JP2018188533A - Polyamide composition and molded article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyamide composition excellent in mechanical property, surface appearance and flame retardancy, and to provide a molded product.SOLUTION: A polyamide composition contains (A) aliphatic polyamide formed from diamine and dicarboxylic acid, (B) semi-aromatic polyamide containing a dicarboxylic acid unit containing at least 75 mol% of an isophthalic acid and a diamine unit containing diamine having 4 or more and 10 or less carbons, (C) a pigment, (D1) a flame retardant and (D2) a flame-retardant auxiliary, where a tanδ peak temperature of the polyamide composition is 90°C or higher, and a weight average molecular weight Mw of the polyamide resin composition is 10,000≤Mw≤40,000. A polyamide resin further contains (E) a polymer containing α,β unsaturated dicarboxylic acid anhydride as a constitutional unit.SELECTED DRAWING: None

Description

  The present invention relates to a polyamide composition and a molded article.

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

In recent years, the use environment of polyamide resins has become severer in terms of heat and dynamics, and changes in physical properties in every environment that have improved mechanical properties, especially the rigidity after water absorption and the rigidity under high temperature use. There is a demand for a polyamide resin material with a low content.
Moreover, in order to improve productivity, the molded object using a polyamide resin may be shape | molded on the high cycle molding conditions performed by raising a molding temperature and lowering mold temperature.

  On the other hand, when molding is performed under a high temperature condition, there is a problem that the molded product may not be stably obtained due to degradation of the polyamide resin or change in fluidity.

Therefore, there is a demand for a polyamide resin that is particularly excellent in the stability of the molded product surface appearance even under the severe molding conditions described above.
In order to meet such requirements, a polyamide made of polyamide 66 / 6I into which an isophthalic acid component is introduced is disclosed as a material that can improve the surface appearance and mechanical properties of a molded product (for example, Patent Document 1). . Further, as a material capable of improving mechanical properties, fluidity, surface appearance, and the like, a polyamide composition comprising a terephthalic acid component and a polyamide 6T / 6I into which an isophthalic acid component is introduced has been disclosed (for example, Patent Documents). 2, 3, 4).

  Further, as a material capable of improving the surface appearance and mechanical properties of a molded article, a polyamide comprising an alloy of polyamide 6T / 6I and polyamide 66 into which a terephthalic acid component and an isophthalic acid component are introduced is disclosed (for example, , See Patent Document 5).

JP-A-6-32980 JP 2000-154316 A JP-A-11-34806 JP2013-119610A International Publication No. 2005-035664

  However, although the techniques disclosed in Patent Documents 1 and 3 improve the rigidity under normal use conditions, there is room for improvement in the rigidity after water absorption and the rigidity under high temperature use.

  Moreover, the polyamide manufactured by the manufacturing technique disclosed in Patent Document 2 has improved rigidity after water absorption and rigidity under high temperature use. However, although the surface appearance of the molded product under general molding conditions is improved, the appearance and stability of the molding surface are deteriorated under severe molding conditions such as high cycle molding conditions. Has the problem.

  As described above, in the prior art, a polyamide copolymer having excellent rigidity after water absorption and rigidity under high-temperature use and little change in physical properties under use in any environment is not yet known. . In addition, it is difficult to suppress a decrease in rigidity after water absorption and under high temperature use while maintaining the balance between mechanical strength and rigidity, which is a characteristic of polyamide copolymers. Compositions and molded articles containing coalesced or polyamide are desired.

  The present invention has been made in view of the above circumstances, and stably provides a polyamide composition and a molded article excellent in mechanical properties (particularly weld strength and Rockwell hardness), surface appearance, and flame retardancy. It is for the purpose.

  As a result of intensive studies to solve the above problems, the present inventors have found that a polyamide composition containing a specific plurality of polyamides can solve the above problems, and have completed the present invention.

That is, the present invention is as follows.
The polyamide composition of the present invention comprises:
(A) an aliphatic polyamide comprising a diamine and a dicarboxylic acid,
(B) a semi-aromatic polyamide containing a dicarboxylic acid unit containing at least 75 mol% of isophthalic acid and a diamine unit containing a diamine having 4 to 10 carbon atoms,
(C) pigment,
(D1) a flame retardant, and (D2) a flame retardant aid,
A polyamide composition comprising:
The tan δ peak temperature of the polyamide composition is 90 ° C or higher,
The weight average molecular weight Mw of the polyamide composition is 10,000 ≦ Mw ≦ 40000.

  The polyamide composition of the present invention may further contain a polymer containing (E) an α, β unsaturated dicarboxylic acid anhydride as a constituent unit.

  In the polyamide composition of the present invention, the total content of (A) aliphatic polyamide and (B) semi-aromatic polyamide having a number average molecular weight Mn of 500 or more and 2000 or less is the total content with respect to 100% by mass of the polyamide composition. It is preferable that it is 0.5 mass% or more and less than 2.5 mass% with respect to the polyamide whole quantity.

  The molecular weight distribution Mw / Mn of the polyamide composition is preferably 2.4 or less.

  The ratio of the amino terminal amount to the total amount of amino terminal amount and carboxyl terminal amount in the polyamide composition {amino terminal amount / (amino terminal amount + carboxyl terminal amount)} is 0.1 or more and less than 0.4. preferable.

  (A) The aliphatic polyamide is preferably polyamide 66.

  (B) The content of isophthalic acid in the dicarboxylic acid unit of the aromatic polyamide is preferably 100 mol%.

  (B) The weight average molecular weight Mw of the semiaromatic polyamide is preferably 10,000 ≦ Mw ≦ 25000.

  (B) The molecular weight distribution Mw / Mn of the semi-aromatic polyamide is preferably 2.4 or less.

  (B) Mw / VR of the semi-aromatic polyamide is preferably 1000 or more and 2000 or less.

  (B) The semi-aromatic polyamide is preferably polyamide 6I.

  (B) The content of the semi-aromatic polyamide is preferably 30% by mass or more and 50% by mass or less with respect to 100% by mass of the total components of the polyamide in the polyamide composition.

  The difference {Mw (A) -Mw (B)} between the weight average molecular weight Mw (A) of the (A) aliphatic polyamide and the weight average molecular weight Mw (B) of the (B) semiaromatic polyamide is 10,000 or more. preferable.

  (B) It is preferable that the terminal of semi-aromatic polyamide is sealed with acetic acid.

  (C) The pigment is a white pigment, and the content of the white pigment is preferably 0.5% by mass or more and 5% by mass or less with respect to 100% by mass of the polyamide composition.

  The white pigment is preferably at least one selected from ZnS and ZnO.

(D1) The flame retardant is brominated polystyrene, and the content of brominated polystyrene is 6% by mass to 15% by mass with respect to 100% by mass of the polyamide composition, and
(D2) The flame retardant aid is Sb ₂ O ₃ , and the content of Sb ₂ O ₃ is preferably 0.1% by mass or more and 4% by mass or less with respect to 100% by mass of the polyamide composition.

  (E) The polymer containing α, β-unsaturated dicarboxylic acid anhydride as a constituent unit is preferably maleic anhydride-modified polyphenylene ether.

  The polyamide composition of the present invention may further contain (F) a filler.

  (F) The filler is glass fiber, and the content of the glass fiber is preferably 40% by mass or more and 60% by mass or less with respect to 100% by mass of the polyamide composition.

  (C) White pigment, (D1) flame retardant, (D2) flame retardant aid, (E) polymer containing α, β unsaturated dicarboxylic acid anhydride in the structural unit, and (F) total content of filler Is preferably 60% by mass or more and 80% by mass or less with respect to 100% by mass of the polyamide composition.

  The molded article of the present invention is formed by molding the polyamide composition of the present invention, and has a surface gloss value of 50 or more.

  ADVANTAGE OF THE INVENTION According to this invention, the polyamide composition and molded article which are excellent in a mechanical property, surface appearance property, and a flame retardance can be provided.

  Hereinafter, the present invention will be described in detail.

[Polyamide composition]
The polyamide composition of the present invention comprises:
(A) an aliphatic polyamide comprising a diamine and a dicarboxylic acid,
(B) a semi-aromatic polyamide containing a dicarboxylic acid unit containing at least 75 mol% of isophthalic acid and a diamine unit containing a diamine having 4 to 10 carbon atoms,
(C) pigment,
(D1) a flame retardant, and (D2) a flame retardant aid,
A polyamide composition comprising:
The tan δ peak temperature of the polyamide composition is 90 ° C or higher,
The weight average molecular weight Mw of the polyamide composition is 10,000 ≦ Mw ≦ 40000.

  In the present invention, “polyamide” means a polymer having an amide (—NHCO—) bond in the main chain. The details of (A) aliphatic polyamide and (B) semi-aromatic polyamide will be described below.

((A) Aliphatic polyamide)
The (A) aliphatic polyamide contained in the polyamide composition of the present invention contains (Aa) an aliphatic dicarboxylic acid unit and (Ab) an aliphatic diamine unit.

((Aa) aliphatic dicarboxylic acid unit)
Examples of the aliphatic dicarboxylic acid constituting the aliphatic dicarboxylic acid unit include, but are not limited to, malonic acid, dimethylmalonic acid, succinic acid, 2,2-dimethylsuccinic acid, and 2,3-dimethyl. Glutaric acid, 2,2-diethylsuccinic acid, 2,3-diethylglutaric acid, glutaric acid, 2,2-dimethylglutaric acid, adipic acid, 2-methyladipic acid, trimethyladipic acid, pimelic acid, suberic acid, azelain C3-C20 linear or branched saturated aliphatic dicarboxylic acids such as acid, sebacic acid, dodecanedioic acid, tetradecanedioic acid, hexadecanedioic acid, octadecanedioic acid, eicosanedioic acid, and diglycolic acid It is done.

(Aa) The aliphatic dicarboxylic acid unit contains an aliphatic dicarboxylic acid having 6 or more carbon atoms, so that the polyamide composition has more excellent heat resistance, fluidity, toughness, low water absorption, rigidity, and the like. This is preferable because of its tendency. The aliphatic dicarboxylic acid unit having 6 or more carbon atoms is not particularly limited, and examples thereof include adipic acid, sebacic acid, dodecanedioic acid, tetradecanedioic acid, hexadecanedioic acid, octadecanedioic acid, and eicosanedioic acid. Can be mentioned. Among these, adipic acid, sebacic acid, and dodecanedioic acid are preferable from the viewpoint of heat resistance of the polyamide composition.
(Aa) The aliphatic dicarboxylic acid which comprises an aliphatic dicarboxylic acid unit may be used individually by 1 type, and may be used in combination of 2 or more type.

  In addition, (A) aliphatic polyamide may further contain a unit derived from a trivalent or higher polyvalent carboxylic acid such as trimellitic acid, trimesic acid, and pyromellitic acid, if necessary. Only one trivalent or higher polyvalent carboxylic acid may be used alone, or two or more polycarboxylic acids may be used in combination.

((A-b) aliphatic diamine unit)
(Ab) The aliphatic diamine constituting the aliphatic diamine unit may be linear or branched.
Examples of the linear aliphatic diamine constituting the aliphatic diamine unit include, but are not limited to, ethylenediamine, propylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octane. Examples thereof include linear saturated aliphatic diamines having 2 to 20 carbon atoms such as methylene diamine, nonamethylene diamine, decamethylene diamine, undecamethylene diamine, dodecamethylene diamine, and tridecamethylene diamine.

The diamine constituting the diamine unit having a substituent branched from the main chain is not limited to the following, but for example, 2-methylpentamethylenediamine (also referred to as 2-methyl-1,5-diaminopentane). ), 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 2-methyl-1,8-octanediamine (also referred to as 2-methyloctamethylenediamine), and 2,4. -C3-C20 branched saturated aliphatic diamines such as dimethyloctamethylenediamine.
Among these, 2-methylpentamethylenediamine and 2-methyl-1,8-octanediamine are preferable, and 2-methylpentamethylenediamine is more preferable. By including such an aliphatic diamine, the polyamide composition tends to be more excellent in heat resistance and rigidity.

  (Ab) The aliphatic diamine unit preferably has 6 or more and 12 or less carbon atoms. A carbon number of 6 or more is preferable because of excellent heat resistance, and a carbon number of 12 or less is preferable because of excellent crystallinity and mold release properties. (Ab) The number of carbon atoms in the diamine unit is more preferably 6 or more and 10 or less.

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

  Specific examples of the (A) aliphatic polyamide used in the polyamide composition of the present invention include polyamide 66 (PA66). Since PA66 is excellent in heat resistance, moldability, and toughness, it is considered as a material suitable for automotive parts.

((B) Semi-aromatic polyamide)
The (B) semi-aromatic polyamide used in the present invention includes a (B-a) dicarboxylic acid unit containing at least 75 mol% of isophthalic acid, and a (B-b) diamine unit containing a diamine having 4 to 10 carbon atoms. Containing polyamide.
The total amount of the isophthalic acid unit and the diamine unit having 4 to 10 carbon atoms is preferably at least 50 mol%, and is 80 to 100 mol% with respect to 100 mol% of all the structural units of (B) polyamide. More preferably, it is more preferably 90 to 100 mol%, and most preferably 100 mol%.
In the present invention, the ratio of the predetermined monomer units constituting the polyamide (B) can be measured by nuclear magnetic resonance spectroscopy (NMR) or the like.

((Ba) dicarboxylic acid unit)
(Ba) The dicarboxylic acid unit contains 75 mol% or more of isophthalic acid (based on the total number of moles of dicarboxylic acid). It is more preferably 80 to 100 mol%, more preferably 90 to 100 mol%, and even more preferably 100 mol%.
(Ba) Polyamide that satisfies mechanical properties, particularly water absorption rigidity, thermal rigidity, fluidity, surface appearance, etc. at the same time when the proportion of the isophthalic acid unit in the dicarboxylic acid unit is 75 mol% or more. A composition can be obtained.

