JP2019127500A - Polyamide composition and molded article - Google Patents

Abstract

To provide: a polyamide composition, which affords pellets having excellent shapes with reduced amount of chips generated, and can provide a molded article having excellent surface appearance; and a molded article using the polyamide composition, the molded article having excellent surface appearance.SOLUTION: The polyamide composition comprises (A) a crystalline polyamide, (B) an amorphous semi-aromatic polyamide, and (C) carbon fibers. The (B) amorphous semi-aromatic polyamide contains, of all dicarboxylic acid units which constitute the (B) amorphous semi-aromatic polyamide, isophthalic acid units in an amount of 75 mole% or more, and of all diamine units which constitute the (B) amorphous semi-aromatic polyamide, diamine units having 4 to 10 carbon atoms in an amount of 50 mole% or more. The molded article is formed by molding the polyamide composition.SELECTED DRAWING: None

Description

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

Polyamides typified by polyamide 6 (hereinafter may be abbreviated as “PA6”) and polyamide 66 (hereinafter may be abbreviated as “PA66”) and the like are excellent in molding processability, mechanical properties and chemical resistance. Because of their excellent properties, they are widely used as various component materials for automobiles, electricity and electronics, for industrial materials, for industrial materials, for daily use, for household goods, and the like.
In recent years, the use environment of polyamide has become severer in terms of heat and dynamics. Mechanical properties, particularly rigidity after water absorption (hereinafter sometimes referred to as “water absorption rigidity”), and rigidity under high temperature use ( Hereinafter, there is a need for a polyamide material which is improved in “stiffness in heat” and which has less change in physical properties in use under any environment.
Moreover, in order to improve productivity, the molded article using polyamide may be shape | molded on the high cycle molding conditions performed by making molding temperature high and lowering | hanging die temperature.

On the other hand, when molding is performed under a high temperature condition, there is a problem that a molded product cannot 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 surface appearance of molded products even under the severe molding conditions described above.

  In order to meet such requirements, as a material capable of improving the surface appearance and mechanical properties of molded articles, a polyamide comprising polyamide 66 / 6I having an isophthalic acid component introduced is disclosed (see, for example, Patent Document 1) ). In addition, as a material capable of improving mechanical properties, fluidity, surface appearance and the like, a polyamide composition comprising polyamide 6T / 6I in which a terephthalic acid component and an isophthalic acid component are introduced is disclosed (for example, patent documents 2, 3).

  Furthermore, in order to improve mechanical properties, particularly rigidity, a polyamide composition containing carbon fibers has been disclosed (see, for example, Patent Documents 4 and 5).

Japanese Patent Application Laid-Open No. 6-032980 JP 2000-154316 A JP 11-349806 A JP, 2013-064106, A Japanese Patent Laying-Open No. 2015-129271

However, although the techniques disclosed in Patent Documents 1 and 3 improve the rigidity under normal use conditions, there is room for improvement in water absorption rigidity and thermal rigidity.
In addition, the polyamide produced by the production 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 cycle molding, there is a problem that the surface appearance and stability of the molded product are reduced.

  Thus, in the prior art, the polyamide copolymer which is excellent in water absorption rigidity and heat rigidity and which hardly changes in physical properties in use under any environment is not yet known. Moreover, it is difficult to suppress the decrease in rigidity after absorption of water and under high temperature use while maintaining the balance between mechanical strength and rigidity, which is a feature of polyamide copolymers, and polyamide co-weights having such physical properties. There is a need for compositions and molded articles comprising coalesced or polyamide.

  Furthermore, in the techniques disclosed in Patent Documents 4 and 5, although the rigidity is significantly improved by containing the carbon fiber, there are problems in the generation amount of chips at the time of extrusion processing and the pellet shape. Moreover, in the polyamide composition which mix | blended especially the high concentration carbon fiber, it was also a subject that the external appearance of a molded piece fell.

  The present invention has been made in view of the above circumstances, and provides a polyamide composition which is excellent in the shape of pellets, has a reduced amount of chips generated, and has a molded article excellent in surface appearance. Moreover, the molded article which is excellent in the surface external appearance using the said polyamide composition is provided.

That is, the present invention includes the following aspects.
The polyamide composition according to the first aspect of the present invention is a polyamide composition containing (A) a crystalline polyamide, (B) an amorphous semi-aromatic polyamide, and (C) a carbon fiber, The (B) amorphous semi-aromatic polyamide contains 75 mol% or more of isophthalic acid units in the total dicarboxylic acid units constituting the (B) amorphous semi-aromatic polyamide, and 50 mol% or more of diamine units having 4 to 10 carbon atoms are contained in all diamine units constituting the crystalline semi-aromatic polyamide.

  In the polyamide composition according to the first aspect, the tan δ peak temperature may be 90 ° C. or more.

  In the polyamide composition according to the first aspect, the content of the (C) carbon fiber in the polyamide composition may be 30% by mass or more and 65% by mass or less.

  In the polyamide composition according to the first aspect, the (A) crystalline polyamide is polyamide 4 (poly α-pyrrolidone), polyamide 6 (polycaproamide), polyamide 11 (polyundecane amide), polyamide 12 (polydodecane) Amide), 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 one or more selected from the group consisting of copolymerized polyamides containing these as constituent components, Also good

  In the polyamide composition according to the first aspect, the content of the non-crystalline polyamide (B) in 100 parts by mass of the total amount of the (A) crystalline polyamide and the (B) non-crystalline semiaromatic polyamide 10 mass parts or more and 50 mass parts or less may be sufficient.

  In the polyamide composition according to the first aspect, the mass of the (B) noncrystalline semiaromatic polyamide and the (C) carbon fiber may satisfy the relationship of the following formula (1).

  In the polyamide composition according to the first aspect, the weight average molecular weight Mw of the polyamide composition may be 15000 or more and 35000 or less.

  In the (B) amorphous semi-aromatic polyamide, the content of the isophthalic acid in the dicarboxylic acid unit may be 100 mol%.

  In the polyamide composition according to the first aspect, the amorphous semi-aromatic polyamide (B) may be polyamide 6I.

  In the polyamide composition according to the first aspect, the weight average molecular weight Mw (B) of the (B) noncrystalline semiaromatic polyamide may be 10000 or more and 25000 or less.

  In the polyamide composition according to the first aspect, the molecular weight distribution Mw (B) / Mn (B) of the (B) amorphous semi-aromatic polyamide may be 2.4 or less.

  The molded article according to the second aspect of the present invention is formed by molding the polyamide composition according to the first aspect.

  The polyamide composition of the above aspect is excellent in the shape of the pellet, the amount of chips generated is reduced, and a molded product excellent in surface appearance can be obtained. The molded product of the above aspect is excellent in surface appearance.

«Polyamide composition»
The polyamide composition of this embodiment contains (A) crystalline polyamide, (B) amorphous semi-aromatic polyamide, and (C) carbon fiber. In addition, the (B) noncrystalline semiaromatic polyamide contains 75 mol% or more of isophthalic acid units in all the dicarboxylic acid units constituting the (B) noncrystalline semiaromatic polyamide, and the above (B ) 50 mol% or more of diamine units having 4 to 10 carbon atoms are contained in all diamine units constituting the amorphous semi-aromatic polyamide.

  In the present specification, “polyamide” means a polymer having an amide (—NHCO—) bond in the main chain.

The polyamide composition of the present embodiment contains (A) crystalline polyamide, B) amorphous semi-aromatic polyamide, and (C) carbon fiber having the above-described configuration, so that water absorption rigidity and heat rigidity are kept good. The shape of the pellets is excellent, and the amount of chips generated can be reduced. Moreover, the molded article excellent in the surface external appearance is obtained by using the polyamide composition of this embodiment.
Details of each component contained in the polyamide composition of the present embodiment will be described below.

<Polyamide>
The polyamide composition of this embodiment contains (A) crystalline polyamide and (B) amorphous semi-aromatic polyamide as polyamide components. Details of each polyamide component will be described below.

[(A) crystalline polyamide]
In the present specification, the “crystalline polyamide” is a polyamide having a heat of fusion of 4 J / g or more when measured at 20 ° C./min with a differential scanning calorimeter. Examples of crystalline polyamides include, but are not limited to, polyamides obtained by ring-opening polymerization of (A-a) lactams, polyamides obtained by self-condensation of (A-b) ω-aminocarboxylic acid, (A-) c) Polyamides obtained by condensing diamine and dicarboxylic acid, and copolymers of these, and the like. The crystalline polyamide may be used alone or in combination of two or more.

Examples of the lactam used for producing the (A-a) polyamide include, but are not limited to, pyrrolidone, caprolactam, undecalactam, dodecalactam and the like.
Examples of the ω-aminocarboxylic acid used for producing the (A-b) polyamide include, but are not limited to, ω-amino fatty acid etc., which is a ring-opening compound of the above-mentioned lactam with water.
In addition, the lactam or the ω-aminocarboxylic acid may be condensed using two or more monomers.

The diamine (monomer) used for producing the (A-c) polyamide is not limited to the following, and for example, linear aliphatic diamine, branched aliphatic diamine, alicyclic diamine, aromatic Group diamine and the like.
Examples of linear aliphatic diamines include, but are not limited to, hexamethylene diamine and pentamethylene diamine.
Examples of branched aliphatic diamines include, but are not limited to, 2-methyl pentane diamine and 2-ethyl hexamethylene diamine.
Examples of alicyclic diamines include, but are not limited to, cyclohexane diamine, cyclopentane diamine, cyclooctane diamine and the like.
Although it does not restrict | limit to the following as aromatic diamine, For example, p-phenylenediamine, m-phenylenediamine etc. are mentioned.
Examples of the dicarboxylic acid (monomer) used for producing the (A-c) polyamide include, but are not limited to, aliphatic dicarboxylic acids, alicyclic dicarboxylic acids, and aromatic dicarboxylic acids.
Examples of aliphatic dicarboxylic acids include, but are not limited to, adipic acid, pimelic acid, sebacic acid and the like.
Although it does not restrict | limit to the following as alicyclic dicarboxylic acid, For example, cyclohexane dicarboxylic acid etc. are mentioned.
Examples of aromatic dicarboxylic acids include, but are not limited to, phthalic acid and isophthalic acid.
The diamine and the dicarboxylic acid as monomers described above may be condensed alone or in combination of two or more.

  The crystalline polyamide (A) may further contain a unit derived from a trivalent or higher polyvalent carboxylic acid such as trimellitic acid, trimesic acid and pyromellitic acid, as necessary. Trivalent or higher polyvalent carboxylic acids may be used alone or in combination of two or more.

Specific examples of the (A) crystalline polyamide contained in the polyamide composition of the present embodiment include polyamide 4 (poly α-pyrrolidone), polyamide 6 (polycaproamide), polyamide 11 (polyundecane amide), and polyamide 12 (polydodecanamide), polyamide 46 (polytetramethylene adipamide), polyamide 56 (polypentamethylene adipamide), polyamide 66 (polyhexamethylene adipamide), polyamide 610 (polyhexamethylene sebacamide) And polyamide 612 (polyhexamethylene dodecamide), polyamide 6T (polyhexamethylene terephthalamide), polyamide 9T (polynonamethylene terephthalamide), and copolymerized polyamides containing these as constituents.
Among them, as the crystalline polyamide (A), polyamide 66 (PA66), polyamide 46 (PA46), or polyamide 610 (PA610) is preferable. PA66 is a material suitable for automobile parts because it is excellent in heat resistance, formability and toughness. In addition, long-chain aliphatic polyamides such as PA610 have excellent chemical resistance and are preferable.

  The content of the (A) crystalline polyamide in the polyamide composition of the present embodiment can be, for example, 50% by mass or more and 99% by mass or less based on the total mass of all the resins contained in the polyamide composition. For example, it can be 60 mass% or more and 95 mass% or less, for example, 70 mass% or more and 85 mass% or less.

[(B) Amorphous semi-aromatic polyamide]
The non-crystalline semi-aromatic polyamide (B) contained in the polyamide composition of the present embodiment is a polyamide containing diamine units and dicarboxylic acid units. (B) Amorphous semi-aromatic polyamide contains 75 mol% or more of isophthalic acid units with respect to all dicarboxylic acid units constituting (B) amorphous semi-aromatic polyamide. And (B) (Bb) a diamine unit containing 50 mol% or more of a diamine unit having 4 to 10 carbon atoms with respect to all diamine units constituting the amorphous semi-aromatic polyamide. Is preferred.
At this time, the total amount of the isophthalic acid unit and the diamine unit having 4 to 10 carbon atoms in (B) the amorphous semi-aromatic polyamide is the total amount of (B) all the structural units of the amorphous semi-aromatic polyamide. On the other hand, 80 mol% or more and 100 mol% or less are preferable, 90 mol% or more and 100 mol% or less are more preferable, and 100 mol% is more preferable.
In the present specification, 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)
As the (B-a) dicarboxylic acid unit, 75 mol% or more of isophthalic acid can be contained with respect to the total number of moles of (B-a) dicarboxylic acid, and it is preferable to contain 80 mol% or more and 100 mol% or less 90 mol% or more and 100 mol% or less is more preferable, and 100 mol% is more preferable.
(Ba) Polyamide composition that satisfies the mechanical properties, particularly water absorption rigidity, thermal rigidity, fluidity, surface appearance, and the like at the same time when the ratio of the isophthalic acid unit in the dicarboxylic acid unit is not less than the above lower limit. Can be obtained.

