JP2023028935A - Polyamide composition and molded article - Google Patents

Abstract

To provide a polyamide composition which is excellent in heat resistance, impact resistance and creep-resistance properties and, in addition, in fire retardancy when formed into a molded article.SOLUTION: There is provided a polyamide composition which comprises a polyamide (A) having a dicarboxylic acid unit having 4 or more and 12 or less carbon atoms and a diamine unit having 4 or more and 12 or less carbon atoms, a phosphorus-based flame retardant (B) and a polymer (C) having an aromatic group in the main chain which has an oxygen index of 27% or more, wherein the content of the polymer (C) is more than 1.0 mass% and less than 10.0 mass% based on the total mass of the polyamide composition, the ratio (B)/(C) of the content of the phosphorus-based flame retardant (B) to the content of the polymer (C) is more than 0.9 and less than 9.0 and the melting peak temperature Tm2 in differential scanning calorimetry according to JIS-K7121 is more than 260°C and 360°C or less.SELECTED DRAWING: None

Description

The present invention relates to polyamide compositions and molded articles.

Due to their excellent mechanical properties and heat resistance, polyamides are widely used in the fields of automobile parts and electrical and electronic parts. In the field of electric and electronic parts, a surface mounting process with high mounting efficiency of parts is widely used, and heat-resistant polyamide, which has high heat resistance and excellent strength, is widely used as a suitable material for forming these parts. In recent years, lead-free solder has been adopted as the solder used in the surface mounting process from the viewpoint of reducing the environmental impact. It is necessary to set the temperature as high as about 260°C. Therefore, heat-resistant polyamides having a relatively high melting point among heat-resistant polyamides are employed as heat-resistant polyamides for forming parts for surface mounting processes.

In the field of electrical and electronic components, flame retardancy is often required for components, and it is often necessary to achieve a rating of V-0 in the UL94 standard of Underwriters Laboratories. BACKGROUND ART Conventionally, materials mixed with brominated flame retardants have generally been used as heat-resistant polyamides forming electrical and electronic parts. However, due to recent heightened environmental awareness, the use of some raw materials containing harmful lead, cadmium and the like is being regulated. Halogen-containing compounds, such as brominated flame retardants, tend to be avoided regardless of their safety and substantial environmental impact evaluation results. demand is increasing.

Several halogen-free flame retardants for blending with polyamides are known. However, in addition to high flame retardancy, flame retardants blended in heat-resistant polyamides with high melting points have high flame retardancy during melt kneading when producing polyamide resin compositions and during molding processing when producing molded products. High heat resistance to withstand temperature is required. In particular, this tendency is conspicuous in electric and electronic parts that undergo the reflow process of the surface mounting process.

Phosphinates are known as halogen-free flame retardants having high flame retardancy and heat resistance. For example, a resin composition containing an aliphatic polyamide, an amorphous semi-aromatic polyamide, and a specific phosphinate is known (see Patent Document 1). A resin composition containing a specific semi-aromatic polyamide and a phosphinate is also known (see Patent Documents 2 and 3).

WO2005/035664 WO2014/148519 WO2014/200082

The level of required properties such as heat resistance, strength, and flame retardancy for polyamide materials has been further improved, and in order to achieve higher levels of physical properties (especially in hot environments), further improvements in polyamide materials are required. is required.
However, although resin compositions such as those described in Patent Documents 1 to 3 can partially improve the problems of conventional PA66 and PPA (polyphthalamide), they have excellent thermal strength, impact resistance, and resistance. Creep properties and flame retardancy are unsatisfactory.

The present invention has been made in view of the above circumstances, and in addition to flame retardancy when molded, a polyamide composition having excellent hot strength, impact resistance, and creep resistance properties, and the polyamide A molded article obtained by molding the composition is provided.

That is, the present invention includes the following aspects.
(1) a polyamide (A) having a dicarboxylic acid unit having 4 to 12 carbon atoms and a diamine unit having 4 to 12 carbon atoms;
a phosphorus-based flame retardant (B);
a polymer (C) having an oxygen index of 27% or more and having an aromatic group in the main chain;
including
The content of the polymer (C) is more than 1.0% by mass and less than 10.0% by mass with respect to the total mass of the polyamide composition,
The content ratio (B)/(C) of the phosphorus-based flame retardant (B) and the polymer (C) is more than 0.9 and less than 9.0,
A polyamide composition, wherein the polyamide (A) has a melting peak temperature Tm2 of more than 260° C. and not more than 360° C. in differential scanning calorimetry according to JIS-K7121.
(2) The polyamide composition of (1), wherein the dicarboxylic acid units comprise terephthalic acid units.
(3) the dicarboxylic acid units include terephthalic acid units and 1,4-cyclohexanedicarboxylic acid units, and the diamine units include aliphatic diamine units;
The terephthalic acid unit content is 50 mol% or more and 90 mol% or less, and the 1,4-cyclohexanedicarboxylic acid unit content is 10 mol% or more and 50 mol%, based on the total molar amount of all dicarboxylic acid units. % or less, the polyamide composition according to (1) or (2).
(4) According to (3), the total content of the terephthalic acid units and the 1,4-cyclohexanedicarboxylic acid units is 90 mol% or more and 100 mol% or less with respect to the total molar amount of all dicarboxylic acid units. of the polyamide composition.
(5) The polyamide (A) has a melting peak temperature Tm2 of 340° C. or more and 360° C. or less obtained when the temperature is raised at 20° C./min in differential scanning calorimetry according to JIS-K7121,
The crystallization enthalpy ΔHc obtained when the temperature is lowered at 20° C./min is 35 J/g or more and 60 J/g or less,
The polyamide composition according to any one of (1) to (4), having a glass transition temperature Tg of 130°C or higher and 160°C or lower.
(6) The polyamide composition according to any one of (1) to (5), wherein the polyamide (A) has a number average molecular weight of 5000 or more and 20000 or less.
(7) The polyamide composition according to any one of (1) to (6), further comprising (D) a filler.
(8) A molded article obtained by molding the polyamide composition according to any one of (1) to (7).

According to the polyamide composition of the above-described aspect, it is possible to provide a polyamide composition which is excellent in flame retardancy, hot strength, impact resistance, and creep resistance when formed into a molded article. The molded article of the above aspect is obtained by molding the polyamide composition, and is excellent in heat strength, impact resistance, and creep resistance in addition to flame retardancy.

EMBODIMENT OF THE INVENTION Hereinafter, the form (henceforth "this embodiment") for implementing this invention is demonstrated in detail. The following embodiments are examples for explaining the present invention, and are not intended to limit the present invention to the following contents. The present invention can be appropriately modified and implemented within the scope of the gist thereof.

As used herein, polyamide means a polymer having an amide bond (--NHCO--) in its main chain.

<<Polyamide composition>>
The polyamide composition of this embodiment is
a polyamide (A) having a dicarboxylic acid unit having 4 to 12 carbon atoms and a diamine unit having 4 to 12 carbon atoms;
a phosphorus-based flame retardant (B);
A polymer (C) having an oxygen index of 27% or more and having an aromatic group in the main chain (hereinafter sometimes simply referred to as "polymer (C)",
including.

The content of the polymer (C) is more than 1.0% by mass and less than 10.0% by mass relative to the total mass of the polyamide composition, preferably more than 1.0% by mass and 8.0% by mass or less, 1.5% by mass or more and 8.0% by mass or less is more preferable, and 2.0% by mass or more and 7.0% by mass or less is even more preferable. By making the content of the polymer (C) equal to or higher than the above lower limit, it is possible to obtain a polyamide composition that is more excellent in flame retardancy. On the other hand, by setting the content of the polymer (C) to the upper limit value or less, a polyamide composition having excellent long-term heat resistance can be obtained.

The content ratio (B)/(C) of the phosphorus-based flame retardant (B) and the polymer (C) is more than 0.9 and less than 9.0, preferably 1.0 or more and 7.0 or less, It is more preferably 1.2 or more and 5.0 or less, and further preferably 1.3 or more and 4.5 or less. By setting the ratio (B)/(C) of the content of (B) the phosphorus-based flame retardant and (C) the polymer within the above range, it is possible to obtain a polyamide composition having excellent strength and creep properties at high temperatures. .

The melting peak temperature Tm2 of the polyamide (A) in differential scanning calorimetry according to JIS-K7121 is higher than 260 ° C., preferably 290 ° C. or higher, more preferably 320 ° C. or higher, 340 ° C. or higher. is more preferable.
On the other hand, the melting peak temperature Tm2 is 360° C. or lower, preferably 355° C. or lower, more preferably 350° C. or lower, particularly preferably 350° C. or lower, and preferably 345° C. or lower. Most preferred.
That is, the melting peak temperature Tm2 is more than 260°C and 360°C or less, preferably 290°C or more and 360°C or less, more preferably 320°C or more and 360°C or less, and 340°C or more and 360°C or less. is even more preferably 340°C or higher and 355°C or lower, even more preferably 340°C or higher and 350°C or lower, particularly preferably 340°C or higher and 350°C or lower, and 340°C or higher and 345°C or higher. °C or less is most preferred. The method of measuring the melting peak temperature Tm2 and the like will be described later in detail.

With the polyamide composition of the present embodiment having the above structure, a molded article having excellent hot strength, impact resistance, and creep resistance in addition to flame retardancy can be obtained.

Next, each constituent component of the polyamide composition of the present embodiment will be described in detail below.

<Polyamide (A)>
Polyamide (A) has a dicarboxylic acid unit having 4 to 12 carbon atoms and a diamine unit having 4 to 12 carbon atoms.
Polyamide (A), in addition to dicarboxylic acid units having 4 to 12 carbon atoms and diamine units having 4 to 12 carbon atoms, dicarboxylic acid units other than dicarboxylic acid units having 4 to 12 carbon atoms, and carbon number It can have diamine units other than 4 to 12 diamine units. These dicarboxylic acid units and diamine units are collectively referred to as dicarboxylic acid units (a) and diamine units (b), respectively.

[Dicarboxylic acid unit (a)]
The dicarboxylic acid unit (a) contains a dicarboxylic acid unit having 4 to 12 carbon atoms, and preferably contains a terephthalic acid unit. The polyamide (A) containing the terephthalic acid unit (a-1) as the dicarboxylic acid unit (a) has higher crystallinity and can impart better heat resistance and mechanical strength to the molded product.

More preferably, the dicarboxylic acid unit (a) contains a terephthalic acid unit (a-1) and a 1,4-cyclohexanedicarboxylic acid unit (a-2). The polyamide (A) containing the 1,4-cyclohexanedicarboxylic acid unit (a-2) as the dicarboxylic acid unit (a) has a higher glass transition temperature, excellent fluidity, and good heat resistance and fluidity due to the molded product. You can give it character.

The content of the terephthalic acid unit (a-1) is preferably 50 mol% or more and 90 mol% or less, more preferably 55 mol% or more and 85 mol% or less, relative to the total molar amount of all dicarboxylic acid units. It is more preferably 60 mol % or more and 80 mol % or less, and particularly preferably 65 mol % or more and 75 mol % or less.

The content of 1,4-cyclohexanedicarboxylic acid units is preferably 10 mol% or more and 50 mol% or less, more preferably 15 mol% or more and 45 mol% or less, relative to the total molar amount of all dicarboxylic acid units. It is more preferably 20 mol % or more and 40 mol % or less, and particularly preferably 25 mol % or more and 35 mol % or less.

The total content of terephthalic acid units and 1,4-cyclohexanedicarboxylic acid units is preferably 90 mol% or more and 100 mol% or less, more preferably 95 mol% or more and 100 mol%, based on the total molar amount of all dicarboxylic acid units. or less, and more preferably 98 mol % or more and 100 mol % or less.

The dicarboxylic acid unit (a) may contain dicarboxylic acid units other than the terephthalic acid unit (a-1) and the 1,4-cyclohexanedicarboxylic acid unit (a-2) within a range that does not impair its effect. Other dicarboxylic acid units include aromatic dicarboxylic acid units, alicyclic dicarboxylic acid units, and aliphatic dicarboxylic acid units, with aromatic dicarboxylic acid units and alicyclic dicarboxylic acid units being preferred.

