JP6970524B2 - Polyamide composition and molded products - Google Patents

Description

The present invention relates to polyamide compositions and molded articles.

Polyamides typified by polyamide 6 (hereinafter, also referred to as “PA6”) and polyamide 66 (hereinafter, also referred to as “PA66”) are excellent in molding processability, mechanical properties, and chemical resistance. It is widely used as a material for various parts such as automobiles, electric and electronic products, industrial materials, industrial materials, daily use and household products.

In recent years, the environment in which polyamide resins are used has become harsh thermally and mechanically, and changes in physical properties in all environments have improved mechanical properties, especially rigidity after water absorption and rigidity under high temperature use. There is a demand for a polyamide resin material with a small amount of water.
Further, in order to improve productivity, a molded product using a polyamide resin may be molded under high cycle molding conditions in which the molding temperature is raised and the mold temperature is lowered.

On the other hand, if molding is performed under high temperature conditions, there is a problem that a stable molded product may not be obtained due to decomposition of the polyamide resin or change in fluidity.

Therefore, in particular, there is a demand for a polyamide resin having excellent stability of the surface appearance of the molded product even under the harsh molding conditions as described above.
In order to meet such demands, a polyamide made of polyamide 66 / 6I into which an isophthalic acid component is introduced is disclosed as a material capable of improving 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 composed of a polyamide 6T / 6I into which a terephthalic acid component and an isophthalic acid component are introduced is disclosed (for example, Patent Document). See 2, 3 and 4).

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

Japanese Unexamined Patent Publication No. 6-32980 Japanese Unexamined Patent Publication No. 2000-154316 Japanese Unexamined Patent Publication No. 11-34806 Japanese Unexamined Patent Publication No. 2013-119610 International Publication No. 2005-055664

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

Further, 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 molded surface are deteriorated under severe molding conditions such as high cycle molding conditions. Has the problem.

As described above, in the prior art, the reality is that a polyamide copolymer having excellent rigidity after water absorption and rigidity under high temperature use and having little change in physical properties when used in all environments is not yet known. .. In addition, it is difficult to suppress the decrease in rigidity after water absorption and under high temperature use while maintaining the balance of mechanical strength and rigidity, which is a characteristic of polyamide copolymers, and it is difficult to suppress the decrease in rigidity after water absorption, and the polyamide copolymer weight having such physical properties. There is a demand for compositions and molded products containing coalesced or polyamides.

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

As a result of diligent studies to solve the above problems, the present inventors have found that a polyamide composition containing a plurality of specific 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 is
(A) Aliphatic polyamide composed of diamine and 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 or more and 10 or less carbon atoms.
(C) Pigment,
(D1) Flame Retardant, and (D2) Flame Retardant Aid,
A polyamide composition containing
The tan δ peak temperature of the polyamide composition is 90 ° C. or higher, and the temperature is 90 ° C. or higher.
The weight average molecular weight Mw of the polyamide composition is 10,000 ≦ Mw ≦ 40,000.

The polyamide composition of the present invention may further contain a polymer containing (E) 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 preferably 0.5% by mass or more and less than 2.5% by mass with respect to the total amount of polyamide.

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 the amino-terminal amount and the 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 semi-aromatic polyamide is preferably 10,000 ≦ Mw ≦ 25,000.

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

(B) The 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.

The content of the semi-aromatic polyamide (B) is preferably 30% by mass or more and 50% by mass or less with respect to 100% by mass of the total constituent 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) semi-aromatic polyamide may be 10,000 or more. preferable.

(B) The ends of the semi-aromatic polyamide are preferably 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 or more and 15% by mass or less 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.

Total content of (C) white pigment, (D1) flame retardant, (D2) flame retardant aid, (E) polymer containing α, β-unsaturated dicarboxylic acid anhydride as a constituent unit, and (F) 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 product of the present invention is formed by molding the above-mentioned polyamide composition of the present invention, and has a surface gloss value of 50 or more.

According to the present invention, it is possible to provide a polyamide composition and a molded product having excellent mechanical properties, surface appearance, and flame retardancy.

Hereinafter, the present invention will be described in detail.

[Polyamide composition]
The polyamide composition of the present invention is
(A) Aliphatic polyamide composed of diamine and 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 or more and 10 or less carbon atoms.
(C) Pigment,
(D1) Flame Retardant, and (D2) Flame Retardant Aid,
A polyamide composition containing
The tan δ peak temperature of the polyamide composition is 90 ° C. or higher, and the temperature is 90 ° C. or higher.
The weight average molecular weight Mw of the polyamide composition is 10,000 ≦ Mw ≦ 40,000.

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

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

((A-a) Aliphatic dicarboxylic acid unit)
The aliphatic dicarboxylic acid constituting the aliphatic dicarboxylic acid unit is not limited to the following, and is, for example, malonic acid, dimethylmalonic acid, succinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethyl. Glutalic 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, azeline Examples include straight-chain or branched saturated aliphatic dicarboxylic acids having 3 to 20 carbon atoms such as acids, sebacic acid, dodecanedioic acid, tetradecanedioic acid, hexadecanedioic acid, octadecanedioic acid, eicosandioic acid, and diglycolic acid. Will be.

(A) The aliphatic dicarboxylic acid unit is more excellent in heat resistance, fluidity, toughness, low water absorption, rigidity and the like of the polyamide composition by containing the aliphatic dicarboxylic acid having 6 or more carbon atoms. It is preferable because it tends to be. 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 eicosandioic 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.
(A) As the aliphatic dicarboxylic acid constituting the aliphatic dicarboxylic acid unit, only one kind may be used alone, or two or more kinds may be used in combination.

The aliphatic polyamide (A) may further contain a unit derived from a trivalent or higher-valent polyvalent carboxylic acid such as trimellitic acid, trimesic acid, and pyromellitic acid, if necessary. As the trivalent or higher-valent polyvalent carboxylic acid, only one type may be used alone, or two or more types may be used in combination.

((A-b) Aliphatic diamine unit)
(A-b) The aliphatic diamine constituting the aliphatic diamine unit may be linear or branched.
The linear aliphatic diamine constituting the aliphatic diamine unit is not limited to the following, and is, for example, ethylenediamine, propylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octa. Examples thereof include linear saturated aliphatic diamines having 2 to 20 carbon atoms such as methylenediamine, nonamethylenediamine, decamethylenediamine, undecamethylenediamine, dodecamethylenediamine, and tridecamethylenediamine.

The diamine constituting the diamine unit having a substituent branched from the main chain is not limited to the following, but is also referred to as, for example, 2-methylpentamethylenediamine (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. -Examples include branched saturated aliphatic diamines having 3 to 20 carbon atoms such as dimethyloctamethylenediamine.
Among these, 2-methylpentamethylenediamine and 2-methyl-1,8-octanediamine are preferable, and 2-methylpentamethylenediamine is more preferable. By containing such an aliphatic diamine, the polyamide composition tends to be excellent in heat resistance, rigidity and the like.

The carbon number of the (A-b) aliphatic diamine unit is preferably 6 or more and 12 or less. When the number of carbon atoms is 6 or more, it is preferable because it is excellent in heat resistance, and when it is 12 or less, it is preferable because it is excellent in crystallinity and releasability. The number of carbon atoms in the (A-b) diamine unit is more preferably 6 or more and 10 or less.

The (A-b) aliphatic diamine may further contain a trivalent or higher valent aliphatic amine such as bishexamethylenetriamine, if necessary.
As the diamine, only one kind may be used alone, or two or more kinds may be used in combination.

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

((B) Semi-aromatic polyamide)
The (B) semi-aromatic polyamide used in the present invention includes a (B) dicarboxylic acid unit containing at least 75 mol% of isophthalic acid and a (B) diamine unit containing a diamine having 4 or more and 10 or less carbon atoms. It is a polyamide containing.
The total amount of the isophthalic acid unit and the diamine unit having 4 or more and 10 or less carbon atoms is preferably 80 to 100 mol% with respect to 100 mol% of all the constituent units of the (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 unit constituting the (B) polyamide 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 contained in an amount of 80 to 100 mol%, further preferably contained in an amount of 90 to 100 mol%, still more preferably contained in an amount of 100 mol%.
(BA) Polyamide that simultaneously satisfies mechanical properties, particularly water absorption rigidity, thermal rigidity, fluidity, surface appearance, etc., when the ratio of the isophthalic acid unit to the dicarboxylic acid unit is 75 mol% or more. The composition can be obtained.

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

-Aromatic dicarboxylic acid unit-
Examples of the aromatic dicarboxylic acid constituting the aromatic dicarboxylic acid unit other than the isophthalic acid unit include, but are not limited to, a dicarboxylic acid having a phenyl group and a naphthyl group. The aromatic group of the aromatic dicarboxylic acid may be unsubstituted or have a substituent.
The substituent is not particularly limited, but is, for example, 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 halogen group such as a chloro group and a bromo group. , A silyl group having 1 to 6 carbon atoms, a sulfonic acid group and a salt thereof (sodium salt, etc.) and the like.
Specifically, but not limited to the following, no terephthalic acid, naphthalenedicarboxylic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, 5-sodiumsulfoisophthalic acid and the like. Examples thereof include aromatic dicarboxylic acids having 8 to 20 carbon atoms substituted with substitutions or predetermined substituents.
As the aromatic dicarboxylic acid constituting the aromatic dicarboxylic acid unit, only one kind may be used alone, or two or more kinds may be used in combination.