  (Ba) The dicarboxylic unit may contain an aromatic dicarboxylic acid unit other than the isophthalic acid unit, an aliphatic dicarboxylic acid unit, and an alicyclic dicarboxylic acid unit.

-Aromatic dicarboxylic acid unit-
The aromatic dicarboxylic acid constituting the aromatic dicarboxylic acid unit other than the isophthalic acid unit is not limited to the following, but examples thereof include a dicarboxylic acid having a phenyl group or a naphthyl group. The aromatic group of the aromatic dicarboxylic acid may be unsubstituted or may have a substituent.
The substituent is not particularly limited, and examples thereof include halogen groups such as an alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 10 carbon atoms, an arylalkyl group having 7 to 10 carbon atoms, a chloro group, and a bromo group. , A silyl group having 1 to 6 carbon atoms, a sulfonic acid group and a salt thereof (such as a sodium salt), and the like.
Specific examples include, but are not limited to, terephthalic acid, naphthalenedicarboxylic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, and 5-sodium sulfoisophthalic acid. Examples thereof include an aromatic dicarboxylic acid having 8 to 20 carbon atoms which is substituted or substituted with a predetermined substituent.
The aromatic dicarboxylic acid which comprises an aromatic dicarboxylic acid unit may be used individually by 1 type, and may be used in combination of 2 or more type.

-Aliphatic dicarboxylic acid unit-
Examples of the aliphatic dicarboxylic acid constituting the aliphatic dicarboxylic acid unit include, but are not limited to, malonic acid, dimethylmalonic acid, succinic acid, 2,2-dimethylsuccinic acid, and 2,3-dimethyl. Glutaric acid, 2,2-diethylsuccinic acid, 2,3-diethylglutaric acid, glutaric acid, 2,2-dimethylglutaric acid, adipic acid, 2-methyladipic acid, trimethyladipic acid, pimelic acid, suberic acid, azelain C3-C20 linear or branched saturated aliphatic dicarboxylic acids such as acid, sebacic acid, dodecanedioic acid, tetradecanedioic acid, hexadecanedioic acid, octadecanedioic acid, eicosanedioic acid, and diglycolic acid It is done.

-Alicyclic dicarboxylic acid unit-
The alicyclic dicarboxylic acid constituting the alicyclic dicarboxylic acid unit (hereinafter also referred to as “alicyclic dicarboxylic acid unit”) is not limited to the following, but for example, the carbon number of the alicyclic structure Is an alicyclic dicarboxylic acid having 3 to 10 carbon atoms, and an alicyclic dicarboxylic acid having 5 to 10 carbon atoms in the alicyclic structure is preferable.
Examples of such alicyclic dicarboxylic acids include, but are not limited to, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, and the like. Can be mentioned. Among these, 1,4-cyclohexanedicarboxylic acid is preferable.
In addition, the alicyclic dicarboxylic acid which comprises an alicyclic dicarboxylic acid unit may be used individually by 1 type, and may be used in combination of 2 or more types.

The alicyclic group of the alicyclic dicarboxylic acid may be unsubstituted or may have a substituent. Examples of the substituent include, but are not limited to, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a tert-butyl group. 4 alkyl groups and the like.
The dicarboxylic acid unit other than the isophthalic acid unit preferably includes an aromatic dicarboxylic acid unit, and more preferably includes an aromatic dicarboxylic acid having 6 or more carbon atoms.
By using such a dicarboxylic acid, the mechanical properties of the polyamide composition, in particular, water absorption rigidity, thermal rigidity, fluidity, and surface appearance tend to be more excellent.

In the present invention, the dicarboxylic acid constituting the (Ba) dicarboxylic acid unit is not limited to the compounds described as the dicarboxylic acid, and may be a compound equivalent to the dicarboxylic acid.
Here, the “compound equivalent to a dicarboxylic acid” refers to a compound that can have a dicarboxylic acid structure similar to the dicarboxylic acid structure derived from the dicarboxylic acid. Examples of such compounds include, but are not limited to, dicarboxylic acid anhydrides and halides.

The (B) semi-aromatic polyamide may further contain a unit derived from a trivalent or higher polyvalent carboxylic acid such as trimellitic acid, trimesic acid, and pyromellitic acid, if necessary.
Only one trivalent or higher polyvalent carboxylic acid may be used alone, or two or more polycarboxylic acids may be used in combination.

((B-b) diamine unit)
(B) The diamine unit constituting the semi-aromatic polyamide includes a diamine having 4 to 10 carbon atoms. Although not limited to the following, for example, an aliphatic diamine unit, an alicyclic amine unit, an aromatic diamine unit and the like can be mentioned.

-Aliphatic diamine unit-
Examples of the aliphatic diamine constituting the aliphatic diamine unit include, but are not limited to, ethylenediamine, propylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, Examples thereof include straight-chain saturated aliphatic diamines having 4 to 20 carbon atoms such as nonamethylenediamine, decamethylenediamine, undecamethylenediamine, dodecamethylenediamine, and tridecamethylenediamine.

-Alicyclic diamine unit-
The alicyclic diamine constituting the alicyclic diamine unit (hereinafter also referred to as “alicyclic diamine”) is not limited to the following, but for example, 1,4-cyclohexanediamine, 1,3 -Cyclohexanediamine, 1,3-cyclopentanediamine, etc. are mentioned.

-Aromatic diamine unit-
The aromatic diamine constituting the aromatic diamine unit is not limited to the following as long as it is an aromatic diamine, and examples thereof include metaxylylenediamine.

(B) Among the diamine units constituting the semi-aromatic polyamide, preferably an aliphatic diamine unit, more preferably a diamine unit having a linear saturated aliphatic group having 4 to 10 carbon atoms, Preferably, it is a diamine unit having a straight-chain saturated aliphatic group having 6 to 10 carbon atoms, and more preferably hexamethylenediamine.
By using such a diamine, it tends to be a polyamide composition having excellent mechanical properties, particularly water absorption rigidity, rigidity under high temperature use (rigidity during heat), fluidity, surface appearance and the like.
In addition, diamine may be used individually by 1 type and may be used in combination of 2 or more types.
(B) The semi-aromatic polyamide is preferably polyamide 6I, 9I, or 10I, and is most preferably polyamide 6I.

The (B) semi-aromatic polyamide may further contain a trivalent or higher polyvalent aliphatic amine such as bishexamethylene triamine, if necessary.
Trivalent or higher polyvalent aliphatic amines may be used alone or in combination of two or more.

  In the present invention, the blending amount of the (B) semi-aromatic polyamide is preferably 5.0% by mass or more and 50.0% by mass or less, more preferably 10. 5% by mass or less with respect to 100% by mass of the total component amount of the polyamide. It is 0 mass% or more and 50 mass% or less, More preferably, it is 15.0 mass% or more and 50 mass% or less, More preferably, it is 20.0 mass% or more and 50 mass% or less, Most preferably, it is 30 mass%. It is 50 mass% or less, Most preferably, it is 30 mass% or more and 45 mass% or less. (B) By making the compounding quantity of semi-aromatic polyamide into the said range, the polyamide composition excellent in a mechanical property is obtained. Moreover, the polyamide composition containing a component typified by an inorganic filler has excellent surface appearance.

(Lactam unit and / or aminocarboxylic acid unit)
(A) Aliphatic polyamide and (B) semi-aromatic polyamide may further contain lactam units and / or aminocarboxylic acid units. By including such a unit, there exists a tendency for the polyamide which is excellent in toughness to be obtained. In addition, the lactam and aminocarboxylic acid which comprise a lactam unit and aminocarboxylic acid here mean the lactam and aminocarboxylic acid which can be condensed (condensed).

  The lactam and aminocarboxylic acid constituting the lactam unit and aminocarboxylic acid unit are not limited to the following, but, for example, lactam and aminocarboxylic acid having 4 to 14 carbon atoms are preferable, and 6 to 12 carbon atoms are preferable. More preferred are lactams and aminocarboxylic acids.

Examples of the lactam constituting the lactam unit include, but are not limited to, butyrolactam, pivalolactam, ε-caprolactam, caprilactam, enantolactam, undecanolactam, laurolactam (dodecanolactam), and the like. Can be mentioned.
Among these, as the lactam, ε-caprolactam, laurolactam and the like are preferable, and ε-caprolactam is more preferable. By including such a lactam, it tends to be a polyamide composition having better toughness.

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

The lactam and aminocarboxylic acid constituting the lactam unit and aminocarboxylic acid unit may be used alone or in combination of two or more.
The total ratio (mol%) of the lactam unit and aminocarboxylic acid unit is preferably 0 to 20 mol%, more preferably 0 to 10 mol%, still more preferably 0 to 5%, based on the whole polyamide. It is.
When the total ratio of the lactam unit and the aminocarboxylic acid unit is within the above range, effects such as improvement in fluidity tend to be obtained.

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

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

The monocarboxylic acid that can be used as the end-capping agent is not limited to the following as long as it has reactivity with an amino group that may be present at the end of the polyamide. 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, and isobutyric acid; alicyclic rings such as cyclohexanecarboxylic acid And aromatic monocarboxylic acids such as benzoic acid, toluic acid, α-naphthalenecarboxylic acid, β-naphthalenecarboxylic acid, methylnaphthalenecarboxylic acid, and phenylacetic acid.
In particular, the end of the aromatic polyamide (B) is preferably sealed with acetic acid from the viewpoint of fluidity and mechanical strength.
A monocarboxylic acid may be used individually by 1 type, and may be used in combination of 2 or more type.

The monoamine that can be used as the end-capping agent is not limited to the following as long as it has reactivity with a carboxyl group that may be present at the end 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; and aniline, toluidine, Examples include aromatic monoamines such as diphenylamine and naphthylamine.
Only one monoamine may be used alone, or two or more monoamines may be used in combination.

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

(Polyamide production method)
When obtaining the polyamide of the present invention, the addition amount of the dicarboxylic acid and the addition amount of the diamine are preferably around the same molar amount. The amount of diamine escaped from the reaction system during the polymerization reaction is also considered in terms of molar ratio, and the molar amount of the diamine is 0.9 to 1.2 with respect to the molar amount 1 of the entire dicarboxylic acid. Is more preferable, 0.95 to 1.1 is more preferable, and 0.98 to 1.05 is still more preferable.
The production method of polyamide is not limited to the following, but for example, dicarboxylic acid constituting a dicarboxylic acid unit, diamine constituting a diamine unit, and, if necessary, a lactam unit and / or an aminocarboxylic acid unit. It is preferable that the method further includes a step of increasing the degree of polymerization of the polyamide by polymerizing the lactam and / or aminocarboxylic acid constituting the polymer to obtain a polymer. Moreover, the sealing process which seals the terminal of the obtained polymer with a terminal sealing agent may be included as needed.

Specific methods for producing polyamide include various methods as exemplified below.
1) A method in which an aqueous solution of a dicarboxylic acid-diamine salt or a mixture of a dicarboxylic acid and a diamine, or a suspension of these waters is heated and polymerized while maintaining a molten state (hereinafter referred to as “hot melt polymerization method”). Say.).
2) A method of increasing the degree of polymerization of the polyamide obtained by the hot melt polymerization method while maintaining the solid state at a temperature below the melting point (hereinafter also referred to as “hot melt polymerization / solid phase polymerization method”).
3) A method of polymerizing a dicarboxylic acid-diamine salt or a mixture of dicarboxylic acid and diamine while maintaining a solid state (hereinafter also referred to as “solid phase polymerization method”).
4) A method of polymerizing using a dicarboxylic acid halide component equivalent to dicarboxylic acid and a diamine component (hereinafter also referred to as “solution method”).
Among them, a production method including a hot melt polymerization method is preferable, and when a polyamide is produced by a hot melt polymerization method, it is preferable to maintain a molten state until the polymerization is completed. In order to maintain the molten state, it is necessary to produce it under polymerization conditions suitable for the polyamide composition. For example, the polymerization pressure in the hot melt polymerization method is controlled to 14 to 25 kg / cm ² (gauge pressure), and while the heating is continued, the pressure in the tank reaches 30 atmospheric pressure (gauge pressure is 0 kg / cm ² ). A method of reducing the pressure while taking more than a minute is mentioned.

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

Hereinafter, as a method for producing polyamide, a method for producing polyamide by a batch-type hot melt polymerization method will be specifically described, but the method for producing polyamide is not limited thereto.
First, for example, an aqueous solution containing about 40 to 60% by mass of a raw material component of polyamide (dicarboxylic acid, diamine, and, if necessary, lactam and / or aminocarboxylic acid) is heated at a temperature of 110 to 180 ° C. and about In a concentration tank operated at a pressure of 0.035 to 0.6 MPa (gauge pressure), the solution is concentrated to about 65 to 90% by mass to obtain a concentrated solution.

Next, the obtained concentrated solution is transferred to an autoclave, and heating is continued until the pressure in the autoclave becomes about 1.2 to 2.2 MPa (gauge pressure).
Thereafter, in the autoclave, the pressure is maintained at about 1.2 to 2.2 MPa (gauge pressure) while removing water and / or gas components, and when the temperature reaches about 220 to 260 ° C., the pressure is reduced to atmospheric pressure ( Gauge pressure is 0 MPa).

By reducing the pressure in the autoclave to atmospheric pressure and then reducing the pressure as necessary, by-product water can be effectively removed.
Thereafter, the autoclave is pressurized with an inert gas such as nitrogen, and the polyamide melt is extruded from the autoclave as a strand. The extruded strand is cooled and cut to obtain polyamide pellets.

(Polyamide polymer end)
Although it does not specifically limit as a polymer terminal of the polyamide used for this invention, It can classify | categorize and define as follows.
That is, 1) amino terminal, 2) carboxyl terminal, 3) terminal by a sealant, and 4) other terminal.

