JP2018012780A - Polyamide, polyamide composition, polyamide composition molded article, and method for producing polyamide - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polyamide excellent in heat resistance, reflow resistance, aging resistance, and releasability.SOLUTION: A polyamide contains (a) a dicarboxylic acid unit containing at least 1,4-cyclohexanedicarboxylic acid and (b) a diamine unit containing at least branched aliphatic diamine, the polyamide having (c) a sulfuric acid relative viscosity ηr of: ηr<2.0, and (d) a total content of active terminals ([NH]+[COOH])μ equiv./g of: 10≤([NH]+[COOH])≤60.SELECTED DRAWING: None

Description

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

  Polyamides represented by polyamide 6 (hereinafter also referred to as “PA6”) and polyamide 66 (hereinafter also referred to as “PA66”) and the like are excellent in molding processability, mechanical properties, and chemical resistance. It is widely used as various parts materials for automobiles, electric and electronic, industrial materials, industrial materials, daily necessities, and household goods.

  As an environmental effort in the automobile industry, a reduction in body weight is required to reduce exhaust emissions. In order to meet this demand, polyamides are increasingly used in place of metals as exterior materials and interior materials for automobiles. Polyamides used for automobile exterior materials and interior materials are required to have higher levels of heat resistance, strength, appearance, and other characteristics. Among these, polyamides used as materials in the engine room are increasingly required to have high heat resistance in order to cope with the increasing tendency of the temperature in the engine room.

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

However, conventional polyamides such as PA6 and PA66 have a low melting point and cannot satisfy these requirements in terms of heat resistance.
In order to solve the problem of heat resistance of conventional polyamides such as PA6 and PA66, high melting point polyamides have been proposed. Specifically, a polyamide composed of terephthalic acid and hexamethylenediamine (hereinafter also referred to as “PA6T”) has been proposed.

  However, since PA6T is a high-melting-point polyamide having a melting point of about 370 ° C., even if an attempt is made to obtain a molded product from PA6T by melt molding, the polyamide undergoes thermal decomposition during the molding process to obtain a molded product having sufficient characteristics. There is a problem that it is difficult.

  In order to solve the problem of thermal decomposition of PA6T, PA6T, aliphatic polyamides such as PA6 and PA66, and amorphous aromatic polyamides (hereinafter referred to as “PA6I”) composed of isophthalic acid and hexamethylenediamine. ) And the like, and a high melting point semi-aromatic polyamide (hereinafter referred to as “6T copolymer polyamide”) composed mainly of terephthalic acid and hexamethylenediamine whose melting point is lowered to about 220 to 340 ° C. And so on.) Etc. have been proposed.

  For example, in Patent Document 1, as a 6T copolymer polyamide, an aromatic polyamide composed of an aromatic dicarboxylic acid and an aliphatic diamine, and the aliphatic diamine is a mixture of hexamethylenediamine and 2-methylpentamethylenediamine ( Hereinafter, “PA6T / 2MPDT” is also disclosed.

  Patent Document 2 discloses a semi-alicyclic polyamide containing 1 to 40% of 1,4-cyclohexanedicarboxylic acid as a dicarboxylic acid unit, and electric and electronic members containing the semi-alicyclic polyamide are disclosed. It is disclosed that the solder heat resistance is improved.

  Furthermore, Patent Document 3 discloses a polyamide resin (hereinafter referred to as “dicarboxylic acid”) containing a terephthalic acid unit and a diamine containing a 1,9-nonanediamine unit and / or a 2-methyl-1,8-octanediamine unit. , "PA9T"), and a polyamide composition comprising titanium oxide, magnesium hydroxide, and a specific reinforcing agent is disclosed, and it is disclosed that this polyamide composition is excellent in heat resistance. Has been.

  Furthermore, Patent Document 4 contains a semi-alicyclic polyamide blended with 70% or more of 1,4-cyclohexanedicarboxylic acid as a dicarboxylic acid unit, titanium oxide, and an inorganic filler, and their mass ratio. A polyamide composition having a predetermined value is disclosed, and it is disclosed that this polyamide composition is excellent in reflow resistance, heat resistance and the like.

JP-T 6-503590 Japanese National Patent Publication No. 11-512476 JP 2006-257314 A JP 2011-219697 A

However, the conventional polyamides or polyamide compositions disclosed in Patent Documents 1 to 4 require further improvement in order to obtain higher level characteristics in heat discoloration resistance, extrusion processability, and molding process stability. It has been.
Therefore, in view of the above-mentioned problems of the prior art, the present invention is excellent in heat resistance, reflow resistance, aging resistance and releasability, polyamide, polyamide composition, and polyamide composition formed by molding the polyamide composition It aims at providing the manufacturing method of a molded article and polyamide.

  As a result of intensive studies to solve the above problems, the present inventors have found that a polyamide having a controlled molecular weight and molecular end composition and a polyamide composition thereof can solve the above problems, and have completed the present invention. It was.

That is, the polyamide of the present invention comprises (a) a dicarboxylic acid unit containing at least 1,4-cyclohexanedicarboxylic acid,
(B) a diamine unit containing at least a branched aliphatic diamine;
A polyamide containing
(C) sulfuric acid relative viscosity ηr is ηr <2.0,
(D) The total amount of active ends ([NH ₂ ] + [COOH]) μeq / g is
10 ≦ [NH ₂ ] + [COOH] ≦ 60
It is.

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

  The content of 1,4-cyclohexanedicarboxylic acid is preferably 100 mol% in the (a) dicarboxylic acid unit.

  It is preferable that content of branched aliphatic diamine is 50-100 mol% in (b) diamine unit.

  The content of the branched aliphatic diamine is preferably 100 mol% in the (b) diamine unit.

  The branched aliphatic diamine preferably has 6 to 12 carbon atoms.

  The branched aliphatic diamine is preferably 2-methyl-pentamethylenediamine or 2-methyl-1,8-octanediamine.

  The branched aliphatic diamine is preferably 2-methyl-pentamethylenediamine.

  The polyamide preferably has two or more types of sealed ends.

  It is preferable that the amino terminal and the carboxyl terminal are sealed.

  It is preferable that the amino terminal is sealed with acetic acid and the carboxyl terminal is sealed with a cyclic amine.

  The amount of cyclic amino terminal of the polyamide is preferably larger than 70 μeq / g.

The trans isomer ratio mol% of 1,4-cyclohexanedicarboxylic acid monomer unit of dicarboxylic acid in polyamide is
71 <trans isomer ratio ≦ 100
It is preferable that

The trans isomer ratio mol% of 1,4-cyclohexanedicarboxylic acid monomer unit in polyamide is
71 <trans isomer ratio ≦ 80
It is preferable that

(D) Active terminal total amount ([NH ₂ ] + [COOH]) μ equivalent / g is:
20 ≦ [NH ₂ ] + [COOH] ≦ 50
It is preferable that

Active end the total amount of amino-terminus weight [NH _2] is the ratio _{([NH 2] + [COOH} ]) [NH 2] / ([NH 2] + [COOH]) is
[NH ₂ ] / ([NH ₂ ] + [COOH]) <0.5
It is preferable that

The polyamide of the present invention has a weight average molecular weight Mw / number average molecular weight Mn, which is a molecular weight distribution,
It is preferable that Mw / Mn <3.5.

  The polyamide composition of the present invention preferably contains the polyamide of the present invention and titanium oxide.

  The polyamide composition of the present invention preferably further contains at least one selected from an inorganic filler, a nucleating agent, 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.

A method for producing a polyamide of the present invention, comprising: (a) a dicarboxylic acid unit containing at least 1,4-cyclohexanedicarboxylic acid; and (b) a diamine unit containing at least a branched aliphatic diamine, wherein the amino terminal amount [NH ₂ ] To the total amount of active terminals ([NH ₂ ] + [COOH]) [NH ₂ ] / ([NH ₂ ] + [COOH])
[NH ₂ ] / ([NH ₂ ] + [COOH]) <0.5, and the total amount of active ends ([NH ₂ ] + [COOH]) μeq / g is 60 ≦ ([NH ₂ ] + [COOH]) <110, and a precursor polyamide having a cyclic amino terminal amount greater than 70 μeq / g is heat-treated at 200 ° C. or more and less than the melting point for 10 hours or more.
Here, melting | fusing point shows melting peak temperature Tm2 mentioned later.

The polyamide 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 a branched aliphatic diamine, and (c) sulfuric acid. The relative viscosity ηr is ηr <2.0, and (d) the active terminal total amount ([NH ₂ ] + [COOH]) μ equivalent / g is 10 ≦ [NH ₂ ] + [COOH] ≦ 60 Since it is a polyamide, it is possible to obtain a polyamide composition molded article having excellent heat resistance, reflow resistance, aging resistance, and releasability.

Further, the method for producing a polyamide 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 a branched aliphatic diamine. active end the total amount of [NH _2] is the ratio _{([NH 2] + [COOH} ]) [NH 2] / ([NH 2] + [COOH]) is,
[NH ₂ ] / ([NH ₂ ] + [COOH]) <0.5, and the total amount of active ends ([NH ₂ ] + [COOH]) μeq / g is 60 ≦ [NH ₂ ] + [COOH The polyamide whose cyclic amino terminal is larger than 70 μeq / g is heat-treated at 200 ° C. or higher and lower than the melting point for 10 hours or longer. By having such a configuration, the sulfuric acid relative viscosity ηr is ηr <2.0, and the active terminal total amount ([NH ₂ ] + [COOH]) μ equivalent / g is 10 ≦ [NH ₂ ] + [COOH ] ≦ 60, and polyamides and polyamide compositions excellent in heat resistance, reflow resistance, aging resistance and releasability can be provided.