-Alphatic dicarboxylic acid unit-
The aliphatic dicarboxylic acid constituting the aliphatic dicarboxylic acid unit is not limited to the following, and is, for example, malonic acid, dimethylmalonic acid, succinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethyl. Glutalic 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, azeline Examples include straight-chain or branched saturated aliphatic dicarboxylic acids having 3 to 20 carbon atoms such as acids, sebacic acid, dodecanedioic acid, tetradecanedioic acid, hexadecanedioic acid, octadecanedioic acid, eicosandioic acid, and diglycolic acid. Will be.

-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 is, for example, the number of carbon atoms in the alicyclic structure. Examples thereof include alicyclic dicarboxylic acids having an alicyclic structure of 3 to 10, and alicyclic dicarboxylic acids having an alicyclic structure having 5 to 10 carbon atoms are preferable.
The alicyclic dicarboxylic acid is not limited to the following, and examples thereof include 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, and 1,3-cyclopentanedicarboxylic acid. Can be mentioned. Of these, 1,4-cyclohexanedicarboxylic acid is preferable.
The alicyclic dicarboxylic acid constituting the alicyclic dicarboxylic acid unit may be used alone or in combination of two or more.

The alicyclic group of the alicyclic dicarboxylic acid may be unsubstituted or have a substituent. The substituent is not limited to the following, but for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group and the like having 1 to 1 carbon atoms. Examples thereof include the alkyl group of 4.
The dicarboxylic acid unit other than the isophthalic acid unit preferably contains an aromatic dicarboxylic acid unit, and more preferably contains an aromatic dicarboxylic acid having 6 or more carbon atoms.
By using such a dicarboxylic acid, the mechanical properties of the polyamide composition, particularly water absorption rigidity, thermal rigidity, fluidity, surface appearance, and the like tend to be more excellent.

In the present invention, the dicarboxylic acid constituting the (BA) dicarboxylic acid unit is not limited to the compound 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 having a dicarboxylic acid structure similar to that of the dicarboxylic acid derived from the dicarboxylic acid. Examples of such compounds include, but are not limited to, anhydrides and halides of dicarboxylic acids.

Further, the semi-aromatic polyamide (B) may further contain a unit derived from a trivalent or higher-valent polyvalent carboxylic acid such as trimellitic acid, trimesic acid, and pyromellitic acid, if necessary.
As the trivalent or higher-valent polyvalent carboxylic acid, only one type may be used alone, or two or more types may be used in combination.

((B-b) diamine unit)
(B) The diamine unit constituting the semi-aromatic polyamide (b) contains a diamine having 4 or more and 10 or less carbon atoms. Examples thereof include, but are not limited to, an aliphatic diamine unit, an alicyclic amine unit, and an aromatic diamine unit.

-Alphatic diamine unit-
The aliphatic diamine constituting the aliphatic diamine unit is not limited to the following, and for example, ethylenediamine, propylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, etc. Examples thereof include linear saturated aliphatic diamines having 4 or more and 20 or less carbon atoms such as nonamethylenediamine, decamethylenediamine, undecamethylenediamine, dodecamethylenediamine, and tridecamethylenediamine.

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

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

(B) Among the diamine units constituting the semi-aromatic polyamide, it is preferably an aliphatic diamine unit, more preferably a diamine unit having a linear saturated aliphatic group having 4 or more and 10 or less carbon atoms, and further. A diamine unit having a linear saturated aliphatic group having 6 to 10 carbon atoms is preferable, and hexamethylenediamine is even more preferable.
By using such a diamine, the polyamide composition tends to be excellent in mechanical properties, particularly water absorption rigidity, rigidity under high temperature use (heat rigidity), fluidity, surface appearance and the like.
As the diamine, only one type may be used alone, or two or more types may be used in combination.
(B) As the semi-aromatic polyamide, polyamides 6I, 9I and 10I are preferable, and polyamide 6I is most preferable.

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

In the present invention, the blending amount of (B) semi-aromatic polyamide is preferably 5.0% by mass or more and 50.0% by mass or less, more preferably 10. It is 0% by mass or more and 50% by mass or less, more preferably 15.0% by mass or more and 50% by mass or less, still more preferably 20.0% by mass or more and 50% by mass or less, and particularly preferably 30% by mass or less. It is 50% by mass or less, and most preferably 30% by mass or more and 45% by mass or less. (B) By setting the blending amount of the semi-aromatic polyamide in the above range, a polyamide composition having excellent mechanical properties can be obtained. Further, the polyamide composition containing a component typified by an inorganic filler has an excellent surface appearance.

(Lactam unit and / or aminocarboxylic acid unit)
The (A) aliphatic polyamide and (B) semi-aromatic polyamide can further contain lactam units and / or aminocarboxylic acid units. By including such a unit, a polyamide having better toughness tends to be obtained. Here, the lactam unit and the lactam and the aminocarboxylic acid constituting the aminocarboxylic acid refer to the lactam and the aminocarboxylic acid that can be combined (reduced).

The lactam and aminocarboxylic acid constituting the lactam unit and the 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. Lactam and aminocarboxylic acids are more preferred.

The lactam constituting the lactam unit is not limited to the following, and examples thereof include butyloractam, pivalolactam, ε-caprolactam, caprolactam, enantractam, undecanolactam, and laurolactam (dodecanolactam). Can be mentioned.
Among them, as the lactam, ε-caprolactam, laurolactam and the like are preferable, and ε-caprolactam is more preferable. The inclusion of such lactam tends to result in 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 acids, which are compounds in which 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, 12-aminododecanoic acid and the like. Further, examples of the aminocarboxylic acid include paraaminomethylbenzoic acid and the like.

The lactam and the aminocarboxylic acid constituting the lactam unit and the aminocarboxylic acid unit may be used alone or in combination of two or more.
The total ratio (mol%) of the lactam unit and the aminocarboxylic acid unit is preferably 0 to 20 mol%, more preferably 0 to 10 mol%, still more preferably 0 to 5% with respect to the total polyamide. Is.
When the total ratio of the lactam unit and the aminocarboxylic acid unit is within the above range, the effect of improving the fluidity or the like tends to be obtained.

(End sealant)
The end of the polyamide used in the present invention may be end-sealed with a known end-sealing agent.
Such an end-capping agent can also be added as a molecular weight modifier when producing a polyamide from the above-mentioned dicarboxylic acid and diamine, and lactam and / or aminocarboxylic acid used as needed.

The terminal encapsulant is not limited to the following, but is not limited to, for example, acid anhydrides such as monocarboxylic acid, monoamine and phthalic anhydride, monoisocyanate, monoacid halides, monoesters and monoalcohols. And so on.
Of these, monocarboxylic acids and monoamines are preferable. Since the ends of the polyamide are sealed with an end sealant, the polyamide composition tends to have better thermal stability.
As the end sealant, only one type may be used alone, or two or more types may be used in combination.

The monocarboxylic acid that can be used as the terminal encapsulant may be any carboxylic acid that has reactivity with an amino group that may be present at the terminal of polyamide, and is not limited to the following, but is, for example, formic acid, acetic acid, and the like. Adipose monocarboxylic acids such as propionic acid, butyric acid, valeric acid, caproic acid, capric acid, lauric acid, tridecylic acid, myristyl acid, palmitic acid, stearic acid, pivalic acid, and isobutyl acid; alicyclic such as cyclohexanecarboxylic acid. Group monocarboxylic acids; and aromatic monocarboxylic acids such as benzoic acid, toluic acid, α-naphthalenecarboxylic acid, β-naphthalenecarboxylic acid, methylnaphthalenecarboxylic acid, and phenylacetic acid.
In particular, the terminal of (B) aromatic polyamide is preferably sealed with acetic acid from the viewpoint of fluidity and mechanical strength.
Only one type of monocarboxylic acid may be used alone, or two or more types may be used in combination.

The monoamine that can be used as the terminal encapsulant may be any one having a reactivity with a carboxyl group that may be present at the terminal of the polyamide, and is not limited to the following, but is, for example, methylamine, ethylamine, and propyl. Adicyclic monoamines such as amines, butylamines, hexylamines, octylamines, decylamines, stearylamines, dimethylamines, diethylamines, dipropylamines, and dibutylamines; alicyclic monoamines such as cyclohexylamines and dicyclohexylamines; and aniline, toluidine, Examples thereof include aromatic monoamines such as diphenylamine and naphthylamine.
Only one type of monoamine may be used alone, or two or more types may be used in combination.

Polyamide compositions containing polyamides terminally sealed with an end sealant tend to be excellent in heat resistance, fluidity, toughness, low water absorption, and rigidity.

(Polyamide manufacturing method)
When the polyamide of the present invention is obtained, the amount of the dicarboxylic acid added and the amount of the diamine added are preferably close to the same molar amount. Considering the amount of diamine escaping to the outside of the reaction system during the polymerization reaction in terms of molar ratio, the total molar amount of diamine is 0.9 to 1.2 with respect to the total molar amount of 1 of the dicarboxylic acid. Is preferable, more preferably 0.95 to 1.1, still more preferably 0.98 to 1.05.
The method for producing a polyamide is not limited to the following, but for example, a dicarboxylic acid constituting a dicarboxylic acid unit, a diamine constituting a diamine unit, and if necessary, a lactam unit and / or an aminocarboxylic acid unit. It is preferable to include a step of polymerizing lactam and / or an aminocarboxylic acid constituting the above to obtain a polymer, and further to include a step of increasing the degree of polymerization of the polyamide. Further, if necessary, a sealing step of sealing the end of the obtained polymer with an end-sealing agent may be included.

