JP2017014397A - Polyamide composition, molding, and reflection plate for led - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyamide composition having excellent molding stability, whiteness, heat aging resistance, thermal discoloration resistance, and light resistance.SOLUTION: A polyamide composition comprises (A) polyamide, (B) inorganic filler, (C) metal hydroxide and/or (D) metal oxide of 0.1-20 mass%, where an Fe concentration in the composition is 5-200 ppm.SELECTED DRAWING: None

Description

  The present invention relates to a polyamide composition, a molded article, and a reflector for LED.

  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. Widely used as various parts materials for automobiles, electric and electronic, industrial materials, industrial materials, daily products and household products.

  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"), a polyamide composition comprising titanium oxide, magnesium hydroxide, and a specific reinforcing material 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 and the like cannot yet be said to have sufficient characteristics in heat discoloration, extrusion processability, and molding process stability. There is a need for further improvements in these properties.

  In view of the above-described problems of the prior art, an object of the present invention is to provide a polyamide composition excellent in molding process stability, whiteness, heat aging resistance, heat discoloration resistance, and light resistance.

As a result of intensive studies in order to solve the above problems, the present inventors contain polyamide, an inorganic filler, a metal hydroxide and / or a metal oxide, and the Fe concentration in the composition is The present inventors have found that a polyamide composition of 5 to 200 ppm can solve the above problems, and have completed the present invention.
That is, the present invention is as follows.

[1]
(A) polyamide,
(B) an inorganic filler;
(C) metal hydroxide and / or (D) 0.1-20% by mass of metal oxide,
And the Fe concentration in the composition is 5 to 200 ppm.
[2]
The polyamide composition according to [1], wherein the (A) polyamide has a melting point of 270 to 350 ° C.
[3]
[1] or [2] wherein the (A) polyamide has (a-1) an alicyclic dicarboxylic acid unit composed of 1,4-cyclohexanedicarboxylic acid and (a) a dicarboxylic acid unit containing 50 mol% or more. ] The polyamide composition as described in.
[4]
The polyamide composition according to any one of [1] to [3], wherein the metal hydroxide (C) is an alkaline earth metal hydroxide.
[5]
The polyamide composition according to any one of [1] to [4], wherein the metal oxide (D) is an alkaline earth metal oxide.
[6]
The polyamide composition according to any one of [1] to [5], wherein (B) the inorganic filler includes wollastonite having an aspect ratio of 20 or less.
[7]
The polyamide composition according to any one of [1] to [6], wherein the Ca concentration is 500 to 45000 ppm.
[8]
The polyamide composition according to any one of [1] to [7], wherein the Mg concentration is 500 to 8000 ppm.
[9]
The polyamide composition according to any one of [1] to [8], wherein a ratio of Ca content to Fe content (Ca / Fe) is 100 or more.
[10]
(E) The polyamide composition according to any one of [1] to [9], further containing 0.1 to 20% by mass of a phosphorus compound.
[11]
(F) The polyamide composition according to any one of [1] to [10], further containing 5% by mass or more of titanium oxide.
[12]
The (B) inorganic filler contains a nucleating agent,
The polyamide composition according to any one of [1] to [11], wherein the content of the nucleating agent in the polyamide composition is 0.001 to 15% by mass.
[13]
[1] A molded article comprising the polyamide composition according to any one of [12].
[14]
[13] The molded article according to [13], which has a reflectivity retention of 95% or more after being exposed for 1000 hours at a position at 100 ° C. and an illuminance of 10 mW / cm ^{2 using a} metal halide lamp type light resistance tester.
[15]
[1] thru | or the reflecting plate for LED containing the polyamide composition in any one of [12].

  According to the present invention, it is possible to provide a polyamide composition having excellent molding process stability, whiteness, heat aging resistance, heat discoloration resistance, and light resistance.

  Hereinafter, a mode for carrying out the present invention (hereinafter referred to as “the present embodiment”) 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.

[Polyamide composition]
The polyamide composition of the present embodiment (hereinafter also simply referred to as “polyamide composition”)
(A) polyamide,
(B) an inorganic filler;
(C) metal hydroxide and / or (D) 0.1-20% by mass of metal oxide,
And the Fe concentration in the composition is 5 to 200 ppm.

((A) Polyamide)
The polyamide (A) used in the present embodiment has (a) a dicarboxylic acid unit and (b) a diamine unit.
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 the present embodiment, the ratio of the predetermined monomer unit constituting the polyamide (A) can be measured by nuclear magnetic resonance spectroscopy (NMR) or the like.
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 embodiment, “polyamide” means a polymer having an amide (—NHCO—) bond in the main chain.

<(A) Dicarboxylic acid unit>
Examples of (a) dicarboxylic acid units include, but are not limited to, (a-1) alicyclic dicarboxylic acid units, (a-2) aromatic dicarboxylic acid units, and (a-3). Aliphatic dicarboxylic acid units are mentioned.
The (a) dicarboxylic acid unit preferably contains 50 to 100 mol% of (a-1) alicyclic dicarboxylic acid units (based on the total number of dicarboxylic acids), more preferably 60 to 100 mol%, and 70 It is more preferable to contain -100 mol%, and it is still more preferable to contain 100 mol%.
(A) When the ratio (mol%) of the (a-1) alicyclic dicarboxylic acid unit in the dicarboxylic acid unit is in the above range, heat resistance, fluidity, toughness, low water absorption, rigidity, etc. are simultaneously obtained. A satisfactory polyamide composition can be obtained.

[(A-1) Alicyclic dicarboxylic acid unit]
The alicyclic dicarboxylic acid constituting the (a-1) alicyclic dicarboxylic acid unit (hereinafter also referred to as “alicyclic dicarboxylic acid unit”) is not limited to the following. An alicyclic dicarboxylic acid having 3 to 10 carbon atoms in the alicyclic structure is exemplified, and an alicyclic dicarboxylic acid having 5 to 10 carbon atoms in the alicyclic structure is preferable.
Specific examples of the (a-1) alicyclic dicarboxylic acid constituting the alicyclic dicarboxylic acid unit are not limited to the following. For example, 1,4-cyclohexanedicarboxylic acid, 1, Examples include 3-cyclohexanedicarboxylic acid and 1,3-cyclopentanedicarboxylic acid. Among these, 1,4-cyclohexanedicarboxylic acid is preferable.
By including the (a-1) alicyclic dicarboxylic acid unit composed of such an alicyclic dicarboxylic acid, the polyamide composition tends to have more excellent heat resistance, low water absorption, rigidity, and the like.
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.
In the polyamide composition of the present embodiment, (A) the polyamide comprises (a-1) an alicyclic dicarboxylic acid unit composed of 1,4-cyclohexanedicarboxylic acid and includes (a) a dicarboxylic acid unit. It is preferable to have. When (A) polyamide has such a (a) dicarboxylic acid unit, the polyamide composition tends to be more excellent in heat resistance, low water absorption, rigidity, and the like.

The alicyclic group of the alicyclic dicarboxylic acid may be unsubstituted or may have a substituent.
Examples of the substituent include, but are not limited to, for example, 1 carbon atom such as 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-1) The alicyclic dicarboxylic acid constituting the alicyclic dicarboxylic acid unit includes 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.
It is known that alicyclic dicarboxylic acids are isomerized at a high temperature, and the trans isomer and cis isomer are in a certain ratio. The cis alicyclic dicarboxylic acid is more trans alicyclic. Compared to dicarboxylic acid, the water solubility of the equivalent salt of alicyclic dicarboxylic acid and 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).
In (A) polyamide, the ratio of the trans isomer in the whole (a-1) alicyclic dicarboxylic acid unit is referred to as “trans isomer ratio”. The trans isomer ratio is preferably 50 to 85 mol%, more preferably 50 to 80 mol%, still more preferably 60 to 80 mol%.
When the trans isomer ratio is within the above range, the polyamide composition of the present embodiment has a high melting point, toughness and rigidity, and in addition to the characteristics such as high thermal transition rigidity (Tg), However, it tends to have a property of simultaneously satisfying fluidity, which is a property contrary to heat resistance, and high crystallinity.
These characteristics are composed of (a-1) an alicyclic dicarboxylic acid unit composed of 1,4-cyclohexanedicarboxylic acid (a) containing 50 mol% or more of (a) a dicarboxylic acid unit and 2-methylpentamethylenediamine. (B-1) (A) a polyamide obtained from a combination with (diamine) a diamine unit containing 50 mol% or more of a diamine unit having a substituent branched from the main chain, and the trans isomer ratio is 50 This is particularly noticeable with the polyamide (A) of ˜85 mol%.
The “trans isomer ratio” can be measured by the method described in Examples described later.

[(A-2) Aromatic dicarboxylic acid unit]
(A-2) The aromatic dicarboxylic acid constituting the aromatic dicarboxylic acid unit is not limited to the following, and examples thereof include a dicarboxylic acid having a phenyl group or a naphthyl group. The aromatic group of the aromatic dicarboxylic acid may be unsubstituted or may have a substituent.
The substituent is not particularly limited, and examples thereof include halogen groups such as an alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 10 carbon atoms, an arylalkyl group having 7 to 10 carbon atoms, a chloro group, and a bromo group. , A silyl group having 1 to 6 carbon atoms, a sulfonic acid group and a salt thereof (such as a sodium salt), and the like.
(A-2) Specific examples of the aromatic dicarboxylic acid constituting the aromatic dicarboxylic acid unit include, but are not limited to, for example, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, 2-chloroterephthalic acid , 2-methyl terephthalic acid, 5-methylisophthalic acid, 5-sodium sulfoisophthalic acid and the like, unsubstituted or substituted C8-20 aromatic dicarboxylic acids and the like.
(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, succinic 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-methyladipic acid, trimethyladipic acid, pimelic acid C3-20 linear or branched saturated aliphatic such as suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, tetradecanedioic acid, hexadecanedioic acid, octadecanedioic acid, eicosanedioic acid, and diglycolic acid And dicarboxylic acid.