  The (B-a) dicarboxylic acid unit may contain an aromatic dicarboxylic acid unit other than an isophthalic acid unit, an aliphatic dicarboxylic acid unit, or an alicyclic dicarboxylic acid unit.

(1) Aromatic Dicarboxylic Acid Unit An aromatic dicarboxylic acid constituting an aromatic dicarboxylic acid unit other than an isophthalic acid unit is not limited to the following, for example, an aromatic group such as a phenyl group and a naphthyl group And dicarboxylic acids having the following. The aromatic group of the aromatic dicarboxylic acid may be unsubstituted or may have a substituent.
The substituent is not particularly limited, and, for example, an alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 10 carbon atoms, an arylalkyl group having 7 to 10 carbon atoms, a halogen group, 1 carbon atom Examples thereof include silyl groups of 6 or less and sulfonic acid groups and salts thereof (sodium salt etc.) and the like.

  Examples of the alkyl group having 1 or more and 4 or less carbon atoms include, but are not limited to, 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. Etc.

  Examples of the aryl group having 6 to 10 carbon atoms include, but are not limited to, phenyl group, tolyl group, xylyl group, and naphthyl group.

  Examples of the arylalkyl group having 7 to 10 carbon atoms include, but are not limited to, a benzyl group.

  Examples of the halogen group include, but are not limited to, a fluoro group, a chloro group, a bromo group, and an iodo group.

  The silyl group having 1 to 6 carbon atoms is not limited to the following, and examples thereof include a trimethylsilyl group and a tert-butyldimethylsilyl group.

  Among them, as an aromatic dicarboxylic acid constituting an aromatic dicarboxylic acid unit other than an isophthalic acid unit, an aromatic dicarboxylic acid having 8 to 20 carbon atoms which is unsubstituted or substituted by a predetermined substituent is preferable.

Specific examples of the aromatic dicarboxylic acid having 8 to 20 carbon atoms that are unsubstituted or substituted with a predetermined substituent include, but are not limited to, for example, terephthalic acid, naphthalenedicarboxylic acid, 2-chloro Examples include terephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, and 5-sodium sulfoisophthalic acid.
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.

(2) Aliphatic dicarboxylic acid unit Examples of the aliphatic dicarboxylic acid constituting the aliphatic dicarboxylic acid unit include linear or branched saturated aliphatic dicarboxylic acids having 3 to 20 carbon atoms.
Examples of the linear saturated aliphatic dicarboxylic acid having 3 to 20 carbon atoms include, but are not limited to, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, and azelaic acid. , Sebacic acid, dodecanedioic acid, tetradecanedioic acid, hexadecanedioic acid, octadecanedioic acid, eicosanedioic acid, diglycolic acid and the like.
Examples of the branched saturated aliphatic dicarboxylic acid having 3 to 20 carbon atoms include, but are not limited to, dimethyl malonic acid, 2,2-dimethyl succinic acid, 2,3-dimethyl glutaric acid, Examples include 2,2-diethylsuccinic acid, 2,3-diethylglutaric acid, 2,2-dimethylglutaric acid, 2-methyladipic acid, trimethyladipic acid, and the like.

(3) Alicyclic dicarboxylic acid unit The alicyclic dicarboxylic acid constituting the alicyclic dicarboxylic acid unit (hereinafter sometimes referred to as "alicyclic dicarboxylic acid unit") is not limited to the following. For example, alicyclic dicarboxylic acids having 3 to 10 carbon atoms in the alicyclic structure may be mentioned. Among these, as the alicyclic dicarboxylic acid, alicyclic dicarboxylic acids having 5 to 10 carbon atoms in the alicyclic structure are 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. It is done. Among these, 1,4-cyclohexanedicarboxylic acid is preferable as the alicyclic dicarboxylic acid.
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 an alkyl group having 1 to 4 carbon atoms. Examples of the alkyl group having 1 to 4 carbon atoms are the same as those exemplified in the above “aromatic dicarboxylic acid unit”.

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.

(B) In the amorphous semi-aromatic polyamide, (B-a) the dicarboxylic acid constituting the dicarboxylic acid unit is not limited to the compounds described as the dicarboxylic acid, but is a compound equivalent to the dicarboxylic acid. It may be.
The “compound equivalent to the dicarboxylic acid” as used herein refers to a compound that can have the same dicarboxylic acid structure as the dicarboxylic acid structure derived from the dicarboxylic acid. Examples of such compounds include, but are not limited to, dicarboxylic acid anhydrides, dicarboxylic acid halides, and the like.

In addition, (B) the amorphous semiaromatic polyamide may further contain a unit derived from a trivalent or higher polyvalent carboxylic acid, as necessary.
Examples of trivalent or higher polyvalent carboxylic acids include trimellitic acid, trimesic acid and pyromellitic acid. These trivalent or higher polyvalent carboxylic acids may be used alone or in combination of two or more.

((B-b) diamine unit)
(B) The diamine unit constituting the amorphous semi-aromatic polyamide preferably includes a diamine unit having 4 to 10 carbon atoms, and a linear saturated fat having 4 to 10 carbon atoms. Group diamine units are more preferable, linear saturated aliphatic diamine units having 6 to 10 carbon atoms are more preferable, and hexamethylene diamine units are particularly preferable.
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.
At this time, the (B) amorphous semi-aromatic polyamide is a diamine unit having 4 to 10 carbon atoms with respect to the total number of moles of the (Bb) diamine unit as the (Bb) diamine unit. Can be contained in an amount of 50 mol% or more.

  Also, (B) the diamine other than the diamine having 4 to 10 carbon atoms constituting the amorphous semi-aromatic polyamide is not limited to the following, for example, aliphatic diamine units, alicyclic diamines Units, aromatic diamine units and the like.

(1) Aliphatic diamine unit As an aliphatic diamine which comprises an aliphatic diamine unit, C4-C20 linear saturated aliphatic diamine etc. are mentioned, for example.
Examples of linear saturated aliphatic diamines having 4 to 20 carbon atoms include, but are not limited to, ethylenediamine, propylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, and the like. Examples include octamethylene diamine, nonamethylene diamine, decamethylene diamine, undecamethylene diamine, dodecamethylene diamine, and tridecamethylene diamine.

(2) Alicyclic diamine unit The alicyclic diamine constituting the alicyclic diamine unit (hereinafter sometimes referred to as "alicyclic diamine") is not limited to the following, 1,4-cyclohexanediamine, 1,3-cyclohexanediamine, 1,3-cyclopentanediamine and the like can be mentioned.

(3) Aromatic Diamine Unit The aromatic diamine constituting the aromatic diamine unit is not limited to the following as long as it is an aromatic-containing diamine. Specific examples of the aromatic diamine include metaxylylenediamine.

  In addition, the diamine which comprises each of these diamine units may be used individually by 1 type, and may be used in combination of 2 or more types.

  The non-crystalline semi-aromatic polyamide (B) contained in the polyamide composition of the present embodiment is preferably polyamide 6I (polyhexamethylene isophthalamide), 9I or 10I, more preferably polyamide 6I.

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

  The content of the (B) amorphous semiaromatic polyamide in the polyamide composition of the present embodiment is 5.0% by mass or more and 45.0% by mass with respect to 100% by mass of the total resin contained in the polyamide composition. It can be set as follows, preferably 10.0 mass% or more and 42.5 mass% or less, more preferably 15.0 mass% or more and 40.0 mass% or less, and 20.0 mass% or more and 37.5 mass% or less Is more 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. By setting the content of the amorphous semiaromatic polyamide (B) in the above-mentioned range, a polyamide composition excellent in mechanical properties, particularly in water absorption stiffness, thermal rigidity, fluidity, surface appearance and the like can be obtained.

[End sealant]
The ends of the polyamide ((A) crystalline polyamide and (B) amorphous semi-aromatic polyamide) contained in the polyamide composition of this embodiment may be end-capped with a known end-capping agent.
Such an end-capping agent can be used as a molecular weight regulator when producing a polyamide from the dicarboxylic acid, the diamine, and, if necessary, at least one of the lactam and the aminocarboxylic acid. Can be added.

Examples of the end capping agent include, but are not limited to, monocarboxylic acids, monoamines, acid anhydrides, monoisocyanates, monoacid halides, monoesters, monoalcohols and the like. Examples of acid anhydrides include, but are not limited to, phthalic anhydride and the like. These end-capping agents may be used alone or in combination of two or more.
Especially, as a terminal blocker, monocarboxylic acid or monoamine is 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.

As a monocarboxylic acid which can be used as an end capping agent, what has the reactivity with the amino group which may exist in the end of polyamide may be used. Specific examples of the monocarboxylic acid include, but are not limited to, aliphatic monocarboxylic acids, alicyclic monocarboxylic acids, and aromatic monocarboxylic acids.
Examples of aliphatic monocarboxylic acids include, but are not limited to, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecyl acid, myristyl acid, palmitic acid, for example. Examples thereof include stearic acid, pivalic acid and isobutyl acid.
As an alicyclic monocarboxylic acid, although it is not limited to the following, cyclohexane carboxylic acid etc. are mentioned, for example.
Examples of the aromatic monocarboxylic acid include, but are not limited to, benzoic acid, toluic acid, α-naphthalenecarboxylic acid, β-naphthalenecarboxylic acid, methylnaphthalenecarboxylic acid, phenylacetic acid and the like.
These monocarboxylic acids may be used alone or in combination of two or more.

The monoamine that can be used as the end-capping agent may be any one that has reactivity with a carboxy group that may be present at the end of the polyamide. Specific examples of monoamines include, but are not limited to, aliphatic monoamines, alicyclic monoamines, and aromatic monoamines.
Examples of the aliphatic amine include, but are not limited to, methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, decylamine, stearylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine Etc.
Examples of the alicyclic amine include, but are not limited to, cyclohexylamine and dicyclohexylamine.
Examples of the aromatic amine include, but are not limited to, aniline, toluidine, diphenylamine, naphthylamine, and the like.
These monoamines may be used alone or in combination of two or more.

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

[Production method of polyamide]
When manufacturing polyamide, it is preferable that the addition amount of dicarboxylic acid and the addition amount of diamine are the equimolar vicinity. Considering the escape of the diamine out of the reaction system during the polymerization reaction in the molar ratio, the molar amount of the whole diamine is preferably 0.9 or more and 1.2 or less with respect to the molar amount 1 of the whole dicarboxylic acid. 0.95 or more and 1.1 or less are preferable, and 0.98 or more and 1.05 or less are more preferable.
The production method of the polyamide is not limited to the following. For example, the dicarboxylic acid constituting the dicarboxylic acid unit, the diamine constituting the diamine unit, and, if necessary, the lactam and amino constituting the lactam unit. And (c) polymerizing at least one of the aminocarboxylic acids constituting the carboxylic acid unit to obtain a polymer.
Moreover, it is preferable to further include the process of raising the polymerization degree of polyamide in the manufacturing method of polyamide.
Moreover, you may include the sealing process which seals the terminal of the obtained polymer with terminal blocker as needed.

Specific methods for producing the polyamide include various methods as exemplified in the following 1) to 4).
1) A method of heating 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, and polymerizing while maintaining the molten state (hereinafter referred to as “heat melting polymerization method” May be called).
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 sometimes referred to as “hot melt polymerization / solid phase polymerization method”).
3) A method of polymerizing a dicarboxylic acid-diamine salt or a mixture of a dicarboxylic acid and a diamine while maintaining a solid state (hereinafter, sometimes referred to as “solid phase polymerization method”).
4) A method of polymerizing using a dicarboxylic acid halide component and a diamine component equivalent to dicarboxylic acid (hereinafter sometimes referred to as “solution method”).
Among these, as a specific method for producing polyamide, a production method including a hot melt polymerization method is preferable. Moreover, when manufacturing polyamide by the hot melt polymerization method, it is preferable to hold | maintain a molten state until superposition | polymerization is complete | finished. As a method of maintaining a molten state, for example, a method of producing under polymerization conditions suitable for the composition of polyamide, and the like can be mentioned. Examples of the polymerization conditions include the conditions shown below. First, the polymerization pressure in the hot melt polymerization method is controlled to 14 kg / cm ² or more and 25 kg / cm ² or less (gauge pressure), and heating is continued. Subsequently, the pressure in the tank is reduced to 30 at least 30 minutes until the pressure in the tank reaches atmospheric pressure (gauge pressure is 0 kg / cm ² ), whereby a polyamide having a desired composition is obtained.

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. Can be mentioned.

