Polyamide resin composition

Abstract

The present invention pertains to a polyamide resin composition that has excellent mechanical physical properties and that exhibits excellent results in an UL94 combustion test. The polyamide resin composition contains an aliphatic polyamide (A), a phosphinate (B), and a phosphazene compound (C). In the polyamide resin composition, the aliphatic polyamide (A) is contained in an amount of 60-85 mass% and the phosphazene compound (C) is contained in an amount of 3-20 mass%.

Description

[Technical field]

[0001] The present invention relates to a polyamide resin composition. [Background technology]

[0002] In recent years, there has been an increasing demand for flame retardant materials in the fields of industrial and consumer equipment and electrical appliances to prevent fires or to prevent the spread of fire. On the other hand, synthetic resins tend to be easily flammable, and although polyamide resins have higher flame retardancy than polyolefin resins, this is not sufficient to meet the increasing demands of recent years. For this reason, there have been inventions in the past that impart high flame retardancy to polyamide resins by using flame retardants.

[0003] For example, a fiber-reinforced polyamide resin based on polyamide 66 and containing several phosphorus-based and nitrogen-based flame retardants has been proposed that has high flame retardancy and glow-wire resistance (see Patent Document 1). Also, a fiber-reinforced polyamide resin composed of an aliphatic polyamide and a partially aromatic polyamide and containing a phosphorus-based flame retardant has been proposed (see Patent Document 2). However, Patent Documents 1 and 2 only describe fiber-reinforced resins. The polyamide resins disclosed in Patent Documents 1 and 2 are not suitable as polyamide resins for use in the manufacture of flexible parts. A polyamide resin composition containing a halogen-free flame retardant has also been proposed (see Patent Document 3). Patent Document 3 is intended for rigid molded products, and all of the resin compositions used in Patent Document 3 are assumed to be fiber-reinforced polyamide resins.

[0004] On the other hand, as a flame-retardant unreinforced polyamide resin, a polyamide molding composition based on polyamide 12 and a polyamide elastomer, containing a flame retardant and a plasticizer has been proposed (see Patent Document 4). [Prior art documents] [Patent documents]

[0005] [Patent Document 1] JP 2007-70627 A [Patent Document 2] Special Publication No. 2007-507566 [Patent Document 3] Special Publication No. 2004-510863 [Patent Document 4] JP 2017-43762 A DISCLOSURE OF THEINVENTION [Problem to be solved by the invention]

[0006] Although Patent Document 4 describes the oxygen index, it does not disclose any technical data on the results of the UL flame test, which is an important indicator of flame retardancy. Therefore, an object of the present invention is to provide a polyamide resin composition that has excellent mechanical properties and shows excellent results in the UL94 flame test. [Means for solving the problem]

[0007] Means for Solving the Problems The present inventors have conducted intensive research to solve the above problems, and have found that a polyamide resin composition containing a phosphinate, and an aliphatic polyamide and a phosphazene compound in a specific ratio has good mechanical properties and shows excellent results in a UL94 flame test.

[0008] That is, the present invention relates to the following. [1] A polyamide resin composition comprising an aliphatic polyamide (A), a phosphinate (B) and a phosphazene compound (C), The aliphatic polyamide (A) is contained in the polyamide resin composition in an amount of 60% by mass or more and 85% by mass or less, The polyamide resin composition includes the phosphazene compound (C) in an amount of 3% by mass or more and 20% by mass or less. [2] The aliphatic polyamide (A) is an aliphatic polyamide having a ratio of the number of methylene groups to the number of amide groups of 5.0 or more; The aliphatic polyamide (A) is contained in an amount of 60% by mass or more and 82% by mass or less based on 100% by mass of the polyamide resin composition, The polyamide resin composition contains the phosphinate (B) in an amount of 15% by mass or more and 20% by mass or less based on 100% by mass of the polyamide resin composition, and The polyamide resin composition according to [1], wherein the phosphazene compound (C) is a cyclic phosphazene compound. [3] Further comprising an elastomeric polymer (D) (excluding the core-shell rubber type graft copolymer (F)) and a phosphorus-containing polymer compound (E), The aliphatic polyamide (A) is contained in an amount of 60% by mass or more and 82% by mass or less based on 100% by mass of the polyamide resin composition, The polyamide resin composition according to [1], wherein the phosphinate (B) is contained in an amount of 15% by mass or more and 20% by mass or less based on 100% by mass of the polyamide resin composition. [4] The polyamide resin composition according to [3], wherein the elastomeric polymer (D) contains a structural unit derived from an unsaturated compound having a carboxyl group and / or an acid anhydride group. [5] The polyamide resin composition according to [3] or [4], wherein the aliphatic polyamide (A) is contained in an amount of 60% by mass or more and 79% by mass or less based on 100% by mass of the polyamide resin composition, and the elastomeric polymer (D) is contained in an amount of 3% by mass or more and 15% by mass or less based on 100% by mass of the polyamide resin composition. [6] The polyamide resin composition according to any one of [3] to [5], wherein the phosphorus-containing polymer compound (E) is represented by the following formula (5): [ka] (In the formula, n1 is an integer of 4 or more.) [7] The polyamide resin composition according to any one of [3] to [6], wherein the aliphatic polyamide (A) is contained in an amount of 60% by mass or more and 76% by mass or less based on 100% by mass of the polyamide resin composition, and the phosphorus-containing polymer compound (E) is contained in an amount of 3% by mass or more and 10% by mass or less based on 100% by mass of the polyamide resin composition. [8] The polyamide resin composition according to any one of [3] to [7], wherein the phosphazene compound (C) is contained in an amount of 3% by mass or more and 10% by mass or less based on 100% by mass of the polyamide resin composition. [9] The polyamide resin composition of [1], further comprising a core-shell rubber type graft copolymer (F).

[10] The polyamide resin composition according to [9], wherein the core-shell rubber type graft copolymer (F) is a silicone-based copolymer.

[11] The polyamide resin composition [9] or

[10] , wherein the core-shell rubber type graft copolymer (F) is contained in an amount of 2% by mass or more and 15% by mass or less based on 100% by mass of the polyamide resin composition.

[12] The polyamide resin composition according to any one of [9] to

[11] , further comprising an impact-resistant material (G) other than the component (F) in an amount of 10% by mass or less based on 100% by mass of the polyamide resin composition.

[13] The polyamide resin composition according to any one of [9] to

[12] , further comprising 10 mass% or less of a flame retardant (H) other than components (B) and (C) based on 100 mass% of the polyamide resin composition.

[14] The polyamide resin composition according to any one of [9] to

[13] , wherein the phosphazene compound (C) is contained in an amount of 3% by mass or more and 10% by mass or less based on 100% by mass of the polyamide resin composition.

[15] The polyamide resin composition according to any one of [1] to

[14] , wherein the phosphazene compound (C) is represented by the following formula (3): [ka] [In the formula, n represents an integer of 3 to 25, and R 1 are the same or different and are unsubstituted or substituted aryl groups, provided that the proportion of unsubstituted aryl groups is 1 It is 0.1 to 100 mol % based on the total amount of the above.

[16] The polyamide resin composition according to any one of [1] to

[15] , wherein the aliphatic polyamide (A) comprises at least one homopolymer selected from the group consisting of polyamide 11, polyamide 12, polyamide 612, polyamide 1010, polyamide 1012, and polyamide 1212, and / or at least one copolymer using two or more raw material monomers forming these.

[17] A molded article comprising the polyamide resin composition according to any one of [1] to

[16] .

[18] A hollow molded article obtained by molding the polyamide resin composition according to any one of [1] to

[16] .

[19] The hollow molded body of

[18] , formed by extrusion molding. Effect of the Invention

[0009] According to the present invention, it is possible to provide a polyamide resin composition which has excellent mechanical properties and shows excellent results in the UL94 flame test. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] [Polyamide resin composition] The polyamide resin composition comprises an aliphatic polyamide (A), a phosphinic acid salt (B) and a phosphazene compound (C), the aliphatic polyamide (A) being contained in the polyamide resin composition in an amount of 60 mass% or more and 85 mass% or less, and the phosphazene compound (C) being contained in the polyamide resin composition in an amount of 3 mass% or more and 20 mass% or less.

[0011] [Aliphatic polyamide (A)] The aliphatic polyamide (A) includes an aliphatic homopolyamide resin and / or an aliphatic copolymer polyamide resin.

[0012] (Aliphatic homopolyamide resin) The aliphatic homopolyamide resin means a polyamide resin in which the monomer component constituting the aliphatic polyamide resin is one type alone. The aliphatic homopolyamide resin may be composed of at least one type of lactam and an aminocarboxylic acid which is a hydrolyzate of the lactam, or may be composed of a combination of one type of aliphatic diamine and one type of aliphatic dicarboxylic acid. Here, when the monomer components constituting the aliphatic polyamide resin are a combination of an aliphatic diamine and an aliphatic dicarboxylic acid, the combination of one type of aliphatic diamine and one type of aliphatic dicarboxylic acid is regarded as one type of monomer component.

[0013] Examples of the aliphatic homopolyamide resin include an aliphatic homopolyamide resin made of an aliphatic diamine and an aliphatic dicarboxylic acid, and an aliphatic homopolyamide resin made of a lactam or an aminocarboxylic acid.

[0014] Examples of monomer components constituting the aliphatic homopolyamide resin include a combination of an aliphatic diamine having 2 to 20 carbon atoms, preferably 4 to 12 carbon atoms, and more preferably 6 to 12 carbon atoms, and an aliphatic dicarboxylic acid having 2 to 20 carbon atoms, preferably 6 to 12 carbon atoms, and more preferably 10 to 12 carbon atoms; and lactam or aminocarboxylic acid having 6 to 12 carbon atoms, preferably 11 or 12 carbon atoms.

[0015] Examples of the aliphatic diamine include ethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, undecamethylenediamine, dodecamethylenediamine, tridecanediamine, tetradecanediamine, pentadecanediamine, hexadecanediamine, heptadecanediamine, octadecanediamine, nonadecanediamine, eicosanediamine, 2-methyl-1,8-octanediamine, and 2,2,4 / 2,4,4-trimethylhexamethylenediamine. Examples of aliphatic dicarboxylic acids include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, octadecanedioic acid, and eicosanedioic acid.

[0016] Examples of lactams include ε-caprolactam, enantholactam, undecane lactam, dodecane lactam, α-pyrrolidone, α-piperidone, etc. Examples of aminocarboxylic acids include 6-aminocaproic acid, 7-aminoheptanoic acid, 9-aminononanoic acid, 11-aminoundecanoic acid, and 12-aminododecanoic acid.

[0017] Aliphatic homopolyamide resins include polyamide 6, polyamide 11, polyamide 12, polyamide 26, polyamide 44, polyamide 45, polyamide 46, polyamide 48, polyamide 49, polyamide 410, polyamide 412, polyamide 54, polyamide 55, polyamide 56, polyamide 58, polyamide 59, polyamide 510, polyamide 512, polyamide 64, polyamide 65, polyamide 66, polyamide 68, polyamide 69, polyamide 70, polyamide 71, polyamide 72, polyamide 73, polyamide 74, polyamide 75, polyamide 76, polyamide 77, polyamide 78, polyamide 79 ...9, polyamide 70, polyamide 71, polyamide 72, polyamide 73, polyamide 74, polyamide 75, polyamide 76, polyamide 78, polyamide 79, polyamide 79, polyamide 79, polyamide 79, polyamide 79, polyamide 79, polyamide 79, poly Examples of the polyamide include polyamide 69, polyamide 610, polyamide 612, polyamide 614, polyamide 616, polyamide 618, polyamide 96, polyamide 98, polyamide 99, polyamide 910, polyamide 912, polyamide 106, polyamide 108, polyamide 109, polyamide 1010, polyamide 1012, polyamide 126, polyamide 128, polyamide 129, polyamide 1210, and polyamide 1212.