  Hereinafter, the present invention will be described in detail. In addition, the following this embodiment is an illustration for demonstrating this invention, and is not the meaning which limits this invention to the following content. The present invention can be implemented with various modifications within the scope of the gist.

The polyamide of the present invention (hereinafter also simply referred to as “polyamide”)
(A) a dicarboxylic acid unit containing at least 1,4-cyclohexanedicarboxylic acid;
(B) a diamine unit containing at least a branched aliphatic diamine,
(C) sulfuric acid relative viscosity ηr is ηr <2.0,
(D) The active terminal total amount ([NH ₂ ] + [COOH]) μ equivalent / g is 10 ≦ [NH ₂ ] + [COOH] ≦ 60.

[(A) Polyamide]
The polyamide (A) of the present invention contains as structural units (a) a dicarboxylic acid unit containing at least 1,4-cyclohexanedicarboxylic acid, and (b) a diamine unit containing at least a branched aliphatic diamine.
The total amount of the above (a) dicarboxylic acid unit and (b) diamine unit is preferably 20 to 100 mol%, and 90 to 100 mol%, based on 100 mol% of all structural units of (A) polyamide. More preferably, it is more preferably 100 mol%.

In addition, the ratio of the predetermined monomer unit which comprises (A) polyamide can be measured by nuclear magnetic resonance spectroscopy (NMR) etc.
In (A) polyamide, the structural unit of (A) polyamide other than (a) dicarboxylic acid unit and (b) diamine unit is not particularly limited. For example, (c) lactam and / or aminocarboxylic acid described later is used. The unit which consists of is mentioned.
In the present invention, “polyamide” means a polymer having an amide (—NHCO—) bond in the main chain.

First, the structural unit of (A) 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.

By containing an aliphatic dicarboxylic acid having 6 or more carbon atoms, the polyamide composition tends to be more excellent in heat resistance, fluidity, toughness, low water absorption, rigidity, and the like.
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, More preferably, the 1,4-cyclohexanedicarboxylic acid is 80 to 95 mol% and the (a-3) aliphatic dicarboxylic acid unit 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 dicarboxylic acid compound, 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, (A) polyamide may further contain the unit derived from trivalent or more polyvalent carboxylic acid, 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>
The (b) diamine unit includes at least (b-1) a branched aliphatic diamine unit. When the (b) diamine unit contains the (b-1) branched aliphatic diamine unit, 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 of the present invention using this polyamide tends to satisfy more excellent fluidity, toughness, rigidity and the like at the same time.
(B) The diamine unit preferably contains 50 to 100 mol% of (b-1) branched aliphatic diamine units (based on the total number of moles of diamine), more preferably 60 to 100 mol%, 85 to 100 mol. %, More preferably 90 to 100 mol%, still more preferably 100 mol%.
(B) When the ratio (mol%) of the branched aliphatic diamine unit in the diamine unit is in the above range, a polyamide having a high glass transition temperature Tg and high crystallinity 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) It is preferable that carbon number of a diamine unit is 6-12. A carbon number of 6 or more is preferable because of excellent heat resistance, and a carbon number of 12 or less is preferable because of excellent crystallinity and releasability. (B) As for carbon number of a diamine unit, 6-10 is more preferable.
Examples of the unit that may be contained in the (b) diamine unit in addition to the (b-1) branched aliphatic diamine unit include (b-2) a linear aliphatic diamine unit. Other diamine units may include (b-3) alicyclic diamine units, (b-4) aromatic diamine units, and the like.

(B-1) Branched aliphatic diamine unit Hereinafter, the (b-1) branched aliphatic diamine unit may be simply referred to as (b-1).
(B-1) The branched aliphatic diamine unit is not limited to the following, but for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, and tert- It has C1-C4 alkyl group etc. of a butyl group.
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 aliphatic diamines having 3 to 20 carbon atoms such as methylene diamine.
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.

(B-2) Linear aliphatic diamine unit Hereinafter, the (b-2) linear aliphatic diamine unit may be simply referred to as (b-2).
The aliphatic diamine constituting (b-2) is not limited to the following, but for example, ethylene diamine, propylene diamine, tetramethylene diamine, pentamethylene diamine, hexamethylene diamine, heptamethylene diamine, octamethylene diamine. , Straight-chain saturated aliphatic diamines having 2 to 20 carbon atoms such as nonamethylenediamine, decamethylenediamine, undecamethylenediamine, dodecamethylenediamine, and tridecamethylenediamine.

(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.
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 proportion (mol%) of the diamine units (b-2) to (b-4) is preferably 0 to less than 50 mol%, and 0 to 40 mol% with respect to the entire diamine unit (b). More preferably, it is more preferably 0 to 30 mol%.
(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 (A) 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 (A) polyamide of the present invention is the above (a) and (b), (c) lactam unit (c-1) and / or aminocarboxylic acid unit (c-), as long as the object of the present invention is not impaired. 2) can be further 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 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 end of the polyamide (A) 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 (A) 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. (A) Since the terminal of the polyamide is sealed with a terminal sealing 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 an amino group that can be present at the terminal of the (A) 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.

In order to obtain the polyamide of the present invention, it is preferable to use a monocarboxylic acid as a terminal blocking agent. The addition amount of the monocarboxylic acid is preferably 0.1 to 2.0 mol%, more preferably 0.3 to 1.5 mol%, and still more preferably 0.5 to mol with respect to the charged diamine. -1.5 mol%. By making such an addition amount, the amino terminal is sealed, and the ratio [NH ₂ ] / ([NH ₂ ] + [COOH]) of the amino terminal amount to the total active terminal amount is less than 0.5. And the sulfuric acid relative viscosity ηr can be made smaller than 2.0.

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 (A) 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.
Only one monoamine may be used alone, or two or more monoamines may be used in combination.

The polyamide composition containing the (A) polyamide end-capped with the end-capping agent tends to be excellent in heat resistance, fluidity, toughness, low water absorption, and rigidity.
Next, a production method for obtaining the polyamide of the present invention will be described.
[(A) Polyamide production method]
The polyamide production method 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 a branched 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
60 ≦ [NH ₂ ] + [COOH] <110,
A precursor polyamide having a cyclic amino terminal amount greater than 70 μequivalent / g is heat-treated at 200 ° C. or higher and lower than the melting point for 10 hours or longer.

That is, the polyamide production method of the present invention is a method in which a precursor polyamide having a specific terminal structure is obtained, and further heat treated at a temperature lower than the melting point to obtain (A) polyamide. As such a production method, a “hot melt polymerization / solid phase polymerization method” is preferable.
Hereinafter, the method for obtaining the precursor polyamide and the heat treatment will be described in detail.

<Method for obtaining precursor polyamide>
The method for obtaining the precursor polyamide is not particularly limited, and examples thereof include the method illustrated 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 the precursor polyamide is produced, it is preferable that (a) the addition amount of the dicarboxylic acid constituting the dicarboxylic acid unit and (b) the addition amount of the diamine constituting the diamine unit are 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 contains a branched aliphatic diamine unit, and the proportion thereof is preferably 10 to 100 mol%, more preferably 50 to 100 mol%, still more preferably 60 to 100 mol%, and 85 to 100 mol%. Is more preferable, 90 to 100 mol% is particularly preferable, and 100 mol% is most preferable. (B-1) is most preferably 2-methyl-5-pentamethylenediamine.

When the precursor polyamide is produced (thermal melt polymerization), a terminal blocking agent may be used for molecular weight and terminal adjustment. The terminal blocking agent is not particularly limited, but acetic acid is preferable. The amount of acetic acid added to the charged diamine is preferably 0.1 to 2.0 mol%, more preferably 0.3 to 1.5 mol%, and still more preferably 0.5 to 1.5 mol% in molar ratio. .
Moreover, when manufacturing precursor polyamide (thermal melt polymerization), you may add a diamine in addition to the (b) diamine unit. Such diamine is preferably 2-methyl-5-pentamethylenediamine. (B) The amount of added diamine with respect to the diamine unit is 1.0 to 6.0 mol%, more preferably 1.5 to 5.0 mol%, still more preferably 2.0 to 4.5 mol% in terms of molar ratio. It is.

Moreover, you may add a phosphorus compound as a heat stabilizer (catalyst) at the time of hot melt polymerization. The heat stabilizer is not particularly limited, but sodium hypophosphite is preferable.
In the method for producing the precursor polyamide, from the viewpoint of the color tone and fluidity of the polyamide, it is preferable to carry out hot melt polymerization while maintaining the trans isomer ratio of the dicarboxylic acid monomer unit in the polyamide at 85% or less. It is more preferable to perform hot melt polymerization while maintaining the trans isomer ratio of the dicarboxylic acid monomer unit at 80% or less.

  (A) It is preferable that the manufacturing method of polyamide 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>
The physical properties of the precursor polyamide are [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]). Less than 0.5, more preferably from 0.2 to less than 0.5, and even more preferably from 0.2 to 0.4. The total amount of active ends ([NH ₂ ] + [COOH]) is preferably 60 or more and less than 110 μeq / g, more preferably 70 or more and less than 110 μeq / g, still more preferably 80 or more and less than 110 μeq / g, and 80 or more and 100 μm. Less than equivalent / g is particularly preferred.
In order to obtain such physical properties of the precursor polyamide, the terminal structure of the polyamide is controlled 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.
Further, the cyclic amino terminal amount is preferably 70 μeq / g or more and 180 μeq / g or less, more preferably 80 μeq / g or more and 150 μeq / g or less, more preferably 1 g of the precursor polyamide. 100 μequivalent / g or more and 140 μequivalent / g or less.
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.