(A-1) As a dicarboxylic acid unit other than the alicyclic dicarboxylic acid unit, (a-3) an aliphatic dicarboxylic acid unit is preferably included, and the dicarboxylic acid unit is composed of an aliphatic dicarboxylic acid having 6 or more carbon atoms. (A-3) It is more preferable that an aliphatic dicarboxylic acid unit is included.
By including such an (a-3) aliphatic dicarboxylic acid unit, the heat resistance, fluidity, toughness, low water absorption, rigidity and the like of the polyamide composition tend to be more excellent.
Among them, (a-3) the aliphatic dicarboxylic acid constituting the aliphatic dicarboxylic acid unit is preferably an aliphatic dicarboxylic acid having 10 or more carbon atoms. By including the (a-3) aliphatic dicarboxylic acid unit composed of such an aliphatic dicarboxylic acid, the heat resistance and low water absorption of the polyamide composition tend to be more excellent.
The aliphatic dicarboxylic acid having 10 or more carbon atoms is not particularly limited, and examples thereof include sebacic acid, dodecanedioic acid, tetradecanedioic acid, hexadecanedioic acid, octadecanedioic acid, and eicosane diacid. 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.

  The proportion (mol%) of the dicarboxylic acid unit other than the (a-1) alicyclic dicarboxylic acid unit in the (a) dicarboxylic acid unit is preferably 0 to 50 mol%, and preferably 0 to 40 mol. % Is more preferable, and 0 to 30 mol% is still more preferable.

Moreover, when (a-3) the aliphatic dicarboxylic acid unit comprised from C10 or more aliphatic dicarboxylic acid is included, the ratio of (a-1) alicyclic dicarboxylic acid unit is 50-99.9. It is preferable that the ratio of mol% and (a-3) aliphatic dicarboxylic acid units is 0.1 to 50 mol%, and (a-1) the ratio of alicyclic dicarboxylic acid units is 60 to 95 mol% and ( a-3) The proportion of aliphatic dicarboxylic acid units is more preferably 5 to 40 mol%, (a-1) the proportion of alicyclic dicarboxylic acid units is 80 to 95 mol%, and (a-3) fat. More preferably, the proportion of the group dicarboxylic acid unit is 5 to 20 mol%.
When the ratio of the aliphatic dicarboxylic acid unit composed of an aliphatic dicarboxylic acid having 10 or more carbon atoms is in the above range, more excellent heat resistance, fluidity, toughness, low water absorption, and There is a tendency to obtain a polyamide composition that simultaneously satisfies rigidity and the like.

In the present embodiment, (a) the dicarboxylic acid constituting the dicarboxylic acid unit is not limited to the compounds described as the dicarboxylic acid, and may be a compound equivalent to the dicarboxylic acid.
Here, the “compound equivalent to dicarboxylic acid” refers to a compound that can have the same dicarboxylic acid structure as the dicarboxylic acid structure derived from the dicarboxylic acid. Examples of such compounds include, but are not limited to, 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.
Only one trivalent or higher polyvalent carboxylic acid may be used alone, or two or more polycarboxylic acids may be used in combination.

<(B) Diamine unit>
(B) The diamine unit is not limited to the following. For example, (b-1) a diamine unit having a substituent branched from the main chain, (b-2) an aliphatic diamine unit, (b- 3) An alicyclic diamine unit, and (b-4) an aromatic diamine unit.
(B) The diamine unit preferably contains a diamine having a substituent branched from the main chain (b-1).
(B) When the diamine unit includes a diamine unit having a substituent branched from the (b-1) main chain, the polyamide composition of the present embodiment has more excellent fluidity, toughness, rigidity, and the like. At the same time, it tends to be satisfactory.
(B) The diamine unit preferably contains 50 mol% or more of the diamine unit having a substituent branched from the main chain (b-1).

[(B-1) Diamine unit having a substituent branched from the main chain]
(B-1) The “substituent branched from the main chain” in the diamine unit having a substituent branched from the main chain is not limited to the following, but for example, a methyl group, an ethyl group, n- Examples thereof include alkyl groups having 1 to 4 carbon atoms such as propyl group, isopropyl group, n-butyl group, isobutyl group, and tert-butyl group.

The diamine constituting the diamine unit having a substituent branched from the main chain (b-1) is not limited to the following. For example, 2-methylpentamethylenediamine (hereinafter referred to as “2- Methyl-1,5-diaminopentane ”), 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 2-methyloctamethylenediamine, and 2,4-dimethyloctane Examples thereof include branched saturated aliphatic diamines having 3 to 20 carbon atoms such as methylenediamine.
Among these, 2-methylpentamethylenediamine is preferable. By including such a diamine unit having a substituent branched from the main chain (b-1), the polyamide composition tends to be superior in heat resistance and rigidity.
In addition, the diamine which comprises the diamine unit which has a substituent branched from the (b-1) main chain may be used individually by 1 type, and may be used in combination of 2 or more types.

(B) The ratio (mol%) of the diamine unit having a substituent branched from the main chain in (b-1) the diamine unit is preferably 50 to 100 mol%, more preferably 60 to 100 mol%. Yes, more preferably 85 to 100 mol%, still more preferably 90 to 100 mol%, still more preferably 100 mol%.
(B) When the ratio of the diamine unit having a substituent branched from the main chain in (b-1) the diamine unit is in the above range, the polyamide composition tends to be excellent in fluidity, toughness, and rigidity. is there.

[(B-2) Aliphatic diamine unit]
The (b-2) aliphatic diamine constituting the aliphatic diamine unit (excluding the (b-1) diamine having a substituent branched from the main chain) is not limited to the following. For example, ethylene diamine, propylene diamine, tetramethylene diamine, pentamethylene diamine, hexamethylene diamine, heptamethylene diamine, octamethylene diamine, nonamethylene diamine, decamethylene diamine, undecamethylene diamine, dodecamethylene diamine, and tridecamethylene diamine C2-C20 linear saturated aliphatic diamine etc. are mentioned.

[(B-3) Alicyclic diamine unit]
The (b-3) alicyclic diamine constituting the alicyclic diamine unit (hereinafter also referred to as “alicyclic diamine”) is not limited to the following, but for example, 1,4- Examples include cyclohexanediamine, 1,3-cyclohexanediamine, and 1,3-cyclopentanediamine.

[(B-4) Aromatic diamine unit]
The aromatic diamine constituting the (b-4) aromatic diamine unit is not limited to the following as long as it is an aromatic diamine, and examples thereof include metaxylylenediamine.

Among the diamine units (b-2) to (b-4), preferably (b-2) an aliphatic diamine unit (excluding the (b-1) diamine unit) and (b-3) fat. It is a cyclic diamine unit, More preferably, it is a (b-2) aliphatic diamine unit comprised from the diamine which has a C4-C13 linear saturated aliphatic group, More preferably, it is C6-C It is (b-2) an aliphatic diamine unit composed of 10 diamines having a linear saturated aliphatic group, and more preferably (b-2) an aliphatic diamine unit composed of hexamethylenediamine.
By including such an (b-2) aliphatic diamine unit, the polyamide composition tends to be superior in heat resistance, fluidity, toughness, low water absorption, rigidity, and the like.
In addition, (b) the diamine which comprises a diamine unit 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 50 mol%, and 0 to 40 mol%, based on the entire (b) diamine unit. It is more preferable, and it is further more preferable that it is 0-30 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)>
(A) Polyamide can further contain (c) a lactam unit (c-1) and / or an aminocarboxylic acid unit (c-2).
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 be condensed (condensed).

  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. Dodecanolactam) and the like.
Among these, as the lactam, ε-caprolactam, laurolactam and the like are preferable, and ε-caprolactam is more preferable. By including the lactam unit (c-1) composed of such a lactam, the polyamide composition tends to be superior in 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- Examples include amino acids.
The aminocarboxylic acid is preferably 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. 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 ends of the polyamide (A) used in this embodiment 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 end 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.
The said monocarboxylic acid may be used individually by 1 type, and may be used in combination of 2 or more type.

The monoamine that can be used as the end-capping agent is not limited to the following as long as it has reactivity with the carboxyl group that can be present at the end of the (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.

((A) Polyamide production method)
(A) As a manufacturing method of polyamide, although not limited to the following, for example, (a) dicarboxylic acid which comprises a dicarboxylic acid unit, (b) diamine which comprises a diamine unit, and as needed It includes a step of polymerizing lactam and / or aminocarboxylic acid constituting the lactam unit (c-1) and / or aminocarboxylic acid unit (c-2) to obtain a polymer, and increases the degree of polymerization of polyamide. It is preferable to further include the step of making it. Moreover, the sealing process which seals the terminal of the obtained polymer with terminal blocker as needed may be included.

(A) As a concrete manufacturing method of polyamide, various methods are mentioned, for example so that it may illustrate below.
1) A method in which an aqueous solution of a dicarboxylic acid-diamine salt or a mixture of a dicarboxylic acid and a diamine, or a suspension of these waters is heated and polymerized while maintaining a molten state (hereinafter referred to as “hot melt polymerization method”). Say.).
2) A method of increasing the degree of polymerization of the polyamide obtained by the hot melt polymerization method while maintaining the solid state at a temperature below the melting point (hereinafter also referred to as “hot melt polymerization / solid phase polymerization method”).
3) An aqueous solution of a dicarboxylic acid-diamine salt or a mixture of dicarboxylic acid and diamine, or a suspension of these waters is heated, and the precipitated prepolymer is melted again with an extruder such as a kneader to increase the degree of polymerization. Method of raising (hereinafter also referred to as “prepolymer / extrusion polymerization method”).
4) An aqueous solution of a dicarboxylic acid-diamine salt or a mixture of a dicarboxylic acid and a diamine, or a suspension of these waters is heated, and the precipitated prepolymer is maintained in a solid state at a temperature below the melting point of the polyamide. A method for increasing the degree of polymerization (hereinafter also referred to as “prepolymer / solid phase polymerization method”).
5) A method of polymerizing a dicarboxylic acid-diamine salt or a mixture of a dicarboxylic acid and a diamine while maintaining a solid state (hereinafter also referred to as “solid phase polymerization method”).
6) A method of polymerizing using a dicarboxylic acid halide component equivalent to dicarboxylic acid and a diamine component (hereinafter also referred to as “solution method”).

