JP5929621B2 - Polyether polyamide composition - Google Patents

Description

  The present invention relates to a polyether polyamide composition, and more particularly to a polyether polyamide composition suitable as a material for automobile parts, electrical parts, electronic parts and the like.

  Rubber with a chemical crosslinking point by vulcanization cannot be recycled and has a high specific gravity. Thermoplastic elastomers, on the other hand, have a phase separation structure in which the physical cross-linking points due to crystals are hard segments and the amorphous portions are soft segments, so they can be easily melt-molded, recycled, and low specific gravity. It has the feature of being. Therefore, it attracts attention in the fields of automobile parts, electrical / electronic parts, sporting goods and the like.

  As the thermoplastic elastomer, various thermoplastic elastomers such as polyolefin, polyurethane, polyester, polyamide, polystyrene, and polyvinyl chloride have been developed. Among them, polyurethane-based, polyester-based, and polyamide-based thermoplastic elastomers are known as elastomers having relatively excellent heat resistance.

  Above all, polyamide elastomers are excellent in flexibility, low specific gravity, friction and wear resistance, elasticity, bending fatigue resistance, low temperature characteristics, molding processability, and chemical resistance, so tubes, hoses, sporting goods, seals, Widely used as a material for packing, automobile parts, electrical parts, electronic parts, etc.

  As the polyamide elastomer, a polyether polyamide elastomer having a polyamide block as a hard segment and a polyether block as a soft segment is known. For example, Patent Documents 1 and 2 disclose polyether polyamide elastomers based on aliphatic polyamides such as polyamide 12.

JP 2004-161964 A JP 2004-346274 A

  In the polyether polyamide elastomer disclosed in Patent Documents 1 and 2, an aliphatic polyamide such as polyamide 12 is used as the polyamide component. However, since the polyamide component has a low melting point, it is used in a high temperature environment. Then, the heat resistance is insufficient.

  On the other hand, polyamides containing a xylylene group in the polymer main chain are also known. Polyamide containing a xylylene group in the polymer main chain is characterized by higher rigidity than aliphatic polyamides such as nylon 6, but it is structurally easy to generate radicals at the benzylmethylene position, so it has thermal stability and heat resistance. Aging property is insufficient.

  The problem to be solved by the present invention is to provide a polyether polyamide composition that maintains the melt-formability, toughness, flexibility and rubber-like properties of a polyamide elastomer and is excellent in thermal stability and heat aging resistance. It is to be.

（式中、ｘ＋ｚは１〜６０、ｙは１〜５０を表し、Ｒ¹はプロピレン基を表す。）
＜２＞上記＜１＞に記載のポリエーテルポリアミド組成物を含む成形品。 The present invention provides the following polyether polyamide composition and molded article.
<1> The diamine structural unit is derived from the polyetherdiamine compound (a-1) and xylylenediamine (a-2) represented by the following general formula (1), and the dicarboxylic acid structural unit has 4 to 20 carbon atoms. A polyether polyamide composition comprising a polyether polyamide (A) derived from an α, ω-linear aliphatic dicarboxylic acid and a stabilizer (B).

(In the formula, x + z represents 1 to 60, y represents 1 to 50, and R ¹ represents a propylene group.)
<2> A molded article comprising the polyether polyamide composition according to the above <1>.

  The polyether polyamide composition of the present invention retains the melt moldability, toughness, flexibility and rubber-like properties of existing polyamide elastomers, and is excellent in thermal stability and heat aging resistance.

（式中、ｘ＋ｚは１〜６０、ｙは１〜５０を表し、Ｒ¹はプロピレン基を表す。） [Polyether polyamide composition]
The polyether polyamide composition of the present invention is derived from the polyetherdiamine compound (a-1) and xylylenediamine (a-2) whose diamine structural unit is represented by the following general formula (1), and is a dicarboxylic acid structural unit. Includes a polyether polyamide (A) derived from an α, ω-linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms and a stabilizer (B).

(In the formula, x + z represents 1 to 60, y represents 1 to 50, and R ¹ represents a propylene group.)

<Polyether polyamide (A)>
The polyether polyamide (A) is derived from the polyetherdiamine compound (a-1) and xylylenediamine (a-2) whose diamine structural unit is represented by the above general formula (1), and the dicarboxylic acid structural unit is carbon. It is derived from an α, ω-linear aliphatic dicarboxylic acid having a number of 4 to 20. By using the polyether polyamide (A), a polyether polyamide composition excellent in mechanical properties such as flexibility and tensile elongation at break can be obtained.

  The diamine structural unit constituting the polyether polyamide (A) is derived from the polyether diamine compound (a-1) and xylylenediamine (a-2) represented by the general formula (1).

(Polyetherdiamine compound (a-1))
The diamine structural unit constituting the polyether polyamide (A) includes a structural unit derived from the polyether diamine compound (a-1) represented by the general formula (1). The numerical value of (x + z) in the general formula (1) is 1 to 60, preferably 2 to 40, more preferably 2 to 30, and still more preferably 2 to 20. Moreover, the numerical value of y is 1-50, Preferably it is 1-40, More preferably, it is 1-30, More preferably, it is 1-20. When the values of x, y, and z are larger than the above ranges, the compatibility of the oligomer or polymer composed of xylylenediamine and dicarboxylic acid generated during the reaction of the melt polymerization is lowered, and the polymerization reaction is difficult to proceed.
Moreover, all R < ¹ > in the said General formula (1) represents a propylene group. The structure of the oxypropylene group represented by —OR ¹ — may be any of —OCH ₂ CH ₂ CH ₂ —, —OCH (CH ₃ ) CH ₂ —, and —OCH ₂ CH (CH ₃ ) —. .

  The weight average molecular weight of the polyetherdiamine compound (a-1) is preferably 180 to 5700, more preferably 200 to 4000, still more preferably 300 to 3000, still more preferably 400 to 2000, and still more preferably 500 to 1800. It is. When the average molecular weight of the polyetherdiamine compound is within the above range, a polymer that exhibits functions as an elastomer such as flexibility and rubber elasticity can be obtained.

(Xylylenediamine (a-2))
The diamine structural unit constituting the polyether polyamide (A) includes a structural unit derived from xylylenediamine (a-2). The xylylenediamine (a-2) is preferably metaxylylenediamine, paraxylylenediamine, or a mixture thereof, metaxylylenediamine, or a mixture of metaxylylenediamine and paraxylylenediamine. It is more preferable.
When xylylenediamine (a-2) is derived from metaxylylenediamine, the resulting polyether polyamide is excellent in flexibility, crystallinity, melt moldability, molding processability, and toughness.
When xylylenediamine (a-2) is derived from a mixture of metaxylylenediamine and paraxylylenediamine, the resulting polyether polyamide has flexibility, crystallinity, melt moldability, moldability, and toughness. Excellent, high heat resistance and high elastic modulus.

  When a mixture of metaxylylenediamine and paraxylylenediamine is used as xylylenediamine (a-2), the ratio of paraxylylenediamine to the total amount of metaxylylenediamine and paraxylylenediamine is preferably It is 90 mol% or less, More preferably, it is 1-80 mol%, More preferably, it is 5-70 mol%. If the ratio of paraxylylenediamine is within the above range, the melting point of the polyether polyamide obtained is preferable because it is not close to the decomposition temperature of the polyether polyamide.

  Ratio of structural unit derived from xylylenediamine (a-2) in diamine structural unit, that is, total amount of polyetherdiamine compound (a-1) and xylylenediamine (a-2) constituting diamine structural unit The ratio of xylylenediamine (a-2) to is preferably 50 to 99.8 mol%, more preferably 50 to 99.5 mol%, still more preferably 50 to 99 mol%. If the proportion of the structural unit derived from xylylenediamine (a-2) in the diamine structural unit is within the above range, the resulting polyether polyamide is excellent in melt moldability, and further, a machine such as strength and elastic modulus. Excellent physical properties.