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 precursor polyamide constant, it is preferable to promote the generation of 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.
<Heat treatment>
The heat treatment in the production method of the present invention is a method of heating the precursor polyamide at 200 ° C. or higher and lower than the melting point (Tm 2).
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. to less than the melting point (Tm 2), more preferably 220 ° C. to less than the melting point (Tm 2), and even more preferably 240 ° C. to less 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 71 mol%. On the other hand, when the melting point is less than (Tm2), it is possible to satisfactorily prevent the polyamide from melting, so that the trans isomer ratio can be made larger than 71 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.

Next, physical properties of the polyamide of the present invention will be described.
[(A) Physical properties of polyamide]
<Trans isomer ratio>
(A) The trans isomer ratio of the dicarboxylic acid monomer unit in the polyamide is preferably more than 71 mol% and 100 mol% or less, more preferably 71 mol% or more and 80 mol% or less.
Since the polyamide of the present invention is highly crystallized because the trans isomer ratio is in the above range, the polyamide and the polyamide composition of the present invention have a high melting point, toughness and rigidity, in addition to the characteristics of being high. It tends to have the property of simultaneously satisfying the thermal rigidity due to the 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 1,4-cyclohexanedicarboxylic acid monomer unit of the polyamide composition molded product can be determined by nuclear magnetic resonance spectroscopy (NMR).

<Sulfuric acid relative viscosity ηr>
(A) The sulfuric acid relative viscosity ηr of the polyamide is preferably larger than 1.2 and smaller than 2.0. It is more preferably larger than 1.6 and smaller than 2.0, more preferably 1.7 or larger and smaller than 2.0. When it is larger than 1.2, the mechanical properties of toughness and rigidity are excellent, and when it is smaller than 2.0, the fluidity and moldability are excellent.
The sulfuric acid relative viscosity ηr at 25 ° C. can be measured at 25 ° C. in 98% sulfuric acid according to JIS-K6920.

<Molecular weight>
(A) As an index of the molecular weight of polyamide, a number average molecular weight Mn, a weight average molecular weight Mw, and a molecular weight distribution Mw / Mn obtained by GPC (gel permeation chromatography) can be used. The larger the Mn, the higher the molecular weight of the (A) polyamide, and the smaller the Mn, the lower the molecular weight of the (A) polyamide.
(A) Mn of polyamide is preferably greater than 10,000, more preferably 11000 or more, and further preferably 12000 or more.
Further, the Mw / Mn of the (A) polyamide is preferably less than 3.5, more preferably 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 is measured by the method described in the following examples.

<Melting peak temperature Tm1, Tm2>
(A) The melting peak temperature Tm1 of the polyamide is preferably 300 ° C. or higher, more preferably 320 ° C. or higher, and further preferably 325 ° C. or higher.
Further, the melting peak temperature Tm1 of the (A) polyamide is preferably 350 ° C. or lower, more preferably 345 ° C. or lower, and further preferably 340 ° C. or lower.
(A) 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 (A) the melting peak temperature Tm1 of the polyamide is 350 ° C. or less, the thermal decomposition of the (A) polyamide in the melt processing such as extrusion and molding tends to be further suppressed.

(A) 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 (A) 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.
(A) 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 (A) polyamide melting peak temperature Tm2 is 350 ° C. or less, (A) thermal decomposition of polyamide in melt processing such as extrusion and molding tends to be further suppressed.
(A) 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>
(A) The heat of fusion ΔHm1 and the crystallization enthalpy ΔHc of the polyamide are each preferably 30 J / g or more, more preferably 35 J / g or more, and further 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.
(A) 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.
(A) The heat of fusion ΔHm1 and the crystallization enthalpy ΔHc of the polyamide can be measured according to JIS-K7121 by the methods described in the Examples below.
The heat of fusion ΔHm1 and crystallization enthalpy ΔHc of the polyamide (A) described above can be measured according to JIS-K7121 by the method described later.
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.
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.

  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.

<Glass transition temperature Tg>
(A) 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.
Further, the glass transition temperature Tg of the (A) polyamide is preferably 170 ° C. or lower, more preferably 165 ° C. or lower, and further preferably 160 ° C. or lower.
(A) 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 (A) polyamide is 170 ° C. or lower, a molded product having a good appearance tends to be obtained.
(A) 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>
The polymer terminal of the polyamide (A) used in the present invention is not particularly limited, but can be classified and defined 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 (A) polyamide 1g, preferably 5~100μ eq / g, more preferably from 5~70μ eq / g, more preferably 5~50μ equivalents / G, even more preferably 5 to 30 μ equivalent / g, and particularly preferably 5 to 20 μ equivalent / 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 100 μequivalent / g, more preferably 5 to 70 μequivalent / g, and still more preferably 5 to 50 μequivalent / g with respect to 1 g of (A) polyamide. g, even more preferably 5 to 40 μequivalent / g, and particularly preferably 5 to 30 μequivalent / 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.

Here, 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 10 to 60 [mu] equivalent / g, preferably 20 to 50 [mu] equivalent / g, based on 1 g of (A) polyamide. In order to make the total amount of active terminals within the above range, it is preferable to seal the amino terminal and carboxyl terminal of (A) polyamide. For sealing the carboxyl end, a cyclic amine described later is preferable. For amino terminal sealing, sealing with a terminal blocking agent is preferable, and the terminal blocking agent is more preferably acetic acid. [NH ₂ ] / ([NH ₂ ] + [COOH]), which is a ratio of the amino terminal amount [NH ₂ ] to the active terminal total amount ([NH ₂ ] + [COOH]), is preferably 0.5. It is less than, More preferably, it is 0.2 or more and less than 0.5, More preferably, it is 0.2 or more and 0.4 or less, Most preferably, it is 0.2 or more and 0.3 or less. The ratio of the total amount of amino terminal and carboxyl terminal and the ratio of amino terminal to the total active terminal is within the above range, so that the trans isomer ratio can be controlled to be greater than 70 and 75 or less. The whiteness, reflow resistance, heat discoloration resistance, and light discoloration resistance of an object 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 amount of the cyclic amino terminus is preferably 70 μeq / g or more and 180 μeq / g or less, more preferably 80 μeq / g or more and 150 μeq / g or less, with respect to 1 g of (A) polyamide. Preferably they are 100 microequivalent / g or more and 140 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.

  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.

[Polyamide composition]
The polyamide composition contains the polyamide and at least one of an inorganic filler, a nucleating agent, a heat stabilizer and a light stabilizer. Furthermore, titanium oxide may be included. By containing such a structural component, a polyamide composition excellent in heat resistance, whiteness, reflow resistance, aging resistance and releasability can be obtained.
Hereinafter, the components of the polyamide composition will be described.

<(B) Titanium oxide>
The polyamide composition of the present invention may further contain (B) titanium oxide.
Examples of (B) titanium oxide include, but are not limited to, titanium monoxide (TiO), dititanium trioxide (Ti ₂ O ₃ ), and titanium dioxide (TiO ₂ ). Of these, titanium dioxide is preferable.

  The crystal structure of (B) titanium oxide is not particularly limited, but is preferably a rutile type from the viewpoint of light resistance of the polyamide composition.

(B) Titanium oxide is preferably in the form of particles, and the number average particle diameter of (B) titanium oxide is preferably 0.1 to 0.8 μm, more preferably 0.15 to 0.4 μm. More preferably, it is 0.15-0.3 micrometer.
(B) When the number average particle diameter of titanium oxide is 0.1 μm or more, the extrusion processability of the polyamide composition tends to be further improved.
(B) When the number average particle diameter of titanium oxide is 0.8 μm or less, the toughness of the polyamide composition tends to be further improved.
(B) The number average particle diameter of titanium oxide can be measured by an electron micrograph. For example, the polyamide composition is put in an electric furnace, the organic matter contained in the polyamide composition is incinerated, and, for example, 100 or more arbitrarily selected titanium oxides from the residue are observed with an electron microscope. By measuring the particle diameter, it is possible to determine the number average particle diameter of (B) titanium oxide.

  (B) Although the manufacturing method of titanium oxide is not limited to the following, for example, a so-called sulfuric acid method in which a titanium sulfate solution is hydrolyzed, or a so-called chlorine method in which titanium halide is oxidized in a gas phase can be mentioned.

(B) It is preferable that the titanium oxide has an inorganic coating layer and / or an organic coating layer on the surface.
In particular, (B) titanium oxide having an inorganic coating layer on the surface of titanium oxide and an organic coating layer on the inorganic coating layer is preferable.

(B) Titanium oxide may be coated using any known method.
The inorganic coating is not limited to the following, but preferably includes, for example, a metal oxide.

The organic coating is not limited to the following, but for example, it preferably contains one or more organic substances selected from the group consisting of carboxylic acids, polyols, alkanolamines, and organosilicon compounds.
Among these, from the viewpoint of light resistance and extrusion processability of the polyamide composition, the surface of (B) titanium oxide is more preferably coated using polyols and organosilicon compounds. From the viewpoint of reducing generated gas, it is more preferable that coating is performed using an organosilicon compound.

  In addition, as (B) titanium oxide, only 1 type may be used independently and 2 or more types may be used in combination.

The content of (B) titanium oxide in the polyamide composition is preferably 5% by mass to 70% by mass, more preferably 20% by mass to 70% by mass, and more preferably 100% by mass with respect to the polyamide composition. Preferably it is 25-60 mass%, More preferably, it is 30-50 mass%.
(B) When the content of titanium oxide is in the above range, the whiteness of the polyamide composition tends to be more excellent.