(A) When manufacturing polyamide, 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 in the vicinity of the same molar amount. .
In consideration of the molar ratio of the escape amount of the diamine constituting the diamine unit (b) during the polymerization reaction in the molar ratio, (a) with respect to the molar amount 1 of the whole dicarboxylic acid constituting the dicarboxylic acid unit, (B) It is preferable that the molar amount of the whole diamine which comprises a diamine unit is 0.9-1.2, More preferably, it is 0.95-1.1, More preferably, it is 0.98-1. 05.

(A) In the polyamide production method, from the viewpoint of the fluidity of the polyamide, it is preferable to carry out the polymerization while maintaining the trans isomer ratio of the alicyclic dicarboxylic acid unit in the polyamide at 85% or less. It is more preferable to carry out the polymerization while maintaining the trans isomer ratio of the group dicarboxylic acid unit at 80% or less.
In particular, when the polymerization is performed while maintaining the trans isomer ratio of the alicyclic dicarboxylic acid unit in the polyamide at 80% or less, a polyamide having a higher color tone and tensile elongation and a high melting point tends to be obtained.

  (A) In the method for producing polyamide, it is preferable to raise the polymerization temperature or lengthen the polymerization time in order to raise the degree of polymerization and raise the melting point of the polyamide. When increasing the polymerization temperature or increasing the polymerization time, it is preferable to perform polymerization while maintaining the trans isomer ratio of the alicyclic dicarboxylic acid unit at 80% or less. Thereby, it exists in the tendency which can suppress the fall of the tensile elongation by the coloring of the (A) polyamide by heating, or heat degradation. Moreover, (A) it exists in the tendency which can suppress that the rate which the molecular weight of a polyamide raises falls remarkably.

  (A) As a method for producing polyamide, it is easy to maintain the trans isomer ratio of the alicyclic dicarboxylic acid unit in the polyamide at 85% or less, and from the viewpoint of excellent color tone of the obtained polyamide, 1) hot melt polymerization and 2) hot melt polymerization / solid phase polymerization are preferred.

(A) In the polyamide production method, the polymerization form is not particularly limited, and may be a batch type or a continuous type.
(A) The polymerization apparatus used for producing the polyamide is not particularly limited, and a known apparatus can be used. For example, an extruder type such as an autoclave type reactor, a tumbler type reactor, and a kneader. A reactor etc. are mentioned.

Hereinafter, as a method for producing (A) polyamide, specific examples of a method for producing polyamide by a batch-type hot melt polymerization method will be shown, but the method for producing (A) polyamide is not limited thereto.
First, for example, an aqueous solution containing about 40 to 60% by mass of a raw material component of polyamide (dicarboxylic acid, diamine, and, if necessary, lactam and / or aminocarboxylic acid) is heated at a temperature of 110 to 180 ° C. and about In a concentration tank operated at a pressure of 0.035 to 0.6 MPa (gauge pressure), it is concentrated to about 65 to 90% by mass to obtain a concentrated solution.
Next, the obtained concentrated solution is transferred to an autoclave, and heating is continued until the pressure in the autoclave reaches about 1.5 to 5.0 MPa (gauge pressure).
Thereafter, in the autoclave, the pressure is maintained at about 1.5 to 5.0 MPa (gauge pressure) while removing water and / or gas components, and when the temperature reaches about 250 to 350 ° C., the pressure is reduced to atmospheric pressure ( Gauge pressure is 0 MPa).
By reducing the pressure in the autoclave to atmospheric pressure and then reducing the pressure as necessary, by-product water can be effectively removed.
Thereafter, the autoclave is pressurized with an inert gas such as nitrogen, and the polyamide melt is extruded from the autoclave as a strand. By cooling and cutting the extruded strand, (A) polyamide pellets are obtained.

Further, specific examples of a method for producing a polyamide by a continuous hot melt polymerization method are shown below.
First, an aqueous solution containing about 40 to 60% by mass of a polyamide raw material component (dicarboxylic acid, diamine and, if necessary, lactam and / or aminocarboxylic acid) is about 40 to 100 ° C. in a container of a preliminary apparatus. Preheat. The preheated aqueous solution is then transferred to a concentration tank / reactor and concentrated to about 70-90% at a pressure of about 0.1-0.5 MPa (gauge pressure) and a temperature of about 200-270 ° C. obtain.
The obtained concentrated solution is discharged into a flasher maintained at a temperature of about 200 to 350 ° C.
Thereafter, the pressure in the flasher is reduced to atmospheric pressure (gauge pressure is 0 MPa). After reducing the pressure in the flasher to atmospheric pressure, the pressure is further reduced as necessary. Thereafter, the polyamide melt is extruded as a strand from the flasher. By cooling and cutting the extruded strand, (A) polyamide pellets can be obtained.

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

1) The amino terminus is a polymer terminus having an amino group (—NH ₂ group) and is derived from a raw material diamine.
The amount of the amino terminal is preferably 5 to 100 μequivalent / g, more preferably 5 to 70 μequivalent / g, and further preferably 5 to 50 μequivalent / g with respect to 1 g of (A) polyamide. Still more preferably, it is 5-30 micro equivalent / g, More preferably, it is 5-20 micro equivalent / g.
When the amount of the amino terminal is in the above range, the polyamide composition tends to have more excellent whiteness, reflow resistance, heat discoloration resistance, light discoloration resistance, hydrolysis resistance, and heat retention stability. The amount of the amino terminus can be measured by neutralization titration.

2) The carboxylic acid terminal is a polymer terminal having a carboxyl group (—COOH group) and is derived from the raw material dicarboxylic acid.
The amount of the carboxylic acid terminal is preferably 5 to 100 μequivalent / g, more preferably 5 to 70 μequivalent / g, and further preferably 5 to 50 μequivalent / g with respect to 1 g of (A) polyamide. Even more preferably, it is 5-30 μeq / g, and even more preferably 5-20 μeq / g. When the amount of the carboxylic acid terminal is within the above range, the polyamide composition tends to be more excellent in whiteness, reflow resistance, heat discoloration resistance, and light discoloration resistance. The amount of the carboxylic acid terminal can be measured by neutralization titration.

  The total amount of the amino-terminated amount and the carboxylic acid-terminated amount is preferably 10 to 200 μequivalent / g, more preferably 10 to 150 μequivalent / g, more preferably 1 A of polyamide (A). Is 10-100 μeq / g, even more preferably 15-50 μeq / g, and even more preferably 20-40 μeq / g. When the total amount of the amino end and the carboxylic end is within the above range, the polyamide composition tends to be more excellent in whiteness, reflow resistance, heat discoloration resistance, and light discoloration resistance.

3) The cyclic amino terminus is a polymer terminus having a cyclic amino group (a group represented by the following (formula 1)).
In the following (Formula 1), R represents a substituent bonded to the carbon constituting the piperidine ring. Specific examples of R are not particularly limited, and examples thereof include a hydrogen atom, a methyl group, an ethyl group, and a t-butyl group.
Further, for example, even when piperidine cyclized by a deammonia reaction of a diamine having a pentamethylenediamine skeleton as a raw material is bonded to the polymer terminal, it becomes the terminal of this cyclic amino group. These structures may be taken when a monomer having a pentamethylenediamine skeleton is included.

3) The amount of the cyclic amino terminal is preferably 30 μe equivalent / g or more and 65 μe equivalent / g or less, more preferably 30 μe equivalent / g or more and 60 μe equivalent / g or less with respect to 1 g of (A) polyamide. Preferably they are 35 microequivalent / g or more and 55 microequivalent / g or less.
When the amount of the cyclic amino terminus is in the above range, the polyamide composition of the present embodiment tends to be more excellent in toughness, hydrolysis resistance, and processability.

  The amount of the cyclic amino terminus can be measured using 1H-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.

The cyclic amino terminus can be generated by a dehydration reaction between a cyclic amine and a carboxylic acid terminus, and can also be generated by a deammonia reaction within the polymer molecule. It can also be produced by adding a diamine having a pentamethylenediamine skeleton, which is a raw material of polyamide, to cyclize by deammonia reaction.
In the present embodiment, 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 (A) the cyclic amino terminal of the polyamide a constant amount, it is preferable to promote the formation of a cyclic amine. Therefore, the reaction temperature for the polymerization of 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, the polymerization temperature, the time for the above reaction temperature of 300 ° C. or more during the polymerization step, the amount of amine added to form a cyclic structure, and the like are controlled appropriately. A method is mentioned.

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

  5) The other terminal is a polymer terminal not classified in the above 1) to 4), for example, a terminal generated by deammonia reaction at the amino terminal, a terminal generated by decarboxylation from the carboxylic acid terminal, etc. Is mentioned.

<Characteristics of (A) polyamide>
(A) The sulfuric acid relative viscosity ηr at 25 ° C. can be used as an index of the molecular weight of the polyamide. The larger the ηr, the higher the molecular weight of the (A) polyamide, and the smaller the ηr, the lower the molecular weight of the (A) polyamide.
(A) 25 degreeC sulfuric acid relative viscosity (eta) of a polyamide becomes like this. Preferably it is 1.5-7.0, More preferably, it is 1.7-6.0, More preferably, it is 1.9-5.5. is there.
(A) When the relative viscosity ηr of sulfuric acid at 25 ° C. of the polyamide is in the above range, it tends to be a polyamide composition that is excellent in mechanical properties such as toughness and rigidity, and moldability. The sulfuric acid relative viscosity ηr at 25 ° C. can be measured under a condition of 1% in 98% sulfuric acid according to JIS-K6920. More specifically, it can be measured by the method described in the following examples.

