JP2017149933A - Phenolic hydroxyl group-containing polyamide resin and composition thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a phenolic hydroxyl group-containing polyamide resin which is excellent in solvent solubility and has high gas barrier properties under high humidity, and a resin composition containing the same.SOLUTION: The phenolic hydroxyl group-containing polyamide resin contains 10 mol% or more of a dicarboxylic acid unit having a phenolic hydroxyl group and 20 mol% or more of an aromatic diamine unit and satisfies the following (1) and (2): (1) the phenolic hydroxyl group content is 500-6,000 eq/t; and (2) when a thin film having a film thickness of 1 μm is formed of the phenolic hydroxyl group-containing polyamide resin, the thin film has an oxygen permeability of 1,000 ml/mday MPa or less at a temperature of 40°C and a humidity of 85% RH.SELECTED DRAWING: None

Description

  The present invention relates to a phenolic hydroxyl group-containing polyamide resin having a high gas barrier property under high humidity, and a phenolic hydroxyl group-containing polyamide resin composition containing the same.

  In recent years, as a material excellent in gas barrier properties, ethylene-vinyl alcohol copolymer (EVOH) and polyamide resin, particularly MXD6 obtained by polycondensation of metaxylenediamine and adipic acid has been actively used. However, although EVOH has an excellent oxygen barrier property under low humidity, it cannot be used as a packaging material under high humidity because the oxygen barrier property greatly decreases under high humidity. On the other hand, MXD6 utilizes the advantage of good thermal stability when melted, and has a multilayer structure by co-extrusion or co-injection molding with thermoplastic resins such as polyethylene terephthalate (hereinafter abbreviated as PET), nylon 6 and polypropylene. Although it is used as a gas barrier layer that constitutes an object, there are problems such as a change in physical properties due to high water absorption derived from an amide bond and oxidative deterioration, and, like EVOH, it has a low barrier property under high humidity. It has been pointed out. In addition, poor solubility in general-purpose solvents due to high cohesive strength derived from amide bonds has been pointed out, and since it will be widely used in processing applications other than molding processing, it is more resistant to chemicals, hydrolysis, and solvent solubility. There is a growing demand for excellent polyamides.

  Examples of the polyamide resin that is amorphous and exhibits gas barrier properties include Patent Documents 1 to 4. In Patent Document 1, a polyamide resin obtained by modifying MXD6 with an aromatic dicarboxylic acid is used. Patent Documents 2 and 3 propose polyamide resins imparted with hydrophobicity by using metaxylylenediamine and hexamethylenediamine as diamine components. Patent Document 4 discloses a polyamide having a gas barrier property even under high humidity by utilizing the high hydrophobicity of an aliphatic diamine having 9 carbon atoms.

JP-A 63-267548 JP-A-1-319531 JP-A-2-60928 JP 2001-302792 A

  When the present inventors examined the background art, it was found that there were the following problems. That is, in the invention disclosed in Patent Document 1, the gas barrier property of this resin also decreases due to moisture absorption. In the inventions disclosed in Patent Documents 2 and 3, since the hydrophobic effect of hexamethylenediamine is small, the hygroscopicity has not been improved. Moreover, in the invention disclosed in Patent Document 4, although the humidity dependency is improved, there is a problem that the gas barrier property itself is low.

  The present invention has been made against the background of such prior art problems. That is, the problem to be solved by the present invention is to provide a phenolic hydroxyl group-containing polyamide resin having a high gas barrier property even under high humidity, and a phenolic hydroxyl group-containing polyamide resin composition containing the same.

  As a result of intensive studies, the present inventors have found that the above problems can be solved by the following means, and have reached the present invention. That is, this invention consists of the following structures.

A phenolic hydroxyl group-containing polyamide resin containing 10 mol% or more of a dicarboxylic acid (A) unit having a phenolic hydroxyl group and 20 mol% or more of an aromatic diamine (B) unit and satisfying the following (1) to (2): .
(1) The amount of phenolic hydroxyl group is 500 to 6000 eq / t. (2) When a thin film having a film thickness of 1 μm is prepared with a phenolic hydroxyl group-containing polyamide resin, the temperature of the thin film is 40 ° C. and the humidity is 85% RH. The oxygen permeability is 1000 ml / m ² · day · MPa or less.

  The phenolic hydroxyl group-containing polyamide resin is preferably a phenolic hydroxyl group-containing polyamide resin composition containing an organic solvent. Furthermore, it is preferable to contain a hardening | curing agent and / or a layered inorganic substance.

  A laminate comprising a layer (A layer) containing the phenolic hydroxyl group-containing polyamide resin and one or more layers (B layer) selected from the group consisting of a film, a sheet, a woven fabric, a nonwoven fabric and paper.

  A packaging material having the laminate as a constituent element.

  The phenolic hydroxyl group-containing polyamide resin of the present invention and the resin composition containing the phenolic resin have a high gas barrier property under high humidity, which has been a difficult problem in the past for polyamide resins, and have a remarkable effect with industrial value. Is. Moreover, since it is excellent in solvent solubility, it can be widely used also as a laminated body apply | coated to various film base materials as a coating layer. Furthermore, the dispersibility of the layered inorganic substance is good due to the presence of the phenolic hydroxyl group, and the gas barrier property can be further enhanced.

<Phenolic hydroxyl group-containing polyamide resin>
The phenolic hydroxyl group-containing polyamide resin of the present invention contains a dicarboxylic acid (A) unit having a phenolic hydroxyl group and an aromatic diamine (B) unit, and (1) the phenolic hydroxyl group amount is 500 to 6000 eq / t. And (2) when a thin film having a film thickness of 1 μm is produced with a phenolic hydroxyl group-containing polyamide resin, the oxygen permeability at a temperature of 40 ° C. and a humidity of 85% RH is 1000 ml / m ² · day · MPa It is a polyamide resin that satisfies the following conditions.

