JP2015155537A - Polyamide resin composition, molded body and manufacturing method of polyamide resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyamide resin composition having excellent physical property during absorption of water and excellent in appearance.

SOLUTION: There is provided a polyamide resin composition containing (A) a polyamide resin and (B) an inorganic reinforcement material and satisfying a condition (e) where (A) is copolymer polyamide and/or polyamide mixture containing a constitutional unit containing dicarboxylic acid having a ring structure and/or diamine having the ring structure and satisfying conditions of (a) to (d). (a) a ratio of the number of carbon/the number of oxygen, C/N is over 7.0. (b) Tg when dried obtained by a viscoelasticity measurement is 70°C or more. (c) a crystallization enthalpy ΔHc obtained when cooled at 20°C/min by a differential scanning calorimetry is 10 J/g or more, (d) difference between a melting point peak temperature Tm and a crystallization peak temperature Tc, Tm-Tc obtained when heated and cooled at 20°C/min by a differential scanning calorimetry is 45°C or more. (e) a ratio between a weight average molecular weight Mw and a number average molecular weight Mn, Mw/Mn, is 2.9 or less.

COPYRIGHT: (C)2015,JPO&INPIT

Description

  The present invention relates to a polyamide resin composition, a molded body, and a method for producing a polyamide resin composition.

  Conventionally, polyamide resins are widely used as various parts materials for clothing, industrial materials, automobiles, electrical / electronics, and industrial use because of their excellent molding processability, mechanical properties and chemical resistance. It has been.

  In recent years, the use environment of polyamide resins has a tendency to become severer in terms of heat and dynamics, and the physical properties in use in harsh environments with improved mechanical properties, in particular, rigidity after water absorption and rigidity under high temperature use. There is a demand for a polyamide resin material with little change and a polyamide resin material with less dependence on molding conditions, which can provide a stable product even under severe molding conditions.

  In order to meet the above-described requirements, as a method for improving the mechanical properties of the polyamide resin material, 40 to 90 mol% of repeating units derived from terephthalic acid and an aliphatic diamine having 4 to 12 carbon atoms, isophthalic acid and 0 to 50 mol% of a repeating unit derived from an aliphatic diamine having 4 to 12 carbon atoms, a repeating unit derived from an aliphatic dicarboxylic acid having 4 to 18 carbon atoms and an aliphatic diamine having 4 to 12 carbon atoms Are disclosed in semi-aromatic polyamides each containing 0 to 60 mol% (see, for example, Patent Document 1).

International Publication No. 97/15610

  However, the conventionally proposed polyamide resin materials still have room for improvement with respect to changes in physical properties during water absorption, and further improvements in the properties of polyamide resin materials during water absorption are required.

  Therefore, in view of the above-described problems of the prior art, an object of the present invention is to provide a polyamide resin composition having excellent physical properties at the time of water absorption and excellent appearance.

As a result of intensive studies to solve the above problems, the present inventors,
(A) In the polyamide resin composition containing the polyamide resin and (B) the inorganic reinforcing material, the (A) polyamide resin in the polyamide composition is measured under a C / N ratio, a glass transition point, and a predetermined condition. Specify the crystallization enthalpy, the difference between the melting point peak temperature (Tm) measured under the specified conditions and the crystallization peak temperature (Tc) (Tm-Tc), and specify the one having the predetermined molecular weight distribution Thus, the inventors have found that the above-mentioned problems can be solved, and have completed the present invention.
That is, the present invention is as follows.

[1]
A polyamide resin composition comprising (A) a polyamide resin and (B) an inorganic reinforcement,
The (A) polyamide resin includes a structural unit of polyamide containing a dicarboxylic acid having a cyclic structure and / or a diamine having a cyclic structure, and satisfies the following conditions (a) to (d):
A copolymerized polyamide and / or a polyamide mixture,
A polyamide resin composition that satisfies the following condition (e).
(A) The ratio of carbon number / nitrogen number (C / N ratio) exceeds 7.0.
(B) The glass transition point at the time of drying calculated | required from a viscoelasticity measurement is 70 (degreeC) or more.
(C) The crystallization enthalpy (ΔHc) obtained by cooling at 20 (° C./min) by differential scanning calorimetry is 10 (J / g) or more.
(D) By differential scanning calorimetry, the difference (Tm−Tc) between the melting point peak temperature (Tm) and the crystallization peak temperature (Tc) obtained when heated and cooled at 20 (° C./min) is 45 (° C.). that's all.
(E) The ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is 2.9 or less.
[2]
(A) The polyamide resin composition according to [1], wherein the dicarboxylic acid constituting the polyamide resin includes terephthalic acid and / or isophthalic acid.
[3]
The polyamide resin composition according to [1] or [2], wherein the (A) polyamide resin satisfies the following conditions (a-1) and (c-1).
(A-1) The ratio of carbon number / nitrogen number (C / N ratio) is 7.2 or more.
(C-1) The crystallization enthalpy (ΔHc) obtained by cooling at 20 (° C./min) by differential scanning calorimetry is 20 (J / g) or more.
[4]
The polyamide resin composition according to any one of [1] to [3], wherein the (A) polyamide resin satisfies the following conditions (a-2), (b-2), and (c-2): object.
(A-2) The ratio of carbon number / nitrogen number (C / N ratio) is 7.3 or more.
(B-2) The glass transition point at the time of drying calculated | required from a viscoelasticity measurement is 80 (degreeC) or more.
(C-2) The crystallization enthalpy (ΔHc) obtained when cooled at 20 (° C./min) by differential scanning calorimetry is 30 (J / g) or more.
[5]
The (A) polyamide resin is
(A-1) 30-50 mol% of structural units of an aliphatic polyamide having a carbon number / nitrogen number ratio (C / N ratio) of 8.0 or more,
(A-2) 20 to 70 mol% of a structural unit composed of hexamethylenediamine and terephthalic acid,
(A-3) 3 to 25 mol% of a structural unit composed of hexamethylenediamine and isophthalic acid,
The polyamide resin composition according to any one of [1] to [4], which is contained.
[6]
(A-1) The structural unit of the aliphatic polyamide whose carbon number / nitrogen number ratio (C / N ratio) is 8.0 or more is:
The polyamide resin composition according to [5], which is one or more structural units selected from the group consisting of PA610, PA612, PA11, PA12, PA1010, and PA1012.
[7]
For 100 parts by mass of the (A) polyamide resin,
(B) The polyamide resin composition according to any one of [1] to [6], which contains 10 to 250 parts by mass of an inorganic reinforcing material.
[8]
For 100 parts by mass of the (A) polyamide resin,
10 to 250 parts by mass of the (B) inorganic reinforcing material,
(C) The polyamide resin composition according to any one of [1] to [7], further including 0.005 to 10 parts by mass of a heat stabilizer.
[9]
For 100 parts by mass of the (A) polyamide resin,
10 to 250 parts by mass of the (B) inorganic reinforcing material,
(D) The polyamide resin composition according to any one of [1] to [8], further including 0.005 to 3 parts by mass of a moldability improver.
[10]
For 100 parts by mass of the (A) polyamide resin,
10 to 250 parts by mass of the (B) inorganic reinforcing material,
(E) The polyamide resin composition according to any one of [1] to [9], further including 1 to 30 parts by mass of a flame retardant.
[11]
A molded article containing the polyamide resin composition according to any one of [1] to [10].
[12]
(A-1) a structural unit of an aliphatic polyamide having a carbon number / nitrogen number ratio (C / N ratio) of 8.0 or more;
(A-2) a structural unit consisting of hexamethylenediamine and terephthalic acid;
(A-3) a structural unit consisting of hexamethylenediamine and isophthalic acid;
(A) a polyamide resin containing
(B) an inorganic reinforcing material;
Is produced by melt kneading with an extruder.

  ADVANTAGE OF THE INVENTION According to this invention, the polyamide resin composition which has the outstanding physical property at the time of water absorption and was excellent also in the external appearance property can be provided.

Hereinafter, a mode for carrying out the present invention (hereinafter simply referred to as “the present embodiment”) will be described in detail.
The following embodiments are examples for explaining the present invention, and are not intended to limit the present invention to the following contents. The present invention can be implemented with appropriate modifications within the scope of the gist thereof.

[Polyamide resin composition]
The polyamide resin composition of this embodiment is
A polyamide resin composition comprising (A) a polyamide resin and (B) an inorganic reinforcement,
The (A) polyamide resin contains a structural unit of polyamide containing a dicarboxylic acid having a cyclic structure and / or a diamine having a cyclic structure, and satisfies the following conditions (a) to (d): It is a polyamide mixture and is a polyamide resin composition that satisfies the following condition (e).
(A) The ratio of carbon number / nitrogen number (C / N ratio) exceeds 7.0.
(B) The glass transition point at the time of drying calculated | required from a viscoelasticity measurement is 70 (degreeC) or more.
(C) The crystallization enthalpy (ΔHc) obtained by cooling at 20 (° C./min) by differential scanning calorimetry is 10 (J / g) or more.
(D) By differential scanning calorimetry, the difference (Tm−Tc) between the melting point peak temperature (Tm) and the crystallization peak temperature (Tc) obtained when heated and cooled at 20 (° C./min) is 45 (° C.). that's all.
(E) The ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is 2.9 or less.

((A) component: polyamide resin)
In the polyamide resin composition of the present embodiment, (A) the polyamide resin is a polymer having an amide bond (—NHCO—) in the main chain.
(A) The polyamide resin is not limited to the following. For example, a polyamide resin obtained by condensation polymerization of a diamine and a dicarboxylic acid, a polyamide resin obtained by ring-opening polymerization of a lactam, and an aminocarboxylic acid self Examples thereof include polyamide resins obtained by condensation, and copolymers obtained by copolymerization of two or more monomers constituting these polyamide resins.
These polyamide resins may be used alone or in combination of two or more.

