JP2018188534A - Polyamide composition and molded article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To stably provide a polyamide composition excellent in mechanical property, in particular, rigidity and surface appearance during water absorption, and a molded product.SOLUTION: A polyamide composition contains (A) crystalline polyamide containing a dicarboxylic acid unit containing at least 75 mol% of an isophthalic acid and a diamine unit containing at least 50 mol% of diamine having 4 to 10 carbon atoms, (B) amorphous semi-aromatic polyamide and (C) polyphenylene ether, where a tanδ peak temperature of the polyamide composition is 90°C or higher, and a weight average molecular weight Mw of the polyamide resin composition is 15,000≤Mw≤35,000. In the polyamide composition, (A) the crystalline polyamide is polyamide 66 or polyamide 610, and (B) the amorphous semi-aromatic polyamide contains 100 mol% of an isophthalic acid in a dicarboxylic acid unit.SELECTED DRAWING: None

Description

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

Polyamides represented by polyamide 6 (hereinafter also referred to as “PA6”) and polyamide 66 (hereinafter also referred to as “PA66”) and the like are excellent in molding processability, mechanical properties, and chemical resistance. Widely used as various parts materials for automobiles, electric and electronic, industrial materials, industrial materials, daily products and household products.
In recent years, the use environment of polyamide has become severer in terms of heat and dynamics, and there is a change in physical properties in use under any environment that has improved mechanical properties, especially rigidity after water absorption and rigidity under high temperature use. Less polyamide material is required.
In addition, a molded body using polyamide may be molded under high cycle molding conditions in which the molding temperature is increased and the mold temperature is lowered in order to improve productivity.

On the other hand, when molding is performed under a high temperature condition, there is a problem that the molded body may not be stably obtained due to degradation of polyamide or change in fluidity.
In particular, there is a demand for polyamides that are excellent in the stability of the molded article surface appearance even under the severe molding conditions described above.

  In order to meet such requirements, a polyamide made of polyamide 66 / 6I into which an isophthalic acid component is introduced is disclosed as a material that can improve the surface appearance and mechanical properties of a molded product (for example, Patent Document 1). . Further, as a material capable of improving mechanical properties, fluidity, surface appearance, and the like, a polyamide composition comprising a terephthalic acid component and a polyamide 6T / 6I into which an isophthalic acid component is introduced has been disclosed (for example, Patent Documents). 2 and 3).

JP-A-6-32980 JP 2000-154316 A JP 11-349806 A

However, although the techniques disclosed in Patent Documents 1 and 3 improve the rigidity under normal use conditions, there is room for improvement in the rigidity after water absorption and the rigidity under high temperature use.
Moreover, although the polyamide manufactured by the manufacturing technique disclosed in Patent Document 2 has improved rigidity after water absorption, rigidity under high temperature use, and surface appearance of a molded product under general molding conditions, Under severe molding conditions such as high cycle molding, there is a problem that the appearance of the surface of the molded product is deteriorated and the stability is lowered.

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

  The present invention has been made in view of the above circumstances, and has mechanical properties, in particular, rigidity during water absorption (hereinafter referred to as water absorption rigidity) and rigidity under high temperature use (hereinafter referred to as heat rigidity). An object of the present invention is to stably provide a polyamide composition and a molded product having excellent fluidity and surface appearance.

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

The polyamide composition of the present invention comprises:
(A) crystalline polyamide,
(B) an amorphous semi-aromatic polyamide, and (C) polyphenylene ether containing a dicarboxylic acid unit containing at least 75 mol% of isophthalic acid and a diamine unit containing at least 50 mol% of a diamine having 4 to 10 carbon atoms A polyamide composition comprising:
The tan δ peak temperature of the polyamide composition is 90 ° C or higher,
The weight average molecular weight Mw of the polyamide composition is 15000 ≦ Mw ≦ 35000.

The total content of the polyamide having a number average molecular weight Mn of 500 or more and 2000 or less is 0. 0 to the total amount of polyamide in the polyamide composition (total of (A) crystalline polyamide and (B) amorphous semi-aromatic polyamide). It is preferable that it is 5 mass% or more and less than 2.5 mass%.
Here, in this invention, the weight average molecular weight Mw and number average molecular weight Mn of a polyamide composition are calculated | required by the measuring method described in the postscript Example.

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

  The ratio of the amino terminal amount to the total amount of amino terminal amount and carboxyl terminal amount {amino terminal amount / (amino terminal amount + carboxyl terminal amount)} is preferably 0.25 or more and less than 0.4.

  (A) The crystalline polyamide is preferably polyamide 66 or polyamide 610.

(B) In the amorphous semi-aromatic polyamide, the content of isophthalic acid in the dicarboxylic acid unit is preferably 100 mol%.
(B) The amorphous semi-aromatic polyamide is preferably polyamide 6I.
(B) The weight average molecular weight Mw of the amorphous semi-aromatic polyamide is preferably 10,000 ≦ Mw ≦ 25000.
(B) The molecular weight distribution Mw / Mn of the amorphous semi-aromatic polyamide is preferably 2.4 or less.

  The difference {Mw (A) -Mw (B)} between the weight average molecular weight Mw (A) of the (A) crystalline polyamide and the weight average molecular weight Mw (B) of the (B) amorphous semi-aromatic polyamide is 2000 or more. Preferably there is.

The polyamide composition of the present invention may further contain a metal phosphite and / or a metal hypophosphite.
The polyamide composition of the present invention may further contain a phosphite compound.

  Further, it may contain a compatibilizer of polyamide ((A) crystalline polyamide and (B) amorphous semi-aromatic polyamide, hereinafter collectively referred to simply as polyamide) and (C) polyphenylene ether.

  Further, the polyamide composition of the present invention further comprises an inorganic filler in an amount of 5 to 250 with respect to a total of 100 parts by mass of (A) crystalline polyamide, (B) amorphous semi-aromatic polyamide and (C) polyphenylene ether. You may contain a mass part.

The molded article of the present invention is formed by molding the polyamide composition of the present invention and has a surface gloss value of 50 or more.
Here, the “surface gloss value” is measured by the method described in Examples described later.

  According to the present invention, it is possible to provide a polyamide composition and a molded article that are excellent in mechanical properties, in particular, water absorption rigidity, thermal rigidity, fluidity, and surface appearance.

  Hereinafter, the present invention will be described in detail.

[Polyamide composition]
The polyamide composition of the present invention contains (A) a crystalline polyamide, a dicarboxylic acid unit containing at least 75 mol% of isophthalic acid, and a diamine unit containing at least 50 mol% of a diamine having 4 to 10 carbon atoms. A polyamide composition containing a crystalline semi-aromatic polyamide and (C) polyphenylene ether, wherein the polyamide composition has a tan δ peak temperature of 90 ° C or higher.

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

((A) crystalline polyamide)
Crystalline polyamide is a polyamide having a heat of fusion of crystal of 4 J / g or more as measured by a differential scanning calorimeter at 20 ° C./min. Although not limited to the following, for example, (a) polyamide obtained by ring-opening polymerization of lactam, (b) polyamide obtained by self-condensation of ω-aminocarboxylic acid, (c) obtained by condensing diamine and dicarboxylic acid. And polyamides thereof, and copolymers thereof. As crystalline polyamide, you may use by 1 type and may be used as a 2 or more types of mixture.

The lactam of (a) is not limited to the following, and examples thereof include pyrrolidone, caprolactam, undecaractam and dodecaractam.
Examples of the ω-aminocarboxylic acid (b) include, but are not limited to, ω-amino fatty acids that are ring-opening compounds of the above lactams with water. As lactam or ω-aminocarboxylic acid, two or more monomers may be used together for condensation.

  The diamine (monomer) of (c) is not limited to the following, but examples thereof include linear aliphatic diamines such as hexamethylene diamine and pentamethylene diamine; 2-methylpentane diamine and 2-ethyl hexamethylene diamine. Branched aliphatic diamines such as: aromatic diamines such as p-phenylenediamine and m-phenylenediamine; and alicyclic diamines such as cyclohexanediamine, cyclopentanediamine and cyclooctanediamine.

The dicarboxylic acid (monomer) of (c) is not limited to the following, but examples thereof include aliphatic dicarboxylic acids such as adipic acid, pimelic acid and sebacic acid; aromatic dicarboxylic acids such as phthalic acid and isophthalic acid; cyclohexane And alicyclic dicarboxylic acids such as dicarboxylic acids. The diamines and dicarboxylic acids as the above-described monomers may be condensed individually by one kind or in combination of two or more kinds.
In addition, (A) crystalline polyamide may further contain the unit derived from polyvalent carboxylic acid more than trivalence, such as trimellitic acid, trimesic acid, and pyromellitic acid, as needed. Only one trivalent or higher polyvalent carboxylic acid may be used alone, or two or more polycarboxylic acids may be used in combination.

Specific examples of the (A) crystalline polyamide used in the polyamide composition of the present invention include polyamide 4 (poly α-pyrrolidone), polyamide 6 (polycaproamide), polyamide 11 (polyundecanamide), polyamide 12 ( Polydodecanamide), polyamide 46 (polytetramethylene adipamide), polyamide 56 (polypentamethylene adipamide), polyamide 66 (polyhexamethylene adipamide), polyamide 610 (polyhexamethylene sebacamide), polyamide 612 (polyhexamethylene dodecamide), polyamide 6T (polyhexamethylene terephthalamide), polyamide 9T (polynonamethylene terephthalamide), and copolymerized polyamides containing these as constituents.
Of these, polyamide 66 (PA66), polyamide 46 (PA46), and polyamide 610 (PA610) are preferable. Since PA66 is excellent in heat resistance, moldability and toughness, it is considered as a material suitable for automobile parts. Further, long-chain aliphatic polyamides such as PA610 are preferred because of their excellent chemical resistance.

((B) amorphous semi-aromatic polyamide)
The (B) amorphous semi-aromatic polyamide used in the present invention contains (Ba) a dicarboxylic acid unit containing at least 75 mol% of isophthalic acid and at least 50 mol% of a diamine having 4 to 10 carbon atoms (B -B) Polyamide containing diamine units.
The total amount of the isophthalic acid unit and the diamine unit having 4 to 10 carbon atoms is preferably 80 to 100 mol% with respect to 100 mol% of all the structural units of the amorphous semi-aromatic polyamide, More preferably, it is 90-100 mol%, and it is further more preferable that it is 100 mol%.
In the present invention, the ratio of the predetermined monomer unit constituting (B) the amorphous semi-aromatic 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 80 to 100 mol%, more preferably 90 to 100 mol%, and even more preferably 100 mol%.
(Ba) Polyamide that satisfies mechanical properties, particularly water absorption rigidity, thermal rigidity, fluidity, surface appearance, etc. at the same time when the proportion of the isophthalic acid unit in the dicarboxylic acid unit is 75 mol% or more. A composition can be obtained.

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

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

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

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

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

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

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

((B-b) diamine unit)
(B) The (b) diamine unit constituting the amorphous semi-aromatic polyamide contains at least 50 mol% of a diamine having 4 to 10 carbon atoms. Examples of diamines other than diamines having 4 to 10 carbon atoms include, but are not limited to, aliphatic diamine units, alicyclic diamine units, and aromatic diamine units.

-Aliphatic diamine unit-
Examples of the aliphatic diamine constituting the aliphatic diamine unit include, but are not limited to, ethylenediamine, propylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, Examples thereof include linear saturated aliphatic diamines having 2 to 20 carbon atoms such as nonamethylene diamine, decamethylene diamine, undecamethylene diamine, dodecamethylene diamine, and tridecamethylene diamine.