<(C) Inorganic filler>
The polyamide composition may further contain (C) an inorganic filler other than the above-described (B) titanium oxide from the viewpoint of mechanical properties such as strength and rigidity.
(C) The inorganic filler is not limited to the following, for example, glass fiber, carbon fiber, calcium silicate fiber, potassium titanate fiber, aluminum borate fiber, glass flake, hydrotalcite, carbonic acid Zinc, zinc oxide, calcium monohydrogen phosphate, wollastonite, silica, zeolite, alumina, boehmite, aluminum hydroxide, silicon oxide, magnesium oxide, calcium silicate, sodium aluminosilicate, magnesium silicate, ketjen black, acetylene Examples thereof include black, furnace black, carbon nanotube, graphite, brass, copper, silver, aluminum, nickel, iron, calcium fluoride, montmorillonite, swellable fluorine mica, and apatite.

  Among these, as the inorganic filler (C), at least one selected from the group consisting of glass fiber, potassium titanate fiber, wollastonite, and clay is preferable, and wollastonite is more preferable.

(C) The number average particle diameter of the inorganic filler is preferably 0.1 to 20 μm, more preferably 0.15 to 15 μm, and still more preferably 0, from the viewpoint of whiteness, toughness and extrusion processability of the polyamide composition. 15 to 10 μm.
By including such (C) inorganic filler, the mechanical strength, appearance, whiteness and the like of the polyamide composition tend to be more excellent.
(C) An inorganic filler may be used individually by 1 type, and may be used in combination of 2 or more type.

The content of the inorganic filler (C) in the polyamide composition is preferably 1 to 30% by mass, more preferably 1 to 20% by mass, and further preferably 100% by mass of the polyamide composition. 1 to 10% by mass.
(C) When content of an inorganic filler exists in said range, the intensity | strength of a polyamide composition, rigidity, and toughness can be maintained with a more sufficient balance.
From the above viewpoint, the content of the (C) inorganic filler is preferably 1% by mass or more, more preferably 2% by mass or more, and further preferably 5% by mass or more.

<(D) Nucleating agent>
The polyamide composition preferably further contains a nucleating agent from the viewpoint of releasability.
“Nucleating agent” refers to a substance that can increase the crystallization peak temperature measured by differential scanning calorimetry when added, and can improve the spherulites of the resulting molded product or make the size uniform. Means that.

Examples of the nucleating agent include, but are not limited to, talc, boron nitride, mica, kaolin, calcium carbonate, barium sulfate, silicon nitride, carbon black, potassium titanate, and molybdenum disulfide. It is done.
A nucleating agent may be used individually by 1 type, and may combine 2 or more types.
Among these, talc, boron nitride, and carbon black are preferable from the viewpoint of the nucleation effect, more preferably talc and boron nitride, and still more preferably talc.

The nucleating agent is preferably in the form of particles, and the number average particle diameter of the nucleating agent is preferably 0.01 to 10 μm, more preferably 0.5 to 5 μm.
When the number average particle diameter of the nucleating agent is within the above range, the nucleating effect tends to be further improved.
For the measurement of the number average particle size of the nucleating agent, the molded article of the polyamide composition is dissolved in a polyamide-soluble solvent such as formic acid, and, for example, 100 or more nucleating agents are obtained from the obtained insoluble components. It can be selected arbitrarily and observed and obtained with an optical microscope or a scanning electron microscope.

The blending amount of the nucleating agent is preferably 0.001 to 15% by mass, more preferably 0.001 to 5% by mass, and still more preferably 0.001 to 100% by mass of the polyamide composition. It is -3 mass%, More preferably, it is 0.5-2.5 mass%.
By making the blending amount of the nucleating agent 0.001% by mass or more with respect to 100% by mass of the polyamide composition, the heat resistance of the polyamide composition is improved favorably, and the blending amount is made 15% by mass or less. As a result, a polyamide composition having excellent toughness can be obtained.

<Heat stabilizer>
The polyamide composition may contain a heat stabilizer from the viewpoint of heat stability. As the heat stabilizer, the following (E) metal hydroxide, (F) phosphorus compound, (G) phenol antioxidant and / or amine antioxidant can be mentioned.

((E) metal hydroxide)
The polyamide composition may contain (E) a metal hydroxide as a heat stabilizer.
(E) The metal hydroxide is represented by a general formula M (OH) x (M represents a metal element, and x represents a number corresponding to the multivalent value of M).
The metal element M is preferably a monovalent or higher metal. Examples of the monovalent or higher metal include, but are not limited to, sodium, potassium, lithium, calcium, magnesium, barium, zinc, aluminum, strontium, and the like. As the metal element M, an alkaline earth metal is preferable.

Examples of the (E) metal hydroxide contained in the polyamide composition include, but are not limited to, sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, Examples thereof include zinc hydroxide and manganese hydroxide. Among these, from the viewpoint that the polyamide composition is excellent in reflow resistance, extrusion process stability, and molding process stability, calcium hydroxide and magnesium hydroxide are preferable, and calcium hydroxide is more preferable.
(E) A metal hydroxide may be used individually by 1 type, and may use 2 or more types together.
Moreover, you may use these (E) metal hydroxide which performed the surface treatment in order to improve adhesiveness and a dispersibility.
Examples of the surface treatment agent include, but are not limited to, for example, silane coupling agents such as aminosilane and epoxysilane, organosilicon compounds such as silicone; organic titanium compounds such as titanium coupling agents; organic acids and polyols And organic substances such as

  The (E) metal hydroxide in the polyamide composition is preferably particulate, and the average particle diameter is preferably 0.05 to 10 μm, more preferably 0.1 to 5 μm. When the average particle diameter is in the above range, the effects of reflow resistance and heat discoloration can be obtained in the polyamide composition.

Moreover, the mass ratio of the particle | grains of 30 micrometers or more with respect to the whole particle | grains of (E) metal hydroxide becomes like this. Preferably it is 1 mass% or less, More preferably, it is 0.1 mass% or less.
(E) By making the mass ratio of the particle | grains 30 micrometers or more with respect to the whole metal hydroxide into the said range, in a polyamide composition, the effect of reflow resistance and heat-resistant discoloration property is acquired.

  The purity of the (E) metal hydroxide in the polyamide composition is preferably 99% or more, more preferably 99.5% or more, and further preferably 99.9% or more. Due to the high purity, the whiteness, reflow resistance, and light discoloration resistance of the polyamide composition tend to be excellent.

The content of the (E) metal hydroxide described above is 0.1 to 20% by mass, preferably 0.1 to 10% by mass, more preferably 0.1 to 10% by mass with respect to 100% by mass of the polyamide composition. 3 to 5% by mass, more preferably 0.3 to 2% by mass, even more preferably 0.5 to 1.5% by mass, and still more preferably 0.5 to 1.0% by mass. It is.
(E) When the content of the metal hydroxide is within the above range, the polyamide composition tends to be more excellent in heat discoloration resistance, extrusion processing stability, and molding processing stability.

The polyamide composition may further contain a metal compound other than the above-described (C) metal hydroxide from the viewpoints of whiteness and heat discoloration.
(E) The metal compound other than the metal hydroxide is not limited to the following, and examples thereof include metal carbonates and metal halides.
(E) Although it does not specifically limit as a metal element contained in metal compounds other than a metal hydroxide, For example, a monovalent or more metal element is preferable. Examples of such metal elements include, but are not limited to, sodium, potassium, lithium, calcium, magnesium barium, zinc, aluminum, strontium, and the like. As the metal element, an alkaline earth metal is preferable.

  The (E) metal hydroxide may be added during the polymerization of the (A) polyamide, but is preferably added during the production of the polyamide composition to be mixed with the (A) polyamide after the polymerization of the (A) polyamide. By adding it during the production of the polyamide composition, the thermal history can be reduced, (E) the decomposition of the metal hydroxide can be suppressed, whiteness, reflow resistance, heat discoloration resistance, extrusion processing And a polyamide composition excellent in molding process stability can be obtained.

((F) phosphorus compound)
The polyamide composition may contain (F) a phosphorus compound as a heat stabilizer.
Examples of (F) phosphorus compounds include, but are not limited to, 1) phosphoric acid, phosphorous acid, hypophosphorous acid, and intramolecular and / or intermolecular condensates thereof, 2) Examples thereof include phosphoric acid, phosphorous acid, hypophosphorous acid, and metal salts of intramolecular and / or intermolecular condensates thereof.
In addition, (F) phosphorus type compound may be used individually by 1 type, and may be used in combination of 2 or more type.

The phosphoric acid, phosphorous acid, hypophosphorous acid, and intramolecular and / or intermolecular condensates thereof in 1) are not limited to the following, but examples include phosphoric acid, pyrophosphoric acid, and metalin. Examples thereof include acids, phosphorous acid, hypophosphorous acid, pyrophosphorous acid, and diphosphorous acid.
The metal salts of the above-mentioned 2) phosphoric acid, phosphorous acid, hypophosphorous acid, and intramolecular and / or intermolecular condensates thereof are not limited to the following. Mention may be made of salts of the compounds with Group 1 and 2 of the periodic table, manganese, zinc and aluminum.

  More preferable (F) phosphorus compounds are selected from the group consisting of metal phosphates, metal phosphites, metal hypophosphites, intramolecular condensates of these metal salts, and intermolecular condensates of these metal salts. One or more selected. By using such a phosphorous compound (F), the polyamide composition tends to be more excellent in whiteness, heat discoloration resistance, heat reflow resistance, and light discoloration resistance.

More preferable (F) phosphorus compound is a phosphorus compound selected from phosphoric acid, phosphorous acid and hypophosphorous acid, group 1 (alkali metal) and group 2 (alkaline earth metal) of the periodic table, manganese , Zinc, and a metal selected from aluminum, or an intramolecular condensate of these metal salts or an intermolecular condensate of these metal salts.
More preferably (F) phosphorus compound is a metal salt containing a phosphorus compound selected from phosphoric acid, phosphorous acid and hypophosphorous acid, and a metal selected from Groups 1 and 2 of the periodic table. is there.

