Polyamide composition, polyamide molded article and composite

Abstract

To provide a polyamide composition having high adhesive strength and excellent heat deformation resistance, heat aging resistance and rigidity and a composite having the polyamide composition.SOLUTION: There is provided a polyamide composition comprising a polyamide (A) and an epoxy resin (B), wherein the polyamide (A) comprises a dicarboxylic acid unit and a diamine unit, the dicarboxylic acid unit comprises 50 mol% or more of a structural unit derived from at least one selected from the group consisting of terephthalic acid and naphthalenedicarboxylic acid, based on 100 mol% of the total dicarboxylic acid units, the diamine unit comprises 60 mol% or more of an aliphatic diamine unit having 7 to 13 carbon atoms based on 100 mol%of the total diamine units, the softening point of the epoxy resin (B), obtained in accordance with JIS K 7196:2012, is 70°C or more and 110°C or less and the content of the epoxy resin (B) in the polyamide composition is more than 0 mass% and 20 mass% or less.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a polyamide composition, a polyamide molded article, and a composite. [Background technology]

[0002] From the viewpoint of weight reduction, molded articles formed from polyamide compositions are widely used as parts in various fields such as sporting goods, automobile parts, etc. When such molded articles are used as parts, a coating film may be applied to the surface of the molded article. For example, Patent Document 1 describes a polyamide resin composition containing a specific amount of a specific copolymer polyamide resin, and describes that the polyamide resin composition has excellent coating film adhesion. Patent Document 2 describes a polyamide resin composition containing a crystalline polyamide resin, a polyalcohol, and an epoxy resin, and describes that the polyamide resin composition has excellent coating film adhesion. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2007-224288 [Patent Document 2] Special Publication No. 2010-532406 Summary of the Invention [Problem to be solved by the invention]

[0004] In recent years, composites formed by bonding a molded article formed from a polyamide composition with a molded article different from the molded article have been used as parts in various fields. The molded article formed from the polyamide composition contained in such composites is required to have not only adhesion to a coating film but also adhesion to a molded article different from the molded article. However, molded articles formed from conventional polyamide compositions have not been satisfactory in adhesion to a coating film or adhesion to a molded article different from the molded article. This has resulted in a problem of insufficient strength of the composite. Furthermore, depending on the type of resin contained in the polyamide composition, there have been problems such as the composite being subject to thermal deformation or having poor heat aging resistance.

[0005] In view of the above problems, the present invention aims to provide a polyamide composition having high adhesive strength and excellent heat distortion resistance, heat aging resistance, and rigidity, a polyamide molded article formed from the polyamide composition, and a composite including the polyamide composition. [Means for solving the problem]

[0006] As a result of intensive research to solve the above problems, the present inventors have conceived the following invention and found that the problems can be solved. That is, the present invention is as follows.

[0007] [1] A polyamide composition containing a polyamide (A) and an epoxy resin (B), The polyamide (A) contains a dicarboxylic acid unit and a diamine unit, the dicarboxylic acid units contain 50 mol% or more of structural units derived from at least one selected from the group consisting of terephthalic acid and naphthalenedicarboxylic acid relative to 100 mol% of all dicarboxylic acid units; The diamine units contain aliphatic diamine units having 7 to 13 carbon atoms in an amount of 60 mol % or more relative to 100 mol % of all diamine units, the softening point of the epoxy resin (B) measured in accordance with JIS K 7196:2012 is 70°C or higher and 110°C or lower; The polyamide composition, wherein the content of the epoxy resin (B) in the polyamide composition is more than 0 mass % and 20 mass % or less. [2] The polyamide composition according to [1] above, wherein the aliphatic diamine unit having 7 to 13 carbon atoms is a structural unit derived from at least one selected from the group consisting of 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, 2-methyl-1,8-octanediamine, 1,10-decanediamine, and 1,12-dodecanediamine. [3] The polyamide composition according to [1] or [2] above, wherein the aliphatic diamine unit having 7 to 13 carbon atoms is a structural unit derived from at least one selected from the group consisting of 1,9-nonanediamine and 2-methyl-1,8-octanediamine. [4] The polyamide composition according to any one of the above [1] to [3], wherein the epoxy equivalent of the epoxy resin (B) is 1500 g / eq or more and 3500 g / eq or less. [5] The polyamide composition according to any one of [1] to [4] above, wherein a test piece made of the polyamide composition has a tensile strength retention rate of 80% or more, measured in accordance with ISO 527-1:2019, before and after heat treatment at 130°C for 1,000 hours. [6] A polyamide molded article formed from the polyamide composition according to any one of the above [1] to [5]. [7] The polyamide molded article according to [6] above, having a coating film on the surface. [8] The polyamide molded article according to [6] or [7] above, which is an exterior panel part. [9] A composite comprising the polyamide molded product according to the above item [6] and a molded product (X) different from the polyamide molded product.

[10] The composite according to the above [9], wherein the molded body (X) contains at least one material selected from the group consisting of organic materials, inorganic materials, and metal materials.

[11] The composite according to

[10] above, having a coating film on the surface.

[12] The composite according to [9] above, which comprises an adhesive layer between the polyamide molded body and the molded body (X).

[13] The composite according to [9] above, which is an outer panel part. [Effects of the Invention]

[0008] According to the present invention, it is possible to provide a polyamide composition having high adhesive strength and excellent heat distortion resistance, heat aging resistance, and rigidity, a polyamide molded article formed from the polyamide composition, and a composite including the polyamide composition. [Brief explanation of the drawings]

[0009] [Figure 1] FIG. 1 is an explanatory diagram illustrating a composite prepared in an example. DETAILED DESCRIPTION OF THE INVENTION

[0010] The following describes an example of an embodiment of the present invention (hereinafter, sometimes referred to as "the present embodiment"). However, the embodiment described below is merely an example for embodying the technical idea of ​​the present invention, and the present invention is not limited to the following description. In addition, although preferred embodiments are shown in this specification, a combination of two or more of the individual preferred embodiments is also a preferred embodiment. When there are several numerical ranges for matters shown as numerical ranges, the lower limit and upper limit can be selectively combined to form a preferred embodiment. In this specification, when a numerical range is stated as "XX to YY", it means "XX or more and YY or less." In addition, in this specification, the term "unit" (where "" indicates a monomer) means "a structural unit derived from". For example, a "dicarboxylic acid unit" means "a structural unit derived from a dicarboxylic acid", and a "diamine unit" means "a structural unit derived from a diamine".