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

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

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

  (B) The amorphous semi-aromatic polyamide is preferably polyamide 6I, 9I, or 10I, and most preferably polyamide 6I.

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

  In the present invention, the blending amount of (B) amorphous semi-aromatic polyamide is preferably 5.0% by mass or more and 45.0% by mass or less with respect to 100% by mass of the total resin contained in the polyamide composition. More preferably, it is 10.0 mass% or more and 42.5 mass% or less, More preferably, it is 15.0 mass% or more and 40.0 mass% or less, More preferably, it is 20.0 mass% or more and 37.5 mass% %, Particularly preferably 22.5% by mass or more and 35.0% by mass or less, and most preferably 22.5% by mass or more and 30.0% by mass or less. (B) By making the compounding quantity of an amorphous semi-aromatic polyamide into the said range, the polyamide composition excellent in mechanical properties, especially water-absorbing rigidity, thermal rigidity, fluidity, etc. is obtained. Moreover, the polyamide composition containing a component typified by an inorganic filler has excellent surface appearance.

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

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

The monocarboxylic acid that can be used as the end-capping agent is not limited to the following as long as it has reactivity with an amino group that may be present at the end of the polyamide. For example, formic acid, acetic acid, Aliphatic monocarboxylic acids such as propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecylic acid, myristic acid, palmitic acid, stearic acid, pivalic acid, and isobutyric acid; alicyclic rings such as cyclohexanecarboxylic acid And aromatic monocarboxylic acids such as benzoic acid, toluic acid, α-naphthalenecarboxylic acid, β-naphthalenecarboxylic acid, methylnaphthalenecarboxylic acid, and phenylacetic acid.
A monocarboxylic acid may be used individually by 1 type, and may be used in combination of 2 or more type.

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

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

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

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

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

Hereinafter, as a method for producing polyamide, a method for producing polyamide by a batch-type hot melt polymerization method will be specifically described, but the method for producing polyamide is not limited thereto.
First, for example, an aqueous solution containing about 40 to 60% by mass of a raw material component of polyamide (dicarboxylic acid, diamine, and, if necessary, lactam and / or aminocarboxylic acid) is heated at a temperature of 110 to 180 ° C. and about In a concentration tank operated at a pressure of 0.035 to 0.6 MPa (gauge pressure), the solution is concentrated to about 65 to 90% by mass to obtain a concentrated solution.
Next, the obtained concentrated solution is transferred to an autoclave, and heating is continued until the pressure in the autoclave becomes about 1.2 to 2.2 MPa (gauge pressure).
Thereafter, in the autoclave, the pressure is maintained at about 1.2 to 2.2 MPa (gauge pressure) while removing water and / or gas components, and when the temperature reaches about 220 to 260 ° C., the pressure is reduced to atmospheric pressure ( Gauge pressure is 0 MPa).
By reducing the pressure in the autoclave to atmospheric pressure and then reducing the pressure as necessary, by-product water can be effectively removed.
Thereafter, the autoclave is pressurized with an inert gas such as nitrogen, and the polyamide melt is extruded from the autoclave as a strand. The extruded strand is cooled and cut to obtain polyamide pellets.

(Polyamide polymer end)
Although it does not specifically limit as a polymer terminal of the polyamide used for this invention, It can classify | categorize and define as follows.
That is, 1) amino terminal, 2) carboxyl terminal, 3) terminal by a sealant, and 4) other terminal.
1) The amino terminus is a polymer terminus having an amino group (—NH ₂ group) and is derived from the diamine unit of the raw material.
2) The carboxyl terminal is a polymer terminal having a carboxyl group (—COOH group) and is derived from the raw material dicarboxylic acid.
3) The terminal by a sealing agent is a terminal formed when a sealing agent is added at the time of superposition | polymerization. Examples of the sealing agent include the above-described end sealing agents.
4) The other terminal is a polymer terminal that is not classified in the above 1) to 3), such as a terminal generated by deammonia reaction at the amino terminal or a terminal generated by decarboxylation from the carboxyl terminal. .

((A) Characteristics of crystalline polyamide)
(A) The molecular weight, melting point Tm2, crystallization enthalpy ΔH, and tan δ peak temperature of the crystalline polyamide can be specifically measured by the method described in Examples described later.
(A) As an index of the molecular weight of the crystalline polyamide, the weight average molecular weight Mw (A) can be used. The weight average molecular weight Mw (A) of the crystalline polyamide is preferably 10000 to 50000, more preferably 15000 to 45000, further preferably 20000 to 40000, and still more preferably 25000 to 35000.

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

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

  (A) As a method for controlling the Mw (A) / Mn (A) of the crystalline polyamide within the above range, for example, phosphoric acid or sodium hypophosphite as an additive at the time of hot melt polymerization of polyamide Examples thereof include a method of adding a known polycondensation catalyst, and a method of controlling polymerization conditions such as heating conditions and reduced pressure conditions.

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

(A) Melting | fusing point Tm2 of crystalline polyamide becomes like this. Preferably it is 220 degreeC or more, More preferably, it is 230 degreeC or more, More preferably, it is 240 degreeC or more.
The melting point Tm2 of the (A) crystalline polyamide is preferably 300 ° C. or lower, more preferably 290 ° C. or lower, further preferably 280 ° C. or lower, and still more preferably 270 ° C. or lower.
(A) When the melting point Tm2 of the crystalline polyamide is 220 ° C. or higher, it tends to be possible to obtain a polyamide composition that is superior in thermal rigidity and the like.
Moreover, when (A) crystalline polyamide has a melting point Tm2 of 300 ° C. or less, thermal decomposition of the polyamide composition in melt processing such as extrusion and molding tends to be further suppressed.

(A) The crystallization enthalpy ΔH of the crystalline polyamide is preferably 4 J / g or more, more preferably 20 J / g or more, and further preferably from the viewpoint of mechanical properties, particularly water absorption rigidity and thermal rigidity. It is 30 J / g or more, more preferably 40 J / g or more, particularly preferably 50 J / g or more, and most preferably 60 J / g or more. Moreover, the upper limit of the crystallization enthalpy ΔH is not particularly limited and is preferably as high as possible.
(A) Examples of the measuring device for the melting point Tm2 and crystallization enthalpy ΔH of crystalline polyamide include Diamond-DSC manufactured by PERKIN-ELMER.

(A) The tan δ peak temperature of the crystalline polyamide is preferably 40 ° C or higher, more preferably 50 to 110 ° C, still more preferably 60 to 100 ° C, and even more preferably 70 to 95 ° C. More preferably, it is 80-90 degreeC. (A) When the tan δ peak temperature of the crystalline polyamide is 40 ° C. or higher, a polyamide composition excellent in water absorption rigidity and thermal rigidity tends to be obtained.
(A) The tan δ peak temperature of the crystalline polyamide can be measured by using, for example, a viscoelasticity measuring / analyzing apparatus (manufactured by Rheology: DVE-V4) as described in the following examples.

((B) Characteristics of amorphous semi-aromatic polyamide)
(B) The molecular weight, melting point Tm2, crystallization enthalpy ΔH, and tan δ peak temperature of the amorphous semi-aromatic polyamide can be specifically measured by the method described in the examples described later.
(B) As an index of the molecular weight of the amorphous semi-aromatic polyamide, the weight average molecular weight Mw (B) can be used. (B) The weight average molecular weight Mw (B) of the amorphous semi-aromatic polyamide is preferably 10,000 to 25000, more preferably 13,000 to 24000, still more preferably 15000 to 23000, and still more preferably 18000. It is -22000, Most preferably, it is 19000-21000.

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

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

(B) As a method of controlling the Mw (B) / Mn (B) of the amorphous semi-aromatic polyamide within the above range, for example, phosphoric acid or hypophosphorous acid as an additive at the time of hot melt polymerization of polyamide A method of adding a known polycondensation catalyst such as sodium can be mentioned. In addition, polymerization conditions such as heating conditions and reduced pressure conditions are controlled to complete the polycondensation reaction at as low a temperature as possible and in a short time. In particular, since (B) amorphous semi-aromatic polyamide does not have a melting point, it is preferable to control the Mw (B) / Mn (B) within the above range by lowering the reaction temperature.
When the aromatic compound unit is contained in the molecular structure of the polyamide, the molecular weight distribution (Mw (B) / Mn (B)) tends to increase as the molecular weight increases. When the molecular weight distribution is within the above range, the proportion of polyamide molecules having a three-dimensional structure of the molecule can be reduced, and the three-dimensional structure of the molecule can be suitably prevented during high temperature processing, and the fluidity is improved. By being able to keep, the surface appearance of the polyamide composition containing the component represented by the inorganic filler can be improved.

  In the present invention, the weight average molecular weight Mw (B) / number average molecular weight Mn (B) of (B) amorphous semi-aromatic polyamide is measured by GPC (gel permeation chromatography) as described in the following examples. ) Using the weight average molecular weight Mw (weight average molecular weight) and the number average molecular weight Mn (B) obtained using

(B) The crystallization enthalpy ΔH of the amorphous semi-aromatic polyamide is preferably less than 4 J / g, more preferably 2 J / g or less, from the viewpoints of mechanical properties, particularly water absorption rigidity and thermal rigidity. More preferably, it is 0 J / g.
(B) As a method of controlling the crystallization enthalpy ΔH of the amorphous semi-aromatic polyamide within the above range, increasing the ratio of the aromatic monomer to the dicarboxylic acid unit can be mentioned. It is important to contain 75 mol% or more of isophthalic acid as a dicarboxylic acid unit, and it is more preferable to contain 100 mol%.
(B) As an apparatus for measuring the crystallization enthalpy ΔH of amorphous semi-aromatic polyamide, for example, Diamond-DSC manufactured by PERKIN-ELMER may be used.

(B) The tan δ peak temperature of the amorphous semi-aromatic polyamide is preferably 90 ° C or higher, more preferably 100 to 160 ° C, still more preferably 110 to 150 ° C, and even more preferably 120 to 120 ° C. It is 145 degreeC, More preferably, it is 130-140 degreeC.
(B) As a method for controlling the tan δ peak temperature of the amorphous semi-aromatic polyamide within the above range, increasing the ratio of the aromatic monomer to the dicarboxylic acid unit can be mentioned. The dicarboxylic acid unit preferably contains 75% by mole or more of isophthalic acid, more preferably 100% by mole.
(B) When the tan δ peak temperature of the amorphous semi-aromatic polyamide is 90 ° C. or higher, a polyamide composition excellent in water absorption rigidity and thermal rigidity tends to be obtained. Moreover, when the tan δ peak temperature of the polyamide composition is 160 ° C. or less, the polyamide composition containing a component typified by an inorganic filler has an excellent surface appearance.
(B) The tan δ peak temperature of the amorphous semi-aromatic polyamide can be measured by using, for example, a viscoelasticity analyzer and the like (Rheology: DVE-V4) as described in the following examples.

  The amount of the amino terminal of the (B) amorphous semi-aromatic polyamide is preferably 5 to 100 μequivalent / g, more preferably 10 to 90 μequivalent / g, and still more preferably 20 to 1 g of polyamide. It is -80 microequivalent / g, More preferably, it is 30-70 microequivalent / g, More preferably, it is 40-60 microequivalent / g. When the amount of the amino terminal is in the above range, a composition excellent in discoloration to heat and light can be obtained. The amount of the amino terminus can be measured by neutralization titration.