[0018] (Aliphatic copolyamide resin) The aliphatic copolyamide resin means a polyamide resin in which the monomer components constituting the aliphatic polyamide resin are a combination of two or more kinds. The aliphatic copolyamide resin is a copolymer of two or more kinds selected from the group consisting of a combination of an aliphatic diamine and an aliphatic dicarboxylic acid, a lactam, and an aminocarboxylic acid. Here, the combination of an aliphatic diamine and an aliphatic dicarboxylic acid is regarded as one type of monomer with a combination of one type of aliphatic diamine and one type of aliphatic dicarboxylic acid.

[0019] Examples of the aliphatic diamine include the same ones as those exemplified as the raw material of the aliphatic homopolyamide resin.

[0020] Examples of the aliphatic dicarboxylic acid include the same as those exemplified as the raw material for the aliphatic homopolyamide resin.

[0021] Examples of lactams include those exemplified as raw materials for aliphatic homopolyamide resins, and examples of aminocarboxylic acids include those exemplified as raw materials for aliphatic homopolyamide resins.

[0022] These aliphatic diamines, aliphatic dicarboxylic acids, lactams and aminocarboxylic acids may be used alone or in combination of two or more.

[0023] The aliphatic copolyamide resin may be one type or a combination of two or more types.

[0024] (Preferred embodiment of aliphatic polyamide (A)) From the viewpoints of mechanical properties (tensile elongation at break) and extrusion moldability, the aliphatic polyamide (A) preferably has a ratio [CH2] / [NHCO] of the number of methylene groups ([CH2]) to the number of amide groups ([NHCO]) (hereinafter, the ratio of the number of methylene groups to the number of amide groups may be referred to as [CH2] / [NHCO]) of 5.0 or more, more preferably 5.0 or more and 15.0 or less, and particularly preferably 7.0 or more and 13.0 or less.

[0025] Aliphatic polyamides (A) having a ratio of the number of methylene groups to the number of amide groups, [CH2] / [NHCO], of 5.0 to 15.0 include polyamide 6: [CH2] / [NHCO]=5.0, polyamide 11: [CH2] / [NHCO]=10.0, polyamide 12: [CH2] / [NHCO]=11.0, polyamide 66: [CH2] / [NHCO]=5.0, polyamide 610: :[CH2] / [NHCO]=7.0, Polyamide 612:[CH2] / [NHCO]=8.0, Polyamide 614:[CH2] / [NHCO]=9.0, Polyamide 616:[CH2] / [NHCO]=10.0, Polyamide 618:[CH2] / [NHCO]=11.0, Polyamide 810:[CH2] / [NHCO]=8.0, Polyamide 812:[CH2] / [N Polyamide 99: [CH2] / [NHCO]=8.0, Polyamide 910: [CH2] / [NHCO]=8.5, Polyamide 912: [CH2] / [NHCO]=9.5, Polyamide 108: [CH2] / [NHCO]=8.0, Polyamide 109: [CH2] / [NHCO]=8.5, Polyamide 1010: [CH2] / [NHCO]=9.0, Polyamide 1012: [CH2] / [NHCO]=9.5, Polyamide 108: [CH2] / [NHCO]=8.0, Polyamide 109: [CH2] / [NHCO]=8.5, Polyamide 1010: [CH2] / [NHCO]=9.0, Examples include amide 1012: [CH2] / [NHCO]=10.0, polyamide 126: [CH2] / [NHCO]=8.0, polyamide 128: [CH2] / [NHCO]=9.0, polyamide 129: [CH2] / [NHCO]=9.5, polyamide 1210: [CH2] / [NHCO]=10.0, and polyamide 1212: [CH2] / [NHCO]=11.0.

[0026] From the viewpoints of mechanical properties and extrusion moldability, the aliphatic polyamide (A) preferably contains at least one homopolymer selected from the group consisting of polyamide 11, polyamide 12, polyamide 612, polyamide 1010, polyamide 1012, and polyamide 1212, and / or at least one copolymer using two or more raw material monomers forming these.

[0027] From the viewpoints of mechanical properties, extrusion moldability and chemical resistance, the aliphatic polyamide (A) more preferably contains polyamide 12 and / or polyamide 11, and particularly preferably consists of polyamide 12 and / or polyamide 11 alone. The aliphatic polyamide (A) may be one type or a combination of two or more types.

[0028] From the viewpoints of mechanical properties and extrusion moldability, the aliphatic polyamide (A) preferably has a relative viscosity of 1.5 or more and 3.5 or less, more preferably 2.0 or more and 3.0 or less, as measured at 25°C by dissolving 1 g of the aliphatic polyamide (A) in 100 ml of 96% sulfuric acid in accordance with JIS K 6920.

[0029] When the aliphatic polyamide (A) contains two or more polyamide resins having different relative viscosities, the relative viscosity of the aliphatic polyamide (A) is preferably measured as described above. However, when the relative viscosity of each polyamide resin and its mixing ratio are known, the relative viscosity of the aliphatic polyamide (A) may be determined by adding up the values ​​obtained by multiplying each relative viscosity by the mixing ratio. The average value thus calculated may be used as the relative viscosity of the aliphatic polyamide (A).

[0030] (Production of polyamide resin) The polyamide resin production apparatus may be a known polyamide production apparatus such as a batch reaction vessel, a single- or multi-vessel continuous reaction apparatus, a tubular continuous reaction apparatus, a kneading reaction extruder such as a single-screw kneading extruder or a twin-screw kneading extruder. The polymerization method may be a known method such as melt polymerization, solution polymerization, or solid-phase polymerization, and may be carried out by repeating normal pressure, reduced pressure, and increased pressure operations. These polymerization methods may be used alone or in appropriate combination.

[0031] [Phosphinate (B)] The phosphinate (B) is a component that imparts flame retardancy to the polyamide resin composition.

[0032] Examples of the phosphinic acid salt (B) include metal phosphinic acid salts of the following formula (1), metal phosphinic acid salts of the following formula (2), and / or polymers thereof, onium salts such as ammonium salts and phosphonium salts, etc. Specific examples of the onium salts of phosphinic acid include those described in WO2008 / 117666.

[0033] The phosphinic acid salt (B) is preferably a metal phosphinic acid salt, and particularly preferably a metal phosphinic acid salt of the following formula (1), a metal phosphinic acid salt of the following formula (2), and / or a polymer thereof.

[0034] [ka]

[0035] [ka]

[0036] (In the formula, R 2 , R 3 are the same or different and are a C1-C8 alkyl group or a C6-C20 aryl group; R 4 is a C1-C10 alkylene group, a C6-C20 arylene group, a C6-C20 arylene group substituted with a C1-C8 alkyl group, or a C1-C10 alkylene group substituted with a C6-C20 aryl group; M is a metal ion of a main group or transition element of Group 2 or 13 of the Periodic Table of the Elements; m is 2 or 3; p is 1 or 3; where x is 1 or 2.

[0037] The C1-C8 alkyl group is a straight or branched alkyl group. Examples of the C1-C8 alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a t-butyl group, and an n-pentyl group. Examples of the C6-C20 aryl group include a phenyl group, a naphthyl group, and a biphenylyl group (such as an o-phenylphenyl group, an m-phenylphenyl group, or a p-phenylphenyl group). The C1-C10 alkylene group is a straight-chain or branched-chain alkylene group. Examples of the C1-C10 alkylene group include a methylene group, an ethylene group, an n-propylene group, an isopropylene group, an n-butylene group, a t-butylene group, an n-pentylene group, an n-octylene group, and an n-dodecylene group. Examples of the C6-C20 arylene group include a phenylene group and a naphthylene group. Examples of the C6-C20 arylene group substituted with a C1-C8 alkyl group include a methylphenylene group, an ethylphenylene group, a t-butylphenylene group, a methylnaphthylene group, an ethylnaphthylene group, and a t-butylnaphthylene group. Examples of the C1-C10 alkylene group substituted with a C6-C20 aryl include a phenylmethylene group, a phenylethylene group, a phenylpropylene group, and a phenylbutylene group.

[0038] Typical elements of Group 2 or Group 13 of the Periodic Table of Elements include Be, Mg, Ca, Sr, Ba, Ra, B, Al, Ga, In, and Tl. Transition metals include Group 12 elements (Zn, Cd, etc.). Thus, transition metals include Ti, Zn, Fe, Zr, Mn, Zn, etc. M is preferably an ion of one or more metals selected from the group consisting of Al, Ca, and Zn. m is the valence of M. For example, when M is Al, m is 3, and when M is Ca or Zn, m is 2. p and x are appropriately set according to m. For example, in formula (2), p and x are set so that 2p=mx.

[0039] Examples of the phosphinic acid in the phosphinic acid salt (B) include dimethylphosphinic acid, ethylmethylphosphinic acid, diethylphosphinic acid, methyl-n-propylphosphinic acid, methylphenylphosphinic acid, diphenylphosphinic acid, methane-di(methylphosphinic acid), ethane-1,2-di(methylphosphinic acid), hexane-1,6-di(methylphosphinic acid), and benzene-1,4-di(methylphosphinic acid).

[0040] The phosphinic acid salt (B) can be prepared by known methods, such as those described in JP 2007-507566 A and EP 0 699 708. The phosphinic acid salt (B) may also be prepared by converting the phosphinic acid in an aqueous solution with a metal carboxylate, a metal hydroxide or a metal oxide essentially into a monomer, and optionally into a polymer depending on the reaction conditions.

[0041] In addition, commercially available products can be used as the phosphinate (B). Commercially available products of the phosphinate (B) include aluminum salts of organic phosphinic acids such as EXOLIT OP1230, EXOLIT OP1240, EXOLIT OP930, and EXOLIT OP935 manufactured by Clariant Co., Ltd. The phosphinic acid salt (B) may be one type or a combination of two or more types.

[0042] [Phosphazene compounds (C)] The phosphazene compound (C) is a component that imparts flame retardancy and mechanical properties to the polyamide resin composition. The phosphazene compound (C) may be a cyclic phosphazene compound or a non-cyclic phosphazene compound. The phosphazene compound (C) is preferably a cyclic phosphazene compound.

[0043] The cyclic phosphazene compound is a compound having a -P=N- bond as a repeating unit. The cyclic phosphazene compound is preferably a compound represented by the following formula (3). [ka] [In the formula, n represents an integer of 3 to 25, and R 1 are the same or different and are unsubstituted or substituted aryl groups, provided that the proportion of unsubstituted aryl groups is 1 It is 0.1 to 100 mol % based on the total amount of the above.

[0044] n is preferably an integer of 3 to 6, and particularly preferably an integer of 3 or 4.

[0045] The unsubstituted aryl group is preferably a C6-C20 aryl group, more preferably a phenyl group, a naphthyl group, a biphenylyl group (e.g., o-phenylphenyl, m-phenylphenyl, p-phenylphenyl group), etc., and particularly preferably a phenyl group.

[0046] The substituent of the substituted aryl group includes an alkyl group, an alkoxy group, a hydroxy group, a (hydroxyaryl) alkyl group, an aryl alkyl group, a hydroxyaryl sulfonyl group, a hydroxyaryloxy group, a glycidyl group, a cyano group, etc. The aryl group in the substituted aryl group is as described above for the unsubstituted aryl group. The alkyl group as the substituent is preferably a C1-C10 alkyl group, and more preferably a C1-C3 alkyl group.

