JP2017155150A - Polyamide composition, polyamide composition molded article and manufacturing method of polyamide composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyamide composition excellent in strength when heated and rigidity when heated and having low water absorption.SOLUTION: There is provided a polyamide composition containing polyamide containing (a) a dicarboxylic acid unit containing at least 1,4-cyclohexane dicarboxylic acid and (b) a diamine unit containing at least aliphatic diamine and having trans isomer ratio mol% of the dicarboxylic acid monomer with 70<trans isomer ratio≤100 and at least one kind of metal compound selected from Li, Na and K, excluding a hypophosphorous acid compound.SELECTED DRAWING: None

Description

  The present invention relates to a polyamide composition, a polyamide composition molded article, and a method for producing a polyamide composition.

As an approach to the environment, for example, in the automobile industry, there is a demand for weight reduction of a vehicle body using a metal substitute material in order to reduce exhaust gas. In order to meet this requirement, polyamide materials are often used as exterior materials and interior materials, and the level of required properties such as heat resistance, strength and appearance of the polyamide materials are further improved. In particular, since the temperature in the engine room is on the rise, there is an increasing demand for higher heat resistance for polyamide materials.
In addition, in the electrical and electronic industries such as home appliances, a polyamide material having high heat resistance that can withstand the rise in melting point of solder is required to cope with lead-free surface mount (SMT) solder.

  From the viewpoint of such heat resistance, a high melting point polyamide has been proposed. For example, a polyamide obtained by polymerizing terephthalic acid and hexamethylenediamine (hereinafter also referred to as PA6T) is known. Although PA6T has the characteristics of low water absorption, high heat resistance, and high chemical resistance, it is a high melting point polyamide having a melting point of about 370 ° C. It is difficult to obtain a molded product having sufficient characteristics due to severe thermal decomposition of the product.

  In order to solve the problems related to the thermal decomposition of PA6T, PA6T is composed of aliphatic polyamide such as polyamide 6 and polyamide 66 (hereinafter also referred to as PA6 and PA66, respectively), amorphous fragrance comprising isophthalic acid and hexamethylenediamine. A high melting point semi-aromatic polyamide (hereinafter also referred to as PA6T copolymer), which has been copolymerized with an aromatic polyamide (hereinafter also referred to as PA6I), etc. and has a melting point lowered to about 220 to 340 ° C. has been proposed. .

  As such a PA6T copolymer, Patent Document 1 discloses an aromatic polyamide (hereinafter referred to as a mixture of hexamethylenediamine and 2-methylpentamethylenediamine), which is composed of an aromatic dicarboxylic acid and an aliphatic diamine. , PA6T / 2MPDT). Although PA6T / 2MPDT can partially improve the problems of the conventional PA6T copolymer, the improvement level in terms of fluidity, moldability, toughness, molded product surface appearance and light resistance is insufficient. .

  As a polyamide having good heat resistance and moldability, a high-melting point aliphatic polyamide (hereinafter also referred to as PA46) composed of adipic acid and tetramethylenediamine is known, but PA46 has a high water absorption rate, and also absorbs water. There is a problem that the dimensional change and the deterioration of the mechanical properties due to the above are remarkably large, and the demand may not be satisfied in terms of the dimensional change required for automobile applications.

  As an alicyclic polyamide composed of an alicyclic dicarboxylic acid and an aliphatic diamine, for example, Patent Documents 2 and 3 include an alicyclic polyamide composed of 1,4-cyclohexanedicarboxylic acid and hexamethylene diamine (hereinafter referred to as PA6C). And semi-alicyclic polyamides (hereinafter also referred to as PA6C copolymers) with other polyamides. However, PA6C and PA6C copolymers disclosed in Patent Documents 2 and 3 also have problems such as high water absorption and insufficient fluidity.

  In Patent Document 4, a polyamide composed of a dicarboxylic acid unit containing 1,4-cyclohexanedicarboxylic acid and a diamine unit containing 2-methyl-1,8-octanediamine has light resistance, toughness, moldability, lightness, In addition, the polyamide is disclosed to be excellent in heat resistance and the like, but this polyamide is also insufficiently improved in terms of toughness, strength and fluidity.

  Patent Document 5 discloses a dicarboxylic acid component containing 10 to 80 mol% of 1,4-cyclohexanedicarboxylic acid having a trans ratio / cis isomer in a molar ratio of 50/50 to 97/3 in all carboxylic acid components; A polyamide obtained by thermal polycondensation with an aliphatic diamine component is described, and a polyamide having a ratio of a trans isomer / cis isomer of a raw material monomer within a predetermined range is excellent in toughness and chemical resistance and moldability It is described that it is excellent.

  Patent Document 6 describes a polyamide obtained by polymerizing a dicarboxylic acid containing an alicyclic dicarboxylic acid and a diamine containing a diamine having a substituent branched from the main chain. Dicarboxylic acid is isomerized at a high temperature and has a fixed ratio, and the cis isomer has a higher water solubility in the equivalent salt with diamine than the trans isomer. It is described that it is preferable that there are many cis-isomers, and that the trans isomer ratio of the entire alicyclic dicarboxylic acid in the polyamide is preferably 50 to 85 mol%.

  Furthermore, Patent Document 7 describes a copolymerized polyamide using a dicarboxylic acid containing an alicyclic dicarboxylic acid and a diamine having 8 or more carbon atoms as raw materials. Similarly, a cis isomer is used as a raw material monomer. It is described that a large amount is preferable, and that the trans isomer ratio in the portion derived from the alicyclic dicarboxylic acid of the copolymerized polyamide is preferably 65 to 80 mol%.

JP-T 6-503590 Japanese National Patent Publication No. 11-512476 Special table 2001-514695 gazette Japanese Patent Laid-Open No. 9-12868 International Publication No. 2002/048239 JP 2010-1111843 A International Publication No. 2012/093722

  In the polyamide described in Patent Document 6 or 7, in addition to the ratio of the trans isomer / cis isomer of the raw material monomer, the trans isomer ratio of the entire alicyclic dicarboxylic acid in the polyamide is within a predetermined range, In addition to the features of high melting point, toughness, and rigidity, it simultaneously achieves high-temperature rigidity due to high glass transition temperature, fluidity, which is usually opposite to heat resistance, and high crystallinity and low water absorption. It is described that it is possible.

However, even if the ratio of the trans isomer / cis isomer of the raw material monomer is adjusted or the ratio of the trans isomer of the polyamide that is the raw material of the molded product is adjusted, it is difficult to maintain the ratio in the molded product. I understood. In order to achieve higher levels of physical properties, further improvements were needed to maintain a high trans isomer ratio in the molded article.
The present invention has been made in view of the above circumstances, and provides a polyamide composition, a polyamide composition molded article, and a method for producing a polyamide composition that are hot strength, hot stiffness, and low water absorption. It is intended.

The polyamide composition of the present invention comprises:
(A) a dicarboxylic acid unit containing at least 1,4-cyclohexanedicarboxylic acid;
(B) a diamine unit containing at least an aliphatic diamine, and a trans isomer ratio mol% of a dicarboxylic acid monomer unit in the polyamide,
70 <trans isomer ratio ≦ 100
A polyamide which is
And at least one metal compound selected from Li, Na, and K (excluding a hypophosphorous acid compound).

  The content of 1,4-cyclohexanedicarboxylic acid is preferably at least 50 mol% in the dicarboxylic acid unit.

  All of the dicarboxylic acid units are preferably 1,4-cyclohexanedicarboxylic acid.

  The aliphatic diamine preferably has 6 to 12 carbon atoms.

  The aliphatic diamine is preferably hexamethylene diamine, 2-methylpentamethylene diamine, 2-methyl-1,8-octane diamine, nonamethylene diamine, decamethylene diamine, or dodecamethylene diamine.

  The aliphatic diamine is preferably 2-methylpentamethylenediamine or decamethylenediamine.

  The metal compound is preferably a Li compound.

  The metal compound is preferably either LiOH or LiCl.

Further, the polyamide in the polyamide composition of the present invention is obtained when the temperature is lowered at 20 ° C./min and the heat of fusion ΔHm1 obtained when the temperature is raised at 20 ° C./min in the differential scanning calorimetry according to JIS-K7121. ΔHm1 / ΔHc, which is the ratio to the crystallization enthalpy ΔHc obtained,
1.0 <ΔHm1 / ΔHc ≦ 2.2
It is preferable that

ΔHm1 / ΔHc is
1.4 ≦ ΔHm1 / ΔHc ≦ 2.2
It is more preferable that

Polyamide has ΔHm1 / ΔHc as y and trans isomer ratio as x.
y ≧ 0.04x−1.8
It is preferable that

  The polyamide preferably has a number average molecular weight Mn of 15,000 or more.

Polyamide has a weight average molecular weight Mw / number average molecular weight Mn indicating a molecular weight distribution,
Mw / Mn <3.5
It is preferable that

The polyamide has a ratio [NH ₂ ] / ([NH ₂ ] + [COOH]), which is a ratio of the amino terminal amount [NH ₂ ] to the total active terminal amount ([NH ₂ ] + [COOH]).
[NH ₂ ] / ([NH ₂ ] + [COOH]) <0.5
It is preferable that

  The polyamide composition of the present invention may further include at least one selected from an inorganic filler, a heat stabilizer, and a light stabilizer.

  The polyamide composition molded article of the present invention is formed by molding the polyamide composition of the present invention further including at least one selected from an inorganic filler, a heat stabilizer, and a light stabilizer.

The method for producing a polyamide composition comprises (a) a dicarboxylic acid unit containing at least 1,4-cyclohexanedicarboxylic acid and (b) a diamine unit containing at least an aliphatic diamine, and has an amino terminal amount [NH ₂ ] active terminal. The ratio of [NH ₂ ] / ([NH ₂ ] + [COOH]) to the total amount ([NH ₂ ] + [COOH]) is [NH ₂ ] / ([NH ₂ ] + [COOH]) <0 A precursor polyamide in which the active terminal total amount ([NH ₂ ] + [COOH]) μeq / g is 100 ≦ [NH ₂ ] + [COOH] ≦ 200,
At least one metal compound selected from Li, Na, and K (excluding a hypophosphorous acid compound);
The precursor polyamide composition containing is heat-treated at 200 ° C. or higher and lower than the melting point for 10 hours or longer.

  And (a) a dicarboxylic acid containing at least 1,4-cyclohexanedicarboxylic acid, and (b) a diamine containing at least an aliphatic diamine, at least one metal compound selected from Li, Na, and K (provided that A step of polymerizing in the presence of (except for a hypophosphorous acid compound) to obtain a precursor polyamide composition may be included.

  The polyamide composition of the present invention is a polyamide containing (a) a dicarboxylic acid unit containing at least 1,4-cyclohexanedicarboxylic acid, and (b) a diamine unit containing at least an aliphatic diamine, The trans isomer ratio mol% of the body unit is 70 <trans isomer ratio ≦ 100, and at least one metal compound selected from Li, Na, and K (excluding a hypophosphite compound) It is a polyamide composition containing. By having such a configuration, a polyamide composition molded article excellent in hot strength, hot stiffness, and low water absorption can be obtained.

Further, the method for producing a polyamide composition of the present invention comprises (a) a dicarboxylic acid unit containing at least 1,4-cyclohexanedicarboxylic acid and (b) a diamine unit containing at least an aliphatic diamine. active end the total amount of _2] is the ratio _{([NH 2] + [COOH} ]) [NH 2] / ([NH 2] + [COOH]) _{is, [NH 2] / ([} NH 2] + [ COOH]) <0.5, and the precursor polyamide in which the active terminal total amount ([NH ₂ ] + [COOH]) μ equivalent / g is 100 ≦ [NH ₂ ] + [COOH] ≦ 200, and Li A precursor polyamide composition containing at least one metal compound selected from N, Na, and K (excluding a hypophosphorous acid compound) is heat-treated at 200 ° C. or higher and lower than the melting point for 10 hours or longer. Than is. By having such a configuration, it is possible to obtain a polyamide and a polyamide composition having a trans isomer ratio mol% of a dicarboxylic acid monomer unit of more than 70 and 100 or less.

Hereinafter, the polyamide composition, the polyamide composition molded article, and the production method thereof according to the present invention will be described in detail.
[(A) Polyamide composition]
The polyamide composition of the present invention is a polyamide containing (a) a dicarboxylic acid unit containing at least 1,4-cyclohexanedicarboxylic acid and (b) a diamine unit containing at least an aliphatic diamine. The trans isomer ratio mol% of the monomer unit is
(A1) polyamide in which 70 <trans isomer ratio ≦ 100;
(A2) and at least one metal compound selected from Li, Na, and K (excluding a hypophosphite compound).
In the present specification, polyamide means a polymer having an amide bond (—NHCO—) in the main chain.

The polyamide of the present invention having the trans isomer ratio as described above can be obtained by the polyamide structural unit and production method described below.
<(A1) Polyamide>
The polyamide in the present invention is a polyamide containing (a) a dicarboxylic acid unit containing at least 1,4-cyclohexanedicarboxylic acid, and (b) a diamine unit containing at least an aliphatic diamine. The trans isomer ratio mol% of the monomer unit is 70 <trans isomer ratio ≦ 100.

First, the structural unit of (A1) polyamide will be described in detail.
((A) dicarboxylic acid unit)
(A) The dicarboxylic acid unit contains at least a 1,4-cyclohexanedicarboxylic acid unit. (A) The dicarboxylic acid unit preferably contains 50 to 100 mol% of 1,4-cyclohexanedicarboxylic acid units (based on the total number of dicarboxylic acids), more preferably 60 to 100 mol%, and 70 to 100 mol. % Is more preferable, and 100 mol% is most preferable.

  (A) When the ratio (mol%) of 1,4-cyclohexanedicarboxylic acid unit in the dicarboxylic acid unit is in the above range, the heat resistance, fluidity, toughness, low water absorption, rigidity, and the like are satisfied at the same time. A polyamide composition can be obtained.

  The units that may be contained in the (a) dicarboxylic acid unit other than 1,4-cyclohexanedicarboxylic acid include (a-1) an alicyclic dicarboxylic acid unit, (a-2) an aromatic dicarboxylic acid unit, and (A-3) Aliphatic dicarboxylic acid units. Hereinafter, unless it is described as (a-1), the term “alicyclic carboxylic acid unit” is used in the sense of including 1,4-cyclohexanedicarboxylic acid.

(A-1) Alicyclic dicarboxylic acid unit (a-1) Other than 1,4-cyclohexanedicarboxylic acid (a-1) The alicyclic dicarboxylic acid constituting the alicyclic dicarboxylic acid unit is not limited to the following. However, examples include alicyclic dicarboxylic acids having 3 to 12 carbon atoms in the alicyclic structure, and alicyclic dicarboxylic acids having 5 to 12 carbon atoms in the alicyclic structure are preferable.
Examples of such (a-1) alicyclic dicarboxylic acid units include, but are not limited to, 1,3-cyclohexanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, and the like. .