The metal salt as such a (F) phosphorus compound is not particularly limited. For example, monosodium phosphate, disodium phosphate, trisodium phosphate, monocalcium phosphate, dicalcium phosphate, phosphoric acid Tricalcium, sodium pyrophosphate, sodium metaphosphate, calcium metaphosphate, sodium hypophosphite, calcium hypophosphite and the like; their anhydrous salts; and their hydrates.
Among these, sodium hypophosphite, calcium hypophosphite, and magnesium hypophosphite are preferable, and calcium hypophosphite and magnesium hypophosphite, which are alkaline earth metal salts, are more preferable. By using such a phosphorus compound (F), it tends to be more excellent in whiteness, heat discoloration resistance, light discoloration resistance and extrusion processability.

  (F) Phosphorus compound selected from the group consisting of the above-mentioned metal phosphates, metal phosphites, metal hypophosphites, intramolecular condensates of these metal salts, and intermolecular condensates of these metal salts Is more preferably a metal hypophosphite salt. (F) When the phosphorus compound is a hypophosphite metal salt, a polyamide composition excellent in extrusion processability and molding process stability can be obtained.

Metal of (F) phosphorus compound selected from the group consisting of metal phosphate, metal phosphite, metal hypophosphite, intramolecular condensate of these metal salts, and intermolecular condensate of these metal salts The species is preferably the same as the metal species of (E) the metal hydroxide.
In particular, the metal species of the (F) phosphorus compound is preferably an alkaline earth metal.
(F) The phosphorus compound is selected from the group consisting of metal salts, intramolecular condensates of metal salts, and intermolecular condensates of metal salts, and (F) the metal species of the phosphorus compound is (E) metal When the metal species of the hydroxide are the same, it is possible to obtain a polyamide composition having improved thermal stability and excellent extrusion processability and molding process stability. Furthermore, by using an alkaline earth metal as the metal species of the (F) phosphorus compound, a more excellent effect can be obtained in the above characteristics.

(F) Phosphorus compound selected from the group consisting of metal phosphates, metal phosphites, metal hypophosphites, intramolecular condensates of these metal salts, and intermolecular condensates of these metal salts, A metal salt containing no anhydrous salt or hydrate is preferred.
(F) By using an anhydrous salt or a metal salt that does not contain a hydrate as the phosphorus compound, the amount of water generated during processing can be suppressed, and a decrease in the molecular weight of polyamide and gas generation can be suppressed. . (F) Polyamide composition having excellent whiteness, reflow resistance, heat discoloration resistance, extrusion processability, and molding process stability by using an anhydrous salt or a metal salt that does not contain hydrates as the phosphorus compound. You can get things.

As the phosphorus compound (F) selected from the group consisting of metal phosphates, metal phosphites, metal hypophosphites, intramolecular condensates of these metal salts, and intermolecular condensates of these metal salts, Those having low deliquescence are preferred, and those having no deliquescence are more preferred.
(F) By using a metal salt with low deliquescence as a phosphorus compound, processing is reduced when mixing each raw material component during production of the polyamide composition, and the amount of water in the raw material component is increased. It is possible to suppress the molecular weight reduction and gas generation of the polyamide at the time. By using a metal salt having low deliquescence, a polyamide composition excellent in whiteness, reflow resistance, heat discoloration resistance, extrusion processability, and molding process stability can be obtained.

(F) The phosphorus compound may include an organic phosphorus compound.
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.

Content of the (F) phosphorus type 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%.
The content of the (F) phosphorus compound in the polyamide composition is preferably greater than (E) the metal hydroxide.
(F) 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.

In the polyamide composition, the phosphorus compound (F) is preferably contained in an amount such that the phosphorus element concentration is 1,400 to 20,000 ppm relative to the polyamide composition, and 2,000 to 20,000 ppm. More preferably, it is contained in an amount of 3,000 to 20,000 ppm, more preferably 3,000 to 10,000 ppm, and even more preferably 4,000. More preferably, it is contained in an amount of ˜6,000 ppm.
When the phosphorus element concentration derived from the phosphorus compound (F) contained in the polyamide composition is in the above range, the polyamide composition has whiteness, reflow resistance, heat discoloration resistance, extrusion process stability, molding process stability. Excellent.

  (F) The phosphorus compound may be added during the polymerization of (A) polyamide, but is added during the production of the polyamide composition mixed with (E) the metal hydroxide described above after polymerizing (A) polyamide. It is preferable to do. By adding it during the production of the polyamide composition, it is possible to reduce the heat history, (F) to suppress the decomposition of the phosphorus compound, etc., whiteness, reflow resistance, heat discoloration resistance, extrusion processability And a polyamide composition excellent in molding process stability can be obtained.

The metal element concentration is determined by ICP (Inductively Coupled Plasma) emission spectroscopic analysis. (E) Metal hydroxide contained in polyamide composition, (F) Phosphorus compound derived metal element / phosphorus concentration Can be measured.
In the polyamide composition, (E) metal hydroxide and (F) phosphorus compound have a combined value of metal element concentrations derived from these components (excluding phosphorus element) of 1,000 to 40,000 ppm. It is preferably contained in an amount, more preferably in an amount of 2,000 to 30,000 ppm, further preferably in an amount of 3,000 to 25,000 ppm, and 4,000 to 20,000. More preferably, it is contained in an amount of 000 ppm, and more preferably in an amount of 5,000 to 10,000 ppm.
When the metal element concentration is in the above range, the polyamide composition tends to be more excellent in reflow resistance and light discoloration resistance.

((G) phenolic antioxidant and / or amine antioxidant)
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.

The content of the phenolic antioxidant in the polyamide composition is preferably 0 to 1% by mass, more preferably 0.01 to 1% by mass, further preferably 100% by mass with respect to 100% by mass of the polyamide composition. 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.

The content of the amine-based antioxidant in the polyamide composition is preferably 0 to 1% by mass, more preferably 0.01 to 1% by mass, further preferably 100% by mass with respect to the polyamide composition. 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.

<Light stabilizer>
The polyamide composition may further 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.

(Amine light stabilizer)
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.

  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, further preferably 100% by mass with respect to 100% by mass of the polyamide composition. 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 ingredients>
In addition to the above-described components, the polyamide composition of the present invention may further contain other components as necessary.
Examples of other components include, but are not limited to, colorants such as pigments and dyes (including colored master batches), mold release agents, flame retardants, fibrillating agents, lubricants, and optical brighteners. , Plasticizers, copper compounds, alkali metal halide compounds, antistatic agents, fluidity improvers, reinforcing agents, spreader rubbers, reinforcing agents and other polymers.
Here, since the above-mentioned other components have greatly different properties, suitable content ratios for the respective components are various. A person skilled in the art can easily set a suitable content for each of the other components described above.

[Production method of polyamide composition]
The method for producing the polyamide composition of the present invention is not particularly limited. (A) Polyamide, and if necessary, titanium oxide, inorganic filler, nucleating agent, heat stabilizer, light stabilizer, other components, etc. The method of mixing each raw material component containing can be used.

  For example, when (B) titanium oxide is contained in the polyamide composition, the mixing method of (A) polyamide and (B) titanium oxide is not limited to the following, but for example, (A) polyamide and the like And (B) titanium oxide are mixed using a tumbler, Henschel mixer, etc., and the resulting mixture is supplied to a melt kneader and kneaded, or is melted with a single or twin screw extruder (A ) A method of blending (B) titanium oxide from a side feeder into a polyamide or the like.

The same method can also be used when blending a heat stabilizer. (A) Polyamide, (E) Metal hydroxide, and (F) Phosphorus compound are mixed, and the resulting mixture is mixed. A method of supplying and kneading to a melt kneader, (A) polyamide or the like made molten by a single or twin screw extruder, (E) a metal hydroxide, (F) a phosphorus compound, from a side feeder, and (G) The method etc. which mix | blend a phenol type / amine type antioxidant are mentioned.
As a method for mixing the heat stabilizer (E) metal hydroxide, (F) phosphorus compound, and (G) phenol / amine antioxidant, a method of blending from a side feeder is preferred. By producing a polyamide composition by a method of blending from a side feeder, the polyamide composition tends to have excellent whiteness, reflow resistance, heat discoloration resistance, light discoloration resistance, and molding process stability.

  The same method can also be used when blending (C) inorganic filler, (A) polyamide etc. and (C) inorganic filler are mixed, and the resulting mixture is fed to a melt kneader. Examples thereof include a kneading method and a method of blending (C) an inorganic filler from a side feeder into (A) polyamide or the like that has been melted with a single or twin screw extruder.

  The method of supplying each component of the polyamide composition to the melt kneader may be a method of supplying all the components to the same supply port at a time, or a method of supplying each component from a different supply port. Good.

  The melt kneading temperature is preferably 250 to 375 ° C. as the resin temperature. The melt kneading time is preferably 0.25 to 5 minutes.

  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.

[Physical properties of polyamide composition]
The physical properties of the polyamide in the polyamide composition of the present invention are equivalent to the physical properties of the polyamide of the present invention. That is, the polyamide of the present invention maintains its original physical properties even after it is melt-kneaded with other additives as necessary to obtain a polyamide composition. For this reason, the polyamide contained in it can be specified by measuring each said physical property about the polyamide in a polyamide composition.
The polyamide composition of the present invention, trans isomer ratio, 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, crystallization peak temperature Tc, crystallization The ratio of the amount of enthalpy ΔHc, glass transition temperature Tg, amino terminal, carboxyl terminal, and amino terminal to the total amount of active terminals can be measured by the method for measuring the physical properties of polyamide described in the examples described later.
When determining the heat of fusion and crystallization enthalpy of the polyamide composition, if it contains inorganic fillers, nucleating agents, lubricants, stabilizers, etc., the value of the heat value is the ratio of polyamide to the composition. Calculate by converting.
Since the measured values of the properties of the polyamide in the polyamide composition of the present invention are in the same range as the measured values of the properties of the polyamide of the present invention, the polyamide composition of the present invention has heat resistance, whiteness, and reflow resistance. Excellent in resistance, aging resistance and releasability.