(Aromatic dicarboxylic acid unit (a-3))
The aromatic dicarboxylic acid constituting the aromatic dicarboxylic acid unit (a-3) is not particularly limited as long as it is an aromatic dicarboxylic acid other than terephthalic acid. dicarboxylic acids having The aromatic moiety may be unsubstituted or may have a substituent. The substituents are not particularly limited, and examples thereof include alkyl groups having 1 to 4 carbon atoms, aryl groups having 6 to 10 carbon atoms, aralkyl groups having 7 to 10 carbon atoms, and halogens such as chloro and bromo groups. groups, silyl groups having 1 to 6 carbon atoms, sulfonic acid groups and salts thereof (sodium salts, etc.), and the like.

Examples of aromatic dicarboxylic acids include, but are not limited to, isophthalic acid, naphthalenedicarboxylic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, and 5-sodium. Examples thereof include aromatic dicarboxylic acids having 8 to 20 carbon atoms which are unsubstituted or substituted with a predetermined substituent such as sulfoisophthalic acid.

The aromatic dicarboxylic acids constituting the aromatic dicarboxylic acid unit (a-3) may be used alone or in combination of two or more.

(Alicyclic dicarboxylic acid unit (a-4))
The alicyclic dicarboxylic acid constituting the alicyclic dicarboxylic acid unit (a-4) is not particularly limited as long as it is an alicyclic dicarboxylic acid other than 1,4-cyclohexanedicarboxylic acid. An alicyclic dicarboxylic acid having an alicyclic structure having 3 or more and 12 or less carbon atoms is mentioned, and an alicyclic dicarboxylic acid having an alicyclic structure having 5 or more and 12 or less carbon atoms is preferable.

Examples of such alicyclic dicarboxylic acids include, but are not limited to, 1,3-cyclohexanedicarboxylic acid and 1,3-cyclopentanedicarboxylic acid.

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

Alicyclic dicarboxylic acids include geometric isomers of trans and cis isomers. As the alicyclic dicarboxylic acid as the raw material monomer, either one of the trans isomer and the cis isomer may be used, or a mixture containing the trans isomer and the cis isomer in a predetermined ratio may be used.

The alicyclic dicarboxylic acids may be used alone or in combination of two or more.

(Aliphatic dicarboxylic acid unit (a-5))
The aliphatic dicarboxylic acid constituting the aliphatic dicarboxylic acid unit (a-5) is not particularly limited, but examples thereof include linear saturated aliphatic dicarboxylic acids and branched saturated aliphatic dicarboxylic acids. be done.

Linear saturated aliphatic dicarboxylic acids include, but are not limited to, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, and dodecanedioic acid. , tetradecanedioic acid, hexadecanedioic acid, octadecanedioic acid, eicosanedioic acid, diglycolic acid, and the like.

Examples of branched saturated aliphatic dicarboxylic acids include, but are not limited to, dimethylmalonic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylglutaric acid, and 2,2-diethylsuccinic acid. , 2,3-diethylglutaric acid, 2,2-dimethylglutaric acid, 2-methyladipic acid, trimethyladipic acid and the like.

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

Among them, a linear saturated aliphatic dicarboxylic acid having 6 or more carbon atoms is preferable as the aliphatic dicarboxylic acid, because the fluidity, toughness, heat resistance, rigidity, etc. of the polyamide tend to be more excellent.

Specific examples of preferred linear saturated aliphatic dicarboxylic acids having 6 or more carbon atoms include adipic acid, sebacic acid, dodecanedioic acid, tetradecanedioic acid, hexadecanedioic acid, octadecanedioic acid, eicosanedioic acid, and the like. be done.

Among them, adipic acid, sebacic acid, or dodecanedioic acid is preferable as the linear saturated aliphatic dicarboxylic acid having 6 or more carbon atoms from the viewpoint of the heat resistance of the polyamide composition.

Moreover, the polyamide (A) may further contain units derived from a polycarboxylic acid having a valence of 3 or more, if necessary, as long as the effect is not impaired. Trivalent or higher polyvalent carboxylic acids include, for example, trimellitic acid, trimesic acid, pyromellitic acid and the like. These trivalent or higher polyvalent carboxylic acids may be used alone, or two or more of them may be used in combination.

[Diamine unit (b)]
The diamine unit (b) includes a diamine unit having 4 to 12 carbon atoms, and an aliphatic diamine unit (b-1) having 4 to 12 carbon atoms (hereinafter simply “aliphatic diamine unit (b-1)” may be referred to as).

The content of the aliphatic diamine unit (b-1) is preferably 50 mol% or more and 100 mol% or less, more preferably 60 mol% or more and 100 mol% or less, relative to the total molar amount of all diamine units. It is more preferably 80 mol % or more and 100 mol % or less, and particularly preferably 100 mol %. When the content of the aliphatic diamine unit (b-1) is within the above range, the glass transition temperature Tg is higher, the crystallinity is higher (that is, ΔHc is higher), and the fluidity, toughness, and tend to be more rigid polyamides.

(Aliphatic diamine unit (b-1))
Examples of the aliphatic diamine constituting the aliphatic diamine unit (b-1) include linear saturated aliphatic diamines and branched saturated aliphatic diamines.

Linear saturated aliphatic diamines include, but are not limited to, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, un Examples include decamethylenediamine and dodecamethylenediamine.

Examples of branched saturated aliphatic diamines include, but are not limited to, 2-methylpentamethylenediamine (also referred to as 2-methyl-1,5-diaminopentane), 2,2,4- trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 2-methyl-1,8-octanediamine (also referred to as 2-methyloctamethylenediamine), 2,4-dimethyloctamethylenediamine and the like. .

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

Among them, the aliphatic diamine preferably has 4, 6, 9, or 10 carbon atoms, and more preferably has 6 carbon atoms, that is, hexamethylenediamine. When the number of carbon atoms in the aliphatic diamine is within the above range, the heat resistance, crystallinity and releasability of the resulting molded article are more excellent.

The diamine unit (b) can contain diamine units other than the aliphatic diamine unit (b-1) within a range that does not impair its effect. Other diamine units include aliphatic diamine units, alicyclic diamine units, and aromatic diamine units.

(Aliphatic diamine unit (b-2))
The aliphatic diamine constituting the aliphatic diamine unit (b-2) is not particularly limited as long as it is an aliphatic diamine other than an aliphatic diamine having 4 or more and 12 or less carbon atoms. Examples include saturated aliphatic diamines and branched saturated aliphatic diamines.

Linear saturated aliphatic diamines include, but are not limited to, ethylenediamine, propylenediamine, tridecamethylenediamine, and the like.

Examples of branched saturated aliphatic diamines include, but are not limited to, methylmethylenediamine, methylethylenediamine, and the like.

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

(Alicyclic diamine unit (b-3))
Examples of the alicyclic diamine constituting the alicyclic diamine unit (b-3) include, but are not limited to, 1,4-cyclohexanediamine, 1,3-cyclohexanediamine, 1,3- cyclopentanediamine and the like.

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

(Aromatic diamine unit (b-4))
Examples of aromatic diamines constituting the aromatic diamine unit (b-4) include meta-xylylenediamine, para-xylylenediamine, para-phenylenediamine and meta-phenylenediamine.

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

In addition, the polyamide (A) may further contain a trivalent or higher polyvalent amine such as bishexamethylenetriamine, if necessary, as long as the effect is not impaired.
The trivalent or higher polyvalent amines may be used alone or in combination of two or more.

[One or more units (c) selected from the group consisting of lactam units and aminocarboxylic acid units]
Polyamide (A) contains one or more units selected from the group consisting of lactam units and aminocarboxylic acid units in addition to the dicarboxylic acid units (a) and diamine units (b) described above, as long as the effects are not impaired. (c) (hereinafter sometimes simply referred to as "lactam unit/aminocarboxylic acid unit (c)") may further be contained. By including such units, there is a tendency to obtain a polyamide composition having more excellent toughness. The lactams and aminocarboxylic acids constituting the lactam units and aminocarboxylic acid units herein refer to lactams and aminocarboxylic acids that can be polymerized or condensation-polymerized.

The lactam and aminocarboxylic acid constituting the lactam unit/aminocarboxylic acid unit (c) are not limited to the following, but for example, lactams and aminocarboxylic acids having 4 to 14 carbon atoms are preferable, and carbon Lactams and aminocarboxylic acids having a number of 6 or more and 12 or less are more preferable.

Examples of lactams include, but are not limited to, butyrolactam, pivalolactam, ε-caprolactam, caprylolactam, enantholactam, undecanolactam, laurolactam (dodecanolactam), and the like.
Among them, the lactam is preferably ε-caprolactam or laurolactam, more preferably ε-caprolactam. Inclusion of such a lactam tends to result in a polyamide composition with better toughness.

Examples of aminocarboxylic acids include, but are not limited to, ω-aminocarboxylic acids and α,ω-amino acids, which are lactam ring-opened compounds.
As the aminocarboxylic acid, a linear or branched saturated aliphatic carboxylic acid having 4 or more and 14 or less carbon atoms substituted with an amino group at the ω-position is preferable. Examples of such aminocarboxylic acids include, but are not limited to, 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid and the like. Moreover, para-aminomethyl benzoic acid etc. are mentioned as an aminocarboxylic acid.

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

The total content of lactam units/aminocarboxylic acid units (c) is preferably 0 mol% or more and 20 mol% or less, and 0 mol% or more, relative to the total molar amount of all structural units of the polyamide (A). It is more preferably 10 mol % or less, and even more preferably 0 mol % or more and 5 mol % or less. When the total content of the lactam unit/aminocarboxylic acid unit (c) is within the above range, the effect of the polyamide composition of the present embodiment is not impaired, and the effect of improving fluidity tends to be obtained more. It is in.

[Terminal blocking agent]
The terminal of polyamide (A) may be terminal-blocked with a known terminal-blocking agent.

Such a terminal blocking agent is used as a molecular weight modifier when producing a polyamide from the above-described dicarboxylic acid and diamine, and one or more selected from the group consisting of lactams and aminocarboxylic acids that are used as necessary. can also be added.

Examples of terminal blockers include, but are not limited to, monocarboxylic acids, monoamines, acid anhydrides such as phthalic anhydride, monoisocyanates, monoacid halides, monoesters, monoalcohols, and the like. is mentioned.

Among these, monocarboxylic acids or monoamines are preferred. By blocking the ends of the polyamide with a terminal blocking agent, the polyamide composition tends to be more excellent in thermal stability. Terminal blockers may be used alone or in combination of two or more.

The monocarboxylic acid that can be used as a terminal blocker may be any one having reactivity with an amino group that may be present at the terminal of the polyamide, and is not limited to the following, for example, formic acid, acetic acid, Aliphatic monocarboxylic acids such as propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecylic acid, myristic acid, palmitic acid, stearic acid, pivalic acid, isobutyric acid; alicyclic acids such as cyclohexanecarboxylic acid monocarboxylic acids; aromatic monocarboxylic acids such as benzoic acid, toluic acid, α-naphthalenecarboxylic acid, β-naphthalenecarboxylic acid, methylnaphthalenecarboxylic acid and phenylacetic acid; Among them, acetic acid is particularly preferred.
Monocarboxylic acids may be used alone or in combination of two or more.

The monoamine that can be used as a terminal blocking agent is not limited to the following, as long as it has reactivity with the carboxyl group that may be present at the terminal of the polyamide. For example, methylamine, ethylamine, propyl Aliphatic monoamines such as amine, butylamine, hexylamine, octylamine, decylamine, stearylamine, dimethylamine, diethylamine, dipropylamine and dibutylamine; alicyclic monoamines such as cyclohexylamine and dicyclohexylamine; aniline, toluidine, diphenylamine, aromatic monoamines such as naphthylamine;
Monoamines may be used alone or in combination of two or more.

Polyamide compositions containing polyamides end-capped with end-capping agents tend to be superior in heat resistance, fluidity, toughness, low water absorption, and rigidity.

<Method for producing polyamide (A)>
Next, a method for producing polyamide (A) will be described.
When producing the polyamide (A), it is preferable that the amount of the dicarboxylic acid and the amount of the diamine added are approximately the same molar amount. Considering the amount of diamine that escapes to the outside of the reaction system during the polymerization reaction, the molar ratio of the total diamine to the total molar amount of the dicarboxylic acid is preferably 0.9 or more and 1.2 or less. , is more preferably 0.95 or more and 1.1 or less, and more preferably 0.98 or more and 1.05 or less.