(A) Melting | fusing point Tm2 of polyamide becomes like this. Preferably it is 270 degreeC or more, More preferably, it is 275 degreeC or more, More preferably, it is 280 degreeC or more.
The melting point Tm2 of the (A) polyamide is preferably 350 ° C. or lower, more preferably 340 ° C. or lower, still more preferably 335 ° C. or lower, and still more preferably 330 ° C. or lower.
(A) When the polyamide has a melting point Tm2 of 270 ° C. or higher, a polyamide composition having superior heat resistance tends to be obtained.
Moreover, when (A) polyamide melting | fusing point Tm2 is 350 degrees C or less, it exists in the tendency which can suppress the thermal decomposition etc. of (A) polyamide in melt processing, such as extrusion and shaping | molding, more.
(A) Melting | fusing point Tm2 of polyamide can be measured according to JIS-K7121 by the method as described in the below-mentioned Example.

(A) The heat of fusion ΔH of the polyamide is preferably 10 J / g or more, more preferably 14 J / g or more, still more preferably 18 J / g or more, and even more preferably 20 J / g or more. Moreover, the upper limit of the heat of fusion ΔH is not particularly limited and is preferably as high as possible.
(A) When the heat of fusion ΔH of polyamide is 10 J / g or more, the heat resistance of the polyamide composition tends to be further improved.
(A) The heat of fusion ΔH of polyamide can be measured in accordance with JIS-K7121 by the method described in the examples below.
Examples of the measuring device for the melting point Tm2 and the heat of fusion ΔH of (A) polyamide described above include Diamond-DSC manufactured by PERKIN-ELMER.

(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.
Moreover, the glass transition temperature of (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 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 of (A) polyamide is 170 ° C. or lower, a molded product having a good appearance tends to be obtained.
(A) The glass transition temperature of polyamide can be measured according to JIS-K7121, as described in the following examples.
Examples of the glass transition temperature measuring device include Diamond-DSC manufactured by PERKIN-ELMER.

((B) inorganic filler)
The polyamide composition of this embodiment contains (B) an inorganic filler.

(B) As an inorganic filler, although not limited to the following, for example, glass fiber, carbon fiber, calcium silicate fiber, potassium titanate fiber, aluminum borate fiber, glass flake, talc, kaolin, mica , Hydrotalcite, calcium carbonate, zinc carbonate, zinc oxide, calcium monohydrogen phosphate, wollastonite, silica, zeolite, alumina, boehmite, aluminum hydroxide, silicon oxide, magnesium oxide, calcium silicate, sodium aluminosilicate, Examples include magnesium silicate, ketjen black, acetylene black, furnace black, carbon nanotube, graphite, brass, copper, silver, aluminum, nickel, iron, calcium fluoride, montmorillonite, swellable fluoromica, and apatite. It is.
Among these, the inorganic filler (B) is preferably at least one selected from the group consisting of glass fiber, potassium titanate fiber, talc, wollastonite, kaolin, mica, calcium carbonate, and clay, and wollastonite. Calcium carbonate is more preferable.
(B) As an inorganic filler, since the Fe concentration in a composition shall be 5-200 ppm, the inorganic filler with few Fe content is preferable. Examples of the inorganic filler having a low Fe content include the use of an inorganic filler having a low Fe content and the use of an inorganic filler from which Fe present as impurities is mechanically removed.
(B) The average particle size of the inorganic filler is preferably 0.01 to 30 μm from the viewpoints of whiteness, mechanical strength, heat aging resistance, surface appearance and extrusion processability of the polyamide resin composition of the present embodiment. 0.5-20 micrometers is more preferable, 1-15 micrometers is still more preferable, 2-10 micrometers is still more preferable, 2-6 micrometers is still more preferable. (B) By setting the average particle size of the inorganic filler to 30 μm or less, a polyamide resin composition excellent in mechanical strength, heat aging resistance, and surface appearance can be obtained, and (B) the average particle size of the inorganic filler When the thickness is 0.01 μm or more, and further 0.01 μm or more, the heat aging resistance, cost, and balance between the handling surface of the powder and the physical properties are improved.
In addition, among (B) inorganic fillers, the number average fiber diameter is defined as the average particle diameter for an inorganic filler having a needle shape such as wollastonite. Furthermore, when the cross section is not a circle, the maximum value of the length is taken as the fiber diameter. Regarding the aspect ratio (L / D) of the weight average fiber length (L) and the number average fiber diameter (D) of the inorganic filler having an acicular shape, whiteness, mechanical strength, heat aging resistance, surface appearance And from a viewpoint of extrudability, 1-30 are preferable, 2-30 are more preferable, 3-25 are more preferable, 5-20 are still more preferable, 5-15 are especially preferable.
As a specific method for measuring the average particle diameter, a scanning electron microscope (SEM) (manufactured by JEOL Ltd., JSM-6700F) was used, and (B) an inorganic filler image was taken at a magnification of 1000 to 50000 times. Then, the particle size is measured from arbitrarily selected 500 inorganic fillers. (B) When the inorganic filler is needle-shaped and the cross section is a circle, the needle diameter is the particle diameter, and when the cross-section is not a circle, the maximum length of the needle-shaped body is the needle diameter. And this is regarded as the particle size.

(B) The inorganic filler may contain a nucleating agent having a nucleating effect from the viewpoint of releasability.
The above-mentioned “nucleating agent” is effective to increase the crystallization temperature measured by thermal differential scanning analysis (DSC) by addition, and to improve the spherulite of the obtained molded product or make the size uniform. Means the substance

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. Can be mentioned.
A nucleating agent may be used individually by 1 type, and may combine 2 or more types.
Among the nucleating agents, talc, boron nitride, and carbon black are preferable from the viewpoint of the nucleating agent effect, more preferably talc and boron nitride, and further 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, still more preferably 0.8. 5 to 3 μm.
When the number average particle diameter of the nucleating agent is within the above range, the nucleating effect tends to be further improved.
The number average particle size of the nucleating agent is such that, for example, 100 or more nucleating agents are obtained from the insoluble components obtained by dissolving the molded article of the polyamide composition of the present embodiment with a solvent in which polyamide such as formic acid is soluble. An agent can be selected arbitrarily, and can be obtained by observing with an optical microscope or a scanning electron microscope.
(B) An inorganic filler may be used individually by 1 type, and may be used in combination of 2 or more type. When two or more types are combined, a combination having different shapes is preferable, and a combination of an inorganic filler having a needle shape and an inorganic filler having a plate shape is more preferable.

<Treatment with surface treatment agent>
(B) The inorganic filler may be subjected to a surface treatment with a silane coupling agent or the like.
The silane coupling agent is not limited to the following examples. For example, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-amino Examples include aminosilanes such as propylmethyldimethoxysilane; mercaptosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane; epoxysilanes; vinylsilanes.
In particular, at least one selected from the above-listed components is preferable, and aminosilanes are more preferable.
The surface treatment agent may be previously treated on the surface of the (B) inorganic filler, or may be added when (A) the polyamide and (B) the inorganic filler are mixed. The amount of the surface treatment agent is preferably in the range of 0.05 parts by mass to 1.5 parts by mass with respect to 100 parts by mass of the (B) inorganic filler.

The content of the inorganic filler (B) in the polyamide composition of the present embodiment is preferably 1 to 50% by mass, more preferably 1 to 40% by mass with respect to 100% by mass of the polyamide composition. More preferably, it is 5-30 mass%, More preferably, it is 10-30 mass%, Most preferably, it is 15-25 mass%.
(B) Content of inorganic filler determines content based on Fe content contained in (B) inorganic filler in order to make Fe concentration in the polyamide composition of this embodiment into 5-200 ppm. It is important to.
(B) When content of an inorganic filler exists in said range, it exists in the tendency for the mechanical strength of the polyamide composition of this embodiment, molding process stability, fluidity | liquidity, and whiteness to be more excellent.
The content of the nucleating agent is preferably 0.001 to 15% by mass, more preferably 0.001 to 5% by mass, and further preferably 100% by mass of the polyamide composition of the present embodiment. Is 0.001 to 3 mass%, and more preferably 0.5 to 2.5 mass%.
By making the content of the nucleating agent 0.001% by mass or more with respect to 100% by mass of the polyamide composition, the molding process stability of the polyamide composition of the present embodiment is improved, and the content of the nucleating agent is also included. By setting the amount to 15% by mass or less, a polyamide composition excellent in mechanical strength, whiteness, heat aging resistance, heat discoloration resistance and light resistance can be obtained.

((C) Metal hydroxide)
The polyamide composition of this embodiment contains (C) a metal hydroxide and / or (D) a metal oxide described later.
(C) The metal hydroxide is preferably represented by the 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.

The (C) metal hydroxide that can be contained in the polyamide composition of the present embodiment is not limited to the following, but for example, sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, water Examples thereof include aluminum oxide, zinc hydroxide, and manganese hydroxide. Among these, from the viewpoint that the polyamide composition of the present embodiment 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.
(C) A metal hydroxide may be used individually by 1 type, and may use 2 or more types together.

Further, these (C) metal oxides may be subjected to surface treatment in order to improve adhesion and 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

((D) Metal oxide)
The metal oxide has the general formula MxOy (M represents a metal element, x and y are 0 <x ≦ 5 and 0 <y ≦ 5, respectively, and satisfy the multivalent value of M × x = 2 × y. It is preferably represented by a number.
In the polyamide composition of this embodiment, it is preferable to use (D) a metal oxide having a specific element as the metal element 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, an alkaline earth metal is preferable.

