JP2012184277A - Polyamide resin composition and molding - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyamide resin composition excellent in rigidity after water absorption (water absorption rigidity), rigidity under high temperature use (rigidity at heating), appearance, and flame retardancy.SOLUTION: The polyamide resin composition includes: (A) a polyamide copolymer; and (B) a phosphinate and/or a diphosphinate. The polyamide copolymer includes: a dicarboxylic acid component unit including (a-p) adipic acid unit, (b-p) isophthalic acid unit, and (c-p) 1,4-cyclohexanedicarboxylic acid unit; and a diamine component unit, wherein the relation of the content (mol%) of the (b-p) and the content (mol%) of the (c-p) based on 100% by mol of the dicarboxylic acid component unit including the (a-p), the (b-p), and the (c-p) satisfies the following formula (1): (the content of the (c-p))>(the content of the (b-p))≥0.1.

Description

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

  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, polyamide resins have been used in environments that are severely thermally and mechanically, maintaining flame retardancy, and improving 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 in physical properties in use below.

  In order to meet the above-described requirements, as a method for improving mechanical properties, polyamide containing 1 to 80 mol% of 1,4-cyclohexanedicarboxylic acid having a trans isomer / cis isomer ratio of 50/50 to 97/3 ( For example, refer to Patent Document 1.), 1 to 40% of the number of chain units of 1,4-cyclohexanedicarboxylic acid and an aliphatic diamine (see, for example, Patent Document 2), 85 to 100 of dicarboxylic acid units. A polyamide (see, for example, Patent Document 3) in which mol% is composed of 1,4-cyclohexanedicarboxylic acid units and 60 to 100 mol% of diamine units is composed of aliphatic diamine units having 6 to 18 carbon atoms is disclosed. . Further, as a method for improving the rigidity after water absorption, it is composed of 30 to 95% by mass of hexamethylene adipamide units, 0 to 40% by mass of hexamethylene terephthalamide units, and 5 to 30% by mass of hexamethylene isophthalamide units. Polyamide is disclosed (for example, refer to Patent Document 4).

International Publication No. 2002/048239 Pamphlet International Publication No. 1997/011108 Pamphlet Japanese Patent Laid-Open No. 9-12868 JP-A-6-32980

However, in the techniques disclosed in Patent Documents 1, 2, and 3, although the rigidity under normal use conditions is improved, the rigidity after water absorption and the rigidity under high temperature use are not sufficiently improved, and the use environment There is a problem that the physical property change due to the bottom becomes large.
Moreover, in the technique disclosed in Patent Document 4, since the rigidity after water absorption is not sufficiently improved, there is a problem that the physical property change due to the use environment becomes large as described above.

  As described above, according to the conventionally disclosed technology, a polyamide copolymer has been proposed that has excellent rigidity after water absorption and rigidity under high-temperature use, and has little change in physical properties under use in any environment. There is no actual situation. In addition, it is difficult to suppress a decrease in rigidity after water absorption and under high temperature use while maintaining the balance between mechanical strength and rigidity, which is a characteristic of polyamide copolymers. There is a need for coalescence and molded products.

  The present invention has been made in view of the above-described problems of the prior art, and has good rigidity after water absorption (water absorption rigidity) and rigidity under high temperature use (rigidity during heat), appearance and flame retardancy. The main object is to provide a polyamide resin composition having excellent properties.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that (ap) adipic acid units, (bp) isophthalic acid units, and (cp) 1,4-cyclohexanedicarboxylic acid units. A polyamide copolymer containing a dicarboxylic acid component unit containing diamine and a diamine component unit, the (ap), (bp), and (cp) constituting the polyamide copolymer The relationship between the content (mol%) of (bp) and the content (mol%) of (cp) in a total of 100 mol% of the dicarboxylic acid component units containing And a polyamide copolymer (A) satisfying
Content of (cp)> Content of (bp) ≧ 0.1 (1)
(B): The present inventors have found that a polyamide resin composition containing a phosphinate and / or a diphosphinate can solve the above problems, and have completed the present invention.
That is, the present invention is as follows.

[1]
(A): a dicarboxylic acid component unit comprising (ap) an adipic acid unit, (bp) isophthalic acid unit, and (cp) 1,4-cyclohexanedicarboxylic acid unit; and a diamine component unit. A polyamide copolymer comprising:
The content (mol%) of the (bp) in the total of 100 mol% of the dicarboxylic acid component units including the (ap), the (bp), and the (cp), and the above A polyamide copolymer whose relationship with the content (mol%) of (cp) satisfies the following formula (1);
Content of (cp)> Content of (bp) ≧ 0.1 (1)
(B): A polyamide resin composition containing a phosphinate and / or a diphosphinate.
[2]
The phosphinic acid salt is a compound represented by the following general formula (I):
The polyamide resin composition according to [1], wherein the diphosphinic acid salt is a compound represented by the following general formula (II).
(In general formula (I) and general formula (II),
R ¹ , R ² , R ³ and R ⁴ are each independently selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, and an arylalkyl group having 7 to 20 carbon atoms. A group to be selected,
R ⁵ is a group selected from the group consisting of an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 10 carbon atoms, an alkylarylene group having 7 to 20 carbon atoms, and an arylalkylene group having 7 to 20 carbon atoms. And
M is a metal (ion) selected from the group consisting of calcium (ion), magnesium (ion), aluminum (ion) and zinc (ion);
m is 2 or 3, n is 1 or 3, and x is 1 or 2. )
[3]
With respect to 100 parts by mass of the (A) polyamide copolymer,
The polyamide resin composition according to the above [1] or [2], wherein the content of the (B) phosphinate and / or diphosphinate is 20 to 90 parts by mass.
[4]
(C) a flame retardant aid;
(D) a polyamide resin composition further containing inorganic fillers 1 to 200,
With respect to 100 parts by mass of the (A) polyamide,
The content of the (B) phosphinate and / or diphosphinate is 20 to 90 parts by mass,
The content of the flame retardant auxiliary (C) is 0.1 to 30 parts by mass,
The polyamide resin composition according to any one of [1] to [3], wherein the content of the (D) inorganic filler is 1 to 200 parts by mass.
[5]
The polyamide resin composition according to [4], wherein the flame retardant aid (C) is zinc borate and / or magnesium hydroxide.
[6]
With respect to a total of 100 mol% of the dicarboxylic acid component units including the (ap), the (bp), and the (cp),
The content of the (ap) adipic acid unit is 40 to 80 mol%,
The content of the (bp) isophthalic acid unit is 0.1 to 25 mol%,
The polyamide resin composition according to any one of [1] to [5], wherein the content of the (cp) 1,4-cyclohexanedicarboxylic acid unit is 15 to 40 mol%.
[7]
The polyamide resin composition according to any one of [1] to [6], wherein the diamine component unit is an aliphatic diamine component unit.
[8]
The polyamide resin composition according to any one of [1] to [7], wherein the diamine component unit is a hexamethylenediamine unit.
[9]
The (A) polyamide copolymer is
(A′-p) a unit comprising adipic acid and hexamethylenediamine,
(B′-p) a unit comprising isophthalic acid and hexamethylenediamine, and
(C′-p) The polyamide resin composition according to any one of [1] to [8], comprising a unit consisting of 1,4-cyclohexanedicarboxylic acid and the hexamethylenediamine.
[10]
The (A) polyamide copolymer is a dicarboxylic acid component containing (am) adipic acid, (bm) isophthalic acid, and (cm) 1,4-cyclohexanedicarboxylic acid, a diamine component, Is a polyamide copolymer obtained by copolymerizing
In the polyamide copolymer, a trans isomer unit (c-1-p) and a cis isomer unit (c-2-p) in the (cp) 1,4-cyclodicarboxylic acid unit, (a -P) When the total of the dicarboxylic acid component unit containing an adipic acid unit and (bp) isophthalic acid unit is 100 mol%, the content (mol%) of the (bp) isophthalic acid unit and the above [C]-[9] wherein the relationship with the content (mol%) of the trans isomer unit in the (c-1-p) 1,4-cyclodicarboxylic acid unit satisfies the following formula (2): The polyamide resin composition according to any one of the above.
(C-1-p) Content of trans isomer unit in 1,4-cyclodicarboxylic acid unit> (bp) Content of isophthalic acid unit ≧ 0.1 (2)
[11]
The dicarboxylic acid component comprising the (am) adipic acid, the (bm) isophthalic acid, and the (cm) 1,4-cyclohexanedicarboxylic acid;
The diamine component;
The polyamide resin composition according to [10], wherein the final polymerization temperature in copolymerization is 270 ° C. or higher.
[12]
The (cm) 1,4-cyclodicarboxylic acid used as a raw material monomer for the copolymer has a trans isomer (c-1-m) and a cis isomer (c-2-m),
The molar ratio of the trans isomer (c-1-m) to the cis isomer (c-2-m) in the (cm) 1,4-cyclodicarboxylic acid ((c-1-m) / (C-2-m)) is a polyamide resin composition according to [10] or [11] above, wherein the ratio is 50/50 to 10/90.
[13]
A molded article comprising the polyamide resin composition according to any one of [1] to [12].
[14]
The molded article according to [13], which is an automobile part.
[15]
The molded product according to [13], which is an electronic component.
[16]
The molded article according to [13], which is a home appliance OA equipment part or a mobile equipment part.

  According to the present invention, there are provided a polyamide resin composition and a molded article that have good rigidity after water absorption (water absorption rigidity) and rigidity under high-temperature use (rigidity during heat), and are excellent in appearance and flame retardancy. can do.

  Hereinafter, a mode for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail. In addition, this invention is not limited to the following embodiment, It can implement by changing variously within the range of the summary.

[Polyamide resin composition]
The polyamide resin composition of this embodiment is
(A): a dicarboxylic acid component unit comprising (ap) adipic acid units, (bp) isophthalic acid units, and (cp) 1,4-cyclohexanedicarboxylic acid units;
A diamine component unit, and a polyamide copolymer comprising:
The total amount of the dicarboxylic acid component units including the (ap), the (bp), and the (cp) constituting the polyamide copolymer is 100 mol%. 100 parts by mass of a polyamide copolymer in which the relationship between the content (mol%) and the content (mol%) of (cp) satisfies the following formula (1):
Content of (cp)> Content of (bp) ≧ 0.1 (1)
(B): A polyamide resin composition containing phosphinate and / or diphosphinate.

