JP7413894B2 - Aliphatic polyamide resin composition - Google Patents

Description

The present invention relates to an aliphatic polyamide resin composition and a hollow molded article containing the same.

In recent years, polyamide resin molded bodies have been manufactured by various molding methods, and typical molding methods include extrusion molding, blow molding, rotational molding, and injection molding. Even for similar shapes, it is possible to choose from multiple molding methods, so we take into consideration various factors such as whether or not we own the equipment used for each molding method, the layout of the factory, and the ease of post-processing. The molding method is selected above.

On the other hand, the properties of polyamide resin suitable for each molding method are different, and even when creating molded articles of the same shape, if the molding method is different, the properties required of the polyamide resin will change. Therefore, different molding methods require the use of different polyamide resin compositions.

For example, in extrusion molding of hollow bodies, a polyamide resin composition containing a specific proportion of polyamide 6/12 resin, a plasticizer, and a modified polyolefin has been proposed, and is said to have excellent moldability (see Patent Document 1).

Furthermore, in blow molding, a polyamide resin composition containing an aromatic polyamide resin, an impact modifier, and a stabilizer has been proposed, and it is said that a blow molded product having a smooth surface appearance can be obtained (see Patent Document 2). ).

: International Publication No. 2013/058027 :Special Publication No. 2006-523763

In these techniques, Patent Document 1 proposes a material suitable for extrusion molding, and Patent Document 2 proposes a material suitable for blow molding. Regardless of the molding method, it is required that the product has a good appearance, for example, but extrusion molding may produce patterns or protrusions on the surface of the product, while blow molding may produce surface irregularities. Sometimes. Therefore, there is a need for a polyamide resin composition that has a good appearance in any molding method. Furthermore, while extrusion molding requires stable continuous production, blow molding requires high parison retention.

Therefore, the present invention provides a polyamide that can be molded with a good appearance when molded by extrusion molding, allows stable continuous production in extrusion molding, and has a good parison retention rate in blow molding. The purpose is to provide a resin composition.

In order to solve the above problems, the present inventors have made extensive studies and found that an aliphatic polyamide resin composition containing an aliphatic polyamide resin (a), an elastomer (b), and a modified fluorine-containing polymer (c) It has been found that a product has an excellent appearance regardless of whether it is molded by extrusion molding or blow molding, and can be molded at low pressures suitable for high-speed molding and long-time molding.
The present invention includes, for example, the following [1] to [11].
[1] An aliphatic polyamide resin composition containing an aliphatic polyamide resin (a), an elastomer (b), and a modified fluorine-containing polymer (c).
[2] The aliphatic polyamide resin composition of [1], wherein the elastomer (b) contains a structural unit derived from an unsaturated compound having a carboxyl group and/or an acid anhydride group.
[3] The aliphatic polyamide resin composition according to [1] or [2], which contains the elastomer (b) in the aliphatic polyamide resin composition in an amount of 10% by mass or more and 25% by mass or less.
[4] The aliphatic polyamide resin composition according to any one of [1] to [3], wherein the aliphatic polyamide (a) has a ratio of the number of methylene groups to the number of amide groups of 8.0 or less.
[5] The aliphatic polyamide resin (a) is at least one homopolymer selected from the group consisting of polyamide 6, polyamide 66, polyamide 6/66, and polyamide 6/12. The aliphatic polyamide resin composition according to any one of [1] to [3].
[6] The fat according to any one of [1] to [5], wherein the modified fluorine-containing polymer (c) is a fluorine-containing polymer modified with (meth)acrylic acid and/or a derivative thereof. Group polyamide resin composition.
[7] The total concentration of carboxyl groups and/or acid anhydride groups possessed by the elastomer (b) is [X] (μeq/g), the content of the elastomer (b) based on 100% by mass of the aliphatic polyamide resin composition. [X]× The aliphatic polyamide resin composition according to any one of [2] to [6], wherein the value of [Y]×[Z] is less than 2,900.
[8] The aliphatic polyamide resin (a) contains polyamide 6,
The aliphatic polyamide resin composition according to any one of [1] to [7], which has an MFR (280° C., 10 kg) of 10 g/10 minutes or more and 20 g/10 minutes or less, as measured by a method according to ISO 1133.
[9] A hollow molded article containing the aliphatic polyamide resin composition according to any one of [1] to [8].
[10] The hollow molded article of [9] which is an extrusion molded product or a blow molded product.

When the aliphatic polyamide resin composition of the present invention is extruded, it is possible to obtain a molded article with a good appearance. Further, stable continuous production is possible in extrusion molding, and the parison retention rate in blow molding is good. Furthermore, the total concentration of carboxyl groups and/or acid anhydride groups possessed by the elastomer (b) is [X] (μeq/g), and the content of the elastomer (b) based on 100% by mass of the aliphatic polyamide resin composition is [Y ] (mass %), [X]×[Y] In an embodiment in which the value of [Z] is less than 2,900, a molded product with a good appearance can be obtained even in blow molding.

In this specification, "(meth)acrylic acid" has the meaning of at least one of acrylic acid and methacrylic acid. "(Meth)acrylic modification" has the meaning of modification of at least one of acrylic acid and methacrylic acid.
In this specification, polytetrafluoroethylene is also referred to as PTFE.

The aliphatic polyamide resin composition includes an aliphatic polyamide resin (a), an elastomer (b), and a modified fluorine-containing polymer (c).
The aliphatic polyamide resin composition has an MFR (280°C, 10 kg) of 10 g/10 minutes or more, measured in accordance with ISO 1133, from the viewpoint of moldability during molding, mechanical properties of the resulting molded product, and appearance. It is preferable that it is less than g/10 minutes. The aliphatic polyamide resin (a) contains polycaproamide (polyamide 6), and it is particularly preferable that the MFR (280°C, 10 kg) is within the above range from the viewpoint of moldability during molding and the appearance of the obtained molded product. .

[Aliphatic polyamide resin (a)]
The aliphatic polyamide resin composition includes an aliphatic polyamide resin (a).
Aliphatic polyamide resin contains an aliphatic group in its constituent repeating units and has an amide bond (-CONH-) in its main chain.
Examples of the aliphatic polyamide resin (a) include aliphatic homopolyamides and aliphatic copolyamides, and these may be used alone or in combination of two or more.

(Aliphatic homopolyamide)
Aliphatic homopolyamide is a polyamide resin consisting of one type of structural unit derived from an aliphatic monomer. The aliphatic homopolyamide may be composed of at least one of one type of lactam and an aminocarboxylic acid that is a hydrolyzate of the lactam, or it may be composed of a combination of one type of diamine and one type of dicarboxylic acid. It may be. Here, the combination of diamine and dicarboxylic acid is considered to be one type of monomer.

Examples of the lactam include ε-caprolactam, enantholactam, undecanelactam, dodecanelactam (ω-laurolactam), α-pyrrolidone, and α-piperidone. Among these, from the viewpoint of polymerization productivity, one selected from the group consisting of ε-caprolactam, undecanelactam, and dodecanelactam is preferred.
Further, examples of aminocarboxylic acids include ε-aminocaproic acid, 7-aminoheptanoic acid, 9-aminononanoic acid, 11-aminoundecanoic acid, and 12-aminododecanoic acid.

Examples of diamines include ethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, peptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, undecamethylenediamine, dodecamethylenediamine, tridecanediamine, Tetradecanediamine, pentadecanediamine, hexadecanediamine, heptadecanediamine, octadecanediamine, nonadecanediamine, eicosanediamine, 2-methyl-1,8-octanediamine, 2,2,4/2,4,4-trimethylhexamethylene Aliphatic diamines such as diamine; 1,3-/1,4-cyclohexyldiamine, bis(4-aminocyclohexyl)methane, bis(4-aminocyclohexyl)propane, bis(3-methyl-4-aminocyclohexyl)methane, (3-Methyl-4-aminocyclohexyl)propane, 1,3-/1,4-bisaminomethylcyclohexane, 5-amino-2,2,4-trimethyl-1-cyclopentanemethylamine, 5-amino-1 , 3,3-trimethylcyclohexanemethylamine, bis(aminopropyl)piperazine, bis(aminoethyl)piperazine, and alicyclic diamines such as norbornane dimethylenediamine.

Examples of 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, and tetradecanedioic acid. , aliphatic dicarboxylic acids such as pentadecanedioic acid, hexadecanedionic acid, octadecanedioic acid, eicosanedioic acid; 1,3-/1,4-cyclohexanedicarboxylic acid, dicyclohexanemethane-4,4'-dicarboxylic acid, norbornane Examples include alicyclic dicarboxylic acids such as dicarboxylic acids.

Specifically, the aliphatic homopolyamides include polyamide 6, polyamide 7, polyamide 11, polyamide 12, polyamide 44, polyamide 45, polyamide 46, polyamide 48, polyamide 49, polyamide 54, polyamide 55, polyamide 56, polyamide 66, polyamide 410, polyamide 412, polyamide 58, polyamide 59, polyamide 510, polyamide 512, polyamide 64, polyamide 65, polyamide 68, polyamide 69, polyamide 610, polyamide 612, polyamide 96, polyamide 98, polyamide 99, polyamide 105, polyamide 616, Examples include polyamide 618, polyamide 910, polyamide 912, polyamide 106, polyamide 108, polyamide 109, polyamide 1010, polyamide 1012, polyamide 125, polyamide 126, polyamide 129, polyamide 1210, polyamide 1212, and polyamide 122. These aliphatic homopolyamides can be used alone or as a mixture of two or more. Among these, polyamide 6 and polyamide 66 are preferred from the viewpoint of availability, economic efficiency, mechanical properties of the obtained molded product, and heat resistance.

(Aliphatic copolymer polyamide)
Aliphatic copolymerized polyamide is a polyamide resin consisting of two or more types of structural units derived from aliphatic monomers. The aliphatic copolyamide is a copolymer of two or more selected from the group consisting of a combination of diamine and dicarboxylic acid, lactam, and aminocarboxylic acid. Here, the combination of diamine and dicarboxylic acid is considered to be one type of monomer.

Examples of the diamine include the same diamines as those exemplified as raw materials for aliphatic homopolyamide. Can be mentioned.

As the dicarboxylic acid, the same ones as those exemplified as raw materials for the aliphatic homopolyamide can be mentioned.

Examples of the lactam include the same lactams as those exemplified as raw materials for aliphatic homopolyamide.
Moreover, as the aminocarboxylic acid, the same ones as those exemplified as the raw material for the aliphatic homopolyamide can be mentioned.
These diamines, dicarboxylic acids, lactams, and aminocarboxylic acids may be used alone or in combination of two or more.

Specific examples of aliphatic copolyamides include copolymers obtained by combining two or more monomers that form polyamides exemplified as aliphatic homopolyamides, and more specifically, polyamide 6/66. , Polyamide 6/69, Polyamide 6/610, Lyamide 6/611, Polyamide 6/612, Polyamide 6/11, Polyamide 6/12, Polyamide 6/66/12, Polyamide 6/66/610, Polyamide 6/66/ 612, polyamide 6/610/12, and aliphatic copolymer polyamide of polyamide 6/612/12. These aliphatic copolyamides can be used alone or as a mixture of two or more.
Among these, a copolymer containing units a derived from polyamide 6/66 and ε-caprolactam or ε-aminocaproic acid, and units b derived from 12-aminododecanoic acid or ω-laurolactam is preferred. In these copolymers, the unit a is preferably contained in an amount of 50% by weight or more, more preferably 70% by weight or more, and even more preferably 75% by weight or more.

Examples of aliphatic copolyamides containing units a derived from ε-caprolactam or ε-aminocaproic acid and units b derived from 12-aminododecanoic acid or ω-laurolactam include polyamide 6/12 and polyamide 6. /66/12, polyamide 6/610/12, polyamide 6/612/12, and mixtures thereof, with polyamide 6/12 and/or polyamide 6/66/12 being more preferred.