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

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

((C) polyphenylene ether)
The (C) polyphenylene ether contained in the polyamide composition of the present invention is a homopolymer and / or copolymer having a repeating structural unit represented by the following general formula (1).
General formula (1):
Here, in general formula (1), O is an oxygen atom, R ¹ , R ² , R ³ and R ⁴ are each independently hydrogen, halogen, a primary or secondary C1-C7 alkyl group, A phenyl group, a C1-C7 haloalkyl group, a C1-C7 aminoalkyl group, a C1-C7 hydrocarbyloxy group, or a halohydrocarbyloxy group (provided that at least two carbon atoms separate the halogen and oxygen atoms) ).

  Specific examples of (C) polyphenylene ether include, for example, poly (2,6-dimethyl-1,4-phenylene ether), poly (2-methyl-6-ethyl-1,4-phenylene ether), poly (2-methyl-6-phenyl-1,4-phenylene ether), poly (2,6-dichloro-1,4-phenylene ether), and further between 2,6-dimethylphenol and other phenols. Polyphenylene such as a copolymer (for example, a copolymer with 2,3,6-trimethylphenol or a copolymer with 2-methyl-6-butylphenol as described in JP-B-52-17880) Also included are ether copolymers.

  Among these, particularly preferred polyphenylene ethers include poly (2,6-dimethyl-1,4-phenylene ether), 2,6-dimethyl-1,4-phenol and 2,3,6-trimethyl-1,4- It is a copolymer with phenol, or a mixture thereof.

  Further, when the copolymer of 2,6-dimethyl-1,4-phenol and 2,3,6-trimethyl-1,4-phenol is 100% by mass based on the total amount of the polyphenylene ether copolymer, A copolymer containing 10 to 30% by mass of 2,3,6-trimethyl-1,4-phenol is preferable, more preferably 15 to 25% by mass, and still more preferably 20 to 25% by mass.

(C) The polyphenylene ether is preferably a polyphenylene ether modified with an α, β unsaturated dicarboxylic acid anhydride from the viewpoint of compatibility with the polyamide.
Examples of the α, β unsaturated dicarboxylic acid anhydride include compounds represented by the following general formula (2).
General formula (2):
In General formula (2), R < ¹ > and R < ² > are respectively independently hydrogen or a C1-C3 alkyl group.
Examples of the α, β unsaturated dicarboxylic acid anhydride include maleic anhydride and methyl maleic anhydride, and maleic anhydride is preferable.

The content of the α, β unsaturated dicarboxylic anhydride component in (C) polyphenylene ether is preferably 0.1 to 50% by mass, more preferably 0.2 to 100% by mass of (C) polyphenylene ether. -20% by mass, more preferably 0.3-5% by mass, particularly preferably 0.3-1% by mass, and most preferably 0.3-0.8% by mass.
By setting the content of the α, β-unsaturated dicarboxylic acid anhydride component to 0.1% by mass or more, it is possible to obtain a polyamide composition having improved compatibility with polyamide and excellent mechanical properties such as toughness and rigidity. . Further, by setting the proportion of the α, β unsaturated dicarboxylic acid anhydride component to 50% by mass or less, the deterioration of the polyamide composition due to the α, β unsaturated dicarboxylic acid anhydride can be prevented.

One of the characteristics of polyphenylene ether is that it is a polyphenylene ether having a low molecular weight, a narrow molecular weight distribution, and a small amount of oligomer.
The (C) polyphenylene ether contained in the polyamide composition of the present invention contains 60% by mass or more, more preferably 65% by mass or more, of a component having a molecular weight of 30000 or less in the polyphenylene ether. When the amount of the component having a molecular weight of 30000 or less is 60% by mass or more, the thin wall fluidity in the mold is excellent. In addition, from the viewpoint of maintaining the toughness of the molded article when it is used as a molded article such as a connector, the preferable upper limit of the component amount having a molecular weight of 30000 or less is 95% by mass, and the more preferable upper limit is 85% by mass, A more preferred upper limit is 80% by mass.

  The amount of a component having a molecular weight of 30,000 or less of polyphenylene ether generally used so far is about 40% by mass with a generally used molecular weight, and about 50% by mass even with what is called a low molecular weight type. . The polyphenylene ether used in the present invention is a low molecular weight type polyphenylene ether further lower than these.

  (C) It is preferable that content of the component of molecular weight 3000 or less of polyphenylene ether is 5 mass% or less, More preferably, it is 4.5 mass% or less, More preferably, it is 4 mass% or less. When the content of the component having a molecular weight of 3000 or less is 5% by mass or less, a change in the color of the molded body during heat exposure is suppressed.

  The number average molecular weight of the (C) polyphenylene ether contained in the polyamide composition of the present invention is not particularly limited. A preferable lower limit is 7000, a more preferable lower limit is 9000, and a more preferable lower limit is 10,000. . Moreover, the preferable upper limit of the number average molecular weight is 15000, the more preferable upper limit is 14000, and the more preferable upper limit is 13000. In order to further suppress the color change of the molded article after heat exposure, the lower limit value of the number average molecular weight is preferably 7000 or more, and in order to further improve the thin wall fluidity in the mold, the upper limit of the number average molecular weight The value is preferably 15000 or less.

  Further, the dispersion ratio of the polyphenylene ether, that is, the ratio of the weight average molecular weight to the number average molecular weight (Mw / Mn) is not particularly limited, and a preferable upper limit is 2.50, and a more preferable upper limit is 2.40. A preferred lower limit is 2.00, and a more preferred lower limit is 2.10. When the dispersion ratio is 2.50 or less, the molecular weight distribution is narrow, indicating that a decrease in the oligomer component, which is a low molecular weight component, or a decrease in the high molecular weight component occurs. In order to reduce the color change of the molded piece after heat exposure, it is preferable to reduce the low molecular weight component.

The polyphenylene ether production methods are roughly divided into two production methods: precipitation polymerization method and solution polymerization method.
The precipitation polymerization method means a polymerization form in which precipitation of polyphenylene ether is obtained in the above concentration range. Specifically, in this polymerization form, as the polymerization of polyphenylene ether proceeds, a sufficiently polymerized one is deposited, and a polymer that is not sufficiently polymerized is dissolved. As the solvent, a mixed solvent of a good solvent of polyphenylene ether such as toluene, xylene and ethylbenzene and a poor solvent of polyphenylene ether such as methanol and butanol is used.

The precipitated polyphenylene ether is considered to be a solid-liquid reaction because the movement of the molecular chain is suppressed and the catalyst is dissolved in the mixed solvent, and the reaction rate of further polymerization is slowed down.
On the other hand, a polyphenylene ether that is in a dissolved state and has not yet been sufficiently polymerized has a polymerization reaction rate maintained, and precipitates when polymerization proceeds and reaches a sufficiently high molecular weight for precipitation. . As a result, the molecular weight distribution of the polyphenylene ether becomes narrower.

  In addition, in the polymerization form as described above, if a particle having a small particle size is precipitated, the surface area is increased in the solid-liquid reaction, so that the reaction is considered to be faster than that having a large particle size. Furthermore, since polyphenylene ether precipitates during the polymerization, the viscosity in the system gradually decreases, the monomer concentration (phenol compound concentration) during polymerization can be increased, and further, the precipitated polyphenylene ether can be filtered. It has an advantage that it can be easily taken out and can be extremely simplified in the process.

  The solution polymerization method is a polymerization method in which polymerization is performed in a good solvent of polyphenylene ether, and no precipitate is deposited during the polymerization. In the solution polymerization method, polyphenylene ether molecules are in a dissolved state, and the molecular weight distribution tends to be broadened. In the solution polymerization method, a powdered polyphenylene ether can be obtained by developing a polymer solution in which polyphenylene ether is dissolved in a poor solvent of polyphenylene ether such as methanol.

  The polymerization method of polyphenylene ether is not particularly limited, but is preferably a precipitation polymerization method. The precipitation polymerization method is suitable for the production of a low molecular weight polyphenylene ether having a narrow molecular weight distribution. The amount of a component having a molecular weight of 30000 or less is 60% by mass or more and the amount of a component having a molecular weight of 3000 or less is 5% by mass or less. Ether can be obtained.

  The intrinsic viscosity (chloroform solution, measured at 30 ° C.) of the (C) polyphenylene ether contained in the polyamide composition of the present invention is not particularly limited, and is preferably in the range of 0.15 to 0.40 dL / g. The range is more preferably 0.20 to 0.35 dL / g, still more preferably 0.25 to 0.35 dL / g, and particularly preferably 0.25 to 0.30 dL / g.

  In the present invention, a mixture obtained by blending two or more polyphenylene ethers having different intrinsic viscosities may be used. Examples of such a mixture include, but are not limited to, a mixture of polyphenylene ether having an intrinsic viscosity of 0.40 dL / g or less and polyphenylene ether having an intrinsic viscosity of 0.45 dL / g or more. Even in this case, it is more preferable that the intrinsic viscosity of the mixture falls within the range of the above-described preferred intrinsic viscosity because a desired effect is easily exhibited.

  In the present invention, the blending amount of (C) polyphenylene ether is preferably 0.5 to 30.0% by mass, more preferably 1 to 100% by mass with respect to 100% by mass of the total resin contained in the polyamide composition. 0% by mass or more and 15.0% by mass or less, more preferably 2.0% by mass or more and 10.0% by mass or less, and still more preferably 3.0% by mass or more and 8.0% by mass or less. Most preferably, it is 3.0 mass% or more and 6.0 mass% or less. (C) By making the compounding quantity of polyphenylene ether into the said range, the polyamide composition excellent in mechanical properties, especially water absorption rigidity, thermal rigidity, fluidity, etc. is obtained. Moreover, the polyamide composition containing a component typified by an inorganic filler has excellent surface appearance.

  In the present invention, a compatibilizing agent may be included for the purpose of enhancing the compatibility between polyamide and polyphenylene ether. Although it does not specifically limit as a compatibilizing agent which can be used in this invention, At least 1 or more types chosen from a citric acid, maleic acid, itaconic acid, and these anhydrides is used from the viewpoint of the handleability and economical efficiency. It is preferable. Among these, maleic acid or its anhydride is more preferable. Since maleic acid or its anhydride can be compatibilized with polyamide and polyphenylene ether in a relatively small amount, it is possible to suppress the color change of the molded piece.

  The content of the compatibilizing agent is preferably 0.05 parts by mass or more and 5 parts by mass or less, more preferably 0.1 parts by mass or more and 3 parts by mass or less with respect to 100 parts by mass of the total resin contained in the polyamide composition. Yes, and more preferably 0.2 parts by mass or more and 2 parts by mass or less. By setting the content of the compatibilizer to 0.05 parts by mass or more, the compatibility with the polyamide is increased, and a polyamide composition having excellent impact resistance can be obtained. Moreover, it can be set as the polyamide composition excellent in fluidity | liquidity by making content of a compatibilizing agent into 5 mass parts or less.