1) The amino terminus is a polymer terminus having an amino group (—NH ₂ group) and is derived from the diamine unit of the raw material.
2) The carboxyl terminal is a polymer terminal having a carboxyl group (—COOH group) and is derived from the raw material dicarboxylic acid.
3) The terminal by a sealing agent is a terminal formed when a sealing agent is added at the time of superposition | polymerization. Examples of the sealing agent include the above-described end sealing agents.
4) The other terminal is a polymer terminal that is not classified in the above 1) to 3), such as a terminal generated by deammonia reaction at the amino terminal or a terminal generated by decarboxylation from the carboxyl terminal. .

((A) Characteristics of aliphatic polyamide)
(A) The molecular weight, melting point Tm2, crystallization enthalpy ΔH, and tan δ peak temperature of the aliphatic polyamide can be specifically measured by the method described in the examples described later.
(A) Mw (A) (weight average molecular weight) can be used as an index of the molecular weight of the aliphatic polyamide. (A) Mw (A) (weight average molecular weight) of the aliphatic polyamide is preferably 10,000 to 50,000, more preferably 15,000 to 45,000, still more preferably 20,000 to 40000, and even more preferably 25,000 to 35,000. It is.

When the Mw (A) (weight average molecular weight) is in the above range, a polyamide composition having excellent mechanical properties, particularly water absorption rigidity, thermal rigidity, fluidity, and the like can be obtained. Moreover, the polyamide composition containing a component typified by an inorganic filler has excellent surface appearance. In addition, the measurement of Mw (weight average molecular weight) can be measured using GPC (gel permeation chromatography) as described in the following Example.
(A) The molecular weight distribution of the aliphatic polyamide uses Mw (weight average molecular weight) / Mn (number average molecular weight) as an index.

  (A) Mw (weight average molecular weight) / Mn (number average molecular weight) of the aliphatic polyamide is preferably 1.8 to 2.2, more preferably 1.9 to 2.1. The lower limit of the molecular weight distribution is 1.0. By setting Mw (weight average molecular weight) / Mn (number average molecular weight) within the above range, a polyamide composition having excellent fluidity and the like can be obtained. Moreover, the polyamide composition containing a component typified by an inorganic filler has excellent surface appearance.

  (A) As a method for controlling the Mw (weight average molecular weight) / Mn (number average molecular weight) of an aliphatic polyamide within the above range, for example, phosphoric acid or hypophosphorous acid as an additive during hot melt polymerization of polyamide Examples thereof include a method of adding a known polycondensation catalyst such as sodium and a method of controlling polymerization conditions such as heating conditions and reduced pressure conditions.

  In the present invention, the measurement of Mw (weight average molecular weight) / Mn (number average molecular weight) of (A) aliphatic polyamide is obtained using GPC (gel permeation chromatography) as described in the following examples. Mw (weight average molecular weight) and Mn (number average molecular weight) can be used for calculation.

(A) Melting | fusing point Tm2 of an aliphatic polyamide becomes like this. Preferably it is 220 degreeC or more, More preferably, it is 230 degreeC or more, More preferably, it is 240 degreeC or more.
Moreover, (A) Melting | fusing point Tm2 of an aliphatic polyamide becomes like this. Preferably it is 300 degrees C or less, More preferably, it is 290 degrees C or less, More preferably, it is 280 degrees C or less, More preferably, it is 270 degrees C or less.
(A) When the melting point Tm2 of the aliphatic polyamide is 220 ° C. or higher, a polyamide composition excellent in thermal rigidity and the like tends to be obtained.
Moreover, (A) When the melting point Tm2 of the aliphatic polyamide is 300 ° C. or less, thermal decomposition of the polyamide composition in melt processing such as extrusion and molding tends to be further suppressed.

  (A) The crystallization enthalpy ΔH of the aliphatic polyamide is preferably 30 J / g or more, more preferably 40 J / g or more, more preferably from the viewpoint of mechanical properties, particularly water absorption rigidity and thermal rigidity. It is 50 J / g or more, more preferably 60 J / g or more. Moreover, the upper limit of the crystallization enthalpy ΔH is not particularly limited and is preferably as high as possible.

(A) As an apparatus for measuring the melting point Tm2 of aliphatic polyamide and the crystallization enthalpy ΔH, for example, Diamond-DSC manufactured by PERKIN-ELMER may be used.
(A) The tan δ peak temperature of the aliphatic polyamide is preferably 40 ° C. or higher, more preferably 50 to 110 ° C., still more preferably 60 to 100 ° C., and even more preferably 70 to 95 ° C. More preferably, it is 80-90 degreeC. (A) When the glass transition temperature of the aliphatic polyamide is 40 ° C. or higher, a polyamide composition excellent in water absorption rigidity and thermal rigidity tends to be obtained.
(A) The tan δ peak temperature of the aliphatic polyamide can be measured by using, for example, a viscoelasticity measurement analyzer or the like (Rheology: DVE-V4) as described in the following examples.

((B) Characteristics of semi-aromatic polyamide)
(B) The molecular weight, melting point Tm2, crystallization enthalpy ΔH, and tan δ peak temperature of the semi-aromatic polyamide can be specifically measured by the method described in Examples described later.
(B) Mw (B) (weight average molecular weight) can be used as an index of the molecular weight of the semi-aromatic polyamide. (B) Mw (weight average molecular weight) of the polyamide is preferably 10,000 to 25,000, more preferably 13,000 to 24,000, still more preferably 15,000 to 23,000, still more preferably 18,000 to 22,000, and particularly preferably. Is 1900-21000.

  When the Mw (B) (weight average molecular weight) is in the above range, a polyamide composition having excellent mechanical properties, particularly water absorption rigidity, thermal rigidity, fluidity and the like can be obtained. Moreover, the polyamide composition containing a component typified by an inorganic filler has excellent surface appearance. In addition, the measurement of Mw (weight average molecular weight) can be measured using GPC (gel permeation chromatography) as described in the following Example.

(B) The molecular weight distribution of the semi-aromatic polyamide uses Mw (weight average molecular weight) / Mn (number average molecular weight) as an index.
(B) Mw (weight average molecular weight) / Mn (number average molecular weight) of the semi-aromatic polyamide is preferably 2.4 or less, more preferably 1.7 to 2.4, and still more preferably 1.8. It is -2.3, More preferably, it is 1.9-2.2, Most preferably, it is 1.9-2.1. The lower limit of Mw (weight average molecular weight) / Mn (number average molecular weight) is 1.0. By setting Mw (weight average molecular weight) / Mn (number average molecular weight) within the above range, a polyamide composition having excellent fluidity and the like can be obtained. Moreover, the polyamide composition containing a component typified by an inorganic filler has excellent surface appearance.

(B) As a method for controlling the Mw (weight average molecular weight) / Mn (number average molecular weight) of the semi-aromatic polyamide within the above range, for example, phosphoric acid or hypophosphorous acid as an additive at the time of hot melt polymerization of polyamide A method of adding a known polycondensation catalyst such as sodium acid can be mentioned. In addition, it is important to control polymerization conditions such as heating conditions and reduced pressure conditions to complete the polycondensation reaction at as low a temperature as possible and in a short time. In particular, if the (B) semi-aromatic polyamide is an amorphous polyamide, it does not have a melting point, which is desirable because the reaction temperature can be lowered.
When the aromatic compound unit is contained in the molecular structure of the polyamide, the molecular weight distribution (Mw / Mn) tends to increase as the molecular weight increases. A high molecular weight distribution indicates a high proportion of polyamide molecules having a three-dimensional molecular structure, and the three-dimensional structure of the molecule is more likely to proceed during high-temperature processing, resulting in a decrease in fluidity, and is representative of inorganic fillers. The polyamide composition containing the components to be deteriorated in surface appearance.

  In the present invention, the measurement of Mw (weight average molecular weight) / Mn (number average molecular weight) of (B) semi-aromatic polyamide is obtained using GPC (gel permeation chromatography) as described in the following examples. The calculated Mw (weight average molecular weight) and Mn (number average molecular weight) can be used for calculation.

  In the present invention, the polyamide formic acid relative viscosity (VR) is the relative viscosity of the polyamide formic acid solution, and can be said to be a relative viscosity obtained by comparing the viscosity of the polyamide formic acid solution with the viscosity of the formic acid itself. In the present specification, the VR is used as an index of the molecular weight and fluidity of polyamide, and the higher the value of VR, the higher the molecular weight and the lower the flow. When measuring VR, it is performed according to ASTM-D789. Specifically, a value measured at 25 ° C. using a solution in which polyamide is dissolved in 90 mass% formic acid (10 mass% water) to 8.4 mass% can be adopted as the VR value. . When the VR is lower than 8, the color tone and mechanical properties are not sufficient, and when the VR is higher than 30, the fluidity is lowered and the molding processability is deteriorated. The VR of (B) semi-aromatic polyamide in this embodiment is 8 or more and 30 or less, preferably 8 or more and 25 or less, more preferably 10 or more and 25 or less, and further preferably 10 or more and 20 or less.

  In the present invention, Mw / VR of polyamide is an indicator of molecular weight and fluidity. (B) The Mw / VR of the semi-aromatic polyamide is preferably 1000 or more and 2000 or less, more preferably 1200 or more and 2000 or less, further preferably 1400 or more and 2000 or less, still more preferably 1500 or more and 2000 or less, and most preferably 1500 or more and 1800 or less. preferable. When Mw / VR is smaller than 1000, for example, the molecular weight becomes low, so the mechanical properties become insufficient. On the other hand, when Mw / VR is larger than 2000, for example, since VR is low, fluidity is high and burrs are generated during molding, which tends to cause molding defects.

(B) The crystallization enthalpy ΔH of the semi-aromatic polyamide is preferably 15 J / g or less, more preferably 10 / g or less, and further preferably from the viewpoint of mechanical properties, particularly water absorption rigidity and thermal rigidity. Is 5 J / g or less, and more preferably 0 J / g.
(B) As a method of controlling the crystallization enthalpy ΔH of the semi-aromatic polyamide within the above range, it is necessary to increase the ratio of the aromatic monomer to the dicarboxylic acid unit. It is important to contain 75 mol% or more of isophthalic acid as the dicarboxylic acid unit, and most preferably 100 mol%.
(B) As a measuring apparatus of the crystallization enthalpy (DELTA) H of semi-aromatic polyamide, Diamond-DSC by PERKIN-ELMER company etc. are mentioned, for example.

(B) The tan δ peak temperature of the semi-aromatic polyamide is preferably 90 ° C or higher, more preferably 100 to 160 ° C, still more preferably 110 to 150 ° C, and even more preferably 120 to 145 ° C. Yes, more preferably 130-140 ° C.
(B) As a method of controlling the tan δ peak temperature of the semiaromatic polyamide within the above range, it is necessary to increase the ratio of the aromatic monomer to the dicarboxylic acid unit. It is important to contain 75 mol% or more of isophthalic acid as the dicarboxylic acid unit, and most preferably 100 mol%.
(B) When the glass transition temperature of the semi-aromatic polyamide is 90 ° C. or higher, a polyamide composition excellent in water absorption rigidity and thermal rigidity tends to be obtained. Moreover, when the glass transition temperature of the polyamide composition is 160 ° C. or lower, the polyamide composition containing a component typified by an inorganic filler has excellent surface appearance.

(B) The tan δ peak temperature of the semi-aromatic polyamide can be measured by using, for example, a viscoelasticity measuring / analyzing apparatus (manufactured by Rheology: DVE-V4) as described in the following examples.
(B) The amount of the amino terminal of the semi-aromatic polyamide is preferably 5 to 100 μequivalent / g, more preferably 10 to 90 μequivalent / g, further preferably 20 to 80 μequivalent to 1 g of polyamide. / G, even more preferably 30 to 70 μeq / g, and even more preferably 40 to 60 μeq / g. When the amount of the amino terminal is in the above range, a composition excellent in discoloration to heat and light can be obtained. The amount of the amino terminus can be measured by neutralization titration.

  (B) The amount of the carboxyl terminal of the semi-aromatic polyamide is preferably 50 to 300 µequivalent / g, more preferably 100 to 280 µequivalent / g, and further preferably 150 to 260 µequivalent with respect to 1 g of polyamide. / G, even more preferably 180 to 250 μeq / g, and even more preferably 200 to 240 μeq / g. When the amount of the carboxyl terminal is within the above range, a polyamide composition having excellent fluidity and the like can be obtained. Moreover, the polyamide composition containing a component typified by an inorganic filler has excellent surface appearance. The amount of the carboxyl terminal can be measured by neutralization titration.

  The total amount of amino end and carboxyl end is preferably 150 to 350 μequivalent / g, more preferably 160 to 300 μequivalent / g, and more preferably 170 to 280 μequivalent to 1 g of polyamide. / G, still more preferably 180 to 270 μeq / g, and even more preferably 190 to 260 μeq / g. When the total amount of the amino terminal amount and the carboxyl terminal amount is in the above range, a polyamide composition excellent in fluidity and the like can be obtained. Moreover, the polyamide composition containing a component typified by an inorganic filler has excellent surface appearance.

((C) Pigment)
The polyamide resin composition of the present invention contains a pigment.
Although it does not specifically limit as a pigment, For example, pigments, such as dyes, such as nigrosine, zinc sulfide, zinc oxide, titanium oxide, and carbon black; aluminum, colored aluminum, nickel, tin, copper, gold, silver, platinum, iron oxide Metal particles such as stainless steel and titanium; metallic pigments such as mica pearl pigment, color graphite, color glass fiber, and color glass flake. Of these, white pigments such as zinc sulfide (ZnS) and zinc oxide (ZnO) are preferable because of mechanical properties such as toughness, strength, and rigidity, and a balance between flame retardancy and coloring.

((D1) Flame retardant)
The flame retardant (D1) used in the present invention is not particularly limited as long as it is a flame retardant containing a halogen element, and examples thereof include a chlorine flame retardant and a bromine flame retardant.
These (D1) flame retardants may be used alone or in combination of two or more.