The method for producing polyamide includes, but is not limited to, the following polymerization step (1) or (2).
(1) A step of polymerizing a combination of a dicarboxylic acid constituting a dicarboxylic acid unit and a diamine constituting a diamine unit to obtain a polymer.
(2) A step of polymerizing at least one selected from the group consisting of lactams constituting lactam units and aminocarboxylic acids constituting aminocarboxylic acid units to obtain a polymer.

Moreover, it is preferable that the method for producing a polyamide further includes, after the polymerization step, a raising step for raising the degree of polymerization of the polyamide. Further, if necessary, a blocking step of blocking terminals of the obtained polymer with a terminal blocking agent may be included after the polymerization step and the rising step.

Specific methods for producing polyamides include, for example, various methods exemplified in 1) to 4) below.
1) Dicarboxylic acid-diamine salts, mixtures of dicarboxylic acids and diamines, lactams, and one or more aqueous solutions or aqueous suspensions selected from the group consisting of aminocarboxylic acids are heated to polymerize while maintaining the molten state. method (hereinafter sometimes referred to as “thermal melt polymerization method”).
2) A method of increasing the degree of polymerization of a polyamide obtained by a hot melt polymerization method while maintaining a solid state at a temperature below the melting point (hereinafter sometimes referred to as "hot melt polymerization/solid phase polymerization method").
3) A method of polymerizing one or more selected from the group consisting of dicarboxylic acid-diamine salts, mixtures of dicarboxylic acids and diamines, lactams, and aminocarboxylic acids while maintaining a solid state (hereinafter referred to as "solid phase polymerization (sometimes referred to as “lawful”).
4) A method of polymerizing using a dicarboxylic acid halide component equivalent to the dicarboxylic acid and a diamine component (hereinafter sometimes referred to as "solution method").

Among them, as a specific method for producing a polyamide, a production method including a solid phase polymerization method is preferable. Moreover, when producing a polyamide by a solid-phase polymerization method, it is preferable to maintain the solid-phase state until the polymerization is completed. In order to maintain the solid phase state, it is necessary to produce the polyamide under polymerization conditions suitable for it. Polymerization conditions include, for example, the conditions shown below. First, the polymerization pressure in the solid phase polymerization method is controlled to 10 kg/cm ² or more and 25 kg/cm ² or less (gauge pressure), and heating is continued. Then, the pressure in the tank is lowered over 30 minutes or more until it reaches the atmospheric pressure (gauge pressure is 0 kg/cm ² ).

In the method for producing polyamide, the form of polymerization is not particularly limited, and may be a batch system or a continuous system.

A polymerization apparatus used for producing polyamide is not particularly limited, and a known apparatus can be used. Specific examples of the polymerization apparatus include an autoclave reactor, a tumbler reactor, and an extruder reactor (kneader, etc.).

As a method for producing a polyamide, a method for producing a polyamide by a batch-type solid-phase polymerization method will be specifically described below, but the method for producing a polyamide is not limited to this.
First, about 40% by mass or more and 60% by mass or less of raw material components for polyamide (combination of dicarboxylic acid and diamine, and at least one selected from the group consisting of lactam and aminocarboxylic acid, if necessary) Prepare an aqueous solution. Then, the aqueous solution is heated to a temperature of 110° C. or higher and 180° C. or lower, and In a concentration tank operated at a pressure of about 0.035 MPa or more and 0.6 MPa or less (gauge pressure), the solution is concentrated to about 65 mass % or more and 90 mass % or less to obtain a concentrated solution.
The resulting concentrated solution is then transferred to an autoclave and heating is continued until the pressure in the autoclave is about 0.8 MPa to 1.5 MPa (gauge pressure).
Then, in an autoclave, the pressure is maintained at about 0.8 MPa or more and 1.5 MPa or less (gauge pressure) while removing at least one of water and gas components. Next, when the temperature reaches approximately 220° C. or higher and 260° C. or lower, the pressure is lowered 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, water produced as a by-product can be effectively removed.
The autoclave is then pressurized with an inert gas such as nitrogen, and the polyamide is discharged from the autoclave as powder.

It is preferable that the method for producing a polyamide further includes a step of increasing the degree of polymerization of the polyamide. Moreover, the sealing process of sealing the terminal of the obtained polymer with a terminal blocking agent may be included as needed.

<Characteristics of Polyamide (A)>
Next, the properties of polyamide (A) will be described.

[Molecular weight]
As indices of the molecular weight of the polyamide (A), the number average molecular weight Mn, weight average molecular weight Mw, and molecular weight distribution Mw/Mn obtained by gel permeation chromatography (GPC) can be used. The higher the Mn, the higher the molecular weight of the polyamide, and the lower the Mn, the lower the molecular weight of the polyamide.

The number average molecular weight Mn of the polyamide (A) is preferably from 5,000 to 20,000, more preferably from 6,000 to 15,000, and even more preferably from 7,000 to 8,000.

Mw/Mn, which indicates the molecular weight distribution of polyamide (A), is preferably less than 3.5, more preferably 3.0 or less. On the other hand, the lower limit of Mw/Mn is not particularly limited, but can be set to 2.1, for example.

When the number average molecular weight Mn and the molecular weight distribution Mw/Mn are within the above ranges, the polyamide composition tends to be more excellent in mechanical properties such as toughness and rigidity, moldability, and the like.

For Mn and Mw, a calibration curve is prepared using the number average molecular weight Mn measured in terms of a PMMA (polymethyl methacrylate) standard sample (manufactured by Polymer Laboratories) to determine the molecular weight of the polyamide. More specifically, it can be measured by the method described in the Examples below.

[Melting peak temperature Tm2]
The melting peak temperature Tm2 of the polyamide (A) is higher than 260°C, preferably 290°C or higher, more preferably 320°C or higher, and even more preferably 340°C or higher.
On the other hand, the melting peak temperature Tm2 is 360° C. or lower, preferably 355° C. or lower, more preferably 350° C. or lower, particularly preferably 350° C. or lower, and preferably 345° C. or lower. Most preferred.
That is, the melting peak temperature Tm2 is more than 260°C and 360°C or less, preferably 290°C or more and 360°C or less, more preferably 320°C or more and 360°C or less, and 340°C or more and 360°C or less. is even more preferably 340°C or higher and 355°C or lower, even more preferably 340°C or higher and 350°C or lower, particularly preferably 340°C or higher and 350°C or lower, and 340°C or higher and 345°C or higher. °C or less is most preferred.
When the melting peak temperature Tm2 of the polyamide (A) is higher than the lower limit or higher than the lower limit, it tends to be possible to obtain a polyamide composition having excellent heat resistance. On the other hand, when the melting peak temperature Tm2 of the polyamide (A) is equal to or lower than the above upper limit, it tends to be possible to suppress thermal decomposition of the polyamide during melt processing such as extrusion and molding.

The melting peak temperature Tm2 of the polyamide (A) can be determined according to JIS-K7121 as described in the examples below. Examples of devices for measuring the melting peak temperature and heat of fusion include Diamond-DSC manufactured by PERKIN-ELMER. A specific method for measuring the melting peak temperature Tm2 of polyamide (A) is as follows. First, after the temperature is raised for the first time, the temperature is maintained for 2 minutes in a molten state at the highest temperature raised, then the temperature is lowered to 30°C at a temperature lowering rate of 20°C/min, and held at 30°C for 2 minutes. After that, when the temperature is similarly increased at a temperature increase rate of 20 ° C./min (at the time of the second temperature increase), the endothermic peak temperature that appears on the highest side of the endothermic peak that appears is taken as the melting peak temperature Tm2 of the polyamide (A) itself. do.

[Enthalpy of crystallization ΔHc]
The enthalpy of crystallization ΔHc of the polyamide (A) is preferably 30 J/g or more and 60 J/g or less, more preferably 35 J/g or more and 60 J/g or less, and 35 J/g or more and 55 J/g or less. is more preferable, and 40 J/g or more and 45 J/g or less is particularly preferable. When the enthalpy of crystallization ΔHc of the polyamide is at least the above lower limit, the heat resistance of the polyamide composition tends to be further improved. On the other hand, when the enthalpy of crystallization ΔHc of the polyamide is equal to or less than the above upper limit, the moldability and impact resistance tend to be excellent.

Crystallization enthalpy ΔHc of polyamide is the peak area of Tc when the temperature of the exothermic peak (crystallization peak) that appears when the polyamide is cooled at a cooling rate of 20 ° C./min is the crystallization peak temperature Tc (° C.). . The crystallization enthalpy ΔHc of polyamide can be measured according to JIS-K7121. As a measuring device, Diamond-DSC manufactured by PERKIN-ELMER can be used as described in the following examples.

[Glass transition temperature Tg]
The glass transition temperature Tg of polyamide (A) is preferably 110° C. or higher, more preferably 120° C. or higher, and even more preferably 130° C. or higher. On the other hand, the glass transition temperature Tg of polyamide (A) is preferably 160° C. or lower, more preferably 155° C. or lower, and even more preferably 150° C. or lower.
That is, the glass transition temperature Tg of the polyamide (A) is preferably 110° C. or higher and 160° C. or lower, more preferably 120° C. or higher and 160° C. or lower, and even more preferably 130° C. or higher and 160° C. or lower. It is preferably 130° C. or higher and 155° C. or lower, and most preferably 130° C. or higher and 150° C. or lower.
When the glass transition temperature Tg of the polyamide is at least the above lower limit, it tends to be possible to obtain a polyamide composition that is more excellent in resistance to heat discoloration and chemical resistance. On the other hand, when the glass transition temperature Tg of the polyamide is equal to or lower than the above upper limit, there is a tendency that a molded product with a better appearance can be obtained.
The glass transition temperature Tg of polyamide can be measured according to JIS-K7121, as described in Examples below. A device for measuring the glass transition temperature Tg includes, for example, Diamond-DSC manufactured by PERKIN-ELMER.

[Polymer terminal amount]
Polyamide polymer ends are not particularly limited, but can be classified and defined as follows.
2) the carboxy terminus; 3) the capped terminus; 4) the other terminus.

1) The amino terminus is a polymer terminus having an amino group ( _--NH2 group) and is derived from the raw material diamine.

The amino terminal amount ([NH ₂ ]) is preferably 5 μmol equivalents/g or more and 100 μmol equivalents/g or less, and preferably 10 μmol equivalents/g or more and 70 μmol equivalents/g or less, relative to 1 g of the polyamide (A). It is more preferably 20 μmol equivalent/g or more and 50 μmol equivalent/g or less, and particularly preferably 25 μmol equivalent/g or more and 40 μmol equivalent/g or less. When the amino terminal amount is within the above range, the polyamide composition tends to be more excellent in whiteness, reflow resistance, heat discoloration resistance, light discoloration resistance, hydrolysis resistance, and heat retention stability.

The amount of amino termini can be measured by neutralization titration. Specifically, 3.0 g of polyamide is dissolved in 100 mL of a 90% by mass phenol aqueous solution, and the resulting solution is titrated with 0.025N hydrochloric acid to determine the amino terminal content (μmol equivalent/g). The end point is determined from the reading of the pH meter.

2) The carboxy terminus is a polymer terminus having a carboxy group (--COOH group), which is derived from the raw material dicarboxylic acid.
The carboxy terminal content ([COOH]) is preferably 5 μmol equivalents/g or more and 150 μmol equivalents/g or less, more preferably 10 μmol equivalents/g or more and 140 μmol equivalents/g or less with respect to 1 g of polyamide (A). Preferably, it is 20 μmol equivalent/g or more and 130 μmol equivalent/g or less, more preferably 30 μmol equivalent/g or more and 120 μmol equivalent/g or less, and 40 μmol equivalent/g or more and 110 μmol equivalent/g or less. Most preferred. When the amount of carboxyl terminals is within the above range, the polyamide composition tends to be more excellent in whiteness, reflow resistance, heat discoloration resistance, and light discoloration resistance.

Carboxy terminal content can be measured by neutralization titration. Specifically, 4.0 g of polyamide is dissolved in 50 mL of benzyl alcohol, and the resulting solution is titrated with 0.1 N NaOH to determine the amount of carboxy terminal (μmol equivalent/g). The endpoint is determined from the color change of the phenolphthalein indicator.

When the amount of amino terminals and the amount of carboxyl terminals are within the above ranges, the polyamide tends to be more excellent in heat discoloration resistance and light discoloration resistance.