<Dicarboxylic acid component (A) having phenolic hydroxyl group>
The dicarboxylic acid (A) unit having a phenolic hydroxyl group needs to be 10 mol% or more when the total amount of all dicarboxylic acid components and all diamine components is 100 mol%. Preferably it is 15 mol% or more, More preferably, it is 20 mol% or more. When there are too few dicarboxylic acid (A) units which have a phenolic hydroxyl group, it exists in the tendency for affinity with an organic solvent to worsen. Moreover, 60 mol% or less is preferable, 50 mol% or less is more preferable, and 45 mol% or less is more preferable. If it exceeds 60 mol%, the total amount of diamine components / total amount of dicarboxylic acid components greatly deviates from 1, and it may be difficult to achieve a high molecular weight sufficient to exhibit gas barrier properties. In addition, gas barrier properties may be reduced.

  In the present invention, examples of the dicarboxylic acid (A) having a phenolic hydroxyl group include 5-hydroxyisophthalic acid (5H-IPA), 4-hydroxyisophthalic acid (4H-IPA), and 2-hydroxyisophthalic acid (2H-IPA). ), 2-hydroxyterephthalic acid (5H-TPA), 2,3-dihydroxyterephthalic acid (2,3H-TPA), 2,5-dihydroxyterephthalic acid (2,5H-TPA), 3-hydroxyphthalic acid (3H) -OPA), 4-hydroxyphthalic acid (3H-OPA) and ester derivatives thereof are used, and these can be used alone or in combination. Preferable are 5-hydroxyisophthalic acid, 4-hydroxyisophthalic acid, 2-hydroxyisophthalic acid, 2-hydroxyterephthalic acid, and 2,5-dihydroxyterephthalic acid.

  Other dicarboxylic acid components can also be used. For example, isophthalic acid, terephthalic acid, 4,4'-biphenyldicarboxylic acid, 3,3'-methylene dibenzoic acid, 4,4'-methylene dibenzoic 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-naphthalene Dicarboxylic acid, 2,6-naphthalenedicarboxylic acid, ethylenediaminebisphthalimide-4,4'-dicarboxylic acid, 3,3'-bis (4-carboxylphenyl) propane, 3,3'-bis (4-carboxylphenyl) hexa Aromatic dica, such as fluoropropane, bis (4-carboxylphenyl) methane, 3,3'-bis (4-carboxylphenyl) hexafluoropropane Bon acid and its derivatives can be exemplified. In addition, alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid and its acid anhydride, succinic acid, adipic acid, azelaic acid, sebacic acid, Examples thereof include aliphatic dicarboxylic acids such as dodecanedioic acid and dimer acid, but are not limited thereto. Isophthalic acid, adipic acid, and sebacic acid are preferable.

<Aromatic diamine component (B)>
The aromatic diamine (B) unit needs to be 20 mol% or more when the total amount of all dicarboxylic acid components and all diamine components is 100 mol%. Preferably it is 25 mol% or more, More preferably, it is 30 mol% or more. When there are too few aromatic diamine (B) units, it exists in the tendency for a mechanical characteristic to fall or for a gas barrier property to fall. Moreover, 60 mol% or less is preferable and 50 mol% or less is more preferable. When it exceeds 60 mol%, the total amount of all dicarboxylic acid components decreases, and it may be difficult to achieve a high molecular weight sufficient to exhibit gas barrier properties.

  In the present invention, examples of the aromatic diamine (B) include p-phenylenediamine, 4,4′-diaminodiphenyl ether, 3,3′-dimethyl-4,4′-diaminodiphenyl ether, and 3,3′-diaminodiphenyl ether. 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, metatolylenediamine, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl thioether, 3, , 3'-dimethyl-4,4'-diaminodiphenyl thioether, 3,3'-diethoxy-4,4'-diaminodiphenyl thioether, 3,3'-diaminodiphenyl thioether, 4,4'-diaminobenzophenone, 3, 3'-dimethyl-4,4'-di Minobenzophenone, 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'-dimethyl bench Gin, 3,3'-dimethoxybenzidine, 3,3'-diaminobiphenyl, p-xylylenediamine, m-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, 3,3'-bis (4-hydroxy-3-aminophenyl) hexafluoro Propane and the like and derivatives thereof are used, and these can be used alone or in combination. Preferred are m-xylylenediamine, p-xylylenediamine, and p-phenylenediamine.

  Other diamine components can also be used, for example, ethylenediamine, 1,4-diaminobutane, hexamethylenediamine, nonamethylenediamine, undecamethylenediamine, dodecamethylenediamine, methylpentamethylenediamine, 2,2,4 -Aliphatic diamines such as trimethylhexamethylenediamine and 2,4,4-trimethylhexamethylenediamine and derivatives thereof, alicyclics such as bis- (4,4'-aminocyclohexyl) methane, isophoronediamine, norbornanediamine, piperazine Examples thereof include, but are not limited to, diamines and derivatives thereof.

<Phenolic hydroxyl group-containing polyamide resin satisfying (1)>
(1) will be described. The amount of phenolic hydroxyl group in the phenolic hydroxyl group-containing polyamide resin of the present invention needs to be 500 to 6000 eq / t. Preferably it is 600 eq / t or more, More preferably, it is 700 eq / t or more. Moreover, 5000 eq / t or less is preferable and 4000 eq / t or less is more preferable. When the amount of the phenolic hydroxyl group is too small, the affinity with an organic solvent and the dispersibility with additives such as layered inorganic substances used in combination tend to be poor. On the other hand, if the amount of the phenolic hydroxyl group is too high, it exhibits hygroscopicity and increases the possibility that the barrier property under high humidity is reduced.