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

[Polymer end of polyamide]
Although it does not specifically limit as a polymer terminal of the polyamide contained in the polyamide composition of this embodiment, it can classify | categorize and define as follows.
That is, 1) an amino terminal, 2) a carboxy terminal, 3) a 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 carboxy terminus is a polymer terminus having a carboxy group (—COOH group) and is derived from the starting 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 blocking agent include the above-mentioned end capping agent.
4) The other end is a polymer end not classified in 1) to 3) described above. Specific examples of the other terminal include a terminal generated by deammonia reaction at the amino terminal, a terminal generated by decarboxylation from the carboxy terminal, and the like.

[Characteristics of (A) crystalline polyamide]
(A) The molecular weight, the melting point Tm2 and the crystallization enthalpy ΔH of the crystalline polyamide can be measured by the methods described in Examples described later.
Further, the tan δ peak temperature of (A) crystalline polyamide can be measured by the following method.

((A) Weight average molecular weight Mw (A) of crystalline polyamide)
(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 10,000 or more and 50000 or less, more preferably 15000 or more and 45000 or less, further preferably 20000 or more and 40000 or less, and particularly preferably 25000 or more and 35000 or less.
When the weight average molecular weight Mw (A) is in the above range, a polyamide composition is obtained which is excellent in mechanical properties, particularly in water absorption rigidity, thermal rigidity, flowability, surface appearance and the like.
In addition, the measurement of weight average molecular weight Mw (A) can be measured using gel permeation chromatography (GPC), as described in the following Example.

((A) Molecular weight distribution of crystalline polyamide Mw (A) / Mn (A))
The molecular weight distribution of the (A) crystalline polyamide is represented by weight average molecular weight Mw (A) / number average molecular weight Mn (A).
The Mw (A) / Mn (A) of the crystalline polyamide (A) can be 1.0 or more, preferably 1.8 or more and 2.2 or less, and more preferably 1.9 or more and 2.1 or less.
When Mw (A) / Mn (A) is in the above-mentioned range, a polyamide composition which is more excellent in fluidity, surface appearance and the like can be obtained.
(A) As a method of controlling Mw / Mn of the crystalline polyamide within the above range, for example, a known polycondensation catalyst such as phosphoric acid or sodium hypophosphite is used as an additive at the time of hot melt polymerization of polyamide. And a method for controlling polymerization conditions such as heating conditions and reduced pressure conditions.
(A) Mw (A) / Mn (A) of the crystalline polyamide, as described in the following examples, weight average molecular weight Mw (A) and number average molecular weight Mn (A) obtained using GPC Can be calculated using.

((A) Melting point Tm2 of crystalline polyamide)
(A) The lower limit of the melting point Tm2 of the crystalline polyamide is preferably 220 ° C, more preferably 230 ° C, and further preferably 240 ° C.
On the other hand, the upper limit of the melting point Tm2 of the crystalline polyamide (A) is preferably 300 ° C, more preferably 290 ° C, further preferably 280 ° C, particularly preferably 270 ° C.
That is, (A) the melting point Tm2 of the crystalline polyamide is preferably 220 ° C. or higher and 300 ° C. or lower, more preferably 230 ° C. or higher and 290 ° C. or lower, further preferably 240 ° C. or higher and 280 ° C. or lower, particularly 240 ° C. or higher and 270 ° C. or lower. preferable.
(A) When the melting point Tm2 of the crystalline polyamide is equal to or higher than the lower limit, the molded article obtained from the polyamide composition tends to have better thermal rigidity.
Moreover, when (A) melting point Tm2 of crystalline polyamide is below the said upper limit, 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.

((A) Crystallization enthalpy ΔH of crystalline polyamide
(A) The lower limit of the crystallization enthalpy ΔH of the crystalline polyamide can be 4 J / g, 20 J / g, or 30 J from the viewpoint of mechanical properties, particularly water absorption rigidity and heat rigidity. / G, 40 J / g, 50 J / g, 60 J / g. On the other hand, the upper limit value of the crystallization enthalpy ΔH of (A) crystalline polyamide 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) tan δ peak temperature of crystalline polyamide)
(A) The tan δ peak temperature of the crystalline polyamide can be 40 ° C. or higher, 50 ° C. or higher and 110 ° C. or lower, 60 ° C. or higher and 100 ° C. or lower, 70 ° C. or higher and 95 ° C. The temperature can be set to 80 ° C. or higher and 90 ° C. or lower.
(A) When the tan δ peak temperature of the crystalline polyamide is equal to or higher than the above lower limit, 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 using, for example, a viscoelasticity measurement analyzer (Rheology: DVE-V4).

[(B) Properties of Amorphous Semi-Aromatic Polyamide]
(B) The molecular weight of the amorphous semiaromatic polyamide can be measured by the method described in the examples described later.
Moreover, (B) Melting | fusing point Tm2, crystallization enthalpy (DELTA) H, tan-delta peak temperature, the amount of amino terminals, and the amount of carboxy terminals of amorphous semi-aromatic polyamide can be measured by the method shown below.

((B) Weight average molecular weight Mw of amorphous semi-aromatic polyamide (B))
As an index of the molecular weight of (B) amorphous semiaromatic polyamide, the weight average molecular weight (Mw (B)) of (B) amorphous semiaromatic polyamide can be used.
(B) The weight average molecular weight (Mw (B)) of the amorphous semi-aromatic polyamide is preferably 10,000 or more and 25,000 or less, more preferably 13,000 or more and 24,000 or less, further preferably 15,000 or more and 23,000 or less, and 18,000 or more and 22,000 or less. Particularly preferred is 19,000 or more and 21,000 or less.
(B) A polyamide composition that is superior in mechanical properties, in particular, water absorption rigidity, thermal rigidity, fluidity, surface appearance, etc., when the weight average molecular weight (Mw (B)) of the amorphous semi-aromatic polyamide is in the above range. The thing is obtained. In addition, the measurement of the weight average molecular weight (Mw (B)) of (B) amorphous semi-aromatic polyamide can be measured using GPC, as it describes in the Example mentioned later.

((B) Molecular weight distribution of amorphous semi-aromatic polyamide Mw (B) / Mn (B))
The molecular weight distribution of the (B) amorphous semi-aromatic polyamide is the weight average molecular weight of the (B) amorphous semi-aromatic polyamide (Mw (B)) / (B) the number average molecular weight of the amorphous semi-aromatic polyamide (Mn (B)) is used as an index.
Mw (B) / Mn (B) can be 2.4 or less, preferably 1.0 or more and 2.4 or less, more preferably 1.7 or more and 2.4 or less, and 1.8 or more and 2.3. The following is more preferable, 1.9 to 2.2 is particularly preferable, and 1.9 to 2.1 is most preferable.
When Mw (B) / Mn (B) is within the above range, a polyamide composition having excellent fluidity, surface appearance and the like can be obtained.

Examples of the method for controlling Mw (B) / Mn (B) within the above range include the methods shown in 1) or 2) below.
1) A method of adding a known polycondensation catalyst such as phosphoric acid or sodium hypophosphite as an additive at the time of hot melt polymerization of polyamide.
2) In addition to the above method 1), the 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, (B) the amorphous semi-aromatic polyamide does not have a melting point, so the reaction temperature can be lowered to control Mw (B) / Mn (B) within the above range.
In addition, when an aromatic compound unit is contained in the molecular structure of the polyamide, the molecular weight distribution (Mw / Mn) tends to be high as the molecular weight increases. (B) When the molecular weight distribution (Mw (B) / Mn (B)) of the amorphous semi-aromatic polyamide is within the above range, the proportion of polyamide molecules having a three-dimensional structure of molecules can be lowered. At the time of high temperature processing, three-dimensional structuring of molecules can be prevented more suitably, and fluidity can be kept better. Thereby, the surface external appearance of the molded article obtained from a polyamide composition can be made more favorable.

  In addition, the measurement of Mw (B) / Mn (B) can be calculated using Mw (B) and Mn (B) obtained using GPC, as described in the Example mentioned later.

((B) Crystallization enthalpy ΔH of amorphous semi-aromatic polyamide
(B) The crystallization enthalpy ΔH of the amorphous semi-aromatic polyamide can be 15 J / g or less, and 10 J / g or less from the viewpoint of mechanical properties, particularly water absorption rigidity and thermal rigidity. And can be 5 J / g or less, and can be 0 J / g.
(B) As a method of controlling the crystallization enthalpy ΔH of the amorphous semi-aromatic polyamide within the above range, for example, a method of increasing the ratio of the aromatic monomer to the dicarboxylic acid unit can be mentioned. From this point of view, (B) the amorphous semiaromatic polyamide is 75 moles of isophthalic acid in all the dicarboxylic acid units constituting the (B) amorphous semiaromatic polyamide as the (Ba) dicarboxylic acid unit. % Or more is preferable, and 100 mol% is more preferable.
(B) As a measuring apparatus of crystallization enthalpy (DELTA) H of amorphous semi-aromatic polyamide, Diamond-DSC made from PERKIN-ELMER, etc. are mentioned, for example.

(Tan δ peak temperature of (B) amorphous semi-aromatic polyamide)
(B) The tan δ peak temperature of the amorphous semiaromatic polyamide can be 90 ° C. or more, can be 100 ° C. or more and 160 ° C. or less, can be 110 ° C. or more and 150 ° C. or less, and 120 The temperature can be in the range of ° C to 145 ° C, and can be in the range of 130 ° C to 140 ° C.
(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. From this point of view, (B) the amorphous semiaromatic polyamide is 75 moles of isophthalic acid in all the dicarboxylic acid units constituting the (B) amorphous semiaromatic polyamide as the (Ba) dicarboxylic acid unit. % Or more is preferable, and 100 mol% is more preferable.
(B) When the tan δ peak temperature of the amorphous semi-aromatic polyamide is equal to or higher than the above lower limit value, it tends to be possible to obtain a polyamide composition excellent in water absorption rigidity and heat rigidity. Further, when the tan δ peak temperature of the polyamide composition is not more than the above upper limit value, a polyamide composition excellent in surface appearance tends to be obtained.
(B) The tan δ peak temperature of the amorphous semi-aromatic polyamide can be measured using, for example, a viscoelasticity measurement analyzer (Rheology: DVE-V4).

((B) Amino terminal amount of amorphous semi-aromatic polyamide)
The amino terminal amount of (B) amorphous semiaromatic polyamide can be 5 μg or more and 100 μg or less, and can be 10 μg or more and 90 μg or less with respect to 1 g of (B) amorphous semiaromatic polyamide 20 μg or more and 80 μg or less, 30 μg or more and 70 μg or less, and 40 μg or more and 60 μg or less.
(B) When the amino terminal amount of the amorphous semi-aromatic polyamide is in the above range, it is possible to obtain a polyamide composition which is excellent in discoloration due to heat and light.
The amino terminal amount can be measured by neutralization titration.

(Carboxy terminal amount of (B) amorphous semi-aromatic polyamide)
The carboxy terminal amount of (B) amorphous semi-aromatic polyamide can be 50 μg or more and 300 μg or less, and can be 100 μg or more and 280 μg or less with respect to 1 g of (B) amorphous semi-aromatic polyamide. 150 μg or more and 260 μg or less, 180 μg or more and 250 μg or less, and 200 μg or more and 240 μg or less.
(B) When the amount of the carboxy terminal of the amorphous semi-aromatic polyamide is in the above range, a polyamide composition excellent in fluidity can be obtained. Further, the surface appearance of a molded product obtained from the polyamide composition is more excellent.
The amount of carboxy terminal can be measured by neutralization titration.

[Total amount of amino terminal amount and carboxy terminal amount of polyamide]
The total amount of the amino terminal amount and the carboxy terminal amount of the polyamide ((A) crystalline polyamide and (B) amorphous semi-aromatic polyamide) is 150 μg or more and 350 μg or less and 160 μg or more and 300 μg with respect to 1 g of polyamide. The following is preferable, 170 to 280 μg is more preferable, 180 to 270 μg is more preferable, and 190 to 260 μg is particularly preferable.
When the total amount of the amino terminal amount and the carboxy terminal amount of the polyamide ((A) crystalline polyamide and (B) amorphous semi-aromatic polyamide) is within the above range, a polyamide composition having excellent fluidity and the like can be obtained. can get. Further, the surface appearance of a molded product obtained from the polyamide composition is more excellent.

[Mass ratio of (B) amorphous semi-aromatic polyamide to the total mass of (A) crystalline polyamide and (B) amorphous semi-aromatic polyamide]
The content of the noncrystalline semiaromatic polyamide (B) is preferably 10 parts by mass to 50 parts by mass with respect to 100 parts by mass of the total amount of the (A) crystalline polyamide and the (B) amorphous semiaromatic polyamide, 15 parts by mass or more and 40 parts by mass or less are more preferable, and 20 parts by mass or more and 30 parts by mass or less are more preferable. When the mass ratio of (B) amorphous semiaromatic polyamide to the total mass of (A) crystalline polyamide and (B) amorphous semiaromatic polyamide is in the above range, the strength and water absorption at 23 ° C. An excellent polyamide composition can be obtained by the balance with the strength at high temperature.