Specific examples of the method for producing the polyamide include various methods as illustrated 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, also referred to as "heat melt polymerization method"). say.).
2) A method of increasing the degree of polymerization of a polyamide obtained by a hot melt polymerization method while maintaining a solid state at a temperature below the melting point (hereinafter, 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 a dicarboxylic acid and a 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 a dicarboxylic acid and a diamine component (hereinafter, also referred to as "solution method").
Above all, a production method including a heat-melt polymerization method is preferable, and when the polyamide is produced by the heat-melt polymerization method, it is preferable to maintain the molten state until the polymerization is completed. In order to maintain the molten state, it is necessary to produce the polyamide composition under suitable polymerization conditions. For example, the polymerization pressure in the thermal melt polymerization method is controlled to 14 to 25 kg / cm ² (gauge pressure), and while heating is continued, until the pressure in the tank reaches atmospheric pressure (gauge pressure is 0 kg / cm ² ) 30. There is a method of lowering the pressure while taking more than a minute.

In the method for producing a 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 known apparatus can be used, for example, an autoclave type reactor, a tumbler type reactor, an extruder type reactor such as a kneader, and the like. Can be mentioned.

Hereinafter, as a method for producing a polyamide, a method for producing a polyamide by a batch-type thermal melt polymerization method will be specifically shown, but the method for producing a polyamide is not limited to this.
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 prepared 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), concentrate to about 65 to 90% by mass to obtain a concentrated solution.

Then, the obtained concentrated solution is transferred to an autoclave, and heating is continued until the pressure in the autoclave reaches about 1.2 to 2.2 MPa (gauge pressure).
Then, 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 lowered to atmospheric pressure (). Gauge pressure is 0 MPa).

By reducing the pressure in the autoclave to atmospheric pressure and then reducing the pressure as necessary, water produced as a by-product can be effectively removed.
Then, 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 strands are cooled and cut to obtain polyamide pellets.

(Polyamide polymer terminal)
The polymer terminal of the polyamide used in the present invention is not particularly limited, but can be classified and defined as follows.
That is, 1) amino terminal, 2) carboxyl terminal, 3) terminal by encapsulant, and 4) other terminal.

1) The amino terminus is _{a polymer terminus having an amino group (-NH 2} groups) and is derived from the diamine unit of the raw material.
2) The carboxyl terminus is a polymer terminus having a carboxyl group (-COOH group) and is derived from the raw material dicarboxylic acid.
3) The end by the encapsulant is the end formed when the encapsulant is added at the time of polymerization. Examples of the encapsulant include the above-mentioned terminal encapsulant.
4) Other terminals are polymer terminals not classified into 1) to 3) described above, and examples thereof include a terminal produced by a decarboxylation reaction of an amino terminal and a terminal produced by a decarboxylation reaction from a 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 Examples described later.
(A) Mw (A) (weight average molecular weight) can be used as an index of the molecular weight of the aliphatic polyamide. The Mw (A) (weight average molecular weight) of the (A) aliphatic polyamide is preferably 1000 to 50000, more preferably 1500 to 45000, still more preferably 20000 to 40000, and even more preferably 2500 to 35000. Is.

When 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. Further, the polyamide composition containing a component typified by an inorganic filler has an excellent surface appearance. The Mw (weight average molecular weight) can be measured by using GPC (gel permeation chromatography) as described in the following examples.
(A) The molecular weight distribution of the aliphatic polyamide uses Mw (weight average molecular weight) / Mn (number average molecular weight) as an index.

(A) The Mw (weight average molecular weight) / Mn (number average molecular weight) of the aliphatic polyamide is preferably 1.8 to 2.2, and 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) in the above range, a polyamide composition having excellent fluidity and the like can be obtained. Further, the polyamide composition containing a component typified by an inorganic filler has an excellent surface appearance.

(A) As a method for controlling Mw (weight average molecular weight) / Mn (number average molecular weight) of the aliphatic polyamide within the above range, for example, phosphoric acid or hypophosphorous acid is used as an additive during thermal 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 (A) Mw (weight average molecular weight) / Mn (number average molecular weight) of the aliphatic polyamide is obtained by using GPC (gel permeation chromatography) as described in the following Examples. It can be calculated using Mw (weight average molecular weight) and Mn (number average molecular weight).

The melting point Tm2 of the (A) aliphatic polyamide is preferably 220 ° C. or higher, more preferably 230 ° C. or higher, and further preferably 240 ° C. or higher.
The melting point Tm2 of the (A) aliphatic polyamide is preferably 300 ° C. or lower, more preferably 290 ° C. or lower, still more preferably 280 ° C. or lower, still more preferably 270 ° C. or lower.
(A) When the melting point Tm2 of the aliphatic polyamide is 220 ° C. or higher, it tends to be possible to obtain a polyamide composition having superior thermal rigidity and the like.
Further, when the melting point Tm2 of the (A) aliphatic polyamide is 300 ° C. or lower, there is a tendency that the thermal decomposition of the polyamide composition in the melt processing such as extrusion and molding can 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, still more preferably 40 J / g or more, from the viewpoint of mechanical properties, particularly water absorption rigidity and thermal rigidity. It is 50 J / g or more, and more preferably 60 J / g or more. Further, the upper limit of the crystallization enthalpy ΔH is not particularly limited, and the higher it is, the more preferable.

Examples of the device for measuring the melting point Tm2 and the crystallization enthalpy ΔH of the (A) aliphatic polyamide include Diamond-DSC manufactured by PERKIN-ELMER.
The tan δ peak temperature of the (A) aliphatic polyamide is preferably 40 ° C. or higher, more preferably 50 to 110 ° C., still more preferably 60 to 100 ° C., still more preferably 70 to 95 ° C. , More preferably 80-90 ° C. (A) When the glass transition temperature of the aliphatic polyamide is 40 ° C. or higher, it tends to be possible to obtain a polyamide composition having excellent water absorption rigidity and thermal rigidity.
(A) The tan δ peak temperature of the aliphatic polyamide can be measured by using, for example, a viscoelasticity measuring and analyzing device (manufactured by 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) The Mw (weight average molecular weight) of the polyamide is preferably 1000 to 25000, more preferably 13000 to 24000, still more preferably 1500 to 23000, still more preferably 18000 to 22000, and particularly preferably. Is 19000 to 21000.

When 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. Further, the polyamide composition containing a component typified by an inorganic filler has an excellent surface appearance. The Mw (weight average molecular weight) can be measured by using GPC (gel permeation chromatography) as described in the following examples.

(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) The 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 further preferably 1.8. It is ~ 2.3, more preferably 1.9 to 2.2, and most preferably 1.9 to 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) in the above range, a polyamide composition having excellent fluidity and the like can be obtained. Further, the polyamide composition containing a component typified by an inorganic filler has an excellent surface appearance.

(B) As a method for controlling 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 is used as an additive during thermal melt polymerization of polyamide. A method of adding a known polycondensation catalyst such as sodium phosphate can be mentioned. It is also important to control the polymerization conditions such as heating conditions and reduced pressure conditions to complete the polycondensation reaction at the lowest possible temperature and in a short time. In particular, if (B) the semi-aromatic polyamide is an amorphous polyamide, it does not have a melting point, so that the reaction temperature can be lowered, which is desirable.
When an aromatic compound unit is contained in the molecular structure of polyamide, the molecular weight distribution (Mw / Mn) tends to increase as the molecular weight increases. A high molecular weight distribution indicates that the proportion of polyamide molecules having a three-dimensional structure of the molecule is high, and the three-dimensional structuring of the molecule is more likely to proceed during high-temperature processing, the fluidity is reduced, and it is typified by an inorganic filler. The surface appearance of the polyamide composition containing the above-mentioned components is deteriorated.

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

In the present invention, the relative viscosity of formic acid (VR) of polyamide is the relative viscosity of the formic acid solution of polyamide, and can be said to be the relative viscosity obtained by comparing the viscosity of the formic acid solution of polyamide with the viscosity of formic acid itself. In the present specification, the above VR is used as an index of the molecular weight and fluidity of the polyamide, and the higher the value of VR, the higher the molecular weight and the lower the fluidity. When measuring VR, it is carried out in accordance with ASTM-D789. Specifically, a value measured at 25 ° C. can be adopted as a VR value by using a solution in which polyamide is dissolved in 90% by mass formic acid (10% by mass of water) so as to be 8.4% by mass. .. If the VR is lower than 8, the color tone and mechanical properties are not sufficient, and if the VR is larger than 30, the fluidity is low and the molding processability is poor. The VR of the (B) semi-aromatic polyamide in the present 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 index 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, further preferably 1500 or more and 2000 or less, and most preferably 1500 or more and 1800 or less. preferable. If Mw / VR is less than 1000, for example, the molecular weight will be low and the mechanical properties will be insufficient. On the other hand, when Mw / VR is larger than 2000, for example, VR is low, so that the 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, still more 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 for 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 that the dicarboxylic acid unit contains 75 mol% or more of isophthalic acid, and most preferably 100 mol%.
(B) Examples of the device for measuring the crystallization enthalpy ΔH of the semi-aromatic polyamide include Diamond-DSC manufactured by PERKIN-ELMER.

(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., still more preferably 120 to 145 ° C. Yes, more preferably 130-140 ° C.
(B) As a method for controlling the tan δ peak temperature 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 that the dicarboxylic acid unit contains 75 mol% or more of isophthalic acid, and most preferably 100 mol%.
(B) When the glass transition temperature of the semi-aromatic polyamide is 90 ° C. or higher, it tends to be possible to obtain a polyamide composition having excellent water absorption rigidity and thermal rigidity. Further, 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 an excellent surface appearance.

