JP2013001836A - Polyamide welded molding - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a welded molding having excellent heat resistance, exhibiting satisfactory moldability and molding appearance and having excellent welding property (weld strength).SOLUTION: The polyamide welded molding comprises a polyamide copolymer containing a dicarboxylic acid component unit containing (a-p) an adipic acid unit, (b-p) an isophthalic acid unit and (c-p) a 1,4-cyclohexane dicarboxylic acid unit and a diamine component unit, wherein the relation of the (b-p) content (mol%) and the (c-p) content (mol%) in the total 100 mol% of the dicarboxylic acid component unit containing the (a-p), (b-p) and (c-p) which constitute the polyamide copolymer satisfies following formula (1): (the content of (c-p))>(the content of (b-p))≥0.1.

Description

  The present invention relates to a polyamide welded 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. Moreover, since intensity | strength improves further by mix | blending glass fiber, it is used widely also in the state reinforced with glass fiber.

  As a method for molding a polyamide resin member, an injection molding method is widely used. However, it is difficult to manufacture a part having a hollow portion or a part having a complicated shape by a single injection molding method. It may be manufactured by welding the members.

  In such welding, various welding techniques, for example, adhesive welding, vibration welding, ultrasonic welding, hot plate welding, injection welding, laser welding techniques and the like are used. However, the adhesive welding has a complicated work, and there is a problem of environmental load such as contamination of the surroundings by a solvent in addition to time loss required for curing.

  On the other hand, other welding methods are simple methods, but as the parts become larger and more complicated, higher welding strength is required, and the strength of the welded part is insufficient, so its use is Was the current situation.

  Polyamide 6 resin has been mainly used for polyamide welding and joining members, but it cannot be used at high temperatures because of poor heat resistance and chemical resistance. On the other hand, the polyamide 66 resin has excellent heat resistance and chemical resistance, but has problems such as low welding strength.

  In Patent Document 1, a member for welding and bonding using a polyamide 66/6 copolymer has been proposed, and although the welding strength is improved, the welding strength is still insufficient. Further, in Patent Document 2, a welded joint member made of a polyamide 66 / 6I copolymer is proposed, and the weld strength is improved, but the strength, elastic modulus, and heat resistance are reduced by copolymerization of the 6I component, It was not satisfactory in terms of mechanical properties.

JP-A-8-337718 JP 2002-348371 A

  As described above, according to the conventionally disclosed technology, there is a demand for a polyamide welded molded article that is excellent in molding processability, maintains a balance between mechanical strength and rigidity, and simultaneously satisfies the welding strength and the appearance of the molded article. Yes.

  The present invention has been made in view of the above-described problems of the prior art, and mainly provides a polyamide welded molded article having good moldability and excellent weld strength and appearance of a welded joint. Objective.

