in the present invention (hereinafter also referred to as polyamide resin (A) or simply component (A)) is a polyamide resin having a hydroxyl group content of 500 to 6000 eq / t. The hydroxyl group content of the hydroxyl-containing polyamide resin (A) is preferably 600 eq / t or more, more preferably 700 eq / t or more. Also, 5000 eq / t or less is preferable, and 4000 eq / t or less is more preferable. When the hydroxyl group content is at least the above lower limit value, the affinity with an organic solvent and the dispersibility with additives such as layered inorganic substances used in combination become good, and the gas barrier property tends to be further improved. Also, if the hydroxyl group content is at most the above upper limit value, the hygroscopicity of the polyamide resin is suppressed, and the gas barrier property under high humidity is kept good. The hydroxyl group content of the hydroxyl-containing polyamide resin (A) can be adjusted by containing a specific amount of a component having a hydroxyl group as the diamine component (a), dicarboxylic acid component (b), etc. constituting the hydroxyl-containing polyamide resin (A).

[0012] The reduced viscosity of the hydroxyl-containing polyamide resin (A) used in the present invention is preferably 0.05 dl / g or more, more preferably 0.1 dl / g or more. Also, it is preferably 2.0 dl / g or less, more preferably 1.5 dl / g or less. When the reduced viscosity is less than 0.05 dl / g, the mechanical properties of the hydroxyl-containing polyamide resin (A) may become low, and when it exceeds 2.0 dl / g, the viscosity during melting becomes high, the processability deteriorates, or the solubility in an organic solvent tends to decrease.

[0013] The glass transition temperature of the hydroxyl-containing polyamide resin (A) used in the present invention is preferably 60°C or more, more preferably 70°C or more. Also, it is preferably 200°C or less, more preferably 190°C or less. When the glass transition temperature is less than 60°C, the mechanical properties of the hydroxyl-containing polyamide resin (A) may become low, and when it exceeds 200°C, the solubility in an organic solvent tends to decrease.

[0014] <Components of hydroxyl group-containing polyamide resin (A)> The hydroxyl group-containing polyamide resin (A) in the present invention is a polymer having repeating units formed by a polycondensation reaction between a polyhydric amine component and a polyhydric carboxylic acid component. The polymer may further have a chemical structure copolymerized with an aminocarboxylic acid component and / or a lactam component. Diamine component (a) is mainly used as the polyhydric amine component, but it is also possible to use trifunctional or higher amine components in combination. Dicarboxylic acid component (b) is mainly used as the polyhydric carboxylic acid component, but it is also possible to use trifunctional or higher carboxylic acid components in combination.

[0015] <Diamine component (a)> <<Aromatic ring-containing diamine (a1) having the structure shown in formula (I)>> The hydroxyl group-containing polyamide resin (A) used in the present invention has an aromatic ring-containing diamine (a1) having the structure shown in formula (I) (hereinafter also referred to as the diamine (a1) of formula (I) or component (a1)) as a constituent component. Equation (I) [ka] (In formula (I), X and Y represent direct bonds or alkylene groups, and R1 to R4 represent hydrogen or monovalent organic groups.) Preferred examples of cases where R1 to R4 are monovalent organic groups include alkyl groups such as methyl and ethyl groups, aryl groups such as phenyl groups, unsaturated hydrocarbon groups such as vinyl groups, and hydroxyl groups.

[0016] In the present invention, the diamine (a1) of formula (I) is, for example, an aromatic diamine without a hydroxyl group such as m-phenylenediamine, 5-methyl-1,3-benzenediamine, 2,4-diaminotoluene, 4,6-dimethyl-1,3-benzenediamine, 4,5,6-trimethyl-1,3-benzenediamine, 4-ethyl-6-methyl-1,3-benzenediamine, an aromatic diamine having a hydroxyl group such as 3,5-diaminophenol, 2,4-diaminophenol, 2,6-diaminophenol, m-xylylenediamine, 5-methyl-1,3-benzenedimethaneamine, 4,6-dimethyl-1,3-benzenedimethaneamine, 2, Aliphatic diamines having aromatic rings but lacking hydroxyl groups, such as 4,6-triethyl-1,3-benzenedimethaneamine, 4,6-bis(1-methylethyl)-1,3-benzenedimethaneamine, and 4,6-bis(1,1-dimethylethyl)-1,3-benzenedimethaneamine; aliphatic diamines having both hydroxyl groups and aromatic rings, such as 3,5-bis(aminomethyl)phenol, 2,4-bis(aminomethyl)phenol, and 2,6-bis(aminomethyl)phenol; and derivatives of the aforementioned aromatic diamines and aliphatic diamines having aromatic rings can be used, and these can be used alone or in combination, but are not limited to these. Among these, m-phenylenediamine and m-xylylenediamine are preferred from the viewpoint of their high interaction ability between benzene rings.

[0017] The diamine (a1) of formula (I) is preferably 1 mol% or more, and more preferably 2 mol% or more, when the total amount of all dicarboxylic acid components and all diamine components constituting the hydroxyl group-containing polyamide resin (A) is set to 100 mol%. The presence of component (a1) in the hydroxyl group-containing polyamide resin (A) enables interaction through hydrophobic bonds between benzene rings, and because it adopts a pseudo-crosslinking structure, the gas barrier properties tend to improve. It is also acceptable for all of the diamine components constituting the hydroxyl group-containing polyamide resin (A) to be component (a1).

[0018] <<Other diamines (a2)>> In the present invention, the diamine component (a) constituting the hydroxyl group-containing polyamide resin (A) may include diamine components other than the diamine (a1) of formula (I) (hereinafter also referred to as other diamine (a2) or (a2) component). Examples of (a2) component include o-phenylenediamine, p-phenylenediamine, 4,4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, metatolylenediamine, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodi Phenylthioether, 3,3'-dimethyl-4,4'-diaminodiphenylthioether, 3,3'-diethoxy-4,4'-diaminodiphenylthioether, 3,3'-diaminodiphenylthioether, 4,4'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobenzophenone, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,3'-dimethoxy-4,4'-diaminodiphenylmethane, 3 ,3',5,5'-tetraethyl-4,4'-diaminodiphenylmethane, 2,2'-bis(3-aminophenyl)propane, 2,2'-bis(4-aminophenyl)propane, 4,4'-diaminodiphenyl sulfoxide, benzidine, 3,3'-dimethylbenzidine, 3,3'-dimethoxybenzidine, 3,3'-diaminobiphenyl, o-xylylenediamine, p-xylylenediamine, bis(4-amino-3-methylphenyl)methane, bis(4- (amino-3,5-dimethylphenyl)methane, bis(4-amino-3-ethylphenyl)methane, bis(4-amino-3,5-diethylphenyl)methane, bis(4-amino-3-propylphenyl)methane, bis(4-amino-3,5-dipropylphenyl)methane, bis(4-amino-3-isopropylphenyl)methane, bis(4-amino-3,5-diisopropylphenyl)methane, 3,3'-dihydroxy-4,4'-diaminobiphenyl, 3,Aromatic diamines such as 3'-bis(4-hydroxy-3-aminophenyl)hexafluoropropane and their derivatives, aliphatic diamines having aromatic rings such as o-xylylenediamine and p-xylylenediamine and their derivatives, aliphatic diamines without aromatic rings such as ethylenediamine, 1,4-diaminobutane, hexamethylenediamine, nonamethylenediamine, undecamethylenediamine, dodecamethylenediamine, methylpentamethylenediamine, 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine and their derivatives, and alicyclic diamines such as bis-(4,4'-aminocyclohexyl)methane, isophoronediamine, norbornanediamine, piperazine and their derivatives can be used, and these can be used alone or in combination, but are not limited to these. Diamines having hydroxyl groups, such as 2,5-diaminophenol, 2,3-diaminophenol, 1,2-diaminoethanol, and 2-piperazinol, and their derivatives, can also be used individually or in combination. When other diamines (a2) are used, it is preferable from the viewpoint of improving mechanical properties that component (a2) contains a diamine component having an aromatic ring, with p-xylylenediamine and p-phenylenediamine being particularly preferred. The aromatic diamine component (a2) is preferably 20 mol% or more, more preferably 25 mol% or more, and even more preferably 30 mol% or more, when the total amount of all dicarboxylic acid components and all diamine components constituting the hydroxyl group-containing polyamide resin (A) is taken as 100 mol%. Furthermore, 60 mol% or less is preferred. When the amount of aromatic diamine component (a2) is within the above range, mechanical properties and gas barrier properties are good.