The polyamide composition of the present invention further comprises a polymer containing an α, β unsaturated dicarboxylic acid anhydride, so that the compatibility between the polyamide and the polyphenylene ether is enhanced, and the polyamide composition is further excellent in mechanical properties such as toughness and rigidity. It can be a thing.
Examples of the polymer containing an α, β unsaturated dicarboxylic acid anhydride used in the present invention include a polymer containing an α, β unsaturated dicarboxylic acid anhydride as a copolymerization component and an α, β unsaturated dicarboxylic acid anhydride. And a polymer modified with 1.
The polymer containing α, β unsaturated dicarboxylic acid anhydride as a copolymerization component includes (B) an aromatic vinyl compound and α, β unsaturated dicarboxylic acid from the viewpoint of enhancing compatibility with the amorphous semi-aromatic polyamide. A copolymer with an acid anhydride is preferred.
As an aromatic vinyl compound used in this invention, the compound represented by following General formula (3) is mentioned, for example.
General formula (3):
In general formula (3), ^{R 3} and ^{R 4} are each independently hydrogen or an alkyl group having 1 to 3 carbon atoms, k is an integer of 1 to 5.
Examples of the aromatic vinyl compound include styrene, α-methylstyrene, p-methylstyrene, and the like, and styrene is preferable.

The proportion of the α, β unsaturated dicarboxylic acid anhydride component in the copolymer of the aromatic vinyl compound and the α, β unsaturated dicarboxylic acid anhydride is determined from the polyamide composition in terms of toughness, fluidity, thermal decomposition resistance, etc. Preferably it is 0.1-50 mass% with respect to 100 mass% of things, More preferably, it is 5-20 mass%, More preferably, it is 8-15 mass%.
By setting the ratio of the α, β unsaturated dicarboxylic acid anhydride component to 0.1% by mass or more, a polyamide composition having excellent mechanical properties such as toughness and rigidity can be obtained. Further, by setting the proportion of the α, β unsaturated dicarboxylic acid anhydride component to 50% by mass or less, the deterioration of the polyamide composition due to the α, β unsaturated dicarboxylic acid anhydride can be prevented.
As the polymer modified with an α, β unsaturated dicarboxylic acid anhydride, a polypropylene resin modified with an α, β unsaturated dicarboxylic acid anhydride is preferable.
The content of the polymer containing α, β unsaturated dicarboxylic acid anhydride is preferably 0.1 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the total resin contained in the polyamide composition.

  The polyamide composition of the present invention comprises an inorganic filler, a nucleating agent, a lubricant and a stabilizer in addition to the above-mentioned (A) crystalline polyamide, (B) amorphous semi-aromatic polyamide, and (C) polyphenylene ether. 1 or more components selected from the group consisting of polymers other than (A), (B) and (C), metal phosphite and / or metal hypophosphite, and phosphite compounds But you can.

(Inorganic filler)
Examples of the inorganic filler include, but are not limited to, glass fiber, carbon fiber, calcium silicate fiber, potassium titanate fiber, aluminum borate fiber, clay, flaky glass, talc, kaolin, mica , Hydrotalcite, calcium carbonate, magnesium carbonate, zinc carbonate, zinc oxide, calcium monohydrogen phosphate, wollastonite, silica, zeolite, alumina, boehmite, aluminum hydroxide, titanium oxide, silicon oxide, magnesium oxide, silicic acid Calcium, sodium aluminosilicate, magnesium silicate, ketjen black, acetylene black, furnace black, carbon nanotube, graphite, brass, copper, silver, aluminum, nickel, iron, calcium fluoride, montmorillonite, swelling Tsu-containing mica and apatite, and the like.

  Among them, from the viewpoint of further improving the mechanical strength, from the group consisting of glass fiber, carbon fiber, wollastonite, kaolin, mica, talc, calcium carbonate, magnesium carbonate, potassium titanate fiber, aluminum borate fiber and clay One or more selected are preferred. Among these, one or more selected from the group consisting of glass fiber, carbon fiber, wollastonite, kaolin, mica, talc, calcium carbonate, and clay is more preferable.

The number average fiber diameter of the glass fiber or carbon fiber is preferably 3 to 30 μm, more preferably 3 to 20 μm, further preferably 3 to 12 μm, and more preferably 3 to 9 μm from the viewpoint of improving toughness and the surface appearance of the molded product. Even more preferred is 4-6 μm.
By setting the number average fiber diameter of the glass fiber or carbon fiber to 30 μm or less, it is possible to obtain a polyamide composition excellent in toughness and the surface appearance of a molded product. On the other hand, when the thickness is 3 μm or more, a polyamide composition having an excellent balance between cost and powder handling surface and physical properties (fluidity) can be obtained. Furthermore, by setting it as 3-9 micrometers, it can be set as the polyamide composition excellent in vibration fatigue characteristics and slidability.

  The cross section of the glass fiber or carbon fiber may be a perfect circle or a flat shape. Examples of such a flat cross section include, but are not limited to, a rectangular shape, an oval shape close to a rectangular shape, an elliptical shape, and a saddle shape with a narrowed central portion in the longitudinal direction. Here, the “flattening ratio” in this specification refers to a value represented by D2 / D1, where D2 is the major axis of the fiber cross section and D1 is the minor axis of the fiber cross section (a perfect circle is a flat shape). The rate is about 1.)

  Among 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 length from the viewpoint of imparting excellent mechanical strength to the polyamide composition. Those having an aspect ratio (L / D) of 10 to 100 between (L) and the number average fiber diameter (D) can be suitably used.

  Further, from the viewpoint of reducing the warpage of the plate-shaped molded article and improving the heat resistance, toughness, low water absorption and heat aging resistance, the flatness is preferably 1.5 or more, more preferably 1.5 to 10. 0.0, more preferably 2.5 to 10.0, and even more preferably 3.1 to 6.0. When the flatness is within the above range, it is preferable that crushing can be effectively prevented during the mixing, kneading, molding, and other processing with other components, and a desired effect can be sufficiently obtained for the molded product.

  The thickness of the glass fiber or carbon fiber having an aspect ratio of 1.5 or more is not limited to the following, but the minor axis D1 of the fiber cross section is 0.5 to 25 μm and the major axis D2 of the fiber cross section is 1.25 to 250 μm. It is preferable that Within the above range, the difficulty of spinning fibers can be effectively avoided, and the strength of the molded product can be improved without reducing the contact area with the resin (polyamide). The short diameter D1 is more preferably 3 to 25 μm, and the flatness is preferably larger than 3.

  These glass fibers and carbon fibers having an aspect ratio of 1.5 or more are obtained by using the methods described in, for example, Japanese Patent Publication No. 3-59019, Japanese Patent Publication No. 4-13300, Japanese Patent Publication No. 4-32775, and the like. Can be manufactured. In particular, in an orifice plate having a large number of orifices on the bottom surface, an orifice plate that surrounds a plurality of orifice outlets and has a convex edge extending downward from the bottom surface, or an outer peripheral tip of a nozzle tip having one or more orifice holes A glass fiber having a flatness ratio of 1.5 or more produced by using any one of the nozzle chips for spinning a modified cross-section glass fiber provided with a plurality of convex edges extending downward from the glass fiber is preferred. In these fibrous reinforcing materials, fiber strands may be used as rovings as they are, or a cutting step may be obtained and used as chopped glass strands.

  Here, the number average fiber diameter and the weight average fiber length in the present specification are values obtained by the following method. The polyamide composition is put in an electric furnace and the contained organic substances are incinerated. From the residue after the treatment, 100 or more glass fibers (or carbon fibers) are arbitrarily selected and observed with a scanning electron microscope (SEM) to measure the fiber diameter of these glass fibers (or carbon fibers). To obtain the number average fiber diameter. In addition, the weight average fiber length is obtained by measuring the fiber length using the SEM photograph of the 100 or more glass fibers (or carbon fibers) taken at a magnification of 1,000 times.

  The glass fiber or carbon fiber may be subjected to a surface treatment with a silane coupling agent or the like. Examples of the silane coupling agent include, but are not limited to, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, and N-β- (aminoethyl) -γ-aminopropylmethyldimethoxy. Examples include aminosilanes such as silane, mercaptosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane, epoxy silanes, and vinyl silanes. Among these, one or more selected from the group consisting of the above-mentioned components is preferable, and aminosilanes are more preferable.

  In addition, for the above glass fiber and carbon fiber, as a sizing agent, a carboxylic acid anhydride-containing unsaturated vinyl monomer and an unsaturated vinyl monomer excluding the carboxylic acid anhydride-containing unsaturated vinyl monomer are used. Copolymers, epoxy compounds, polyurethane resins, acrylic acid homopolymers, copolymers of acrylic acid with other copolymerizable monomers, and their primary, secondary and tertiary amines A salt and a copolymer containing an unsaturated vinyl monomer containing a carboxylic acid anhydride and an unsaturated vinyl monomer excluding the unsaturated vinyl monomer containing a carboxylic acid anhydride may be included. These may be used alone or in combination of two or more.

  Among them, from the viewpoint of the mechanical strength of the resulting polyamide composition, as a sizing agent, unsaturated vinyl monomer excluding unsaturated vinyl monomer containing carboxylic acid anhydride and unsaturated vinyl monomer containing carboxylic acid anhydride A copolymer containing a polymer as a constituent unit, an epoxy compound, a polyurethane resin, and a combination thereof are preferable. More preferably, a copolymer containing a carboxylic acid anhydride-containing unsaturated vinyl monomer and an unsaturated vinyl monomer excluding the carboxylic acid anhydride-containing unsaturated vinyl monomer as constituent units, and a polyurethane resin, and It is a combination of these.

Glass fiber and carbon fiber are continuously produced by drying the fiber strand produced by applying the sizing agent to the fiber using a known method such as a roller-type applicator in the known fiber production process. Obtained by reaction.
The fiber strand may be used as it is as roving, or may be used as a chopped glass strand after further obtaining a cutting step.
The sizing agent preferably imparts (adds) an equivalent of 0.2 to 3% by mass, more preferably an equivalent of 0.3 to 2% by mass, based on 100% by mass of glass fiber or carbon fiber. (Added. That is, from the viewpoint of maintaining the fiber bundling, the addition amount of the bundling agent is preferably 0.2% by mass or more as a solid content with respect to 100% by mass of the glass fiber or the carbon fiber. On the other hand, from the viewpoint of improving the thermal stability of the resulting polyamide composition, the amount of sizing agent added is preferably 3% by mass or less. The strand may be dried after the cutting step, or may be cut after the strand is dried.

  Inorganic fillers other than glass fibers and carbon fibers are not limited to the following from the viewpoint of improving the strength, rigidity and surface appearance of the molded product, for example, wollastonite, kaolin, mica, talc, Calcium carbonate, magnesium carbonate, potassium titanate fiber, aluminum borate fiber, and clay are preferred. More preferably wollastonite, kaolin, mica, talc, calcium carbonate and clay, more preferably wollastonite, kaolin, mica, talc, even more preferably wollastonite, mica, especially Wollastonite is preferable. These inorganic fillers may be used individually by 1 type, and may be used in combination of 2 or more type.

  The average particle diameter of the inorganic filler other than glass fibers and carbon fibers is preferably 0.01 to 38 μm, more preferably 0.03 to 30 μm, from the viewpoint of improving the toughness and the surface appearance of the molded product. ˜25 μm is more preferable, 0.10 to 20 μm is still more preferable, and 0.15 to 15 μm is particularly preferable.

  By setting the average particle size of the inorganic filler other than the glass fiber and the carbon fiber to 38 μm or less, a polyamide composition excellent in toughness and the surface appearance of the molded product can be obtained. On the other hand, when the thickness is 0.1 μm or more, a polyamide composition having an excellent balance between cost and powder handling surface and physical properties (fluidity, etc.) can be obtained.

  Here, among inorganic fillers, those having a needle-like shape such as wollastonite have a number average fiber diameter (hereinafter, also simply referred to as “average fiber diameter”) as an average particle diameter. When the cross section is not a circle, the maximum value of the length is defined as the (number average) fiber diameter.

