JP5942109B2 - Polyamide composition and molded body obtained by molding polyamide composition - Google Patents

Description

  The present invention relates to a polyamide composition and a molded body obtained by molding the polyamide composition.

  Polyamides represented by polyamide 6 and polyamide 66 (hereinafter sometimes abbreviated as “PA6” and “PA66”, respectively) and the like are excellent in molding processability, mechanical properties, and chemical resistance. Conventionally, it has been widely used as various parts materials for automobiles, electric and electronic, industrial materials, industrial materials, daily use, household products and the like.

  Such polyamides are required to be further improved in the future.

  For example, in the automobile industry, a reduction in body weight is required to reduce exhaust gas as an environmental effort. In order to meet such demands, polyamides are increasingly used in place of metals as automobile exterior materials and interior materials. Polyamides used for automotive exterior materials and interior materials are required to have higher levels of heat resistance, strength, appearance, and other characteristics. In particular, polyamides used for materials in the engine room are increasingly required to have high heat resistance because the temperature in the engine room tends to increase.

  In addition, in the electrical and electronic industries such as home appliances, lead-free surface mount (SMT) solder is being promoted. Polyamides used for materials such as home appliances are required to have high heat resistance that can withstand the rise in melting point of solder accompanying the lead-free solder.

  Polyamides such as PA6 and PA66 have a low melting point, and cannot satisfy the demand for high heat resistance as described above.

  In order to solve the problems relating to high heat resistance such as PA6 and PA66, high melting point polyamides have been proposed.

  Specifically, a polyamide composed of terephthalic acid and hexamethylenediamine (hereinafter sometimes abbreviated as “PA6T”) has been proposed.

  Further, a semi-alicyclic polyamide (hereinafter referred to as “PA6C”) composed of an alicyclic polyamide (hereinafter sometimes referred to as “PA6C”) composed of 1,4-cyclohexanedicarboxylic acid and hexamethylenediamine and another polyamide. (In some cases, it is abbreviated as “copolymerized polyamide”) (see, for example, Patent Documents 1 and 2).

  Specifically, Patent Document 1 discloses that the semi-alicyclic polyamide electrical and electronic members containing 1 to 40% 1,4-cyclohexanedicarboxylic acid as dicarboxylic acid units have excellent solder heat resistance. It is disclosed. Patent Document 2 discloses that semi-alicyclic polyamide automobile parts are excellent in fluidity and toughness.

  Furthermore, a polyamide comprising a dicarboxylic acid unit containing 1,4-cyclohexanedicarboxylic acid and a diamine unit containing 2-methyl-1,8-octanediamine is light resistance, toughness, moldability, lightness, heat resistance, etc. (For example, refer to Patent Document 3).

  On the other hand, it is disclosed that a composition containing polyamide 66 resin and glass fiber having a fiber diameter of 5 to 25 μm is excellent in welding strength (see, for example, Patent Document 4). It is also disclosed that the impact resistance of the polyamide 6 resin is improved by blending glass fibers having an average diameter of 3 to 8 μm with the polyamide 6 resin (see, for example, Patent Document 5).

Japanese National Patent Publication No. 11-512476 Special table 2001-514695 gazette Japanese Patent Laid-Open No. 9-12868 JP-A-9-176484 JP 60-38459 A

  In recent years, a polyamide composition having mechanical strength, toughness, heat resistance, and vibration fatigue resistance, which are further superior to conventional ones, has been demanded when the polyamide composition is used as a material for parts for automobile engine rooms. Also, in the field of electrical and electronic parts and the like, the polyamide composition has excellent strength, toughness, heat resistance and dimensional stability when used as a material for parts that have been made smaller and more precise. Is required. However, the conventional polyamide compositions as disclosed in Patent Documents 1 to 5 are insufficiently improved.

  Therefore, in the present invention, a polyamide composition having excellent mechanical strength, toughness, heat resistance, dimensional stability, vibration fatigue resistance, slidability, and low water absorption, and a molded body using the same. The purpose is to provide.

  As a result of intensive studies aimed at solving the above-described problems of the prior art, the present inventors have found that at least one unit composed of alicyclic dicarboxylic acid and one unit composed of diamine having 8 or more carbon atoms. A polyamide composition containing a copolymerized polyamide containing a unit composed of a specific copolymerization component and a fibrous reinforcing material having a number average fiber diameter of 3 to 9 μm can solve the above-mentioned problems of the prior art. As a result, the present invention has been completed.

  That is, the present invention is as follows.

[1]
(A) (a) a unit composed of at least one alicyclic dicarboxylic acid, (b) one unit composed of a diamine having 8 or more carbon atoms, and (c) the following (c-1) to (c- A unit comprising at least one copolymer component selected from the group consisting of 3), and a copolymerized polyamide,
(B) a fibrous reinforcing material having a number average fiber diameter of 3 to 9 μm;
Containing a polyamide composition;
(C-1) a dicarboxylic acid other than the (a) alicyclic dicarboxylic acid,
(C-2) a diamine having fewer carbon atoms than the diamine of (b),
(C-3) Lactam and / or aminocarboxylic acid.

[2]
The polyamide composition according to [1], wherein the (B) fibrous reinforcing material is glass fiber.

[3]
The polyamide composition according to [1] or [2], wherein the (B) fibrous reinforcing material has a weight average fiber length of 100 to 500 μm in the polyamide composition.

[4]
The (B) fibrous reinforcing material is composed of a unit composed of a carboxylic acid anhydride-containing unsaturated vinyl monomer and an unsaturated vinyl monomer (excluding the carboxylic acid anhydride-containing unsaturated vinyl monomer). The polyamide composition according to any one of [1] to [3], which is a fibrous reinforcing material treated with a sizing agent including a copolymer containing units.

[5]
The polyamide composition according to any one of [1] to [4], wherein the (a) alicyclic dicarboxylic acid is 1,4-cyclohexanedicarboxylic acid.

[6]
In the suggested scanning calorimetry according to JIS-7121 of the (A) copolymerized polyamide, the difference between the crystallization peak temperature T _pc-1 obtained when cooled at 20 ° C./min and the glass transition temperature T _g ( The polyamide composition according to any one of [1] to [5], wherein T _pc-1 −T _g ) is 140 ° C. or higher.

[7]
The polyamide composition according to any one of [1] to [6], wherein the ratio of the number of carbon atoms to the number of amide groups (carbon number / amide group number) in the (A) copolymerized polyamide is 8 or more.

[8]
In the suggested scanning calorimetry according to JIS-7121 of the (A) copolymerized polyamide, the melting peak temperature T _pm obtained when the temperature is raised at 20 ° C./min, and when the temperature is raised again at 20 ° C./min The polyamide composition according to any one of [1] to [7], wherein the difference (T _pm -T _pm-1 ) from the obtained melting peak temperature T _pm-1 is 30 ° C or lower.

[9]
The trans isomer ratio in the portion derived from the (a) alicyclic dicarboxylic acid in the (A) copolymerized polyamide is 65 to 80 mol%, according to any one of [1] to [8]. Polyamide composition.

[10]
The ratio (amino end amount / (amino end amount + carboxyl end amount)) of the amino terminal amount to the total amount of amino terminal amount and carboxyl terminal amount in the (A) copolymerized polyamide is 0.5 or more and less than 1.0. The polyamide composition according to any one of [1] to [9].

[11]
The polyamide composition according to any one of [1] to [10], wherein (b) the diamine having 8 or more carbon atoms is decamethylenediamine.

[12]
The polyamide composition according to any one of [1] to [11], wherein the (c-1) dicarboxylic acid is an aliphatic dicarboxylic acid having 10 or more carbon atoms.

[13]
The polyamide composition according to any one of [1] to [12], wherein the (c-1) dicarboxylic acid is sebacic acid and / or dodecanedioic acid.

[14]
The polyamide composition according to any one of [1] to [11], wherein the (c-1) dicarboxylic acid is isophthalic acid.

[15]
The polyamide composition according to any one of [1] to [14], wherein the (c-2) diamine is an aliphatic diamine having 4 to 7 carbon atoms.

[16]
In the differential scanning calorimetry according to JIS-K7121 of the (A) copolymerized polyamide, when it is cooled again at a crystallization peak temperature T _pc-1 obtained by cooling at 20 ° C./min and at 50 ° C./min. The polyamide composition according to any one of [1] to [15], wherein the difference from the crystallization peak temperature T _pc-2 obtained in ( ₁ ) to (T _pc-1 −T _pc-2 ) is 10 ° C. or less.

[17]
The content of the unit consisting of the copolymer component (c) is 7.5 mol% or more and 20.0 mol% or less with respect to 100 mol% of the total content of all structural units of the copolymer (A). The polyamide composition according to any one of [1] to [16].

[18]
The polyamide composition according to any one of [1] to [17], wherein the biomass plasticity of the (A) copolymerized polyamide is 25% or more.

[19]
With respect to 100 parts by mass of the (A) copolymerized polyamide,
The polyamide composition according to any one of [1] to [18], wherein the content of the (B) fibrous reinforcing material is 1 to 200 parts by mass.

[20]
(C) Phenol-based heat stabilizer, phosphorus-based heat stabilizer, amine-based heat stabilizer, elements of Group Ib, Group IIb, Group IIIa, Group IIIb, Group IVa and Group IVb of the periodic table The polyamide composition according to any one of [1] to [19], further comprising at least one heat stabilizer selected from the group consisting of metal salts of: and alkali metal and alkaline earth metal halides.

[21]
The polyamide composition according to [20], wherein the heat stabilizer (C) is a mixture of a copper salt and an alkali metal or alkaline earth metal halide.

[22]
(D) The polyamide composition according to any one of [1] to [21], further comprising at least one nucleating agent selected from the group consisting of boron nitride, talc and carbon black.

[23]
[1] A molded article comprising the polyamide composition according to any one of [22].

[24]
A sliding component comprising the polyamide composition according to any one of [1] to [22].

  According to the present invention, a polyamide composition excellent in mechanical strength, toughness, heat resistance, dimensional stability, vibration fatigue resistance, slidability, and low water absorption and a molded body using the same are obtained. It is done.

  Hereinafter, a mode for carrying out the present invention (hereinafter referred to as the present embodiment) will be described in detail.

  The present invention is not limited to the following embodiments, and various modifications can be made within the scope of the gist.

[Polyamide composition]
The polyamide composition of this embodiment contains (A) a specific copolymer polyamide and (B) a specific fibrous reinforcement.

≪ (A) Copolymer polyamide≫
The (A) copolymerized polyamide used in this embodiment contains a unit comprising the following component (a), a unit comprising the following component (b) and a unit comprising the following component (c).

(A) At least one alicyclic dicarboxylic acid.
(B) One kind of diamine having 8 or more carbon atoms.
(C) Specific at least one copolymer component.

  In the present embodiment, polyamide means a polymer having an amide (—NHCO—) bond in the main chain.

  Hereinafter, the components (a), (b) and (c) will be described in detail.

[(A) Alicyclic dicarboxylic acid]
Although it does not specifically limit as (a) alicyclic dicarboxylic acid (henceforth "alicyclic dicarboxylic acid") used for this embodiment, For example, carbon number of an alicyclic structure is 3-10. Examples thereof include alicyclic dicarboxylic acids, preferably alicyclic dicarboxylic acids having 5 to 10 carbon atoms in the alicyclic structure. Specific examples of (a) alicyclic dicarboxylic acids include, but are not limited to, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, and the like.

  The (a) alicyclic dicarboxylic acid used in the present embodiment may be unsubstituted or may have a substituent.

  Although it does not specifically limit as the said substituent, For example, C1-C4 alkyl groups, such as a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, and tert-butyl group Etc.

  The (a) alicyclic dicarboxylic acid used in the present embodiment is preferably 1,4-cyclohexanedicarboxylic acid from the viewpoints of heat resistance, low water absorption, strength, rigidity, and the like.

  As (a) alicyclic dicarboxylic acid used for this embodiment, you may use by 1 type and may be used in combination of 2 or more types.

  An alicyclic dicarboxylic acid has a geometric isomer of a trans isomer and a cis isomer. As the alicyclic dicarboxylic acid as a raw material monomer, either a trans isomer or a cis isomer may be used, or a mixture of various proportions of a trans isomer and a cis isomer may be used.

  Alicyclic dicarboxylic acids are isomerized at a high temperature to have a certain ratio, and the cis isomer has a higher water solubility in the equivalent salt with diamine than the trans isomer. The acid is preferably 50/50 to 0/100, more preferably 40/60 to 10/90, and even more preferably 35/65 to 15/85 in terms of a trans isomer / cis isomer ratio. It is.

The trans / cis ratio (molar ratio) of the alicyclic dicarboxylic acid can be determined by liquid chromatography (HPLC) or nuclear magnetic resonance spectroscopy (NMR). Here, the trans isomer / cis isomer ratio (molar ratio) in the present specification is determined by ¹ H-NMR.

[(B) Diamine having 8 or more carbon atoms]
(B) The diamine having 8 or more carbon atoms used in the present embodiment is not particularly limited as long as it is a diamine having 8 or more carbon atoms. For example, an unsubstituted linear aliphatic diamine may be a methyl group, an ethyl group, or n. A branched aliphatic diamine having a substituent such as an alkyl group having 1 to 4 carbon atoms such as a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a tert-butyl group; It may be a group diamine. The number of carbon atoms in (b) diamine used in the present embodiment is preferably 8-20, more preferably 8-15, and still more preferably 8-12.

  Although it does not specifically limit as a specific example of (b) C8 or more diamine used for this embodiment, For example, octamethylenediamine, 2-methyloctamethylenediamine, nonamethylenediamine, decamethylenediamine, undecamethylenediamine , Dodecamethylenediamine, tridecamethylenediamine, 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 2-methyloctamethylenediamine, 2,4-dimethyloctamethylenediamine, metaxyl Examples include range amine, orthoxylylene diamine, and paraxylylene diamine.

  (B) The diamine having 8 or more carbon atoms used in the present embodiment is octamethylenediamine, 2-methyloctamethylenediamine, nonamethylenediamine, decamethylenediamine from the viewpoints of heat resistance, low water absorption, strength and rigidity. , Undecamethylene diamine and dodecamethylene diamine are preferable, more preferably 2-methyloctamethylene diamine, nonamethylene diamine, decamethylene diamine, undecamethylene diamine, and dodecamethylene diamine, and still more preferably decamethylene diamine, Dodecamethylenediamine, particularly preferably decamethylenediamine.

  In addition, in this embodiment, when combining 2 or more types of diamines having 8 or more carbon atoms, the diamine having the largest number of carbon atoms is used as the component (b), and other diamines having 8 or more carbon atoms are described later (c-2). Ingredients.

[(C) Copolymerization component]
The (c) copolymerization component used in this embodiment is (c-1) a dicarboxylic acid other than (a) the alicyclic dicarboxylic acid, (c-2) a diamine having fewer carbon atoms than the diamine of (b), And (c-3) at least one selected from the group consisting of lactams and / or aminocarboxylic acids.

  The copolymerized polyamide (A) used in the present embodiment contains a unit composed of at least one copolymer component selected from the group consisting of the above (c-1) to (c-3). , Excellent in low water absorption, low blocking property, releasability and plasticization time stability. Moreover, the copolymerized polyamide composition containing the copolymerized polyamide (A) is excellent in vibration fatigue characteristics, surface appearance and continuous productivity.

  The copolymer polyamide (A) used in the present embodiment is particularly excellent in low water absorption and surface appearance when it contains units composed of the copolymer component (c-1). Moreover, when the copolymer polyamide (A) used for this embodiment contains the unit which consists of a copolymerization component of said (c-2), it is excellent in especially intensity | strength, high temperature strength, low blocking property, and mold release property. Furthermore, the copolymerized polyamide (A) used in the present embodiment is particularly excellent in high temperature strength and releasability when it contains a unit composed of the copolymer component (c-3).