Methods for controlling the ratio of the amino terminal amount to the total amount of active terminals include, for example, a method of controlling the amount of diamine and terminal blocker added as additives during hot melt polymerization of polyamide, and the polymerization conditions. .

3) Terminals formed by a capping agent are terminals formed when a capping agent is added during polymerization. The terminal blocking agent mentioned above is mentioned as a blocking agent.

4) Other terminals are polymer terminals not classified in 1) to 3) above, and include terminals generated by deammonification of amino terminals and terminals generated by decarboxylation of carboxylic acid terminals. be done.

The properties of these polyamides (A) maintain the properties of the original polyamide even after being melt-kneaded with other additives as necessary to form a polyamide composition, and have equivalent measured values. It is possible to specify the properties of the polyamide contained therein by measuring each physical property by the method for measuring the properties of the polyamide described in the examples below.
When determining the heat of fusion and the enthalpy of crystallization of the polyamide composition, if inorganic fillers, nucleating agents, lubricants, stabilizers, etc. are included, the above heat value is the ratio of polyamide to the polyamide composition Calculate by converting with

The content of the polyamide (A) can be, for example, 10.0% by mass or more and 90.0% by mass or less, and 20.0% by mass or more and 80.0% by mass or less, relative to the mass of the polyamide composition. , 30.0% by mass or more and 70.0% by mass or less, and 35.0% by mass or more and 65.0% by mass or less. When the content of the polyamide (A) is within the above range, the properties of the polyamide (A) can be fully exhibited in the polyamide composition without impairing the properties.

<Phosphorus flame retardant (B)>
(B) The phosphorus-based flame retardant is not particularly limited as long as it is a flame retardant containing phosphorus. The flame retardant is not particularly limited as long as it contains a phosphorus element. Examples of phosphorus flame retardants include phosphate ester flame retardants, melamine polyphosphate flame retardants, phosphazene flame retardants, phosphinic acid flame retardants, and red phosphorus flame retardants.

Among them, the phosphorus flame retardant is preferably a phosphate ester flame retardant, a melamine polyphosphate flame retardant, a phosphazene flame retardant or a phosphinic acid flame retardant, and particularly preferably a phosphinic acid flame retardant. .

Specific examples of the phosphinic acid-based flame retardant include, for example, phosphinates represented by the following general formula (1) (hereinafter sometimes abbreviated as "phosphinate (1)"), the following general formula (2 ) (hereinafter sometimes abbreviated as “diphosphinate (2)”), condensates thereof, and the like.

In general formula (1), R ¹¹ and R ¹² are each independently an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms. M ⁿ¹¹⁺ is an n11-valent metal ion. M is an element belonging to group 2 or group 15 of the periodic table or a transition element. n11 is 2 or 3; When n11 is 2 or 3, multiple R ¹¹ and R ¹² may be the same or different.
In general formula (2), R ²¹ and R ²² are each independently an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms. Y ²¹ is an alkylene group having 1 to 10 carbon atoms or an arylene group having 6 to 10 carbon atoms. M′ ^m21+ is an m21 valent metal ion. M' is an element belonging to group 2 or group 15 of the periodic table or a transition element. n21 is an integer of 1 or more and 3 or less. When n21 is 2 or 3, multiple R ²¹ , R ²² and Y ²¹ may be the same or different. m21 is 2 or 3; x is 1 or 2; When x is 2, multiple M' may be the same or different. n21, x and m21 are integers satisfying the relational expression 2*n21=m21*x.

[R ¹¹ , R ¹² , R ²¹ and R ²² ]
R ¹¹ , R ¹² , R ²¹ and R ²² are each independently an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms. When n11 is 2 or 3, a plurality of R ¹¹ and R ¹² may be the same or different, but are preferably the same for ease of production. When n21 is 2 or 3, the plurality of R ²¹ and R ²² may be the same or different, but are preferably the same for ease of production.

The alkyl group may be chain-like or cyclic, but is preferably chain-like. The chain alkyl group may be linear or branched. Linear alkyl groups include, for example, methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group and the like. Examples of branched chain alkyl groups include 1-methylethyl group, 1-methylpropyl group, 2-methylpropyl group, 1,1-dimethylethyl group, 1-methylbutyl group, 2-methylbutyl group and 3-methylbutyl group. , 1,1-dimethylpropyl group, 1,2-dimethylpropyl group, 2,2-dimethylpropyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group, 1,1-dimethylbutyl group, 1,2-dimethylbutyl group, 1,3-dimethylbutyl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, 3,3-dimethylbutyl group, 1- Examples include ethylbutyl group, 2-ethylbutyl group, 1,1,2-trimethylpropyl group and the like.

Examples of aryl groups include phenyl groups and naphthyl groups.

Alkyl groups and aryl groups may have substituents. Examples of substituents on the alkyl group include aryl groups having 6 or more and 10 or less carbon atoms. Examples of substituents on the aryl group include alkyl groups having 1 to 6 carbon atoms.
Specific examples of the alkyl group having a substituent include a benzyl group and the like.
Specific examples of the aryl group having a substituent include a tolyl group and a xylyl group.

Among them, R ¹¹ , R ¹² , R ²¹ and R ²² are preferably alkyl groups having 1 to 6 carbon atoms, more preferably methyl or ethyl groups.

[ ^Y21 ]
Y ²¹ is an alkylene group having 1 to 10 carbon atoms or an arylene group having 6 to 10 carbon atoms. When n21 is 2 or 3, a plurality of ^Y21 may be the same or different, but are preferably the same for ease of production.

The alkylene group may be chain or cyclic, but is preferably chain. The chain alkylene group may be linear or branched. Examples of linear alkylene groups include methylene, ethylene, trimethylene, tetramethylene, etc., pentamethylene, hexamethylene and the like. Examples of branched alkylene groups include 1-methylethylene group and 1-methylpropylene group.

The arylene group includes, for example, a phenylene group and a naphthylene group.

An alkylene group and an arylene group may have a substituent. Examples of substituents on the alkylene group include aryl groups having 6 or more and 10 or less carbon atoms. Examples of substituents on the arylene group include alkyl groups having 1 to 6 carbon atoms.

Specific examples of the alkylene group having a substituent include a phenylmethylene group, a phenylethylene group, a phenyltrimethylene group, a phenyltetramethylene group and the like.

Specific examples of the arylene group having a substituent include methylphenylene group, ethylphenylene group, tert-butylphenylene group, methylnaphthylene group, ethylnaphthylene group, tert-butylnaphthylene group and the like.

Among them, Y ²¹ is preferably an alkylene group having 1 to 10 carbon atoms, more preferably a methylene group or an ethylene group.

[M and M']
M and M' are each independently an ion of an element belonging to group 2 or group 15 of the periodic table or an ion of a transition element. Examples of ions of elements belonging to Group 2 of the element cycle include calcium ions and magnesium ions. Examples of ions of elements belonging to group 15 of the periodic table include bismuth ions. Examples of transition element ions include zinc ions and aluminum ions.
Also, when x is 2, the multiple M' may be the same or different, but the same is preferred for ease of production.
Among them, M and M' are preferably calcium, zinc or aluminum, more preferably calcium or aluminum.

[x]
x represents the number of M' and is 1 or 2; x can be appropriately selected according to the type of M' and the number of diphosphinic acids.

[n11 and n21]
n11 represents the number of phosphinic acids and the valence of M, and is 2 or 3; n11 can be appropriately selected according to the type and valence of M.
n21 represents the number of diphosphinic acids and is an integer of 1 or more and 3 or less. n21 can be appropriately selected according to the type and number of M'.

[m21]
m21 represents the valence of M' and is 2 or 3;
n21, x and m21 are integers satisfying the relational expression 2*n21=m21*x.

Specific examples of preferred phosphinates (1) include calcium dimethylphosphinate, magnesium dimethylphosphinate, aluminum dimethylphosphinate, zinc dimethylphosphinate, calcium ethylmethylphosphinate, magnesium ethylmethylphosphinate, and ethylmethylphosphine. aluminum acid, zinc ethylmethylphosphinate, calcium diethylphosphinate, magnesium diethylphosphinate, aluminum diethylphosphinate, zinc diethylphosphinate, calcium methyl-n-propylphosphinate, magnesium methyl-n-propylphosphinate, methyl-n - aluminum propylphosphinate, zinc methyl-n-propylphosphinate, calcium methanedi(methylphosphinate), magnesium methanedi(methylphosphinate), aluminum methanedi(methylphosphinate), zinc methanedi(methylphosphinate), benzene-1 , 4-(dimethylphosphinate) calcium, benzene-1,4-(dimethylphosphinate) magnesium, benzene-1,4-(dimethylphosphinate) aluminum, benzene-1,4-(dimethylphosphinate) zinc, methyl Calcium phenylphosphinate, magnesium methylphenylphosphinate, aluminum methylphenylphosphinate, zinc methylphenylphosphinate, calcium diphenylphosphinate, magnesium diphenylphosphinate, aluminum diphenylphosphinate, zinc diphenylphosphinate and the like. Among them, calcium diethylphosphinate or aluminum diethylphosphinate is particularly preferable as the phosphinate (1) because of its excellent flame retardancy.

Specific examples of preferred diphosphinates (2) include calcium methanedi(methylphosphinate), magnesium methanedi(methylphosphinate), aluminum methanedi(methylphosphinate), zinc methanedi(methylphosphinate), and benzene-1. ,4-di(methylphosphinate)calcium, benzene-1,4-di(methylphosphinate)magnesium, benzene-1,4-di(methylphosphinate)aluminum, benzene-1,4-di(methylphosphinate) ) zinc and the like.

The method for producing phosphinates is not particularly limited. 08-073720) and the like. Specifically, it is produced in an aqueous solution using phosphinic acid and a metal carbonate, metal hydroxide or metal oxide. These are essentially monomeric compounds, but also polymeric phosphinates, which are condensates with a degree of condensation of 1 or more and 3 or less, depending on the reaction conditions and under certain circumstances.

The content of the phosphorus-based flame retardant (B) is preferably 0.1% by mass or more and 30.0% by mass or less, more preferably 5.0% by mass or more and 20.0% by mass or less, relative to the mass of the polyamide composition. It is preferably 5.0% by mass or more and 15.0% by mass or less, and particularly preferably 8.0% by mass or more and 12.0% by mass or less. By setting the content of the phosphorus-based flame retardant (B) to the above lower limit or more, a polyamide composition having more excellent flame retardancy can be obtained. On the other hand, by setting the content of the phosphorus-based flame retardant (B) to the above upper limit or less, a polyamide composition having excellent flame retardancy can be obtained without impairing the properties of the polyamide (A).

<Polymer (C) having an oxygen index of 27% or more and having an aromatic group in the main chain>
(C) The polymer is not particularly limited as long as it has an oxygen index of 27% or more. Specific examples of the (C) polymer include polyphenylene sulfide, polyphenylene ether, maleic anhydride-modified polyphenylene ether, polysulfone, polyetheretherketone, polyetherimide, polyamideimide, and polyethersulfone. Among them, the (C) polymer is preferably polyphenylene sulfide, polyphenylene ether, maleic anhydride-modified polyphenylene ether, or polysulfone, and more preferably polyphenylene sulfide, polyphenylene ether, or maleic anhydride-modified polyphenylene ether.

In general, the "oxygen index" is an index of the flammability of a material, and is expressed by the minimum oxygen concentration (% by volume) required for the material to sustain combustion. Oxygen index can be measured according to ISO 4589-2.

<Filler (D)>
Preferably, the polyamide composition of the present embodiment further contains a filler (D).
The polyamide composition of the present embodiment contains the phosphorus-based flame retardant (B), the polymer (C), and the filler (D), so that it has excellent flame retardancy, heat resistance, and thermal stability. and have a higher melting point.

The filler is not particularly limited, and known materials can be used.
For example, glass fiber, carbon fiber, calcium silicate fiber, potassium titanate fiber, aluminum borate fiber, glass flake, talc, kaolin, mica, hydrotalcite, calcium carbonate, magnesium carbonate, zinc carbonate, zinc oxide, phosphoric acid Calcium monohydrogen, wollastonite, silica, zeolite, alumina, boehmite, aluminum hydroxide, titanium oxide, silicon oxide, magnesium oxide, calcium silicate, sodium aluminosilicate, magnesium silicate, ketjen black, acetylene black, furnace black , carbon nanotubes, graphite, brass, copper, silver, aluminum, nickel, iron, calcium fluoride, clay, montmorillonite, swelling fluoromica, silicon nitride, and apatite.
The filler may be used alone or in combination of two or more.