  About the weight average fiber length (hereinafter, also simply referred to as “average fiber length”) of the above-mentioned needle-like shape, the preferred range of the above-mentioned number average fiber diameter, and the following weight average fiber length (L) A numerical range calculated from a preferable range of the aspect ratio (L / D) with the number average fiber diameter (D) is preferable.

  Regarding the aspect ratio (L / D) of the weight average fiber length (L) and the number average fiber diameter (D) of the needle-shaped one, the surface appearance of the molded product is improved, and the metal such as an injection molding machine From the viewpoint of preventing wear of the sexual parts, 1.5 to 10 is preferable, 2.0 to 5 is more preferable, and 2.5 to 4 is more preferable.

  Further, the inorganic filler other than glass fiber and carbon fiber may be subjected to surface treatment using a silane coupling agent, a titanate coupling agent, or the like. Examples of the silane coupling agent include, but are not limited to, aminosilanes such as γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, and N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane. , Mercaptosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane, epoxy silanes, and vinyl silanes. Among these, one or more selected from the components listed above are preferable, and aminosilanes are more preferable. Such a surface treating agent may be previously treated on the surface of the inorganic filler, or may be added when the polyamide and the inorganic filler are mixed. Moreover, the addition amount of the surface treatment agent is preferably 0.05 to 1.5% by mass with respect to 100% by mass of the inorganic filler.

  The content of the inorganic filler is preferably 5 to 250 parts by mass with respect to 100 parts by mass in total of (A) crystalline polyamide, (B) amorphous semi-aromatic polyamide and (C) polyphenylene ether. More preferably, it is 30-250 mass parts, More preferably, it is 50-240 mass parts, More preferably, it is 50-200 mass parts, Most preferably, it is 50-150 mass parts.

  Obtained by setting the content of the inorganic filler to 5 parts by mass or more with respect to a total of 100 parts by mass of (A) crystalline polyamide, (B) amorphous semi-aromatic polyamide, and (C) polyphenylene ether. The effect which improves the intensity | strength and rigidity of the polyamide composition obtained is expressed. On the other hand, by setting the content of the inorganic filler to 250 parts by mass or less, a polyamide composition excellent in extrudability and moldability can be obtained.

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

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

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

(lubricant)
Examples of the lubricant include, but are not limited to, higher fatty acids, higher fatty acid metal salts, higher fatty acid esters, and higher fatty acid amides.
One type of lubricant may be used alone, or two or more types may be used in combination.

Examples of higher fatty acids include, for example, stearic acid, palmitic acid, behenic acid, erucic acid, oleic acid, lauric acid, and montanic acid, which are saturated or unsaturated, linear or branched aliphatic having 8 to 40 carbon atoms. Examples thereof include monocarboxylic acids, and stearic acid and montanic acid are preferred.
As the higher fatty acid, one kind may be used, or two or more kinds may be used in combination.

A higher fatty acid metal salt is a metal salt of a higher fatty acid.
The metal element constituting the higher fatty acid metal salt is preferably a group 1, 2, 3 element of the periodic table of elements, zinc, aluminum or the like, more preferably first, such as calcium, sodium, potassium, magnesium, etc. Examples include Group 2 elements, aluminum, and the like.
Examples of the higher fatty acid metal salt include, but are not limited to, calcium stearate, aluminum stearate, zinc stearate, magnesium stearate, calcium montanate, sodium montanate, calcium palmitate, and the like. A metal salt of montanic acid and a metal salt of stearic acid are preferred.
A higher fatty acid metal salt may be used individually by 1 type, and may be used in combination of 2 or more types.

The higher fatty acid ester is an esterified product of a higher fatty acid and an alcohol. An ester of an aliphatic carboxylic acid having 8 to 40 carbon atoms and an aliphatic alcohol having 8 to 40 carbon atoms is preferable.
Examples of the aliphatic alcohol include, but are not limited to, stearyl alcohol, behenyl alcohol, and lauryl alcohol.
Examples of the higher fatty acid ester include, but are not limited to, stearyl stearate and behenyl behenate.
As a higher fatty acid ester, one type may be used alone, or two or more types may be used in combination.

A higher fatty acid amide is an amide compound of a higher fatty acid.
The higher fatty acid amide is preferably stearic acid amide, oleic acid amide, erucic acid amide, ethylene bis stearyl amide, ethylene bis oleyl amide, N-stearyl stearyl amide, N-stearyl erucamide, more preferably ethylene bisstearyl. Amides and N-stearyl erucamide.
Only one type of higher fatty acid amide may be used alone, or two or more types may be used in combination.

The content of the lubricant in the polyamide composition of the present invention is preferably 0.001 to 1 part by weight, more preferably 0.03 to 0.5 parts by weight with respect to 100 parts by weight of the polyamide. is there.
When the content of the lubricant is within the above range, it is possible to obtain a polyamide composition having excellent releasability and plasticizing time stability and excellent toughness, and a polyamide obtained by breaking the molecular chain. Can be prevented.

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

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

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

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

Examples of the phosphorus-based heat stabilizer include, but are not limited to, pentaerythritol phosphite compounds, trioctyl phosphite, trilauryl phosphite, tridecyl phosphite, octyl diphenyl phosphite, trisisodecyl. Phosphite, phenyl diisodecyl phosphite, phenyl di (tridecyl) phosphite, diphenyl isooctyl phosphite, diphenyl isodecyl phosphite, diphenyl (tridecyl) phosphite, triphenyl phosphite, tris (nonylphenyl) phosphite, tris (2 , 4-di-t-butylphenyl) phosphite, tris (2,4-di-t-butyl-5-methylphenyl) phosphite, tris (butoxyethyl) phosphite, 4,4′-butylidene- Bis (3-methyl-6-t-butylphenyl-tetra-tridecyl) diphosphite, tetra (C12-C15 mixed alkyl) -4,4′-isopropylidene diphenyldiphosphite, 4,4′-isopropylidenebis (2 -T-butylphenyl) -di (nonylphenyl) phosphite, tris (biphenyl) phosphite, tetra (tridecyl) -1,1,3-tris (2-methyl-5-t-butyl-4-hydroxyphenyl) Butane diphosphite, tetra (tridecyl) -4,4′-butylidenebis (3-methyl-6-tert-butylphenyl) diphosphite, tetra (C1-C15 mixed alkyl) -4,4′-isopropylidene diphenyl diphosphite , Tris (mono, dimixed nonylphenyl) phosphite, 4,4'-isopropylide Bis (2-t-butylphenyl) -di (nonylphenyl) phosphite, 9,10-di-hydro-9-oxa-9-oxa-10-phosphaphenanthrene-10-oxide, tris (3 5-di-t-butyl-4-hydroxyphenyl) phosphite, hydrogenated-4,4′-isopropylidene diphenyl polyphosphite, bis (octylphenyl) -bis (4,4′-butylidenebis (3-methyl-) 6-t-butylphenyl))-1,6-hexanol diphosphite, hexatridecyl-1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) diphosphite, tris (4 4′-isopropylidenebis (2-t-butylphenyl)) phosphite, tris (1,3-stearoyloxyisopropyl) phosphite 2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite, 2,2-methylenebis (3-methyl-4,6-di-t-butylphenyl) 2-ethylhexyl phosphite, Tetrakis (2,4-di-t-butyl-5-methylphenyl) -4,4′-biphenylene diphosphite and tetrakis (2,4-di-t-butylphenyl) -4,4′-biphenylenedi A phosphite is mentioned.
These may be used alone or in combination of two or more.

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

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

  When using a phosphorus-based heat stabilizer, the content of the phosphorus-based heat stabilizer in the polyamide composition is preferably 0.01 to 1% by mass, more preferably 100% by mass with respect to the polyamide composition. 0.1 to 1% by mass. When the content of the phosphorus-based heat stabilizer is within the above range, the heat aging resistance of the polyamide composition can be further improved and the amount of gas generated can be reduced.

  Examples of amine heat stabilizers include, but are not limited to, 4-acetoxy-2,2,6,6-tetramethylpiperidine, 4-stearoyloxy-2,2,6,6-tetra. Methylpiperidine, 4-acryloyloxy-2,2,6,6-tetramethylpiperidine, 4- (phenylacetoxy) -2,2,6,6-tetramethylpiperidine, 4-benzoyloxy-2,2,6 6-tetramethylpiperidine, 4-methoxy-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, 4-cyclohexyloxy-2,2,6 6-tetramethylpiperidine, 4-benzyloxy-2,2,6,6-tetramethylpiperidine, 4-phenoxy-2,2,6,6-tetramethyl Peridine, 4- (ethylcarbamoyloxy) -2,2,6,6-tetramethylpiperidine, 4- (cyclohexylcarbamoyloxy) -2,2,6,6-tetramethylpiperidine, 4- (phenylcarbamoyloxy)- 2,2,6,6-tetramethylpiperidine, bis (2,2,6,6-tetramethyl-4-piperidyl) -carbonate, bis (2,2,6,6-tetramethyl-4-piperidyl)- Oxalate, bis (2,2,6,6-tetramethyl-4-piperidyl) -malonate, bis (2,2,6,6-tetramethyl-4-piperidyl) -sebacate, bis (2,2,6, 6-tetramethyl-4-piperidyl) -adipate, bis (2,2,6,6-tetramethyl-4-piperidyl) -terephthalate, 1,2-bis (2, , 6,6-tetramethyl-4-piperidyloxy) -ethane, α, α′-bis (2,2,6,6-tetramethyl-4-piperidyloxy) -p-xylene, bis (2,2, 6,6-tetramethyl-4-piperidyltolylene-2,4-dicarbamate, bis (2,2,6,6-tetramethyl-4-piperidyl) -hexamethylene-1,6-dicarbamate, tris ( 2,2,6,6-tetramethyl-4-piperidyl) -benzene-1,3,5-tricarboxylate, tris (2,2,6,6-tetramethyl-4-piperidyl) -benzene-1, 3,4-tricarboxylate, 1- [2- {3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy} butyl] -4- [3- (3,5-di- t-Butyl-4-hydroxyfe L) propionyloxy] 2,2,6,6-tetramethylpiperidine, 1,2,3,4-butanetetracarboxylic acid, 1,2,2,6,6-pentamethyl-4-piperidinol and β, β , Β ′, β′-tetramethyl-3,9- [2,4,8,10-tetraoxaspiro (5,5) undecane] diethanol. These may be used alone or in combination of two or more.

  When the amine heat stabilizer is used, the content of the amine heat stabilizer in the polyamide composition is preferably 0.01 to 1% by mass, more preferably 0 to 100% by mass of the polyamide composition. 0.1 to 1% by mass. When the content of the amine heat stabilizer is within the above range, the heat aging resistance of the polyamide composition can be further improved, and the amount of gas generated can be reduced.

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

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

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

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

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

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

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

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

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

(Other polymers)
Polymers other than the above (A) crystalline polyamide, (B) amorphous semi-aromatic polyamide and (C) polyphenylene ether are not limited to the following, but examples include polyester, liquid crystal polyester, polyphenylene sulfide, Polycarbonate, polyarylate, phenol resin, epoxy resin and the like can be mentioned.

  Examples of the polyester include, but are not limited to, polybutylene terephthalate, polytrimethylene terephthalate, polyethylene terephthalate, and polyethylene naphthalate.