By including such (a-1) alicyclic dicarboxylic acid units, the heat resistance, low water absorption, rigidity, etc. of the polyamide composition tend to be more excellent.
In addition, (a-1) alicyclic dicarboxylic acid which comprises an alicyclic dicarboxylic acid unit may be used individually by 1 type, and may be used in combination of 2 or more types.

The alicyclic group of the alicyclic dicarboxylic acid unit may be unsubstituted or may have a substituent.
Examples of the substituent include, but are not limited to, for example, 1 to 1 carbon atoms of a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a tert-butyl group. 4 alkyl groups and the like.

(A-2) Aromatic dicarboxylic acid unit (a-2) The aromatic dicarboxylic acid constituting the aromatic dicarboxylic acid unit is not limited to the following, but for example, a dicarboxylic acid having a phenyl group or a naphthyl group. Examples include acids. The aromatic group of the aromatic dicarboxylic acid unit may be unsubstituted or may have a substituent.
Although it does not specifically limit as a substituent, For example, halogen groups, such as a C1-C4 alkyl group, a C6-C10 aryl group, a C7-C10 aralkyl group, a chloro group, and a bromo group, carbon Examples thereof include silyl groups of 1 to 6, sulfonic acid groups and salts thereof (sodium salts, etc.).

Examples of the aromatic dicarboxylic acid unit include, but are not limited to, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, and 5-methylisophthalic acid. And an aromatic dicarboxylic acid having 8 to 20 carbon atoms which is unsubstituted or substituted with a predetermined substituent such as 5-sodium sulfoisophthalic acid.
(A-2) The aromatic dicarboxylic acid which comprises an aromatic dicarboxylic acid unit may be used individually by 1 type, and may be used in combination of 2 or more type.

(A-3) Aliphatic dicarboxylic acid unit (a-3) The aliphatic dicarboxylic acid constituting the aliphatic dicarboxylic acid unit is not limited to the following, but examples thereof include malonic acid, dimethylmalonic acid, and succinic acid. Acid, 2,2-dimethylsuccinic acid, 2,3-dimethylglutaric acid, 2,2-diethylsuccinic acid, 2,3-diethylglutaric acid, glutaric acid, 2,2-dimethylglutaric acid, adipic acid, 2- 3 to 3 carbon atoms such as methyl adipic acid, trimethyl adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, tetradecanedioic acid, hexadecanedioic acid, octadecanedioic acid, eicosanedioic acid, and diglycolic acid 20 linear or branched saturated aliphatic dicarboxylic acids and the like.

(A-3) When the aliphatic dicarboxylic acid unit contains an aliphatic dicarboxylic acid having 6 or more carbon atoms, the heat resistance, fluidity, toughness, low water absorption, rigidity, and the like of the polyamide composition are more excellent. This is preferable because of its tendency.
Among them, (a-3) the aliphatic dicarboxylic acid unit is preferably an aliphatic dicarboxylic acid having 10 or more carbon atoms. By using such a dicarboxylic acid, the heat resistance and low water absorption of the polyamide composition tend to be more excellent.

The aliphatic dicarboxylic acid unit 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, sebacic acid and dodecanedioic acid are preferable from the viewpoint of heat resistance of the polyamide composition.
(A-3) As the aliphatic dicarboxylic acid constituting the aliphatic dicarboxylic acid unit, only one kind may be used alone, or two or more kinds may be used in combination.

  (A) The proportion (mol%) of dicarboxylic acid other than 1,4-cyclohexadicarboxylic acid unit in the dicarboxylic acid unit is preferably 0 to 50 mol%, and preferably 0 to 40 mol%. More preferably, it is more preferably 0 to 30 mol%.

When the aliphatic dicarboxylic acid unit (a-3) having 10 or more carbon atoms is contained, 1,4-cyclohexanedicarboxylic acid is 50 to 99.9 mol% and (a-3) the aliphatic dicarboxylic acid unit is It is preferably 0.1 to 50 mol%, more preferably 60 to 95 mol% of 1,4-cyclohexanedicarboxylic acid and (a-3) 5 to 40 mol% of an aliphatic dicarboxylic acid unit, It is more preferable that 1,4-cyclohexanedicarboxylic acid is 80 to 95 mol% and (a-3) aliphatic dicarboxylic acid is 5 to 20 mol%.
Polyamide that satisfies the excellent heat resistance, fluidity, toughness, low water absorption, rigidity, etc. at the same time when the ratio of the aliphatic dicarboxylic acid unit (a-3) having 10 or more carbon atoms is in the above range. There is a tendency to obtain a composition.

(A) The dicarboxylic acid constituting the dicarboxylic acid unit is not limited to the compounds described as the dicarboxylic acid, and may be a compound equivalent to the dicarboxylic acid.
Here, the “compound equivalent to dicarboxylic acid” refers to a compound that can have the same dicarboxylic acid structure as the dicarboxylic acid structure derived from the dicarboxylic acid. Examples of such compounds include dicarboxylic acid anhydrides and halides.

Moreover, (A1) polyamide may further contain the unit derived from polyvalent carboxylic acid more than trivalence, such as trimellitic acid, trimesic acid, and pyromellitic acid, as needed.
Trivalent or higher polyvalent carboxylic acids may be used alone or in combination of two or more.
The alicyclic dicarboxylic acid constituting the alicyclic dicarboxylic acid unit has a trans isomer and a cis geometric 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 containing a trans isomer and a cis isomer in a predetermined ratio may be used.

((B) diamine unit)
(B) The diamine unit contains at least an aliphatic diamine. This aliphatic diamine may be linear or branched. (B) The diamine unit is not limited to the following. For example, (b-1) an aliphatic diamine unit having a substituent branched from the main chain, and (b-2) a linear aliphatic diamine Examples include units. Other diamine units may include (b-3) alicyclic diamine units, (b-4) aromatic diamine units, and the like.

  (B) The aliphatic diamine unit preferably has 6 to 12 carbon atoms. A carbon number of 6 or more is preferable because of excellent heat resistance and low water absorption, and a carbon number of 12 or less is preferable because of high temperature strength and crystallinity. (B) As for carbon number of a diamine unit, 6-10 is more preferable.

  (B) The diamine unit preferably includes (b-1) an aliphatic diamine having a substituent branched from the main chain. (B) Since the diamine unit includes (b-1) a diamine unit having a substituent branched from the main chain, a polyamide having a high glass transition temperature Tg and high crystallinity (ie, high ΔHm1 / ΔHc) is obtained. Can be obtained. For this reason, the polyamide composition of the present invention using this polyamide tends to satisfy more excellent fluidity, toughness, rigidity and the like at the same time.

(B-1) Aliphatic diamine unit having a substituent branched from the main chain Hereinafter, (b-1) an aliphatic diamine unit having a substituent branched from the main chain is simply described as (b-1). There is.
The “substituent branched from the main chain” in (b-1) is not limited to the following, but for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl Group, an alkyl group having 1 to 4 carbon atoms of a tert-butyl group, and the like.

The diamine constituting such (b-1) is not limited to the following, but for example, 2-methylpentamethylenediamine (also referred to as 2-methyl-1,5-diaminopentane), 2 2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 2-methyl-1,8-octanediamine (also referred to as 2-methyloctamethylenediamine), and 2,4-dimethylocta Examples thereof include branched saturated aliphatic diamines having 3 to 20 carbon atoms such as methylenediamine.
Among these, 2-methylpentamethylenediamine and 2-methyl-1,8-octanediamine are preferable, and 2-methylpentamethylenediamine is more preferable. By including such (b-1), it tends to be a polyamide composition that is superior in heat resistance and rigidity.
In addition, the diamine which comprises (b-1) may be used individually by 1 type, and may be used in combination of 2 or more type.

The (b) diamine unit more preferably contains 10 mol% or more of (b-1). (B) The proportion (mol%) of (b-1) in the diamine unit is preferably 10 to 100 mol%, more preferably 20 to 100 mol%, and still more preferably 30 to 100 mol%. is there.
(B) When the ratio of (b-1) in the diamine unit is in the above range, a polyamide having a high glass transition temperature Tg and high crystallinity (that is, high ΔHm1 / ΔHc) can be obtained. For this reason, the polyamide composition using this polyamide tends to be a polyamide composition that is superior in fluidity, toughness, and rigidity.

(B-2) Linear aliphatic diamine unit Hereinafter, the (b-2) linear aliphatic diamine unit may be simply referred to as (b-2).
The linear aliphatic diamine constituting (b-2) is not limited to the following, and examples thereof include ethylene diamine, propylene diamine, tetramethylene diamine, pentamethylene diamine, hexamethylene diamine, heptamethylene diamine, and octane. Examples thereof include linear saturated aliphatic diamines having 2 to 20 carbon atoms such as methylene diamine, nonamethylene diamine, decamethylene diamine, undecamethylene diamine, dodecamethylene diamine, and tridecamethylene diamine.

(B-3) Alicyclic diamine unit Hereinafter, the (b-3) alicyclic diamine unit may be simply referred to as (b-3).
The alicyclic diamine (hereinafter, also referred to as “alicyclic diamine”) constituting (b-3) is not limited to the following, and examples thereof include 1,4-cyclohexanediamine and 1,3. -Cyclohexanediamine, 1,3-cyclopentanediamine, etc. are mentioned.

(B-4) Aromatic diamine unit Hereinafter, the (b-4) aromatic diamine unit may be simply referred to as (b-4).
Examples of the aromatic diamine constituting (b-4) include metaxylylenediamine, paraxylylenediamine, paraphenylenediamine, metaphenylenediamine, and the like.

Among the diamine units (b-2) to (b-4), preferably (b-2) and (b-3), more preferably a linear saturated aliphatic group having 4 to 13 carbon atoms. A diamine unit (b-2) having a straight-chain saturated aliphatic group having 6 to 12 carbon atoms, more preferably hexamethylenediamine or nonamethylenediamine. , Decamethylenediamine and dodecamethylenediamine, most preferably decamethylenediamine.
By using such a diamine, the polyamide composition tends to be excellent in heat resistance, fluidity, toughness, low water absorption, rigidity, and the like.
In addition, diamine may be used individually by 1 type and may be used in combination of 2 or more types.

The total ratio (mol%) of the diamine units (b-2) to (b-4) is preferably 80 mol% or less and 70 mol% or less with respect to the entire (b) diamine unit. More preferred.
(B) When the total ratio of the diamine units (b-2) to (b-4) in the diamine unit is within the above range, the polyamide composition tends to be excellent in fluidity, toughness, and rigidity.

The (A1) polyamide may further contain a trivalent or higher polyvalent aliphatic amine such as bishexamethylenetriamine, if necessary.
Trivalent or higher polyvalent aliphatic amines may be used alone or in combination of two or more.

((C) Lactam unit (c-1) and / or aminocarboxylic acid unit (c-2))
The (A1) polyamide of the present invention is not limited to (a) and (b) described above, but (c) a lactam unit (c-1) and / or an aminocarboxylic acid unit (c) as long as the object of the present invention is not impaired. -2) can further be contained.
By including such a unit, a polyamide composition that is superior in toughness tends to be obtained. In addition, the lactam and aminocarboxylic acid which comprise a lactam unit (c-1) and / or aminocarboxylic acid (c-2) here mean the lactam and aminocarboxylic acid which can superpose | polymerize or condensation-polymerize.

  The lactam and aminocarboxylic acid constituting the lactam unit (c-1) and the aminocarboxylic acid unit (c-2) are not limited to the following, but for example, lactam and amino having 4 to 14 carbon atoms Carboxylic acids are preferred, and lactams having 6 to 12 carbon atoms and aminocarboxylic acids are more preferred.

The lactam constituting the lactam unit (c-1) is not limited to the following. Noractam) and the like.
Among them, as the lactam, ε-caprolactam, laurolactam and the like are preferable, and ε-caprolactam is more preferable. By including such a lactam, it tends to be a polyamide composition having better toughness.

  The aminocarboxylic acid constituting the aminocarboxylic acid unit (c-2) is not limited to the following, and examples thereof include ω-aminocarboxylic acid and α, ω-amino acid which are compounds in which a lactam is opened. Is mentioned.

  As the aminocarboxylic acid, a linear or branched saturated aliphatic carboxylic acid having 4 to 14 carbon atoms in which the ω position is substituted with an amino group is preferable. Examples of such aminocarboxylic acids include, but are not limited to, 6-aminocaproic acid, 11-aminoundecanoic acid, and 12-aminododecanoic acid. Examples of the aminocarboxylic acid include paraaminomethylbenzoic acid.

  The lactam and aminocarboxylic acid constituting the lactam unit (c-1) and the aminocarboxylic acid unit (c-2) may each be used alone or in combination of two or more. .

The total ratio (mol%) of the lactam unit (c-1) and the aminocarboxylic acid unit (c-2) is preferably 0 to 20 mol%, more preferably 0 to 0%, based on the whole (A) polyamide. It is 10 mol%, More preferably, it is 0 to 5%.
When the total ratio of the lactam unit (c-1) and the aminocarboxylic acid unit (c-2) is within the above range, effects such as improvement of fluidity tend to be obtained.

(End sealant)
The terminal of (A1) polyamide used in the present invention may be end-capped with a known end-capping agent.
Such an end-capping agent is also added as a molecular weight regulator in the production of (A1) polyamide from the above-described dicarboxylic acid and diamine and lactam and / or aminocarboxylic acid used as necessary. Can do.

Examples of end-capping agents include, but are not limited to, acid anhydrides such as monocarboxylic acids, monoamines, and phthalic anhydride, monoisocyanates, monoacid halides, monoesters, and monoalcohols. Etc.
Among these, monocarboxylic acid and monoamine are preferable. (A1) Since the end of the polyamide is sealed with an end-capping agent, the polyamide composition tends to be more excellent in thermal stability. Only one type of end capping agent may be used alone, or two or more types may be used in combination.

The monocarboxylic acid that can be used as the end-capping agent is not limited to the following as long as it has reactivity with the amino group that can be present at the terminal of the (A1) polyamide. For example, formic acid Aliphatic monocarboxylic acids such as acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecylic acid, myristic acid, palmitic acid, stearic acid, pivalic acid, and isobutyric acid; cyclohexanecarboxylic acid, etc. And aromatic monocarboxylic acids such as benzoic acid, toluic acid, α-naphthalenecarboxylic acid, β-naphthalenecarboxylic acid, methylnaphthalenecarboxylic acid, and phenylacetic acid. Of these, acetic acid is particularly preferred.
A monocarboxylic acid may be used individually by 1 type, and may be used in combination of 2 or more type.

The monoamine that can be used as the end-capping agent is not limited to the following as long as it has reactivity with the carboxyl group that can be present at the end of the (A1) polyamide, but for example, methylamine, Aliphatic monoamines such as ethylamine, propylamine, butylamine, hexylamine, octylamine, decylamine, stearylamine, dimethylamine, diethylamine, dipropylamine, and dibutylamine; alicyclic monoamines such as cyclohexylamine and dicyclohexylamine; and aniline , Aromatic monoamines such as toluidine, diphenylamine, and naphthylamine.
Monoamines may be used alone or in combination of two or more.