(A) The polyamide resin is a polyamide resin having a carbon number / nitrogen number ratio (C / N) ratio exceeding 7.0 ((a) above).
The ratio of carbon number / nitrogen number (C / N ratio) exceeds 7.0 (A) The polyamide resin is a polyamide resin in which the ratio of carbon number to nitrogen number in the polyamide constituent unit exceeds 7.0. is there.
Such polyamide (unit) is not limited to the following, but examples include polyamide 11 (polyundecanamide), polyamide 12 (polydodecanamide), polyamide 610 (polyhexamethylene sebacamide), polyamide 612 (polyhexamethylene dodecamide), polyamide 116 (polyundecamethylene adipamide), polyamide 1010 (polydecamethylene sebacamide), polyamide 1012 (polydecamethylene dodecamide), polyamide 1210 (polydodecamethylene sebaca) Amide), polyamide 1212 (polydodecamethylene dodecamide), polyamide TMHT (trimethylhexamethylene terephthalamide), polyamide 6T (polyhexamethylene terephthalamide), polyamide 2Me-5T (poly-2-methyl) Pentamethylene terephthalamide (Me represents a methyl group; the same shall apply hereinafter)), polyamide 9T (polynonamethylene terephthalamide), 2Me-8T (poly-2-methyloctamethylene terephthalamide), polyamide 6I (polyhexamethylene) Isophthalamide), polyamide 6C (polyhexamethylenecyclohexanedicarboxamide), polyamide 2Me-5C (poly-2-methylpentamethylenecyclohexanedicarboxamide), polyamide 9C (polynonamethylenecyclohexanedicarboxamide), 2Me-8C (poly-2-methyl) Octamethylenecyclohexanedicarboxamide), polyamide PACM12 (polybis (4-aminocyclohexyl) methane dodecamide), polyamide dimethyl PACM12 (polybis (3 Methyl-aminocyclohexyl) methane dodecamide, polyamide MXD6 (polymetaxylylene adipamide), polyamide 10T (polydecamethylene terephthalamide), polyamide 11T (polyundecamethylene terephthalamide), polyamide 12T (polydodecamethylene terephthalamide) And polyamides (units) such as polyamide 10C (polydecamethylenecyclohexanedicarboxamide), polyamide 11C (polyundecamethylenecyclohexanedicarboxamide), and polyamide 12C (polydodecamethylenecyclohexanedicarboxamide).
(A) The polyamide resin may be only one kind of the above polyamide, may be a polyamide mixture using two or more kinds in combination, or may be a copolymer polyamide having two or more kinds of the above polyamide units. Good.
Preferably, polyamide 11 (polyundecanamide), polyamide 12 (polydodecanamide), polyamide 610 (polyhexamethylene sebacamide), polyamide 612 (polyhexamethylene dodecane), polyamide 1010 (polydecane methylene sebacamide), Examples include polyamide 1012 (polydecamethylene dodecamide), polyamide 6T (polyhexamethylene terephthalamide), polyamide 6I (polyhexamethylene isophthalamide), and polyamide 6C (polyhexamethylenecyclohexanedicarboxamide).

When the (A) polyamide resin has a ratio of carbon number / nitrogen number (C / N) exceeding 7.0, an effect of improving low water absorption can be obtained. The C / N is preferably 7.2 or more, and more preferably 7.3 or more.
The C / N can be controlled by monomer selection.
In order to obtain the C / N from the polyamide resin composition, the C / N may be determined by ¹ H-NMR as follows.
The polyamide resin composition pellets are dissolved by heating with heavy hexafluoroisopropanol to a concentration of about 5% by mass, and analyzed by ¹ H-NMR (for example, JEOL Nuclear Magnetic Resonance Analyzer JNM ECA-500). And calculating the integral ratio to determine the contents of diamine and dicarboxylic acid constituting the polyamide resin.
In the polyamide resin, an average value of the number of carbon atoms per amide group (the number of carbons / the number of amide groups) is obtained by calculation, and is defined as a carbon number / nitrogen number ratio (C / N).
Specifically, the ratio of the number of carbons to the number of amide groups (number of carbons / number of amide groups) is determined by dividing the number of carbons contained in the molecular main chain by the number of amide groups contained in the molecular main chain. The ratio of nitrogen number (C / N).

(A) A polyamide resin contains the structural unit of the polyamide containing the dicarboxylic acid which has a cyclic structure, and / or the diamine which has a cyclic structure.
The structural unit of polyamide containing a dicarboxylic acid having a cyclic structure and / or a diamine having a cyclic structure means a structural unit of polyamide in which the dicarboxylic acid and / or diamine has a cyclic structure, and the structural unit of the polyamide. As a preferable example, a polyamide constituent unit containing a dicarboxylic acid or a diamine having a cyclic structure such as a benzene ring or a cyclohexane ring is preferable.
Examples of such a diamine having a cyclic structure and a dicarboxylic acid having a cyclic structure include, but are not limited to, for example, metaxylylenediamine, paraxylylenediamine, paraphenylenediamine, terephthalic acid, isophthalic acid, Naphthalenedicarboxylic acid, cyclohexanedicarboxylic acid, specifically 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid; 1,3-cyclopentanedicarboxylic acid and the like can be mentioned.
Preferred are metaxylylenediamine, paraxylylenediamine, terephthalic acid, isophthalic acid and 1,4-cyclohexanedicarboxylic acid.

The structural unit of the polyamide containing a dicarboxylic acid having a cyclic structure and / or a diamine having a cyclic structure is not limited to the following, but examples include polyamide TMHT (trimethylhexamethylene terephthalamide), polyamide 6T (polyhexa Methylene terephthalamide), polyamide 2Me-5T (poly 2-methylpentamethylene terephthalamide (Me represents a methyl group; the same shall apply hereinafter)), polyamide 9T (polynonamethylene terephthalamide), 2Me-8T (poly 2) -Methyloctamethylene terephthalamide), polyamide 6I (polyhexamethylene isophthalamide), polyamide 6C (polyhexamethylenecyclohexanedicarboxamide), polyamide 2Me-5C (poly-2-methylpentamethylenecyclohexane) Sandicarboxamide), polyamide 9C (polynonamethylenecyclohexanedicarboxamide), 2Me-8C (poly-2-methyloctamethylenecyclohexanedicarboxamide), polyamide PACM12 (polybis (4-aminocyclohexyl) methane dodecamide), polyamide dimethyl PACM12 (polybis (3-methyl-aminocyclohexyl) methane dodecamide, polyamide MXD6 (polymetaxylylene adipamide), polyamide 10T (polydecamethylene terephthalamide), polyamide 11T (polyundecamethylene terephthalamide), polyamide 12T (polydodecamethylene) Terephthalamide), polyamide 10C (polydecamethylenecyclohexanedicarboxamide), polyamide 11C (polyundecamethylene) Cyclohexane dicarboxamide), polyamide 12C (poly dodecamethylene cyclohexane dicarboxamide), and the like.
These polyamide structural units may be used alone or in combination of two or more.
Polyamide 6T (polyhexamethylene terephthalamide) and polyamide 6I (polyhexamethylene isophthalamide) are preferable.

(A) The polyamide resin has a glass transition point of 70 ° C. or higher when dried, which is determined from viscoelasticity measurement (above (b)).
Although the glass transition point at the time of drying calculated | required from a viscoelasticity measurement is not limited to the following, For example, it measures on conditions with a frequency of 10 Hz and a temperature increase rate of 3 degree-C / min using the GABO Explexer 150N. The peak temperature of the loss elastic modulus corresponding to α-dispersion is defined as the glass transition point.
(A) The glass transition point of polyamide resin shall be 70 degreeC or more from a viewpoint of the physical property at the time of water absorption, Preferably it is 80 degreeC or more, More preferably, it is 90 degreeC or more.
(A) As a method for controlling the glass transition point during drying of the polyamide resin within the above range, for example, (A) polyamide resin is (A-1) carbon number / nitrogen number ratio (C / N ratio). Are composed of aliphatic polyamide structural units of 8.0 or more, (A-2) structural units composed of hexamethylenediamine and terephthalic acid, (A-3) structural units composed of hexanemethylenediamine and isophthalic acid, and And (A-1) 30-50 mol%, (A-2) 20-70 mol%, and (A-3) 3-25 mol%.

(A) The crystallization enthalpy (ΔHc) obtained when the polyamide resin is cooled at 20 (° C./min) by differential scanning calorimetry is 10 (J / g) ≧ (above (c)).
The crystallization enthalpy (ΔHc) obtained by cooling at 20 (° C./min) by differential scanning calorimetry can be measured by differential scanning calorimetry (DSC) according to JIS-K7121.
Specifically, it can be measured as follows.
As the measuring device, Diamond-DSC manufactured by PERKIN-ELMER can be used.
The measurement conditions are such that about 10 mg of the sample is heated from 30 ° C. to 350 ° C. at a temperature increase rate of 20 ° C./min in a nitrogen atmosphere. Subsequently, after being kept at 350 ° C. for 3 minutes, it is cooled from 350 ° C. to 30 ° C. at a cooling rate of 20 ° C./min. The exothermic peak appearing at this time is defined as a crystallization peak, and the crystallization peak area is defined as a crystallization enthalpy (ΔHc).

(A) The crystallization enthalpy of the polyamide resin is 10 J / g or more, preferably 20 J / g or more, more preferably 30 J / g or more, from the viewpoints of heat resistance, low blocking properties and releasability. It is.
(A) Although the upper limit of the crystallization enthalpy of a polyamide resin is not specifically limited, it is 100 J / g or less.
(A) As a method for controlling the crystallization enthalpy of the polyamide resin within the above range, for example, there is a method for controlling the blending ratio to the above range using the above components (A-1) to (A-3). Can be mentioned.

(A) The difference (Tm−Tc) between the melting point peak temperature (Tm) and the crystallization peak temperature (Tc) obtained when the polyamide resin is heated and cooled at 20 (° C./min) by differential scanning calorimetry. 45 (° C.) or more (above (d)).
By differential scanning calorimetry, the difference (Tm−Tc) between the melting point peak temperature (Tm) and the crystallization peak temperature (Tc) obtained when heated and cooled at 20 (° C./min) is Diamond manufactured by PERKIN-ELMER. -It can be measured by DSC.
The measurement conditions are such that about 10 mg of the sample is heated from 30 ° C. to 350 ° C. at a temperature increase rate of 20 ° C./min in a nitrogen atmosphere.
Subsequently, after being kept at 350 ° C. for 3 minutes, it is cooled from 350 ° C. to 30 ° C. at a cooling rate of 20 ° C./min.
The exothermic peak appearing at this time is defined as a crystallization peak, and the crystallization peak temperature is defined as (Tc). Subsequently, after maintaining at 30 ° C. for 3 minutes, the temperature is increased again from 30 ° C. to 350 ° C. at a temperature increase rate of 20 ° C./min. The endothermic peak that appears on the highest temperature side at this time is defined as the melting peak temperature (Tm).

(A) The polyamide resin has a difference (Tm−Tc) between the melting peak temperature (Tm) and the crystallization peak temperature (Tc) of 45 ° C. or higher, preferably 47 ° C. or higher, and preferably 50 ° C. or higher. It is more preferable that
(A) In the polyamide resin, when the difference (Tm−Tc) between the melting peak temperature (Tm) and the crystallization peak temperature (Tc) is within the above range, a polyamide resin excellent in surface appearance can be obtained.
(A) In the polyamide resin, as a method for controlling the difference (Tm−Tc) between the melting peak temperature (Tm) and the crystallization peak temperature (Tc) within the above range, for example, (A-1) to (A) A-3) The method etc. which control a compounding ratio to the range mentioned above etc. are mentioned using a component.