  Examples of the chlorinated flame retardant include chlorinated paraffin, chlorinated polyethylene, dodecachloropentacyclooctadeca-7,15-diene (Dechlorane Plus 25 <registered trademark> manufactured by Occidental Chemical), and heptic anhydride. Can be mentioned.

  Examples of brominated flame retardants include hexabromocyclododecane (HBCD), decabromodiphenyl oxide (DBDPO), octabromodiphenyl oxide, tetrabromobisphenol A (TBBA), bis (tribromophenoxy) ethane, and bis (pentabromo). Phenoxy) ethane (BPBPE), tetrabromobisphenol A epoxy resin (TBBA epoxy), tetrabromobisphenol A carbonate (TBBA-PC), ethylene (bistetrabromophthal) imide (EBTBPI), ethylene bispentabromodiphenyl, tris (tri Bromophenoxy) triazine (TTBPTA), bis (dibromopropyl) tetrabromobisphenol A (DBP-TBBA), bis (dibromopropyl) tetrabromobi Phenol S (DBP-TBBS), brominated polyphenylene ether (including poly (di) bromophenylene ether) (BrPPE), brominated polystyrene (including polydibromostyrene, polytribromostyrene, crosslinked brominated polystyrene, etc.) ( BrPS), brominated cross-linked aromatic polymer, brominated epoxy resin, brominated phenoxy resin, brominated styrene-maleic anhydride polymer, tetrabromobisphenol S (TBBS), tris (tribromoneopentyl) phosphate (TTBNPP) , Polybromotrimethylphenylindane (PBPI), and tris (dibromopropyl) -isocyanurate (TDBPIC).

  (D1) As a flame retardant, bromine is used from the viewpoint of suppressing the amount of corrosive gas generated during melt processing such as extrusion and molding, and from the viewpoint of mechanical properties such as the expression of flame retardancy, toughness and rigidity. Preferred are brominated polystyrene (including poly (di) bromophenylene ether) and brominated polystyrene (including polydibromostyrene, polytribromostyrene, crosslinked brominated polystyrene, etc.), and more preferred is brominated polystyrene.

  The method for producing brominated polystyrene is not particularly limited. For example, after polystyrene is produced by polymerizing a styrene monomer, the benzene ring of polystyrene is brominated or brominated styrene monomer (bromo And styrene, dibromostyrene, tribromostyrene, etc.).

  The bromine content in the brominated polystyrene is preferably 55 to 75% by mass. By setting the bromine content to 55% by mass or more, the amount of bromine required for flame retardancy can be satisfied with a small amount of brominated polystyrene, and heat resistance is maintained without impairing the properties of the polyamide copolymer. In addition, a polyamide resin composition excellent in fluidity, toughness, low water absorption, rigidity, and flame retardancy can be obtained. Further, by setting the bromine content to 75% by mass or less, a polyamide resin composition that hardly causes thermal decomposition during melt processing such as extrusion or molding, can suppress gas generation, and is excellent in heat discoloration resistance. Can be obtained.

((D2) Flame retardant aid)
The polyamide resin composition of this invention can be made into the polyamide resin composition which is excellent by a flame retardance by containing the flame retardant adjuvant (D2).
The flame retardant aid (D2) used in the present invention is not particularly limited. For example, diantimony trioxide (Sb ₂ O ₃ ), diantimony tetroxide, diantimony pentoxide, sodium antimonate, etc. Antimony oxides; tin oxides such as tin monoxide and tin dioxide; iron oxides such as ferric oxide and gamma iron oxide; other zinc oxide, zinc borate, calcium oxide, aluminum oxide (alumina), aluminum oxide (Boehmite), silicon oxide (silica), titanium oxide, zirconium oxide, manganese oxide, molybdenum oxide, cobalt oxide, bismuth oxide, chromium oxide, nickel oxide, copper oxide, and tungsten oxide; magnesium hydroxide, And metal hydroxides such as aluminum hydroxide; aluminum, iron, titanium, manga Metal powders such as zinc, molybdenum, cobalt, bismuth, chromium, tin, antimony, nickel, copper, and tungsten; metal carbonates such as zinc carbonate, calcium carbonate, magnesium carbonate, and barium carbonate; magnesium borate, boric acid And metal borates such as calcium and aluminum borate; and silicone.
These (D2) flame retardant aids may be used alone or in combination of two or more.

(D2) Flame retardant aids used in the present invention include antimony oxides such as antimony trioxide, diantimony tetroxide, diantimony pentoxide, and sodium antimonate from the viewpoint of flame retardant effect; magnesium hydroxide Tin oxides such as tin monoxide and tin dioxide; iron oxides such as ferric oxide and gamma iron oxide; zinc oxide and zinc borate are preferred, and diantimony trioxide, diantimony tetroxide, and pentoxide Antimony oxides such as diantimony; magnesium hydroxide and zinc borate are more preferred, antimony oxides and / or magnesium hydroxide are more preferred, and antimony trioxide and magnesium hydroxide are particularly preferred.
In order to increase the flame retardant effect, it is preferable to use a flame retardant aid (D2) having an average particle size of 0.01 to 10 μm.
The average particle size can be measured using a laser diffraction scattering method particle size distribution measuring device or a precision particle size distribution measuring device.

((E) Polymer containing α, β unsaturated dicarboxylic acid anhydride as constituent unit)
The polyamide resin composition of the present invention may further contain (E) a polymer containing α, β-unsaturated dicarboxylic acid anhydride as a constituent unit. (E) By containing the polymer which contains (alpha), (beta) unsaturated dicarboxylic anhydride in a structural unit, it can be set as the polyamide resin composition excellent in mechanical physical properties, such as toughness and rigidity, and a flame retardance.

Examples of the polymer containing (E) α, β unsaturated dicarboxylic acid anhydride as a constituent unit used in the present invention include, for example, a polymer containing α, β unsaturated dicarboxylic acid anhydride as a copolymerization component, and α, β And polymers modified with unsaturated dicarboxylic acid anhydrides.
Examples of the α, β unsaturated dicarboxylic acid anhydride include compounds represented by the following general formula (1).

General formula (1):

In General formula (1), R < ¹ > and R < ² > are respectively independently hydrogen or a C1-C3 alkyl group.

Examples of the α, β unsaturated dicarboxylic acid anhydride include maleic anhydride and methyl maleic anhydride, and maleic anhydride is preferable. Examples of the polymer containing an α, β unsaturated dicarboxylic acid anhydride as a copolymerization component include a copolymer of an aromatic vinyl compound and an α, β unsaturated dicarboxylic acid anhydride.
Examples of the polymer modified with α, β unsaturated dicarboxylic acid anhydride include polyphenylene ether and polypropylene modified with α, β unsaturated dicarboxylic acid anhydride. In particular, maleic anhydride-modified polyphenylene ether is preferable.
As a polymer containing an α, β unsaturated dicarboxylic acid anhydride as a copolymerization component, an aromatic vinyl compound and an α, β unsaturated compound are used from the viewpoint of efficiency to improve flame retardancy (expressed with a small amount of addition). A copolymer with a dicarboxylic acid anhydride is preferred.

  As an aromatic vinyl compound used in this invention, the compound represented by following General formula (2) is mentioned, for example.

General formula (2):

In general formula (2), ^{R 3} and ^{R 4} are each independently hydrogen or an alkyl group having 1 to 3 carbon atoms, k is an integer of 1 to 5.

  Examples of the aromatic vinyl compound include styrene, α-methylstyrene, p-methylstyrene, and the like, and styrene is preferable.

  In the present invention, when the polymer containing α, β unsaturated dicarboxylic acid anhydride as a constituent unit contains an aromatic vinyl compound component, the aromatic vinyl compound component is (D1) a flame retardant (brominated polystyrene or the like). And the α, β-unsaturated dicarboxylic acid anhydride moiety (B) has an affinity or reaction with the semi-aromatic polyamide, thereby helping to disperse the flame retardant (D1) in the polyamide matrix. Can be finely dispersed.

  The ratio of aromatic vinyl compound component and α, β unsaturated dicarboxylic acid anhydride component in the copolymer of aromatic vinyl compound and α, β unsaturated dicarboxylic acid anhydride is flame retardant, fluidity, thermal decomposition From the viewpoint of properties, the aromatic vinyl compound component is preferably 50 to 99% by mass, and the α, β unsaturated dicarboxylic anhydride component is preferably 1 to 50% by mass. The proportion of the α, β unsaturated dicarboxylic anhydride component is more preferably 5 to 20% by mass, and further preferably 8 to 15% by mass.

  By setting the proportion of the α, β unsaturated dicarboxylic anhydride component to 1% by mass or more, a polyamide resin composition excellent in mechanical properties such as toughness and rigidity and flame retardancy can be obtained. Moreover, deterioration of the polyamide resin composition due to the α, β unsaturated dicarboxylic acid anhydride can be prevented by setting the proportion of the α, β unsaturated dicarboxylic acid anhydride component to 50% by mass or less.

  As the polymer modified with an α, β unsaturated dicarboxylic acid anhydride, a polyphenylene ether resin or a polypropylene resin modified with an α, β unsaturated dicarboxylic acid anhydride is preferable. The content of the polymer modified with α, β unsaturated dicarboxylic anhydride is preferably 0.05% by mass or more and 5% by mass or less with respect to 100% by mass of the polyamide composition.

((F) Filler)
The polyamide resin composition of the present invention may further contain (F) a filler. (F) By containing a filler, it can be set as the polyamide resin composition which is further excellent in mechanical physical properties, such as toughness and rigidity.

The (F) filler used in the present invention is not particularly limited, and examples thereof include glass fiber, carbon fiber, calcium silicate fiber, potassium titanate fiber, aluminum borate fiber, glass flake, talc, and kaolin. , Mica, hydrotalcite, calcium carbonate, zinc carbonate, zinc oxide, calcium monohydrogen phosphate, 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 nanotube, Graphite, Brass, Copper, Silver, Aluminum, Nickel, Iron, Calcium fluoride, Montmorillonite, Swelling fluorine Mother, and apatite, and the like.
(F) As a filler, you may use by 1 type and may be used in combination of 2 or more types.

  (F) As filler, from the viewpoint of rigidity and strength, glass fiber, carbon fiber, glass flake, talc, kaolin, mica, calcium carbonate, calcium monohydrogen phosphate, wollastonite, silica, carbon nanotube, graphite , Calcium fluoride, montmorillonite, swellable fluorine mica, apatite, and the like are preferable.

  (F) The filler is more preferably glass fiber or carbon fiber, and among glass fiber and carbon fiber, the number average fiber diameter is 3 to 30 μm, the weight average fiber length is 100 to 750 μm, and the weight average fiber Those having an aspect ratio (L / D) of 10 to 100 between the length (L) and the number average fiber diameter (D) are more preferably used from the viewpoint of developing high characteristics.

  Further, as the filler (F), glass fibers are more preferable, and among the glass fibers, the number average fiber diameter is 3 to 30 μm, the weight average fiber length is 10 to 500 μm, and the aspect ratio (L / D ) Is more preferably 3 to 100.

  (F) The measurement of the number average fiber diameter and the weight average fiber length of the filler is carried out by dissolving the molded article of the polyamide resin composition with a solvent in which polyamide is soluble, such as formic acid, and from the obtained insoluble components, For example, 100 or more fillers can be selected arbitrarily, and can be obtained by observing with an optical microscope or a scanning electron microscope.

(Content of each component)
The content of the pigment (C) in the polyamide resin composition of the present invention is preferably 0.5% by mass or more and 5% by mass or less, and more preferably 3% by mass or less with respect to 100% by mass of the polyamide composition. Particularly, (C) the pigment is a white pigment, and the content of the white pigment is 0.5% by mass or more and 5% by mass or less based on 100% by mass of the polyamide composition. Particularly preferred from the viewpoint of mechanical strength.

  The content of the flame retardant (D1) in the polyamide resin composition of the present invention is preferably 0.1% by mass or more and 30% by mass or less, more preferably 5 to 20% with respect to 100% by mass of the polyamide composition. It is mass%, More preferably, it is 5-15 mass%.

  The content of the flame retardant aid (D2) in the polyamide resin composition is preferably 0.1 to 10% by mass, more preferably 1 to 10% by mass with respect to 100% by mass of the polyamide composition. . (D2) By containing a flame retardant aid in the above range, a polyamide resin composition having further excellent flame retardancy can be obtained. In addition, by setting the content of (D2) the flame retardant aid to 10% by mass or less, the viscosity at the time of melt processing can be controlled within an appropriate range, the torque at the time of extrusion is increased, and the moldability at the time of molding. And the appearance of the molded product can be suppressed. Moreover, a polyamide resin composition having excellent toughness can be obtained without impairing the properties of polyamide having excellent mechanical properties such as toughness and rigidity.

  (D2) By making content of a flame-retardant adjuvant into 0.1 mass% or more, the polyamide resin composition excellent in a flame retardance can be obtained. In addition, by setting the content of the flame retardant (D1) to 15% by mass or less, generation of decomposition gas at the time of melt-kneading, decrease in fluidity at the time of molding, and adhesion of pollutants to the molding die are suppressed. be able to. Furthermore, deterioration of mechanical properties such as toughness and rigidity and appearance of the molded product can be suppressed.

A particularly preferable combination is (D1) the flame retardant is brominated polystyrene, the brominated polystyrene content is 6% by mass to 15% by mass with respect to 100% by mass of the polyamide composition, and (D2) difficult The fuel additive is diantimony trioxide (Sb ₂ O ₃ ), and the content of diantimony trioxide (Sb ₂ O ₃ ) is 0.1% by mass or more and 4% by mass or less with respect to 100% by mass of the polyamide composition. It is.