  A polyamide composition containing (A1) polyamide end-capped with a terminal capping agent tends to be excellent in heat resistance, fluidity, toughness, low water absorption, and rigidity.

<(A2) At least one metal compound selected from Li, Na, and K (excluding a hypophosphite compound)>
The polyamide composition of the present invention contains (A2) at least one metal compound selected from Li, Na, and K (excluding a hypophosphorous acid compound). Hereinafter, these are simply referred to as the component (A2). Examples of the component (A2) include LiCl, LiOH (anhydrous or monohydrate), NaCl, KCl, and the like. By including the component (A2), the isomerization reaction to the trans isomer is promoted, and a high trans isomer ratio can be achieved. Therefore, the polyamide composition of the present invention tends to be excellent in heat resistance, fluidity, strength, hot strength, rigidity, and hot stiffness.
Among Li, Na, and K, from the viewpoint of achieving a high trans isomer ratio, a Li compound is preferable, and LiCl or LiOH is more preferable. The concentration of the component (A2) relative to the polyamide (A1) is preferably 1 to 5000 ppm, more preferably 10 to 3000 ppm, and most preferably 50 to 2000 ppm. The component (A2) may be added as a catalyst at the time of polymerization of polyamide, or may be added at the time of kneading or injection molding after polymerization. From the viewpoint of achieving a high trans isomer ratio, it is preferably added as a polymerization catalyst.

<Additives>
The polyamide composition (A) of the present invention may contain at least one selected from an inorganic filler, a heat stabilizer, and a light stabilizer. (A) By containing an inorganic filler as a polyamide composition, it has excellent heat resistance and stability under heat, and has a high melting point. In addition, by containing the above components, the polyamide composition does not impair the properties of the polyamide, and the polyamide composition satisfies heat resistance, stability during heat, etc., and is particularly excellent in strength and moldability. Become. Hereinafter, (A) the other component which may be contained in a polyamide composition is demonstrated.

(Inorganic filler)
The inorganic filler that can be used in the present invention is not particularly limited, and a known material can be used.
For example, glass fiber, carbon fiber, calcium silicate fiber, potassium titanate fiber, aluminum borate fiber, glass flake, talc, kaolin, mica, hydrotalcite, calcium carbonate, magnesium carbonate, zinc carbonate, zinc oxide, phosphoric acid Calcium monohydrogen, wollastonite, 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 nanotubes, graphite, brass, copper, silver, aluminum, nickel, iron, calcium fluoride, clay, montmorillonite, swellable fluorine mica, silicon nitride, and apatite.
An inorganic filler may be used individually by 1 type, and may be used in combination of 2 or more types.

Among the inorganic fillers, the glass fiber and the carbon fiber may have a round shape or a flat shape in cross section.
Examples of the flat cross section include a rectangle, an oval close to a rectangle, an ellipse, and a bowl shape with a narrowed central portion in the longitudinal direction.

  Among glass fibers and carbon fibers, from the viewpoint of imparting excellent mechanical properties to the polyamide composition, in the polyamide composition, the number average fiber diameter is 3 to 30 μm, and the weight average fiber length is 100 to 750 μm. Glass fibers or carbon fibers having an aspect ratio (L / D) of 10 to 100 between the weight average fiber length (L) and the number average fiber diameter (D) are preferably used.

  (A) The number average fiber diameter of the inorganic filler in the polyamide composition is, for example, that the polyamide composition is put in an electric furnace, the organic matter contained in the polyamide composition is incinerated, and from the residue, for example, 100 or more A number average fiber diameter can be calculated | required by selecting glass fiber arbitrarily, observing with a SEM (Scanning Electron Microscope) photograph, and measuring a fiber diameter.

(A) As for the weight average fiber length of the inorganic filler in the polyamide composition, glass fiber is arbitrarily selected in the same manner, and the fiber length is measured by using an SEM photograph at a magnification of 1000 times. Can be measured.
As the inorganic filler, reinforcing fibers having a weight average fiber length of 1 to 15 mm are more preferable. The weight average fiber length of such reinforcing fibers is 1 to 15 mm, preferably 3 to 12 mm, from the viewpoint of improving mechanical strength, rigidity and moldability.

The weight average fiber length of the reinforcing fibers is the length of 400 reinforcing fibers arbitrarily selected using an image analyzer after observing with an optical microscope after burning or dissolving only the polyamide of the polyamide composition. It is calculated | required by measuring thickness and calculating an average value.
Here, when the length of each reinforcing fiber is L1, L2,..., L400, the calculation formula for the weight average fiber length for each reinforcing fiber is expressed by the following formula. In the following formula, “i” is an integer from 1 to 400.
Weight average fiber length = Σ (Li ² ) / ΣLi
In addition, a weight average fiber length is a value applied with respect to the reinforcing fiber of the state contained in the polyamide composition of this invention. That is, the weight average fiber length of the reinforcing fiber before blending with the polyamide is not limited to the above.

The material of the reinforcing fiber is not particularly limited as long as it is a reinforcing fiber generally used for polyamide.
For example, inorganic fiber such as glass fiber, carbon fiber, boron fiber, metal fiber (eg, stainless fiber, aluminum fiber, copper fiber), polyparaphenylene terephthalamide fiber, polymetaphenylene terephthalamide fiber, polyparaffin Organic materials such as phenylene isophthalamide fiber, polymetaphenylene isophthalamide fiber, wholly aromatic polyamide fiber such as fiber obtained from condensate of diaminodiphenyl ether and terephthalic acid or isophthalic acid, or wholly aromatic liquid crystal polyester fiber Is mentioned.

As reinforcing fiber, the said material may be used independently and 2 or more types may be used together. Especially, it is preferable that it is 1 or more types chosen from a glass fiber, a carbon fiber, a boron fiber, and a metal fiber from a viewpoint of an improvement of mechanical strength and rigidity, and a glass fiber and / or a carbon fiber are more preferable.
The reinforcing fiber is not particularly limited with respect to the average fiber diameter in the single fiber, but, for example, those having a diameter of 5 to 25 μm are generally used.

The average fiber diameter of single fibers is obtained by observing the reinforcing fibers to be used under an optical microscope and calculating the average value when measuring 400 fiber diameters arbitrarily selected using an image analyzer. It is done.
Further, as the reinforcing fiber, it is preferable to use roving which is a continuous fiber obtained by bundling single fibers.

-Surface treatment agent-
An inorganic filler such as glass fiber or carbon fiber may be surface-treated with a surface treatment agent such as a silane coupling agent.
The silane coupling agent is not particularly limited, and examples thereof include γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, and N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane. And aminosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane; epoxysilanes; vinylsilanes and the like. Of these, aminosilanes are preferable.
As the silane coupling agent, one kind may be used alone, or two or more kinds may be used in combination.

-Bundling agent-
Fibrous inorganic fillers such as glass fibers and carbon fibers are further used as sizing agents, copolymers and epoxy compounds containing carboxylic anhydride-containing unsaturated vinyl monomers and unsaturated vinyl monomers as constituent units , Polyurethane resins, and homopolymers of acrylic acid, copolymers of acrylic acid and other copolymerizable monomers, and salts thereof with primary, secondary, or tertiary amines.

In particular, from the viewpoint of mechanical properties (particularly strength) of the polyamide composition, a copolymer containing a carboxylic acid anhydride-containing unsaturated vinyl monomer and an unsaturated vinyl monomer as structural units (containing carboxylic acid anhydride) A copolymer containing an unsaturated vinyl monomer and an unsaturated vinyl monomer excluding an unsaturated vinyl monomer containing a carboxylic acid anhydride as a structural unit), an epoxy compound, and a polyurethane resin are preferred, and a carboxylic acid anhydride More preferred are a copolymer containing a contained unsaturated vinyl monomer and an unsaturated vinyl monomer as structural units, and a polyurethane resin.
As the sizing agent, one type may be used alone, or two or more types may be used in combination.

  The carboxylic acid anhydride-containing unsaturated vinyl monomer constituting the copolymer containing the carboxylic acid anhydride-containing unsaturated vinyl monomer and the unsaturated vinyl monomer as structural units is not particularly limited. Examples thereof include maleic anhydride, itaconic anhydride, and citraconic anhydride, and maleic anhydride is preferred.

  Further, the unsaturated vinyl monomer constituting the copolymer containing carboxylic acid anhydride-containing unsaturated vinyl monomer and unsaturated vinyl monomer as structural units is not particularly limited, for example , Styrene, α-methylstyrene, ethylene, propylene, butadiene, isoprene, chloroprene, 2,3-dichlorobutadiene, 1,3-pentadiene, cyclooctadiene, methyl methacrylate, methyl acrylate, ethyl acrylate, and ethyl methacrylate. Styrene and butadiene are preferred.

  Examples of the copolymer containing a carboxylic acid anhydride-containing unsaturated vinyl monomer and an unsaturated vinyl monomer as structural units include, for example, a copolymer of maleic anhydride and butadiene, a maleic anhydride and ethylene. Copolymers and copolymers of maleic anhydride and styrene are preferred.

The weight average molecular weight of the copolymer containing a carboxylic acid anhydride-containing unsaturated vinyl monomer and an unsaturated vinyl monomer as constituent units is preferably 2,000 or more, which improves the fluidity of the polyamide composition. From the viewpoint, it is more preferably 2,000 to 1,000,000, and further preferably 2,000 to 1,000,000.
The weight average molecular weight can be measured by gel permeation chromatography (GPC).

  The epoxy compound is not particularly limited, and examples thereof include ethylene oxide, propylene oxide, butene oxide, pentene oxide, hexene oxide, heptene oxide, octene oxide, nonene oxide, decene oxide, undecenoxide, and dodecene oxide. , Pentadecene oxide, eicosene oxide and the like; glycidol, epoxypentanol, 1-chloro-3,4-epoxybutane, 1-chloro-2-methyl-3,4-epoxybutane, 1,4 -Dichloro-2,3-epoxybutane, cyclopentene oxide, cyclohexene oxide, cycloheptene oxide, cyclooctene oxide, methylcyclohexene oxide, vinylcyclohexene Alicyclic epoxy compounds such as oxide and epoxidized cyclohexene methyl alcohol; terpene epoxy compounds such as pinene oxide; aromatic epoxy compounds such as styrene oxide, p-chlorostyrene oxide and m-chlorostyrene oxide; epoxidized soybean oil; And epoxidized linseed oil.

  The polyurethane resin is not particularly limited, and those generally used as a sizing agent can be used. For example, isocyanates such as m-xylylene diisocyanate (XDI), 4,4′-methylenebis (cyclohexyl isocyanate) (HMDI), and isophorone diisocyanate (IPDI), polyester-based and polyether-based diols, Those synthesized from can be suitably used.

  As a homopolymer of acrylic acid (polyacrylic acid), the weight average molecular weight is preferably 1,000 to 90,000, more preferably 1,000 to 25,000.

The polyacrylic acid may be in the form of a salt with a primary, secondary, or tertiary amine.
The amine is not particularly limited, and examples thereof include triethylamine, triethanolamine, and glycine.

The degree of neutralization of polyacrylic acid by having a salt form means the ratio of the acrylic acid component forming a salt out of the acrylic acid component of polyacrylic acid, and other concomitant drugs (silane coupling agents, etc.) From the viewpoint of improving the stability of the mixed solution with) and reducing the amine odor, it is preferably 20 to 90%, more preferably 40 to 60%.
The weight average molecular weight of the salt-form polyacrylic acid is preferably 3,000 to 50,000, and is preferably 3,000 or more from the viewpoint of improving the converging property of glass fibers and carbon fibers. From the viewpoint of improving the mechanical properties of the product, it is preferably 50,000 or less.

  The other copolymerizable monomer in the copolymer of acrylic acid and other copolymerizable monomer is not particularly limited, and examples thereof include acrylic acid, maleic acid, and methacrylic acid, which are monomers having a hydroxyl group and / or a carboxyl group. Vinyl acetic acid, crotonic acid, isocrotonic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid. As the other copolymerizable monomer, a monomer that is an ester of a monomer having a hydroxyl group and / or a carboxyl group can be suitably used.

The copolymer of acrylic acid and other copolymerizable monomers preferably has a weight average molecular weight of 1,000 to 90,000, more preferably 1,000 to 25,000.
The copolymer of acrylic acid and other copolymerizable monomers may be in the form of a salt with a primary, secondary, or tertiary amine.
The amine is not particularly limited, and examples thereof include triethylamine, triethanolamine, and glycine.

The degree of neutralization of the copolymer by having a salt form means the proportion of the acid component forming a salt in the acid component of the copolymer, and the mixed solution with other concomitant drugs (such as a silane coupling agent) From the viewpoint of improving stability and from the viewpoint of reducing amine odor, it is preferably 20 to 90%, more preferably 40 to 60%.
The weight average molecular weight of the salt-form copolymer is preferably 3,000 to 50,000, and is preferably 3,000 or more from the viewpoint of improving the convergence of glass fibers and carbon fibers. From the viewpoint of improving mechanical properties, it is preferably 50,000 or less.

The fibrous inorganic filler such as glass fiber and carbon fiber containing a sizing agent is obtained by using the above sizing agent in a known glass fiber or carbon fiber manufacturing process using a known method such as a roller type applicator. It is obtained by reacting continuously by drying fiber strands produced by applying to a fibrous inorganic filler such as carbon fiber.
The fiber strand may be used as it is as roving, or may be used as a chopped glass strand after further obtaining a cutting step.

  The sizing agent preferably imparts (adds) a solid content of 0.2 to 3% by mass with respect to 100% by mass of a fibrous inorganic filler such as glass fiber or carbon fiber. It is more preferable to apply (add) mass%.

  From the viewpoint of maintaining the bundling of fibrous inorganic fillers such as glass fibers and carbon fibers, the amount of sizing agent added is 100% by mass with respect to 100% by mass of fibrous inorganic fillers such as glass fibers and carbon fibers. Is preferably 0.2% by mass or more. From the viewpoint of improving the thermal stability of the polyamide composition, the addition amount of the sizing agent is preferably 3% by mass or less as the solid content. Moreover, drying of a strand may be performed after a cutting process, and you may cut | disconnect, after drying a strand.

When wollastonite is used as the inorganic filler constituting the polyamide composition, the polyamide composition has a number average fiber diameter of 3 to 30 μm, a weight average fiber length of 10 to 500 μm, and an aspect ratio (L / Those in which D) is 3 to 100 are preferably used.
As the inorganic filler, when talc, mica, kaolin, silicon nitride or the like is used, the polyamide composition preferably has a number average fiber diameter of 0.1 to 3 μm.