The metal oxide (D) that can be contained in the polyamide composition of the present embodiment is not limited to the following, but examples thereof include calcium oxide, magnesium oxide, aluminum oxide, zinc oxide, manganese oxide, and tin oxide. Is mentioned. Among these, from the viewpoint that the polyamide composition of the present embodiment is excellent in heat discoloration resistance, extrusion processing stability, and molding processing stability, calcium oxide and magnesium oxide are preferable, and calcium oxide is more preferable.
The (D) metal oxide may be used alone or as a mixture of two or more.

Moreover, you may use these metal oxides which surface-treated 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 (C) metal hydroxide and / or (D) metal oxide in the polyamide composition of the present embodiment is preferably particulate, and the average particle diameter is preferably 0.05 to 10 μm, more Preferably it is 0.1-5 micrometers. When the average particle diameter of (C) the metal hydroxide and / or (D) the metal oxide is within the above range, the polyamide composition has the effects of reflow resistance and heat discoloration resistance.

Further, the mass ratio of the particles of 30 μm or more to the whole particles of (C) metal hydroxide and / or (D) metal oxide is preferably 1% by mass or less, more preferably 0.1% by mass or less. is there.
(C) By making the mass ratio of the particle | grains 30 micrometers or more with respect to the whole metal hydroxide and / or the (D) metal hydroxide into the said range, in a polyamide composition, the effect of reflow resistance and heat-resistant discoloration is effective. can get.

  The purity of (C) metal hydroxide and / or (D) metal oxide in the polyamide composition is preferably 99% or more, more preferably 99.5% or more, and further preferably 99.9%. That's it. Due to the high purity of (C) metal hydroxide and / or (D) metal oxide, the whiteness, reflow resistance, and light discoloration resistance of the polyamide composition tend to be excellent.

The content of the above-mentioned (C) metal hydroxide and / or (D) metal oxide is 0.1 to 20% by mass, preferably 0.1 to 10% by mass with respect to 100% by mass of the polyamide composition. %, More preferably 0.3 to 5% by mass, still more preferably 0.3 to 2% by mass, still more preferably 0.5 to 1.5% by mass, and still more preferably 0.5 to 1.0% by mass.
When the content of (C) metal hydroxide and / or (D) metal oxide is within the above range, the polyamide composition is more excellent in heat discoloration resistance, extrusion stability, and molding stability.

The polyamide composition of this embodiment may further contain a metal compound other than the above-described (C) metal hydroxide and (D) metal oxide from the viewpoints of whiteness and heat discoloration.
Examples of the metal compound other than (C) metal hydroxide and (D) metal oxide include, but are not limited to, metal carbonates and metal halides.
Although it does not specifically limit as a metal element contained in (C) metal hydroxide and metal compounds other than (D) metal oxide, 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.

  (C) Metal hydroxide and / or (D) Metal oxide may be added during polymerization of (A) polyamide. (A) Polyamide composition mixed with (A) polyamide after polymerization of polyamide It is preferable to add at the time of manufacture. By adding it during the production of the polyamide composition, it is possible to reduce the thermal history, to suppress the decomposition of (C) metal hydroxide and / or (D) metal oxide, etc. A polyamide composition having excellent reflow properties, heat discoloration resistance, extrusion processability, and molding process stability can be obtained.

((E) Phosphorus compound)
The polyamide composition of the present embodiment may further contain (E) a phosphorus compound.
Examples of (E) 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, (E) phosphorus compound may be used individually by 1 type, and may be used in combination of 2 or more type.

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

  More preferable (E) 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 containing such a phosphorus compound (E), the polyamide composition of the present embodiment tends to be excellent in whiteness, heat discoloration resistance, heat reflow resistance, and light discoloration resistance.

More preferable (E) phosphorus compounds are 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 (E) a 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 the (E) phosphorus compound is not particularly limited, and examples thereof include monosodium phosphate, disodium phosphate, trisodium phosphate, monocalcium phosphate, dicalcium phosphate, phosphorus Tricalcium acid, 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 containing such a phosphorus compound (E), the polyamide composition of this embodiment tends to be more excellent in whiteness, heat discoloration resistance, light discoloration resistance and extrusion processability.

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

(E) Phosphorus compound metal 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 The species is preferably the same as the metal species of (C) metal hydroxide and / or (D) metal oxide.
In particular, the metal species of the phosphorus compound (E) is preferably an alkaline earth metal.
(E) The phosphorus compound is selected from the group consisting of metal salts, intramolecular condensates of metal salts, and intermolecular condensates of metal salts, and (E) the metal species of the phosphorus compound is (C) metal When the metal species of the hydroxide and / or the (D) metal oxide are the same, a thermal stability is enhanced, and a polyamide composition excellent in extrusion processability and molding process stability can be obtained. Furthermore, by using an alkaline earth metal as the metal species of the (E) phosphorus compound, a more excellent effect can be obtained in the above characteristics.

(E) Phosphorus compounds 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.
(E) By using a metal salt that does not contain an anhydrous salt or hydrate as the phosphorus compound, the amount of water generated during processing can be suppressed, and a decrease in the molecular weight and gas generation of polyamide can be suppressed. . (E) Polyamide composition having excellent whiteness, reflow resistance, heat discoloration resistance, extrusion processability, and molding process stability by using anhydrous salts and metal salts that do not contain hydrates as phosphorus compounds You can get things.

(E) Phosphorus compounds 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.
(E) By using a metal salt with low deliquescence as a phosphorus compound, processing is reduced when mixing each raw material component during the 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.

(E) The phosphorus compound may include an organic phosphorus compound.
Examples of the organophosphorus compounds include, but are not limited to, pentaerythritol phosphite compounds, trioctyl phosphites, trilauryl phosphites, tridecyl phosphites, octyl diphenyl phosphites, trisisodecyls. Phosphite, 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′-butyryl Den-bis (3-methyl-6-tert-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-hydroxy) Phenyl) butanediphosphite, tetra (tridecyl) -4,4′-butylidenebis (3-methyl-6-tert-butylphenyl) diphosphite, tetra (C1-C15 mixed alkyl) -4,4′-isopropylidenediphenyldi Phosphite, tris (mono, dimixed nonylphenyl) phosphite, 9,10-di-hydride Rho-9-oxa-9-oxa-10-phosphaphenanthrene-10-oxide, tris (3,5-di-t-butyl-4-hydroxyphenyl) phosphite, hydrogenated-4,4′- Isopropylidene diphenyl polyphosphite, bis (octylphenyl) -bis (4,4′-butylidenebis (3-methyl-6-tert-butylphenyl)), 1,6-hexanol diphosphite, hexatridecyl-1, 1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) diphosphite, tris (4,4′-isopropylidenebis (2-t-butylphenyl)) phosphite, tris (1,3 -Stearoyloxyisopropyl) phosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite, 2, -Methylenebis (3-methyl-4,6-di-t-butylphenyl) 2-ethylhexyl phosphite, tetrakis (2,4-di-t-butyl-5-methylphenyl) -4,4'-biphenylenediphos Phyto, and tetrakis (2,4-di-t-butylphenyl) -4,4′-biphenylene diphosphite.
The organic phosphorus compound may be used alone or in combination of two or more.

  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, -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- Tyl-4-methylphenyl-stearyl-pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl-cyclohexyl-pentaerythritol diphosphite, 2,6-di-t-butyl-4- Methylphenyl-benzyl-pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl-ethylcellosolve-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-nonyl Phenyl-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, 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-pentae Rithritol diphosphite, bis (2,6-di-t-amyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-octyl-4-methylphenyl) pentaerythritol diphosphite Examples include phosphites and bis (2,4-dicumylphenyl) pentaerythritol diphosphites.
The pentaerythritol 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.

The content of the (E) phosphorus compound in the polyamide composition of the present embodiment is preferably 0.1 to 20.0% by mass with respect to 100% by mass of the polyamide composition. More 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 0.5 to 2.0% by mass, particularly preferably 0.5 to 1.5% by mass.
The (E) phosphorus compound in the polyamide composition of the present embodiment preferably contains more than (C) metal hydroxide and / or (D) metal oxide.
(E) When the content of the phosphorus compound is within the above range, the polyamide composition of this embodiment tends to be excellent in whiteness, reflow resistance, heat discoloration resistance, extrusion stability, and molding stability. It is in.

In the polyamide composition of the present embodiment, the phosphorus compound (E) is preferably contained in an amount such that the phosphorus element concentration is 1,400 to 20,000 ppm relative to the polyamide composition. More preferably, it is contained in an amount of 20,000 ppm, more preferably 3,000 to 20,000 ppm, and even more preferably 3,000 to 10,000 ppm. More preferably, it is contained in an amount of 4,000 to 6,000 ppm.
When the phosphorus element concentration derived from the phosphorus compound (E) 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.
In addition, the phosphorus element density | concentration derived from the (E) phosphorus type compound contained in a polyamide composition can be measured with the measuring method of the metal element density | concentration described in the Example mentioned later.

  (E) Phosphorus compound may be added during polymerization of (A) polyamide, but after (A) polyamide is polymerized, (C) metal hydroxide and / or (D) metal oxide described above, It is preferable to add at the time of manufacture of the polyamide composition to be mixed. By adding the (E) phosphorus compound during the production of the polyamide composition, the thermal history of the (E) phosphorus compound can be reduced, and the decomposition of the (E) phosphorus compound can be suppressed, A polyamide composition having excellent whiteness, reflow resistance, heat discoloration resistance, extrusion processability, and molding process stability can be obtained.

In the polyamide composition of the present embodiment, (B) an inorganic filler, (C) a metal hydroxide and / or (D) a metal oxide, and (E) a phosphorus compound, if necessary, (F) Arbitrary components such as titanium oxide are included in an amount such that the total value of Fe concentrations derived from these components is 5 to 200 ppm, preferably 10 to 180 ppm, and preferably 10 to 160 ppm. It is more preferable that it is contained in an amount of 10 to 140 ppm. When the Fe concentration contained in the polyamide composition is in the above range, the polyamide composition is excellent in molding process stability, whiteness, heat aging resistance, and heat discoloration.
In addition, the Fe concentration contained in the polyamide composition can be measured by a method for measuring a metal concentration described in Examples described later.