[0011] [Polyamide composition] The polyamide composition according to the present embodiment is a polyamide composition containing a polyamide (A) and an epoxy resin (B), wherein the polyamide (A) contains dicarboxylic acid units and diamine units, the dicarboxylic acid units contain 50 mol% or more of structural units derived from at least one selected from the group consisting of terephthalic acid and naphthalenedicarboxylic acid, relative to 100 mol% of all dicarboxylic acid units, and the diamine units contain 60 mol% or more of aliphatic diamine units having 7 to 13 carbon atoms, the softening point of the epoxy resin (B) obtained in accordance with JIS K 7196:2012 is 70°C or more and 110°C or less, and the content of the epoxy resin (B) in the polyamide composition is more than 0 mass% and 20 mass% or less.

[0012] The polyamide composition according to the present embodiment has high adhesive strength and is excellent in heat distortion resistance, heat aging resistance, and rigidity. Although the details of the reasons for this are unknown, it is presumed to be due to the following reasons. The polyamide composition according to the present embodiment contains a polyamide (A) and an epoxy resin (B). Hydroxyl groups are generated by reaction of the end groups of the polyamide (A) with the epoxide contained in the epoxy resin (B). It is believed that the generated hydroxyl groups provide the polyamide composition with high adhesive strength, excellent heat distortion resistance, and excellent heat aging resistance. The epoxy resin (B) contained in the polyamide composition according to the present embodiment has a softening point of 70° C. or more and 110° C. or less. When the polyamide composition contains an epoxy resin (B) having such a specific softening point, the generated components having hydroxyl groups are prevented from evaporating during melt-kneading, and it is believed that the polyamide composition exhibits excellent heat distortion resistance and heat aging resistance. Furthermore, the epoxy resin (B) is less likely to bleed out during molding. When the polyamide composition is heated, a crosslinking reaction between the polyamide (A) and the epoxy resin (B) proceeds. For these reasons, it is believed that the heat aging resistance of the polyamide composition is further improved. Furthermore, although the polyamide composition contains polyamide (A) and epoxy resin (B), the rigidity of the polyamide (A) is maintained, so the polyamide composition also has excellent rigidity.

[0013] <Polyamide (A)> The polyamide (A) according to the present embodiment contains dicarboxylic acid units and diamine units, and the dicarboxylic acid units contain 50 mol % or more of structural units derived from at least one selected from the group consisting of terephthalic acid and naphthalenedicarboxylic acid relative to 100 mol % of all dicarboxylic acid units, and the diamine units contain 60 mol % or more of aliphatic diamine units having 7 to 13 carbon atoms relative to 100 mol % of all diamine units.

[0014] (dicarboxylic acid unit) The polyamide (A) according to the present embodiment contains a dicarboxylic acid unit. Preferred examples of the dicarboxylic acid unit include aromatic dicarboxylic acid units such as terephthalic acid unit, naphthalenedicarboxylic acid unit, isophthalic acid unit, 1,4-phenylenedioxydiacetic acid unit, 1,3-phenylenedioxydiacetic acid unit, diphenic acid unit, diphenylmethane-4,4'-dicarboxylic acid unit, diphenylsulfone-4,4'-dicarboxylic acid unit, and 4,4'-biphenyldicarboxylic acid unit. Examples of the naphthalenedicarboxylic acid unit include a 2,6-naphthalenedicarboxylic acid unit, a 2,7-naphthalenedicarboxylic acid unit, and a 1,4-naphthalenedicarboxylic acid unit, with the 2,6-naphthalenedicarboxylic acid unit being preferred.

[0015] Examples of the dicarboxylic acid unit include units derived from aliphatic dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, dimethylmalonic acid, 2,2-diethylsuccinic acid, 2,2-dimethylglutaric acid, 2-methyladipic acid, trimethyladipic acid, and dimer acid; and alicyclic dicarboxylic acids such as 1,3-cyclopentanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, cycloheptanedicarboxylic acid, cyclooctanedicarboxylic acid, and cyclodecanedicarboxylic acid. The unit derived from these dicarboxylic acids may be of one type only, or may be of two or more types.

[0016] The dicarboxylic acid units contained in the polyamide (A) according to the present embodiment contain 50 mol% or more of structural units derived from at least one selected from the group consisting of terephthalic acid and naphthalenedicarboxylic acid, relative to 100 mol% of all dicarboxylic acid units. When the dicarboxylic acid units contain 50 mol% or more of structural units derived from at least one selected from the group consisting of terephthalic acid and naphthalenedicarboxylic acid, the polyamide has excellent heat distortion resistance, and a polyamide composition having excellent heat distortion resistance can be obtained. From the viewpoint of obtaining a polyamide composition having even better heat distortion resistance, the polyamide (A) used in the present invention preferably contains 75 mol% or more, more preferably 90 mol% or more, and even more preferably 100 mol% of at least one selected from the group consisting of terephthalic acid units and naphthalenedicarboxylic acid units, relative to 100 mol% of all dicarboxylic acid units.

[0017] Furthermore, from the viewpoint of improving heat resistance, rigidity, and chemical resistance, the dicarboxylic acid units preferably contain 50 mol% or more, more preferably 75 mol% or more, even more preferably 90 mol% or more, and even more preferably 100 mol% of structural units derived from terephthalic acid relative to 100 mol% of all dicarboxylic acid units.

[0018] (diamine units) The polyamide (A) according to the present embodiment contains 60 mol % or more of aliphatic diamine units having 7 to 13 carbon atoms relative to 100 mol % of all diamine units. When 60 mol % or more of all diamine units are aliphatic diamine units having 7 to 13 carbon atoms, the resulting polyamide has excellent heat distortion resistance, and a polyamide composition having excellent heat distortion resistance can be obtained. The polyamide (A) according to the present embodiment preferably contains 75 mol % or more, more preferably 90 mol % or more, and even more preferably 100 mol % of aliphatic diamine units having 7 to 13 carbon atoms relative to 100 mol % of all diamine units.