<Phenolic hydroxyl group-containing polyamide resin satisfying (2)>
(2) will be described. The phenolic hydroxyl group-containing polyamide resin of the present invention has an oxygen permeability of 1000 ml / m ² · day · MPa at a temperature of 40 ° C. and a humidity of 85% RH when a thin film having a film thickness of 1 μm is produced from the resin. It is necessary that:

  The thin film was prepared by applying the phenolic hydroxyl group-containing polyamide resin composition (resin varnish) of the present invention to a corona-treated surface of a PET film substrate (Toyobo Ester (registered trademark) film E5100, manufactured by Toyobo Co., Ltd., thickness 50 μm), It coat | covers with a wire bar (# 10) so that the film thickness after drying may be set to 1 micrometer. Next, a laminate of a thin film / PET film substrate in which a phenolic hydroxyl group-containing polyamide resin layer (hereinafter also referred to as a thin film or a coating layer) having a thickness of 1 μm is laminated by drying at 150 ° C. for 1 minute and 210 ° C. for 1 minute. (Hereinafter also referred to as a coat film).

Next, the oxygen permeability under the conditions of 40 ° C. and 85% relative humidity is measured using an oxygen permeability measuring apparatus (trade name: OX-TRAN 2/21, manufactured by Mocon). The oxygen permeability is measured by allowing oxygen to permeate from the thin film (coating layer) side to the PET film side.
The oxygen permeability of the thin film (coating layer) of the coat film was calculated using the following formula. It shows that gas barrier property is so high that oxygen permeability is low.
P = DFT / (1 / R-1 / Rcoat)
Rcoat = Oxygen permeability of coated film (ml / m ² · day · MPa)
R = Oxygen permeability of substrate (PET) film in coated film (ml / m ² · day · MPa)
DFT = thin film (coating layer) thickness (mm)
P = Oxygen permeability of thin film (coating layer) (ml / m ² · day · MPa)

The oxygen permeability needs to be 1000 ml / m ² · day · MPa or less, preferably 800 ml / m ² · day · MPa or less, more preferably 600 ml / m ² · day · MPa or less. More preferably, it is 400 ml / m ² · day · MPa or less. If the oxygen permeability is too high, the gas barrier property is insufficient, and application to packaging materials and the like may be difficult.

The phenolic hydroxyl group-containing polyamide resin of the present invention has an oxygen permeability of 1000 ml / m ² · day · MPa or less under the conditions of a thin film at 23 ° C. and a relative humidity of 65% when a coated film is produced by the above method. It is preferable. More preferably, it is 800 ml / m < ² > * day * MPa or less, More preferably, it is 600 ml / m < ² > * day * MPa or less, Most preferably, it is 400 ml / m < ² > * day * MPa or less. By reducing the oxygen permeability at a relative humidity of 65%, the range of application to packaging materials and the like can be expanded.

  The phenolic hydroxyl group-containing polyamide resin of the present invention polycondenses the aromatic diamine component (B) capable of constituting the diamine unit and the dicarboxylic acid component (A) having a phenol hydroxyl group capable of constituting the dicarboxylic acid unit. The degree of polymerization can be controlled by adjusting polycondensation conditions and the like. A small amount of monoamine or monocarboxylic acid may be added as a molecular weight modifier during polycondensation. Further, in order to suppress the polycondensation reaction and obtain a desired degree of polymerization, the ratio (molar ratio) between the diamine component and the carboxylic acid component constituting the phenolic hydroxyl group-containing polyamide resin may be adjusted by shifting from 1. . In this case, in addition to the above components, a (polyhydric) alcohol component, a (polyhydric) epoxy component, and the like can be copolymerized.

<Polymerization method>
The phenolic hydroxyl group-containing polyamide resin can be produced by performing a known amidation condensation polymerization reaction. For example, although a normal pressure dropping method is mentioned, it is not limited to this.

  In the normal pressure dropping method, a diamine component is continuously dropped into a mixture obtained by heating and melting a dicarboxylic acid component under normal pressure, and polycondensation is performed while removing condensed water. The polycondensation reaction is performed while raising the temperature of the reaction system so that the reaction temperature does not fall below the melting point of the polyamide resin to be produced.

  The polyamide resin produced by the polycondensation method can be used as it is, but may be subjected to a step for further increasing the degree of polymerization. Further examples of the step of increasing the degree of polymerization include reactive extrusion in an extruder and solid phase polymerization. As a heating device used in solid phase polymerization, a continuous heating drying device, a tumble dryer, a conical dryer, a rotary drum heating device called a rotary dryer, etc., and a rotary blade inside a nauta mixer are provided. A conical heating device can be preferably used, but a known method and device can be used without being limited thereto. In particular, when solid-phase polymerization of polyamide resin is performed, the heating device of the rotating drum type among the above-mentioned devices can seal the inside of the system and facilitate polycondensation in a state where oxygen that causes coloring is removed. Are preferably used.

  The logarithmic viscosity of the phenolic hydroxyl group-containing polyamide resin of the present invention is preferably 0.05 dl / g or more, and more preferably 0.1 dl / g or more. Moreover, it is preferable that it is 4.0 dl / g or less, and it is more preferable that it is 3.5 dl / g or less. When the logarithmic viscosity is less than 0.05 dl / g, the mechanical properties of the phenolic hydroxyl group-containing polyamide resin may be low. When it exceeds 4.0 dl / g, the viscosity at the time of melting is high and the workability is high. It tends to be worse and the solubility in organic solvents tends to decrease.

  The glass transition temperature of the phenolic hydroxyl group-containing polyamide resin of the present invention is preferably 60 ° C. or higher, and more preferably 70 ° C. or higher. Moreover, it is preferable that it is 200 degrees C or less, and it is more preferable that it is 190 degrees C or less. When the glass transition temperature is less than 60 ° C, the mechanical properties of the phenolic hydroxyl group-containing polyamide resin may be lowered, and when it exceeds 200 ° C, the solubility in an organic solvent tends to be lowered.

<Organic solvent>
The phenolic hydroxyl group-containing polyamide resin of the present invention may be diluted at an arbitrary ratio using a known organic solvent. These are also important for adjusting the viscosity to be applicable when applied to the substrate.