The diamine structural unit constituting the polyether polyamide (A) is derived from the polyether diamine compound (a-1) and xylylenediamine (a-2) represented by the general formula (1) as described above. However, if it is a range which does not impair the effect of this invention, you may include the structural unit derived from another diamine compound.
Examples of the diamine compound that can constitute a diamine constituent unit other than the polyetherdiamine compound (a-1) and xylylenediamine (a-2) include tetramethylenediamine, pentamethylenediamine, 2-methylpentanediamine, hexamethylenediamine, Aliphatic diamines such as heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, dodecamethylenediamine, 2,2,4-trimethyl-hexamethylenediamine, 2,4,4-trimethylhexamethylenediamine; 3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, bis (4-aminocyclohexyl) methane, 2,2-bis (4 -A Nocyclohexyl) propane, bis (aminomethyl) decalin, alicyclic diamines such as bis (aminomethyl) tricyclodecane; aromatic rings such as bis (4-aminophenyl) ether, paraphenylenediamine, bis (aminomethyl) naphthalene Examples of diamines having ss are not limited thereto.

(Dicarboxylic acid structural unit)
The dicarboxylic acid structural unit constituting the polyether polyamide (A) is derived from an α, ω-linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms. Examples of the α, ω-linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms include succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, 1,10-decanedicarboxylic acid, 1, 11-undecanedicarboxylic acid, 1,12-dodecanedicarboxylic acid and the like can be exemplified, but among these, at least one selected from the group consisting of adipic acid and sebacic acid is preferably used from the viewpoint of crystallinity and high elasticity. These dicarboxylic acids may be used alone or in combination of two or more.

The dicarboxylic acid structural unit constituting the polyether polyamide (A) is derived from the α, ω-linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms as described above, but within the range not impairing the effect of the present invention. If it exists, you may include the structural unit derived from other dicarboxylic acid.
Examples of dicarboxylic acids that can constitute dicarboxylic acid structural units other than α, ω-linear aliphatic dicarboxylic acids having 4 to 20 carbon atoms include aliphatic dicarboxylic acids such as oxalic acid and malonic acid; terephthalic acid, isophthalic acid, 2 Aromatic dicarboxylic acids such as 1,6-naphthalenedicarboxylic acid and the like can be exemplified, but are not limited thereto.
When a mixture of an α, ω-linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms and isophthalic acid is used as the dicarboxylic acid component, the molding processability of the polyether polyamide (A) is improved, and the glass transition The temperature rises, thereby improving the heat resistance. The molar ratio of α, ω-linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms and isophthalic acid (α, ω-linear aliphatic dicarboxylic acid / isophthalic acid having 4 to 20 carbon atoms) is 50/50 to 99/1 is preferable, and 70/30 to 95/5 is more preferable.

(Physical properties of polyether polyamide (A))
The polyether polyamide (A) has a highly crystalline polyamide block formed from xylylenediamine (a-2) and an α, ω-linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms as a hard segment. By using the polyether block derived from the etherdiamine compound (a-1) as a soft segment, it is excellent in melt moldability and moldability. Furthermore, the obtained polyether polyamide is excellent in toughness, flexibility, crystallinity, heat resistance and the like.

  The relative viscosity of the polyether polyamide (A) is preferably in the range of 1.1 to 3.0, more preferably in the range of 1.1 to 2.9 from the viewpoints of moldability and melt mixing with other resins. More preferably, it is in the range of 1.1 to 2.8. The relative viscosity is measured by the method described in the examples.

  The melting point of the polyether polyamide (A) is preferably in the range of 170 to 270 ° C, more preferably in the range of 175 to 270 ° C, still more preferably 180 to 270 ° C, and still more preferably 180 to 260 ° C, from the viewpoint of heat resistance. Range. The melting point is measured by the method described in the examples.

  From the viewpoint of flexibility, the tensile elongation at break of the polyether polyamide (A) (measurement temperature: 23 ° C., humidity: 50% RH) is preferably 100% or more, more preferably 200% or more, still more preferably 250% or more, More preferably, it is 300% or more.

  The tensile modulus (measurement temperature: 23 ° C., humidity: 50% RH) of the polyether polyamide (A) is preferably 100 MPa or more, more preferably 200 MPa or more, still more preferably 300 MPa or more, from the viewpoint of flexibility and mechanical strength. Preferably it is 400 MPa or more, preferably 500 MPa or more.

(Production of polyether polyamide (A))
Manufacture of polyether polyamide (A) is not specifically limited, It can carry out by arbitrary methods and superposition | polymerization conditions. For example, a diamine component (a diamine such as a polyether diamine compound (a-1) and xylylenediamine (a-2)) and a dicarboxylic acid component (an α, ω-linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms) A polyether polyamide (A) can be produced by a method in which a salt comprising a dicarboxylic acid is heated in a pressurized state in the presence of water and polymerized in a molten state while removing added water and condensed water. Further, a diamine component (diamine such as polyether diamine compound (a-1) and xylylenediamine (a-2)) is a dicarboxylic acid component in a molten state (α, ω-linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms). The polyether polyamide (A) can also be produced by a method in which it is directly added to a dicarboxylic acid such as an acid and polycondensed under normal pressure. In this case, in order to keep the reaction system in a uniform liquid state, the diamine component is continuously added to the dicarboxylic acid component, and the reaction system is heated up so that the reaction temperature does not fall below the melting point of the generated oligoamide and polyamide. However, polycondensation proceeds.
At this time, among the diamine components, the polyether diamine compound (a-1) may be previously charged in the reaction tank together with the dicarboxylic acid component. By preparing the polyether diamine compound (a-1) in the reaction vessel in advance, thermal degradation of the polyether diamine compound (a-1) can be suppressed. Also in that case, in order to keep the reaction system in a uniform liquid state, a diamine component other than the polyether diamine compound (a-1) is continuously added to the dicarboxylic acid component, and during this time, an oligoamide and a polyamide that generate a reaction temperature. The polycondensation proceeds while the temperature of the reaction system is raised so that it does not fall below the melting point.

  Diamine component (diamine such as polyether diamine compound (a-1) and xylylenediamine (a-2)) and dicarboxylic acid component (dicarboxylic such as α, ω-linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms) The molar ratio (diamine component / dicarboxylic acid component) to (acid) is preferably in the range of 0.9 to 1.1, more preferably in the range of 0.93 to 1.07, and still more preferably in the range of 0.95 to 1. The range is 05, more preferably 0.97 to 1.02. If the molar ratio is within the above range, high molecular weight tends to proceed.

  The polymerization temperature is preferably 150 to 300 ° C, more preferably 160 to 280 ° C, still more preferably 170 to 270 ° C. When the polymerization temperature is within the above temperature range, the polymerization reaction proceeds rapidly. In addition, since thermal decomposition of monomers, oligomers in the middle of polymerization, polymers, and the like hardly occurs, the properties of the obtained polymer are good.

  The polymerization time is usually 1 to 5 hours after the diamine component starts to be dropped. By setting the polymerization time within the above range, the molecular weight of the polyether polyamide (A) can be sufficiently increased, and coloring of the obtained polymer can be suppressed.

  The polyether polyamide (A) is preferably produced by a melt polycondensation (melt polymerization) method by adding a phosphorus atom-containing compound. As the melt polycondensation method, a method in which a diamine component is dropped into a dicarboxylic acid component melted at normal pressure and polymerized in a molten state while removing condensed water is preferable.

  In the polycondensation system of the polyether polyamide (A), a phosphorus atom-containing compound can be added as long as the characteristics are not inhibited. Phosphorus atom-containing compounds that can be added include dimethylphosphinic acid, phenylmethylphosphinic acid, hypophosphorous acid, sodium hypophosphite, potassium hypophosphite, lithium hypophosphite, ethyl hypophosphite, phenylphosphonite. Acid, sodium phenylphosphonite, potassium phenylphosphonite, lithium phenylphosphonite, ethyl phenylphosphonite, phenylphosphonic acid, ethylphosphonic acid, sodium phenylphosphonate, potassium phenylphosphonate, lithium phenylphosphonate, phenyl Examples include diethyl phosphonate, sodium ethylphosphonate, potassium ethylphosphonate, phosphorous acid, sodium hydrogen phosphite, sodium phosphite, triethyl phosphite, triphenyl phosphite, pyrophosphorous acid, etc. Special Hypophosphite metal salts such as sodium hypophosphite, potassium hypophosphite, and lithium hypophosphite are preferably used because they are highly effective in promoting the amidation reaction and have excellent anti-coloring effects. Sodium phosphite is preferred. The phosphorus atom-containing compounds that can be used in the present invention are not limited to these compounds. The addition amount of the phosphorus atom-containing compound added to the polycondensation system is preferably 1 to 1000 ppm, more preferably 5 to 1000 ppm, in terms of phosphorus atom concentration in the polyether polyamide, from the viewpoint of good appearance and moldability. More preferably, it is 10 to 1000 ppm.