[0019] Examples of diamine units contained in the polyamide (A) according to the present embodiment include units derived from linear aliphatic diamines such as 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,11-undecanediamine, 1,12-dodecanediamine, and 1,13-tridecanediamine; branched aliphatic diamines such as 2,2,4-trimethyl-1,6-hexanediamine, 2,4,4-trimethyl-1,6-hexanediamine, 2-methyl-1,8-octanediamine, and 5-methyl-1,9-nonanediamine; alicyclic diamines such as methylcyclohexanediamine and isophoronediamine; and aromatic diamines such as p-phenylenediamine, m-phenylenediamine, xylylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, and 4,4'-diaminodiphenyl ether. The unit derived from these diamines may be contained in one kind or in two or more kinds.

[0020] Examples of the aliphatic diamine unit having 7 to 13 carbon atoms include the above-mentioned linear aliphatic diamines and branched aliphatic diamines.

[0021] The aliphatic diamine unit having 7 to 13 carbon atoms is preferably a structural unit derived from at least one selected from the group consisting of 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, 2-methyl-1,8-octanediamine, 1,10-decanediamine, and 1,12-dodecanediamine. Since a polyamide composition having even more excellent heat distortion resistance can be obtained, the aliphatic diamine units having 7 to 13 carbon atoms are more preferably units derived from at least one selected from the group consisting of 1,9-nonanediamine and 2-methyl-1,8-octanediamine, and even more preferably 1,9-nonanediamine units and 2-methyl-1,8-octanediamine units. When the aliphatic diamine units contain both units derived from 1,9-nonanediamine and 2-methyl-1,8-octanediamine, the molar ratio of 1,9-nonanediamine units to 2-methyl-1,8-octanediamine units, 1,9-nonanediamine units / 2-methyl-1,8-octanediamine units, is preferably in the range of 95 / 5 to 5 / 95, more preferably 90 / 10 to 10 / 90, and even more preferably 85 / 15 to 15 / 85.

[0022] (aminocarboxylic acid unit and / or lactam unit) The polyamide (A) according to the present embodiment may contain an aminocarboxylic acid unit and / or a lactam unit. Examples of the aminocarboxylic acid unit include units derived from 11-aminoundecanoic acid, 12-aminododecanoic acid, etc. The aminocarboxylic acid unit may be one type only, or two or more types may be contained. The content of the aminocarboxylic acid unit in the polyamide is preferably 50 mol % or less, more preferably 20 mol % or less, and even more preferably 10 mol % or less, relative to 100 mol % of all monomer units constituting the polyamide.

[0023] Examples of the lactam units include units derived from ε-caprolactam, enantholactam, undecane lactam, lauryllactam, α-pyrrolidone, α-piperidone, etc. The lactam units may be of one type only, or may be of two or more types. The content of lactam units in the polyamide is preferably 50 mol% or less, more preferably 20 mol% or less, and even more preferably 10 mol% or less, relative to 100 mol% of all monomer units constituting the polyamide.

[0024] (Type of polyamide (A)) In the present embodiment, the polyamide (A) is a semi-aromatic polyamide containing structural units derived from at least one selected from the group consisting of terephthalic acid and naphthalenedicarboxylic acid, i.e., dicarboxylic acid units containing 50 mol % or more aromatic dicarboxylic acid units, and diamine units containing 60 mol % or more aliphatic diamine units having 7 to 13 carbon atoms.

[0025] Representative semi-aromatic polyamides include polynonamethylene terephthalamide (polyamide 9T), poly(2-methyloctamethylene) terephthalamide (polyamide M8T), polynonamethylene terephthalamide / poly(2-methyloctamethylene) terephthalamide copolymer (polyamide 9T / M8T), polynonamethylene naphthalene dicarboxamide (polyamide 9N), polynonamethylene naphthalene dicarboxamide / poly(2-methyloctamethylene) naphthalene dicarboxamide copolymer (polyamide 9N / M8N), polydecamethylene terephthalamide (polyamide 10T), and copolymers of polyamide 10T and polyundecaneamide (polyamide 11) (polyamide 10T / 11), and polydodecamethylene terephthalamide (polyamide 12).

[0026] Among these, polyamide 10T / 11, polynonamethylene naphthalene dicarboxamide (polyamide 9N), polynonamethylene naphthalene dicarboxamide / poly(2-methyloctamethylene) naphthalene dicarboxamide copolymer (polyamide 9N / M8N), polynonamethylene terephthalamide (polyamide 9T), polynonamethylene terephthalamide / poly(2-methyloctamethylene) terephthalamide copolymer (polyamide 9T / M8T), and poly At least one selected from decamethylene terephthalamide (polyamide 10T) is preferred, and at least one selected from polynonamemethylene naphthalene dicarboxamide / poly(2-methyloctamethylene) naphthalene dicarboxamide copolymer (polyamide 9N / M8N), polynonamemethylene terephthalamide / poly(2-methyloctamethylene) terephthalamide copolymer (polyamide 9T / M8T), polyamide 10T, and polyamide 12T is more preferred. From the viewpoints of ensuring moldability and rigidity at high temperatures, polynonamemethylene terephthalamide / poly(2-methyloctamethylene) terephthalamide copolymer (polyamide 9T / M8T) is even more preferred.

[0027] (Melting Point) In the present embodiment, the melting point of the polyamide (A) is preferably 250° C. or higher, more preferably 285° C. or higher, and even more preferably 290° C. or higher, from the viewpoint of excellent heat deformation resistance, and is preferably 330° C. or lower, more preferably 320° C. or lower, and even more preferably 310° C. or lower.

[0028] (Amount of terminal amino groups) In the present embodiment, the polyamide (A) preferably has a terminal amino group content (hereinafter also referred to as "terminal amino group amount") ([NH2]) of 5 to 45 μeq / g, more preferably 10 to 30 μeq / g, and even more preferably 10 to 25 μeq / g. If the terminal amino group content ([NH2]) is 45 μeq / g or less, the polyamide resin composition has good heat aging resistance. The amount of terminal amino groups ([NH2]) refers to the amount of terminal amino groups (unit: μeq) contained in 1 g of polyamide (A) and can be determined by neutralization titration using an indicator. The amount of terminal amino groups ([NH2]) is specifically measured by the procedure described in the Examples.