Among the fillers, the glass fiber and the carbon fiber may have a circular cross section or a flat cross section. Examples of the flattened cross section include a rectangular shape, an oval shape close to a rectangle, an elliptical shape, and a cocoon shape with a constricted central portion in the longitudinal direction.

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

The number average fiber diameter of the inorganic filler in the polyamide composition is obtained, for example, by placing the polyamide composition in an electric furnace, incinerating the organic matter contained in the polyamide composition, and removing, for example, 100 or more glass fibers from the residue. The number average fiber diameter can be obtained by selecting arbitrarily, observing with an SEM photograph, and measuring the fiber diameter.

Similarly, the weight average fiber length of the filler in the polyamide composition is determined by arbitrarily selecting glass fibers and measuring the fiber length using an SEM photograph at a magnification of 1000 times to measure the weight average fiber length. can be done.

As the filler, reinforcing fibers having a weight-average fiber length of 1 mm or more and 15 mm or less are more preferable. The weight average fiber length of such reinforcing fibers is preferably 1 mm or more and 15 mm or less, more preferably 3 mm or more and 12 mm or less, from the viewpoint of improving mechanical strength, rigidity and moldability.

In addition, the weight average fiber length of the reinforcing fiber is observed using an optical microscope after removing only the polyamide of the polyamide composition by burning or dissolving, and the length of 400 reinforcing fibers arbitrarily selected using an image analyzer. It is obtained by measuring the thickness and calculating the average value.
Here, when the length of each reinforcing fiber is set to L1, L2, . In the following formula, "i" takes an integer of 1 or more and 400 or less.

Weight average fiber length = Σ(Li ² )/ΣLi

The weight average fiber length is a value applied to the reinforcing fibers contained in the polyamide composition of the present embodiment. That is, the weight-average fiber length of the reinforcing fibers before blending with the polyamide is not limited to the above.

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

As the reinforcing fibers, the above materials may be used alone, or two or more of them may be used in combination. Among them, from the viewpoint of improving mechanical strength and rigidity, it is preferably one or more selected from the group consisting of glass fiber, carbon fiber, boron fiber, and metal fiber, and more preferably glass fiber or carbon fiber.

Although the reinforcing fibers are not particularly limited in terms of the average fiber diameter of the single fibers, those having a diameter of 5 μm or more and 25 μm or less, for example, are generally used.

The average fiber diameter of the single fiber is obtained by observing the reinforcing fiber to be used under an optical microscope and calculating the average value when measuring the diameter of 400 arbitrarily selected fibers using an image analyzer. be done.
As the reinforcing fibers, rovings, which are continuous fibers obtained by bundling single fibers, are preferably used.

[Surface treatment agent]
Inorganic fillers such as glass fibers and carbon fibers may be surface-treated with a surface treatment agent such as a silane coupling agent.
The silane coupling agent is not particularly limited, and examples include γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, and N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane. mercaptosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane; epoxysilanes; vinylsilanes and the like. Among them, aminosilanes are preferred.
As the silane coupling agent, one type may be used alone, or two or more types may be used in combination.

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

Among them, from the viewpoint of the mechanical properties (among others, strength) of the polyamide composition, a copolymer containing a carboxylic anhydride-containing unsaturated vinyl monomer and an unsaturated vinyl monomer as structural units (carboxylic anhydride-containing Copolymers containing unsaturated vinyl monomers and unsaturated vinyl monomers excluding carboxylic acid anhydride-containing unsaturated vinyl monomers as structural units), epoxy compounds, and polyurethane resins are preferred, and carboxylic acid anhydrides are preferred. Copolymers and polyurethane resins containing unsaturated vinyl monomers and unsaturated vinyl monomers as structural units are more preferable.
The sizing agent may be used singly or in combination of two or more.

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

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

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

A copolymer containing a carboxylic acid anhydride-containing unsaturated vinyl monomer and an unsaturated vinyl monomer as structural units has a weight average molecular weight of 2,000 or more from the viewpoint of improving the fluidity of the polyamide composition. more preferably 2,000 or more and 1,000,000 or less, and even more preferably 2,000 or more and 1,000,000 or less.
A weight average molecular weight can be measured by GPC.

Epoxy compounds are not particularly limited, and examples include ethylene oxide, propylene oxide, butene oxide, pentene oxide, hexene oxide, heptene oxide, octene oxide, nonene oxide, decene oxide, undecene oxide, and dodecene oxide. , pentadecene oxide, eicosene oxide; glycidol, epoxypentanol, 1-chloro-3,4-epoxybutane, 1-chloro-2-methyl-3,4-epoxybutane, 1,4 - Alicyclic epoxy compounds such as dichloro-2,3-epoxybutane, cyclopentene oxide, cyclohexene oxide, cycloheptene oxide, cyclooctene oxide, methylcyclohexene oxide, vinylcyclohexene oxide, and epoxidized cyclohexene methyl alcohol; terpene-based epoxy compounds; aromatic epoxy compounds such as styrene oxide, p-chlorostyrene oxide and m-chlorostyrene oxide; epoxidized soybean oil; and epoxidized linseed oil.

Polyurethane resins are not particularly limited, and those commonly used as sizing agents can be used. For example, m-xylylene diisocyanate (XDI), 4,4′-methylenebis(cyclohexyl isocyanate) (HMDI), isophorone diisocyanate (IPDI) and other isocyanates synthesized from polyester-based and polyether-based diols. can be preferably used.

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

Polyacrylic acid may be in salt form with primary, secondary, or tertiary amines.
Amines are not particularly limited, and examples thereof include triethylamine, triethanolamine, glycine, and the like.

The degree of neutralization of polyacrylic acid by having a salt form means the ratio of the acrylic acid component forming a salt among the acrylic acid components of polyacrylic acid, and other concomitant agents (silane coupling agents, etc. ) and from the viewpoint of reducing amine odor, the content is preferably 20% or more and 90% or less, more preferably 40% or more and 60% or less.

The weight average molecular weight of the salt-form polyacrylic acid is preferably 3,000 or more and 50,000 or less. When the weight-average molecular weight is at least the above lower limit, the bundling properties of glass fibers and carbon fibers can be further improved. On the other hand, when the weight average molecular weight is equal to or less than the above upper limit, the mechanical properties of the polyamide composition can be further improved.

Other copolymerizable monomers in the copolymer of acrylic acid and other copolymerizable monomers are not particularly limited, and are, for example, monomers having one or more functional groups selected from the group consisting of hydroxyl groups and carboxyl groups. Some examples include acrylic acid, maleic acid, methacrylic acid, vinylacetic acid, crotonic acid, isocrotonic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid. As other copolymerizable monomers, monomers that are esters of monomers having one or more functional groups selected from the group consisting of hydroxyl groups and carboxyl groups can be preferably used.

The copolymer of acrylic acid and other copolymerizable monomer preferably has a weight average molecular weight of 1,000 to 90,000, more preferably 1,000 to 25,000.

Copolymers of acrylic acid and other copolymerizable monomers may be in salt form with primary, secondary, or tertiary amines.

Amines are not particularly limited, and examples thereof include triethylamine, triethanolamine, glycine, and the like.

The degree of neutralization of a copolymer by having a salt form refers to the proportion of the acid component forming a salt among the acid components of the copolymer, and the degree of neutralization of the mixed solution with other concomitant agents (such as silane coupling agents). From the viewpoint of improving stability and reducing amine odor, it is preferably 20% or more and 90% or less, more preferably 40% or more and 60% or less.

The weight average molecular weight of the copolymer in salt form is preferably between 3,000 and 50,000. When the weight-average molecular weight is at least the above lower limit, the bundling properties of glass fibers and carbon fibers can be further improved. On the other hand, when the weight average molecular weight is equal to or less than the above upper limit, the mechanical properties of the polyamide composition can be further improved.

A fibrous filler such as glass fiber or carbon fiber containing a sizing agent is obtained by applying the sizing agent to the glass fiber or carbon fiber by using a known method such as a roller applicator in a known glass fiber or carbon fiber manufacturing process. It is obtained by continuously reacting by drying a fiber strand produced by applying it to a fibrous filler such as carbon fiber.

The fiber strands may be used as they are as rovings, or may be further subjected to a cutting process and used as chopped glass strands.

The sizing agent is preferably added (added) at a solid content of 0.2% by mass or more and 3% by mass or less with respect to 100% by mass of a fibrous filler such as glass fiber or carbon fiber. It is more preferable to provide (add) at least 2% by mass.
When the amount of the bundling agent added is equal to or more than the above lower limit, the bundling of the fibrous filler such as glass fiber or carbon fiber can be maintained. On the other hand, when the amount of the sizing agent added is equal to or less than the above upper limit, the thermal stability of the polyamide composition can be further improved.

Further, the strand may be dried after the cutting step, or the strand may be cut after drying.

When wollastonite is used as a filler constituting the polyamide composition, the polyamide composition has a number average fiber diameter of 3 μm or more and 30 μm or less, a weight average fiber length of 10 μm or more and 500 μm or less, and an aspect ratio Those having (L/D) of 3 or more and 100 or less are preferably used.

When talc, mica, kaolin, silicon nitride, or the like is used as the filler, those having a number average fiber diameter of 0.1 μm or more and 3 μm or less in the polyamide composition are preferable.

The content of the filler (D) can be, for example, 10.0% by mass or more and 90.0% by mass or less, and 15.0% by mass or more and 75.0% by mass, relative to the total mass of the polyamide composition. % or less, 20.0 mass % or more and 60.0 mass % or less, and 25.0 mass % or more and 50.0 mass % or less. When the content of the filler (D) is within the above range, it is possible to obtain a polyamide composition that is superior in flame retardancy, heat resistance, and thermal stability and has a higher melting point.

<Other components (E)>
The polyamide composition of the present embodiment can contain another component (E) in addition to the above components (A) to (D).
For example, the polyamide composition may further contain at least one selected from heat stabilizers (E1) and light stabilizers (E2). By further including at least one selected from a heat stabilizer and a light stabilizer, the polyamide composition can improve heat resistance, heat stability, etc. without impairing the properties of the polyamide (A). While being satisfactory, it is furthermore excellent in terms of strength and molding processability.

[Heat stabilizer (E1)]
Examples of heat stabilizers (E1) include, but are not limited to, phenol-based heat stabilizers, phosphorus-based heat stabilizers, amine-based heat stabilizers, Groups Ib, IIb, and IIIa of the periodic table. , metal salts of elements of groups IIIb, IVa and IVb, halides of alkali metals and alkaline earth metals, and the like.

Phenolic heat stabilizers include, but are not limited to, hindered phenol compounds. Hindered phenol compounds have the property of imparting excellent heat resistance and light resistance to resins such as polyamides and fibers.

Examples of the hindered phenol compound include, but are not limited to, N,N'-hexane-1,6-diylbis[3-(3,5-di-tert-butyl-4-hydroxyphenylprop onamide), pentaerythrityl-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], N,N'-hexamethylenebis(3,5-di-tert-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-tetraoxaspiro[5,5]undecane, 3,5-di-tert -butyl-4-hydroxybenzylphosphonate-diethyl ester, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 1,3,5 -tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanuric acid and the like.
These hindered phenol compounds may be used alone or in combination of two or more.
In particular, from the viewpoint of improving heat aging resistance, the hindered phenol compound includes N,N'-hexane-1,6-diylbis[3-(3,5-di-tert-butyl-4-hydroxyphenylpropionamide )] is preferred.

When using a phenolic heat stabilizer, the content of the phenolic heat stabilizer in the polyamide composition is preferably 0% by mass or more and 1% by mass or less with respect to the total mass of the polyamide composition, and 0.01% by mass 1 mass % or less is more preferable, and 0.1 mass % or more and 1 mass % or less is still more preferable.
When the content of the phenolic heat stabilizer is within the above range, the heat aging resistance of the polyamide composition can be further improved and the amount of gas generated can be further reduced.