[0047] Examples of the substituted aryl group include aryl groups substituted with an alkyl group {e.g., tolyl (o-tolyl, m-tolyl, p-tolyl, etc.), xylyl (3,4-xylyl, 3,5-xylyl, 2,3-xylyl, 2,4-xylyl, 2,5-xylyl, 2,6-xylyl, etc.), ethylphenyl, cumyl (o-cumyl, m-cumyl, p-cumyl, phenylcumyl, etc.), butylphenyl (2-t-butylphenyl, 4-t-butylphenyl, 2,4-di-t-butylphenyl, 2,6-di-t-butylphenyl, 3-methyl-6-t-butylphenyl, 2,6-di-t-butyl-4-methylphenyl, etc.), amylphenyl (2,4-di-t-amylphenyl, 2,6-di-t-amylphenyl, etc.), cyclohexylphenyl, nyl, trimethylphenyl, methylnaphthyl, etc.}, alkoxyphenyl groups (o-methoxyphenyl, m-methoxyphenyl, p-methoxyphenyl groups, etc.), hydroxyphenyl groups (o-hydroxyphenyl, m-hydroxyphenyl, p-hydroxyphenyl groups, p-(p'-hydroxyphenyl)phenyl groups, etc.), (hydroxyaryl)alkylaryl groups (p-[2-(p'-hydroxyphenyl)isopropyl]phenyl groups, etc.), (hydroxyarylsulfonyl)aryl groups (p-(p'-hydroxyphenylsulfonyl)phenyl groups), (hydroxyaryloxy)aryl groups (p-(p'-hydroxyphenyloxy)phenyl groups, etc.), glycidylphenyl, cyanophenyl, and the like.

[0048] The substituted aryl group is preferably a phenyl group substituted with a C1-C3 alkyl group (for example, o-tolyl, m-tolyl, p-tolyl, 2,4-xylyl, 2,6-xylyl, 3,5-xylyl group) and / or a cyanophenyl group.

[0049] In formula (3), the proportion of unsubstituted aryl groups is R 1 With respect to the total amount of the above, the amount is preferably 0.1 to 100 mol %, more preferably 50 to 100 mol %, further preferably 70 to 100 mol %, and particularly preferably 100 mol %.

[0050] Specific examples of the cyclic phosphazene compound include 2,2,4,4,6,6-hexaphenoxycyclotriphosphazene (compound with n=3), 2,2,4,4,6,6,8,8-octaphenoxycyclotetraphosphazene (compound with n=4), and 2,2,4,4,6,6,8,8,10,10-decaphenoxycyclopentaphosphazene (compound with n=5). Phosphazene compound (C) may be a commercially available product. Examples of commercially available phosphazene compound (C) include Rabitol FP-110, Rabitol FP-300, and Rabitol FP-390 manufactured by Fushimi Pharmaceutical Co., Ltd. The phosphazene compound (C) may be one type or a combination of two or more types. For example, the phosphazene compound (C) may be a mixture of two or more types of cyclic phosphazene compounds having different n.

[0051] [Additional ingredients] The polyamide resin composition may contain further components within the range not impairing the effects of the present invention, such as components (D) to (H) described below, other thermoplastic resins, plasticizers, antioxidants, heat stabilizers, UV absorbers, light stabilizers, antistatic agents, crystallization accelerators, and colorants. Each of the additional components may be one type or a combination of two or more types.

[0052] [Elastomer polymer (D) (excluding core-shell rubber type graft copolymer (F))] The elastomeric polymer (D) is a component that imparts impact resistance to the polyamide resin composition. The elastomeric polymer (D) does not include the core-shell rubber type graft copolymer (F) described below.

[0053] Examples of the elastomeric polymer (D) include polyolefin resins such as high density polyethylene (HDPE), medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), ultra-high molecular weight polyethylene (UHMWPE), polypropylene (PP), polybutene (PB), polymethylpentene (TPX), and saponified ethylene / vinyl acetate copolymer (EVOH); polystyrene resins such as polystyrene (PS), syndiotactic polystyrene (SPS), methyl methacrylate / styrene copolymer (MS), and methyl methacrylate / styrene / butadiene copolymer (MBS); the above polyolefin resins and polystyrene resins containing functional groups such as carboxyl groups and their salts, acid anhydride groups, and epoxy groups; polybutylene terephthalate (PBT), polyethylene terephthalate (PET), polyethylene isophthalate (PEI), poly(ethylene terephthalate / ethylene isophthalate) copolymer (PET / PEI), polytrimethylene terephthalate (PT Polyester-based resins such as polycyclohexanedimethylene terephthalate (PCT), polyethylene naphthalate (PEN), polybutylene naphthalate (PBN), polyarylate (PAR), liquid crystal polyester (LCP), polylactic acid (PLA), and polyglycolic acid (PGA); polyether-based resins such as polyacetal (POM) and polyphenylene ether (PPO); polysulfone-based resins such as polysulfone (PSU), polyethersulfone (PESU), and polyphenylsulfone (PPSU) polythioether-based resins such as polyphenylene sulfide (PPS) and polythioether sulfone (PTES); polyketone-based resins such as polyketone (PK), polyether ketone (PEK), polyether ether ketone (PEEK), polyether ketone ketone (PEKK), polyether ether ketone (PEEEK), polyether ether ketone ketone (PEEKK), polyether ketone ketone ketone (PEKKK), and polyether ketone ether ketone ketone (PEKEKK);Polynitrile resins such as polyacrylonitrile (PAN), polymethacrylonitrile, acrylonitrile / styrene copolymer (AS), methacrylonitrile / styrene copolymer, acrylonitrile / butadiene / styrene copolymer (ABS), and acrylonitrile / butadiene copolymer (NBR); polymethacrylate resins such as polymethyl methacrylate (PMMA) and polyethyl methacrylate (PEMA); polyvinyl alcohol (PVA), polyvinylidene chloride (PVDC), polyvinyl chloride (PVC), vinyl chloride / vinylidene chloride copolymer, and vinylidene chloride / methyl acrylate copolymer; cellulose resins such as cellulose acetate and cellulose butyrate; polycarbonate resins such as polycarbonate (PC); polyimide resins such as thermoplastic polyimide (TPI), polyetherimide, polyesterimide, polyamideimide (PAI), and polyesteramideimide; thermoplastic polyurethane resins; polyamide elastomer, polyurethane elastomer, polyester elastomer, polyfluoride, Fluorine-containing polymers such as polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVF), polytetrafluoroethylene (PTFE), polychlorofluoroethylene (PCTFE), tetrafluoroethylene / ethylene copolymer (ETFE), ethylene / chlorotrifluoroethylene copolymer (ECTFE), tetrafluoroethylene / hexafluoropropylene copolymer (FEP), tetrafluoroethylene / hexafluoropropylene / vinylidene fluoride copolymer (THV), tetrafluoroethylene / hexafluoropropylene / vinylidene fluoride / perfluoro(alkyl vinyl ether) copolymer, tetrafluoroethylene / perfluoro(alkyl vinyl ether) copolymer (PFA), tetrafluoroethylene / hexafluoropropylene / perfluoro(alkyl vinyl ether) copolymer, chlorotrifluoroethylene / perfluoro(alkyl vinyl ether) / tetrafluoroethylene copolymer (CPT), and the above-mentioned fluorine-containing polymers containing a functional group reactive to an amino group. The elastomeric polymer (D) may be one type or a combination of two or more types.;

[0054] From the viewpoint of compatibility with the aliphatic polyamide (A), the elastomeric polymer (D) is preferably an elastomeric polymer containing a structural unit derived from an unsaturated compound having a carboxyl group and / or an acid anhydride group.Specific examples of the elastomeric polymer (D) include (ethylene and / or propylene) / α-olefin copolymers, (ethylene and / or propylene) / (α,β-unsaturated carboxylic acid and / or α,β-unsaturated carboxylic acid ester) copolymers, and aromatic vinyl compound / conjugated diene compound block copolymers, each of which contains a structural unit derived from an unsaturated compound having a carboxyl group and / or an acid anhydride group, and these may be used alone or in combination.

[0055] The (ethylene and / or propylene) / α-olefin copolymer is a polymer obtained by copolymerizing ethylene and / or propylene with an α-olefin having 3 or more carbon atoms. Examples of the α-olefin having 3 or more carbon atoms include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 9-methyl-1-decene, 11-methyl-1-dodecene, and 12-ethyl-1-tetradecene. These can be used alone or in combination of two or more.

[0056] The copolymer may also be one obtained by copolymerizing a polyene such as a non-conjugated diene. Examples of the non-conjugated diene include 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 1,4-octadiene, 1,5-octadiene, 1,6-octadiene, 1,7-octadiene, 2-methyl-1,5-hexadiene, 6-methyl-1,5-heptadiene, 7-methyl-1,6-octadiene, 4-ethylidene-8-methyl-1,7-nonadiene, 4,8-dimethyl-1,4,8-decatriene (DMDT), dicyclopentadiene, ... Examples of the aryl group include butyl ether, cyclohexadiene, cyclooctadiene, 5-vinylnorbornene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene-2-norbornene, 6-chloromethyl-5-isopropylidene-2-norbornene, 2,3-diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, and 2-propenyl-2,5-norbornadiene. These may be used alone or in combination.

[0057] The (ethylene and / or propylene) / (α,β-unsaturated carboxylic acid and / or α,β-unsaturated carboxylic acid ester) copolymer is a polymer obtained by copolymerizing ethylene and / or propylene with α,β-unsaturated carboxylic acid and / or α,β-unsaturated carboxylic acid ester monomers. Examples of the α,β-unsaturated carboxylic acid monomers include acrylic acid, methacrylic acid, maleic acid, and itaconic acid. Examples of the α,β-unsaturated carboxylic acid ester monomers include methyl esters, ethyl esters, propyl esters, butyl esters, pentyl esters, hexyl esters, heptyl esters, octyl esters, nonyl esters, decyl esters, 2-ethylhexyl esters, and hydroxyethyl esters of these α,β-unsaturated carboxylic acids. These may be used alone or in combination.

[0058] The aromatic vinyl compound / conjugated diene compound block copolymer is a block copolymer consisting of an aromatic vinyl compound polymer block and a conjugated diene compound polymer block, and a block copolymer having at least one aromatic vinyl compound polymer block and at least one conjugated diene compound polymer block is used. In the block copolymer, the unsaturated bond in the conjugated diene compound polymer block may be hydrogenated.

[0059] The aromatic vinyl compound polymer block is a polymer block mainly composed of units derived from an aromatic vinyl compound. In this case, examples of the aromatic vinyl compound include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 1,5-dimethylstyrene, 2,4-dimethylstyrene, vinylnaphthalene, vinylanthracene, 4-propylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, and 4-(phenylbutyl)styrene, and these can be used alone or in combination. In addition, the aromatic vinyl compound polymer block may have a small amount of units composed of other unsaturated monomers, depending on the case.

