Resin composition, pellets, and molded article

Abstract

Provided are a resin composition, pellets, and a molded article. This resin composition contains a xylylenediamine-based polyamide resin and an aliphatic polyamide resin. The xylylenediamine-based polyamide resin contains a structural unit derived from a diamine and a structural unit derived from a dicarboxylic acid. 70 mol% or more of the structural unit derived from the diamine is derived from xylylenediamine. 70 mol% or more of the structural unit derived from the dicarboxylic acid is derived from an α,ω-linear aliphatic dicarboxylic acid having 11-20 carbon atoms. The aliphatic polyamide resin contains a structural unit containing −(CH2)n1− (where n1 is 3 to 6) and a structural unit containing −(CH2)n2− (where n2 is 7 to 20).

Description

Resin composition, pellets, and molded products

[0001] The present invention relates to a resin composition, a pellet, and a molded article, and more particularly to a resin composition containing a polyamide resin as a main component.

[0002] Polyamide resins are applied in various fields due to their excellent performance in various fields. In particular, blending two or more polyamide resins has been practiced to achieve desired performance. For example, Patent Document 1 discloses a polyamide resin composition containing 100 parts by mass of a polyamide resin (Z) containing 70% by mass or more and 98% by mass or less of a semi-aromatic polyamide (A) and 30% by mass or more and 2% by mass or less of an aliphatic polyamide (B), 0.03 parts by mass or more and 0.3 parts by mass or less of a compound (C) and / or a compound (D), and 0.03 parts by mass or more and 0.3 parts by mass or less of a hindered phenol-based antioxidant (E), wherein the semi-aromatic polyamide (A) contains diamine units containing 70 mol% or more of units derived from m-xylylenediamine and / or p-xylylenediamine relative to the total diamine units, and a total dicarboxylic acid unit. The polyamide resin composition disclosed is a polyamide resin composition comprising dicarboxylic acid units containing 70 mol % or more of units derived from an aliphatic dicarboxylic acid having 6 to 12 carbon atoms relative to the above-mentioned compound (C), wherein the compound (C) is a polyalkylene glycol (C1) having a number average molecular weight of 4,000 or less, or a partial ester compound (C2) of a polyalkylene glycol and a fatty acid, the compound (D) is a partial ester compound (D1) of a trihydric or higher alcohol and a fatty acid, or a partial ester compound (D2) of an alkylene oxide adduct of a trihydric or higher alcohol and a fatty acid, and the hindered phenol-based antioxidant (E) has a predetermined structure.

[0003] Furthermore, Patent Document 2 discloses the use of at least one MXDZ polyamide obtained from the polycondensation of meta-xylylenediamine (MXD) with a C6 to C18 aliphatic (Z) dicarboxylic acid, particularly C6 to C12, in a mixture comprising at least one aliphatic polyamide A obtained from the polycondensation of units selected from XY units obtained from the polycondensation of a C6 to C12 lactam, a C6 to C12 amino acid, and a C4 to C18 aliphatic diamine (X), particularly C4 to C12, and a C6 to C18 aliphatic dicarboxylic acid (Y), particularly C6 to C12, circular cross-section glass fiber, and optionally at least one impact modifier and / or at least one additive, for limiting warpage of the composition during processing, particularly by injection or compression molding, wherein the MXDZ polyamide and the mixture constitute a composition having an MXDZ / A weight ratio of 0.11 to 0.83, particularly 0.11 to 0.66.

[0004] JP 2012-107217 A, JP 2019-531394 A

[0005] Here, when a polyamide resin composition is molded using a mold such as an injection molder, one of the challenges is to properly solidify the polyamide resin composition even within the mold. More specifically, when molding using a mold such as an injection molder, it is required that the resin composition be properly crystallized within the mold. Furthermore, depending on the application, even if crystallization progresses sufficiently within the mold, poor barrier properties can become a problem. The present invention aims to solve this problem and to provide a resin composition, pellets, and molded articles that can be properly crystallized within a mold and have excellent barrier properties.

[0006] In light of the above-mentioned problems, the present inventors have conducted research and found that the above-mentioned problems can be solved by using, in a resin composition containing a xylylenediamine-based polyamide resin and an aliphatic polyamide resin, an aliphatic dicarboxylic acid having a relatively long chain length as a raw material monomer for the xylylenediamine-based polyamide resin, and using an aliphatic polyamide resin having a relatively short chain length and an aliphatic polyamide resin having a relatively long chain length. Specifically, the above-mentioned problems have been solved by the following means. <1> A resin composition comprising a xylylenediamine-based polyamide resin and an aliphatic polyamide resin, wherein the xylylenediamine-based polyamide resin contains diamine-derived structural units and dicarboxylic acid-derived structural units, wherein 70 mol % or more of the diamine-derived structural units are derived from xylylenediamine, and 70 mol % or more of the dicarboxylic acid-derived structural units are derived from an α,ω-linear aliphatic dicarboxylic acid having 11 to 20 carbon atoms, and wherein the aliphatic polyamide resin has a -(CH ２ ) ｎ１ -(n1 is 3 to 6) and -(CH ２ ) ｎ２ A resin composition comprising a structural unit containing -(n2 is 7 to 20).<2> The resin composition according to<1>, wherein 10 to 90 mol % of the diamine-derived structural units in the xylylenediamine-based polyamide resin are derived from meta-xylylenediamine and 90 to 10 mol % are derived from para-xylylenediamine (provided that the total of meta-xylylenediamine and para-xylylenediamine does not exceed 100 mol %).<3> The resin composition according to<1>, wherein 70 mol % or more of the dicarboxylic acid-derived structural units in the xylylenediamine-based polyamide resin are derived from dodecanedioic acid and / or tetradecanedioic acid. <4> The resin composition according to <1>, wherein 10 to 90 mol % of the diamine-derived structural units in the xylylenediamine-based polyamide resin are derived from metaxylylenediamine, and 90 to 10 mol % are derived from paraxylylenediamine (however, the total of metaxylylenediamine and paraxylylenediamine does not exceed 100 mol %), and 70 mol % or more of the dicarboxylic acid-derived structural units in the xylylenediamine-based polyamide resin are derived from dodecanedioic acid and / or tetradecanedioic acid. <5> The aliphatic polyamide resin is a polyamide resin having a -(CH２ ) ｎ１ -(n1 is 3 to 6) and -(CH ２ ) ｎ２ -(n2 is 7 to 20). <6> The resin composition according to any one of <1> to <4>, which is a copolymer containing a structural unit containing -(n2 is 7 to 20). <6> The resin composition according to any one of <1> to <4>, wherein the aliphatic polyamide resin contains at least one selected from polyamide 610 and polyamide 612. <7> The resin composition according to any one of <1> to <6>, wherein a mass ratio of the xylylenediamine-based polyamide resin to the aliphatic polyamide resin is 5:95 to 80:20. <8> Pellets of the resin composition according to any one of <1> to <7>. <9> A molded article formed from the resin composition according to any one of <1> to <7>.

[0007] According to the present invention, it is possible to appropriately crystallize a resin composition in a mold, and to provide a resin composition having excellent barrier properties, as well as pellets and molded articles.

[0008] Hereinafter, an embodiment of the present invention (hereinafter simply referred to as "the present embodiment") will be described in detail. Note that the following present embodiment is an example for explaining the present invention, and the present invention is not limited to this embodiment. Note that in this specification, the expression "to" is used to mean that the numerical values ​​before and after it are included as the lower limit and upper limit. In this specification, various physical property values ​​and characteristic values ​​are those at 23°C unless otherwise specified.