  One type of (c) copolymerization component combined with (a) alicyclic dicarboxylic acid and (b) C8 or more diamine may be combined, and two or more types may be combined. As an example of combination, (c-1), (c-2) and (c-3) can be freely combined. For example, two types from (c-1) may be used, Two types may be combined from c-2) and (c-3), or one type from (c-1) and one type from (c-2).

  In the present embodiment, the content of the unit comprising (c) the copolymerization component is preferably 5.0 mol% or more and 22.22% with respect to 100 mol% in total of the content of all the structural units of the copolymerized polyamide (A). It is 5 mol% or less, More preferably, it is 7.5 mol% or more and 20.0 mol% or less, More preferably, it is 10.0 mol% or more and 18.0 mol% or less. (C) Copolymer polyamide (A) excellent in strength, high-temperature strength, low water absorption, low blocking property, releasability and plasticizing time stability by adjusting the content of the unit comprising the copolymer component within the above range. It can be. Moreover, the copolymerized polyamide composition containing the copolymerized polyamide (A) is excellent in vibration fatigue characteristics, surface appearance and continuous productivity.

[(C-1) (a) Dicarboxylic acid other than alicyclic dicarboxylic acid]
(C-1) The dicarboxylic acid other than the (a) alicyclic dicarboxylic acid used in the present embodiment is not particularly limited, and examples thereof include aliphatic dicarboxylic acids and aromatic dicarboxylic acids.

  Examples of the aliphatic dicarboxylic acid include, but are not limited to, for example, malonic acid, dimethyl malonic acid, succinic acid, 2,2-dimethyl succinic acid, 2,3-dimethyl glutaric acid, 2,2-diethyl succinic acid, 2, 3-diethylglutaric acid, glutaric acid, 2,2-dimethylglutaric acid, adipic acid, 2-methyladipic acid, trimethyladipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, tetradecanedioic acid, Examples thereof include linear or branched aliphatic dicarboxylic acids having 3 to 20 carbon atoms such as hexadecanedioic acid, octadecanedioic acid, eicosanedioic acid, and diglycolic acid.

  The aromatic dicarboxylic acid is not particularly limited, and examples thereof include terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, and 5-sodium sulfoisophthalic acid. Or an aromatic dicarboxylic acid having 8 to 20 carbon atoms which is unsubstituted or substituted with various substituents.

  Although it does not specifically limit as various substituents, For example, halogens, such as a C1-C4 alkyl group, a C6-C10 aryl group, a C7-C10 arylalkyl group, a chloro group, and a bromo group Groups, silyl groups having 1 to 6 carbon atoms, and sulfonic acid groups and salts thereof such as sodium salts.

  (C-1) The dicarboxylic acid other than (a) the alicyclic dicarboxylic acid used in the present embodiment is preferably aliphatic in terms of heat resistance, fluidity, toughness, low water absorption, strength, rigidity, and the like. Dicarboxylic acids, more preferably aliphatic dicarboxylic acids having 6 or more carbon atoms.

  Among these, (c-1) the dicarboxylic acid other than the (a) alicyclic dicarboxylic acid is preferably an aliphatic dicarboxylic acid having 10 or more carbon atoms from the viewpoint of heat resistance and low water absorption.

  The aliphatic dicarboxylic acid having 10 or more carbon atoms is not particularly limited, and examples thereof include sebacic acid, dodecanedioic acid, tetradecanedioic acid, hexadecanedioic acid, octadecanedioic acid, and eicosanedioic acid.

  Among these, as the (c-1) dicarboxylic acid other than the (a) alicyclic dicarboxylic acid, sebacic acid and / or dodecanedioic acid are preferable from the viewpoint of heat resistance and the like.

  (C-1) The dicarboxylic acid other than (a) the alicyclic dicarboxylic acid used in the present embodiment is preferably aromatic in terms of heat resistance, fluidity, toughness, low water absorption, strength, rigidity, and the like. Dicarboxylic acid, more preferably aromatic dicarboxylic acid having 8 or more carbon atoms.

  Among them, (c-1) As the dicarboxylic acid other than the (a) alicyclic dicarboxylic acid, isophthalic acid is preferable from the viewpoint of heat resistance, fluidity, surface appearance, and the like.

  Furthermore, (c-1) the dicarboxylic acid other than the (a) alicyclic dicarboxylic acid is a trivalent or higher valent group such as trimellitic acid, trimesic acid, and pyromellitic acid within a range not impairing the object of the present embodiment. A polyvalent carboxylic acid may be included.

  As the polyvalent carboxylic acid, one kind may be used, or two or more kinds may be used in combination.

  There is no particular limitation on the ratio (mol%) of (a) alicyclic dicarboxylic acid in (a) alicyclic dicarboxylic acid and (c-1) dicarboxylic acid other than (a) alicyclic dicarboxylic acid. 50-100 mol% is preferable, More preferably, it is 60-100 mol%, More preferably, it is 70-100 mol%. Copolymer polyamide excellent in strength, high temperature strength, low water absorption, low blocking property, releasability and plasticizing time stability when the proportion of (a) alicyclic dicarboxylic acid is 50 to 100 mol% (A). Moreover, the copolymerized polyamide composition containing the copolymerized polyamide (A) is excellent in vibration fatigue characteristics, surface appearance and continuous productivity.

  The dicarboxylic acid used in the present embodiment is not limited to the compounds described as the dicarboxylic acid, and may be a compound equivalent to the dicarboxylic acid.

  The compound equivalent to the dicarboxylic acid is not particularly limited as long as it can be a dicarboxylic acid structure similar to the dicarboxylic acid structure derived from the dicarboxylic acid, and examples thereof include anhydrides and halides of dicarboxylic acids.

[(C-2) Diamine with Less Carbon Number than Diamine in (b)]
(C-2) used in the present embodiment is not particularly limited as long as it is a diamine having a carbon number smaller than that of the diamine (b), and examples thereof include aliphatic diamines, alicyclic diamines, and aromatic diamines. It is done.

  Examples of the aliphatic diamine include, but are not limited to, ethylene diamine, propylene diamine, tetramethylene diamine, pentamethylene diamine, hexamethylene diamine, heptamethylene diamine, octamethylene diamine, nonamethylene diamine, decamethylene diamine, undecamethylene diamine. , Linear aliphatic diamines such as dodecamethylenediamine and tridecamethylenediamine, 2-methylpentamethylenediamine, 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 2- Examples thereof include branched aliphatic diamines such as methyloctamethylenediamine and 2,4-dimethyloctamethylenediamine.

  The alicyclic diamine (also referred to as alicyclic diamine) is not particularly limited, and examples thereof include 1,4-cyclohexanediamine, 1,3-cyclohexanediamine, and 1,3-cyclopentanediamine. It is done.

  The aromatic diamine is an aromatic diamine and is not particularly limited, and examples thereof include metaxylylenediamine, orthoxylylenediamine, paraxylylenediamine, and the like.

  (C-2) The diamine having a smaller number of carbon atoms than the diamine (b) used in the present embodiment is preferably aliphatic in terms of heat resistance, fluidity, toughness, low water absorption, strength and rigidity. A diamine and an alicyclic diamine, more preferably an aliphatic diamine having 4 to 13 carbon atoms, still more preferably an aliphatic diamine having 4 to 10 carbon atoms, and particularly preferably 4 to 7 carbon atoms. Is an aliphatic diamine.

  Furthermore, (c-2) the diamine having a smaller number of carbon atoms than the diamine (b) may contain a trivalent or higher polyvalent aliphatic amine such as bishexamethylenetriamine within the range not impairing the object of the present embodiment. Good.

  As the polyvalent aliphatic amine, one kind may be used, or two or more kinds may be used in combination.

  The ratio (mol%) of the diamine having 8 or more carbon atoms in (b) the diamine having 8 or more carbon atoms, and (c-2) the diamine having less carbon atoms than the diamine (b) is particularly limited. However, it is preferably 40 to 100 mol%, more preferably 50 to 100 mol%, still more preferably 60 to 100 mol%. (B) Copolymer having excellent strength, high temperature strength, low water absorption, low blocking property, releasability and plasticizing time stability when the proportion of the diamine having 8 or more carbon atoms is 40 to 100 mol%. Polyamide (A) can be used. Moreover, the copolymerized polyamide composition containing the copolymerized polyamide (A) is excellent in vibration fatigue characteristics, surface appearance and continuous productivity.

  When obtaining the copolymerized polyamide (A) used in the present embodiment, the addition amount of the dicarboxylic acid and the addition amount of the diamine are preferably around the same molar amount. The amount of diamine escaped from the reaction system during the polymerization reaction is also considered in terms of molar ratio, and the molar amount of the diamine is 0.9 to 1.2 with respect to the molar amount 1 of the entire dicarboxylic acid. Is more preferable, 0.95 to 1.1 is more preferable, and 0.98 to 1.05 is still more preferable.

[(C-3) Lactam and / or aminocarboxylic acid]
The (c-3) lactam and / or aminocarboxylic acid used in this embodiment means a lactam and / or aminocarboxylic acid that can be condensed (condensed).

  The copolymerized polyamide (A) used in this embodiment comprises (a) a unit composed of an alicyclic dicarboxylic acid, (b) a unit composed of a diamine having 8 or more carbon atoms, and (c-3) a lactam and / or amino. (C-3) the lactam and / or aminocarboxylic acid is preferably a lactam having 4 to 14 carbon atoms and / or an aminocarboxylic acid having 4 to 14 carbon atoms. More preferably, it is a lactam having 6 to 12 and / or an aminocarboxylic acid having 6 to 12 carbon atoms.

  Although it does not specifically limit as a lactam, For example, a butyrolactam, pivalolactam, (epsilon) -caprolactam, a caprilolactam, an enantolactam, undecanolactam, a laurolactam (dodecanolactam), etc. are mentioned.

  Among these, as the lactam, from the viewpoint of toughness, ε-caprolactam, undecanolactam, laurolactam and the like are preferable, and ε-caprolactam and laurolactam are more preferable.

  The aminocarboxylic acid is not particularly limited, and examples thereof include ω-aminocarboxylic acid and α, ω-amino acid which are compounds in which the lactam is ring-opened.

  The aminocarboxylic acid is preferably a linear or branched saturated aliphatic carboxylic acid having 4 to 14 carbon atoms substituted with an amino group at the ω position, and is not particularly limited. For example, 6-aminocaproic acid, 11 -Aminoundecanoic acid, 12-aminododecanoic acid, etc. are mentioned, As a paracarboxylic acid, paraaminomethylbenzoic acid etc. are mentioned.

  Among these, as the aminocarboxylic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid and the like are more preferable from the viewpoint of low water absorption and toughness.

  When (c-3) lactam and / or aminocarboxylic acid is used in obtaining the copolymerized polyamide (A) used in the present embodiment, the amount (mol%) of (c-3) is not particularly limited. However, it is preferable that the molar amount of each monomer of (a) an alicyclic dicarboxylic acid, (b) a diamine having 8 or more carbon atoms, and (c-3) lactam and / or aminocarboxylic acid is preferably 0.8. It is 5 mol% or more and 20 mol% or less, and more preferably 2 mol% or more and 18 mol% or less. (C-3) Copolymer polyamide having excellent heat resistance, low water absorption, strength, releasability, etc., when the addition amount of lactam and / or aminocarboxylic acid is 0.5 mol% or more and 20 mol% or less. (A).

In the present embodiment, the content of each structural unit in the copolymerized polyamide (A) can be measured by ¹ H-NMR, and can be measured in detail by the method described in the examples below. it can.

[End sealant]
In this embodiment, when polymerizing the copolymerized polyamide (A), in addition to the components (a) to (c), a known end-capping agent can be further added for molecular weight adjustment.

  The end capping agent is not particularly limited, and examples thereof include monocarboxylic acids, monoamines, acid anhydrides such as phthalic anhydride, monoisocyanates, monoacid halides, monoesters, and monoalcohols. From the viewpoint of thermal stability, monocarboxylic acids and monoamines are preferred.

  As the terminal blocking agent, one kind may be used, or two or more kinds may be used in combination.

  The monocarboxylic acid that can be used as the end-capping agent is not particularly limited as long as it has reactivity with an amino group. For example, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid Aliphatic monocarboxylic acids such as lauric acid, tridecylic acid, myristic acid, palmitic acid, stearic acid, pivalic acid, and isobutyric acid; alicyclic monocarboxylic acids such as cyclohexanecarboxylic acid; and benzoic acid, toluic acid, α -Aromatic monocarboxylic acids such as naphthalenecarboxylic acid, β-naphthalenecarboxylic acid, methylnaphthalenecarboxylic acid, and phenylacetic acid;

  As monocarboxylic acid, you may use by 1 type and may be used in combination of 2 or more types.

  The monoamine that can be used as the end-capping agent is not particularly limited as long as it has reactivity with a carboxyl group. For example, methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, decylamine, stearyl Aliphatic monoamines such as amine, dimethylamine, diethylamine, dipropylamine, and dibutylamine; alicyclic monoamines such as cyclohexylamine and dicyclohexylamine; and aromatic monoamines such as aniline, toluidine, diphenylamine, and naphthylamine; It is done.

  Monoamines may be used alone or in combination of two or more.

[Characteristics of copolymerized polyamide (A)]
In the copolymerized polyamide (A) used in this embodiment, the part derived from (a) alicyclic dicarboxylic acid exists as a geometric isomer of a trans isomer and a cis isomer.

  In the copolymerized polyamide (A) used in this embodiment, the trans isomer ratio in the part derived from (a) the alicyclic dicarboxylic acid is the entire part derived from the alicyclic dicarboxylic acid in the copolymerized polyamide (A). The ratio which is a trans isomer is represented. The trans isomer ratio is preferably 50 to 85 mol%, more preferably 50 to 80 mol%, and still more preferably 65 to 80 mol%.

  As the raw material (a) alicyclic dicarboxylic acid, it is preferable to use an alicyclic dicarboxylic acid having a trans isomer / cis isomer ratio (molar ratio) of 50/50 to 0/100 as described above. On the other hand, it is preferable that the trans isomer ratio in the part derived from (a) alicyclic dicarboxylic acid in the copolymerized polyamide (A) is within the above range (for example, 50 to 80 mol%).

  When the trans isomer ratio is within the above range, the copolymer polyamide (A) has high melting point, toughness, strength, rigidity, and plasticity time stability, and also has a high Tg thermal rigidity. Ordinarily, it has the property of simultaneously satisfying fluidity, which is a property contrary to heat resistance, and high crystallinity. Moreover, the copolymerized polyamide composition containing the copolymerized polyamide (A) is excellent in surface appearance and continuous productivity.

The method for controlling the trans isomer ratio in the portion derived from (a) the alicyclic dicarboxylic acid in the copolymerized polyamide (A) is not particularly limited, but for example, the copolymer polyamide (A) Examples thereof include a polymerization method and a method for controlling polymerization conditions. When producing the copolymerized polyamide (A) by the hot melt polymerization method, it is preferable to maintain the molten state until the polymerization is completed. In order to maintain a molten state, it is preferable to produce it under polymerization conditions suitable for the constituent components of the copolymerized polyamide (A). Specifically, for example, the polymerization pressure is controlled to a high pressure of 23 to 50 kg / cm ² (gauge pressure), preferably 25 kg / cm ² (gauge pressure) or more, and the pressure in the tank is atmospheric pressure while heating is continued. Examples include a method of reducing pressure while taking 30 minutes or more until the gauge pressure becomes 0 kg / cm ² .

In this embodiment, the trans isomer ratio in the copolymerized polyamide (A) is such that, for example, 30-40 mg of the copolymerized polyamide (A) is dissolved in 1.2 g of hexafluoroisopropanol deuteride, and the resulting solution is It can obtain | require by measuring by < ¹ > H-NMR. Specifically, in the case of 1,4-cyclohexanedicarboxylic acid, a peak area of 1.98 ppm derived from the trans isomer and 1.77 ppm and 1.86 ppm derived from the cis isomer in ¹ H-NMR measurement. The trans isomer ratio can be determined from the ratio to the peak area.