<(C) carbon fiber>
The carbon fiber (C) contained in the polyamide composition of the present embodiment may have a perfect circular shape or a flat shape in cross section. 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, “flatness” 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. For example, a perfect circle has a flatness ratio of about 1.

  Among them, from the viewpoint of imparting excellent mechanical strength to the polyamide composition, the number average fiber diameter is 3 μm or more and 30 μm or less, the weight average fiber length is 100 μm or more and 750 μm or less, and the weight average fiber length (l) Carbon fibers having an aspect ratio (l / d) of 10 or more and 100 or less with respect to the number average fiber diameter (d) are preferably used.

  Here, the “number average fiber diameter (d)” and “weight average fiber length (l)” in the present specification can be determined by the following method. First, the polyamide composition is placed in an electric furnace, and the contained organic matter is incinerated. From the residue after the treatment, select 100 or more carbon fibers arbitrarily, observe with a scanning electron microscope (SEM), and determine the number average fiber diameter by measuring the fiber diameter of these carbon fibers Can. In addition, the weight average fiber length can be determined by measuring the fiber length using an SEM photograph of the 100 or more carbon fibers taken at a magnification of 1000 times.

The carbon fiber may further contain a sizing agent.
Examples of the sizing agent include copolymers and epoxy compounds containing, as structural units, unsaturated vinyl monomers containing carboxylic acid anhydrides and unsaturated vinyl monomers excluding unsaturated vinyl monomers containing carboxylic acid anhydrides. , Polyurethane resins, homopolymers of acrylic acid, copolymers of acrylic acid and other copolymerizable monomers, and salts thereof with primary, secondary and tertiary amines. One of these focusing agents may be used alone, or two or more thereof may be used in combination.
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 One or more selected from the group consisting of a copolymer containing an epoxy compound as a constituent unit, an epoxy compound and a polyurethane resin is preferred. Also selected from the group consisting of copolymers and polyurethane resins containing as constituent units carboxylic anhydride-containing unsaturated vinyl monomers and unsaturated vinyl monomers excluding carboxylic anhydride-containing unsaturated vinyl monomers. One or more of the following are more preferable.

The carbon fiber reacts continuously 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. It is obtained by
The fiber strand may be used as it is as a roving or it may be used as a chopped glass strand after obtaining a cutting step.

The sizing agent preferably imparts (adds) about 0.2% by mass or more and 3% by mass or less as a solid content with respect to the total mass of the carbon fiber, and about 0.3% by mass or more and 2% by mass or less. It is more preferable to add (add). When the addition amount of the sizing agent is not less than the above lower limit as the solid content with respect to the total mass of the carbon fibers, the sizing of the fibers can be more effectively maintained. On the other hand, when the addition amount of the sizing agent is not more than the above upper limit value as the solid content with respect to the total mass of the carbon fibers, the thermal stability of the obtained polyamide composition is further improved.
Drying of the strand may be performed after the cutting step, or may be cut after drying the strand.

The number average fiber diameter of the carbon fibers is preferably 3 μm or more and 30 μm or less, more preferably 3 μm or more and 20 μm or less, further preferably 3 μm or more and 12 μm or less, and more preferably 3 μm or more and 9 μm or less from the viewpoint of improving toughness and the surface appearance of the molded product. Is particularly preferable, and 4 to 6 μm is the most preferable.
By setting the number average fiber diameter of the carbon fibers to the upper limit value or less, it is possible to obtain a polyamide composition that is more excellent in toughness and the surface appearance of a molded product. On the other hand, by setting the number average fiber diameter of the carbon fibers to be equal to or greater than the above lower limit value, a polyamide composition having an excellent balance between cost and powder handling surface and physical properties (fluidity, etc.) can be obtained. Furthermore, by setting the number average fiber diameter of the carbon fibers to 3 μm or more and 9 μm or less, a polyamide composition excellent in vibration fatigue characteristics and slidability can be obtained.

[Inorganic filler other than carbon fiber]
The polyamide composition of this embodiment may further contain an inorganic filler other than carbon fibers in addition to (C) carbon fibers.
As an inorganic filler other than carbon fiber, wollastonite, kaolin, mica, talc, calcium carbonate, magnesium carbonate, potassium titanate fiber, aluminum borate fiber from the viewpoint of improving the strength, rigidity and surface appearance of a molded article Or clay is preferred. More preferred is wollastonite, kaolin, mica, talc, calcium carbonate or clay. More preferred is wollastonite, kaolin, mica or talc. Wollastonite, mica or talc are particularly preferred. These inorganic fillers may be used alone or in combination of two or more.

The average particle diameter of the inorganic filler other than carbon fiber is preferably 0.01 μm or more and 38 μm or less, more preferably 0.03 μm or more and 30 μm or less, and more preferably 0.05 μm or more and 25 μm from the viewpoint of improving toughness and the surface appearance of the molded product. The following are more preferable, 0.10 μm or more and 20 μm or less are more preferable, and 0.15 μm or more and 15 μm or less are particularly preferable.
By setting the average particle size of inorganic fillers other than carbon fibers to the upper limit or less, a polyamide composition having superior toughness and surface appearance of a molded product can be obtained. On the other hand, when the average particle size is at least the above lower limit value, a polyamide composition having an excellent balance between cost and powder handling surface and physical properties (fluidity, etc.) can be obtained.

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

  The number average particle length of the above-mentioned needle-like inorganic filler (hereinafter, may be simply referred to as “average particle length”) may be a preferable range of the above-mentioned number average particle diameter and the following number average particle diameter ( A numerical range calculated from a preferable range of the aspect ratio (l / d) of the number average particle length (l) to d) is preferable.

  Although it has a needle-like shape, the aspect ratio (l / d) of number average particle length (l) to number average particle diameter (s) improves the surface appearance of a molded article, and an injection molding machine etc. From the viewpoint of preventing wear of the metallic part, 1.5 to 10 is preferable, 2.0 to 5 is more preferable, and 2.5 to 4 is more preferable.

Moreover, you may surface-treat inorganic fillers other than carbon fiber using a silane coupling agent, a titanate coupling agent, etc.
Examples of the silane coupling agent include, but are not limited to, amino silanes, mercapto silanes, epoxy silanes, and vinyl silanes.
Examples of aminosilanes include γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane, and the like.
Examples of mercaptosilanes include γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, and the like.
One of these silane coupling agents may be used alone, or two or more thereof may be used in combination.
Among them, aminosilanes are preferable as the silane coupling agent.
Such a surface treatment agent may be previously treated on the surface of the inorganic filler, or may be added when mixing the polyamide and the inorganic filler. The amount of the surface treatment agent added is preferably 0.05% by mass or more and 1.5% by mass or less based on the total mass of the inorganic filler.

The total content of the inorganic filler is 5 parts by mass or more and 250 parts by mass or less with respect to 100 parts by mass of the total polyamide ((A) crystalline polyamide and (B) amorphous semiaromatic polyamide) in the polyamide composition Is preferable, 30 to 250 parts by mass is more preferable, 50 to 240 parts by mass is more preferable, 50 to 200 parts by mass is particularly preferable, and 50 to 150 parts by mass is the most preferable. .
By setting the total content of the inorganic filler to the above lower limit value or more with respect to 100 parts by mass of the total polyamide in the polyamide composition, the effect of further improving the strength and the rigidity of the obtained polyamide composition is expressed . On the other hand, by setting the total content of the inorganic filler to the above upper limit value or less with respect to 100 parts by mass of the total polyamide in the polyamide composition, it is possible to obtain a polyamide composition more excellent in extrudability and moldability. .

Further, the content of (C) carbon fiber is preferably 30% by mass to 65% by mass, more preferably 30% by mass to 60% by mass, and more preferably 35% by mass to 60% by mass with respect to the total mass of the polyamide composition. % Or less is more preferable.
(C) By making content of carbon fiber more than the said lower limit with respect to the total mass of a polyamide composition, the effect which improves the intensity | strength and rigidity of the obtained polyamide composition more is expressed. On the other hand, by setting the content of (C) the carbon fiber to the upper limit value or less with respect to the total mass of the polyamide composition, a polyamide composition that is more excellent in extrudability and moldability can be obtained.

Moreover, it is preferable that the content mass of (B) amorphous semi-aromatic polyamide and (C) carbon fiber in the polyamide composition of this embodiment satisfy | fills the relationship of following formula (1).

  When the contained mass of (B) amorphous semi-aromatic polyamide and (C) carbon fiber in the polyamide composition of the present embodiment satisfies the relationship of the above-mentioned formula (1), the water absorption rigidity and the thermal rigidity are good. Thus, a polyamide composition having an excellent surface appearance and pellet shape and reduced chip generation is obtained.

<(D) Nucleating agent>
The polyamide composition of this embodiment may further contain (D) a nucleating agent in addition to the components (A) to (C).

The nucleating agent means a substance which can obtain at least one of the following effects (1) to (3) by addition.
(1) The effect of raising the crystallization peak temperature of the polyamide composition.
(2) The effect of reducing the difference between the extrapolation start temperature and the extrapolation end temperature of the crystallization peak.
(3) The effect of refining the spherulites of the resulting molded product or making the size uniform.

Examples of the nucleating agent include, but are not limited to, talc, boron nitride, mica, kaolin, silicon nitride, carbon black, potassium titanate, molybdenum disulfide and the like. Only one type of nucleating agent may be used alone, or two or more types may be used in combination.
Among them, as the nucleating agent, talc or boron nitride is preferable from the viewpoint of the nucleating agent effect.

Further, since the effect of the nucleating agent is high, the number average particle size of the nucleating agent is preferably 0.01 μm or more and 10 μm or less.
The number average particle diameter of the nucleating agent can be measured using the following method. First, the molded product is dissolved in a solvent in which polyamide such as formic acid is soluble. Next, for example, 100 or more nucleating agents are arbitrarily selected from the obtained insoluble components. Subsequently, it can obtain | require by observing by an optical microscope, a scanning electron microscope, etc., and measuring a particle size.

The content of the nucleating agent in the polyamide composition of the present embodiment is based on 100 parts by mass of the total polyamide ((A) crystalline polyamide and (B) amorphous semi-aromatic polyamide) in the polyamide composition. 0.001 to 1 part by weight is preferable, 0.001 to 0.5 part by weight is more preferable, and 0.001 to 0.09 part by weight is further preferable.
By setting the content of the nucleating agent to the above lower limit value or more with respect to 100 parts by mass of the polyamide, the heat resistance of the polyamide composition tends to be further improved. By setting it to the above upper limit value or less with respect to 100 parts by mass, a polyamide composition that is superior in toughness can be obtained.

<(E) Lubricant>
The polyamide composition of the present embodiment may further contain (E) a lubricant in addition to the components (A) to (C).

  The lubricant contained in the polyamide composition of the present embodiment is not particularly limited, and examples thereof include higher fatty acids, higher fatty acid metal salts, higher fatty acid esters, and higher fatty acid amides.

[Higher fatty acids]
Examples of the higher fatty acid include linear or branched, saturated or unsaturated aliphatic monocarboxylic acids having 8 to 40 carbon atoms.
Examples of the linear or branched, saturated or unsaturated aliphatic monocarboxylic acid having 8 to 40 carbon atoms include lauric acid, palmitic acid, stearic acid, behenic acid, montanic acid and the like.
Examples of the branched saturated aliphatic monocarboxylic acid having 8 to 40 carbon atoms include isopalmitic acid and isostearic acid.
Examples of the linear unsaturated aliphatic monocarboxylic acid having 8 to 40 carbon atoms include oleic acid and erucic acid.
Examples of the branched unsaturated aliphatic monocarboxylic acid having 8 to 40 carbon atoms include isooleic acid and the like.
One of these higher fatty acids may be used alone, or two or more of these higher fatty acids may be used in combination.
Of these, stearic acid or montanic acid is preferred as the higher fatty acid.

[Higher fatty acid metal salt]
The higher fatty acid metal salt is a metal salt of higher fatty acid.
Examples of the metal element of the metal salt include Group 1 element, Group 2 element and Group 3 element, zinc, aluminum and the like in the periodic table.
Examples of the element of Group 1 of the Periodic Table of the Elements include sodium and potassium.
Examples of the group 2 element of the Periodic Table of the Elements include calcium and magnesium.
Examples of the Group 3 element in the Periodic Table of the Elements include scandium, yttrium and the like.
Especially, as a metal element, the 1st and 2nd group element of an element periodic table, or aluminum is preferable, and sodium, potassium, calcium, magnesium, or aluminum is more preferable.

Specific examples of the higher fatty acid metal salt include calcium stearate, aluminum stearate, zinc stearate, magnesium stearate, calcium montanate, sodium montanate, calcium palmitate and the like.
One of these higher fatty acid metal salts may be used alone, or two or more thereof may be used in combination.
Among them, metal salts of montanic acid or metal salts of stearic acid are preferable as the higher fatty acid metal salt.