  The content of the polymer containing (E) α, β unsaturated dicarboxylic acid anhydride in the polyamide resin composition as a constituent unit is preferably 0.1 to 20% by mass with respect to 100% by mass of the polyamide composition. Yes, more preferably 0.5 to 20% by mass, still more preferably 1 to 15% by mass, and particularly preferably 2 to 10% by mass. (E) Increasing the fine dispersion effect of (D1) flame retardant in the polyamide resin composition by compatibilization by containing a polymer containing α, β unsaturated dicarboxylic acid anhydride in the above range in the above range. Thus, a polyamide resin composition excellent in flame retardancy and strength improvement effect can be obtained. (E) By setting the content of the polymer containing α, β unsaturated dicarboxylic acid anhydride as a constituent unit to 20% by mass or less, the properties of polyamide having excellent mechanical properties such as toughness and rigidity are not impaired. A polyamide resin composition having excellent strength and the like can be obtained.

  The content of the filler (F) in the polyamide resin composition is preferably 1 to 80% by mass, more preferably 10 to 70% by mass, and still more preferably 30 to 100% by mass of the polyamide composition. It is -70 mass%, More preferably, it is 30-60 mass%, Most preferably, it is 40-60 mass%.

(F) By containing the filler in the above range, mechanical properties such as the strength and rigidity of the polyamide resin composition are improved satisfactorily, and the content of the inorganic filler is 70% by mass or less. A polyamide resin composition having excellent moldability can be obtained.
In the present invention, (C) a pigment, (D1) a flame retardant, (D2) a flame retardant aid, (E) a polymer containing α, β unsaturated dicarboxylic acid anhydride as a structural unit, (F) a filler, The total content is preferably 60 to 80% by mass or less with respect to 100% by mass of the polyamide resin composition. More preferably, it is 10-90 mass%, More preferably, it is 30-80 mass%, More preferably, it is 40-80 mass%. By setting the total amount to 10% by mass or more, it is possible to obtain a polyamide composition having excellent strength, rigidity, flame retardancy, and the like, and having excellent melt viscosity and excellent workability.

In the polyamide composition of the present invention, additives that are conventionally used for polyamide within a range that does not impair the object of the present invention, such as moldability improver, deterioration inhibitor, nucleating agent, lubricant, stabilizer, In addition, polymers other than the polyamide in the present invention can also be contained.
Since the content of the additive varies depending on the type and use of the polyamide composition, it is not particularly limited as long as the object of the present invention is not impaired.

(Formability improver)
If necessary, a moldability improving agent may be added to the polyamide resin composition of the present invention as long as the object of the present invention is not impaired. Although it does not specifically limit as a moldability improving agent, A higher fatty acid, a higher fatty acid metal salt, a higher fatty acid ester, a higher fatty acid amide, etc. are mentioned.

  Examples of higher fatty acids include, for example, stearic acid, palmitic acid, behenic acid, erucic acid, oleic acid, lauric acid, and montanic acid, which are saturated or unsaturated, linear or branched aliphatic having 8 to 40 carbon atoms. A monocarboxylic acid etc. are mentioned. Among these, stearic acid and montanic acid are preferable.

A higher fatty acid metal salt is a metal salt of a higher fatty acid.
As the metal element of the metal salt, group 1, 2, 3 elements of the periodic table, zinc, aluminum, etc. are preferable, group 1, 2, elements such as calcium, sodium, potassium, and magnesium, and aluminum Etc. are more preferable.
Examples of the higher fatty acid metal salt include calcium stearate, aluminum stearate, zinc stearate, magnesium stearate, calcium montanate, sodium montanate, calcium palmitate and the like. Among these, a metal salt of montanic acid and a metal salt of stearic acid are preferable.

The higher fatty acid ester is an esterified product of a higher fatty acid and an alcohol.
Esters of an aliphatic carboxylic acid having 8 to 40 carbon atoms and an aliphatic alcohol having 8 to 40 carbon atoms are preferred. Examples of the aliphatic alcohol include stearyl alcohol, behenyl alcohol, and lauryl alcohol. Examples of higher fatty acid esters include stearyl stearate and behenyl behenate.

A higher fatty acid amide is an amide compound of a higher fatty acid.
Examples of the higher fatty acid amide include stearic acid amide, oleic acid amide, erucic acid amide, ethylene bisstearyl amide, ethylene bisoleyl amide, N-stearyl stearic acid amide, N-stearyl erucic acid amide and the like.

  These higher fatty acids, higher fatty acid metal salts, higher fatty acid esters, and higher fatty acid amides may be used singly or in combination of two or more.

(Degradation inhibitor)
In the polyamide resin composition of the present invention, a degradation inhibitor is added to the polyamide resin composition of the present invention for the purpose of improving thermal degradation, thermal discoloration prevention, heat aging resistance, and weather resistance, as long as the purpose of the present invention is not impaired. It may be added.
Although it does not specifically limit as a deterioration inhibitor, For example, Copper compounds, such as copper acetate and copper iodide; Phenol stabilizers, such as a hindered phenol compound; A phosphite stabilizer, A hindered amine stabilizer; A triazine stabilizer A benzotriazole stabilizer, a benzophenone stabilizer, a cyanoacrylate stabilizer, a salicylate stabilizer; and a sulfur stabilizer.
One of these deterioration inhibitors may be used alone, or two or more thereof may be used in combination.

(Nucleating agent)
The nucleating agent means that the addition increases the crystallization peak temperature of the polyamide composition, reduces the difference between the extrapolation start temperature and the extrapolation end temperature of the crystallization peak, It means a substance that can achieve the effect of miniaturizing or making the size uniform.
Examples of the nucleating agent include, but are not limited to, talc, boron nitride, mica, kaolin, calcium carbonate, barium sulfate, silicon nitride, carbon black, potassium titanate, and molybdenum disulfide. It is done.
Only one type of nucleating agent may be used alone, or two or more types may be used in combination.

The nucleating agent is preferably talc or boron nitride from the viewpoint of the nucleating agent effect.
Moreover, since a nucleating agent effect is high, the nucleating agent whose number average particle diameter is 0.01-10 micrometers is preferable.
The number average particle size of the nucleating agent is determined by dissolving the molded article in a solvent in which polyamide such as formic acid is soluble, and arbitrarily selecting, for example, 100 or more nucleating agents from the obtained insoluble components, It can be determined by observing and measuring with an optical microscope or a scanning electron microscope.

In the polyamide composition of the present invention, the content of the nucleating agent is preferably 0.001 to 1 part by mass, more preferably 0.001 to 0.5 part with respect to 100 parts by mass of the polyamide of the present invention. It is a mass part, More preferably, it is 0.001-0.09 mass part.
By setting the content of the nucleating agent to 0.001 part by mass or more with respect to 100 parts by mass of the polyamide, the heat resistance of the polyamide composition is improved, and the content of the nucleating agent is set to 100 parts by mass of the polyamide. By setting it to 1 part by mass or less with respect to parts, a polyamide composition having excellent toughness can be obtained.

(Stabilizer)
Examples of the stabilizer include, but are not limited to, for example, phenol-based heat stabilizers, phosphorus-based heat stabilizers, amine-based heat stabilizers, and groups 3, 4, and 11 to 14 of the periodic table. Metal salts of these elements, and halides of alkali metals and alkaline earth metals.

  Examples of the phenol-based heat stabilizer include, but are not limited to, hindered phenol compounds. The hindered phenol compound has a property of imparting excellent heat resistance and light resistance to resins and fibers such as polyamide.

Examples of the hindered phenol compound include, but are not limited to, for example, N, N′-hexane-1,6-diylbis [3- (3,5-di-t-butyl-4-hydroxyphenylpropylene). Onamide), pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], N, N′-hexamethylenebis (3,5-di-t-butyl- 4-hydroxy-hydrocinnamamide), triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 3,9-bis {2- [3- (3 -T-butyl-4-hydroxy-5-methylphenyl) propynyloxy] -1,1-dimethylethyl} -2,4,8,10-tetraoxapyro [5,5] undecane, , 5-Di-tert-butyl-4-hydroxybenzylphosphonate-diethyl ester, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene And 1,3,5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanuric acid.
These may be used alone or in combination of two or more.
In particular, N, N′-hexane-1,6-diylbis [3- (3,5-di-t-butyl-4-hydroxyphenylpropionamide)] is preferable from the viewpoint of improving heat aging resistance.

  When using a phenol-based heat stabilizer, the content of the phenol-based heat stabilizer in the polyamide composition is preferably 0.01 to 1% by mass, more preferably 0, with respect to 100% by mass of the polyamide composition. 0.1 to 1% by mass. When content of a phenol type heat stabilizer exists in said range, the heat-resistant aging property of a polyamide composition can be improved further, and also the amount of gas generation can be reduced.

Examples of the phosphorus-based heat stabilizer include, but are not limited to, pentaerythritol phosphite compounds, trioctyl phosphite, trilauryl phosphite, tridecyl phosphite, octyl diphenyl phosphite, trisisodecyl. Phosphite, phenyl diisodecyl phosphite, phenyl di (tridecyl) phosphite, diphenyl isooctyl phosphite, diphenyl isodecyl phosphite, diphenyl (tridecyl) phosphite, triphenyl phosphite, tris (nonylphenyl) phosphite, tris (2 , 4-di-t-butylphenyl) phosphite, tris (2,4-di-t-butyl-5-methylphenyl) phosphite, tris (butoxyethyl) phosphite, 4,4′-butylidene- Bis (3-methyl-6-t-butylphenyl-tetra-tridecyl) diphosphite, tetra (C12-C15 mixed alkyl) -4,4'-isopropylidene diphenyldiphosphite, 4,4'-isopropylidenebis (2 -T-butylphenyl) -di (nonylphenyl) phosphite, tris (biphenyl) phosphite, tetra (tridecyl) -1,1,3-tris (2-methyl-5-t-butyl-4-hydroxyphenyl) Butane diphosphite, 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'-isopropylidene (2-t-butylphenyl) -di (nonylphenyl) phosphite, 9,10-di-hydro-9-oxa-9-oxa-10-phosphaphenanthrene-10-oxide, tris (3 5-di-t-butyl-4-hydroxyphenyl) phosphite, hydrogenated-4,4′-isopropylidene diphenyl polyphosphite, bis (octylphenyl) -bis (4,4′-butylidenebis (3-methyl-) 6-t-butylphenyl))-1,6-hexanol diphosphite, hexatridecyl-1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) diphosphite, tris (4 4′-isopropylidenebis (2-t-butylphenyl)) phosphite, tris (1,3-stearoyloxyisopropyl) phosphite 2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite, 2,2-methylenebis (3-methyl-4,6-di-t-butylphenyl) 2-ethylhexyl phosphite, tetrakis (2,4-di-t-butyl-5-methylphenyl) -4,4'-biphenylene diphosphite and tetrakis (2,4-di-t-butylphenyl) -4,4'-biphenylene diphos Fight is mentioned.
These may be used alone or in combination of two or more.

Among those listed above, pentaerythritol type phosphite compound and / or tris (2,4-di-t-butylphenyl) from the viewpoint of further improving the heat aging resistance of the polyamide composition and reducing the gas generation amount. Phosphites are preferred. Examples of the pentaerythritol type phosphite compound include, but are not limited to, 2,6-di-t-butyl-4-methylphenyl-phenyl-pentaerythritol diphosphite, 2,6-di- t-butyl-4-methylphenyl-methyl-pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl-2-ethylhexyl-pentaerythritol diphosphite, 2,6-di-t- Butyl-4-methylphenyl-isodecyl-pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl-lauryl-pentaerythritol diphosphite, 2,6-di-t-butyl-4- Methylphenyl-isotridecyl-pentaerythritol diphosphite, 2,6-di-t-butyl -4-methylphenyl-stearyl pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl cyclohexyl-pentaerythritol diphosphite, 2,6-di-t-butyl-4-methyl Phenyl-benzyl-pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl ethyl cellosolve-pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl-butyl Carbitol-pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl-octylphenyl-pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl-nonylphenyl Pentaerythritol diphosphite, bis (2,6-di t-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-butyl-4-ethylphenyl) pentaerythritol diphosphite, 2,6-di-t-butyl-4- Methylphenyl-2,6-di-t-butylphenyl-pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl-2,4-di-t-butylphenyl-pentaerythritol diphosphite Phyto, 2,6-di-t-butyl-4-methylphenyl-2,4-di-t-octylphenyl-pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl-2 -Cyclohexylphenyl-pentaerythritol diphosphite, 2,6-di-t-amyl-4-methylphenyl-phenyl pentaeryth Tritol diphosphite, bis (2,6-di-t-amyl-4-methylphenyl) pentaerythritol diphosphite, and bis (2,6-di-t-octyl-4-methylphenyl) pentaerythritol di A phosphite is mentioned.
These may be used alone or in combination of two or more.

  Among the pentaerythritol type phosphite compounds listed above, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, bis, from the viewpoint of reducing the gas generation amount of the polyamide composition. (2,6-di-t-butyl-4-ethylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-amyl-4-methylphenyl) pentaerythritol diphosphite, and bis (2, One or more selected from the group consisting of 6-di-t-octyl-4-methylphenyl) pentaerythritol diphosphite is preferred, and bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol Diphosphite is more preferred.

  When using a phosphorus-based heat stabilizer, the content of the phosphorus-based heat stabilizer in the polyamide composition is preferably 0.01 to 1% by mass, more preferably 100% by mass with respect to the polyamide composition. 0.1 to 1% by mass. When the content of the phosphorus-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 reduced.