[0019] <Dicarboxylic acid containing a hydroxyl group (b1)> In the present invention, the dicarboxylic acid component (b) constituting the hydroxyl group-containing polyamide resin (A) is not particularly limited, but for example, a hydroxyl group can be imparted to the polyamide resin by introducing a dicarboxylic acid (b1) having a hydroxyl group. As the dicarboxylic acid (b1) having a hydroxyl group, for example, aromatic dicarboxylic acids and their ester derivatives such as 5-hydroxyisophthalic acid, 4-hydroxyisophthalic acid, 2-hydroxyisophthalic acid, 2-hydroxyterephthalic acid, 2,3-dihydroxyterephthalic acid, 2,5-dihydroxyterephthalic acid, 3-hydroxyorthophthalic acid, and 4-hydroxyorthophthalic acid can be used, and these can be used alone or in combination. Preferably, 5-hydroxyisophthalic acid, 4-hydroxyisophthalic acid, 2-hydroxyisophthalic acid, 2-hydroxyterephthalic acid, and 2,5-dihydroxyterephthalic acid are used.

[0020] The amount of hydroxyl-containing dicarboxylic acid (b1) is preferably 10 mol% or more, when the total amount of all dicarboxylic acid components and all diamine components is taken as 100 mol%. More preferably, it is 15 mol% or more, and even more preferably 20 mol% or more. If the amount of hydroxyl-containing dicarboxylic acid (b1) units is too small, the solubility in organic solvents and affinity with compounds having metalloxane bonds tend to be poor. Furthermore, it is preferably 60 mol% or less, more preferably 50 mol% or less, and even more preferably 45 mol% or less. If it exceeds 60 mol%, the ratio of total diamine component amount to total dicarboxylic acid component amount deviates significantly from 1, which can make it difficult to achieve a sufficiently high molecular weight to exhibit gas barrier properties. In addition, the gas barrier properties may decrease.

[0021] Furthermore, a dicarboxylic acid component (a2) (hereinafter also referred to as component (b2)) that does not contain a hydroxyl group can be used in combination with the hydroxyl group-containing polyamide resin (A) as the dicarboxylic acid component (b). (b2) Examples of components include aromatic dicarboxylic acids and their derivatives such as isophthalic acid, terephthalic acid, 4,4'-biphenyldicarboxylic acid, 3,3'-methylenedibenzoic acid, 4,4'-methylenedibenzoic acid, 4,4'-oxydibenzoic acid, 3,4'-oxydibenzoic acid, 4,4'-thiodibenzoic acid, 3,3'-carbonyldibenzoic acid, 4,4'-carbonyldibenzoic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, ethylenediaminebisphthalimide-4,4'-dicarboxylic acid, 3,3'-bis(4-carboxylphenyl)propane, 3,3'-bis(4-carboxylphenyl)hexafluoropropane, bis(4-carboxylphenyl)methane, and 3,3'-bis(4-carboxylphenyl)hexafluoropropane. Furthermore, examples of alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid and their acid anhydrides, and aliphatic dicarboxylic acids such as succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, and dimer acid can be given, but are not limited to these. When a dicarboxylic acid component (a2) without a hydroxyl group is used in combination, isophthalic acid is preferred from the viewpoint of improving mechanical properties due to its high interaction ability between benzene rings, and adipic acid and sebacic acid are preferred from the viewpoint of providing flexibility when formed into a coated film.

[0022] The hydroxyl group-containing polyamide resin (A) used in the present invention can be produced by polycondensing a diamine component (a) that can constitute the diamine unit and a dicarboxylic acid component (b) having a hydroxyl group that can constitute the dicarboxylic acid unit, and the degree of polymerization can be controlled by adjusting the polycondensation conditions. A small amount of monoamine or monocarboxylic acid may be added as a molecular weight modifier and end-capturing agent during polycondensation. In addition, in order to suppress the polycondensation reaction and achieve a desired degree of polymerization, the ratio (molar ratio) of the diamine component and the carboxylic acid component constituting the hydroxyl group-containing polyamide resin may be adjusted by shifting it from 1. Furthermore, it is also possible to copolymerize alcohol components of trivalent or higher hydride, carboxylic acid components of trivalent or higher hydride, etc., in addition to the above components.

[0023] <Polymerization method> A hydroxyl group-containing polyamide resin (A) can be produced by carrying out a known amidation condensation polymerization reaction. For example, the atmospheric pressure drop method can be used, but is not limited thereto.

[0024] In the atmospheric pressure dropwise method, the diamine component (a) is continuously added dropwise to a mixture of the heated and melted dicarboxylic acid component (b) under atmospheric pressure, and polycondensation is carried out while removing condensation water. The polycondensation reaction is carried out while raising the temperature of the reaction system so that the reaction temperature does not fall below the melting point of the resulting polyamide resin.

[0025] The polyamide resin produced by the polycondensation method described above can be used as is, but it may also undergo further steps to increase the degree of polymerization. Examples of steps to further increase the degree of polymerization include reactive extrusion in an extruder and solid-phase polymerization. Suitable heating devices for solid-phase polymerization include continuous heating and drying devices, tumble dryers, conical dryers, rotary dryers, and other rotary drum type heating devices, as well as conical heating devices equipped with rotating blades inside, known as Nauta mixers. However, the method is not limited to these, and any known methods and devices can be used. In particular, when performing solid-phase polymerization of polyamide resin, a rotary drum type heating device is preferred among the above-mentioned devices because it can seal the system and facilitate polycondensation while removing oxygen, which causes discoloration.

[0026] <Compounds containing metalloxane bonds (B)> Compound (B) having a metalloxane bond used in the present invention (hereinafter also referred to as compound (B) or simply component (B)) is a compound having a metalloxane bond, that is, a bond represented by a metal atom (M)-oxygen atom (O)-metal atom (M). Compound (B) used in the present invention is, for example, a compound having a structure represented by the following formula (II).

[0027] Formula (II) [ka]

[0028] In the above formula (II), M is a metal atom, O is an oxygen atom, and R 11 R represents alkyl groups, aryl groups such as phenyl groups, unsaturated hydrocarbon groups such as methacryloxy groups and vinyl groups, organic functional groups such as glycidoxy groups, amino groups and hydroxyl groups, and hydrolyzable groups. 12 k represents a hydrocarbon group or a hydrogen atom. k is an integer of 2 or more, and l and m are integers of 0 or 1 or more. The number of k, l, and m may be the same or different for each repeating unit. Also, R 11 , R 12 The type may be the same or different for each repeating unit.

[0029] In compound (B), the metal atom (M) is a metallic element that can take on a structure as exemplified by formula (II), and is exemplified below, but is not limited to these examples. For example, examples include Group 13 elements such as boron (B), aluminum (Al), gallium (Ga), indium (In), and thallium (Tl); Group 14 elements such as carbon (C), silicon (Si), germanium (Ge), tin (Sn), and lead (Pb); Group 4 elements such as titanium (Ti) and zirconium (Zr); and metallic elements such as zinc (Zn), calcium (Ca), tellurium (Te), magnesium (Mg), nickel (Ni), chromium (Cr), barium (Ba), tantalum (Ta), molybdenum (Mo), and terbium (Tb). Among these, Group 4, Group 13, and Group 14 elements are preferred due to their high adhesion to the silica-based metal vapor deposition layer, Zr, Ti, Al, and Si are more preferred, and Si is even more preferred. You can use one or more of these in combination.