[Higher fatty acid ester]
The higher fatty acid ester is an esterified product of higher fatty acid and alcohol.
The higher fatty acid ester is preferably an ester of an aliphatic carboxylic acid having 8 to 40 carbon atoms and an aliphatic alcohol having 8 to 40 carbon atoms.
Examples of the aliphatic alcohol having 8 to 40 carbon atoms include stearyl alcohol, behenyl alcohol, lauryl alcohol, and the like.
Specific examples of the higher fatty acid ester include stearyl stearate and behenyl behenate.
Each of these higher fatty acid esters may be used alone or in combination of two or more.

[Higher fatty acid amide]
A higher fatty acid amide is an amide compound of a higher fatty acid.
Examples of the higher fatty acid amide include stearic acid amide, oleic acid amide, erucic acid amide, ethylene bisstearyl amide, ethylene bisoleyl amide, N-stearyl stearic acid amide, N-stearyl erucic acid amide and the like.
Each of these higher fatty acid amides may be used alone or in combination of two or more.

The content of the lubricant in the polyamide composition of the present embodiment is 0.001 with respect to 100 parts by mass of the polyamide ((A) crystalline polyamide and (B) amorphous aromatic polyamide) in the polyamide composition. It is preferably no less than 1 part by mass and no greater than 1 part by mass, and more preferably no less than 0.03 parts by mass and no greater than 0.5 parts by mass.
When the content of the lubricant is within the above range, it is possible to obtain a polyamide composition that is excellent in releasability and plasticization time stability and excellent in toughness. In addition, the extreme molecular weight reduction of the polyamide due to the molecular chain breakage can be more effectively prevented.

<(F) Heat stabilizer>
The polyamide composition of the present embodiment may further contain (F) a heat stabilizer in addition to the components (A) to (C).

  Examples of the heat stabilizer include, but are not limited to, phenol heat stabilizers, phosphorus heat stabilizers, amine heat stabilizers, and Groups 3, 4 and 11 to 14 of the Periodic Table of the Elements. And metal halides of alkali metals and alkaline earth metals, and the like.

[Phenolic heat stabilizer]
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-tetraoxaspiro [5,5] undecane 3,5-di-tert-butyl-4-hydroxybenzylphosphonate-diethyl ester, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) Examples thereof include benzene and 1,3,5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanuric acid.
These hindered phenol compounds may be used alone or in combination of two or more.
In particular, from the viewpoint of improving heat aging resistance, the hindered phenol compound may be N, N′-hexane-1,6-diylbis [3- (3,5-di-t-butyl-4-hydroxyphenylpropionamide). )] Is preferred.

When a phenol-based heat stabilizer is used, the content of the phenol-based heat stabilizer in the polyamide composition is preferably 0.01% by mass or more and 1% by mass or less based on the total mass of the polyamide composition. More than 1% by mass is preferable.
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 more.

[Phosphorus-based heat stabilizer]
Examples of phosphorus-based heat stabilizers include, but are not limited to, pentaerythritol-type phosphite compounds, trioctyl phosphite, trilauryl phosphite, tridecyl phosphite, octyl diphenyl phosphite, and tris isodecyl. Phosphite, phenyldiisodecyl 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, di mixed nonylphenyl) phosphite, 4,4'-isopropylidene (2-t-butylphenyl) -di (nonylphenyl) phosphite, 9,10-di-hydro-9-oxa-9-oxa-10-phosphaphenanthrene-10-oxide, tris (3 5-di-t-butyl-4-hydroxyphenyl) phosphite, hydrogenated-4,4′-isopropylidene diphenyl polyphosphite, bis (octylphenyl) -bis (4,4′-butylidenebis (3-methyl-) 6-t-butylphenyl))-1,6-hexanol diphosphite, hexatridecyl-1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) diphosphite, tris (4 4′-isopropylidenebis (2-t-butylphenyl)) phosphite, tris (1,3-stearoyloxyisopropyl) phosphite 2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite, 2,2-methylenebis (3-methyl-4,6-di-t-butylphenyl) 2-ethylhexyl phosphite, tetrakis (2,4-di-t-butyl-5-methylphenyl) -4,4'-biphenylene diphosphite, tetrakis (2,4-di-t-butylphenyl) -4,4'-biphenylene diphosphite Etc.
These phosphorus heat stabilizers may be used alone or in combination of two or more.
Among them, as a phosphorus-based heat stabilizer, a pentaerythritol-type phosphite compound and tris (2,4-di-t-butylphenyl) from the viewpoint of further improving the heat aging resistance of the polyamide composition and reducing the amount of gas generation. 1) At least one selected from the group consisting of phosphites is 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-tert-butylphenyl-pentaerythritol diphosphite, 2,6-di-tert-butyl-4-methylphenyl-2,4-di-tert-butylphenyl-pentaerythritol diphos Phyto, 2,6-di-tert-butyl-4-methylphenyl-2,4-di-tert-octylphenyl-pentaerythritol diphosphite, 2,6-di-tert-butyl-4-methylphenyl-2 -Cyclohexylphenyl-pentaerythritol diphosphite, 2,6-di-t-amyl-4-methylphenyl-phenyl pentaerythritol Tritol diphosphite, bis (2,6-di-t-amyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-octyl-4-methylphenyl) pentaerythritol diphos Fight etc. are mentioned.
One of these pentaerythritol-type phosphite compounds may be used alone, or two or more thereof may be used in combination.

  Among them, as a pentaerythritol-type phosphite compound, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2 (2-di-t-butyl-4-methylphenyl), from the viewpoint of reducing the gas generation amount of the polyamide composition. , 6-di-t-butyl-4-ethylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-amyl-4-methylphenyl) pentaerythritol diphosphite, and bis (2,6 -(Di-t-octyl-4-methylphenyl) pentaerythritol diphosphite is preferably one or more selected from the group consisting of bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphos The fight 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% by mass or more and 1% by mass or less based on the total mass of the polyamide composition, 0.1 More preferably, the content is from 1% by mass 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 generation can be further reduced.

[Amine heat stabilizer]
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 and 1,2,2,6,6-pentamethyl-4-piperidinol and β, β, and a condensate with β ′, β′-tetramethyl-3,9- [2,4,8,10-tetraoxaspiro (5,5) undecane] diethanol.
These amine heat stabilizers may be used alone or in combination of two or more.

When an amine heat stabilizer is used, the content of the amine heat stabilizer in the polyamide composition is preferably 0.01% by mass or more and 1% by mass or less based on the total mass of the polyamide composition, 0.1 More preferably, the content is from 1% by mass to 1% by mass.
When the content of the amine-based heat stabilizer is within the above range, the heat aging resistance of the polyamide composition can be further improved, and the amount of gas generation can be further reduced.

[Metal salts of elements of Groups 3, 4 and 11 to 14 of the Periodic Table of the Elements]
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.
Among them, copper salts are preferable from the viewpoint of further improving the heat aging resistance of the polyamide composition. Such copper salts include, but are not limited to, for example, copper halide, copper acetate, copper propionate, copper benzoate, copper adipate, copper terephthalate, copper isophthalate, copper salicylate, copper nicotinate, stearic acid Copper, copper complex salts in which copper is coordinated to a chelating agent, and the like can be mentioned.
Examples of the copper halide include copper iodide, cuprous bromide, cupric bromide, cuprous chloride and the like.
Examples of the chelating agent include ethylenediamine, ethylenediaminetetraacetic acid and the like.
These copper salts may be used alone or in combination of two or more.
Among them, the copper salt is preferably at least one selected from the group consisting of copper iodide, cuprous bromide, cupric bromide, cuprous chloride and copper acetate, and consists of copper iodide and copper acetate. One or more selected from the group is more preferred. When the above-mentioned preferred copper salts are used, the heat aging resistance is superior, and metal corrosion of the screw or cylinder part during extrusion (hereinafter sometimes referred to simply as "metal corrosion") is more effectively suppressed. A possible polyamide composition is obtained.

  When using a copper salt as a heat stabilizer, the content of the copper salt in the polyamide composition is 0 with respect to the total mass of the polyamide ((A) crystalline polyamide and (B) amorphous semiaromatic polyamide). .01 mass% or more and 0.60 mass% or less are preferable, and 0.02 mass% or more and 0.40 mass% or less are more preferable.

  When the content of the copper salt is in the above range, the heat aging resistance of the polyamide composition can be further improved, and the deposition of copper and metal corrosion can be more effectively suppressed.

Further, the content of the copper element derived from the above copper salt is selected from the viewpoint of improving the heat aging resistance of the polyamide composition. 10 mass parts or more and 2000 mass parts or less are preferable with respect to ⁶ mass parts (1 million mass parts), 30 mass parts or more and 1500 mass parts or less are more preferable, and 50 mass parts or more and 500 mass parts or less are more preferable.

[Alkali metal and alkaline earth metal halides]
Examples of halides of alkali metals and alkaline earth metals include, but are not limited to, potassium iodide, potassium bromide, potassium chloride, sodium iodide, sodium chloride and the like.
One of these alkali metal and alkaline earth metal halides may be used alone, or two or more thereof may be used in combination.
Among them, at least one member selected from the group consisting of potassium iodide and potassium bromide is preferable as a halide of an alkali metal and an alkaline earth metal, from the viewpoint of the improvement of the heat aging resistance and the suppression of metal corrosion. Potassium is more preferred.

When alkali metal and alkaline earth metal halides are used, the content of alkali metal and alkaline earth metal halides in the polyamide composition is determined based on polyamide ((A) crystalline polyamide and (B) amorphous semi-crystalline. The amount is preferably 0.05 parts by mass or more and 20 parts by mass or less, and more preferably 0.2 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the aromatic polyamide.
When the content of alkali metal and alkaline earth metal halide is within the above range, the heat resistance aging property of the polyamide composition can be further improved, and copper precipitation and metal corrosion can be more effectively suppressed. it can.

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

The content ratio of the copper salt to the halide of the alkali metal and the alkaline earth metal is preferably 2/1 or more and 40/1 or less, as the molar ratio of halogen to copper (halogen / copper), 5/1 or more and 30 / 1 or less is more preferable.
When the molar ratio of halogen to copper (halogen / copper) is within the above range, the heat aging resistance of the polyamide composition can be further improved.
Moreover, when the molar ratio of halogen to copper (halogen / copper) is not less than the above lower limit value, copper precipitation and metal corrosion can be more effectively suppressed. On the other hand, when the molar ratio of halogen to copper (halogen / copper) is equal to or less than the above upper limit, corrosion of a screw or the like of a molding machine can be more effectively prevented without substantially impairing mechanical properties (toughness etc.).

<(G) Other resins>
The polyamide composition of this embodiment may further contain (G) other resins in addition to the components (A) to (C).

  Examples of other resins contained in the polyamide composition of the present embodiment include, but are not limited to, polyester, liquid crystal polyester, polyphenylene sulfide, polycarbonate, polyarylate, phenol resin, epoxy resin and the like.

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

The content of the other resin in the polyamide composition of the present embodiment is preferably 1 part by mass or more and 200 parts by mass or less, and 5 parts by mass or more and 100 parts by mass with respect to 100 parts by mass in total of all resin components in the polyamide composition. Part or less is more preferable, and 5 parts by mass or more and 50 parts by mass or less are more preferable.
When the content of the other resin in the polyamide composition of the present embodiment is in the above range, it is possible to obtain a polyamide composition which is more excellent in heat resistance and releasability.

<(H) At least one member selected from the group consisting of metal phosphite and metal hypophosphite>
The polyamide composition of the present embodiment further includes at least one selected from the group consisting of (H) a metal phosphite and a metal hypophosphite in addition to the components (A) to (C). You may contain.

As metal phosphite and metal hypophosphite contained in the polyamide composition of the present embodiment, for example, phosphorous acid, hypophosphorous acid, pyrophosphorous acid or phosphorous acid, and the periodic table Examples thereof include salts with Group 1 and Group 2 elements, manganese, zinc, aluminum, ammonia, alkylamines, cycloalkylamines, and diamines.
Especially, as a metal phosphite salt and a metal hypophosphite, sodium hypophosphite, calcium hypophosphite, or magnesium hypophosphite is preferable.
By including at least one selected from the group consisting of these metal phosphites and metal hypophosphites, it is possible to obtain a polyamide composition which is more excellent in extrusion processability and molding process stability.

<(I) Phosphite compound>
The polyamide composition of the present embodiment may further contain (I) a phosphite compound in addition to the components (A) to (C).

Examples of the phosphite compound contained in the polyamide composition of the present embodiment include triphenyl phosphite and tributyl phosphite.
By adding a phosphite compound, a polyamide composition that is more excellent in extrusion processability and molding process stability can be obtained.