  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-tetramethyl Peridine, 4- (ethylcarbamoyloxy) -2,2,6,6-tetramethylpiperidine, 4- (cyclohexylcarbamoyloxy) -2,2,6,6-tetramethylpiperidine, 4- (phenylcarbamoyloxy)- 2,2,6,6-tetramethylpiperidine, bis (2,2,6,6-tetramethyl-4-piperidyl) -carbonate, bis (2,2,6,6-tetramethyl-4-piperidyl)- Oxalate, bis (2,2,6,6-tetramethyl-4-piperidyl) -malonate, bis (2,2,6,6-tetramethyl-4-piperidyl) -sebacate, bis (2,2,6, 6-tetramethyl-4-piperidyl) -adipate, bis (2,2,6,6-tetramethyl-4-piperidyl) -terephthalate, 1,2-bis (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-piperidyltolylene-2,4-dicarbamate, bis (2,2,6,6-tetramethyl-4-piperidyl) -hexamethylene-1,6-dicarbamate, tris ( 2,2,6,6-tetramethyl-4-piperidyl) -benzene-1,3,5-tricarboxylate, tris (2,2,6,6-tetramethyl-4-piperidyl) -benzene-1, 3,4-tricarboxylate, 1- [2- {3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy} butyl] -4- [3- (3,5-di- t-Butyl-4-hydroxyfe L) propionyloxy] 2,2,6,6-tetramethylpiperidine, 1,2,3,4-butanetetracarboxylic acid, 1,2,2,6,6-pentamethyl-4-piperidinol and β, β , Β ′, β′-tetramethyl-3,9- [2,4,8,10-tetraoxaspiro (5,5) undecane] diethanol. These may be used alone or in combination of two or more.

  When the amine heat stabilizer is used, the content of the amine heat stabilizer in the polyamide composition is preferably 0.01 to 1% by mass, more preferably 0 to 100% by mass of the polyamide composition. 0.1 to 1% by mass. When the content of the amine 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 reduced.

  The metal salts of the elements of Groups 3, 4, and 11-14 of the Periodic Table of Elements are not limited as long as they are salts of metals belonging to these groups. From the viewpoint of further improving the heat aging resistance of the polyamide composition, a copper salt is preferable. Examples of the copper salt include, but are not limited to, copper halides (copper iodide, cuprous bromide, cupric bromide, cuprous chloride, etc.), copper acetate, copper propionate, benzoic acid. Examples thereof include copper, copper adipate, copper terephthalate, copper isophthalate, copper salicylate, copper nicotinate and copper stearate, and a copper complex in which copper is coordinated to a chelating agent such as ethylenediamine and ethylenediaminetetraacetic acid. These may be used alone or in combination of two or more.

  Among the copper salts listed above, preferably one or more selected from the group consisting of copper iodide, cuprous bromide, cupric bromide, cuprous chloride and copper acetate, more preferably Copper iodide and / or copper acetate. When the above-mentioned more preferable copper salt is used, a polyamide composition having excellent heat aging resistance and capable of effectively suppressing metal corrosion of the screw and cylinder part during extrusion (hereinafter also simply referred to as “metal corrosion”) is provided. can get.

  When using a copper salt, the content of the copper salt in the polyamide composition is preferably 0.01 to 0.60 mass%, more preferably 0.02 to 0.40, based on 100 mass% of the polyamide. % By mass. When the content of the copper salt is within the above range, the heat aging resistance of the polyamide composition can be further improved, and copper precipitation and metal corrosion can be effectively suppressed.

Also, concentration of the copper elements derived from the copper salts described above, from the viewpoint of improving the thermal aging resistance of the polyamide composition, the polyamic ¹⁰⁶ parts, preferably 10 to 2,000 parts by weight, more preferably It is 30-1500 mass parts, More preferably, it is 50-500 mass parts.

  Alkali metal and alkaline earth metal halides include, but are not limited to, for example, potassium iodide, potassium bromide, potassium chloride, sodium iodide and sodium chloride, and mixtures thereof. . Among these, potassium iodide and / or potassium bromide is preferable from the viewpoint of improving heat aging resistance and suppressing metal corrosion, and more preferably potassium iodide.

  When the alkali metal and alkaline earth metal halide is used, the content of the alkali metal and alkaline earth metal halide in the polyamide composition is preferably 0.05 to 20 mass with respect to 100 parts by mass of the polyamide. Part, more preferably 0.2 to 10 parts by mass. When the content of the alkali metal and alkaline earth metal halide is within the above range, the polyamide composition can be further improved in heat aging resistance, and copper precipitation and metal corrosion can be effectively suppressed.

  The stabilizer components described above may be used alone or in combination of two or more. Among these, from the viewpoint of further improving the heat aging resistance of the polyamide composition, a mixture of a copper salt and a halide of an alkali metal and an alkaline earth metal is preferable.

  The ratio of copper salt to alkali metal and alkaline earth metal halide is preferably 2/1 to 40/1, more preferably 5 /, as the molar ratio of halogen to copper (halogen / copper). 1-30 / 1. In the above-mentioned range, the heat aging resistance of the polyamide composition can be further improved.

  When the above halogen / copper is 2/1 or more, it is preferable because precipitation of copper and metal corrosion can be effectively suppressed. On the other hand, when the halogen / copper is 40/1 or less, corrosion of the screw of the molding machine and the like can be prevented without substantially impairing mechanical properties (toughness and the like).

(Other resins)
If necessary, other resins may be added to the polyamide resin composition of the present invention as long as the object of the present invention is not impaired.
Such a resin is not particularly limited, and examples thereof include a thermoplastic resin and a rubber component described later.

Examples of the thermoplastic resin include polystyrene resins such as atactic polystyrene, isotactic polystyrene, syndiotactic polystyrene, AS (acrylonitrile-styrene copolymer) resin, and ABS (acrylonitrile-butadiene-styrene copolymer) resin. Polyester resins such as polyethylene terephthalate and polybutylene terephthalate; nylon polyamides other than polyamide used in the present invention; polyether resins such as polycarbonate, polyphenylene ether, polysulfone and polyethersulfone; condensation systems such as polyphenylene sulfide and polyoxymethylene Resin; Acrylic resin such as polyacrylic acid, polyacrylic acid ester, polymethyl methacrylate, etc .; polyethylene, polypropylene, polybutene, polyethylene Polyvinyl chloride, halogen-containing vinyl compound resin polyvinylidene chloride; - Len propylene copolymer polyolefin resins such as phenolic resins, epoxy resins and the like.
One type of these thermoplastic resins may be used alone, or two or more types may be used in combination.

Examples of the rubber component include natural rubber, polybutadiene, polyisoprene, polyisobutylene, neoprene, polysulfide rubber, thiocol rubber, acrylic rubber, urethane rubber, silicone rubber, epichlorohydrin rubber, styrene-butadiene block copolymer (SBR), Hydrogenated styrene-butadiene block copolymer (SEB), styrene-butadiene-styrene block copolymer (SBS), hydrogenated styrene-butadiene-styrene block copolymer (SEBS), styrene-isoprene block copolymer (SIR) ), Hydrogenated styrene-isoprene block copolymer (SEP), styrene-isoprene-styrene block copolymer (SIS), hydrogenated styrene-isoprene-styrene block copolymer (SEPS), steel -Butadiene random copolymer, hydrogenated styrene-butadiene random copolymer, styrene-ethylene-propylene random copolymer, styrene-ethylene-butylene random copolymer, ethylene-propylene copolymer (EPR), ethylene- (1-butene) copolymer, ethylene- (1-hexene) copolymer, ethylene- (1-octene) copolymer, ethylene-propylene-diene copolymer (EPDM), butadiene-acrylonitrile-styrene- Core shell rubber (ABS), methyl methacrylate-butadiene-styrene-core shell rubber (MBS), methyl methacrylate-butyl acrylate-styrene-core shell rubber (MAS), octyl acrylate-butadiene-styrene-core shell rubber (MABS), alkyl Acrylate - butadiene - acrylonitrile - styrene core-shell rubbers (AABS), butadiene - styrene - core shell rubber (SBR), methyl methacrylate - include core-shell type, etc. such as a siloxane-containing core-shell rubber, including butyl acrylate siloxane.
These rubber components may be used alone or in combination of two or more.

(Manufacturing method of polyamide resin composition)
As a manufacturing method of the polyamide resin composition of the present invention, (A) aliphatic polyamide and (B) semi-aromatic polyamide, (C) pigment, (D1) flame retardant, (D2) flame retardant aid, if necessary (E) It will not specifically limit if it is a method of mixing the polymer which contains (alpha), (beta) unsaturated dicarboxylic acid anhydride in a structural unit, and (F) filler.

  (A) aliphatic polyamide and (B) semi-aromatic polyamide, (C) pigment, (D1) flame retardant, (D2) flame retardant aid, (E) α, β unsaturated dicarboxylic anhydride Examples of the mixing method of the polymer containing and the filler (F) include, for example, (A) aliphatic polyamide, (B) semi-aromatic polyamide, (C) pigment, and (D1) flame retardant, and ( D2) A flame retardant aid, (E) a polymer containing α, β-unsaturated dicarboxylic acid anhydride as a constituent unit, and (F) at least one selected from the group consisting of fillers using a Henschel mixer or the like Mixing and supplying to a melt-kneader and kneading, or (A) an aliphatic polyamide, (B) a semi-aromatic polyamide and (D1) a flame retardant, and optionally (C) Pigment, (D2) flame retardant aid and / or (E) α, β unsaturated dicarbo A method of blending a polymer containing acid anhydride in advance with a Henschel mixer or the like into a melt kneader and kneading, and optionally blending (F) filler from the side feeder, etc. Is mentioned.

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

The temperature of the melt kneading is preferably a temperature that is about 1 to 100 ° C. higher than the melting point of the (A) aliphatic polyamide, more preferably about 10 to 50 ° C.
The shear rate in the kneader is preferably about 100 sec ⁻¹ or more, and the average residence time during kneading is preferably about 0.5 to 5 minutes.

  As an apparatus for performing melt kneading, a known apparatus, for example, a melt kneader such as a single or twin screw extruder, a Banbury mixer, and a mixing roll is preferably used.

  The compounding quantity of each component at the time of manufacturing the polyamide resin composition of this invention is the same as content of each component in the polyamide resin composition mentioned above.

(Physical properties of polyamide composition)
Specifically, the molecular weight, the melting point Tm2, the crystallization enthalpy ΔH, and the tan δ peak temperature of the polyamide composition of the present invention can be measured by the methods described in Examples described later.
Mw (weight average molecular weight) can be used as an index of the molecular weight of the polyamide composition. Mw (weight average molecular weight) of the polyamide composition is 10,000 to 40000, preferably 17000 to 35000, more preferably 20000 to 35000, still more preferably 22000 to 34000, and still more preferably 24,000 to 33000. And most preferably 25000-32000. When Mw (weight average molecular weight) is in the above range, a polyamide having excellent mechanical properties, in particular, water absorption rigidity, thermal rigidity, fluidity and the like can be obtained. Moreover, the polyamide composition containing the component typified by the filler is excellent in surface appearance.
Examples of a method for controlling the Mw of the polyamide composition within the above range include using (A) an aliphatic polyamide and (B) a semiaromatic polyamide having a Mw within the above-described range.
In addition, the measurement of Mw (weight average molecular weight) can be measured using GPC (gel permeation chromatography) as described in the following Example.

  The total content of the polyamide having a number average molecular weight Mn of 500 or more and 2000 or less is preferably 0.5% by mass or more and less than 2.5% by mass, more preferably 0.8%, based on the total amount of polyamide in the polyamide composition. % By mass or more and less than 2.5% by mass, more preferably 1.0% by mass or more and less than 2.5% by mass, still more preferably 1.2% by mass or more and less than 2.5% by mass, Preferably they are 1.4 mass% or more and less than 2.5 mass%. A polyamide composition containing a component having a number average molecular weight Mn of not less than 500 and not more than 2000 mass%, which is excellent in fluidity and typified by an inorganic filler, has a surface appearance. It can be excellent. Moreover, gas generation at the time of shaping | molding can be suppressed by being less than 2.5 mass%.

As a method of controlling the total content of the polyamide having a number average molecular weight Mn of 500 or more and 2000 or less within the above range, the molecular weight of the (B) semi-aromatic polyamide is important, and Mw (weight average molecular weight) is preferably 10000-25000.
In addition, the total content of the polyamide having a number average molecular weight Mn of 500 or more and 2000 or less with respect to the total mass of the polyamide is determined from an elution curve under measurement conditions in Examples described later using GPC.
When other components that are soluble in a solvent that dissolves the polyamide are contained in the composition containing (A) an aliphatic polyamide and (B) a semi-aromatic polyamide during GPC measurement, the polyamide is insoluble. However, after the other components are extracted and removed using a soluble solvent, GPC measurement is performed. Further, an inorganic filler or the like that is insoluble in a solvent that dissolves the polyamide resin is dissolved in a solvent that dissolves the polyamide composition, and then filtered to remove insoluble matters, and then GPC measurement is performed.

  The difference {Mw (A) -Mw (B)} between the weight average molecular weight Mw (A) of the (A) aliphatic polyamide and the weight average molecular weight Mw (B) of the (B) semiaromatic polyamide is 10,000 or more. More preferably, it is 11000 or more, More preferably, it is 12000 or more, More preferably, it is 13000 or more, Most preferably, it is 14000 or more. When {Mw (A) -Mw (B)} is 10,000 or more, (B) a semi-aromatic polyamide forms a microsize domain, and a composition excellent in water absorption rigidity and heat rigidity can be obtained. .

The molecular weight distribution of the polyamide composition of the present invention uses Mw (weight average molecular weight) / Mn (number average molecular weight) as an index.
Mw (weight average molecular weight) / Mn (number average molecular weight) of the polyamide composition of the present invention is preferably 2.4 or less, more preferably 1.7 to 2.3, and still more preferably 1.8 to 2.3. 2.2, more preferably 1.9 to 2.1. The lower limit of the molecular weight distribution is 1.0. By setting Mw (weight average molecular weight) / Mn (number average molecular weight) within the above range, a polyamide composition having excellent fluidity and the like can be obtained. Moreover, the polyamide composition containing a component typified by an inorganic filler has excellent surface appearance.