[0009] In this specification, unless otherwise specified, the number average molecular weight is a value measured by the following method. The number average molecular weight (Mn) is measured using gel permeation chromatography (GPC) measurement, using a standard polymethyl methacrylate (PMMA) equivalent value. Two columns packed with a styrene polymer are used as the packing material, and hexafluoroisopropanol (HFIP) with a sodium trifluoroacetate concentration of 2 mmol / L is used as the solvent. The resin concentration is 0.02 mass%, the column temperature is 40 ° C, the flow rate is 0.3 mL / min, and the measurement is performed using a refractive index detector (RI). In addition, the calibration curve is measured by dissolving six levels of PMMA in HFIP.

[0010] In this specification, the melting point (Tm) is a value measured in accordance with ISO 11357 according to differential scanning calorimetry (DSC), unless otherwise specified. Using a differential scanning calorimeter, the resin is placed in the measurement pan of the differential scanning calorimeter, heated to a temperature above the melting point at a heating rate of 10 ° C. / min under a nitrogen atmosphere, and then rapidly cooled before measurement. The measurement conditions are a heating rate of 10 ° C. / min, held at 280 ° C. for 5 minutes, and then measured at a heating rate of -5 ° C. / min to 100 ° C. to determine the melting point (Tm). As the differential scanning calorimeter, a "DSC-60" manufactured by Shimadzu Corporation is used. If the measurement methods described in the standards shown in this specification differ depending on the fiscal year, unless otherwise specified, they will be based on the standards as of January 1, 2023.

[0011] The resin composition of the present embodiment contains a xylylenediamine-based polyamide resin and an aliphatic polyamide resin, the xylylenediamine-based polyamide resin contains diamine-derived structural units and dicarboxylic acid-derived structural units, 70 mol % or more of the diamine-derived structural units are derived from xylylenediamine, 70 mol % or more of the dicarboxylic acid-derived structural units are derived from an α,ω-linear aliphatic dicarboxylic acid having 11 to 20 carbon atoms, and the aliphatic polyamide resin contains -(CH ２ ) ｎ１ -(n1 is 3 to 6) and -(CH ２ ) ｎ２The xylylenediamine-based polyamide resin is characterized by including a structural unit containing - (n2 is 7 to 20). This structure allows the resin composition to be appropriately crystallized in a mold, and a resin composition with excellent barrier properties can be obtained. The reason for this is presumably due to the use of a long-carbon-chain aliphatic dicarboxylic acid (a C11-C20 α,ω-linear aliphatic dicarboxylic acid) as a raw material monomer for the xylylenediamine-based polyamide resin. Specifically, a polyamide resin in which 70 mol % or more of the diamine-derived structural units are derived from xylylenediamine is a resin that is difficult to crystallize, even among polyamide resins. Representative examples of such xylylenediamine-based polyamide resins that are difficult to crystallize include polyamide resins synthesized from xylylenediamine and a C10 α,ω-linear aliphatic dicarboxylic acid (sebacic acid) and resins synthesized from xylylenediamine and adipic acid. In this embodiment, by deriving 70 mol % or more of the dicarboxylic acid-derived structural units from α,ω-linear aliphatic dicarboxylic acids having 11 to 20 carbon atoms, the chain length becomes relatively long, which is presumably due to the increased mobility of the xylylenediamine-based polyamide resin molecules themselves. Furthermore, it is presumed that a longer chain length tends to lower the glass transition temperature, making the polyamide molecules more mobile even at low temperatures. It is surprising that this slight difference in the number of carbon chains significantly contributes to the acceleration of the crystallization rate. Furthermore, in this embodiment, by using a specific aliphatic polyamide resin, molded products with excellent barrier properties can be obtained without reducing mold crystallinity.

[0012] <Xylylenediamine-Based Polyamide Resin> The resin composition of this embodiment contains a polyamide resin (sometimes simply referred to as a "xylylenediamine-based polyamide resin" in this specification) that contains diamine-derived structural units and dicarboxylic acid-derived structural units, and in which 70 mol % or more of the diamine-derived structural units are derived from xylylenediamine. Such xylylenediamine-based polyamide resins are polyamide resins that are excellent in various performances, and the resin composition of this embodiment also exhibits these excellent physical properties.

[0013] The diamine-derived structural units of the xylylenediamine-based polyamide resin are more preferably 75 mol% or more, even more preferably 80 mol% or more, even more preferably 90 mol% or more, still more preferably 95 mol% or more, and particularly preferably 99 mol% or more, of xylylenediamine (preferably paraxylylenediamine and / or metaxylylenediamine).

[0014] The xylylenediamine is preferably paraxylylenediamine and / or metaxylylenediamine. The xylylenediamine preferably contains 0 to 100 mol% metaxylylenediamine and 100 to 0 mol% paraxylylenediamine (provided that the total of metaxylylenediamine and paraxylylenediamine does not exceed 100 mol%), more preferably 10 to 100 mol% metaxylylenediamine and 90 to 0 mol% paraxylylenediamine, even more preferably 10 to 90 mol% metaxylylenediamine and 90 to 10 mol% paraxylylenediamine, still more preferably 40 to 90 mol% metaxylylenediamine and 60 to 10 mol% paraxylylenediamine, and even more preferably 60 to 90 mol% metaxylylenediamine and 40 to 10 mol% paraxylylenediamine. In the xylylenediamine-based polyamide resin, the total of the paraxylylenediamine-derived structural units and metaxylylenediamine-derived structural units preferably accounts for 80 mol% or more, more preferably 85 mol% or more, even more preferably 90 mol% or more, even more preferably 95 mol% or more, even more preferably 98 mol% or more, and even more preferably 99 mol% or more of the diamine-derived structural units. The upper limit of the total of the paraxylylenediamine-derived structural units and metaxylylenediamine-derived structural units is 100 mol%. By setting the metaxylylenediamine content to 10 mol% or more, the appearance of the test piece surface tends to be further improved when injection molding is performed under low mold temperature conditions. Furthermore, by setting the paraxylylenediamine content to 10 mol% or more, crystallization can be promoted at a lower mold temperature.

[0015] Diamines other than metaxylylenediamine and paraxylylenediamine that can be used as raw diamine components for xylylenediamine-based polyamide resins include aliphatic diamines such as tetramethylenediamine, pentamethylenediamine, 2-methylpentanediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, dodecamethylenediamine, 2,2,4-trimethyl-hexamethylenediamine, and 2,4,4-trimethylhexamethylenediamine; 1,3-bis( Examples of the diamine include alicyclic diamines such as bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, bis(4-aminocyclohexyl)methane, 2,2-bis(4-aminocyclohexyl)propane, bis(aminomethyl)decalin, and bis(aminomethyl)tricyclodecane; and diamines having an aromatic ring such as bis(4-aminophenyl)ether, paraphenylenediamine, and bis(aminomethyl)naphthalene, and these can be used alone or in combination of two or more.

[0016] On the other hand, the dicarboxylic acid-derived structural units of the xylylenediamine-based polyamide resin are preferably 75 mol% or more, more preferably 80 mol% or more, even more preferably 85 mol% or more, still more preferably 90 mol% or more, even more preferably 95 mol% or more, and particularly preferably 99 mol% or more, of which the dicarboxylic acid-derived structural units are preferably derived from an α,ω-linear aliphatic dicarboxylic acid having 11 to 20 carbon atoms.

[0017] The α,ω-linear aliphatic dicarboxylic acid having 11 to 20 carbon atoms that is preferably used as the raw dicarboxylic acid component of the xylylenediamine-based polyamide resin is preferably an α,ω-linear aliphatic dicarboxylic acid having 11 to 16 carbon atoms, and more preferably an α,ω-linear aliphatic dicarboxylic acid having 12 to 14 carbon atoms. Specific examples of the α,ω-linear aliphatic dicarboxylic acid having 11 to 20 carbon atoms include dodecanedioic acid, tridecanedioic acid, and tetradecanedioic acid. Among these, at least one of dodecanedioic acid and / or tetradecanedioic acid is preferred, with dodecanedioic acid being more preferred, as the melting point of the polyamide resin is in a range suitable for molding.