Examples of phosphorus-based heat stabilizers include, but are not limited to, pentaerythritol-type phosphite compounds, trioctylphosphite, trilaurylphosphite, tridecylphosphite, octyldiphenylphosphite, trisisodecyl Phosphite, phenyldiisodecylphosphite, phenyldi(tridecyl)phosphite, diphenylisooctylphosphite, diphenylisodecylphosphite, diphenyl(tridecyl)phosphite, triphenylphosphite, tris(nonylphenyl)phosphite, tris(2 ,4-di-tert-butylphenyl)phosphite, tris(2,4-di-tert-butyl-5-methylphenyl)phosphite, tris(butoxyethyl)phosphite, 4,4'-butylidene-bis( 3-methyl-6-tert-butylphenyl-tetra-tridecyl)diphosphite, tetra(C12-C15 mixed alkyl)-4,4'-isopropylidene diphenyl diphosphite, 4,4'-isopropylidenebis(2-tert -butylphenyl)-di(nonylphenyl)phosphite, tris(biphenyl)phosphite, tetra(tridecyl)-1,1,3-tris(2-methyl-5-tert-butyl-4-hydroxyphenyl)butanedi Phosphites, tetra(tridecyl)-4,4'-butylidenebis(3-methyl-6-tert-butylphenyl) diphosphite, tetra(C1-C15 mixed alkyl)-4,4'-isopropylidene diphenyl diphosphite, tris (mono, dimixed nonylphenyl) phosphite, 4,4′-isopropylidenebis(2-tert-butylphenyl)-di(nonylphenyl)phosphite, 9,10-di-hydro-9-oxa-9- Oxa-10-phosphaphenanthrene-10-oxide, tris(3,5-di-tert-butyl-4-hydroxyphenyl)phosphite, hydrogenated-4,4′-isopropylidene diphenyl polyphosphite, bis (Octylphenyl)-bis(4,4′-butylidenebis(3-methyl-6-tert-butylphenyl))-1,6-hexanol diphosphite, hexatridecyl-1,1,3-tris(2- methyl-4-hydroxy-5-tert-butylphenyl)diphosphite, tris(4,4'-isopropylidenebis(2-tert-butylphenyl) )) phosphite, tris(1,3-stearoyloxyisopropyl)phosphite, 2,2-methylenebis(4,6-di-tert-butylphenyl)octylphosphite, 2,2-methylenebis(3-methyl- 4,6-di-tert-butylphenyl)2-ethylhexylphosphite, tetrakis(2,4-di-tert-butyl-5-methylphenyl)-4,4'-biphenylenediphosphite, tetrakis(2,4 -di-tert-butylphenyl)-4,4'-biphenylene diphosphite and the like.
These phosphorus-based heat stabilizers may be used alone or in combination of two or more.
Among them, as the phosphorus-based heat stabilizer, pentaerythritol type phosphite compound or tris(2,4-di-t-butyl Phenyl)phosphite is preferred, and pentaerythritol-type phosphite compound is more preferred.

Examples of pentaerythritol-type phosphite compounds include, but are not limited to, 2,6-di-tert-butyl-4-methylphenyl-phenyl-pentaerythritol diphosphite, 2,6-di- tert-butyl-4-methylphenyl-methyl-pentaerythritol diphosphite, 2,6-di-tert-butyl-4-methylphenyl-2-ethylhexyl-pentaerythritol diphosphite, 2,6-di-tert- Butyl-4-methylphenyl-isodecyl-pentaerythritol diphosphite, 2,6-di-tert-butyl-4-methylphenyl-lauryl-pentaerythritol diphosphite, 2,6-di-tert-butyl-4- Methylphenyl-isotridecyl-pentaerythritol diphosphite, 2,6-di-tert-butyl-4-methylphenyl-stearyl pentaerythritol diphosphite, 2,6-di-tert-butyl-4-methylphenyl cyclohexyl -pentaerythritol diphosphite, 2,6-di-tert-butyl-4-methylphenyl-benzyl-pentaerythritol diphosphite, 2,6-di-tert-butyl-4-methylphenyl ethyl cellosolve-pentaerythritol Diphosphite, 2,6-di-tert-butyl-4-methylphenyl-butylcarbitol-pentaerythritol diphosphite, 2,6-di-tert-butyl-4-methylphenyl-octylphenyl-pentaerythritol diphosphite phosphites, 2,6-di-tert-butyl-4-methylphenyl-nonylphenyl pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, Bis(2,6-di-tert-butyl-4-ethylphenyl) pentaerythritol diphosphite, 2,6-di-tert-butyl-4-methylphenyl-2,6-di-tert-butylphenyl-penta Erythritol diphosphite, 2,6-di-tert-butyl-4-methylphenyl-2,4-di-tert-butylphenyl-pentaerythritol diphosphite, 2,6-di-tert-butyl-4-methyl Phenyl-2,4-di-tert-octylphenyl-pentaerythritol diphosphite, 2,6-di-tert-butyl-4-methylphenyl -2-cyclohexylphenyl-pentaerythritol diphosphite, 2,6-di-tert-amyl-4-methylphenyl-phenyl pentaerythritol diphosphite, bis(2,6-di-tert-amyl-4 -methylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-octyl-4-methylphenyl)pentaerythritol diphosphite and the like.
These pentaerythritol-type phosphite compounds may be used alone or in combination of two or more.

Among them, as the pentaerythritol-type phosphite compound, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, bis(2 ,6-di-tert-butyl-4-ethylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-amyl-4-methylphenyl)pentaerythritol diphosphite, bis(2,6-di -tert-octyl-4-methylphenyl)pentaerythritol diphosphite or bis(2,4-dicumylphenyl)pentaerythritol diphosphite are preferred.

When using a phosphorus-based heat stabilizer, the content of the phosphorus-based heat stabilizer in the polyamide composition is preferably 0.1% by mass or more and 20.0% by mass or less with respect to the total mass of the polyamide composition, and 0 0.2% by mass or more and 7.0% by mass or less is more preferable, 0.5% by mass or more and 3.0% by mass or less is still more preferable, and 0.55% by mass or more and 2.5% by mass or less is even more preferable. 55% by mass or more and 2.0% by mass or less is particularly preferable, and 0.55% by mass or more and 1.5% by mass or less is most preferable.
When the content of the phosphorus-based heat stabilizer is within the above range, the polyamide composition tends to be more excellent in whiteness, reflow resistance, heat discoloration resistance, extrusion processing stability, and molding processing stability.

Examples of amine heat stabilizers 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-dimethyldenyl)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, aromatic amines such as N-phenyl-N'-1,3-dimethylbutyl-p-phenylenediamine and N-(1-methylheptyl)-N'-phenyl-p-phenylenediamine;
These amine heat stabilizers may be used alone or in combination of two or more.

When using an amine-based heat stabilizer, the content of the amine-based heat stabilizer in the polyamide composition is preferably 0% by mass or more and 1% by mass or less with respect to the total mass of the polyamide composition, and 0.01% by mass. 1 mass % or less is more preferable, and 0.1 mass % or more and 1 mass % or less is still more preferable.
When the content of the amine-based heat stabilizer is within the above range, the heat aging resistance of the polyamide composition can be further improved, and the amount of gas generated can be further reduced.

The metal salts of the elements of Groups Ib, IIb, IIIa, IIIb, IVa, and IVb of the periodic table are not particularly limited, and are preferably copper salt.

The copper salt is not particularly limited, and examples thereof include copper halides (copper iodide, cuprous bromide, cupric bromide, cuprous chloride, etc.), copper acetate, copper propionate, and benzoin. Copper complex salts in which copper is coordinated to a chelating agent such as copper acid, copper adipate, copper terephthalate, copper isophthalate, copper salicylate, copper nicotinate and copper stearate, ethylenediamine, ethylenediaminetetraacetic acid, and the like. Among them, it is preferably one or more selected from the group consisting of copper iodide, cuprous bromide, cupric bromide, cuprous chloride, and copper acetate, and more copper iodide or copper acetate. preferable. When the above metal salts, especially copper salts, are used, a polyamide composition having excellent heat aging resistance and capable of suppressing metal corrosion (hereinafter simply referred to as "metal corrosion") of screw and cylinder parts during extrusion is obtained. be able to.
The above metal salts may be used alone or in combination of two or more.

When using a copper salt, the amount of the copper salt in the polyamide composition is preferably 0.01% by mass or more and 0.2% by mass or less with respect to the total mass of the polyamide composition, and 0.02% by mass. % or more and 0.15 mass % or less. When the blending amount is within the above range, the heat aging resistance is further improved, and copper precipitation and metal corrosion can be further suppressed.

Further, from the viewpoint of improving heat aging resistance, the content concentration of the copper element is preferably 10 mass ppm or more and 500 mass ppm or less, and 30 mass ppm or more and 500 mass ppm with respect to the total mass of the polyamide composition. It is more preferably 50 mass ppm or more and 300 mass ppm or less.

Halides of alkali metals and alkaline earth metals are not particularly limited, and examples thereof include potassium iodide, potassium bromide, potassium chloride, sodium iodide, sodium chloride, and mixtures thereof. Among them, potassium iodide, potassium bromide, or a mixture thereof is preferred, and potassium iodide is more preferred, from the viewpoint of improving heat aging resistance and suppressing metal corrosion.
The above halides may be used alone or in combination of two or more.

When alkali metal and alkaline earth metal halides are used to prepare the polyamide composition, the amount of the alkali and alkaline earth metal halides in the polyamide composition is 0 with respect to the total mass of the polyamide composition. 05% by mass or more and 5% by mass or less, and more preferably 0.2% by mass or more and 25% by mass or less. When the blending amount is within the above range, the heat aging resistance is further improved, and copper precipitation and metal corrosion can be further suppressed.

Mixtures of copper salts and halides of alkali and alkaline earth metals can be suitably used as heat stabilizers in polyamide compositions. The ratio of the copper salt to the alkali and alkaline earth metal halides is such that the molar ratio of halogen to copper (halogen/copper) is preferably 2/1 or more and 40/1 or less, and 5/1 or more and 30/ It is more preferable to be 1 or less.
When the molar ratio (halogen/copper) is within the above range, the heat aging resistance of the polyamide composition can be further improved. Further, when the molar ratio (halogen/copper) is equal to or higher than the above lower limit, copper deposition and metal corrosion can be further suppressed. When the molar ratio (halogen/copper) is equal to or less than the above upper limit, corrosion of the screw of the molding machine can be further prevented without substantially impairing mechanical properties such as toughness.

[Light stabilizer (E2)]
The light stabilizer (E2) has a property of imparting excellent heat resistance and light resistance to resins such as polyamides and fibers. Light stabilizers include amine-based light stabilizers.

Examples of amine heat stabilizers 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-tetramethylpiperidine, 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-tetra methyl-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, 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-tetramethyl-4-piperidyl tolylene-2,4-dicarbamate, bis ( 2,2,6,6-tetramethyl-4-piperidyl)-hexamethylene-1,6-dicarbamate, tris(2,2,6,6-tetramethyl-4-piperidyl)-benzene-1,3, 5-tricarboxylate, tris(2,2,6,6-tetramethyl-4-piperidyl)-benzene-1,3,4-tricarboxylate, 1-[2-{3-(3,5-di -tert-butyl-4-hydroxyphenyl)propionyloxy}butyl]-4-[3-(3,5-di-tert-butyl-4- Hydroxyphenyl)propionyloxy]2,2,6,6-tetramethylpiperidine, 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6,6-pentamethyl-4-piperidinol and β,β , β', β'-tetramethyl-3,9-[2,4,8,10-tetraoxaspiro(5,5)undecane]diethanol.
These amine heat stabilizers may be used alone or in combination of two or more.

Among them, amine light stabilizers include 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, N,N'-bis-2,2,6,6-tetramethyl-4-piperidinyl-1,3- Benzenedicarboxamide or tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate are preferred.
Further, amine light stabilizers include bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, N,N'-bis-2,2,6,6-tetramethyl-4-piperidinyl -1,3-benzenedicarboxamide or tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate is more preferred, and N,N'- More preferred is bis-2,2,6,6-tetramethyl-4-piperidinyl-1,3-benzenedicarboxamide.

The content of the amine light stabilizer is preferably 0% by mass or more and 2% by mass or less, more preferably 0.01% by mass or more and 2% by mass or less, relative to the total mass of the polyamide composition. , more preferably 0.1% by mass or more and 2% by mass. When the content of the amine light stabilizer is within the above range, the light stability and heat aging resistance of the polyamide composition can be further improved, and the amount of generated gas can be further reduced.