  The organic solvent used is not particularly limited, but N, N-dimethylformamide, N, N-dimethylacetamide, N, N-dimethylpropionamide, 1,3-dimethylimidazolidinone, N-methyl-2-pyrrolidone, N Amide solvents such as ethyl-2-pyrrolidone, ketone solvents such as cyclohexanone and cyclopentanone, lactone solvents such as γ-butyrolactone, and known solvents such as phenol and benzyl alcohol can be used. Among these, N, N-dimethylacetamide and benzyl alcohol are preferable from the viewpoint of solubility. These organic solvents can be used alone or in combination of two or more.

  The content of the organic solvent is preferably 80% by weight or more, more preferably 90% by weight or more, still more preferably 95% by weight or more, and 100% by weight with respect to the whole organic solvent. It is particularly preferred. If the amount is too small, the solubility of the phenolic hydroxyl group-containing polyamide resin may decrease.

  Further, as long as the effect of the present invention is not hindered, some of the above solvents are aromatic solvents such as toluene and xylene, aliphatic solvents such as hexane, heptane and octane, methanol, ethanol, propyl alcohol, butanol and the like. Alcohol solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diethyl ether and tetrahydrofuran, and ether solvents such as methyl acetate, ethyl acetate and butyl acetate can be mixed.

  The phenolic hydroxyl group-containing polyamide resin of the present invention is preferably dissolved in the organic solvent at 160 ° C. by 10% by mass or more. More preferably, it is 15 mass% or more, More preferably, it is 20 mass% or more. By dissolving 10% by mass or more, application to the substrate becomes easy.

<Curing agent>
The phenolic hydroxyl group-containing polyamide resin of the present invention can contain a curing agent having reactivity with a phenolic hydroxyl group, a carboxyl group, or an amino group for the purpose of improving chemical resistance and adhesion. As said hardening | curing agent, various hardening | curing agents, such as amino resins, such as a melamine type and a benzoguanamine type, a polyvalent isocyanate compound, a polyvalent oxazoline compound, a polyvalent epoxy compound, a phenol resin, can be used. In particular, melamine-based amino resins and polyisocyanate compounds are preferable because they have high reactivity, can be cured at low temperatures, and can provide high adhesive strength. Multivalent metal salts can also be used as curing agents.

  When using these hardening | curing agents, it is preferable that the content is 5-50 mass parts with respect to 100 mass parts of phenolic hydroxyl group containing polyamide resins of this invention, and it is more preferable that it is 10-30 mass parts. . When the blending amount of the curing agent is less than 5 parts by mass, the curability tends to be insufficient, and when it exceeds 50 parts by mass, the coating film tends to be too hard.

  Suitable polyhydric epoxy compounds as curing agents for use in the present invention include novolac polyhydric epoxy resins, bisphenol polyhydric epoxy resins, trisphenolmethane polyhydric epoxy resins, amino group-containing polyhydric epoxy resins, and copolymers. Type polyvalent epoxy resin. Examples of novolak-type polyvalent epoxy resins are those obtained by reacting novolaks obtained by reacting phenols such as phenol, cresol, alkylphenol and formaldehyde in the presence of an acidic catalyst with epichlorohydrin and / or methyl epichlorohydrin. Can be mentioned. Examples of bisphenol type polyvalent epoxy resins include those obtained by reacting bisphenols such as bisphenol A, bisphenol F, and bisphenol S with epichlorohydrin and / or methyl epichlorohydrin, and diglycidyl ethers of bisphenol A and the bisphenols. The thing obtained by making epichlorohydrin and / or methyl epichlorohydrin react with a condensate can be mentioned. Examples of the trisphenol methane type polyvalent epoxy resin include those obtained by reacting trisphenol methane, tris-resole methane and the like with epichlorohydrin and / or methyl epichlorohydrin. Examples of amino group-containing polyvalent epoxy resins include glycidylamines such as tetraglycidyldiaminodiphenylmethane, triglycidylparaaminophenol, tetraglycidylbisaminomethylcyclohexanone, N, N, N ′, N′-tetraglycidyl-m-xylenediamine and the like. The system can be mentioned. Examples of copolymer type polyhydric epoxy resins include copolymers of glycidyl methacrylate and styrene, copolymers of glycidyl methacrylate and styrene and methyl methacrylate, or copolymers of glycidyl methacrylate and cyclohexylmaleimide, etc. Can do.

  A curing catalyst can be used for the curing reaction of the polyvalent epoxy compound used in the present invention. For example, imidazole compounds such as 2-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, and triethylamine , Triethylenediamine, N'-methyl-N- (2-dimethylaminoethyl) piperazine, 1,8-diazabicyclo (5,4,0) -undecene-7 and 1,5-diazabicyclo (4,3,0)- Tertiary amines such as nonene-5 and 6-dibutylamino-1,8-diazabicyclo (5,4,0) -undecene-7, and tertiary amines such as phenol, octylic acid and quaternized tetraphenylborate Compounds converted to amine salts with salts, triallylsulfonium hexafluoroantimonate and dia Le iodonium hexafluoroantimonate Mona bets and cationic catalysts include triphenylphosphine and the like. Of these, 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 the like, and compounds obtained by converting these tertiary amines into amine salts with phenol, octylic acid or the like or quaternized tetraphenylborate salts are thermosetting and heat resistant, It is preferable in terms of adhesion to metal and storage stability after blending. It is preferable that the compounding quantity in that case is 0.01-1.0 mass part of compounding quantity with respect to 100 mass parts of phenolic hydroxyl group containing polyamide resins. If it is this range, the effect with respect to reaction of a phenolic hydroxyl group-containing polyamide resin and an epoxy compound will increase further, and a firm coating film can be obtained.

  Examples of the phenol resin suitable as the curing agent used in the present invention include alkylated phenols and / or condensates of cresols and formaldehyde. Specifically, alkylated phenols alkylated with alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, 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, phenyl o- Mention may be made of condensates of cresol, p-phenylphenol, xylenol and the like with formaldehyde.