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 The present inventors have found that a polyamide fusion-molded article comprising a polyamide resin composition containing a polyamide copolymer (A) satisfying the above requirements can solve the above-mentioned problems, and completed the present invention.
Content of (cp)> Content of (bp) ≧ 0.1 (1)
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 total amount of the dicarboxylic acid component units including the (ap), the (bp), and the (cp) constituting the polyamide copolymer is 100 mol%. A welded molded article containing 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)
[2]
(A) 100 parts by mass of polyamide copolymer, (B) 1 to 300 parts by mass of inorganic filler,
The weld-molded product according to [1], comprising a polyamide resin composition containing
[3]
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 content of the (cp) 1,4-cyclohexanedicarboxylic acid unit is 15 to 40 mol%,
The welded molded product according to [1] or [2].
[4]
The welded molded article according to any one of [1] to [3], wherein the diamine component unit is an aliphatic diamine component unit.
[5]
The welded molded article according to [4], wherein the diamine component unit is a hexamethylenediamine unit.
[6]
A polyamide copolymer obtained by copolymerizing a dicarboxylic acid component containing (am) adipic acid, (bm) isophthalic acid, and (cm) 1,4-cyclohexanedicarboxylic acid, and a diamine component. A polymer comprising:
In a total of 100 mol% of units derived from each of the dicarboxylic acid component including the (cm) 1,4-cyclodicarboxylic acid, the (am) adipic acid, and the (bm) isophthalic acid, The content (mol%) of units derived from (bp) isophthalic acid and the units of trans isomers of units derived from (c-1-p) 1,4-cyclodicarboxylic acid in the polyamide copolymer The weld-molded product according to any one of [1] to [5], wherein (A) the polyamide copolymer contains a relationship with the content (mol%) that satisfies the following formula (2).
(C-1-p) Content of units of trans isomers of units derived from 1,4-cyclodicarboxylic acid> (bp) Content of units derived from isophthalic acid ≧ 0.1 2)
[7]
The dicarboxylic acid component comprising the (am) adipic acid, the (bm) isophthalic acid, and the (cm) 1,4-cyclohexanedicarboxylic acid;
The diamine component;
The fusion-molded article according to [6], wherein the final polymerization temperature in the copolymerization is 270 ° C. or higher.
[8]
The molar ratio of the trans isomer (c-1-m) to the cis isomer (c-2-m) in the (cm) 1,4-cyclodicarboxylic acid used as a raw material monomer for the copolymerization ( (C-1-m) / (c-2-m)) is a welded molded article according to [6] or [7], wherein 50/50 to 10/90.
[9]
The welded molded article according to any one of [1] to [8], which is an automobile part.
[10]
The welded molded product according to any one of [1] to [8], which is an electronic component.
[11]
The welded molded product according to any one of [1] to [8], which is a home appliance OA device component or a portable device component.

  According to the present invention, it is possible to provide a weld-molded article comprising a polyamide resin composition containing a polyamide copolymer which has good heat resistance and moldability and is excellent in weld strength and appearance of a weld joint. .

It is a conceptual diagram which shows the dimension of the flat plate at the time of vibration welding, a set state, and a vibration direction.

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.
That is, the present invention is a welded molded article comprising the polyamide resin composition shown below.

[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%. It is a polyamide resin composition containing a polyamide copolymer in which the relationship between the content (mol%) and the content (mol%) of (cp) satisfies the following formula (1).
((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) The relation of the content (mol%) of (cp) is a polyamide copolymer satisfying the following formula (1).

Thereby, not only it is excellent in heat resistance, but it can be set as the polyamide resin composition which is excellent in the welding strength of a welding junction part, and a shaping | molding external appearance property.
Content of (cp)> Content of (bp) ≧ 0.1 (1)

<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) relation is a polyamide copolymer which satisfies the above formula (1).

By setting the composition ratio within the above range and satisfying the relationship of the above formula (1), it is possible to obtain a polyamide resin composition having excellent welding strength at the welded joint and excellent molding appearance and heat resistance.
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, and examples thereof include aliphatic diamines, aromatic diamines, and diamines having substituents branched from the main chain. Among these, aliphatic Diamine is preferred.

Examples of the aliphatic diamine include ethylene diamine, propylene diamine, tetramethylene diamine, pentamethylene diamine, heptamethylene diamine, hexamethylene diamine, octamethylene diamine, nonamethylene diamine, decamethylene diamine, undecamethylene diamine, dodecamethylene diamine, And straight-chain saturated aliphatic diamines having 2 to 20 carbon atoms such as tridecamethylenediamine. Among these aliphatic diamine components, hexamethylene diamine is preferable from the viewpoint of rigidity.
Examples of the aromatic diamine include metaxylylenediamine.

Examples of the diamine having a substituent branched from the main chain include 2-methylpentamethylenediamine (also referred to as 2-methyl-1,5-diaminopentane), 2,2,4-trimethylhexamethylenediamine, Examples thereof include branched saturated aliphatic diamines having 3 to 20 carbon atoms such as 2,4,4-trimethylhexamethylenediamine, 2-methyloctamethylenediamine, and 2,4-dimethyloctamethylenediamine.
One of these diamine components may be used alone, or two or more of these diamine components may be used in combination.

<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.

<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, and when it is 100,000 or less, a decrease in moldability 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. More specifically, for example, measurement can be performed using “DSC-7” manufactured by PERKIN-ELMER.