[0018] Examples of dicarboxylic acid components other than those mentioned above include α,ω-linear aliphatic dicarboxylic acids having 10 or less carbon atoms, such as adipic acid and sebacic acid; phthalic acid compounds, such as isophthalic acid, terephthalic acid and orthophthalic acid; and isomers of naphthalenedicarboxylic acid, such as 1,2-naphthalenedicarboxylic acid, 1,3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 1,6-naphthalenedicarboxylic acid, 1,7-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid and 2,7-naphthalenedicarboxylic acid. These can be used alone or in combination of two or more.

[0019] Although the xylylenediamine-based polyamide resin is primarily composed of diamine-derived structural units and dicarboxylic acid-derived structural units, other structural units are not completely excluded. It goes without saying that the resin may contain structural units derived from lactams such as ε-caprolactam and laurolactam, and aliphatic aminocarboxylic acids such as aminocaproic acid and aminoundecanoic acid. Here, "major component" refers to the structural units constituting the xylylenediamine-based polyamide resin in which the combined number of diamine-derived structural units and dicarboxylic acid-derived structural units is the largest among all structural units. In this embodiment, the combined total of the diamine-derived structural units and dicarboxylic acid-derived structural units in the xylylenediamine-based polyamide resin preferably accounts for 90% by mass or more of all structural units, more preferably 95% by mass or more, even more preferably 97% by mass or more, and even more preferably 99% by mass or more.

[0020] It is also preferable to use a polyamide resin produced using biomass raw materials (biomass polyamide resin) as the xylylenediamine-based polyamide resin. Using biomass polyamide resin can reduce the environmental impact. Mass balance certified (ISCC PLUS) raw material monomers can also be used. Mass balance certification means that the amount of renewable raw materials and bio-based raw materials used at each factory or production facility and the amount of products produced and shipped are quantified, and the quality is guaranteed.

[0021] The melting point of the xylylenediamine-based polyamide resin is preferably 150°C or higher, more preferably 180°C or higher, and even more preferably 200°C or higher, and is preferably 350°C or lower, more preferably 330°C or lower, and even more preferably 300°C or lower.

[0022] The lower limit of the number average molecular weight (Mn) of the xylylenediamine-based polyamide resin is preferably 6,000 or more, more preferably 8,000 or more, and even more preferably 10,000 or more, and is preferably 100,000 or less, more preferably 50,000 or less. Within such ranges, the heat resistance, elastic modulus, dimensional stability, and moldability are improved.

[0023] <Aliphatic Polyamide Resin> The resin composition of this embodiment contains an aliphatic polyamide resin. The aliphatic polyamide resin used in this embodiment is intended to include an alicyclic polyamide resin, but is preferably a linear polyamide resin. In this embodiment, the aliphatic polyamide resin is preferably a -(CH ２ ) ｎ１ A structural unit containing -(n1 is 3 to 6) (hereinafter, sometimes referred to as "structural unit n1") and -(CH ２ ) ｎ２- (n2 is 7 to 20) (hereinafter, sometimes referred to as "structural unit n2"). The aliphatic polyamide resin may be a mixture of a polyamide resin containing the structural unit n1 and a polyamide resin containing the structural unit n2, or a copolymer containing the structural unit n1 and the structural unit n2. Alternatively, the aliphatic polyamide resin may be a mixture of a polyamide resin containing the structural unit n1, a polyamide resin containing the structural unit n2, and a copolymer containing the structural unit n1 and the structural unit n2.

[0024] n1 is preferably 4 or more and 6 or less. The aliphatic polyamide resin used in this embodiment is a -(CH ２ ) ｎ１ The structural unit n1 may be a structural unit containing - and having a different value of n1. ２ ) ｎ１ -C(=O)-, -NH-(CH ２ ) ｎ１ -NH- and -C(=O)-(CH ２ ) ｎ１ Structural units represented by one or more of -C(=O)- preferably account for 90% by mass or more, and more preferably 95% by mass or more, of all structural units n1.

[0025] n2 is preferably 8 or more, more preferably 9 or more, and is preferably 18 or less, more preferably 16 or less, even more preferably 14 or less, and even more preferably 12 or less. The aliphatic polyamide resin used in this embodiment has a -(CH ２ ) ｎ２ The structural unit n2 may be a structural unit containing - and having a different value of n2. ２ ) ｎ２ -C(=O)-, -NH-(CH ２ ) ｎ２ -NH- and -C(=O)-(CH ２ ) ｎ２ Structural units represented by two or more types of —C(═O)— preferably account for 90% by mass or more, and more preferably 95% by mass or more, of all structural units n2.

[0026] The aliphatic polyamide resin used in this embodiment preferably has a mass ratio of the structural unit n1 to the structural unit n2 of 9:1 to 1:9, more preferably 9:1 to 3:7, even more preferably 9:1 to 5:5, even more preferably 8:2 to 5:5, and even more preferably 8:2 to 6:4. The aliphatic polyamide resin used in this embodiment may contain only one type of structural unit n1 and one type of structural unit n2, or two or more types. The aliphatic polyamide resin used in this embodiment preferably has the structural unit n1 and the structural unit n2 combined to account for 90% by mass or more of the total structural units, more preferably 95% by mass or more, and it is even more preferable that all structural units other than the terminal groups are the structural unit n1 and the structural unit n2. The aliphatic polyamide resin used in this embodiment may be partially (for example, less than 5% by mass, even less than 3% by mass, particularly less than 1% by mass) substituted with an aromatic monomer or another monomer.

[0027] Examples of aliphatic polyamide resins include polyamide 610, polyamide 611, polyamide 612, polyamide 410, a mixture of polyamide 6 and polyamide 10, a mixture of polyamide 6 and polyamide 11, a mixture of polyamide 6 and polyamide 12, and a mixture of polyamide 4 and polyamide 10, and more preferably contains at least one selected from polyamide 610, polyamide 611, and polyamide 612, and even more preferably contains at least one selected from polyamide 610 and polyamide 612. The aliphatic polyamide resin may be a blend of three or more aliphatic polyamide resins, such as a blend of polyamide 6, polyamide 12, and polyamide 610.

[0028] <Polyamide Resin Blend Form> In the resin composition of this embodiment, the mass ratio of the xylylenediamine-based polyamide resin to the aliphatic polyamide resin is preferably 5:95 to 80:20. More specifically, the content of the aliphatic polyamide resin in the resin composition of this embodiment is, relative to 100 parts by mass of the total of the xylylenediamine-based polyamide resin and the aliphatic polyamide resin, preferably 5 parts by mass or more, more preferably 10 parts by mass or more, even more preferably 15 parts by mass or more, even more preferably 20 parts by mass or more, even more preferably 30 parts by mass or more, even more preferably 40 parts by mass or more, and preferably 95 parts by mass or less, more preferably 90 parts by mass or less, even more preferably 85 parts by mass or less, even more preferably 80 parts by mass or less, even more preferably 70 parts by mass or less, and even more preferably 60 parts by mass or less. By setting the content at or above the lower limit, the in-mold crystallization effect at low temperatures tends to be further improved. Furthermore, by making the content equal to or less than the upper limit, the effects of lowering the water absorption rate, increasing the chemical resistance, increasing the fogging resistance, and increasing the barrier properties tend to be further improved.

[0029] The resin composition of this embodiment may or may not contain polyamide resins other than aliphatic polyamide resins and xylylenediamine-based polyamide resins. Examples of polyamide resins other than aliphatic polyamide resins and xylylenediamine-based polyamide resins include semi-aromatic polyamide resins other than xylylenediamine-based polyamide resins. Examples of semi-aromatic polyamide resins include terephthalic acid-based polyamide resins (polyamide 6T, polyamide 9T, polyamide 10T). The resin composition of this embodiment preferably does not substantially contain polyamide resins other than aliphatic polyamide resins and xylylenediamine-based polyamide resins. "Substantially free" means that the content of polyamide resins other than aliphatic polyamide resins and xylylenediamine-based polyamide resins contained in the resin composition is less than 10% by mass of the total amount of polyamide resins other than aliphatic polyamide resins and xylylenediamine-based polyamide resins, preferably less than 5% by mass, more preferably less than 3% by mass, and even more preferably less than 1% by mass.