[Other additives (E3)]
The polyamide composition can also contain other additives (E3) that are commonly used in polyamides, as long as they do not impair the purpose of the present embodiment. Other additives (E3) include, for example, coloring agents such as pigments and dyes (including coloring masterbatches), fibrillating agents, lubricants, fluorescent bleaching agents, plasticizers, ultraviolet absorbers, antistatic agents, flow Properties improvers, reinforcing agents, spreading agents, nucleating agents, rubbers, reinforcing agents, other polymers, and the like.

<Method for producing polyamide composition>
The method of adding the constituent components (A) to (E) of the polyamide composition includes polyamide (A), phosphorus-based flame retardant (B), polymer (C), and, if necessary, filler (D) and other constituent components (E) described above are not particularly limited.

As a method for mixing the constituent materials of the polyamide composition, for example, a method of mixing using a Henschel mixer or the like and supplying it to a melt kneader and kneading, or a method of mixing polyamide (A) and polymer in a molten state with a single screw or twin screw extruder A method of blending (C) with the phosphorus flame retardant (B), the filler (D) and other constituent components (E) from a side feeder, and the like can be mentioned.

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

The melt-kneading temperature is preferably about 250° C. or higher and 375° C. or lower in terms of resin temperature.

The melt-kneading time is preferably about 0.5 minutes or more and 5 minutes or less.

The apparatus for melt-kneading is not particularly limited, and known apparatuses such as single-screw or twin-screw extruders, Banbury mixers, mixing rolls, and other melt-kneaders can be used.

The method for producing the polyamide composition when the filler (D) contained in the polyamide composition is a reinforcing fiber having a weight average fiber length of 1 mm or more and 15 mm or less is not particularly limited. For example, a pultrusion method in which polyamide (A) is melt-kneaded with a twin-screw extruder and the molten polyamide (A) is impregnated into a reinforcing fiber roving to obtain a polyamide-impregnated strand, or Reference Document 4 (JP 2008- No. 221574), a method of sufficiently impregnating the polyamide by twisting the impregnated strand in a helical shape can be mentioned.

≪Molded product≫
The molded article of this embodiment is obtained by molding the polyamide composition described above.
The molded article of the present embodiment has a high crystallization enthalpy ΔHc and a high glass transition temperature Tg, and is excellent in hot strength, hot stiffness, impact resistance, and creep resistance, so that it can be suitably used for automobile parts. can.

<Manufacturing method of molded product>
The molded article of the present embodiment can be obtained by subjecting the above polyamide composition to known molding methods such as press molding, injection molding, gas-assisted injection molding, welding molding, extrusion molding, blow molding, film molding, blow molding, multi-layer molding, It can be obtained by molding using melt spinning or the like.

<Application>
The molded article of the present embodiment has excellent hot strength, hot stiffness, and impact resistance, and has improved creep resistance as shown in the following examples. It can be suitably used as a material for various parts such as industrial materials, extrusion applications, daily necessities and household goods.

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

Automotive air intake system parts include, for example, air intake manifolds, intercooler inlets, exhaust pipe covers, inner bushes, bearing retainers, engine mounts, engine head covers, resonators, throttle bodies and the like.

Automotive cooling system parts include, for example, chain covers, thermostat housings, outlet pipes, radiator tanks, oil pumps, delivery pipes and the like.

Automotive fuel system parts include, for example, fuel delivery pipes and gasoline tank cases.

Interior parts include, for example, instrument panels, console boxes, glove boxes, steering wheels, trims, and the like.

Exterior parts include, for example, moldings, lamp housings, front grilles, mudguards, side bumpers, door mirror stays, roof rails, and the like.

The electrical parts are not particularly limited, and examples thereof include connectors, wire harness connectors, motor parts, lamp sockets, sensor-mounted switches, combination switches, and the like.

Electrical and electronic applications include, for example, connectors, switches, relays, printed wiring boards, housings for electronic components, electrical outlets, noise filters, coil bobbins, motor end caps, and the like.

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

For everyday and household items, for example, buttons, food containers, office furniture, and the like.

Extrusion applications include, for example, films, sheets, filaments, tubes, rods, hollow molded articles, and the like.

EXAMPLES Hereinafter, the present embodiment will be described in more detail with reference to examples, but the present embodiment is not limited to the examples.
Raw materials used in Examples and Comparative Examples and methods for measuring physical properties are shown below.
In this example, 1 kg/cm ² means 0.098 MPa.

<Raw materials of polyamide (A)>
[Raw material of dicarboxylic acid unit (a)]
(1) Terephthalic acid (TPA): manufactured by Tokyo Chemical Industry Co., Ltd. (2) 1,4-cyclohexanedicarboxylic acid (CHDA): manufactured by Eastman Chemical, trade name: 1,4-CHDA HP grade (trans/cis (molar ratio) = 25/75)
(3) Isophthalic acid (IPA): manufactured by Tokyo Chemical Industry Co., Ltd.

[Raw material of diamine unit (b)]
(1) Hexamethylenediamine (C6DA): manufactured by Tokyo Chemical Industry Co., Ltd. (2) 2-Methylpentamethylenediamine (2MC5DA): manufactured by Tokyo Chemical Industry Co., Ltd. (3) Nonamethylenediamine (C9DA): manufactured by Aldrich (4 ) 2-Methyloctamethylenediamine (2MC8DA): prepared according to the method described in reference 5 (JP-A-05-17413).
(5) 1,10-decanediamine (C10DA): manufactured by Tokyo Chemical Industry Co., Ltd.

<Commercially available polyamide (A)>
(1) Polyamide (A-12): Polyamide 66 (manufactured by Asahi Kasei, trade name: 1300-301)
(2) Polyamide (A-13): Polyamide 1 containing 4T (manufactured by DSM, trade name: TD100)
(3) Polyamide (A-14): Polyamide 2 containing 4T (manufactured by DSM, trade name: DX100)

<Phosphorus flame retardant (B)>
B-1: Phosphinic acid-based flame retardant: aluminum diethylphosphinate (manufactured by Clariant, trade name: "Exolit OP1230")
B-2: Phosphinic acid-based flame retardant: calcium diethylphosphinate (manufactured by Taihei Kagaku Sangyo Co., Ltd.)

<Polymer (C) having an oxygen index of 27% or more and having an aromatic group in the main chain>
C-1: Polyphenylene sulfide (PPS) (manufactured by DIC) (oxygen index: 46%, molecular weight: 30000)
C-2: Maleic anhydride-modified polyphenylene ether (m-PPE) (manufactured by Asahi Kasei Corporation) (oxygen index: 28%, molecular weight: 54000)

<Filler (D)>
D-1: Glass fiber (GF) manufactured by Nippon Electric Glass Product name: ECS03T275H Average fiber diameter (average particle diameter) 10 μm (perfect circle), cut length 3 mm

<Method for measuring physical properties of polyamide (A)>
[Physical properties 1]
(Constituent unit content of polyamide (A))
The specific dicarboxylic acid unit content (mol%) is obtained by calculation as (number of moles of specific dicarboxylic acid added as raw material monomer) / (number of moles of all dicarboxylic acids added as raw material monomer) x 100. rice field.

The specific diamine unit content (mol %) was obtained by calculation as (number of moles of specific diamine added as raw material monomer)/(number of moles of all diamines added as raw material monomer)×100.
In addition, the number of moles of diamine added as an additive at the time of polymerization is not included in the denominator and numerator when calculating with the above formula.

[Physical properties 2]
(Melting peak temperatures Tm1 and Tm2 (°C) of polyamide (A), enthalpy of crystallization ΔHc (J/g))
It was measured using a Diamond-DSC manufactured by PERKIN-ELMER in accordance with JIS-K7121. The measurement conditions appear when about 10 mg of polyamide is heated to 280° C. or more and 370° C. or less according to the melting point (Tm) of the sample at a heating rate of 20° C./min in a nitrogen atmosphere (at the time of the first temperature rise). The melting peak temperature that appeared on the highest temperature side of the endothermic peak (melting peak) was defined as Tm1 (°C). Moreover, the melting peak temperature Tm2 of polyamide (A) was measured as follows. After the first temperature rise, the temperature was maintained for 2 minutes in a molten state at the highest temperature rise, then the temperature was lowered to 30°C at a temperature lowering rate of 20°C/min, and held at 30°C for 2 minutes. After that, when the temperature was similarly increased at a temperature increase rate of 20° C./min (during the second temperature increase), the endothermic peak temperature that appeared on the highest side of the endothermic peak that appeared was taken as the melting peak temperature Tm2 of the polyamide itself.

The temperature of the exothermic peak (crystallization peak) that appears when the temperature is lowered at a cooling rate of 20° C./min is defined as the crystallization peak temperature Tc (° C.), and the total peak area of Tc is defined as the crystallization enthalpy ΔHc (J/g). bottom.

[Physical properties 3]
(Glass transition temperature Tg (°C) of polyamide (A))
The glass transition temperature Tg (° C.) was measured according to JIS-K7121 using a Diamond-DSC manufactured by PERKIN-ELMER. Measurement conditions were as follows: a sample in a molten state obtained by melting polyamide on a hot stage (EP80 manufactured by Mettler) was rapidly cooled using liquid nitrogen and solidified to obtain a measurement sample. Using 10 mg of the sample, the temperature was raised from 30° C. to 350° C. at a heating rate of 20° C./min, and the glass transition temperature Tg (° C.) was measured.

[Physical properties 4]
(molecular weight)
The number average molecular weight Mn, the weight average molecular weight Mw, and the molecular weight distribution Mw/Mn were measured by PMMA (polymethyl methacrylate) standard sample (manufactured by Polymer Laboratory Co., Ltd.). As GPC columns, TSK-GEL GMHHR-M and G1000HHR were used.

<Evaluation method>
[Manufacturing of molded products]
Each polyamide composition obtained in Examples and Comparative Examples was injection-molded into a multi-purpose test piece (type A) according to ISO 3167 to obtain a molded article. The obtained molded article was evaluated using the methods shown below.

[Evaluation 1]
(High temperature tensile strength (MPa))
Using the molded product (multi-purpose test piece), a tensile test was performed at a tensile speed of 5 mm/min under an environment of 120° C. in accordance with ISO 527 to measure the tensile strength (MPa).

[Evaluation 2]
(Charpy impact strength)
Charpy impact strength (kJ/m ² ) was measured according to ISO 179 using a molded product (multipurpose test piece).

[Evaluation 3]
(creep strain)
The molded product is installed in a creep test (model C100-6) manufactured by Toyo Seiki, and a tensile test is performed under a 120 ° C environment with a test load of 85 MPa. (%) was measured.

[Production of test piece for flame retardancy evaluation]
A test piece for flame retardancy evaluation (length 127 mm, width 12.7 mm, thickness 0.4 mm) was placed in an injection molding machine (PS40E manufactured by Nissei Kogyo Co., Ltd.) with a UL test piece mold (mold temperature = 120 ° C. ) was attached, and each polyamide composition was molded at a cylinder temperature of 360°C. The injection pressure was the full filling pressure + 2% pressure when molding the test piece for flame retardancy evaluation.

[Evaluation 4]
(Flame retardance)
The measurement was performed using the method of UL94 (the standard established by Under Writers Laboratories Inc., USA). The flame retardant grade was evaluated according to the UL94 standard (vertical burning test) to determine which grade was V-0, V-1, or V-2. Incidentally, the smaller the numerical value of the grade, the higher the flame retardancy, and the flame retardancy of V-0 was evaluated as having no practical problem.

<Method for producing polyamide (A)>
[Production Example 1]
(Production of polyamide (A-1))
A polymerization reaction of polyamide was carried out as follows by a hot melt polymerization method.
A mixture of 1695 g (10.2 mol) of TPA and 310 g (1.8 mol) of CHDA as dicarboxylic acid, 1395 g (12.0 mol) of C6DA as diamine and 300 g of distilled water was prepared.

The resulting mixture was charged into an autoclave having an internal volume of 5.4 L (manufactured by Nitto Koatsu), and the inside of the autoclave was replaced with nitrogen. When the temperature inside the autoclave tank (hereinafter also simply referred to as "inside the tank") is heated from room temperature to 80 ° C., the gauge pressure (hereinafter, all pressures in the tank are referred to as gauge pressure), about 2 0 kg/cm ² (G) was shown and maintained. When the heating was continued for a while, the pressure valve was opened, and the mixture was left until normal temperature and normal pressure returned to obtain a prepolymer. The obtained prepolymer was pulverized and further treated as follows.