[0029] (end-capping agent) The polyamide (A) according to the present embodiment may have its molecular chain terminal groups blocked with a terminal blocking agent.

[0030] As the terminal blocking agent, a monofunctional compound having reactivity with a terminal amino group or a terminal carboxyl group can be used. Specific examples include monocarboxylic acids, acid anhydrides, monoisocyanates, monoacid halides, monoesters, monoalcohols, and monoamines. From the viewpoints of reactivity and the stability of the blocked terminals, monocarboxylic acids are preferred as terminal blocking agents for terminal amino groups, and monoamines are preferred as terminal blocking agents for terminal carboxyl groups. From the viewpoints of ease of handling, monocarboxylic acids are more preferred as terminal blocking agents.

[0031] The monocarboxylic acid used as the terminal blocking agent is not particularly limited as long as it is reactive with an amino group. Examples of the monocarboxylic acid include aliphatic monocarboxylic acids such as acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, stearic acid, pivalic acid, and isobutyric acid; alicyclic monocarboxylic acids such as cyclopentanecarboxylic acid and cyclohexanecarboxylic acid; aromatic monocarboxylic acids such as benzoic acid, toluic acid, α-naphthalenecarboxylic acid, β-naphthalenecarboxylic acid, methylnaphthalenecarboxylic acid, and phenylacetic acid; and mixtures thereof. Among these, at least one selected from the group consisting of acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, stearic acid, and benzoic acid is preferred in terms of reactivity, stability of the blocked terminal, cost, and the like.

[0032] The monoamine used as the terminal blocking agent is not particularly limited as long as it is reactive with a carboxyl group. Examples of the monoamine include aliphatic monoamines such as methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, decylamine, stearylamine, dimethylamine, diethylamine, dipropylamine, and dibutylamine; alicyclic monoamines such as cyclohexylamine and dicyclohexylamine; aromatic monoamines such as aniline, toluidine, diphenylamine, and naphthylamine; and mixtures thereof. Among these, at least one selected from the group consisting of butylamine, hexylamine, octylamine, decylamine, stearylamine, cyclohexylamine, and aniline is preferred from the viewpoints of reactivity, high boiling point, stability of the blocked terminal, and cost.

[0033] In the polyamide (A) according to the present embodiment, the total content of the dicarboxylic acid units, diamine units, and end-capping agent units is preferably 80 to 100 mol%, more preferably 85 to 100 mol%, even more preferably 90 to 100 mol%, and still more preferably 95 to 100 mol%, relative to 100 mol% of all monomer units in the polyamide (A), from the viewpoint of obtaining a polyamide composition having excellent heat distortion resistance and rigidity.

[0034] (Method for producing polyamide (A)) The polyamide (A) can be produced by any known method for producing polyamides, such as a solution polymerization method or an interfacial polymerization method using an acid chloride, a dicarboxylic acid, and a diamine as raw materials, a melt polymerization method, a solid-state polymerization method, or a melt extrusion polymerization method using a dicarboxylic acid and a diamine as raw materials.

[0035] Catalysts that can be used in producing the polyamide (A) include, for example, phosphoric acid, phosphorous acid, hypophosphorous acid, and salts or esters thereof. Examples of the salts or esters of phosphoric acid, phosphorous acid, and hypophosphorous acid include salts or hydrates of phosphoric acid, phosphorous acid, or hypophosphorous acid with metals such as potassium, sodium, magnesium, vanadium, calcium, zinc, cobalt, manganese, tin, tungsten, germanium, titanium, and antimony; ammonium salts of phosphoric acid, phosphorous acid, or hypophosphorous acid; and ethyl esters, isopropyl esters, butyl esters, hexyl esters, isodecyl esters, octadecyl esters, decyl esters, stearyl esters, and phenyl esters of phosphoric acid, phosphorous acid, or hypophosphorous acid. Among these, at least one catalyst selected from the group consisting of sodium hypophosphite monohydrate and phosphorous acid is preferred.

[0036] <Epoxy resin (B)> The epoxy resin (B) according to the present embodiment has a softening point determined in accordance with JIS K 7196:2012 of 70°C or more and 110°C or less, and its content in the polyamide composition is more than 0 mass% and 20 mass% or less. The epoxy resin (B) according to the present embodiment is preferably a compound having epoxy groups at least at both ends. The presence or absence of epoxy groups can be determined by a time-of-flight mass spectrometer (TOF-MS).

[0037] When the softening point of the epoxy resin (B) according to the present embodiment is 70°C or higher, evaporation during melt-kneading and bleeding out during molding are suppressed, and a polyamide composition having excellent heat distortion resistance and heat aging resistance is obtained. Furthermore, when the softening point of the epoxy resin (B) according to the present embodiment is 110°C or lower, the moldability of the polyamide composition is good. The softening point of the epoxy resin (B) according to the present embodiment is preferably 80° C. or higher, more preferably 85° C. or higher, and even more preferably 90° C. or higher, from the viewpoint of obtaining a polyamide composition having excellent heat distortion resistance and heat aging resistance. Also, from the viewpoint of moldability, the softening point is preferably 105° C. or lower, more preferably 100° C. or lower, and even more preferably 95° C. or lower. The softening point of the epoxy resin (B) can be measured by the method described in JIS K 7196:2012, specifically by the method described in the examples.

[0038] The epoxy equivalent of the epoxy resin (B) according to the present embodiment is preferably 1500 g / eq or more, more preferably 1700 g / eq or more, and even more preferably 1750 g / eq or more, from the viewpoint of obtaining a polyamide composition having high adhesive strength and excellent heat distortion resistance and heat aging resistance, and is preferably 3500 g / eq or less, more preferably 3300 g / eq or less, and even more preferably 3000 g / eq or less, from the viewpoint of adhesiveness. That is, the epoxy equivalent of the epoxy resin (B) is preferably 1500 to 3500 g / eq, more preferably 1700 to 3300 g / eq, and even more preferably 1750 to 3000 g / eq. The epoxy equivalent of the epoxy resin (B) can be measured by the method described in JIS K 7236:2009, and specifically, by the method described in the examples.