In the polyamide resin composition of the present embodiment, the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is 2.9 or less (the above (e)).
The ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) can be used as an index of the molecular weight distribution of the (A) polyamide resin.
The ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the polyamide resin composition of this embodiment is (A) the strength of the polyamide resin, the high temperature strength, and the fluidity of the polyamide resin composition. In view of the above, it is assumed that it is 2.9 or less, preferably 2.8 or less, and more preferably 2.7 or less. The lower limit of the molecular weight distribution is preferably 2.0.

By making the ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the polyamide resin composition of the present embodiment to 2.9 or less, (B) an inorganic reinforcing material to be described later is contained. The polyamide resin composition is excellent in surface appearance.
As a method for controlling the Mw (weight average molecular weight) / Mn (number average molecular weight) of the polyamide resin composition within the above range, for example, (A) phosphoric acid or hypochlorous acid as an additive at the time of hot melt polymerization of the polyamide resin Examples thereof include a method of adding a known polycondensation catalyst such as sodium phosphate, and a method of controlling polymerization conditions such as heating conditions and reduced pressure conditions.
The measurement of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of a polyamide resin composition can be performed using GPC (gel permeation chromatography) as described in Examples described later.
In addition, the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the polyamide resin composition are substantially obtained as the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the (A) polyamide resin.

In the (A) polyamide resin, the dicarboxylic acid constituting the (A) polyamide resin preferably contains terephthalic acid and / or isophthalic acid.
Specifically, it is preferable to contain (A-1) a structural unit composed of hexamethylenediamine and terephthalic acid and / or (A-2) a structural unit composed of hexamethylenediamine and isophthalic acid. Thereby, the effect of heat resistance improvement is acquired.
(A-2) The structural unit consisting of hexamethylenediamine and terephthalic acid is a polyamide 6T (polyhexamethylene terephthalamide) unit.
(A-3) The structural unit consisting of hexamethylenediamine and isophthalic acid is a polyamide 6I (polyhexamethyleneisophthalamide) unit.

The (A) polyamide resin containing a dicarboxylic acid having a cyclic structure and / or a diamine having a cyclic structure may be a crystalline polyamide or an amorphous polyamide.
Examples of the crystalline polyamide include polyamide 6T. By using crystalline polyamide as the component (A-2), the effect of improving heat resistance can be obtained.
Examples of the amorphous polyamide include polyamide 6I. By using amorphous polyamide as the component (A-3), the effect of improving fluidity can be obtained.

In said (A) polyamide resin, content of the structural unit of the (A-1) aliphatic polyamide whose carbon number / nitrogen number ratio (C / N ratio) is 8.0 or more shall be 20-80 mol%. It is preferable.
(A) polyamide resin excellent in heat resistance etc. is obtained as content of the structural unit of (A-1) is 20 mol% or more. When the content of the structural unit (A-1) is 80 mol% or less, a (A) polyamide resin having excellent moldability is obtained. More preferably, it is 24-60 mol%, More preferably, it is 28-55 mol%, More preferably, it is 30-50 mol%, More preferably, it is 31-50 mol%.

  (A-1) The structural unit of the aliphatic polyamide having a carbon number / nitrogen number ratio (C / N ratio) of 8.0 or more is PA610 (polyhexamethylene sebacamide), PA612 (polyhexamethylene dodecamide). ), PA11 (polyundecanamide), PA12 (polydodecanamide), PA1010 (polydecanamethylene sebamide), and PA1012 (polydecanamidodecanamide). Is preferred. Thereby, in (A) polyamide resin, the effect of water absorption reduction is acquired.

In the (A) polyamide resin, the content of the structural unit (A-2) composed of hexamethylenediamine and terephthalic acid is preferably 0.1 to 80 mol%.
When the content of the structural unit (A-2) is 80 mol% or less, the (A) polyamide resin having excellent heat resistance can be obtained. When the amount is 0.1 mol or more, an effect of improving heat resistance is obtained. More preferably, it is 5-75 mol%, More preferably, it is 15-70 mol%, More preferably, it is 20-70 mol%, More preferably, it is 25-65 mol%.

In the (A) polyamide resin, the content of the structural unit (A-3) composed of hexamethylenediamine and isophthalic acid is preferably 0.1 to 50 mol%.
It can be set as the (A) polyamide resin which is excellent in fluidity | liquidity in content of the structural unit of (A-3) being 50 mol% or less. When the amount is 0.1 mol or more, an effect of improving heat resistance is obtained. More preferably, it is 1-40 mol%, More preferably, it is 2-30 mol%, More preferably, it is 3-25 mol%.

(A) The polyamide resin may be a copolymerized polyamide or a polyamide mixture as long as it satisfies the above conditions (a) to (d).
(A) When the polyamide resin is a copolymerized polyamide, it may be a random copolymer or a block (graft) copolymer.

As a manufacturing method of a random copolymer, the following manufacturing methods are mentioned as a suitable example.
<Method for producing random copolymer>
(A) Although it does not specifically limit as a manufacturing method of the said polyamide resin in case a polyamide resin is a random copolymer, For example, the method shown to the following 1) -8) is applicable.
1) An aqueous solution of dicarboxylic acid and diamine or a suspension of water, or a mixture of dicarboxylic acid and diamine salt and other components such as lactam and / or aminocarboxylic acid (hereinafter, these are abbreviated as “the mixture”) A method in which an aqueous solution or a suspension of water is heated and polymerized while maintaining a molten state (hereinafter, also referred to as “hot melt polymerization method”);
2) A method of heating an aqueous solution or a suspension of water of a dicarboxylic acid and a diamine or a mixture thereof and removing the precipitated prepolymer (“prepolymer method”);
3) A method of increasing the degree of polymerization while maintaining the solid state of the polyamide obtained by the hot melt polymerization method at a temperature below the melting point (“hot melt polymerization / solid phase polymerization method”);
4) A method in which an aqueous solution or a suspension of water of a dicarboxylic acid and a diamine or a mixture thereof is heated, and the precipitated prepolymer is melted again with an extruder such as a kneader to increase the degree of polymerization (“prepolymer · Extrusion polymerization method ");
5) A method in which an aqueous solution or a suspension of water of dicarboxylic acid and diamine or a mixture thereof is heated, and the precipitated prepolymer is further maintained in a solid state at a temperature below the melting point of polyamide to increase the degree of polymerization (“ Prepolymer / solid phase polymerization method));
6) A method of polymerizing a dicarboxylic acid and a diamine or a mixture thereof while maintaining a solid state (“monomer / solid phase polymerization method”);
7) A method of polymerizing “a salt of dicarboxylic acid and diamine” or a mixture thereof while maintaining a solid state (“salt / solid phase polymerization method”);
8) A method of polymerization using a dicarboxylic acid halide and a diamine equivalent to a dicarboxylic acid (“solution method”).
Among the above production methods, the hot melt polymerization method is preferable from the viewpoint of productivity.

The polymerization form of the random copolymer is not particularly limited, and may be a batch type or a continuous type.
The polymerization apparatus is not particularly limited, and a known apparatus such as an autoclave type reactor, a tumbler type reactor, an extruder type reactor such as a kneader, or the like can be used.

(A) In the manufacturing process of a polyamide resin, when the monomer of a polyamide resin is polymerized, an end-capping agent can be further added to adjust the molecular weight.
It does not specifically limit as a terminal blocker, A well-known thing can be used.

Examples of the end-capping agent include, but are not limited to, acid anhydrides such as monocarboxylic acid, monoamine, and phthalic anhydride; monoisocyanates, monoacid halides, monoesters, and monoalcohols. Etc.
Among these, monocarboxylic acid and monoamine are preferable from the viewpoint of the thermal stability of the polyamide resin.
These may be used alone or in combination of two or more.

The monocarboxylic acid that can be used as the end-capping agent is not limited to the following as long as it has reactivity with an amino group. For example, formic acid, acetic acid, propionic acid, butyric acid, valeric acid , Caproic acid, caprylic acid, lauric acid, tridecylic acid, myristic acid, palmitic acid, stearic acid, pivalic acid, isobutyric acid and other aliphatic monocarboxylic acids; cyclohexanecarboxylic acid and other alicyclic monocarboxylic acids; benzoic acid, And aromatic monocarboxylic acids such as toluic acid, α-naphthalenecarboxylic acid, β-naphthalenecarboxylic acid, methylnaphthalenecarboxylic acid, and phenylacetic acid.
These may be used alone or in combination of two or more.

The monoamine that can be used as the end-capping agent is not limited to the following as long as it has reactivity with a carboxyl group. For example, methylamine, ethylamine, propylamine, butylamine, hexylamine, Aliphatic monoamines such as octylamine, decylamine, stearylamine, dimethylamine, diethylamine, dipropylamine, dibutylami; Alicyclic monoamines such as cyclohexylamine, dicyclohexylamine; Aromatic monoamines such as aniline, toluidine, diphenylamine, naphthylamine; etc. Is mentioned.
These may be used alone or in combination of two or more.

Examples of the acid anhydride that can be used as the end-capping agent include, but are not limited to, phthalic anhydride, maleic anhydride, benzoic anhydride, acetic anhydride, hexahydrophthalic anhydride, and the like.
These may be used alone or in combination of two or more.

Examples of the monoisocyanate that can be used as the end-capping agent include, but are not limited to, phenyl isocyanate, tolyl isocyanate, dimethylphenyl isocyanate, cyclohexyl isocyanate, butyl isocyanate, and naphthyl isocyanate.
These may be used alone or in combination of two or more.

Examples of monoacid halides that can be used as end-capping agents include, but are not limited to, benzoic acid, diphenylmethane carboxylic acid, diphenyl sulfone carboxylic acid, diphenyl sulfoxide carboxylic acid, diphenyl sulfide carboxylic acid, diphenyl ether carboxylic acid. And halogen-substituted monocarboxylic acids such as monocarboxylic acids such as acid, benzophenone carboxylic acid, biphenyl carboxylic acid, α-naphthalene carboxylic acid, β-naphthalene carboxylic acid, and anthracene carboxylic acid.
These may be used alone or in combination of two or more.

Monoesters that can be used as end-capping agents include, but are not limited to, for example, glycerin monopalmitate, glycerin monostearate, glycerin monobehenate, glycerin monomontanate, pentaerythritol monopalmitate, Pentaerythritol monostearate, pentaerythritol monobehenate, pentaerythritol monomontanate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monobehenate, sorbitan monomontanate, sorbitan dimontanate, sorbitan trimontanate, sorbitol monomono Palmitate, sorbitol monostearate, sorbitol monobehenate, sorbitol tribehenate, sorbitol monobetanate, sorbitol Rujimontaneto, and the like.
These may be used alone or in combination of two or more.