(B) The tan δ peak temperature of the semi-aromatic polyamide can be measured by using, for example, a viscoelasticity measuring and analyzing device (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 μe equivalent / g, more preferably 10 to 90 μe equivalent / g, still more preferably 20 to 80 μe equivalent, relative to 1 g of polyamide. It is / g, more preferably 30 to 70 μe equivalents / g, and even more preferably 40 to 60 μe equivalents / g. When the amount of the amino terminal is in the above range, the composition can be excellent in discoloration due to heat or light. The amount of 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 μe equivalent / g, more preferably 100 to 280 μe equivalent / g, still more preferably 150 to 260 μe equivalent, relative to 1 g of polyamide. / G, even more preferably 180-250 μe equivalents / g, and even more preferably 200-240 μe equivalents / g. When the amount of the carboxyl terminal is in the above range, a polyamide composition having excellent fluidity and the like can be obtained. Further, the polyamide composition containing a component typified by an inorganic filler has an excellent surface appearance. The amount of carboxyl terminus can be measured by neutralization titration.

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

((C) Pigment)
The polyamide resin composition of the present invention contains a pigment.
The pigment is not particularly limited, and is, for example, a dye such as niglocin, a pigment such as zinc sulfide, zinc oxide, titanium oxide and carbon black; aluminum, colored aluminum, nickel, tin, copper, gold, silver, platinum and iron oxide. , Stainless steel, and metal particles such as titanium; metallic pigments such as mica pearl pigments, colored graphite, colored glass fibers, and colored glass flakes. Among them, zinc sulfide (ZnS) and zinc oxide (ZnO), which are white pigments, are preferable because of their mechanical properties such as toughness, strength and rigidity, and the balance between flame retardancy and coloring.

((D1) Flame Retardant)
The (D1) flame retardant 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 chlorine-based flame retardants and brominated flame retardants.
These (D1) flame retardants may be used alone or in combination of two or more.

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

Examples of the brobromo-based flame retardant 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), ethylenebispentabromodiphenyl, tris (tri) Brobromophenoxy) triazine (TTBPTA), bis (dibromopropyl) tetrabromobisphenol A (DBP-TBBA), bis (dibromopropyl) tetrabromobisphenol S (DBP-TBBS), brominated polyphenylene ether (poly (di) bromophenylene ether) (Including BrPPE), brominated polystyrene (including polydibromostyrene, polytribromostyrene, cross-linked 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), polybromotrimethylphenyl indane (PBPI), and tris (dibromopropyl) -isosocyanurate ( TDBPIC) and the like.

(D1) As the 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 flame retardancy, toughness and rigidity. Polyphenylene ether (including poly (di) bromophenylene ether and the like) and brominated polystyrene (including polydibromostyrene, polytribromostyrene, crosslinked brominated polystyrene and the like) are preferable, and brominated polystyrene is more preferable.

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

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 not impaired without impairing the properties of the polyamide copolymer. , A polyamide resin composition having excellent 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 is less likely to cause thermal decomposition during melt processing such as extrusion or molding, can suppress gas generation, and has excellent heat-resistant discoloration. Can be obtained.

((D2) Flame retardant aid)
The polyamide resin composition of the present invention can be made into a polyamide resin composition having better flame retardancy by containing (D2) a flame retardant aid.
The (D2) flame-retardant aid used in the present invention is not particularly limited, and is, for example, diantimony trioxide (Sb ₂ O ₃ ), diantimony trioxide, diantimony pentoxide, sodium antimonate, and the like. Antimony trioxide; tin oxide such as tin monoxide and tin dioxide; iron oxide such as ferric oxide and γ iron oxide; other zinc oxide, zinc borate, calcium oxide, aluminum oxide (alumina), aluminum oxide Metal oxides such as (bemite), 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; metal powders such as aluminum, iron, titanium, manganese, zinc, molybdenum, cobalt, bismuth, chromium, tin, antimony, nickel, copper, and tungsten; zinc carbonate, calcium carbonate, Metallic carbonates such as magnesium carbonate and barium carbonate; metal borates such as magnesium borate, calcium borate, and aluminum borate; and silicones; and the like.
These (D2) flame retardant aids may be used alone or in combination of two or more.

The (D2) flame-retardant aid used in the present invention includes antimony oxides such as diantimony trioxide, diantimony trioxide, diantimony trioxide, and sodium antimonate; magnesium hydroxide from the viewpoint of flame-retardant effect. , Tin oxides such as tin monoxide and tin dioxide; iron oxides such as ferric oxide and γ iron oxide; zinc oxide and zinc borate are preferable, and diantimony trioxide, diantimony trioxide and pentoxide are preferable. Antimony oxides such as diantimony; magnesium hydroxide and zinc borate are more preferred, antimony oxide and / or magnesium hydroxide are even more preferred, and diantimony trioxide and magnesium hydroxide are particularly preferred.
In order to increase the flame retardant effect, it is preferable to use a flame retardant aid having an average particle size of 0.01 to 10 μm (D2).
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 a constituent unit)
The polyamide resin composition of the present invention may further contain a polymer containing (E) α, β unsaturated dicarboxylic acid anhydride as a constituent unit. (E) By containing a polymer containing α, β unsaturated dicarboxylic acid anhydride as a constituent unit, a polyamide resin composition having excellent mechanical properties such as toughness and rigidity and flame retardancy can be obtained.

Examples of the polymer containing (E) α, β-unsaturated dicarboxylic acid anhydride used in the present invention include a polymer containing α, β-unsaturated dicarboxylic acid anhydride as a copolymerization component and α, β. Examples thereof include a polymer modified with an unsaturated dicarboxylic acid anhydride.
Examples of the α and β unsaturated dicarboxylic acid anhydride include compounds represented by the following general formula (1).

General formula (1):

In the general formula (1), R ¹ and R ² are independently hydrogen or an alkyl group having 1 to 3 carbon atoms.

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

Examples of the aromatic vinyl compound used in the present invention include compounds represented by the following general formula (2).

General formula (2):

In the general formula (2), R ³ and R ⁴ are independently hydrogen or an alkyl group having 1 to 3 carbon atoms, and 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). In addition, the α, β unsaturated dicarboxylic acid anhydride moiety has an affinity or reaction with (B) a semi-aromatic polyamide, thereby helping the (D1) flame retardant to be dispersed in the polyamide matrix, and the flame retardant. Is considered to be able to be finely dispersed.

The proportions of the aromatic vinyl compound component and the α, β-unsaturated dicarboxylic acid anhydride component in the copolymer of the aromatic vinyl compound and the α, β-unsaturated dicarboxylic acid anhydride are flame-retardant, fluid, and heat-resistant decomposition. From the viewpoint of properties and the like, it is preferable that the aromatic vinyl compound component is 50 to 99% by mass and the α, β unsaturated dicarboxylic acid anhydride component is 1 to 50% by mass. The proportion of the α, β unsaturated dicarboxylic acid anhydride component is more preferably 5 to 20% by mass, still more preferably 8 to 15% by mass.

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

As the polymer modified with the α, β unsaturated dicarboxylic acid anhydride, a polyphenylene ether resin or a polypropylene resin modified with the α, β unsaturated dicarboxylic acid anhydride is preferable. The content of the polymer modified with the α, β unsaturated dicarboxylic acid 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 the filler, a polyamide resin composition having further excellent mechanical properties such as toughness and rigidity can be obtained.

The (F) filler used in the present invention is not particularly limited, and is, for example, glass fiber, carbon fiber, calcium silicate fiber, potassium titanate fiber, aluminum borate fiber, glass flake, talc, kaolin. , Mica, hydrotalcite, calcium carbonate, zinc carbonate, zinc oxide, calcium monohydrogen phosphate, wollastonite, silica, zeolite, alumina, boehmite, aluminum hydroxide, titanium oxide, silicon oxide, magnesium oxide, calcium silicate , Sodium aluminosilicate, magnesium silicate, Ketjen black, acetylene black, furnace black, carbon nanotubes, graphite, brass, copper, silver, aluminum, nickel, iron, calcium fluoride, montmorillonite, swelling fluoromother, and apatite, etc. Can be mentioned.
(F) As the filler, one type may be used, or two or more types may be used in combination.

(F) As the 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 fluoromamma, and apatite are preferred.

As the filler, glass fibers and carbon fibers are more preferable, and among the glass fibers and carbon fibers, 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 the length (L) and the number average fiber diameter (D) of 10 to 100 are more preferably used from the viewpoint of exhibiting high characteristics.

Further, as the filler (F), glass fiber is 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 described above. ) Is 3 to 100, which is more preferably used.

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

(Contents 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, more preferably 3% by mass or less, based on 100% by mass of the polyamide composition. In particular, the color tone and mechanical properties (C) are that 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 with respect to 100% by mass of the polyamide composition. Especially preferable from the viewpoint of mechanical strength).

The content of the (D1) flame retardant 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% by mass, based on 100% by mass of the polyamide composition. It is by mass, more preferably 5 to 15% by mass.

The content of the (D2) flame-retardant aid in the polyamide resin composition is preferably 0.1 to 10% by mass, more preferably 1 to 10% by mass, based on 100% by mass of the polyamide composition. .. (D2) By containing the flame retardant aid in the above range, a polyamide resin composition having further excellent flame retardancy can be obtained. Further, by setting the content of (D2) 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 increases, and the formability at the time of molding can be controlled. And deterioration of the appearance of the molded product can be suppressed. Further, it is possible to obtain a polyamide resin composition having excellent toughness and the like without impairing the properties of the polyamide having excellent mechanical properties such as toughness and rigidity.