[0039] Examples of the epoxy resin (B) include bisphenol-type epoxy resins such as bisphenol A-type epoxy resins and bisphenol F-type epoxy resins; biphenyl-type epoxy resins such as biphenyl-type epoxy resins and tetramethylbiphenyl-type epoxy resins; novolac-type epoxy resins such as phenol novolac-type epoxy resins, cresol novolac-type epoxy resins, bisphenol A novolac-type epoxy resins, and biphenyl novolac-type epoxy resins; triphenylmethane-type epoxy resins; tetraphenylethane-type epoxy resins; dicyclopentadiene-phenol addition reaction-type epoxy resins; phenol aralkyl-type epoxy resins; naphthol novolac-type epoxy resins, naphthol aralkyl-type epoxy resins, naphthol-phenol co-condensed novolac-type epoxy resins, naphthol-cresol co-condensed novolac-type epoxy resins, diglycidyloxynaphthalene, and phosphorus-containing epoxy resins. Among these, bisphenol-type epoxy resins are preferred, and bisphenol A-type epoxy resins are more preferred, from the viewpoint of obtaining a polyamide composition having high adhesive strength and excellent heat distortion resistance and heat aging resistance. The epoxy resin (B) may be used alone or in combination of two or more kinds.

[0040] The epoxy resin (B) may be a crosslinked epoxy resin or an uncrosslinked epoxy resin, but from the viewpoint of heat aging resistance, an uncrosslinked epoxy resin is preferred. From the viewpoint of heat aging resistance, the epoxy resin (B) is preferably linear. From the viewpoint of heat aging resistance, the epoxy resin (B) is preferably a thermoplastic resin.

[0041] As the epoxy resin (B), commercially available products such as the Epiclon (registered trademark) series from DIC Corporation and the jER (registered trademark) series from Mitsubishi Chemical Corporation can be used.

[0042] <Inorganic fillers> The polyamide composition according to the present embodiment may contain the above polyamide (A) and epoxy resin (B), and may further contain an inorganic filler, if necessary. The inorganic filler is not particularly limited, and known fillers can be used as long as they do not impair the effects of the present invention. Examples of inorganic fillers include glass flakes, talc, kaolin, mica, silicon nitride, hydrotalcite, calcium carbonate, zinc carbonate, titanium oxide, calcium hydrogen phosphate, wollastonite, silica, zeolite, alumina, boehmite, aluminum hydroxide, calcium silicate, sodium aluminosilicate, magnesium silicate, ketjen black, acetylene black, furnace black, carbon nanotubes, graphite, graphene, brass, copper, silver, aluminum, nickel, iron, calcium fluoride, montmorillonite, swellable fluoromica, and apatite. Among these, at least one selected from the group consisting of talc, wollastonite, and calcium carbonate is preferred, and talc is more preferred. These inorganic fillers may be used alone or in combination.

[0043] <Other additives> The polyamide composition according to the present embodiment may contain other additives in addition to the polyamide (A) and epoxy resin (B) as required. Examples of other additives include stabilizers such as copper compounds; antioxidants such as hindered phenol antioxidants, hindered amine antioxidants, phosphorus-based antioxidants, and thio-based antioxidants; colorants such as carbon black; ultraviolet absorbers; light stabilizers; antistatic agents; flame retardants such as brominated polymers, antimony oxide, metal hydroxides, and phosphinates; flame retardant assistants; nucleating agents; plasticizers; lubricants; glidants; dispersants; oxygen absorbers; hydrogen sulfide adsorbents; mold release agents; organic fibrous fillers such as wholly aromatic polyamide fibers; and impact modifiers such as α-olefin copolymers and rubber.

[0044] <Content of each ingredient> The content of polyamide (A) in the polyamide composition is preferably 75 to 99.9% by mass. Within this range, a polyamide composition having higher adhesive strength and more excellent heat distortion resistance, heat aging resistance, and rigidity can be obtained. From this viewpoint, the content of polyamide (A) in the polyamide composition is more preferably 78 to 99% by mass, even more preferably 80 to 98% by mass, and even more preferably 82 to 97% by mass.

[0045] The polyamide composition may contain a polyamide other than the polyamide (A), but from the viewpoint of favorably exhibiting the effects of the present invention, it is preferable that the polyamide composition does not contain a polyamide other than the polyamide (A). The content of polyamides other than polyamide (A) in the polyamide composition is preferably 10% by mass or less, more preferably 5% by mass or less, even more preferably 1% by mass or less, and still more preferably 0% by mass.

[0046] The content of the epoxy resin (B) in the polyamide composition is more than 0% by mass and not more than 20% by mass. When the content of the epoxy resin (B) in the polyamide composition according to this embodiment is more than 0% by mass, a polyamide composition having high adhesive strength and excellent heat distortion resistance, heat aging resistance, and rigidity can be obtained. Furthermore, when the content of the epoxy resin (B) in the polyamide composition according to this embodiment is not more than 20% by mass, the epoxy resin (B) can be uniformly dispersed in the polyamide composition, resulting in a polyamide composition with a uniform composition. The content of the epoxy resin (B) in the polyamide composition according to this embodiment is preferably 1% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more, from the viewpoint of obtaining a polyamide composition having higher adhesive strength and being more excellent in heat distortion resistance, heat aging resistance, and rigidity. From the viewpoint of obtaining a polyamide composition with a more uniform composition, the content is preferably 18% by mass or less, more preferably 15% by mass or less, and even more preferably 13% by mass or less.

[0047] The content of the inorganic filler is not particularly limited as long as it does not impair the effects of the present invention, but from the viewpoint of mechanical strength, it is preferably 0.01 to 4 mass %, more preferably 0.02 to 3 mass %, and even more preferably 0.04 to 2 mass % in the polyamide composition.

[0048] The content of the above other additives is not particularly limited as long as it does not impair the effects of the present invention, but is preferably 0.01 to 5 mass %, more preferably 0.02 to 4 mass %, and even more preferably 0.04 to 3 mass % in the polyamide composition.

[0049] <Physical properties of polyamide composition> (tensile strength) The tensile strength of a test piece made of the polyamide composition, measured in accordance with ISO 527-1: 2019, is preferably 75 MPa or more, more preferably 80 MPa or more, and even more preferably 82 MPa or more, from the viewpoint of rigidity. Furthermore, from the viewpoint of moldability, a higher tensile strength is preferable, and specifically, it may be 300 MPa or less. The test piece can be obtained by injection molding a polyamide composition. For example, a dumbbell-shaped tensile test piece (Type A1) prepared in accordance with JIS K7139:2009 can be used as the test piece. Alternatively, the test piece can be obtained by cutting it out from a polyamide molded product. Specifically, the test piece is preferably obtained by the method described in the Examples.