  In the present invention, the content of the polymer other than (A) crystalline polyamide, (B) amorphous semi-aromatic polyamide and (C) polyphenylene ether is 1 with respect to 100 parts by mass of the total resin contained in the polyamide composition. -200 mass parts is preferable, More preferably, it is 5-100 mass parts, More preferably, it is 5-50 mass parts. By setting the content of the polymer other than polyamide in the polyamide composition of the present invention within the above range, a polyamide composition having excellent heat resistance and releasability can be obtained.

(Metal phosphite and / or metal hypophosphite)
The polyamide composition of the present invention may contain a metal phosphite salt and / or a metal hypophosphite salt. Examples of the metal phosphite and / or metal hypophosphite include phosphorous acid, hypophosphorous acid, pyrophosphorous acid, diphosphorous acid, and groups 1 and 2 of the periodic table, manganese, zinc , Salts with aluminum, ammonia, alkylamines, cycloalkylamines, and diamines. Of these, sodium hypophosphite, calcium hypophosphite, and magnesium hypophosphite are preferable. By including a metal phosphite salt and / or a metal hypophosphite salt, a polyamide composition excellent in extrusion processability and molding process stability can be obtained.

(Phosphite compound)
The polyamide composition of the present invention may further contain a phosphite compound. Examples of the phosphite compound include triphenyl phosphite and tributyl phosphite. By adding a phosphite compound, a polyamide composition excellent in extrusion processability and molding process stability can be obtained.
As phosphite compounds, trioctyl phosphite, trilauryl phosphite, tridecyl phosphite, octyl-diphenyl phosphite, trisisodecyl phosphite, phenyl diisodecyl phosphite, phenyl di (tridecyl) phosphite, diphenyl isooctyl phosphite Phyto, diphenylisodecyl phosphite, diphenyl tridecyl phosphite, triphenyl phosphite, tris (nonylphenyl) phosphite, tris (2,4-di-t-butylphenyl) phosphite, bis [2,4-bis (1,1-dimethylethyl) -6-methylphenyl] ethyl phosphite, bis (2,4-di-t-butylphenyl) pentaerythritol-di-phosphite, bis (2,6-di-t-butyl) -4-methyl Phenyl) pentaerythritol-di-phosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite, 4,4′-butylidene-bis (3-methyl-6-tert-butylphenyl) -Di-tridecyl) phosphite, 1,1,3-tris (2-methyl-4-ditridecylphosphite-5-t-butyl-phenyl) butane, 4,4'-isopropylidenebis (phenyl-dialkylphos Phyto), tris (2,4-di-t-butylphenyl) phosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite, bis (2,6-di-t-) Butyl-4-methylphenyl) pentaerythritol di-phosphite and the like.
As the phosphite compound, one kind of phosphite compound may be used, or two or more kinds of phosphite compounds may be used in combination.

  In the polyamide composition of the present invention, additives conventionally used in the polyamide composition, for example, colorants such as pigments and dyes (including colored master batches), difficulty, and the like within the range not impairing the object of the present invention. A flame retardant, a fibrillating agent, a fluorescent bleaching agent, a plasticizer, an antioxidant, an ultraviolet absorber, an antistatic agent, a fluidity improver, a spreading agent, an elastomer and the like can also be contained.

  When the polyamide composition of the present invention contains other raw materials that can be included in the polyamide composition described above, the content of the other raw materials varies depending on the type and use of the polyamide composition. Therefore, there is no particular limitation as long as the object of the present invention is not impaired.

[Method for producing polyamide composition]
As a method for producing the polyamide composition of the present invention, a production method comprising a step of melt-kneading raw material components including the above-mentioned (A) crystalline polyamide, (B) amorphous semi-aromatic polyamide, and (C) polyphenylene ether. If it is, it will not specifically limit. For example, a method in which a raw material component containing the above-described polyamide is melt-kneaded with an extruder and the set temperature of the extruder is set to a melting peak temperature Tm2 + 30 ° C. or less of the polyamide composition described below is preferable.

  As a method of melt-kneading raw material components including polyamide, for example, a method in which polyamide and other raw materials are mixed using a tumbler, a Henschel mixer, etc., and supplied to a melt-kneader, kneaded, or single-screw or twin-screw extrusion Examples include a method of blending other raw materials from the side feeder into the polyamide melted by a machine.

  In the method of supplying the components constituting the polyamide 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 melt kneading temperature is preferably about 250 to 350 ° C. as the resin temperature.
The melt kneading time is preferably about 0.25 to 5 minutes.
The apparatus for performing the melt kneading is not particularly limited, and a known apparatus such as a single or twin screw extruder, a Banbury mixer, a mixing roll, or the like can be used.

[Physical properties of polyamide composition]
Specifically, the molecular weight, the melting point Tm2, the crystallization enthalpy ΔH, and the tan δ peak temperature of the polyamide composition of the present invention can be measured by the methods described in Examples described later.
Mw (weight average molecular weight) can be used as an index of the molecular weight of the polyamide composition. Mw (weight average molecular weight) of the polyamide composition is 15000 to 35000, preferably 17000 to 35000, more preferably 20000 to 35000, still more preferably 22000 to 34000, and still more preferably 24,000 to 33000. And most preferably 25000-32000. When Mw (weight average molecular weight) is in the above range, a polyamide having excellent mechanical properties, in particular, water absorption rigidity, thermal rigidity, fluidity and the like can be obtained. Moreover, the polyamide composition containing a component typified by an inorganic filler has excellent surface appearance.
Examples of a method for controlling the Mw of the polyamide composition within the above range include using (A) a crystalline polyamide and (B) an amorphous semi-aromatic polyamide having a Mw within the above range.
In addition, the measurement of Mw (weight average molecular weight) can be measured using GPC (gel permeation chromatography) as described in the following Example.

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

As a method for controlling the total content of polyamides having a number average molecular weight Mn of 500 or more and 2000 or less within the above range, the molecular weight of (B) amorphous semi-aromatic polyamide is important, and the weight average molecular weight Mw (B ) Is preferably 10,000 to 25,000.
In addition, the total content of the polyamide having a number average molecular weight Mn of 500 or more and 2000 or less with respect to the total mass of the polyamide is determined from an elution curve under measurement conditions in Examples described later using GPC.
When other components that are soluble in the solvent in which the polyamide is dissolved are contained in the composition containing (A) crystalline polyamide and (B) amorphous semi-aromatic polyamide during GPC measurement, A polyamide is insoluble, but other components are soluble in a solvent, and other components are extracted and removed, and then GPC measurement is performed. In addition, an inorganic filler or the like that is insoluble in a solvent that dissolves polyamide is dissolved in a solvent that dissolves the polyamide composition, then filtered to remove insoluble matters, and then GPC measurement is performed.

  The difference {Mw (A) -Mw (B)} between the weight average molecular weight Mw (A) of the (A) crystalline polyamide and the weight average molecular weight Mw (B) of the (B) amorphous semi-aromatic polyamide is 2000 or more. Preferably, it is 5000 or more, more preferably 8000 or more, still more preferably 10,000 or more, and most preferably 12000 or more. When {Mw (A) -Mw (B)} is 2000 or more, (B) an amorphous semi-aromatic polyamide forms a microsize domain, and a composition excellent in water absorption rigidity and thermal rigidity is obtained. be able to.

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

As a method for controlling the Mw / Mn of the polyamide composition within the above range, (M) the Mw (B) / Mn (B) of the amorphous semi-aromatic polyamide may be set to the above-described range.
When the aromatic compound unit is contained in the molecular structure of the polyamide composition, the molecular weight distribution (Mw / Mn) tends to increase as the molecular weight increases. When the molecular weight distribution is within the above range, the proportion of polyamide molecules having a three-dimensional structure of the molecule can be reduced, and the three-dimensional structure of the molecule can be suitably prevented during high temperature processing, and the fluidity is improved. By being able to keep, the surface appearance of the polyamide composition containing the component represented by the inorganic filler can be improved.

  In the present invention, Mw / Mn of the polyamide composition is Mw (weight average molecular weight) and Mn (number average molecular weight) obtained using GPC (gel permeation chromatography) as described in the following examples. Can be calculated using.

The melting point Tm2 of the polyamide composition is preferably 200 ° C or higher, more preferably 220 to 270 ° C, still more preferably 230 to 265 ° C, still more preferably 240 to 260 ° C, and particularly preferably. 250-260 ° C.
When the melting point Tm2 of the polyamide composition is 200 ° C. or more, it tends to be able to obtain a polyamide composition that is superior in thermal rigidity and the like.
Moreover, when melting | fusing point Tm2 of a polyamide composition is 270 degrees C or less, it exists in the tendency which can suppress the thermal decomposition etc. of the polyamide composition in melt processing, such as extrusion and shaping | molding, more.

The crystallization enthalpy ΔH of the polyamide composition is preferably 10 J / g or more, more preferably 14 J / g or more, and further preferably 18 J / g, from the viewpoint of mechanical properties, particularly water absorption rigidity and thermal rigidity. It is above, More preferably, it is 20 J / g or more. Moreover, the upper limit of the crystallization enthalpy ΔH is not particularly limited and is preferably as high as possible.
As a method for controlling the crystallization enthalpy ΔH of the polyamide composition within the above range, for example, the blending ratio of (A) crystalline polyamide, (B) amorphous semi-aromatic polyamide, and (C) polyphenylene ether is described above. The method etc. which control to a range are mentioned.
Examples of the measuring device for the melting point Tm2 and crystallization enthalpy ΔH of the polyamide composition include Diamond-DSC manufactured by PERKIN-ELMER.

The tan δ peak temperature of the polyamide composition is 90 ° C or higher, more preferably 100 ° C or higher, still more preferably 110 ° C or higher, and still 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, a polyamide composition excellent in water absorption rigidity and heat rigidity tends to be obtained. Further, when the tan δ peak temperature of the polyamide composition is 150 ° C. or less, the polyamide composition containing a component typified by an inorganic filler has an excellent surface appearance.
Examples of the method for controlling the tan δ peak temperature of the polyamide composition within the above range include, for example, the ranges described above for the blending ratio of (A) crystalline polyamide, (B) amorphous semi-aromatic polyamide, and (C) polyphenylene ether. And the like.

The crystallization peak temperature Tc (° C.) obtained when the polyamide composition of the present invention is cooled at 20 ° C./min is preferably 160 to 240 ° C.
The crystallization peak temperature Tc (° C) of the polyamide composition is more preferably 170 ° C to 230 ° C, further preferably 180 ° C to 225 ° C, still more preferably 190 ° C to 220 ° C, and particularly preferably. Is 200 ° C. to 215 ° C.
When the crystallization peak temperature Tc (° C.) of the polyamide composition is 160 ° C. or higher, a polyamide composition having excellent releasability during molding can be obtained. Moreover, when the crystallization peak temperature Tc (° C.) of the polyamide composition is 240 ° C. or less, the polyamide composition containing a component typified by an inorganic filler has excellent surface appearance.

The measurement of the melting | fusing point crystallization peak temperature Tc of the polyamide composition used for this invention can be performed according to JIS-K7121 by the method as described in the below-mentioned Example.
Examples of the measuring device for the crystallization peak temperature Tc include Diamond-DSC manufactured by PERKIN-ELMER. Examples of the method for controlling the crystallization peak temperature Tc of the polyamide within the above range include, for example, the above-described ranges of the blending ratio of (A) crystalline polyamide, (B) amorphous semi-aromatic polyamide, and (C) polyphenylene ether. And the like.