Units derived from ε-caprolactam or ε-aminocaproic acid from the viewpoint of easy availability, economic efficiency, and ensuring sufficient physical properties such as mechanical properties, chemical resistance, and flexibility of the resulting molded product. In the copolymer containing a and units b derived from 12-aminododecanoic acid or ω-laurolactam, the units a derived from ε-caprolactam or ε-aminocaproic acid preferably contain 50% by mass or more, and more It is preferable to select the content as appropriate so as to preferably satisfy the content of 70% by weight or more, more preferably 75% by weight or more.

The aliphatic polyamide resin has a ratio of the number of methylene groups ([CH ₂ ]) to the number of amide groups ([NHCO]) [CH ₂ ]/[NHCO] (hereinafter, the ratio of the number of methylene groups to the number of amide groups is [CH ₂ ]/[NHCO]). ) is preferably 8.0 or less, more preferably 7.0 or less, and even more preferably 6.0 or less.

Examples of aliphatic polyamides in which the ratio [CH ₂ ]/[NHCO] of the number of methylene groups to the number of amide groups is 8.0 or less include polycaproamide (polyamide 6): [CH ₂ ]/[NHCO]=5.0; Polyamide 26: [CH ₂ ]/[NHCO] = 3.0, Polyamide 44: [CH ₂ ]/[NHCO] = 3.0, Polyamide 45: [CH ₂ ]/[NHCO] = 3.5, (Polyamide 46: [CH ₂ ]/[NHCO] = 4.0, Polyamide 48: [CH ₂ ]/[NHCO] = 5.0, Polyamide 49: [CH ₂ ]/[NHCO] = 5.5, Polyamide 410: [CH ₂ ]/[NHCO] = 6.0, Polyamide 412: [CH ₂ ]/[NHCO] = 7.0, Polyamide 54: [CH ₂ ]/[NHCO] = 3.5, Polyamide 55: [CH ₂ ]/[NHCO] = 4.0, Polyamide 56: [CH ₂ ]/[NHCO] = 4.5, Polyamide 58: [CH ₂ ]/[NHCO] = 5.5, Polyamide 59: [CH ₂ ] / [NHCO] = 6.0, Polyamide 510: [CH ₂ ] / [NHCO] = 6.5, Polyamide 512: [CH ₂ ] / [NHCO] = 7.5, Polyamide 64: [CH ₂ ] / [ NHCO] = 4.0, Polyamide 65: [CH ₂ ]/[NHCO] = 4.5, Polyamide 66: [CH ₂ ]/[NHCO] = 5.5, Polyamide 68: [CH ₂ ]/[NHCO] = 6.0, Polyamide 69: [CH ₂ ]/[NHCO] = 6.5, Polyamide 610: [CH ₂ ]/[NHCO] = 7.0, Polyamide 96: [CH ₂ ]/[NHCO] = 6 .5, Polyamide 98: [CH ₂ ]/[NHCO] = 7.5, Polyamide 105): [CH ₂ ]/[NHCO] = 6.5, Polyamide 106: [CH ₂ ]/[NHCO] = 7. 0, polyamide 125: [CH ₂ ]/[NHCO] = 7.5. In addition, as the aliphatic polyamide in which the ratio [CH ₂ ]/[NHCO] of the number of methylene groups to the number of amide groups is 8.0 or less, several types of raw material monomers forming at least one type of homopolymer described above were used. Also included are at least one copolymer. These can be used alone or in combination of two or more.

When the aliphatic polyamide resin (a) is a copolymer, the ratio [CH ₂ ]/[NHCO] of the number of methylene groups to the number of amide groups is the same as that of the homopolymer of the monomers constituting the constituent repeating units of the copolymer. It can be determined by multiplying the ratio of the number of methylene groups to the number of amide groups [CH ₂ ]/[NHCO] by the molar ratio of its constituent repeating units and adding them together for all constituent repeating units.
When the aliphatic polyamide resin (a) is a mixture of two or more types of aliphatic polyamide resins, the ratio [CH ₂ ]/[NHCO] of the number of methylene groups to the number of amide groups is the ratio of the number of methylene groups to the number of amide groups in each aliphatic polyamide resin. It can be determined by adding the value obtained by multiplying the ratio [CH ₂ ]/[NHCO] to the number of amide groups by the mixing ratio expressed in molar ratio for all aliphatic polyamide resins.

The aliphatic polyamide resin (a) is selected from the group consisting of polyamide 6, polyamide 66, polyamide 6/66, and polyamide 6/12 from the viewpoint of availability, economy, mechanical properties of the obtained molded product, and heat resistance. It is preferable that it is at least one selected from the group consisting of:

The relative viscosity of the aliphatic polyamide resin (a) measured in accordance with JIS K-6920 under the conditions of 96% sulfuric acid, 1% polymer concentration, and 25°C ensures the mechanical properties of the resulting molded product. In addition, from the viewpoint of ensuring desirable moldability of the molded product by setting the viscosity at the time of melting within an appropriate range, it is preferably 3.0 or more and 5.0 or less, and 3.5 or more and 4.5 or less. More preferred.

The aliphatic polyamide resin (a) is produced by polymerizing or copolymerizing the polyamide raw material in the presence of an amine by a known method such as melt polymerization, solution polymerization, solid phase polymerization, or the like. Alternatively, it can be produced by melt-kneading in the presence of amines after polymerization. As described above, amines can be added at any stage during polymerization or at any stage during melt-kneading after polymerization, but it is preferable to add them at any stage during polymerization.

[Elastomer (b)]
The aliphatic polyamide composition contains an elastomer (b). Elastomer (b) may be modified with carboxylic acid and/or acid anhydride. The elastomer (b) modified with a carboxylic acid and/or acid anhydride has a structural unit derived from an unsaturated compound having a carboxyl group and/or an acid anhydride group.
The elastomer (b) is an (ethylene and/or propylene)/α-olefin copolymer containing a structural unit derived from an unsaturated compound having a carboxyl group and/or an acid anhydride group; /or propylene)/(α,β-unsaturated carboxylic acid and/or α,β-unsaturated carboxylic acid ester) copolymer, aromatic vinyl compound/conjugated diene compound block copolymer, carboxyl group and/or or (ethylene and/or propylene)/α-olefin copolymer, (ethylene and/or propylene)/(α,β-unsaturated Examples include copolymers based on carboxylic acid and/or α,β-unsaturated carboxylic acid esters, and block copolymers based on aromatic vinyl compounds/conjugated diene compounds, and these may be used alone or in combination of two or more. . Among these, preferred are (ethylene and/or propylene)/α-olefin copolymers containing structural units derived from unsaturated compounds having carboxyl groups and/or acid anhydride groups.

The above (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. -Olefins include, for example, 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. Also, 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, cyclohexadiene, cyclooctadiene, 5-vinylnorbornene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene-2-norbornene, 6-chloromethyl -5-isopropenyl-2-norbornene, 2,3-diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, 2-propenyl-2,5-norbornadiene, etc. Polyenes may be copolymerized. These can be used alone or in combination of two or more.

(ethylene and/or propylene)/(α,β-unsaturated carboxylic acid and/or α,β-unsaturated carboxylic acid ester) copolymer is ethylene and/or propylene and α,β-unsaturated carboxylic acid. and/or a copolymer of α,β-unsaturated carboxylic acid ester monomer. Examples of the α,β-unsaturated carboxylic acid monomer include acrylic acid and methacrylic acid. Examples of α,β-unsaturated carboxylic acid ester monomers include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, and acrylic acid. Pentyl acrylate, pentyl methacrylate, hexyl acrylate, hexyl methacrylate, heptyl acrylate, heptyl methacrylate, octyl acrylate, octyl methacrylate, nonyl acrylate, nonyl methacrylate, decyl acrylate, decyl methacrylate, acrylic acid 2 -ethylhexyl, 2-ethylhexyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, monomethyl maleate, monomethyl itaconate, dimethyl maleate, and dimethyl itaconate. These can be used alone or in combination of two or more.

Further, the aromatic vinyl compound/conjugated diene compound-based block copolymer is a block copolymer consisting of an aromatic vinyl compound-based polymer block and a conjugated diene compound-based polymer block, and the aromatic vinyl compound-based polymer A block copolymer having at least one block and at least one conjugated diene compound polymer block is used. In the block copolymer, unsaturated bonds in the conjugated diene compound polymer block may be hydrogenated.

The aromatic vinyl compound-based polymer block is a polymer block mainly composed of units derived from an aromatic vinyl compound. Examples of aromatic vinyl compounds in this case include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 1,5-dimethylstyrene, 2,4-dimethylstyrene, vinylnaphthalene, vinylanthracene, -propylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, and 4-(phenylbutyl)styrene, and one or more of these can be used. Further, the aromatic vinyl compound polymer block may optionally contain a small amount of units made of other unsaturated monomers.

Conjugated diene compound polymer blocks include, for example, 1,3-butadiene, chloroprene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 4-methyl-1,3-pentadiene, 1 , 3-hexadiene is a polymer block formed from one or more conjugated diene compounds, and in a hydrogenated aromatic vinyl compound/conjugated diene compound block copolymer, the conjugated diene compound polymer Some or all of the unsaturated bond parts in the combined block have become saturated bonds due to 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 an aromatic vinyl compound/conjugated diene compound block copolymer and/or its hydrogenated product, one aromatic vinyl compound polymer block and one conjugated diene compound polymer block are linear chains. Three polymer blocks are bonded in a linear chain in the order of diblock copolymer, aromatic vinyl compound polymer block - conjugated diene compound polymer block - aromatic vinyl compound polymer block. Preferably, one or more triblock copolymers and their hydrogenated products are used, including unhydrogenated or hydrogenated styrene/butadiene block copolymers, unhydrogenated or hydrogenated styrene/isoprene block copolymers, and hydrogenated triblock copolymers. Polymer, unhydrogenated or hydrogenated styrene/butadiene/styrene block copolymer, unhydrogenated or hydrogenated styrene/isoprene/styrene block copolymer, unhydrogenated or hydrogenated styrene/(ethylene/butadiene)/styrene Examples include block copolymers, unhydrogenated or hydrogenated styrene/(isoprene/butadiene)/styrene block copolymers, and the like. These can be used alone or in combination of two or more.

Examples of unsaturated compounds having carboxyl groups that may form constituent units of the elastomer (b) include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, mesaconic acid, citraconic acid, and glutaconic acid. acids, cis-4-cyclohexene-1,2-dicarboxylic acid, endobicyclo-[2.2.1]-5-heptene-2,3-dicarboxylic acid, and the α,β-union of metal salts of these carboxylic acids. Examples include saturated carboxylic acids. These can be used alone or in combination of two or more. Examples of the unsaturated compound having an acid anhydride group that may form a structural unit of the elastomer (b) include maleic anhydride, itaconic anhydride, citraconic anhydride, endobicyclo-[2.2.1]- Examples include dicarboxylic anhydrides having α,β-unsaturated bonds such as 5-heptene-2,3-dicarboxylic anhydride. These can be used alone or in combination of two or more. Among these, dicarboxylic acid anhydrides having α,β-unsaturated bonds are preferred, and maleic anhydride and itaconic anhydride are more preferred.

The concentration of carboxyl groups and/or acid anhydride groups in the elastomer (b) should be 25 μeq/g or more and 200 μeq/g or less, from the viewpoint of improving low-temperature impact resistance and fluidity of the resulting aliphatic polyamide composition. is preferable, and more preferably 50 μeq/g or more and 150 μeq/g or less.

The carboxyl group and/or acid anhydride group concentration in the elastomer (b) was determined by dissolving the elastomer in a toluene solution, using a sample solution prepared by adding ethanol, and using phenolphthalein as an indicator. It can be measured by titration with .1N KOH ethanol solution.

[Modified fluorine-containing polymer (c)]
The fluorine-containing polymer in the modified fluorine-containing polymer (c) is a polymer (homopolymer or copolymer) having a constituent repeating unit derived from at least one fluorine-containing monomer. . There are no particular limitations as long as the fluorine-containing polymer can be heat-melt processed.

Examples of the modification mode include a mode in which a functional group other than a fluoro group is introduced into the fluorine-containing polymer, and the functional group is introduced into the fluorine-containing polymer, and the modified fluorine-containing polymer It does not matter whether it is introduced at the end of the molecule (c), the side chain or the main chain. Moreover, the functional group may be used alone or in combination of two or more types in the modified fluorine-containing polymer (c).
Modification is preferable from the viewpoint of the appearance of the molded product and molding stability.