[0030] A method for obtaining the metalloxane bond-containing compound (B) used in the present invention is, for example, by hydrolysis and condensation reactions of a compound (p) in which a hydrolyzable group such as an alkoxy group is bonded to a metal atom (M).

[0031] The number of MO bonds constituting the metalloxane bond in compound (B) is preferably more than 2 on average per metal atom (M). When the number of MO bonds constituting the metalloxane bond is more than 2 on average per metal atom (M), compound (B) has a metalloxane bond (MOMOM), and its gas barrier properties can be improved. Such a bond can be formed, for example, by using a compound (p) that has more than 2 hydrolyzable groups per metal atom (M).

[0032] The following are specific examples of compounds (p) in which Si is used as the metal element, but the examples are not limited to these. For example, tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane, tetra-i-butoxysilane, tetra-sec-butoxysilane, and tetra-t-butoxysilane; methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, i-propyltrimethoxysilane, i-propyltriethoxysilane, phenyltri Ethoxysilane, benzyltrimethoxysilane, benzyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-Epoxycyclohexyl)ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-(meth)acrylooxypropyltrimethoxysilane, 3-(meth)acrylooxypropyltriethoxysilane, γ-mercaptopropyltriethoxysilane, γ-ureidopropyltriethoxysilane, γ-ureidopropyltrimethoxysilane, γ-(2-ureidoethyl)aminopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropyltrimethoxysilane, γ-(2-aminoethyl)aminopropyltrimethoxysilane, γ-H Trialkoxysilanes such as droxypropyltrimethoxysilane, γ-hydroxypropyltriethoxysilane, N-β-(N-vinylbenzylaminoethyl)-γ-aminopropyltrimethoxysilane hydrochloride, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, di-n-propyldimethoxysilane, di-n-propyldiethoxysilane, di-i-propyldimethoxysilane, di-i-propyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β-(3,Examples include dialkoxysilanes such as 4-epoxycyclohexyl)ethyltrimethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropylethyldimethoxysilane, γ-isocyanatopropylethyldiethoxysilane, and γ-(2-aminoethyl)aminopropylmethyldimethoxysilane; tetraacyloxysilanes such as tetraacetyloxysilane and tetrapropionyloxysilane; triacyloxysilanes such as methyltriacetyloxysilane and ethyltriacetyloxysilane; diacyloxysilanes such as dimethyldiacetyloxysilane and diethyldiacetyloxysilane, and modified versions thereof. Of these, tetraalkoxysilanes and trialkoxysilanes are preferred because the resulting compound (B) is well compatible with the polyamide resin (A) and forms sufficient crosslinking points, resulting in a coating with good gas barrier properties. Tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, and phenyltriethoxysilane are more preferred. Furthermore, when alkoxysilanes having reactive functional groups are used, a bond can be formed between the polyamide resin (A) and compound (B), improving gas barrier properties and the toughness of the coating.

[0033] Specific examples of compound (p) using Zr, Ti, and Al are given below, but are not limited to these. Examples include zirconium alkoxide compounds such as tetrapropoxyzirconium and tetrabutoxyzirconium; titanium alkoxide compounds such as tetramethoxytitanium, tetraethoxytitanium, tetraisopropoxytitanium, tetra-n-propoxytitanium, tetra-n-butoxytitanium, tetra-tert-butoxytitanium, and tetra-sec-butoxytitanium; aluminum alkoxide compounds such as trimethoxyaluminum, triethoxyaluminum, triisopropoxyaluminum, tri-n-propoxyaluminum, tri-n-butoxyaluminum, tri-tert-butoxyaluminum, and tri-sec-butoxyaluminum, and modified versions thereof.

[0034] To carry out the hydrolysis or condensation reaction of compound (p), for example, water, a catalyst to promote the hydrolysis or condensation reaction, and an organic solvent are used.

[0035] The hydrolysis and condensation reactions of compound (p) are promoted under both acidic and basic conditions. Suitable catalysts under acidic conditions include mineral acids such as hydrochloric acid, nitric acid, and sulfuric acid, and organic acids such as phosphoric acid, acetic acid, citric acid, oxalic acid, and p-toluenesulfonic acid. Suitable catalysts under basic conditions include inorganic bases such as sodium hydroxide, calcium hydroxide, and magnesium hydroxide, and organic bases such as ammonia, pyridine, triethylamine, N,N-dimethylbenzylamine, tripropylamine, tributylamine, and tripentylamine. Furthermore, catalysts may be used separately for hydrolysis and for polycondensation. Among these, hydrochloric acid and nitric acid, which provide acidic conditions, are particularly preferred. The above catalysts may be used individually or in combination of two or more.

[0036] The amount of catalyst added is not particularly limited, and any amount can be added as long as the solution does not instantly gel. For example, the amount of catalyst added is preferably 0.001 to 10 equivalents per 100 equivalents of hydrolyzable groups of compound (p).

[0037] The degree of hydrolysis of compound (p) is preferably 70% or more, and more preferably 80% or more. A degree of hydrolysis above the aforementioned lower limit increases the efficiency of the condensation reaction, and because the condensation reaction proceeds uniformly, the uniformity of the resulting coating film is also increased, allowing for stable gas barrier properties. The degree of hydrolysis can be measured by Raman spectroscopy as described in the examples.

[0038] The degree of condensation reaction of compound (p) is preferably 50% or more, and preferably 60% or more. The higher the degree of condensation reaction, the more metalloxane bonds are formed, resulting in a denser crosslinking density in the gas barrier coating layer and enabling high gas barrier properties. The degree of condensation reaction can be measured by infrared spectroscopy (IR) as described in the examples.

[0039] The metalloxane-containing compound (B) that can be used in the present invention is not limited to the above examples, and one or more of them can be used in combination. When two or more are used in combination, M may be the same metal element, or two or more metal elements may be selected and combined.

[0040] In the present invention, the content of the compound (B) having metalloxane bonds is not particularly limited, but is preferably 1 to 150 parts by mass, more preferably 3 to 130 parts by mass, and even more preferably 5 to 100 parts by mass, per 100 parts by mass of the hydroxyl group-containing polyamide resin (A). When the content of the compound (B) having metalloxane bonds is above the lower limit, hardness and gas barrier properties tend to be further improved. Conversely, when it is below the upper limit, film-forming properties and flexibility tend to be further improved.

[0041] The hydroxyl group-containing polyamide resin composition of the present invention, when used to prepare a thin film with a thickness of 1 μm, exhibits an oxygen permeability of 1000 ml(STP) / m² at a temperature of 23°C and a relative humidity (RH) of 85%. 2It is preferable that the pressure be less than or equal to day·MPa, and more preferably 800 ml(STP) / m². 2 The pressure is less than or equal to day·MPa, and more preferably 600 ml(STP) / m². 2 The oxygen permeability should be less than or equal to day·MPa. If the oxygen permeability is too high, the gas barrier properties will be insufficient, which may make it difficult to apply to packaging materials, etc.

[0042] Next, a method for producing the hydroxyl group-containing polyamide resin composition according to this invention will be described. The method for producing the hydroxyl group-containing polyamide resin composition of the present invention is not particularly limited as long as it contains a polyamide resin (A) and a compound (B). It may be prepared by mixing the polyamide resin (A) and the compound (B), or by preparing the compound (B) in situ from compound (p). For example, one method involves adding water and a catalyst to a hydroxyl group-containing polyamide resin (A) dissolved in an organic solvent, then mixing in compound (p) to make the solution completely miscible, and then performing a hydrolysis reaction and a condensation reaction at a predetermined temperature. Another method involves adding an organic solvent, water, and a catalyst to compound (p), then mixing in a hydroxyl group-containing polyamide resin (A) dissolved in an organic solvent to make the solution completely miscible, and then performing a hydrolysis reaction and a condensation reaction at a predetermined temperature. Furthermore, when using a compound (p) having a reactive functional group, it may be reacted with the hydroxyl group-containing polyamide resin (A) beforehand.