[0060] The conjugated diene compound polymer block is a polymer block formed from one or more conjugated diene compounds such as 1,3-butadiene, chloroprene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 4-methyl-1,3-pentadiene, and 1,3-hexadiene. In a hydrogenated aromatic vinyl compound / conjugated diene compound block copolymer, a part or all of the unsaturated bonds in the conjugated diene compound polymer block are converted to saturated bonds by hydrogenation. The molecular structure of the aromatic vinyl compound / conjugated diene compound block copolymer and its hydrogenated product may be linear, branched, radial, or any combination thereof. Among these, as the aromatic vinyl compound / conjugated diene compound block copolymer and / or its hydrogenated product, a diblock copolymer in which one aromatic vinyl compound polymer block and one conjugated diene compound polymer block are linearly bonded, a triblock copolymer in which three polymer blocks are linearly bonded in the order of aromatic vinyl compound polymer block-conjugated diene compound polymer block-aromatic vinyl compound polymer block, and one or more of their hydrogenated products are preferably used, and examples thereof include unhydrogenated or hydrogenated styrene / butadiene block copolymers, unhydrogenated or hydrogenated styrene / isoprene block copolymers, unhydrogenated or hydrogenated styrene / butadiene / styrene block copolymers, unhydrogenated or hydrogenated styrene / isoprene / styrene block copolymers, unhydrogenated or hydrogenated styrene / (ethylene / butadiene) / styrene block copolymers, and unhydrogenated or hydrogenated styrene / (isoprene / butadiene) / styrene block copolymers. These can be used alone or in combination.

[0061] Examples of the unsaturated compound having a carboxyl group forming the structural unit of the elastomeric polymer (D) include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, mesaconic acid, citraconic acid, glutaconic acid, cis-4-cyclohexene-1,2-dicarboxylic acid, endobicyclo-[2.2.1]-5-heptene-2,3-dicarboxylic acid, as well as metal salts, alkyl esters, hydroxyalkyl esters, and aminoalkyl esters of these carboxylic acids. Examples of the unsaturated compound having an acid anhydride group forming the structural unit of the elastomeric polymer (D) include dicarboxylic acid anhydrides having an α,β-unsaturated bond, such as maleic anhydride, itaconic anhydride, citraconic anhydride, and endobicyclo-[2.2.1]-5-heptene-2,3-dicarboxylic anhydride. These can be used alone or in combination. Among these, dicarboxylic acid anhydrides having an α,β-unsaturated bond are preferred, and maleic anhydride and itaconic anhydride are more preferred.

[0062] The carboxyl group and / or acid anhydride group concentration in the elastomeric polymer (D) is preferably 25 μeq / g or more and 200 μeq / g or less, and more preferably 50 μeq / g or more and 150 μeq / g or less, from the viewpoints of impact resistance and fluidity.

[0063] The carboxyl group and / or acid anhydride group concentration in the elastomeric polymer (D) can be measured by dissolving the elastomeric polymer in a toluene solution, adding ethanol to prepare a sample solution, and titrating the solution with a 0.1 N KOH ethanol solution using phenolphthalein as an indicator.

[0064] When two or more kinds of elastomeric polymers having different carboxyl group and / or acid anhydride group concentrations are used as the elastomeric polymer (D), the carboxyl group and / or acid anhydride group concentration in the elastomeric polymer (D) is preferably measured by neutralization titration with a 0.1 N KOH ethanol solution using a sample solution prepared using toluene and ethanol and phenolphthalein as an indicator. However, when the carboxyl group and / or acid anhydride group concentrations of each elastomeric polymer and their mixing ratios are known, the carboxyl group and / or acid anhydride group concentration of each elastomeric polymer and the mixing ratio are multiplied by each carboxyl group and / or acid anhydride group concentration and the average value calculated by adding up the values ​​may be used as the carboxyl group and / or acid anhydride concentration of the elastomeric polymer (D).

[0065] [Phosphorus-containing polymer compounds (E)] The phosphorus-containing polymer compound (E) is a component that imparts flame retardancy to the polyamide resin composition. The phosphorus-containing polymer compound (E) may be one type or a combination of two or more types. In terms of mechanical properties and flame retardancy, the phosphorus-containing polymer compound (E) preferably contains a repeating unit having a group represented by formula (4). [ka]

[0066] The phosphorus-containing polymer compound (E) is particularly preferably a compound represented by the following formula (5). [ka] [In the formula, n1 is an integer of 4 or more, preferably an integer of 6 or more and 100 or less, and particularly preferably an integer of 10 or more and 60 or less.]

[0067] [Core-shell rubber type graft copolymer (F)] The core-shell rubber type graft copolymer (F) is a component that imparts moldability, flame retardancy, and impact resistance to the polyamide resin composition. The core-shell rubber type graft copolymer (F) is a copolymer having a core-shell structure, in which a polymer component that is a rubber component forms a core layer, and a monomer component that can be copolymerized with this polymer component is graft-copolymerized as a shell layer. The shell layer may be two or more layers. The core-shell rubber type graft copolymer (F) may be one type or a combination of two or more types.

[0068] From the viewpoint of moldability, flame retardancy, and low-temperature impact resistance, the core-shell rubber type graft copolymer (F) is preferably a silicone-based copolymer. When the core-shell rubber type graft copolymer (F) is a silicone-based copolymer, the core layer may contain silicone units, the shell layer may contain silicone units, or the core layer and the shell layer may contain silicone units. From the viewpoint of further improving moldability, flame retardancy, and low-temperature impact resistance, it is preferable that the core layer contains silicone units.

[0069] The glass transition temperature of the polymer component forming the core layer is usually 0° C. or lower, preferably −10° C. or lower, more preferably −20° C. or lower, and even more preferably −30° C. or lower. Specific examples of the polymer component forming the core layer include polybutadiene, polyisoprene, polyalkyl acrylates such as polybutyl acrylate, poly(2-ethylhexyl acrylate), and butyl acrylate-2-ethylhexyl acrylate copolymers, silicone-based rubbers such as polyorganosiloxane rubber, butadiene-acrylic composites, IPN (Interpenetrating Polymer Network)-type composite rubbers consisting of polyorganosiloxane rubber and polyalkyl acrylate rubber, styrene-butadiene copolymers, ethylene-α-olefin-based copolymers such as ethylene-propylene copolymers, ethylene-butene copolymers, and ethylene-octene copolymers, ethylene-acrylic copolymers, and fluororubbers. These may be used alone or in combination of two or more. Among these, from the standpoint of mechanical properties and surface appearance, polybutadiene, polyalkyl acrylate, polyorganosiloxane, a composite of polyorganosiloxane and polyalkyl acrylate, and butadiene-styrene copolymer are preferred, and polyorganosiloxane and a composite of polyorganosiloxane and polyalkyl acrylate are more preferred.

[0070] Specific examples of the monomer component constituting the shell layer and capable of graft copolymerization with the polymer component of the core layer include aromatic vinyl compounds, vinyl cyanide compounds, (meth)acrylic acid ester compounds, (meth)acrylic acid compounds, epoxy group-containing (meth)acrylic acid ester compounds such as glycidyl (meth)acrylate, maleimide compounds such as maleimide, N-methylmaleimide, and N-phenylmaleimide, α,β-unsaturated carboxylic acid compounds such as maleic acid, phthalic acid, and itaconic acid, and their anhydrides (e.g., maleic anhydride, etc.). These monomer components may be used alone or in combination of two or more. Among these, from the standpoint of mechanical properties and surface appearance, aromatic vinyl compounds, vinyl cyanide compounds, (meth)acrylic acid ester compounds, and (meth)acrylic acid compounds are preferred, and (meth)acrylic acid ester compounds are more preferred. Specific examples of the (meth)acrylic acid ester compound include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, cyclohexyl (meth)acrylate, and octyl (meth)acrylate, of which methyl (meth)acrylate and ethyl (meth)acrylate are preferred, and methyl (meth)acrylate is more preferred.

[0071] Examples of the core-shell rubber graft copolymer (F) include diene-based core-shell rubber polymers such as methyl methacrylate-butadiene-styrene copolymer resin (MBS resin) and acrylonitrile-butadiene-styrene copolymer resin (ABS resin); acrylic-based core-shell rubber polymers such as acrylate-styrene-acrylonitrile copolymer resin (ASA resin) and acrylate-methyl methacrylate copolymer resin; silicone-based core-shell rubber polymers (silicone copolymers) such as silicone-acrylate-methyl methacrylate copolymer resin and silicone-acrylate-acrylonitrile-styrene copolymer resin; and modified versions of these with maleic anhydride, glycidyl methacrylate, etc.

[0072] Commercially available core-shell rubber graft copolymers (F) include products using silicone-based core-shell rubber polymers: Metablen (registered trademark) S-2001, S-2006, S-2501, S-2030, S-2100, S-2200, SRK200A, SX-005, and SX-006 (manufactured by Mitsubishi Chemical Corporation); products using diene-based core-shell rubber polymers: Paraloid (registered trademark) EXL-2655 (manufactured by Rohm & Haas), Metablen (registered trademark) C-223A, C -215A, C-201A, C-140A, E-860A, E-870A, E-875A (manufactured by Mitsubishi Chemical Corporation); product names using acrylic core-shell type rubber polymers include: Staphyloid (registered trademark) AC-3355, TR-2122 (manufactured by Aica Kogyo Co., Ltd.), Paraloid (registered trademark) EXL-2611, EXL-3387 (manufactured by Rohm & Haas), Metablen (registered trademark) W-300A, W-450A, W-600A, W377 (manufactured by Mitsubishi Chemical Corporation), and the like.

[0073] The core-shell rubber type graft copolymer (F) preferably has a particulate shape. When the core-shell rubber type graft copolymer (F) has a particulate shape, the volume average particle diameter (D50) of the particles is preferably 100 nm or more, more preferably 250 nm or more, and 800 nm or less, from the viewpoints of moldability, flame retardancy, impact resistance, and the appearance of the molded product. The core-shell rubber type graft copolymer (F) particles having a volume average particle diameter (D50) in the above range can be prepared by emulsion polymerization.

[0074] The volume average particle diameter of the particles of the core-shell rubber type graft copolymer (F) is the average diameter measured on a volume basis, and is the value of the median diameter (D50) at 50%. The volume average particle diameter (D50) can be measured by a laser diffraction / scattering method, an image analysis method, a Coulter method, a centrifugal sedimentation method, etc. The volume average particle diameter (D50) of the above particles is preferably determined by measurement by a laser diffraction / scattering method.

[0075] [Impact-resistant material (G) other than component (F)] The impact-resistant material (G) other than the component (F) (hereinafter, also referred to as the other impact-resistant material (G)) is a component that imparts impact resistance to the polyamide resin composition. Examples of the other impact-resistant material (G) include the components described in the component (D). The other impact resistant materials (G) may be one type or a combination of two or more types.

[0076] [Flame retardant (H) other than components (B) and (C)] The flame retardant (H) other than the components (B) and (C) (hereinafter also referred to as the other flame retardant (H)) is a component that further imparts flame retardancy to the polyamide resin composition. Examples of the other flame retardant (H) include phosphorus-containing compounds (including the phosphorus-containing polymer compound (E)), halogen-containing compounds, boron-containing compounds, etc. The other flame retardants (H) may be one type or a combination of two or more types.

[0077] From the viewpoint of flame retardancy, the other flame retardant (H) is preferably a phosphorus-containing polymer compound (E).