The functional group other than the fluoro group introduced into the fluorine-containing polymer is preferably a functional group that is reactive with an amino group, and examples of the functional group that is reactive with an amino group include a carboxyl group and an acid group. Carboxyl groups and/or derivatives thereof such as anhydride groups, carboxylic acid ester groups, carboxylic acid metal salts, carboxylic imide groups, carboxylic acid amide groups; sulfo groups, sulfonate salts, epoxy groups, cyano groups, carbonate groups , and a haloformyl group. Among these, from the viewpoint of the appearance and moldability of the molded article, carboxyl groups and/or groups of derivatives thereof are preferable, and it is preferable that the fluorine-containing polymer has at least carboxyl groups and/or groups of derivatives thereof.
As the mode of modification for introducing a carboxyl group and/or a derivative thereof, modification with a carboxylic acid and/or a derivative thereof is preferable from the viewpoint of the appearance and moldability of the molded article, and unsaturated carboxylic acid and/or Modification with a derivative thereof is more preferred, and modification with (meth)acrylic acid and/or a derivative thereof is even more preferred. Note that carboxylic acids and/or derivatives thereof also include acid anhydrides.

Examples of carboxylic acids and their derivatives 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, endo Bicyclo-[2.2.1]-5-heptene-2,3-dicarboxylic acid and metal salts of these carboxylic acids, monomethyl maleate, monomethyl itaconate, methyl acrylate, ethyl acrylate, butyl acrylate, acrylic acid 2-ethylhexyl, hydroxyethyl acrylate, methyl methacrylate, 2-ethylhexyl methacrylate, hydroxyethyl methacrylate, aminoethyl methacrylate, dimethyl maleate, dimethyl itaconate, vinyl acetate, vinyl chloroacetate, vinyl lactate, vinyl butyrate, Vinyl pivalate, vinyl benzoate, vinyl crotonate, maleic anhydride, itaconic anhydride, citraconic anhydride, endobicyclo-[2.2.1]-5-heptene-2,3-dicarboxylic anhydride, maleimide, N-ethylmaleimide, N-butylmaleimide, N-phenylmaleimide, acrylamide, methacrylamide, glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, glycidyl itaconate, and glycidyl citraconate. These can be used alone or in combination of two or more. Among these, acrylic acid, methacrylic acid, acrylic acid derivatives, and methacrylic acid derivatives are preferred.

As a method for introducing a functional group other than a fluoro group into the modified fluorine-containing polymer (c), (i) during polymerization of the fluorine-containing polymer, a copolymerizable group having a functional group other than a fluoro group is used. A method of copolymerizing monomers, (ii) a method of introducing a functional group other than a fluoro group to the molecular terminal of a fluorine-containing polymer during polymerization using a polymerization initiator, a chain transfer agent, etc., and (iii) a method of increasing reactivity. Examples include a method of grafting a compound (graft compound) having a functional group other than a fluoro group and a functional group other than a fluoro group that can be grafted onto a fluorine-containing polymer. These introduction methods can be used alone or in combination as appropriate. The modified fluorine-containing polymer (c) produced from the above (i) and (ii) is preferred. Regarding (iii), JP-A-7-18035, JP-A-7-25952, JP-A-7-25954, JP-A-7-173230, JP-A-7-173446, JP-A-7- Please refer to the manufacturing method disclosed in Japanese Patent Publication No. 173447 and Japanese Patent Publication No. 10-503236.

(i) In a method of copolymerizing a copolymerizable monomer having a functional group other than a fluoro group (hereinafter sometimes abbreviated as a functional group-containing monomer) during the production of a fluorine-containing polymer. Examples of the functional group-containing monomer include functional group-containing non-fluorine monomers, functional group-containing fluorine-containing monomers, and the like.

Examples of the functional group-containing non-fluorine monomer include the compounds exemplified as the above-mentioned carboxylic acids and derivatives thereof, and are determined in consideration of copolymerization reactivity with the fluorine-containing monomer used. By selecting an appropriate functional group-containing non-fluorine monomer, polymerization will proceed well and it will be easier to introduce the functional group-containing non-fluorine monomer uniformly into the main chain, resulting in less unreacted monomer. , which has the advantage of reducing impurities.

The functional group-containing fluorine-containing monomer has the general formula CX ³ X ⁴ =CX ⁵ -(R ⁷ ) _n -Y (where Y is -COOM (M represents a hydrogen atom or an alkali metal). , a carboxyl group-derived group, -SO ₃ M (M represents a hydrogen atom or an alkali metal), a sulfonic acid-derived group, an epoxy group, and -CN, and X ³ , X ⁴ and X ^{5 are} the same or different and represent a hydrogen atom or a fluorine atom (however, if X ³ , X ^{4 and} ), ^R7 is an alkylene group having 1 to 40 carbon atoms, a fluorine-containing oxyalkylene group having 1 to 40 carbon atoms, a fluorine-containing alkylene group having ether bond and having 1 to 40 carbon atoms, or a fluorine-containing oxyalkylene group having an ether bond and having 1 to 40 carbon atoms, where n is 0 or 1). These can be used alone or in combination of two or more.
The carboxyl group-derived group that is Y in the general formula is, for example, a group derived from the general formula -C(=O)Q ¹ (wherein Q ¹ is -OR ⁸ , -NH ₂ , F, Cl, Br, or I and R ⁸ represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 22 carbon atoms. These can be used alone or in combination of two or more.
The sulfonic acid-derived group that is Y in the general formula is, for example, a group derived from the general formula -SO ₂ Q ² (wherein Q ² represents -OR ⁹ , -NH ₂ , F, Cl, Br, or I, and R ⁹ represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 22 carbon atoms.
The Y is preferably -COOH, -SO ₃ H, -SO ₃ Na, -SO ₂ F, or -CN.

Examples of the functional group-containing fluorine-containing monomer include perfluoroacrylic acid fluoride, 1-fluoroacrylic acid fluoride, acrylic acid fluoride, 1-trifluoromethacrylic acid fluoride, and perfluoroacrylic acid fluoride in the case of a functional group having a carbonyl group. Mention may be made of butenoic acid. These can be used alone or in combination of two or more.

The content of the functional group-containing monomer in the modified fluorine-containing polymer (c) is determined by the following: during processing at high temperatures, poor adhesion, coloring, and foaming, and during use at high temperatures, peeling due to decomposition, coloring, and foaming. From the viewpoint of preventing the occurrence of elution, etc., it is preferably 0.01 mol% or more and 5 mol% or less, more preferably 0.015 mol% or more and 4 mol% or less, based on the total polymerized units. , more preferably 0.02 mol% or more and 3 mol% or less. When the content of the functional group-containing monomer in the modified fluoropolymer (c) is within the above range, the polymerization rate during production will not decrease, and the modified fluoropolymer (c) c) has excellent adhesion to the mating material to be laminated. The method of adding the functional group-containing monomer is not particularly limited, and it may be added all at once at the start of polymerization, or may be added continuously during polymerization. The addition method is appropriately selected depending on the decomposition reactivity of the polymerization initiator and the polymerization temperature, but as the functional group-containing monomer is consumed during polymerization, the consumed amount can be continuously or intermittently added. It is preferable to supply the functional group-containing monomer into the polymerization tank and maintain the concentration of the functional group-containing monomer within this range.
The content of the functional group-containing monomer in the modified fluoropolymer (c) is 0.01 mol% based on the total polymerized units. This corresponds to the content of functional group residues in (c) being 100 per 1×10 ⁶ main chain carbon atoms of the modified fluorine-containing polymer (c). In addition, 5 mol% refers to the content of functional group residues in the modified fluorine-containing polymer (c) based on the total polymerized units in the modified fluorine-containing polymer (c). This corresponds to 50,000 carbon atoms compared to 1×10 ⁶ main chain carbon atoms of the fluorine-containing polymer (c).
As long as the above content is satisfied, it may be a mixture of a fluorine-containing polymer into which a functional group is introduced and a fluorine-containing polymer into which a functional group is not introduced.

(ii) In a method of introducing a functional group other than a fluoro group to the molecular end of a fluorine-containing polymer using a polymerization initiator or the like, the number of carbon atoms in the main chain in the modified fluorine-containing polymer (c) is 10 ^{to 6} . The number of terminal functional groups (other than fluoro groups) ensures sufficient heat resistance, and during processing at high temperatures, adhesion failure, coloring, foaming, and when used at high temperatures, peeling due to decomposition, coloring, foaming, elution, etc. From the viewpoint of preventing this, the number is preferably 150 or more and 3,000 or less, more preferably 200 or more and 2,000 or less, and even more preferably 300 or more and 1,000 or less.
Further, as long as the number of functional groups is satisfied, it may be a mixture of a fluorine-containing polymer into which a functional group is introduced and a fluorine-containing polymer into which no functional group is introduced.

On the other hand, examples of fluoromonomers used in the production of fluoropolymers include tetrafluoroethylene (TFE), trifluoroethylene, vinylidene fluoride (VDF), vinyl fluoride (VF), and chlorotrifluoroethylene ( CTFE), trichlorofluoroethylene, hexafluoropropylene (HFP), CF ₂ =CFOR ^f1 (here, R ^f1 represents a perfluoroalkyl group having 1 to 10 carbon atoms and which may contain an etheric oxygen atom. ), CF ₂ =CF-OCH ₂ -R ^f2 (here, R ^f2 represents a perfluoroalkylene group having 1 to 10 carbon atoms and which may contain an ether oxygen atom), CF ₂ =CF ( CF ₂ ) _p OCF=CF ₂ (here, p is 1 or 2), CH ₂ =CX ¹ (CF ₂ ) _n X ² (here, X ¹ and X ² are each independently hydrogen represents an atom or a fluorine atom, and n is an integer of 2 or more and 10 or less. These can be used alone or in combination of two or more.

Specific examples of the general formula CF ₂ =CFOR ^f1 include CF ₂ =CFOCF ₂ (perfluoro(methyl vinyl ether): PMVE), CF ₂ =CFOCF ₂ CF ₃ (perfluoro (ethyl vinyl ether): PEVE), CF ₂ = CFOCF ₂ CF ₂ CF ₃ (perfluoro(propyl vinyl ether): PPVE), CF ₂ = CFOCF ₂ CF ₂ CF ₂ CF ₃ (perfluoro (butyl vinyl ether): PBVE), CF ₂ =CFO(CF ₂ ) ₈ F Examples include perfluoro(alkyl vinyl ether) (hereinafter sometimes referred to as PAVE) such as (perfluoro(octyl vinyl ether): POVE). These can be used alone or in combination of two or more. Among these, CF ₂ =CFOCF ₂ and CF ₂ =CFOCF ₂ CF ₂ CF ₃ are preferred.

Furthermore ^, the general formula CH ₂ = ^{CX 1 (} CF ₂ ⁾ _n n in the compound represented by ) is ensured to ensure the effect of modifying the fluorine-containing polymer (for example, suppressing the occurrence of cracks during molding of the copolymer and in molded products), and to obtain sufficient polymerization reactivity. From this point of view, it is an integer of 2 or more and 10 or less. Specifically, _CH2 =CF( _CF2 ) _2F , _CH2 =CF( _CF2 ) _3F , CH2=CF( _CF2 ) _4F , _{CH2 =} CF( _CF2 ) _5F , CH ₂ =CF( _CF2 ) _8F , _CH2 =CF( _CF2 )2H, _CH2 =CF( _CF2 ) _3H , _CH2 =CF( _{CF2 ) 4H} , _CH2 =CF( _CF2) ) _5H , _CH2 =CF( _CF2 ) _8H , _CH2 =CH( _CF2 ) _2F , _CH2 =CH( _CF2 ) _3F , _CH2 =CH( _CF2 ) _4F , _CH2 =CH( _CF2 ) _5F , _CH2 =CH( _CF2 ) _8F , _CH2 =CH( _CF2 ) _2H , _CH2 =CH( _CF2 ) _3H , _CH2 =CH( _CF2 ) _4H , _CH2 =CH( _CF2 ) _5H , _CH2 =CH( _CF2 ) _8H , and the like. These can be used alone or in combination of two or more. Among these, from the viewpoint of the balance between chemical barrier properties and environmental stress cracking resistance of the modified fluorine-containing polymer (c), _CH2 =CH( _CF2 ) _nF or _CH2 =CF( _CF2 ) A compound represented by _n H is preferred, and n in the formula is more preferably 2 or more and 4 or less.