(Heat stabilizer)
Further, the (A) polyamide composition may contain a heat stabilizer. As a thermal stabilizer, phosphorus stabilizer (phosphorus compound), phenolic antioxidant, amine antioxidant, Group Ib, Group IIb, Group IIIa, Group IIIb, Group IVa of the periodic table And one or more selected from the group consisting of metal salts of Group IVb elements and halides of alkali metals and alkaline earth metals. Specific examples of the heat stabilizer are shown below.

-Phosphorus stabilizer (phosphorus compound)-
Examples of phosphorus compounds include organic phosphorus compounds.
Examples of organic phosphorus compounds include, but are not limited to, pentaerythritol phosphite compounds, trioctyl phosphites, trilauryl phosphites, tridecyl phosphites, octyl diphenyl phosphites, trisisodecyl phosphites. Phyto, phenyl diisodecyl phosphite, phenyl di (tridecyl) phosphite, diphenyl isooctyl phosphite, diphenyl isodecyl phosphite, diphenyl (tridecyl) phosphite, triphenyl phosphite, 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-t-butylphenyl-tetra-tridecyl) diphosphite, tetra (C12-C15 mixed alkyl) -4,4'-isopropylidene diphenyldiphosphite, 4,4'-isopropylidenebis ( 2-t-butylphenyl) -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′-isopropylidenediphenyldiphos Phyto, 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-stearoyl) Oxyisopropyl) phosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite, 2,2- Tylene bis (3-methyl-4,6-di-t-butylphenyl) 2-ethylhexyl phosphite, tetrakis (2,4-di-t-butyl-5-methylphenyl) -4,4'-biphenylene diphosphite And tetrakis (2,4-di-t-butylphenyl) -4,4′-biphenylene diphosphite.
An organophosphorus compound may be used individually by 1 type, and may be used in combination of 2 or more type.

  Among the organophosphorus compounds listed above, pentaerythritol phosphite compounds, tris (2,4-di-t-butylphenyl), from the viewpoint of further improving the heat aging resistance of the polyamide composition and reducing the generated gas. ) Phosphites are preferred, and pentaerythritol phosphite compounds are more preferred.

Examples of the pentaerythritol type phosphite compound include, but are not limited to, 2,6-di-t-butyl-4-methylphenyl-phenyl-pentaerythritol diphosphite, 2,6-di- t-butyl-4-methylphenyl-methyl-pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl-2-ethylhexyl-pentaerythritol diphosphite, 2,6-di-t- Butyl-4-methylphenyl-isodecyl-pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl-lauryl-pentaerythritol diphosphite, 2,6-di-t-butyl-4- Methylphenyl-isotridecyl-pentaerythritol diphosphite, 2,6-di-t-butyl -4-methylphenyl-stearyl-pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl-cyclohexyl-pentaerythritol diphosphite, 2,6-di-t-butyl-4-methyl Phenyl-benzyl-pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl-ethyl cellosolve-pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl-butyl Carbitol-pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl-octylphenyl-pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl-nonylphenyl -Pentaerythritol diphosphite, 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- Methylphenyl-2,6-di-t-butylphenyl-pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl-2,4-di-t-butylphenyl-pentaerythritol diphosphite Phyto, 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-phenyl-pentaeryth Tritol diphosphite, bis (2,6-di-t-amyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-octyl-4-methylphenyl) pentaerythritol diphos And bis (2,4-dicumylphenyl) pentaerythritol diphosphite.
A pentaerythritol type phosphite compound 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, bis (2,6-di-t-octyl-4-methylphenyl) penta Erythritol diphosphite and bis (2,4-dicumylphenyl) pentaerythritol diphosphite are preferred.

(A) Content of the phosphorus compound in a polyamide composition is 0.1-20.0 mass% with respect to 100 mass% of polyamide compositions. Preferably it is 0.2-7.0 mass%, More preferably, it is 0.5-3.0 mass%, More preferably, it is 0.5-2.5 mass%, More preferably, it is 0.5 It is -2.0 mass%, More preferably, it is 0.5-1.5 mass%.
When the content of the phosphorus compound is within the above range, the polyamide composition tends to be excellent in whiteness, reflow resistance, heat discoloration resistance, extrusion process stability, and molding process stability.

-Phenol-based antioxidant and / or amine-based antioxidant-
(A) The polyamide composition may contain a phenol-based antioxidant and / or an amine-based antioxidant as a heat stabilizer.
Examples of phenolic antioxidants include, but are not limited to, hindered phenolic compounds. Phenol-based antioxidants, particularly hindered phenol compounds, have the property of imparting heat resistance and light resistance to resins such as polyamide and fibers.

Examples of the hindered phenol compound include, but are not limited to, for example, N, N′-hexane-1,6-diylbis [3- (3,5-di-t-butyl-4-hydroxyphenylpropylene). Onamide), pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], N, N′-hexamethylenebis (3,5-di-t-butyl- 4-hydroxy-hydrocinnamamide), triethylene glycol-bis [3- (3-tert-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-tetraoxaspiro [5,5] undecane 3,5-di-tert-butyl-4-hydroxybenzylphosphonate-diethyl ester, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) Examples include benzene and 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanuric acid.
Among these, from the viewpoint of improving heat aging resistance, the hindered phenol compound may be N, N′-hexane-1,6-diylbis [3- (3,5-di-t-butyl-4-hydroxyphenylpropionamide). )] Is preferred.
In addition, the phenolic antioxidant mentioned above may be used individually by 1 type, and may be used in combination of 2 or more type.

(A) Content of the phenolic antioxidant in the polyamide composition is preferably 0 to 1% by mass, more preferably 0.01 to 1% by mass with respect to 100% by mass of the polyamide composition. More preferably, it is 0.1 to 1% by mass.
When the content of the phenolic antioxidant is within the above range, the polyamide composition tends to be superior in heat aging resistance and lower in the amount of generated gas.

Examples of amine-based antioxidants include, but are not limited to, poly (2,2,4-trimethyl-1,2-dihydroquinoline, 6-ethoxy-1,2-dihydro-2, 2,4-trimethylquinoline, phenyl-α-naphthylamine, 4,4-bis (α, α-dimethyldendyl) diphenylamine, (p-toluenesulfonylamido) diphenylamine, N, N′-diphenyl-p-phenylenediamine, N, N′-di-β-naphthyl-p-phenylenediamine, N, N′-di (1,4-dimethylpentyl) -p-phenylenediamine, N-phenyl-N′-isopropyl-p-phenylenediamine, N-phenyl-N′-1,3-dimethylbutyl-p-phenylenediamine, N- (1-methylheptyl) -N′-phenyl-p-pheny Aromatic amines such as Njiamin the like.
The amine antioxidant includes an aromatic amine compound. Only one amine antioxidant may be used alone, or two or more amine antioxidants may be used in combination.

(A) The content of the amine antioxidant in the polyamide composition is preferably 0 to 1% by mass, more preferably 0.01 to 1% by mass with respect to 100% by mass of the polyamide composition. More preferably, it is 0.1 to 1% by mass.
When the content of the amine-based antioxidant is within the above range, the polyamide composition tends to be more excellent in heat aging resistance and lower in the amount of generated gas.

-Metal salts of elements of Group Ib, Group IIb, Group IIIa, Group IIIb, Group IVa, and Group IVb of the periodic table, and halides of alkali metals and alkaline earth metals-
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 and is preferably a heat stabilizer. Copper salt.
The copper salt is not particularly limited. For example, copper halide (copper iodide, cuprous bromide, cupric bromide, cuprous chloride, etc.), copper acetate, copper propionate, benzoic acid Examples thereof include copper oxide, copper adipate, copper terephthalate, copper isophthalate, copper salicylate, copper nicotinate and copper stearate, and a copper complex salt in which copper is coordinated to a chelating agent such as ethylenediamine and ethylenediaminetetraacetic acid. Especially, it is preferable that it is 1 or more types selected from the group which consists of copper iodide, cuprous bromide, cupric bromide, cuprous chloride, and copper acetate. Copper iodide and / or copper acetate Is more preferable. When the above metal salt, especially copper salt, is used, a polyamide composition having excellent heat aging resistance and capable of suppressing metal corrosion (hereinafter also simply referred to as “metal corrosion”) of screws and cylinders during extrusion is obtained. be able to.

The said metal salt may be used individually by 1 type, and may be used in combination of 2 or more types.
When using a copper salt, the compounding amount of the copper salt in the polyamide composition is preferably 0.01 to 0.2 parts by mass, more preferably 0.02 to 0 parts per 100 parts by mass of the polyamide composition. 15 parts by mass. When the amount is within the above range, the heat aging resistance is further improved, and copper precipitation and metal corrosion can be suppressed.

  Moreover, from the viewpoint of improving the heat aging resistance, the content of copper element is preferably 10 to 500 ppm, more preferably 30 to 500 ppm, and still more preferably 50 to 300 ppm with respect to the total amount of the polyamide composition. .

(A) Alkali metal and alkaline earth metal halide contained in the polyamide composition is not particularly limited, and examples thereof include potassium iodide, potassium bromide, potassium chloride, sodium iodide and sodium chloride. And mixtures thereof. Among these, potassium iodide and potassium bromide, and a mixture thereof are preferable, and potassium iodide is more preferable from the viewpoint of improving heat aging resistance and suppressing metal corrosion.
As said halide, 1 type may be used independently and 2 or more types may be used in combination.

  (A) In the case of using alkali metal and alkaline earth metal halides for the preparation of the polyamide composition, the blending amount of the alkali and alkaline earth metal halide in the polyamide composition is based on 100 parts by mass of the polyamide composition. The amount is preferably 0.05 to 5 parts by mass, and more preferably 0.2 to 2 parts by mass. When the amount is within the above range, the heat aging resistance is further improved, and copper precipitation and metal corrosion can be suppressed.

  (A) In a polyamide composition, a mixture of a copper salt and a halide of an alkali or alkaline earth metal can be suitably used as a heat stabilizer. The ratio of the copper salt to the alkali and alkaline earth metal halide may be included in the polyamide composition so that the molar ratio of halogen to copper (halogen / copper) is 2/1 to 40/1. Preferably, it is 5/1 to 30/1.

  When the molar ratio (halogen / copper) is within the above range, the heat aging resistance of the (A) polyamide composition can be further improved. Moreover, when the molar ratio (halogen / copper) is 2/1 or more, it is preferable because copper precipitation and metal corrosion can be suppressed. When the molar ratio (halogen / copper) is 40/1 or less, corrosion of the screws of the molding machine can be prevented without substantially impairing mechanical properties such as toughness, which is preferable.

(Light stabilizer)
(A) The polyamide composition may contain a light stabilizer from the viewpoint of light stability. The light stabilizer has a property of imparting excellent heat resistance and light resistance to resins such as polyamide and fibers. Examples of the light stabilizer include amine light stabilizers.

Examples of the amine light stabilizer include, but are not limited to, 4-acetoxy-2,2,6,6-tetramethylpiperidine, 4-stearoyloxy-2,2,6,6-tetra. Methylpiperidine, 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-tetramethyl Peridine, 4- (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-tetramethyl) -4-piperidyl) adipate, bis (2,2,6,6-tetramethyl-4-piperidyl) terephthalate, bis (1,2,2,6,6-pen) Methyl-4-piperidyl) carbonate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) oxalate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) malonate, bis ( 1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) adipate, bis (1,2,2,6,6- Pentamethyl-4-piperidyl) terephthalate, N, N′-bis-2,2,6,6-tetramethyl-4-piperidinyl-1,3-benzenedicarboxamide, 1,2-bis (2,2,6) , 6-Tetramethyl-4-piperidyloxy) ethane, α, α′-bis (2,2,6,6-tetramethyl-4-piperidyloxy) -p-xylene, bis (2,2,6,6) -Tetra Methyl-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, N, N ′, N ″, N ′ ″-tetrakis- (4,6-bis- (butyl- ( N-methyl-2,2,6,6-tetramethylpiperidin-4-yl) amino) -triazin-2-yl) -4,7-diazadecane-1,10-diamine, dibutylamine-1,3,5 -Triazine-N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) -1,6-hexamethylenediamine and N- (2,2,6,6-tetramethyl-4- Polycondensate with piperidyl) butylamine, poly [ {6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl} {(2,2,6,6-tetramethyl-4-piperidyl) imino } Hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) imino}], tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4- Butanetetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, tris (2,2,6,6-tetramethyl- 4-piperidyl) -benzene-1,3,4-tricarboxylate, 1- [2- {3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy} butyl] -4- [ 3- (3,5-di-t- Til-4-hydroxyphenyl) propionyloxy] 2,2,6,6-tetramethylpiperidine, and 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6,6-pentamethyl-4- Examples include condensates of piperidinol and β, β, β ′, β′-tetramethyl-3,9- [2,4,8,10-tetraoxaspiro (5,5) undecane] diethanol.
Only one amine light stabilizer may be used alone, or two or more amine stabilizers may be used in combination.

Examples of amine light stabilizers include bis (2,2,6,6-tetramethyl-4-piperidyl) carbonate, bis (2,2,6,6-tetramethyl-4-piperidyl) oxalate, and bis (2, 2,6,6-tetramethyl-4-piperidyl) malonate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (2,2,6,6-tetramethyl-4-piperidyl) ) Adipate, bis (2,2,6,6-tetramethyl-4-piperidyl) terephthalate, N, N′-bis-2,2,6,6-tetramethyl-4-piperidinyl-1,3-benzenedi Carboxamide and tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate are preferred.
Among these, as the amine light stabilizer, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, N, N′-bis-2,2,6,6-tetramethyl-4 -Piperidinyl-1,3-benzenedicarboxamide, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate are more preferred, N, N ′ -Bis-2,2,6,6-tetramethyl-4-piperidinyl-1,3-benzenedicarboxamide is more preferred.

  (A) The content of the amine light stabilizer in the polyamide composition is preferably 0 to 2% by mass, more preferably 0.01 to 2% by mass with respect to 100% by mass of the polyamide composition. More preferably, it is 0.1 to 2% by mass. When the content of the amine light stabilizer is within the above range, the light stability and heat aging resistance of the polyamide composition can be further improved, and the amount of generated gas can be further reduced.

(Other additives)
(A) In the polyamide composition, additives that are conventionally used for polyamides, for example, colorants such as pigments and dyes (including colored master batches), flame retardants, and fibrillation, as long as the object of the present invention is not impaired. Agents, lubricants, fluorescent bleaches, plasticizers, UV absorbers, antistatic agents, fluidity improvers, fillers, reinforcing agents, spreading agents, nucleating agents, rubber, reinforcing agents, and other polymers It can also be contained.

  The method of adding at least one selected from inorganic fillers, heat stabilizers, and light stabilizers, or other additives, etc. is at least selected from (A1) polyamide and (A2) Li, Na, and K. If it is the method of mixing the composition which consists of 1 type of metal compounds (however, except a hypophosphite compound), and an inorganic filler and the other additive mentioned above as needed, it will be specifically limited. It is not a thing.