In the polyamide composition of the present embodiment, (B) an inorganic filler, (C) a metal hydroxide and / or (D) a metal oxide, and (E) an optional component such as a phosphorus compound, if necessary, It is preferable that the total value of Ca concentration derived from these components is included in an amount of 0 to 60000 ppm, more preferably included in an amount of 0 to 45000 ppm, and further included in an amount of 500 to 45000 ppm. It is particularly preferable that it is contained in an amount of 20000 to 45000 ppm. When the Ca concentration contained in the polyamide composition is in the above range, the polyamide composition is excellent in molding process stability, whiteness, heat aging resistance, and heat discoloration.
In addition, Ca concentration contained in a polyamide composition can be measured by the measuring method of the metal concentration described in the Example mentioned later.

In the polyamide composition of the present embodiment, (B) an inorganic filler, (C) a metal hydroxide and / or (D) a metal oxide, and (E) a phosphorus compound, if necessary, (F) Arbitrary components such as titanium oxide are preferably included in an amount such that the total Mg concentration derived from these components is 0 to 12000 ppm, more preferably 0 to 8000 ppm, and more preferably 500 to 8000 ppm. More preferably, it is contained in an amount of 500 to 3000 ppm. When the Mg concentration contained in the polyamide composition is in the above range, the polyamide composition is excellent in molding process stability, whiteness, and heat discoloration resistance.
The Mg concentration contained in the polyamide composition can be measured by a method for measuring a metal element concentration described in Examples described later.
In the polyamide composition of the present embodiment, the ratio of Ca content to Fe content (Ca / Fe) is preferably 100 or more, more preferably 200 to 1000, and more preferably 300 to 800. More preferably. The ratio of the Ca content to the Fe content (Ca / Fe) in the polyamide composition is in the above range, so that the polyamide composition has improved molding process stability, whiteness, heat aging resistance, and heat discoloration. It tends to be even better.
The metal element concentration can be measured by the method for measuring the metal element concentration described in the examples.

((F) Titanium oxide)
The polyamide composition of this embodiment may further contain (F) titanium oxide.
Examples of (F) titanium oxide include, but are not limited to, titanium oxide (TiO), dititanium trioxide (Ti ₂ O ₃ ), and titanium dioxide (TiO ₂ ).
Of these, titanium dioxide is preferable.

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

(F) The titanium oxide is preferably in the form of particles, and the number average particle diameter of the (F) 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.
(F) 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.
(F) When the number average particle diameter of titanium oxide is 0.8 μm or less, the mechanical strength of the polyamide composition tends to be further improved.
(F) 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, and the organic matter contained in the polyamide composition is incinerated. By measuring the particle diameter, it is possible to determine the number average particle diameter of (F) titanium oxide.

  (F) 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.

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

(F) The titanium oxide particles 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 the (F) titanium oxide particles is more preferably coated with polyols and organosilicon compounds. From the viewpoint of reducing the generated gas, it is more preferable to coat using an organosilicon compound.

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

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

(Phenolic antioxidant and / or amine antioxidant)
The polyamide composition of the present embodiment may contain a phenol-based antioxidant and / or an amine-based antioxidant from the viewpoint of thermal stability.

  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, N, N′-hexane-1,6-diylbis [3- (3,5-di-t-butyl-4-hydroxy). Phenylpropionamide), 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-tert-butyl-4-hydroxy-5-methylphenyl) propynyloxy] -1,1-dimethylethyl} -2,4,8,10-tetraoxapyro [5,5] undeca 3,5-di-t-butyl-4-hydroxybenzylphosphonate-diethyl ester, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl ) 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-hydroxyphenylpropion). Amide)] 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 of the present embodiment is preferably 0 to 1% by mass, more preferably 0.01 to 1% by mass with respect to 100% by mass of the polyamide composition. Yes, more preferably 0.1 to 1% by mass.
When the content of the phenolic antioxidant is within the above range, the polyamide composition of the present embodiment 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.
In the present embodiment, 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 of the present embodiment is preferably 0 to 1% by mass, more preferably 0.01 to 1% by mass with respect to 100% by mass of the polyamide composition. Yes, more preferably 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.

(Amine light stabilizer)
The polyamide composition of this embodiment may further contain an amine light stabilizer from the viewpoint of light stability.

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.
The amine light stabilizer may be used alone or in combination of two or more.

Examples of the amine light stabilizer 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-benzene Dicarboxyamide 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 of the present embodiment is preferably 0 to 2% by mass, more preferably 0.01 to 2% by mass with respect to 100% by mass of the polyamide composition. Yes, more preferably 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.

(Silicone compound)
The polyamide composition of this embodiment may contain a silicone compound from the viewpoint of releasability.

  Examples of the silicone compound include, but are not limited to, epoxy-modified reactive silicone oil, amino-modified silicone oil, and carboxy-modified silicone oil.

  The content of the silicone compound in the polyamide composition of the present embodiment is preferably 0.1 to 1% by mass, more preferably 0.1 to 0.8% by mass with respect to 100% by mass of the polyamide composition. More preferably, it is 0.2-0.6 mass%.

(Other ingredients)
In addition to the above-described components, the polyamide composition of this embodiment 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. , Plasticizer, copper compound, alkali metal halide compound, antioxidant, stabilizer, UV absorber, antistatic agent, fluidity improver, filler, reinforcing agent, spreading agent, nucleating agent, rubber, 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 embodiment is not particularly limited, and the (A) polyamide, (B) inorganic filler, (C) metal hydroxide and / or (D) metal oxide, and further necessary. Each raw material containing (E) phosphorus compound, (F) titanium oxide, phenolic antioxidant and / or amine antioxidant, amine light stabilizer, nucleating agent, other components, etc. A method of mixing the components can be used.

  When (F) titanium oxide is contained in the polyamide composition of the present embodiment, the mixing method of (A) polyamide and (F) titanium oxide is not limited to the following. For example, (A) ) Mixing polyamide and the like with (F) titanium oxide using a tumbler, Henschel mixer, etc., supplying the resulting mixture to a melt kneader, kneading, or using a single or twin screw extruder (A) The method etc. which mix | blend (F) titanium oxide from a side feeder to the polyamide etc. are mentioned.

The same method can also be used when (C) a metal hydroxide and / or (D) a metal oxide, (E) a phosphorus compound, (A) polyamide or the like and (C) a metal hydroxide. And / or (D) a metal oxide and (E) a phosphorus compound are mixed, and the resulting mixture is supplied to a melt kneader and kneaded, or in a molten state with a single or twin screw extruder. (A) A method of blending (C) a metal hydroxide and / or (D) a metal oxide, (E) a phosphorus-based compound from the side feeder into the polyamide (A).
As a mixing method of (C) metal hydroxide and / or (D) metal oxide and (E) phosphorus compound, a method of blending from a side feeder is preferable. 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 (B) inorganic filler, (A) polyamide etc. and (B) 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 (B) 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 25 ° C. sulfuric acid relative viscosity ηr, the melting point Tm2, the heat of fusion ΔH, and the glass transition temperature Tg of the polyamide composition of the present embodiment can be measured by the same method as that for the polyamide (A). Specifically, it can measure by the method as described in the Example mentioned later.
Moreover, when the measured value in a polyamide composition exists in the range similar to a preferable range as a measured value of the said polyamide, the polyamide composition excellent in heat resistance, a moldability, and chemical resistance can be obtained.

The crystallization peak temperature Tc (° C.) obtained when the polyamide composition of the present embodiment is cooled at 100 ° C./min is preferably 240 to 290 ° C.
The crystallization peak temperature Tc (° C.) of the polyamide composition is more preferably 245 ° C. or more, further preferably 250 ° C. or more, still more preferably 255 ° C. or more, and still more preferably 260 ° C. or more. is there. The crystallization peak temperature Tc (° C.) of the polyamide composition is more preferably 280 ° C. or less, more preferably 275 ° C. or less, and further preferably 270 ° C. or less.
When the crystallization peak temperature Tc (° C.) of the polyamide composition is 240 ° C. or higher, a polyamide composition having excellent releasability at the time of molding can be obtained. In addition, since the crystallization peak temperature Tc (° C.) of the polyamide composition is 290 ° C. or less, the gate seal at the time of molding does not become too fast, and the polyamide composition can satisfactorily mold fine parts such as thin molded products. Can be obtained.
In the present embodiment, the melting point crystallization peak temperature Tc of the polyamide composition can be measured in accordance with JIS-K7121 by the method described in Examples described later.
Examples of the measuring device for the crystallization peak temperature Tc include Diamond-DSC manufactured by PERKIN-ELMER.

The polyamide composition of the present embodiment preferably has a difference (Tc−Tg) between the crystallization peak temperature Tc (° C.) obtained when cooled at 100 ° C./min and the glass transition temperature Tg is 90 ° C. or higher. More preferably, it is 95 ° C. or higher, more preferably 100 ° C. or higher, still more preferably 105 ° C. or higher, and still more preferably 110 ° C. or higher.
As the difference (Tc−Tg) between the crystallization peak Tc (° C.) obtained when the polyamide composition of the present embodiment is cooled at 100 ° C./min and the glass transition temperature Tg is larger, the temperature range capable of crystallization is wider. , Which means that it is easy to crystallize sufficiently in the mold.
The polyamide composition in which the difference (Tc−Tg) between the crystallization peak temperature Tc (° C.) obtained when the polyamide composition of the present embodiment is cooled at 100 ° C./min and the glass transition temperature Tg is 90 ° C. or more. Is excellent in releasability during molding. Although the upper limit of the difference (Tc−Tg) between the crystallization peak temperature Tc (° C.) obtained when the polyamide composition of the present embodiment is cooled at 100 ° C./min and the glass transition temperature Tg is not particularly limited, It is preferable that it is 300 degrees C or less.