  The biomass plasticity of the copolymerized polyamide (A) used in this embodiment is preferably 25% or more. Biomass plasticity means the ratio of the unit comprised by the raw material derived from biomass among copolymer polyamide (A), and is computed by the method described in the following Example. A more preferable bioplastic degree is 30% or more. Although the upper limit of the biomass plasticity degree of the copolymer polyamide (A) used for this embodiment is not specifically limited, For example, it is 80%.

  The biomass-derived raw material as used herein means a monomer that can be synthesized using a component such as a plant as a starting material among the components (a) to (c) that are components of the copolymerized polyamide (A). . Although it does not specifically limit as a raw material derived from biomass, For example, it synthesize | combines from the component of a sebacic acid, a decamethylenediamine, 11-amino undecanoic acid which can be synthesize | combined from the ricinoleic acid triglyceride which is a main component of a castor oil, and the component of a sunflower seed. Examples include azelaic acid that can be synthesized, pentamethylenediamine, and γ-aminobutyric acid that can be synthesized from cellulose.

  Biomass is accumulated by absorbing carbon dioxide in the atmosphere through photosynthesis. Therefore, even when carbon dioxide is released into the atmosphere by combustion after using plastics made from these materials, it is originally in the atmosphere. Therefore, the carbon dioxide concentration in the atmosphere does not increase.

  Therefore, the high degree of biomass plasticity in the copolymerized polyamide (A) is very effective for reducing the environmental load. Examples of a method for increasing the degree of biomass plasticity of the copolymerized polyamide (A) include a method for increasing the blending ratio of the above-described biomass-derived raw materials when the copolymerized polyamide (A) is produced.

  The molecular weight of the copolymerized polyamide (A) used in the present embodiment is based on sulfuric acid relative viscosity ηr at 25 ° C.

  The sulfuric acid relative viscosity ηr at 25 ° C. of the copolymerized polyamide (A) used in the present embodiment is preferably 1.5 to 7.0 in terms of mechanical properties such as toughness, strength and rigidity, and moldability, More preferably, it is 1.7-6.0, More preferably, it is 1.9-5.5.

  As a method for controlling the sulfuric acid relative viscosity ηr at 25 ° C. of the copolymerized polyamide (A) within the above range, for example, a diamine as an additive at the time of hot melt polymerization of the copolymerized polyamide (A) and an end-capping agent Examples thereof include a method of controlling the addition amount and polymerization conditions.

  In this embodiment, the measurement of the sulfuric acid relative viscosity ηr at 25 ° C. of the copolymerized polyamide (A) can be performed according to JIS-K6920 as described in the following examples.

The melting peak temperature (melting point) T _pm-1 of the copolymerized polyamide (A) used in the present embodiment is preferably 280 ° C. or higher, more preferably 280 ° C. or higher and 330 ° C. or lower, from the viewpoint of heat resistance. More preferably, it is 300 ° C. or higher and 330 ° C. or lower, and particularly preferably 310 ° C. or higher and 325 ° C. or lower. A copolymerized polyamide (A) having a melting peak temperature T _pm-1 of 330 ° C. or lower is preferable because thermal decomposition in melt processing such as extrusion and molding can be suppressed.

As a method for controlling the melting peak temperature (melting point) T _pm-1 of the copolymerized polyamide (A) within the above range, for example, the constituent components of the copolymerized polyamide (A) are the above components (a) to (c). And a method of controlling the blending ratio of the copolymer component to the above-described range.

  In this embodiment, the melting peak temperature (melting point), the crystallization peak temperature, and the crystallization enthalpy of the copolymerized polyamide (A) can be measured by differential scanning calorimetry (DSC) according to JIS-K7121. . Specifically, it can be measured as follows.

As the measuring device, Diamond-DSC manufactured by PERKIN-ELMER can be used. The measurement conditions are such that about 10 mg of the sample is heated from 50 ° C. to 350 ° C. at a temperature increase rate of 20 ° C./min in a nitrogen atmosphere. The endothermic peak that appears at this time is the melting peak, and the peak that appears on the highest temperature side is the melting peak temperature _Tpm . Subsequently, after being kept at 350 ° C. for 3 minutes, it is cooled from 350 ° C. to 50 ° C. at a cooling rate of 20 ° C./min. The exothermic peak appearing at this time is defined as a crystallization peak, the crystallization peak temperature is _defined as T _pc-1 , and the crystallization peak area is defined as a crystallization enthalpy. Subsequently, after maintaining at 50 ° C. for 3 minutes, the temperature is increased again from 50 ° C. to 350 ° C. at a temperature increase rate of 20 ° C./min. The endothermic peak that appears on the highest temperature side at this time is the melting peak temperature T _pm-1, and the endothermic peak that appears on the lowest temperature side is the melting peak temperature T _pm-2 . When there is one endothermic peak appearing at this time, the endothermic peaks are defined as melting peak temperatures T _pm-1 and T _pm-2 (T _pm-1 = T _pm-2 ). Further, after being kept at 350 ° C. for 3 minutes, it is cooled from 350 ° C. to 50 ° C. at a cooling rate of 50 ° C./min. The crystallization peak temperature appearing at this time is _defined as T _pc-2 .

The copolymer polyamide (A) used in the present embodiment preferably has a difference (T _pm -T _pm-1 ) between the melting peak temperature T _pm and the melting peak temperature T _pm-1 of 30 ° C. or less. The temperature is more preferably in the range of 20 ° C, and further preferably in the range of 0 to 10 ° C. In the copolymerized polyamide (A), the smaller the difference between the melting peak temperature T _pm and the melting peak temperature T _pm-1 (T _pm -T _pm-1 ), the smaller the (a) alicyclic ring in the copolymerized polyamide (A). This means that the part derived from the group dicarboxylic acid has a thermodynamically stable structure. The copolymerized polyamide (A) in which the difference (T _pm -T _pm-1 ) between the melting peak temperature T _pm and the melting peak temperature T _pm-1 is in the above range is excellent in plasticization time stability. Moreover, the copolymerized polyamide composition containing the copolymerized polyamide (A) is excellent in surface appearance and continuous productivity. In the copolymerized polyamide (A), as a method for controlling the difference between the melting peak temperature _Tpm and the melting peak temperature _Tpm-1 ( _Tpm - _Tpm-1 ) within the above range, for example, a copolymerized polyamide ( The component (A) is the components (a) to (c) described above, the blending ratio of the copolymer component is in the above-described range, and is derived from the (a) alicyclic dicarboxylic acid in the copolymer polyamide (A). The method of controlling the trans isomer ratio in a part within the range of 65-80 mol% is mentioned.

The melting peak temperature T _pm-2 of the copolymerized polyamide (A) used in the present embodiment is preferably 270 ° C. or more, more preferably 270 to 320 ° C. from the viewpoint of heat resistance, and 280 to 320 ° C. More preferably, it is in the range of 310 ° C.

As a method for controlling the melting peak temperature (melting point) T _pm-2 of the copolymerized polyamide (A) within the above range, for example, the constituent components of the copolymerized polyamide (A) are the above components (a) to (c). And a method of controlling the blending ratio of the copolymer component to the above-described range.

Furthermore, the copolymer polyamide (A) used in this embodiment has a difference (T _pm-1 -T _pm-2 ) between the melting peak temperature T _pm-1 and the melting peak temperature T _pm-2 of 30 ° C. or less. Is preferable, and it is more preferable that it is the range of 10-20 degreeC. When the difference (T _pm-1 -T _pm-2 ) between the melting peak temperature T _pm-1 and the melting peak temperature T _pm-2 in the copolymerized polyamide (A) is within the above range, release properties and low blocking are achieved. From the viewpoint of sex.

As a method of controlling the difference (T _pm-1 -T _pm-2 ) between the melting peak temperature T _pm-1 and the melting peak temperature T _pm-2 in the copolymerized polyamide (A) within the above range, for example, Examples include a method in which the constituent components of the polymerized polyamide (A) are the above components (a) to (c) and the blending ratio of the copolymer components is controlled within the above-described range.

The crystallization peak temperature T _pc-1 of the copolymerized polyamide (A) used in this embodiment is preferably 250 ° C. or higher, more preferably 260 ° C. or higher and 300 ° C. or lower, from the viewpoints of low blocking properties and releasability. It is.

As a method for controlling the crystallization peak temperature T _pc-1 of the copolymerized polyamide (A) within the above range, for example, the components (a) to (c) are used as the constituent components of the copolymerized polyamide (A). Examples include a method of controlling the blending ratio of the polymerization components within the above-described range.

The crystallization peak temperature T _pc-2 of the copolymerized polyamide (A) used in the present embodiment is preferably 240 ° C. or higher from the viewpoint of low blocking properties and releasability, and is in the range of 240 to 280 ° C. Is more preferable.

As a method for controlling the crystallization peak temperature T _pc-2 of the copolymerized polyamide (A) within the above range, for example, the constituent components of the copolymerized polyamide (A) are the above components (a) to (c), Examples include a method of controlling the blending ratio of the polymerization components within the above-described range.

Furthermore, in the copolymerized polyamide (A) used in the present embodiment, the difference (T _pc-1 −T _pc-2 ) between the crystallization peak temperature T _pc-1 and the crystallization peak temperature T _pc-2 is 10 ° C. or less. It is preferable that In the copolymerized polyamide (A), the smaller the difference (T _pc-1 -T _pc-2 ) between the crystallization peak temperature T _pc-1 and the crystallization peak temperature T _pc-2 , the faster the crystallization speed becomes. It means that the crystal structure of the polymerized polyamide is stable. When the difference (T _pc-1 -T _pc-2 ) between the crystallization peak temperature T _pc-1 and the crystallization peak temperature T _pc-2 in the copolymerized polyamide (A) is within the above range, low blocking property, It is preferable from the viewpoint of releasability.

As a method for controlling the difference (T _pc-1 -T _pc-2 ) between the crystallization peak temperature T _pc-1 and the crystallization peak temperature T _pc-2 in the copolymerized polyamide (A) within the above range, for example, And a method of controlling the blending ratio of the copolymer component within the above-described range by using the components (a) to (c) as components of the copolymer polyamide (A). In order to reduce (T _pc-1 -T _pc-2 ) and to make the copolymer polyamide (A) have a stable crystal structure, the components (a) to (a) which are constituent components of the copolymer polyamide (A) are used. c) The number of carbon atoms of the component is set to an even number, the carbon chain is linear, and the ratio of the number of carbons to the number of amide groups in the copolymerized polyamide (A) (carbon number / amide group number) is 8 or more. It is preferable to make it less than 9.

  The crystallization enthalpy of the copolymerized polyamide (A) used in the present embodiment is preferably 10 J / g or more, more preferably 15 J / g or more, from the viewpoints of heat resistance, low blocking properties, and releasability. More preferably, it is 20 J / g or more. Although the upper limit of the crystallization enthalpy of the copolymer polyamide (A) used for this embodiment is not specifically limited, For example, it is 100 J / g or less.

  As a method for controlling the crystallization enthalpy of the copolymerized polyamide (A) within the above range, for example, the ratio of the number of carbons to the number of amide groups (carbon number / amide group number) in the copolymerized polyamide (A) is 8 or more. And a method of controlling the blending ratio of the copolymer component within the above-mentioned range by using the components (a) to (c) as components of the copolymer polyamide (A).

  The glass transition temperature Tg of the copolymerized polyamide (A) used in the present embodiment is preferably 90 ° C. or higher and 170 ° C. or lower, more preferably 90 ° C. or higher and 140 ° C. or lower, and further preferably 100 ° C. or higher and 140 ° C. or lower. It is. By setting the glass transition temperature Tg to 90 ° C. or higher, a copolymerized polyamide (A) having excellent heat resistance and chemical resistance can be obtained. Moreover, by setting the glass transition temperature to 170 ° C. or lower, a molded product having a good surface appearance can be obtained from the copolymerized polyamide (A).

  As a method for controlling the glass transition temperature Tg of the copolymerized polyamide (A) within the above range, for example, the components (a) to (c) are used as the components of the copolymerized polyamide (A), and the components of the copolymerized component are blended. Examples include a method of controlling the ratio within the above-described range.

  In the present embodiment, the glass transition temperature Tg can be measured by differential scanning calorimetry (DSC) according to JIS-K7121. Specifically, it can measure by the method as described in the Example mentioned later.

The copolymerized polyamide (A) used in the present embodiment has a difference (T _pc) between the crystallization peak temperature T _pc-1 obtained when cooled at 20 ° C./min and the glass transition temperature Tg in differential scanning calorimetry. ₋₁ −Tg) is preferably 140 ° C. or higher, more preferably 145 ° C. or higher, and further preferably 150 ° C. or higher. In the copolymerized polyamide (A), the larger the difference (T _pc-1 -Tg) between the crystallization peak temperature T _pc-1 and the glass transition temperature Tg, the wider the temperature range that can be crystallized. ) Is stable. The copolymerized polyamide (A) having a difference between the crystallization peak temperature T _pc-1 and the glass transition temperature Tg (T _pc-1 -Tg) of 140 ° C. or more is excellent in low blocking property and releasability. Although the upper limit of the difference (T _pc-1 -Tg) between the crystallization peak temperature T _pc-1 and the glass transition temperature Tg is not particularly limited, it is, for example, 300 ° C. or less.

As a method for controlling the difference (T _pc-1 -Tg) between the crystallization peak temperature T _pc-1 and the glass transition temperature Tg in the copolymerized polyamide (A), for example, the constituent components of the copolymerized polyamide (A) are: A method of controlling the blending ratio of the copolymer component within the above-described range as the above components (a) to (c) can be mentioned. In order to increase (T _pc-1 -Tg) and to make the copolymer polyamide (A) have a stable crystal structure, the number of carbon atoms of the copolymer components (a) to (c) should be an even number. In addition, it is preferable that the carbon chain is linear, or the ratio of carbon number to amide group number (carbon number / amide group number) in the copolymerized polyamide (A) is 8 or more and less than 9.

  The polymer terminal of the copolymerized polyamide (A) used in this embodiment is classified and defined as follows.

  That is, 1) amino terminal, 2) carboxyl terminal, 3) terminal by a sealant, and 4) other terminal.

  The polymer terminal of the copolymerized polyamide (A) means a terminal part of a polymer chain obtained by polymerizing dicarboxylic acid and diamine by an amide bond. The polymer terminal of the copolymerized polyamide (A) is one or more of these terminals 1) to 4).

1) The amino terminal is a polymer terminal to which an amino group (—NH ₂ group) is bonded, and is derived from a raw material diamine.

  2) The carboxyl end is a polymer end to which a carboxyl group (—COOH group) is bonded, and is derived from the raw material dicarboxylic acid.

  3) The terminal by a sealing agent is the terminal terminal of the polymer sealed by the terminal sealing agent added at the time of superposition | polymerization, for example, carboxylic acid or an amine.

  4) The other terminal is a polymer terminal not classified in the above 1) to 4), and is not particularly limited. For example, the amino terminal is decarboxylated from the terminal generated by deammonia reaction or the carboxyl terminal. Examples include the generated terminal.

  The ratio of the amino terminal amount to the total amount of the amino terminal amount and the carboxyl terminal amount in the copolymerized polyamide (A) used in this embodiment {amino terminal amount / (amino terminal amount + carboxyl terminal amount)} is not particularly limited, Preferably it is 0.3 or more, More preferably, it is 0.5 or more, More preferably, it is 0.7 or more. The upper limit of the ratio of the amino terminal amount to the total amount of amino terminal amount and carboxyl terminal amount {amino terminal amount / (amino terminal amount + carboxyl terminal amount)} in the copolymer polyamide (A) used in the present embodiment is 1. It is preferably less than 0. By setting the ratio of the amino terminal amount to the total amount of the amino terminal amount and the carboxyl terminal amount in the copolymerized polyamide (A) to 0.3 or more, the strength, toughness, thermal stability and resistance of the copolymerized polyamide (A) are increased. Hydrolyzability can be improved. Moreover, the copolymerized polyamide composition containing the copolymerized polyamide (A) is excellent in vibration fatigue characteristics.