[0078] [Other thermoplastic resins] Other thermoplastic resins include polyolefin resins such as high density polyethylene (HDPE), medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), ultra-high molecular weight polyethylene (UHMWPE), polypropylene (PP), polybutene (PB), polymethylpentene (TPX), and saponified ethylene / vinyl acetate copolymer (EVOH); polystyrene resins such as polystyrene (PS), syndiotactic polystyrene (SPS), methyl methacrylate / styrene copolymer (MS), and methyl methacrylate / styrene / butadiene copolymer (MBS); the above polyolefin resins and polystyrene resins containing functional groups such as carboxyl groups and their salts, acid anhydride groups, and epoxy groups; polybutylene terephthalate (PBT), polyethylene terephthalate (PET), polyethylene isophthalate (PEI), poly(ethylene terephthalate / ethylene isophthalate) copolymer (PET / PEI), polytrimethylene terephthalate (PTT), and the like. Polyester-based resins such as polycyclohexanedimethylene terephthalate (PCT), polyethylene naphthalate (PEN), polybutylene naphthalate (PBN), polyarylate (PAR), liquid crystal polyester (LCP), polylactic acid (PLA), and polyglycolic acid (PGA); polyether-based resins such as polyacetal (POM) and polyphenylene ether (PPO); polysulfone-based resins such as polysulfone (PSU), polyethersulfone (PESU), and polyphenylsulfone (PPSU), etc. polythioether-based resins such as polyphenylene sulfide (PPS) and polythioether sulfone (PTES); polyketone-based resins such as polyketone (PK), polyether ketone (PEK), polyether ether ketone (PEEK), polyether ketone ketone (PEKK), polyether ether ketone (PEEEK), polyether ether ketone ketone (PEEKK), polyether ketone ketone ketone (PEKKK), and polyether ketone ether ketone ketone (PEKEKK);Examples of the polynitrile resins include polyacrylonitrile (PAN), polymethacrylonitrile, acrylonitrile / styrene copolymer (AS), methacrylonitrile / styrene copolymer, acrylonitrile / butadiene / styrene copolymer (ABS), and acrylonitrile / butadiene copolymer (NBR); polymethacrylate resins such as polymethyl methacrylate (PMMA) and polyethyl methacrylate (PEMA); and polyvinyl resins such as polyvinyl alcohol (PVA), polyvinylidene chloride (PVDC), polyvinyl chloride (PVC), vinyl chloride / vinylidene chloride copolymer, and vinylidene chloride / methyl acrylate copolymer.

[0079] Other thermoplastic resins include cellulose-based resins such as cellulose acetate and cellulose butyrate; polyimide-based resins such as thermoplastic polyimide (TPI), polyetherimide, polyesterimide, polyamideimide (PAI), and polyesteramideimide; thermoplastic polyurethane-based resins; polyamide elastomers, polyurethane elastomers, polyester elastomers, polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVF), polytetrafluoroethylene (PTFE), polychlorofluoroethylene (PCTFE), tetrafluoroethylene / ethylene copolymer (ETFE), ethylene / chlorotrifluoroethylene copolymer (ECTFE), tetrafluoroethylene / hexafluoroethylene copolymer (ECTFE), and tetrafluoroethylene / hexafluoroethylene copolymer (ECTFE). Fluorine-containing polymers such as tetrafluoroethylene / hexafluoropropylene / vinylidene fluoride copolymer (FEP), tetrafluoroethylene / hexafluoropropylene / vinylidene fluoride copolymer (THV), tetrafluoroethylene / hexafluoropropylene / vinylidene fluoride / perfluoro(alkyl vinyl ether) copolymer, tetrafluoroethylene / perfluoro(alkyl vinyl ether) copolymer (PFA), tetrafluoroethylene / hexafluoropropylene / perfluoro(alkyl vinyl ether) copolymer, chlorotrifluoroethylene / perfluoro(alkyl vinyl ether) / tetrafluoroethylene copolymer (CPT), and the above-mentioned fluorine-containing polymers containing a functional group reactive to an amino group. The other thermoplastic resins may be one or a combination of two or more.

[0080] [Plasticizer] Examples of the plasticizer include those described in JP 2017-43762 A, such as N-butylbenzenesulfonamide, N-octylbenzenesulfonamide, N-ethylhexylbenzenesulfonamide, N-cyclohexylbenzenesulfonamide, toluenesulfonamide, and N-alkyltoluenesulfonamide.

[0081] Specific examples of additional components other than the above-mentioned components include components that are usually used in polyamide resin compositions.

[0082] [Content of each ingredient] The total content of each component in the polyamide resin composition is as follows. The aliphatic polyamide (A) is contained in 100% by mass of the polyamide resin composition in an amount of 60% by mass or more and 85% by mass or less. If the content of the aliphatic polyamide (A) is less than 60% by mass, the mechanical properties tend to be poor. If the content of the aliphatic polyamide (A) is more than 85% by mass, the results of the UL94 combustion test tend to be poor. From the viewpoints of mechanical properties, chemical resistance, and heat resistance, the aliphatic polyamide (A) is preferably contained in 100% by mass of the polyamide resin composition in an amount of 60% by mass or more and 82% by mass or less, more preferably in an amount of 60% by mass or more and 79% by mass or less, even more preferably in an amount of 60% by mass or more and 76% by mass or less, even more preferably in an amount of 62% by mass or more and 75% by mass or less, and particularly preferably in an amount of 64% by mass or more and 72% by mass or less. In addition, the amount of the aliphatic polyamide (A) in 100% by mass of the polyamide resin composition is not particularly limited as long as it is in the range of 60% by mass or more and is the remainder of the contents of each component described below.

[0083] The phosphazene compound (C) is contained in the polyamide resin composition in an amount of 3% by mass or more and 20% by mass or less. If the content of the phosphazene compound (C) in the polyamide resin composition exceeds 20% by mass, the mechanical strength at low temperatures (e.g., −30 to −60° C.) decreases. If the content of the phosphazene compound (C) in the polyamide resin composition is less than 3% by mass, the results of the UL94 flammability test are poor.

[0084] The contents of component (B), other thermoplastic resins and plasticizers in the polyamide resin composition are as follows.

[0085] From the viewpoints of flame retardancy and mechanical properties, the phosphinate (B) is contained in the polyamide resin composition in an amount of preferably 15 mass% or more and 20 mass% or less, more preferably 16 mass% or more and 19 mass% or less, and particularly preferably 16 mass% or more and 18 mass% or less.

[0086] The content of the other thermoplastic resin in the polyamide resin composition is preferably 20 parts by mass or less, and particularly preferably 15 parts by mass or less, relative to 100 parts by mass of the polyamide resin composition. The content of the other thermoplastic resin in the polyamide resin composition is preferably more than 0 part by mass, and particularly preferably 1 part by mass or more, relative to 100 parts by mass of the polyamide resin composition.

[0087] From the viewpoint of excellent volatility resistance, the content of the plasticizer in the polyamide resin composition is preferably 5% by mass or less, more preferably 1% by mass or less, in the polyamide resin composition. In addition, when low-temperature impact resistance of a molded product is required, it is particularly preferable that the polyamide resin composition does not contain a plasticizer, since there is a concern that the inclusion of a plasticizer may decrease the low-temperature impact resistance.

[0088] [Additional ingredients and possible variations in the amount of each ingredient] Regarding the additional components in the polyamide resin composition and the contents of each component, possible first to third embodiments are as follows. [1] In the first aspect, the aliphatic polyamide (A) is an aliphatic polyamide (A1) having a ratio of the number of methylene groups to the number of amide groups of 5.0 or more, the phosphazene compound (C) is a cyclic phosphazene compound (C1), and the polyamide resin composition contains 60% to 82% by mass of the aliphatic polyamide (A1) having a ratio of the number of methylene groups to the number of amide groups of 5.0 or more, and 15% to 20% by mass of the phosphinic acid salt (B) in 100% by mass. The polyamide resin composition according to the first aspect further has excellent surface properties and melting properties, and shows excellent results in an oxygen index test.

[0089] In the first embodiment, the polyamide resin composition may contain, or may not contain, as further components, an elastomer polymer (D) (excluding the core-shell rubber type graft copolymer (F)), the core-shell rubber type graft copolymer (F) and other impact resistant materials (G). In the first embodiment, the polyamide resin composition may contain other flame retardants (H).

[0090] In the first embodiment, the contents of each component are as follows in addition to those described above.

[0091] From the viewpoints of mechanical properties, surface properties and flame retardancy, the phosphazene compound (C) is preferably contained in the polyamide resin composition in an amount of 5% by mass or more and 15% by mass or less.

[0092] The total content of further components other than the other thermoplastic resins and the plasticizers in the polyamide resin composition is preferably 20 parts by mass or less, and particularly preferably 15 parts by mass or less, per 100 parts by mass of the polyamide resin composition.

[0093] [2] The second aspect further comprises an elastomeric polymer (D) (excluding the core-shell rubber type graft copolymer (F)) and a phosphorus-containing polymer compound (E), and comprises 60% by mass or more and 82% by mass or less of the aliphatic polyamide (A) in 100% by mass of the polyamide resin composition, and comprises 15% by mass or more and 20% by mass or less of the phosphinic acid salt (B) in 100% by mass of the polyamide resin composition. The polyamide resin composition according to the second aspect further has better mechanical properties and excellent extrusion moldability, and shows excellent results in an oxygen index test.

[0094] In the second embodiment, when the polyamide resin composition contains another impact resistant material (G) as a further component, the content is calculated as the elastomer polymer (D) (excluding the core-shell rubber type graft copolymer (F)). In the second embodiment, the polyamide resin composition may or may not contain the core-shell rubber type graft copolymer (F) as a further component.

[0095] In the second embodiment, other flame retardants (H) may or may not be included.

[0096] In the second embodiment, the contents of each component are as follows in addition to those described above.

[0097] From the viewpoints of impact resistance, fluidity and flame retardancy, the elastomer polymer (D) (excluding the core-shell rubber type graft copolymer (F)) is preferably contained in an amount of 3% by mass to 15% by mass, more preferably 3% by mass to 10% by mass, and particularly preferably 3% by mass to 7% by mass in 100% by mass of the polyamide resin composition. When the elastomer polymer (D) (excluding the core-shell rubber type graft copolymer (F)) is contained in an amount of 3% by mass to 15% by mass in 100% by mass of the polyamide resin composition, it is preferable that the aliphatic polyamide (A) is contained in an amount of 60% by mass to 79% by mass in 100% by mass of the polyamide resin composition.

[0098] From the viewpoints of mechanical properties, surface properties and flame retardancy, the phosphazene compound (C) is preferably contained in an amount of 3 mass% or more and 10 mass% or less, more preferably 4 mass% or more and 8 mass% or less, and particularly preferably 5 mass% or more and 7 mass% or less, based on 100 mass% of the polyamide resin composition.

[0099] From the viewpoint of mechanical properties and flame retardancy, the phosphorus-containing polymer compound (E) is preferably contained in an amount of 3% by mass to 10% by mass, more preferably 3% by mass to 8% by mass, particularly preferably 4% by mass to 7% by mass, based on 100% by mass of the polyamide resin composition. When the phosphorus-containing polymer compound (E) is contained in an amount of 3% by mass to 10% by mass, the aliphatic polyamide (A) is preferably contained in an amount of 60% by mass to 76% by mass, based on 100% by mass of the polyamide resin composition.

[0100] The total content of the elastomeric polymer (D) (excluding the core-shell rubber type graft copolymer (F)), the phosphorus-containing polymer compound (E), other thermoplastic resins, and further components other than the plasticizer in the polyamide resin composition is preferably 20 parts by mass or less, and particularly preferably 15 parts by mass or less, per 100 parts by mass of the polyamide resin composition.

[0101] [3] The polyamide resin composition according to the third aspect further comprises a core-shell rubber type graft copolymer (F). The polyamide resin composition according to the third aspect further has particularly excellent mechanical properties.

[0102] In the third embodiment, the contents of each component are as follows in addition to those described above.