[0030] In the case of a reinforced resin composition containing a reinforcing filler described below, the total content of the polyamide resins (xylylenediamine-based polyamide resin, aliphatic polyamide resin, and other polyamide resins blended as needed) in the resin composition of this embodiment is preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 65% ​​by mass or more, and preferably 80% by mass or less, and more preferably 75% by mass or less. In the case of a non-reinforced resin composition not containing a reinforcing filler described below, the total content of the polyamide resins (xylylenediamine-based polyamide resin, aliphatic polyamide resin, and other polyamide resins blended as needed) in the resin composition of this embodiment is preferably 85% by mass or more, more preferably 90% by mass or more, even more preferably 95% by mass or more, and preferably 99.9% by mass or less.

[0031] <Other Components> The resin composition of this embodiment may contain components other than those described above. Examples of the other components include thermoplastic resins other than polyamide resins, reinforcing fillers, and resin additives. Examples of resin additives include nucleating agents, release agents, heat stabilizers, light stabilizers, antioxidants, UV inhibitors, alkalis, colorants, hydrolysis resistance improvers, matting agents, plasticizers, dispersants, antistatic agents, antigelling agents, and flame retardants. The total content of the resin additives is preferably 20.0 mass% or less of the resin composition, more preferably 10.0 mass% or less, even more preferably 5.0 mass% or less, and even more preferably 1.0 mass% or less. Only one type of other additive may be used, or two or more types may be used in combination. For details of the other additives, please refer to the descriptions in paragraphs 0130 to 0155 of Japanese Patent No. 4,894,982, the contents of which are incorporated herein by reference. Further, the resin composition of the present embodiment can be blended with the additives described in paragraphs 0047 to 0103 of WO 2021 / 241471 within the scope of the present invention, and the contents thereof are incorporated herein.

[0032] In addition, in the resin composition of this embodiment, the contents of the xylylenediamine-based polyamide resin, the aliphatic polyamide resin, and other components that are blended as necessary are adjusted so that the total of each component is 100 mass %.

[0033] <<Reinforcing Filler>> The resin composition of this embodiment may contain a reinforcing filler. By containing a reinforcing filler, the mechanical strength of the resulting molded article can be improved. The reinforcing filler that can be used in this embodiment is not particularly limited in terms of type, etc., and may be any of fibers, fillers, flakes, beads, etc., but fibers are preferred.

[0034] When the reinforcing filler is a fiber, it may be either a short fiber or a long fiber, with a long fiber being preferred.

[0035] Examples of raw materials for the reinforcing filler include inorganic substances such as glass, carbon (carbon fiber, etc.), alumina, boron, ceramic, metal (steel, etc.), asbestos, clay, zeolite, potassium titanate, barium sulfate, titanium oxide, silicon oxide, aluminum oxide, and magnesium hydroxide, and organic substances such as plants (including kenaf, bamboo, etc.), aramid, polyoxymethylene, aromatic polyamide, polyparaphenylene benzobisoxazole, and ultra-high molecular weight polyethylene, with glass being preferred.

[0036] The resin composition of this embodiment preferably contains glass fiber as a reinforcing filler. The glass fiber is selected from glass compositions such as A-glass, C-glass, E-glass, R-glass, D-glass, M-glass, and S-glass, with E-glass (alkali-free glass) being particularly preferred. The number-average fiber diameter of the glass fiber monofilament is typically 1 to 25 μm, preferably 5 to 17 μm. By setting the number-average fiber diameter to 1 μm or more, the moldability of the resin composition tends to be further improved. By setting the number-average fiber diameter to 25 μm or less, the appearance of the resulting molded article and the reinforcing effect tend to be improved. The glass fiber may be a monofilament or a twist of multiple monofilaments. The glass fiber may be in the form of chopped strand (e.g., glass fiber cut to a length of 1 to 10 mm) or milled fiber (i.e., glass fiber pulverized to a length of approximately 10 to 500 μm), with chopped strand being preferred. Glass fibers of different forms can also be used in combination. The glass fiber may have a cross section that is circular, polygonal, or irregular. The irregular cross section has a flattening ratio, which is the ratio of the major axis to the minor axis of the cross section perpendicular to the longitudinal direction of the fiber, of, for example, 1.5 to 10, preferably 2.5 to 10, more preferably 2.5 to 8, and even more preferably 2.5 to 5.

[0037] The glass fiber may be surface-treated with, for example, a silane-based compound, an epoxy-based compound, a urethane-based compound, or the like, or may be oxidized, in order to improve its affinity with the resin component, as long as the properties of the resin composition of this embodiment are not significantly impaired.

[0038] The reinforcing filler used in this embodiment may be a reinforcing filler having electrical conductivity. Specific examples include metals, metal oxides, conductive carbon compounds, and conductive polymers, with conductive carbon compounds being preferred.

[0039] The content of the reinforcing filler (preferably glass fiber) in the resin composition of this embodiment is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, even more preferably 30 parts by mass or more, and even more preferably 40 parts by mass or more, per 100 parts by mass of the xylylenediamine-based polyamide resin and the aliphatic polyamide resin combined. By setting the content at or above the lower limit, the mechanical strength of the resulting molded article tends to be further increased. Furthermore, the content of the reinforcing filler (preferably glass fiber) is preferably 100 parts by mass or less, more preferably 90 parts by mass or less, even more preferably 85 parts by mass or less, even more preferably 80 parts by mass or less, and even more preferably 75 parts by mass or less, per 100 parts by mass of the xylylenediamine-based polyamide resin and the aliphatic polyamide resin combined. By setting the content at or below the upper limit, the appearance of the molded article tends to be improved, and the flowability of the resin composition tends to be further improved.

[0040] The content of the reinforcing filler (preferably glass fiber) in the resin composition of this embodiment is preferably 20% by mass or more, more preferably 25% by mass or more, and preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 35% by mass or less. The resin composition of this embodiment may contain only one type of reinforcing filler (preferably glass fiber), or may contain two or more types. When two or more types are contained, it is preferable that the total amount is in the above range.

[0041] <<Nucleating Agent>> The resin composition of this embodiment may contain a nucleating agent. The inclusion of a nucleating agent can improve the appearance of the resulting molded article. The nucleating agent may be organic or inorganic, but inorganic nucleating agents are preferred. Examples include graphite, molybdenum disulfide, barium sulfate, talc, mica, calcium carbonate, sodium phosphate, boron nitride, and kaolin. Preferably, the nucleating agent contains one or more selected from talc, mica, calcium carbonate, and boron nitride, more preferably one or more selected from talc and calcium carbonate, and even more preferably talc. Talc may be surface-treated with at least one compound selected from polyorganohydrogensiloxanes and organopolysiloxanes. In this case, the amount of the siloxane compound attached to the talc is preferably 0.1 to 5% by mass of the talc.

[0042] The lower limit of the number average particle size of the nucleating agent is preferably 0.1 μm or more, and more preferably 0.5 μm or more. The upper limit of the number average particle size of the nucleating agent is preferably 40 μm or less, more preferably 30 μm or less, even more preferably 28 μm or less, even more preferably 15 μm or less, and even more preferably 10 μm or less. By setting the number average particle size to 40 μm or less, the number of nucleating agents that become nuclei increases compared to the amount of nucleating agent blended, and the crystal structure tends to be more stable.