  Examples of suitable amino resins as curing agents used in the present invention include formaldehyde adducts such as urea, melamine, and benzoguanamine, and alkyl ether compounds obtained by alkoxylating these compounds with alcohols having 1 to 6 carbon atoms. be able to. Specific examples include methoxylated methylol urea, methoxylated methylol-N, N-ethyleneurea, methoxylated methylol dicyandiamide, methoxylated methylol melamine, methoxylated methylol benzoguanamine, butoxylated methylol melamine, butoxylated methylol benzoguanamine and the like. Preferred are methoxylated methylol melamine, butoxylated methylol melamine and methylolated benzoguanamine, each of which can be used alone or in combination.

  The polyvalent isocyanate compound suitable as the curing agent used in the present invention may be either a low molecular compound or a high molecular compound. Examples of the low molecular compound include aliphatic isocyanate compounds such as tetramethylene diisocyanate and hexamethylene diisocyanate, aromatic polyvalent isocyanate compounds such as toluene diisocyanate, diphenylmethane diisocyanate, and xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate, and hydrogenated xylylene diisocyanate. And alicyclic polyvalent isocyanates such as isophorone diisocyanate. Moreover, trimers of these polyvalent isocyanate compounds can be exemplified. Examples of the polymer compound include a terminal isocyanate group-containing compound obtained by reacting a compound having a plurality of active hydrogens with an excess of the low-molecular polyisocyanate compound. Examples of the compound having a plurality of active hydrogens include polyhydric alcohols such as ethylene glycol, propylene glycol, trimethylolpropane, glycerin and sorbitol, polyhydric amines such as ethylenediamine, hydroxyl groups such as monoethanolamine, diethanolamine and triethanolamine And compounds having an amino group, polyester polyols, polyether polyols, polyamides, and other active hydrogen-containing polymers.

  The polyvalent isocyanate compound may be a blocked isocyanate. Examples of the isocyanate blocking agent include phenols such as phenol, thiophenol, methylthiophenol, cresol, xylenol, resorcinol, nitrophenol, and chlorophenol, oximes such as acetoxime, methyl ethyl ketoxime, and cyclohexanone oxime, methanol, ethanol, propanol, Alcohols such as butanol, halogen-substituted alcohols such as ethylene chlorohydrin and 1,3-dichloro-2-propanol, tertiary alcohols such as t-butanol and t-pentanol, ε-caprolactam, δ-valero Examples include lactams such as lactam, γ-butyrolactam, β-propyllactam, and other aromatic amines, imides, acetylacetone, acetoacetate ester, ethyl malonate. Examples include active methylene compounds such as tellurium, mercaptans, imines, ureas, diaryl compounds and sodium bisulfite. The blocked isocyanate is obtained by subjecting the above isocyanate compound, isocyanate compound and isocyanate blocking agent to an addition reaction by a conventionally known appropriate method.

  The polyvalent oxazoline compound suitable as a curing agent used in the present invention is a compound having an oxazoline group in the molecule, and a polymer containing an oxazoline group is particularly preferable, and an addition polymerizable oxazoline group-containing monomer alone or other monomer And can be prepared by polymerization. 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, 2-isopropenyl-5-ethyl-2-oxazoline, and the like can be mentioned, and one or a mixture of two or more thereof can be used. Among these, 2-isopropenyl-2-oxazoline is preferred because it is easily available industrially. The other monomer is not limited as long as it is a monomer copolymerizable with an addition polymerizable oxazoline group-containing monomer. For example, alkyl (meth) acrylate (the alkyl group includes a methyl group, an ethyl group, an n-propyl group, an isopropyl group, (meth) acrylic acid esters such as n-butyl group, isobutyl group, t-butyl group, 2-ethylhexyl group, cyclohexyl group); acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, styrene Unsaturated carboxylic acids such as sulfonic acid and its salts (sodium salt, potassium salt, ammonium salt, tertiary amine salt, etc.); Unsaturated nitriles such as acrylonitrile, methacrylonitrile; (meth) acrylamide, N-alkyl ( (Meth) acrylamide, N, N-dialkyl (meth) acrylamide, As the alkyl group, unsaturated amides such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, 2-ethylhexyl group and cyclohexyl group); vinyl acetate Vinyl esters such as 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, and the like, and one or more of these monomers can be used.

  As the curing agent used in the present invention, a commercially available curing agent can be used, such as polyisocyanate compounds such as Duranate (registered trademark) 24A-100, TPA-100, TLA-100, manufactured by Asahi Kasei Corporation, Nagaseke A polyvalent epoxy resin such as Denacor (registered trademark) EX-411 or EX-321 manufactured by Mitex Corporation can be used.

<Layered inorganic material>
The phenolic hydroxyl group-containing polyamide resin of the present invention can contain a layered inorganic substance. By containing a layer compound, a phenolic hydroxyl group-containing polyamide resin composition having improved gas barrier properties can be provided. The layered inorganic substance may be a natural product or a synthetic product, and a typical example thereof is a layered silicate. Examples of layered silicates include swelling of smectite clay minerals such as montmorillonite, hectorite, fluorine hectorite, saponite, hydelite, stevensite, Na-type fluorine teniolite, Na-type tetrasilicon fluorine mica, Li-type tetrasilicon fluorine mica, etc. Sexual synthetic mica, vermiculite, fluorine vermiculite, halloysite and the like. Among these, swellable synthetic mica such as Na-type tetrasilicon fluorine mica and Li-type tetrasilicon fluorine mica is particularly preferable. The content of the layered inorganic substance 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 with respect to 100 parts by mass of the phenolic hydroxyl group-containing polyamide resin. When the content is small, the gas barrier effect may be lowered. When the content is large, the coating film strength may be lowered.