Specific examples of the phosphite compound include, for example, trioctyl phosphite, trilauryl phosphite, tridecyl phosphite, octyl-diphenyl phosphite, trisisodecyl phosphite, phenyl diisodecyl phosphite, phenyl di (tridecyl) phos Phyto, diphenylisooctyl phosphite, diphenyl isodecyl 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-methylphenyl) pentaerythritol-di-phosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite, 4,4′-butylidene-bis (3-methyl-6) -T-butylphenyl-di-tridecyl) phosphite, 1,1,3-tris (2-methyl-4-ditridecylphosphite-5-t-butyl-phenyl) butane, 4,4'-isopropylidenebis (Phenyl-dialkyl phosphite), tris (2,4-di-t-butylphenyl) phosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite, bis (2,6 And -di-t-butyl-4-methylphenyl) pentaerythritol-di-phosphite and the like.
One of these phosphite compounds may be used alone, or two or more of these phosphite compounds may be used in combination.

<(J) Other additives>
The polyamide composition of the present embodiment is conventionally used for polyamide in addition to the components (A) to (C) described above, as long as the effects of the polyamide composition of the present embodiment are not impaired (J) Others Additives can also be included. (J) Other additives include, for example, colorants (including colored masterbatches) such as pigments and dyes, flame retardants, fibrillating agents, fluorescent bleaches, plasticizers, antioxidants, ultraviolet light absorbers, electrostatic charges There may be mentioned inhibitors, flow improvers, spreading agents, elastomers and the like.

  The content of (J) other additives in the polyamide composition of the present embodiment varies depending on the type, use of the polyamide composition, and the like, so long as the effects of the polyamide composition of the present embodiment are not impaired. There is no particular restriction.

<Method of producing polyamide composition>
As a method for producing the polyamide composition of the present embodiment, the raw material components including the (A) crystalline polyamide, the (B) noncrystalline semiaromatic polyamide, and the (C) carbon fiber are melt-kneaded. If it is a manufacturing method including a process, it will not be limited in particular.
For example, the process of melt-kneading the above-mentioned (A) crystalline polyamide, the above-mentioned (B) amorphous semi-aromatic polyamide, the above-mentioned (C) carbon fiber, and the raw material component containing with an extruder, and setting of the extruder A method in which the temperature is a melting peak temperature Tm2 + 30 ° C. or lower of the polyamide composition described later is preferable.

As a method of melt-kneading the raw material component containing polyamide, the method of the following (1) or (2) etc. are mentioned, for example.
(1) A method of mixing polyamide and other raw materials using a tumbler, a Henschel mixer or the like, supplying to a melt kneader and kneading.
(2) A method of blending other raw materials from a side feeder into polyamide which has been melted by a single-screw or twin-screw extruder.

  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 one time, or the components may be supplied from different supply ports.

The melt-kneading temperature is preferably about 250 ° C. or more and 350 ° C. or less at the resin temperature.
The melting and kneading time is preferably about 0.25 minutes to 5 minutes.
The apparatus for performing melt kneading is not particularly limited, and a known apparatus such as a single or twin screw extruder, a Banbury mixer, a melt kneader (such as a mixing roll) and the like can be used.

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

<Physical properties of polyamide composition>
Specifically, the tan δ peak temperature of the polyamide composition of the present embodiment can be measured by the method described in the examples described later.
Further, the molecular weight, melting point Tm2, crystallization enthalpy ΔH, crystallization peak temperature Tc, amino terminal amount / (amino terminal amount + carboxy terminal amount) of the polyamide composition of the present embodiment, and the gloss value of the obtained molded product are as follows: It can measure by the method shown to.

[Weight average molecular weight (Mw) of polyamide composition]
A weight average molecular weight (Mw) can be used as a parameter | index of the molecular weight of a polyamide composition.
The weight average molecular weight (Mw) of the polyamide composition is preferably 15000 or more and 35000 or less, more preferably 17000 or more and 35000 or less, further preferably 20000 or more and 35000 or less, particularly preferably 22000 or more and 34000 or less, and most preferably 24000 or more and 33000 or less. .
When the weight average molecular weight (Mw) of the polyamide composition is in the above-mentioned range, a polyamide which is more excellent in mechanical properties, particularly in water absorption rigidity, thermal rigidity, flowability and the like can be obtained. In addition, molded articles obtained from the polyamide composition become more excellent in surface appearance.
As a method of controlling the Mw of the polyamide composition within the above range, it is possible to use one in which the weight average molecular weight of the (A) crystalline polyamide and the (B) amorphous semiaromatic polyamide is in the above range, etc. Be
In addition, measurement of Mw of a polyamide composition can be measured using GPC.

[Total content of those having a number average molecular weight Mn of 500 or more and 2000 or less among total polyamides in the polyamide composition]
Among the total polyamide in the polyamide composition, the total content of those having a number average molecular weight Mn of 500 or more and 2000 or less is 0.5% by mass or more and 2.5% by mass with respect to the total mass of the polyamide in the polyamide composition. % Can be less than 0.8% by mass and less than 2.5% by mass, can be 1.0% by mass or more and less than 2.5% by mass, 1.2% by mass or more It can be less than 2.5% by mass, and can be 1.4% by mass or more and less than 2.5% by mass.
Of the total polyamide in the polyamide composition, the number average molecular weight Mn is not less than 500 and not more than 2000, so that the molded product obtained from the polyamide composition is excellent in fluidity because the content is not less than the above lower limit value. Excellent surface appearance. Moreover, by being less than the said upper limit, the gas generation at the time of shaping | molding can be suppressed more effectively.

Examples of a method for controlling the total content of those having a number average molecular weight Mn of 500 or more and 2000 or less among the total polyamide in the polyamide composition within the above range include, for example, (B) Molecular weight of amorphous semi-aromatic polyamide And the like. At this time, the weight average molecular weight (Mw (B)) of the (B) amorphous semi-aromatic polyamide is preferably 10,000 to 25,000.
In addition, the total content of those whose number average molecular weight Mn is 500 or more and 2000 or less among the total polyamide in the polyamide composition can be determined from an elution curve obtained using GPC.
In addition, during GPC measurement, the composition containing (A) crystalline polyamide and (B) amorphous semi-aromatic polyamide contains other components that are soluble in a solvent that dissolves the polyamide. In this case, GPC measurement can be performed after extracting and removing other components using a solvent in which the polyamide is insoluble but the other components are soluble. Also, (C) inorganic fillers such as carbon fibers that are insoluble in the solvent in which the polyamide is dissolved are dissolved in the solvent in which the polyamide composition is dissolved, and then filtered to remove insoluble materials, and then GPC measurement is performed. It can be carried out.

[(A) Difference between weight average molecular weight Mw (A) of crystalline polyamide and (B) weight average molecular weight Mw (B) of amorphous semi-aromatic polyamide {Mw (A) -Mw (B)}]
The difference {Mw (A) -Mw (B)} between the weight average molecular weight Mw (A) of (A) crystalline polyamide and the weight average molecular weight Mw (B) of (B) amorphous semi-aromatic polyamide is 2000 or more. And can be 5000 or more, can be 8000 or more, can be 10000 or more, and can be 12000 or more. When {Mw (A) -Mw (B)} is greater than or equal to the above lower limit, (B) a non-crystalline semi-aromatic polyamide forms a microsize domain and is excellent in water absorption rigidity and thermal rigidity. It can be a thing.

[Molecular weight distribution of polyamide composition]
The molecular weight distribution of the polyamide composition of the present embodiment is represented by weight average molecular weight (Mw) / number average molecular weight (Mn).
The lower limit value of the weight average molecular weight (Mw) / number average molecular weight (Mn) of the polyamide composition of the present embodiment can be 1.0, can be 1.7, and can be 1.8. And can be 1.9.
On the other hand, the upper limit value of Mw / Mn of the polyamide composition of the present embodiment can be 2.4, can be 2.3, and can be 2.2.
That is, Mw / Mn of the polyamide composition of the present embodiment can be 2.4 or less, can be 1.0 or more and 2.4 or less, and can be 1.7 or more and 2.3 or less It can be 1.8 or more and 2.3 or less, and can be 1.9 or more and 2.1 or less.
When Mw / Mn is in the above range, a polyamide composition which is more excellent in fluidity or the like tends to be obtained. In addition, molded articles obtained from polyamide compositions tend to be more excellent in surface appearance.

As a method of controlling Mw / Mn of the polyamide composition within the above range, a method of setting Mw (B) / Mn (B) of the (B) amorphous semiaromatic polyamide within the above range can be mentioned.
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 in the above range, the proportion of polyamide molecules having a three-dimensional structure of molecules can be further lowered, three-dimensional structure formation of molecules can be more suitably prevented during high temperature processing, and flowability You can keep better. This tends to make it possible to improve the surface appearance of molded articles obtained from the polyamide composition.
Mw / Mn of the polyamide composition can be calculated using the weight average molecular weight (Mw) and number average molecular weight (Mn) obtained by using GPC.

[Melting point Tm2 of polyamide composition]
The melting point Tm2 of the polyamide composition can be 200 ° C or higher, can be 220 ° C or higher and 270 ° C or lower, can be 230 ° C or higher and 265 ° C or lower, and can be 240 ° C or higher and 260 ° C or lower. It can be set to 250 ° C. or higher and 260 ° C. or lower.
When the melting point Tm2 of the polyamide composition is not less than the above lower limit value, it tends to be able to obtain a polyamide composition that is superior in thermal rigidity and the like.
On the other hand, when the melting point Tm2 of the polyamide composition is not more than the above upper limit value, the thermal decomposition of the polyamide composition in the melt processing such as extrusion and molding tends to be further suppressed.

[Crystallization enthalpy ΔH of polyamide composition]
The lower limit value of the crystallization enthalpy ΔH of the polyamide composition can be 10 J / g, can be 14 J / g, and can be 18 J / g, from the viewpoint of mechanical properties, particularly water absorption rigidity, thermal rigidity. Can be 20 J / g. On the other hand, the upper limit value of the crystallization enthalpy ΔH is not particularly limited and is preferably as high as possible.
As a method of controlling the crystallization enthalpy ΔH of the polyamide composition within the above range, for example, a method of controlling the contents of (A) crystalline polyamide and (B) amorphous semi-aromatic polyamide within the above range, etc. Is mentioned.
As a measuring apparatus of melting | fusing point Tm2 and crystallization enthalpy (DELTA) H of a polyamide composition, Diamond-DSC made from PERKIN-ELMER, etc. are mentioned, for example.

[Tan δ peak temperature of polyamide composition]
The lower limit of the tan δ peak temperature of the polyamide composition is preferably 90 ° C, more preferably 100 ° C, still more preferably 110 ° C, and particularly preferably 120 ° C.
The upper limit of the tan δ peak temperature of the polyamide composition is preferably 150 ° C, more preferably 140 ° C, and even more preferably 130 ° C.
That is, the tan δ peak temperature of the polyamide composition is preferably 90 ° C. or higher and 150 ° C. or lower, more preferably 100 ° C. or higher and 140 ° C. or lower, further preferably 110 ° C. or higher and 130 ° C. or lower, and particularly preferably 120 ° C. or higher and 130 ° C. or lower.
When the tan δ peak temperature of the polyamide composition is equal to or higher than the above lower limit, a polyamide composition excellent in water absorption rigidity and thermal rigidity tends to be obtained. In addition, when the tan δ peak temperature of the polyamide composition is less than or equal to the above upper limit value, a molded article obtained from the polyamide composition becomes more excellent in surface appearance.
Examples of the method of controlling the tan δ peak temperature of the polyamide composition within the above range include a method of controlling the blending ratio of (A) crystalline polyamide and (B) amorphous semi-aromatic polyamide to the above range. Can be mentioned.

[Crystallization peak temperature Tc obtained when the polyamide composition is cooled at 20 ° C./min]
The crystallization peak temperature Tc (° C.) obtained when the polyamide composition is cooled at 20 ° C./min can be 160 ° C. or higher and 240 ° C. or lower, 170 ° C. or higher and 230 ° C. or lower, 180 The temperature can be in the range of ° C to 225 ° C, can be in the range of 190 ° C to 220 ° C, and can be in the range of 200 ° C to 215 ° C.
When the crystallization peak temperature Tc (° C.) of the polyamide composition is equal to or higher than the lower limit, a polyamide composition that is more excellent in releasability during molding can be obtained.
On the other hand, when the crystallization peak temperature Tc (° C.) of the polyamide composition is not more than the above upper limit value, the surface appearance of the molded product obtained from the polyamide composition becomes more excellent.

The melting point crystallization peak temperature Tc of the polyamide composition of the present embodiment can be measured according to JIS-K7121.
As a measuring apparatus of crystallization peak temperature Tc, Diamond-DSC made from PERKIN-ELMER, etc. are mentioned, for example.
Examples of the method of controlling the crystallization peak temperature Tc of the polyamide within the above range include a method of controlling the blending ratio of (A) crystalline polyamide and (B) amorphous semi-aromatic polyamide within the above range. Be

[Mass ratio of amino terminus to total mass of amino terminus amount and carboxy terminus amount in polyamide composition {amino terminus amount / (amino terminus amount + carboxy terminus amount)}]
The ratio of the mass of amino terminal to the total mass of the amount of amino terminal and the amount of carboxy terminal in the polyamide composition {amino terminal amount / (amino terminal amount + carboxy terminal amount)} is 0.25 or more and less than 0.4. And can be 0.35 or more and less than 0.4, and can be 0.25 or more and less than 0.35. When the ratio of the mass of the amino terminus to the total mass of the amino terminus and the carboxy terminus is equal to or more than the above lower limit, the corrosion of the extruder or the molding machine can be suppressed more effectively. When the ratio of the mass of the amino terminus to the total mass of the amount of the amino terminus and the amount of the carboxy terminus is less than the above upper limit value, it is possible to obtain a polyamide composition excellent by color change to heat or light.
The amino terminal amount and the carboxy terminal amount can be measured by neutralization titration, and the ratio of the mass of the amino terminal to the total mass of the amino terminal amount and the carboxy terminal amount by the measured amino terminal amount and carboxy terminal amount {amino terminal The amount / (amino terminal amount + carboxy terminal amount)} can be calculated.