((A) polyamide copolymer)
(A) Polyamide copolymer (in this specification, (A): may be described as a polyamide copolymer or a polyamide copolymer (A)) is (ap) an adipic acid unit, (b -P) a polyamide copolymer containing a dicarboxylic acid component unit containing an isophthalic acid unit and a (cp) 1,4-cyclohexanedicarboxylic acid unit, and a diamine component unit, the polyamide copolymer constituting the polyamide copolymer Content (mol%) of (bp) in a total of 100 mol% of the dicarboxylic acid component units including (ap), (bp), and (cp) It is a polyamide copolymer whose relationship with the content (mol%) of (cp) satisfies the following formula (1).
Content of (cp)> Content of (bp) ≧ 0.1 (1)
By containing such a polyamide copolymer (A), it is possible to obtain a polyamide resin composition not only excellent in water absorption rigidity and thermal rigidity, but also excellent in molded appearance.

<Dicarboxylic acid component>
The composition ratio of the dicarboxylic acid component unit in the (A) polyamide copolymer is the (ap) adipic acid unit, (bp) isophthalic acid unit, and (cp) 1,4-cyclohexane. Preferably, the content of (ap) adipic acid unit is 40 to 80 mol% and the content of (bp) isophthalic acid unit is 100 mol% in total of dicarboxylic acid component units including dicarboxylic acid units. The content of 0.1 to 25 mol% and (cp) 1,4-cyclohexanedicarboxylic acid unit is 15 to 40 mol%, and the more preferable composition ratio is the content of (ap) adipic acid unit Is 45 to 80 mol%, (bp) the content of isophthalic acid units is 1 to 25 mol%, and (cp) the content of 1,4-cyclohexanedicarboxylic acid units is 20 to 40 mol% And (bp) (C-p) and the relation is a polyamide copolymer which satisfies the above formula (1).
By including the polyamide copolymer (A) having a composition ratio within the above range and satisfying the relationship of the formula (1), a polyamide having further excellent water absorption rigidity and thermal rigidity without deteriorating the molding appearance. It can be set as a resin composition.
In addition, the ratio of each composition which comprises a polyamide copolymer can be calculated | required with a nuclear magnetic resonance apparatus (NMR).

<Diamine component>
The diamine component unit in the (A) polyamide copolymer is not particularly limited, but examples include component units such as aliphatic diamine, aromatic diamine, and diamine having a substituent branched from the main chain, and among these, From the viewpoint of productivity, an aliphatic diamine component unit is preferred.

  Examples of the aliphatic diamine component unit include ethylene diamine, propylene diamine, tetramethylene diamine, pentamethylene diamine, heptamethylene diamine, hexamethylene diamine, octamethylene diamine, nonamethylene diamine, decamethylene diamine, undecamethylene diamine, dodecamethylene. Component units, such as C2-C20 linear saturated aliphatic diamine, such as diamine and tridecamethylenediamine, are mentioned. Among these aliphatic diamine component units, hexamethylene diamine component units are preferable from the viewpoint of rigidity.

  Examples of the aromatic diamine component unit include component units such as metaxylylenediamine.

  Examples of the diamine component unit having a substituent branched from the main chain include 2-methylpentamethylenediamine (also referred to as 2-methyl-1,5-diaminopentane), 2,2,4-trimethylhexamethylene. Component units such as branched saturated aliphatic diamines having 3 to 20 carbon atoms such as diamine, 2,4,4-trimethylhexamethylenediamine, 2-methyloctamethylenediamine, and 2,4-dimethyloctamethylenediamine are exemplified. .

  Each of these diamine component units may be included alone or in combination of two or more.

<Other copolymer components>
(A) The polyamide copolymer has (am) adipic acid, (bm) isophthalic acid, and (cm) 1,4-cyclohexanedicarboxylic acid as long as the object of the present embodiment is not impaired. Other aliphatic dicarboxylic acids, alicyclic dicarboxylic acids, aromatic dicarboxylic acids, polycondensable amino acids, lactams, and the like can be used as copolymerization components.

  Examples of aliphatic dicarboxylic acids other than (am) adipic acid, (bm) isophthalic acid, and (cm) 1,4-cyclohexanedicarboxylic acid include malonic acid, dimethylmalonic acid, succinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylglutaric acid, 2,2-diethylsuccinic acid, 2,3-diethylglutaric acid, glutaric acid, 2,2-dimethylglutaric acid, 2-methyladipic acid, trimethyl C3-C20 straight chain such as adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, tetradecanedioic acid, hexadecanedioic acid, octadecanedioic acid, eicosanedioic acid, and diglycolic acid Examples include branched saturated aliphatic dicarboxylic acids.

  Examples of the alicyclic dicarboxylic acid include 1,3-cyclohexanedicarboxylic acid and 1,3-cyclopentanedicarboxylic acid. An alicyclic dicarboxylic acid etc. whose number is 5-10 are mentioned. The alicyclic dicarboxylic acid may be unsubstituted or may have a substituent.

Examples of the aromatic dicarboxylic acid include unsubstituted or various substitutions such as terephthalic acid, naphthalenedicarboxylic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, and 5-sodium sulfoisophthalic acid. And aromatic dicarboxylic acids having 8 to 20 carbon atoms substituted with a group.
Examples of the various substituents include halogen groups such as alkyl groups having 1 to 6 carbon atoms, aryl groups having 6 to 12 carbon atoms, arylalkyl groups having 7 to 20 carbon atoms, chloro groups and bromo groups, and carbon numbers. Examples thereof include 3 to 10 alkylsilyl groups, and sulfonic acid groups and groups such as sodium salts thereof.

  Examples of the polycondensable amino acid include 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, paraaminomethylbenzoic acid and the like.

  Examples of the lactam include butyl lactam, pivalolactam, caprolactam, capryl lactam, enantolactam, undecanolactam, dodecanolactam and the like.

  These dicarboxylic acid components, amino acid components, and lactam components may be used alone or in combination of two or more.

  The (A) polyamide copolymer comprises (a′-p) a unit composed of adipic acid and hexamethylene diamine, (b′-p) a unit composed of isophthalic acid and hexamethylene diamine, and (c′-p). It is preferable that a unit comprising 1,4-cyclohexanedicarboxylic acid and hexamethylenediamine is included. By containing the polyamide copolymer (A) containing such units, it is possible to obtain a polyamide resin composition that is further excellent in water absorption rigidity and high-temperature rigidity.

<End sealant>
As a raw material for the (A) polyamide copolymer, an end-capping agent can be further added in order to adjust the molecular weight or improve hot water resistance. For example, when polymerizing the (A) polyamide copolymer, a known end-capping agent can be further added.

  The terminal blocking agent is not particularly limited, and examples thereof include acid anhydrides such as monocarboxylic acid, monoamine, and phthalic anhydride, monoisocyanates, monoacid halides, monoesters, and monoalcohols. Among them, monocarboxylic acids and monoamines are preferable from the viewpoint of production cost. These terminal blocking agents may be used alone or in combination of two or more.

  The monocarboxylic acid used as a terminal blocking agent is not particularly limited as long as it is a monocarboxylic acid having reactivity with an amino group. For example, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, Aliphatic monocarboxylic acids such as lauric acid, tridecylic acid, myristic acid, palmitic acid, stearic acid, pivalic acid, and isobutyric acid; cycloaliphatic monocarboxylic acids such as cyclohexanecarboxylic acid; benzoic acid, toluic acid, α-naphthalene And aromatic monocarboxylic acids such as carboxylic acid, β-naphthalenecarboxylic acid, methylnaphthalenecarboxylic acid, and phenylacetic acid. These monocarboxylic acids may be used alone or in combination of two or more.

  The monoamine used as the end-capping agent is not particularly limited as long as it is a monoamine having reactivity with a carboxyl group. For example, methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, decylamine, stearylamine Aliphatic monoamines such as dimethylamine, diethylamine, dipropylamine, and dibutylamine; alicyclic monoamines such as cyclohexylamine and dicyclohexylamine; aromatic monoamines such as aniline, toluidine, diphenylamine, and naphthylamine; These monoamines may be used alone or in combination of two or more.

<Number average molecular weight>
The molecular weight of the (A) polyamide copolymer is not particularly limited, but from the viewpoint of moldability and mechanical properties, the number average molecular weight (Mn) is preferably 7000 to 100,000, more preferably 7500 to 50,000. Yes, more preferably from 10,000 to 40,000.
The number average molecular weight (Mn) is determined by gel permeation using, for example, hexafluoroisopropanol (HFIP) in which 0.1 mol% of sodium trifluoroacetate is dissolved as a solvent and polymethyl methacrylate (PMMA) as a standard sample. It can be determined by chromatography (GPC).
When the number average molecular weight (Mn) of the (A) polyamide copolymer is 7000 or more, there is a tendency that a decrease in toughness can be further suppressed. Tend.

<Melting point>
The melting point of the (A) polyamide copolymer is preferably 210 to 340 ° C, more preferably 230 to 330 ° C, still more preferably 240 to 320 ° C, and still more preferably 240 to 300 ° C. is there.
The melting point can be measured according to JIS K7121. Specifically, it can measure using "DSC-7" by PERKIN-ELMER, for example.
More specifically, using 8 mg of the sample, the temperature is raised to 400 ° C. under a temperature rising rate of 20 ° C./min, and the peak temperature of the obtained melting curve is taken as the melting point.
When the melting point of the polyamide copolymer (A) is 210 ° C. or higher, there is a tendency to further suppress deterioration in chemical resistance and heat resistance, and when it is 340 ° C. or lower, thermal decomposition during molding is further reduced. There is a tendency to be able to suppress.

<Glass transition temperature>
The glass transition temperature of said (A) polyamide copolymer becomes like this. Preferably it is 50-110 degreeC, More preferably, it is 50-100 degreeC, More preferably, it is 50-90 degreeC.
The glass transition temperature can be measured according to JIS K7121. More specifically, for example, it can be measured as follows using “DSC-7” manufactured by PERKIN-ELMER.
First, the sample is melted on a hot stage (for example, “EP80” manufactured by Mettler Co.), and the molten sample is rapidly cooled in liquid nitrogen and solidified to obtain a measurement sample. Using 10 mg of the measurement sample, the glass transition temperature can be measured by raising the temperature in the range of 30 to 300 ° C. under a temperature rising rate of 20 ° C./min.
When the glass transition temperature of the (A) polyamide copolymer is 50 ° C. or higher, it is difficult to cause a decrease in heat resistance and chemical resistance, and an increase in water absorption can be effectively prevented. Moreover, when the glass transition temperature of the (A) polyamide copolymer is 110 ° C. or lower, a polyamide resin composition having further improved molding appearance can be obtained.