[0043] When the resin composition of this embodiment contains a nucleating agent, the content thereof is preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, even more preferably 0.1 parts by mass or more, and even more preferably 0.4 parts by mass or more, per 100 parts by mass of the xylylenediamine-based polyamide resin and the aliphatic polyamide resin combined. The upper limit of the content of the nucleating agent is preferably 5 parts by mass or less, more preferably 3 parts by mass or less, and even more preferably 2 parts by mass or less, per 100 parts by mass of the xylylenediamine-based polyamide resin and the aliphatic polyamide resin combined. The resin composition of this embodiment may contain only one type of nucleating agent, or two or more types. When two or more types are contained, the total amount is preferably within the above range.

[0044] <<Release Agent>> The resin composition of this embodiment may contain a release agent. Examples of release agents include aliphatic carboxylic acids, salts of aliphatic carboxylic acids, esters of aliphatic carboxylic acids and alcohols, aliphatic hydrocarbon compounds having a number average molecular weight of 200 to 15,000, polysiloxane-based silicone oils, ketone waxes, and fatty acid amides. Preferred are aliphatic carboxylic acids, salts of aliphatic carboxylic acids, esters of aliphatic carboxylic acids and alcohols, and fatty acid amides, with fatty acid amides being more preferred. For details of the release agent, please refer to paragraphs 0055 to 0061 of JP 2018-095706 A, the contents of which are incorporated herein by reference. When the resin composition of this embodiment contains a release agent, the content thereof is preferably 0.05 to 3 parts by mass, more preferably 0.1 to 1 part by mass, and even more preferably 0.2 to 0.8 parts by mass, per 100 parts by mass of the combined xylylenediamine-based polyamide resin and aliphatic polyamide resin. The resin composition of the present embodiment may contain only one type of release agent, or may contain two or more types. When two or more types are contained, the total amount is preferably in the above range.

[0045] <Method for producing resin composition> In the present embodiment, the method for producing the resin composition is not particularly limited, and a wide variety of known methods for producing thermoplastic resin compositions can be adopted. Specifically, the resin composition can be produced by pre-mixing the components using various mixers such as a tumbler or a Henschel mixer, and then melt-kneading them using a Banbury mixer, a roll, a Brabender, a single-screw extruder, a twin-screw extruder, a kneader, or the like.

[0046] Alternatively, for example, a resin composition can be produced by premixing only some of the components, or by premixing only some of the components, and feeding the mixture using a feeder to an extruder for melt-kneading. Furthermore, for example, a masterbatch can be produced by premixing some of the components, feeding the mixture to an extruder for melt-kneading, and then mixing this masterbatch again with the remaining components to produce pellets. Side-feeding of glass fibers is also preferred.

[0047] <Uses of Resin Composition and Molded Articles> The molded article of this embodiment is formed from the resin composition or pellets of this embodiment. The manufacturing method of the molded article of this embodiment is not particularly specified. One example is an injection-molded article molded by injection molding. For example, the molded article of this embodiment may be molded directly by various molding methods after melt-kneading the components, or may be molded by melt-kneading the components and pelletizing them, and then melting and molding them again by various molding methods.

[0048] The method for molding the molded article is not particularly limited, and any conventionally known molding method can be used, such as injection molding, injection compression molding, extrusion molding, profile extrusion, transfer molding, blow molding, gas-assisted blow molding, blow molding, extrusion blow molding, IMC (in-mold coating molding), rotational molding, multilayer molding, two-color molding, insert molding, sandwich molding, foam molding, and pressure molding.

[0049] The shape of the molded article of the present embodiment is not particularly limited and can be appropriately selected depending on the use and purpose of the molded article. Examples include plate-like, plate-like, rod-like, sheet-like, film-like, cylindrical, ring-like, circular, elliptical, gear-like, polygonal, irregular-shaped, hollow, frame-like, box-like, and panel-like shapes.

[0050] The fields of use of the resin composition, pellets, and molded articles of this embodiment are not particularly specified, and are widely used in automobile and other transportation vehicle parts, general machine parts, precision machine parts, electronic and electrical equipment parts, office equipment parts, building materials and housing-related parts, medical devices, leisure sports goods, play equipment, medical products, everyday items such as food packaging films, defense and aerospace products, etc. The resin composition of this embodiment is also preferably used for hollow structures such as hoses and tubes. For details of these, please refer to the descriptions in paragraphs 0077 to 0079 of WO 2022 / 219988, the contents of which are incorporated herein by reference.

[0051] The present invention will be explained in more detail below with reference to examples. The materials, amounts used, ratios, treatment contents, treatment procedures, etc. shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. If the measuring instruments used in the examples are difficult to obtain due to discontinuation or the like, measurements can be made using other instruments with equivalent performance.

[0052] 1. Raw materials The following raw materials were used:

[0053]

[0054] Synthesis Example 1: Polyamide Resin MP12(30) A precisely weighed amount of 60 mol of dodecanedioic acid was placed in a jacketed reactor equipped with a stirrer, partial condenser, condenser, thermometer, dropping tank, and nitrogen gas inlet tube. The atmosphere was thoroughly purged with nitrogen and the temperature was raised to 180°C under a small nitrogen stream to dissolve the dodecanedioic acid and create a uniform fluid state. To this mixture, 60 mol of para- / meta-xylylenediamine, in which 30 mol% of the diamine component was para-xylylenediamine and 70 mol% was meta-xylylenediamine, was added dropwise over 160 minutes with stirring. During this time, the internal pressure of the reaction system was maintained at atmospheric pressure, and the internal temperature was continuously raised to 240°C. Water distilled with the addition of para- / meta-xylylenediamine was removed from the system via the partial condenser and condenser. After the dropwise addition of para- / meta-xylylenediamine was completed, the liquid temperature was maintained at 240°C and the reaction was continued for 10 minutes. The pressure inside the reaction system was then continuously reduced to 600 Torr over 10 minutes, and the reaction was continued for 20 minutes. During this time, the reaction temperature was continuously raised to 250° C. After the reaction was completed, the inside of the reactor was pressurized with nitrogen gas to 0.3 MPa, and the polymer was taken out as a strand from a nozzle at the bottom of the polymerization vessel. After cooling with water, the strand was cut into pellets to obtain pellets of a melt polymer.

[0055] Synthesis Example 2: Polyamide Resin MP12(40) A precisely weighed amount of 60 mol of dodecanedioic acid was placed in a jacketed reactor equipped with a stirrer, partial condenser, condenser, thermometer, dropping tank, and nitrogen gas inlet tube. The atmosphere was thoroughly purged with nitrogen and the temperature was raised to 180°C under a small nitrogen stream to dissolve the dodecanedioic acid and create a uniform fluid state. To this mixture, 60 mol of para- / meta-xylylenediamine, in which 40 mol% of the diamine component was para-xylylenediamine and 60 mol% was meta-xylylenediamine, was added dropwise over 160 minutes with stirring. During this time, the internal pressure of the reaction system was maintained at atmospheric pressure, and the internal temperature was continuously raised to 250°C. Water distilled with the addition of para- / meta-xylylenediamine was removed from the system via the partial condenser and condenser. After the dropwise addition of para- / meta-xylylenediamine was completed, the liquid temperature was maintained at 250°C and the reaction was continued for 10 minutes. The pressure inside the reaction system was then continuously reduced to 600 Torr over 10 minutes, and the reaction was continued for 20 minutes. During this time, the reaction temperature was continuously raised to 260°C. After the reaction was completed, the inside of the reactor was pressurized with nitrogen gas to 0.3 MPa, and the polymer was taken out as a strand from a nozzle at the bottom of the polymerization vessel. After cooling with water, the strand was cut into pellets to obtain pellets of a melt polymer.