Monoalcohols that can be used as end-capping agents include, but are not limited to, for example, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol. , Pentadecanol, hexadecanol, heptadecanol, octadecanol, nonadecanol, eicosanol, docosanol, tricosanol, tetracosanol, hexacosanol, heptacosanol, octacosanol, triacontanol (over, linear, branched) Oleyl alcohol, behenyl alcohol, phenol, cresol (o-, m-, p-isomer), biphenol (o-, m-, p-isomer), 1-naphthol, 2-naphthol, etc. It is below.
These may be used alone or in combination of two or more.

As a manufacturing method of a block (graft) copolymer, the following manufacturing methods are mentioned as a suitable example.
<Method for producing block (graft) copolymer>
(A) When the polyamide resin is a block (graft) copolymer, examples of the method for producing the block (graft) copolymer include (A-1), (A-2), and (A- What is necessary is just to perform block copolymerization by combining suitably 3 or more types of polyamide so that the structural unit of 3) may be included.
The (A) polyamide resin may be a copolymer polyamide containing two or more kinds of polyamides, or may be a combination of different copolymer polyamides.
For example, a block (graft) copolymer of a polyamide comprising the component (A-1) and a polyamide comprising the components (A-2) and (A-3), the component (A-1) and the component (A-2) A block (graft) copolymer containing two or more types of copolymer polyamides comprising a polyamide comprising component) and (A-3), and a polyamide comprising components (A-1) and (A-3), (A-2) block (graft) copolymer comprising two or more types of copolymerized polyamide, and (A-1) component and (A-2) component polyamide component and (A-2) component And a block (graft) copolymer obtained by combining a copolymer polyamide comprising the component (A-3).

The method for block copolymerization is not particularly limited. For example, various methods can be adopted as described below.
For example, a method of obtaining a block copolymer by melting and extruding a metal phosphite salt, a phosphite compound and / or a molecular weight modifier when melt kneading at least two kinds of polyamides as raw materials Is mentioned. Specifically, the method described in the patent document (Japanese Patent Laid-Open No. 2011-26396) can be adopted, and when at least two kinds of polyamide components are used, the polyamide-polyamide exchange reaction is accelerated.

In the step of producing the block copolymer, for example, various kneaders (for example, uniaxial or multiaxial kneaders, kneaders, hensil mixers, ball mills, planetary mills, Banbury mixers, rolls, Brabender plastograms, etc.) are used. be able to.
Among these, the melt kneading method is preferable from the viewpoint of industrial cost.
In the melt kneading, it is preferable to use a single screw extruder or a twin screw extruder, and it is more preferable to use a twin screw extruder.

<Method for producing polyamide mixture>
(A) When a polyamide resin is a polyamide mixture, the following manufacturing methods are mentioned as a manufacturing method of the said polyamide mixture.
The polyamide mixture is a combination of three or more kinds of polyamides appropriately mixed so as to include the structural unit (A-1), the structural unit (A-2), and the structural unit (A-3). Is obtained.
For example, a mixture of a polyamide comprising (A-1) and a polyamide comprising (A-2) and (A-3), a polyamide comprising (A-1) and (A-2) (A-3) a mixture comprising two or more types of copolymerized polyamides, a (A-1) component and a (A-3) component polyamide, and a (A-2) component copolymerized polyamide Or a mixture comprising a polyamide component comprising the components (A-1) and (A-2) and a copolymer polyamide comprising the components (A-2) and (A-3). The polymers can be combined as appropriate.
The mixing method is not particularly limited, and for example, various methods can be adopted as described below.

(A) When the polyamide resin is a polyamide mixture, the method for producing the polyamide mixture is not particularly limited. For example, at least two kinds of polyamides (including the case of a copolymerized polyamide) are used as raw materials. The method of melt-kneading is mentioned.
For example, various kneaders (for example, uniaxial or multi-axial kneaders, kneaders, hensil mixers, ball mills, planetary mills, Banbury mixers, rolls, Brabender plastograms, etc.) can be used.
Among these, the melt kneading method is preferable from the viewpoint of industrial cost. In the melt kneading, it is preferable to use a single screw extruder or a twin screw extruder, and it is more preferable to use a twin screw extruder.

((B) component: inorganic reinforcing material)
The polyamide resin composition of the present embodiment contains (B) an inorganic reinforcing material (hereinafter sometimes referred to as a reinforcing material, (B) component, (B)).
(B) The inorganic reinforcing material is not particularly limited as long as it improves the strength and / or rigidity of the material. For example, glass fiber, carbon fiber, calcium silicate fiber, titanium Potassium acid fiber, aluminum borate fiber, flaky glass, talc, kaolin, mica, hydrotalcite, calcium carbonate, zinc carbonate, zinc oxide, calcium monohydrogen phosphate, wollastonite, silica, zeolite, alumina, boehmite, Aluminum hydroxide, titanium oxide, silicon oxide, magnesium oxide, calcium silicate, sodium aluminosilicate, magnesium silicate, ketjen black, acetylene black, furnace black, carbon nanotube, graphite, brass, copper, silver, aluminum, nickel, Iron, fluorinated cal Um, mica, montmorillonite, swelling fluorine mica, and an apatite like.
Among these, from the viewpoint of increasing strength and rigidity, glass fiber, carbon fiber, flaky glass, talc, kaolin, mica, calcium carbonate, calcium monohydrogen phosphate, wollastonite, silica, carbon nanotube, graphite, fluorine Calcium hydride, montmorillonite, swellable fluoromica and apatite are preferred.
More preferably, glass fiber, carbon fiber, wollastonite, talc, mica, kaolin and silicon nitride are used.
As the above-mentioned (B) inorganic reinforcing material, only one kind may be used alone, or two or more kinds may be used in combination.

  Among the glass fibers and carbon fibers, from the viewpoint that excellent mechanical properties can be imparted to the polyamide resin composition, the number average fiber diameter is 3 to 30 μm, and the weight average fiber length in the polyamide resin composition Is 100 to 750 μm, and the aspect ratio of the weight average fiber length to the number average fiber diameter (value obtained by dividing the weight average fiber length by the number average fiber diameter) is preferably 10 to 100.

  Of the wollastonite, from the viewpoint that excellent mechanical properties can be imparted to the polyamide resin composition, the number average fiber diameter is 3 to 30 μm, and in the polyamide resin composition, the weight average fiber length Is preferably 10 to 500 μm and the aspect ratio is 3 to 100.

  Of the talc, mica, kaolin and silicon nitride, those having a number average fiber diameter of 0.1 to 3 μm are preferred from the viewpoint that excellent mechanical properties can be imparted to the polyamide resin composition.

  Here, regarding the number average fiber diameter and the weight average fiber length, the polyamide resin composition is put in an electric furnace, the contained organic matter is incinerated, and, for example, 100 or more (B) inorganic reinforcing materials are obtained from the residue. The number average fiber diameter can be measured by arbitrarily selecting, observing with SEM, and measuring the fiber diameter of these (B) inorganic reinforcements, and using the SEM photograph at a magnification of 1000 times, the fiber length By measuring the weight average fiber length can be obtained.

The (B) inorganic reinforcing material may be subjected to a surface treatment with a silane coupling agent or the like.
Examples of the silane coupling agent include, but are not limited to, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, and N-β- (aminoethyl) -γ-aminopropylmethyl. Aminosilanes such as dimethoxysilane; mercaptosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane; epoxysilanes; vinylsilanes. As the silane coupling agent, aminosilanes are particularly preferable.

The glass fiber or carbon fiber may further contain a sizing agent.
Examples of the sizing agent include, but are not limited to, for example, a carboxylic acid anhydride-containing unsaturated vinyl monomer and an unsaturated vinyl monomer excluding the carboxylic acid anhydride-containing unsaturated vinyl monomer; , Epoxy compounds, polycarbodiimide compounds, polyurethane resins, acrylic acid homopolymers, copolymers of acrylic acid and other copolymerizable monomers, and their primary, secondary and tertiary copolymers. Examples include salts with secondary amines.
These sizing agents may be used alone or in combination of two or more.
In particular, from the viewpoint of the mechanical strength of the polyamide resin composition, the carboxylic acid anhydride-containing unsaturated vinyl monomer and the unsaturated vinyl monomer excluding the carboxylic acid anhydride-containing unsaturated vinyl monomer are structural units. A copolymer, an epoxy compound, a polycarbodiimide compound, a polyurethane resin, and a combination thereof are preferably used, and the carboxylic acid anhydride-containing unsaturated vinyl monomer and the carboxylic acid anhydride-containing unsaturated vinyl monomer are excluded. A copolymer containing a saturated vinyl monomer as a structural unit, a polycarbodiimide compound, a polyurethane resin, and a combination thereof are more preferable.

Among the copolymers containing carboxylic acid anhydride-containing unsaturated vinyl monomers and unsaturated vinyl monomers excluding the carboxylic acid anhydride-containing unsaturated vinyl monomers as constituent units, the carboxylic acid anhydride-containing copolymer Examples of the unsaturated vinyl monomer include, but are not limited to, maleic anhydride, itaconic anhydride, and citraconic anhydride, and maleic anhydride is particularly preferable.
On the other hand, the unsaturated vinyl monomer excluding the carboxylic acid anhydride-containing unsaturated vinyl monomer means an unsaturated vinyl monomer different from the carboxylic acid anhydride-containing unsaturated vinyl monomer. The unsaturated vinyl monomer excluding the acid anhydride-containing unsaturated vinyl monomer is not limited to the following, for example, styrene, α-methylstyrene, ethylene, propylene, butadiene, isoprene, chloroprene, Examples include 2,3-dichlorobutadiene, 1,3-pentadiene, cyclooctadiene, methyl methacrylate, methyl acrylate, ethyl acrylate, and ethyl methacrylate. Of these, styrene and butadiene are particularly preferable.

  Among these material combinations as sizing agents, from a copolymer of maleic anhydride and butadiene, a copolymer of maleic anhydride and ethylene, and a copolymer of maleic anhydride and styrene, and mixtures thereof One or more selected from the group consisting of

  Further, the copolymer containing the carboxylic acid anhydride-containing unsaturated vinyl monomer and the unsaturated vinyl monomer excluding the carboxylic acid anhydride-containing unsaturated vinyl monomer as constituent units has a weight average molecular weight. It is preferably 2,000 or more. Moreover, from a viewpoint of the fluidity | liquidity improvement of a polyamide resin composition, More preferably, it is 2,000-1,000,000, More preferably, it is 2,000-1,000,000. The weight average molecular weight can be measured by GPC.