  As the layered inorganic material, those having a particle size in the range of 10 to 1000 angstroms are preferably used, and more preferably 100 to 500 angstroms. If the particle size is less than 10 angstroms, the layered inorganic substance cannot be sufficiently dispersed in the polyamide molecule, and if it exceeds 1000 angstroms, the tensile strength of the phenolic hydroxyl group-containing polyamide resin composition may be reduced. Therefore, it is not preferable. Further, as the layered inorganic substance, a layer having a unit structure (hereinafter referred to as a unit layer) having a thickness of about 10 angstroms and a distance between unit layers exceeding 10 angstroms is preferable. The layered inorganic material is blended with the phenolic hydroxyl group-containing polyamide resin by a known method. For example, a predetermined amount of layered inorganic material may be added to the system in the polymerization step of the phenolic hydroxyl group-containing polyamide resin, or after preparing the phenolic hydroxyl group-containing polyamide resin, dry blending, melting using an extruder Examples thereof include a kneading method and a method of adding a resin varnish after adjustment.

<Additives>
In the present invention, various additives may be contained in order to impart other functionality to the coating layer within a range not impairing the effects of the present invention. Examples of the additive include inorganic or organic particles, pigments, dyes, antistatic agents, leveling agents, fluorescent dyes, fluorescent whitening agents, plasticizers, dispersants, ultraviolet absorbers, pigment dispersants, and anti-settling agents. Agents, antifoaming agents, antifoaming agents, anti-skinning agents, anti-sagging agents, delustering agents, thickeners, fungicides, antiseptics, conductive agents, or flame retardants. Furthermore, a resin other than the phenolic hydroxyl group-containing polyamide resin, for example, a polyester resin, a polyurethane resin, a polyimide resin, a polyamideimide resin, another polyamide resin, or the like can be appropriately blended. Since the phenolic hydroxyl group value of the phenolic hydroxyl group-containing polyamide resin is large, the dispersibility of various pigments is large, and a paint having a high concentration can be produced.

  In the present invention, particles that can be contained in the coating layer include silica, kaolinite, talc, light calcium carbonate, heavy calcium carbonate, zeolite, alumina, barium sulfate, carbon black, zinc oxide, zinc sulfate, carbonic acid. Inorganic particles such as zinc, zirconium dioxide, titanium dioxide, satin white, aluminum silicate, diatomaceous earth, calcium silicate, aluminum hydroxide, hydrous halloysite, magnesium carbonate, magnesium hydroxide, acrylic or methacrylic, vinyl chloride, acetic acid Vinyl, nylon, styrene / acrylic, styrene / butadiene, polystyrene / acrylic, polystyrene / isoprene, polystyrene / isoprene, methyl methacrylate / butyl methacrylate, melamine, poly Boneto system, urea, epoxy, urethane, phenolic, diallyl phthalate, and organic particles of a polyester or the like.

  In this invention, you may contain a metal compound etc. in the range which does not impair the effect of this invention. The metal constituting the metal compound is not particularly limited, and monovalent metals such as lithium, sodium, potassium, rubidium, and cesium, and magnesium, calcium, zirconium, zinc, copper, cobalt, iron, nickel, aluminum, and the like. A bivalent or higher metal is mentioned. The metal compound is a compound containing the above metal, and examples of the compound include oxides, hydroxides, halides, inorganic salts such as carbonates, bicarbonates, phosphates, sulfates, acetates, Examples thereof include carboxylates such as formate, stearate, citrate, malate and maleate, and organic acid salts such as sulfonate, and oxides and carbonates are preferred. Moreover, you may use a metal simple substance as a metal compound. In particular, an iron ion compound such as iron chloride is preferable from the viewpoint of easy reaction with a phenolic hydroxyl group, and a magnesium ion compound such as magnesium oxide is preferable from the viewpoint of easy reaction with a carboxylic acid. Due to these interaction effects, an improvement in barrier properties can be expected.

<Laminated body>
The phenolic hydroxyl group-containing polyamide resin and composition of the present invention are a layer (B layer) selected from the group consisting of a layer (A layer) containing a phenolic hydroxyl group-containing polyamide resin and a film, sheet, woven fabric, nonwoven fabric and paper. Can be laminated to form a laminate. For example, the laminate is applied with the phenolic hydroxyl group-containing polyamide resin composition (resin varnish) of the present invention on a layer (B layer) selected from the group consisting of a film, a sheet, a woven fabric, a nonwoven fabric, and paper and dried. Can be easily obtained. The resin varnish of the present invention exhibits strong adhesion to films, sheets, woven fabrics, nonwoven fabrics and papers made of various raw materials. In particular, it exhibits high adhesion to films and sheets made from polylactic acid, polyester, polyurethane, polyamide, cellulose, starch, vinyl chloride, vinylidene chloride, chlorinated polyolefin and these chemically modified substances. Moreover, since it shows high adhesive force also to various metal vapor deposition films, it is also useful to use it as a laminate having a three-layer structure of the A layer / metal vapor deposition layer / B layer. Although the metal and B layer used for a metal vapor deposition layer are not specifically limited, Especially the adhesive force of an aluminum vapor deposition film and the phenolic hydroxyl group containing polyamide resin varnish of this invention is large. It is considered that the phenolic hydroxyl group-containing polyamide resin varnish of the present invention exhibits high adhesion to various metal vapor deposited films because of the high phenolic hydroxyl value of the polyester resin of the present invention. These laminates are suitable for use as packaging materials, for example, and are particularly suitable as food packaging materials.

  Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited by the following examples, but may be implemented with appropriate modifications within a scope that can meet the gist of the present invention. These are all included in the technical scope of the present invention.

  Hereinafter, unless otherwise specified, “part” represents “part by mass”. The measurement and evaluation methods employed in the present specification are as follows.

<Resin composition>
A resin sample was dissolved in deuterated chloroform or deuterated dimethyl sulfoxide, and ¹ H-NMR analysis and ¹³ C-NMR analysis were performed as necessary using an NMR apparatus 400-MR manufactured by VARIAN. The composition was determined and expressed in mole%.
Moreover, the amount of phenolic hydroxyl groups (eq / t) was calculated by the following formula based on the resin composition.
Amount of phenolic hydroxyl group (eq / t) = (Σ (P / 100 × Q)) × 10 ⁶ / (Σ (R / 100) × Z)
P = content of each phenolic hydroxyl group-containing component (mol%)
Q = number of phenolic hydroxyl groups in one molecule of each phenolic hydroxyl group-containing component R = content of each constituent component (mol%)
Z = molecular weight of each component

<Glass transition temperature>
Based on JIS K7121 (1987), the glass transition temperature was calculated | required from the DSC curve using the differential scanning calorimeter DSC (the Seiko Instruments Inc. make, DSC200).