[0056] Synthesis Example 3: PXD12 Polyamide Resin A precisely weighed amount of 60 mol of dodecanedioic acid was placed in a jacketed reactor equipped with a stirrer, partial condenser, condenser, thermometer, dropping tank, and nitrogen gas inlet tube. The atmosphere was thoroughly purged with nitrogen and the temperature was raised to 180°C under a small nitrogen stream to dissolve the dodecanedioic acid and achieve a uniform fluid state. To this, 60 mol of paraxylylenediamine was added dropwise over 160 minutes with stirring. During this time, the internal pressure of the reaction system was maintained at atmospheric pressure, and the internal temperature was continuously raised to 290°C. Water distilled with the dropwise addition of paraxylylenediamine was removed from the system via the partial condenser and condenser. After the dropwise addition of paraxylylenediamine was completed, the liquid temperature was maintained at 290°C and the reaction was continued for 10 minutes. The internal pressure of the reaction system was then continuously reduced to 600 Torr over 10 minutes, after which the reaction was continued for 20 minutes. During this time, the reaction temperature was continuously raised to 300° C. After the reaction was completed, the inside of the reactor was pressurized with nitrogen gas to 0.3 MPa, and the polymer was taken out as a strand from a nozzle at the bottom of the polymerization vessel, cooled with water, and cut into pellets to obtain pellets of a melt polymer product.

[0057] Synthesis Example 4: Polyamide Resin MP14(30) A precisely weighed amount of 60 mol of tetradecanedioic acid was placed in a jacketed reactor equipped with a stirrer, partial condenser, condenser, thermometer, dropping tank, and nitrogen gas inlet tube. The atmosphere was thoroughly purged with nitrogen and the temperature was raised to 180°C under a small nitrogen stream to dissolve the tetradecanedioic acid and achieve a uniform fluid state. To this mixture, 60 mol of para- / meta-xylylenediamine, in which 30 mol% of the diamine component was para-xylylenediamine and 70 mol% was meta-xylylenediamine, was added dropwise over 160 minutes with stirring. During this time, the internal pressure of the reaction system was maintained at atmospheric pressure, and the internal temperature was continuously raised to 240°C. Water distilled with the addition of para- / meta-xylylenediamine was removed from the system via the partial condenser and condenser. After the dropwise addition of para- / meta-xylylenediamine was completed, the liquid temperature was maintained at 240°C and the reaction was continued for 10 minutes. The pressure inside the reaction system was then continuously reduced to 600 Torr over 10 minutes, and the reaction was continued for 20 minutes. During this time, the reaction temperature was continuously raised to 250° C. After the reaction was completed, the inside of the reactor was pressurized with nitrogen gas to 0.3 MPa, and the polymer was taken out as a strand from a nozzle at the bottom of the polymerization vessel. After cooling with water, the strand was cut into pellets to obtain pellets of a melt polymer.

[0058] Synthesis Example 5: Polyamide Resin MP10: 60 mol of precisely weighed sebacic acid was placed in a jacketed reactor equipped with a stirrer, partial condenser, condenser, thermometer, dropping tank, and nitrogen gas inlet tube. The atmosphere was thoroughly purged with nitrogen and the temperature was raised to 180°C under a small nitrogen stream to dissolve the sebacic acid and achieve a uniform fluid state. To this was added dropwise 60 mol of para / meta-xylylenediamine, in which 30 mol% of the diamine component was para-xylylenediamine and 70 mol% was meta-xylylenediamine, with stirring over 160 minutes. During this time, the internal pressure of the reaction system was maintained at atmospheric pressure, and the internal temperature was continuously raised to 250°C. Water distilled with the addition of para-xylylenediamine was removed from the system via the partial condenser and condenser. After the dropwise addition of para-xylylenediamine was completed, the liquid temperature was maintained at 250°C and the reaction was continued for 10 minutes. The pressure inside the reaction system was then continuously reduced to 600 Torr over 10 minutes, and the reaction was continued for 20 minutes. During this time, the reaction temperature was continuously raised to 260°C. After the reaction was completed, the inside of the reactor was pressurized with nitrogen gas to 0.3 MPa, and the polymer was taken out as a strand from a nozzle at the bottom of the polymerization vessel. After cooling with water, the strand was cut into pellets to obtain pellets of a melt polymer.

[0059] 2. Examples 1-1 to 1-8, Reference Examples 1-1 to 1-3, Comparative Examples 1-1 to 1-9 <Compounds> The components shown in Table 1 were weighed out to the proportions shown in Tables 2 to 5 (proportions of each component are in mass%), and the components other than the glass fiber were blended in a tumbler. The blend was then fed into the base of a twin-screw extruder (Shibaura Machine Co., Ltd., TEM26SS) and melted. The glass fiber was then side-fed to produce pellets of the resin composition. The temperature of the twin-screw extruder was set to 240 to 280°C.

[0060] <CE10 Barrier Property> The pellets obtained by the above manufacturing method were dried at 120°C for 4 hours, and then injection-molded into flat test specimens (2 mm thick) using an injection molding machine (NEX140III, manufactured by Nissei Plastic Industrial Co., Ltd.) under conditions of a cylinder temperature of 200-300°C, a mold temperature of 90°C, and a molding cycle of 50 seconds. For compositions that could not crystallize in the mold at 90°C, annealing was performed at 150°C for 1 hour. 15 cc of a mixed solvent consisting of toluene (45% by volume), isooctane (45% by volume), and ethanol (10% by volume) was placed in an aluminum cup with a diameter of 38 mm. The flat test specimen was placed on top of the packing, and an aluminum lid with a hole the same size as the packing and the cup's mouth was attached and screwed in place. The gas permeability coefficient (g·mm / m) was calculated from the change in weight before and after storage for 1,000 hours in a constant temperature bath at 60°C. ２ The gas permeability coefficient (g mm / m ２ ・day) = [(mass before storage - mass after storage) × (thickness of test piece)] / [(area of ​​the mouth of the aluminum cup) × (number of days of storage)] 5: 5.5 g mm / m ２ ・Less than day 4:5.5g・mm / m ２ ・day over 7.0g・mm / m ２ ・Less than day 3: 7.0g・mm / m ２ ・Day super 8.5g・mm / m ２ ・Less than day 2: 8.5g・mm / m ２ ・day over 10.0 g・mm / m ２ ・Less than day 1:10.0g・mm / m ２ ・Day super

[0061] <Flexural Modulus (GPa)> The resin composition (pellets) obtained by the above-mentioned manufacturing method was dried at 80°C for 12 hours, and then ISO tensile test specimens (4 mm thick) were injection molded using an injection molding machine (Nissei Plastic Industrial Co., Ltd., "NEX140III") under conditions of a cylinder temperature of 200 to 300°C, a mold temperature of 90°C, and a molding cycle of 50 seconds. For compositions that could not crystallize in the mold at 90°C, annealing was performed at 150°C for 1 hour. In accordance with ISO 178, the flexural modulus (unit: GPa) was measured using the above ISO tensile test specimens (4 mm thick) under an environment of a temperature of 23°C and a humidity of 50%. 5: 7.0 GPa or more 4: 6.5 GPa or more but less than 7.0 GPa 3: 6.0 GPa or more but less than 6.5 GPa 2: 5.5 GPa or more but less than 6.0 GPa 1: Less than 5.5 GPa