  Examples of the epoxy compound include, but are not limited to, ethylene oxide, propylene oxide, butene oxide, pentene oxide, hexene oxide, heptene oxide, octene oxide, nonene oxide, decene oxide, undecene oxide, Aliphatic epoxy compounds such as dodecene oxide, pentadecene oxide, eicosene oxide; glycidol, epoxypentanol, 1-chloro-3,4-epoxybutane, 1-chloro-2-methyl-3,4 -Epoxybutane, 1,4-dichloro-2,3-epoxybutane, cyclopentene oxide, cyclohexene oxide, cycloheptene oxide, cyclooctene oxide, methylcyclohexene oxide, vinyl Alicyclic epoxy compounds such as hexene oxide and epoxidized cyclohexene methyl alcohol; Terpene epoxy compounds such as pinene oxide; Aromatic epoxy compounds such as styrene oxide, p-chlorostyrene oxide and m-chlorostyrene oxide; Epoxidized soybean oil And epoxidized linseed oil.

  The polycarbodiimide compound can be obtained by condensing a compound containing one or more carbodiimide groups (—N═C═N—).

  The degree of condensation of the polycarbodiimide compound is preferably 1-20, and more preferably 1-10. When the degree of condensation of the polycarbodiimide compound is in the range of 1 to 20, a good aqueous solution or dispersion of the sizing agent can be obtained. Furthermore, when the condensation degree is in the range of 1 to 10, a better aqueous solution or aqueous dispersion is obtained.

Moreover, it is preferable that the said polycarbodiimide compound is a polycarbodiimide compound which has a polyol segment partially.
By having a polyol segment, the polycarbodiimide compound is easily water-soluble and can be more suitably used as a sizing agent for glass fibers or carbon fibers.

These polycarbodiimide compounds can be obtained by decarboxylating a diisocyanate compound in the presence of a known carbodiimidization catalyst such as 3-methyl-1-phenyl-3-phospholene-1-oxide.
As the diisocyanate compound, aromatic diisocyanates, aliphatic diisocyanates and alicyclic diisocyanates, and mixtures thereof can be used.
Examples of the diisocyanate compound include, but are not limited to, for example, 1,5-naphthalene diisocyanate, 4,4′-diphenylmethane diisocyanate, 4,4′-diphenyldimethylmethane diisocyanate, 1,3-phenylene diisocyanate, 1 , 4-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, a mixture of 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate, hexamethylene diisocyanate, cyclohexane-1,4 -Diisocyanate, xylylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, methylcyclohexane diisocyanate, tetramethylxylylene diisocyanate Aneto, like 2,6-diisopropylphenyl isocyanate and 1,3,5-triisopropylbenzene 2,4-diisocyanate. And the polycarbodiimide compound which has two isocyanate groups at the terminal is obtained by carbodiimidizing these diisocyanate compounds. Of these, dicyclohexylmethane carbodiimide can be suitably used from the viewpoint of improving reactivity.

For the polycarbodiimide compound having two isocyanate groups at the terminal, a method of further converting the monoisocyanate compound into an equimolar amount of carbodiimide, or a method of reacting an equimolar amount with a polyalkylene glycol monoalkyl ether to generate a urethane bond, etc. A polycarbodiimide compound having one isocyanate group at the terminal is obtained.
Examples of the monoisocyanate compound include, but are not limited to, hexyl isocyanate, phenyl isocyanate, and cyclohexyl isocyanate.
Examples of the polyalkylene glycol monoalkyl ether include, but are not limited to, polyethylene glycol monomethyl ether and polyethylene glycol monoethyl ether.

  The polyurethane resin is not particularly limited as long as it is generally used as a sizing agent. For example, m-xylylene diisocyanate (XDI), 4,4′-methylenebis (cyclohexyl isocyanate). Those synthesized from an isocyanate such as (HMDI) or isophorone diisocyanate (IPDI) and a polyester or polyether diol can be suitably used.

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

  The monomer constituting the copolymer of acrylic acid and other copolymerizable monomer and forming the copolymer with acrylic acid is not limited to the following, but has, for example, a hydroxyl group and / or a carboxyl group Among the monomers, one or more selected from the group consisting of acrylic acid, maleic acid, methacrylic acid, vinyl acetic acid, crotonic acid, isocrotonic acid, fumaric acid, itaconic acid, citraconic acid and mesaconic acid may be mentioned (however, acrylic Except for acid only). In addition, it is preferable that the said other copolymerizable monomer has 1 or more types of ester monomers among the said monomers.

The polymer of acrylic acid (including both homopolymers and copolymers) may be in the form of a salt.
The acrylic acid polymer salts include, but are not limited to, primary, secondary, and tertiary amine salts. Examples of the salt of the acrylic acid polymer include, but are not limited to, a triethylamine salt, a triethanolamine salt, and a glycine salt.
The degree of neutralization is preferably 20 to 90%, preferably 40 to 60% from the viewpoint of improving the stability of the mixed solution with other concomitant drugs (such as a silane coupling agent) and reducing the amine odor. Is more preferable.

  The weight average molecular weight of the acrylic acid polymer forming the salt is not particularly limited, but is preferably in the range of 3,000 to 50,000. 3,000 or more are preferable from the viewpoint of improving the converging property of glass fiber or carbon fiber, and 50,000 or less are preferable from the viewpoint of improving mechanical properties when a polyamide resin composition is obtained.

Glass fiber or carbon fiber containing a sizing agent is a fiber obtained by applying the above sizing agent to glass fiber or carbon fiber using a known method such as a roller type applicator in the manufacturing process of known glass fiber or carbon fiber. It is obtained by producing a strand, drying it and reacting it continuously.
The fiber strand may be used as a roving as it is as glass fiber or carbon fiber, or may be used as a chopped strand after obtaining a cutting step.
The sizing agent preferably imparts (adds) 0.2 to 3% by mass, more preferably 0.3 to 2% by mass (as a solid fraction), with respect to 100% by mass of glass fiber or carbon fiber. Added. From the viewpoint of maintaining the bundling of the glass fiber or carbon fiber, the addition amount of the bundling agent is preferably 0.2% by mass or more as a solid content with respect to 100% by mass of the glass fiber or carbon fiber. On the other hand, from the viewpoint of improving the thermal stability of the polyamide resin composition, it is preferably 3% by mass or less. Moreover, drying of a strand may be performed after a cutting process, and you may cut | disconnect, after drying a strand.

The polyamide resin composition of the present embodiment contains (A) a polyamide resin and (B) an inorganic reinforcing material. The content of (B) inorganic reinforcing material in the polyamide resin composition of the present embodiment is preferably 10 to 250 parts by mass of (B) inorganic reinforcing material with respect to 100 parts by mass of (A) polyamide resin.
(B) By making content of an inorganic reinforcement material 10 mass parts or more, the improvement effect of intensity | strength is acquired more fully. Moreover, favorable productivity is obtained at an extrusion process by setting it as 250 mass parts or less.
When (A) polyamide resin and (B) inorganic reinforcing material are melt-kneaded, generally, (A) polyamide resin and (B) inorganic reinforcing material tend to generate heat due to shear and the resin temperature tends to rise. (B) The greater the content of the inorganic reinforcement, the greater the amount of heat generated by shearing and the higher the resin temperature. The polyamide resin containing the structural unit (A-2) has a tendency to gel as the resin temperature increases. The gel viscosity increases the melt viscosity, and the fluidity during molding decreases, so the surface appearance tends to deteriorate. However, since the polyamide resin composition of this embodiment satisfies (A) the polyamide resin satisfies the above-described conditions (a) to (d) and satisfies the above-described condition (e), the (A) polyamide resin Even when 250 parts by mass of (B) inorganic reinforcing material is included with respect to 100 parts by mass of resin, gelation due to an increase in the resin temperature during melt-kneading can be suppressed, and a molded product having a good surface appearance can be obtained. It has the characteristics.
The content of the (B) inorganic reinforcing material is more preferably 20 to 150 parts by mass, further preferably 25 to 100 parts by mass, and still more preferably 30 to 100 parts by mass of the (A) polyamide resin. -60 mass parts.

((C) component: heat stabilizer)
The polyamide resin composition of the present embodiment can further contain (C) a heat stabilizer (hereinafter sometimes referred to as a heat stabilizer, a component (C), and (C)).

(C) The thermal stabilizer is not limited to the following as long as it can improve thermal deterioration suppression of materials, prevention of discoloration during heating, heat aging resistance, and weather resistance. For example, copper acetate And copper stabilizers of copper compounds such as copper iodide, phenol stabilizers such as hindered phenol compounds, phosphite stabilizers, hindered amine stabilizers, triazine stabilizers, sulfur stabilizers and the like.
Moreover, ultraviolet absorbers, such as said antioxidant, such as alkylphenol, alkylene bisphenol, and alkylphenol thioether, salicylic acid ester, benzotriazole, and hydroxybenzophenone, are also mentioned.

In the polyamide resin composition of the present embodiment, when (C) the heat stabilizer is added, the content of the (C) heat stabilizer is (C) heat stable with respect to 100 parts by mass of the (A) polyamide resin. It is preferable that it is 0.005-10 mass parts of agents.
(C) By making content of a heat stabilizer 0.005 mass part or more, the improvement effect of heat stability is fully acquired. Moreover, favorable productivity is obtained at an extrusion process by setting it as 10 mass parts or less.

((D) component: moldability improving agent)
The polyamide resin composition of the present embodiment may further contain (D) a moldability improving agent (hereinafter, sometimes referred to as a moldability improving agent, a component (D), or (D)).

  The (D) moldability improver (also referred to as a lubricant or a plasticizer) is not limited to the following as long as it improves the plasticity and mold release properties during molding. Examples include higher fatty acids, higher fatty acid metal salts, higher fatty acid esters, higher fatty acid amides, and waxes.

  Examples of the higher fatty acid include, but are not limited to, for example, saturated or unsaturated having 8 to 40 carbon atoms such as stearic acid, palmitic acid, behenic acid, erucic acid, oleic acid, lauric acid, and montanic acid. Saturated linear or branched aliphatic monocarboxylic acid and the like can be mentioned. Among these, stearic acid and montanic acid are preferable from the viewpoint of suppressing gas generation during melt processing and suppressing mold deposits on the mold during molding.

The higher fatty acid metal salt is a metal salt of a higher fatty acid.
As a metal element which comprises a metal salt, the 1st, 2nd, 3rd group element of an element periodic table, zinc, aluminum, etc. are preferable, and calcium, sodium, potassium, magnesium, etc. are more preferable.
Examples of the higher fatty acid metal salt include, but are not limited to, calcium stearate, aluminum stearate, zinc stearate, magnesium stearate, calcium montanate, sodium montanate, calcium palmitate, and the like. . Among these, a metal salt of montanic acid and a metal salt of stearic acid are preferable from the viewpoints of suppressing gas generation during melt processing and suppressing mold deposit on the mold during molding.