((A) Polyamide copolymer production method)
(A) It does not specifically limit as a manufacturing method of a polyamide copolymer, A well-known method can be used.
For example, a solution of adipic acid, isophthalic acid, 1,4-cyclohexanedicarboxylic acid, hexamethylenediamine, and a mixture of other components as necessary, or an aqueous suspension is heated and polymerized while maintaining the molten state. Method (hot melt polymerization method);
A method of increasing the degree of polymerization of a polyamide copolymer obtained by a hot melt polymerization method while maintaining a solid state at a temperature below the melting point (hot melt polymerization / solid phase polymerization method);
Aqueous solution or water suspension of adipic acid, isophthalic acid, 1,4-cyclohexanedicarboxylic acid, hexamethylenediamine, and other components as necessary, is heated, and the precipitated prepolymer is further extruded into a kneader, etc. Method of increasing the degree of polymerization by melting again with a machine (prepolymer / extrusion polymerization method);
Adipic acid, isophthalic acid, 1,4-cyclohexanedicarboxylic acid, hexamethylenediamine, and if necessary, an aqueous solution or a water suspension of a mixture with other components is heated, and the precipitated prepolymer is further below the melting point of the polyamide. A method of increasing the degree of polymerization while maintaining a solid state at a temperature (prepolymer / solid phase polymerization method);
A method of polymerizing adipic acid, isophthalic acid, 1,4-cyclohexanedicarboxylic acid, hexamethylenediamine, if necessary, a mixture with other components, solid salt or polycondensate while maintaining the solid state (solid phase weight Legal).

(A) It does not specifically limit as a polymerization form of a polyamide copolymer, A batch type or a continuous type may be sufficient.
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.

Among the above production methods, the hot melt polymerization method is preferable from the viewpoint of productivity. Examples of the hot melt polymerization method include a batch type hot melt polymerization method. The polymerization temperature condition of the batch-type hot melt polymerization method is not particularly limited, but is preferably 100 ° C. or higher, more preferably 120 ° C. or higher, and further preferably 170 ° C. or higher from the viewpoint of productivity.
For example, a mixture of adipic acid, isophthalic acid, 1,4-cyclohexanedicarboxylic acid, and hexamethylenediamine, a solid salt, an aqueous solution, or the like is stirred at a temperature of 110 to 200 ° C., and water vapor is increased to about 60 to 90%. Is gradually removed and concentrated by heating. Subsequently, heating is continued until the internal pressure becomes about 1.5 to 5.0 MPa (gauge pressure). Thereafter, the pressure is maintained at about 1.5 to 5.0 MPa (gauge pressure) while removing water and / or gas components, and the internal temperature is preferably 250 ° C. or higher, more preferably 260 ° C. or higher, more preferably 270 ° C. or higher. At this point, a hot melt polymerization method can be used in which water and / or gas components are removed and the pressure is gradually released and polycondensation is performed under normal pressure or reduced pressure.
Furthermore, a solid phase polymerization method in which a mixture, a solid salt, or a polycondensate of adipic acid, isophthalic acid, 1,4-cyclohexanedicarboxylic acid, and hexamethylenediamine is subjected to thermal polycondensation at a temperature below the melting point is used. Can do.
These methods may be combined as necessary.

For example, as described above, (a′-p) a unit composed of adipic acid and hexamethylenediamine, (b′-p) a unit composed of isophthalic acid and hexamethylenediamine, and (c′-p) 1,4- A polyamide copolymer containing units composed of cyclohexanedicarboxylic acid and hexamethylenediamine can be produced by a hot melt polymerization method.
(A) The structural unit of the polyamide copolymer can be confirmed by a nuclear magnetic resonance apparatus (NMR).

The (A) polyamide copolymer comprises a dicarboxylic acid component composed of (am) adipic acid, (bm) isophthalic acid, and (cm) 1,4-cyclohexanedicarboxylic acid, and a diamine component. It is preferably a polyamide copolymer obtained by copolymerization. In the polyamide copolymer, a unit of trans isomer (c-1-p) in (cp) 1,4-cyclodicarboxylic acid unit. ) And cis isomer units (c-2-p), (ap) adipic acid units, and (bp) isophthalic acid units, the total amount of dicarboxylic acid component units is 100 mol%, (A) Content (mol%) of the (bp) isophthalic acid unit constituting the polyamide copolymer and a unit of trans isomer in the (c-1-p) 1,4-cyclodicarboxylic acid unit Content of Relationship between the mole%) preferably satisfies the following formula (2).
(C-1-p) Content of trans isomer unit in 1,4-cyclodicarboxylic acid unit> (bp) Content of isophthalic acid unit ≧ 0.1 (2)
(A) When the polyamide copolymer satisfies the above formula (2), the obtained polyamide resin composition can further improve the water absorption rigidity and the high-temperature rigidity without impairing the molded appearance.
The content of the trans isomer unit in the (c-1-p) 1,4-cyclodicarboxylic acid unit and the content of the (bp) isophthalic acid unit are determined by NMR, respectively.

(A) In the polymerization step of the polyamide copolymer, a dicarboxylic acid component containing (am) adipic acid, (bm) isophthalic acid, and (cm) 1,4-cyclohexanedicarboxylic acid, and a diamine The final polymerization temperature in copolymerization with the component is preferably 270 ° C. or higher, more preferably 280 ° C. or higher, and further preferably 290 ° C. or higher. The upper limit of the final polymerization temperature is not particularly limited, but is preferably 300 ° C. or lower. As a result, the content of the trans isomer unit (c-1-p) of 1,4-cyclohexanedicarboxylic acid in the polyamide copolymer can be increased, and the water absorption rigidity and hot time can be increased without impairing the molding appearance. A polyamide resin composition having further excellent rigidity can be obtained.
For example, when adopting the above-described hot melt polymerization method, it is preferable to carry out polycondensation at normal pressure or reduced pressure while keeping the final polymerization temperature within the above temperature range.

(A) In the polymerization step of the polyamide copolymer, when an extrusion type reactor such as a kneader is used, the conditions for extrusion are not particularly limited, but the degree of vacuum is preferably about 0 to 0.07 MPa.
The extrusion temperature is preferably about 1 to 100 ° C. higher than the melting point determined by differential scanning calorimetry (DSC) measurement according to JIS K7121. The shear rate is preferably about 100 (sec ⁻¹ ) or more, and the average residence time is preferably about 0.1 to 15 minutes. By setting it as said extrusion conditions, generation | occurrence | production of problems, such as coloring and high molecular weight being unable to be suppressed, can be suppressed effectively.

(A) In the polymerization step of the polyamide copolymer, a predetermined polymerization catalyst may be used.
The polymerization catalyst is not particularly limited as long as it is a known catalyst used in the production of polyamide. For example, phosphoric acid, phosphorous acid, hypophosphorous acid, orthophosphorous acid, pyrophosphorous acid, phenylphosphinic acid , Phenylphosphonic acid, 2-methoxyphenylphosphonic acid, 2- (2′-pyridyl) ethylphosphonic acid, and metal salts thereof.
Examples of the metal of the metal salt include potassium, sodium, magnesium, vanadium, calcium, zinc, cobalt, manganese, tin, tungsten, germanium, titanium, and antimony.
In addition, as the polymerization catalyst, phosphate esters such as ethyl ester, isopropyl ester, butyl ester, hexyl ester, decyl ester, isodecyl ester, octadecyl ester, stearyl ester, and phenyl ester can also be used.

As described above, (C) 1,4-cyclohexanedicarboxylic acid used as a raw material monomer in the polymerization step of (A) polyamide copolymer has a geometric isomer of a trans isomer and a cis isomer. Exists.
(Cm) 1,4-cyclohexanedicarboxylic acid used as a raw material monomer may use either a trans isomer or a cis isomer, or a mixture of trans isomer and cis isomer in various ratios. It may be used as
(Cm) 1,4-cyclodicarboxylic acid is isomerized at a high temperature to have a certain ratio, and the cis isomer is higher in water solubility of the equivalent salt with diamine than the trans isomer. When the (cm) 1,4-cyclodicarboxylic acid used as a monomer has a trans isomer (c-1-m) and a cis isomer (c-2-m), the (cm) 1, The molar ratio of trans isomer (c-1-m) to cis isomer (c-2-m) in 4-cyclodicarboxylic acid ((c-1-m) / (c-2-m)) is Preferably it is 50 / 50-10 / 90, More preferably, it is 40 / 60-10 / 90, More preferably, it is 35 / 65-15 / 85.
By setting (c-1-m) / (c-2-m) in the above range, it is possible to obtain a polyamide resin composition that is further excellent in water absorption rigidity and thermal rigidity without impairing the molding appearance. (C-1-m) / (c-2-m) can be measured using a nuclear magnetic resonance apparatus (NMR).

((B) phosphinic acid salt and / or diphosphinic acid)
The polyamide resin composition of the present embodiment includes the (A) polyamide copolymer and (B) phosphinate and / or diphosphinate (hereinafter, both may be collectively referred to as “phosphinate”). And a polyamide resin composition.
Examples of phosphinates include compounds represented by the following general formula (I).
Examples of the diphosphinic acid salt include compounds represented by the following general formula (II).
In general formula (I) and general formula (II), R < ¹ >, R < ² >, R < ³ > and R < ⁴ > are each independently an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, and R ⁵ is a group selected from the group consisting of arylalkyl groups having 7 to 20 carbon atoms, R ⁵ is an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 10 carbon atoms, and an alkylarylene group having 7 to 20 carbon atoms. And a group selected from the group consisting of aryl alkylene groups having 7 to 20 carbon atoms, and M is selected from the group consisting of calcium (ion), magnesium (ion), aluminum (ion) and zinc (ion). M is 2 or 3, n is 1 or 3, and x is 1 or 2.