<Preparation of coated film sample>
The phenolic hydroxyl group-containing polyamide resin varnish obtained in Examples and Comparative Examples was applied to the corona-treated surface of a 50 μm thick substrate (PET) film (Toyobo Co., Ltd., Toyobo Ester (registered trademark) film E5100). After coating using wire bar # 10, the coated film sample was obtained by drying at 150 ° C. for 1 minute and at 210 ° C. for 1 minute.

<Logarithmic viscosity>
In accordance with JIS K 7367-5 (2000), 0.1 g of a phenolic hydroxyl group-containing polyamide resin was sampled, and a 1,1,2,2-tetrachloroethane / phenol = 40/60 (weight ratio) mixed solution was used. , Measured at 30 ° C.

The gas barrier performance of the produced coated film was evaluated by oxygen permeability.
<Oxygen permeability>
For the coated film, oxygen under the conditions of 23 ° C., relative humidity 65%, or 23 ° C., relative humidity 80% using an oxygen permeability measuring device (trade name: OX-TRAN 2/21, manufactured by Mocon) The transmittance was measured. The oxygen permeability was measured by transmitting oxygen from the thin film (coating layer) side to the PET film side.
The oxygen permeability of the thin film (coating layer) of the coat film was calculated using the following formula. It shows that gas barrier property is so high that oxygen permeability is low.
P = DFT / (1 / R-1 / Rcoat)
Rcoat = Oxygen permeability of coated film (ml / m ² · day · MPa)
R = Oxygen permeability of substrate (PET) film in coated film (ml / m ² · day · MPa)
DFT = thin film (coating layer) thickness (mm)
P = Oxygen permeability of thin film (coating layer) (ml / m ² · day · MPa)

Hereinafter, the abbreviations of the compounds shown in the text and tables in the examples indicate the following compounds, respectively.
H-IPA: hydroxyisophthalic acid H-TPA: hydroxyterephthalic acid AA: adipic acid SA: sebacic acid IPA: isophthalic acid MXDA: metaxylenediamine PXDA: paraxylenediamine PPD: p-phenylenediamine HMDA: hexamethylenediamine DMAc: dimethyl Acetamide BzlOH: benzyl alcohol

<Solvent solubility>
The phenolic hydroxyl group-containing polyamide resin was dissolved in an organic solvent at 160 ° C. so that the resin concentration was 20% by mass. After stirring for 2 hours, the solution state was observed and evaluated according to the following criteria.
○: Completely dissolved.
Δ: Almost dissolved, but slightly turbid.
X: Almost no dissolution.

Example A-1
Phenolic hydroxyl group-containing polyamide resin no. Production of 1 A 500 ml glass flask equipped with a thermometer, a stirrer, and a Liebig condenser was charged with 25 parts of 5-hydroxyisophthalic acid, 25 parts of adipic acid, and 50 parts of metaxylylenediamine, and the polymerization system was maintained while circulating nitrogen gas. The temperature was raised to 170 ° C., and the temperature was raised to 255 ° C. at a rate of 3 ° C./min. After stirring for 15 minutes at 255 ° C., the contents were taken out and cooled. The obtained phenolic hydroxyl group-containing polyamide resin No. Table 1 shows the composition, logarithmic viscosity, phenolic hydroxyl group amount, and the like.

Examples A-1 to A-7, Comparative Examples B-1 to B-4
Phenolic hydroxyl group-containing polyamide resin no. Production of phenolic hydroxyl group-containing polyamide resin No. 2-11 1 except that the raw materials and the ratios thereof were changed and the phenolic hydroxyl group-containing polyamide resin No. 1 was changed. 2 to 11 were synthesized, and phenolic hydroxyl group-containing polyamide resin No. 2 was synthesized. Evaluation similar to 1 was performed. The evaluation results are shown in Tables 1 and 2.

Phenolic hydroxyl group-containing polyamide resin no. No. 8 is outside the scope of the present invention because the dicarboxylic acid unit having a phenolic hydroxyl group is less than 10 mol% and the phenolic hydroxyl group amount is less than 500 eq / t. Phenolic hydroxyl group-containing polyamide resin no. No. 9 is outside the scope of the present invention because the amount of phenolic hydroxyl group exceeds 6000 eq / t. Phenolic hydroxyl group-containing polyamide resin no. No. 10 is outside the scope of the present invention because the aromatic diamine unit is less than 20 mol%. Phenolic hydroxyl group-containing polyamide resin no. No. 11 is out of the scope of the present invention because the oxygen permeability exceeds 1000 ml / m ² · day · MPa.

Example C-1
Production and evaluation of phenolic hydroxyl group-containing polyamide resin varnish A phenolic hydroxyl group-containing polyamide resin No. 1 was added to a 500 ml glass flask equipped with a thermometer, a stirrer and a Liebig condenser. 20 parts of 1 and 80 parts of dimethylacetamide were charged, heated to 160 ° C. and stirred for 2 hours, and then the contents were taken out and cooled to produce a phenolic hydroxyl group-containing polyamide resin varnish 1. The obtained varnish was applied to a film substrate by the method described above, and the oxygen permeability of the obtained coated film sample was evaluated. The results are shown in Table 3.

Examples C-2 to C-7
In the same manner as in Example C-1, except that the raw materials and the ratios thereof were changed to produce a phenolic hydroxyl group-containing polyamide resin varnish to produce phenolic hydroxyl group-containing polyamide resin varnishes C-2 to C-7. . Furthermore, it applied to the film base material similarly to Example C-1, and the oxygen permeability of the obtained coat film sample was evaluated. The results are shown in Table 3. All showed high solvent solubility and high gas barrier properties (low oxygen permeability) even under high humidity.