  Moreover, it is preferable to add an alkali metal compound in combination with the phosphorus atom-containing compound into the polycondensation system of the polyether polyamide (A). To prevent coloring of the polymer during polycondensation, a sufficient amount of the phosphorus atom-containing compound needs to be present, but in some cases it may lead to gelation of the polymer, so that the amidation reaction rate is adjusted. In addition, it is preferable to coexist an alkali metal compound. As the alkali metal compound, an alkali metal hydroxide or an alkali metal acetate is preferable. Examples of the alkali metal compound that can be used in the present invention include lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, lithium acetate, sodium acetate, potassium acetate, rubidium acetate, cesium acetate, and the like. However, it can be used without being limited to these compounds. When an alkali metal compound is added to the polycondensation system, the value obtained by dividing the number of moles of the compound by the number of moles of the phosphorus atom-containing compound is preferably 0.5 to 1, more preferably 0.8. It is 55-0.95, More preferably, it is 0.6-0.9. Within the above range, the effect of suppressing the promotion of the amidation reaction of the phosphorus atom-containing compound is moderate, so that the polycondensation reaction rate decreases due to excessive suppression of the reaction, the thermal history of the polymer increases, and the polymer An increase in gelation of can be avoided.

  The sulfur atom concentration of the polyether polyamide (A) is preferably 1 to 200 ppm, more preferably 10 to 150 ppm, and still more preferably 20 to 100 ppm. Within the above range, not only can the increase in the yellowness (YI value) of the polyether polyamide during production be suppressed, but also an increase in the YI value during melt molding of the polyether polyamide can be suppressed. The YI value of the molded product thus obtained can be lowered.

  Further, when sebacic acid is used as the dicarboxylic acid, the sulfur atom concentration is preferably 1 to 500 ppm, more preferably 1 to 200 ppm, still more preferably 10 to 150 ppm, and particularly preferably 20 to 100 ppm. . Within the above range, an increase in the YI value when polymerizing the polyether polyamide can be suppressed. Moreover, the increase in the YI value when the polyether polyamide is melt-molded can be suppressed, and the YI value of the obtained molded product can be lowered.

  Similarly, when using sebacic acid as dicarboxylic acid, it is preferable that the sodium atom concentration is 1-500 ppm, More preferably, it is 10-300 ppm, More preferably, it is 20-200 ppm. Within the above range, the reactivity when synthesizing the polyether polyamide is good, it is easy to control to an appropriate molecular weight range, and furthermore, the amount of alkali metal compound to be blended for the purpose of adjusting the amidation reaction rate described above can be reduced. Can be reduced. In addition, the viscosity increase can be suppressed when the polyether polyamide is melt-molded, and the moldability is good and the generation of kogation during the molding process can be suppressed, so the quality of the resulting molded product tends to be good. is there.

  Such sebacic acid is preferably derived from a plant. Since plant-derived sebacic acid contains sulfur compounds and sodium compounds as impurities, polyether polyamides having units derived from plant-derived sebacic acid as constituent units have a YI value without adding an antioxidant. And the YI value of the obtained molded product is low. Moreover, it is preferable to use plant-derived sebacic acid without excessive purification of impurities. Since it is not necessary to purify excessively, it is advantageous in terms of cost.

  99-100 mass% is preferable, as for the purity of sebacic acid in the case of plant origin, 99.5-100 mass% is more preferable, and 99.6-100 mass% is still more preferable. Within this range, the quality of the resulting polyether polyamide is good, and it is preferable because it does not affect the polymerization.

For example, the other dicarboxylic acid (1,10-decamethylene dicarboxylic acid and the like) contained in sebacic acid is preferably 0 to 1% by mass, more preferably 0 to 0.7% by mass, and 0 to 0.6% by mass. Is more preferable. Within this range, the quality of the resulting polyether polyamide is good, and it is preferable because it does not affect the polymerization.
The monocarboxylic acid (octanoic acid, nonanoic acid, undecanoic acid, etc.) contained in sebacic acid is preferably 0 to 1% by mass, more preferably 0 to 0.5% by mass, and 0 to 0.4% by mass. Further preferred. Within this range, the quality of the resulting polyether polyamide is good, and it is preferable because it does not affect the polymerization.

  The hue (APHA) of sebacic acid is preferably 100 or less, more preferably 75 or less, and still more preferably 50 or less. This range is preferable because the polyether polyamide obtained has a low YI value. In addition, APHA can be measured by the Standard Oils for the Analysis of Fats, Oils and Related Materials of the Japan Oil Chemistry Society (Japan Oil Chemist's Society).

  The polyether polyamide (A) obtained by melt polycondensation is once taken out, pelletized, and dried before use. In order to further increase the degree of polymerization, solid phase polymerization may be performed. As a heating device used in drying or solid-phase polymerization, a continuous heating drying device, a rotary drum type heating device called a tumble dryer, a conical dryer, a rotary dryer or the like, and a rotary blade inside a nauta mixer are used. Although a conical heating apparatus provided with can be used suitably, a well-known method and apparatus can be used without being limited to these.

<Stabilizer (B)>
The stabilizer (B) used in the present invention is preferably an amine compound (B1), an organic sulfur compound (B2), a phenol compound (B3), phosphorus, from the viewpoint of improving thermal stability and heat aging resistance. It is at least one selected from the group consisting of a system compound (B4) and an inorganic compound (B5). Furthermore, from the viewpoint of improving the processing stability, heat stability and heat aging resistance during melt molding, and from the viewpoint of appearance of the molded product, in particular, coloring prevention, the amine compound (B1), the organic sulfur compound (B2) and Particularly preferred is at least one selected from the group consisting of inorganic compounds (B5).

(Amine compound (B1))
As the amine compound (B1), an aromatic secondary amine compound is preferable, a compound having a diphenylamine skeleton, a compound having a phenylnaphthylamine skeleton, and a compound having a dinaphthylamine skeleton are more preferable, and a compound having a diphenylamine skeleton and phenyl A compound having a naphthylamine skeleton is more preferable.

Specifically, p, p′-dialkyldiphenylamine (carbon number of alkyl group: 8 to 14), octylated diphenylamine (for example, manufactured by BASF, trade name: IRGANOX 5057, manufactured by Ouchi Shinsei Chemical Co., Ltd.) Product name: available as NOCRACK AD-F), 4,4′-bis (α, α-dimethylbenzyl) diphenylamine (for example, Ouchi Shinsei Chemical Co., Ltd., product name: available as NOCRACK CD), p- (p-toluenesulfonylamide) diphenylamine (for example, Ouchi Shinsei Chemical Co., Ltd., trade name: available as NOCRACK TD), N, N′-diphenyl-p-phenylenediamine (for example, Ouchi Shinsei) Chemical Industry Co., Ltd., trade name: available as NOCRACK DP), N-phenyl-N′-isopropyl-p-phenylenediamine For example, Ouchi Shinsei Chemical Co., Ltd., trade name: available as NOCRACK 810-NA), N-phenyl-N ′-(1,3-dimethylbutyl) -p-phenylenediamine (for example, Ouchi Shinsei) Chemical Industry Co., Ltd., trade name: available as NOCRACK 6C), and N-phenyl-N ′-(3-methacryloyloxy-2-hydroxypropyl) -p-phenylenediamine (for example, Ouchi Shinsei Chemical Industry ( N-phenyl-1-naphthylamine (for example, Ouchi Shinsei Chemical Co., Ltd., trade name: Nocrack PA) And N, N′-di-2-naphthyl-p-phenylenediamine (for example, manufactured by Ouchi Shinsei Chemical Industry Co., Ltd., trade name: NOCRACK White) Compounds having a phenyl naphthylamine skeleton such as 2,2′-dinaphthylamine, 1,2′-dinaphthylamine, and compounds having a dinaphthylamine skeleton such as 1,1′-dinaphthylamine; Although a mixture can be illustrated, it is not limited to these.
Among these, 4,4′-bis (α, α-dimethylbenzyl) diphenylamine, N, N′-di-2-naphthyl-p-phenylenediamine and N, N′-diphenyl-p-phenylenediamine are preferable, N, N′-di-2-naphthyl-p-phenylenediamine and 4,4′-bis (α, α-dimethylbenzyl) diphenylamine are particularly preferred.