(A) As a method of mixing the constituent materials of the polyamide composition, for example, a method of mixing using a Henschel mixer or the like, supplying to a melt kneader and kneading, or a polyamide melted with a single screw or twin screw extruder, The method of mix | blending an inorganic filler and another additive from a side feeder is mentioned.
In the method of supplying the components constituting the polyamide composition to the melt kneader, all the components (polyamide, inorganic filler, etc.) may be supplied to the same supply port at the same time, and the components are supplied to different supply ports. You may supply from.

The melt kneading temperature is preferably about 250 to 375 ° C. as the resin temperature.
The melt kneading time is preferably about 0.5 to 5 minutes.
The apparatus for performing melt kneading is not particularly limited, and a known apparatus, for example, a melt kneader such as a single-screw or twin-screw extruder, a Banbury mixer, and a mixing roll can be used.

  The method for producing the polyamide composition when the inorganic filler contained in the polyamide composition is a reinforcing fiber having a weight average fiber length of 1 to 15 mm is not particularly limited. A pultrusion method in which polyamide is melt-kneaded with a twin screw extruder and the molten polyamide is impregnated into a roving of reinforcing fibers to obtain a polyamide-impregnated strand, or as described in JP 2008-221574 A A method in which the polyamide is sufficiently impregnated by a step of twisting the material into a spiral shape.

[(A) Physical properties of polyamide composition]
Next, the physical properties of the (A1) polyamide in the (A) polyamide composition of the present invention will be described.
<Trans isomer ratio>
The trans isomer ratio of the dicarboxylic acid monomer unit of the (A1) polyamide in the (A) polyamide composition of the present invention is greater than 70 mol% and 100 mol% or less. The trans isomer ratio is more preferably more than 71 mol% and 100 mol% or less, further preferably more than 75 mol% and 90 mol% or less, and more preferably 80 mol% or more and 90 mol% or less.
Since the (A1) polyamide in the (A) polyamide composition of the present invention is highly crystallized because the trans isomer ratio is within the above range, the polyamide composition of the present invention has a high melting point, toughness and rigidity. In addition to the feature of being superior, it tends to have the property of simultaneously satisfying the thermal rigidity due to the high glass transition temperature (Tg), the fluidity, which is usually a property contrary to heat resistance, and the high crystallinity. .

As described above, the trans isomer ratio of the dicarboxylic acid monomer unit in such a polyamide can be controlled by controlling the carboxyl terminal amount of the polyamide and the method for producing the polyamide of the present invention.
The trans isomer ratio (molar ratio) of the polyamide of the molded polyamide composition can be determined by nuclear magnetic resonance spectroscopy (NMR).

<Sulfuric acid relative viscosity ηr>
(A1) The sulfuric acid relative viscosity ηr of the polyamide uses the sulfuric acid relative viscosity ηr at 25 ° C. as an index. (A1) The polyamide has a sulfuric acid relative viscosity ηr at 25 ° C. of preferably 1.5 or more. More preferably, it is 2.3 to 5.0, and most preferably 2.5 to 4.0. Effective methods for controlling the relative viscosity ηr of sulfuric acid at 25 ° C. for polyamides include, for example, methods for controlling the addition amount of diamine and end-capping agent as additives during hot melt polymerization of polyamide, and polymerization conditions. Method.

When the sulfuric acid relative viscosity ηr at 25 ° C. is 1.5 or more, the (A) polyamide composition is excellent in mechanical properties such as toughness and strength. From the viewpoint of melt fluidity, a polyamide composition having excellent fluidity can be obtained when the sulfuric acid relative viscosity ηr at 25 ° C. of the polyamide is 5.0 or less.
The sulfuric acid relative viscosity at 25 ° C. can be measured at 25 ° C. in 98% sulfuric acid according to JIS-K6920.

<Molecular weight>
As an index of the molecular weight of the polyamide, a number average molecular weight Mn obtained by GPC (gel permeation chromatography), a weight average molecular weight Mw, and a molecular weight distribution Mw / Mn can be used. The larger the Mn, the higher the molecular weight of the (A1) polyamide, and the smaller the Mn, the lower the molecular weight of the (A1) polyamide.
(A1) The number average molecular weight Mn of the polyamide is preferably 15,000 or more, more preferably 16,000 or more, and further preferably 17,000 or more.
Moreover, Mw / Mn which shows the molecular weight distribution of (A1) polyamide becomes like this. Preferably it is less than 3.5, More preferably, it is 3.0 or less.
When the number average molecular weight Mn and the molecular weight distribution Mw / Mn are in the above ranges, it tends to be a polyamide composition having excellent mechanical properties such as toughness and rigidity, and moldability. In addition, Mn and Mw can produce | generate a calibration curve using the number average molecular weight Mn measured by PMMA (polymethylmethacrylate) standard sample (made by a polymer laboratory company), and can obtain | require the molecular weight of polyamide. More specifically, it can be measured by the method described in the following examples.

<Melting peak temperature Tm1, Tm2>
(A1) The melting peak temperature Tm1 of the polyamide is preferably 300 ° C. or higher, more preferably 310 ° C. or higher.
The melting peak temperature Tm1 of (A1) polyamide is preferably 350 ° C. or lower, more preferably 345 ° C. or lower, and further preferably 340 ° C. or lower.
(A1) When the melting peak temperature Tm1 of the polyamide is 300 ° C. or higher, a polyamide composition excellent in heat resistance tends to be obtained.
Moreover, when (A1) polyamide melting peak temperature Tm1 is 350 ° C. or less, (A1) thermal decomposition of polyamide in melt processing such as extrusion and molding tends to be further suppressed.

(A1) The melting peak temperature Tm2 of the polyamide is preferably 270 ° C. or higher, more preferably 275 ° C. or higher, and further preferably 280 ° C. or higher.
The melting peak temperature Tm2 of the (A1) polyamide is preferably 350 ° C. or lower, more preferably 340 ° C. or lower, further preferably 335 ° C. or lower, and still more preferably 330 ° C. or lower.
(A1) When the melting peak temperature Tm2 of the polyamide is 270 ° C. or higher, a polyamide composition excellent in heat resistance tends to be obtained.
Moreover, when (A1) polyamide melting peak temperature Tm2 is 350 ° C. or less, (A1) thermal decomposition of polyamide in melt processing such as extrusion and molding tends to be further suppressed.
(A1) The melting peak temperatures Tm1 and Tm2 of the polyamide can be measured according to JIS-K7121 by the method described in Examples below.

<Heat of fusion ΔHm1, ΔHm2, crystallization enthalpy ΔHc>
(A1) The heat of fusion ΔHm1 and crystallization enthalpy ΔHc of the polyamide are each preferably 30 J / g or more, more preferably 35 J / g or more, and still more preferably 40 J / g or more. Moreover, the upper limit of the heat of fusion ΔHm1 and the crystallization enthalpy ΔHc is not particularly limited and is preferably as high as possible.
(A1) When the heat of fusion ΔHm1 and the crystallization enthalpy ΔHc of the polyamide are each 30 J / g or more, the heat resistance of the polyamide composition tends to be further improved.
(A1) The heat of fusion ΔHm1 and crystallization enthalpy ΔHc of the polyamide can be measured according to JIS-K7121 by the method described later.
(A1) The heat of fusion ΔHm2 of the polyamide is preferably 20 J / g or more, more preferably 25 J / g or more, and further preferably 30 J / g or more. Moreover, the upper limit of the heat of fusion ΔHm2 is not particularly limited and is preferably as high as possible.
(A1) When the heat of fusion ΔHm2 of the polyamide is 20 J / g or more, the heat resistance of the polyamide composition tends to be further improved.

<Ratio of heat of fusion ΔHm1 and crystallization enthalpy ΔHc ΔHm1 / ΔHc>
The heat of fusion ΔHm1 is a heat of fusion reflecting the heat history received by the polyamide during heat treatment or cooling, and is different from the heat of fusion inherent in the polyamide. On the other hand, ΔHc is a crystallization enthalpy obtained through a cooling process (slow cooling) after complete melting, and is equal to the heat of fusion inherent in polyamide. Therefore, ΔHm1 / ΔHc means the ratio between the heat of fusion inherent in polyamide and the heat of fusion of polyamide subjected to a thermal history. For example, when heat treatment is performed at a temperature lower than the melting point, crystallization proceeds and ΔHm1 increases, so that ΔHm1 / ΔHc ≧ 1. In the case of rapid cooling, crystallization does not proceed and ΔHm1 becomes small, so ΔHm1 / ΔHc <1.
The ratio (ΔHm1 / ΔHc) of (A1) polyamide heat of fusion ΔHm1 and crystallization enthalpy ΔHc (ΔHm1 / ΔHc) in the (A) polyamide composition of the present invention is preferably more than 1.0 and not more than 2.2 from the viewpoint of heat resistance. More preferably, it is larger than 1.4 and is 2.2 or less, more preferably 1.5 or more and 2.2 or less, particularly preferably 1.6 or more and 2.2 or less, and 1.7 or more. Most preferred is 2.2 or less.

  (A1) When the ratio of heat of fusion ΔHm1 of the polyamide and crystallization enthalpy ΔHc ΔHm1 / ΔHc is y and the trans isomer ratio is x, it is preferable that y ≧ 0.04x−1.8. There is a tendency for the heat resistance of the to improve.

<Difference between melting peak temperature Tm1 and crystallization peak temperature Tc of polyamide (Tm1-Tc)>
(A1) When the difference (Tm1−Tc) between the melting peak temperature Tm1 and the crystallization peak temperature Tc of the polyamide is in the range higher than 40 ° C. and lower than 90 ° C., the polyamide composition has excellent fluidity and improved release properties. Tend to. Tm1-Tc is preferably higher than 40 ° C and lower than 90 ° C, and more preferably 50 ° C to 80 ° C.

  The measurement of the heat of fusion ΔHm1 and the crystallization enthalpy ΔHc of the polyamide can be carried out according to JIS-K7121, and the heat of fusion ΔHm1 is measured when the temperature of the polyamide is raised at a heating rate of 20 ° C./min (the first temperature rise). The endothermic peak appearing on the highest temperature side of the endothermic peak (melting peak) appearing at the time) is the peak area of Tm when the melting peak temperature is Tm (° C.). When there are a plurality of endothermic peaks, a peak having ΔH of 1 J / g or more is regarded as a peak, the highest temperature is defined as a melting peak temperature Tm1, and ΔHm1 is a sum of peak areas. The crystallization enthalpy ΔHc is the Tc value when the temperature of the exothermic peak (crystallization peak) that appears when the polyamide composition molded article is cooled at a temperature decrease rate of 20 ° C./min is the crystallization peak temperature Tc (° C.). It is the peak area. As the measuring device, Diamond-DSC manufactured by PERKIN-ELMER can be used as described in the following examples.

Further, the melting peak temperature Tm2 and the heat of fusion ΔHm2 of polyamide can be measured as follows. After the first temperature increase, the temperature is maintained for 2 minutes in the molten state at the maximum temperature increase, then the temperature is decreased to 30 ° C. at a temperature decrease rate of 20 ° C./min, maintained at 30 ° C. for 2 minutes, and then the temperature increase rate is 20 The endothermic peak temperature that appears at the highest temperature side of the endothermic peak that appears when the temperature is similarly raised at the same temperature (° C./min) is the melting peak temperature Tm2 of the polyamide itself, and the peak area at this melting peak temperature. Is the heat of fusion ΔHm2 of the polyamide.
The measurement of the melting peak temperature Tm2 and the heat of fusion ΔHm2 of polyamide can be performed according to JIS-K7121 as described in the following examples. As an apparatus for measuring the melting peak temperature and the heat of fusion, for example, Diamond-DSC manufactured by PERKIN-ELMER may be used.

<Glass transition temperature Tg>
(A1) The glass transition temperature Tg of the polyamide is preferably 90 ° C. or higher, more preferably 110 ° C. or higher, still more preferably 120 ° C. or higher, even more preferably 130 ° C. or higher, and even more preferably. Is 135 ° C. or higher.
The glass transition temperature Tg of (A1) polyamide is preferably 170 ° C. or lower, more preferably 165 ° C. or lower, and further preferably 160 ° C. or lower.
(A1) When the glass transition temperature Tg of polyamide is 90 ° C. or higher, a polyamide composition excellent in heat discoloration resistance and chemical resistance tends to be obtained. Moreover, when the glass transition temperature Tg of (A1) polyamide is 170 ° C. or lower, a molded product having a good appearance tends to be obtained.
(A1) The glass transition temperature Tg of polyamide can be measured according to JIS-K7121, as described in the following examples.
Examples of the measuring device for the glass transition temperature Tg include Diamond-DSC manufactured by PERKIN-ELMER.

<Polymer end>
Although it does not specifically limit as a polymer terminal of the polyamide used for this invention, It can classify | categorize and define as follows.
That is, 1) amino terminal, 2) carboxyl terminal, 3) cyclic amino terminal, 4) terminal by sealing agent, and 5) other terminal.

1) the amino terminus is a polymer end with an amino group (-NH ₂ group), derived from (b) diamine units of the raw material.
Amino-terminal amount _([NH 2]), to the (A1) Polyamide 1g, preferably 5~100μ eq / g, more preferably from 5~70μ eq / g, more preferably 5~50μ equivalents / G, even more preferably 5-30 μeq / g, and even more preferably 5-20 μeq / g.
When the amino terminal amount is in the above range, the whiteness, reflow resistance, heat discoloration resistance, light discoloration resistance, hydrolysis resistance, and heat retention stability of the polyamide composition tend to be more excellent. The amino terminal amount can be measured by neutralization titration. Specifically, 3.0 g of polyamide is dissolved in 100 mL of a 90 mass% phenol aqueous solution, and the obtained solution is titrated with 0.025N hydrochloric acid to obtain the amino terminal amount (μ equivalent / g). The end point is determined from the indicated value of the pH meter.

2) The carboxyl terminal is a polymer terminal having a carboxyl group (—COOH group) and is derived from the raw material (a) dicarboxylic acid.
The carboxyl terminal amount ([COOH]) is preferably 5 to 150 μequivalent / g, more preferably 5 to 140 μequivalent / g, and still more preferably 5 to 130 μequivalent / g with respect to 1 g of (A1) polyamide. g, even more preferably 5 to 120 μeq / g, and even more preferably 5 to 110 μeq / g. When the carboxyl end amount is in the above range, the whiteness, reflow resistance, heat discoloration resistance, and light discoloration resistance of the polyamide composition tend to be more excellent. The carboxyl end amount can be measured by neutralization titration. Specifically, 4.0 g of polyamide is dissolved in 50 mL of benzyl alcohol, and the obtained solution is titrated with 0.1 N NaOH to obtain the carboxyl terminal amount (μ equivalent / g). The end point is determined from the discoloration of the phenolphthalein indicator.