The modified fluorine-containing polymer (c) is based on a non-fluorine-containing monomer in addition to the fluorine-containing monomer and a monomer having a functional group reactive with an amino group. It may contain polymerized units. Examples of non-fluorine-containing monomers include olefins having 2 to 4 carbon atoms such as ethylene, propylene, and isobutene; halogenated vinyl compounds such as vinyl chloride and vinylidene chloride; methyl vinyl ether (MVE) and ethyl vinyl ether (EVE). , butyl vinyl ether (BVE), isobutyl vinyl ether (IBVE), cyclohexyl vinyl ether (CHVE), glycidyl vinyl ether, and other vinyl ethers. These can be used alone or in combination of two or more. Among these, ethylene and propylene are preferred, and ethylene is more preferred.

Among the modified fluorine-containing polymers (c), from the viewpoint of heat resistance, chemical resistance, and chemical barrier properties, tetrafluoroethylene homopolymer (E0), at least from vinylidene fluoride units (VDF units) A copolymer (E2) consisting of at least a tetrafluoroethylene unit (TFE unit) and an ethylene unit (E unit), a copolymer (E2) consisting of at least a tetrafluoroethylene unit (TFE unit), a hexafluoropropylene unit (HFP units), and PAVE represented by the general formula CF ₂ =CFOR ^f1 (where R ^f1 represents a perfluoroalkyl group having 1 to 10 carbon atoms and which may contain an etheric oxygen atom). A copolymer (E3) consisting of at least two types selected from the group consisting of PAVE units derived from PAVE units, a copolymer (E4) consisting of at least chlorotrifluoroethylene units (CTFE units), at least chlorotrifluoroethylene units It is preferable that each of the copolymers (E5) consisting of (CTFE units) and tetrafluoroethylene units (TFE units) be modified. Among these, modified tetrafluoroethylene homopolymers and copolymers containing tetrafluoroethylene units (TFE units) are more preferred, and modified tetrafluoroethylene homopolymers are even more preferred.

As the polymer (E1) consisting of at least vinylidene fluoride units (VDF units) (hereinafter sometimes referred to as VDF polymer (E1)), for example, vinylidene fluoride homopolymer (polyvinylidene fluoride (PVDF unit) )) (E1-1),
A copolymer consisting of VDF units and TFE units, in which the content of VDF units is 30 mol% or more and 99 mol% or less, based on the entire monomer excluding the functional group-containing monomer, and TFE A copolymer (E1-2) whose unit content is 1 mol% or more and 70 mol% or less,
A copolymer consisting of VDF units, TFE units, and trichlorofluoroethylene units, in which the content of VDF units is 10 mol% or more and 90 mols based on the total monomers excluding the functional group-containing monomers. % or less, a copolymer (E1-3) in which the content of TFE units is 0 mol% or more and 90 mol% or less, and the content of trichlorofluoroethylene units is 0 mol% or more and 30 mol% or less,
A copolymer consisting of VDF units, TFE units, and HFP units, in which the content of VDF units is 10 mol% or more and 90 mol% or less based on the entire monomer excluding the functional group-containing monomer. , a copolymer (E1-4) in which the content of TFE units is 0 mol% or more and 90 mol% or less, and the content of HFP units is 0 mol% or more and 30 mol% or less.

In the copolymer (E1-4), the content of VDF units is 15 mol% or more and 84 mol% or less, and the content of TFE units is 15 mol% or more and 84 mol% or less, based on the entire monomer excluding the functional group-containing monomer. is preferably 15 mol% or more and 84 mol% or less, and the content of HFP units is preferably 0 mol% or more and 30 mol% or less.

At least, as a copolymer (E2) consisting of tetrafluoroethylene units (TFE units) and ethylene units (E units) (hereinafter sometimes referred to as TFE copolymer (E2)), for example, the above-mentioned functional Examples include polymers in which the content of TFE units is 20 mol% or more with respect to the entire monomer excluding the group-containing monomer, and furthermore, the entire monomer excluding the functional group-containing monomer described below. , the content of TFE units is 20 mol% or more and 80 mol% or less, the content of E units is 20 mol% or more and 80 mol% or less, and the content of units derived from monomers copolymerizable with these. Examples include copolymers in which the amount is 0 mol% or more and 60 mol% or less.

The copolymerizable monomer includes hexafluoropropylene (HFP), the general formula CF ₂ =CFOR ^f1 (where R ^f1 may include an etheric oxygen atom having 1 to 10 carbon atoms). represents a perfluoroalkyl group), the general formula CH ₂ =CX ¹ (CF ₂ ) _n X ² (where X ¹ and X ² independently represent a hydrogen atom or a fluorine atom, and n is is an integer greater than or equal to 10 and less than 10). These can be used alone or in combination of two or more.

As the TFE copolymer (E2), for example,
TFE unit, E unit, ^{and the} general formula CH ₂ =CX ¹ (CF ₂ ⁾ _n A copolymer consisting of fluoroolefin units derived from a fluoroolefin represented by the following integer: 30 mol% or more and 70 mol% or less, the content of E units is 20 mol% or more and 55 mol% or less, and ^the general formula _CH2 = ^CX1 ( _CF2 ) _nX2 (wherein ^X1 and ² each independently represent a hydrogen atom or a fluorine atom, and n is an integer of 2 or more and 10 or less.) The content of fluoroolefin units derived from the fluoroolefin represented by is 0 mol% or more and 10 mol% A copolymer (E2-1) which is the following,
A copolymer consisting of TFE units, E units, HFP units, and units derived from monomers copolymerizable with these, with respect to the entire monomer excluding the functional group-containing monomer, The content of TFE units is 30 mol% or more and 70 mol% or less, the content of E units is 20 mol% or more and 55 mol% or less, the content of HFP units is 1 mol% or more and 30 mol% or less, and copolymerized with these. A copolymer (E2-2) in which the content of units derived from possible monomers is 0 mol% or more and 10 mol% or less,
TFE unit, E unit, and the general formula CF ₂ =CFOR ^f1 (here, R ^f1 represents a perfluoroalkyl group having 1 to 10 carbon atoms and optionally containing an etheric oxygen atom). A copolymer consisting of PAVE units derived from PAVE, in which the content of TFE units is 30 mol% or more and 70 mol% or less, based on the entire monomer excluding the functional group-containing monomer, and E The content of the unit is 20 mol% or more and 55 mol% or less, and the general formula CF ₂ =CFOR ^f1 (here, R ^f1 is perfluoroalkyl having 1 to 10 carbon atoms and optionally containing an etheric oxygen atom) Examples include a copolymer (E2-3) in which the content of PAVE units derived from PAVE represented by (representing a group) is 0 mol% or more and 10 mol% or less.

At least, a tetrafluoroethylene unit (TFE unit), a hexafluoropropylene unit (HFP unit), and the general formula CF ₂ =CFOR ^f1 (here, R ^f1 is an etheric oxygen atom having 1 to 10 carbon atoms) A copolymer (E3) consisting of at least two types selected from the group consisting of PAVE units derived from PAVE represented by For example,
A copolymer consisting of TFE units and HFP units, in which the content of TFE units is preferably 70 mol% or more and 95 mol% or less based on the entire monomer excluding the functional group-containing monomer. is 85 mol% or more and 93 mol% or less, and the content of HFP units is 5 mol% or more and 30 mol% or less, preferably 7 mol% or more and 15 mol% or less (E3-1),
Derived from TFE unit and PAVE represented by the general formula CF ₂ =CFOR ^f1 (where R ^f1 represents a perfluoroalkyl group having 1 to 10 carbon atoms and which may contain an etheric oxygen atom) A copolymer consisting of one or more types of PAVE units, in which the content of TFE units is 70 mol% or more and 95 mol% based on the entire monomer excluding the functional group-containing monomer. Derived from PAVE represented by the following and the general formula CF ₂ =CFOR ^f1 (here, R ^f1 represents a perfluoroalkyl group having 1 to 10 carbon atoms and which may contain an etheric oxygen atom). A copolymer (E3-2) in which the content of one or more PAVE units is 5 mol% or more and 30 mol% or less,
TFE units, HFP units, and the general formula CF ₂ =CFOR ^f1 (here, R ^f1 represents a perfluoroalkyl group having 1 to 10 carbon atoms and which may contain an etheric oxygen atom). A copolymer consisting of one or more PAVE units derived from PAVE, in which the content of TFE units is 70 mol% with respect to the entire monomer excluding the functional group-containing monomer. 95 mol% or less, HFP units and the general formula CF ₂ =CFOR ^f1 (here, R ^f1 represents a perfluoroalkyl group having 1 to 10 carbon atoms and which may contain an etheric oxygen atom). Examples include a copolymer (E3-3) in which the total content of one or more PAVE units derived from the expressed PAVE is 5 mol% or more and 30 mol% or less.

A copolymer composed of at least chlorotrifluoroethylene units (CTFE units) is a copolymer composed of CTFE units [-CFCl-CF ₂ -], and further composed of ethylene units (E units) and/or fluorine-containing monomer units. It is a chlorotrifluoroethylene copolymer (E4) (hereinafter sometimes referred to as CTFE copolymer (E4)).
The fluorine-containing monomer in the CTFE copolymer (E4) is not particularly limited as long as it is other than CTFE, but includes vinylidene fluoride (VDF), hexafluoropropylene (HFP), and the general formula CF ₂ =CFOR. PAVE represented by ^f1 (here, R ^f1 represents a perfluoroalkyl group having 1 to 10 carbon atoms and which may contain an etheric oxygen atom), the general formula CH ₂ =CX ¹ (CF ₂ ) _n X ² (wherein, X ¹ and X ² each independently represent a hydrogen atom or a fluorine atom, and n is an integer of 2 or more and 10 or less), and the like. These can be used alone or in combination of two or more.

The CTFE copolymer (E4) is not particularly limited, and includes, for example, CTFE/PAVE copolymer, CTFE/VDF copolymer, CTFE/HFP copolymer, CTFE/E copolymer, CTFE/PAVE/E Examples include copolymers, CTFE/VDF/E copolymers, CTFE/HFP/E copolymers, and the like. These can be used alone or in combination of two or more.

The content of CTFE units in the CTFE copolymer (E4) is preferably 15 mol% or more and 70 mol% or less, and 18 mol% based on the total monomers excluding the functional group-containing monomer. More preferably, the content is 65 mol% or less. On the other hand, the content of E units and/or fluorine-containing monomer units is preferably 30 mol% or more and 85 mol% or less, more preferably 35 mol% or more and 82 mol% or less.

The copolymer (E5) consisting of at least chlorotrifluoroethylene units (CTFE units) and tetrafluoroethylene units (TFE units) contains CTFE units [-CFCl-CF ₂ -], TFE units [-CF ₂ -CF ₂ -], and a chlorotrifluoroethylene copolymer composed of monomer units copolymerizable with CTFE and TFE (hereinafter sometimes referred to as CTFE/TFE copolymer (E5)).

The copolymerizable monomer in the CTFE/TFE copolymer (E5) is not particularly limited as long as it is other than CTFE and TFE, but vinylidene fluoride (VDF), hexafluoropropylene (HFP), PAVE represented by the general formula CF ₂ =CFOR ^f1 (here, R ^f1 represents a perfluoroalkyl group having 1 to 10 carbon atoms and which may contain an etheric oxygen atom), the general formula CH ₂ ^{= CX 1} ( _{CF 2} ⁾ n Fluorine-containing monomers such as olefins; olefins having 2 to 4 carbon atoms such as ethylene, propylene, and isobutene; non-fluorine such as vinyl ethers such as methyl vinyl ether (MVE), ethyl vinyl ether (EVE), and butyl vinyl ether (BVE) Containing monomers may be mentioned. These can be used alone or in combination of two or more. Among these, PAVE represented by the general formula CF ₂ =CFOR ^f1 (where R ^f1 represents a perfluoroalkyl group having 1 to 10 carbon atoms and which may contain an etheric oxygen atom) Preferably, perfluoro(methyl vinyl ether) (PMVE) and perfluoro(propyl vinyl ether) (PPVE) are more preferable, and from the viewpoint of heat resistance, PPVE is even more preferable.