[0062] <Fogging Test (%)> The resin composition (pellets) obtained by the above-mentioned production method was dried at 80 ° C. for 12 hours, and then an injection molding machine (manufactured by Nissei Plastic Industrial Co., Ltd., "NEX140III") was used to injection-molde a φ80 mm × 2 mm thick test piece under conditions of a cylinder temperature of 280 ° C., a mold temperature of 90 ° C., and a molding cycle of 50 seconds. With reference to ISO 6452, a φ80 mm × 2 mm thick test piece was conditioned at 23 ° C., 50% RH, and 16 hours, and then a fogging test was performed using a fogging tester WF-2 (manufactured by Suga Test Instruments Co., Ltd.) at a test temperature of 150 ° C. and a test time of 3 hours. Thereafter, the glass plate was left to stand at 23 ° C., 50% RH, and 1 hour. Using a gloss meter PG-IIM (manufactured by Nippon Denshoku Industries Co., Ltd.), the glass specular gloss before and after the test was measured, and the glass haze was calculated. <<Method for measuring specular gloss>> Before the fogging test, the specular gloss of the glass plate was measured at four points. Then, the fogging test was carried out. After the fogging test, the glass plate was left to stand for 1 hour, and the specular gloss was measured again at four points. Glass haze (%) = R ２ / R １ x100 R １ : Specular gloss of glass before fogging test R ２: Specular gloss of glass after fogging test Glass haze was evaluated as follows: 5: 90% or more 4: 75% or more but less than 90% 3: 60% or more but less than 75% 2: 45% or more but less than 60% 1: Less than 45%

[0063] <Acid resistance (%)> The above ISO tensile test piece (4 mm thick) was immersed in a 10% by mass aqueous solution of hydrogen chloride at 23°C for 90 days, and the flexural modulus was measured in the same manner as above. The retention rate of the flexural modulus after immersion relative to that before immersion was calculated. The evaluation was as follows: 5: 80% or more 4: 60% or more but less than 80% 3: 40% or more but less than 60% 2: 20% or more but less than 40% 1: Less than 20%

[0064] <Ethyl acetate resistance (%)> The above ISO tensile test piece (4 mm thick) was immersed in ethyl acetate at 23°C for 90 days, and the flexural modulus was measured in the same manner as above. The retention rate of the flexural modulus after immersion relative to that before immersion was calculated. The evaluation was as follows: 5: 95% or more 4: 90% or more but less than 95% 3: 85% or more but less than 90% 2: 80% or more but less than 85% 1: Less than 80%

[0065] <Zinc Chloride Resistance (%)> The above ISO tensile test piece (4 mm thick) was immersed in a 50 mass % zinc chloride aqueous solution at 23°C for 90 days, and the flexural modulus was measured in the same manner as above. The retention rate of the flexural modulus after immersion relative to that before immersion was calculated. The unit is %. The evaluation was as follows: 5: 80% or more 4: 75% or more but less than 80% 3: 65% or more but less than 75% 2: 60% or more but less than 65% 1: Less than 60%

[0066] <Water Absorption (%)> The ISO tensile test specimens were processed into the ISO 178 recommended test specimens (80 mm x 10 mm x 4 mm thick), and the molded specimens were immersed in water at 23°C for 90 days, and then their masses were measured to determine the water absorption. The difference between the mass after immersion and the mass before immersion was taken as the water absorption. The water absorption was evaluated as follows: 5: 1.5% or less 4: More than 1.5% and 2.0% or less 3: More than 2.0% and 2.5% or less 2: More than 2.5% and 3.0% or less 1: More than 3.0%

[0067] <In-mold crystallization> The pellets obtained by the above manufacturing method were dried at 120 ° C. for 4 hours, and then injection molded using an injection molding machine (manufactured by Nissei Plastic Industrial Co., Ltd., "NEX140III") under the following conditions: cylinder temperature 200-300 ° C., mold temperature 90 ° C., cooling time 30 seconds, pressure holding time 15 seconds, and cycle time 50 seconds. A three-stage plate having a length of 100 mm and a width of 60 mm and a thickness of 3 mm (length 40 mm), 2 mm (length 30 mm), and 1 mm (length 30 mm) was obtained. The 1 mm-thick portion of the three-stage plate was evaluated for in-mold crystallization by the presence or absence of a peak in the heat of crystallization Hch when heated at 10 ° C. / min using a differential scanning calorimeter (manufactured by Shimadzu Corporation, DSC-60A). Evaluation was performed as follows. 5: The heat of crystallization Hch is less than 0.1 J / g (crystallization occurs at a mold temperature of 90°C) 1: The heat of crystallization Hch is 0.1 J / g or more (crystallization does not occur at a mold temperature of 90°C)

[0068] <Overall evaluation> Based on the above results, an overall evaluation was made. Specifically, the evaluation was made as follows: 5: No points for each evaluation item were 1 (all were 2 or more), and the total points for the evaluation items was 35 or more. 4: No points for each evaluation item were 1 (all were 2 or more), and the total points for the evaluation items was 30 or more but less than 35. 3: No points for each evaluation item were 1 (all were 2 or more), and the total points for the evaluation items was less than 30. 2: There was a point for each evaluation item that was 1, and the total points for the evaluation items was more than 25. 1: There was a point for each evaluation item that was 1, and the total points for the evaluation items was 25 or less.

[0069]

[0070]

[0071]

[0072]

[0073] 2. Examples 2-1 to 2-8, Reference Examples 2-1 to 2-3, Comparative Examples 2-1 to 2-9 <Compounds> The components shown in Table 1 were weighed and blended in a tumbler to obtain the proportions shown in Tables 6 to 9 (proportions of each component are in mass%). The blend was then charged into the base of a twin-screw extruder (TEM26SS, manufactured by Shibaura Machine Co., Ltd.) and melted to produce pellets of the resin composition. The temperature of the twin-screw extruder was set to 240 to 280°C.

[0074] <Barrier Properties> The pellets obtained by the above manufacturing method were dried at 120°C for 4 hours, and then molded into a 100 μm film using a film molding machine at a cylinder temperature of 200 to 300°C. 15 cc of a mixed solvent consisting of toluene (45% by volume), isooctane (45% by volume), and ethanol (10% by volume) was placed in an aluminum cup with a diameter of 38 mm, and a flat test piece or film was placed on top of the packing. An aluminum lid with a hole of the same size as the packing and the mouth of the cup was attached and fastened with screws. The gas permeability coefficient (g mm / m) was calculated from the change in weight before and after storage for 1000 hours in a constant temperature bath at 60°C. ２ The gas permeability coefficient (g mm / m ２ ・day) = [(mass before storage - mass after storage) × (thickness of test piece)] / [(area of ​​the mouth of the aluminum cup) × (number of days of storage)] 5: 8.0 g mm / m ２ ・Less than day 4:8.0g・mm / m ２ ・day over 9.0 g・mm / m ２ ・Less than day 3:9.0g・mm / m ２ ・day over 10.0 g・mm / m ２ ・Less than day 2: 10.0g・mm / m ２ ・day over 11.0 g・mm / m ２ ・Less than day 1:11.0g・mm / m ２ ・Day super

[0075] <Flexural Modulus (GPa)> The resin composition (pellets) obtained by the above-described manufacturing method was dried at 80°C for 12 hours, and then an ISO tensile test piece (4 mm thick) was injection molded using an injection molding machine (manufactured by Nissei Plastic Industrial Co., Ltd., "NEX140III") under conditions of a cylinder temperature of 200 to 300°C, a mold temperature of 90°C, and a molding cycle of 50 seconds. For compositions that could not crystallize in the mold at 90°C, annealing was performed at 150°C for 1 hour. In accordance with ISO 178, the flexural modulus (unit: GPa) was measured using the above ISO tensile test piece (4 mm thick) under an environment of a temperature of 23°C and a humidity of 50%. Evaluation was performed as follows. 5: 2.4 GPa or more 4: 2.2 GPa or more and less than 2.4 GPa 3: 2.0 GPa or more and less than 2.2 GPa 2: 1.8 GPa or more and less than 2.0 GPa 1: Less than 1.8 GPa

[0076] <Fogging Test (%)> The resin composition (pellets) obtained by the above-mentioned production method was dried at 80 ° C. for 12 hours, and then an injection molding machine (manufactured by Nissei Plastic Industrial Co., Ltd., "NEX140III") was used to injection-molde a φ80 mm × 2 mm thick test piece under conditions of a cylinder temperature of 280 ° C., a mold temperature of 90 ° C., and a molding cycle of 50 seconds. With reference to ISO 6452, the φ80 mm × 2 mm thick test piece was conditioned at 23 ° C., 50% RH, and 16 hours, and then a fogging test was performed using a fogging tester WF-2 (manufactured by Suga Test Instruments Co., Ltd.) at a test temperature of 150 ° C. and a test time of 3 hours. The glass plate was then left to stand at 23 ° C., 50% RH, and 1 hour. The glass specular gloss before and after the test was measured using a gloss meter PG-IIM (manufactured by Nippon Denshoku Industries Co., Ltd.), and the glass haze was calculated.