[0050] (tensile modulus) The tensile modulus of a test piece made of the polyamide composition, measured in accordance with ISO 527-1: 2019, is preferably 2.5 GPa or more, more preferably 2.7 GPa or more, and even more preferably 2.9 GPa or more, from the viewpoint of rigidity. Furthermore, from the viewpoint of moldability, a higher modulus is preferable, and specifically, it may be 30 GPa or less. The test piece can be obtained by injection molding a polyamide composition. For example, a dumbbell-shaped tensile test piece (Type A1) prepared in accordance with JIS K7139:2009 can be used as the test piece. Alternatively, the test piece can be obtained by cutting it out from a polyamide molded product. Specifically, the test piece is preferably obtained by the method described in the Examples.

[0051] (heat distortion temperature) The heat distortion temperature of a test piece made of the polyamide composition, measured in accordance with ISO 527-1:2019, is preferably 100°C or higher, more preferably 105°C or higher, and even more preferably 110°C or higher, from the viewpoints of heat distortion resistance and heat aging resistance. From the viewpoint of moldability, the higher the temperature, the better. Specifically, the temperature is determined by the polyamide (A) contained in the polyamide composition, and is preferably 330°C or lower, more preferably 320°C or lower, and even more preferably 300°C or lower. The test piece can be obtained by injection molding a polyamide composition. For example, a dumbbell-shaped tensile test piece (Type A1) prepared in accordance with JIS K7139:2009 can be used as the test piece. Alternatively, the test piece can be obtained by cutting it out from a polyamide molded product. Specifically, the test piece is preferably obtained by the method described in the Examples.

[0052] (Tensile strength retention rate) In a test piece made of the polyamide composition, the retention of tensile strength measured in accordance with ISO527-1:2019 before and after heat treatment at 130°C for 1000 hours is preferably 60% or more, more preferably 70% or more, and even more preferably 80% or more, from the viewpoint of heat aging resistance. The retention rate of tensile strength is a value calculated from the following formula (X). Tensile strength retention rate (%) = (tensile strength after 1000 hours / initial tensile strength) × 100 Formula (X) In the above formula (X), the tensile strength after 1000 hours refers to a tensile strength measured in accordance with ISO 527-1:2019 using a test piece made of a polyamide composition after it has been left to stand for 1000 hours in a thermostatic chamber set at 130°C, and the initial tensile strength refers to a tensile strength measured in accordance with ISO 527-1:2019 using a test piece after it has been produced (a tensile strength measured in accordance with ISO 527-1:2019 using a test piece that has not been left to stand for 1000 hours in a thermostatic chamber set at 130°C). The test piece can be obtained by injection molding a polyamide composition. For example, a dumbbell-shaped tensile test piece (Type A1) prepared in accordance with JIS K7139:2009 can be used as the test piece. Alternatively, the test piece can be obtained by cutting it out from a polyamide molded product. Specifically, the test piece is preferably obtained by the method described in the Examples.

[0053] <Method of producing polyamide composition> The method for producing the polyamide composition is not particularly limited, and any known method can be used, such as a method of melt-kneading the polyamide (A), the epoxy resin (B), and optional components other than the polyamide (A) and the epoxy resin (B). The melt-kneading method is not particularly limited, and any method capable of uniformly mixing the above components can be preferably used. For example, a single-screw extruder, a twin-screw extruder, a kneader, a Banbury mixer, etc. are preferably used. The melt-kneading conditions are not particularly limited, and an example is a method in which melt-kneading is performed for about 1 to 30 minutes at a temperature range about 10 to 50°C higher than the melting point of polyamide (A).

[0054] [Polyamide molding] The polyamide molded article according to the present embodiment is formed from the polyamide composition according to the present embodiment. The polyamide molded article can be obtained by molding the polyamide composition according to the present embodiment using various molding methods such as injection molding, blow molding, extrusion molding, compression molding, stretch molding, vacuum molding, and foam molding.

[0055] The polyamide molded article may have a coating film on its surface. The coating film is a cured film of a coating material, and is obtained by applying the coating material to the surface of the polyamide molded article and, if necessary, subjecting it to a curing treatment such as drying, heating, or irradiation with active energy rays. The coating material can be selected depending on the purpose. The coating film also includes an undercoat layer (primer layer) and the like.

[0056] [Complex] The composite according to the present embodiment comprises the polyamide molded article according to the present embodiment and a molded article (X) different from the polyamide molded article. The molded body (X) preferably contains at least one material selected from the group consisting of organic materials, inorganic materials, and metal materials, and more preferably contains a metal material. Examples of organic materials include thermoplastic resins, rubber, thermosetting resins, etc. Among these, thermoplastic resins are preferred from the viewpoint of moldability. As the thermoplastic resin, for example, at least one selected from the group consisting of polyamide, polyester, polyphenylene sulfide, polyethylene, polypropylene, polycarbonate, polyetherimide, polyethersulfone, and polyphenylene ether can be used. The inorganic material may be, for example, at least one selected from the group consisting of glass and ceramics. Examples of metal materials include aluminum, copper, iron, gold, silver, zinc, tin, lead, stainless steel, alloys thereof, etc. Among these, at least one selected from the group consisting of aluminum, copper, iron, and stainless steel is preferred.

[0057] The composite according to the present embodiment may have a coating film on the surface thereof. The coating film on the surface of the composite is the same as the coating film on the polyamide molded article.

[0058] The composite according to this embodiment preferably includes an adhesive layer between the polyamide molded body and the molded body (X). From the viewpoint of adhesiveness, the adhesive layer is preferably formed using an adhesive. Examples of adhesives include epoxy adhesives, urethane adhesives, and acrylic adhesives. Among these, epoxy adhesives are preferred from the viewpoint of adhesiveness. The thickness of the adhesive layer is not particularly limited, but is preferably 5 to 100 μm, more preferably 10 to 70 μm, and even more preferably 20 to 60 μm.