[0043] The hydrolysis and condensation reactions of compound (p), or the mixing and reaction of their reaction products with the hydroxyl group-containing polyamide resin (A), can be controlled by temperature conditions. Any temperature range in which the hydroxyl group-containing polyamide resin (A), the metalloxane-bonded compound (B), and the organic solvent do not freeze or volatilize can be applied. The higher the temperature, the faster the hydrolysis and condensation reactions of compound (p). The lower the temperature, the more controllable the hydrolysis and condensation reactions of compound (p).

[0044] A hydroxyl group-containing polyamide resin (A) and a compound (B) having a metalloxane bond may form a bond as needed.

[0045] <Organic solvents> The hydroxyl group-containing polyamide resin (A) and the compound having a metalloxane bond (B) used in the present invention may be diluted and dissolved in any proportion using an organic solvent. The organic solvent used is not particularly limited, but it is desirable that it dissolves both the hydroxyl group-containing polyamide resin (A) and the compound having a metalloxane bond (B). The organic solvent can also be used to uniformly mix the compound having a metalloxane bond (B) and the hydroxyl group-containing polyamide resin (A), and to adjust the viscosity to a level suitable for application when coating them onto a substrate.

[0046] The amount of organic solvent added is not particularly limited, but the solid content concentration in the resulting varnish is preferably 2 to 90% by mass, and more preferably 10 to 70% by mass. If it is less than 2% by mass, the amount of volatile solvent increases, which is undesirable from an environmental protection standpoint. On the other hand, if it is more than 70% by mass, the solubility tends to decrease or the viscosity tends to become too high. By adjusting the solid content concentration appropriately, it is also possible to control the progress of the hydrolysis reaction and condensation reaction of compound (p).

[0047] The organic solvents used are not particularly limited, but aromatic solvents such as toluene and xylene, aliphatic solvents such as hexane, heptane, and octane, alcoholic solvents such as methanol, ethanol, propyl alcohol, butanol, and benzyl alcohol, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and cyclopentanone, ether solvents such as diethyl ether and tetrahydrofuran, ester solvents such as methyl acetate, ethyl acetate, and butyl acetate, amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethylpropionamide, 1,3-dimethylimidazolidinone, N-methyl-2-pyrrolidone, and N-ethyl-2-pyrrolidone, lactone solvents such as γ-butyrolactone, and phenols can be used. Among these, N,N-dimethylacetamide and benzyl alcohol are preferred from the viewpoint of solubility of the hydroxyl group-containing polyamide resin (A) and compound (B). These organic solvents can be used individually or in combination of two or more.

[0048] Furthermore, water can be used as a solvent, to the extent that it does not hinder the effects of the present invention. In this case, the hydroxyl group-containing polyamide resin (A) is dissolved in the aforementioned organic solvent, and water is added in the presence of a basic compound to facilitate mixing with water. The hydroxyl groups become hydrophilic due to the basic compound, thereby improving their affinity for water.

[0049] Examples of basic compounds that can be used include ammonia, organic amine compounds, and inorganic basic compounds.

[0050] Specific examples of the aforementioned organic amine compounds include triethylamine, N,N-diethylethanolamine, N,N-dimethylethanolamine, aminoethanolamine, N-methyl-N,N-diethanolamine, isopropylamine, iminobispropylamine, ethylamine, diethylamine, 3-ethoxypropylamine, 3-diethylaminopropylamine, sec-butylamine, propylamine, methylaminopropylamine, dimethylaminopropylamine, methyliminobispropylamine, 3-methoxypropylamine, monoethanolamine, diethanolamine, triethanolamine, morpholine, N-methylmorpholine, and N-ethylmorpholine. Among these organic amine compounds, using highly hydrophilic ethanolamines, particularly triethanolamine, can improve the hydrophilicity of the hydroxyl group-containing polyamide resin (A).

[0051] Specific examples of the inorganic basic compounds mentioned above include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; alkali metal carbonates and bicarbonates such as sodium bicarbonate and sodium carbonate; and ammonium carbonate.

[0052] When using the basic compound, it is necessary to use an amount that can neutralize at least some of the hydroxyl groups in the hydroxyl group-containing polyamide resin (A). Specifically, it is desirable to add 0.5 to 10 equivalents relative to the amount of hydroxyl groups in the hydroxyl group-containing polyamide resin (A). If the addition ratio of the basic compound is too low, the hydrophilicity of the hydroxyl group-containing polyamide resin (A) will be low and it will tend to become insoluble when water is added. If it is too high, the pH of the solution will become high, which may make it difficult to control the subsequent sol-gel reaction.

[0053] In the present invention, various additives such as curing agents, layered inorganic materials, dispersants, and plasticizers can be included as needed, as long as they do not impair the effects of the present invention.

[0054] <Hardening agent> The hydroxyl group-containing polyamide resin composition of the present invention may contain a curing agent that is reactive to hydroxyl groups, carboxyl groups, or amino groups for the purpose of improving chemical resistance and adhesion. Various curing agents can be used as the curing agent, such as amino resins such as melamine-based and benzoguanamine-based resins, polyvalent isocyanate compounds, polyvalent oxazoline compounds, polyvalent epoxy compounds, and phenolic resins. Melamine-based amino resins and polyvalent isocyanate compounds are particularly preferred because they are highly reactive, allow curing at low temperatures, and provide high adhesive strength. Polyvalent metal salts can also be used as curing agents.

[0055] When using these curing agents, their content is preferably 5 to 50 parts by mass, and more preferably 10 to 30 parts by mass, per 100 parts by mass of hydroxyl group-containing polyamide resin. If the amount of curing agent is less than 5 parts by mass, the curing ability tends to be insufficient, and if it exceeds 50 parts by mass, the coating film tends to become too hard.

[0056] Suitable polyvalent epoxy compounds for use as curing agents in the present invention include novolac-type polyvalent epoxy resins, bisphenol-type polyvalent epoxy resins, trisphenolmethane-type polyvalent epoxy resins, amino group-containing polyvalent epoxy resins, copolymer-type polyvalent epoxy resins, and the like. An example of a novolac-type polyvalent epoxy resin is one obtained by reacting novolacs, which are produced by reacting phenols such as phenol, cresol, and alkylphenol with formaldehyde under an acidic catalyst, with epichlorohydrin and / or methyl epichlorohydrin. An example of a bisphenol-type polyvalent epoxy resin is one obtained by reacting bisphenols such as bisphenol A, bisphenol F, and bisphenol S with epichlorohydrin and / or methyl epichlorohydrin, or one obtained by reacting a condensate of diglycidyl ether of bisphenol A and the bisphenols with epichlorohydrin and / or methyl epichlorohydrin. Examples of trisphenolmethane-type polyvalent epoxy resins include those obtained by reacting trisphenolmethane, triscresolmethane, etc., with epichlorohydrin and / or methylepichlorohydrin. Examples of amino group-containing polyvalent epoxy resins include glycidylamine-based resins such as tetraglycidyldiaminodiphenylmethane, triglycidylparaaminophenol, tetraglycidylbisaminomethylcyclohexanone, and N,N,N',N'-tetraglycidyl-m-xylenediamine. Examples of copolymer-type polyvalent epoxy resins include copolymers of glycidyl methacrylate and styrene, copolymers of glycidyl methacrylate, styrene, and methyl methacrylate, or copolymers of glycidyl methacrylate and cyclohexylmaleimide, etc.