  Specifically, using 8 mg of the sample, the temperature is raised to 350 ° 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 is 210 ° C. or higher, the chemical resistance and the heat resistance tend to be further suppressed, and when it is 340 ° C. or lower, the thermal decomposition during molding tends to be further suppressed.

<Glass transition temperature>
The glass transition temperature of said (A) polyamide copolymer becomes like this. Preferably it is 55-110 degreeC, More preferably, it is 60-105 degreeC, More preferably, it is 60-100 degreeC.

  The glass transition temperature can be measured according to JIS K7121. More specifically, for example, measurement can be performed 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 is 55 ° 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. In addition, when the glass transition temperature is 110 ° C. or lower, a product having a more excellent molded 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 (thermal melt polymerization method); Method of increasing the degree of polymerization of the polyamide copolymer obtained by the hot melt polymerization method while maintaining the solid state at a temperature below the melting point (thermal melt polymerization / solid phase polymerization method); An extruder such as a kneader is further heated with an aqueous solution or water suspension of a mixture of acid, isophthalic acid, 1,4-cyclohexanedicarboxylic acid, hexamethylenediamine, and other components as necessary, and water. Method of increasing the degree of polymerization by re-melting with (a prepolymer / extrusion polymerization method); adipic acid, isophthalic acid, 1,4-cyclohexanedicarbo Heat the aqueous solution of the mixture of acid, hexamethylenediamine, and other components as necessary, or a suspension of water, and the degree of polymerization while maintaining the solid state at a temperature below the melting point of the polyamide. Method of raising (prepolymer / solid phase polymerization method); adipic acid, isophthalic acid, 1,4-cyclohexanedicarboxylic acid, hexamethylenediamine, if necessary, a mixture with other components, solid salt or polycondensate, Examples thereof include a method of polymerizing (solid phase polymerization method) while maintaining a solid state.

  (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. Although it does not specifically limit as polymerization temperature conditions of a batch type hot-melt-polymerization method, From a viewpoint of productivity, Preferably it is 100 degreeC or more, More preferably, it is 120 degreeC or more, More preferably, it is 170 degreeC or more.

  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.

  The structural unit of the polyamide copolymer can be confirmed by a nuclear magnetic resonance apparatus (NMR).

  (A) In the polymerization step of the polyamide copolymer, a dicarboxylic acid component consisting of (am) adipic acid, (bm) isophthalic acid, and (cm) 1,4-cyclohexanedicarboxylic acid, and a diamine Derived from each of the dicarboxylic acid components, including (cm) 1,4-cyclodicarboxylic acid, (am) adipic acid, and (bm) isophthalic acid The total content of the units to be 100 mol%, (A) the content (mol%) of units derived from the (bp) isophthalic acid constituting the polyamide copolymer and (c-1-p) 1, It is preferable to obtain a polyamide copolymer satisfying the following formula (2) in relation to the content (mol%) of a trans isomer unit of a unit derived from 4-cyclodicarboxylic acid.

  (A) By satisfy | filling following formula (2), a polyamide copolymer can improve weld strength and heat resistance further, without impairing shaping | molding external appearance property.

(C-1-p) Content of units of trans isomers of units derived from 1,4-cyclodicarboxylic acid> (bp) Content of units derived from isophthalic acid ≧ 0.1 2)
The content of units derived from the trans isomer of (c-1-p) 1,4-cyclodicarboxylic acid and the content of units derived from (bp) isophthalic acid are each determined by NMR. .

  (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 internal temperature in copolymerization with the components is preferably 270 ° C. or higher, more preferably 280 ° C. or higher, and further preferably 290 ° C. or higher. Thereby, the content of the trans isomer unit (c-1) of 1,4-cyclohexanedicarboxylic acid in the polyamide copolymer can be increased, and the welding strength and heat resistance can be further improved without impairing the molding appearance. An excellent polyamide resin composition can be obtained.

  For example, when employing the above-described hot melt polymerization method, it is preferable to carry out polycondensation at normal pressure or reduced pressure while keeping the final internal 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 catalyst is not particularly limited as long as it is a known one used for the production of polyamide. For example, phosphoric acid, phosphorous acid, hypophosphorous acid, orthophosphorous acid, pyrophosphorous acid, phenylphosphinic acid, phenylphosphonic acid. Examples include acid, 2-methoxyphenylphosphonic acid, 2- (2′-pyridyl) ethylphosphonic acid, and metal salts thereof.