[Gloss value of molded articles obtained from polyamide composition]
The surface gloss value of the molded article obtained from the polyamide composition can be 50 or more, can be 55 or more, and can be 60 or more. When the surface gloss value of the polyamide composition is the above lower limit value or more, it is more suitably used as a molding material for various parts such as for automobiles, for electric and electronic applications, for industrial materials, for industrial materials, for daily use and household products. It can be used.
The surface gloss value can be measured by the method described in the examples below.

«Molded goods»
The molded article of the present embodiment is formed by molding the polyamide composition of the above-described embodiment.
The molded article of the present embodiment is excellent in mechanical properties, particularly in terms of water absorption rigidity, thermal rigidity and surface appearance.

The molded product of this embodiment is obtained by molding the polyamide composition using 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 melt spinning. And generally known plastic molding methods.

<Use>
Since the molded article of the present embodiment is obtained from the above-described polyamide composition, it is excellent in water absorption rigidity, thermal rigidity and surface appearance. Therefore, the molded product of the present embodiment is various parts such as automobile parts, electric and electronic parts, household appliance parts, OA (Office Automation) equipment parts, portable equipment parts, industrial equipment parts, daily necessities and household goods, It can be suitably used for extrusion applications and the like. Among them, the molded article of the present embodiment is suitably used as an automobile part, an electric and electronic part, a home electric appliance part, an OA equipment part or a mobile equipment part.

  Examples of automobile parts include, but are not limited to, intake system parts, cooling system parts, fuel system parts, interior parts, exterior parts, electrical parts and the like.

The automobile intake system parts are not particularly limited, and examples thereof 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.
The automobile cooling system parts are not particularly limited, and examples thereof include a chain cover, a thermostat housing, an outlet pipe, a radiator tank, an alternator, a delivery pipe and the like.
Although there is no particular limitation on automobile fuel system parts, for example, a fuel delivery pipe, a gasoline tank case and the like can be mentioned.
The automobile interior parts are not particularly limited, and examples thereof include an instrumental panel, a console box, a glove box, a steering wheel, and a trim.
The exterior parts of the automobile are not particularly limited, and examples thereof include a molding, a lamp housing, a front grill, a mud guard, a side bumper, a door mirror stay, a roof rail and the like.
Examples of the automotive electrical components include, but are not limited to, connectors, wire harness connectors, motor parts, lamp sockets, sensor in-vehicle switches, combination switches, and the like.

Examples of the electrical and electronic components include, but are not limited to, connectors, reflectors for light emitting devices, switches, relays, printed wiring boards, housings for electronic components, outlets, noise filters, coil bobbins, motor end caps, and the like.
In addition to light emitting diodes (LEDs), semiconductor packages such as photo diodes such as laser diodes (LDs), photo diodes, charge coupled devices (CCDs), and complementary metal oxide semiconductors (CMOS) as light emitting device reflectors Can be used widely.

  The portable device parts are not particularly limited, and examples thereof include casings and structures of a mobile phone, a smartphone, a personal computer, a portable game device, a digital camera and the like.

  Examples of the industrial equipment parts include, but are not limited to, gears, cams, insulating blocks, valves, power tool parts, agricultural machinery parts, engine covers, and the like.

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

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

The molded article of this embodiment is particularly suitable for exterior structural materials among these various uses. The structural material for exterior is a mechanical component or structural component that requires surface processability of a molded product (for example, texture processing, high surface glossiness, etc.) and that requires relatively large strength and rigidity.
Specific examples of the exterior structural material include OA equipment field products, automobile parts, electrical field products, and other field products.
Examples of OA equipment field products include furniture such as desk legs, chair legs, seats, cabins, wagon parts, and notebook personal computer housings.
Examples of automobile parts include door mirror stays, wheel rims, wheel caps, wipers, motor fans, seat lock parts, gears, lamp housings, wheel rims, wheel spokes, saddles, saddle posts, handles, stands, and cargo beds. .
Examples of the electrical field article include a pulley, a gear, and a hot air fan housing.
Examples of other field products include valve housings, nails, screws, bolts, bolts and nuts.

Moreover, since the molded article of the present embodiment is excellent in surface appearance, it is preferably used also as a molded article in which a coating film is formed on the surface of the molded article.
The method for forming the coating film is not particularly limited as long as it is a known method, and for example, the coating method such as a spray method or an electrostatic coating method can be used.
The paint used for coating is not particularly limited as long as it is a known one. For example, a melamine cross-linked polyester polyol resin paint, an acrylic urethane paint, or the like can be used.
Among these, the molded product of the present embodiment is excellent in mechanical strength, toughness, heat resistance, vibration fatigue resistance, and is more suitable as a component material for automobiles. Are particularly suitable as component materials for gears, bearings. Moreover, since it is excellent in mechanical strength, toughness, and heat resistance, it is more suitable as component materials for electricity and electronics.

Hereinafter, the present invention will be described in detail by way of specific examples and comparative examples, but the present invention is not limited to the following examples.
In the examples, 1 kg / cm ² means 0.098 MPa.
Hereinafter, the (A) crystalline polyamide, the (B) amorphous semi-aromatic polyamide, and the (C) carbon fiber used in Examples and Comparative Examples will be described.

<Components>
[(A) crystalline polyamide]
A-1 to A-5: Polyamide 66 (The production method is as described later)
A-6: Polyamide MXD6 resin “Renny” (registered trademark) # 6002 (manufactured by Mitsubishi Engineering Plastics) (Tm: 238 ° C., Tc: 161 ° C.)
A-7: Polyamide 6 SF1013A (manufactured by Ube Industries) (Tm224 ° C.)

[(B) Amorphous semi-aromatic polyamide]
B-1: Polyamide 6I Mw (B) = 35000, Mw (B) / Mn (B) = 2
B-2: Polyamide 6I T-40 (manufactured by LANXESS CORPORATION) Mw (B) = 44000, Mw (B) / Mn (B) = 2.8

[(C) Carbon fiber]
C-1: Carbon fiber HTC413 (manufactured by Toho Tenax)
C-2: Carbon fiber TR60NE (Mitsubishi Rayon Co., Ltd.)

<Method of Producing (A) Crystalline Polyamide and (B) Amorphous Semi-Aromatic Polyamide>
[material]
The (A) crystalline polyamide and the (B) amorphous semi-aromatic polyamide used in the examples and comparative examples were produced using the following (a) and (b) as appropriate.
((A) dicarboxylic acid)
a-1: Adipic acid (ADA) (manufactured by Wako Pure Chemical Industries)
a-2: Isophthalic acid (IPA) (manufactured by Wako Pure Chemical Industries, Ltd.)
((B) diamine)
b-1: 1,6-diaminohexane (hexamethylenediamine) (C6DA) (manufactured by Tokyo Chemical Industry)

Synthesis Example 1 Synthesis of Crystalline Polyamide A-1 (Polyamide 66) The polymerization reaction of polyamide was carried out as follows by the “heat melting polymerization method”.
First, 1500 g of equimolar salt of adipic acid and hexamethylene diamine was dissolved in 1500 g of distilled water to prepare an equimolar 50 mass% uniform aqueous solution of the raw material monomer. 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 ° C. or more and 150 ° C. or less, water vapor was gradually withdrawn and concentrated to a solution concentration of 70% by mass. 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 polymerization was 265.degree.
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 at 100 ° C. in a nitrogen atmosphere for 12 hours to obtain crystalline polyamide A-1. .
Crystalline polyamide A-1 (polyamide 66) obtained had a weight average molecular weight (Mw) of 35000 and a weight average molecular weight (Mw (A)) / number average molecular weight (Mn (A)) = 2. The amino end group concentration of polyamide A-1 (polyamide 66) was 45 μmol / g, and the carboxy end group concentration was 60 μmol / g.

Synthesis Example 2 Synthesis of Crystalline Polyamide A-2 (Polyamide 66) The same as Synthesis Example 1 except that 900 g of adipic acid was further added to a 50% by mass equimolar aqueous solution of the raw material monomer prepared in Synthesis Example 1. Crystalline polyamide A-2 was obtained using the method.
The obtained crystalline polyamide A-2 (polyamide 66) had Mw (A) = 35000 and Mw (A) / Mn (A) = 2. The amino end group concentration of crystalline polyamide A-2 (polyamide 66) was 33 μmol / g, and the carboxy end group concentration was 107 μmol / g.

Synthesis Example 3 Synthesis of Crystalline Polyamide A-3 (Polyamide 66) In the same manner as in Synthesis Example 1 except that 900 g of hexamethylene diamine was further added to a 50% by mass equimolar aqueous solution of the raw material monomer prepared in Synthesis Example 1. The crystalline polyamide A-3 was obtained using the method of
Crystalline polyamide A-3 (polyamide 66) obtained had Mw = 35000 and Mw / Mn = 2. The amino end group concentration of crystalline polyamide A-3 (polyamide 66) was 78 μmol / g, and the carboxy end group concentration was 52 μmol / g.

Synthesis Example 4 Synthesis of Crystalline Polyamide A-4 (Polyamide 66) The polymerization reaction of polyamide was carried out as follows by the “heat melting polymerization method”.
First, 1500 g of equimolar salt of adipic acid and hexamethylene diamine was dissolved in 1500 g of distilled water to prepare an equimolar 50 mass% uniform aqueous solution of the raw material monomer. 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 ° C. or higher and 150 ° C. or lower, the water vapor was gradually withdrawn 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.
Then, it was pressurized with nitrogen and formed into a strand from the lower spinning nozzle (nozzle), water cooled, cut, discharged in the form of pellets, and dried at 100 ° C. under a nitrogen atmosphere for 12 hours to obtain a polyamide. The obtained polyamide had Mw = 35000 and Mw / Mn = 2. Thereafter, the pellet was subjected to solid phase polymerization at 200 ° C. for 6 hours to obtain crystalline polyamide A-4.
The obtained crystalline polyamide A-4 (polyamide 66) had Mw (A) = 70000 and Mw (A) / Mn (A) = 3.0. Crystalline polyamide A-4 (polyamide 66) had an amino end group concentration of 45 μmol / g and a carboxy end group concentration of 60 μmol / g.

Synthesis Example 5 Synthesis of Crystalline Polyamide A-5 (Polyamide 66) The polymerization reaction of polyamide was carried out as follows by the “heat melting polymerization method”.
First, 1500 g of equimolar salt of adipic acid and hexamethylene diamine was dissolved in 1500 g of distilled water to prepare an equimolar 50 mass% uniform aqueous solution of the raw material monomer. 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 ° C. or higher and 150 ° C. or lower, the water vapor was gradually withdrawn 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 5 minutes. At this time, the final internal temperature of polymerization was 265.degree.
Then, it pressurized with nitrogen and made strand shape from the lower spinning nozzle (nozzle), carried out water cooling, cut and discharged in pellet form, dried at 100 ° C. under nitrogen atmosphere for 12 hours to obtain crystalline polyamide A-5. .
Crystalline polyamide A-5 (polyamide 66) obtained had Mw (A) = 25000 and Mw (A) / Mn (A) = 2. Crystalline polyamide A-5 (polyamide 66) had an amino end group concentration of 60 μmol / g and a carboxy end group concentration of 80 μmol / g.

[Synthesis Example 6] Synthesis of Amorphous Semi-Aromatic Polyamide B-1 (Polyamide 6I) A polyamide polymerization reaction was carried out by the "hot melt polymerization method" as follows.
First, 1500 g of equimolar salt of isophthalic acid and hexamethylene diamine and 1.5 mol% excess of adipic acid with respect to the total equimolar salt component are dissolved in 1500 g of distilled water, and 50 mol% of the raw material monomer is equimolar. A homogeneous aqueous solution was prepared.
While stirring at a temperature of 110 ° C. or higher and 150 ° C. or lower, the water vapor was gradually withdrawn 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 polymerization was 265.degree.
Then, it is pressurized with nitrogen and made into strands from the lower spinning nozzle (nozzle), water cooled, cut and discharged in the form of pellets, dried at 100 ° C. under nitrogen atmosphere for 12 hours, amorphous semi-aromatic polyamide B- 1 was obtained.
The obtained noncrystalline semiaromatic polyamide B-1 (polyamide 6I) had Mw (B) = 35000 and Mw (B) / Mn (B) = 2.