[0057] A curing catalyst can be used in the curing reaction of the polyvalent epoxy compound used in the present invention. Examples include imidazole compounds such as 2-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, and 1-cyanoethyl-2-ethyl-4-methylimidazole; tertiary amines such as triethylamine, triethylenediamine, N'-methyl-N-(2-dimethylaminoethyl)piperazine, 1,8-diazabicyclo(5,4,0)-undecene-7, 1,5-diazabicyclo(4,3,0)-nonene-5, and 6-dibutylamino-1,8-diazabicyclo(5,4,0)-undecene-7; compounds obtained by amine salting these tertiary amines with phenol, octic acid, or quaternized tetraphenylborate salts; cationic catalysts such as triallylsulfonium hexafluoroantimonate and diallyiodonium hexafluoroantimonate; and triphenylphosphine. Of these, tertiary amines such as 1,8-diazabicyclo(5,4,0)-undecene-7, 1,5-diazabicyclo(4,3,0)-nonene-5, and 6-dibutylamino-1,8-diazabicyclo(5,4,0)-undecene-7, and compounds obtained by amine salting these tertiary amines with phenol, octic acid, or quaternized tetraphenyl borate salts, are preferred in terms of thermosetting properties, heat resistance, adhesion to metals, and storage stability after compounding. The amount added is preferably 0.01 to 1.0 parts by mass per 100 parts by mass of hydroxyl group-containing polyamide resin. Within this range, the effect on the reaction between the hydroxyl group-containing polyamide resin and the epoxy compound is further enhanced, and a strong coating film can be obtained.

[0058] Suitable phenolic resins for use as curing agents in the present invention include, for example, condensates of alkylated phenols and / or cresols with formaldehyde. Specifically, examples include alkylated phenols alkylated with alkyl groups such as methyl, ethyl, propyl, isopropyl, and butyl groups, p-tert-amylphenol, 4,4'-sec-butylidenephenol, p-tert-butylphenol, o-cresol, m-cresol, p-cresol, p-cyclohexylphenol, 4,4'-isopropylidenephenol, p-nonylphenol, p-octylphenol, 3-pentadecylphenol, phenol, α-phenylo-cresol, p-phenylphenol, xylenol, and condensates of formaldehyde.

[0059] Suitable amino resins for use as curing agents in the present invention include, for example, urea, melamine, formaldehyde adducts such as benzoguanamine, and alkyl ether compounds obtained by alkoxyling these compounds with an alcohol having 1 to 6 carbon atoms. Specifically, examples include methoxylated methylolurea, methoxylated methylol-N,N-ethyleneurea, methoxylated methyloldicyandiamide, methoxylated methylolmelamine, methoxylated methylolbenzoguanamine, butoxylated methylolmelamine, and butoxylated methylolbenzoguanamine. Methoxylated methylolmelamine, butoxylated methylolmelamine, and methylollated benzoguanamine are preferred, and each can be used alone or in combination.

[0060] Suitable polyvalent isocyanate compounds for use as curing agents in the present invention may be either low-molecular-weight compounds or high-molecular-weight compounds. Examples of low-molecular-weight compounds include aliphatic isocyanate compounds such as tetramethylene diisocyanate and hexamethylene diisocyanate, aromatic polyvalent isocyanate compounds such as toluene diisocyanate, diphenylmethane diisocyanate and xylylene diisocyanate, and alicyclic polyvalent isocyanates such as hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate and isophorone diisocyanate. Trimers of these polyvalent isocyanate compounds can also be used. Examples of high-molecular-weight compounds include terminal isocyanate group-containing compounds obtained by reacting a compound having multiple active hydrogens with an excess amount of the low-molecular-weight polyisocyanate compound. Examples of compounds containing multiple active hydrogens include polyhydric alcohols such as ethylene glycol, propylene glycol, trimethylolpropane, glycerin, and sorbitol; polyhydric amines such as ethylenediamine; compounds having hydroxyl and amino groups such as monoethanolamine, diethanolamine, and triethanolamine; and active hydrogen-containing polymers such as polyester polyols, polyether polyols, and polyamides.

[0061] The polyvalent isocyanate compound may also be a blocked isocyanate. Examples of isocyanate blocking agents include phenols such as phenol, thiophenol, methylthiophenol, cresol, xylenol, resorcinol, nitrophenol, and chlorophenol; oximes such as acetoxime, methyl ethyl ketoxime, and cyclohexanone oxime; alcohols such as methanol, ethanol, propanol, and butanol; halogen-substituted alcohols such as ethylene chlorohydrin and 1,3-dichloro-2-propanol; tertiary alcohols such as t-butanol and t-pentanol; lactams such as ε-caprolactam, δ-valerolactam, γ-butyrolactam, and β-propiolactam; and others such as aromatic amines, imides, active methylene compounds such as acetylacetone, acetoacetate ester, and ethyl malonate ester, mercaptans, imines, ureas, diaryl compounds, and sodium bisulfite. Blocked isocyanates are obtained by adding the above-mentioned isocyanate compound and an isocyanate blocking agent using a conventionally known method.

[0062] Suitable polyvalent oxazoline compounds for use as curing agents in the present invention are compounds having an oxazoline group in the molecule, and polymers containing an oxazoline group are particularly preferred. These can be produced by polymerization of an addition-polymerizable oxazoline group-containing monomer alone or with other monomers. Examples of addition-polymerizable oxazoline group-containing monomers include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2-oxazoline, 2-isopropenyl-4-methyl-2-oxazoline, and 2-isopropenyl-5-ethyl-2-oxazoline. One or more of these can be used. Among these, 2-isopropenyl-2-oxazoline is industrially readily available and therefore preferred. Other monomers are not limited as long as they are copolymerizable with addition-polymerizable oxazoline group-containing monomers, for example (meth)acrylic acid esters such as alkyl (meth)acrylates (alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, 2-ethylhexyl, and cyclohexyl groups); unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, styrene sulfonic acid and their salts (sodium salt, potassium salt, ammonium salt, tertiary amine salt, etc.); unsaturated nitriles such as acrylonitrile and methacrylonitrile; (meth)acrylamide, N-alkyl(meth)acrylamide Examples of unsaturated amides include lylamide, N,N-dialkyl(meth)acrylamide (alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, 2-ethylhexyl, and cyclohexyl); vinyl esters such as vinyl acetate and vinyl propionate; vinyl ethers such as methyl vinyl ether and ethyl vinyl ether; α-olefins such as ethylene and propylene; halogen-containing α,β-unsaturated monomers such as vinyl chloride, vinylidene chloride, and vinyl fluoride; and α,β-unsaturated aromatic monomers such as styrene and α-methylstyrene. One or more of these monomers can be used.

[0063] As the curing agent used in the present invention, commercially available curing agents can be used, including polyisocyanate compounds such as Duranate® 24A-100, TPA-100, and TLA-100 manufactured by Asahi Kasei Corporation, and polyvalent epoxy resins such as Denacol® EX-411 and EX-321 manufactured by Nagase ChemteX Corporation.

[0064] <Layered inorganic material> The hydroxyl group-containing polyamide resin composition of the present invention may contain layered inorganic materials. By including layered compounds, a hydroxyl group-containing polyamide resin composition with further improved gas barrier properties can be provided. The layered inorganic materials may be natural or synthetic products, and a typical example is a layered silicate. Examples of layered silicates include smectite-type clay minerals such as montmorillonite, hectorite, fluoridehectorite, saponite, hydelite, and stivunsite; swelling synthetic micas such as Na-type fluoriteniolite, Na-type tetrasilicon fluorimica, and Li-type tetrasilicon fluorimica; vermiculite, fluoridevermiculite, and halloysite. Among these, swelling synthetic micas such as Na-type tetrasilicon fluorimica and Li-type tetrasilicon fluorimica are particularly preferred. The content of the layered inorganic material is preferably in the range of 0.01 to 10 parts by mass, and more preferably in the range of 0.1 to 5 parts by mass, per 100 parts by mass of the hydroxyl group-containing polyamide resin (A). If the content is too low, the effect of improving gas barrier properties may not be achieved. If the content is too high, the strength of the coating film may decrease.

[0065] As for the layered inorganic material, it is preferable to use one with a particle size of 100 μm or less as measured using a laser diffraction scattering particle size analyzer. If the particle size exceeds 100 μm, it may lead to a decrease in the tensile strength of the hydroxyl group-containing polyamide resin composition.