The higher fatty acid ester is an esterified product of higher fatty acid and alcohol.
Among these, from the viewpoints of suppressing gas generation during melt processing and mold deposit suppression to the mold during molding, an aliphatic carboxylic acid having 8 to 40 carbon atoms and an aliphatic alcohol having 8 to 40 carbon atoms are used. Esters are preferred.
Here, as the higher fatty acid, those described above can be used.
Examples of the aliphatic alcohol include, but are not limited to, stearyl alcohol, behenyl alcohol, lauryl alcohol, and the like.
Examples of the higher fatty acid ester include, but are not limited to, stearyl stearate and behenyl behenate.

The higher fatty acid amide is an amide compound of higher fatty acid.
Examples of the higher fatty acid amide include, but are not limited to, stearic acid amide, oleic acid amide, erucic acid amide, ethylene bisstearyl amide, ethylene bis oleyl amide, N-stearyl stearyl amide, N-stearyl erucamide. Examples include acid amides.
Of these, stearic acid amide, erucic acid amide, ethylene bisstearyl amide, and N-stearyl erucic acid amide are preferable from the viewpoint of suppressing gas generation during melt processing and mold deposits on the mold during molding. Bisstearyl amide and N-stearyl erucamide are more preferred.

  Examples of the wax include montanic acid wax, polyethylene wax, polypropylene wax, and silicone wax.

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

In the polyamide resin composition of this embodiment, when (D) the moldability improver is added, the content of the (D) moldability improver is (D) molded with respect to 100 parts by mass of the (A) polyamide resin. It is preferable that it is 0.005-3 mass parts of property improvement agent.
(D) By making content of a moldability improving agent 0.005 mass part or more, improvement effects, such as plasticization property and mold release property, are fully acquired. Moreover, favorable productivity is obtained at an extrusion process by setting it as 3 mass parts or less.

((E) component: flame retardant)
In the polyamide resin composition of this embodiment, (E) a flame retardant (Hereinafter, it may describe as a flame retardant, (E) component, and (E).) May further be included.

  The flame retardant (E) is not limited to the following as long as it improves the flame retardancy, and examples thereof include non-halogen flame retardants and halogen-based flame retardants.

  The (E) flame retardant is preferably a non-halogen flame retardant or a bromine flame retardant from the viewpoints of suppressing gas generation during melt processing and suppressing mold deposits on the mold during molding.

  Examples of the non-halogen flame retardant include, but are not limited to, phosphorus flame retardants such as red phosphorus, ammonium phosphate, or ammonium polyphosphate, aluminum hydroxide, magnesium hydroxide, dolomite, hydro Hydrates of metal hydroxides or inorganic metal compounds such as talcite, calcium hydroxide, barium hydroxide, basic magnesium carbonate, zirconium hydroxide, tin oxide, zinc stannate, zinc hydroxystannate, and zinc borate , Inorganic compound flame retardants such as boric acid compounds such as zinc metaborate and barium metaborate, melamine, melam, melem, melon (product obtained by deammonation of 3 to 3 molecules of melem above 300 ° C), melamine cyanurate , Melamine phosphate, melamine polyphosphate, succinoguanamine, adipoguanamine Methyl glutarate log guanamine, triazine flame retardant such as melamine resins, silicone resins, silicone oils, silicone flame retardants such as silica.

  Examples of the brominated flame retardant include, but are not limited to, for example, compounds composed of brominated polystyrene, brominated polyphenylene ether, brominated bisphenol type epoxy polymer, and brominated crosslinked aromatic polymer. Examples include at least one flame retardant selected. Flame retardant aids such as antimony trioxide can also be used in combination.

In the polyamide resin composition of the present embodiment, when (E) a flame retardant is added, the content of the (E) flame retardant is (E) 1 to 30 flame retardants per 100 parts by mass of the polyamide resin. It is preferable that it is a mass part.
(E) By making content of a flame retardant 1 mass part or more, the improvement effect of a flame retardance is fully acquired. Moreover, favorable productivity is acquired at an extrusion process by setting it as 30 mass parts or less, and the big fall of a mechanical physical property can also be suppressed.

(Other components that can be included in the polyamide resin composition)
The polyamide resin composition of this embodiment can contain other components other than the above-described components (A) to (E) as needed, as long as the purpose of the present embodiment is not impaired.
Examples of the other components include usual additives used for other polymers and (A) polyamide resins, such as colorants and crystal nucleating agents.

  Examples of the other polymer include, but are not limited to, polyethylene, polypropylene, polystyrene, ABS resin, polyacetal, polyethylene terephthalate, polybutylene terephthalate, polyamide, polycarbonate, (modified) polyphenylene ether, polyphenylene sulfide, Examples include cycloolefin polymer, liquid crystal polyester, polyetherimide, polysulfone, polyethersulfone, polyamideimide, thermoplastic polyimide, polyetherketone, polyetheretherketone, fluororesin, and polybenzimidazole.

  Examples of the colorant include, but are not limited to, dyes such as nigrosine, pigments such as titanium oxide and carbon black; aluminum, colored aluminum, nickel, tin, copper, gold, silver, platinum, and oxidation. Metal particles such as iron, stainless steel, and titanium; metallic pigments such as mica pearl pigment, color graphite, color glass fiber, and color glass flake.

  Examples of the crystal nucleating agent include, but are not limited to, boron nitride and talc.

[Production method of polyamide resin composition]
The method for producing the polyamide resin composition of the present embodiment is not particularly limited as long as it is a method of mixing (A) a polyamide resin and (B) an inorganic reinforcing material, and a conventionally known method can be applied. .
Preferably, (A-1) a structural unit of an aliphatic polyamide having a carbon number / nitrogen number ratio (C / N ratio) of 8.0 or more, and (A-2) a structural unit consisting of hexamethylenediamine and terephthalic acid And (A-3) (A) polyamide containing a structural unit composed of hexamethylenediamine and isophthalic acid, and (B) an inorganic reinforcing material are melt-kneaded by an extruder.

〔Molding〕
The molded article of the polyamide resin composition includes the polyamide resin composition of the present embodiment described above.
The molded product of this embodiment can be manufactured by molding by a known molding method.
Since the molded product of this embodiment is excellent in mechanical properties such as tensile strength and surface appearance even at the time of water absorption, automobile parts, electrical parts, electronic parts, portable electronic equipment parts, mechanical / industrial parts, office equipment parts, It can be used for a wide range of applications such as aviation and space parts.

EXAMPLES Hereinafter, although a specific Example is given and this invention is demonstrated in detail, this invention is not limited to a following example.
In addition, the raw material and evaluation method which were applied to the Example are as follows.

〔material〕
(A) Polyamide resin As a raw material of the polyamide resin composition, a polyamide resin was produced according to Production Examples 1 to 13 described later.

(B) Reinforcing Material GF (Glass Fiber) Made by Nippon Electric Glass Product Name ECS03T275H Average fiber diameter (average particle diameter) 10 μm (round), cut length 3 mm

〔Evaluation method〕
(Test piece manufacturing method)
A test piece was produced using the polyamide resin composition produced in Examples described later.
A Type 3 dumbbell molded body conforming to ISO 37 was manufactured and used as a test piece.
Specifically, a dumbbell molded body was manufactured according to the following method.
First, a small injection molding machine jacket (manufactured by DSM, “Xplore”) was connected to the strand outlet of the small laboratory kneader. And the said resin composition (polyamide resin composition) of the molten state was inject | poured in the small injection molding machine jacket. When the polyamide resin composition was injected into the small injection molding machine jacket, the jacket temperature was set to 310 ° C.
Next, the small injection molding machine jacket was removed from the small laboratory kneader, and this small injection molding machine jacket was set in a mold of a Type 3 dumbbell conforming to ISO 37.
And the polyamide resin composition in the inside of a small injection molding machine jacket was extruded into the metal mold | die using the pressure cylinder connected to the small injection molding machine jacket rear part.
The injection conditions were as follows.
-Kneading time 2 minutes, injection pressure 11 bar, injection time 30 seconds-Mold temperature of polyamide resin composition: 80 ° C

(Tensile strength)
A dumbbell test piece of ISO37 Type 3 (length 16 mm × width 4 mm × thickness 2 mm of a parallel portion at a central portion between dumbbell chucks) was prepared.
Using a tensile tester (manufactured by Shimadzu Corporation, “Autograph AG-5000D”), the tensile strength of the dumbbell was measured at 23 ° C. with a distance between chucks of 25 mm and a tensile speed of 50 mm / min.
In addition, the tensile strength was performed about the water absorption test piece in 23 degreeC.
The water absorption test piece was obtained by immersing the dumbbell piece in a container containing 80 ° C. water and immediately heating it in an oven set at 80 ° C. for 96 hours.

(Water absorption rate)
An oven set at 80 ° C. by dipping three ISO37 Type 3 dumbbell test pieces each having a length of 16 mm (width of the central portion between dumbbell chucks × 4 mm × width 2 mm) in a container containing 80 ° C. water. And heated.
After 24 hours, the dumbbell test piece was taken out of the container, wiped off water, and naturally cooled over 15 minutes.
The mass of the dumbbell specimen before and after immersion was determined, and the water absorption was determined.

(Carbon / nitrogen ratio (C / N)
(A) In the polyamide resin, the average value of the number of carbon atoms per amide group (carbon number / amide group number) was obtained by calculation, and the ratio (C / N) of carbon number / nitrogen number was obtained. Specifically, the ratio of the number of carbons to the number of amide groups (number of carbons / number of amide groups) is determined by dividing the number of carbons contained in the molecular main chain by the number of amide groups contained in the molecular main chain. The nitrogen number ratio (C / N) was used.

(Dry glass transition point obtained from viscoelasticity measurement)
A dumbbell test piece of ISO37 Type 3 (length 15 mm × width 4 mm × thickness 2 mm of a parallel portion at the center between dumbbell chucks) was prepared.
Using a viscoelasticity measuring and analyzing apparatus (manufactured by GABO: EPLEXOR), a temperature dispersion spectrum of dynamic viscoelasticity was measured under the following conditions.
Measurement mode: tensile, waveform: sine wave, frequency: 8 Hz, temperature range: −100 ° C. to 300 ° C., temperature increase step: 3 ° C./min, static load: 140 N.
The tan δ which is the peak value of α relaxation of the loss tangent of the test piece obtained by the above measuring method was taken as the glass transition point.