In the polyamide composition of the present invention, the ratio of the amino terminal amount to the total amount of amino terminal amount and carboxyl terminal amount {amino terminal amount / (amino terminal amount + carboxyl terminal amount)} is preferably 0.25 or more and less than 0.4. 0.35 or more and less than 0.4 is more preferable, and 0.25 or more and less than 0.35 is more preferable. When the ratio of the amino terminal amount to the total amount of the amino terminal amount and the carboxyl terminal amount is 0.25 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.
The amino terminal amount and the carboxyl terminal amount can be measured by the method shown in the Examples below, and the ratio of the amino terminal amount to the total amount of the amino terminal amount and the carboxyl terminal amount by the measured amino terminal amount and the carboxyl terminal amount { Amino terminal amount / (amino terminal amount + carboxyl terminal amount)} can be calculated.

The surface gloss value of the polyamide composition of the present invention is preferably 50 or more, more preferably 55 or more, and still more preferably 60 or more. When the surface gloss value of the polyamide composition is 50 or more, it is suitably used as a molding material for various parts such as automobiles, electric and electronic, industrial materials, industrial materials, and daily and household products. be able to.
The surface gloss value can be measured by the method shown in Examples described later.

[Molding]
The molded article of the present invention is formed by molding the polyamide composition described above.
The molded article of the present invention is excellent in mechanical properties, in particular, water absorption rigidity, thermal rigidity, fluidity, and surface appearance.
The molded article of the present invention can be obtained, for example, by molding the above-mentioned polyamide composition by a known molding method.
Known molding methods include, but are not limited to, for example, press molding, injection molding, gas assist injection molding, welding molding, extrusion molding, blow molding, film molding, hollow molding, multilayer molding, and melting. Commonly known plastic molding methods such as spinning can be listed.

  Since the molded article of the present invention is obtained from the above-mentioned polyamide composition, it is excellent in moldability, mechanical strength, low water absorption, and surface appearance. Therefore, the molded article of the present invention includes various parts for various sliding parts, automobile parts, electrical and electronic parts, home appliance parts, OA (Office Automation) equipment parts, portable equipment parts, industrial equipment parts, daily necessities and household goods. Moreover, it can be suitably used for extrusion applications. Among these, the molded article of the present invention is suitably used as an automobile part, an electronic part, a home appliance part, an OA equipment part, or a portable equipment part.

  Although it does not specifically limit as an automotive component, For example, an intake system component, a cooling system component, a fuel system component, an interior component, an exterior component, an electrical component, etc. are mentioned.

  The automobile intake system parts are not particularly limited, and examples include an air intake manifold, an intercooler inlet, an exhaust pipe cover, an inner bush, a bearing retainer, an engine mount, an engine head cover, a resonator, and a throttle body. .

  Although it does not specifically limit as a motor vehicle cooling system component, For example, a chain cover, a thermostat housing, an outlet pipe, a radiator tank, an alternator, a delivery pipe, etc. are mentioned.

  Although it does not specifically limit in an automotive fuel system component, For example, a fuel delivery pipe, a gasoline tank case, etc. are mentioned.

  Although it does not specifically limit as a motor vehicle interior part, For example, an instrument panel, a console box, a glove box, a steering wheel, a trim, etc. are mentioned.

  Although it does not specifically limit as a motor vehicle exterior component, For example, a mall, a lamp housing, a front grille, a mud guard, a side bumper, a door mirror stay, a roof rail, etc. are mentioned.

  Although it does not specifically limit as an automotive electrical component, For example, a connector, a wire harness connector, a motor component, a lamp socket, a sensor vehicle switch, a combination switch, etc. are mentioned.

Although it does not specifically limit as an electrical and electronic component, For example, a connector, the reflector for light-emitting devices, a switch, a relay, a printed wiring board, the housing of an electronic component, an electrical outlet, a noise filter, a coil bobbin, a motor end cap, etc. are mentioned. In addition to light-emitting diodes (LEDs), reflectors for light-emitting devices are used in semiconductor packages such as photo-diodes such as laser diodes (LD), photo diodes, charge-coupled devices (CCD), and complementary metal oxide semiconductors (CMOS). Can be widely used.
Although it does not specifically limit as portable apparatus components, For example, housing | casings, structures, etc., such as a mobile phone, a smart phone, a personal computer, a portable game device, a digital camera, etc. are mentioned.

  Although it does not specifically limit as industrial equipment components, For example, a gear, a cam, an insulation block, a valve, an electric tool component, an agricultural equipment component, an engine cover etc. are mentioned.

  Although it does not specifically limit as household goods and household goods, For example, a button, a food container, an office furniture etc. are mentioned.

  Although it does not specifically limit as an extrusion use, For example, it is used for a film, a sheet | seat, a filament, a tube, a rod, a hollow molded article, etc.

  Among these various uses, the molded article obtained from the polyamide composition of the present invention is particularly suitable for a structural material for exterior use. The structural material for the exterior is a mechanical part or a structural part that requires a surface workability of a molded product (for example, embossing workability, high surface glossiness, etc.) and a relatively large strength and rigidity. Legs, chair legs, seats, cabins, wagon parts and other furniture items, notebook computer housing and other OA equipment items, door mirror stays, wheel rims, wheel caps, wipers, motor fans, seat lock parts, gears, Automotive parts such as lamp housings, electrical parts such as pulleys, gears, hot air blower housings, etc., and other parts such as wheel rims, wheel spokes, saddles, saddle posts, handles, stands, cargo platforms, etc., valve housings, nails , Screws, bolts, bolts and nuts.

Moreover, since the molded product obtained from the polyamide composition of the present invention is excellent in surface appearance, it is also preferably used as a molded product having a coating film formed on the surface of the molded product. The formation method of the coating film is not particularly limited as long as it is a known method, and for example, it can be performed by coating such as a spray method or an electrostatic coating method. The paint used for the coating is not particularly limited as long as it is a known one, and a melamine cross-linked polyester polyol resin paint, an acrylic urethane paint, or the like can be used.
Among them, the polyamide composition of the present invention is suitable as an automotive part material because it is excellent in mechanical strength, toughness, heat resistance, and vibration fatigue resistance, and is also excellent in slidability. It is particularly suitable as a component material for gears and bearings. Moreover, since it is excellent in mechanical strength, toughness, and heat resistance, it is suitable as a component material for electric and electronic use.

EXAMPLES Hereinafter, although a specific Example and a comparative example are given and this invention is demonstrated in detail, this invention is not limited to a following example. In this example, 1 kg / cm ² means 0.098 MPa.

  First, (A) crystalline polyamide, (B) amorphous semi-aromatic polyamide, (C) polyphenylene ether and inorganic filler used in Examples and Comparative Examples are shown below.

(A) Crystalline polyamide A-1: Polyamide 66 Mw = 35000, Mw / Mn = 2

(B) Amorphous semi-aromatic polyamide B-1: Polyamide 6I Mw = 35000, Mw / Mn = 2
B-2: Polyamide 6I T-40 (manufactured by LANXESS, Mw = 44000, Mw / Mn = 2.8)
B-3: Polyamide 6I / 6T Griboly 21 (Mus Mw = 27000, Mw / Mn = 2.2, isophthalic acid ratio of dicarboxylic acid unit is 70 mol%)

(C) Polyphenylene ether C-1: Polyphenylene ether (reduced viscosity (0.5 g / dl chloroform solution, measured at 30 ° C.) 0.52)
C-2: Maleic anhydride-modified polyphenylene ether

Inorganic filler (1) Glass fiber Made by Nippon Electric Glass Brand name ECS03T275H Number average fiber diameter (average particle diameter) 10 μm (circular shape), cut length 3 mm
In this example, the average fiber diameter of the glass fibers was measured as follows.
First, the polyamide composition was placed in an electric furnace, and the organic matter contained in the polyamide composition was incinerated. From the residue after the treatment, 100 or more glass fibers arbitrarily selected were observed with a scanning electron microscope (SEM), and the number average fiber diameter was determined by measuring the fiber diameter of these glass fibers. .

The (A) crystalline polyamide and (B) amorphous semi-aromatic polyamide used in Examples and Comparative Examples were produced using the following (a) and (b) as appropriate.
((A) dicarboxylic acid)
(1) Adipic acid (ADA) (manufactured by Wako Pure Chemical Industries)
(2) Isophthalic acid (IPA) (manufactured by Wako Pure Chemical Industries)
((B) Diamine)
(1) 1,6-diaminohexane (hexamethylenediamine) (C6DA) (manufactured by Tokyo Chemical Industry)

[Production of polyamide]
Next, the manufacturing method of (A) crystalline polyamide (A-1) and (B) amorphous semi-aromatic polyamide (B-1) is demonstrated.

(A-1: Polyamide 66)
The polyamide polymerization reaction was carried out as follows by the “hot melt polymerization method”.
1500 g of an equimolar salt of adipic acid and hexamethylenediamine was dissolved in 1500 g of distilled water to prepare an equimolar 50% by mass aqueous solution of raw material monomers. This aqueous solution was charged into an autoclave having an internal volume of 5.4 L and purged with nitrogen.
While stirring at a temperature of 110 to 150 ° C., water vapor was gradually removed to a solution concentration of 70% by mass and concentrated. Thereafter, the internal temperature was raised to 220 ° C. At this time, the autoclave was pressurized to 1.8 MPa. The reaction was continued for 1 hour while gradually removing water vapor and maintaining the pressure at 1.8 MPa until the internal temperature reached 245 ° C.
Next, the pressure was reduced over 1 hour. Thereafter, the inside of the autoclave was maintained under a reduced pressure of 650 torr with a vacuum apparatus for 10 minutes. At this time, the final internal temperature of the polymerization was 265 ° C.
Thereafter, it was pressurized with nitrogen to form a strand from the lower nozzle (nozzle), water-cooled, cut, discharged in a pellet form, and dried in a nitrogen atmosphere at 100 ° C. for 12 hours to obtain a polyamide. Mw = 35000 and Mw / Mn = 2.

(B-1: Polyamide 6I)
The polyamide polymerization reaction was carried out as follows by the “hot melt polymerization method”.
1500 g of equimolar salt of isophthalic acid and hexamethylenediamine and 1.5 mol% excess adipic acid with respect to all equimolar salt components are dissolved in 1500 g of distilled water to prepare a uniform aqueous solution of 50 mol% of equimolar raw material monomers. did.
While stirring at a temperature of 110 to 150 ° C., water vapor was gradually removed to a solution concentration of 70% by mass and concentrated. Thereafter, the internal temperature was raised to 220 ° C. At this time, the autoclave was pressurized to 1.8 MPa. The reaction was continued for 1 hour while gradually removing water vapor and maintaining the pressure at 1.8 MPa until the internal temperature reached 245 ° C.
Next, the pressure was reduced over 30 minutes. Thereafter, the inside of the autoclave was maintained under a reduced pressure of 650 torr with a vacuum apparatus for 10 minutes. At this time, the final internal temperature of the polymerization was 265 ° C.
Thereafter, it was pressurized with nitrogen to form a strand from the lower nozzle (nozzle), water-cooled, cut, discharged in a pellet form, and dried in a nitrogen atmosphere at 100 ° C. for 12 hours to obtain a polyamide. Mw = 20000 and Mw / Mn = 2.

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

[Production of polyamide composition]
(Examples 1-3 and Comparative Examples 1-3)
Using the above (A) crystalline polyamide, (B) amorphous semi-aromatic polyamide and (C) polyphenylene ether in the types and proportions shown in Table 1 below, a polyamide composition was produced as follows.
The polyamide obtained above was dried in a nitrogen stream and adjusted to a moisture content of about 0.2% by mass, and then used as a raw material for the polyamide composition.