〔Molding〕
The molded product of this embodiment contains the above-mentioned polyamide composition.
The molded product of this embodiment is excellent in reflow resistance, heat discoloration resistance, and light discoloration resistance, and can be suitably used for a reflector or the like.
The molded product of this embodiment can be obtained, for example, by molding the above-described polyamide composition by a known molding method.
The known molding method is not limited to the following, for example, press molding, injection molding, gas assist injection molding, welding molding, extrusion molding, blow molding, film molding, hollow molding, multilayer molding, and Commonly known plastic molding methods such as melt spinning can be mentioned.

  By including the above-mentioned polyamide composition, the molded product of this embodiment is excellent in heat resistance, moldability, mechanical strength, and low water absorption. Therefore, the above-mentioned polyamide composition can be suitably used as various parts materials for automobiles, electric and electronic use, industrial materials, daily use and household goods, and also suitably used for extrusion applications. be able to.

The molded product of this embodiment is preferably a metal halide lamp type light resistance tester having a reflectance retention of 95% or more after being exposed for 1000 hours at a position where the illuminance is 10 mW / cm ² at 100 ° C. The reflectance retention is more preferably 98% or more, and further preferably 99% or more.
In order to make the reflectance retention rate 95% or more, it is effective to contain the (E) phosphorus compound in the above-mentioned polyamide composition.
Moreover, the said reflectance retention of a molded article can be measured by the method described in the Example mentioned later.

The molded product of this embodiment can be used as various component materials.
Examples of the automotive parts include, but are not limited to, intake system parts, cooling system parts, fuel system parts, interior parts, exterior parts, and electrical parts.

  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 use, it is not limited to the following. For example, connectors, switches, relays, printed wiring boards, electronic component housings, outlets, noise filters, coil bobbins, LED reflectors, LED reflectors, etc. 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 and household items 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 product containing the polyamide composition of the present embodiment can be suitably used as a reflector.
In the reflector, the (A) polyamide, the (C) metal hydroxide and / or (D) metal oxide, and (E) a phosphorus compound are used in combination, thereby reflecting by heat. The decrease in rate can be effectively suppressed.
About the said reflectance, it can measure by the method described in the Example mentioned later, and in the reflector containing the polyamide composition of this embodiment, the fall of a reflectance can be suppressed effectively by the combination mentioned above. Has been verified in an example described later.

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

〔raw materials〕
((A) Polyamide)
The polyamide (A) used in the examples and comparative examples was produced using the following (a) and (b) as appropriate.
<(A) Dicarboxylic acid>
(A-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))
(A-2) Terephthalic acid (Wako Pure Chemical Industries, Ltd.)
<(B) Diamine>
(B-1) 2-methylpentamethylenediamine (2MC5DA) (manufactured by Tokyo Chemical Industry)
(B-2) 1,9-nonamethylenediamine (C9DA) (manufactured by Aldrich)
(B-3) 2-Methyloctamethylenediamine (2MC9DA) (produced with reference to the production method described in JP-A No. 05-17413)

((B) inorganic filler)
(B-1) Wollastonite NYCO Product Name ASPECT-4000 Number average fiber diameter (average particle diameter) 10.0 μm, weight average fiber length 112 μm, aspect ratio 11.2
(B-2) Wollastonite Made by NYCO Product name Nyglos8 Number average fiber diameter (average particle diameter) 8.0 μm, weight average fiber length 136 μm, aspect ratio 17

((D) Metal oxide)
(D-1) Calcium oxide purity 99.9% (Wako Pure Chemical Industries, Ltd.)
(D-2) Magnesium oxide Wako first grade (Wako Pure Chemical Industries, Ltd.)

((E) Phosphorus compound)
(E-1) Calcium hypophosphite (manufactured by Wako Pure Chemical Industries, Ltd., decomposition start temperature 340 ° C.)

((F) Titanium oxide)
(F-1) 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 (F) titanium oxide was measured as follows by an electron micrograph.
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 (F) titanium oxide was calculated | required by measuring these particle diameters.

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

(Silicone compound)
Epoxy-modified reactive silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KF-105, viscosity (25 ° C.) 15 mm ² / s, functional group equivalent = 490 g / mol)

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

[Method of identifying dicarboxylic acid unit in polyamide]
[Calculation of mol% of alicyclic dicarboxylic acid unit (a-1)]
The mol% of the alicyclic dicarboxylic acid unit (a-1) was obtained by calculation using the following formula.
Formula: mol% of alicyclic dicarboxylic acid unit (a-1) = (mol number of alicyclic dicarboxylic acid added as raw material monomer / mol number of all dicarboxylic acids added as raw material monomer) × 100

[Method for measuring physical properties]
(1) Melting point Tm2 (° C) of polyamide, heat of fusion ΔH (J / g), crystallization peak temperature Tc (° C)
In accordance with JIS-K7121, the melting point Tm2 (° C.) and heat of fusion ΔH (J / g) of polyamide were measured using Diamond-DSC manufactured by PERKIN-ELMER.
Specifically, it measured as follows.
First, in a nitrogen atmosphere, about 10 mg of a sample was heated from room temperature to 300 to 350 ° C. according to the melting point of the sample at a temperature rising rate of 20 ° C./min. The temperature of the endothermic peak (melting peak) appearing at this time was defined as Tm1 (° C.). Next, the temperature was maintained for 2 minutes at the highest temperature rise. At this maximum temperature, the polyamide was in a molten state. Thereafter, the temperature is lowered to 30 ° C. at a temperature lowering rate of 100 ° C./min. The exothermic peak appearing at this time is defined as a crystallization peak, and the crystallization peak temperature is defined as Tc. Then, after hold | maintaining for 2 minutes at 30 degreeC, it heated up at 30-degree C / min from 300 degreeC to 300-350 degreeC according to melting | fusing point of the sample. The maximum peak temperature of the endothermic peak (melting peak) appearing at this time was the melting point Tm2 (° C.), and the total peak area was the heat of fusion ΔH (J / g). When there were a plurality of peaks, those having ΔH of 1 J / g or more were regarded as peaks, and the endothermic peak temperature having the maximum ΔH was defined as the melting point Tm2 (° C.). For example, when there are two peaks, an endothermic peak temperature of 295 ° C. (ΔH = 20 J / g) and an endothermic peak temperature of 325 ° C. (ΔH = 25 J / g), the melting point Tm2 is 325 ° C., and ΔH = 25 J / g. It was.

(2) Trans isomer ratio of part derived from (a-1) alicyclic dicarboxylic acid in polyamide (A) Trans isomer ratio of part derived from (a-1) alicyclic dicarboxylic 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 1H-NMR using the obtained solution.
(A-1) When the alicyclic dicarboxylic acid is 1,4-cyclohexanedicarboxylic acid, the peak area of 1.98 ppm derived from the trans isomer and the peaks of 1.77 ppm and 1.86 ppm derived from the cis isomer The trans isomer ratio was determined from the ratio of the area.

(3) 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 the DSC in the range of 30 to 350 ° C. under a temperature rising rate of 20 ° C./min, and the glass transition temperature Tg (° C.) observed at the time of the temperature rising. Was measured.

(4) 25 ° C. sulfuric acid relative viscosity ηr of polyamide
The sulfuric acid relative viscosity ηr at 25 ° C. was measured according to JIS-K6810.
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) Metal element concentration (B) Inorganic filler, (C) Metal hydroxide, (D) Metal oxide contained in the polyamide composition by ICP emission spectroscopy (ICPS-8100, manufactured by Shimadzu Corporation) (E) Phosphorus compound, (F) Fe concentration, Ca concentration, and Mg concentration derived from titanium oxide were calculated. As a pretreatment, 0.1 g of a sample was precisely weighed in a TFM (tetrafluorometaxeal) decomposition vessel, sulfuric acid, nitric acid and hydrofluoric acid were added, and pressure decomposition was performed with a microwave decomposition apparatus. The decomposition solution was made up to a volume of 50 ml to obtain a measurement solution.

(6) Formability The pellets of the polyamide composition produced in the examples and comparative examples described later are molded using an injection molding machine [PS-40E: manufactured by Nissei Resin Co., Ltd.], so that the length is 60 mm x the width is 60 mm. X A molded product having a thickness of 1.0 mm was produced.
During the molding, injection + holding time 2 seconds, cooling time 6 seconds, mold temperature 130 ° C., and molten resin temperature (A) polyamide melting point Tm2 + 10 ° C. were set.
The formability evaluation was determined as follows. It was evaluated that obtaining a molded product without problems would lead to improvement in productivity.
A: A molded product was obtained without any problem.
○: The mold was released without any problem, but a burr was generated.
Δ: Sprue sometimes remained in the mold.
X: The releasability was insufficient, and the molded product adhered to the mold or deformed.
(7) Gas at the time of molding The molding of the above (6) was continuously performed 100 shots, and the gas vent after the molding was visually confirmed.
The evaluation of gas generation during molding was as follows. It was evaluated that obtaining a molded product without problems would lead to improvement in productivity.
◎: There are no deposits on the gas vent. ○: There are deposits on the gas vent. △: There are deposits on the gas vent and it is clogging. ×: There are deposits on the gas vent and there is clogging. (8) Initial whiteness 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 the molding, the injection + holding time was 10 seconds, the cooling time was 15 seconds, the mold temperature was set to 120 ° C., and the temperature of the molten polyamide composition was set to (A) melting point Tm2 + 10 ° C.
Hunter whiteness of the obtained molded piece was measured using a color difference meter ZE-2000 manufactured by Nippon Denshoku.