In the present embodiment, examples of the alkyl group include a linear or branched saturated aliphatic group.
In the present embodiment, examples of the aryl group include an aromatic group having 6 to 20 carbon atoms which is unsubstituted or substituted with various substituents, and includes a phenyl group, a benzyl group, an o-toluyl group, 2, 3 -A xylyl group etc. are mentioned.

The polyamide resin composition of the present embodiment contains (B) a phosphinic acid salt, so that the properties of the polyamide copolymer excellent in heat resistance, fluidity, toughness, low water absorption, and rigidity are not impaired. The resin composition can also be a polyamide resin composition having excellent heat resistance, fluidity, toughness, low water absorption, rigidity, and excellent flame retardancy.
Moreover, even if the polyamide resin composition of this embodiment contains a phosphinate, it is excellent in light resistance, and is excellent also as a color tone of a polyamide resin composition.

As the phosphinic acid salt (B) used in the present embodiment, as described in European Patent Application Publication No. 699708 and Japanese Patent Application Laid-Open No. 8-73720, etc., phosphinic acid and metal carbonate, metal hydroxide are used. It can manufacture in aqueous solution using metal components, such as a thing or a metal oxide.
These are essentially monomeric compounds, but depending on the reaction conditions, polymeric phosphinates having a degree of condensation of 1 to 3 are also included depending on the environment.

  (B) Examples of the phosphinic acid and diphosphinic acid in the phosphinic acid salt include dimethylphosphinic acid, ethylmethylphosphinic acid, diethylphosphinic acid, methyl-n-propylphosphinic acid, methandi (methylphosphinic acid), and benzene-1,4. -Di (methylphosphinic acid), methylphenylphosphinic acid, diphenylphosphinic acid, etc. are mentioned.

  (B) As a metal ion component in a phosphinic acid salt, calcium ion, magnesium ion, aluminum ion, zinc ion etc. are mentioned, for example.

Examples of (B) phosphinic acid salts include calcium dimethylphosphinate, magnesium dimethylphosphinate, aluminum dimethylphosphinate, zinc dimethylphosphinate, calcium ethylmethylphosphinate, magnesium ethylmethylphosphinate, aluminum ethylmethylphosphinate, ethyl Zinc methylphosphinate, calcium diethylphosphinate, magnesium diethylphosphinate, aluminum diethylphosphinate, zinc diethylphosphinate, calcium methyl-n-propylphosphinate, magnesium methyl-n-propylphosphinate, methyl-n-propylphosphinic acid Aluminum, zinc methyl-n-propylphosphinate, methylenebis (methylphosphinate) calcium, methylenebis ( Chlorophosphinic acid) magnesium, methylenebis (methylphosphinic acid) aluminum, methylenebis (methylphosphinic acid) zinc, phenylene-1,4-bis (methylphosphinic acid) calcium, phenylene-1,4-bis (methylphosphinic acid) magnesium, Phenylene-1,4-bis (methylphosphinic acid) aluminum, phenylene-1,4-bis (methylphosphinic acid) zinc, calcium methylphenylphosphinate, magnesium methylphenylphosphinate, aluminum methylphenylphosphinate, methylphenylphosphinic acid Examples include zinc, calcium diphenylphosphinate, magnesium diphenylphosphinate, aluminum diphenylphosphinate, and zinc diphenylphosphinate.
These (B) phosphinic acid salts may be used alone or in combination of two or more.

  (B) As the phosphinate, from the viewpoint of flame retardancy and electrical properties of the polyamide resin composition, and from the viewpoint of synthesis of phosphinate, calcium dimethylphosphinate, aluminum dimethylphosphinate, zinc dimethylphosphinate, ethyl Calcium methylphosphinate, aluminum ethylmethylphosphinate, zinc ethylmethylphosphinate, calcium diethylphosphinate, aluminum diethylphosphinate, and zinc diethylphosphinate are preferred.

(B) As the phosphinic acid salt, the particle size of the phosphinic acid salt is 100 μm or less in terms of mechanical properties such as toughness and rigidity of the molded product obtained by molding the polyamide resin composition and the appearance of the molded product. It is preferable to use as a pulverized powder, and it is more preferable to use a powder pulverized to 50 μm or less.
When the powdered (B) phosphinate having an average particle size of 0.5 to 20 μm is used, not only a polyamide resin composition exhibiting high flame retardancy can be obtained, but also the strength of the molded product is remarkably increased. Therefore, it is more preferable.
In the present embodiment, the average particle size can be measured using a laser diffraction / scattering particle size distribution measuring device or a precision particle size distribution measuring device.

  (B) The phosphinic acid salt is not necessarily completely pure, and some unreacted products or by-products may remain.

The polyamide resin composition of this embodiment may further contain either (C) a flame retardant aid, (D) an inorganic filler, or both.
((C) Flame retardant aid)
The polyamide resin composition of this embodiment can be made into a polyamide resin composition that is further excellent in flame retardancy by further containing (C) a flame retardant aid.

(C) Although it does not specifically limit as a flame retardant adjuvant, For example, antimony oxides, such as antimony trioxide, diantimony tetroxide, diantimony pentoxide, sodium antimonate; tin monoxide, dioxide Tin oxide such as tin; iron oxides such as ferric oxide and gamma iron oxide; other zinc oxide, zinc borate, calcium oxide, aluminum oxide (alumina), aluminum oxide (boehmite), silicon oxide (silica), oxidation Metal oxides such as titanium, zirconium oxide, manganese oxide, molybdenum oxide, cobalt oxide, bismuth oxide, chromium oxide, tin oxide, nickel oxide, copper oxide, and tungsten oxide; metal water such as magnesium hydroxide and aluminum hydroxide Oxides; aluminum, iron, titanium, manganese, zinc, molybdenum, cobalt, Metal powders such as smus, chromium, tin, antimony, nickel, copper, and tungsten; metal carbonates such as zinc carbonate, calcium carbonate, magnesium carbonate, and barium carbonate; magnesium borate, calcium borate, aluminum borate, etc. Metal borate; as well as silicone.
(C) Flame retardant aids include zinc oxide, iron oxide, calcium oxide, aluminum oxide (alumina), aluminum oxide (boehmite), silicon oxide (silica), titanium oxide, zirconium oxide, manganese oxide, molybdenum oxide, oxidation Metal oxides such as cobalt, bismuth oxide, chromium oxide, tin oxide, antimony oxide, nickel oxide, copper oxide, and tungsten oxide; metal hydroxides such as magnesium hydroxide and aluminum hydroxide; aluminum, iron, titanium, Metal powders such as manganese, zinc, molybdenum, cobalt, bismuth, chromium, tin, antimony, nickel, copper, and tungsten; metal carbonates such as zinc carbonate, calcium carbonate, magnesium carbonate, and barium carbonate; zinc borate, boron Magnesium oxide, calcium borate, and Metal borates such as aluminum borate, etc., as well as silicone are preferable.
These (C) flame retardant aids may be used alone or in combination of two or more.

(B) As a flame retardant aid used together with the phosphinate, calcium oxide, aluminum oxide (alumina), aluminum hydroxide (boehmite), magnesium hydroxide, and zinc borate are used from the viewpoint of flame retardancy. A metal borate such as is preferable, and zinc borate and / or magnesium hydroxide is more preferable.
The zinc borate, more preferably zinc borate represented by _{xZnO · yB 2 O 3 · zH} 2 O (x> 0, y> 0, z ≧ 0), more preferably, 2ZnO · 3B ₂ O Examples thereof include zinc borate represented by ₃ · 3.5H ₂ O, 4ZnO · B ₂ O ₃ · H ₂ O, and 2ZnO · 3B ₂ O ₃ .
These metal borates may be treated with a surface treatment agent such as a silane coupling agent and a titanate coupling agent.
(C) The average particle diameter of the flame retardant aid is preferably 30 μm or less, more preferably 15 μm or less, and even more preferably 7 μm or less.

((D) inorganic filler)
The polyamide resin composition of this embodiment can be made into a polyamide resin composition that is further excellent in mechanical properties such as toughness and rigidity by further containing (D) an inorganic filler.

The inorganic filler (D) used in the present embodiment is not particularly limited, and examples thereof include glass fiber, carbon fiber, calcium silicate fiber, potassium titanate fiber, aluminum borate fiber, glass flake, and 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, silica Calcium oxide, sodium aluminosilicate, magnesium silicate, ketjen black, acetylene black, furnace black, carbon nanotube, graphite, brass, copper, silver, aluminum, nickel, iron, calcium fluoride, montmorillonite, swelling Fluorine mica, and apatite, and the like.
(D) As an inorganic filler, you may use by 1 type and may be used in combination of 2 or more types.

  (D) As an inorganic filler, in terms of rigidity and strength, glass fiber, carbon fiber, glass flake, talc, kaolin, mica, calcium carbonate, calcium monohydrogen phosphate, wollastonite, silica, carbon nanotube, Graphite, calcium fluoride, montmorillonite, swellable fluorine mica, apatite, and the like are preferable.

(D) As an inorganic filler, glass fiber and carbon fiber are more preferable. Among glass fiber and carbon fiber, the number average fiber diameter is 3 to 30 μm, the weight average fiber length is 100 to 750 μm, and the weight average Those having an aspect ratio (L / D) between the fiber length and the number average fiber diameter of 10 to 100 are more preferably used from the viewpoint of expressing high characteristics.
The inorganic filler (D) is more preferably wollastonite. Among the wollastonites, the number average fiber diameter is 3 to 30 μm, the weight average fiber length is 10 to 500 μm, and the aspect ratio ( Those having L / D) of 3 to 100 are more preferably used. Furthermore, as the (E) inorganic filler, talc, mica, kaolin, silicon nitride, and the like are more preferable. Among talc, mica, kaolin, silicon nitride, and the like, the number average fiber diameter is 0.1 to 3 μm. Those are more preferably used.

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

(Content of each component)
In the polyamide resin composition of the present embodiment, the content of (B) phosphinate in the polyamide resin composition, and (C) a flame retardant aid and / or (D) an inorganic filler that can be optionally added. The content is not particularly limited.
The content of the (B) phosphinic acid salt in the polyamide resin composition is preferably 20 to 90 parts by mass, more preferably 25 to 80 parts by mass with respect to 100 parts by mass of the (A) polyamide. Preferably it is 30-60 mass parts.
(B) By making content of a phosphinic acid salt into 20 mass parts or more, the polyamide resin composition excellent in a flame retardance can be obtained. Moreover, the fall of the fluidity | liquidity at the time of a shaping | molding process can be suppressed by making content of (B) phosphinate into 90 mass parts or less. Furthermore, it is possible to suppress deterioration of mechanical properties such as rigidity and appearance of the molded product.