The CTFE/TFE copolymer (E5) is not particularly limited, and includes, for example, CTFE/TFE copolymer, CTFE/TFE/HFP copolymer, CTFE/TFE/VDF copolymer, and CTFE/TFE/PAVE copolymer. Examples include polymers, CTFE/TFE/E copolymers, CTFE/TFE/HFP/PAVE copolymers, CTFE/TFE/VDF/PAVE copolymers, and the like. These can be used alone or in combination of two or more. Among these, CTFE/TFE/PAVE copolymers and CTFE/TFE/HFP/PAVE copolymers are preferred.

The total content of CTFE units and TFE units in the CTFE/TFE copolymer (E5) is determined from the viewpoint of ensuring good moldability, environmental stress cracking resistance, chemical barrier properties, heat resistance, and mechanical properties. The content of monomer units copolymerizable with CTFE and TFE is preferably 90 mol% or more and 99.9 mol% or less based on the entire monomers excluding the functional group-containing monomer. is preferably 0.1 mol% or more and 10 mol% or less.

The content of CTFE units in the CTFE/TFE copolymer (E5) is determined from the viewpoint of ensuring good moldability, environmental stress cracking resistance, and chemical barrier properties, to a total amount of 100% of the CTFE units and TFE units. It is preferably 15 mol% or more and 80 mol% or less, more preferably 17 mol% or more and 70 mol% or less, and even more preferably 19 mol% or more and 65 mol% or less.

In the CTFE/TFE copolymer (E5), when the monomer copolymerizable with CTFE and TFE is PAVE, the content of PAVE units is the total amount of the monomers excluding the functional group-containing monomer. It is preferably 0.5 mol% or more and 7 mol% or less, more preferably 1 mol% or more and 5 mol% or less.

In the CTFE/TFE copolymer (E5), when the monomers copolymerizable with CTFE and TFE are HFP and PAVE, the total content of HFP units and PAVE units is equal to the total content of the functional group-containing monomers. It is preferably 0.5 mol% or more and 7 mol% or less, and more preferably 1 mol% or more and 5 mol% or less, based on the total monomers excluding .

The TFE copolymer (E3), CTFE copolymer (E4), and CTFE/TFE copolymer (E5) have excellent chemical barrier properties, particularly barrier properties against alcohol-containing gasoline. The permeability coefficient of alcohol-containing gasoline is determined by placing a sheet obtained from the resin to be measured into a permeability coefficient measuring cup containing a mixed solvent of isooctane/toluene/ethanol, which is a mixture of isooctane, toluene, and ethanol in a volume ratio of 45:45:10. , is a value calculated from the mass change measured at 60°C. The alcohol-containing gasoline permeability coefficient of the TFE copolymer (E3), CTFE copolymer (E4), and CTFE/TFE copolymer (E5) is 1.5 g·mm/(m ² ·day) or less. It is preferably 0.01 g·mm/(m ² ·day) or more and 1 g·mm/(m ² ·day) or less, and more preferably 0.02 g·mm/(m 2·day) or more and 0.02 g·mm/(m ² ·day) or more. It is more preferable that it is 8 g·mm/(m ² ·day) or less.

The modified fluorine-containing polymer (c) can be obtained by (co)polymerizing by a conventional polymerization method using monomers constituting the polymer. Among these, a method based on radical polymerization is mainly used. That is, the means for initiating polymerization is not particularly limited as long as it proceeds radically, but for example, it may be initiated by an organic or inorganic radical polymerization initiator, heat, light, ionizing radiation, or the like.

The method for producing the modified fluorine-containing polymer (c) is not particularly limited, and a polymerization method using a commonly used radical polymerization initiator can be used. Polymerization methods include bulk polymerization, solution polymerization using organic solvents such as fluorinated hydrocarbons, chlorinated hydrocarbons, fluorinated chlorinated hydrocarbons, alcohols, and hydrocarbons, and aqueous media and appropriate organic solvents as necessary. Known methods such as suspension polymerization using an aqueous medium and emulsion polymerization using an aqueous medium and an emulsifier can be employed.
Moreover, the polymerization can be carried out as a batchwise or continuous operation using a one-tank or multi-vet stirring type polymerization apparatus, a tubular polymerization apparatus, or the like.

As a radical polymerization initiator, the decomposition temperature at which the half-life is 10 hours is preferably 0°C or more and 100°C or less, more preferably 20°C or more and 90°C or less. Specific examples include 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2-methylvaleronitrile), and 2,2'-azobis(2,4-dimethylvaleronitrile). '-Azobis(2-cyclopropylpropionitrile), 2,2'-dimethyl azobisisobutyrate, 2,2'-azobis[2-(hydroxymethyl)propionitrile], 4,4'-azobis(4-cyano azo compounds such as pentenoic acid); hydroperoxides such as hydrogen peroxide, t-butyl hydroperoxide, and cumene hydroperoxide; dialkyl peroxides such as di-t-butyl peroxide and dicumyl peroxide; acetyl peroxide , isobutyryl peroxide, octanoyl peroxide, benzoyl peroxide, lauroyl peroxide, and other non-fluorinated diacyl peroxides; methyl ethyl ketone peroxide, cyclohexanone peroxide, and other ketone peroxides; diisopropyl peroxydicarbonate and other peroxides; Carbonate; peroxy ester such as t-butylperoxypivalate, t-butylperoxyisobutyrate, t-butylperoxyacetate; (Z(CF ₂ ) _p COO) ₂ (here, Z is a hydrogen atom , a fluorine atom, or a chlorine atom, and p is an integer of 1 to 10.) Fluorine-containing diacyl peroxides such as compounds represented by Examples include oxides. These can be used alone or in combination of two or more.

Furthermore, when producing the modified fluorine-containing polymer (c), it is also preferable to use a conventional chain transfer agent in order to adjust the molecular weight. Examples of chain transfer agents include alcohols such as methanol and ethanol; 1,3-dichloro-1,1,2,2,3-pentafluoropropane, 1,1-dichloro-1-fluoroethane, 1,2-dichloro- Chlorofluorohydrocarbons such as 1,1,2,2-tetrafluoroethane, 1,1-dichloro-1-fluoroethane, 1,1,2-trichloro-1,2,2-trifluoroethane; pentane, hexane Hydrocarbons such as , cyclohexane; and chlorohydrocarbons such as carbon tetrachloride, chloroform, methylene chloride, and methyl chloride. These can be used alone or in combination of two or more.

The polymerization conditions are not particularly limited, and the polymerization temperature is preferably 0°C or higher and 100°C or lower, more preferably 20°C or higher and 90°C or lower. In order to avoid a decrease in heat resistance due to the formation of ethylene-ethylene chains in the polymer, low temperatures are generally preferred. The polymerization pressure is appropriately determined depending on other polymerization conditions such as the type and amount of solvent used, vapor pressure, and polymerization temperature, but is preferably 0.1 MPa or more and 10 MPa or less, and 0.5 MPa or more and 3 MPa or less. It is more preferable. The polymerization time is preferably 1 hour or more and 30 hours or less.

The modified fluorine-containing polymer (c) preferably has a high molecular weight from the viewpoint of moldability, and preferably has an average molecular weight of 6 million or more. The average molecular weight is calculated by the following formula according to ASTM D4591. Log Mw=27.5345-12.1405D (wherein, Mw represents weight average molecular weight and D represents standard specific gravity). Furthermore, the molecular weight is controlled by the concentration of monomers used in polymerization, the concentration of polymerization initiators, the concentration of chain transfer agents, temperature, and the like.

When using a particulate modified fluorine-containing polymer (c), it is also preferable to blend it into the aliphatic polyamide resin composition as a mixed powder with particles of other resins.

The mixed powder is obtained by mixing an aqueous dispersion of modified fluoropolymer particles with an aqueous dispersion of other resin particles and turning the mixture into a powder by coagulation or spray drying, or by mixing a modified fluoropolymer particle aqueous dispersion with an aqueous dispersion of other resin particles and turning the mixture into powder by coagulation or spray drying, or by mixing the modified fluoropolymer particle aqueous dispersion with an aqueous dispersion of other resin particles and turning the mixture into powder by coagulation or spray drying. After polymerizing monomers constituting other resins in the presence of an aqueous dispersion, the monomers constituting the other resins are pulverized by coagulation or spray drying, or the aqueous dispersion of fluorine-containing polymer particles and the aqueous dispersion of other resin particles are combined. It can be obtained by emulsion polymerizing vinyl monomers in a mixed dispersion and then pulverizing the resultant mixture by coagulation or spray drying.

The modified fluorine-containing polymer particle aqueous dispersion can be obtained by emulsion polymerization using a fluorine-containing surfactant.

The other resin constituting the mixed powder is not particularly limited, but from the viewpoint of dispersibility, it is preferable that it has a high affinity with the aliphatic polyamide resin (a).

Specific examples of monomers for producing other resins include styrene, α-methylstyrene, p-methylstyrene, o-methylstyrene, t-butylstyrene, o-ethylstyrene, p-chlorostyrene, - Aromatic vinyl monomers such as chlorostyrene, 2,4-dichlorostyrene, p-methoxystyrene, o-methoxystyrene, 2,4-dimethylstyrene; methyl acrylate, methyl methacrylate, ethyl acrylate, methacrylic acid Ethyl, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, dodecyl acrylate, dodecyl methacrylate, tridecyl acrylate, tridecyl methacrylate, octadecyl acrylate, octadecyl methacrylate, acrylic acid (Meth)acrylic acid ester monomers such as cyclohexyl and cyclohexyl methacrylate; Vinyl cyanide monomers such as acrylonitrile and methacrylonitrile; α,β-unsaturated carboxylic acids such as maleic anhydride; N-phenylmaleimide, N -Maleimide monomers such as methylmaleimide and N-cyclohexylmaleimide; Epoxy group-containing monomers such as glycidyl methacrylate; Vinyl ether monomers such as vinyl methyl ether and vinyl ethyl ether; Carvone such as vinyl acetate and vinyl butyrate Examples include acid vinyl monomers; olefin monomers such as ethylene, propylene, and isobutylene; and diene monomers such as butadiene, isoprene, and dimethylbutadiene.
These monomers can be used alone or in combination of two or more.

Among these monomers, one or more monomers selected from the group consisting of aromatic vinyl monomers and vinyl cyanide monomers are preferred from the viewpoint of affinity with the aliphatic polyamide resin (a). Examples include monomers containing 30% by weight or more of the monomer. Particularly preferred are monomers containing 30% by weight or more of one or more monomers selected from the group consisting of styrene and acrylonitrile.

The mixed powder can be powdered by pouring the aqueous dispersion into hot water in which metal salts such as calcium chloride and magnesium sulfate are dissolved, and drying after salting out and coagulating, or by spray drying. . __
The particle size of the modified fluorine-containing polymer (c) in the mixed powder is not particularly limited, but is preferably 10 μm or less. The particle diameter is a value measured by dynamic light scattering method.
Note that the content of the modified fluorine-containing polymer (c) described below does not include other resins in the mixed powder.

(Aliphatic polyamide resin composition)
The content of aliphatic polyamide (a) in the aliphatic polyamide resin composition is preferably 65% by mass or more and 95% by mass or less, and 70% by mass or more, based on 100% by mass of the aliphatic polyamide resin composition. It is more preferably 90% by mass or less, and even more preferably 75% by mass or more and 88% by mass or less. When the content of aliphatic polyamide (a) is within the above range, the molded product obtained is excellent in terms of moldability, mechanical properties, and heat resistance.

The content of the elastomer (b) in the aliphatic polyamide resin composition is preferably 4% by mass or more and 35% by mass or less, and 7% by mass or more and 30% by mass, based on 100% by mass of the aliphatic polyamide resin composition. % or less, and even more preferably 10% by mass or more and 25% by mass or less. When the content of the elastomer (b) is within the above range, the resulting molded product is excellent in terms of moldability and mechanical properties.