  As a method of controlling the ratio {amino terminal amount / (amino terminal amount + carboxyl terminal amount)} of amino terminal amount to total amount of amino terminal amount and carboxyl terminal amount in copolymerized polyamide (A), for example, copolymerized polyamide Examples thereof include a method of controlling the addition amount of the diamine and the end-capping agent as additives during the hot melt polymerization (A) and the polymerization conditions.

  The amount of amino terminal bound to the polymer terminal is measured by neutralization titration. Specifically, 3.0 g of polyamide is dissolved in 100 mL of 90% by mass phenol aqueous solution, and the resulting solution is titrated with 0.025N hydrochloric acid, and the amino terminal amount is determined based on the titration result. The end point is determined from the indicated value of the pH meter.

  The amount of carboxyl terminal bound to the polymer terminal is measured by neutralization titration. Specifically, 4.0 g of polyamide is dissolved in 50 mL of benzyl alcohol, and the resulting solution is titrated with 0.1N NaOH, and the carboxyl end amount is determined based on the titration result. The end point is determined from the discoloration of the phenolphthalein indicator.

  In the copolymerized polyamide (A) used in the present embodiment, the ratio of carbon number to amide group number (carbon number / amide group number) is preferably 8 or more, more preferably 8.2 or more, from the viewpoint of low water absorption. Is less than 9. The ratio of carbon number to amide group number (carbon number / amide group number) is an index indicating the amino group concentration of the copolymerized polyamide (A). By making the ratio of the number of carbon atoms to the number of amide groups (carbon number / amide group number) within the above range, the strength, high-temperature strength, low water absorption, low blocking property, releasability, and plasticization time stability were excellent. A copolymerized polyamide (A) and a copolymerized polyamide composition excellent in vibration fatigue characteristics, surface appearance, and continuous productivity can be provided.

  Examples of a method for controlling the ratio of the number of carbon atoms to the number of amide groups (carbon number / amide group number) in the copolymerized polyamide (A) include the components (a) to (c) described above as constituent components of the copolymerized polyamide (A). And a method of controlling the blending ratio of the copolymer component within the above-described range.

  The index indicating the amino group concentration (carbon number / amide group number) can be obtained by calculating the average value of the number of carbon atoms per amide group in the copolymerized polyamide (A). Specifically, it can be determined by the method described in Examples described later.

[Production method of copolymerized polyamide (A)]
Although it does not specifically limit as a manufacturing method of the copolyamide (A) used for this embodiment, For example, (a) at least 1 sort (s) of alicyclic dicarboxylic acid, and (b) 1 type of C8 or more are mentioned, for example. And (c) a method for producing a copolymerized polyamide comprising a step of polymerizing at least one copolymer component.

  The method for producing the copolymerized polyamide (A) used in the present embodiment preferably further includes a step of increasing the degree of polymerization of the copolymerized polyamide.

Although it does not specifically limit as a specific manufacturing method of the copolyamide (A) used for this embodiment, For example, various methods are mentioned so that it may illustrate below:
1) A method in which an aqueous solution or a suspension of water of a dicarboxylic acid, a diamine salt or a mixture thereof is heated and polymerized while maintaining a molten state (hereinafter sometimes referred to as “hot melt polymerization method”).

  2) A method of increasing the degree of polymerization while maintaining the solid state of the polyamide obtained by the hot melt polymerization method at a temperature below the melting point (hereinafter sometimes abbreviated as “hot melt polymerization / solid phase polymerization method”).

  3) A method of polymerizing using a dicarboxylic acid halide component equivalent to a dicarboxylic acid and a diamine component (“solution method”).

Among them, a production method including a hot melt polymerization method is preferable, and when the copolymerized polyamide (A) is produced by the hot melt polymerization method, it is preferable to maintain a molten state until the polymerization is completed. In order to maintain a molten state, it is preferable to produce it under polymerization conditions suitable for the composition of the copolymerized polyamide (A). Specifically, for example, the polymerization pressure in the hot melt polymerization method is controlled to a high pressure of 23 to 50 kg / cm ² (gauge pressure), preferably 25 kg / cm ² (gauge pressure) or more, and while heating is continued, A method in which the pressure is lowered while taking 30 minutes or more until the internal pressure becomes atmospheric pressure (gauge pressure is 0 kg / cm ² ) can be mentioned. The copolymerized polyamide (A) obtained by such a production method can satisfy the characteristics such as the trans isomer ratio described above.

  In the method for producing the copolymerized polyamide (A) used in the present embodiment, from the viewpoint of fluidity of the copolymerized polyamide (A), it is derived from (a) the alicyclic dicarboxylic acid in the copolymerized polyamide (A) to be obtained. It is preferable to carry out the polymerization while maintaining the trans isomer ratio of the portion at 85% or less. In particular, by maintaining the trans isomer ratio at 80% or less, more preferably from 65 to 80%, the copolymer polyamide (A) having excellent color tone, tensile elongation and plasticization time stability and having a high melting point can be obtained. Can be obtained. Moreover, the copolymerized polyamide composition containing the copolymerized polyamide (A) is excellent in surface appearance and continuous productivity.

  In the method for producing the copolyamide (A) used in the present embodiment, in order to increase the degree of polymerization and increase the melting point of the copolyamide (A), the heating temperature is increased and / or the heating time is increased. May be lengthened. In that case, there is a possibility that the tensile elongation is lowered due to coloring of the copolymerized polyamide (A) by heating or thermal degradation. In addition, the rate of increase in molecular weight may be significantly reduced.

  The copolymerized polyamide (A) is colored by maintaining the trans isomer ratio in the portion derived from the (a) alicyclic dicarboxylic acid in the copolymerized polyamide (A) at 80% or less. It is possible to prevent a decrease in tensile elongation and stability in plasticizing time due to heat deterioration, and a decrease in surface appearance and continuous productivity of the copolymerized polyamide composition containing the copolymerized polyamide (A). Can be prevented.

  As a method for producing the copolyamide (A) used in the present embodiment, a method of producing a copolyamide by 1) a hot melt polymerization method and 2) a hot melt polymerization / solid phase polymerization method is preferable. With such a production method, it is easy to maintain the trans isomer ratio in the portion derived from (a) the alicyclic dicarboxylic acid in the copolymerized polyamide (A) at 80% or less. The resulting copolymerized polyamide (A) is excellent in color tone and plasticization time stability. Furthermore, the copolymerized polyamide composition containing the copolymerized polyamide (A) is excellent in surface appearance and continuous productivity.

  In the method for producing the copolyamide (A) used in the present embodiment, the polymerization form may be a batch type or a continuous type.

  The polymerization apparatus is not particularly limited, and examples thereof include known apparatuses such as an autoclave type reactor, a tumbler type reactor, and an extruder type reactor such as a kneader.

  Although it does not specifically limit as a more specific manufacturing method of the copolymerization polyamide (A) used for this embodiment, For example, a copolymerization polyamide can be manufactured with the batch type hot-melt-polymerization method described below.

  Although it does not specifically limit as a method of manufacturing copolyamide by a batch type hot-melt-polymerization method, For example, the following methods are mentioned. When producing a copolymerized polyamide by a hot melt polymerization method, it is preferable to maintain a molten state until the polymerization is completed. In order to maintain a molten state, it is preferable to produce it under polymerization conditions suitable for the composition of the copolymerized polyamide (A).

Using water as a solvent, an aqueous solution of about 40 to 60% by mass containing the constituent components of the copolyamide (A) (the above components (a) to (c)) was heated to 110 to 180 ° C. In a concentration tank operated at a pressure of 6 kg / cm ² (gauge pressure), the solution is concentrated to about 65 to 90% by mass to obtain a concentrated solution. The concentrated solution is then transferred to an autoclave and heating is continued until the pressure in the vessel is about 23-50 kg / cm ² (gauge pressure). Thereafter, the pressure is maintained at about 23 to 50 kg / cm ² (gauge pressure) while removing water and / or gas components. Here, in order to maintain the molten state, a pressure suitable for the constituent component of the copolymerized polyamide is preferable. Especially when a diamine having a large carbon number is used, the pressure in the container is 25 kg / cm ² (gauge pressure) or more. It is preferable that When the temperature in the container reaches about 250 to 350 ° C., the pressure in the container is reduced to atmospheric pressure (gauge pressure is 0 kg / cm ² ). Here, in order to maintain a molten state, it is preferable to reduce the pressure while continuing heating and taking 30 minutes or more. By reducing the pressure to atmospheric pressure and then reducing the pressure as necessary, by-product water can be effectively removed. Thereafter, pressurization is performed with an inert gas such as nitrogen to extrude the polyamide melt as a strand. The final temperature of the resin temperature (liquid temperature) is preferably higher by 10 ° C. or more than T _pm-1 in order to maintain a molten state. The strand can be cooled and cut to obtain copolymerized polyamide pellets.

≪ (B) Fibrous reinforcement≫
The polyamide composition of this embodiment contains the above-mentioned (A) copolymer polyamide and (B) a fibrous reinforcing material having a number average fiber diameter of 3 to 9 μm.

  The polyamide composition of this embodiment is excellent in heat resistance, toughness, fluidity, rigidity, etc. by containing (B) a fibrous reinforcing material having a number average fiber diameter of 3 to 9 μm. Without impairing the properties of the polymerized polyamide, in addition to these properties, it is excellent in mechanical strength, dimensional stability and vibration fatigue resistance.

  (B) The fibrous reinforcing material is not particularly limited as long as the number average fiber diameter is 3 to 9 μm, and examples thereof include glass fibers, carbon fibers, calcium silicate fibers, potassium titanate fibers, and aluminum borate fibers. Can be mentioned.

  In particular, the (B) fibrous reinforcing material is preferably glass fiber or carbon fiber from the viewpoint of strength and rigidity, and glass fiber is particularly preferable from the viewpoint of vibration fatigue resistance.

  (B) One type of fibrous reinforcing material may be used, or two or more types may be used in combination.

  (B) The number average fiber diameter of a fibrous reinforcement is 3-9 micrometers, Preferably it is 4-8 micrometers, More preferably, it is 4-6.

  In the polyamide composition, (B) the fibrous reinforcing material has a weight average fiber length of preferably 100 to 500 μm, more preferably 150 to 450 μm, and further preferably 200 to 400. When the weight average fiber length is within the above range, the polyamide composition is more excellent in mechanical strength, dimensional stability and vibration fatigue resistance.

  In this embodiment, the number average fiber diameter of the (B) fibrous reinforcing material can be used as it is if there is a nominal value by the manufacturer of the product when using a commercially available product as the (B) fibrous reinforcing material. When there is no nominal value, it can be easily obtained from the measured value with a microscope. Specifically, the number average fiber diameter of the (B) fibrous reinforcing material is determined by the following method. 100 or more arbitrarily selected (B) fibrous reinforcing materials are observed with a scanning electron microscope (SEM), and the fiber diameters of these (B) fibrous reinforcing materials are measured. Based on the measured values, The number average fiber diameter can be determined.

  Moreover, the weight average fiber length of the (B) fibrous reinforcement in the polyamide composition of this embodiment is calculated | required with the following method. Using the SEM photograph of the 100 or more (B) fibrous reinforcing materials photographed at a magnification of 1,000 times, the fiber length of each fibrous reinforcing material was measured, and the weight average fiber based on the measured values You can ask for the length.

  (B) By making the number average fiber diameter of the fibrous reinforcing material 3 μm or more, the mechanical strength, heat resistance, rigidity and the like of the polyamide composition of the present embodiment are improved, and by making it 9 μm or less, the mechanical strength is improved. A polyamide composition having excellent strength, toughness, heat resistance, dimensional stability and vibration fatigue resistance can be obtained.

  In the polyamide composition of the present embodiment, the content of the (B) fibrous reinforcing material is preferably 0.1 to 200 parts by mass, more preferably 100 parts by mass of the (A) copolymerized polyamide described above. Is 1 to 200 parts by mass, more preferably 5 to 150 parts by mass.

  (B) By making the content of the fibrous reinforcing material 0.1 parts by mass or more with respect to 100 parts by mass of the (A) copolymerized polyamide, mechanical properties such as toughness and rigidity of the polyamide composition of the present embodiment are obtained. Moreover, the polyamide composition which is excellent in moldability is obtained by making the content of (B) fibrous reinforcing material 200 parts by mass or less with respect to 100 parts by mass of (A) copolymerized polyamide.

  (B) When a fibrous reinforcement is glass fiber, E glass composition, C glass composition, S glass composition, alkali-resistant glass composition etc. are mentioned as a specific composition.

The tensile strength of the glass fiber is arbitrary, but is usually 290 kg / mm ² or more.

  Among these, E glass is preferable from the viewpoint of easy availability.

  These glass fibers are not particularly limited, but are surface-treated with a silane coupling agent such as γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-aminopropyltriethoxysilane. It is preferable. The adhesion amount of the silane coupling agent is preferably 0.01% by mass or more based on the glass fiber weight (total amount of the glass fiber and the surface treatment agent).

  Further, (B) the fibrous reinforcing material can be treated with a sizing agent, if necessary.

  As the sizing agent, a unit composed of a unit composed of a carboxylic acid anhydride-containing unsaturated vinyl monomer and a unit composed of an unsaturated vinyl monomer (excluding the carboxylic acid anhydride-containing unsaturated vinyl monomer) Copolymers, epoxy compounds, polyurethane resins, homopolymers of acrylic acid, copolymers of acrylic acid and other copolymerizable monomers, and salts of these with primary, secondary and tertiary amines, etc. Can be mentioned.

  These may be used individually by 1 type and may be used in combination of 2 or more type.

  In particular, from the viewpoint of mechanical strength of the polyamide composition, a unit composed of a carboxylic acid anhydride-containing unsaturated vinyl monomer and an unsaturated vinyl monomer (excluding the carboxylic acid anhydride-containing unsaturated vinyl monomer). And a combination thereof, and a combination thereof. Among these, a carboxylic acid anhydride-containing unsaturated vinyl monomer is preferable from the viewpoint of toughness and vibration fatigue resistance. And a copolymer containing a unit consisting of a unit consisting of an unsaturated vinyl monomer (excluding the carboxylic acid anhydride-containing unsaturated vinyl monomer) as a constituent unit. A copolymer comprising an unsaturated vinyl monomer and a unit composed of an unsaturated vinyl monomer (excluding the carboxylic anhydride-containing unsaturated vinyl monomer) as constituent units The combination of coalescing and polyurethane resins are more preferred.

≪Inorganic filler other than (B) ≫
The polyamide composition of this embodiment may use a predetermined inorganic filler in addition to the above (B): fibrous reinforcing material having a number average fiber diameter of 3 to 9 μm.

  In the molded body containing the polyamide composition of the present embodiment, from the viewpoint of reducing the occurrence of warpage and reducing the dimensional anisotropy, (B): fibrous reinforcement having a number average fiber diameter of 3 to 9 μm It is preferable to include an inorganic filler other than the material.

  The inorganic filler is not particularly limited, and examples thereof include glass flakes, glass beads, hollow glass beads, talc, kaolin, mica, hydrotalcite, calcium carbonate, zinc carbonate, zinc oxide, calcium monohydrogen phosphate, Lastite, silica, zeolite, alumina, boehmite, aluminum hydroxide, titanium oxide, silicon oxide, magnesium oxide, calcium silicate, sodium aluminosilicate, magnesium silicate, ketjen black, acetylene black, furnace black, carbon nanotube, graphite , Brass, copper, silver, aluminum, nickel, iron, calcium fluoride, montmorillonite, swellable fluorine mica, and apatite.

  These inorganic fillers may be surface-treated.

  As the inorganic filler, one kind may be used, or two or more kinds may be used in combination.