(Organic sulfur compound (B2))
As the organic sulfur compound (B2), a mercaptobenzimidazole compound, a dithiocarbamic acid compound, a thiourea compound and an organic thioacid compound are preferable, and a mercaptobenzimidazole compound and an organic thioacid compound are more preferable.

Specifically, 2-mercaptobenzimidazole (for example, Ouchi Shinsei Chemical Co., Ltd., trade name: available as NOCRACK MB), 2-mercaptomethylbenzimidazole (for example, Ouchi Shinsei Chemical Co., Ltd.) And a mercaptobenzimidazole compound such as a metal salt of 2-mercaptobenzimidazole; dilauryl-3,3′-thiodipropionate (for example, manufactured by API Corporation) Product name: DLTP “Yoshitomi”, manufactured by Sumitomo Chemical Co., Ltd., product name: SUMILIZER TPL-R), dimyristyl-3,3′-thiodipropionate (for example, product name manufactured by API Corporation) : DMTP “Yoshitomi”, manufactured by Sumitomo Chemical Co., Ltd., trade name: S Available as MILIZER TPM), distearyl-3,3′-thiodipropionate (for example, manufactured by API Corporation, trade name: DSTP “Yoshitomi”, manufactured by Sumitomo Chemical Co., Ltd., trade name: SUMILIZER TPS) Organic thioic acid compounds such as pentaerythritol tetrakis (3-laurylthiopropionate) (available from Sumitomo Chemical Co., Ltd., trade name: SUMILIZER TP-D); diethyldithiocarbamic acid Dithiocarbamic acid compounds such as metal salts and metal salts of dibutyldithiocarbamic acid; and 1,3-bis (dimethylaminopropyl) -2-thiourea (for example, manufactured by Ouchi Shinsei Chemical Co., Ltd., trade name: NOCRACK NS) -10-N) and tributylthio Thiourea-based compounds arsenide; or mixtures thereof may be cited, but is not limited thereto.
Among these, 2-mercaptobenzimidazole, 2-mercaptomethylbenzimidazole, dimyristyl-3,3′-thiodipropionate, distearyl-3,3′-thiodipropionate and pentaerythritol tetrakis (3-laurylthio) Propionate) is preferred, pentaerythritol tetrakis (3-laurylthiopropionate), 2-mercaptobenzimidazole, and dimyristyl-3,3′-thiodipropionate are more preferred, and pentaerythritol tetrakis (3-laurylthio). Propionate) is particularly preferred.
The molecular weight of the organic sulfur compound (B2) is usually 200 or more, preferably 500 or more, and the upper limit is usually 3,000.

It is preferable to use the amine compound (B1) and the organic sulfur compound (B2) in combination. By using these in combination, the heat aging resistance of the polyamide resin composition tends to be better than when used alone.
As a suitable combination of the amine compound (B1) and the organic sulfur compound (B2), 4,4′-bis (α, α-dimethylbenzyl) diphenylamine and N, N′-di-2-naphthyl-p- Selected from at least one amine compound (B1) selected from phenylenediamine, dimyristyl-3,3′-thiodipropionate, 2-mercaptomethylbenzimidazole, and pentaerythritol tetrakis (3-laurylthiopropionate) And a combination with at least one organic sulfur compound (B2). Furthermore, a combination in which the amine compound (B1) is N, N′-di-2-naphthyl-p-phenylenediamine and the organic sulfur compound (B2) is pentaerythritol tetrakis (3-laurylthiopropionate) is more. preferable.
Moreover, when using together an amine type compound (B1) and an organic sulfur type compound (B2), from a viewpoint of an improvement of heat aging resistance, it is content ratio (mass ratio) in the polyether polyamide composition of this invention, The amine compound (B1) / organic sulfur compound (B2) is preferably 0.05 to 15, more preferably 0.1 to 5, and still more preferably 0.2 to 2.

(Phenolic compound (B3))
Examples of the phenolic compound (B3) include 2,2′-methylenebis (4-methyl-6-t-butylphenol) (for example, available from AP Corporation, trade name: Yoshinox 425), 4, 4′-butylidenebis (6-t-butyl-3-methylphenol) (for example, manufactured by ADEKA Corporation, trade name: ADK STAB AO-40, manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumilizer BBM-S) ), 4,4′-thiobis (6-t-butyl-3-methylphenol) (for example, manufactured by Kawaguchi Chemical Industries, Ltd., trade name: available as Antage Crystal), 3,9-bis [2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl] -2,4, , 10-tetraoxaspiro [5.5] undecane (for example, manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumilizer GA-80, manufactured by ADEKA Corporation, trade name: available as ADK STAB AO-80), triethylene Glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate] (for example, available as BASF Corporation, trade name: Irganox® 245), 1,6-hexanediol -Bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (for example, available from BASF, trade name: Irganox 259), 2,4-bis- (n-octylthio) -6- (4-Hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine (eg BASF Manufactured, trade name: Irganox 565), pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (for example, product name: Irganox 1010, manufactured by BASF) Made by ADEKA, trade name: available as ADK STAB AO-60, 2,2-thio-diethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (for example, produced by BASF) , Trade name: available as Irganox 1035), octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (for example, manufactured by BASF, trade name: Irganox 1076, manufactured by ADEKA Corporation, product) Name: Available as ADK STAB AO-50), N, N'-F Samethylene bis (3,5-di-t-butyl-4-hydroxy-hydrocinnamamide) (for example, available from BASF, trade name: Irganox 1098), 3,5-di-t-butyl-4-hydroxy Benzylphosphonate-diethyl ester (for example, available from BASF, trade name: Irganox 1222), 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4 -Hydroxybenzyl) benzene (for example, manufactured by BASF, trade name: available as Irganox 1330), tris- (3,5-di-t-butyl-4-hydroxybenzyl) -isocyanurate (for example, manufactured by BASF, Product name: Irganox 3114, manufactured by ADEKA Corporation, product name: Acquired as ADK STAB AO-20 Possible), 2,4-bis [(octylthio) methyl] -o-cresol (for example, available as BASF AG, trade name: Irganox 1520), isooctyl-3- (3,5-di-t-butyl-4 -Hydroxyphenyl) propionate (for example, manufactured by BASF, trade name: available as Irganox 1135) and the like can be exemplified, but are not limited thereto.
Among these, octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 1,6-hexanediol-bis [3- (3,5-di-t-butyl-4- Hydroxyphenyl) propionate], pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], N, N′-hexamethylenebis (3,5-di-t-butyl- 4-hydroxy-hydrocinnamamide), 3,9-bis [2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl] -2 , 4,8,10-tetraoxaspiro [5.5] undecane and N, N′-hexamethylenebis (3,5-di-tert-butyl-4-hydroxy-hydrocin Hindered phenolic compound of Muamido) are preferred.

(Phosphorus compound (B4))
As the phosphorus compound (B4), a phosphite compound and a phosphonite compound are preferable.

  Examples of phosphite compounds include distearyl pentaerythritol diphosphite (for example, manufactured by ADEKA, trade name: ADK STAB PEP-8, manufactured by Johoku Chemical Industry Co., Ltd., trade name: JPP-2000). ), Dinonylphenyl pentaerythritol diphosphite (for example, manufactured by ADEKA, trade name: available as ADK STAB PEP-4C), bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite ( For example, manufactured by BASF, trade name: Irgafos 126, manufactured by ADEKA, trade name: ADKAPEP-24G), bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite (For example, ADEKA Corporation, trade name: Adekas Bis (2,6-di-t-butyl-4-ethylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-butyl-4-isopropylphenyl) penta Erythritol diphosphite, bis (2,4,6-tri-t-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-butyl-4-sec-butylphenyl) pentaerythritol diphosphite Bis (2,6-di-t-butyl-4-t-octylphenyl) pentaerythritol diphosphite, bis (2,4-dicumylphenyl) pentaerythritol diphosphite, etc. 2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,4-di Mill phenyl) pentaerythritol diphosphite (e.g., (Ltd.) ADEKA Corporation, trade name: ADK STAB PEP-45 available as) is preferable.