The prepolymer obtained above was charged into the same autoclave, and the internal temperature was raised to 240° C. over 30 minutes. At this time, the pressure valve of the autoclave was kept closed and the pressure showed 10 kg/cm ² . After that, the pressure valve was opened, and heating was continued for 6 hours and 30 minutes while maintaining this state. After replacing the inside of the tank with nitrogen again, the pressure valve was closed, heating was stopped, and the mixture was allowed to stand until the temperature reached normal temperature.

Again, the internal temperature was raised to 240° C. over 30 minutes. At this time, the pressure valve of the autoclave was kept closed and the pressure showed 10 kg/cm ² . After that, the pressure valve was opened, and heating was continued for 6 hours and 30 minutes while maintaining this state. After replacing the inside of the tank with nitrogen again, the pressure valve was closed, heating was stopped, and the mixture was allowed to stand until the temperature reached normal temperature to obtain polyamide (A-1) (polyamide 6T/6C).

[Production Example 2]
(Production of polyamide (A-2))
Polyamide (A-2) was prepared in the same manner as in Production Example 1 except that 1595 g (9.6 mol) of TPA and 413 g (2.4 mol) of CHDA were used as dicarboxylic acids and 1395 g (12.0 mol) of C6DA were used as diamines. (Polyamide 6T/6C) was obtained.

[Production Example 3]
(Production of polyamide (A-3))
Polyamide (A-3) was prepared in the same manner as in Production Example 1 except that 1495 g (9.0 mol) of TPA and 517 g (3.0 mol) of CHDA were used as dicarboxylic acids and 1395 g (12.0 mol) of C6DA were used as diamines. (Polyamide 6T/6C) was obtained.

[Production Example 4]
(Production of polyamide (A-4))
Polyamide (A-4) was prepared in the same manner as in Production Example 1 except that 1395 g (8.4 mol) of TPA and 620 g (3.6 mol) of CHDA were used as dicarboxylic acids and 1395 g (12.0 mol) of C6DA were used as diamines. (Polyamide 6T/6C) was obtained.

[Production Example 5]
(Production of polyamide (A-5))
Polyamide (A-5) was prepared in the same manner as in Production Example 1 except that 1296 g (7.8 mol) of TPA and 723 g (4.2 mol) of CHDA were used as dicarboxylic acids and 1395 g (12.0 mol) of C6DA were used as diamines. (Polyamide 6T/6C) was obtained.

[Production Example 6]
(Production of polyamide (A-6))
Polyamide (A-6) was prepared in the same manner as in Production Example 1 except that 1196 g (7.2 mol) of TPA and 826 g (4.8 mol) of CHDA were used as dicarboxylic acids and 1395 g (12.0 mol) of C6DA were used as diamines. (Polyamide 6T/6C) was obtained.

[Production Example 7]
(Production of polyamide (A-7))
Polyamide (A-7) was prepared in the same manner as in Production Example 1 except that 1096 g (6.6 mol) of TPA and 930 g (5.4 mol) of CHDA were used as dicarboxylic acids and 1395 g (12.0 mol) of C6DA were used as diamines. (Polyamide 6T/6C) was obtained.

[Production Example 8]
(Production of polyamide (A-8))
Polyamide (A-8) was prepared in the same manner as in Production Example 1 except that 1395 g (8.4 mol) of TPA and 598 g (3.6 mol) of IPA were used as dicarboxylic acids and 1395 g (12.0 mol) of C6DA were used as diamines. (Polyamide 6T/6I) was obtained.

[Production Example 9]
(Production of polyamide (A-9))
Polyamide (A-9) was prepared in the same manner as in Production Example 1 except that 1994 g (12.0 mol) of TPA was used as the dicarboxylic acid, and 976 g (8.4 mol) of C6DA and 418 g (3.6 mol) of 2MC5DA were used as the diamine. (Polyamide 6T/2Me5T) was obtained.

[Production Example 10]
(Production of polyamide (A-10))
Polyamide (A-10) was prepared in the same manner as in Production Example 1 except that 1994 g (12.0 mol) of TPA was used as the dicarboxylic acid, and 1519 g (9.6 mol) of C9DA and 380 g (2.4 mol) of 2MC8DA were used as the diamine. (Polyamide 9T/2Me8T) was obtained.

[Production Example 11]
(Production of polyamide (A-11))
Polyamide (A-11) (polyamide 10T) was obtained in the same manner as in Production Example 1 except that 1994 g (12.0 mol) of TPA was used as the dicarboxylic acid and 2068 g (12.0 mol) of C10DA was used as the diamine.

Table 1 shows the composition and physical properties of the polyamide obtained in each production example and commercially available polyamide.

<Production of Polyamide Composition>
[Examples 1 to 19 and Comparative Examples 1 to 3]
(Production of polyamide compositions PA-a1 to PA-a19 and PA-b1 to PA-b3)
Polyamides (A-1) to (A-11) or commercially available polyamides (A-12) to (A-14) obtained in Production Examples 1 to 11 above and each of the above raw materials are shown in Tables 2 to 3 below. Using the types and proportions described in Section 4, a polyamide composition was prepared as follows.

Incidentally, the polyamides (A-1) to (A-11) obtained in the above Production Examples 1 to 11 were dried in a nitrogen stream to adjust the moisture content to about 0.2% by mass, and then the polyamide composition. It was used as a raw material for

A polyamide composition was produced using polyamide (A), phosphorus flame retardant (B), polymer (C) and filler (D).
Specifically, a twin-screw extruder (TEM35 manufactured by Toshiba Machine Co., Ltd., L / D = 47.6 (D = 37 mmφ), set temperature Tm2 + 10 ° C. (when using the polyamide obtained above, 349 + 10 = 359 ° C.) and a screw rotation speed of 300 rpm), a polyamide composition was produced as follows. Polyamide (A) (61 parts by mass) and polymer (C) (5 parts by mass) with adjusted moisture content are supplied from the top feed port provided at the most upstream part of the twin-screw extruder, and the twin-screw extruder From the side feed port on the downstream side (the state in which the resin supplied from the top feed port is sufficiently melted), phosphorus-based flame retardant (B) (9 parts by mass) and filler (D) (25 parts by mass) are added ( Polyamide (A): Polymer (C): Phosphorus-based flame retardant (B): Filler (D) = 61: 5: 9: 25) supplied at a mass ratio, and the melt-kneaded product extruded from the die head was extruded into strands. and pelletized to obtain pellets of the polyamide composition.

Tables 2 to 4 below show the composition of each polyamide composition obtained and the evaluation results of molded articles formed from the polyamide composition.

As shown in Tables 2 to 4, components (A) to (C) are included, the content of component (C) is 2.0% by mass or more and 7.0% by mass or less, and component (B) / component ( Polyamide compositions PA-a1 to PA-a19 (implemented The molded articles obtained from Examples 1 to 19) were excellent in hot strength, impact resistance, and creep resistance in addition to flame retardancy.
In addition, polyamide compositions PA-a1 to PA-a4 and PA-a11 to 13 having different contents of terephthalic acid units and contents of 1,4-cyclohexanedicarboxylic acid units relative to the total molar amount of all dicarboxylic acid units (Examples 1 to 4 and 11 to 13), the lower the content of terephthalic acid units and the higher the content of 1,4-cyclohexanedicarboxylic acid units, the higher the hot strength and impact resistance of the resulting molded article. There was a tendency to be superior in terms of sex. Further, when the content of terephthalic acid units is 65 mol% or less, or 80 mol% or more, and the content of 1,4-cyclohexanedicarboxylic acid units is 20 mol% or less, or 35 mol% or more, Molded articles tend to be more excellent in creep resistance, the content of terephthalic acid units is 60 mol% or 85 mol%, and the content of 1,4-cyclohexanedicarboxylic acid units is 15 mol% or 40 mol%. When it was mol %, there was a tendency for the creep resistance to be particularly excellent.
Further, in comparison of the polyamide compositions PA-a4 and PA-a14 (Examples 4 and 14) having different types of dicarboxylic acid units to be combined, the polyamide composition PA- having a terephthalic acid unit and a 1,4-cyclohexanedicarboxylic acid unit A4 tended to be superior in hot strength, impact resistance, and creep resistance.
Further, polyamide compositions PA-a4 and PA-a7 to PA-a8 (Examples 4 and 7 to 8) having different blending amounts of component (C), and polyamide compositions PA-a9 and PA-a10 (Examples In the comparison of 9 and 10), there was a tendency that as the amount of component (C) decreased, the hot strength and impact resistance tended to be more excellent. On the other hand, there was a tendency that as the blending amount of component (C) increased, the creep resistance was more excellent.
Further, in comparison of the polyamide compositions PA-a4 and PA-a10 (Examples 4 and 10) having different types of component (C), it is better to use the polymer (C-1) as the component (C) at hot strength , impact resistance, and creep resistance tended to be better.
Further, in comparison of polyamide compositions PA-a4 and PA-a5 (Examples 4 and 5) having different blending ratios of component (D) to component (A), blending of component (D) to component (A) As the ratio increased, the hot strength, impact resistance, and creep resistance tended to be more excellent.

On the other hand, although components (A) to (C) are included, the content of component (C) is 1.0% by mass or 10.0% by mass, and the mass ratio of component (B) / component (C) is 9 .0 or 0.9 polyamide compositions PA-b1 to PA-b2 (Comparative Examples 1 and 2), and the polyamide composition PA-b3 (comparative The molded article obtained in Example 3) was not excellent in all of hot strength, impact resistance, creep resistance and flame retardancy.

According to the polyamide composition of the present embodiment, it is possible to provide a polyamide composition which is excellent in flame retardancy when formed into a molded article, as well as in hot strength, impact resistance, and creep resistance. The molded article of the present embodiment is obtained by molding the polyamide composition, and is excellent in flame retardancy, hot strength, impact resistance, and creep resistance. Therefore, the molded article of the present embodiment can be suitably used as various parts for automobiles, electric and electronic parts, industrial materials, and daily and household goods.

Claims (8)

a polyamide (A) having a dicarboxylic acid unit having 4 to 12 carbon atoms and a diamine unit having 4 to 12 carbon atoms;
a phosphorus-based flame retardant (B);
a polymer (C) having an oxygen index of 27% or more and having an aromatic group in the main chain;
including
The content of the polymer (C) is more than 1.0% by mass and less than 10.0% by mass with respect to the total mass of the polyamide composition,
The content ratio (B)/(C) of the phosphorus-based flame retardant (B) and the polymer (C) is more than 0.9 and less than 9.0,
A polyamide composition, wherein the polyamide (A) has a melting peak temperature Tm2 of more than 260° C. and not more than 360° C. in differential scanning calorimetry according to JIS-K7121. 2. The polyamide composition of claim 1, wherein said dicarboxylic acid units comprise terephthalic acid units. The dicarboxylic acid units comprise terephthalic acid units and 1,4-cyclohexanedicarboxylic acid units, and the diamine units comprise aliphatic diamine units,
The terephthalic acid unit content is 50 mol% or more and 90 mol% or less, and the 1,4-cyclohexanedicarboxylic acid unit content is 10 mol% or more and 50 mol%, based on the total molar amount of all dicarboxylic acid units. % or less, the polyamide composition according to claim 1 or 2. The polyamide composition according to claim 3, wherein the total content of the terephthalic acid units and the 1,4-cyclohexanedicarboxylic acid units is 90 mol% or more and 100 mol% or less with respect to the total molar amount of all dicarboxylic acid units. thing. In the differential scanning calorimetry of the polyamide (A) according to JIS-K7121, the melting peak temperature Tm2 obtained when the temperature is raised at 20 ° C./min is 340 ° C. or higher and 360 ° C. or lower,
The crystallization enthalpy ΔHc obtained when the temperature is lowered at 20° C./min is 35 J/g or more and 60 J/g or less,
The polyamide composition according to any one of claims 1 to 4, which has a glass transition temperature Tg of 130°C or higher and 160°C or lower. The polyamide composition according to any one of claims 1 to 5, wherein the polyamide (A) has a number average molecular weight of 5000 or more and 20000 or less. The polyamide composition according to any one of claims 1 to 6, further comprising (D) a filler. A molded article obtained by molding the polyamide composition according to any one of claims 1 to 7.