(D2) By setting the content of the flame retardant aid to 0.1% by mass or more, a polyamide resin composition having excellent flame retardancy can be obtained. Further, by setting the content of the (D1) flame retardant to 15% by mass or less, it is possible to suppress the generation of decomposition gas during melt-kneading, the decrease in fluidity during molding, and the adhesion of contaminating substances to the molding die. be able to. Further, it is possible to suppress deterioration of mechanical properties such as toughness and rigidity and appearance of the molded product.

In a particularly preferable combination, (D1) the flame retardant is brominated polystyrene, the content of brominated polystyrene is 6% by mass or more and 15% by mass or less with respect to 100% by mass of the polyamide composition, and (D2) difficult. The flame retardant 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. Is.

The content of the polymer containing (E) α, β unsaturated dicarboxylic acid anhydride as a constituent unit in the polyamide resin composition is preferably 0.1 to 20% by mass with respect to 100% by mass of the polyamide composition. It is more preferably 0.5 to 20% by mass, further preferably 1 to 15% by mass, and particularly preferably 2 to 10% by mass. (E) By containing a polymer containing α, β unsaturated dicarboxylic acid anhydride as a constituent unit in the above range, the effect of finely dispersing the (D1) flame retardant in the polyamide resin composition by compatibilization is enhanced. It is possible to obtain a polyamide resin composition having excellent flame retardancy and strength improving effect. Further, by setting the content of the polymer containing (E) α, β unsaturated dicarboxylic acid anhydride as a constituent unit to 20% by mass or less, the properties of the polyamide having excellent mechanical characteristics 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 (F) filler in the polyamide resin composition is preferably 1 to 80% by mass, more preferably 10 to 70% by mass, and further preferably 30 with respect to 100% by mass of the polyamide composition. It is ~ 70% by mass, more preferably 30-60% by mass, and most preferably 40-60% by mass.

(F) By containing the filler in the above range, the mechanical properties such as strength and rigidity of the polyamide resin composition are satisfactorily improved, and by setting the content of the inorganic filler to 70% by mass or less, A polyamide resin composition having excellent moldability can be obtained.
In the present invention, a polymer containing (C) a pigment, (D1) a flame retardant, (D2) a flame retardant aid, (E) α, β unsaturated dicarboxylic acid anhydride as a constituent unit, and (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. It is more preferably 10 to 90% by mass, further preferably 30 to 80% by mass, and even more preferably 40 to 80% by mass. When the total amount is 10% by mass or more, a polyamide composition having excellent strength, rigidity, flame retardancy and the like, and having an appropriate melt viscosity and excellent processability can be obtained.

The polyamide composition of the present invention includes additives commonly used for polyamides, for example, moldability improvers, deterioration inhibitors, nucleating agents, lubricants, stabilizers, as long as the object of the present invention is not impaired. It is also possible to contain a polymer other than the polyamide in the present invention.
Since the content of the additive varies depending on the type, the use of the polyamide composition, and the like, it is not particularly limited as long as it does not impair the object of the present invention.

(Moldability 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. The moldability improving agent is not particularly limited, and examples thereof include higher fatty acids, higher fatty acid metal salts, higher fatty acid esters, higher fatty acid amides, and the like.

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 fatty acids having 8 to 40 carbon atoms. Examples thereof include monocarboxylic acid. Of these, stearic acid and montanic acid are preferred.

The higher fatty acid metal salt is a metal salt of a higher fatty acid.
As the metal element of the metal salt, Group 1 and 2 and 3 elements of the Periodic Table of the Elements, zinc, aluminum and the like are preferable, and Group 1 and 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 preferable. Examples of the aliphatic alcohol include stearyl alcohol, behenyl alcohol, lauryl alcohol and the like. Examples of the higher fatty acid ester include stearyl stearate and behenic behenate.

The higher fatty acid amide is an amide compound of a higher fatty acid.
Examples of the higher fatty acid amide include stearate amide, oleic acid amide, erucate amide, ethylene bisstearyl amide, ethylene bisoleyl amide, N-stearyl steayl amide, N-stearyl erucate amide and the like.

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

(Deterioration inhibitor)
The polyamide resin composition of the present invention contains, if necessary, a deterioration inhibitor for the purpose of improving thermal deterioration, heat discoloration prevention, heat aging resistance, and weather resistance, as long as the object of the present invention is not impaired. It may be added.
The deterioration inhibitor is not particularly limited, but for example, a copper compound such as copper acetate and copper iodide; a phenol-based stabilizer such as a hindered phenol compound; a phosphite-based stabilizer; a hindered amine-based stabilizer; a triazine-based stabilizer. Examples include benzotriazole-based stabilizers, benzophenone-based stabilizers, cyanoacrylate-based stabilizers, salicylate-based stabilizers; and sulfur-based stabilizers.
One of these deterioration inhibitors may be used alone, or two or more of them may be used in combination.

(Nucleating agent)
The nucleating agent is a spherulite of a molded product obtained by increasing the crystallization peak temperature of the polyamide composition by adding it, reducing the difference between the extrapolation start temperature and the extrapolation end temperature of the crystallization peak. It means a substance that can obtain the effect of crystallization or homogenization of size.
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, molybdenum disulfide and the like. Be done.
As the nucleating agent, only one type 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 effect of the nucleating agent.
Further, since the effect of the nucleating agent is high, a nucleating agent having a number average particle size of 0.01 to 10 μm is preferable.
For the number average particle size of the nucleating agent, for example, 100 or more nucleating agents are arbitrarily selected from the insoluble components obtained by dissolving the molded product in a solvent in which polyamide such as formic acid is soluble. It can be obtained by observing and measuring with an optical microscope, a scanning electron microscope, or the like.

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 by mass with respect to 100 parts by mass of the polyamide of the present invention. It is by mass, more preferably 0.001 to 0.09 parts by mass.
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 100 parts by mass of the polyamide. By setting the amount to 1 part by mass or less with respect to the part, a polyamide composition having excellent toughness can be obtained.

(Stabilizer)
Stabilizers are not limited to the following, but are, for example, phenol-based heat stabilizers, phosphorus-based heat stabilizers, amine-based heat stabilizers, and Group 3, Group 4 and Group 11-14 of the Periodic Table of the Elements. Examples thereof include metal salts of the elements of the above, and halides of alkali metals and alkaline earth metals.

Examples of the phenolic 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.

The hindered phenol compound is not limited to the following, and is, for example, N, N'-hexane-1,6-diylbis [3- (3,5-di-t-butyl-4-hydroxyphenylpropi). Onamide), pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], N, N'-hexamethylenebis (3,5-di-t-butyl-) 4-Hydroxy-hydrosinnamamide), triethylene glycol-bis [3- (3-t-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, 3,5-di-t -Butyl-4-hydroxybenzylphosphonate-diethyl ester, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, and 1,3. Examples thereof include 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, from the viewpoint of improving heat resistance aging, N, N'-hexane-1,6-diylbis [3- (3,5-di-t-butyl-4-hydroxyphenylpropionamide)] is preferable.

When a phenolic heat stabilizer is used, the content of the phenolic heat stabilizer in the polyamide composition is preferably 0.01 to 1% by mass, more preferably 0, based on 100% by mass of the polyamide composition. .1-1% by mass. When the content of the phenolic heat stabilizer is within the above range, the heat-resistant aging property of the polyamide composition can be further improved, and the amount of gas generated can be further reduced.

The phosphorus-based heat stabilizer is not limited to, but is not limited to, for example, pentaerythritol type phosphite compound, trioctylphosphite, trilaurylphosphite, tridecylphosphite, octyldiphenylphosphite, trisisodecyl. 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) butanji Phosphite, Tetra (tridecyl) -4,4'-butylidenebis (3-methyl-6-t-butylphenyl) diphosphite, Tetra (C1-C15 mixed alkyl) -4,4'-isopropyridene diphenyldiphosphite, Tris (Mono-dimixed nonylphenyl) phosphite, 4,4'-isopropylidenebis (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, hydride-4,4'-isopropridendiphenylpolyphosphite, bis (Octylphenyl) -bis (4,4'-butylidenebis (3-methyl-6-t-butylphenyl))-1,6-hexanoldiphosphite, 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) octylphosphite, 2,2-methylenebis (3-methyl-4,6-di-t-butylphenyl) 2-ethylhexylphos Fight, Tetrakiss (2,4-di-t-butyl-5-methylphenyl) -4,4'-biphenylenediphosphite, and Tetrakiss (2,4-di-t-butylphenyl) -4,4'- Biphenirange phosphite can be mentioned.
These may be used alone or in combination of two or more.

Among those listed above, pentaerythritol-type phosphite compounds and / or tris (2,4-di-t-butylphenyl) are used from the viewpoint of further improving the heat-resistant aging property of the polyamide composition and reducing the amount of gas generated. Phenyl phosphite is preferred. The pentaerythritol-type phosphite compound is not limited to the following, and is, for example, 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-methylphenyl-benzyl-pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl ethylcellosolve-pentaerythritol Diphosphite, 2,6-di-t-butyl-4-methylphenyl-butylcarbitol-pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl-octylphenyl-pentaerythritol di Phosphite, 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-penta Ellisritol diphosphite, 2,6-di-t-butyl-4-methylphenyl-2,4-di-t-butylphenyl-pentaerythritol diphosphite, 2,6-di-t-butyl-4-methyl Phenyl-2,4-di-t-octylphenyl-pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl-2-cyclohexylphenyl-pentaerythritol diphosphite, 2,6-di -T-Amil-4-methylphenyl-phenyl pentaeris Tritor diphosphite, bis (2,6-di-t-amyl-4-methylphenyl) pentaerythritol diphosphite, and bis (2,6-di-t-octyl-4-methylphenyl) pentaerythritol di Phenylphite can be 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 amount of gas generated in 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, 6-di-t-octyl-4-methylphenyl) pentaerythritol One or more selected from the group consisting of diphosphite is preferable, and bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol is preferable. Diphosfite is more preferred.