[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 polyamide composition described above.
The polyamide composition molded article maintains a high trans isomer ratio of dicarboxylic acid monomer units, is excellent in reflow resistance, heat discoloration resistance, and light discoloration resistance, and can be suitably used for a reflector or the like.

[Production Method of Polyamide Composition Molded Product]
The polyamide composition molded article can be obtained, for example, by molding the above-described polyamide composition by a known molding method.
Known molding methods include, but are not limited to, for example, press molding, injection molding, gas assist injection molding, welding molding, extrusion molding, blow molding, film molding, hollow molding, multilayer molding, and melting. Commonly known plastic molding methods such as spinning can be listed.

[Physical properties of molded products]
The polyamide composition molded article is excellent in heat resistance, whiteness, reflow resistance, aging resistance, and mold releasability. The initial reflectance is preferably 96.5% or more. Further, the reflectance retention after the reflow process is preferably 95% or more, and more preferably 96.2% or more. The aging retention is preferably 86% or more, and more preferably 86.5% or more.

[Use of polyamide composition molded product]
By including the above-mentioned polyamide composition, the polyamide composition molded article is excellent in heat resistance, moldability, mechanical strength, and low water absorption. Therefore, the above-mentioned polyamide composition can be suitably used as various component materials such as reflectors, automobiles, electric and electronic, industrial materials, daily necessities and household goods, and for extrusion applications. It can be used suitably.

  The reflectance retention of the polyamide composition molded article can be measured by the method described in the examples described later.

The polyamide composition can be used as various component materials.
Although it is not limited to the following for automobiles, for example, intake system parts, cooling system parts, fuel system parts, interior parts, exterior parts, electrical parts and the like can be mentioned.

  Examples of the vehicle intake system parts include, but are not limited to, 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. It is done.

  Examples of the automobile cooling system parts include, but are not limited to, a chain cover, a thermostat housing, an outlet pipe, a radiator tank, an oil netter, and a delivery pipe.

  The automobile fuel system parts include, but are not limited to, a fuel delivery pipe and a gasoline tank case.

  Examples of automobile interior parts include, but are not limited to, an instrument panel, a console box, a glove box, a steering wheel, and a trim.

  Examples of automobile exterior parts include, but are not limited to, malls, lamp housings, front grilles, mud guards, side bumpers, door mirror stays, roof rails, and the like.

  Examples of the automobile electrical component include, but are not limited to, a connector, a wire harness connector, a motor component, a lamp socket, a sensor on-vehicle switch, and a combination switch.

  For electrical and electronic applications, but not limited to the following, for example, reflectors such as connectors, switches, relays, printed wiring boards, electronic component housings, outlets, noise filters, coil bobbins, and LEDs (light emitting diodes) And LED reflectors and motor end caps.

  Examples of industrial equipment include, but are not limited to, gears, cams, insulating blocks, valves, power tool parts, agricultural equipment parts, engine covers, and the like.

  Examples of daily goods and household goods include, but are not limited to, buttons, food containers, and office furniture.

  Extrusion applications include, but are not limited to, for example, films, sheets, filaments, tubes, rods, and hollow molded products.

[Method for suppressing reduction in reflectance due to heat of reflector]
As described above, a molded article containing the polyamide composition of the present invention can be suitably used as a reflector.
In the reflection plate, by using a combination of (A) polyamide, (E) metal hydroxide, and (F) phosphorus compound, it is possible to effectively suppress a decrease in reflectance due to heat.
About a reflectance, it can measure by the method described in the Example mentioned later. It has been verified in Examples to be described later that the above-described combination can effectively suppress a decrease in reflectance in a reflector containing the polyamide composition of the present invention.

  EXAMPLES Hereinafter, although a specific Example and a comparative example are given and this invention is demonstrated in detail, this invention is not limited to a following example.

The raw materials used in the polyamide compositions of Examples and Comparative Examples, and methods for measuring physical properties of the polyamide and polyamide composition molded articles are shown below.
In this example, 1 kg / cm ² means 0.098 MPa.

〔raw materials〕
(A) Polyamide The (A) polyamide used in the examples and comparative examples was produced using the following (a) and (b) as appropriate.
(A) Dicarboxylic acid (1) 1,4-cyclohexanedicarboxylic acid (CHDA) (manufactured by Eastman Chemical Co., Ltd., trade name: 1,4-CHDA HP grade (trans isomer / cis isomer = 25/75))
(B) Diamine (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) Undecamethylenediamine (C11DA) (manufactured by Tokyo Chemical Industry Co., Ltd.)
(6) Dodecamethylenediamine (C12DA) (manufactured by Tokyo Chemical Industry Co., Ltd.)

(C) Monocarboxylic acid (1) Acetic acid (manufactured by Wako Pure Chemical Industries, Ltd.)
(2) Benzoic acid (Wako Pure Chemical Industries, Ltd.)

(B) Titanium oxide TiO ₂ (manufactured by Ishihara Sangyo Co., Ltd., trade name: Taipei (registered trademark) CR-63, number average particle size: 0.21 μm, coating: alumina, silica and siloxane compound)
In addition, the number average particle diameter of (B) titanium oxide was measured as follows by an electron micrograph method.
The polyamide compositions of Examples and Comparative Examples to be described later are placed in an electric furnace, the organic matter contained in the polyamide composition is incinerated, and 100 or more titanium oxides arbitrarily selected from the residue are observed with an electron microscope. And the number average particle diameter of (B) titanium oxide was calculated | required by measuring these particle sizes.

(C) Inorganic filler Wollastonite (number average fiber diameter 8 μm)
In addition, (C) The number average fiber diameter of an inorganic filler puts the polyamide composition of the Example and comparative example which are mentioned later into an electric furnace, and incinerates the organic substance contained in a polyamide composition. From the residue, 100 or more arbitrarily selected wollastonite was observed with a scanning electron microscope (SEM), and the number average fiber diameter was determined by measuring the fiber diameter of these wollastonites.

(D) Nucleating agent Talc (made by Nippon Talc Co., Ltd., trade name: MICRO ACE (registered trademark) L-1 average particle size 5 μm)

(E) Metal hydroxide, calcium hydroxide, purity 99.9% (manufactured by Wako Pure Chemical Industries, Ltd.)

(F) Phosphorus compound Calcium hypophosphite (manufactured by Wako Pure Chemical Industries, Ltd., decomposition start temperature 340 ° C.)

(G) Phenol-based antioxidant Phenol-based antioxidant (manufactured by BASF, trade name: IRGANOX (registered trademark) 1098)

[Calculation of unit amount of structural unit in polyamide]
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.
Further, the mol% of the aliphatic diamine was obtained by calculation as (number of moles of aliphatic diamine added as raw material monomer / number of moles of all diamine units added as 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 temperature Tm1 · Tm2 (° C.), heat of fusion ΔHm1 · ΔHm2 (J / g), crystallization peak temperature Tc (° C.), crystallization enthalpy ΔHc (J / g)
In accordance with JIS-K7121, using Diamond-DSC manufactured by PERKIN-ELMER, melting peak temperatures Tm1, Tm2 (° C.), heat of fusion ΔHm1 (J / g), crystallization peak temperature Tc (° C.), and The crystallization enthalpy ΔHc was measured.
Specifically, it measured as follows.

  First, it appears when about 10 mg of a sample ((A) polyamide) is heated to 300 to 350 ° C. according to the melting point of the sample at a temperature increase rate of 20 ° C./min (at the first temperature increase) in a nitrogen atmosphere. The melting peak temperature that appeared on the highest temperature side of the endothermic peak (melting peak) was Tm1 (° C.), and the peak area of Tm1 was the heat of fusion ΔHm1 (J / g). The melting peak temperature (melting point) Tm2 and the heat of fusion ΔHm2 of the raw material 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 amount of 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. Specifically, it measured as follows. The sample was melted on a hot stage (EP80 manufactured by Mettler), and the obtained sample in a molten state was rapidly cooled using liquid nitrogen and solidified to obtain a measurement sample. 10 mg of the measurement sample was heated by DSC in the range of 30 to 350 ° C. under the condition of a heating rate of 20 ° C./min, and the glass transition temperature Tg (° C.) observed at the time of temperature increase was measured. did.

(3) Trans isomer ratio of polyamide (A) The trans isomer ratio of the portion derived from 1,4-cyclohexadicarboxylic acid in polyamide was measured as follows.
30-40 mg of polyamide was dissolved in 1.2 g of hexafluoroisopropanol deuteride, and the trans isomer ratio was measured by ¹ H-NMR (ECA500 manufactured by JEOL) using the resulting solution.
When the alicyclic dicarboxylic acid is 1,4-cyclohexanedicarboxylic acid, the ratio between the peak area of 1.98 ppm derived from the trans isomer and the peak areas of 1.77 ppm and 1.86 ppm derived from the cis isomer From which the trans isomer ratio was determined.