The total amount of the amino terminal amount ([NH ₂ ]) and the carboxyl terminal amount ([COOH]) is defined as the active terminal total amount ([NH ₂ ] + [COOH]). The total amount of active terminals is preferably 10 to 200 μeq / g, more preferably 10 to 150 μeq / g, and still more preferably 10 to 130 μeq / g, based on 1 g of (A1) polyamide.
In addition, [NH ₂ ] / ([NH ₂ ] + [COOH]), which is the ratio of the amino terminal amount to the total active terminal amount, is preferably less than 0.5, more preferably less than 0.4, More preferably, it is less than 0.3. ΔHm1 / ΔHc can be controlled to be greater than 1.0 and less than or equal to 2.2 because the ratio of the amino terminal amount and the carboxyl terminal amount and the ratio of the amino terminal amount to the active terminal total amount are within the above ranges. The heat discoloration resistance and light discoloration resistance of the polyamide composition tend to be more excellent.

  Examples of the method for controlling the ratio of the amino terminal amount to the total active terminal amount include a method of controlling the addition amount of diamine and terminal blocking agent as additives during hot melt polymerization of polyamide, and the polymerization conditions. .

3) The cyclic amino terminus is a polymer terminus having a cyclic amino group (a group represented by the following (formula 1)).
In the following (Formula 1), R represents a substituent bonded to the carbon constituting the piperidine ring. Specific examples of R include a hydrogen atom, a methyl group, an ethyl group, and a t-butyl group.
Further, for example, even when piperidine cyclized by a deammonia reaction of a diamine having a pentamethylenediamine skeleton as a raw material is bonded to the polymer terminal, it becomes the terminal of this cyclic amino group. These structures may be taken when a monomer having a pentamethylenediamine skeleton is included.

3) The amount of the cyclic amino terminal is preferably 0 μe equivalent / g or more and 65 μe equivalent / g or less, more preferably 10 μe equivalent / g or more and 60 μequivalent / g or less, with respect to 1 g of (A1) polyamide. Preferably they are 20 microequivalent / g or more and 55 microequivalent / g or less.
When the amount of the cyclic amino terminus is in the above range, the polyamide composition of the present invention tends to have better toughness, hydrolysis resistance, and processability.

The amount of the cyclic amino terminus can be measured using ¹ H-NMR. For example, there is a method of calculation based on the integral ratio of hydrogen bonded to carbon adjacent to the nitrogen atom of the heterocyclic ring of nitrogen and hydrogen bonded to carbon adjacent to the nitrogen atom of the amide bond of the polyamide main chain.

  Cyclic amino terminal can be generated by dehydration reaction of cyclic amine and carboxyl terminal, and can also be generated by deammonia reaction of amino terminal in the polymer molecule. Cyclic amine is added as end-capping agent. It can also be produced by the diamine having a pentamethylenediamine skeleton, which is a raw material for polyamide, and cyclizing by deammonia reaction.

In the present invention, the cyclic amino terminal is preferably derived from a raw material diamine.
Without adding cyclic amine as an end-capping agent at the initial stage of polymerization, the cyclic amino terminal is generated from the raw material diamine, so that the low molecular weight carboxylic acid terminal is prevented from being blocked at the initial stage of polymerization. Thus, the polymerization reaction rate of the polyamide is maintained high, and as a result, a high molecular weight product tends to be easily obtained. As described above, when a cyclic amine is generated during the reaction, the carboxylic acid terminal is sealed with the cyclic amine at a later stage of the polymerization, so that a high molecular weight polyamide is easily obtained.

  Cyclic amines that generate a cyclic amino terminus can be generated as a by-product during the polymerization reaction of the polyamide. In this cyclic amine formation reaction, the higher the reaction temperature, the higher the reaction rate. Therefore, in order to make the cyclic amino terminal of the (A1) polyamide constant, it is preferable to promote the formation of a cyclic amine. Therefore, the reaction temperature for the polymerization of the precursor polyamide is preferably 300 ° C. or higher, and more preferably 320 ° C. or higher.

  As a method for adjusting these cyclic amino ends to a certain amount, control is performed by appropriately adjusting the polymerization temperature, the holding time of the reaction temperature of 300 ° C. or more during the polymerization step, the addition amount of the amine forming the cyclic structure, and the like. The method of doing is mentioned.

  4) The terminal by a sealing agent is a terminal formed when a sealing agent is added at the time of superposition | polymerization. Examples of the sealing agent include the above-described end sealing agents.

5) The other terminal is a polymer terminal not classified in the above 1) to 4), such as a terminal generated by deammonia reaction at the amino terminal or a terminal generated by decarboxylation from the carboxylic acid terminal. It is done.
The physical properties of the (A1) polyamide in the (A) polyamide composition of the present invention are the same as those of the original (A1) polyamide even after melt-kneading with other additives as necessary to obtain a composition. The physical properties are maintained and have equivalent measurement values, and (A) by measuring each of the above physical properties in the polyamide composition, the physical properties of the (A1) polyamide contained therein can be specified. Is possible.

  (A) Polyamide composition in the present invention (A1) Polyamide ratio of trans isomer, sulfuric acid relative viscosity ηr, number average molecular weight Mn, molecular weight distribution Mw / Mn, melting peak temperature Tm1, Tm2, heat of fusion ΔHm1, ΔHm2 The ratio of the crystallization peak temperature Tc, crystallization enthalpy ΔHc, glass transition temperature Tg, amino terminus, carboxyl terminus, and amino terminus amount to the total amount of active terminus was measured by the method for measuring the physical properties of polyamide described in the examples described later. can do.

  When determining the heat of fusion and crystallization enthalpy of the polyamide composition, if it contains an inorganic filler, nucleating agent, lubricant, stabilizer, etc., the value of the heat value is the ratio of the polyamide to the composition. Convert and calculate.

Next, a production method for obtaining the polyamide composition of the present invention will be described.
[(A) Polyamide composition production method]
The production method of the polyamide composition (A) of the present invention comprises (a) a dicarboxylic acid unit containing at least 1,4-cyclohexanedicarboxylic acid and (b) a diamine unit containing at least an aliphatic diamine,
[NH ₂ ] / ([NH ₂ ] + [COOH]), which is the ratio of the amino terminal amount [NH ₂ ] to the total active terminal amount ([NH ₂ ] + [COOH]),
[NH ₂ ] / ([NH ₂ ] + [COOH]) <0.5,
Active terminal total amount ([NH ₂ ] + [COOH]) μeq / g is
100 ≦ ([NH ₂ ] + [COOH]) ≦ 200
And a precursor polyamide composition comprising (A2) at least one metal compound selected from Li, Na, and K (excluding a hypophosphite compound) The heat treatment is performed for less than 10 hours.

That is, in the method for producing a polyamide composition (A) of the present invention, a polyamide composition (hereinafter referred to as a precursor polyamide composition) is composed of a polyamide having a specific terminal structure (precursor polyamide) and a component (A2). And (A) a method of obtaining a polyamide composition by heat treatment at 200 ° C. or higher and lower than the melting point. As such a production method, a “hot melt polymerization / solid phase polymerization method” is preferable.
Hereinafter, the method for obtaining the precursor polyamide composition and the heat treatment will be described in detail.

<Method for obtaining precursor polyamide composition>
The precursor polyamide composition is not particularly limited, and examples thereof include the methods exemplified below.
1) A method in which an aqueous solution or a suspension of water of a dicarboxylic acid / diamine salt or a mixture thereof is heated and polymerized while maintaining a molten state (hereinafter referred to as hot melt polymerization method).
2) A method in which an aqueous solution or suspension of water of a dicarboxylic acid / diamine salt or a mixture thereof is heated, and the precipitated prepolymer is melted again with an extruder such as a kneader to increase the degree of polymerization (hereinafter referred to as prepolymer · Called the extrusion polymerization method).
3) A method of polymerizing using a dicarboxylic acid halide equivalent to a dicarboxylic acid and a diamine (hereinafter referred to as a solution method).
Among them, the hot melt polymerization method is preferable from the viewpoint of increasing the molecular weight by polymerization in a short time and suppressing gelation.

When producing the precursor polyamide composition, for the precursor polyamide in the precursor polyamide composition, (a) the addition amount of the dicarboxylic acid constituting the dicarboxylic acid unit, and (b) the addition of the diamine constituting the diamine unit The amount is preferably about the same molar amount.
(A) The dicarboxylic acid unit preferably contains 50 to 100 mol% of 1,4-cyclohexanedicarboxylic acid units (based on the total number of dicarboxylic acids), more preferably 60 to 100 mol%, and 70 to 100 mol. % Is more preferable, and 100 mol% is most preferable.

It is known that alicyclic dicarboxylic acids are isomerized at high temperatures, and the trans isomer and cis isomer are in a certain ratio, and the cis alicyclic dicarboxylic acid is more trans alicyclic dicarboxylic acid. Compared with an acid, the water solubility of an equivalent salt of an alicyclic dicarboxylic acid and a diamine tends to be higher. From this, the trans isomer / cis isomer ratio (molar ratio) of the alicyclic dicarboxylic acid as the raw material monomer is preferably 50/50 to 0/100, more preferably 40/60 to 10/90. More preferably, it is 35/65 to 15/85.
The trans / cis ratio (molar ratio) of the alicyclic dicarboxylic acid can be determined by liquid chromatography (HPLC) or nuclear magnetic resonance spectroscopy (NMR).

  (B) The diamine unit preferably includes (b-1) a diamine unit having a substituent branched from the main chain, and the ratio is preferably 10 to 100 mol%, more preferably 20 to 100 mol%, 30 More preferred is ˜100 mol%. (B-1) is most preferably 2-methylpentamethylenediamine.

  When the precursor polyamide composition is produced (thermal melt polymerization), a diamine may be added in addition to (b) in order to adjust the molecular weight and terminal of the precursor polyamide in the precursor polyamide composition. As the diamine to be added, 2-methylpentamethylenediamine is preferable. (B) The amount of added diamine with respect to diamine is 0-5.0 mol% by mole ratio, More preferably, it is 0-2.0 mol%, More preferably, it is 0-1.0 mol%.

When the precursor polyamide composition is produced (thermal melt polymerization), it is preferable to add a catalyst. The catalyst is preferably an alkali metal compound, and more preferably at least one metal compound selected from Li, Na, and K as the A2 component (excluding a hypophosphorous acid compound) is added as a catalyst. Among these, Li compounds are more preferable, and LiCl and LiOH are most preferable. The concentration of the component (A2) relative to the (A1) polyamide is preferably 1 to 5000 ppm, more preferably 10 to 3000 ppm, and still more preferably 50 to 2000 ppm.
When other than at least one metal compound selected from Li, Na, and K as the A2 component is used as the catalyst, the A2 component may be added before the heat treatment.

  In the method for producing the precursor polyamide composition, (A1) From the viewpoint of the color tone and fluidity of the polyamide, the trans isomer ratio of the alicyclic dicarboxylic acid unit in the precursor polyamide is maintained at 85% or less and is melted by heat. It is preferable to perform polymerization, and it is particularly preferable to perform hot melt polymerization while maintaining the trans isomer ratio of the alicyclic dicarboxylic acid unit at 80% or less.

  (A) It is preferable that the manufacturing method of a polyamide composition further includes the process of raising the polymerization degree of polyamide. Moreover, the sealing process which seals the terminal of the obtained polymer with a terminal sealing agent may be included as needed.

(Physical properties of precursor polyamide in precursor polyamide composition)
The physical property of the precursor polyamide in the precursor polyamide composition is the ratio of the amino terminal amount [NH ₂ ] to the active terminal total amount ([NH ₂ ] + [COOH]) [NH ₂ ] / ([NH ₂ ] + [COOH]) is preferably less than 0.5, more preferably less than 0.01 to less than 0.5, and even more preferably 0.05 to 0.4. The active terminal total amount ([NH ₂ ] + [COOH]) is preferably 100 to 200 μeq / g, more preferably 100 to 180 μeq / g, and still more preferably 100 to 160 μeq / g.
In order to obtain the physical properties of such a precursor polyamide composition, the terminal structures of the precursor polyamide are adjusted by adjusting the amount of the structural units (a) to (c) of the polyamide, the end-capping agent and the additional diamine. Can be obtained by controlling.

<Heat treatment>
The heat treatment in the production method of the present invention is a method of heating the precursor polyamide composition at a temperature lower than the melting point (Tm2).
The heat treatment method is not particularly limited as long as heating at 200 ° C. or more and less than the melting point (Tm2) is possible. For example, apparatuses such as a dryer, an autoclave, an electric furnace, a gear oven, a hot plate, and a molding die This can be done by using The heat treatment may be performed in the air, may be performed in an inert gas atmosphere, for example, a nitrogen gas atmosphere, or may be performed in a reduced pressure environment. As the heat treatment method, a solid phase polymerization method in which constituent units such as monomers and precursor polyamide are polymerized in a solid state at a temperature lower than the melting point is preferable.

The heat treatment temperature is 200 ° C. or higher and lower than the melting point (Tm 2), more preferably 220 ° C. to lower than the melting point (Tm 2), and further preferably 240 ° C. or higher and lower than the melting point (Tm 2). By making it 200 degreeC or more, the trans isomer ratio of the 1, 4- cyclohexane dicarboxylic acid monomer unit in polyamide can be made larger than 70 mol%. On the other hand, when the melting point (Tm2) is set, the polyamide can be prevented from being melted satisfactorily, so that the trans isomer ratio can be made larger than 70 mol%. The heat treatment time can be appropriately selected depending on the heat treatment temperature. For example, when the heat treatment time is 200 to 240 ° C., it is preferably 10 to 72 hours, more preferably about 10 to 48 hours.
As described above, the polyamide composition is obtained by heat-treating the precursor polyamide composition.

[Polyamide composition molded product]
The polyamide composition molded article of the present invention (hereinafter sometimes simply referred to as a molded article) is formed by molding the above-mentioned (A) polyamide composition.
The polyamide composition molded article maintains a high trans isomer ratio of the dicarboxylic acid monomer unit, and is excellent in hot strength, hot stiffness, and low water absorption, so it can be suitably used for automotive parts. it can.

[Production Method of Polyamide Composition Molded Product]
The polyamide composition molded article of the present invention is obtained by forming the above polyamide composition into a known molding method such as press molding, injection molding, gas assist injection molding, welding molding, extrusion molding, blow molding, film molding, hollow molding, and multilayer molding. And can be obtained by molding using melt spinning or the like.
The polyamide composition molded article of the present invention may be heat-treated at 200 ° C. or higher in order to further increase the trans isomer ratio and cause crystallization as necessary.