As an apparatus for producing the polyamide composition, a twin screw extruder [ZSK-26MC: manufactured by Coperion (Germany)] was used.
The twin screw extruder has an upstream supply port in the first barrel from the upstream side of the extruder, a downstream first supply port in the sixth barrel, and a downstream second supply port in the ninth barrel. Had. In the twin screw extruder, L / D was 48 and the number of barrels was 12.
In the twin-screw extruder, the temperature from the upstream supply port to the die was set to (A-1) polyamide melting point Tm2 + 20 ° C., screw rotation speed 250 rpm, and discharge rate 25 kg / h.

After the dry blending of (A) crystalline polyamide, (B) amorphous semi-aromatic polyamide, and (C) polyphenylene ether, the upstream side of the twin-screw extruder so as to have the types and proportions described in Table 1 below Glass fiber (GF) is supplied as an inorganic filler from the first supply port on the downstream side of the twin-screw extruder, and the melt-kneaded material extruded from the die head is cooled in a strand shape and pelletized. Polyamide composition pellets (including glass fibers) were obtained.
The obtained polyamide composition pellets were dried in a nitrogen stream, and the water content in the polyamide composition was reduced to 500 ppm or less.

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

(1) Melting peak temperature Tm2 (melting point), crystallization peak temperature Tc, crystallization enthalpy According to JIS-K7121, it measured using Diamond-DSC by PERKIN-ELMER. Specifically, it measured as follows.
First, in a nitrogen atmosphere, about 10 mg of a sample was heated from room temperature to 300 to 350 ° C. according to the melting point of the sample at a temperature rising rate of 20 ° C./min. The maximum peak temperature of the endothermic peak (melting peak) appearing at this time was defined as Tm1 (° C.). Next, the temperature was maintained for 2 minutes at the highest temperature rise. At this maximum temperature, the polyamide was in a molten state. Thereafter, the temperature is decreased to 30 ° C. at a temperature decrease rate of 20 ° C./min. The exothermic peak appearing at this time was defined as a crystallization peak, the crystallization peak temperature was defined as Tc, and the crystallization peak area was defined as a crystallization enthalpy ΔH (J / g). Then, after hold | maintaining at 30 degreeC for 2 minute (s), it heated up by 30 degreeC / min from 30 degreeC to 280-300 degreeC according to melting | fusing point of the sample. The maximum peak temperature of the endothermic peak (melting peak) appearing at this time was defined as the melting point Tm2 (° C.).

(2) tan δ peak temperature Using a viscoelasticity analyzer (Rheology: DVE-V4), the temperature dispersion spectrum of dynamic viscoelasticity of a test piece obtained by cutting a parallel part of an ASTM D1822 TYPE L test piece into a strip shape. Measurement was performed under the following conditions. In addition, the test piece dimension was 3.1 mm (width) x 2.9 mm (thickness) x 15 mm (length: distance between gripping tools).
Measurement mode: tensile, waveform: sine wave, frequency: 3.5 Hz, temperature range: 0 ° C. to 180 ° C., heating step: 2 ° C./min, static load: 400 g, displacement amplitude: 0.75 μm. The ratio E2 / E1 between the storage elastic modulus E1 and the loss elastic modulus E2 was tan δ, and the highest temperature was the tan δ peak temperature.

(3) Mw (weight average molecular weight), Mn (number average molecular weight), molecular weight distribution Mw / Mn, Mw (A) -Mw (B)
Mw (weight average molecular weight), Mn (number average molecular weight), Mw (A) and Mw (B) are GPC (gel permeation chromatography, manufactured by Tosoh Corporation, HLC-8020, hexafluoroisopropanol solvent, and PMMA ( Polymethylmethacrylate) standard sample (converted by Polymer Laboratories) was used for measurement. Moreover, Mw (A) -Mn (B) and molecular weight distribution Mw / Mn were calculated from the values. The content (% by mass) of the number average molecular weight Mn of 500 or more and 2000 or less is from the elution curve (vertical axis: signal intensity obtained from the detector, horizontal axis: elution time) of each sample obtained using GPC. It was calculated from the area of the region having a number average molecular weight of 500 or more and less than 2000 surrounded by the baseline and the elution curve, and the area of the region surrounded by the baseline and the elution curve.

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

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

([NH ₂ ] / ([NH ₂ ] + [COOH]) is calculated from the amino terminal amount ([NH ₂ ]) and the carboxyl terminal amount ([COOH]) measured in (4) and (5) above. did.

(6) Surface gloss value A flat plate molded piece was produced as follows.
Using an injection molding machine [NEX50III-5EG: manufactured by Nissei Plastic Industry Co., Ltd.], cooling time is 25 seconds, screw rotation speed is 200 rpm, mold temperature is Tan δ peak temperature + 5 ° C., cylinder temperature = (Tm2 + 10) ° C. to (Tm2 + 30) A flat plate molded piece (6 cm × 9 cm, thickness 2 mm) was produced by appropriately adjusting the injection pressure and the injection speed so that the filling time was in the range of 1.6 ± 0.1 seconds.
A 60-degree gloss was measured for the central part of the flat plate molded piece thus produced using a gloss meter (IG320 manufactured by HORIBA) in accordance with JIS-K7150.
The larger the measured value, the better the surface appearance.

(7) MD (mold deposit) during molding
The above-mentioned molding (6) was continuously performed for 100 shots, and the gas vent after the molding was visually confirmed.
The evaluation of gas generation during molding was as follows. It was evaluated that obtaining a molded product without problems would lead to improvement in productivity.
(Evaluation criteria)
A: There is no deposit on the gas vent. B: There is an deposit on the gas vent. C: There is an deposit on the gas vent. It is clogging. D: There is an deposit on the gas vent.

(8) Tensile strength Using an injection molding machine [PS-40E: manufactured by Nissei Plastic Industry Co., Ltd.], each was molded into a multipurpose test piece A-type molded piece in accordance with ISO 3167. The specific molding conditions were injection + holding time 25 seconds, cooling time 15 seconds, mold temperature 80 ° C., and molten resin temperature set to the high temperature melting peak temperature (Tm2) + 20 ° C. of polyamide.
Using the obtained multipurpose test piece A-type molded piece, in accordance with ISO 527, under a temperature condition of 80 ° C., a tensile test was performed at a tensile rate of 50 mm / min, and the tensile yield stress was measured to obtain the tensile strength. .

(9) Weld strength A mold in which molten resin flows from both ends in the length direction of a length of 127 mm, a width of 12.7 mm, and a thickness of 1.6 mm, and a weld is formed at the center in the length direction. Molding was performed with the attached injection molding machine (PS40E manufactured by Nissei Kogyo Co., Ltd.) to obtain a test piece. A tensile test was carried out by a method based on ASTM D638 except that the formed test piece was set to a distance between chucks of 50 mm and a tensile speed of 50 mm / min to obtain a tensile strength.

(10) Flexural modulus after water absorption (80 ° C)
An ISO dumbbell having a thickness of 4 mm was produced and used as a test piece. The ISO dumbbell was allowed to stand in a constant temperature and humidity (23 ° C., 50 RH%) atmosphere to reach water absorption equilibrium, and then the flexural modulus was measured under a temperature condition of 80 ° C. according to ISO 178.

  As shown in Table 1, (A) a crystalline polyamide, containing a dicarboxylic acid unit containing at least 75 mol% of isophthalic acid, and a diamine unit containing at least 50 mol% of a diamine having 4 to 10 carbon atoms (B) A polyamide composition comprising a crystalline semi-aromatic polyamide and (C) polyphenylene ether, wherein the polyamide composition has a Tanδ peak temperature of 90 ° C. or higher, and the weight average molecular weight Mw of the polyamide composition is 15000 ≦ Mw In Example 1 in which the polyamide composition of the present invention satisfying ≦ 35000 was molded, (C) Comparative Example 1 containing no polyphenylene ether, (A) crystalline polyamide, (B) amorphous semi-aromatic polyamide, and (C) Comparison in which the weight average molecular weight Mw of the polyamide composition is greater than 35000 even if it contains polyphenylene ether As compared to 2 or 3, in particular, surface appearance, MD during molding, has excellent tensile strength, and flexural modulus after water absorption.

  The polyamide composition of the present invention is excellent in mechanical properties, in particular, water absorption rigidity, thermal rigidity, fluidity, surface appearance, etc., for automobiles, electric and electronic, industrial materials, industrial materials, and daily use and It has industrial applicability, such as being able to be suitably used as a molding material for various parts such as for household goods.

Claims (15)

(A) crystalline polyamide,
(B) an amorphous semi-aromatic polyamide containing a dicarboxylic acid unit containing at least 75 mol% of isophthalic acid and a diamine unit containing at least 50 mol% of a diamine having 4 to 10 carbon atoms,
And (C) polyphenylene ether,
A polyamide composition comprising:
The tan δ peak temperature of the polyamide composition is 90 ° C. or higher,
The polyamide composition whose weight average molecular weight Mw of the said polyamide composition is 15000 <= Mw <= 35000.   The polyamide composition according to claim 1, wherein the total content of the polyamide having a number average molecular weight Mn of 500 or more and 2000 or less is 0.5% by mass or more and less than 2.5% by mass with respect to the total amount of polyamide in the polyamide composition. object.   The polyamide composition according to claim 1 or 2, wherein a molecular weight distribution Mw / Mn of the polyamide composition is 2.4 or less.   The ratio of amino terminal amount to total amount of amino terminal amount and carboxyl terminal amount {amino terminal amount / (amino terminal amount + carboxyl terminal amount)} is 0.25 or more and less than 0.4. 2. The polyamide composition according to item 1.   The polyamide composition according to any one of claims 1 to 4, wherein the crystalline polyamide (A) is polyamide 66 or polyamide 610.   The polyamide composition according to any one of claims 1 to 5, wherein in the (B) amorphous semi-aromatic polyamide, the content of the isophthalic acid in the dicarboxylic acid unit is 100 mol%.   The polyamide composition according to any one of claims 1 to 6, wherein the (B) amorphous semi-aromatic polyamide is polyamide 6I.   The weight average molecular weight Mw (B) of said (B) amorphous semi-aromatic polyamide is 10000 <= Mw <= 25000, The polyamide composition of any one of Claims 1-7.   9. The polyamide composition according to claim 1, wherein the (B) amorphous semi-aromatic polyamide has a molecular weight distribution Mw (B) / Mn (B) of 2.4 or less.   The difference {Mw (A) -Mw (B)} between the weight average molecular weight Mw (A) of the (A) crystalline polyamide and the weight average molecular weight Mw (B) of the (B) amorphous semiaromatic polyamide is 2000. It is the above, The polyamide composition of any one of Claims 1-9.   Furthermore, the polyamide composition of any one of Claims 1-10 containing a phosphorous acid metal salt and / or a hypophosphite metal salt.   Furthermore, the polyamide composition of any one of Claims 1-11 containing a phosphite compound.   Furthermore, the polyamide composition of any one of Claims 1-12 containing the compatibilizer of the said polyamide and the said (C) polyphenylene ether.   The inorganic filler is further contained in an amount of 5 to 250 parts by mass with respect to a total of 100 parts by mass of the (A) crystalline polyamide, the (B) amorphous semi-aromatic polyamide and the (C) polyphenylene ether. The polyamide composition according to any one of ˜13.   A molded product obtained by molding the polyamide composition according to any one of claims 1 to 14, and having a surface gloss value of 50 or more.