Examples of the phosphonite compound include tetrakis (2,4-di-t-butylphenyl) -4,4′-biphenylenediphosphonite (for example, available from BASF, trade name: Irgafos P-EPQ), Tetrakis (2,5-di-t-butylphenyl) -4,4′-biphenylenediphosphonite, tetrakis (2,3,4-trimethylphenyl) -4,4′-biphenylenediphosphonite, tetrakis (2, 3-dimethyl-5-ethylphenyl) -4,4′-biphenylenediphosphonite, tetrakis (2,6-di-t-butyl-5-ethylphenyl) -4,4′-biphenylenediphosphonite, tetrakis ( 2,3,4-tributylphenyl) -4,4′-biphenylenediphosphonite, tetrakis (2,4,6-tri-t-butylphenyl) Enyl) -4,4′-biphenylenediphosphonite and the like, and tetrakis (2,4-di-t-butylphenyl) -4,4′-biphenylenediphosphonite is particularly preferable.
Further, the combined use of a phenolic compound and a phosphorus compound is preferable because it exhibits an effect of improving the color tone.

(Inorganic compound (B5))
As the inorganic compound (B5), a copper compound and a halide are preferable.
The copper compound used as the inorganic compound (B5) is a copper salt of various inorganic acids or organic acids, and excludes halides described later. The copper may be either cuprous or copper, and specific examples thereof include copper chloride, copper bromide, copper iodide, copper phosphate, copper stearate, hydrotalcite, styreneite, pyro Examples include natural minerals such as light.
Examples of the halide used as the inorganic compound (B5) include alkali metal or alkaline earth metal halides; ammonium halides and quaternary ammonium halides of organic compounds; alkyl halides, halogens. Organic halides such as allyl iodide, and specific examples thereof include ammonium iodide, stearyltriethylammonium bromide, benzyltriethylammonium iodide, and the like. Among these, alkali metal halide salts such as potassium chloride, sodium chloride, potassium bromide, potassium iodide, sodium iodide and the like are preferable.

  A combined use of a copper compound and a halide, particularly a combined use of a copper compound and a halogenated alkali metal salt, is preferable because it exhibits excellent effects in terms of heat discoloration and weather resistance (light resistance). For example, when a copper compound is used alone, the molded product may be colored reddish brown by copper, and this coloring is not preferable depending on the application. In this case, discoloration to reddish brown can be prevented by using a copper compound and a halide together.

  The content of the stabilizer (B) in the polyether polyamide composition of the present invention is preferably 0.01-1 part by mass, more preferably 0.01-0. 8 parts by mass, more preferably 0.1 to 0.5 parts by mass. By setting the content to 0.01 parts by mass or more, the effect of improving thermal discoloration and improving weather resistance / light resistance can be sufficiently exerted, and by setting the content to 1 part by mass or less, the appearance of the molded product Defects and deterioration of mechanical properties can be suppressed.

<Other ingredients>
The polyether polyamide composition of the present invention includes a matting agent, an ultraviolet absorber, a nucleating agent, a plasticizer, a flame retardant, an antistatic agent, an anti-coloring agent, an anti-gelling agent, etc., as long as the properties are not inhibited. An additive can be mix | blended as needed.

  The polyether polyamide composition of the present invention can be blended with a thermoplastic resin such as a polyamide resin, a polyester resin, or a polyolefin resin, if necessary, as long as the characteristics are not impaired.

  Polyamide resins include polycaproamide (nylon 6), polyundecanamide (nylon 11), polydodecanamide (nylon 12), polytetramethylene adipamide (nylon 46), polyhexamethylene adipamide (nylon 66) , Polyhexamethylene azelamide (nylon 69), polyhexamethylene sebamide (nylon 610), polyundecamethylene adipamide (nylon 116), polyhexamethylene dodecamide (nylon 612), polyhexamethylene terephthalamide (Nylon 6T (T represents a terephthalic acid component unit; the same applies hereinafter)), polyhexamethylene isophthalamide (Nylon 6I (I represents an isophthalic acid component unit; the same applies hereinafter)), polyhexamethylene terephthalate Isophthalamide Nylon 6TI), polyheptamethylene terephthalamide (nylon 9T), polymetaxylylene adipamide (nylon MXD6 (MXD represents m-xylylenediamine component unit; the same applies hereinafter)), polymetaxylylene sebacamide ( Nylon MXD10), polyparaxylylene sebacamide (nylon PXD10 (PXD represents p-xylylenediamine component unit)), 1,3- or 1,4-bis (aminomethyl) cyclohexane and adipic acid. Polyamide resins obtained by polycondensation (nylon 1,3- / 1,4-BAC6 (BAC represents a bis (aminomethyl) cyclohexane component unit)) and copolymerized amides thereof can be used. .

  Examples of the polyester resin include polyethylene terephthalate resin, polyethylene terephthalate-isophthalate copolymer resin, polyethylene-1,4-cyclohexanedimethylene-terephthalate copolymer resin, polyethylene-2,6-naphthalene dicarboxylate resin, polyethylene-2,6. -Naphthalene dicarboxylate-terephthalate copolymer resin, polyethylene-terephthalate-4,4'-biphenyldicarboxylate copolymer resin, poly-1,3-propylene-terephthalate resin, polybutylene terephthalate resin, polybutylene-2,6- Naphthalene dicarboxylate resin. More preferable polyester resins include polyethylene terephthalate resin, polyethylene terephthalate-isophthalate copolymer resin, polybutylene terephthalate resin, and polyethylene-2,6-naphthalenedicarboxylate resin.

  Examples of the polyolefin resin include polyethylene such as low density polyethylene (LDPE), linear low density polyethylene (LLDPE), very low density polyethylene (VLDPE), medium density polyethylene (MDPE), and high density polyethylene (HDPE); Polypropylene such as a polymer, a random or block copolymer of propylene and ethylene or α-olefin; and a mixture of two or more of these. Most of polyethylene is a copolymer of ethylene and α-olefin. The polyolefin resin includes a modified polyolefin resin modified with a carboxyl group-containing monomer such as a small amount of acrylic acid, maleic acid, methacrylic acid, maleic anhydride, fumaric acid, and itaconic acid. The modification is usually performed by copolymerization or graft modification.

  By using the polyether polyamide composition of the present invention for at least a part of thermoplastic resins such as polyamide resin, polyester resin, polyolefin resin, etc., it is possible to obtain toughness and flexibility by molding methods such as injection molding, extrusion molding, blow molding and the like. A molded article having excellent properties and impact resistance can be obtained.

[Physical properties of polyether polyamide composition]
The relative viscosity of the polyether polyamide composition of the present invention is preferably in the range of 1.1 to 3.0, more preferably 1.1 to 2.9, from the viewpoints of moldability and melt mixing with other resins. More preferably, it is the range of 1.1-2.8. The relative viscosity is measured by the method described in the examples.

  The melting point of the polyether polyamide composition is preferably in the range of 170 to 270 ° C, more preferably in the range of 175 to 270 ° C, and still more preferably in the range of 180 to 270 ° C, from the viewpoint of heat resistance. The melting point is measured by the method described in the examples.

  The number average molecular weight (Mn) of the polyether polyamide composition is preferably in the range of 8,000 to 200,000, more preferably 9,000 to 150,000, from the viewpoints of moldability and melt mixing with other resins. The range is more preferably 10,000 to 100,000. The said number average molecular weight (Mn) is measured by the method as described in an Example.

In the polyether polyamide composition of the present invention, from the viewpoint of heat aging resistance, the tensile strength retention calculated by the following formula is preferably 75% or more, more preferably 85% or more, still more preferably 90% or more, Preferably it is 100% or more.
Tensile strength retention (%) = [Stress at break of film after heat treatment at 130 ° C. for 72 hours (MPa) / Stress at break of film before heat treatment at 130 ° C. for 72 hours (MPa)] × 100
Here, the stress at break of the film is measured by the method described in Examples.