When a phosphorus-based heat stabilizer is used, the content of the phosphorus-based heat stabilizer in the polyamide composition is preferably 0.01 to 1% by mass, more preferably 0.01 to 1% by mass, based on 100% by mass of 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-resistant aging property of the polyamide composition can be further improved, and the amount of gas generated can be further reduced.

The amine-based heat stabilizer is not limited to the following, and is, for example, 4-acetoxy-2,2,6,6-tetramethylpiperidine, 4-stearoyloxy-2,2,6,6-tetra. Methylpiperidine, 4-acryloyloxy-2,2,6,6-tetramethylpiperidine, 4- (phenylacetoxy) -2,2,6,6-tetramethylpiperidine, 4-benzoyloxy-2,2,6 6-Tetramethylpiperidine, 4-methoxy-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, 4-cyclohexyloxy-2,2,6 6-Tetramethylpiperidine, 4-benzyloxy-2,2,6,6-tetramethylpiperidine, 4-phenoxy-2,2,6,6-tetramethylpiperidine, 4- (ethylcarbamoyloxy) -2,2 , 6,6-Tetramethylpiperidine, 4- (cyclohexylcarbamoyloxy) -2,2,6,6-tetramethylpiperidine, 4- (phenylcarbamoyloxy) -2,2,6,6-tetramethylpiperidine, bis (2,2,6,6-tetramethyl-4-piperidyl) -carbonate, bis (2,2,6,6-tetramethyl-4-piperidyl) -oxalate, bis (2,2,6,6-tetra Methyl-4-piperidyl) -malonate, bis (2,2,6,6-tetramethyl-4-piperidyl) -sevacate, bis (2,2,6,6-tetramethyl-4-piperidyl) -adipate, bis (2,2,6,6-tetramethyl-4-piperidyl) -terephthalate, 1,2-bis (2,2,6,6-tetramethyl-4-piperidyloxy) -ethane, α, α'-bis (2,2,6,6-tetramethyl-4-piperidyloxy) -p-xylene, bis (2,2,6,6-tetramethyl-4-piperidyltrilen-2,4-dicarbamate, bis (2,2,6,6-tetramethyl-4-piperidyloxy) 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-hydroxyphenyl) Enyl) propionyloxy] 2,2,6,6-tetramethylpiperidine, and 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6,6-pentamethyl-4-piperidinol and β, β , Β', β'-Tetramethyl-3,9- [2,4,8,10-tetraoxaspiro (5,5) undecane] Condensate with diethanol. These may be used alone or in combination of two or more.

When an amine-based heat stabilizer is used, the content of the amine-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. .1-1% by mass. When the content of the amine-based heat stabilizer is within the above range, the heat-resistant aging property of the polyamide composition can be further improved, and the amount of gas generated can be further reduced.

The metal salts of the elements of Group 3, Group 4 and Groups 11 to 14 of the Periodic Table of the Elements are not limited as long as they are salts of metals belonging to these groups. From the viewpoint of further improving the heat-resistant aging property of the polyamide composition, a copper salt is preferable. The copper salt is not limited to the following, and is, for example, copper halide (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 copper complex salts in which copper is coordinated with a chelating agent such as ethylenediamine and ethylenediamine tetraacetic acid. These may be used alone or in combination of two or more.

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

When a copper salt is used, the content of the copper salt in the polyamide composition is preferably 0.01 to 0.60% by mass, more preferably 0.02 to 0.40% with respect to 100% by mass of the polyamide. It is mass%. When the content of the copper salt is within the above range, the heat-resistant aging property 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 to 1500 parts by mass, more preferably 50 to 500 parts by mass.

Alkali metals and alkali earth metal halides include, but are not limited to, potassium iodide, potassium bromide, potassium chloride, sodium iodide and sodium chloride, and mixtures thereof. .. Among them, potassium iodide and / or potassium bromide is preferable, and potassium iodide is more preferable, from the viewpoint of improving heat-resistant aging property and suppressing metal corrosion.

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

As the component of the stabilizer described above, only one kind may be used alone, or two or more kinds may be used in combination. Above all, a mixture of a copper salt and a halide of an alkali metal and an alkaline earth metal is preferable from the viewpoint of further improving the heat-resistant aging property of the polyamide composition.

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

When the above-mentioned 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, it is preferable because it can prevent corrosion of screws and the like of the molding machine without 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-based resins such as atactic polystyrene, isotactic polystyrene, syndiotactic polystyrene, AS (acrylonitrile-styrene copolymer) resin, and ABS (acrylonitrile-butadiene-styrene copolymer) resin. Polyester resin such as polyethylene terephthalate and polybutylene terephthalate; Nylon Polyamide other than polyamide used in the present invention; Polyether resin such as polycarbonate, polyphenylene ether, polysulfone and polyether sulfone; Condensation system such as polyphenylene sulfide and polyoxymethylene Resins: Acrylic resins such as polyacrylic acid, polyacrylic acid esters, and polymethylmethacrylate; polyolefin resins such as polyethylene, polypropylene, polybutene, and ethylene-propylene copolymers; halogen-containing vinyls such as polyvinyl chloride and polyvinylidene chloride. Compound-based resins; phenolic resins; epoxy resins and the like can be mentioned.
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), and the like. 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), styrene-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 Combined, 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 rubber (MABS) AABS), butadiene-styrene-core-shell rubber (SBR), core-shell types such as siloxane-containing core-shell rubber such as methyl methacrylate-butyl acrylate siloxane can be mentioned.
One type of these rubber components may be used alone, or two or more types may be used in combination.

(Manufacturing method of polyamide resin composition)
The method for producing the polyamide resin composition of the present invention includes (A) an aliphatic polyamide, (B) a semi-aromatic polyamide, (C) a pigment, (D1) a flame retardant, and (D2) a flame retardant aid, if necessary. The method is not particularly limited as long as it is a method of mixing (E) a polymer containing α, β unsaturated dicarboxylic acid anhydride as a constituent unit and (F) a filler.

The constituent units are (A) aliphatic polyamide, (B) semi-aromatic polyamide, (C) pigment, (D1) flame retardant, (D2) flame retardant aid, and (E) α, β unsaturated dicarboxylic acid anhydride. As a method of mixing the polymer containing the polymer and the filler (F), for example, (A) aliphatic polyamide, (B) semi-aromatic polyamide, (C) pigment and (D1) flame retardant, and optionally ( D2) A flame retardant, (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 a filler, using a Henshell mixer or the like. (A) aliphatic polyamide, (B) semi-aromatic polyamide and (D1) flame retardant, optionally (C). A mixture of a pigment, a flame retardant aid and / or a polymer containing (E) α, β unsaturated dicarboxylic acid anhydride as a constituent unit in advance using a Henshell mixer or the like is supplied to a melt kneader. After kneading and kneading, a method of blending the (F) filler from the side feeder is optionally 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 about 1 to 100 ° C. higher than the melting point of the (A) aliphatic polyamide, and more preferably a temperature about 10 to 50 ° C. higher.
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 such as a single-screw or twin-screw extruder, a Banbury mixer, and a melt-kneader such as a mixing roll is preferably used.

The blending amount of each component in producing the polyamide resin composition of the present invention is the same as the content of each component in the above-mentioned polyamide resin composition.

(Physical characteristics of polyamide composition)
Specifically, the molecular weight, melting point Tm2, crystallization enthalpy ΔH, and tan δ peak temperature of the polyamide composition of the present invention can be measured by the method described in Examples described later.
Mw (weight average molecular weight) can be used as an index of the molecular weight of the polyamide composition. The Mw (weight average molecular weight) of the polyamide composition is 1000 to 40,000, preferably 17,000 to 35,000, more preferably 2000 to 35,000, still more preferably 22,000 to 34,000, and even more preferably 24,000 to 33,000. The most preferable is 2500 to 32000. When Mw (weight average molecular weight) is in the above range, a polyamide having excellent mechanical properties, particularly water absorption rigidity, thermal rigidity, fluidity and the like can be obtained. Further, the polyamide composition containing a component typified by a filler has an excellent surface appearance.
Examples of the method for controlling the Mw of the polyamide composition within the above range include using Mw of (A) an aliphatic polyamide and (B) a semi-aromatic polyamide in the above range.
The Mw (weight average molecular weight) can be measured by using GPC (gel permeation chromatography) as described in the following examples.

The total content of 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 with respect to the total amount of polyamide in the polyamide composition. It is more than mass% 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, and most It is preferably 1.4% by mass or more and less than 2.5% by mass. The polyamide composition having a number average molecular weight Mn of 500 or more and 2000 or less and having a content of 0.5% by mass, which is excellent in fluidity and contains a component typified by an inorganic filler, has a surface appearance. It can be excellent. Further, when it is less than 2.5% by mass, gas generation during molding can be suppressed.