[0059] [Examples of use] The polyamide molded article and composite according to the present embodiment can be suitably used for, for example, various bicycle parts (sprockets, cranks, transmissions, pedals, hubs, bottom brackets), etc. Furthermore, since the polyamide molded article and composite according to the present embodiment have excellent adhesion to various coating materials, they can be suitably used as housings for various products and exterior panel parts for automobiles, etc. As an exterior panel part for an automobile, they can be suitably used as at least one member selected from the group consisting of fenders, hoods, fuel lids, charging lids, side mirrors, back door panels, door panels, and roof panels. [Example]

[0060] The present invention will be specifically explained below with reference to examples and comparative examples, but the present invention is not limited to these.

[0061] The measurements and evaluations in the examples and comparative examples were carried out according to the methods shown below.

[0062] 1. Terminal amino group content The amount of terminal amino groups in polyamide (A) was measured by dissolving 1 g of each polyamide obtained in the Production Examples in 35 mL of phenol, adding 2 mL of methanol to prepare a sample solution. Using thymol blue as an indicator, titration was carried out using a 0.01 N hydrochloric acid solution to measure the terminal amino group content ([NH2], unit: μeq / g) of polyamide (A). 2. Softening point The softening point of the epoxy resin (B) was determined in accordance with JIS K 7196: 2012. More specifically, the softening point was determined by measuring in the penetration mode of a thermomechanical analyzer (TMA) in a dry air ambient atmosphere while increasing the temperature at a rate of 5°C per minute.

[0063] 3. Epoxy equivalent The epoxy equivalent of the epoxy resin (B) was determined in accordance with JIS K 7236: 2009. More specifically, it was measured by indicator titration using a perchloric acid-acetic acid solution.

[0064] 4. Tensile strength and tensile modulus (Preparation of test specimens) Using the polyamide compositions obtained in the Examples and Comparative Examples, dumbbell-shaped tensile test specimens (Type A1) were prepared in accordance with JIS K 7139: 2009. Specifically, using an injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd., mold clamping force: 100 tons, screw diameter: φ32 mm), a cylinder temperature was set to 320°C, an actual mold temperature was set to 140°C, and a T-runner mold was used to prepare dumbbell-shaped tensile test specimens (Type A1) (4 mm thick, total length 170 mm, parallel portion length 80 mm, parallel portion width 10 mm) at an injection speed of 130 mm / sec. (measurement) Using the dumbbell-shaped tensile test specimen (Type A1) prepared by the above method, tensile properties were measured in accordance with ISO 527-1:2019. Specifically, the tensile strength and tensile modulus at 23°C were measured using an autograph (Instron, Universal Testing Machine 5969, video extensometer used). Note that the higher the tensile strength and tensile modulus values ​​of the dumbbell 0012-type tensile test specimen, the more excellent the rigidity.

[0065] 5. Heat distortion temperature The dumbbell-shaped tensile test specimen (Type A1) prepared by the method described in "4. Tensile Properties" above was cut to prepare a test specimen (4 mm thick, 80 mm total length, 10 mm width), and the heat distortion temperature (°C) was measured using an HDT tester (S-3M, manufactured by Toyo Seiki Seisaku-sho, Ltd.) in accordance with ISO75:2013. Note that the higher the heat distortion temperature of the dumbbell-shaped tensile test specimen, the better its heat distortion resistance.

[0066] 6. Tensile strength retention (heat aging resistance) The dumbbell-shaped tensile test specimen (Type A1) prepared by the method described in "4. Tensile Properties" above was left to stand for 1000 hours in a thermostatic chamber (DE-303, manufactured by Mita Sangyo Co., Ltd.) set at 130°C. After 1000 hours, the test specimen was removed from the thermostatic chamber and the tensile strength at 23°C was measured using the same method as described in "3. Tensile Strength and Tensile Modulus" above. The tensile strength retention rate was calculated from the obtained tensile strength (tensile strength after 1000 hours) and the initial tensile strength (tensile strength obtained in "4. Tensile strength and tensile modulus") using the following formula (X). Tensile strength retention rate (%) = (tensile strength after 1000 hours / initial tensile strength) × 100 Formula (X) The higher the tensile strength retention rate, the more excellent the heat aging resistance.

[0067] 7.Adhesive strength (Preparation of the complex) Using an injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd., clamping force: 100 tons, screw diameter: φ32 mm), a cylinder temperature was set to 320°C, an actual mold temperature was set to 140°C, and a T-runner mold was used to produce composite test pieces (2 mm thick, 25 mm × 100 mm) from the polyamide compositions (pellets) obtained in the examples and comparative examples at an injection speed of 130 mm / sec. The surfaces of the obtained composite test piece and metal piece (JIS K 6850:1999 aluminum test piece, manufactured by Standard Test Piece Co., Ltd., 1.6 mm thick, 25 mm × 100 mm) were washed with acetone and air-dried. The surface of the metal piece was then polished with #240 abrasive paper. Next, as shown in Figure 1, an adhesive (3M® Scotch-Weld® two-part epoxy adhesive DP125, clear, manufactured by 3M Japan Ltd.) was applied to the adhesive margin (6 mm) of the composite test piece, and the metal piece was placed on the adhesive surface. The test pieces were then pressed together to prevent air bubbles from being trapped in the adhesive. The test pieces were then left standing at 50°C for 2 hours, and then at 23°C for 3 days to cure the adhesive, yielding a composite (see Figure 1). (measurement) The adhesive strength of the composites prepared by the above method was measured in accordance with JIS K 6850:1999. Specifically, a tensile test was performed using an autograph (Instron Corporation, Universal Testing Machine 5969, using a video extensometer) at 23°C with a chuck distance of 115 mm, a tensile speed of 20 mm / min, and a gripping distance of 38 mm. The peel force was measured and used as the adhesive strength. A 2.0 mm thick spacer was placed between the autograph chuck and the metal specimen, and a 1.6 mm thick spacer was placed between the autograph chuck and the composite specimen, with the adhesive surface positioned near the center of the chuck.