[Production of Polyether Polyamide Composition]
The polyether polyamide composition of the present invention is obtained by blending the polyether polyamide (A) with the stabilizer (B) and other components. The blending method is not particularly limited, and a method of adding a stabilizer (B) or the like to the polyether polyamide (A) in a molten state in the reaction vessel, or a stabilizer (B) or the like for the polyether polyamide (A). Examples of the method include dry blending and melt-kneading using an extruder.
Examples of the method for melt-kneading the polyether polyamide composition of the present invention include a method for melt-kneading using various commonly used extruders such as a single-screw or twin-screw extruder, among these, A method using a twin screw extruder is preferred from the viewpoint of productivity, versatility and the like. At that time, the melt kneading temperature is preferably set in the range of not less than the melting point of the polyether polyamide (A) and not more than 80 ° C. higher than the melting point, and more than 10 ° C. higher than the melting point of the component (A). It is more preferable to set the temperature within a range of 60 ° C. or higher. By setting the melt kneading temperature to be equal to or higher than the melting point of the polyether polyamide (A), solidification of the component (A) can be suppressed, and by setting the temperature to 80 ° C. or lower than the melting point, the component (A) Thermal degradation can be suppressed.
The residence time in melt-kneading is preferably adjusted to a range of 1 to 10 minutes, and more preferably adjusted to a range of 2 to 7 minutes. By making the residence time 1 minute or more, the dispersion of the polyether polyamide (A) and the stabilizer (B) becomes sufficient, and by making the residence time 10 minutes or less, the polyether polyamide (A) is thermally deteriorated. Can be suppressed.
The screw of the twin-screw extruder preferably has at least one reverse screw element portion and / or a kneading disc portion, and it is preferable to perform melt-kneading while partially retaining the polyether polyamide composition in the portion.
The melt-kneaded polyether polyamide composition may be directly extruded and formed into a molded product such as a film, or may be formed into various molded products by once performing pelletization and then performing extrusion molding or injection molding again.

[Molding]
The molded article of the present invention contains the polyether polyamide composition, and can be obtained by molding the polyether polyamide composition of the present invention into various forms by a conventionally known molding method. Examples of the molding method include injection molding, blow molding, extrusion molding, compression molding, vacuum molding, press molding, direct blow molding, rotational molding, sandwich molding, and two-color molding.
A molded article containing the polyether polyamide composition of the present invention has excellent thermal stability and heat aging resistance, and is suitable for automobile parts, electrical parts, electronic parts and the like. In particular, a hose, a tube, or a metal coating material is preferable as a molded product containing the polyamide resin composition.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these. In this example, various measurements were performed by the following methods.

1) Relative viscosity (ηr)
A 0.2 g sample was precisely weighed and dissolved in 20 ml of 96% sulfuric acid at 20-30 ° C. with stirring. After complete dissolution, 5 ml of the solution was quickly taken into a Cannon Fenceke viscometer, and left for 10 minutes in a thermostatic bath at 25 ° C., and then the drop time (t) was measured. Further, the dropping time (t ₀ ) of 96% sulfuric acid itself was measured in the same manner. The relative viscosity was calculated from t and t _{0 according} to the following equation.
Relative viscosity = t / t ₀

2) Number average molecular weight (Mn)
First, the sample was dissolved in a phenol / ethanol mixed solvent and a benzyl alcohol solvent, respectively, and the carboxyl end group concentration and amino end group concentration were determined by neutralization titration with hydrochloric acid and sodium hydroxide aqueous solution. The number average molecular weight was determined by the following formula from the quantitative values of the amino end group concentration and the carboxyl end group concentration.
Number average molecular weight = 2 × 1,000,000 / ([NH ₂ ] + [COOH])
[NH ₂ ]: Amino end group concentration (μeq / g)
[COOH]: Carboxyl end group concentration (μeq / g)

3) Differential scanning calorimetry (glass transition temperature, crystallization temperature and melting point)
The differential scanning calorific value was measured according to JIS K7121 and K7122. Using a differential scanning calorimeter (manufactured by Shimadzu Corporation, trade name: DSC-60), each sample was charged into a DSC measurement pan and heated to 300 ° C. at a temperature increase rate of 10 ° C./min in a nitrogen atmosphere. The measurement was performed after the pre-cooling pretreatment. The measurement conditions were a temperature rising rate of 10 ° C./min and holding at 300 ° C. for 5 minutes, and then a temperature falling rate of −5 ° C./min was measured up to 100 ° C., and the glass transition temperature Tg, crystallization temperature Tch and melting point Tm were Asked.

4) Tensile test (tensile modulus, tensile elongation at break and tensile strength retention)
(Measurement of tensile modulus and elongation at break)
The tensile modulus and tensile elongation at break were measured according to JIS K7161. The produced film having a thickness of about 100 μm was cut into 10 mm × 100 mm to obtain a test piece. Using a tensile tester (manufactured by Toyo Seiki Seisakusho Co., Ltd., Strograph), a tensile test was conducted under the conditions of a measurement temperature of 23 ° C., a humidity of 50% RH, a distance between chucks of 50 mm, and a tensile speed of 50 mm / min. Rate and tensile elongation at break were determined.

(Measurement of tensile strength retention)
First, the film was heat-treated at 130 ° C. for 72 hours with a hot air dryer. Next, the film before and after heat treatment was subjected to a tensile test according to JIS K7127, and the stress (MPa) at break was obtained. In addition, the apparatus uses a tensile tester (manufactured by Toyo Seiki Seisakusho Co., Ltd., Strograph), the test piece width is 10 mm, the distance between chucks is 50 mm, the tensile speed is 50 mm / min, the measurement temperature is 23 ° C., and the measurement is performed. The humidity was measured as 50% RH. The ratio of stress at break before and after heat treatment was defined as the tensile strength retention, and the tensile strength retention (%) was calculated from the following formula. Higher tensile strength retention means better heat aging resistance.
Tensile strength retention (%) = [Stress at break of film after heat treatment at 130 ° C. for 72 hours (MPa) / Stress at break of film before heat treatment at 130 ° C. for 72 hours (MPa)] × 100

5) Yellowness: YI value measurement The YI value was measured according to JIS K-7105. The produced film having a thickness of about 100 μm was cut into 50 mm × 50 mm to obtain a test piece. As the measuring device, a haze measuring device (manufactured by Nippon Denshoku Industries Co., Ltd., model: COH-300A) was used.

6) Sulfur atom concentration (unit: ppm)
Dicarboxylic acid or polyether polyamide was tableted with a press machine and subjected to X-ray fluorescence analysis (XRF). A fluorescent X-ray analyzer (trade name: ZSX Primus, manufactured by Rigaku Corporation) was used, and an Rh tube (4 kW) was used as the tube. A polypropylene film was used as the analysis window film, and an EZ scan was performed in an irradiation area of 30 mmφ under a vacuum atmosphere.

Example 1-1
A reaction vessel having a volume of about 3 L equipped with a stirrer, a nitrogen gas inlet, and a condensed water outlet was charged with 584.60 g of adipic acid, 0.6613 g of sodium hypophosphite monohydrate and 0.4606 g of sodium acetate, The interior was sufficiently purged with nitrogen, and then melted at 170 ° C. while supplying nitrogen gas at 20 ml / min. While gradually raising the temperature to 260 ° C., 489.34 g of metaxylylenediamine (MXDA) (manufactured by Mitsubishi Gas Chemical Co., Ltd.) and polyether diamine (manufactured by HUNTSMAN, USA, trade name: ED-900) 359. 28 g of the mixed liquid was dropped and polymerization was performed for about 2 hours to obtain a polyether polyamide. ηr = 1.35, [COOH] = 73.24 μeq / g, [NH ₂ ] = 45.92 μeq / g, Mn = 16784, Tg = 42.1 ° C., Tch = 89.7 ° C., Tm = 227.5 ° C.
Next, 100 parts by mass of the obtained polyether polyamide and N, N′-di-2-naphthyl-p-phenylenediamine (manufactured by Ouchi Shinsei Chemical Co., Ltd., trade name: NOCRACK White, stable) as a stabilizer (B1-1)) is dry blended and extruded at a temperature of 260 ° C. in a twin screw extruder equipped with a screw having a diameter of 30 mm and a T die, and an unstretched film having a thickness of about 100 μm is formed. Obtained.
The said tensile test was done using the obtained film. The results are shown in Table 1.

Examples 1-2 to 1-5
A film was obtained in the same manner as in Example 1-1 except that the type of stabilizer in Example 1-1 was changed as described in Table 1, and the tensile test was performed. The results are shown in Table 1.

Comparative Example 1-1
A reaction vessel equipped with a stirrer, a nitrogen gas inlet, and a condensed water outlet was charged with 584.5 g of adipic acid, 0.6210 g of sodium hypophosphite monohydrate and 0.4325 g of sodium acetate in a vessel. The interior was sufficiently purged with nitrogen, and then melted at 170 ° C. while supplying nitrogen gas at 20 ml / min. While gradually raising the temperature to 260 ° C., 544.80 g of metaxylylenediamine (MXDA) (manufactured by Mitsubishi Gas Chemical Co., Ltd.) was added dropwise thereto and polymerization was performed for about 2 hours to obtain polyamide. ηr = 2.10, [COOH] = 104.30 μeq / g, [NH ₂ ] = 24.58 μeq / g, Mn = 15500, Tg = 86.1 ° C., Tch = 153.0 ° C., Tm = 239.8 ° C.
The obtained polyamide was extruded at a temperature of 260 ° C. to prepare an unstretched film having a thickness of about 100 μm.
The said tensile test was done using the obtained film. The results are shown in Table 1.