(B) The molecular weight of the semi-aromatic polyamide is important as a method for controlling the total content of the polyamide having a number average molecular weight Mn of 500 or more and 2000 or less, and Mw (weight average molecular weight) is preferable. It is 1000 to 25000.
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 by using GPC from the elution curve under the measurement conditions in the examples described later.
If the composition containing (A) aliphatic polyamide and (B) semi-aromatic polyamide at the time of GPC measurement contains other components that are soluble in the solvent that dissolves the polyamide, the polyamide is insoluble. However, for the other component, a soluble solvent is used to extract and remove the other component, and then 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 the insoluble matter, 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) semi-aromatic polyamide may be 10,000 or more. It is preferable, more preferably 11000 or more, still more preferably 12000 or more, still more preferably 13000 or more, and most preferably 14000 or more. When {Mw (A) -Mw (B)} is 10,000 or more, the semi-aromatic polyamide (B) forms a micro-sized domain, and a composition having excellent water absorption rigidity and thermal 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.
The 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, still more preferably 1.8 to. It is 2.2, and even 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) in the above range, a polyamide composition having excellent fluidity and the like can be obtained. Further, the polyamide composition containing a component typified by an inorganic filler has an excellent surface appearance.

As a method for controlling 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 used. It is important to keep it within the above range.
When an 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 that the proportion of polyamide molecules having a three-dimensional structure of the molecule is high, and the three-dimensional structuring of the molecule is more likely to proceed during high-temperature processing, the fluidity is reduced, and it is typified by an inorganic filler. The surface appearance of the polyamide composition containing the above-mentioned components is deteriorated.

In the present invention, the measurement of Mw (weight average molecular weight) / Mn (number average molecular weight) of the polyamide composition is performed by using GPC (gel permeation chromatography) as described in the following Examples. It can be calculated using (weight average molecular weight) and Mn (number average molecular weight).

The tan δ peak temperature of the polyamide composition is 90 ° C. or higher. It is more preferably 100 ° C. or higher, further preferably 110 ° C. or higher, and even more preferably 120 ° C. or higher.
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, it tends to be possible to obtain a polyamide composition having excellent water absorption rigidity and thermal rigidity. Further, when the tan δ peak temperature of the polyamide composition is 150 ° C. or lower, the polyamide composition containing a component typified by an inorganic filler has an excellent surface appearance.
Examples of the method for controlling the tan δ peak temperature of the polyamide composition within the above range include a method for controlling the blending ratio of (A) aliphatic polyamide and (B) semi-aromatic polyamide within the above range.

In the polyamide composition of the present invention, the ratio of the amino-terminal amount to the total amount of the amino-terminal amount and the 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 further 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 can be obtained. The surface gloss value of the polyamide composition of the present invention is more preferably 55 or more, still more preferably 60 or more. Since 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.

The method for obtaining the molded product is not particularly limited, and a known molding method can be used.
For example, extrusion molding, injection molding, vacuum molding, blow molding, injection compression molding, decorative molding, molding of other materials, gas assisted injection molding, foam injection molding, low pressure molding, ultra-thin wall injection molding (ultra-high speed injection molding), In addition, molding methods such as in-mold composite molding (insert molding, outsert molding) can be mentioned.

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

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.
Hereinafter, the constituent components of the polyamide composition used in this example and comparative example will be described.

(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 (G21 manufactured by Ms, 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) (SACHTORITH HD-S) was used.

[(D1) Flame Retardant]
(D1) Polystyrene brominated (manufactured by ALBEMARLLE CORPORATION, trade name "SAYTEX® HP-7010G" (bromine content determined by elemental analysis: 63% by mass))
Was used.

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

[(E) Polymer containing α, β unsaturated dicarboxylic acid anhydride as a 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.

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

(A-1: Polyamide 66)
The polymerization reaction of the polyamide was carried out as follows by the "heat 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 uniform aqueous solution of the raw material monomer. This aqueous solution was placed in an autoclave having an internal volume of 5.4 L and substituted with nitrogen.
While stirring at a temperature of 110 to 150 ° C., water vapor was gradually removed and concentrated to a solution concentration of 70% by mass. After that, the internal temperature was raised to 220 ° C. At this time, the autoclave was boosted to 1.8 MPa. The reaction was carried out for 1 hour as it was until the internal temperature reached 245 ° C., while the water vapor was gradually removed and the pressure was maintained at 1.8 MPa.
Next, the pressure was reduced over 1 hour. Then, the inside of the autoclave was maintained under a reduced pressure of 650 torr for 10 minutes with a vacuum device. At this time, the final internal temperature of the polymerization was 265 ° C.
Then, it was pressurized with nitrogen to form a strand from the lower spun (nozzle), water-cooled, cut and discharged as a pellet, and dried at 100 ° C. in a nitrogen atmosphere for 12 hours to obtain a polyamide. Mw = 35000 and Mw / Mn = 2.0.

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

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

(B-5: Polyamide 66 / 6I)
The polymerization reaction of the polyamide was carried out as follows by the "heat melt polymerization method".
1044 g of an homomolar salt of adipic acid and hexamethylenediamine, 456 g of an equimolar salt of isophthalic acid and hexamethylenediamine, and 1500 g of adipic acid in an excess of 0.5 mol% with respect to the total equimolar salt component were dissolved in 1500 g of distilled water. An equimolar 50% by mass uniform aqueous solution of the raw material monomer was prepared.
While stirring at a temperature of 110 to 150 ° C., water vapor was gradually removed and concentrated to a solution concentration of 70% by mass. After that, the internal temperature was raised to 220 ° C. At this time, the autoclave was boosted to 1.8 MPa. The reaction was carried out for 1 hour as it was until the internal temperature reached 245 ° C., while the water vapor was gradually removed and the pressure was maintained at 1.8 MPa.
Next, the pressure was reduced over 1 hour. Then, the inside of the autoclave was maintained under a reduced pressure of 650 torr for 10 minutes with a vacuum device. At this time, the final internal temperature of the polymerization was 265 ° C.
Then, it was pressurized with nitrogen to form a strand from the lower spun (nozzle), water-cooled, cut and discharged as a pellet, and dried at 100 ° C. in a nitrogen atmosphere 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) with a reduced viscosity (0.5 g / dl chloroform solution, measured at 30 ° C.) obtained by oxidative polymerization of 2,6-dimethylphenol (hereinafter, 100 parts by weight of polyphenylene ether) and 1.0 part by weight of maleic anhydride as a compatibilizer are located upstream (hereinafter abbreviated as top-F), in the center of the extruder and downstream near the die. Side-1 of a twin-screw extruder (Werner & Pfluiderer: ZSK-40) having supply ports (hereinafter, the central part of the extruder is abbreviated as side-1 and the downstream side near the die is abbreviated as side-2) at two locations on the side. And side-2 are closed, and a dry blend of polyphenylene ether and maleic anhydride is supplied from top-F under the conditions of a cylinder set temperature of 320 ° C., a screw rotation of 300 rpm, and a discharge rate of 20.15 kg / hr. Then, the mixture was melt-kneaded, taken out in the form of strands, cooled in a strand bath (water tank), and granulated with a cutter to obtain pellets of maleic anhydride-modified polyphenylene ether.

[Manufacturing of polyamide composition]
Using the above (A) aliphatic polyamide and (B) semi-aromatic polyamide in the types and ratios shown in Table 1 below, a polyamide composition was produced as follows.
The polyamide obtained above was dried in a nitrogen stream to adjust the water content to 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 pellets of the polyamide composition. The obtained pellets of the polyamide composition were dried in a nitrogen stream to reduce the water content in the polyamide composition to 500 ppm or less.

[Method for measuring physical properties of polyamide composition]
The following various evaluations were carried out using the polyamide composition after adjusting the water 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., set the cylinder temperature to 290 ° C and the mold temperature to 100 ° C, and under the injection molding conditions of 10 seconds for injection and 10 seconds for cooling, a molded product conforming to JIS-K7139. Molded. This molded product was measured under the following conditions using a dynamic viscoelasticity evaluation device (EPLEXOR 500N manufactured by GABO). Measurement mode: tension, measurement frequency: 8.00 Hz, temperature rise rate: 3 ° C / min, temperature range: -100 to 250 ° C. The ratio E2 / E1 of the storage elastic modulus E1 and the loss elastic modulus E2 was defined as Tanδ, and the highest temperature was defined as the Tanδ peak temperature.

<Molecular weight and terminal of polyamide composition>
( Molecular weight of polyamide composition (Mn, Mw / Mn)
The Mw (weight average molecular weight) / Mn (number average molecular weight) of the polyamide compositions obtained in Examples and Comparative Examples is GPC (Gel Permeation Chromatography, manufactured by Toso Co., Ltd., HLC-8020, hexafluoroisopropanol solvent, PMMA. (Polymethylmethacrylate) Calculated using Mw and Mn measured with a standard sample (converted by Polymer Laboratory). As the GPC column, TSK-GEL GMHHR-M and G1000HHR were used.

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

(Carboxylic acid terminal amount ([COOH]))
In the polyamide compositions obtained in Examples and Comparative Examples, the amount of carboxyl terminus bonded to the polymer terminus was measured by neutralization titration as follows.
4.0 g of the polyamide composition was dissolved in 50 mL of benzyl alcohol, and the obtained solution was titrated with 0.1 N NaOH to determine the carboxyl terminal amount (μe equivalent / g). The end point was determined from the discoloration of the phenolphthalein indicator.