Moreover, when the polyamide resin composition of this embodiment further contains (C) a flame retardant aid and (D) inorganic fillers 1 to 200, with respect to 100 parts by mass of the (A) polyamide, The content of the (B) phosphinate and / or diphosphinate is 20 to 90 parts by mass, the content of the flame retardant aid (C) is 0.1 to 30 parts by mass, and (D ) The content of the inorganic filler is preferably 1 to 200 parts by mass.
The content of the flame retardant aid (C) in the polyamide resin composition is preferably 0.1 to 30 parts by mass, more preferably 1 to 30 parts per 100 parts by mass of the (A) polyamide copolymer. It is a mass part, More preferably, it is 1-20 mass parts, Most preferably, it is 2-15 mass parts.
(C) By mix | blending a flame retardant adjuvant, the polyamide resin composition which is further excellent in a flame retardance can be obtained. In addition, by setting the content of (C) the flame retardant auxiliary to 30 parts by mass or less, it is possible to control the viscosity at the time of melt processing to an appropriate range, increase in torque at the time of extrusion, and formability at the time of molding. The decrease and the deterioration of the appearance of the molded product can be suppressed. Moreover, a polyamide resin composition having excellent rigidity can be obtained without impairing the properties of the polyamide copolymer having excellent mechanical properties such as rigidity.

The content of the inorganic filler (D) in the polyamide resin composition is preferably 1 to 200 parts by weight, more preferably 1 to 150 parts by weight, with respect to 100 parts by weight of the polyamide copolymer. Preferably it is 5-150 mass parts.
(D) By containing an inorganic filler in the said range, mechanical properties, such as toughness and rigidity of a polyamide resin composition, are improved favorably, and the content of (D) inorganic filler is 200 parts by mass or less. By doing so, a polyamide resin composition excellent in moldability can be obtained.

(Other additives)
The polyamide resin composition of the present embodiment is deteriorated as necessary for the purpose of improving thermal deterioration, preventing discoloration during heat, heat aging resistance, and weather resistance, as long as the purpose of the present embodiment is not impaired. An inhibitor may be added.
The deterioration inhibitor is not particularly limited. For example, copper compounds such as copper acetate and copper iodide, phenol stabilizers such as hindered phenol compounds, phosphite stabilizers, hindered amine stabilizers, and triazine stabilizers. And at least one kind of deterioration inhibitor selected from the group consisting of sulfur stabilizers and the like.
These deterioration inhibitors may be used alone or in combination of two or more.

If necessary, the polyamide resin composition of the present embodiment may be blended with a moldability improving agent as long as the purpose of the present embodiment is not impaired.
The moldability improver is not particularly limited, and examples thereof include at least one moldability improver selected from the group consisting of higher fatty acids, higher fatty acid metal salts, higher fatty acid esters, higher fatty acid amides, and the like.

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

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

The higher fatty acid ester is an esterified product of the higher fatty acid and alcohol.
Among these, an ester of an aliphatic carboxylic acid having 8 to 40 carbon atoms and an aliphatic alcohol having 8 to 40 carbon atoms is preferable from the viewpoint of moldability.
Examples of the alcohol include stearyl alcohol, behenyl alcohol, and lauryl alcohol. Examples of higher fatty acid esters include stearyl stearate and behenyl behenate.

The higher fatty acid amide is an amide compound of the higher fatty acid.
Examples of the higher fatty acid amide include stearic acid amide, oleic acid amide, erucic acid amide, ethylene bisstearyl amide, ethylene bisoleyl amide, N-stearyl stearyl amide, N-stearyl erucic amide, and the like.
Among these, from the viewpoint of moldability, preferably stearic acid amide, erucic acid amide, ethylene bisstearyl amide, and N-stearyl erucic acid amide, more preferably ethylene bisstearyl amide and N-stearyl erucic acid amide. is there. These higher fatty acids, higher fatty acid metal salts, higher fatty acid esters, and higher fatty acid amides may be used singly or in combination of two or more.

You may add a coloring agent to the polyamide resin composition of this embodiment in the range which does not impair the objective of this embodiment as needed.
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, iron oxide, stainless steel, and titanium. And at least one colorant selected from the group consisting of metallic pigments such as mica pearl pigments, color graphite, color glass fibers, and color glass flakes.

In the polyamide resin composition of this embodiment, you may mix | blend another resin in the range which does not impair the objective of this embodiment as needed.
Other resins are not particularly limited, and include thermoplastic resins and rubber components.

Examples of the thermoplastic resin include polystyrene resins such as atactic polystyrene, isotactic polystyrene, syndiotactic polystyrene, AS resin, and ABS resin; polyester resins such as polyethylene terephthalate and polybutylene terephthalate; Other polyamides such as 612, 66 / 6I; polyether resins such as polycarbonate, polyphenylene ether, polysulfone, and polyethersulfone; condensation resins such as polyphenylene sulfide and polyoxymethylene; polyacrylic acid, polyacrylic acid ester, poly Acrylic resins such as methyl methacrylate; Polyolefin resins such as polyethylene, polypropylene, polybutene, and ethylene-propylene copolymers; polyvinyl chloride, polyvinyl chloride Halogen-containing vinyl compound resin of emissions and the like; phenol resins, epoxy resins and the like.
These thermoplastic resins may be used individually by 1 type, and may be used in combination of 2 or more types.

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

[Production method of polyamide resin composition]
The method for producing the polyamide resin composition in the present embodiment is not particularly limited as long as it is a method of mixing (A) a polyamide copolymer and (B) a phosphinate. Moreover, as a manufacturing method of the polyamide resin composition in this embodiment, the method of further mixing (C) a flame retardant adjuvant and / or (D) inorganic filler is mentioned. Furthermore, you may further mix the other additive mentioned above.
As a mixing method of (A) polyamide copolymer and (B) phosphinate, for example, (A) polyamide copolymer and (B) phosphinate, and optionally (C) a flame retardant aid and And / or (D) a method in which an inorganic filler is mixed using a Henschel mixer and the like, supplied to a melt kneader and kneaded, or (A) a polyamide copolymer and (B) phosphinic acid by a single or twin screw extruder After the salt and, optionally, (C) flame retardant aid are mixed in advance using a Henschel mixer, etc. are supplied to the melt-kneader and optionally kneaded, (D) inorganic filler is blended from the side feeder. The method of doing is mentioned.
In the method of supplying the components constituting the polyamide resin composition to the melt kneader, all the components may be supplied to the same supply port at once, or the components may be supplied from different supply ports. .

The temperature of the melt kneading is preferably a temperature about 1 to 100 ° C., more preferably about 10 to 50 ° C. higher than the melting point of the (A) polyamide copolymer.
The shear rate in the kneader is preferably about 100 sec ⁻¹ or more, and the average residence time during kneading is preferably about 0.5 to 5 minutes.
As an apparatus for performing melt kneading, a known apparatus, for example, a melt kneader such as a single or twin screw extruder, a Banbury mixer, and a mixing roll is preferably used.

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

[Molded product of polyamide resin composition]
The molded article of the polyamide resin composition of the present embodiment includes the above-described polyamide resin composition, and is obtained by molding the polyamide resin composition by a predetermined method.
The molding method is not particularly limited as long as it can obtain a molded product from the above-described polyamide resin composition, and a known molding method can be used.
For example, extrusion molding, injection molding, vacuum molding, blow molding, injection compression molding, decorative molding, other material molding, gas assist injection molding, gunshot injection molding, low pressure molding, ultra thin injection molding (ultra high speed injection molding), And molding methods such as in-mold composite molding (insert molding, outsert molding) and the like.

Since the molded article of the present embodiment includes the above-described polyamide resin composition, it has excellent rigidity after water absorption (water absorption rigidity) and rigidity under high temperature use (heat rigidity), and further, appearance and flame retardancy. And can be used for various purposes.
Although it does not specifically limit as a molded article of this embodiment, For example, it is suitable in a motor vehicle part, an electrical component, an electronic component, a household appliance OA equipment part, a portable equipment part, a machine / industrial part, an office equipment part, an aerospace part Can be used.

Examples of automobile parts include automobile interior / outer plate / exterior parts, automobile engine compartment parts, automobile electrical parts, and the like.
Examples of electrical / electronic components include connectors, switches, relays, printed wiring boards, electronic component housings, outlets, noise filters, coil bobbins, and motor end caps.
Examples of the portable device parts include a cellular phone, a smartphone, a personal computer, a portable game device, a case such as a digital camera, a structure, and the like.
Moreover, since the molded product of this embodiment is excellent in surface appearance, it is preferably used as a molded product in which a coating film is formed on the surface of the molded product. The method for forming the coating film is not particularly limited as long as it is a known method. For example, the coating film can be formed by spraying, electrostatic coating, or the like. The paint used for coating is not particularly limited as long as it is a known one, and a melamine cross-linked polyester polyol resin paint, an acrylic urethane paint, or the like can be used.

Hereinafter, the present embodiment will be described more specifically by way of examples. However, the present embodiment is not limited to these examples.
The structures of the materials used in the examples and comparative examples, the methods for measuring physical properties, the molding methods, and the evaluation methods are shown below.

[Measuring method of material structure and physical properties]
(Number average molecular weight (Mn) of polyamide copolymer)
The number average molecular weight of the polyamide copolymer was determined by gel permeation chromatography (GPC).
The apparatus is “HLC-8020” manufactured by Tosoh Corporation, the detector is a differential refractometer (RI), the solvent is hexafluoroisopropanol (HFIP) in which 0.1 mol% of sodium trifluoroacetate is dissolved, the column Used 2 pieces of “TSKgel-GMHHR-H” and 1 piece of “G1000HHR” manufactured by Tosoh Corporation.
The solvent flow rate was 0.6 mL / min, and the sample concentration was 1 to 3 (mg sample) / 1 (mL solvent), which was filtered through a filter to remove insolubles, thereby obtaining a measurement sample.
Based on the obtained elution curve, the number average molecular weight (Mn) was calculated in terms of polymethyl methacrylate (PMMA).