Comparative Example 1-2
The polyether polyamide obtained in Example 1-1 was extruded at a temperature of 260 ° C. to produce an unstretched film having a thickness of about 100 μm.
The said tensile test was done using the obtained film. The results are shown in Table 1.

The abbreviations in the table are as follows.
ED-900: Polyether diamine manufactured by HUNTSMAN, USA. According to the catalog of HUNTSMAN, USA, the approximate number of x + z in the general formula (1) is 6.0, the approximate number of y is 12.5, and the approximate weight average molecular weight is 900.
Stabilizer (B1-1): N, N′-di-2-naphthyl-p-phenylenediamine (manufactured by Ouchi Shinsei Chemical Co., Ltd., trade name: NOCRACK White)
Stabilizer (B1-2): 4,4′-bis (α, α-dimethylbenzyl) diphenylamine (Ouchi Shinsei Chemical Co., Ltd., trade name: NOCRACK CD)
Stabilizer (B2-1): Pentaerythritol tetrakis (3-lauryl thiopropionate) (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumilyzer TP-D)
Stabilizer (B2-2): 2-mercaptobenzimidazole (Ouchi Shinsei Chemical Co., Ltd., trade name: NOCRACK MB)
Stabilizer (B3-1): 3,9-bis [2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl] -2,4 , 8,10-tetraoxaspiro [5.5] undecane (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumilizer GA-80)
Stabilizer (B3-2): N, N′-hexamethylenebis (3,5-di-tert-butyl-4-hydroxy-hydrocinnamamide) (manufactured by BASF, trade name: Irganox 1098)
Stabilizer (B4-1): Bis (2,4-dicumylphenyl) pentaerythritol diphosphite (manufactured by ADEKA CORPORATION, trade name: ADK STAB PEP-45)
Stabilizer (B4-2): Tetrakis (2,4-di-t-butylphenyl) -4,4'-biphenylenediphosphonite (3,5-di-t-butyl-4-hydroxy-hydrocinnamamide (Product name: Irgafos P-EPQ, manufactured by BASF)
Stabilizer (B5-1): Sodium iodide (Wako Pure Chemical Industries, Ltd.)
Stabilizer (B5-2): Potassium chloride (Wako Pure Chemical Industries, Ltd.)

Example 2-1
A reaction vessel having a volume of about 3 L equipped with a stirrer, a nitrogen gas inlet, and a condensed water outlet was charged with 584.60 g of adipic acid, 0.6626 g of sodium hypophosphite monohydrate and 0.4616 g of sodium acetate. The interior was sufficiently purged with nitrogen, and then melted at 170 ° C. while supplying nitrogen gas at 20 ml / min. While gradually raising the temperature to 260 ° C., 343.22 g of metaxylylenediamine (MXDA) (Mitsubishi Gas Chemical Co., Ltd.) and 147.10 g of paraxylenediamine (PXDA) (Mitsubishi Gas Chemical Co., Ltd.) were added. (Molar ratio (MXDA / PXDA = 70/30)) and polyether diamine (trade name: ED-900, manufactured by HUNTSMAN, USA) 360.00 g of a mixed solution was added dropwise to perform polymerization for about 2 hours to obtain a polyether polyamide. Got. ηr = 1.34, [COOH] = 75.95 μeq / g, [NH ₂ ] = 61.83 μeq / g, Mn = 14516, Tg = 33.2 ° C., Tch = 73.9 ° C., Tm = 246.2 ° C.
Next, 100 parts by mass of the obtained polyether polyamide and N, N′-di-2-naphthyl-p-phenylenediamine (manufactured by Ouchi Shinsei Chemical Co., Ltd., trade name: NOCRACK White, stable) as a stabilizer (B1-1)) is dry blended and extruded at a temperature of 270 ° C. in a twin screw extruder equipped with a screw having a diameter of 30 mm and a T die, and an unstretched film having a thickness of about 100 μm is formed. Obtained.
The said tensile test was done using the obtained film. The results are shown in Table 2.

Examples 2-2 to 2-5
A film was obtained in the same manner as in Example 2-1, except that the type of stabilizer in Example 2-1 was changed as shown in Table 2, and the tensile test was performed. The results are shown in Table 2.

Comparative Example 2-1
A reaction vessel equipped with a stirrer, a nitrogen gas inlet, and a condensed water outlet is charged with 730.8 g of adipic acid, 0.6322 g of sodium hypophosphite monohydrate and 0.4404 g of sodium acetate in a vessel. The interior was sufficiently purged with nitrogen, and then melted at 170 ° C. while supplying nitrogen gas at 20 ml / min. While gradually raising the temperature to 275 ° C., 476.70 g of metaxylylenediamine (MXDA) (Mitsubishi Gas Chemical Co., Ltd.) and paraxylylenediamine (PXDA) (Mitsubishi Gas Chemical Co., Ltd.) 204. A mixed solution of 30 g (molar ratio (MXDA / PXDA = 70/30)) was dropped, and polymerization was performed for about 2 hours to obtain polyamide. ηr = 2.07, [COOH] = 55.70 μeq / g, [NH ₂ ] = 64.58 μeq / g, Mn = 16623, Tg = 89.0 ° C., Tch = 135.0 ° C., Tm = 257.0 ° C.
The obtained polyamide was extruded at a temperature of 275 ° C. to prepare an unstretched film having a thickness of about 100 μm.
The said tensile test was done using the obtained film. The results are shown in Table 2.

Comparative Example 2-2
The polyether polyamide obtained in Example 2-1 was extruded at a temperature of 270 ° C. to produce an unstretched film having a thickness of about 100 μm.
The said tensile test was done using the obtained film. The results are shown in Table 2.

Example 3-1.
In a reaction vessel having a volume of about 3 L equipped with a stirrer, a nitrogen gas inlet, and a condensed water outlet, 687.65 g of sebacic acid (sulfur atom concentration 70 ppm), 0.6612 g of sodium hypophosphite monohydrate and 0 of sodium acetate 4605 g was charged and the inside of the container was sufficiently purged with nitrogen, and then melted at 170 ° C. while supplying nitrogen gas at 20 ml / min. While gradually raising the temperature to 260 ° C., 416.77 g of metaxylylenediamine (MXDA) (manufactured by Mitsubishi Gas Chemical Co., Ltd.) and polyether diamine (manufactured by HUNTSMAN, USA, trade name: ED-900) 306. 00 g of the mixed solution was dropped and polymerization was performed for about 2 hours to obtain a polyether polyamide. ηr = 1.33, [COOH] = 96.88 μeq / g, [NH ₂ ] = 37.00 μeq / g, Mn = 14939, Tg = 22.2 ° C., Tch = 43.0 ° C., Tm = 182.8 ° C. The sulfur atom concentration in the polyether polyamide was 34 ppm.
Next, 100 parts by mass of the obtained polyether polyamide and 4,4′-bis (α, α-dimethylbenzyl) diphenylamine (manufactured by Ouchi Shinsei Chemical Co., Ltd., trade name: NOCRACK CD, stable) as a stabilizer (B1-2)) is dry blended with 0.5 parts by weight, and extruded at a temperature of 235 ° C. with a twin screw extruder equipped with a screw having a diameter of 30 mm and a T die, and an unstretched film having a thickness of about 100 μm is formed. Obtained.
Using the obtained film, the tensile test and the YI value were measured. The results are shown in Table 3.

Examples 3-2 to 3-5
A film was obtained in the same manner as in Example 3-1, except that the type of stabilizer in Example 3-1 was changed as shown in Table 3, and the tensile test and the YI value were measured. The results are shown in Table 3.