The content of the modified fluorine-containing polymer (c) in the aliphatic polyamide resin composition shall be 0.1% by mass or more and 5% by mass or less based on 100% by mass of the aliphatic polyamide resin composition. The content is preferably 0.3% by mass or more and 4% by mass or less, and even more preferably 0.5% by mass or more and 3% by mass or less. When the content of the modified fluorine-containing polymer (c) is within the above range, the resulting molded product is excellent in terms of moldability, mechanical properties, and appearance.

The aliphatic polyamide resin composition may be a mixture of the aliphatic polyamide resin (a), the elastomer (b), and a thermoplastic resin other than the modified fluorine-containing polymer (c). The total content of the aliphatic polyamide resin (a), elastomer (b), and modified fluorine-containing polymer (c) should be 80% by mass or more based on 100% by mass of the aliphatic polyamide resin composition. is preferable, and more preferably 85% by mass or more.

Other thermoplastic resins to be mixed include high-density polyethylene (HDPE), medium-density polyethylene (MDPE), low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), ultra-high molecular weight polyethylene (UHMWPE), and polypropylene. (PP), polybutene (PB), polyolefin resins such as polymethylpentene (TPX); polystyrene (PS), syndiotactic polystyrene (SPS), methyl methacrylate/styrene copolymer (MS), methyl methacrylate/ Polystyrene resins such as styrene/butadiene copolymer (MBS); 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), polycyclohexane dimethylene terephthalate (PCT), Polyester resins such as polyethylene naphthalate (PEN), polybutylene naphthalate (PBN), polyarylate (PAR), liquid crystal polyester (LCP), polylactic acid (PLA), polyglycolic acid (PGA); polyacetal (POM), Polyether resins such as polyphenylene ether (PPO); polysulfone resins such as polysulfone (PSU), polyether sulfone (PESU), and polyphenylsulfone (PPSU); polyphenylene sulfide (PPS), polythioether sulfone (PTES) Polythioether resins such as polyketone (PK), polyether ketone (PEK), polyether ether ketone (PEEK), polyether ketone ketone (PEKK), polyether ether ether ketone (PEEEK), polyether ether ketone ketone ( Polyketone resins such as PEEKK), polyetherketoneketoneketone (PEKKK), and polyetherketoneetherketoneketone (PEKEKK); polyacrylonitrile (PAN), polymethacrylonitrile, acrylonitrile/styrene copolymer (AS), methacrylonitrile Polynitrile resins such as nitrile/styrene copolymer, acrylonitrile/butadiene/styrene copolymer (ABS), acrylonitrile/butadiene copolymer (NBR); polymethyl methacrylate (PMMA), polyethyl methacrylate (PEMA), etc. polymethacrylate resin; polyvinyl alcohol (PVA), polyvinylidene chloride (PVDC), polyvinyl chloride (PVC), vinyl chloride/vinylidene chloride copolymer, vinylidene chloride/methyl acrylate copolymer, etc.; 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 resin; examples include polyamide elastomer, polyurethane elastomer, polyester elastomer, etc., and in some cases, 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), tetrafluoro Examples include fluororesins such as ethylene/hexafluoropropylene/perfluoro(alkyl vinyl ether) copolymer and chlorotrifluoroethylene/perfluoro(alkyl vinyl ether)/tetrafluoroethylene copolymer (CPT). These can be used alone or in combination of two or more.

The aliphatic polyamide resin composition may further contain a conductive filler.
Conductivity means that, for example, if a flammable fluid such as gasoline comes into continuous contact with an insulator such as resin, static electricity may accumulate and cause a fire. It means to have electrical properties. This makes it possible to prevent explosions due to static electricity generated during transport of fluid such as fuel.
The conductive filler includes all fillers added to impart conductivity to the resin, and includes granular, flake, and fibrous fillers.

Particulate fillers include carbon black, graphite, and the like. Examples of the flaky filler include aluminum flakes, nickel flakes, nickel coated mica, and the like. Further, examples of the fibrous filler include metal fibers such as carbon fibers, carbon-coated ceramic fibers, carbon whiskers, carbon nanotubes, aluminum fibers, copper fibers, brass fibers, and stainless steel fibers. These can be used alone or in combination of two or more. Among these, carbon nanotubes and carbon black are preferred.

Carbon nanotubes are referred to as hollow carbon fibrils, which have an outer region consisting of many essentially continuous layers of regularly arranged carbon atoms and an inner hollow region, with each layer and the hollow region are substantially concentrically disposed about the cylindrical axis of the fibril. Furthermore, it is preferable that the regularly arranged carbon atoms in the outer region are graphitic, and the diameter of the hollow region is 2 nm or more and 20 nm or less. The outer diameter of the carbon nanotube is preferably 3.5 nm or more and 70 nm or less, and 4 nm or more and 60 nm or less, from the viewpoint of providing sufficient dispersibility in the resin and good conductivity of the resulting resin molded body. It is more preferable. The aspect ratio (length/outer diameter ratio) of the carbon nanotubes is preferably 5 or more, more preferably 100 or more, and even more preferably 500 or more. By satisfying this aspect ratio, it is easy to form a conductive network, and excellent conductivity can be exhibited even when a small amount is added.

Carbon black includes all carbon blacks that are generally used for imparting electrical conductivity. Preferred carbon blacks include acetylene black obtained by incomplete combustion of acetylene gas, and acetylene black obtained by incomplete combustion in a furnace using crude oil as a raw material. Examples include, but are not limited to, furnace black such as Ketjen black produced by Kotchen Black, oil black, naphthalene black, thermal black, lamp black, channel black, roll black, and disk black. These can be used alone or in combination of two or more. Among these, acetylene black and furnace black are more preferred.

Furthermore, various carbon powders are produced with different characteristics such as particle size, surface area, DBP oil absorption, and ash content. Although there are no restrictions on the properties of the carbon black, it is preferable to have a good chain structure and a high agglomeration density. It is not preferable to incorporate a large amount of carbon black from the viewpoint of impact resistance, and from the viewpoint of obtaining excellent electrical conductivity with a smaller amount, the average particle size is preferably 500 nm or less, and preferably 5 nm or more and 100 nm or less. More preferably, it is 10 nm or more and 70 nm or less, and the surface area (BET method) is preferably 10 m ² /g or more, more preferably 30 m ² /g or more, and 50 m ² /g or more. It is more preferable that the DBP (dibutyl phthalate) oil absorption amount is 50 ml/100 g or more, more preferably 100 ml/100 g, and even more preferably 150 ml/100 g or more. Further, the ash content is preferably 0.5% by mass or less, more preferably 0.3% by mass or less. The DBP oil absorption amount herein is a value measured by the method specified in ASTM D-2414. Further, the volatile content of carbon black is preferably less than 1% by mass.
These conductive fillers may be surface-treated with a titanate-based, aluminum-based, silane-based, or other surface treatment agent. Furthermore, it is also possible to use granulated materials in order to improve melt-kneading workability.

The content of the conductive filler varies depending on the type of conductive filler used, so it cannot be absolutely specified, but from the viewpoint of balance with conductivity, fluidity, mechanical strength, etc., the content of the aliphatic polyamide resin composition 100 mass It is generally preferred that the amount is 3 parts by mass or more and 30 parts by mass or less.
In addition, from the viewpoint of obtaining sufficient antistatic performance, the conductive filler preferably has a surface resistivity value of 10 ⁸ Ω/square or less, and more preferably 10 ⁶ Ω/square or less, from the viewpoint of obtaining sufficient antistatic performance. preferable. However, addition of the conductive filler tends to cause deterioration in strength and fluidity. Therefore, it is desirable that the content of the conductive filler be as small as possible if the target conductivity level can be obtained.

Furthermore, the aliphatic polyamide resin composition may contain antioxidants such as phenolic and phosphorus antioxidants, heat stabilizers, ultraviolet absorbers, light stabilizers, additive impregnation agents, lubricants, and inorganic fillers, as necessary. additives, antistatic agents, flame retardants, crystallization promoters, colorants, etc. may be added.

The aliphatic polyamide resin composition has a total concentration of carboxyl groups and acid anhydride groups in the elastomer (b) of [X] (μeq/g), based on 100% by mass of the aliphatic polyamide resin composition of the elastomer (b). When the content is [Y] (mass%) and the content of the modified fluorine-containing polymer (c) based on 100 mass% of the aliphatic polyamide resin composition is [Z] (mass%), [X ]×[Y]×[Z] is preferably less than 2,900, more preferably 300 or more and less than 2,900, even more preferably 400 or more and 2,000 or less, and 600 or more and 1,750 or less. It is more preferable that When the value of [X]×[Y]×[Z] is within the above range, the tube and blow-molded product are excellent in terms of appearance and moldability.

[Method for producing aliphatic polyamide resin composition]
The method of mixing the aliphatic polyamide resin (a), elastomer (b), modified fluorine-containing polymer (c), and other optional components is not particularly limited, and various conventionally known methods may be used. Can be adopted. For example, using a tumbler and/or mixer, the pellets of aliphatic polyamide resin (a), elastomer (b), and modified fluorine-containing polymer (c) are mixed together in the above-mentioned mixing ratio. A method of uniformly dry blending, a method of pre-dry blending the three components together with other ingredients added as necessary at the concentration used during molding, and a method of melt-kneading, a method of blending some of the components and then melt-kneading, It can be produced by a method in which the remaining components are further blended and melt-kneaded, or by a method in which some of the components are blended and then the remaining components are mixed using a side feeder during melt-kneading. A masterbatch in which each component is mixed with a thermoplastic resin can also be used as pellets. Melt-kneading can be performed using a kneading machine such as a single-screw extruder, a twin-screw extruder, a kneader, or a Banbury mixer.

[Applications of aliphatic polyamide resin composition]
The aliphatic polyamide resin composition can be suitably used for producing blow molded products by blow molding. Furthermore, it can be suitably used for manufacturing extrusion molded products by extrusion molding.
There are no particular restrictions on the method for producing a blow molded product from an aliphatic polyamide resin by blow molding, and any known method can be used. Generally, blow molding may be performed after forming a parison using a normal blow molding machine. Preferably, the resin temperature during parison formation is 10°C to 70°C higher than the melting point of the aliphatic polyamide resin composition.

The method for producing an extrusion molded product from an aliphatic polyamide resin by extrusion molding is not particularly limited, and any known method can be used.
It is also possible to obtain a multilayered structure by coextruding it with a polyolefin such as polyethylene or another thermoplastic resin and then blow molding it. In that case, it is also possible to provide an adhesive layer between the aliphatic polyamide resin composition layer and another thermoplastic resin layer such as polyolefin. In the case of a multilayer structure, the aliphatic polyamide resin composition of the present invention can be used for both the outer layer and the inner layer.

Blow molded products by blow molding and extrusion molded products by extrusion molding include, but are not particularly limited to, spoilers, air intake ducts, intake manifolds, resonators, fuel tanks, gas tanks, hydraulic oil tanks, fuel filler tubes, fuel delivery pipes, and others. Automotive parts such as various hoses, tubes and tanks, mechanical parts such as power tool housings and pipes, electrical and electronic parts such as tanks, tubes, hoses and films, household and office supplies, building material related parts, and furniture. Examples include parts, with blow molded products being preferred. The hollow molded product is preferably a molded product selected from the group consisting of pipes, tubes, hoses, and tanks.

EXAMPLES Below, the present invention will be specifically explained with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

In addition, methods for analysis and measuring physical properties in Examples and Comparative Examples, and materials used in Examples and Comparative Examples are shown.

The material properties of the aliphatic polyamide resin composition were measured by the following method.

[Relative viscosity]
It was measured in accordance with JIS K-6920 in 96% sulfuric acid, at a polyamide concentration of 1%, and at a temperature of 25°C.

[Fluidity (MFR)]
The fluidity of the aliphatic polyamide resin composition was measured by a method based on ISO 1133 at a measurement temperature of 280° C. and a load of 10 kg.