[0066] <Other additives> In the present invention, various additives may be included to impart other functionalities to the coating layer, to the extent that the effects of the present invention are not impaired. Examples of such additives include inorganic or organic particles different from the layered inorganic material, pigments, dyes, antistatic agents, leveling agents, fluorescent dyes, fluorescent whitening agents, plasticizers, dispersants, ultraviolet absorbers, pigment dispersants, anti-settling agents, anti-foaming agents, anti-skinning agents, anti-sagging agents, matting agents, thickeners, antifungal agents, preservatives, conductive agents, inorganic fillers, impact resistance modifiers, organophosphorus compounds, nucleating agents such as polyetheretherketones, anti-coloring agents such as hypophosphates, antioxidants such as hindered phenols and hindered amines, heat stabilizers, lubricants, or flame retardants. Furthermore, resins other than the hydroxyl group-containing polyamide resin (A), such as polyester resins, polyurethane resins, polyimide resins, polyamide-imide resins, and other polyamide resins, may be appropriately blended. Because hydroxyl group-containing polyamide resins have a high hydroxyl value, they exhibit high dispersibility of various pigments, making it possible to produce high-concentration paints.

[0067] In the present invention, examples of particles that can be contained in the coating layer include inorganic particles such as silica, kaolinite, talc, light calcium carbonate, heavy calcium carbonate, zeolite, alumina, barium sulfate, carbon black, zinc oxide, zinc sulfate, zinc carbonate, zirconium dioxide, titanium dioxide, satin white, aluminum silicate, diatomaceous earth, calcium silicate, aluminum hydroxide, hydrated halloysite, magnesium carbonate, and magnesium hydroxide; and organic particles such as acrylic or methacrylic, vinyl chloride, vinyl acetate, nylon, styrene / acrylic, styrene / butadiene, polystyrene / acrylic, polystyrene / isoprene, methyl methacrylate / butyl methacrylate, melamine, polycarbonate, urea, epoxy, urethane, phenol, diallyl phthalate, and polyester.

[0068] In the present invention, metal compounds other than compound (B) may be included as long as they do not impair the effects of the present invention. The metals constituting the metal compound are not particularly limited and include monovalent metals such as lithium, sodium, potassium, rubidium, and cesium, and divalent or higher metals such as magnesium, calcium, zirconium, zinc, copper, cobalt, iron, nickel, and aluminum. The metal compound is a compound containing the above metals, and examples of compounds include oxides, hydroxides, halides, inorganic salts such as carbonates, bicarbonates, phosphates, and sulfates, carboxylates such as acetates, formates, stearates, citrates, malates, and maleates, and organic acid salts such as sulfonates, with oxides and carbonates being preferred. In addition, elemental metals may be used as the metal compound. In particular, iron ion compounds such as iron chloride are preferred from the viewpoint of readily reacting with hydroxyl groups, and magnesium ion compounds such as magnesium oxide are preferred from the viewpoint of readily reacting with carboxylic acids. Due to the interaction effect of these, an improvement in gas barrier properties can be expected.

[0069] The method of compounding the various additives, such as the curing agent mentioned above, is not particularly limited. For example, they may be added in advance to the hydroxyl group-containing polyamide resin (A) or its organic solvent solution, or to the compound (B) having a metalloxane bond. The method of adding them to the hydroxyl group-containing polyamide resin (A) is not particularly limited. For example, methods include adding a predetermined amount of the various additives into the system during the polymerization step of the polyamide resin (A), dry blending after preparing the polyamide resin (A), or melt kneading using an extruder. Furthermore, when adding the various additives to a solution, it is desirable to go through processing steps such as stirring or ultrasonic irradiation to improve dispersibility.

[0070] <Laminate> The hydroxyl group-containing polyamide resin composition of the present invention can be laminated onto a substrate layer selected from the group consisting of films, sheets, metal vapor-deposited layers, woven fabrics, nonwoven fabrics, and paper to form a laminate. The laminate can be easily obtained, for example, by coating at least one side of a substrate layer selected from the group consisting of films, sheets, metal vapor-deposited layers, woven fabrics, nonwoven fabrics, and paper with the hydroxyl group-containing polyamide resin composition (resin varnish) of the present invention and drying it. The hydroxyl group-containing polyamide resin composition of the present invention can exhibit strong adhesion to films, sheets, metal vapor-deposited layers, woven fabrics, nonwoven fabrics, and paper made from various raw materials. The film or sheet of the above-mentioned substrate layer is not particularly limited, but examples include polymer resin films or sheets made from at least one resin selected from polylactic acid, polyester, polyurethane, polyamide, cellulose, starch, vinyl chloride, vinylidene chloride, chlorinated polyolefin, etc., and mixed resins thereof, or laminates of such polymer resin films or sheets. The film or sheet may be an unstretched film or a stretched film. Furthermore, these polymer materials may contain additives as needed, such as known antistatic agents, ultraviolet absorbers, plasticizers, lubricants, and colorants. The surface of the substrate may also be subjected to known treatments such as corona discharge, flame treatment, ultraviolet treatment, and anchor coating to improve adhesion.

[0071] Furthermore, since it exhibits high adhesion to various metal vapor-deposited films, a vapor-deposited film in which a metal vapor-deposited layer is formed on the surface of the resin film may be used as the substrate. In this case, the hydroxyl group-containing polyamide resin composition of the present invention may be coated onto the vapor-deposited surface of the vapor-deposited film. The metal used for the metal vapor-deposited layer is not particularly limited, but the adhesion between silica vapor-deposited films and aluminum vapor-deposited films and the hydroxyl group-containing polyamide resin composition of the present invention is particularly strong. The high adhesion of the hydroxyl group-containing polyamide resin composition of the present invention to various metal vapor-deposited layers is thought to be due to the high hydroxyl value of the hydroxyl group-containing polyamide resin composition of the present invention and the effect of the interaction between the compound (B) having a metalloxane bond and the metal vapor-deposited layer. These laminates can be used as gas barrier films and are suitable for use as packaging materials, for example, and are particularly suitable as food packaging materials.

[0072] The coating method for the hydroxyl group-containing polyamide resin composition of the present invention can be any known coating method that forms a layer made of the hydroxyl group-containing polyamide resin composition of the present invention on the surface of a substrate, and is not particularly limited. Examples include gravure coating, spin coater, reverse roll coating, wire bar coating, spray coater, die coating, etc. The above coating may be performed before or after the stretching of the film.

[0073] The drying conditions for the gas barrier coating layer formed by coating the above substrate with the hydroxyl group-containing polyamide resin composition of the present invention are not particularly limited, but can be set at a temperature below the melting point and softening point of the substrate, and can be set at a temperature at which the crosslinking reaction is sufficiently carried out.

[0074] The laminate coated with the hydroxyl group-containing polyamide resin composition of the present invention and dried may be subjected to aging. The temperature and time of this aging are not particularly limited, but 20 to 120°C for 1 to 200 hours is preferred, and 30 to 70°C for 10 to 150 hours is more preferred. Aging increases the crosslinking density of the gas barrier coating layer, so that high barrier properties can be achieved even under high humidity conditions. [Examples]

[0075] Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited by the following examples, and it is also possible to make appropriate modifications within the range that conforms to the spirit of the present invention and implement them, and all of them are included in the technical scope of the present invention.

[0076] In the following, unless otherwise specified, "parts" represent parts by mass. Also, the measurement and evaluation methods adopted in this specification are as follows.

[0077] (Resin composition and amount of hydroxyl groups) The hydroxyl group-containing polyamide resin (A) sample was dissolved in deuterated chloroform or deuterated dimethyl sulfoxide, and using a VARIAN NMR apparatus 400-MR, 1 H-NMR analysis, and if necessary 13 C-NMR analysis was performed, and the resin composition was determined from the integration ratio and expressed in mol%. Also, based on the above resin composition, the amount of hydroxyl groups (eq / t) was calculated by the following formula. Amount of hydroxyl groups (eq / t) = (Σ(P / 100) × Q) × 10 6 / (Σ(R / 100) × Z) P = Content of each hydroxyl group-containing component (mol%) Q = Number of hydroxyl groups in one molecule of each hydroxyl group-containing component R = Content of each constituent component (mol%) Z = Molecular weight of each constituent component

[0078] (Glass transition temperature) In accordance with JIS K7121 (1987), using a differential scanning calorimeter DSC (manufactured by Seiko Instruments Inc., DSC200), in the endothermic curve obtained in this process, the temperature of the intersection of the baseline before the endothermic peak appears and the tangent line towards the endothermic peak was taken as the glass transition temperature (Tg, unit: °C).