(9) Hunter whiteness after heat treatment The molded piece obtained in (8) above was heat-treated in a hot air dryer at 150 ° C for 300 hours. Hunter whiteness of the molded piece after the heat treatment was measured.
(10) Crack generation during long-term aging (after heat treatment) (%)
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 the molding, the injection + holding time was 10 seconds, the cooling time was 15 seconds, the mold temperature was set to 120 ° C., and the molten resin temperature was set to (A) the melting point Tm2 + 10 ° C. of the polyamide. The obtained molded piece was heat-treated in a hot air dryer at 180 ° C. Evaluation evaluation of crack generation during long-term aging was as follows.
A: No cracks occurred after 300 hours.
○: No cracks occurred after 200 hours, and cracks occurred after 300 hours.
Δ: No cracks occurred after 100 hours, and cracks occurred after 200 hours.
X: Cracks occurred after 100 hours.

(11) Reflectivity retention ratio during metal halide exposure test (%)
The molded piece obtained in the above (8) was subjected to a metal halide exposure treatment for 1000 hours using a metal halide lamp type light resistance tester (manufactured by Iwasaki Electric Co., Ltd.) at 100 ° C. The illuminance at the position where the molded piece was installed was 10 mW / cm ² .
The molded piece before and after the metal halide exposure treatment was irradiated with light having a wavelength of 450 nm, the reflectance of the light was measured with a Hitachi spectrophotometer (U-3310), and the reflectance retention was calculated.

[(A) Production of polyamide]
(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 mixed solution and 15 g (0.15 mol) of 2MC5DA, which is an additive at the time of melt polymerization, were charged into an autoclave (made by Nitto Koatsu Co., Ltd.) having an internal volume of 5.4 L.
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.
Until the pressure in the autoclave tank (hereinafter, also simply referred to as “inside the tank”) reaches about 2.5 kg / cm ² as gauge pressure (hereinafter, all pressure in the tank is expressed as gauge pressure). Heating was continued. At this time, the liquid temperature was about 145 ° C.
While maintaining the pressure in the tank at about 2.5 kg / cm ² , heating was continued while removing water out of the system, and the solution was concentrated until the concentration of the aqueous solution in the tank was 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 .
While maintaining the pressure in the tank at about 30 kg / cm ² , the water was removed from the system, and heating was continued until the temperature reached 50 ° C. (about 295 ° C.) lower than the final temperature (about 345 ° C.). 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 345 ° C.
While maintaining the resin temperature in the tank, the inside of the tank was maintained for 10 minutes under a reduced pressure of 100 torr 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). Furthermore, the strand-like product was cooled with water and cut to obtain pellets of polyamide (polyamide pellets).
10 kg of polyamide pellets obtained by using the melt polymerization were 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 polyamide pellets were heated at 260 ° C. for 6 hours with stirring while nitrogen was passed through the vacuum dryer at 1 L / min. Thereafter, the temperature in the vacuum dryer is lowered to about 50 ° C. with nitrogen flowing, and the polyamide pellets are taken out from the vacuum dryer in the form of pellets, and polyamide (hereinafter also referred to as “PA-1”). Obtained.
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.
As a result of the measurement, the polyamide (PA-1) had a melting point Tm2 of 327 ° C., a glass transition temperature Tg of 150 ° C., a trans isomer ratio of 71%, and a sulfuric acid relative viscosity of 25 ° C. of 3.1.

(Production Example 2)
CHDA 782 g (4.54 mol), C9DA 575 g (3.63 mol), and 2MC9DA 144 g (0.91 mol) were dissolved in 1500 g of distilled water to prepare an aqueous mixture of 50% by mass of the starting monomer.
The obtained water mixture and 11 g (0.07 mol) of C9DA, which is an additive at the time of melt polymerization, were charged into an autoclave (made by Nitto Koatsu Co., Ltd.) having an internal volume of 5.4 L.
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. Heating was continued until the pressure in the autoclave tank reached about 2.5 kg / cm ² as a gauge pressure. At this time, the liquid temperature was about 145 ° C.
Heating was continued while removing water out of the system in order to keep the pressure in the tank at about 2.5 kg / cm ^2, and the solution was concentrated until the concentration of the aqueous solution in the tank was about 75% by mass. The removal of water was stopped, and heating was continued until the pressure in the tank reached about 30 kg / cm ² .
Heating was continued until the temperature reached about 50 ° C. (about 290 ° C.) lower than the final temperature (about 340 ° C.) while removing water out of the system in order to keep the pressure in the tank at about 30 kg / cm ² . While further heating, the pressure in the tank was reduced to atmospheric pressure (gauge pressure was 0 kg / cm ² ) over 90 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 for 30 minutes under a reduced pressure of 400 torr 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 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.
As a result of the measurement, the polyamide (PA-2) had a melting point Tm2 of 316 ° C., a glass transition temperature Tg of 119 ° C., a trans isomer ratio of 70%, and a sulfuric acid relative viscosity at 25 ° C. of 2.4.

(Production Example 3)
Polyamide 9T (hereinafter also abbreviated as “PA-3”) was produced according to the method described in Example 1 of JP-A-7-228689.
At that time, terephthalic acid was used as the starting dicarboxylic acid, and 1,9-nonamethylenediamine and 2-methyloctamethylenediamine [1,9-nonamethylenediamine: 2-methyloctamethylenediamine = 80: 20 (molar ratio)] was used.
Specifically, the above raw materials, distilled water and the like were put into a 20 liter autoclave to obtain a water mixture. Next, the inside of the autoclave was replaced with nitrogen. Thereafter, the water mixture in the autoclave was stirred at 100 ° C. for 30 minutes.
Next, the internal temperature of the autoclave was raised to 210 ° C. over 2 hours. At that time, the autoclave was pressurized to 22 kg / cm ² .
After the reaction was continued for 1 hour, the internal temperature of the autoclave was raised to 230 ° C. Thereafter, the internal temperature of the autoclave was kept constant at 230 ° C. for 2 hours, and the reaction was carried out while gradually removing water vapor and maintaining the pressure in the autoclave at 22 kg / cm ² .
Next, the pressure in the autoclave was lowered to 10 kg / cm ² over 30 minutes, and the reaction was further continued for 1 hour to obtain a prepolymer.
The obtained prepolymer was dried at 100 ° C. under reduced pressure for 12 hours and pulverized to a size of 2 mm or less. The pulverized prepolymer was subjected to solid phase polymerization at 230 ° C. and 0.1 mmHg for 10 hours to obtain polyamide (PA-3).
Each characteristic of this polyamide (PA-3) was measured based on the said measuring method.
As a result of the measurement, the polyamide (PA-3) had a melting point Tm2 of 298 ° C., a glass transition temperature Tg of 122 ° C., and a sulfuric acid relative viscosity of 2.6 ° C. of 2.6.

[Production of polyamide composition]
(Examples 1-10 and Comparative Examples 1-4)
Using the polyamides (PA-1) to (PA-3) obtained in Production Examples 1 to 3 and the raw materials in the types and proportions described in Table 1 below, the polyamide composition is as follows: Manufactured.

  The polyamide (PA-1) obtained in Production Example 1 was used as a raw material for the polyamide composition after drying in a nitrogen stream and adjusting the water content to about 0.2% by mass.

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 in the ninth barrel. Had a mouth. 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 was set to the melting point Tm2 + 20 ° C. of each (A) polyamide produced in the above production example, the screw rotation speed was set to 250 rpm, and the discharge amount was set to 25 kg / h. .

(A) Polyamide, (D) Metal oxide, and (E) Phosphorous compound were dry-blended and supplied from the upstream supply port of the twin-screw extruder so that the types and ratios described in Table 1 were obtained.
Next, when manufacturing the polyamide composition shown in Table 1, (F) titanium oxide was supplied from the downstream 1st supply port of the said twin-screw extruder by the kind and ratio of Table 1 below.
Furthermore, (B) inorganic filler was supplied from the downstream second supply port of the twin-screw extruder in the types and proportions shown in Table 1 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.
The evaluation results are shown in Table 1 below.

  As shown in Table 1, it was found that the polyamide compositions of Examples 1 to 10 were excellent in moldability, initial whiteness, whiteness after heat treatment, long-term aging properties, and reflectance retention during a metal halide exposure test. It was.

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

Claims (15)

(A) polyamide,
(B) an inorganic filler;
(C) metal hydroxide and / or (D) 0.1-20% by mass of metal oxide,
And the Fe concentration in the composition is 5 to 200 ppm.   The polyamide composition according to claim 1, wherein the (A) polyamide has a melting point of 270 to 350 ° C.   The said (A) polyamide has (a-1) an alicyclic dicarboxylic acid unit comprised from 1, 4- cyclohexane dicarboxylic acid and contains (a) dicarboxylic acid unit containing 50 mol% or more. The polyamide composition described.   The polyamide composition according to any one of claims 1 to 3, wherein the metal hydroxide (C) is an alkaline earth metal hydroxide.   The polyamide composition according to any one of claims 1 to 4, wherein the metal oxide (D) is an alkaline earth metal oxide.   The polyamide composition according to any one of claims 1 to 5, wherein the inorganic filler (B) includes wollastonite having an aspect ratio of 20 or less.   The polyamide composition according to any one of claims 1 to 6, wherein the Ca concentration is 500 to 45000 ppm.   The polyamide composition according to any one of claims 1 to 7, wherein the Mg concentration is 500 to 8000 ppm.   The polyamide composition according to any one of claims 1 to 8, wherein a ratio of Ca content to Fe content (Ca / Fe) is 100 or more.   (E) Polyamide composition as described in any one of Claims 1 thru | or 9 which further contains 0.1-20 mass% of phosphorus compounds.   (F) The polyamide composition according to any one of claims 1 to 10, further comprising 5% by mass or more of titanium oxide. The (B) inorganic filler contains a nucleating agent,
The polyamide composition according to any one of claims 1 to 11, wherein the content of the nucleating agent in the polyamide composition is 0.001 to 15 mass%.   A molded article comprising the polyamide composition according to any one of claims 1 to 12. The molded article according to claim 13, wherein the reflectance retention after exposure for 1000 hours at a position where the light resistance tester is 100 ° C. and the illuminance is 10 mW / cm ² is 95% or more.   The reflecting plate for LED containing the polyamide composition as described in any one of Claims 1 thru | or 12.