[0103] From the viewpoints of moldability, flame retardancy, and low-temperature impact resistance, the core-shell rubber type graft copolymer (F) is preferably contained in an amount of 2% by mass or more and 15% by mass or less, more preferably 3% by mass or more and 13% by mass or less, and particularly preferably 5% by mass or more and 10% by mass or less, based on 100% by mass of the polyamide resin composition.

[0104] From the viewpoints of mechanical properties, surface properties and flame retardancy, the phosphazene compound (C) is preferably contained in an amount of 3 mass% or more and 10 mass% or less, more preferably 4 mass% or more and 8 mass% or less, and particularly preferably 5 mass% or more and 7 mass% or less, based on 100 mass% of the polyamide resin composition.

[0105] From the viewpoint of impact resistance and flame retardancy, the other impact resistant material (G) is preferably contained in an amount of 10 mass% or less, more preferably 1 mass% or more and 7 mass% or less, and particularly preferably 3 mass% or more and 5 mass% or less, based on 100 mass% of the polyamide resin composition. In the third embodiment, when the polyamide resin composition contains an elastomer polymer (D) (excluding the core-shell rubber type graft copolymer (F)) as a further component, the content of these is calculated as the other impact resistant material (G).

[0106] From the viewpoint of mechanical properties and flame retardancy, the other flame retardant (H) is preferably contained in an amount of 10 mass% or less, more preferably 2 mass% or more and 8 mass% or less, and particularly preferably 3 mass% or more and 7 mass% or less, based on 100 mass% of the polyamide resin composition. In the third embodiment, when the polyamide resin composition contains a phosphorus-containing polymer compound (E) as a further component, the content of this is calculated as the other flame retardant (H).

[0107] The total content of further components other than the other impact-resistant materials (G), other flame retardants (H), other thermoplastic resins and plasticizers in the polyamide resin composition is preferably 20 parts by mass or less, and particularly preferably 15 parts by mass or less, per 100 parts by mass of the polyamide resin composition.

[0108] [Method of producing polyamide resin composition] The method for producing the polyamide resin composition is not particularly limited, and a method for mixing each component can be adopted. Here, the method for mixing the aliphatic polyamide (A), the phosphinate (B), the phosphazene compound (C), and other components as necessary is not particularly limited, and various conventionally known methods can be adopted. For example, the polyamide resin composition can be produced by a method in which pellets of the aliphatic polyamide (A), the phosphinate (B), and the phosphazene compound (C) are uniformly dry-blended to the above-mentioned mixing ratio using a tumbler and / or mixer, or a method in which the aliphatic polyamide (A), the phosphinate (B), and the phosphazene compound (C) are dry-blended in advance with other components added as necessary at the concentration used during molding, and melt-kneaded. The melt-kneading can be carried out using a kneader such as a single-screw extruder, a twin-screw extruder, a kneader, or a Banbury mixer.

[0109] [Uses of polyamide resin composition] The polyamide resin composition can be used as a molded article containing the polyamide resin composition. The molded article containing the polyamide resin composition can be used for various applications such as automobile parts, railway parts, mechanical parts such as electric tool housings, industrial materials, industrial materials, electrical parts, electronic parts, medical parts, food packaging parts, household goods, office supplies, building materials, furniture parts, etc. The molded article containing the polyamide resin composition can be used for the above-mentioned applications for the purpose of fire prevention. The desired molded article can be obtained by molding the polyamide resin composition. As the molding method, any melt molding method such as extrusion molding, blow molding, injection molding, etc. can be adopted. The shape of the molded article containing the polyamide resin composition is arbitrary, and examples thereof include a film shape, a sheet shape, a hollow shape (tube shape, hose shape, bottle shape, etc.). When the shape of the molded article containing the polyamide resin composition is a film shape or a sheet shape, it may be post-processed to form a hollow molded article. In addition, the molded products can be used as automobile parts, such as fuel parts (fuel tanks such as gasoline tanks and oil tanks; fuel transport parts such as fuel delivery pipes, fuel rails, fuel tubes, and fuel hoses); intake system parts or exhaust system parts (air ducts, intake manifolds, air cleaners, air cleaner boxes, resonators, throttle bodies, pneumatic hoses, pneumatic tubes, etc.); automobile exterior panels and exterior structural members (air spoilers, fenders, bumpers, suspension boots, etc.); and other automobile parts (hose joints, hydraulic tubes, hydraulic hoses, seat covers, etc.). Examples of molded articles used as railway parts include electrical wire covering materials (coating materials, covering materials) and seat covers. Examples of molded articles used as electric or electronic parts include plugs, fans, and the like. Examples of molded articles used as building material-related parts include fire walls.

[0110] [Further aspects] From the viewpoint of surface properties and mechanical properties, the polyamide resin composition preferably does not contain one or more selected from the group consisting of phosphorous acid, inorganic zinc compounds, silica, coal ash, zeolite, silicate, polymetaxylylene adipamide (PAMXD6), polycarbonate resins, polyphenylene ether (PPE), phenol aralkyl resins, and epoxy resins. From the viewpoint of surface properties and mechanical properties, the polyamide resin composition preferably does not contain a reinforcing material (e.g., inorganic fillers having shapes such as fibrous, powdery, granular, plate-like, needle-like, cross-like, and mat-like, and organic fibers such as glass fibers and carbon fibers). Furthermore, from the viewpoint of properties required for its application, a molded article containing the polyamide resin composition preferably does not contain a reinforcing material (e.g., inorganic fillers having shapes such as fibrous, powdery, granular, plate-like, needle-like, cross-like, and mat-like, and organic fibers such as glass fibers and carbon fibers). EXAMPLES

[0111] The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to these.

[0112] [Materials used in the Examples and Comparative Examples] 1. Aliphatic polyamide (A) (1) Polyamide 12 (A-1): Polyamide 12 (A-1) is polyamide 12 (A-1) produced by the following: In a 70-liter pressure-resistant reactor equipped with a stirrer, 19.73 kg (100.0 mol) of dodecane lactam, 258.3 g (0.909 mol) of stearic acid, and 0.5 L of distilled water were charged, and the inside of the polymerization tank was replaced with nitrogen, and then the tank was heated to 180°C, and the reaction system was stirred at this temperature to make the inside of the reaction system uniform. The temperature inside the polymerization tank was then raised to 270°C, and polymerization was carried out for 2 hours under stirring while adjusting the pressure inside the tank to 3.5 MPa. Thereafter, the pressure was released to normal pressure over about 2 hours, and then the pressure was reduced to 53 kPa, and polymerization was carried out under reduced pressure for 5 hours. Nitrogen was then introduced into the autoclave, and after the pressure was restored to normal pressure, the strands were extracted from the lower nozzle of the reaction tank and cut to obtain pellets. The pellets were dried under reduced pressure to obtain polyamide 12 with a relative viscosity of 1.67 (hereinafter, this polyamide 12 is referred to as "polyamide 12 (A-1)"). (2) Polyamide 12 (A-2) (manufactured by Ube Industries, Ltd., UBESTA (registered trademark), relative viscosity 2.26)

[0113] 2. Phosphinate (B) (1) Metal phosphinate (B-1) (Exolit OP1230, manufactured by Clariant Produkte GmbH) (2) Phosphinic acid metal salt (B-2) (Exolit (registered trademark) OP935, manufactured by Clariant Produkte GmbH)

[0114] 3. Phosphazene compounds (C) (1) Cyclic phosphazene compound (C-1): 2,2,4,4,6,6-hexaphenoxycyclotriphosphazene (manufactured by Fushimi Pharmaceutical Co., Ltd., Rabitol (registered trademark) FP-110)

[0115] 4. Elastomer polymer (D) (1) Maleic anhydride modified ethylene / 1-butene copolymer (D-1) (manufactured by Mitsui Chemicals, Inc., Tafmer (registered trademark) MH5010 (total concentration of carboxyl group and acid anhydride group: 50 μeq / g))

[0116] 5. Phosphorus-containing polymer compounds (E) (1) 2-(9,10-dihydroxy-9-oxa-10-oxide-10-phosphaphenanthren-10-yl)methylsuccinic acid bis-(2-hydroxyethyl)-ester polymer (E-1) (manufactured by Sanko Co., Ltd., ME-P8, average molecular weight: 10,000) (E-1) is expressed by the following formula (5). [ka]

[0117] 6. Core-shell rubber type graft copolymer (F) (1) Alkyl methacrylate-alkyl acrylate-dimethylsiloxane copolymer (F-1) (Mitsubishi Chemical Corporation, Metablen (registered trademark) SX-005, core-shell rubber particles in which the core is polydimethylsiloxane and the shell is a copolymer of alkyl methacrylate and alkyl acrylate)

[0118] 7.Other impact-resistant materials (G) (1)(G-1):(G-1) is the same as (D-1).

[0119] 8.Other flame retardants (H) (1) Melamine polyphosphate (H-1) (BASF Ltd., Melapur 200 70) (2) Melamine cyanurate (H-2) (Nissan Chemical Industries, Ltd., MC-6000) (3)(H-3):(H-3) is the same as (E-1).

[0120] 9. Plasticizers (I) (1) N-Butylbenzenesulfonamide (I-1) (Proviron, BBSA)

[0121] [Example 1] Production of polyamide resin composition (A1-1) Polyamide 12 (A-1) was mixed with phosphinic acid metal salt (B-1) and cyclic phosphazene compound (C-1) in advance, and fed into a twin-screw melt kneader (manufactured by Japan Steel Works, Ltd., model: TEX44), melt-kneaded at a cylinder temperature of 180°C to 270°C, and the molten resin was extruded in the form of a strand, which was then introduced into a water tank, cooled, cut, and vacuum-dried to obtain pellets of a polyamide 12 composition consisting of 100 parts by mass of polyamide 12 (A-1) / phosphinic acid metal salt (B-1) / cyclic phosphazene compound (C-1)=78.3 / 18.7 / 3.0 (mass%) in total (hereinafter, this polyamide 12 composition is referred to as "polyamide composition (A1-1)"). The amount of steam generated during the production of polyamide composition (A1-1) was clearly smaller than the amount generated when using BBSA (N-butylbenzenesulfonamide), a common plasticizer.

[0122] [Example 2] Preparation of polyamide 12 composition (A1-2) Except for changing the amount of polyamide 12 (A-1), phosphinic acid metal salt (B-1) and cyclic phosphazene compound (C-1), a pellet of polyamide 12 composition consisting of 100 parts by mass of polyamide 12 (A-1) / phosphinic acid metal salt (B-1) / cyclic phosphazene compound (C-1)=75.0 / 18.7 / 6.3 (mass%) was obtained in the same manner as in the preparation of polyamide 12 composition (A1-1) (hereinafter, this polyamide 12 composition is referred to as "polyamide composition (A1-2)"). The amount of steam generated during the preparation of polyamide composition (A1-2) was obviously less than the amount generated when using BBSA (N-butylbenzenesulfonamide), a general plasticizer.

[0123] [Example 3] Preparation of polyamide 12 composition (A1-3) Except for changing the amount of polyamide 12 (A-1), phosphinic acid metal salt (B-1) and cyclic phosphazene compound (C-1), a pellet of polyamide 12 composition consisting of 100 mass parts in total of polyamide 12 (A-1) / phosphinic acid metal salt (B-1) / cyclic phosphazene compound (C-1)=71.3 / 18.7 / 10.0 (mass%) was obtained in the same manner as the preparation of polyamide 12 composition (A1-1) (hereinafter, this polyamide 12 composition is referred to as "polyamide composition (A1-3)"). The amount of steam generated during the preparation of polyamide composition (A1-3) was obviously less than the amount generated when using BBSA (N-butylbenzenesulfonamide), a general plasticizer.