(Trans isomer ratio of 1,4-cyclohexanedicarboxylic acid in polyamide copolymer, and structural unit in polyamide copolymer)
The trans isomer ratio of 1,4-cyclohexanedicarboxylic acid in the polyamide copolymer was measured by ¹ H-NMR after dissolving 30-40 mg of the polyamide copolymer in 1.2 g of hexafluoroisopropanol deuteride.
As a device, “JNM ECA-500” manufactured by JEOL Ltd. was used. In the case of 1,4-cyclohexanedicarboxylic acid, the trans isomer ratio (trans isomer / cis isomer) was determined from the ratio between the peak area derived from the trans isomer and the peak area derived from the cis isomer.
Moreover, the ratio of the structural unit in a polyamide copolymer was measured by < ¹ > H-NMR, and it calculated | required from the ratio of the peak area derived from each component.
The peaks used for the ratio calculation are shown below.
<Trans / cis ratio of 1,4-cyclohexanedicarboxylic acid in polyamide copolymer>
Transpeak: 1.98 ppm
Cis peak: 1.77 ppm, 1.86 ppm
<Ratio of structural units in polyamide copolymer>
1,4-cyclohexanedicarboxylic acid: peak used for the above trans / cis ratio Adipic acid: 2.3 ppm, 2.4 ppm
Isophthalic acid: 3.5ppm
Hexamethylenediamine: 3.28 ppm, 3.5 ppm

(Mole ratio of trans / cis of raw material 1,4-cyclohexanedicarboxylic acid)
Using a HPLC (high performance liquid chromatography) apparatus, the molar ratio of trans / cis in 1,4-cyclohexanedicarboxylic acid as a raw material monomer was measured.
As an HPLC apparatus, LC-10A manufactured by Shimadzu Corporation was used. The 1,4-cyclohexanedicarboxylic acid monomer is separated into a trans component (elution time of about 11 minutes) and a cis component (elution time of about 14.5 minutes) by a gradient elution method using a reverse phase column. It calculated | required by ratio of peak area.
Details of the HPLC analysis conditions are shown below.
Equipment: Shimadzu Corporation LC-10A vp
Reversed phase (C30) column: Nomura Chemical Co., Ltd. Develosil PRAQUEUS
Temperature: 40 ° C
Flow rate: 1.0 mL / min
Detection: UV214nm
Mobile phase A: water (containing 0.1% by mass of trifluoroacetic acid)
Mobile phase B: water / acetonitrile = 10/90 (containing 0.1% by mass of trifluoroacetic acid)
Mobile phase mixing ratio: B = 0 → 100% (15 minutes)
Sample concentration: 10 mg / mL
(Solvent: (water / acetonitrile = 50/50)
Sample solution injection volume: 20 mL

(Melting point (℃))
The melting point was measured using “DSC-7” manufactured by PERKIN-ELMER according to JIS K7121.
The measurement conditions are as follows. The temperature of an endothermic peak (melting peak) that appears when about 10 mg of a sample is heated at a rate of temperature increase of 20 ° C./min in a nitrogen atmosphere is Tm 1 (° C.). The temperature is lowered to 30 ° C. at a temperature drop rate of 20 ° C./min, held for 2 minutes, held for 2 minutes, and then the peak temperature of the endothermic peak (melting peak) that appears when the temperature is raised at a temperature rise rate of 20 ° C./min (° C.)).

(Glass transition temperature (℃))
The glass transition temperature was measured using “DSC-7” manufactured by PERKIN-ELMER according to JIS K7121.
First, the sample was melted on a hot stage (“EP80” manufactured by Mettler), and the molten sample was quenched in liquid nitrogen and solidified to obtain a measurement sample.
A 10 mg sample for measurement was heated in the range of 30 to 300 ° C. under a temperature rising rate of 20 ° C./min, and the glass transition temperature was measured.

[Production of molded product for water absorption rigidity and thermal rigidity evaluation]
The molded product was produced as follows using an injection molding machine.
As the injection molding machine, “PS40E” manufactured by Nissei Resin Co., Ltd. was used. The mold temperature was set to 100 ° C., and an ISO test piece having a thickness of 4 mm was obtained under injection molding conditions of 17 seconds for injection and 20 seconds for cooling. The cylinder temperature was set to a temperature condition about 30 ° C. higher than the melting point of the polyamide copolymer determined according to the melting point measurement method.

(Measurement of flexural modulus)
As described above, an ISO dumbbell having a thickness of 4 mm was produced and used as a test piece.
Using the obtained test piece, the flexural modulus was measured according to ISO178.

(Measurement of flexural modulus after water absorption)
Using the ISO dumbbell as a test piece, it was immersed in warm water at 80 ° C. for 24 hours, and the flexural modulus (flexural modulus after water absorption) was measured according to ISO178.
Wet retention, which is an index of water absorption rigidity, was determined using the following formula. The higher the wet retention rate, the better the water absorption rigidity.
Wet retention (%) = after water absorption (Wet) flexural modulus / before water absorption (Dry) flexural modulus × 100

(Measurement of flexural modulus at 100 ° C)
Using a test piece having a thickness of 4 mm produced as described above, the flexural modulus (100 ° C. flexural modulus) was measured in accordance with ISO178 under an atmosphere of 100 ° C. The retention rate at 100 ° C., which is an index of thermal rigidity, was determined using the following formula. The higher the 100 ° C. retention, the better the thermal rigidity.
100 ° C. retention rate (%) = 100 ° C. flexural modulus / before water absorption (Dry) flexural modulus × 100

[Production of molded product for evaluation of molding appearance]
The molded product was produced as follows using an injection molding machine.
As the injection molding machine, “IS150E” manufactured by Toshiba Machine Co., Ltd. was used. A test piece having a length of 130 mm, a width of 130 mm and a thickness of 4 mm was obtained under the injection molding conditions of an injection temperature of 12 seconds and cooling of 20 seconds with the mold temperature set to 90 ° C. The cylinder temperature was set to a temperature condition about 30 ° C. higher than the melting point of the polyamide copolymer determined according to the melting point measurement method.

(Measurement of appearance)
Using a handy gloss meter “IG320” manufactured by HORIBA, Ltd., a 60 ° C. reflection gloss value of the molded product for evaluation of the molded appearance was determined.

[Evaluation of flame retardancy]
Measurements were made using the method of UL94 (standard established by Under Writers Laboratories Inc., USA). The specimen (length 127 mm, width 12.7 mm, thickness 1/32 inch) is attached to the injection molding machine (PS40E manufactured by Nissei Resin Co., Ltd.) with the mold of the UL specimen (mold temperature = Tg + 20 ° C.). Then, molding was performed at a cylinder temperature = Tm2 + 20 ° C. The injection pressure was the full filling pressure at the time of forming the UL test piece + 2% pressure. The flame retardant grade conformed to UL94 standard (vertical combustion test).

[Polyamide copolymer (A)]
(material)
The following compounds were used in the production of polyamide copolymers in Examples and Comparative Examples.
(1) Adipic acid Wako Pure Chemical Industries, Ltd. Product name: Adipic acid (2) 1,4-cyclohexanedicarboxylic acid, Eastman Chemical product name: 1,4-CHDA HP grade (trans isomer / cis isomer (mol) Ratio) = 25/75)
(3) Isophthalic acid Wako Pure Chemical Industries, Ltd. Product name: Isophthalic acid (4) Hexamethylenediamine Wako Pure Chemical Industries, Ltd. Product name: Hexamethylenediamine

<Production Example 1: Production of polyamide copolymer (A1)>
Adipic acid 517.0 g (3.54 mol), isophthalic acid 55.1 g (0.33 mol), and trans-cis / cis-isomer molar ratio 25/75 285.5 g (1 .66 mol) and 642.3 g (5.53 mol) of hexamethylenediamine were dissolved in 1500 g of distilled water to prepare an equimolar 50 mass% homogeneous aqueous solution of the raw material monomer.
This aqueous solution was charged into an autoclave having an internal volume of 5.4 L and purged with nitrogen.
While stirring at a temperature of 110 to 150 ° C., water vapor was gradually removed to concentrate the solution concentration to 70% by mass. Thereafter, the internal temperature was raised to 218 ° C. At this time, the autoclave was pressurized to 1.8 MPa. Then, until the internal temperature reached 270 ° C., the reaction was continued for 1 hour while gradually removing water vapor and maintaining the pressure at 1.8 MPa.
Next, the pressure was reduced to 1 MPa over 1 hour, and the polymerization was further continued for 15 minutes while flowing nitrogen into the autoclave to obtain a polyamide copolymer. At this time, the final polymerization arrival temperature of the polymerization was 290 ° C.
The obtained polyamide copolymer was pulverized to a size of 2 mm or less and dried at 100 ° C. in a nitrogen atmosphere for 12 hours. The trans isomer ratio of the 1,4-cyclodicarboxylic acid component contained in the obtained polyamide copolymer was 69.8 mol%.
The composition of the obtained polyamide copolymer (A1) is shown in Table 1 below. The proportion of the structural units of the polyamide copolymer shown in Table 1 below was determined by analyzing the obtained copolymer by ¹ H-NMR.
The molecular weight, melting point, and glass transition temperature of the obtained polyamide copolymer (A1) were evaluated by the methods described above. The evaluation results are shown in Table 1 below.

<Production Example 2: Production of polyamide copolymer (A2)>
440.6 g (3.02 mol) of adipic acid, 91.1 g (0.55 mol) of isophthalic acid, 330.6 g (1) of 1,4-cyclohexanedicarboxylic acid having a trans / cis molar ratio of 25/75 .92 mol), and the polyamide copolymer was polymerized by the method described in Production Example 1 except that 637.4 g (5.49 mol) of hexamethylenediamine was used.
At this time, the final polymerization arrival temperature of the polymerization was 291 ° C. The trans isomer ratio of the 1,4-cyclodicarboxylic acid component contained in the obtained polyamide copolymer was 71.4 mol%.
The composition of the obtained polyamide copolymer (A2) is shown in Table 1 below. The proportion of the structural units of the polyamide copolymer shown in Table 1 below was determined by analyzing the obtained copolymer by ¹ H-NMR.
The molecular weight, melting point, and glass transition temperature of the obtained polyamide copolymer (A2) were evaluated by the methods described above. The evaluation results are shown in Table 1 below.