  As the inorganic filler, wollastonite is more preferable. Among the wollastonites, those having a number average fiber diameter of 3 to 30 μm, a weight average fiber length of 10 to 500 μm, and an aspect ratio (weight average fiber length / number average fiber diameter) of 3 to 100 are further included. Preferably used.

  Furthermore, as the inorganic filler, talc, mica, kaolin, silicon nitride and the like are more preferable. Among talc, mica, kaolin, and silicon nitride, those having a number average fiber diameter of 0.1 to 3 μm are more preferably used.

  The number average fiber diameter and the weight average fiber length of the inorganic filler are measured by dissolving a polyamide composition molded article in a polyamide-soluble solvent such as formic acid. More than fibrous reinforcements and inorganic fillers are arbitrarily selected and observed with an optical microscope, a scanning electron microscope or the like, or the molded product is incinerated with, for example, an electric furnace, etc. It is obtained by arbitrarily selecting a fibrous reinforcing material and an inorganic filler, and observing and measuring with an optical microscope, a scanning electron microscope, or the like.

≪ (C) Thermal stabilizer≫
The polyamide composition of the present embodiment includes (C) a phenol-based heat stabilizer, a phosphorus-based heat stabilizer, an amine-based heat stabilizer, Group Ib, Group IIb, Group IIIa, Group IIIb of the periodic table, It may further contain at least one heat stabilizer selected from the group consisting of metal salts of Group IVa and Group IVb elements, and alkali metal and alkaline earth metal halides.

(Phenolic heat stabilizer)
Although it does not restrict | limit especially as a phenol type heat stabilizer, For example, a hindered phenol compound is mentioned.

  Phenol-based heat stabilizers, particularly hindered phenol compounds, have the property of imparting heat resistance and light resistance to resins such as polyamide and fibers.

  The hindered phenol compound is not particularly limited. For example, N, N′-hexane-1,6-diylbis [3- (3,5-di-t-butyl-4-hydroxyphenylpropionamide), penta Erythrityl-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], N, N′-hexamethylenebis (3,5-di-tert-butyl-4-hydroxy-hydro Cinnamamide), triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], 3,9-bis {2- [3- (3-t-butyl- 4-hydroxy-5-methylphenyl) propynyloxy] -1,1-dimethylethyl} -2,4,8,10-tetraoxapyro [5,5] undecane, 3,5-di- -Butyl-4-hydroxybenzylphosphonate-diethyl ester, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, and 1,3,3 5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanuric acid.

  A phenol type heat stabilizer may be used individually by 1 type, and may be used in combination of 2 or more type.

  In particular, as a phenol-based heat stabilizer, N, N′-hexane-1,6-diylbis [3- (3,5-di-t-butyl-4-hydroxyphenylpropion) is used from the viewpoint of improving heat aging resistance. Amide)] is preferred.

  When using a phenol-based heat stabilizer, the content of the phenol-based heat stabilizer in the polyamide composition is preferably 0.01 to 1 part by weight with respect to 100 parts by weight of the copolymerized polyamide (A), and more Preferably it is 0.1-1 mass part. When the content of the phenol-based heat stabilizer in the polyamide composition is within the above range, the heat aging resistance of the polyamide composition can be further improved, and the amount of generated gas can be reduced.

(Phosphorus heat stabilizer)
The phosphorus-based heat stabilizer is not particularly limited. For example, pentaerythritol phosphite compound, trioctyl phosphite, trilauryl phosphite, tridecyl phosphite, octyl diphenyl phosphite, trisisodecyl phosphite, phenyl diisodecyl Phosphite, phenyldi (tridecyl) phosphite, diphenylisooctylphosphite, diphenylisodecylphosphite, diphenyl (tridecyl) phosphite, triphenylphosphite, tris (nonylphenyl) phosphite, tris (2,4-di-) t-butylphenyl) phosphite, tris (2,4-di-t-butyl-5-methylphenyl) phosphite, tris (butoxyethyl) phosphite, 4,4′-butylidene-bis (3-methyl 6-tert-butylphenyl-tetra-tridecyl) diphosphite, tetra (C12-C15 mixed alkyl) -4,4′-isopropylidene diphenyldiphosphite, 4,4′-isopropylidenebis (2-t-butyl) Phenyl) di (nonylphenyl) phosphite, tris (biphenyl) phosphite, tetra (tridecyl) -1,1,3-tris (2-methyl-5-tert-butyl-4-hydroxyphenyl) butanediphosphite, Tetra (tridecyl) -4,4′-butylidenebis (3-methyl-6-tert-butylphenyl) diphosphite, tetra (C1-C15 mixed alkyl) -4,4′-isopropylidene diphenyldiphosphite, tris (mono, Dimixed nonylphenyl) phosphite, 9,10-di-hydro-9-oxa-9- Oxa-10-phosphaphenanthrene-10-oxide, tris (3,5-di-tert-butyl-4-hydroxyphenyl) phosphite, hydrogenated-4,4′-isopropylidene diphenyl polyphosphite, bis (Octylphenyl) bis (4,4′-butylidenebis (3-methyl-6-tert-butylphenyl)) 1,6-hexanol diphosphite, hexatridecyl-1,1,3-tris (2-methyl- 4-hydroxy-5-t-butylphenyl) diphosphite, tris (4,4′-isopropylidenebis (2-t-butylphenyl)) phosphite, tris (1,3-stearoyloxyisopropyl) phosphite, 2, 2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite, 2,2-methylenebis (3-methyl) -4,6-di-tert-butylphenyl) 2-ethylhexyl phosphite, tetrakis (2,4-di-tert-butyl-5-methylphenyl) -4,4'-biphenylenediphosphite, and tetrakis (2 , 4-di-t-butylphenyl) -4,4′-biphenylene diphosphite.

  These may be used alone or in combination of two or more.

  Among the phosphorus-based heat stabilizers, among those listed above, from the viewpoint of further improving the heat aging resistance of the polyamide composition and reducing the generated gas, a pentaerythritol phosphite compound, tris (2,4-di- t-Butylphenyl) phosphite is preferred.

  The pentaerythritol type phosphite compound is not particularly limited. For example, (2,6-di-t-butyl-4-methylphenyl) phenylpentaerythritol diphosphite, (2,6-di-t-butyl) -4-methylphenyl) methylpentaerythritol diphosphite, (2,6-di-t-butyl-4-methylphenyl) 2-ethylhexylpentaerythritol diphosphite, (2,6-di-t-butyl-4) -Methylphenyl) isodecylpentaerythritol diphosphite, (2,6-di-t-butyl-4-methylphenyl) laurylpentaerythritol diphosphite, (2,6-di-t-butyl-4-methylphenyl) ) Isotridecyl pentaerythritol diphosphite, (2,6-di-t-butyl-4) Methylphenyl) stearylpentaerythritol diphosphite, (2,6-di-t-butyl-4-methylphenyl) cyclohexylpentaerythritol diphosphite, (2,6-di-t-butyl-4-methylphenyl) benzyl Pentaerythritol diphosphite, (2,6-di-t-butyl-4-methylphenyl) ethyl cellosolve pentaerythritol diphosphite, (2,6-di-t-butyl-4-methylphenyl) butyl carbitol penta Erythritol diphosphite, (2,6-di-t-butyl-4-methylphenyl) octylphenyl pentaerythritol diphosphite, (2,6-di-t-butyl-4-methylphenyl) nonylphenyl pentaerythritol di Phosphite, bis (2,6-di-t-butyl 4-methylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-butyl-4-ethylphenyl) pentaerythritol diphosphite, (2,6-di-t-butyl-4-methyl) Phenyl) (2,6-di-t-butylphenyl) pentaerythritol diphosphite, (2,6-di-t-butyl-4-methylphenyl) (2,4-di-t-butylphenyl) pentaerythritol Diphosphite, (2,6-di-t-butyl-4-methylphenyl) (2,4-di-t-octylphenyl) pentaerythritol diphosphite, (2,6-di-t-butyl-4 -Methylphenyl) (2-cyclohexylphenyl) pentaerythritol diphosphite, (2,6-di-t-amyl-4-methylphenyl) phenylpen Taerythritol diphosphite, bis (2,6-di-t-amyl-4-methylphenyl) pentaerythritol diphosphite, and bis (2,6-di-t-octyl-4-methylphenyl) penta An example is erythritol diphosphite.

  These may be used alone or in combination of two or more.

  Among the pentaerythritol type phosphite compounds listed above, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-butyl-4-) Ethylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-amyl-4-methylphenyl) pentaerythritol diphosphite, and bis (2,6-di-t-octyl-4-methylphenyl) Pentaerythritol diphosphite is preferred, and bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite is more preferred.

  When using a phosphorus-based heat stabilizer, the content of the phosphorus-based heat stabilizer in the polyamide composition is preferably 0.01 to 1 part by weight with respect to 100 parts by weight of the copolymerized polyamide (A). Preferably it is 0.1-1 mass part.

  When the content of the phosphorus-based heat stabilizer in the polyamide composition is within the above range, the heat aging resistance of the polyamide composition can be further improved, and the amount of generated gas can be reduced.

(Amine heat stabilizer)
The amine heat stabilizer is not particularly limited, and examples thereof include 4-acetoxy-2,2,6,6-tetramethylpiperidine, 4-stearoyloxy-2,2,6,6-tetramethylpiperidine, 4- Acryloyloxy-2,2,6,6-tetramethylpiperidine, 4- (phenylacetoxy) -2,2,6,6-tetramethylpiperidine, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine 4-methoxy-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, 4-cyclohexyloxy-2,2,6,6-tetramethylpiperidine 4-benzyloxy-2,2,6,6-tetramethylpiperidine, 4-phenoxy-2,2,6,6-tetramethylpiperidine, -(Ethylcarbamoyloxy) -2,2,6,6-tetramethylpiperidine, 4- (cyclohexylcarbamoyloxy) -2,2,6,6-tetramethylpiperidine, 4- (phenylcarbamoyloxy) -2,2 , 6,6-tetramethylpiperidine, bis (2,2,6,6-tetramethyl-4-piperidyl) -carbonate, bis (2,2,6,6-tetramethyl-4-piperidyl) -oxalate, bis (2,2,6,6-tetramethyl-4-piperidyl) -malonate, bis (2,2,6,6-tetramethyl-4-piperidyl) -sebacate, bis (2,2,6,6-tetra Methyl-4-piperidyl) -adipate, bis (2,2,6,6-tetramethyl-4-piperidyl) -terephthalate, 1,2-bis (2,2,6,6- Tramethyl-4-piperidyloxy) -ethane, α, α′-bis (2,2,6,6-tetramethyl-4-piperidyloxy) -p-xylene, bis (2,2,6,6-tetramethyl) -4-piperidyltolylene-2,4-dicarbamate, bis (2,2,6,6-tetramethyl-4-piperidyl) -hexamethylene-1,6-dicarbamate, tris (2,2,6, 6-tetramethyl-4-piperidyl) -benzene-1,3,5-tricarboxylate, tris (2,2,6,6-tetramethyl-4-piperidyl) -benzene-1,3,4-tricarboxy 1- [2- {3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy} butyl] -4- [3- (3,5-di-t-butyl-4- Hydroxyphenyl) propi Nyloxy] 2,2,6,6-tetramethylpiperidine, 1,2,3,4-butanetetracarboxylic acid, 1,2,2,6,6-pentamethyl-4-piperidinol and β, β, β ′ , Β′-tetramethyl-3,9- [2,4,8,10-tetraoxaspiro (5,5) undecane] diethanol.

  These may be used alone or in combination of two or more.

  When the amine heat stabilizer is used, the content of the amine heat stabilizer in the polyamide composition is preferably 0.01 to 1 part by mass with respect to 100 parts by mass of the copolymerized polyamide (A). Preferably it is 0.1-1 mass part. When the content of the amine heat stabilizer in the polyamide composition is within the above range, the heat aging resistance of the polyamide composition can be further improved, and the amount of generated gas can be further reduced.

(Metal salts of elements of Group Ib, Group IIb, Group IIIa, Group IIIb, Group IVa and Group IVb of the periodic table)
The metal salt of the elements of Group Ib, Group IIb, Group IIIa, Group IIIb, Group IVa, and Group IVb of the periodic table is not particularly limited, but is preferably a copper salt.

  Although it does not specifically limit as a copper salt, For example, copper halide (copper iodide, cuprous bromide, cupric bromide, cuprous chloride, etc.), copper acetate, copper propionate, copper benzoate, Examples include copper adipate, copper terephthalate, copper isophthalate, copper salicylate, copper nicotinate and copper stearate, and copper complex salts in which copper is coordinated to a chelating agent such as ethylenediamine and ethylenediaminetetraacetic acid.

  These may be used alone or in combination of two or more.

  Among the copper salts listed above, at least one selected from the group consisting of copper iodide, cuprous bromide, cupric bromide, cuprous chloride and copper acetate is preferred, and copper iodide and more preferably / Or copper acetate.

  When such a preferable copper salt is used, a polyamide composition having excellent heat aging resistance and capable of suppressing metal corrosion of the screw or cylinder during extrusion (hereinafter also simply referred to as “metal corrosion”) can be obtained.

  When using a copper salt, the content of the copper salt in the polyamide composition is preferably 0.01 to 0.2 parts by mass, more preferably 0.000 parts by mass with respect to 100 parts by mass of the copolyamide (A). 02 to 0.15 parts by mass.

  When the content of the copper salt in the polyamide composition is within the above range, the heat aging resistance of the polyamide composition can be further improved, and copper precipitation and metal corrosion can be suppressed.

  Further, from the viewpoint of improving the heat aging resistance of the polyamide composition, the copper element content is preferably 10 to 500 ppm, more preferably 30 to 500 ppm, and even more preferably 50, based on the total amount of the polyamide composition. ~ 300 ppm.

(Alkali metal and alkaline earth metal halides)
Alkali metal and alkaline earth metal halides are not particularly limited, and examples thereof include potassium iodide, potassium bromide, potassium chloride, sodium iodide and sodium chloride, and mixtures thereof.

  In particular, the alkali metal and alkaline earth metal halides are preferably potassium iodide and potassium bromide, and mixtures thereof from the viewpoint of improving the heat aging resistance of the polyamide composition and suppressing metal corrosion. More preferred is potassium iodide.

  When the alkali metal and alkaline earth metal halide is used, the content of the alkali metal and alkaline earth metal halide in the polyamide composition is preferably 0 with respect to 100 parts by mass of the copolymerized polyamide (A). 0.05 to 5 parts by mass, and more preferably 0.2 to 2 parts by mass. When it is within the above range, the heat aging resistance is further improved, and copper precipitation and metal corrosion can be suppressed.

  The component of the (C) heat stabilizer mentioned above may be used individually by 1 type, and may be used in combination of 2 or more type. In particular, the component (C) is preferably a mixture of a copper salt and an alkali metal or alkaline earth metal halide.

  The ratio of the copper salt to the alkali metal and alkaline earth metal halide is included in the polyamide composition so that the molar ratio of halogen to copper (halogen / copper) is 2/1 to 40/1. Is more preferable, and 5/1 to 30/1 is more preferable. When the molar ratio of halogen to copper (halogen / copper) is within the above range, the heat aging resistance of the polyamide composition can be further improved.

  When the halogen / copper is 2/1 or more, it is preferable because copper precipitation and metal corrosion can be suppressed.

  On the other hand, when the halogen / copper is 40/1 or less, corrosion of the screw or the like of the molding machine can be prevented without substantially impairing mechanical properties such as toughness of the polyamide composition.

≪ (D) Nucleating agent≫
The polyamide composition of the present embodiment can further contain (D) a nucleating agent. (D) As the nucleating agent, for example, the crystallization peak temperature is increased by addition, the difference between the extrapolation start temperature and the extrapolation end temperature of the crystallization peak is reduced, or the spherulite of the obtained molded product is fine It means a substance that can achieve the effect of making it uniform or making its size uniform. (D) The nucleating agent is not particularly limited, and examples thereof include talc, boron nitride, mica, kaolin, calcium carbonate, barium sulfate, silicon nitride, carbon black, potassium titanate, and molybdenum disulfide.