(Crystallation enthalpy obtained when cooled at 20 ° C./min by differential scanning calorimetry)
The crystallization enthalpy of the polyamide resin contained in the polyamide resin compositions obtained in Examples and Comparative Examples was measured using Diamond-DSC manufactured by PERKIN-ELMER according to JIS-K7121.
The measurement was performed in a nitrogen atmosphere.
First, about 10 mg of the sample was heated from 30 ° C. to 350 ° C. at a temperature rising rate of 20 ° C./min.
Subsequently, after being kept at 350 ° C. for 3 minutes, it was cooled from 350 ° C. to 30 ° C. at a cooling rate of 20 ° C./min. The exothermic peak appearing at this time was defined as a crystallization peak, and the crystallization peak area was defined as a crystallization enthalpy.

(Differential scanning temperature measurement (Tm−Tc) between the melting point peak temperature (Tm) and the crystallization peak temperature (Tc) obtained when heated and cooled at 20 ° C./min)
The crystallization enthalpy of the polyamide resin contained in the polyamide resin compositions obtained in Examples and Comparative Examples was measured using Diamond-DSC manufactured by PERKIN-ELMER according to JIS-K7121.
The measurement was performed in a nitrogen atmosphere.
First, about 10 mg of the sample was heated from 30 ° C. to 350 ° C. at a temperature rising rate of 20 ° C./min.
Subsequently, after being kept at 350 ° C. for 3 minutes, it was cooled from 350 ° C. to 30 ° C. at a cooling rate of 20 ° C./min. The exothermic peak appearing at this time was defined as a crystallization peak, which was defined as a crystallization peak temperature (Tc).
Subsequently, after maintaining at 30 ° C. for 3 minutes, the temperature was raised again from 30 ° C. to 350 ° C. at a temperature rising rate of 20 ° C./min. The peak that appeared on the highest temperature side at this time was defined as the melting peak temperature Tm, and the difference (Tm−Tc) between the melting point peak temperature (Tm) and the crystallization peak temperature (Tc).

(Mw (weight average molecular weight) / Mn (number average molecular weight))
Mw (weight average molecular weight) / Mn (number average molecular weight) of the polyamide resin compositions obtained in Examples and Comparative Examples is GPC (gel permeation chromatography, manufactured by Tosoh Corporation, HLC-8020, hexafluoroisopropanol solvent). And Mw (weight average molecular weight) and number average molecular weight (Mn) measured with a PMMA (polymethyl methacrylate) standard sample (manufactured by Polymer Laboratories).
As a sample, a solution obtained by dissolving 3.0 mg of polyamide and a polyamide composition in 3 mL of hexafluoroisopropanol (added with 0.005N sodium trifluoroacetate) and filtering through a 0.45 μm filter was used for measurement. The measurement conditions were as follows.
Solvent: hexafluoroisopropanol (added 0.005N sodium trifluoroacetate)
Flow rate: 0.5 mL / min Sample injection amount: 0.1 mL
Temperature: 30 ° C

(Surface appearance (60 ° gloss))
Flat plate molded pieces were produced from the polyamide resin composition pellets obtained in the examples and comparative examples as follows.
Using an injection molding machine [PS40E: manufactured by Nissei Plastic Co., Ltd.], set cooling time 15 seconds, screw rotation speed 200 rpm, mold temperature Tg + 20 ° C., cylinder temperature = (Tm + 10) ° C. to (Tm + 30) ° C. The injection pressure and the injection speed were appropriately adjusted so that the time was in the range of 0.5 ± 0.1 seconds, and a flat plate molded piece (80 mm × 80 mm, thickness 3 mm) was produced from the polyamide composition pellets.
The central portion of the flat plate molded piece thus produced was measured for 60 ° gloss according to JIS-K7150 using a gloss meter (IG320 manufactured by HORIBA).
The larger the measured value, the better the surface appearance.

The production example of polyamide resin is shown below.
[Production Example 1: Production of polyamide copolymer (A1)]
1600 kg of equimolar salt of hexamethylenediamine and sebacic acid was added to distilled water to obtain a 50% by mass aqueous solution of raw material monomers. The obtained aqueous solution was charged into an autoclave of about 4,000 liters having a discharge nozzle at the bottom, and the inside of the autoclave was replaced with nitrogen while mixing at 50 ° C. Subsequently, the temperature was raised from 50 ° C. to about 150 ° C. over about 1 hour.
At that time, in order to keep the pressure in the autoclave at about 0.15 MPa (gauge pressure), heating was continued while removing water out of the system.
Thereafter, the autoclave was sealed, and the temperature was raised from 150 ° C. to about 220 ° C. over about 1 hour to raise the pressure to about 1.77 MPa (gauge pressure).
Subsequently, the temperature was raised from about 220 ° C. to about 270 ° C. over about 1 hour, while the pressure was maintained at about 1.77 MPa while heating was performed by removing water from the system.
Thereafter, the pressure was reduced to atmospheric pressure over about 1 hour. After the atmospheric pressure was reached, the strand was discharged from the lower nozzle into a strand, water-cooled, and cut to obtain pellets. The obtained pellets were dried in a nitrogen stream at 90 ° C. for 4 hours.

[Production Example 2: Production of polyamide copolymer (A2)]
An aqueous solution of hexamethylene diammonium terephthalate (6T salt) and hexamethylene diammonium isophthalate (6I salt) prepared so as to be 70 mol% hexamethylene terephthalamide units and 30 mol% hexamethylene isophthalamide units (solid raw material concentration 50 Mass%) was charged into a 500 mL autoclave, and the inside of the autoclave was sufficiently purged with nitrogen, and then reacted for 1 hour at a temperature of about 250 ° C. and a pressure of about 3.5 MPa.
Thereafter, the pressure was extracted into a receiver set at a pressure lower by about 1.0 MPa, dried, and then melt polymerized using a twin screw extruder.

[Production Example 3: Production of polyamide copolymer (A3)]
Raw materials were prepared so that the copolymerization ratios shown in Table 1 were obtained, and polymerization was carried out in the same manner as in Production Example 2 under other conditions to produce polyamide copolymers.

[Production Example 4: Production of polyamide copolymer (A4)]
An aqueous solution (solid raw material) of hexamethylene diammonium terephthalate (6T salt) and hexamethylene diammonium sebacanoate (610 salt) prepared to be 55 mol% of hexamethylene terephthalamide units and 45 mol% of hexamethylene sebacamide units Was charged into a 500 mL autoclave and the autoclave was sufficiently purged with nitrogen, and then the temperature was raised to about 140 ° C.
At this time, in order to maintain the pressure in the tank at a gauge pressure of about 0.2 MPa, heating was continued while removing water out of the system, and the mixture was concentrated to about 80%.
Thereafter, removal of water was once stopped, the temperature was raised to about 260 ° C., and when the pressure reached about 3.5 MPa, heating was continued while removing water so as to keep the pressure constant again.
Thereafter, after the temperature rose to 300 ° C., the pressure was slowly reduced to atmospheric pressure (gauge pressure was 0 kg / cm ² ) while continuing heating and finally applying for about 30 minutes to obtain a polyamide copolymer.
At this time, the final internal temperature of the polymerization was about 340 ° C.
The obtained polyamide copolymer was pulverized to a size of 5 mm or less and dried at 80 ° C. in a nitrogen atmosphere for 12 hours.

[Production Examples 5 and 6: Production of polyamide copolymers (A5) and (A6)]
Raw materials were prepared so as to have the copolymerization ratios shown in Tables 1 and 2 below, respectively, and polymerization was carried out in the same manner as in Production Example 4 under other conditions to produce polyamide copolymers.

[Production Example 7: Production of polyamide copolymer (A7)]
Hexamethylene diammonium terephthalate (6T salt), hexamethylene diammonium sebacanoate prepared to be 65 mol% hexamethylene terephthalamide unit, 20 mol% hexamethylene sebacamide unit, 15 mol% hexamethylene isophthalamide unit (610 salt), an aqueous solution of hexamethylene diammonium isophthalate (6I salt) (solid raw material concentration 50 mass%) was charged into a 500 mL autoclave, and the autoclave was sufficiently purged with nitrogen, and then the temperature was raised to about 140 ° C. Warm up.
At this time, in order to maintain the pressure in the tank at a gauge pressure of about 0.2 MPa, heating was continued while removing water out of the system, and the mixture was concentrated to about 80%.
Thereafter, removal of water was once stopped, the temperature was raised to about 260 ° C., and when the pressure reached about 3.5 MPa, heating was continued while removing water so as to keep the pressure constant again. Thereafter, the pressure was extracted into a receiver set at a pressure lower by about 1.0 MPa, dried, and then melt polymerized using a twin screw extruder.

[Production Example 8: Production of polyamide copolymer (A8)]
Hexamethylene diammonium terephthalate (6T salt), hexamethylene diammonium sebacanoate prepared to be 60 mol% hexamethylene terephthalamide unit, 30 mol% hexamethylene sebacamide unit, 10 mol% hexamethylene isophthalamide unit (610 salt), an aqueous solution of hexamethylene diammonium isophthalate (6I salt) (solid raw material concentration: 50% by mass) was charged into a 500 mL autoclave, and the autoclave was sufficiently purged with nitrogen. The temperature was raised to 200 ° C.
At this time, heating is continued while maintaining the pressure in the tank at a gauge pressure of about 1.0 MPa, and the temperature is raised to about 280 ° C. in 3 to 5 hours. Thereafter, the pressure was returned to atmospheric pressure over about 2 hours, the temperature was raised to 285 ° C. while injecting nitrogen gas into the system, and the reaction was completed over about 1-2 hours. The pressure was increased by about 1.0 MPa, the reaction product was discharged in a strand shape, cooled in a cooling bath, and then cut into a pellet shape.

[Production Examples 9 to 13: Production of polyamide copolymers (A9) to (A13)]
Raw materials were prepared so as to have a copolymerization ratio shown in Table 2 below, and polymerization was carried out in the same manner as in Production Example 8 under other conditions to produce a polyamide copolymer.

[Example 1]
53.8 parts by mass of (B) inorganic reinforcing material was added to 100 parts by mass of the polyamide component consisting of 66.7 parts by mass of the polyamide copolymer (A4) and 33.3 parts by mass of the polyamide copolymer (A2).
A polyamide resin composition was produced in accordance with the method using the small laboratory kneader described above.
Using the polyamide resin composition, the tensile strength of the water absorption test piece at 23 ° C. and the 60 ° gloss of the dried flat plate molded piece were determined.
Moreover, the water absorption was calculated | required by the method mentioned above.
The evaluation results are shown in Table 3 below.