(4) (A) Sulfuric acid relative viscosity ηr of polyamide
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) Polyamide molecular weight (Mn, Mw / Mn)
Mw (weight average molecular weight) / Mn (number average molecular weight) of the polyamides obtained in Examples and Comparative Examples is GPC (gel permeation chromatography, manufactured by Tosoh Corporation, HLC-8020, hexafluoroisopropanol solvent, PMMA (poly It was calculated using Mw and Mn measured by methyl methacrylate) standard sample (manufactured by Polymer Laboratories). In addition, TSK-GEL GMHHR-M and G1000HHR were used for the GPC column.

(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 total amount of active terminals ([NH ₂ ] + [COOH]) and the amount of amino terminal The ratio ([NH ₂ ] / ([NH ₂ ] + [COOH])) to the total amount of active terminals was calculated.
(8) Cyclic amino terminal amount (μ equivalent / g)
The amount of cyclic amino terminals was measured using ¹ H-NMR.
Hydrogen signal (chemical shift value 3.5 to 4.0 ppm) bonded to the carbon adjacent to the nitrogen atom of the heterocyclic ring of nitrogen and hydrogen signal (chemical shift bonded to the carbon adjacent to the nitrogen atom of the amide bond of the polyamide main chain) The cyclic amino terminal amount was calculated using an integration ratio of 3.0 to 3.5 ppm). The total number of polymer terminals used at that time was calculated as 2 / Mn × 1,000,000 using Mn measured by GPC.

[Measurement method of physical properties of polyamide composition molded article]
(9) Initial reflectance (%)
The pellets of the polyamide composition produced in Examples and Comparative Examples to be described later are molded using an injection molding machine [PS-40E: manufactured by Nissei Resin Co., Ltd.], so that length 60 mm × width 60 mm × thickness 1. A 0 mm molded piece was produced.
During molding, the total time of injection and pressure holding time was 5 seconds, the cooling time was 15 seconds, the mold temperature was set to Tg + 10 ° C., and the temperature of the molten polyamide composition was set to (A) the melting peak temperature Tm2 + 10 ° C. of polyamide.
The reflectance of the obtained molded piece with respect to light having a wavelength of 450 nm was measured with a Hitachi spectrophotometer (U-3310).

(10) Reflectivity retention after reflow process (%)
The pellets of the polyamide composition produced in Examples and Comparative Examples to be described later are molded using an injection molding machine [PS-40E: manufactured by Nissei Resin Co., Ltd.], so that length 60 mm × width 60 mm × thickness 1. A 0 mm molded piece was produced.
During molding, the total time of injection and holding time was 5 seconds, cooling time was 15 seconds, the mold temperature was set to Tg + 10 ° C., and the molten resin temperature was set to (A) the melting peak temperature Tm2 + 10 ° C. of polyamide. The obtained molded piece was heat-treated (reflow process) three times in a hot air reflow furnace (280 ° C. × 10 seconds).
The reflectance with respect to 450 nm light of the molded piece before and after the heat treatment (reflow process) was measured with a Hitachi spectrophotometer (U-3310), and the reflectance retention after the reflow process was calculated.

(11) Aging retention rate (%)
The molded piece after the reflow process obtained as described above was heat-treated in a hot air dryer at 150 ° C. for 300 hours.
The reflectance of the molded piece after heat treatment with respect to 450 nm light was measured with a Hitachi spectrophotometer (U-3310), and the aging retention was calculated in comparison with the reflectance before heat treatment.

(12) Releasability By molding the polyamide composition pellets produced in the examples and comparative examples described below using an injection molding machine (PS-40E: manufactured by Nissei Resin Co., Ltd.), the length is 60 mm × width. A molded product of 60 mm × 1.0 mm thickness was produced.
During molding, the total time of injection and holding time was 2 seconds, the mold temperature was set to Tg + 10 ° C., and the molten resin temperature was set to the melting peak temperature Tm2 + 10 ° C. of (A) polyamide.
The cooling time was adjusted, and the shortest cooling time for releasing the molded product from the mold without any problem was evaluated as the releasability. It was determined that shortening the cooling time would lead to improved productivity.

[(A) Production of polyamide]
Hereinafter, production examples of polyamide will be described. The materials, blending ratios and polymerization conditions of each component are shown in Table 1, and the properties of the obtained polyamide are shown in Table 2.
(Production Example 1)
CHDA 896 g (5.20 mol) and 2MC5DA 604 g (5.20 mol) were dissolved in 1500 g of distilled water to prepare an equimolar 50 mass% water mixture of the raw material monomers.
The obtained water mixture, 27 g (0.23 mol) of 2MC5DA, 4.1 g (0.07 mol) of acetic acid and 1.3 g of sodium hypophosphite monohydrate, which are additives at the time of melt polymerization. An autoclave (manufactured by Nitto Koatsu) with an internal volume of 5.4 L was charged.

Next, it heated until the liquid temperature (internal temperature) in an autoclave became 50 degreeC. Thereafter, the inside of the autoclave was purged with nitrogen. The pressure inside the tank of the autoclave (hereinafter also simply referred to as “inside the tank”) is about 2.5 kg / cm ² as gauge pressure (hereinafter, all the pressure inside the tank is expressed as gauge pressure (G)). Heating was continued until At this time, the liquid temperature was about 145 ° C.
While maintaining 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 aqueous solution in the tank was concentrated to a concentration of about 85% by mass.

The removal of water was stopped, and heating was continued until the pressure in the tank reached about 30 kg / cm ² (G).

In order to keep the pressure in the tank at about 30 kg / cm ² (G), heating was continued until the temperature reached 15 ° C. (about 330 ° C.) lower than the final temperature (about 345 ° C.) while removing water from the system. While further heating, the pressure in the tank was reduced to atmospheric pressure (gauge pressure was 0 kg / cm ² ) over 60 minutes. The heater temperature was adjusted so that the final temperature of the resin temperature (liquid temperature) in the tank was about 340 ° C.

While maintaining the resin temperature in the tank, the inside of the tank was maintained under a reduced pressure of 100 torr (1.33 × 10 ⁴ Pa) for 10 minutes with a vacuum apparatus. Then, the inside of the tank was pressurized with nitrogen, and the product was discharged in a strand form from the lower nozzle (nozzle). Further, the strand-like product was cooled with water and cut to obtain a pellet-like precursor polyamide (precursor polyamide pellet). The total active terminal amount ([NH ₂ ] + [COOH]) of this precursor polyamide was 98 μeq / g, and the ratio of the amino terminal amount [NH ₂ ] to the active terminal total amount ([NH ₂ ] + [COOH]). [NH ₂ ] / ([NH ₂ ] + [COOH]) was 0.40, and the amount of cyclic amino terminus was 132 μeq / g.

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 1 L / min in the vacuum dryer. Thereafter, the temperature in the vacuum dryer was lowered to about 50 ° C. while nitrogen was circulated to produce a pellet-like polyamide. The polyamide pellets were taken out from the vacuum dryer to obtain polyamide (hereinafter also referred to as “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)
CHDA 896 g (5.20 mol) and 2MC5DA 604 g (5.20 mol) were dissolved in 1500 g of distilled water to prepare an equimolar 50 mass% water mixture of the raw material monomers.
The obtained water mixed solution, 20 g (0.17 mol) of 2MC5DA, 3.1 g (0.05 mol) of acetic acid and 1.3 g of sodium hypophosphite monohydrate, which are additives at the time of melt polymerization. An autoclave (manufactured by Nitto Koatsu) with an internal volume of 5.4 L was charged. The polymerization conditions are such that the pressure in the tank is maintained at about 30 kg / cm ² (G), and water is removed from the system while being heated to 25 ° C. lower than the final temperature (about 345 ° C.) (about 320 ° C.). According to Production Example 1 except that. The total active terminal amount ([NH ₂ ] + [COOH]) of the obtained precursor polyamide was 92 μeq / g, the total active terminal amount of amino terminal amount [NH ₂ ] ([NH ₂ ] + [COOH]). The ratio to [NH ₂ ] / ([NH ₂ ] + [COOH]) was 0.41, and the cyclic amino terminal amount was 122 μeq / g.

10 kg of precursor polyamide pellets obtained by using melt polymerization was placed in 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 1 L / min in the vacuum dryer. Thereafter, the temperature in the vacuum dryer was lowered to about 50 ° C. with nitrogen flowing, and the polyamide pellets were removed from the vacuum dryer in the form of pellets to obtain polyamide (hereinafter also referred to as “PA-2”). .

  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 3)
CHDA 896 g (5.20 mol) and 2MC5DA 604 g (5.20 mol) were dissolved in 1500 g of distilled water to prepare an equimolar 50 mass% water mixture of the raw material monomers.
The obtained water mixture, 18 g (0.16 mol) of 2MC5DA, 1.6 g (0.03 mol) of acetic acid and 1.3 g of sodium hypophosphite monohydrate, which are additives at the time of melt polymerization. An autoclave (manufactured by Nitto Koatsu) with an internal volume of 5.4 L was charged. The polymerization conditions are such that the pressure in the tank is maintained at about 30 kg / cm ² (G), and water is removed from the system while heating to a temperature (about 310 ° C.) 35 ° C. lower than the final temperature (about 345 ° C.). According to Production Example 1 except that. The total active terminal amount ([NH ₂ ] + [COOH]) of this precursor polyamide is 93 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 0.4, and the cyclic amino terminal amount was 95 μeq / g.

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 1 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 removed from the vacuum dryer in the form of pellets to obtain polyamide (hereinafter also referred to as “PA-3”). .