Depending on the measured amino-terminal amount ([NH ₂ ]) and carboxyl-terminal amount ([COOH]), the _{ratio of the total active-terminal amount ([NH 2} ] + [COOH]) and the amino-terminal amount to the total active-terminal 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 moldability and appearance>
The device used was "FN3000" manufactured by Nissei Kogyo Co., Ltd.
The cylinder temperature was set to 290 ° C., the mold temperature was set to 100 ° C., and molding was performed up to 100 shots using the polyamide resin composition under injection molding conditions of 10 seconds for injection and 10 seconds for cooling, and the molded product (ISO test piece). Got
Regarding the moldability, when the mold was released during molding, the ratio of sticking to the mold was evaluated as 10% or less out of 100 shots A, more than 10% 20% or less B, more than 20% 50% or less C, 50%. Super is D.
Further, regarding the appearance of the obtained molded product, the surface gloss value of 60 or more was evaluated as A, 55 or more and 59 or less was evaluated as B, 50 or more and 54 or less was evaluated as C, and the value lower than 50 was evaluated as D.

<Evaluation of flame retardancy>
The measurement was performed using the method of UL94 (standard defined by Under Writer's Laboratories Inc. in the United States). For the test piece (length 127 mm, width 12.7 mm, thickness 1.6 mm), attach the UL test piece mold (mold temperature = 100 ° C) to an injection molding machine (PS40E manufactured by Nissei Kogyo Co., Ltd.). It was produced by molding a polyamide resin composition at a cylinder temperature of 290 ° C. The injection pressure was the complete filling pressure at the time of molding the UL test piece + 2%. The flame retardancy grade conformed to UL94 standard (vertical combustion test).

<Weld strength>
An injection molding machine equipped with a mold so that molten resin flows from both ends in the length direction of a shape having a length of 127 mm, a width of 12.7 mm, and a thickness of 1.6 mm, and a weld is formed in the central part in the length direction. Molding was performed by (PS40E manufactured by Nissei Kogyo Co., Ltd.) to obtain a test piece. A tensile test was carried out by a method conforming to ASTMD638 except that the formed test piece had a chuck distance of 50 mm and a tensile speed of 50 mm / min, and the tensile strength was determined. 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 tensile strength was measured by a method according to ASTMD638. The tensile strength retention rate after water absorption was calculated using the following formula.
Tensile retention rate after water absorption (%) = Tensile strength after water absorption / Tensile strength before water absorption x 100

<Rockwell hardness>
The device used was "FN3000" manufactured by Nissei Kogyo Co., Ltd.
A molded product (ISO test piece) was obtained using the polyamide resin composition under injection molding conditions of setting the cylinder temperature to 290 ° C. and the mold temperature to 100 ° C. for 10 seconds for injection and 10 seconds for cooling. The Rockwell hardness (M scale) was measured using a hardness tester (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 rate 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 x 100

[Example 1]
Polyamide (A-1) and (B-1) from the top feed port provided at the uppermost stream of the extruder using a TEM35 mm twin-screw extruder (set temperature: 280 ° C before, screw rotation speed 300 rpm) manufactured by Toshiba Machinery Co., Ltd. ), (C) Pigment, (D1) Flame Retardant, (D2) Flame Retardant Auxiliary, and (E) Polymer containing α, β unsaturated dicarboxylic acid anhydride as a constituent unit. Then, the (F) filler 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. Then, pelletizing was performed to obtain a polyamide resin composition pellet. The blending amount was (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). ) The flame retardant aid was 2.0% by mass, (E) 3.5% by mass of the polymer containing α, β unsaturated dicarboxylic acid anhydride as a constituent unit, and (F) 55% by mass of the filler.

Further, using the obtained polyamide resin composition, a molded product was manufactured by the above method, and the moldability, appearance, weld strength, Rockwell hardness, and flame retardancy at the time of molding were evaluated. The evaluation results are shown in Table 1 below.

[Example 2]
The same procedure as in Example 1 was carried out except that the blending amounts were changed to 16.2% by mass of (A-1) polyamide and 10.8% by mass of (B-1) polyamide.

[Example 3]
The same procedure as in Example 1 was carried out except that the blending amounts were changed to (A-1) polyamide 16.5% by mass, (B-4) polyamide 11.0% by mass, and (D1) flame retardant 10.0% by mass. bottom.

[Example 4]
The same procedure as in Example 1 was carried out except that the blending amounts were changed to (A-1) polyamide 14.8% by mass and (B-1) polyamide 12.2% by mass.

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

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

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

[Comparative Example 5]
The blending amount was 18.4% by mass of (A-1) polyamide, 12.1% by mass of (B-2) polyamide, and 0% by mass of the polymer containing (E) α, β unsaturated dicarboxylic acid anhydride as a constituent unit. It was carried out in the same manner as in Example 1 except that it was changed to.

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

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

As is clear from the results shown in Table 1, the polyamide composition of the present invention contains 75 mol% or more of isophthalic acid as the dicarboxylic acid unit of (B) semi-aromatic polyamide, so that the Tanδ peak temperature of the polyamide composition is high. became. As a result, the polyamide composition molded products of Examples 1 to 4 had excellent properties of weld strength and Rockwell hardness in addition to flame retardancy. Further, since the weight average molecular weight Mw of the polyamide composition was in the range of 10000 ≦ Mw ≦ 40,000, in addition to the above-mentioned characteristics, the moldability and the appearance were also excellent.

In contrast, Comparative Example 1 did not contain (B) semi-aromatic polyamide, and in Comparative Examples 3, 6 and 7, the dicarboxylic acid unit of (B) semi-aromatic polyamide contained less than 75 mol% of isophthalic acid. Therefore, the molded product of the polyamide composition was insufficient in flame retardancy, weld strength, rockwell hardness, moldability, and appearance.
In Comparative Example 2, (B) the dicarboxylic acid unit of the semi-aromatic polyamide contains 75 mol% or more of isophthalic acid, but (A) does not contain the aliphatic polyamide, so that the appearance, flame retardancy, weld strength, and Rockwell hardness are not contained. Was unbalanced and inadequate. In Comparative Example 4, (B) the dicarboxylic acid unit of the semi-aromatic polyamide contains 75 mol% or more of isophthalic acid, but since the weight average molecular weight Mw is large, the balance between appearance, flame retardancy, weld strength, and Rockwell hardness is balanced. It was bad and inadequate. In Comparative Example 5, (B) the dicarboxylic acid unit of the 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 it does not contain the polymer containing it, the physical property balance of the molded product of the polyamide composition was insufficient.

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

Claims (22)

(A) Aliphatic polyamide composed of diamine and 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 or more and 10 or less carbon atoms.
(C) Pigment,
(D1) Flame Retardant, and (D2) Flame Retardant Aid,
A polyamide composition containing
The tan δ peak temperature of the polyamide composition is 90 ° C. or higher, and the temperature is 90 ° C. or higher.
The weight average molecular weight Mw of the polyamide composition is
Polyamide composition in which 10000 ≦ Mw ≦ 40,000. The polyamide composition according to claim 1, further comprising (E) a polymer containing an 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 with respect to the total amount of polyamide in the polyamide composition 2 The polyamide composition according to claim 1 or 2, which is less than 5.5% by mass. The polyamide composition according to any one of claims 1 to 3, wherein the polyamide composition has a molecular weight distribution Mw / Mn of 2.4 or less. A claim that the ratio of the amino-terminal amount to the total amount of the amino-terminal amount and the 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 4. 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 a polyamide 66. The polyamide composition according to any one of claims 1 to 6, wherein the content of the isophthalic acid in the dicarboxylic acid unit of the semi-aromatic polyamide (B) is 100 mol%. The polyamide composition according to any one of claims 1 to 7, wherein the weight average molecular weight Mw (B) of the semi-aromatic polyamide (B) is 10,000 ≦ Mw ≦ 25,000. The polyamide composition according to any one of claims 1 to 8, 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 Mw / VR of the semi-aromatic polyamide (B) is 1000 or more and 2000 or less. The polyamide composition according to any one of claims 1 to 10, wherein the semi-aromatic polyamide (B) is polyamide 6I. The first item according to any one of claims 1 to 11, wherein the content of the semi-aromatic polyamide (B) is 30% by mass or more and 50% by mass or less with respect to 100% by mass of the total constituent components 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 the end of the semi-aromatic polyamide (B) is sealed with acetic acid. One of claims 1 to 14, wherein the pigment (C) 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 or more and 15% by mass or less with respect to 100% by mass of the polyamide composition, and the (D2) difficulty Any of claims 1 to 16 in which the flame retardant is Sb ₂ O ₃ and _{the content of the 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 item 1. A polyamide resin composition containing a polymer containing (E) α, β-unsaturated dicarboxylic acid anhydride as a constituent unit, and a polymer containing the above-mentioned (E) α, β-unsaturated dicarboxylic acid anhydride as a constituent unit. The polyamide composition according to any one of claims 2 to 17, wherein the polyamide composition is a maleic anhydride-modified polyphenylene ether. The polyamide composition according to any one of claims 1 to 18, wherein the pigment (C) is a white pigment and further contains a filler (F). The polyamide composition according to claim 19, wherein the filler (F) is 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. (E) A polyamide resin composition containing a polymer containing an α, β unsaturated dicarboxylic acid anhydride as a constituent unit, wherein the (C) white pigment, the (D1) flame retardant, and the (D2) flame retardant. The total content of the auxiliary agent, the polymer containing the (E) α, β-unsaturated dicarboxylic acid anhydride as a constituent unit, and the (F) filler is 60% by mass with respect to 100% by mass of the polyamide composition. The polyamide composition according to claim 19 or 20, which is 80% by mass or more. A molded product obtained by molding the polyamide composition according to any one of claims 1 to 21.