[0068] <Production Example 1> (Preparation of Polyamide A-1) 8091.0 g (48.70 mol) of terephthalic acid, 7969.4 g (50.35 mol) of a mixture of 1,9-nonanediamine and 2-methyl-1,8-octanediamine [former / latter = 80 / 20 (molar ratio)], 354.1 g (2.90 mol) of benzoic acid, 16.2 g of sodium hypophosphite monohydrate (0.1% by mass relative to the total mass of the raw materials), and 8.3 L of distilled water were placed in a 40 L autoclave and purged with nitrogen. The mixture was stirred at 100°C for 30 minutes, and the temperature inside the autoclave was raised to 220°C over 2 hours. At this time, the pressure inside the autoclave rose to 2 MPa. Heating was continued for 5 hours while maintaining the pressure at 2 MPa, and water vapor was gradually released to allow the reaction. Next, the pressure was reduced to 1.3 MPa over 30 minutes, and the reaction was allowed to continue for another hour, yielding a prepolymer. The resulting prepolymer was dried at 100°C under reduced pressure for 12 hours and pulverized to a particle size of 2 mm or less. This was subjected to solid-state polymerization at 230°C and 13 Pa (0.1 mmHg) for 10 hours to obtain a polyamide. The amount of terminal amino groups was 18 μeq / g. This polyamide is referred to as "Polyamide A-1."

[0069] <Production Example 2> (Preparation of Polyamide A-2) Polyamide A-2 was obtained by polymerization in the same manner as Polyamide A-1, except that the amount of 1,9-nonanediamine and 2-methyl-1,8-octanediamine (former / latter = 80 / 20 (molar ratio)) added was changed to 8064.4 g (50.95 mol). The amount of terminal amino groups was 70 μeq / g. This polyamide is referred to as "Polyamide A-2" for short.

[0070] <Examples 1 and 2, and Comparative Examples 1 to 3> Polyamide (A), epoxy resin (B), epoxy group-containing compound, inorganic filler, antioxidant, and mold release agent were premixed in the proportions shown in Table 1 and fed into the upstream hopper of a twin-screw extruder (twin-screw extruder manufactured by the Plastics Engineering Research Institute, screw diameter φ30 mm, L / D=32, rotation speed 150 rpm, output rate 10 kg / h). The mixture was melt-kneaded and extruded at a cylinder temperature of 320°C, and then cooled and cut to produce a pellet-shaped polyamide composition. The polyamide composition thus obtained was subjected to the above-mentioned evaluations, and the results are shown in Table 1.

[0071] The components shown in Table 1 are as follows: [Polyamide (A)] A-1: Polyamide A-1 obtained in Production Example 1 A-2: Polyamide A-2 obtained in Production Example 2

[0072] [Epoxy resin (B)] B-1: DIC Corporation, product name "Epiclon (registered trademark) HM-091", bisphenol A type epoxy resin, solid, softening point: 94°C, epoxy equivalent: 2340g / eq B-2: DIC Corporation, product name "Epiclon (registered trademark) 7050, bisphenol A type epoxy resin, solid, softening point: 92°C, epoxy equivalent: 1900 g / eq

[0073] [Epoxy group-containing compound] Lotader AX8900: SK Geo Centric, product name "LOTADER (registered trademark) AX8900", ethylene acrylate elastomer modified with glycidyl methacrylate, softening point: -40°C

[0074] [Inorganic filler] ML112: TALC ML112, manufactured by Fuji Talc Co., Ltd.

[0075] [Antioxidants] GA-80: Sumitomo Chemical Co., Ltd., product name "SUMILIZER GA-80", hindered phenol antioxidant

[0076] [Release agent] LICOWAX OP: Clariant Chemicals Co., Ltd., product name "LICOWAX OP"

[0077] [Table 1]

[0078] As is clear from Table 1, the polyamide compositions according to the Examples have high adhesive strength and are excellent in heat distortion resistance, heat aging resistance, and rigidity, while the polyamide compositions according to the Comparative Examples are inferior in at least one of adhesive strength, heat distortion resistance, heat aging resistance, and rigidity.

Claims

1. A polyamide composition containing a polyamide (A) and an epoxy resin (B), The polyamide (A) contains a dicarboxylic acid unit and a diamine unit, the dicarboxylic acid units contain 50 mol% or more of structural units derived from at least one selected from the group consisting of terephthalic acid and naphthalenedicarboxylic acid, relative to 100 mol% of all dicarboxylic acid units; The diamine units contain 60 mol% or more aliphatic diamine units having 7 to 13 carbon atoms relative to 100 mol% of all diamine units, The softening point of the epoxy resin (B) measured in accordance with JIS K 7196:2012 is 70°C or higher and 110°C or lower, The polyamide composition, wherein the content of the epoxy resin (B) in the polyamide composition is more than 0 mass% and 20 mass% or less.

2. 2. The polyamide composition according to claim 1, wherein the aliphatic diamine unit having 7 to 13 carbon atoms is a structural unit derived from at least one selected from the group consisting of 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, 2-methyl-1,8-octanediamine, 1,10-decanediamine, and 1,12-dodecanediamine.

3. 2. The polyamide composition according to claim 1, wherein the aliphatic diamine unit having 7 to 13 carbon atoms is a structural unit derived from at least one selected from the group consisting of 1,9-nonanediamine and 2-methyl-1,8-octanediamine.

4. 2. The polyamide composition according to claim 1, wherein the epoxy equivalent of the epoxy resin (B) is 1500 g / eq or more and 3500 g / eq or less.

5. 2. The polyamide composition according to claim 1, wherein a test piece made of the polyamide composition has a tensile strength retention of 80% or more as measured in accordance with ISO 527-1:2019 before and after heat treatment at 130°C for 1000 hours.

6. A polyamide molded article formed from the polyamide composition according to any one of claims 1 to 5.

7. The polyamide molded article according to claim 6, which has a coating film on its surface.

8. The polyamide molded article according to claim 7, which is an outer panel part.

9. A composite comprising the polyamide molded article according to claim 6 and a molded article (X) different from the polyamide molded article.

10. The composite according to claim 9 , wherein the molded body (X) contains at least one material selected from the group consisting of an organic material, an inorganic material, and a metal material.

11. The composite according to claim 10, having a coating on the surface thereof.

12. The composite according to claim 9, which comprises an adhesive layer between the polyamide molded body and the molded body (X).

13. 10. The composite of claim 9, which is a skin component.

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