<Physical properties and evaluation>
The physical properties of the crystalline polyamides A-1 to A-7, the amorphous aromatic polyamides B-1 to B-2, and the respective polyamide compositions were measured using the following methods.
Moreover, various evaluation was implemented by the following method using each polyamide composition and each molded article obtained by the Example and the comparative example.

[Various physical properties of (A) crystalline polyamide and (B) amorphous aromatic polyamide]
[Physical property 1] Melting peak temperature Tm2 (melting point), crystallization peak temperature Tc, crystallization enthalpy ΔH
According to JIS-K7121, it measured using PERKIN-ELMER Diamond-DSC made. Specifically, it was measured as follows.
First, in a nitrogen atmosphere, about 10 mg of each polyamide was heated from room temperature to about 300 ° C. to 350 ° C. at a rate of temperature increase of 20 ° C./min depending on the melting point of the sample. The maximum peak temperature of the endothermic peak (melting peak) appearing at this time was defined as Tm1 (° C.). Next, it was kept at the highest temperature rise for 2 minutes. At this maximum temperature, the polyamide was in a molten state. Thereafter, the temperature was lowered to 30 ° C. at a temperature lowering 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 at a temperature increase rate of 20 degrees C / min. The maximum peak temperature of the endothermic peak (melting peak) appearing at this time was defined as the melting point Tm2 (° C.).

[Physical property 2] Weight average molecular weight (Mw), number average molecular weight (Mn), molecular weight distribution Mw / Mn
The weight average molecular weight (Mw) and the number average molecular weight (Mn) were measured using gel permeation chromatography (GPC). The measurement conditions were as follows.
(Measurement condition)
Apparatus: Tosoh Corporation HLC-8020
Solvent: Hexafluoroisopropanol Measurement: PMMA (polymethyl methacrylate) standard sample (manufactured by Polymer Laboratories)

  Moreover, molecular weight distribution Mw / Mn was calculated from the obtained value.

[Physical property 3] Amino end group concentration and carboxy end group concentration of polyamide (1) Amino end group concentration ([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 90% by mass aqueous phenol solution, and the obtained solution was titrated with 0.025 N hydrochloric acid to determine the amount of amino terminal (μ equivalent / g). The end point was determined from the reading of the pH meter.

(2) Carboxy terminal group concentration ([COOH])
The amount of carboxy terminal bound to the polymer terminal was measured by neutralization titration as follows.
4.0 g of polyamide was dissolved in 50 mL of benzyl alcohol, and the obtained solution was titrated with 0.1 N NaOH to determine the amount of carboxy terminal (μ equivalent / g). The end point was determined from the color change of the phenolphthalein indicator.

[Physical properties of polyamide composition]
[Physical Property 4] Tan δ Peak Temperature of Polyamide Composition Using a viscoelasticity measurement analyzer (Rheology: DVE-V4), the parallel part of the ASTM D1822 TYPE L specimen prepared from each polyamide composition was cut into a strip shape. The temperature dispersion spectrum of the dynamic viscoelasticity of the test piece was measured 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 jaws). The ratio E2 / E1 of the storage elastic modulus E1 to the loss elastic modulus E2 is tan δ, and the highest temperature is the tan δ peak temperature.
(Measurement condition)
Measurement mode: Tensile Waveform: Sine wave Frequency: 3.5Hz
Temperature range: 0 ° C to 180 ° C Heating step: 2 ° C / min
Static load: 400g
Displacement amplitude: 0.75 μm

[Evaluation of Polyamide Composition and Molded Article]
[Evaluation 1] Surface Gloss Value The central portion of the flat plate molded piece obtained in Examples and Comparative Examples was measured for 60 degree gloss according to JIS-K7150 using a gloss meter (IG320 manufactured by HORIBA). The larger the measured value, the better the surface appearance.

[Evaluation 2] Pellet shape The pellet shape of the polyamide compositions obtained in Examples and Comparative Examples was visually confirmed. The evaluation criteria for the pellet shape were as follows. It was evaluated that obtaining a pellet with a good shape would lead to an improvement in productivity.
(Evaluation criteria)
5: no fuzz, cylindrical substantially uniform shape pellet 4: no fuzz, most of cylindrical shape pellets of uniform shape 3: some fuzz, most cylindrical shapes are uniform Pellets with a shape 2: Fluffy, cylindrical non-uniform pellets 1: Fluffy, irregularly shaped pellets

[Evaluation 3] Chip amount The chip amount at the time of manufacture of the polyamide compositions in Examples and Comparative Examples was visually confirmed. The evaluation criteria for the amount of chips were as follows. It was evaluated that the small amount of chips leads to the improvement of productivity.
(Evaluation criteria)
5: almost no chips 4: some fine chips are present 3: fine chips are noticeable but large chips are not present 2: some fine chips are present, some large chips are present 1: There are quite a few fine chips and large chips

[Evaluation 4] Tensile strength A tensile test was conducted at a tensile speed of 50 mm / min under a temperature condition of 80 ° C. in accordance with ISO 527 using molded pieces of multi-purpose test piece A obtained in Examples and Comparative Examples. , Tensile yield stress was measured, and was taken as tensile strength.

[Evaluation 5] Bending Strength The multi-purpose test piece A-shaped molded pieces obtained in Examples and Comparative Examples were cut to obtain test pieces of 80 mm long × 10 mm wide × 4 mm thick. The bending strength was measured according to ISO178.

[Evaluation 6] Notched Charpy Impact Strength The multi-purpose test piece A-shaped molded pieces obtained in Examples and Comparative Examples were cut to obtain test pieces of 80 mm long × 10 mm wide × 4 mm thick. The notched Charpy impact strength (kJ / m ² ) was measured using the test piece while conforming to ISO 179.

<Production of polyamide composition>
[Examples 1 to 11 and Comparative Examples 1 to 5]
(1) Production of Polyamide Composition Using the (A) crystalline polyamide, the (B) amorphous semi-aromatic polyamide and the (C) carbon fiber described above so as to have types and proportions described in Table 1 below. Each polyamide composition was produced by the following method.
The crystalline polyamides A-1 to A-5 and the non-crystalline aromatic polyamide B-1 synthesized above are dried in a nitrogen stream to adjust the water content to about 0.2 mass%, It used as a raw material of a polyamide composition.

As a manufacturing apparatus of a polyamide composition, a twin-screw extruder [ZSK-26MC: manufactured by Copellion (Germany)] was used.
The twin-screw extruder has an upstream feed port in the first barrel from the upstream side of the extruder, a downstream first feed port in the sixth barrel, and a downstream second feed port in the ninth barrel. Had. Moreover, in the twin-screw extruder, the extruder length (L1) / screw diameter (D1) was 48, and the number of barrels was 12.
In the twin-screw extruder, the temperature from the upstream supply port to the die was set to the melting point Tm 2 + 20 ° C of each polyamide, and the screw rotation speed was set to 250 rpm, and the discharge amount was 25 kg / h.

  As a specific production method using the above-mentioned production apparatus, after dry blending of (A) crystalline polyamide and (B) amorphous semi-aromatic polyamide, it is supplied from the upstream feed port of a twin-screw extruder, (C) Carbon fibers were supplied from the downstream first feed port of the twin-screw extruder, and the melt-kneaded product extruded from the die head was cooled in the form of a strand and pelletized to obtain pellets of each polyamide composition. 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.

(2) Production of Molded Product 1 (Flat Plate Molded Piece) Subsequently, using the injection molding machine (NEX 50 III-5 EG, manufactured by Nissei Resin Industry Co., Ltd.), the pellets of each obtained polyamide composition were subjected to the following conditions The injection pressure and the injection speed were appropriately adjusted so that the filling time was in the range of 1.6 ± 0.1 seconds, and flat plate molded pieces (6 cm × 9 cm, thickness 2 mm) were produced. About each obtained flat plate shaping | molding piece, surface glossiness evaluation was performed by said method. The results are shown in Tables 1 and 2.
(Production conditions)
Cooling time: 25 seconds Screw speed: 200 rpm
Mold temperature: Tan δ peak temperature + 5 ° C
Cylinder temperature: (Tm2 + 10) ° C or higher and (Tm2 + 30) ° C or lower

(3) Production of Molded Article 2 (Molded Piece of Multipurpose Test Piece A) Next, with respect to the obtained pellets of each polyamide composition, using an injection molding machine (PS-40E, manufactured by Nisshin Resin Co., Ltd.) In accordance with ISO 3167, each was molded into a multi-purpose specimen A-shaped molded piece. Specific molding conditions were as follows: injection + holding time 25 seconds, cooling time 15 seconds, mold temperature 80 ° C., and molten resin temperature set at the high temperature melting peak temperature (Tm2) + 20 ° C. of the polyamide. About each obtained multi-purpose test piece A type molded piece, the tensile strength, bending strength, and notched Charpy impact strength were evaluated by the above-described methods. The results are shown in Tables 1 and 2. In addition, regarding “weight average molecular weight Mw” in Table 1 and Table 2, “−” indicates that it has not been measured.

  From Tables 1 and 2, a polyamide composition comprising (A) crystalline polyamide, (B) amorphous aromatic polyamide and (C) carbon fiber, wherein (B) amorphous aromatic polyamide is B) In all the dicarboxylic acid units constituting the amorphous semiaromatic polyamide, carbon is contained in all diamine units containing 75 mol% or more of the isophthalic acid unit and constituting the (B) amorphous semiaromatic polyamide The polyamide composition (Examples 1 to 11) containing 50 mol% or more of diamine units of several 4 to 10 has various mechanical properties (tensile strength) than the polyamide compositions (Comparative Examples 1 to 5) which do not have the above configuration. Further, while maintaining good bending strength and notched Charpy strength), the surface appearance and pellet shape were excellent, and the amount of chips generated was reduced.

  Moreover, according to the increase in content of crystalline polyamide A-1, reduction of a pellet shape and a chip from the comparison of the polyamide composition (Example 1, 9-11) from which content of crystalline polyamide A-1 differs. And the surface gloss of the molded product tended to be better.

  The polyamide composition of the present embodiment is excellent in the shape of the pellet, the amount of chips generated is reduced, and a molded product having an excellent surface appearance can be obtained. The molded article of the present embodiment can be suitably used as a molding material for various parts, such as for automobiles, for electric and electronics, for industrial materials, for industrial materials, for daily use and household products.

Claims (12)

(A) crystalline polyamide;
(B) Amorphous semi-aromatic polyamide,
(C) carbon fiber;
A polyamide composition containing
The (B) amorphous semi-aromatic polyamide contains 75 mol% or more of isophthalic acid units in all the dicarboxylic acid units constituting the (B) amorphous semi-aromatic polyamide, and the (B) non-non-polyamide The polyamide composition which contains 50 mol% or more of C4 or more and 10 or less diamine unit in all the diamine units which comprise crystalline semi-aromatic polyamide.   The polyamide composition according to claim 1, wherein the tan δ peak temperature is 90 ° C or higher.   The polyamide composition according to claim 1 or 2, wherein a content of the (C) carbon fiber in the polyamide composition is 30% by mass or more and 65% by mass or less.   The crystalline polyamide (A) is polyamide 4 (polyα-pyrrolidone), polyamide 6 (polycaproamide), polyamide 11 (polyundecanamide), polyamide 12 (polydodecanamide), polyamide 46 (polytetramethylene adipa). Amide), polyamide 56 (polypentamethylene adipamide), polyamide 66 (polyhexamethylene adipamide), polyamide 610 (polyhexamethylene sebacamide), polyamide 612 (polyhexamethylene dodecamide), polyamide 6T (poly The hexamethylene terephthalamide), polyamide 9T (polynonane methylene terephthalamide), and one or more selected from the group consisting of copolyamides containing these as a constituent component according to any one of claims 1 to 3. Polyamide composition.   The content of the (B) amorphous polyamide is 10 parts by mass to 50 parts by mass with respect to 100 parts by mass of the total amount of the (A) crystalline polyamide and the (B) amorphous semiaromatic polyamide. The polyamide composition as described in any one of 1-4. The polyamide composition as described in any one of Claims 1-5 with which the content mass of said (B) amorphous semi-aromatic polyamide and said (C) carbon fiber satisfy | fills the relationship of following formula (1).

  The weight average molecular weight Mw of the said polyamide composition is 15000 or more and 35000 or less, The polyamide composition as described in any one of Claims 1-6.   The polyamide composition according to any one of claims 1 to 7, 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 8, wherein the (B) amorphous semi-aromatic polyamide is polyamide 6I.   The polyamide composition according to any one of claims 1 to 9, wherein the weight average molecular weight Mw (B) of the (B) amorphous semiaromatic polyamide is 10000 or more and 25000 or less.   The polyamide composition according to any one of claims 1 to 10, wherein the molecular weight distribution Mw (B) / Mn (B) of the (B) amorphous semiaromatic polyamide is 2.4 or less.   The molded article formed by shape | molding the polyamide composition as described in any one of Claims 1-11.