The heat treatment method for the polyamide composition molded body is not particularly limited as long as heating at 200 ° C. or higher is possible. For example, an apparatus such as an electric furnace, a gear oven, a hot plate, or a molding die is used. Can be performed. The heat treatment may be performed in the air, may be performed in an inert gas atmosphere, for example, a nitrogen gas atmosphere, or may be performed in a reduced pressure environment. The heat treatment temperature is 200 ° C or higher, preferably 220 ° C to 300 ° C, more preferably 240 ° C to 300 ° C. By setting it as 200 degreeC or more, the trans isomer ratio of the 1, 4- cyclohexane dicarboxylic acid monomer unit in a molded article can be made larger than 70 mol%. On the other hand, by setting the temperature to 300 ° C. or lower, it is possible to prevent the molded product from being melted satisfactorily, so that the trans isomer ratio can be made larger than 70 mol%. The heat treatment time can be appropriately selected depending on the size and thickness of the molded product and the heat treatment temperature. For example, when the heat treatment time is 200 to 240 ° C., it is preferably 1 to 72 hours, more preferably about 1 to 48 hours.
By this method, a polyamide composition molded article having excellent heat resistance, strength, hot strength, rigidity, hot stiffness, and hot stability can be obtained.

[Use of polyamide composition molded product]
The polyamide composition molded article of the present invention is excellent in heat resistance, strength, heat strength, rigidity, heat stiffness, heat stability, and has LLC (Long Life Coolant) resistance as shown in the following examples. Since it is improved, it can be suitably used as various parts materials for automobiles, electric and electronic, industrial materials, extrusion applications, daily necessities and household goods.

  It is not particularly limited for automobiles, and is used for, for example, intake system parts, cooling system parts, fuel system parts, interior parts, exterior parts, and electrical parts.

  Examples of the vehicle intake system parts include 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, and a throttle body.

  Examples of the automobile cooling system parts include a chain cover, a thermostat housing, an outlet pipe, a radiator tank, an oil netter, and a delivery pipe.

  Examples of automobile fuel system parts include fuel delivery pipes and gasoline tank cases.

  Examples of the interior parts include an instrument panel, a console box, a glove box, a steering wheel, and a trim.

  Examples of exterior parts include a mall, a lamp housing, a front grille, a mud guard, a side bumper, a door mirror stay, and a roof rail.

  The electrical component is not particularly limited, and examples thereof include a connector, a wire harness connector, a motor component, a lamp socket, a sensor on-vehicle switch, and a combination switch.

  Examples of electrical and electronic products include connectors, switches, relays, printed wiring boards, electronic component housings, outlets, noise filters, coil bobbins, and motor end caps.

  Examples of industrial materials include gears, cams, insulating blocks, valves, power tool parts, agricultural equipment parts, engine covers, and the like.

  Examples of daily necessities and household goods include buttons, food containers, and office furniture.

  Examples of extrusion applications include films, sheets, filaments, tubes, rods, and hollow molded articles.

EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited to an Example.
Measuring methods for raw materials and physical properties used in Examples and Comparative Examples are shown below.
In this example, 1 kg / cm ² means 0.098 MPa.

[Raw material of polyamide]
<(A) Raw material of dicarboxylic acid unit>
(1) 1,4-cyclohexanedicarboxylic acid (CHDA) manufactured by Eastman Chemical Co., Ltd. Product name: 1,4-CHDA HP grade (trans isomer / cis isomer (molar ratio) = 25/75)
<(B) Raw material of diamine unit>
(1) 2-methylpentamethylenediamine (2MC5DA) (manufactured by Tokyo Chemical Industry Co., Ltd.)
(2) Nonamethylenediamine (C9DA) (Aldrich)
(3) 2-methyloctamethylenediamine (2MC8DA) (manufactured with reference to the production method described in JP-A No. 05-17413)
(4) Hexamethylenediamine (C6DA) (manufactured by Tokyo Chemical Industry Co., Ltd.)
(5) Decamethylenediamine (C10DA) (manufactured by Tokyo Chemical Industry Co., Ltd.)
(6) Undecamethylenediamine (C11DA) (manufactured by Tokyo Chemical Industry Co., Ltd.)
(7) Dodecamethylenediamine (C12DA) (manufactured by Tokyo Chemical Industry Co., Ltd.)

〔Additive〕
<Polymerization catalyst>
(1) Lithium chloride (LiCl) (Wako Pure Chemical Industries, Ltd.)
(2) Lithium hydroxide monohydrate (LiOH.H ₂ O) (Wako Pure Chemical Industries, Ltd.)
(3) Sodium chloride (NaCl) (Wako Pure Chemical Industries, Ltd.)
(4) Potassium chloride (KCl) (manufactured by Wako Pure Chemical Industries, Ltd.)
(5) Sodium hypophosphite monohydrate (NaH ₂ PO ₂ .H ₂ O) (manufactured by Taihei Chemical Industrial Co., Ltd.)

[Inorganic filler]
Glass fiber (GF) manufactured by Nippon Electric Glass Co., Ltd. Product name: ECS03T275H Average fiber diameter (average particle diameter) 10 μm (circular shape), cut length 3 mm

[Calculation of polyamide unit amount]
The mole% of 1,4-cyclohexanedicarboxylic acid is calculated by (Mole number of 1,4-cyclohexanedicarboxylic acid added as raw material monomer / Mole number of all dicarboxylic acid units added as raw material monomer) × 100. It was.
The mol% of the aliphatic diamine was determined by calculation as (number of moles of aliphatic diamine added as a raw material monomer / number of moles of all diamine units added as a raw material monomer) × 100.
In addition, when calculating by the above formula, the denominator and numerator do not include the number of moles of aliphatic diamine added as an additive during melt polymerization.

[Method of measuring physical properties of polyamide]
(1) Polyamide melting peak temperatures Tm1, Tm2 (° C.), heat of fusion ΔHm1, ΔHm2 (J / g), crystallization enthalpy ΔHc (J / g)
According to JIS-K7121, it measured using Diamond-DSC by PERKIN-ELMER. The measurement conditions were as follows: when about 10 mg of the polyamide obtained in Examples and Comparative Examples was heated to 300 to 350 ° C. according to the melting point (Tm) of the sample at a heating rate of 20 ° C./min in the nitrogen atmosphere (first time) The melting peak temperature appearing on the highest temperature side of the endothermic peak (melting peak) appearing at the time of temperature rise was Tm1 (° C.), and the peak area of Tm1 was the heat of fusion ΔHm1 (J / g). The melting peak temperature Tm2 and the heat of fusion ΔHm2 of the starting polyamide can be measured as follows. After the first temperature increase, the temperature is maintained for 2 minutes in the molten state at the maximum temperature increase, then the temperature is decreased to 30 ° C. at a temperature decrease rate of 20 ° C./min, maintained at 30 ° C. for 2 minutes, and then the temperature increase rate is 20 The endothermic peak temperature that appears at the highest temperature side of the endothermic peak that appears when the temperature is similarly raised at the same temperature (° C./min) is the melting peak temperature Tm2 of the polyamide itself, and the peak area at Tm2 is the polyamide area. The heat of fusion ΔHm2

In addition, when there were a plurality of endothermic peaks appearing at the first temperature increase, those having ΔH of 1 J / g or more were regarded as peaks. For example, when there are two endothermic peaks that appear at the first temperature increase, melting point 295 ° C., ΔH = 20 J / g, melting point 325 ° C., ΔH = 5 J / g, the melting peak temperature Tm1 is higher. The value of 325 ° C. and ΔHm1 were 25 J / g of the total value of all peaks.
The temperature of the exothermic peak (crystallization peak) that appears when the temperature is lowered at a rate of temperature decrease of 20 ° C./min is defined as the crystallization peak temperature Tc (° C.), and the total peak area of Tc is the crystallization enthalpy ΔHc (J / g). did.

(2) Glass transition temperature Tg (° C) of polyamide
The glass transition temperature Tg (° C.) was measured using Diamond-DSC manufactured by PERKIN-ELMER according to JIS-K7121. The measurement conditions were as follows: a sample obtained by melting the polyamide obtained in Examples and Comparative Examples on a hot stage (EP80 manufactured by Mettler) was rapidly cooled and solidified using liquid nitrogen, and the measurement sample and did. Using 10 mg of the sample, the glass transition temperature was measured by raising the temperature in the range of 30 to 350 ° C. under a temperature raising speed of 20 ° C./min.

(3) Trans isomer ratio 30-40 mg of polyamides obtained in Examples and Comparative Examples were dissolved in 1.2 g of hexafluoroisopropanol deuterated and measured by ¹ H-NMR (ECA500 manufactured by JEOL). The trans isomer ratio of the 1,4-cyclohexanedicarboxylic acid monomer unit of the polyamide is 2.00 ppm peak area derived from the trans isomer, and 1.77 ppm and 1.87 ppm peak area ratio derived from the cis isomer. I asked for it.

(4) Polyamide sulfuric acid relative viscosity ηr
The relative viscosity ηr of sulfuric acid at 25 ° C. of the polyamides obtained in the examples and comparative 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 a temperature of 25 ° C. was obtained using the obtained solution. The sulfuric acid relative viscosity ηr was measured under the conditions.

(5) Molecular weight Number average molecular weight Mn, weight average molecular weight Mw, molecular weight distribution Mw / Mn are GPC (gel permeation chromatography, manufactured by Tosoh Corporation, HLC-8020, hexafluoroisopropanol solvent, PMMA (polymethyl methacrylate) standard sample. A calibration curve was prepared using the number average molecular weight Mn measured by Polymer Laboratories Co., Ltd., and the molecular weight of the polyamide obtained in this example and comparative example was determined.The GPC column was TSK-GEL GMHHR. -M and G1000HHR were used.

(6) Amino terminal amount ([NH ₂ ])
In the polyamides obtained in the examples and comparative examples, the amount of amino terminal bound to the polymer terminal was measured by neutralization titration as follows.
3.0 g of polyamide was dissolved in 100 mL of a 90 mass% phenol aqueous solution, and the obtained solution was titrated with 0.025N hydrochloric acid to determine the amino terminal amount (μ equivalent / g). The end point was determined from the indicated value of the pH meter.

(7) Carboxyl end amount ([COOH])
In the polyamides obtained in the examples and comparative 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 resulting solution was titrated with 0.1N NaOH to obtain the carboxyl end amount (μ equivalent / g). The end point was determined from the discoloration of the phenolphthalein indicator.

Based on the amino terminal amount ([NH ₂ ]) and carboxyl terminal amount ([COOH]) measured by (6) and (7), the active terminal total amount ([NH ₂ ] + [COOH]) and amino terminal amount activity The ratio ([NH ₂ ] / ([NH ₂ ] + [COOH])) relative to the total amount of terminals was calculated.

[Measurement method of physical properties of polyamide composition molded article]
(8) Tensile strength (MPa), tensile modulus (GPa), breaking strain (%)
Using the polyamide composition molded articles (multipurpose test pieces) obtained in Examples and Comparative Examples, a tensile test was performed in accordance with ISO 527 under a 120 ° C. environment and a tensile speed of 5 mm / min, and the tensile strength and tensile elasticity. The rate and breaking strain were measured.

(9) Water absorption rate (%)
The molded product of the polyamide composition obtained in Examples and Comparative Examples was immersed in distilled water at 80 ° C. for 24 hours, and the weight change rate before and after immersion was taken as the water absorption rate.

(10) Tensile strength retention rate after immersion (%) (in Tables 2 and 3, described as LLC resistance (retention rate))
Tensile strength retention (%) after immersion of the polyamide composition molded articles obtained in Examples and Comparative Examples was measured as follows. The multipurpose test piece (3 mm thickness) of (8) above is immersed in an ethylene glycol 50% aqueous solution at 120 ° C. for 24 hours and 720 hours and left at room temperature, and then the tensile test of the method of (8) is performed. Tensile strength was measured. The ratio of the tensile strength measured after immersion for 720 hours to the tensile strength measured after immersion for 24 hours was determined as the tensile strength retention after immersion.

  (A) The manufacture example of a polyamide composition is demonstrated below. Table 1 describes the types, blending ratios, and polymerization methods of (A1) polyamide and (A2) metal compound in each production example.

[Production Example 1]
Polyamide was polymerized by the hot melt polymerization method as follows.
CHDA 802 g (4.66 mol) as a dicarboxylic acid unit, 2MC5DA 216 g (1.86 mol) and C10DA 482 g (2.80 mol) as a diamine unit are dissolved in 1500 g of distilled water, and an equimolar aqueous solution of about 50% by mass of the raw material monomer is obtained. Was made.

The obtained aqueous solution was charged into an autoclave having an internal volume of 5.4 L (manufactured by Nitto Koatsu), and further 1.3 g of LiCl was added to the autoclave as a catalyst. The temperature was maintained until the liquid temperature (internal temperature) reached 50 ° C., and the inside of the autoclave was purged with nitrogen. The pressure in the autoclave tank (hereinafter, also simply referred to as “inside the tank”) is about 2.5 kg / cm ² (G) as gauge pressure (hereinafter, all pressure in the tank is expressed as gauge pressure). The liquid temperature was continuously heated from about 50 ° C. until the temperature reached (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 (G), heating was continued while removing water out of the system, and the solution was concentrated until the concentration of the aqueous solution reached about 75% by mass (the liquid in this system). The temperature 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 (G) (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 (G), heating was continued until the final temperature (330 ° C. described later) −40 ° C. (here, 290 ° C.) while removing water out of the system. . After the liquid temperature rises to the final temperature (330 ° C. described later) −40 ° C. (290 ° C. here), the heating continues and the pressure in the tank reaches 30 at 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) in the tank was about 330 ° C. While the resin temperature was kept at about 330 ° C., the inside of the tank was maintained under a reduced pressure of about 50 kPa for 20 minutes with a vacuum apparatus 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 a precursor polyamide pellet (precursor polyamide pellet). . The total active terminal amount ([NH ₂ ] + [COOH]) of this precursor polyamide is 161 μeq / g, the ratio of the amino terminal amount [NH ₂ ] to the active terminal total amount ([NH ₂ ] + [COOH]). [NH ₂ ] / ([NH ₂ ] + [COOH]) was 0.15.

10 kg of the precursor polyamide pellets obtained by using melt polymerization was put into a conical ribbon vacuum dryer (trade name “ribocorn RM-10V” manufactured by Okawara Seisakusho Co., Ltd.), and the inside of the vacuum dryer was sufficiently substituted with nitrogen.
The precursor polyamide pellets were heated at 240 ° C. for 10 hours with stirring while flowing nitrogen at 10 L / min in the vacuum dryer. Thereafter, the temperature in the vacuum dryer was lowered to about 50 ° C. while circulating nitrogen, and the polyamide pellets were taken out from the vacuum dryer in the form of pellets to obtain polyamide (PA-1).
The obtained polyamide was dried in a nitrogen stream to adjust the moisture content to less than about 0.2% by mass, and then each property of the polyamide was measured based on the above measurement method.

[Production Example 2]
A polyamide (PA-2) was obtained in the same manner as in Production Example 1 except that the catalyst LiCl was LiOH monohydrate and the amount thereof was 0.1 g.
In addition, the active terminal total amount ([NH ₂ ] + [COOH]) of the precursor polyamide before heat treatment of the obtained polyamide was 133 μeq / g, the amino terminal amount [NH ₂ ] active terminal total amount ([NH _2] + [COOH] is the _{ratio) [NH 2] / ([} NH 2] + [COOH]) was 0.23.