Comparative Examples C-8 to C-11
In the same manner as in Example C-1, except that the raw materials and ratios thereof were changed, an attempt was made to produce a phenolic hydroxyl group-containing polyamide resin varnish. About what obtained the varnish, it apply | coated to the film base material similarly to Example C-1, and the oxygen permeability of the obtained coat film sample was evaluated. The results are shown in Table 4.

  In Comparative Example C-8, a large amount of undissolved resin was present even after 2 hours of stirring, and a large amount of undissolved resin remained even after stirring for 1 hour. The polyamide resin used in Comparative Example C-8 is out of the scope of the present invention because the dicarboxylic acid unit having a phenolic hydroxyl group is less than 10 mol% and the phenolic hydroxyl group amount is less than 500 eq / t. It is presumed that the polyamide resin has crystallinity and the dissolution hardly progressed.

  In Comparative Example C-9, the solvent solubility was good, but the barrier property under high humidity was greatly reduced. Polyamide resin No. used in Comparative Example C-9 No. 9 is outside the scope of the present invention because the amount of phenolic hydroxyl group exceeds 6000 eq / t. It is presumed that the amount of phenolic hydroxyl group is too high, so that it shows humidity dependency.

  Although Comparative Example C-10 had good solvent solubility, it did not show barrier properties under low humidity and high humidity. Polyamide resin No. used in Comparative Example C-10 No. 10 is outside the scope of the present invention because the aromatic diamine unit is less than 20 mol%. Since there are few aromatic diamine units, it is estimated that the mechanical properties of the obtained coating film are weak, and gas barrier properties were not exhibited due to the occurrence of cracks and the like.

In Comparative Example C-11, although the solvent solubility was good, the oxygen permeability was more than 1000 ml / m ² · day · MPa. Polyamide resin No. used in Comparative Example C-11 No. 11 is presumed to be because the logarithmic viscosity was less than 0.05 dl / g, the mechanical properties of the obtained coating film were weak, and oxygen barrier properties were not exhibited.

Example D-1
To 100 parts of the C-1 varnish filtrate filtered through a 100 mesh filter cloth, 3.5 parts of a curing agent (Duranate (registered trademark) TPA100 manufactured by Asahi Kasei Co., Ltd.), a polyisocyanate compound, is added to obtain D-1. It was.

Example D-2
4.4 parts of a curing agent (Duranate TPA100 manufactured by Asahi Kasei Co., Ltd.), which is a polyisocyanate compound, was added to 100 parts of the C-2 varnish filtrate filtered through a 100 mesh filter cloth to obtain D-2. An adhesion test was performed using the above (D-1) and (D-2). In addition, preparation and evaluation of the coated plate followed the following method. The results are shown in Table 5.

Preparation of coated plate (test plate) After coating (D-1) and (D-2) on a hot dip galvanized steel plate, it was dried at 150 ° C. for 10 minutes and then baked at 140 ° C. for 30 minutes. The film thickness was 5 μm.

<Evaluation of adhesion>
According to JIS-K5600-5-6 (1999) grid pattern-tape method, parallel straight lines of 6 vertical and horizontal lines are drawn at 1 mm intervals so as to reach the substrate with a cutter knife on the coating film surface of the test plate. 25 squares of 1 mm × 1 mm were created. A cellophane pressure-sensitive adhesive tape was adhered to the surface, and the degree of cell peeling when the tape was rapidly peeled was observed and evaluated according to the following criteria.
(Double-circle): Coating film peeling is not seen at all.
○: The coating film was slightly peeled, but 20 or more squares remained.
(Triangle | delta): A coating film peels and the remaining number of squares is 10 or more and less than 20.
X: The coating film was peeled off, and the remaining number of cells was less than 10.

Example E-1
To 100 parts of the C-1 varnish filtrate filtered through a 100-mesh filter cloth, 0.6 part of a lipophilic plate-like synthetic mica (Somasif (registered trademark) MEE manufactured by Katakura Corp.) is added as a layered inorganic substance. -1 was obtained.

Example E-2
To 100 parts of the C-2 varnish filtrate filtered through a 100-mesh filter cloth, 1.2 parts of lipophilic plate-like synthetic mica (Somasif (registered trademark) MEE manufactured by Katakura Corp.) is added as a layered inorganic substance. -2 was obtained. Using the above (E-1) and (E-2), it was applied to a film substrate by the method described above, and the oxygen permeability of the obtained coated film sample was evaluated. The results are shown in Table 6.

  The phenolic hydroxyl group-containing polyamide resin of the present invention and the resin composition containing the same can provide a coating film having a high gas barrier property under high humidity.

Claims (6)

A phenolic hydroxyl group-containing polyamide resin containing 10 mol% or more of a dicarboxylic acid (A) unit having a phenolic hydroxyl group and 20 mol% or more of an aromatic diamine (B) unit and satisfying the following (1) to (2): .
(1) The amount of phenolic hydroxyl group is 500 to 6000 eq / t. (2) When a thin film having a film thickness of 1 μm is prepared with a phenolic hydroxyl group-containing polyamide resin, the temperature of the thin film is 40 ° C. and the humidity is 85% RH. The oxygen permeability is 1000 ml / m ² · day · MPa or less.   A phenolic hydroxyl group-containing polyamide resin composition comprising the phenolic hydroxyl group-containing polyamide resin according to claim 1 and an organic solvent.   Furthermore, the phenolic hydroxyl group containing polyamide resin composition of Claim 1 or 2 containing a hardening | curing agent.   Furthermore, the phenolic hydroxyl group containing polyamide resin composition in any one of Claims 1-3 containing a layered inorganic substance.   A laminate comprising a layer (A layer) containing the phenolic hydroxyl group-containing polyamide resin according to claim 1 and one or more layers (B layer) selected from the group consisting of a film, a sheet, a woven fabric, a nonwoven fabric and paper. body.   The packaging material which has the laminated body of Claim 5 as a component.