[0079] (Logarithmic viscosity) In accordance with JIS K7367-5 (2000), a 0.1 g sample of hydroxyl group-containing polyamide resin was dissolved in 20 ml of a 1,1,2,2-tetrachloroethane / phenol = 40 / 60 (mass ratio) mixed solution and measured at 30°C.

[0080] (Particle size of layered compound) The particle size and particle size distribution described above were measured using a laser diffraction scattering particle size analyzer, and the measurement principle is based on "Particle Size Measurement Technology" (edited by the Japan Society of Powder Technology, published by Nikkan Kogyo Shimbun, November 1, 1994). The measuring instrument used was a Shimadzu SALD-2000 model.

[0081] (Preparation of coated film samples) A 50 μm thick substrate (PET) film (manufactured by Toyobo Co., Ltd., Toyobo Ester® Film E5100) was corona-treated, and the hydroxyl group-containing polyamide resin compositions obtained in the examples and comparative examples were applied using a wire bar #10. The film was then dried at 150°C for 1 minute and at 210°C for 1 minute to obtain a coated film sample.

[0082] <Progress of the hydrolysis reaction of compound (p)> The polyester resin compositions obtained in the examples and comparative examples were placed in glass bottles and Raman measurements were performed using a RAMAN-11 from Nanophoton Inc. If necessary, peaks that do not change before and after the reaction (e.g., approximately 1640 cm², attributed to the C=O stretching mode of the amide group) were identified. -1 The peak, approximately 1610 cm, is attributed to the aromatic stretching mode. -1 Normalized by the peak of the compound (p), and showing the bond before hydrolysis after the reaction (M-OR 12 Based on the peak intensity corresponding to ), the progress (%) of the hydrolysis reaction of compound (p) was calculated using the following formula. For example, when M is Si, the peak originating from Si-OEt is 650 cm². -1 It was detected in the vicinity. The degree of hydrolysis of compound (p) (%) = 100 - {(M-OR after reaction) 12 (Peak intensity of compound (p)) / (M-OR of compound (p))12 (Peak intensity) × 100

[0083] <Evaluation of the progress of the condensation reaction of compound (p)> The fabricated coated film was subjected to IR measurement (ATR method, Ge crystal, incident angle 45°, Spectra-Tech Thunderdoe) using an Agilent Cary670FTIR with a resolution of 4 cm. -1 The evaluation was performed over 64 cumulative trials. If necessary, the spectrum of the substrate (PET) film, or the spectrum of a sample coated only with hydrophilic group-containing polyester resin (A) using the method described above, was subtracted. Based on the peak intensities corresponding to the bond (M-OH) and metalloxane bond (MO) after hydrolysis, the progress (%) of the condensation reaction of compound (p) was calculated using the following formula. For example, when M=Si, the peak originating from Si-OH is 950 cm⁻¹. -1 Nearby, the peak originating from Si-O is at 1054 cm. -1 It was detected in the vicinity. The degree of condensation reaction of compound (p) (%) = Peak intensity of metalloxane bond (MO) / (Peak intensity of metalloxane bond (MO) + Peak intensity of bond after hydrolysis (M-OH)) × 100

[0084] <Solvent solubility> A hydroxyl group-containing polyamide resin (A) was dissolved in the organic solvent shown in Table 2 at 160°C to a resin concentration of 20% by mass. After stirring for 2 hours, the solution state was observed and evaluated according to the following criteria. ○: The resin has completely dissolved. △: The resin was almost completely dissolved, but a slight cloudiness remained. ×: The resin hardly dissolved at all.

[0085] <Oxygen permeability> The gas barrier performance of the fabricated coated film was evaluated by its oxygen permeability. The oxygen permeability of the coated film was measured using an oxygen permeability measuring device (MOCON, product name: OX-TRAN2 / 22L) under conditions of 23°C and 85% relative humidity. Oxygen permeability was measured by allowing oxygen to permeate from the thin film (coated layer) to the PET film. The oxygen permeability of the thin film (coated layer) of the coating film was calculated using the following formula. A lower oxygen permeability indicates higher gas barrier properties. P = DFT / (1 / Rcoat - 1 / R) Rcoat = Oxygen permeability of coated film (ml(STP) / m 2 (·day·MPa) R = Oxygen permeability of the substrate (PET) film in coated film (ml(STP) / m 2 (·day·MPa) DFT = Thickness of the thin film (coated layer) (μm) P = Oxygen permeability per 1 μm of thin film (coated layer) thickness (ml(STP) / m 2 (·day·MPa)

[0086] (Preparation of coated panels (test panels)) A hydroxyl group-containing polyamide resin composition was applied to a hot-dip galvanized steel sheet to a dry film thickness of 5 μm. After drying at 150°C for 10 minutes, the sheet was baked at 140°C for 30 minutes to prepare a test plate.

[0087] <Evaluation of adhesion> In accordance with JIS-K5600-5-6 (1999) Adhesion (Cross-cut method), six parallel vertical and six parallel horizontal lines were drawn at 1 mm intervals on the surface of the coating film of the test plate using a utility knife, so as to reach the substrate, creating 25 1 mm x 1 mm grids. Cellophane adhesive tape was adhered to the surface, and the degree of peeling of the grids when the tape was rapidly removed was observed and evaluated according to the following criteria. ◎: No paint peeling was observed at all. ○: The paint film peeled off slightly, but more than 20 grid lines remained. △: The paint film had peeled off, and the number of remaining squares was between 10 and 20. ×: The paint film had peeled off, and fewer than 10 squares remained.

[0088] In the following examples, the abbreviations for the compounds shown in the text and tables refer to the following compounds, respectively. 5H-IPA: 5-hydroxyisophthalic acid 2,5H-TPA: 2,5-dihydroxyterephthalic acid AA: Adipic acid SA: Sebaciate MXDA: Metaxylylenediamine PXDA: Paraxylylenediamine HMDA: Hexamethylenediamine DMAc: Dimethylacetamide BzlOH: Benzyl alcohol TEOS: Tetraethoxysilane PhTES: Phenyletriethoxysilane DPDES: Diphenyldiethoxysilane ALTIP: Aluminum triisopropoxide

[0089] (Synthesis Example 1) Production of hydroxyl group-containing polyamide resin (A-1) 25 moles of 5-hydroxyisophthalic acid, 25 moles of adipic acid, and 50 moles of metaxylylenediamine were charged into a 500 ml glass flask equipped with a thermometer, stirrer, and Liebig condenser. The polymerization system was heated to 170°C while circulating nitrogen gas, and then heated to 255°C at a heating rate of 3°C / min. After stirring at 255°C for 15 minutes, the contents were removed and cooled. The composition, logarithmic viscosity, glass transition temperature, and amount of hydroxyl groups of the obtained hydroxyl group-containing polyamide resin (A-1) are shown in Table 1.

[0090] (Synthesis Examples 2-6) Manufacturing of hydroxyl group-containing polyamide resins (A-2) to (A-6) Hydroxyl group-containing polyamide resins (A-2) to (A-6) were synthesized in the same manner as in Synthesis Example 1, except that the raw materials and their ratios were changed as shown in Table 1. The resin properties of the obtained hydroxyl group-containing polyamide resins (A-2) to (A-6) are shown in Table 1.