[Production Example 3]
A polyamide (PA-3) was obtained in the same manner as in Production Example 1 except that the amount of the catalyst LiOH • monohydrate was 1.3 g.
In addition, the active terminal total amount ([NH ₂ ] + [COOH]) of the precursor polyamide before heat treatment of the obtained polyamide was 129 μeq / g, the amino terminal amount [NH ₂ ] active terminal total amount ([NH _2] + [COOH] is the _{ratio) [NH 2] / ([} NH 2] + [COOH]) was 0.38.

[Production Example 4]
A polyamide (PA-4) was obtained in the same manner as in Production Example 1 except that the amount of the catalyst LiOH • monohydrate was 2.6 g.
In addition, the active terminal total amount ([NH ₂ ] + [COOH]) of the precursor polyamide before heat treatment of the obtained polyamide was 147 μeq / g, the amino terminal amount [NH ₂ ] active terminal total amount ([NH _2] + [COOH] is the _{ratio) [NH 2] / ([} NH 2] + [COOH]) was 0.48.

[Production Example 5]
CHDA 795 g (4.62 mol) as dicarboxylic acid units, 2MC5DA 188 g (1.62 mol) and C10DA 517 g (3.00 mol) as diamine units were dissolved in 1500 g of distilled water, and an equimolar aqueous solution of about 50% by mass of raw material monomers was obtained. A polyamide (PA-5) was obtained in the same manner as in Production Example 3 except that was prepared.
The total active terminal amount ([NH ₂ ] + [COOH]) of the precursor polyamide before heat treatment of the obtained polyamide was 134 μeq / g, and the total active terminal amount of amino terminal amount [NH ₂ ] ([NH _2] + [COOH] is the _{ratio) [NH 2] / ([} NH 2] + [COOH]) was 0.38.

[Production Example 6]
Production Example 1 except that CHDA 896 g (5.20 mol) as a dicarboxylic acid unit and 2MC5DA 604 g (5.20 mol) as a diamine unit were dissolved in 1500 g of distilled water to prepare an equimolar aqueous solution of about 50% by mass of the raw material monomer. In the same manner as above, polyamide (PA-6) was obtained.
In addition, the active terminal total amount ([NH ₂ ] + [COOH]) of the precursor polyamide before heat treatment of the obtained polyamide was 161 μeq / g, and the amino terminal amount [NH ₂ ] active terminal total amount ([NH _2] + [COOH] is the _{ratio) [NH 2] / ([} NH 2] + [COOH]) was 0.15.

[Production Example 7]
A polyamide (PA-7) was obtained in the same manner as in Production Example 1 except that the amount of catalyst NaCl was 1.3 g, and the amount of 2MC5DA additional diamine was 12 g.
In addition, the active terminal total amount ([NH ₂ ] + [COOH]) of the precursor polyamide before heat treatment of the obtained polyamide was 120 μeq / g, the amino terminal amount [NH ₂ ] active terminal total amount ([NH _2] + [COOH] is the _{ratio) [NH 2] / ([} NH 2] + [COOH]) was 0.49.

[Production Example 8]
Polyamide (PA-8) was obtained in the same manner as in Production Example 1 except that the amount of catalyst KCl was 1.3 g, and the amount of 2MC5DA additional diamine was 12 g.
In addition, the active terminal total amount ([NH ₂ ] + [COOH]) of the precursor polyamide before the heat treatment of the obtained polyamide was 121 μeq / g, the amino terminal amount [NH ₂ ] active terminal total amount ([NH _2] + [COOH] is the _{ratio) [NH 2] / ([} NH 2] + [COOH]) was 0.48.

[Production Example 9]
Polyamide (PA-9) was obtained in the same manner as in Production Example 1 except that the amount of 2MC5DA additional diamine was 13 g, and the precursor polyamide pellets obtained by subsequent melt polymerization were dried at 150 ° C. for 10 hours in a vacuum dryer. It was.
In addition, the active terminal total amount ([NH ₂ ] + [COOH]) of this precursor polyamide is 123 μ equivalent / g, the active terminal total amount of amino terminal amount [NH ₂ ] ([NH ₂ ] + [COOH]). [NH ₂ ] / ([NH ₂ ] + [COOH]), which is the ratio to, was 0.55.

[Production Example 10]
A polyamide (PA-10) was obtained in the same manner as in Production Example 9 except that the precursor polyamide pellets obtained by melt polymerization were dried at 190 ° C. for 10 hours with a vacuum dryer.

[Production Example 11]
The polymerization method was in accordance with the production method described in Patent Document 7 (Japanese Patent Publication No. 64-2131).
1007 g (5.85 mol) of CHDA, 832 g (4.46 mol) of C11DA, and 161 g (1.39 mol) of C6DA were dissolved in 500 g of distilled water to prepare an equimolar aqueous solution of about 80% by mass of raw material monomers.
The obtained aqueous solution was charged into an autoclave (made by Nitto High Pressure Co., Ltd.) having an internal volume of 5.4 L, kept warm until the liquid temperature (internal temperature) reached 50 ° C., and the autoclave was purged with nitrogen. The liquid temperature is continuously heated from about 50 ° C. to 210 ° C., and the pressure in the autoclave tank is referred to as gauge pressure (hereinafter, all the pressure in the tank is expressed as gauge pressure (G)), 17.5 kg / Heating was continued while removing water out of the system to maintain cm ² (G). Thereafter, the internal temperature was raised to 320 ° C., and the pressure was reduced while taking about 120 minutes until the pressure in the tank reached atmospheric pressure (gauge pressure was 0 kg / cm ² ). Thereafter, nitrogen gas was allowed to flow through the tank for 30 minutes, and the heater temperature was adjusted so that the final temperature of the resin temperature (liquid temperature) was about 323 ° C. 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 a copolymer polyamide pellet (PA-11).

[Production Example 12]
The polymerization method was in accordance with the production method described in (International Publication No. 2008-149862).
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 and 1.3 g of sodium hypophosphite monohydrate were charged into an internal volume 5.4 L autoclave (manufactured by Nitto Koatsu) and kept warm until the liquid temperature (internal temperature) reached 50 ° C. The inside of the autoclave was purged 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 maintained at 160 ° C. for 30 minutes, and while continuing to heat while removing the steam from the system, the solution was concentrated until the concentration of the aqueous solution reached 70% by mass. The removal of water was stopped and heating was continued until the internal pressure of 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 (PA-12).

[Production Example 13]
The polymerization method was in accordance with the production method described in JP-A-9-12868.
CHDA 770 g (4.47 mol), C9DA (nonamethylenediamine) 609 g (3.85 mol), 2MC8DA (2-methyl-1,8-octanediamine) 107 g (0.68 mol), benzoic acid 13.8 g (0 .11 mol), 1.5 g of sodium hypophosphite monohydrate and 1500 g of distilled water were charged into an internal volume 5.4 L autoclave (manufactured by Nitto Koatsu) and purged 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 this time, the autoclave was heated up to 22 kg / cm ² . The reaction was continued as it was for 1 hour, then the temperature was raised to 230 ° C., and then the temperature was maintained at 230 ° C. for 2 hours, and 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. The prepolymer was dried at 100 ° C. under reduced pressure for 12 hours and pulverized to a size of 2 mm or less. This was solid-phase polymerized at 230 ° C. under 0.1 mmHg for 10 hours to obtain a polyamide (PA-13).

[Examples 1 to 8 and Comparative Examples 1 to 5]
Using the polyamides (PA-1) to (PA-13) obtained in Production Examples 1 to 13 and the raw materials in the types and proportions described in Tables 2 and 3 below, a polyamide composition is obtained. Produced as follows.

  The polyamides (PA-1 to PA-13) obtained in Production Examples 1 to 13 were dried in a nitrogen stream and the moisture content was adjusted to about 0.2% by mass. Used as.

A polyamide composition was produced using the polyamide pellets and glass fibers obtained above.
Specifically, a twin-screw extruder (TEM35 manufactured by Toshiba Machine Co., Ltd., L / D = 47.6 (D = 37 mmφ), set temperature Tm2 + 10 ° C. (310 + 20 = 330 when the polyamide obtained above is used) C.) and a screw rotational speed of 250 rpm), a polyamide composition was produced as follows. The polyamide (65 parts by mass) with the moisture content adjusted is supplied from a top feed port provided at the most upstream part of the twin screw extruder, and the downstream side of the twin screw extruder (resin supplied from the top feed port is Glass fiber (35 parts by mass) is supplied as an inorganic filler from the side feed port in a sufficiently melted state) at a mass ratio of (polyamide: glass fiber = 65: 35), and the melt-kneaded product extruded from the die head is supplied. It was cooled in a strand form and pelletized to obtain polyamide composition pellets.

(Production of polyamide composition molded product)
The obtained polyamide composition was molded into a multi-purpose test piece (A type) by injection molding in accordance with ISO 3167 to obtain a molded polyamide composition product. Various physical properties of the obtained polyamide composition molded article were measured based on the above methods. The measurement results are shown in Table 2 and Table 3.

  As is clear from the results shown in Table 2, the (A1) polyamide of the present invention is trans isomerized by the addition of (A2) any of Li, Na, and K metal compounds (excluding hypophosphite compounds). The body ratio was improved, and the ratio of heat of fusion ΔHm1 / crystallization enthalpy ΔHc, which is an index of crystal growth, was increased. As a result, the polyamide composition molded articles of Examples 1 to 8 had excellent properties in hot strength and hot stiffness. In general, when a polymer absorbs water, degradation occurs due to hydrolysis and chemical permeation, and so-called LLC resistance is lowered. However, the molded product containing the (A1) polyamide of the present invention shows the tensile strength retention after immersion. The LLC resistance was improved. The penetration rate (degradation rate) of LLC differs between the amorphous part and the crystalline part of the molded product, and the amorphous part deteriorates faster than the crystalline part. The (A1) polyamide of the present invention is a non-crystalline part after molding of the composition. As a result of the decrease in the crystal portion and the increase in the crystal portion (ΔHm), it is considered that the LLC resistance was improved.

  On the other hand, as shown in Table 3, in Comparative Examples 1 and 2, there was no addition of any of the metal compounds (excluding the hypophosphite compound) of (A2) Li, Na, and K. A1) The trans isomer ratio of polyamide is as low as 70 mol%. As a result, the hot strength, the hot stiffness, and the LLC resistance were insufficient. In Comparative Examples 3, 4, and 5, the ratio of the trans isomer of (A1) polyamide was 82 to 85 mol%, but the branching ratio in the polymer skeleton was low, and the crystal growth index ΔHm1 / ΔHc was 1. .1 to 1.3, which is lower than the examples, was insufficient in terms of hot strength, hot stiffness and LLC resistance.

  The polyamide composition molded article of the present invention has industrial applicability as various parts for automobiles, electric and electronic use, industrial materials, daily use and household goods.

Claims (18)

(A) a dicarboxylic acid unit containing at least 1,4-cyclohexanedicarboxylic acid;
(B) a diamine unit containing at least an aliphatic diamine;
A polyamide containing
The trans isomer ratio mol% of the dicarboxylic acid monomer unit in the polyamide is
70 <trans isomer ratio ≦ 100
A polyamide which is
A polyamide composition comprising: at least one metal compound selected from Li, Na, and K (excluding a hypophosphorous acid compound).   The polyamide composition according to claim 1, wherein a content of the 1,4-cyclohexanedicarboxylic acid is at least 50 mol% in the dicarboxylic acid unit.   The polyamide composition according to claim 2, wherein all of the dicarboxylic acid units are 1,4-cyclohexanedicarboxylic acid.   The polyamide composition according to any one of claims 1 to 3, wherein the aliphatic diamine has 6 to 12 carbon atoms.   The polyamide composition according to claim 4, wherein the aliphatic diamine is hexamethylenediamine, 2-methylpentamethylenediamine, 2-methyl-1,8-octanediamine, nonamethylenediamine, decamethylenediamine, or dodecamethylenediamine. .   The polyamide composition according to claim 5, wherein the aliphatic diamine is 2-methylpentamethylenediamine or decamethylenediamine.   The polyamide composition according to any one of claims 1 to 6, wherein the metal compound is a Li compound.   The polyamide composition according to claim 7, wherein the metal compound is any one of LiOH and LiCl. In the differential scanning calorimetry according to JIS-K7121, the ratio of the heat of fusion ΔHm1 obtained when the polyamide is heated at 20 ° C./min and the crystallization enthalpy ΔHc obtained when the polyamide is cooled at 20 ° C./min. ΔHm1 / ΔHc is
1.0 <ΔHm1 / ΔHc ≦ 2.2
The polyamide composition according to any one of claims 1 to 8. The ΔHm1 / ΔHc is
1.4 ≦ ΔHm1 / ΔHc ≦ 2.2
The polyamide composition according to claim 9. When the polyamide has the ΔHm1 / ΔHc as y and the trans isomer ratio as x,
y ≧ 0.04x−1.8
The polyamide composition according to claim 9 or 10.   The polyamide composition according to any one of claims 1 to 11, wherein the polyamide has a number average molecular weight Mn of 15,000 or more. The polyamide has a weight average molecular weight Mw / number average molecular weight Mn indicating a molecular weight distribution.
Mw / Mn <3.5
The polyamide composition according to any one of claims 1 to 12. [NH ₂ ] / ([NH ₂ ] + [COOH]), wherein the polyamide is a ratio of the amino terminal amount [NH ₂ ] to the total active terminal amount ([NH ₂ ] + [COOH]),
[NH ₂ ] / ([NH ₂ ] + [COOH]) <0.5
The polyamide composition according to any one of claims 1 to 13.   The polyamide composition according to any one of claims 1 to 14, further comprising at least one selected from an inorganic filler, a heat stabilizer, and a light stabilizer.   A polyamide composition molded article obtained by molding the polyamide composition according to claim 15. (A) a dicarboxylic acid unit containing at least 1,4-cyclohexanedicarboxylic acid and (b) a diamine unit containing at least an aliphatic diamine, and the total amount of active terminals ([NH ₂ ] +) of amino terminal amount [NH ₂ ] [NH ₂ ] / ([NH ₂ ] + [COOH]), which is the ratio to [COOH]) is [NH ₂ ] / ([NH ₂ ] + [COOH]) <0.5, and the total active ends A precursor polyamide having an amount ([NH ₂ ] + [COOH]) μeq / g of 100 ≦ ([NH ₂ ] + [COOH]) ≦ 200;
At least one metal compound selected from Li, Na, and K (excluding a hypophosphorous acid compound);
A process for producing a polyamide composition comprising heat-treating a precursor polyamide composition containing at least 200 ° C. and less than the melting point for 10 hours or more.   (A) a dicarboxylic acid containing at least 1,4-cyclohexanedicarboxylic acid, and (b) a diamine containing at least an aliphatic diamine, at least one metal compound selected from the above Li, Na, and K 18. The method for producing a polyamide composition according to claim 17, further comprising a step of polymerizing in the presence of a phosphorous acid compound to obtain the precursor polyamide composition.