As a method of controlling the Mw (weight average molecular weight) / Mn (number average molecular weight) of the polyamide composition within the above range, (B) Mw (weight average molecular weight) / Mn (number average molecular weight) of the semi-aromatic polyamide is set. It is important to make the above-mentioned range.
When the aromatic compound unit is contained in the molecular structure of the polyamide composition, the molecular weight distribution (Mw / Mn) tends to increase as the molecular weight increases. A high molecular weight distribution indicates a high proportion of polyamide molecules having a three-dimensional molecular structure, and the three-dimensional structure of the molecule is more likely to proceed during high-temperature processing, resulting in a decrease in fluidity, and is representative of inorganic fillers. The polyamide composition containing the components to be deteriorated in surface appearance.

  In the present invention, the measurement of Mw (weight average molecular weight) / Mn (number average molecular weight) of the polyamide composition was carried out using MPC (gel permeation chromatography) as described in the following examples. Weight average molecular weight) and Mn (number average molecular weight) can be used for calculation.

The tan δ peak temperature of the polyamide composition is 90 ° C. or higher. More preferably, it is 100 degreeC or more, More preferably, it is 110 degreeC or more, More preferably, it is 120 degreeC or more.
The tan δ peak temperature of the polyamide composition is preferably 150 ° C. or lower, more preferably 140 ° C. or lower, and further preferably 130 ° C. or lower.
When the tan δ peak temperature of the polyamide composition is 90 ° C. or higher, a polyamide composition excellent in water absorption rigidity and heat rigidity tends to be obtained. Further, when the tan δ peak temperature of the polyamide composition is 150 ° C. or less, the polyamide composition containing a component typified by an inorganic filler has an excellent surface appearance.
Examples of the method of controlling the tan δ peak temperature of the polyamide composition within the above range include a method of controlling the blending ratio of (A) aliphatic polyamide and (B) semi-aromatic polyamide to the above-described ranges.

  In the polyamide composition of the present invention, the ratio of the amino terminal amount to the total amount of amino terminal amount and carboxyl terminal amount {amino terminal amount / (amino terminal amount + carboxyl terminal amount)} is preferably 0.1 or more and less than 0.4. 0.35 or more and less than 0.4 is more preferable, and 0.25 or more and less than 0.35 is more preferable. When the ratio of the amino terminal amount to the total amount of the amino terminal amount and the carboxyl terminal amount is 0.1 or more, corrosion of the extruder or the molding machine can be suppressed. When the ratio of the amino terminal amount to the total amount of the amino terminal amount and the carboxyl terminal amount is less than 0.4, a composition excellent in discoloration to heat and light can be obtained.

[Molding]
By molding the polyamide resin composition of the present invention, a molded product having a surface gloss value of 50 or more is obtained. The surface gloss value of the polyamide composition of the present invention is more preferably 55 or more, and still more preferably 60 or more. When the surface gloss value of the polyamide composition is 50 or more, it is suitably used as a molding material for various parts such as automobiles, electric and electronic, industrial materials, industrial materials, and daily and household products. be able to.

It does not specifically limit as a method of obtaining a molded article, A well-known shaping | molding method can be used.
For example, extrusion molding, injection molding, vacuum molding, blow molding, injection compression molding, decorative molding, other material molding, gas assist injection molding, gunshot injection molding, low pressure molding, ultra thin injection molding (ultra high speed injection molding), And molding methods such as in-mold composite molding (insert molding, outsert molding) and the like.

(Use)
The molded article of the present invention contains the above-described polyamide resin composition, is excellent in mechanical properties (particularly weld strength and hardness), surface appearance, flame retardancy, etc., and can be used for various applications.
For example, it can be suitably used in the automotive field, electrical / electronic field, machine / industrial field, office equipment field, aerospace field.

Hereinafter, the present invention will be described in detail with reference to specific examples and comparative examples, but the present invention is not limited to the following examples.
Hereafter, the structural component of the polyamide composition used for the present Example and the comparative example is demonstrated.

(Structural component)
[(A) Aliphatic polyamide]
A-1: Polyamide 66
A-2: Polyamide 6 (SF1013A manufactured by Ube Industries)

[(B) Semi-aromatic polyamide]
B-1: Polyamide 6I
B-2: Polyamide 6I (T40 manufactured by LANXESS, Mw = 44000, Mw / Mn = 2.8, VR31, Mw / VR = 1419)
B-3: Polyamide 6I / 6T (M21 G21, Mw = 27000, Mw / Mn = 2.2, Mw / VR = 1000, VR27, Mw / VR = 1000, isophthalic acid ratio of dicarboxylic acid unit is 70 mol) %)
B-4: Polyamide 6I (high molecular weight)
B-5: Polyamide 66 / 6I

[(C) Pigment]
(C) Zinc sulfide (ZnS) (SACHTOLITH HD-S) was used.

[(D1) Flame retardant]
(D1) Brominated polystyrene (trade name “SAYTEX (registered trademark) HP-7010G, manufactured by ALBEMARL CORPORATION” (bromine content determined by elemental analysis: 63 mass%))
Was used.

[(D2) Flame retardant aid]
(D2) Antimony trioxide (trade name “antimony trioxide” manufactured by Daiichi FRF Co., Ltd.) was used.

[(E) Polymer containing α, β unsaturated dicarboxylic acid anhydride as constituent unit]
(E) Maleic anhydride-modified polyphenylene ether was used.

[(F) Filler]
(F) Glass fiber (GF) (manufactured by Nippon Electric Glass, trade name “ECS03T275H” average fiber diameter 10 μmφ, cut length 3 mm) was used.

[Production of polyamide]
Next, (A) aliphatic polyamide (A-1), (B) semi-aromatic polyamide (B-1), (B-4), (B-5) and α, β unsaturated dicarboxylic anhydride A method for producing the polymer (E) contained in the structural unit will be described.

(A-1: Polyamide 66)
The polyamide polymerization reaction was carried out as follows by the “hot melt polymerization method”.
1500 g of an equimolar salt of adipic acid and hexamethylenediamine was dissolved in 1500 g of distilled water to prepare an equimolar 50% by mass aqueous solution of raw material monomers. This aqueous solution was charged into an autoclave having an internal volume of 5.4 L and purged with nitrogen.
While stirring at a temperature of 110 to 150 ° C., water vapor was gradually removed to a solution concentration of 70% by mass and concentrated. Thereafter, the internal temperature was raised to 220 ° C. At this time, the autoclave was pressurized to 1.8 MPa. The reaction was continued for 1 hour while gradually removing water vapor and maintaining the pressure at 1.8 MPa until the internal temperature reached 245 ° C.
Next, the pressure was reduced over 1 hour. Thereafter, the inside of the autoclave was maintained under a reduced pressure of 650 torr with a vacuum apparatus for 10 minutes. At this time, the final internal temperature of the polymerization was 265 ° C.
Thereafter, it was pressurized with nitrogen to form a strand from the lower nozzle (nozzle), water-cooled, cut, discharged in a pellet form, and dried in a nitrogen atmosphere at 100 ° C. for 12 hours to obtain a polyamide. Mw = 35000 and Mw / Mn = 2.0.

(B-1: Polyamide 6I)
The polyamide polymerization reaction was carried out as follows by the “hot melt polymerization method”.
1500 g of equimolar salt of isophthalic acid and hexamethylenediamine, and 1.5 mol% excess adipic acid and 0.5 mol% of acetic acid with respect to all equimolar salt components are dissolved in 1500 g of distilled water, etc. A 50 mass% homogeneous aqueous solution was prepared.
While stirring at a temperature of 110 to 150 ° C., water vapor was gradually removed to a solution concentration of 70% by mass and concentrated. Thereafter, the internal temperature was raised to 220 ° C. At this time, the autoclave was pressurized to 1.8 MPa. The reaction was continued for 1 hour while gradually removing water vapor and maintaining the pressure at 1.8 MPa until the internal temperature reached 245 ° C.
Next, the pressure was reduced over 30 minutes. Thereafter, the inside of the autoclave was maintained under a reduced pressure of 650 torr with a vacuum apparatus for 10 minutes. At this time, the final internal temperature of the polymerization was 265 ° C.
Thereafter, it was pressurized with nitrogen to form a strand from the lower nozzle (nozzle), water-cooled, cut, discharged in a pellet form, and dried in a nitrogen atmosphere at 100 ° C. for 12 hours to obtain a polyamide. Mw = 20000, Mw / Mn = 2.0, VR12, Mw / VR = 1667.

(B-4: Polyamide 6I)
The polyamide polymerization reaction was carried out as follows by the “hot melt polymerization method”.
1500 g of equimolar salt of isophthalic acid and hexamethylenediamine, 1.0 mol% excess adipic acid and 0.5 mol% of acetic acid with respect to all equimolar salt components were dissolved in 1500 g of distilled water, etc. A homogeneous 50% by mass aqueous solution was prepared.
While stirring at a temperature of 110 to 150 ° C., water vapor was gradually removed to a solution concentration of 70% by mass and concentrated. Thereafter, the internal temperature was raised to 220 ° C. At this time, the autoclave was pressurized to 1.8 MPa. The reaction was continued for 1 hour while gradually removing water vapor and maintaining the pressure at 1.8 MPa until the internal temperature reached 245 ° C.
Next, the pressure was reduced over 30 minutes. Thereafter, the inside of the autoclave was maintained under a reduced pressure of 650 torr with a vacuum apparatus for 10 minutes. At this time, the final internal temperature of the polymerization was 265 ° C.
Thereafter, it was pressurized with nitrogen to form a strand from the lower nozzle (nozzle), water-cooled, cut, discharged in a pellet form, and dried in a nitrogen atmosphere at 100 ° C. for 12 hours to obtain a polyamide. Mw = 25000, Mw / Mn = 2.1, VR16, Mw / VR = 1563.

(B-5: Polyamide 66 / 6I)
The polyamide polymerization reaction was carried out as follows by the “hot melt polymerization method”.
Adipic acid and hexamethylenediamine equimolar salt 1044g, isophthalic acid and hexamethylenediamine equimolar salt 456g, and 0.5 mol% excess adipic acid with respect to all equimolar salt components were dissolved in 1500 g of distilled water, An equimolar 50 mass% uniform aqueous solution of raw material monomers was prepared.
While stirring at a temperature of 110 to 150 ° C., water vapor was gradually removed to a solution concentration of 70% by mass and concentrated. Thereafter, the internal temperature was raised to 220 ° C. At this time, the autoclave was pressurized to 1.8 MPa. The reaction was continued for 1 hour while gradually removing water vapor and maintaining the pressure at 1.8 MPa until the internal temperature reached 245 ° C.
Next, the pressure was reduced over 1 hour. Thereafter, the inside of the autoclave was maintained under a reduced pressure of 650 torr with a vacuum apparatus for 10 minutes. At this time, the final internal temperature of the polymerization was 265 ° C.
Thereafter, it was pressurized with nitrogen to form a strand from the lower nozzle (nozzle), water-cooled, cut, discharged in a pellet form, and dried in a nitrogen atmosphere at 100 ° C. for 12 hours to obtain a polyamide. Mw = 28000, Mw / Mn = 2.3, and the isophthalic acid ratio of the dicarboxylic acid unit was 30 mol%.

(E: maleic anhydride modified polyphenylene ether)
Poly (2,6-dimethyl-1,4-phenylene ether) having a reduced viscosity (0.5 g / dl chloroform solution, measured at 30 ° C.) of 0.52 obtained by oxidative polymerization of 2,6-dimethylphenol 100 parts by weight of polyphenylene ether), 1.0 part by weight of maleic anhydride as a compatibilizer, one upstream (hereinafter abbreviated as top-F), the central part of the extruder, and the downstream near the die Side-1 of a twin-screw extruder (manufactured by Werner & Pfleiderer: ZSK-40) having supply ports (hereinafter abbreviated as side-1 at the central portion of the extruder and side-2 at the downstream side close to the die). And side-2 in a closed state, under conditions of a cylinder set temperature of 320 ° C., a screw rotation of 300 rpm, and a discharge rate of 20.15 kg / hr. Supply dry blend of ether and maleic anhydride from top-F, melt knead and take out into strand form, cool in strand bath (water tank), granulate with cutter, and pellet of maleic anhydride modified polyphenylene ether Obtained.

[Production of polyamide composition]
Using the above (A) aliphatic polyamide and (B) semi-aromatic polyamide in the types and proportions shown in Table 1 below, a polyamide composition was produced as follows.
The polyamide obtained above was dried in a nitrogen stream and adjusted to a moisture content of about 0.2% by mass, and then used as a raw material for the polyamide composition.

  Melt kneading was carried out by the method described in the following examples to obtain polyamide composition pellets. The obtained polyamide composition pellets were dried in a nitrogen stream, and the water content in the polyamide composition was reduced to 500 ppm or less.

[Method for measuring physical properties of polyamide composition]
The following various evaluation was implemented using the polyamide composition after adjusting the moisture content. The evaluation results are shown in Table 1 below.

<Tanδ peak temperature>
Using a PS40E injection molding machine manufactured by Nissei Kogyo Co., Ltd., a cylinder temperature of 290 ° C., a mold temperature of 100 ° C., and injection molding conditions of 10 seconds for injection and 10 seconds for cooling, a molded body conforming to JIS-K7139 Molded. This molded body was measured under the following conditions using a dynamic viscoelasticity evaluation apparatus (manufactured by GABO, EPLEXOR500N). Measurement mode: tensile, measurement frequency: 8.00 Hz, temperature increase rate: 3 ° C./min, temperature range: minus 100 to 250 ° C. The ratio E2 / E1 between the storage elastic modulus E1 and the loss elastic modulus E2 was Tanδ, and the highest temperature was the Tanδ peak temperature.