[0091] [Table 1]

[0092] <Example 1> Production and evaluation of hydroxyl group-containing polyamide resin composition (C-1) In a 500 ml glass flask equipped with a thermometer, stirrer, and Liebig condenser, 3.9 parts by mass of hydroxyl group-containing polyamide resin (A-1) and 92.92 parts by mass of benzyl alcohol were charged. The mixture was heated to 160°C and stirred for 2 hours until completely dissolved. After cooling, a hydroxyl group-containing polyamide resin varnish was obtained. To the obtained varnish, 2.72 parts of tetraethoxysilane, 0.004 parts of nitric acid, and 0.466 parts of water were added dropwise, and the mixture was stirred at room temperature for 12 hours. Tetraethoxysilane was hydrolyzed, and a condensate of the resulting metalloxane compound was formed. A hydroxyl group-containing polyamide resin composition (C-1) was obtained by mixing the metalloxane compound with the hydroxyl group-containing polyamide resin. The obtained composition was applied to a film substrate using the method described above, and the oxygen permeability of the resulting coated film sample was evaluated. The results are shown in Table 2.

[0093] <Examples 2-6, Comparative Examples 3-4> Hydroxyl group-containing polyamide resin compositions (C-2) to (C-6) and (C-9) to (C-10) were prepared in the same manner as in Example 1, except that the type and amount of raw materials were changed. Furthermore, as in Example 1, the compositions were applied to a film substrate, and the oxygen permeability of the resulting coated film samples was evaluated. The results are shown in Tables 2 and 3.

[0094] <Example 7> 100 parts of hydroxyl group-containing polyamide resin composition (C-1) were mixed with 0.7 parts of a curing agent, which is a polyisocyanate compound (Duranate® TPA100, manufactured by Asahi Kasei Corporation), to obtain hydroxyl group-containing polyamide resin composition (D-1). An adhesion test was performed using (D-1). The results are shown in Table 4.

[0095] <Example 8> To 100 parts of hydroxyl group-containing polyamide resin composition (C-1), 0.5 parts of lipophilic plate-like synthetic mica (Somasif® MEE, manufactured by Katakura Coop Agri Co., Ltd., particle size 5-20 μm) was added as a layered inorganic material to obtain hydroxyl group-containing polyamide resin composition (E-1). Using (E-1), it was applied to a film substrate in the same manner as in Example 1, and the oxygen permeability of the obtained coated film sample was evaluated. The results are shown in Table 5.

[0096] <Comparative Example 1> An attempt was made to prepare a hydroxyl group-containing polyamide resin composition (C-7) using the same method as in Example 1, except that the type and amount of raw materials used were changed. However, since the hydroxyl group-containing polyamide resin (A-3) did not dissolve in the organic solvent, a coated film sample could not be prepared, and the oxygen permeability could not be evaluated.

[0097] <Comparative Example 2> In a 500 ml glass flask equipped with a thermometer, stirrer, and Liebig condenser, 4.35 parts of hydroxyl group-containing polyamide resin (A-1) and 93.39 parts of benzyl alcohol were charged. The mixture was heated to 160°C and stirred for 2 hours until completely dissolved. After cooling, a hydroxyl group-containing polyamide resin varnish was obtained. To the obtained varnish, 2.26 parts of tetraethoxysilane were added dropwise, and without adding water or catalyst, the mixture was stirred at room temperature for 12 hours to obtain hydroxyl group-containing polyamide resin varnish (C-8). The obtained composition was applied to a film substrate using the method described above, but no film was formed, and a coated film sample could not be obtained, so the oxygen permeability could not be evaluated.

[0098] [Table 2]

[0099] [Table 3]

[0100] [Table 4]

[0101] [Table 5]

[0102] As can be seen from Table 2, the hydroxyl group-containing polyamide resin compositions in Examples 1 to 6 all exhibited good solvent solubility and high gas barrier properties even under high humidity. Furthermore, Example 7, which contained a curing agent, showed good adhesion. In Example 8, the gas barrier properties were further improved by incorporating a layered inorganic material.

[0103] On the other hand, in Comparative Example 1, a large amount of undissolved resin remained in the polyamide resin (A-3) even after stirring for 2 hours, and a large amount of undissolved resin still remained even after continuing stirring for another hour. The polyamide resin used in Comparative Example 1 has a hydroxyl group content of less than 500 eq / t, and is therefore outside the scope of the present invention. It is presumed that the low hydroxyl group content and the crystallinity of the polyamide resin prevented dissolution from progressing very well.

[0104] Comparative Example 2 involved applying the composition to a film substrate, but no film was formed, making it impossible to obtain a coated film sample. Comparative Example 2 did not contain compound (B) having a metalloxane bond and was therefore outside the scope of the present invention. It is presumed that the reaction to form compound (B) having a metalloxane bond hardly proceeded because no catalyst was added, resulting in poor film-forming properties.

[0105] Comparative Example 3 exhibited almost no gas barrier properties. The polyamide resin (A-4) used in Comparative Example 3 has a hydroxyl group content exceeding 6000 eq / t, and is therefore outside the scope of the present invention. It is presumed that the high hydroxyl group content and the composition in which the total diamine component content / total dicarboxylic acid component content deviate significantly from 1 made it difficult to achieve a sufficiently high molecular weight to exhibit gas barrier properties, and that the high hydroxyl group content reduced gas barrier properties under high humidity conditions.

[0106] Comparative Example 4 exhibited almost no gas barrier properties. The polyamide resin (A-5) used in Comparative Example 4 is outside the scope of the present invention because component (c) is less than 1 mol% when the total amount of all dicarboxylic acid components and all diamine components constituting the hydroxyl group-containing polyamide resin (A) is set to 100 mol%. It is presumed that because the amount of component (c) was small, there was almost no interaction due to hydrophobic bonding between benzene rings, and therefore the gas barrier properties were not sufficiently exhibited. [Industrial applicability]

[0107] The hydroxyl group-containing polyamide resin composition of the present invention can provide a coating film with high gas barrier properties under high humidity conditions. Therefore, it can be used as a gas barrier film by coating it onto a film, and is suitable for use as a packaging material, for example, and is particularly optimal as a food packaging material.

Claims

1. A hydroxyl group-containing polyamide resin composition comprising a hydroxyl group-containing polyamide resin (A) that satisfies the following conditions (1) and (2), and a compound (B) having a metalloxane bond. (1) The amount of hydroxyl groups is 500 to 6000 eq / t. (2) When the total amount of all dicarboxylic acid components and all diamine components constituting the hydroxyl group-containing polyamide resin (A) is set to 100 mol%, it contains 1 mol% or more of the diamine (a1) of the following formula (I). Equation (I) 【Chemistry 1】 (In formula (I), X and Y represent direct bonds or alkylene groups, and R1 to R4 represent hydrogen or monovalent organic groups.)

2. The hydroxyl group-containing polyamide resin composition according to claim 1, wherein the compound (B) having a metalloxane bond contains at least one metal element selected from silicon, titanium, aluminum, and zirconium.

3. The hydroxyl group-containing polyamide resin composition according to claim 1, wherein the compound (B) having a metalloxane bond is a compound derived from at least one of a trifunctional metal alkoxy compound and a tetrafunctional metal alkoxy compound.

4. The hydroxyl group-containing polyamide resin composition according to claim 1, wherein the aromatic diamine (c) in which the two amino groups constituting the hydroxyl group-containing polyamide resin (A) are located on substituents that are each positioned at the meta position of the aromatic ring is metaxylylenediamine.

5. The hydroxyl group-containing polyamide resin composition according to claim 1, further containing an organic solvent.

6. The hydroxyl group-containing polyamide resin composition according to claim 1, further containing a curing agent.

7. The hydroxyl group-containing polyamide resin composition according to claim 1, further containing a layered inorganic material.

8. A laminate comprising a layer made of a hydroxyl group-containing polyamide resin composition according to any one of claims 1 to 7, and one or more layers selected from the group consisting of film, sheet, metal vapor-deposited layer, woven fabric, nonwoven fabric, and paper.

9. A packaging material having the laminate described in claim 8 as a component.

10. A gas barrier material having a layer made of a hydroxyl group-containing polyamide resin composition according to any one of claims 1 to 7.

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