  (D) A nucleating agent may be used by 1 type and may be used in combination of 2 or more types.

  (D) The nucleating agent is preferably at least one selected from the group consisting of boron nitride, talc and carbon black from the viewpoint of the nucleating agent effect.

  The polyamide composition of this embodiment can further improve mechanical strength, toughness, heat resistance, and dimensional stability, which are the effects of the present invention, by including (D) a nucleating agent.

  When (D) the nucleating agent is used, the content of the (D) nucleating agent in the polyamide composition is preferably 0.01 to 2 parts by mass with respect to 100 parts by mass of the copolymerized polyamide (A), and more Preferably it is 0.02-0.5 mass part. When the content of the (D) nucleating agent in the polyamide composition is within the above range, the mechanical strength, heat resistance and dimensional stability of the polyamide composition can be further improved.

≪Polymers other than copolymerized polyamide (A) ≫
The polyamide composition of this embodiment may contain a polymer other than the copolymerized polyamide (A).

  The polymer other than the copolymerized polyamide (A) is not particularly limited. For example, a polyamide other than the copolymerized polyamide (A), polyester, liquid crystal polyester, polyphenylene sulfide, polyphenylene ether, polycarbonate, polyarylate, phenol resin, epoxy resin Etc.

  The polyamide other than the copolymerized polyamide (A) is not particularly limited. For example, polyamide 66, polyamide 56, polyamide 46, polyamide 610, polyamide 612, polyamide 6T, polyamide 6I, polyamide 6, polyamide 11, polyamide 12, polyamide MXD6 etc. are mentioned, These homopolymers or copolymers are mentioned.

  The polyester is not particularly limited, and examples thereof include polybutylene terephthalate, polytrimethylene terephthalate, polyethylene terephthalate, and polyethylene naphthalate.

  In the polyamide composition of the present embodiment, the content of the polymer other than the copolymerized polyamide (A) is preferably 1 to 200 parts by mass, more preferably 5 to 100 parts per 100 parts by mass of the copolymerized polyamide (A). It is a mass part, More preferably, it is 5-50 mass parts. By setting the content of the polymer other than the copolymerized polyamide (A) within the above range, a polyamide composition having excellent heat resistance and releasability can be obtained.

≪Other ingredients≫
The polyamide composition of the present embodiment may further contain other components as necessary within the range not impairing the effects of the present embodiment, in addition to the components described above.

  The polyamide composition of the present embodiment may contain, for example, an antioxidant, an ultraviolet absorber, a photodegradation inhibitor, a plasticizer, a lubricant, a release agent, a flame retardant, a colorant, a dyeing agent, a pigment, and the like. In addition, other thermoplastic resins may be contained. Here, since the above-mentioned other components are greatly different in properties, there are various suitable contents for each component that hardly impair the effects of the present embodiment.

  A person skilled in the art can easily set a suitable content for each of the other components described above.

[Production method of polyamide composition]
The method for producing the polyamide composition of the present embodiment is not particularly limited as long as it is a method of mixing raw material components including the (A) copolymerized polyamide and (B) the fibrous reinforcing material.

  (A) Although it does not specifically limit as a mixing method of the raw material component containing copolymer polyamide and (B) fibrous reinforcement, For example, (A) copolymer polyamide and (B) fibrous reinforcement are Henschel mixer etc. (B) Fibrous reinforcing material is blended from the side feeder into the melted kneading method with a melt kneader or the melted kneading machine with a single screw or twin screw extruder (A) Methods and the like.

  In the method of supplying the components constituting the polyamide composition to the melt kneader, all the components may be supplied to the same supply port at once, or the components may be supplied from different supply ports.

  The melt kneading temperature is preferably 250 to 375 ° C. as the resin temperature.

  The melt kneading time is preferably 0.25 to 5 minutes.

  An apparatus for performing the melt-kneading is not particularly limited, and a known apparatus such as a single- or twin-screw extruder, a Banbury mixer, and a mixing roll can be used.

  The relative viscosity ηr at 25 ° C., the melting point Tm2, the heat of fusion ΔH, and the glass transition temperature Tg of the polyamide composition of the present embodiment can be measured by the same method as the measurement method for the (A) copolymerized polyamide.

  In addition, a polyamide composition having excellent heat resistance, moldability, and chemical resistance is obtained by having a measured value in the polyamide composition in a range similar to a preferable range as the measured value of the (A) copolymer polyamide. Can do.

[Molded body]
The molded body of the present embodiment includes the above-described polyamide composition. Examples of the molded body include sliding parts.

  The molded body of the present embodiment can be obtained by molding the above polyamide composition using a known molding method. The molding method is not particularly limited, and is generally known, for example, press molding, injection molding, gas assist injection molding, welding molding, extrusion molding, blow molding, film molding, hollow molding, multilayer molding, and melt spinning. The plastic molding method is mentioned.

  The molded body of the present embodiment is excellent in heat resistance, toughness, rigidity, low water absorption, and also excellent in heat aging resistance.

[Use]
The polyamide composition of the present embodiment is suitably used for various parts materials such as automobiles, electric and electronic, portable equipment, industrial equipment, daily necessities, household goods, and extrusion applications.

  Although it does not specifically limit as an object for motor vehicles, For example, it uses for an intake system component, a cooling system component, a fuel system component, an interior component, an exterior component, an electrical component, etc.

  Although it does not specifically limit as a motor vehicle intake system component, For example, an air intake manifold, an intercooler inlet, an exhaust pipe cover, an inner bush, a bearing retainer, an engine mount, an engine head cover, a resonator, a throttle body, etc. are mentioned.

  Although it does not specifically limit as a motor vehicle cooling system component, For example, a chain cover, a thermostat housing, an outlet pipe, a radiator tank, an oil noter, a delivery pipe, etc. are mentioned.

  Although it does not specifically limit in a vehicle fuel system component, For example, a fuel delivery pipe, a gasoline tank case, etc. are mentioned.

  Although it does not specifically limit as a vehicle interior component, For example, an instrument panel, a console box, a glove box, a steering wheel, a trim, etc. are mentioned.

  Although it does not specifically limit as a motor vehicle exterior component, For example, a mall, a lamp housing, a front grille, a mud guard, a side bumper, a door mirror stay, a roof rail, etc. are mentioned.

  Although it does not specifically limit as a motor vehicle electrical component, For example, a connector, a wire harness connector, a motor component, a lamp socket, a sensor vehicle-mounted switch, a combination switch etc. are mentioned.

  Although it does not specifically limit as an electrical and electronic component, For example, a connector, the reflector for light-emitting devices, a switch, a relay, a printed wiring board, the housing of an electronic component, an electrical outlet, a noise filter, a coil bobbin, a motor end cap, etc. are mentioned. In addition to light-emitting diodes (LEDs), reflectors for light-emitting devices are used in semiconductor packages such as photo-diodes such as laser diodes (LD), photo diodes, charge-coupled devices (CCD), and complementary metal oxide semiconductors (CMOS). Can be widely used.

  Although it does not specifically limit as portable apparatus components, For example, housing | casings, structures, etc., such as a mobile telephone, a smart phone, a personal computer, a portable game device, a digital camera, etc. are mentioned.

  Although it does not specifically limit as industrial equipment components, For example, a gear, a cam, an insulation block, a valve, an electric tool component, an agricultural equipment component, an engine cover etc. are mentioned.

  Although it does not specifically limit as household goods and household goods, For example, a button, a food container, office furniture, etc. are mentioned.

  Although it does not specifically limit as an extrusion use, For example, it uses for a film, a sheet | seat, a filament, a tube, a stick | rod, a hollow molded article, etc.

  Among these various uses, the molded product obtained from the polyamide composition of the present embodiment has a thin-walled portion (for example, a thickness of 0.5 mm), and further undergoes a heat treatment process (for example, SMT). It is particularly suitable for electrical and electronic parts such as connectors, reflectors for light emitting devices and switches.

  Moreover, since the molded product obtained from the polyamide composition of this embodiment is excellent in surface appearance, it is preferably used as a molded product having a coating film formed on the surface of the molded product. The method for forming the coating film is not particularly limited as long as it is a known method, and for example, it can be performed by coating such as spraying or electrostatic coating. The paint used for the coating is not particularly limited as long as it is a known one, and a melamine cross-linked polyester polyol resin paint, an acrylic urethane paint, or the like can be used.

  Among these, the polyamide composition of the present embodiment is suitable as a component material for automobiles because it is excellent in mechanical strength, toughness, heat resistance, and vibration fatigue resistance, and is also excellent in slidability. It is particularly suitable as a component material for gears and bearings. Moreover, since it is excellent in mechanical strength, toughness, heat resistance, and dimensional stability, it is suitable as a component material for electric and electronic use.

  Hereinafter, the present embodiment will be described more specifically with reference to examples and comparative examples, but the present embodiment is not limited to only these examples.

The raw materials and measurement methods used in Examples and Comparative Examples are shown below. In this example, 1 kg / cm ² means 0.098 MPa.

[Raw material of polyamide composition]
(A) Copolymer polyamide, (B) Fibrous reinforcing material, (C) Thermal stabilizer, (D) Nucleating agent, etc. used as raw materials for the polyamide composition are shown below.

≪ (A) Copolymer polyamide etc.≫
(1) Polyamide (PA-1) obtained by polymerizing 1,4-cyclohexanedicarboxylic acid, decamethylenediamine and sebacic acid described in Production Example 1
(2) Polyamide obtained by polymerizing 1,4-cyclohexanedicarboxylic acid, decamethylenediamine and isophthalic acid described in Production Example 2 (PA-2)
(3) Polyamide obtained by polymerizing 1,4-cyclohexanedicarboxylic acid, octamethylenediamine and isophthalic acid described in Production Example 3 (PA-3)
(4) Polyamide obtained by polymerizing 1,4-cyclohexanedicarboxylic acid, decamethylenediamine and 1,6-diaminohexane described in Production Example 4 (PA-4)
(5) Polyamide obtained by polymerizing 1,4-cyclohexanedicarboxylic acid, decamethylenediamine, 1,6-diaminohexane and sebacic acid described in Production Example 5 (PA-5)
(6) Polyamide obtained by polymerizing 1,4-cyclohexanedicarboxylic acid, undecamethylenediamine and 1,6-diaminohexane described in Production Example 6 (PA-6)
(7) Polyamide obtained by polymerizing 1,4-cyclohexanedicarboxylic acid, 1,12-diaminododecane and 1,6-diaminohexane described in Production Example 7 (PA-7)
(8) Polyamide obtained by polymerizing 1,4-cyclohexanedicarboxylic acid, 1,12-diaminododecane and 1,10-diaminodecane described in Production Example 8 (PA-8)
(9) Polyamide obtained by polymerizing 1,4-cyclohexanedicarboxylic acid, decamethylenediamine and ε-caprolactam described in Production Example 9 (PA-9)
(10) Polyamide obtained by polymerizing 1,4-cyclohexanedicarboxylic acid, decamethylenediamine and 11-aminoundecanoic acid described in Production Example 10 (PA-10)
(11) Polyamide obtained by polymerizing 1,4-cyclohexanedicarboxylic acid, 1,12-diaminododecane and 1,6-diaminohexane described in Production Example 11 (PA-11)
(12) Polyamide 66 (PA-12) obtained by polymerizing hexamethylenediamine and adipic acid
(13) Polyamide obtained by polymerizing 1,4-cyclohexanedicarboxylic acid described in Comparative Production Example 1, hexamethylenediamine, and ε-caprolactam (PA-13)
(14) Polyamide 9T (PA-14) described in Comparative Production Example 2
It shows below about dicarboxylic acid, diamine, caprolactam, etc. which comprise (A) copolymerization polyamide etc. of manufacture examples 1-11 and comparative manufacture examples 1 and 2.

<Dicarboxylic acid>
(1) 1,4-cyclohexanedicarboxylic acid (CHDA)
Product name: 1,4-CHDA HP grade (trans isomer / cis isomer = 25/75)
(Eastman Chemical)
(2) Sebacic acid (C10DC)
Product name: Sebacic acid TA (manufactured by Ito Oil Co., Ltd.)
(3) Isophthalic acid (IPA) (manufactured by Wako Pure Chemical Industries, Ltd.)
(4) Terephthalic acid (TPA) (manufactured by Wako Pure Chemical Industries, Ltd.)

<Diamine>
(1) 1,10-diaminodecane (decamethylenediamine) (C10DA) (manufactured by Tokyo Chemical Industry)
(2) 1,6-diaminohexane (hexamethylenediamine) (C6DA) (manufactured by Tokyo Chemical Industry)
(3) Octamethylenediamine (C8DA) (manufactured by Tokyo Chemical Industry Co., Ltd.)
(4) Undecamethylenediamine (C11DA) (manufactured by Tokyo Chemical Industry Co., Ltd.)
(5) 1,12-diaminododecane (dodecamethylenediamine) (C12DA) (manufactured by Tokyo Chemical Industry)
(6) 1,9-Diaminononane (nonamethylenediamine) (C9DA) (manufactured by Tokyo Chemical Industry)
(7) 2-Methyloctamethylenediamine (2MC8DA) The 2-methyloctamethylenediamine was produced with reference to the production method described in JP-A No. 05-17413.

<Caprolactam, etc.>
(1) ε-caprolactam (CPL) (manufactured by Wako Pure Chemical Industries)
(2) 11-aminoundecanoic acid (11AU) (manufactured by Aldrich)

≪ (B) Fibrous reinforcement, etc.≫
(1) Glass fiber (GF-1) treated with a sizing agent containing a maleic anhydride copolymer as in Production Example A described later. Number average fiber diameter of GF-1: 7 μm.
(2) Glass fiber (GF-2) treated with a sizing agent containing a maleic anhydride copolymer as in Production Example B described later. Number average fiber diameter of GF-2: 5 μm.
(3) Glass fiber (GF-3) treated with a sizing agent containing urethane resin as in Production Example C described later. Number average fiber diameter of GF-3: 7 μm.
(4) Glass fiber (GF-4) treated with a sizing agent containing a maleic anhydride copolymer as described in Production Example D described later. Number average fiber diameter of GF-4: 10 μm.

  In this example, the number average fiber diameter of each glass fiber was determined by the following method. 100 or more arbitrarily selected glass fibers were observed with a scanning electron microscope (SEM), the fiber diameters of these glass fibers were measured, and the number average fiber diameter was determined based on the measured values.

<Converging agent>
The components constituting the sizing agent such as (B) fibrous reinforcing material in Production Examples A to D described later are shown below.

(1) Polyurethane resin emulsion Product name: Bondic (registered trademark) 1050 (Dainippon Ink Co., Ltd.)
(Aqueous solution with a solid content of 50% by mass)
(2) Maleic anhydride copolymer emulsion Product name: Acro Binder (registered trademark) BG-7 (manufactured by Sanyo Chemical Industries, Ltd.)
(Aqueous solution with a solid content of 25% by mass)
(3) Aminosilane coupling agent Product name: KBE-903 (manufactured by Shin-Etsu Chemical Co., Ltd.)
γ-Aminopropyltriethoxysilane (4) Lubricant Brand name: Carnauba wax (manufactured by Hiroyuki Kato)

≪ (C) Thermal stabilizer≫
(1) Copper iodide (CuI) (manufactured by Wako Pure Chemical Industries, Ltd.)
(2) Potassium iodide (KI) (Wako Pure Chemical Industries, Ltd.)