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

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

(Carboxyl terminal amount ([COOH]))
In the polyamides obtained in the examples and comparative examples, the amount of carboxyl terminal bound to the polymer terminal was measured by neutralization titration as follows.
4.0 g of polyamide was dissolved in 50 mL of benzyl alcohol, and the resulting solution was titrated with 0.1N NaOH to obtain the carboxyl end amount (μ equivalent / g). The end point was determined from the discoloration of the phenolphthalein indicator.

Based on the measured amino terminal amount ([NH ₂ ]) and carboxyl terminal amount ([COOH]), the active terminal total amount ([NH ₂ ] + [COOH]) and the ratio of the amino terminal amount to the active terminal total amount ([[ NH ₂ ] / ([NH ₂ ] + [COOH])) was calculated.

<Formic acid solution viscosity VR>
Polyamide was dissolved in formic acid and measured according to JIS K6810.

<Evaluation of formability and appearance>
The apparatus used was “FN3000” manufactured by Nissei Industry Co., Ltd.
The cylinder temperature is set to 290 ° C, the mold temperature is set to 100 ° C, and molding is performed up to 100 shots using the polyamide resin composition under injection molding conditions of 10 seconds for injection and 10 seconds for cooling. Got.
Formability is evaluated when 10% or less of the 100 shots is fixed to the mold at the time of mold release during molding A, more than 10%, 20% or less B, more than 20%, 50% or less C, 50% The super is D.
In addition, regarding the appearance of the obtained molded body, the surface gloss value was 60 or more as evaluation A, 55 or more and 59 or less as evaluation B, 50 or more and 54 or less as evaluation C, and value lower than 50 as evaluation D.

<Evaluation of flame retardancy>
Measurements were made using the method of UL94 (standard established by Under Writers Laboratories Inc., USA). The test piece (length 127 mm, width 12.7 mm, thickness 1.6 mm) was attached to the injection molding machine (PS40E manufactured by Nissei Kogyo Co., Ltd.) with a UL test piece mold (mold temperature = 100 ° C.), It was produced by molding a polyamide resin composition at a cylinder temperature of 290 ° C. The injection pressure was the full filling pressure at the time of forming the UL test piece + 2% pressure. The flame retardant grade conformed to UL94 standard (vertical combustion test).

<Weld strength>
An injection molding machine equipped with a mold in which molten resin flows from both ends in the length direction having a length of 127 mm, a width of 12.7 mm, and a thickness of 1.6 mm, and a weld is formed at the center in the length direction. Molding was performed with (Nissei Kogyo Co., Ltd. PS40E) to obtain a test piece. A tensile test was carried out by a method based on ASTM D638 except that the formed test piece was set to a distance between chucks of 50 mm and a tensile speed of 50 mm / min to obtain a tensile strength. Moreover, after leaving a test piece in a constant temperature and humidity (23 degreeC, 50RH%) atmosphere and reaching water absorption equilibrium, the tensile strength was measured by the method based on ASTMD638. The tensile strength retention after water absorption was determined using the following formula.
Tensile retention after water absorption (%) = Tensile strength after water absorption / Tensile strength before water absorption × 100

<Rockwell hardness>
The apparatus used was “FN3000” manufactured by Nissei Industry Co., Ltd.
A molded body (ISO test piece) was obtained using the polyamide resin composition under the injection molding conditions of 10 seconds for injection and 10 seconds for cooling, with the cylinder temperature set at 290 ° C. and the mold temperature set at 100 ° C. Rockwell hardness (M scale) was measured using a hardness meter (ARK-F3000, manufactured by Akashi Seisakusho Co., Ltd.). Further, the test piece was left in a constant temperature and humidity (23 ° C., 50 RH%) atmosphere to reach water absorption equilibrium, and then the Rockwell hardness was measured. The Rockwell hardness retention after water absorption was determined using the following formula.
Rockwell hardness retention after water absorption (%) = Rockwell hardness after water absorption / Rockwell hardness before water absorption × 100

[Example 1]
Using a TEM 35 mm twin screw extruder (set temperature: 280 ° C. in front, screw rotation speed 300 rpm) manufactured by Toshiba Machine Co., Ltd., polyamide (A-1) and (B-1) from the top feed port provided in the most upstream part of the extruder ), (C) pigment, (D1) flame retardant, (D2) flame retardant aid, and (E) a polymer containing α, β unsaturated dicarboxylic anhydride as a constituent unit is supplied in advance. Then, the filler (F) is supplied from the side feed port on the downstream side of the extruder (the resin supplied from the top feed port is sufficiently melted), and the melt-kneaded product extruded from the die head is cooled in a strand shape. And pelletized to obtain polyamide resin composition pellets. The blending amounts are (A-1) polyamide 17.5% by mass, (B-1) polyamide 9.5% by mass, (C) pigment 2.0% by mass, (D1) flame retardant 10.5% by mass, (D2 ) 2.0% by mass of a flame retardant auxiliary, (E) 3.5% by mass of a polymer containing α, β unsaturated dicarboxylic acid anhydride as a constituent unit, and (F) 55% by mass of a filler.

  Moreover, using the obtained polyamide resin composition, a molded product was produced by the above-described method, and the moldability, appearance, weld strength, Rockwell hardness, and flame retardance during molding were evaluated. The evaluation results are shown in Table 1 below.

[Example 2]
It implemented similarly to Example 1 except having changed the compounding quantity into (A-1) 16.2 mass% of polyamide, and (B-1) polyamide 10.8 mass%.

[Example 3]
The same as in Example 1 except that the blending amount was changed to (A-1) 16.5% by mass of polyamide, (B-4) 11.0% by mass of polyamide, and (D1) 10.0% by mass of flame retardant. did.

[Example 4]
It implemented similarly to Example 1 except having changed the compounding quantity into (A-1) polyamide 14.8 mass% and (B-1) polyamide 12.2 mass%.

[Comparative Example 1]
The same procedure as in Example 1 was performed except that the blending amount was changed to (A-1) polyamide 27.5% by mass, (B-1) polyamide 0% by mass, and (D1) flame retardant 10.0% by mass.

[Comparative Example 2]
The same procedure as in Example 1 was carried out except that the blending amount was changed to (A-1) polyamide 0 mass%, (B-1) polyamide 27.5 mass%, and (D1) flame retardant 10.0 mass%.

[Comparative Example 3]
The same procedure as in Example 1 was carried out except that the blending amount was changed to (A-1) polyamide 0% by mass, (B-5) polyamide 22.5% by mass, and (D1) flame retardant 15.0% by mass.

[Comparative Example 4]
The same as in Example 1 except that the blending amount was changed to (A-1) polyamide 22.0% by mass, (B-2) polyamide 9.5% by mass, and (D1) flame retardant 6.0% by mass. did.

[Comparative Example 5]
The blending amount is (A-1) 18.4% by mass of polyamide, (B-2) polyamide 12.1% by mass, (E) 0% by mass of polymer containing α, β-unsaturated dicarboxylic acid anhydride as a structural unit, The same procedure as in Example 1 was performed except that

[Comparative Example 6]
The same as in Example 1 except that the blending amount was changed to (A-1) polyamide 20.0% by mass, (B-3) polyamide 8.5% by mass, and (D1) flame retardant 9.0% by mass. did.

[Comparative Example 7]
The same as in Example 1 except that the blending amount was changed to (A-2) polyamide 20.0% by mass, (B-3) polyamide 8.5% by mass, and (D1) flame retardant 9.0% by mass. did.

  As is clear from the results shown in Table 1, the polyamide composition of the present invention has a high Tan δ peak temperature because the dicarboxylic acid unit of the (B) semi-aromatic polyamide contains 75% by mole or more of isophthalic acid. became. As a result, the polyamide composition molded articles of Examples 1 to 4 had excellent properties in terms of weld strength and Rockwell hardness in addition to flame retardancy. Moreover, when the weight average molecular weight Mw of the polyamide composition was in the range of 10,000 ≦ Mw ≦ 40000, in addition to the above properties, the moldability and the appearance were excellent.

In contrast, Comparative Example 1 does not contain (B) semi-aromatic polyamide, and in Comparative Examples 3, 6, and 7, the dicarboxylic acid unit of (B) semi-aromatic polyamide contains less than 75 mol% of isophthalic acid. Therefore, the polyamide composition molded article has insufficient flame retardancy, weld strength, Rockwell hardness, moldability, and appearance.
In Comparative Example 2, the dicarboxylic acid unit of (B) the semi-aromatic polyamide contains 75 mol% or more of isophthalic acid, but (A) the aliphatic polyamide is not included, so the appearance and flame retardancy, weld strength, Rockwell hardness The balance was poor and insufficient. In Comparative Example 4, the dicarboxylic acid unit of the (B) semi-aromatic polyamide contains 75 mol% or more of isophthalic acid, but the weight average molecular weight Mw is large, so that the balance between appearance and flame retardancy, weld strength, and Rockwell hardness is achieved. It was bad and insufficient. In Comparative Example 5, the dicarboxylic acid unit of (B) semi-aromatic polyamide contains 75 mol% or more of isophthalic acid, but the weight average molecular weight Mw is large, and (E) α, β unsaturated dicarboxylic acid anhydride is used as a constituent unit Since the containing polymer was not contained, the physical property balance of the polyamide composition molded article was insufficient.

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

Claims (22)

(A) an aliphatic polyamide comprising a diamine and a dicarboxylic acid,
(B) a semi-aromatic polyamide containing a dicarboxylic acid unit containing at least 75 mol% of isophthalic acid and a diamine unit containing a diamine having 4 to 10 carbon atoms,
(C) pigment,
(D1) a flame retardant, and (D2) a flame retardant aid,
A polyamide composition comprising:
The tan δ peak temperature of the polyamide composition is 90 ° C. or higher,
The weight average molecular weight Mw of the polyamide composition is
A polyamide composition satisfying 10,000 ≦ Mw ≦ 40000.   The polyamide composition according to claim 1, further comprising (E) a polymer containing α, β unsaturated dicarboxylic acid anhydride as a constituent unit.   The total content of the (A) aliphatic polyamide and the (B) semi-aromatic polyamide having a number average molecular weight Mn of 500 or more and 2000 or less is 0.5% by mass or more and 2% by mass with respect to the total amount of polyamide in the polyamide composition. The polyamide composition according to claim 1 or 2, which is less than 5% by mass.   The polyamide composition according to any one of claims 1 to 3, wherein a molecular weight distribution Mw / Mn of the polyamide composition is 2.4 or less.   The ratio of the amino terminal amount to the total amount of amino terminal amount and carboxyl terminal amount in the polyamide composition {amino terminal amount / (amino terminal amount + carboxyl terminal amount)} is 0.1 or more and less than 0.4. Item 5. The polyamide composition according to any one of Items 1 to 4.   The polyamide composition according to any one of claims 1 to 5, wherein the (A) aliphatic polyamide is polyamide 66.   The polyamide composition according to any one of claims 1 to 6, wherein a content of the isophthalic acid in the dicarboxylic acid unit of the (B) semi-aromatic polyamide is 100 mol%.   8. The polyamide composition according to claim 1, wherein the (B) semi-aromatic polyamide has a weight average molecular weight Mw (B) of 10,000 ≦ Mw ≦ 25000.   9. The polyamide composition according to claim 1, wherein the (B) semi-aromatic polyamide has a molecular weight distribution Mw / Mn of 2.4 or less.   The polyamide composition according to any one of claims 1 to 9, wherein the (B) semi-aromatic polyamide has an Mw / VR of 1000 or more and 2000 or less.   The polyamide composition according to any one of claims 1 to 10, wherein the (B) semi-aromatic polyamide is polyamide 6I.   12. The content of the (B) semi-aromatic polyamide is 30% by mass or more and 50% by mass or less with respect to 100% by mass of the total component amount of the polyamide in the polyamide composition. Polyamide composition.   The difference {Mw (A) -Mw (B)} between the weight average molecular weight Mw (A) of the (A) aliphatic polyamide and the weight average molecular weight Mw (B) of the (B) semi-aromatic polyamide is 10,000 or more. The polyamide composition according to any one of claims 1 to 12.   The polyamide composition according to any one of claims 1 to 13, wherein a terminal of the (B) semi-aromatic polyamide is sealed with acetic acid.   The (C) pigment is a white pigment, and the content of the white pigment is 0.5% by mass or more and 5% by mass or less with respect to 100% by mass of the polyamide composition. The polyamide composition described.   The polyamide composition according to claim 15, wherein the white pigment is at least one selected from ZnS and ZnO. The flame retardant (D1) is brominated polystyrene, and the content of the brominated polystyrene is 6% by mass to 15% by mass with respect to 100% by mass of the polyamide composition, and
The flame retardant aid (D2) is Sb ₂ O ₃ , and the content of Sb ₂ O ₃ is 0.1% by mass or more and 4% by mass or less with respect to 100% by mass of the polyamide composition. The polyamide composition according to any one of 1 to 16.   The polyamide composition according to any one of claims 2 to 17, wherein the polymer containing (E) an α, β unsaturated dicarboxylic acid anhydride as a constituent unit is a maleic anhydride-modified polyphenylene ether.   The polyamide composition according to any one of claims 1 to 18, further comprising (F) a filler.   The polyamide composition according to claim 19, wherein the filler (F) is a glass fiber, and the content of the glass fiber is 40% by mass or more and 60% by mass or less with respect to 100% by mass of the polyamide composition.   The (C) white pigment, the (D1) flame retardant, the (D2) flame retardant aid, the (E) a polymer containing α, β unsaturated dicarboxylic acid anhydride as a constituent unit, and the (F) filling 21. The polyamide composition according to claim 19 or 20, wherein a total content of the material is 60% by mass or more and 80% by mass or less with respect to 100% by mass of the polyamide composition.   A molded article obtained by molding the polyamide composition according to any one of claims 1 to 21, and having a surface gloss value of 50 or more.