  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 4)
CHDA 896 g (5.20 mol) and 2MC5DA 604 g (5.20 mol) were dissolved in 1500 g of distilled water to prepare an equimolar 50 mass% water mixture of the raw material monomers.
The resulting water mixture, 24 g (0.21 mol) of 2MC5DA, 3.7 g (0.06 mol) of acetic acid, and 1.3 g of sodium hypophosphite monohydrate, which are additives at the time of melt polymerization. An autoclave (manufactured by Nitto Koatsu) with an internal volume of 5.4 L was charged. The polymerization conditions were such that the pressure in the tank was maintained at about 30 kg / cm ² (G), and water was removed from the system while heating to a temperature (about 295 ° C.) that was 50 ° C. lower than the final temperature (about 345 ° C.). According to Production Example 1 except that. The total active terminal amount ([NH ₂ ] + [COOH]) of this precursor polyamide was 102 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 0.55, and the cyclic amino terminal amount was 55 μeq / g.

10 kg of precursor polyamide pellets obtained by using melt polymerization was placed in 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 120 ° C. for 24 hours with stirring while flowing nitrogen at 1 L / min in the vacuum dryer. Thereafter, the temperature in the vacuum dryer was lowered to about 50 ° C. with nitrogen flowing, and the polyamide pellets were removed from the vacuum dryer in the form of pellets to obtain polyamide (hereinafter also referred to as “PA-4”). .

  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 5)
The procedure was the same as in Production Example 4 except for the drying conditions.
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 210 ° C. for 24 hours with stirring while flowing nitrogen at 1 L / min in the vacuum dryer. Thereafter, the temperature in the vacuum dryer was lowered to about 50 ° C. with nitrogen flowing, and the polyamide pellets were removed from the vacuum dryer in the form of pellets to obtain polyamide (hereinafter also referred to as “PA-5”). .

  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 6)
CHDA 896 g (5.20 mol) and 2MC5DA 604 g (5.20 mol) were dissolved in 1500 g of distilled water to prepare an equimolar 50 mass% water mixture of the raw material monomers.
An autoclave (with an inner volume of 5.4 L) containing 1.6 g (0.03 mol) of acetic acid and 1.3 g of sodium hypophosphite monohydrate, which are additives during melt polymerization, was obtained. Nitto High Pressure). The polymerization conditions and drying conditions were in accordance with Production Example 1.

  The obtained polyamide (hereinafter also referred to as “PA-6”) is dried in a nitrogen stream to adjust the moisture content to less than about 0.2% by mass, and then the properties of the polyamide are determined based on the above measurement methods. Measured.

(Production Example 7)
The polymerization method was in accordance with the production method described in (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 was continuously heated from about 50 ° C. to 210 ° C., and heating was continued while removing water out of the system in order to keep the pressure in the autoclave tank at 17.5 kg / cm ² as a gauge pressure. 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 copolymer polyamide pellets.

  Each physical property of the obtained polyamide (hereinafter also referred to as “PA-7”) was measured based on the above method.

(Production Example 8)
The polymerization method was in accordance with the production method described in (International Publication No. 2008-149862 pamphlet).
CHDA 726 g (4.22 mol), C12DA 675 g (3.37 mol), and C6DA 99 g (0.85 mol) were dissolved in 1500 g of distilled water to prepare an equimolar aqueous solution of about 50% by mass of the raw material monomer.
The obtained aqueous solution was charged into an internal volume 5.4 L autoclave (manufactured by Nitto Koatsu), kept warm until the liquid temperature (internal temperature) reached 50 ° C., and 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 (hereinafter also referred to as “PA-8”).

(Production Example 9)
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. and 0.1 mmHg for 10 hours to obtain polyamide (hereinafter also referred to as “PA-9”).

[Production of polyamide composition]
(Examples 1-3 and Comparative Examples 1-6)
Using the polyamides (PA-1) to (PA-9) obtained in Production Examples 1 to 9 and the raw materials in the types and proportions shown in Table 2 below, the polyamide composition is as follows. Manufactured.

  The polyamides (PA-1 to PA-9) obtained in Production Examples 1 to 9 were dried in a nitrogen stream and the moisture content was adjusted to about 0.2% by mass. Used as.

As an apparatus for producing the polyamide composition, a twin screw extruder [ZSK-26MC: manufactured by Coperion (Germany)] was used.
The twin screw extruder has an upstream supply port in the first barrel from the upstream side of the extruder, a downstream first supply port in the sixth barrel, and a downstream second supply port in the ninth barrel. Had. In the twin-screw extruder, L / D (extruder cylinder length / extruder cylinder diameter) was 48, and the number of barrels was 12.
In the twin screw extruder, the temperature from the upstream supply port to the die is set to the melting peak temperature Tm2 + 10 ° C. of each (A) polyamide produced in the above production example, the screw rotation speed is set to 250 rpm, and the discharge amount is set to 25 kg / h. did.

(A) Polyamide, (D) Nucleating agent, (E) Metal hydroxide, (F) Phosphorus compound, and (G) Phenol antioxidant so that it may become the kind and ratio of Table 2. Was dry blended and then fed from the upstream feed port of the twin screw extruder.
Next, (B) titanium oxide was supplied from the downstream first supply port of the twin-screw extruder in the types and proportions shown in Table 2 below.
Furthermore, (C) inorganic filler was supplied from the downstream second supply port of the twin-screw extruder in the types and proportions shown in Table 2 below.
The raw materials supplied as described above were melt-kneaded with a twin-screw extruder to produce polyamide composition pellets.
The obtained polyamide composition pellets were dried in a nitrogen stream, and the water content in the polyamide composition was reduced to 500 ppm or less.
Various evaluations were performed as described above using the polyamide composition after adjusting the water content.
Tables 1 and 2 are shown below.

As shown in Table 2, it was found that the polyamide compositions of Examples 1 to 3 had high initial reflectivity, reflectivity retention after the reflow process, and reflectivity retention after the heat treatment, and were excellent in releasability. .
On the other hand, the comparative example in which the 25 ° C. sulfuric acid relative viscosity ηr and the active terminal total amount ([NH ₂ ] + [COOH]) are out of the scope of the present invention is particularly in the reflectance retention and the aging retention after the reflow process. Inferior to Example. From the above results, it was shown that the polyamide composition of the present invention is excellent in reflectance retention, aging retention and releasability, and therefore can be suitably used for LED reflectors.

  The polyamide composition of the present invention has industrial applicability as various component materials for LED reflectors, automobiles, electrical and electronic products, industrial materials, daily products and household products.

Claims (21)

(A) a dicarboxylic acid unit containing at least 1,4-cyclohexanedicarboxylic acid;
(B) a diamine unit containing at least a branched aliphatic diamine;
A polyamide containing
(C) sulfuric acid relative viscosity ηr is ηr <2.0,
(D) Total amount of active terminals ([NH ₂ ] + [COOH]) μ equivalent / g is 10 ≦ ([NH ₂ ] + [COOH]) ≦ 60
Is a polyamide.   The polyamide according to claim 1, wherein a content of the 1,4-cyclohexanedicarboxylic acid is at least 50 mol% in the (a) dicarboxylic acid unit.   The polyamide according to claim 2, wherein a content of the 1,4-cyclohexanedicarboxylic acid is 100 mol% in the (a) dicarboxylic acid unit.   Content of the said branched aliphatic diamine is 50-100 mol% in (b) diamine unit, The polyamide of any one of Claims 1-3.   The polyamide according to claim 4, wherein the content of the branched aliphatic diamine is 100 mol% in (b) diamine units.   The polyamide according to any one of claims 1 to 5, wherein the branched aliphatic diamine has 6 to 12 carbon atoms.   The polyamide according to claim 6, wherein the branched aliphatic diamine is 2-methyl-pentamethylenediamine or 2-methyl-1,8-octanediamine.   The polyamide according to claim 7, wherein the branched aliphatic diamine is 2-methyl-pentamethylenediamine.   The polyamide according to any one of claims 1 to 8, wherein the polyamide has two or more kinds of sealed ends.   The polyamide according to claim 9, wherein the amino terminal and carboxyl terminal are sealed.   The polyamide according to claim 9 or 10, wherein the amino terminal is sealed with acetic acid, and the carboxyl terminal is sealed with a cyclic amine.   The polyamide according to any one of claims 1 to 11, wherein a cyclic amino terminal amount of the polyamide is larger than 70 µeq / g. The trans isomer ratio mol% of 1,4-cyclohexanedicarboxylic acid monomer unit of dicarboxylic acid in the polyamide is
71 <trans isomer ratio ≦ 100
The polyamide according to any one of claims 1 to 12. The trans isomer ratio mol% of 1,4-cyclohexanedicarboxylic acid monomer unit of dicarboxylic acid in the polyamide is
71 <trans isomer ratio ≦ 80
The polyamide according to claim 13. (D) The total amount of active ends ([NH ₂ ] + [COOH]) μeq / g is
20 ≦ [NH ₂ ] + [COOH] ≦ 50
The polyamide according to any one of claims 1 to 14. [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
The polyamide according to any one of claims 1 to 15. The weight average molecular weight Mw / number average molecular weight Mn as the molecular weight distribution is
The polyamide according to any one of claims 1 to 16, wherein Mw / Mn <3.5.   A polyamide composition comprising the polyamide according to any one of claims 1 to 17 and titanium oxide.   The polyamide composition according to claim 18, further comprising at least one selected from an inorganic filler, a nucleating agent, a heat stabilizer, and a light stabilizer.   A polyamide composition molded article obtained by molding the polyamide composition according to claim 18 or 19. (A) a dicarboxylic acid unit containing at least 1,4-cyclohexanedicarboxylic acid;
(B) a diamine unit containing at least a branched 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, and the total amount of active ends ([NH ₂ ] + [COOH]) μeq / g is 60 ≦ ([NH ₂ ] + [COOH]) <110 and a polyamide production method in which a precursor polyamide having a cyclic amino terminal amount greater than 70 μeq / g is heat-treated at 200 ° C. or more and less than the melting point for 10 hours or more.