[0124] [Example 4] Preparation of polyamide 12 composition (A1-4) Except for changing the amount of polyamide 12 (A-1), phosphinic acid metal salt (B-1) and cyclic phosphazene compound (C-1), a pellet of polyamide 12 composition consisting of 100 mass parts in total of polyamide 12 (A-1) / phosphinic acid metal salt (B-1) / cyclic phosphazene compound (C-1)=66.3 / 18.7 / 15.0 (mass%) was obtained in the same manner as the preparation of polyamide 12 composition (A1-1) (hereinafter, this polyamide 12 composition is referred to as "polyamide composition (A1-4)"). The amount of steam generated during the preparation of polyamide composition (A1-4) was obviously less than the amount generated when using BBSA (N-butylbenzenesulfonamide), a general plasticizer.

[0125] [Example 5] Preparation of polyamide 12 composition (A1-5) Except for changing the amount of polyamide 12 (A-1), phosphinic acid metal salt (B-1) and cyclic phosphazene compound (C-1), a pellet of polyamide 12 composition consisting of 100 mass parts in total of polyamide 12 (A-1) / phosphinic acid metal salt (B-1) / cyclic phosphazene compound (C-1)=77.7 / 16.0 / 6.3 (mass%) was obtained in the same manner as the preparation of polyamide 12 composition (A1-1) (hereinafter, this polyamide 12 composition is referred to as "polyamide composition (A1-5)"). The amount of steam generated during the preparation of polyamide composition (A1-5) was obviously less than the amount generated when using BBSA (N-butylbenzenesulfonamide), a general plasticizer.

[0126] [Example 6] Preparation of polyamide 12 composition (A1-6) Except for changing the amount of polyamide 12 (A-1), phosphinic acid metal salt (B-1) and cyclic phosphazene compound (C-1), a pellet of polyamide 12 composition consisting of 100 parts by mass of polyamide 12 (A-1) / phosphinic acid metal salt (B-1) / cyclic phosphazene compound (C-1)=83.7 / 10.0 / 6.3 (mass%) was obtained in the same manner as in the preparation of polyamide 12 composition (A1-1) (hereinafter, this polyamide 12 composition is referred to as "polyamide composition (A1-6)"). The amount of steam generated during the preparation of polyamide composition (A1-6) was obviously less than the amount generated when using BBSA (N-butylbenzenesulfonamide), a general plasticizer.

[0127] [Example 7] Preparation of polyamide 12 composition (A1-7) Except for changing the amount of polyamide 12 (A-1), phosphinic acid metal salt (B-1) and cyclic phosphazene compound (C-1), a pellet of polyamide 12 composition consisting of 100 mass parts in total of polyamide 12 (A-1) / phosphinic acid metal salt (B-1) / cyclic phosphazene compound (C-1)=80.7 / 13.0 / 6.3 (mass%) was obtained in the same manner as the preparation of polyamide 12 composition (A1-1) (hereinafter, this polyamide 12 composition is referred to as "polyamide composition (A1-7)"). The amount of steam generated during the preparation of polyamide composition (A1-7) was obviously less than the amount generated when using BBSA (N-butylbenzenesulfonamide), a general plasticizer.

[0128] [Example 8] Preparation of polyamide 12 composition (A1-8) Except for changing the amount of polyamide 12 (A-1), phosphinic acid metal salt (B-1) and cyclic phosphazene compound (C-1), a pellet of polyamide 12 composition consisting of polyamide 12 (A-1) / phosphinic acid metal salt (B-1) / cyclic phosphazene compound (C-1)=80.0 / 10.0 / 10.0 (mass%) was obtained in the same manner as the preparation of polyamide 12 composition (A1-1) (hereinafter, this polyamide 12 composition is referred to as "polyamide composition (A1-7)"). The amount of steam generated during the preparation of polyamide composition (A1-7) was obviously less than the amount generated when using BBSA (N-butylbenzenesulfonamide), a general plasticizer.

[0129] [Comparative Example 1] Preparation of polyamide 12 composition (A2-1) A pellet of polyamide 12 composition consisting of 100 parts by mass of polyamide 12 (A-1) / metal phosphinate (B-1)=81.3 / 18.7 (mass%) was obtained in the same manner as in the preparation of polyamide 12 composition (A1-1), except that cyclic phosphazene compound (C-1) was not used (hereinafter, this polyamide 12 composition is referred to as "polyamide composition (A2-1)"). The amount of steam generated during the preparation of polyamide composition (A2-1) was obviously less than the amount generated when using BBSA (N-butylbenzenesulfonamide), a common plasticizer.

[0130] [Comparative Example 2] Preparation of polyamide 12 composition (A2-2) Except for changing the cyclic phosphazene compound (C-1) to melamine polyphosphate (H-1), the same method as that for the production of polyamide 12 composition (A1-1) was used to obtain a pellet of polyamide 12 composition consisting of 100 parts by mass of polyamide 12 (A-1) / metal phosphinate (B-1) / melamine polyphosphate (H-1)=78.3 / 18.7 / 3.0 (mass%) (hereinafter, this polyamide 12 composition is referred to as "polyamide composition (A2-2)"). The amount of steam generated during the production of polyamide composition (A2-2) was obviously less than the amount generated when using BBSA (N-butylbenzenesulfonamide), a common plasticizer.

[0131] [Comparative Example 3] Preparation of polyamide 12 composition (A2-3) Except for changing the cyclic phosphazene compound (C-1) to melamine cyanurate (H-2), the same method as that for the production of polyamide 12 composition (A1-1) was used to obtain a pellet of polyamide 12 composition consisting of 100 parts by mass of polyamide 12 (A-1) / metal phosphinate (B-1) / melamine cyanurate (H-2)=78.3 / 18.7 / 3.0 (mass%) (hereinafter, this polyamide 12 composition is referred to as "polyamide composition (A2-3)"). The amount of steam generated during the production of polyamide composition (A2-3) was obviously less than the amount generated when using BBSA (N-butylbenzenesulfonamide), a common plasticizer.

[0132] The properties of the polyamide resin compositions of Examples 1 to 8 and Comparative Examples 1 to 3 were measured by the following methods. The results are summarized in Table 1. [Method of measuring characteristics] [Relative Viscosity] The measurements were performed in 96% sulfuric acid at a polyamide concentration of 1% and at a temperature of 25°C in accordance with the test method described in JIS K-6920.

[0133] [Tensile elongation at break] A tensile test was performed and the tensile elongation at break was measured in accordance with the test methods described in ISO 527-1 and 2, except that the tensile test speed was changed to 5 mm / min. If the tensile elongation at break was 35% or more, it was determined that the material had sufficient mechanical properties.

[0134] [Combustion test (UL94 equivalent test)] Flame tests were conducted on 1 / 16-inch-thick test pieces in accordance with the test method described in UL94. Based on the UL94 standard, the test pieces were rated as "V-0", "V-2" or "out of spec".

[0135] [Superficiality] A strand of the polyamide resin composition extruded from the twin-screw melt kneader was sampled, and the surface properties were measured by visual inspection and touch. When no protrusions were observed on the strand, it was marked with ◯, when few protrusions were observed on the strand, it was marked with △, and when many protrusions were observed on the strand, it was marked with ×.

[0136] [MFR (Melt Flow Rate)] The MFR (melt flow rate) was measured under conditions of 190°C and 1,000g in accordance with the test method described in ISO 1133. If the MFR was 5.0 or higher, it was determined that the material had sufficient melting properties.

[0137] [Oxygen Index] The oxygen index was measured according to the test method described in ISO 4589-2. An oxygen index of 30% or more was determined to have sufficient flame retardancy.

[0138] [Table 1]

[0139] As is clear from Table 1, the polyamide composition of Comparative Example 1, which did not contain the phosphazene compound (C), had poor mechanical properties. The polyamide compositions of Comparative Examples 2 and 3, which contained a flame retardant other than the phosphazene compound (C), had poor mechanical properties. On the other hand, the polyamide compositions of Examples 1 to 8 had good results in the mechanical properties and combustion tests. Furthermore, the polyamide compositions of Examples 1 to 5 had good results in the surface properties, mechanical properties, melting properties, combustion tests, and oxygen index tests.

[0140] [Example 9] Production of polyamide resin composition (A1-9) Polyamide 12 (A-2) was mixed in advance with a metal phosphinate (B-2), a cyclic phosphazene compound (C-1), an elastomeric polymer (D-1), and a phosphorus-containing polymer compound (E-1), and the resulting mixture was fed into a twin-screw melt kneader (manufactured by The Japan Steel Works, Ltd., model: TEX44), melt-kneaded at a cylinder temperature of 210°C to 230°C, and the molten resin was extruded in the form of strands, which were then introduced into a water tank, cooled, cut, and vacuum-dried. As a result, pellets of a polyamide 12 composition consisting of 100 parts by mass of polyamide 12 (A-2) / D-1 metal phosphinate (B-2) / cyclic phosphazene compound (C-1) / elastomeric polymer (D-1) / phosphorus-containing polymer compound (E-1)=65.00 / 18.75 / 6.25 / 5.00 / 5.00 (mass%) were obtained (hereinafter, this polyamide 12 composition is referred to as "polyamide resin composition (A1-9)").

[0141] [Example 10] Production of polyamide resin composition (A1-10) Except for changing the amounts of polyamide 12 (A-2) and metal phosphinate (B-2) added, the same method as in Example 9 was used to obtain pellets of a polyamide 12 composition consisting of 100 parts by mass of polyamide 12 (A-2) / metal phosphinate (B-2) / cyclic phosphazene compound (C-1) / elastomeric polymer (D-1) / phosphorus-containing polymer compound (E-1)=73.75 / 10.00 / 6.25 / 5.00 / 5.00 (mass%) (hereinafter, this polyamide 12 composition is referred to as "polyamide resin composition (A1-10)").

[0142] [Comparative Example 4] Production of polyamide resin composition (A2-4) A pellet of a polyamide 12 composition consisting of 100 parts by mass of polyamide 12 (A-2) / metal phosphinate (B-2) / elastomeric polymer (D-1) / phosphorus-containing polymer compound (E-1)=71.25 / 18.75 / 5.00 / 5.00 (mass%) was obtained in the same manner as in Example 9, except that the cyclic phosphazene compound (C-1) was not used and the amount of polyamide 12 (A-2) was increased accordingly (hereinafter, this polyamide 12 composition is referred to as "polyamide resin composition (A2-4)").

[0143] [Comparative Example 5] Production of polyamide resin composition (A2-5) Comparative Example 5 relates to a polyamide resin composition produced based on JP2017-43762A and not containing the phosphazene compound (C). Polyamide 12 (A-2) and metal phosphinate (B-2) were mixed in advance and fed to a twin-screw melt kneader (manufactured by Japan Steel Works, Ltd., model: TEX44). Meanwhile, plasticizer (I-1) was injected from a metering pump into the middle of the cylinder of the twin-screw melt kneader. The cylinder temperature was 210°C to 230°C, and the molten resin was extruded in the form of a strand. The strand was then introduced into a water tank, cooled, cut, and vacuum dried to obtain pellets of a polyamide 12 composition consisting of 100 parts by mass of polyamide 12 (A-2) / metal phosphinate (B-2) / plasticizer (I-1)=66.00 / 25.00 / 9.00 (mass%) in total (hereinafter, this polyamide 12 composition is referred to as "polyamide resin composition (A2-5)").