Comparative Example 3-1
809.0 g of sebacic acid (sulfur atom concentration 0 ppm), 0.6210 g of sodium hypophosphite monohydrate, and sodium acetate 0 were added to a reaction vessel having a volume of about 3 L equipped with a stirrer, a nitrogen gas inlet, and a condensed water outlet. 4325 g was charged and the inside of the container was sufficiently purged with nitrogen, and then melted at 170 ° C. while supplying nitrogen gas at 20 ml / min. While gradually raising the temperature to 260 ° C., 544.80 g of metaxylylenediamine (MXDA) (manufactured by Mitsubishi Gas Chemical Co., Ltd.) was added dropwise thereto and polymerization was performed for about 2 hours to obtain polyamide. ηr = 1.80, [COOH] = 88.5 μeq / g, [NH ₂ ] = 26.7 μeq / g, Mn = 17300, Tg = 61.2 ° C., Tch = 11.1 ° C., Tm = 191.5 ° C.
The obtained polyamide was extruded at a temperature of 220 ° C. to prepare an unstretched film having a thickness of about 100 μm.
Using the obtained film, the tensile test and the YI value were measured. The results are shown in Table 3.

Comparative Example 3-2
The polyether polyamide obtained in Example 3-1 was extruded at a temperature of 220 ° C. to prepare an unstretched film having a thickness of about 100 μm.
Using the obtained film, the tensile test and the YI value were measured. The results are shown in Table 3.

Example 4-1
A reaction vessel equipped with a stirrer, a nitrogen gas inlet, and a condensed water outlet is charged with 687.65 g of sebacic acid, 0.6612 g of sodium hypophosphite monohydrate, and 0.4605 g of sodium acetate. The interior was sufficiently purged with nitrogen, and then melted at 170 ° C. while supplying nitrogen gas at 20 ml / min. While gradually raising the temperature to 260 ° C., 291.74 g of metaxylylenediamine (MXDA) (Mitsubishi Gas Chemical Co., Ltd.) and paraxylylenediamine (PXDA) (Mitsubishi Gas Chemical Co., Ltd.) 125. A mixture of 306.00 g of 03 g (molar ratio (MXDA / PXDA = 70/30)) and polyetherdiamine (manufactured by HUNTSMAN, USA, trade name: ED-900) was added dropwise to perform polymerization for about 2 hours. Polyamide was obtained. ηr = 1.36, [COOH] = 66.35 μeq / g, [NH ₂ ] = 74.13 μeq / g, Mn = 14237, Tg = 16.9 ° C., Tch = 52.9 ° C., Tm = 201.9 ° C.
Next, 100 parts by mass of the obtained polyether polyamide and N, N′-di-2-naphthyl-p-phenylenediamine (manufactured by Ouchi Shinsei Chemical Co., Ltd., trade name: NOCRACK White, stable) as a stabilizer (B1-1)) is dry blended and extruded at a temperature of 250 ° C. with a twin screw extruder equipped with a screw having a diameter of 30 mm and a T-die, and an unstretched film having a thickness of about 100 μm is formed. Obtained.
The said tensile test was done using the obtained film. The results are shown in Table 4.

Examples 4-2 to 4-5
A film was obtained in the same manner as in Example 4-1, except that the type of stabilizer in Example 4-1 was changed as described in Table 4, and the tensile test was performed. The results are shown in Table 4.

Examples 4-6 to 4-8
Except having changed the addition amount of the stabilizer in Example 4-1 or 4-2 as shown in Table 4, a film was obtained in the same manner as in Example 4-1 or 4-2, and the tensile test was performed. went. The results are shown in Table 4.

Examples 4-9 to 4-11
A film was obtained in the same manner as in Example 4-1, except that the type and addition amount of the stabilizer in Example 4-1 were changed as shown in Table 4, and the tensile test was performed. The results are shown in Table 4.

Comparative Example 4-1
A reaction vessel having a volume of about 3 L equipped with a stirrer, a nitrogen gas inlet, and a condensed water outlet was charged with 829.2 g of sebacic acid, 0.6365 g of sodium hypophosphite monohydrate and 0.4434 g of sodium acetate. The interior was sufficiently purged with nitrogen, and then melted at 170 ° C. while supplying nitrogen gas at 20 ml / min. While gradually raising the temperature to 260 ° C., 390.89 g of metaxylylenediamine (MXDA) (Mitsubishi Gas Chemical Co., Ltd.) and paraxylylenediamine (PXDA) (Mitsubishi Gas Chemical Co., Ltd.) 167. A mixed solution of 53 g (molar ratio (MXDA / PXDA = 70/30)) was dropped, and polymerization was performed for about 2 hours to obtain polyamide. ηr = 2.20, [COOH] = 81.8 μeq / g, [NH ₂ ] = 26.9 μeq / g, Mn = 18400, Tg = 65.9 ° C., Tch = 100.1 ° C., Tm = 213.8 ° C.
The obtained polyamide was extruded at a temperature of 240 ° C. to prepare an unstretched film having a thickness of about 100 μm.
The said tensile test was done using the obtained film. The results are shown in Table 4.

Comparative Example 4-2
The polyether polyamide obtained in Example 4-1 was extruded at a temperature of 260 ° C. to produce an unstretched film having a thickness of about 100 μm.
The said tensile test was done using the obtained film. The results are shown in Table 4.

  From the results of Tables 1 to 4, it can be seen that the polyether polyamide composition of the present invention is a material that is excellent in melt moldability, crystallinity, and flexibility, and also excellent in thermal stability and heat aging resistance.

  The polyether polyamide composition of the present invention retains the melt moldability, toughness, flexibility and rubber-like properties of existing polyamide elastomers, and is excellent in thermal stability and heat aging resistance. Therefore, the polyether polyamide composition of the present invention is used for various industrial parts, gears and connectors for machinery and electrical precision equipment, fuel tubes around automobile engines, connector parts, sliding parts, belts, hoses, silencer gears, etc. It can be suitably applied to parts, electronic parts, sporting goods and the like.

Claims (14)

The diamine structural unit is derived from the polyetherdiamine compound (a-1) and xylylenediamine (a-2) represented by the following general formula (1), and the dicarboxylic acid structural unit is α to ω having 4 to 20 carbon atoms. - look-containing polyether polyamide (a) and stabilizers from the linear aliphatic dicarboxylic acid (B),
The polyether polyamide composition whose ratio of the structural unit derived from xylylenediamine (a-2) in a diamine structural unit is 50-99.8 mol% .

(In the formula, x + z represents 1 to 60, y represents 1 to 50, and R ¹ represents a propylene group.)   The stabilizer (B) is at least one selected from the group consisting of an amine compound (B1), an organic sulfur compound (B2), a phenol compound (B3), a phosphorus compound (B4), and an inorganic compound (B5). The polyether polyamide composition of claim 1 which is a seed.   The polyether polyamide composition of Claim 1 or 2 whose content of a stabilizer (B) is 0.01-1 mass part with respect to 100 mass parts of polyether polyamide (A).   The polyether polyamide composition according to any one of claims 1 to 3, wherein the xylylenediamine (a-2) is metaxylylenediamine, paraxylylenediamine, or a mixture thereof.   The polyether polyamide composition according to any one of claims 1 to 4, wherein the xylylenediamine (a-2) is metaxylylenediamine.   The polyether polyamide composition according to any one of claims 1 to 4, wherein the xylylenediamine (a-2) is a mixture of metaxylylenediamine and paraxylylenediamine.   The polyether polyamide composition according to claim 6, wherein the ratio of paraxylylenediamine to the total amount of metaxylylenediamine and paraxylylenediamine is 90 mol% or less.   The polyether polyamide composition according to any one of claims 1 to 7, wherein the α, ω-linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms is at least one selected from the group consisting of adipic acid and sebacic acid. object. The polyether polyamide composition according to any one of claims 1 to 8 , wherein the polyether polyamide composition has a relative viscosity of 1.1 to 3.0. The polyether polyamide composition according to any one of claims 1 to 9 , wherein the polyether polyamide composition has a melting point of 170 to 270 ° C. The polyether polyamide composition according to any one of claims 1 to 10 , wherein the tensile strength retention calculated by the following formula is 75% or more.
Tensile strength retention (%) = [Stress at break of film after heat treatment at 130 ° C. for 72 hours (MPa) / Stress at break of film before heat treatment at 130 ° C. for 72 hours (MPa)] × 100 Stabilizer (B) is at least one selected from the group consisting of an amine compound (B1), organosulfur compounds (B2) and the inorganic compound (B5), according to any one of claims 1 to 11 Polyether polyamide composition. Molded article comprising a polyether polyamide composition according to any one of claims 1 to 12. The molded article according to claim 13 , which is a hose, a tube, or a metal coating material.