≪ (D) Nucleating agent≫
(1) Boron nitride (BN)
Product name: DENKABORON NITRIDE SP-2 (manufactured by Denki Kagaku Kogyo Co., Ltd.)
(2) Talc Product name: Microace (registered trademark) L-1 (manufactured by Nippon Talc)
(3) Carbon black (CB)
Product name: Mitsubishi (registered trademark) carbon black # 2300 (Mitsubishi Chemical Corporation)

[Measuring method]
(1) Melting peak temperature (melting point), crystallization peak temperature, crystallization enthalpy Melting peak temperature (melting point), crystallization peak temperature and crystallization enthalpy of copolymerized polyamides obtained in Production Examples and Comparative Production Examples According to JIS-K7121, measurement was performed as follows using Diamond-DSC manufactured by PERKIN-ELMER. The measurement was performed under a nitrogen atmosphere. First, about 10 mg of the sample was heated from 50 ° C. to 350 ° C. at a temperature increase rate of 20 ° C./min. The endothermic peak appearing at this time was taken as the melting peak, and the peak appearing on the highest temperature side was taken as the melting peak temperature _Tpm . Subsequently, after being kept at 350 ° C. for 3 minutes, it was cooled from 350 ° C. to 50 ° C. at a cooling rate of 20 ° C./min. The exothermic peak appearing at this time was defined as a crystallization peak, the crystallization peak temperature was _defined as T _pc-1 , and the crystallization peak area was defined as a crystallization enthalpy. Subsequently, after maintaining at 50 ° C. for 3 minutes, the temperature was increased again from 50 ° C. to 350 ° C. at a temperature increase rate of 20 ° C./min. The peak that appeared on the highest temperature side at this time was defined as the melting peak temperature _Tpm-1, and the peak that appeared on the lowest temperature side was defined as the melting peak temperature _Tpm-2 . Further, after being kept at 350 ° C. for 3 minutes, it was cooled from 350 ° C. to 50 ° C. at a cooling rate of 50 ° C./min. The crystallization peak temperature appearing at this time was _defined as T _pc-2 .

(2) Glass transition temperature The glass transition temperatures of the copolymerized polyamides and the like obtained in the production examples and comparative production examples were measured as follows using Diamond-DSC manufactured by PERKIN-ELMER according to JIS-K7121. First, the sample was melted on a hot stage (EP80 manufactured by Mettler). The obtained sample in the molten state was quenched with liquid nitrogen and solidified to obtain a measurement sample. Using 10 mg of the measurement sample, the glass transition temperature Tg was measured by raising the temperature in the range of 30 to 350 ° C. under the condition of a temperature elevation rate of 20 ° C./min.

(3) Sulfuric acid relative viscosity ηr at 25 ° C
The sulfuric acid relative viscosity ηr at 25 ° C. of the copolymerized polyamide obtained in Production Examples and Comparative Production Examples was measured according to JIS-K6920. Specifically, a 1% concentration solution ((polyamide 1 g) / (98% sulfuric acid 100 mL)) was prepared using 98% sulfuric acid and measured under a temperature condition of 25 ° C.

(4) Trans isomerization rate The trans isomerization rate in the part derived from alicyclic dicarboxylic acid, such as copolymer polyamide obtained by the manufacture example and the comparative manufacture example, was calculated | required as follows.

30-40 mg of polyamide was dissolved in 1.2 g of hexafluoroisopropanol deuteride, and ¹ H-NMR was measured using the resulting solution. In the case of 1,4-cyclohexanedicarboxylic acid, from the ratio of the peak area of 1.98 ppm derived from the trans isomer and the peak areas of 1.77 ppm and 1.86 ppm derived from the cis isomer in ¹ H-NMR measurement. The trans isomer ratio in the part derived from alicyclic dicarboxylic acid such as copolymerized polyamide was determined.

(5) Amino terminal amount ([NH ₂ ])
In the copolymerized polyamides and the like obtained in Production Examples and Comparative Production Examples, the amount of amino terminals bonded to the polymer terminals was measured by neutralization titration as follows.

  3.0 g of polyamide was dissolved in 100 mL of 90% by weight phenol aqueous solution, and the resulting solution was titrated with 0.025N hydrochloric acid, and the amino terminal amount (μ equivalent / g) was determined based on the titration result. The end point was determined from the indicated value of the pH meter.

(6) Amount of carboxyl terminal ([COOH])
In the copolymerized polyamides and the like obtained in Production Examples and Comparative Production Examples, the amount of carboxyl terminal bound to the polymer terminal was measured by neutralization titration as follows.

  4.0 g of polyamide was dissolved in 50 mL of benzyl alcohol, and the obtained solution was titrated with 0.1N NaOH, and the carboxyl end amount (μ equivalent / g) was determined based on the titration result. The end point was determined from the discoloration of the phenolphthalein indicator.

(7) Ratio of carbon number to amide group number (carbon number / amide group number)
In the copolymerized polyamides and the like obtained in Production Examples and Comparative Production Examples, the average number of carbon atoms per amide group (carbon number / amide group number) was determined by calculation. Specifically, the ratio of the number of carbons to the number of amide groups (carbon number / number of amide groups) was determined by dividing the number of carbons contained in the molecular species main chain by the number of amide groups contained in the molecular main chain. The ratio of the number of carbon atoms to the number of amide groups (carbon number / amide group number) was used as an index indicating the amino group concentration in the copolymerized polyamide or the like.

(8) Biomass plastic degree In the copolymerized polyamides and the like obtained in the production examples and comparative production examples, the mass% of the units composed of biomass-derived raw materials was calculated as the biomass plastic degree. Specifically, pentamethylene diamine which uses sebacic acid as a raw material and uses sebacic acid, 1,10-diaminodecane, 11-aminoundecanoic acid and glucose as raw materials was used as a biomass-derived raw material. And in the copolymer polyamide etc. which were obtained by the manufacture example and the comparative manufacture example, the ratio of the unit derived from sebacic acid and 1,10- diaminodecane was computed, and the said ratio was made into the biomass plastic degree. In the polymerization of polyamide, 2 moles of water molecules are formed from two hydrogen atoms in the diamine, two oxygen atoms in the dicarboxylic acid, and two hydrogen atoms when forming the amide bond. It was calculated taking this into consideration.

(9) Content of each structural unit in copolymerized polyamide The content of each structural unit in the copolymerized polyamide was quantified by ¹ H-NMR measurement as follows. The copolymerized polyamide pellets are dissolved in heavy hexafluoroisopropanol by heating to a concentration of about 5% by mass, and analyzed by ¹ H-NMR using JEOL nuclear magnetic resonance analyzer JNM ECA-500. By calculating the integral ratio, the content of each structural unit such as diamine and dicarboxylic acid constituting the copolymer polyamide was determined.

(10) Weight average fiber length of glass fiber (μm)
The polyamide composition pellets obtained in the examples and comparative examples were incinerated by heating in an electric furnace at 650 ° C. for 2 hours. The weight average fiber length was determined by measuring the fiber length of 100 glass fibers arbitrarily selected from the residue using an SEM photograph at a magnification of 1000 times.

(11) Tensile fracture stress (MPa), tensile fracture strain (%)
By molding the polyamide composition pellets prepared in Examples and Comparative Examples described later using an injection molding machine (PS-40E: manufactured by Nissei Plastic Co., Ltd.), a molded piece of ISO 3167, a multi-purpose test piece A type is obtained. Created. In the molding, the injection + pressure holding time was 25 seconds, the cooling time was 15 seconds, the mold temperature was set to 120 ° C., and the molten resin temperature was set to (A) the melting peak temperature T _pm-1 + 20 ° C. of the copolymerized polyamide.

  The obtained multipurpose test piece (A type) was subjected to a tensile test at a tensile speed of 5 mm / min in accordance with ISO 527, and the tensile fracture stress and tensile fracture strain were measured.

(12) Bending strength (MPa), bending deflection (mm)
The multipurpose test piece (A type) prepared in the above (11) was cut to prepare a test piece of length 80 mm × width 10 mm × thickness 4 mm. Using this test piece, a bending test was performed at a test speed of 2 mm / min in accordance with ISO 178, and the bending strength was measured. Further, the amount of deflection (displacement) when the test piece breaks was defined as the amount of bending deflection.

(13) Charpy impact strength (kJ / m ² )
The multipurpose test piece (A type) prepared in the above (11) was cut to prepare a test piece of length 80 mm × width 10 mm × thickness 4 mm. Using this test piece, notch Charpy impact strength according to ISO 179 / 1eA, and notch impact strength according to ISO 179 / 1eU were measured by an edgewise impact method. The notched Charpy strength was measured with a 2J hammer and the notched Charpy strength was measured with a 4J hammer. In addition, what did not fracture | rupture at the time of a test was described as NB. Those that did not break indicate the strongest impact strength.

(14) Deflection temperature under load (℃)
The multipurpose test piece (A type) prepared in the above (11) was cut to prepare a test piece of length 80 mm × width 10 mm × thickness 4 mm. Using this test piece, the deflection temperature under load was measured by the flatwise method in accordance with ISO 75 under a bending stress of 1.80 MPa.

(15) Warpage (mm)
Test pieces of 60 mm × 60 mm × 1 mm were prepared by molding the polyamide composition pellets prepared in Examples and Comparative Examples described later using an injection molding machine (PS-40E: manufactured by Nissei Resin Co., Ltd.). In the molding, the injection + holding time was 10 seconds, the cooling time was 15 seconds, the mold temperature was set to 120 ° C., and the molten resin temperature was set to (A) the melting peak temperature T _pm-1 + 20 ° C. of the copolymerized polyamide. As the mold, a mold of type D1 was used according to ISO 294-3.

  This test piece is left in a constant temperature and humidity (23 ° C., 50 RH%) atmosphere for 24 hours, placed on a horizontal surface, and an arbitrary one of the four corners is fixed to the horizontal surface. Was measured as the amount of warpage.

(16) Warpage after annealing (mm)
Test pieces were prepared by molding polyamide composition pellets prepared in Examples and Comparative Examples described later using an injection molding machine (PS-40E: manufactured by Nissei Resin Co., Ltd.). Specifically, by filling a polyamide composition pellet from a fan gate having a length of 125 mm, a width of 12.5 mm, and a thickness of 0.5 mm into a cavity having a side of 125 mm and a thickness of 0.3 mm, A test piece was prepared. In the molding, injection + holding time 10 seconds, cooling time 10 seconds, mold temperature (A) polyamide Tg + 10 ° C., molten resin temperature (A) copolymer polyamide polyamide melting peak temperature T _pm-1 + 20 ° C. Set.

  This test piece was allowed to stand in a constant temperature and humidity (23 ° C., 50 RH%) atmosphere for 24 hours, and then heated in an oven at 170 ° C. for 2 hours for annealing treatment. The test piece after the annealing treatment was placed on a horizontal surface, the side on the gate side was fixed to a horizontal surface, and the rising height of the opposite end surface was measured as the amount of warpage after annealing. In all the test pieces, the amount of warpage of the test piece before annealing was less than 0.5 mm.

(17) Bending vibration fatigue properties Polyamide composition pellets produced in Examples and Comparative Examples described later are molded into JIS K7119-1972 by using an injection molding machine (PS-40E: manufactured by Nissei Resin Co., Ltd.). The described type I specimen (fatigue property evaluation specimen, dimensions: length × width (b) × thickness = 80 mm × 20 mm × 3 mm, R = 40 mm) was prepared. In the molding, the injection + holding time was 10 seconds, the cooling time was 15 seconds, the mold temperature was set to 120 ° C., and the molten resin temperature was set to (A) the melting peak temperature T _pm-1 + 20 ° C. of the copolymerized polyamide.

  Using the obtained test piece, in accordance with JIS K7119-1972, using a repeated vibration fatigue tester (manufactured by Toyo Seiki Seisakusho Co., Ltd.), the number of breaks at 120 ° C., 20 Hz, maximum bending stress 70 MPa It was measured.

(18) Friction coefficient Using the multipurpose test piece (A type) created in (11) above, a reciprocating friction and wear tester (AFT-15MS: manufactured by Toyo Seimitsu Co., Ltd.), load 500 g, linear velocity 30 mm / sec, Under a condition of a distance of 20 mm, a reciprocating test was performed 10,000 times at an environmental temperature of 23 ° C., and a 10,000th coefficient of friction was measured. As the counterpart material, a SUS ball (SUS304, R = 2.5 mm) was used.

(19) Wear depth (μm)
With respect to the shaved portion of the multipurpose test piece after the evaluation of the friction coefficient in (18) above, Rmax was measured using a surface roughness meter (Surfcom: manufactured by Tokyo Seimitsu Co., Ltd.) to evaluate the wear depth.

(20) Water absorption rate (%)
About the multipurpose test piece (A type) created by said (11), the mass before the following water absorption test (mass before water absorption) was measured in the absolutely dry state after shaping | molding.

<Water absorption test>
The test piece was immersed in pure water at 80 ° C. for 48 hours. Then, the test piece was taken out from water, the surface adhering moisture was wiped off, and it was left for 30 minutes in a constant temperature and humidity (23 ° C., 50 RH%) atmosphere.

  The mass of the test piece after the water absorption test (mass after water absorption) was measured.

  The increment of the mass after water absorption with respect to the mass before water absorption was taken as the water absorption amount, the ratio of the water absorption amount with respect to the mass before water absorption was determined by the number of trials n = 3, and the average value was made the water absorption rate (%).

[Production example of polyamide]
<Production Example 1>
The polyamide polymerization reaction was carried out as follows by the “hot melt polymerization method”.

  Dicarboxylic acid: CHDA 650 g (3.78 mol), sebacic acid: C10DC85 g (0.42 mol) and diamine: C10DA 720 g (4.18 mol) were dissolved in distilled water 1500 g, and equimolar 50 mass% homogeneous aqueous solution of raw material monomers. Was made.

  To this homogeneous aqueous solution, 17 g (0.10 mol) of diamine: C10DA was added.

  The aqueous solution thus obtained was charged into an autoclave having an internal volume of 5.4 L (manufactured by Nitto Koatsu) and heated until the liquid temperature (internal temperature) reached 50 ° C., and the interior of the autoclave was purged with nitrogen.

Until the pressure in the autoclave tank (hereinafter also simply referred to as “inside the tank”) is about 2.5 kg / cm ² as gauge pressure (hereinafter, all pressure in the tank is expressed as gauge pressure). The liquid temperature was continuously heated from about 50 ° C. (the liquid temperature in this system was about 145 ° C.). In order to keep the pressure in the tank at about 2.5 kg / cm ² , water was removed from the system while heating was continued until the concentration of the aqueous solution reached about 75% by mass (the liquid temperature in this system was It was about 160 ° C.). The removal of water was stopped, and heating was continued until the pressure in the tank reached about 30 kg / cm ² (the liquid temperature in this system was about 245 ° C.). In order to keep the pressure in the tank at about 30 kg / cm ² , heating was continued until the final temperature (355 ° C. described later) −50 ° C. (here, 305 ° C.) was reached while removing water out of the system. After the liquid temperature rises to the final temperature (355 ° C. described later) −50 ° C. (here, 305 ° C.), the heating continues while the pressure in the tank reaches atmospheric pressure (gauge pressure is 0 kg / cm ² ). The pressure dropped while taking about a minute.

Thereafter, the heater temperature was adjusted so that the final temperature of the resin temperature (liquid temperature) was about 355 ° C. The resin temperature was kept at about 355 ° C., and the inside of the tank was maintained under a reduced pressure of about 53.3 kPa (400 torr) with a vacuum apparatus for 30 minutes to obtain a polymer. Thereafter, the obtained polymer was pressurized with nitrogen to form a strand from the lower nozzle (nozzle), water-cooled, cut and discharged in a pellet form to obtain copolymer polyamide pellets. The content of each structural unit in the obtained copolyamide was measured by ¹ H-NMR as described above. From the measurement results, it was confirmed that the content of each structural unit such as diamine and dicarboxylic acid constituting the copolymerized polyamide was in a proportion as prepared.

  The obtained copolymer polyamide was dried in a nitrogen stream, and the water content was adjusted to about 0.2% by mass. Table 2 below shows the measurement results of the adjusted copolyamide based on the above measurement method.