[Examples 2 to 11]
Raw materials were blended so that the composition ratios shown in Table 2 were obtained, and the other conditions were the same as in Example 1 to produce a polyamide resin composition.
Using the polyamide resin composition, the tensile strength of the water absorption test piece at 23 ° C. and the 60 ° gloss of the dried flat plate molded piece were determined.
Moreover, the water absorption was calculated | required by the method mentioned above.
The evaluation results are shown in Tables 3 and 4 below.

[Comparative Example 1]
A polyamide resin composition containing 100 parts by mass of the polyamide copolymer (A1) and 53.8 parts by mass of the (B) inorganic reinforcing material was manufactured in accordance with the method using the small laboratory kneader described above. .
Using the polyamide resin composition, the tensile strength of the water absorption test piece at 23 ° C. and the 60 ° gloss of the dried flat plate molded piece were determined.
Moreover, the water absorption was calculated | required by the method mentioned above.
The evaluation results are shown in Table 5 below.

[Comparative Example 2]
A polyamide resin composition containing 100 parts by mass of the polyamide copolymer (A2) and (B) 53.8 parts by mass of the inorganic reinforcing material was produced in accordance with the above-described method using a small laboratory kneader. .
Using the polyamide resin composition, the tensile strength of the water absorption test piece at 23 ° C. and the 60 ° gloss of the dried flat plate molded piece were determined.
Moreover, the water absorption was calculated | required by the method mentioned above.
The evaluation results are shown in Table 5 below.

[Comparative Example 3]
A polyamide resin composition containing 100 parts by mass of the polyamide copolymer (A3) and (B) 53.8 parts by mass of the inorganic reinforcing material was produced in accordance with the method using the small laboratory kneader described above. .
Using the polyamide resin composition, the tensile strength of the water absorption test piece at 23 ° C. and the 60 ° gloss of the dried flat plate molded piece were determined.
Moreover, the water absorption was calculated | required by the method mentioned above.
The evaluation results are shown in Table 5 below.

[Comparative Example 4]
A polyamide resin composition containing 100 parts by mass of the polyamide copolymer (A4) and (B) 53.8 parts by mass of the inorganic reinforcing material was manufactured in accordance with the method using the small laboratory kneader described above. .
Using the polyamide resin composition, the tensile strength of the water absorption test piece at 23 ° C. and the 60 ° gloss of the dried flat plate molded piece were determined.
Moreover, the water absorption was calculated | required by the method mentioned above.
The evaluation results are shown in Table 5 below.

[Comparative Example 5]
A polyamide resin composition containing 100 parts by mass of the polyamide copolymer (A5) and 53.8 parts by mass of the reinforcing material (B) was produced in accordance with the method using the small laboratory kneader described above.
Using the polyamide resin composition, the tensile strength of the water absorption test piece at 23 ° C. and the 60 ° gloss of the dried flat plate molded piece were determined.
Moreover, the water absorption was calculated | required by the method mentioned above.
The evaluation results are shown in Table 5 below.

[Comparative Example 6]
A polyamide resin composition containing 100 parts by mass of the polyamide copolymer (A6) and (B) 53.8 parts by mass of the inorganic reinforcing material was produced in accordance with the method using the small laboratory kneader described above. .
Using the polyamide resin composition, the tensile strength of the water absorption test piece at 23 ° C. and the 60 ° gloss of the dried flat plate molded piece were determined.
Moreover, the water absorption was calculated | required by the method mentioned above.
The evaluation results are shown in Table 5 below.

[Comparative Example 7]
53.8 parts by mass of (B) inorganic reinforcing material was blended with 100 parts by mass of the polyamide component consisting of 70 parts by mass of the polyamide copolymer (A1) and 30 parts by mass of the polyamide copolymer (A2).
A polyamide resin composition was produced in accordance with the method using the small laboratory kneader described above.
Using the polyamide resin composition, the tensile strength of the water absorption test piece at 23 ° C. and the 60 ° gloss of the dried flat plate molded piece were determined.
Moreover, the water absorption was calculated | required by the method mentioned above.
The evaluation results are shown in Table 5 below.

[Comparative Example 8]
53.8 parts by mass of (B) inorganic reinforcing material was blended with 100 parts by mass of the polyamide component consisting of 25 parts by mass of the polyamide copolymer (A1) and 75 parts by mass of the polyamide copolymer (A3).
A polyamide resin composition was produced in accordance with the method using the small laboratory kneader described above.
Using the polyamide resin composition, the tensile strength of the water absorption test piece at 23 ° C. and the 60 ° gloss of the dried flat plate molded piece were determined.
Moreover, the water absorption was calculated | required by the method mentioned above.
The evaluation results are shown in Table 5 below.

[Comparative Example 9]
(B) Inorganic reinforcing material 53.8 parts by mass was blended with 100 parts by mass of the polyamide component consisting of 70 parts by mass of the polyamide copolymer (A1) and 30 parts by mass of the polyamide copolymer (A3).
A polyamide resin composition was produced in accordance with the method using the small laboratory kneader described above.
Using the polyamide resin composition, the tensile strength of the water absorption test piece at 23 ° C. and the 60 ° gloss of the dried flat plate molded piece were determined.
Moreover, the water absorption was calculated | required by the method mentioned above.
The evaluation results are shown in Table 5 below.

[Comparative Example 10]
A polyamide resin composition containing 100 parts by mass of a polyamide copolymer (A7) and (B) 53.8 parts by mass of an inorganic reinforcing material was produced in accordance with the above-described method using a small laboratory kneader. .
Using the polyamide resin composition, the tensile strength of the water absorption test piece at 23 ° C. and the 60 ° gloss of the dried flat plate molded piece were determined.
Moreover, the water absorption was calculated | required by the method mentioned above.
The evaluation results are shown in Table 5 below.

[Comparative Example 11]
A polyamide resin composition containing 100 parts by mass of the polyamide copolymer (A8) and 53.8 parts by mass of the reinforcing material (B) was produced in accordance with the method using the small laboratory kneader described above.
Using the polyamide resin composition, the tensile strength of the water absorption test piece at 23 ° C. and the 60 ° gloss of the dried flat plate molded piece were determined.
Moreover, the water absorption was calculated | required by the method mentioned above.
The evaluation results are shown in Table 5 below.

  In Table 5, “-” means an amorphous polyamide having no melting point Tm, meaning that measurement is impossible.

  As shown in Tables 3 and 4, it was confirmed that the polyamide resin composition of each example was excellent in physical properties and surface appearance upon water absorption.

  The polyamide resin composition of the present invention has industrial applicability in fields such as automobile parts, electronic and electrical parts, industrial machine parts, various gears, and extrusion applications.

Claims (12)

A polyamide resin composition comprising (A) a polyamide resin and (B) an inorganic reinforcement,
The (A) polyamide resin includes a structural unit of polyamide containing a dicarboxylic acid having a cyclic structure and / or a diamine having a cyclic structure, and satisfies the following conditions (a) to (d):
A copolymerized polyamide and / or a polyamide mixture,
A polyamide resin composition that satisfies the following condition (e).
(A) The ratio of carbon number / nitrogen number (C / N ratio) exceeds 7.0.
(B) The glass transition point at the time of drying calculated | required from a viscoelasticity measurement is 70 (degreeC) or more.
(C) The crystallization enthalpy (ΔHc) obtained by cooling at 20 (° C./min) by differential scanning calorimetry is 10 (J / g) or more.
(D) By differential scanning calorimetry, the difference (Tm−Tc) between the melting point peak temperature (Tm) and the crystallization peak temperature (Tc) obtained when heated and cooled at 20 (° C./min) is 45 (° C.). that's all.
(E) The ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is 2.9 or less.   The polyamide resin composition according to claim 1, wherein the dicarboxylic acid constituting the polyamide resin (A) contains terephthalic acid and / or isophthalic acid. The polyamide resin composition according to claim 1 or 2, wherein the (A) polyamide resin satisfies the following conditions (a-1) and (c-1).
(A-1) The ratio of carbon number / nitrogen number (C / N ratio) is 7.2 or more.
(C-1) The crystallization enthalpy (ΔHc) obtained by cooling at 20 (° C./min) by differential scanning calorimetry is 20 (J / g) or more. The polyamide resin composition according to any one of claims 1 to 3, wherein the (A) polyamide resin satisfies the following conditions (a-2), (b-2), and (c-2).
(A-2) The ratio of carbon number / nitrogen number (C / N ratio) is 7.3 or more.
(B-2) The glass transition point at the time of drying calculated | required from a viscoelasticity measurement is 80 (degreeC) or more.
(C-2) The crystallization enthalpy (ΔHc) obtained by cooling at 20 (° C./min) by differential scanning calorimetry is 30 (J / g) or more. The (A) polyamide resin is
(A-1) 30-50 mol% of structural units of an aliphatic polyamide having a carbon number / nitrogen number ratio (C / N ratio) of 8.0 or more,
(A-2) 20 to 70 mol% of a structural unit composed of hexamethylenediamine and terephthalic acid,
(A-3) 3 to 25 mol% of a structural unit composed of hexamethylenediamine and isophthalic acid,
The polyamide resin composition according to any one of claims 1 to 4, which is contained. (A-1) The structural unit of the aliphatic polyamide whose carbon number / nitrogen number ratio (C / N ratio) is 8.0 or more is:
The polyamide resin composition according to claim 5, wherein the polyamide resin composition is at least one structural unit selected from the group consisting of PA610, PA612, PA11, PA12, PA1010, and PA1012. For 100 parts by mass of the (A) polyamide resin,
(B) The polyamide resin composition as described in any one of Claims 1 thru | or 6 containing 10-250 mass parts of inorganic reinforcement. For 100 parts by mass of the (A) polyamide resin,
10 to 250 parts by mass of the (B) inorganic reinforcing material,
(C) The polyamide resin composition according to any one of claims 1 to 7, further comprising 0.005 to 10 parts by mass of a heat stabilizer. For 100 parts by mass of the (A) polyamide resin,
10 to 250 parts by mass of the (B) inorganic reinforcing material,
(D) The polyamide resin composition according to any one of claims 1 to 8, further comprising 0.005 to 3 parts by mass of a moldability improver. For 100 parts by mass of the (A) polyamide resin,
10 to 250 parts by mass of the (B) inorganic reinforcing material,
(E) The polyamide resin composition according to any one of claims 1 to 9, further comprising 1 to 30 parts by mass of a flame retardant.   The molded article containing the polyamide resin composition as described in any one of Claims 1 thru | or 10. (A-1) a structural unit of an aliphatic polyamide having a carbon number / nitrogen number ratio (C / N ratio) of 8.0 or more;
(A-2) a structural unit consisting of hexamethylenediamine and terephthalic acid;
(A-3) a structural unit consisting of hexamethylenediamine and isophthalic acid;
(A) a polyamide resin containing
(B) an inorganic reinforcing material;
Is produced by melt kneading with an extruder.