<Production Example 3: Production of polyamide copolymer (A3)>
Adipic acid 509.4 g (3.49 mole), isophthalic acid 128.7 g (0.77 mole), and trans-cis / cis mole ratio 25/75, 219.1 g (1 .27 mol) and 642.9 g (5.53 mol) of hexamethylenediamine were used to polymerize the polyamide copolymer by the method described in Production Example 1. At this time, the final polymerization arrival temperature of the polymerization was 292 ° C.
The trans isomer ratio of the 1,4-cyclodicarboxylic acid component contained in the obtained polyamide copolymer was 71.8 mol%.
The composition of the obtained polyamide copolymer (A3) is shown in Table 1 below. The proportion of structural units of the polyamide copolymer shown in Table 1 was determined by analyzing the obtained copolymer by ¹ H-NMR.
The molecular weight, melting point, and glass transition temperature of the obtained polyamide copolymer (A3) were evaluated by the methods described above. The evaluation results are shown in Table 1 below.

<Production Example 4: Production of polyamide copolymer (A4)>
Adipic acid 433.3 g (2.97 mol), isophthalic acid 173.3 g (1.04 mol), and trans-cis / cis-isomer molar ratio 25/75 255.3 g (1 .48 mol), and a polyamide copolymer was polymerized by the method described in Production Example 1 except that 638.1 g (5.49 mol) of hexamethylenediamine was used. At this time, the final polymerization arrival temperature of the polymerization was 293 ° C.
The trans isomer ratio of the 1,4-cyclodicarboxylic acid component contained in the obtained polyamide copolymer was 72.0 mol%.
The composition of the obtained polyamide copolymer (A4) is shown in Table 1 below. The proportion of the structural units of the polyamide copolymer shown in Table 1 below was determined by analyzing the obtained copolymer by ¹ H-NMR.
The molecular weight, melting point, and glass transition temperature of the obtained polyamide copolymer (A4) were evaluated by the methods described above. The evaluation results are shown in Table 1 below.

<Production Example 5: Production of polyamide copolymer (A5)>
Adipic acid 595.3 g (4.07 mol), isophthalic acid 83.4 g (0.50 mol), 172.9 g (1 mol) of 1,4-cyclohexanedicarboxylic acid having a trans / cis molar ratio of 25/75 0.0000 mol) and 648.4 g (5.58 mol) of hexamethylenediamine, the polyamide copolymer was polymerized by the method described in Production Example 1. At this time, the final polymerization arrival temperature of the polymerization was 290 ° C.
The trans isomer ratio of the 1,4-cyclodicarboxylic acid component contained in the obtained polyamide copolymer was 72.2 mol%.
The composition of the obtained polyamide copolymer (A5) is shown in Table 1 below. The proportion of the structural units of the polyamide copolymer shown in Table 1 below was determined by analyzing the obtained copolymer by ¹ H-NMR.
The molecular weight, melting point, and glass transition temperature of the obtained polyamide copolymer (A5) were evaluated by the methods described above. The evaluation results are shown in Table 1 below.

<Production Example 6: Production of polyamide copolymer (A6)>
337.5 g (2.28 mol) of adipic acid, 207.6 g (1.25 mol) of isophthalic acid, 327.5 g of 1,4-cyclohexanedicarboxylic acid having a trans / cis molar ratio of 25/75 (1 .90 mol), and a polyamide copolymer was polymerized by the method described in Production Example 1 except that 631.4 g (5.43 mol) of hexamethylenediamine was used. At this time, the final polymerization arrival temperature of the polymerization was 290 ° C.
The trans isomer ratio of the 1,4-cyclodicarboxylic acid component contained in the obtained polyamide copolymer was 70.2 mol%.
The composition of the obtained polyamide copolymer (A6) is shown in Table 1 below. The proportion of the structural units of the polyamide copolymer shown in Table 1 below was determined by analyzing the obtained copolymer by ¹ H-NMR.
The molecular weight, melting point, and glass transition temperature of the obtained polyamide copolymer (A6) were evaluated by the methods described above. The evaluation results are shown in Table 1 below.

<Production Example 7: Production of polyamide copolymer (A7)>
331.6 g (2.28 mol) of adipic acid, 135.2 g (0.81 mol) of isophthalic acid, 401.6 g (2 of 1,4-cyclohexanedicarboxylic acid having a trans / cis molar ratio of 25/75 .33 mol), and a polyamide copolymer was polymerized by the method described in Production Example 1 except that 630.3 g (5.42 mol) of hexamethylenediamine was used. At this time, the final polymerization arrival temperature of the polymerization was 292 ° C.
The trans isomer ratio of the 1,4-cyclodicarboxylic acid component contained in the obtained polyamide copolymer was 72.1 mol%.
The composition of the obtained polyamide copolymer (A7) is shown in Table 1 below. The proportion of the structural units of the polyamide copolymer shown in Table 1 below was determined by analyzing the obtained copolymer by ¹ H-NMR.
The obtained polyamide copolymer (A7) was evaluated for the molecular weight, melting point, and glass transition temperature by the methods described above. The evaluation results are shown in Table 1 below.

<Production Example 8: Production of polyamide copolymer (A8)>
Adipic acid 268.1g (1.83mol), isophthalic acid 233.1g (1.40mol), 1,4-cyclohexanedicarboxylic acid 371.7g (2 .16 mol), and a polyamide copolymer was polymerized by the method described in Production Example 1 except that 627.1 g (5.40 mol) of hexamethylenediamine was used. At this time, the final polymerization arrival temperature of the polymerization was 291 ° C.
The trans isomer ratio of the 1,4-cyclodicarboxylic acid component contained in the obtained polyamide copolymer was 72.3 mol%.
The composition of the obtained polyamide copolymer (A8) is shown in Table 1 below. The proportion of the structural units of the polyamide copolymer shown in Table 1 below was determined by analyzing the obtained copolymer by ¹ H-NMR.
The obtained polyamide copolymer (A8) was evaluated for the molecular weight, melting point, and glass transition temperature by the methods described above. The evaluation results are shown in Table 1 below.

<Production Example 9: Polyamide copolymer (A9)>
692.2 g (4.74 mol) of adipic acid, 74.9 g (0.45 mol) of isophthalic acid, 77.7 g of 1,4-cyclohexanedicarboxylic acid having a trans / cis molar ratio of 80/20 (0 .45 mol) and 655.2 g (5.64 mol) of hexamethylenediamine were dissolved in 1500 g of distilled water to prepare an equimolar 50 mass% homogeneous aqueous solution of the raw material monomer. This aqueous solution was charged into an autoclave having an internal volume of 5.4 L and purged with nitrogen. While stirring at a temperature of 110 to 150 ° C., water vapor was gradually removed to a solution concentration of 70% by mass and concentrated. Thereafter, the internal temperature was raised to 218 ° C. At this time, the autoclave was pressurized to 1.8 MPa. The reaction was continued for 1 hour while gradually removing water vapor and maintaining the pressure at 1.8 MPa until the temperature reached 253 ° C. for 1 hour.
Next, the pressure was reduced to 1 MPa over 1 hour, and the polymerization was further continued for 15 minutes while flowing nitrogen into the autoclave to obtain a polyamide copolymer.
This was pulverized to a size of 2 mm or less and dried in a nitrogen atmosphere at 100 ° C. for 12 hours.
The composition of the obtained polyamide copolymer (A9) is shown in Table 1 below. The proportion of the structural units of the polyamide copolymer shown in Table 1 below was determined by analyzing the obtained copolymer by ¹ H-NMR.
The obtained polyamide copolymer (A9) was evaluated for the molecular weight, melting point, and glass transition temperature by the methods described above. The evaluation results are shown in Table 1 below.

<Production Example 10: Polyamide copolymer (A10)>
Adipic acid 595.9 g (4.08 mol), isophthalic acid 129.9 g (0.78 mol), 125.0 g of 1,4-cyclohexanedicarboxylic acid having a trans / cis molar ratio of 80/20 (0 .73 mol), and the polyamide copolymer was polymerized by the method described in Production Example 9 except that the hexamethylenediamine was 649.1 g (5.59 mol).
The composition of the obtained polyamide copolymer (A10) is shown in Table 1 below. The proportion of the structural units of the polyamide copolymer shown in Table 1 below was determined by analyzing the obtained copolymer by ¹ H-NMR.
The obtained polyamide copolymer (A10) was evaluated for the molecular weight, melting point, and glass transition temperature by the methods described above. The evaluation results are shown in Table 1 below.

<Production Example 11: Polyamide copolymer (A11)>
Adipic acid 317.5 g (2.17 mol), isophthalic acid 270.7 g (1.63 mol), 1,4-cyclohexanedicarboxylic acid 280.6 g (1 mole ratio of trans / cis isomer) is 80/20 0.663 mol), and a polyamide copolymer was polymerized by the method described in Production Example 9 except that 631.2 g (5.43 mol) of hexamethylenediamine was used.
The composition of the obtained polyamide copolymer (A11) is shown in Table 1 below. The proportion of the structural units of the polyamide copolymer shown in Table 1 below was determined by analyzing the obtained copolymer by ¹ H-NMR.
The molecular weight, melting point, and glass transition temperature of the obtained polyamide copolymer (A11) were evaluated by the methods described above. The evaluation results are shown in Table 1 below.

<Production Example 12: Polyamide copolymer (A12)>
Adipic acid 509.9 g (3.49 mol), isophthalic acid 174.8 g (1.05 mol), 1,4-cyclohexanedicarboxylic acid 171.7 g (1 mole ratio of trans / cis isomer) is 80/20 (1 0.0000 mole) and 643.6 g (5.54 mole) of hexamethylenediamine were used to polymerize the polyamide copolymer by the method described in Production Example 9.
The composition of the obtained polyamide copolymer (A12) is shown in Table 1 below. The proportion of the structural units of the polyamide copolymer shown in Table 1 below was determined by analyzing the obtained copolymer by ¹ H-NMR.
The molecular weight, melting point, and glass transition temperature of the obtained polyamide copolymer (A12) were evaluated by the methods described above. The evaluation results are shown in Table 1 below.