<Production Examples 2 to 10, Comparative Production Example 1>
Polyamide in the same manner as in Production Example 1 except that the compounds and amounts shown in Table 1 below were used as dicarboxylic acid, diamine and caprolactam, and the final temperature of the resin temperature was changed to the temperature shown in Table 1 below. ("The hot melt polymerization method"). The content of each structural unit in the obtained copolyamide was measured by ¹ H-NMR as described above. From the measurement results, it was confirmed that the content of each structural unit such as diamine and dicarboxylic acid constituting the copolymerized polyamide was in a proportion as prepared.

  Table 2 below shows the results of measurements performed on the obtained copolyamide based on the above measurement method.

<Production Example 11>
The polyamide polymerization reaction was carried out as follows by the “prepolymer / solid phase polymerization method”.

  The polymerization method was in accordance with the production method described in Patent Document 8 (International Publication No. 2008/149862 pamphlet).

  CHDA 726 g (4.22 mol), C12DA 675 g (3.37 mol), and C6DA 99 g (0.85 mol) were dissolved in 1500 g of distilled water to prepare an equimolar aqueous solution of about 50% by mass of the raw material monomer.

  The obtained aqueous solution was charged into an autoclave (made by Nitto Koatsu Co., Ltd.) having an internal volume of 5.4 L, kept warm until the liquid temperature (internal temperature) reached 50 ° C., and the inside of the autoclave was replaced with nitrogen.

The solution in the autoclave was stirred and the internal temperature was raised to 160 ° C. over 50 minutes. Thereafter, the internal temperature was kept at 160 ° C. for 30 minutes, and heating was continued while removing water vapor from the autoclave to the outside of the system, and the aqueous solution was concentrated to a concentration of about 70% by mass. The removal of water was stopped, and heating was continued until the pressure in the tank reached about 35 kg / cm ² (the liquid temperature in this system was about 250 ° C.). In order to keep the pressure in the tank at about 35 kg / cm ² , the prepolymer was obtained by reacting for 1 hour until the final temperature reached 300 ° C. while removing water out of the system.

The prepolymer was pulverized to a size of 3 mm or less, and then dried at 100 ° C. for 24 hours in an atmosphere in which nitrogen gas was flowed at a flow rate of 20 L / min. Thereafter, the prepolymer was subjected to solid phase polymerization at 280 ° C. for 10 hours in an atmosphere in which nitrogen gas was flowed at a flow rate of 200 mL / min to obtain polyamide. The content of each structural unit in the obtained copolyamide was measured by ¹ H-NMR as described above. From the measurement results, it was confirmed that the content of each structural unit such as diamine and dicarboxylic acid constituting the copolymerized polyamide was in a proportion as prepared. The polyamide components and polymerization conditions are shown in Table 1. Moreover, it measured based on the said method about each physical property of the obtained polyamide. The measurement results are shown in Table 2.

<Comparative Production Example 2>
Polyamide 9T (hereinafter abbreviated as “PA9T”) was produced with reference to the method described in Example 1 of JP-A-7-228689. At that time, the terephthalic acid unit was a dicarboxylic acid unit. On the other hand, 1,9-nonamethylenediamine unit and 2-methyloctamethylenediamine unit [1,9-nonamethylenediamine unit: 2-methyloctamethylenediamine unit = 80: 20 (molar ratio)] were used as diamine units.

The raw materials shown in Table 1 and 1500 g of distilled water were placed in an autoclave (made by Nitto Koatsu Co., Ltd.) having an internal volume of 5.4 L (non-uniform slurry state) and replaced with nitrogen. The mixture was stirred at 100 ° C. for 30 minutes, and the internal temperature was raised to 210 ° C. over 2 hours. At that time, the autoclave was pressurized to 22 kg / cm ² . The reaction was continued for 1 hour, then the temperature was raised to 230 ° C., and then the temperature was kept constant at 230 ° C. for 2 hours. The reaction was carried out while gradually removing water vapor and keeping the pressure at 22 kg / cm ² . Next, the pressure was reduced to 10 kg / cm ² over 30 minutes, and the reaction was further continued for 1 hour to obtain a prepolymer. This was dried at 100 ° C. under reduced pressure for 12 hours and pulverized to a size of 2 mm or less. This was subjected to solid phase polymerization at 230 ° C. and 0.1 mmHg for 10 hours to obtain PA9T. The content of each structural unit in the obtained PA9T was measured by ¹ H-NMR as described above. From the measurement results, it was confirmed that the content of each structural unit in PA9T was in the proportion as prepared.

  The measurement results obtained based on the above-described measurement method for the obtained PA9T are shown in Table 2 below.

[Production example of glass fiber]
<Production Example A>
First, the solid content is 2% by mass of polyurethane resin, 4% by mass of maleic anhydride-butadiene copolymer, 0.6% by mass of γ-aminopropyltriethoxysilane, and 0.1% by mass of carnauba wax. Dilution with water gave a glass fiber sizing agent. The obtained glass fiber sizing agent was adhered to a melt-proofed glass fiber having a number average fiber diameter of 7 μm by an applicator provided in the middle of being wound around a rotating drum. Then, roving of the glass fiber bundle surface-treated with the said glass fiber sizing agent was obtained by drying the glass fiber to which the glass fiber sizing agent was adhered. At that time, the glass fiber was made to be a bundle of 1,000 pieces. The adhesion amount of the glass fiber sizing agent to the glass fiber was 0.6% by mass. This was cut into a length of 3 mm to obtain a chopped strand (hereinafter also abbreviated as “GF-1”).

<Production Example B>
A chopped strand (hereinafter also abbreviated as “GF-2”) was obtained in the same manner as in Production Example A, except that glass fibers having a number average fiber diameter of 5 μm were used. The adhesion amount of the glass fiber sizing agent to the glass fiber was 0.7% by mass.

<Production Example C>
First, it diluted with water so that it might become 6 mass% of polyurethane resins, 0.6 mass% of (gamma) -aminopropyl triethoxysilane, and 0.1 mass% of carnauba wax as solid content, and the glass fiber sizing agent was obtained. . A chopped strand (hereinafter also abbreviated as “GF-3”) was obtained in the same manner as in Production Example A, except that the obtained glass fiber sizing agent was used. The adhesion amount of the glass fiber sizing agent to the glass fiber was 0.6% by mass.

<Production Example D>
A chopped strand (hereinafter also abbreviated as “GF-4”) was obtained in the same manner as in Production Example A, except that glass fibers having a number average fiber diameter of 10 μm were used. The adhesion amount of the glass fiber sizing agent to the glass fiber was 0.5% by mass.

[Production Example of Polyamide Composition]
<Example 1>
The copolymerized polyamide obtained in Production Example 1 was dried in a nitrogen stream, and the moisture content was adjusted to about 0.2% by mass.

In the production example of the polyamide composition, L / D (length of the cylinder of the extruder) having an upstream supply port in the first barrel from the upstream side of the extruder and a downstream supply port in the ninth barrel. A twin screw extruder [ZSK-26MC: manufactured by Coperion (Germany)] having a diameter / cylinder diameter of 48 = 48 (the number of barrels: 12) was used. In the twin-screw extruder, the range from the upstream supply port to the die was set to the melting peak temperature T _pm-1 + 20 ° C. (348 ° C. in Example 1) of the copolymerized polyamide produced by the above production example or comparative production example. . In the twin-screw extruder, the screw rotation speed was 300 rpm and the discharge rate was 25 kg / h.

  After dry blending (A) copolymer polyamide, (C) heat stabilizer, and (D) nucleating agent so as to have the ratio shown in Table 3 below, it is supplied to the twin screw extruder from the upstream supply port, Glass fiber (GF), which is (B) a fibrous reinforcing material, was supplied from the downstream supply port to the twin-screw extruder, and melt-kneaded to produce polyamide composition pellets. The weight average fiber length of the glass fibers in the obtained polyamide composition pellets was 305 μm.

  The obtained polyamide composition pellets were dried in a nitrogen stream to reduce the water content to 500 ppm or less. The obtained polyamide composition pellets are processed into a predetermined molded body as described above, and tensile fracture stress, tensile fracture strain, bending strength, bending deflection, Charpy impact strength, deflection temperature under load, warpage, warpage after annealing. Bending vibration fatigue properties, friction coefficient, wear depth, and water absorption were evaluated. The evaluation results are shown in Table 5. Moreover, the weight average fiber length of the glass fiber in a multipurpose test piece (A type) was 292 micrometers.

<Examples 2 to 16, Comparative Examples 1 to 10>
Polyamide composition pellets were produced in the same manner as in Example 1 except that each raw material composition had the ratio shown in Table 3 or 4 below. The obtained polyamide composition pellets are processed into a predetermined molded body as described above, and tensile fracture stress, tensile fracture strain, bending strength, bending deflection, Charpy impact strength, deflection temperature under load, warpage, and after annealing. Warpage, bending vibration fatigue properties, friction coefficient, wear depth, and water absorption were evaluated. The evaluation results are shown in Table 5 or 6 below.

As shown in Tables 5 and 6 above, the polyamide compositions of Examples 1 to 16 have high mechanical strength due to high tensile fracture stress and flexural strength when compared with the polyamide compositions of Comparative Examples 1 to 10. Excellent tensile fracture strain, bending deflection, and Charpy impact strength, excellent toughness, high deflection temperature under load, excellent heat resistance, low warpage, and low warpage after annealing. It was excellent. Furthermore, it was excellent in low water absorption and vibration fatigue resistance.

  In particular, when Example 4 is compared with Comparative Examples 1, 3, 6, and 8, at least one alicyclic dicarboxylic acid, one diamine having 8 or more carbon atoms, and at least one copolymer component are mainly used. The polyamide composition of this embodiment containing a copolymerized polyamide as a component and a fibrous reinforcing material having a number average fiber diameter of 7 μm is a polyamide composition containing a fibrous reinforcing material having a number average fiber diameter of 10 μm. In contrast, it was found that the bending strength, Charpy impact strength, deflection temperature under load, warpage after annealing, bending vibration fatigue characteristics, low water absorption, and slidability were improved. On the other hand, from the viewpoint of warping after annealing and low water absorption, as can be seen from Comparative Examples 8, 9, and 10, this is a problem that was not found in conventional polyamides containing terephthalic acid as a main component, and is used in this embodiment. This was a problem specific to polyamide.

  According to the present invention, a polyamide composition excellent in mechanical strength, toughness, heat resistance and dimensional stability, and excellent in vibration fatigue resistance, slidability and low water absorption can be obtained. The polyamide composition of the present invention can be suitably used as a molding material for various parts such as automobiles, electric and electronic, industrial equipment, industrial materials, and daily and household products. Has availability.

Claims (23)

(A) (a) a unit composed of at least one alicyclic dicarboxylic acid, (b) one unit composed of a diamine having 8 or more carbon atoms, and (c) the following (c-1) to (c- A unit comprising at least one copolymer component selected from the group consisting of 3), and a copolymerized polyamide,
(B) a fibrous reinforcing material having a number average fiber diameter of 3 to 9 μm;
Containing ,
(B) The polyamide composition in which the fibrous reinforcing material is glass fiber ;
(C-1) a dicarboxylic acid other than the (a) alicyclic dicarboxylic acid,
(C-2) a diamine having fewer carbon atoms than the diamine of (b),
(C-3) Lactam and / or aminocarboxylic acid. The polyamide composition according to claim 1, wherein the (B) fibrous reinforcing material has a weight average fiber length of 100 to 500 µm in the polyamide composition. The (B) fibrous reinforcing material is composed of a unit composed of a carboxylic acid anhydride-containing unsaturated vinyl monomer and an unsaturated vinyl monomer (excluding the carboxylic acid anhydride-containing unsaturated vinyl monomer). The polyamide composition according to claim 1 or 2 , which is a fibrous reinforcing material treated with a sizing agent containing a copolymer containing units. The polyamide composition according to any one of claims 1 to 3 , wherein the (a) alicyclic dicarboxylic acid is 1,4-cyclohexanedicarboxylic acid. In the suggested scanning calorimetry according to JIS-7121 of the (A) copolymerized polyamide, the difference between the crystallization peak temperature T _pc-1 obtained when cooled at 20 ° C./min and the glass transition temperature T _g ( The polyamide composition according to any one of claims 1 to 4 , wherein T _pc-1 -T _g ) is 140 ° C or higher. The polyamide composition according to any one of claims 1 to 5 , wherein a ratio of the number of carbon atoms to the number of amide groups (carbon number / amide group number) in the (A) copolymerized polyamide is 8 or more. In the suggested scanning calorimetry according to JIS-7121 of the (A) copolymerized polyamide, the melting peak temperature T _pm obtained when the temperature is raised at 20 ° C./min, and when the temperature is raised again at 20 ° C./min The polyamide composition according to any one of claims 1 to 6 , wherein a difference ( _Tpm - _Tpm-1 ) from the obtained melting peak temperature _Tpm-1 is 30 ° C or lower. The trans isomer ratio in the part derived from the (a) alicyclic dicarboxylic acid in the (A) copolymerized polyamide is 65 to 80 mol%, according to any one of claims 1 to 7 . Polyamide composition. The ratio (amino end amount / (amino end amount + carboxyl end amount)) of the amino terminal amount to the total amount of the amino terminal amount and the carboxyl terminal amount in the (A) copolymerized polyamide is 0.5 or more and less than 1.0. The polyamide composition according to any one of claims 1 to 8 , wherein The polyamide composition according to any one of claims 1 to 9 , wherein the (b) diamine having 8 or more carbon atoms is decamethylenediamine. The polyamide composition according to any one of claims 1 to 10 , wherein the (c-1) dicarboxylic acid is an aliphatic dicarboxylic acid having 10 or more carbon atoms. The polyamide composition according to any one of claims 1 to 11 , wherein the (c-1) dicarboxylic acid is sebacic acid and / or dodecanedioic acid. The polyamide composition according to any one of claims 1 to 10 , wherein the (c-1) dicarboxylic acid is isophthalic acid. The polyamide composition according to any one of claims 1 to 13 , wherein the (c-2) diamine is an aliphatic diamine having 4 to 7 carbon atoms. In the differential scanning calorimetry according to JIS-K7121 of the (A) copolymerized polyamide, when it is cooled again at a crystallization peak temperature T _pc-1 obtained by cooling at 20 ° C./min and at 50 ° C./min. The polyamide composition according to any one of claims 1 to 14 , wherein a difference (T _pc-1 -T _pc-2 ) from the crystallization peak temperature T _pc-2 obtained in 1 is 14C or less. The content of the unit consisting of the copolymer component (c) is 7.5 mol% or more and 20.0 mol% or less with respect to 100 mol% of the total content of all structural units of the copolymer (A). The polyamide composition according to any one of claims 1 to 15 . The polyamide composition according to any one of claims 1 to 16 , wherein the biomass plasticity of the (A) copolymerized polyamide is 25% or more. With respect to 100 parts by mass of the (A) copolymerized polyamide,
The polyamide composition according to any one of claims 1 to 17 , wherein a content of the (B) fibrous reinforcing material is 1 to 200 parts by mass. (C) Phenol-based heat stabilizer, phosphorus-based heat stabilizer, amine-based heat stabilizer, elements of Group Ib, Group IIb, Group IIIa, Group IIIb, Group IVa and Group IVb of the periodic table The polyamide composition according to any one of claims 1 to 18 , further comprising at least one heat stabilizer selected from the group consisting of metal salts of the above, and halides of alkali metals and alkaline earth metals. The polyamide composition according to claim 19 , wherein the heat stabilizer (C) is a mixture of a copper salt and an alkali metal or alkaline earth metal halide. (D) The polyamide composition according to any one of claims 1 to 20 , further comprising at least one nucleating agent selected from the group consisting of boron nitride, talc and carbon black. Shaped body comprising a polyamide composition according to any one of claims 1 to 21. A sliding component comprising the polyamide composition according to any one of claims 1 to 21 .