[Total concentration of carboxyl groups and acid anhydride groups in elasmeric polymer (b) [X]]
A predetermined amount of elastomer sample was placed in a three-neck eggplant-shaped flask, dissolved in 170 mL of toluene, and then 30 mL of ethanol was added. Using a sample solution prepared, a 0.1N KOH ethanol solution was prepared using phenolphthalein as an indicator. Titration was performed to determine the total concentration of carboxyl groups and acid anhydride groups.

(1) Extrusion moldability Measured by the following method.
[Tube forming stability]
The molding stability of the tube when taken out of the extrusion molding machine was evaluated based on the following criteria.
○: Continuous molding is possible, and stable molding is possible without pulsation.
Δ: Continuous molding is possible, but slight pulsation occurs.
×: Continuous molding is impossible and pulsation occurs.

[Appearance (smoothness)]
The smoothness of the outer surface of the tube after extrusion molding was visually observed for the presence or absence of striped patterns (chatter marks) occurring in the circumferential direction, and evaluated based on the following criteria.
○: No striped patterns (chattering marks), protrusions, etc. are observed with the naked eye on the outer surface of the tube.
Δ: Minute striped patterns (chatter marks), protrusions, etc. are observed with the naked eye on the outer surface of the tube.
×: Large striped patterns (chatter marks), protrusions, etc. are observed with the naked eye on the outer surface of the tube.

[Resin pressure]
The resin pressure in the extruder was measured during extrusion molding of the tube. For measurement, a pressure gauge was attached to the extruder and the value was read. When the pressure is low, the load on the equipment can be reduced and continuous molding can be performed stably.

(2) Blow moldability Measured by the following method.
[Surface properties of blow molded products]
The surface properties of the blow molded products were confirmed by visually observing the inner surface of the molded products and by directly touching them with fingers, and evaluated according to the following criteria.
○: There is no unevenness or roughness on the inner surface of the molded product.
Δ: There is no unevenness on the inner surface of the molded product, but there is some roughness.
×: There are irregularities and roughness on the inner surface of the molded article.

[Drawdown characteristics]
After taking out a 1 m parison from a blow molding machine, the parison length was measured 2 seconds and 5 seconds later. The smaller the drawdown amount, the higher the parison retention rate and the better the blow moldability, so if the change from the initial value at any time was 20 cm or less in absolute value, it was judged to have good drawdown characteristics. .

[Materials used in Examples and Comparative Examples]
Aliphatic polyamide resin (a)
Polyamide 6(a-1): Polyamide 6 with a relative viscosity of 4.1
Polyamide 6/12 (a-2): Polyamide 6/12 consisting of 80% by mass of ε-caprolactam and 20% by mass of 12-aminododecanoic acid and having a relative viscosity of 3.9.
Polyamide 6/66 (a-3): Polyamide 6/66) consisting of 85% by mass of ε-caprolactam and 15% by mass of hexamethylenediamine adipate and having a relative viscosity of 4.0.

Elastomer (b)
Elastomer (b-1): Tafmer MH5020 (manufactured by Mitsui Chemicals, maleic anhydride-modified ethylene/butene copolymer, acid anhydride concentration: 100 μeq/g)
Elastomer (b-2): Tafmer MH5040 (manufactured by Mitsui Chemicals, maleic anhydride-modified ethylene/butene copolymer, acid anhydride concentration: 200 μeq/g)

Modified PTFE (c)
PTFE (c-1) modified with acrylic acid: Metablen A-3800 (manufactured by Mitsubishi Chemical Corporation, acrylic modified polytetrafluoroethylene)
Unmodified PTFE (c-2): Fluon PTFE L169E (manufactured by AGC Corporation, polytetrafluoroethylene)

[Aliphatic polyamide resin composition]
[Example 1]
Production of polyamide 6 composition (A-1) Polyamide 6 (a-1), elastomer (b-1), modified PTFE (c-1), and as an antioxidant, bis[3-[3-(tert -butyl)-4-hydroxy-5-methylphenyl]propanoic acid]2,4,8,10-tetraoxaspiro[5.5]undecane-3,9-diylbis(2-methylpropane-2,1-diyl ) (manufactured by Sumitomo Chemical Co., Ltd., SUMILIZER GA-80), as an antioxidant, pentaerythritol tetrakis [3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (manufactured by BASF Japan, Irganox 1010), 3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5. 5] Undecane (ADEKA Co., Ltd., ADEKA STAB PEP-36) and polyoxyethylene (20) sorbitan monolaurate (Marubishi Yuka Kogyo Co., Ltd., Valu 7220) as an impregnating agent are mixed in advance. , supplied to a twin-screw melt kneader (manufactured by Coperion Co., Ltd., model: ZSK, cylinder diameter 32 mm, L/D48), and melted and kneaded at a cylinder temperature of 240°C to 250°C, screw rotation of 400 rpm, and a discharge rate of 60 kg/hrs. After extruding the resin into a strand, it was introduced into a water tank, cooled, cut, and vacuum dried to form polyamide 6 (a-1) / elastomer (b-1) / modified PTFE (c-1) = A polyamide 6 composition (A -1) Pellets were obtained (in the composition, polyamide 6 (a-1) / elastomer (b-1) / modified PTFE (c-1) = 86.3 / 11.9 / 1.0 (mass) %)).The total concentration [X] (μeq/g) of carboxyl groups and acid anhydride groups possessed by the elastomer (b-1) of this material is 100 μeq/g, and the aliphatic polyamide resin of the elastomer (b-1) The content [Y] (mass%) based on 100% by mass of the composition is 11.9% by mass, and the content [Z] (mass) of the modified PTFE (c-1) based on 100% by mass of the aliphatic polyamide resin composition. %) is 1.0% by mass, and [X] × [Y] × [Z] is 1,190. In addition, the value of MFR (280 ° C., 10 kg) of polyamide 6 composition (A-1) was 17g/10min.

[Example 2]
Production of polyamide 6 composition (A-2) In the production of polyamide 6 composition (A-1), the amounts of elastomer (b-1) and modified PTFE (c-1) were changed, and polyamide 6 (a- Polyamide 6 composition (A- 2) pellets were obtained (in the composition, polyamide 6 (a-1) / elastomer (b-1) / modified PTFE (c-1) = 83.8 / 14.9 / 0.5 (mass) %)). The total concentration [X] (μeq/g) of carboxyl groups and acid anhydride groups possessed by the elastomer (b-1) of this material is 100 μeq/g, and 100 mass of the aliphatic polyamide resin composition of the elastomer (b-1) is %, the content [Y] (mass %) is 14.9 mass %, and the content [Z] (mass %) of the modified PTFE (c-1) with respect to 100 mass % of the aliphatic polyamide resin composition is 0. .5% by mass, and [X]×[Y]×[Z] is 745. Further, the MFR value (280° C., 10 kg) of the polyamide 6 composition (A-2) was 18 g/10 min.

[Example 3]
Production of polyamide 6 composition (A-3) In the production of polyamide 6 composition (A-1), the amount of elastomer (b-1) was changed, and polyamide 6 (a-1)/elastomer (b-1)/ Pellets of polyamide 6 composition (A-3) were obtained in the same manner except that modified PTFE (c-1) = 84/15/1 (mass ratio) (in the composition, polyamide 6 (a-1)/elastomer (b-1)/modified PTFE (c-1) = 83.3/14.9/1.0 (mass%)). The total concentration [X] (μeq/g) of carboxyl groups and acid anhydride groups possessed by the elastomer (b-1) of this material is 100 μeq/g, and 100 mass of the aliphatic polyamide resin composition of the elastomer (b-1) is %, the content [Y] (mass %) is 14.9 mass %, and the content [Z] (mass %) of the modified PTFE (c-1) with respect to 100 mass % of the aliphatic polyamide resin composition is 1. .0% by mass, and [X]×[Y]×[Z] is 1,490. Further, the MFR value (280° C., 10 kg) of the polyamide 6 composition (A-3) was 15 g/10 min.

[Example 4]
Production of polyamide 6 composition (A-4) In the production of polyamide 6 composition (A-1), the amounts of elastomer (b-1) and modified PTFE (c-1) were changed to produce polyamide 6 (a-4). Pellets of polyamide 6 composition (A-4) were prepared in the same manner except that 1)/elastomer (b-1)/modified PTFE (c-1) = 82/15/3 (mass ratio). (In the composition, polyamide 6 (a-1)/elastomer (b-1)/modified PTFE (c-1) = 81.3/14.9/3.0 (mass%)). The total concentration [X] (μeq/g) of carboxyl groups and acid anhydride groups possessed by the elastomer (b-1) of this material is 100 μeq/g, and 100 mass of the aliphatic polyamide resin composition of the elastomer (b-1) is %, the content [Y] (mass %) is 14.9 mass %, and the content [Z] (mass %) of the modified PTFE (c-1) with respect to 100 mass % of the aliphatic polyamide resin composition is 3. .0% by mass, and [X]×[Y]×[Z] is 4,470. Further, the MFR value (280° C., 10 kg) of the polyamide 6 composition (A-4) was 6 g/10 min.

[Example 5]
Production of polyamide 6 composition (A-5) Polyamide 6 composition was produced in the same manner as in the production of polyamide 6 composition (A-2) except that elastomer (b-1) was changed to elastomer (b-2). Pellets of product (A-5) were obtained (in the composition, polyamide 6 (a-1)/elastomer (b-2)/modified PTFE (c-1) = 83.8/14.9/0 .5 (mass%)). The total concentration [X] (μeq/g) of carboxyl groups and acid anhydride groups possessed by the elastomer (b-2) of this material is 200 μeq/g, and 100 mass of the aliphatic polyamide resin composition of the elastomer (b-2) is %, the content [Y] (mass %) is 14.9 mass %, and the content [Z] (mass %) of the modified PTFE (c-1) with respect to 100 mass % of the aliphatic polyamide resin composition is 0. .5% by mass, and [X]×[Y]×[Z] is 1,490. Further, the MFR value (280° C., 10 kg) of the polyamide 6 composition (A-5) was 11 g/10 min.

[Example 6]
Production of polyamide 6 composition (A-6) Polyamide 6 composition was produced in the same manner as in the production of polyamide 6 composition (A-3) except that elastomer (b-1) was changed to elastomer (b-2). Pellets of product (A-6) were obtained (in the composition, polyamide 6 (a-1)/elastomer (b-2)/modified PTFE (c-1) = 83.3/14.9/1 .0 (mass%)). The total concentration [X] (μeq/g) of carboxyl groups and acid anhydride groups possessed by the elastomer (b-2) of this material is 200 μeq/g, and 100 mass of the aliphatic polyamide resin composition of the elastomer (b-2) is %, the content [Y] (mass %) is 14.9 mass %, and the content [Z] (mass %) of the modified PTFE (c-1) with respect to 100 mass % of the aliphatic polyamide resin composition is 1. .0% by mass, and [X]×[Y]×[Z] is 2,980. Further, the MFR value (280° C., 10 kg) of the polyamide 6 composition (A-6) was 4 g/10 min.

[Example 7]
Production of polyamide 6/12 composition (A-7) In the production of polyamide 6 composition (A-2), polyamide 6 (a-1) was changed to polyamide 6/12 (a-2), and elastomer (b -1) by changing the amount of polyamide 6/12 (a-2)/elastomer (b-1)/modified PTFE (c-1) = 79.5/20/0.5 (mass ratio). Pellets of polyamide 6/12 composition (A-7) were obtained in the same manner except that (in the composition, polyamide 6/12 (a-2)/elastomer (b-1)/modified PTFE (c-1) = 78.8/19.8/0.5 (mass%)). The total concentration [X] (μeq/g) of carboxyl groups and acid anhydride groups possessed by the elastomer (b-1) of this material is 100 μeq/g, and 100 mass of the aliphatic polyamide resin composition of the elastomer (b-1) is %, the content [Y] (mass%) is 19.8% by mass, and the content [Z] (mass%) of the modified PTFE (c-1) with respect to 100% by mass of the aliphatic polyamide resin composition is 0. .5% by mass, and [X]×[Y]×[Z] is 990. Further, the MFR value (280° C., 10 kg) of the polyamide 6/12 composition (A-7) was 13 g/10 min.