[0077] <<Method for measuring specular gloss>> Before the fogging test, the specular gloss of the glass plate was measured at four points. Then, the fogging test was carried out. After the fogging test, the glass plate was left to stand for 1 hour, and the specular gloss was measured again at four points. Glass haze (%) = R ２ / R １ x100 R １ : Specular gloss of glass before fogging test R ２ : Specular gloss of glass after fogging test Glass haze was evaluated as follows.

[0078] The glass haze was evaluated as follows: 5: 80% or more 4: 75% or more and less than 80% 3: 70% or more and less than 75% 2: 65% or more and less than 70% 1: Less than 65%

[0079] <Acid resistance (%)> The above ISO tensile test piece (4 mm thick) was immersed in a 10% by mass aqueous hydrogen chloride solution at 23°C for 90 days, and the flexural modulus was measured in the same manner as above. The retention rate of the flexural modulus after immersion relative to that before immersion was calculated. The evaluation was as follows: 5: 80% or more 4: 70% or more but less than 80% 3: 60% or more but less than 70% 2: 50% or more but less than 60% 1: Less than 50%

[0080] <Ethyl acetate resistance (%)> The above ISO tensile test piece (4 mm thick) was immersed in ethyl acetate at 23°C for 90 days, and the flexural modulus was measured in the same manner as above. The retention rate of the flexural modulus after immersion relative to that before immersion was calculated. The evaluation was as follows: 5: 95% or more 4: 90% or more but less than 95% 3: 85% or more but less than 90% 2: 80% or more but less than 85% 1: Less than 80%

[0081] <Zinc chloride resistance (%)> The above ISO tensile test piece (4 mm thick) was immersed in a 50 mass % zinc chloride aqueous solution at 23°C for 90 days, and the flexural modulus was measured in the same manner as above. The retention rate of the flexural modulus after immersion relative to that before immersion was calculated. Evaluation was performed as follows. The zinc chloride resistance was evaluated as follows: 5: 75% or more 4: 70% or more but less than 75% 3: 65% or more but less than 70% 2: 60% or more but less than 65% 1: Less than 60%

[0082] <Water absorption (%)> The ISO tensile test specimens were processed into the ISO 178 recommended test specimens (80 mm x 10 mm x 4 mm thick), and the molded specimens were immersed in water at 23°C for 90 days, and then their masses were measured to determine the water absorption. The difference between the mass after immersion and the mass before immersion was taken as the water absorption. The evaluation was as follows: 5: 2.0% or less 4: More than 2.0% and 2.5% or less 3: More than 2.5% and 3.0% or less 2: More than 3.0% and 3.5% or less 1: More than 3.5%

[0083] <In-mold crystallization> The pellets obtained by the above manufacturing method were dried at 120 ° C for 4 hours, and then injection molded using an injection molding machine (Nissei Plastic Industrial Co., Ltd., "NEX140III") under the following conditions: cylinder temperature 200-300 ° C, mold temperature 90 ° C, cooling time 30 seconds, pressure holding time 15 seconds, and cycle time 50 seconds. A three-stage plate measuring 100 mm long x 60 mm wide and having thicknesses of 3 mm (40 mm long), 2 mm (30 mm long), and 1 mm (30 mm long) was obtained. The 1 mm-thick portion of the three-stage plate was evaluated for in-mold crystallization by the presence or absence of a peak in the heat of crystallization Hch when heated at 10 ° C / min using a differential scanning calorimeter (Shimadzu Corporation, DSC-60A). Evaluation was performed as follows. 5: The heat of crystallization Hch is less than 0.1 J / g (crystallization occurs at a mold temperature of 90°C) 1: The heat of crystallization Hch is 0.1 J / g or more (crystallization does not occur at a mold temperature of 90°C)

[0084] <Overall evaluation> Based on the above results, an overall evaluation was made. Specifically, the evaluation was made as follows: 5: No points for each evaluation item were 1 (all were 2 or more), and the total points for the evaluation items was 35 or more. 4: No points for each evaluation item were 1 (all were 2 or more), and the total points for the evaluation items was 30 or more but less than 35. 3: No points for each evaluation item were 1 (all were 2 or more), and the total points for the evaluation items was less than 30. 2: There was a point for each evaluation item that was 1, and the total points for the evaluation items was more than 25. 1: There was a point for each evaluation item that was 1, and the total points for the evaluation items was 25 or less.

[0085]

[0086]

[0087]

[0088]

[0089] As is clear from the above results, the resin composition was able to be appropriately crystallized in the mold, and a molded article with excellent barrier properties was obtained. In contrast, when the xylylenediamine-based polyamide resin was outside the range of the present invention, the crystallization in the mold was insufficient.

Claims

1. A polyamide resin comprising a xylylenediamine-based polyamide resin and an aliphatic polyamide resin, the xylylenediamine-based polyamide resin comprising a diamine-derived structural unit and a dicarboxylic acid-derived structural unit, 70 mol % or more of the diamine-derived structural units being derived from xylylenediamine, 70 mol % or more of the dicarboxylic acid-derived structural units being derived from an α,ω-linear aliphatic dicarboxylic acid having 11 to 20 carbon atoms, and the aliphatic polyamide resin comprising -(CH ２ ) ｎ１ -(n1 is 3 to 6)-containing structural unit and -(CH ２ ) ｎ２ A resin composition comprising a structural unit containing -(n2 is 7 to 20).

2. The resin composition according to claim 1, wherein 10 to 90 mol % of the diamine-derived structural units in the xylylenediamine-based polyamide resin are derived from meta-xylylenediamine, and 90 to 10 mol % are derived from para-xylylenediamine (however, the total of meta-xylylenediamine and para-xylylenediamine does not exceed 100 mol %).

3. The resin composition according to claim 1, wherein 70 mol % or more of the dicarboxylic acid-derived structural units in the xylylenediamine-based polyamide resin are derived from dodecanedioic acid and / or tetradecanedioic acid.

4. The resin composition according to claim 1, wherein 10 to 90 mol % of the diamine-derived structural units in the xylylenediamine-based polyamide resin are derived from meta-xylylenediamine and 90 to 10 mol % are derived from para-xylylenediamine (provided that the sum of meta-xylylenediamine and para-xylylenediamine does not exceed 100 mol %), and 70 mol % or more of the dicarboxylic acid-derived structural units in the xylylenediamine-based polyamide resin are derived from dodecanedioic acid and / or tetradecanedioic acid.

5. The aliphatic polyamide resin is -(CH ２ ) ｎ１ -(n1 is 3 to 6)-containing structural unit and -(CH ２ ) ｎ２ The resin composition according to any one of claims 1 to 4, which is a copolymer containing a structural unit containing -(n2 is 7 to 20).

6. The resin composition according to any one of claims 1 to 4, wherein the aliphatic polyamide resin comprises at least one selected from polyamide 610 and polyamide 612.

7. A resin composition according to any one of claims 1 to 6, wherein the mass ratio of the xylylenediamine-based polyamide resin to the aliphatic polyamide resin is 5:95 to 80:

20.

8. Pellets of the resin composition according to any one of claims 1 to 7.

9. A molded article formed from the resin composition according to any one of claims 1 to 7.

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