<Production Example 13: Polyamide copolymer (A13)>
Adipic acid 509.4 g (3.49 mole), isophthalic acid 128.7 g (0.77 mole), and trans-cis / cis mole ratio 25/75, 219.1 g (1 .27 mol) and 642.9 g (5.53 mol) of hexamethylenediamine were dissolved in 1500 g of distilled water to prepare an equimolar 50% by mass aqueous solution of the raw material monomer.
This aqueous solution was charged into an autoclave having an internal volume of 5.4 L and purged with nitrogen. While stirring at a temperature of 110 to 150 ° C., water vapor was gradually removed to a solution concentration of 70% by mass and concentrated. Thereafter, the internal temperature was raised to 218 ° C. At this time, the autoclave was pressurized to 1.8 MPa. The reaction was continued for 1 hour while gradually removing water vapor and maintaining the pressure at 1.8 MPa until the temperature reached 253 ° C. for 1 hour.
Next, the pressure was reduced to 1 MPa over 1 hour, and the polymerization was further continued for 15 minutes while flowing nitrogen into the autoclave to obtain a polyamide copolymer. At this time, the final polymerization arrival temperature of the polymerization was 275 ° C.
This was pulverized to a size of 2 mm or less and dried in a nitrogen atmosphere at 100 ° C. for 12 hours.
The trans isomer ratio of the 1,4-cyclodicarboxylic acid component contained in the obtained polyamide copolymer was 56.7 mol%.
The composition of the obtained polyamide copolymer (A13) is shown in Table 1 below. The proportion of the structural units of the polyamide copolymer shown in Table 1 below was determined by analyzing the obtained copolymer by ¹ H-NMR.
The molecular weight, melting point, and glass transition temperature of the obtained polyamide copolymer (A13) were evaluated by the methods described above. The evaluation results are shown in Table 1 below.

(B) Phosphinate (B1) Aluminum diethylphosphinate (DEPAl) produced by referring to the production method described in JP-A-08-73720.

(C) Flame retardant aid (C1) Zinc borate 2ZnO.3B ₂ O ₃ .3.5H ₂ O U.S. S. Borax product name Firebrake (registered trademark) ZB

(D) Inorganic filler (D1) Glass fiber (GF) Made by Nippon Electric Glass Product name ECS03T275H Average fiber diameter 10 μmφ, cut length 3 mm

[Polyamide resin composition]
<Example 1>
Using a TEM 35 mm twin-screw extruder manufactured by Toshiba Machine Co., Ltd. (set temperature: a temperature approximately 30 ° C. higher than the melting point of the polyamide copolymer determined according to the melting point measurement method described above, screw rotation speed 300 rpm), A blend of (A) a polyamide copolymer, (B) a phosphinate and / or diphosphinate, and (C) a flame retardant aid is supplied from the provided top feed port, and the downstream side of the extruder ( (D) Inorganic filler is supplied from the side feed port in a state where the resin supplied from the top feed port is sufficiently melted, and the melt-kneaded product extruded from the die head is cooled in a strand form, pelletized, and polyamide Resin composition pellets were obtained. The blending amount is (B) 45.0 parts by mass of phosphinate and / or diphosphinate, (C) 7.0 parts by mass of flame retardant aid, and (A) 100 parts by mass of polyamide copolymer. D) The inorganic filler was 70.0 parts by mass.
By the above-described methods, the above-described bending elastic moduli (water absorption rigidity and thermal rigidity), appearance, and flame retardancy were evaluated. The evaluation results are shown in Table 2 below.

<Examples 2-9, Comparative Examples 1-4>
Instead of the polyamide copolymer of Production Example 1, a polyamide resin composition was obtained by the method described in Example 1 except that each of the polyamide copolymers of Production Examples 2 to 13 was used.
By the above-described methods, the above-described bending elastic moduli (water absorption rigidity and thermal rigidity), appearance, and flame retardancy were evaluated. The evaluation results are shown in Table 2 below.

As shown in Table 2, the molded products obtained from the polyamide resin compositions of the respective examples all have excellent water absorption rigidity and thermal rigidity without impairing the molding appearance, and further flame retardancy. It was confirmed to be excellent.
On the other hand, the relationship between the content (mol%) of (bp) isophthalic acid units and the content (mol%) of (cp) 1,4-cyclohexanedicarboxylic acid units is (b−p) = ( a molded product obtained from the polyamide resin compositions of Comparative Examples 1 and 3 comprising a polyamide copolymer of cp), and a comparison comprising a polyamide copolymer of (bp)> (cp) It was confirmed that the molded articles obtained from the polyamide resin compositions of Examples 2 and 4 were greatly reduced in water absorption rigidity and heat rigidity at 100 ° C.
Furthermore, the relationship between the content (mol%) of (bp) isophthalic acid units and the content (mol%) of (cp) 1,4-cyclohexanedicarboxylic acid units is (cp)> (b -P) and the content of the trans isomer unit in the (c-1-p) 1,4-cyclodicarboxylic acid unit> (bp) the content of the isophthalic acid unit> 0.1 The molded product obtained from the polyamide resin composition of Example 3 containing a polyamide copolymer has much higher water absorption rigidity and thermal rigidity than the molded product obtained from the polyamide resin composition of Example 9. It was confirmed that

  The polyamide resin composition of the present invention has industrial applicability as a molding material for various parts in the automotive field, electrical / electronic field, portable device field, machine / industrial field, office equipment field, aerospace field. ing.

Claims (16)

(A): a dicarboxylic acid component unit comprising (ap) an adipic acid unit, (bp) isophthalic acid unit, and (cp) 1,4-cyclohexanedicarboxylic acid unit; and a diamine component unit. A polyamide copolymer comprising:
The content (mol%) of the (bp) in the total of 100 mol% of the dicarboxylic acid component units including the (ap), the (bp), and the (cp), and the above A polyamide copolymer whose relationship with the content (mol%) of (cp) satisfies the following formula (1);
Content of (cp)> Content of (bp) ≧ 0.1 (1)
(B): A polyamide resin composition containing a phosphinate and / or a diphosphinate. The phosphinic acid salt is a compound represented by the following general formula (I):
The polyamide resin composition according to claim 1, wherein the diphosphinic acid salt is a compound represented by the following general formula (II).
(In general formula (I) and general formula (II),
R ¹ , R ² , R ³ and R ⁴ are each independently selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, and an arylalkyl group having 7 to 20 carbon atoms. A group to be selected,
R ⁵ is a group selected from the group consisting of an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 10 carbon atoms, an alkylarylene group having 7 to 20 carbon atoms, and an arylalkylene group having 7 to 20 carbon atoms. And
M is a metal (ion) selected from the group consisting of calcium (ion), magnesium (ion), aluminum (ion) and zinc (ion);
m is 2 or 3, n is 1 or 3, and x is 1 or 2. ) With respect to 100 parts by mass of the (A) polyamide copolymer,
The polyamide resin composition according to claim 1 or 2, wherein the content of the (B) phosphinate and / or diphosphinate is 20 to 90 parts by mass. (C) a flame retardant aid;
(D) a polyamide resin composition further containing inorganic fillers 1 to 200,
With respect to 100 parts by mass of the (A) polyamide,
The content of the (B) phosphinate and / or diphosphinate is 20 to 90 parts by mass,
The content of the flame retardant auxiliary (C) is 0.1 to 30 parts by mass,
The polyamide resin composition according to any one of claims 1 to 3, wherein the content of the (D) inorganic filler is 1 to 200 parts by mass.   The polyamide resin composition according to claim 4, wherein the flame retardant aid (C) is zinc borate and / or magnesium hydroxide. With respect to a total of 100 mol% of the dicarboxylic acid component units including the (ap), the (bp), and the (cp),
The content of the (ap) adipic acid unit is 40 to 80 mol%,
The content of the (bp) isophthalic acid unit is 0.1 to 25 mol%,
The polyamide resin composition according to any one of claims 1 to 5, wherein a content of the (cp) 1,4-cyclohexanedicarboxylic acid unit is 15 to 40 mol%.   The polyamide resin composition according to any one of claims 1 to 6, wherein the diamine component unit is an aliphatic diamine component unit.   The polyamide resin composition according to any one of claims 1 to 7, wherein the diamine component unit is a hexamethylenediamine unit. The (A) polyamide copolymer is
(A′-p) a unit comprising adipic acid and hexamethylenediamine,
(B′-p) a unit comprising isophthalic acid and hexamethylenediamine, and
The polyamide resin composition according to any one of claims 1 to 8, comprising a unit consisting of (c'-p) 1,4-cyclohexanedicarboxylic acid and the hexamethylenediamine. The (A) polyamide copolymer is a dicarboxylic acid component containing (am) adipic acid, (bm) isophthalic acid, and (cm) 1,4-cyclohexanedicarboxylic acid, a diamine component, Is a polyamide copolymer obtained by copolymerizing
In the polyamide copolymer, a trans isomer unit (c-1-p) and a cis isomer unit (c-2-p) in the (cp) 1,4-cyclodicarboxylic acid unit, (a -P) When the total of the dicarboxylic acid component unit containing an adipic acid unit and (bp) isophthalic acid unit is 100 mol%, the content (mol%) of the (bp) isophthalic acid unit and the above The relationship between the content (mol%) of the trans isomer unit in the (c-1-p) 1,4-cyclodicarboxylic acid unit satisfies the following formula (2). The polyamide resin composition according to one item.
(C-1-p) Content of trans isomer unit in 1,4-cyclodicarboxylic acid unit> (bp) Content of isophthalic acid unit ≧ 0.1 (2) The dicarboxylic acid component comprising the (am) adipic acid, the (bm) isophthalic acid, and the (cm) 1,4-cyclohexanedicarboxylic acid;
The diamine component;
The polyamide resin composition according to claim 10, wherein the final polymerization temperature in copolymerization is 270 ° C or higher. The (cm) 1,4-cyclodicarboxylic acid used as a raw material monomer for the copolymer has a trans isomer (c-1-m) and a cis isomer (c-2-m),
The molar ratio of the trans isomer (c-1-m) to the cis isomer (c-2-m) in the (cm) 1,4-cyclodicarboxylic acid ((c-1-m) / The polyamide resin composition according to claim 10 or 11, wherein (c-2-m)) is 50/50 to 10/90.   A molded article comprising the polyamide resin composition according to any one of claims 1 to 12.   The molded article according to claim 13, which is an automobile part.   The molded article according to claim 13 which is an electronic component.   The molded article according to claim 13, which is a home appliance OA equipment part or a mobile equipment part.