[Example 8]
Production of polyamide 6/66 composition (A-8) In the production of polyamide 6 composition (A-3), the same procedure was carried out except that polyamide 6 (a-1) was changed to polyamide 6/66 (a-3). By the method, pellets of polyamide 6/66 composition (A-8) were obtained (in the composition, polyamide 6/66 (a-3)/elastomer (b-1)/modified PTFE (c-1) )=83.3/14.9/1.0 (mass%)). The total concentration [X] (μeq/g) of carboxyl groups and acid anhydride groups possessed by the elastomer (b-1) of this material is 100 μeq/g, and 100 mass of the aliphatic polyamide resin composition of the elastomer (b-1) is %, the content [Y] (mass %) is 14.9 mass %, and the content [Z] (mass %) of the modified PTFE (c-1) with respect to 100 mass % of the aliphatic polyamide resin composition is 1. .0% by mass, and [X]×[Y]×[Z] is 1,490. Further, the MFR value (280° C., 10 kg) of the polyamide 6/66 composition (A-8) was 5 g/10 min.

[Comparative example 1]
Production of polyamide 6 composition (A-9) Polyamide 6 (a-1) was produced in the same manner as in the production of polyamide 6 composition (A-1) except that modified PTFE (c-1) was not used. / Elastomer (b-1) = 88/12 (mass ratio) pellets of polyamide 6 composition (A-9) were obtained (in the composition, polyamide 6 (a-1) / elastomer (b-1) = 87.3/11.9 (mass%)). Since the content [Z] (mass %) of modified PTFE (c) based on 100 mass % of the aliphatic polyamide resin composition is 0 mass %, [X] × [Y] × [Z] is 0. Become. Further, the MFR value (280° C., 10 kg) of the polyamide 6 composition (A-9) was 27 g/10 min.

[Comparative example 2]
Production of polyamide 6 composition (A-10) Polyamide 6 (a-1) was produced in the same manner as in the production of polyamide 6 composition (A-2) except that modified PTFE (c-1) was not used. Pellets of polyamide 6 composition (A-10) with /elastomer (b-1) = 85/15 (mass ratio) were obtained (in the composition, polyamide 6 (a-1) / elastomer (b-1) = 84.3/14.9 (mass%)). Since the content [Z] (mass %) of modified PTFE (c) based on 100 mass % of the aliphatic polyamide resin composition is 0 mass %, [X] × [Y] × [Z] is 0. Become. Further, the MFR value (280° C., 10 kg) of the polyamide 6 composition (A-10) was 21 g/10 min.

[Comparative example 3]
Production of polyamide 6 composition (A-11) Polyamide 6 (a-1)/ Pellets of polyamide 6 composition (A-11) with elastomer (b-1) = 80/20 (mass ratio) were obtained (in the composition, polyamide 6 (a-1)/elastomer (b-1) = 79 .3/19.8 (mass%)). Since the content [Z] (mass %) of modified PTFE (c) based on 100 mass % of the aliphatic polyamide resin composition is 0 mass %, [X] × [Y] × [Z] is 0. Become. Further, the MFR value (280° C., 10 kg) of the polyamide 6 composition (A-11) was 15 g/10 min.

[Comparative example 4]
Production of polyamide 6 composition (A-12) In the production of polyamide 6 composition (A-9), elastomer (b-1) was changed to elastomer (b-2), and the amount of (b-2) was changed. Pellets of polyamide 6 composition (A-12) were obtained in the same manner except that polyamide 6 (a-1)/elastomer (b-2) = 90/10 (mass ratio) (composition Among them, polyamide 6 (a-1)/elastomer (b-2) = 89.2/9.9 (mass%)). Since the content [Z] (mass %) of modified PTFE (c) based on 100 mass % of the aliphatic polyamide resin composition is 0 mass %, [X] × [Y] × [Z] is 0. Become. Further, the MFR value (280° C., 10 kg) of the polyamide 6 composition (A-12) was 17 g/10 min.

[Comparative example 5]
Production of polyamide 6 composition (A-13) In production of polyamide 6 composition (A-12), the amount of elastomer (b-2) was changed, and polyamide 6 (a-1)/elastomer (b-2) = Pellets of polyamide 6 composition (A-13) were obtained in the same manner except that the mass ratio was 85/15 (in the composition, polyamide 6 (a-1)/elastomer (b-2)). =84.3/14.9 (mass%)). Since the content [Z] (mass %) of modified PTFE (c) based on 100 mass % of the aliphatic polyamide resin composition is 0 mass %, [X] × [Y] × [Z] is 0. Become. Further, the MFR value (280° C., 10 kg) of the polyamide 6 composition (A-13) was 4 g/10 min.

[Comparative example 6]
Production of polyamide 6 composition (A-14) Polyamide 6 (a-1)/modified polyamide 6 composition (A-1) was produced in the same manner except that the elastomer (b-1) was not used. Pellets of a polyamide 6 composition (A-14) with modified PTFE (c-1) = 99/1 (mass ratio) were obtained (in the composition, polyamide 6 (a-1)/modified PTFE (c-1) was 1) = 98.2/1.0 (mass%)). The total concentration [X] (μeq/g) of carboxyl groups and acid anhydride groups possessed by the elastomer (b) and the content [Y] (mass %) based on 100 mass % of the aliphatic polyamide resin composition of the elastomer (b) are Since it is 0% by mass, [X]×[Y]×[Z] is 0. Further, the MFR value (280°C, 10 kg) of the polyamide 6 composition (A-14) was 25 g/10 min.

[Comparative Example 7]
Production of polyamide 6/12 composition (A-15) Polyamide 6/12 composition (A-7) was produced using the same method except that modified PTFE (c-1) was not used. Pellets of polyamide 6/12 composition (A-15) with elastomer 12(a-2)/elastomer (b-1) = 80/20 (mass ratio) were obtained (in the composition, polyamide 6/12(a-1) 2)/elastomer (b-1) = 79.3/19.8 (mass%)). Since the content [Z] (mass %) of modified PTFE (c) based on 100 mass % of the aliphatic polyamide resin composition is 0 mass %, [X] × [Y] × [Z] is 0. Become. Further, the MFR value (280° C., 10 kg) of the polyamide 6/12 composition (A-15) was 23 g/10 min.

[Comparative example 8]
Production of polyamide 6/66 composition (A-16) Polyamide 6/66 composition (A-8) was produced using the same method except that modified PTFE (c-1) was not used. Pellets of polyamide 6/66 composition (A-16) with 66 (a-3)/elastomer (b-1) = 85/15 (mass ratio) were obtained (in the composition, polyamide 6/66 (a- 3)/elastomer (b-1) = 84.3/14.9 (mass%)). Since the content [Z] (mass %) of modified PTFE (c) based on 100 mass % of the aliphatic polyamide resin composition is 0 mass %, [X] × [Y] × [Z] is 0. Become. Further, the MFR value (280° C., 10 kg) of the polyamide 6/66 composition (A-16) was 9 g/10 min.

[Comparative Example 9]
Production of polyamide 6 composition (A-17) Same method except that modified PTFE (c-1) was changed to unmodified PTFE (c-2) in production of polyamide 6 composition (A-3) , pellets of polyamide 6 composition (A-17) with polyamide 6 (a-1) / elastomer (b-1) / modified PTFE (c-2) = 84/15/1 (mass ratio) (In the composition, polyamide 6 (a-1)/elastomer (b-1)/modified PTFE (c-2) = 83.3/14.9/1.0 (mass%)). The total concentration [X] (μeq/g) of carboxyl groups and acid anhydride groups possessed by the elastomer (b-1) of this material is 100 μeq/g, and 100 mass of the aliphatic polyamide resin composition of the elastomer (b-1) is %, the content [Y] (mass%) is 14.9% by mass, and the content [Z] (mass%) of the modified PTFE (c-2) with respect to 100% by mass of the aliphatic polyamide resin composition is 1. .0% by mass, and [X]×[Y]×[Z] is 1,490. Further, the MFR value (280° C., 10 kg) of the polyamide 6 composition (A-17) was 7 g/10 min.

[Tube extrusion molding]
Polyamide 6 compositions (A-1) to (A-17) were molded into a tubular body using a PAL32 (manufactured by Milfer) single-layer tube molding machine. Polyamide 6 compositions (A-1) to (A-6), (A-9) to (A-14), (A-17) and polyamide 6/66 compositions (A-8), (A-16) ), the extrusion molding machine was set at 270°C to 300°C, and the polyamide 6/12 compositions (A-7) and (A-15) were molded by setting the extrusion molding machine at 240°C to 260°C. went.
Table 1 shows the results of the tube forming. Note that the unit of composition in the table is mass %, and the entire resin composition is 100 mass %.

As is clear from the comparison between Examples 1 to 8 and Comparative Examples 1 to 5, 7, and 8, it can be seen that the inclusion of modified PTFE improves the tube molding stability and the appearance of the molded product.
Modified PTFE from comparison of Example 1 and Comparative Example 1, Examples 2 to 4 and Comparative Example 2, Examples 5 to 6 and Comparative Example 5, Example 7 and Comparative Example 7, and Example 8 and Comparative Example 8 It can be confirmed that the resin pressure in the extrusion molding machine is reduced by adding . When modified PTFE is added, the MFR value decreases, so even though the resin viscosity increases, the resin pressure decreases, which reduces the burden on the equipment and allows for long-time molding and high-speed molding. It can be said that it is suitable for molding.
A comparison between Examples 3 and 6 and Comparative Example 6 revealed that when the elastomer (b) was not included, the tube molding stability and the appearance of the molded product were not improved as in the case where the elastomer (b) was included.
A comparison between Example 3 and Comparative Example 9 shows that when unmodified PTFE (c-2) is used, the tube molding stability and the appearance of the molded product are not as good as when modified PTFE is used. No improvement or decrease in resin pressure could be confirmed.

[Blow molding]
Blow moldability was confirmed using a blow molding machine DA-50 model with an accumulation head manufactured by Plako Co., Ltd. The measurement conditions were a cylinder temperature of 240°C, a screw rotation speed of 40 rpm, a die diameter of 50 mm, a cylindrical 3-liter bottle mold, and a molded product at a mold temperature of 60°C.
The results of the blow molding are shown in Table 2. Note that the unit of composition in the table is mass %, and the entire resin composition is 100 mass %.

In all of Examples 1 to 8, the drawdown characteristics were 20 cm or less after 2 and 5 seconds, which was good. In particular, in Examples 1 to 3, 5, and 7 to 8 in which [X]×[Y]×[Z] was within the range of less than 2,900, the surface properties of the blow-molded products were also good.

Claims (6)

A blow molded article of an aliphatic polyamide resin composition comprising an aliphatic polyamide resin (a), an elastomer (b) and a modified fluorine-containing polymer (c),
The elastomer (b) is a maleic anhydride-modified ethylene/butene copolymer,
The modified fluorine-containing polymer (c) is a fluorine-containing polymer modified with (meth)acrylic acid and/or a derivative thereof,
The total concentration of carboxyl groups and acid anhydride groups that the elastomer (b) has is [X] (μeq/g), and the content of the elastomer (b) based on 100% by mass of the aliphatic polyamide resin composition is [Y] (mass %), [X] x [Y] A blow-molded product having a [Z] value of less than 2,900. The blow-molded article according to claim 1, wherein the aliphatic polyamide resin composition contains the elastomer (b) in an amount of 10% by mass or more and 25% by mass or less. The blow-molded article according to claim 1 or 2, wherein the aliphatic polyamide (a) has a ratio of the number of methylene groups to the number of amide groups of 8.0 or less. The aliphatic polyamide resin (a) is at least one homopolymer selected from the group consisting of polyamide 6 and polyamide 66, at least one type selected from the group consisting of polyamide 6/66, and polyamide 6/12. A blow molded article according to claim 1 or 2. The aliphatic polyamide resin (a) contains polycaproamide (polyamide 6),
The blow molded article according to any one of claims 1 to 4, which has an MFR (280°C, 10 kg) of 10 g/10 minutes or more and 20 g/10 minutes or less, as measured by a method based on ISO 1133. The blow molded article according to any one of claims 1 to 5, which is a hollow molded article.