[0144] [Example 11] Production of polyamide resin composition (A1-11) Polyamide 12 (A-2) was mixed in advance with core-shell rubber type graft copolymer (F-1), metal phosphinate (B-2) and cyclic phosphazene compound (C-1), and the mixture was fed to a twin-screw melt kneader (manufactured by Japan Steel Works, Ltd., model: TEX44), melt-kneaded at a cylinder temperature of 210°C to 230°C, and the molten resin was extruded in the form of a strand, which was then introduced into a water tank, cooled, cut and vacuum dried to obtain pellets of a polyamide 12 composition consisting of 100 parts by mass of polyamide 12 (A-2) / metal phosphinate (B-2) / cyclic phosphazene compound (C-1) / core-shell rubber type graft copolymer (F-1)=70.00 / 18.75 / 6.25 / 5.00 (mass%) in total (hereinafter, this polyamide 12 composition is referred to as "polyamide resin composition (A1-11)").

[0145] [Example 12] Production of polyamide resin composition (A1-12) Further, in the same manner as in Example 11, except that other impact-resistant materials (G-1) were used and the amount of polyamide 12 (A-2) was changed, pellets of a polyamide 12 composition consisting of 100 parts by mass of polyamide 12 (A-2) / metal phosphinate (B-2) / cyclic phosphazene compound (C-1) / core-shell rubber type graft copolymer (F-1) / other impact-resistant materials (G-1) = 67.00 / 18.75 / 6.25 / 5.00 / 3.00 (mass%) were obtained (hereinafter, this polyamide 12 composition is referred to as "polyamide resin composition (A1-12)").

[0146] [Example 13] Production of polyamide resin composition (A1-13) Further, in the same manner as in Example 11, except that another flame retardant (H-3) was used and the amount of polyamide 12 (A-2) was changed, pellets of a polyamide 12 composition consisting of 100 parts by mass of polyamide 12 (A-2) / metal phosphinate (B-2) / cyclic phosphazene compound (C-1) / core-shell rubber type graft copolymer (F-1) / other flame retardant (H-3) = 65.00 / 18.75 / 6.25 / 5.00 / 5.00 (mass%) were obtained (hereinafter, this polyamide 12 composition is referred to as "polyamide resin composition (A1-13)").

[0147] [Example 14] Production of polyamide resin composition (A1-14) Except for changing the amounts of polyamide 12 (A-2) and core-shell rubber type graft copolymer (F-1) added, the same method as in Example 11 was used to obtain pellets of a polyamide 12 composition consisting of 100 parts by mass of polyamide 12 (A-2) / metal phosphinate (B-2) / cyclic phosphazene compound (C-1) / core-shell rubber type graft copolymer (F-1) = 65.00 / 18.75 / 6.25 / 10.00 (mass%) (hereinafter, this polyamide 12 composition is referred to as "polyamide resin composition (A1-14)").

[0148] [Example 15] Production of polyamide resin composition (A1-15) Except for not using the core-shell rubber type graft copolymer (F-1) and changing the amount of polyamide 12 (A-2), the same method as in Example 11 was used to obtain pellets of a polyamide 12 composition consisting of 100 parts by mass of polyamide 12 (A-2) / metal phosphinate (B-2) / cyclic phosphazene compound (C-1) = 75.00 / 18.75 / 6.25 (mass%) (hereinafter, this polyamide 12 composition is referred to as "polyamide resin composition (A1-15)").

[0149] The properties of the polyamide resin compositions of Examples 9 to 15 and Comparative Examples 4 to 5 were measured by the following methods. The results are summarized in Tables 2 to 4. [Method of measuring characteristics] [Preparation of test specimens] Using the pellets of Examples 9 to 15 and Comparative Examples 4 to 5, test pieces suitable for each test were prepared under the following injection molding conditions. <Injection molding conditions> Cylinder temperature: 270℃ Mold temperature: 80℃ Average injection speed in the mold: 50mm / sec Cooling time: 5 seconds

[0150] [Combustion test (UL94 equivalent test)] Flame tests were conducted on 1 / 16-inch-thick test pieces in accordance with the test method described in UL94. Based on the UL94 standard, the test pieces were rated as "V-0", "V-2" or "out of spec".

[0151] [Tensile elongation at break] Tensile tests were conducted in accordance with the test methods described in ISO 527-1 and 2 to measure the tensile elongation at break. If the tensile elongation at break was 35% or more, it was determined that the material had sufficient mechanical properties. If the tensile elongation at break was 100% or more, it was determined that the material had more sufficient mechanical properties, and if the tensile elongation at break was 130% or more, it was determined that the material had particularly sufficient mechanical properties.

[0152] [Oxygen Index] The oxygen index was measured according to the test method described in ISO 4589-2. An oxygen index of 30% or more was determined to have sufficient flame retardancy.

[0153] The moldability of the hollow molded article (tube) was evaluated by the following method.

[0154] [Tube extrusion] The polyamide resin compositions of Examples 9 to 15 and Comparative Examples 4 to 5 were each molded into a tubular body using a PAL32 (Milfur) single-layer tube molding machine, with the extrusion temperature set at 190° C. to 210° C., and with a target outer diameter of 8 mm and thickness of 1 mm. Tubes moldable with dimensional errors of 0.1 mm or less in outer diameter and thickness were determined to have good tube moldability.

[0155] The tensile elongation at break and low-temperature impact resistance of the hollow molded articles (tubes) of Example 11 and Comparative Example 5 were evaluated by the following methods.

[0156] [Tensile elongation at break (tube)] The tube obtained by "tube extrusion molding" was subjected to a tensile test in accordance with the test method described in SAE J 2260 to measure the tensile elongation at break.

[0157] [Low temperature impact resistance (tube)] Using the tubes obtained by "tube extrusion molding", low-temperature impact resistance tests were performed on the tubes at -40℃ and -60℃ in accordance with the test method described in SAE J 2260 to check whether cracks occurred in the tubes. The results were reported as the number of tubes with cracks divided by the number of tubes tested.

[0158] [Table 2]

[0159] As shown in Table 2, the polyamide resin composition of Comparative Example 4, which does not contain the phosphazene compound (C), was inferior in mechanical properties and tube moldability. The polyamide resin composition of Comparative Example 5, which was produced based on JP2017-43762A, was out of specification in the combustion test and had poor flame retardancy. On the other hand, the polyamide resin composition of Example 9 showed good results in all of the combustion test, oxygen index, tensile elongation at break, and tube moldability. Also, the polyamide resin composition of Example 10 showed good results in the combustion test and tensile elongation at break. Here, the polyamide resin compositions of Examples 9 and 10 had a tensile elongation at break of 130% or more, and had particularly sufficient mechanical properties.

[0160] [Table 3]

[0161] [Table 4]

[0162] From Table 3, it can be seen that the polyamide resin compositions of Examples 11 to 15 show good results in the combustion test and mechanical properties. Here, the polyamide resin compositions of Examples 11 to 14 had a tensile elongation at break of 130% or more, and had particularly sufficient mechanical properties. Moreover, the polyamide resin composition of Example 15 had a tensile elongation at break of 100% or more, and had even more sufficient mechanical properties. Moreover, from Table 4, it can be seen that the polyamide resin composition of Example 11 has excellent mechanical properties and low-temperature impact resistance as a tube. On the other hand, in Comparative Example 5, cracks were confirmed in the low-temperature impact resistance test of the tube.

Claims

1. A polyamide resin composition comprising an aliphatic polyamide (A), a phosphinate (B) and a phosphazene compound (C), The aliphatic polyamide (A) is contained in an amount of 60% by mass or more and 79% by mass or less based on 100% by mass of the polyamide resin composition, The phosphinate (B) is contained in an amount of 16% by mass or more and 20% by mass or less based on 100% by mass of the polyamide resin composition, The polyamide resin composition comprises the phosphazene compound (C) in an amount of 5% by mass or more and 20% by mass or less based on 100% by mass of the polyamide resin composition.

2. The aliphatic polyamide (A) is an aliphatic polyamide having a ratio of the number of methylene groups to the number of amide groups of 5.0 or more, The polyamide resin composition according to claim 1, wherein the phosphazene compound (C) is a cyclic phosphazene compound.

3. The polyamide resin composition according to claim 1, further comprising an elastomeric polymer (D) (excluding the core-shell rubber type graft copolymer (F)) and a phosphorus-containing polymer compound (E).

4. 4. The polyamide resin composition according to claim 3, wherein the elastomeric polymer (D) contains a structural unit derived from an unsaturated compound having a carboxyl group and / or an acid anhydride group.

5. 5. The polyamide resin composition according to claim 3, wherein the aliphatic polyamide (A) is contained in an amount of 60% by mass or more and 76% by mass or less based on 100% by mass of the polyamide resin composition, and the elastomeric polymer (D) is contained in an amount of 3% by mass or more and 15% by mass or less based on 100% by mass of the polyamide resin composition.

6. The polyamide resin composition according to claim 3 or 4, wherein the phosphorus-containing polymer compound (E) is represented by the following formula (5): 【Chemistry 1】 [In the formula, n1 is an integer of 4 or more.]

7. 5. The polyamide resin composition according to claim 3, wherein the aliphatic polyamide (A) is contained in an amount of 60% by mass or more and 76% by mass or less based on 100% by mass of the polyamide resin composition, and the phosphorus-containing polymer compound (E) is contained in an amount of 3% by mass or more and 10% by mass or less based on 100% by mass of the polyamide resin composition.

8. The polyamide resin composition according to claim 3 or 4, wherein the phosphazene compound (C) is contained in an amount of 5% by mass or more and 10% by mass or less based on 100% by mass of the polyamide resin composition.

9. The polyamide resin composition according to claim 1, further comprising a core-shell rubber type graft copolymer (F).

10. The polyamide resin composition according to claim 9, wherein the core-shell rubber type graft copolymer (F) is a silicone-based copolymer.

11. The polyamide resin composition according to claim 9 or 10, wherein 100% by mass of the polyamide resin composition contains 60% by mass or more and 76% by mass or less of the aliphatic polyamide (A), and 100% by mass of the core-shell rubber type graft copolymer (F).

12. The polyamide resin composition according to claim 9 or 10, comprising 10 mass% or less of an impact resistant material (G) other than the component (F) per 100 mass% of the polyamide resin composition.

13. The polyamide resin composition according to claim 9 or 10, comprising 10 mass% or less of a flame retardant (H) other than the components (B) and (C) based on 100 mass% of the polyamide resin composition.

14. The polyamide resin composition according to claim 9 or 10, wherein the phosphazene compound (C) is contained in an amount of 5% by mass or more and 10% by mass or less based on 100% by mass of the polyamide resin composition.

15. The polyamide resin composition according to any one of claims 1 to 4, 9 and 10, wherein the phosphazene compound (C) is represented by the following formula (3): 【Chemistry 2】 [In the formula, n represents an integer of 3 to 25, and R １ are the same or different and are unsubstituted or substituted aryl groups, provided that the proportion of unsubstituted aryl groups is １ It is 0.1 to 100 mol % based on the total amount of

16. The polyamide resin composition according to any one of claims 1 to 4, 9 and 10, wherein the aliphatic polyamide (A) comprises at least one homopolymer selected from the group consisting of polyamide 11, polyamide 12, polyamide 612, polyamide 1010, polyamide 1012 and polyamide 1212, and / or at least one copolymer using two or more raw material monomers forming the homopolymer.

17. A molded article comprising the polyamide resin composition according to any one of claims 1 to 16.

18. A blow molded article molded from the polyamide resin composition according to any one of claims 1 to 16.

19. The hollow molded article according to claim 18, which is molded by an extrusion molding method.

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