  Examples of the metal of the metal salt include metal salts such as potassium, sodium, magnesium, vanadium, calcium, zinc, cobalt, manganese, tin, tungsten, germanium, titanium, and antimony, and ammonium salts.

  Further, 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, (cm) 1,4-cyclohexanedicarboxylic acid used as a raw material monomer in the polymerization step of the (A) polyamide copolymer has a trans isomer and a cis geometric isomer.

  (Cm) 1,4-cyclohexanedicarboxylic acid used as a raw material monomer may use either the trans isomer or the cis isomer, or may be used as a mixture in various ratios of the trans isomer and the cis isomer. Good.

  (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 an equivalent salt with diamine than the trans isomer. The molar ratio of the trans isomer (c-1-m) to the cis isomer (c-2-m) in the (cm) 1,4-cyclodicarboxylic acid used ((c-1-m) / (c -2-m)) is preferably 50/50 to 10/90, more preferably 40/60 to 10/90, and even more preferably 35/65 to 15/85.

  By setting the trans isomer / cis isomer ratio in the above range, it is possible to obtain a polyamide resin composition having further excellent welding strength and heat resistance without impairing the molding appearance. The trans isomer / cis isomer ratio can be measured using a nuclear magnetic resonance apparatus (NMR).

((B) inorganic filler)
The inorganic filler (B) used in the present embodiment is not limited to the following, for example, glass fiber, carbon fiber, calcium silicate fiber, potassium titanate fiber, aluminum borate fiber, glass flake, talc, Kaolin, mica, hydrotalcite, calcium carbonate, zinc carbonate, zinc oxide, calcium monohydrogen phosphate, wollastonite, silica, zeolite, alumina, boehmite, aluminum hydroxide, titanium oxide, silicon oxide, magnesium oxide, silicic acid Calcium, sodium aluminosilicate, magnesium silicate, ketjen black, acetylene black, furnace black, carbon nanotube, graphite, brass, copper, silver, aluminum, nickel, iron, calcium fluoride, mica, montmorillonite, swellable Containing mica and apatite and the like.

Among these, glass fiber, carbon fiber, wollastonite, kaolin, mica, talc, calcium carbonate, magnesium carbonate, potassium titanate, aluminum borate, and clay are preferable from the viewpoint of strength and surface appearance. More preferred are glass fiber, carbon fiber, wollastonite, kaolin, mica and talc, still more preferred are glass fiber, wollastonite and mica, and most preferred is glass fiber. The above-mentioned inorganic fillers may be used alone or in combination of two or more.
First, as a glass fiber or carbon fiber, the cross section may be a perfect circle shape or a flat shape. Examples of such a flat cross section include, but are not limited to, a rectangular shape, an oval shape close to a rectangular shape, an elliptical shape, and a saddle shape with a narrowed central portion in the longitudinal direction.

  Among glass fibers and carbon fibers, the number average fiber diameter is 3 to 30 μm, the weight average fiber length is 100 to 750 μm, and the weight average fiber length from the viewpoint of imparting excellent mechanical strength to the welded molded product. Those having an aspect ratio (L / D) of 10 to 100 between (L) and the number average fiber diameter (D) are preferably used.

  Here, the number average fiber diameter and the weight average fiber length of the glass fiber and carbon fiber in the present specification are values obtained by the following method. The welded molded product is placed in an electric furnace and the contained organic matter is incinerated. From the residue after the treatment, 100 or more glass fibers and carbon fibers are arbitrarily selected, and these glass fibers are observed with a scanning electron microscope (SEM) (manufactured by JEOL Ltd., JSM-6700F). The number average fiber diameter is measured by measuring the fiber diameter of the carbon fiber. In addition, the weight average fiber length is obtained by measuring the fiber length using SEM photographs of the 100 or more glass fibers and carbon fibers taken at a magnification of 1,000 times.

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

  In addition, for the above glass fiber and carbon fiber, as a sizing agent, an unsaturated vinyl monomer excluding the carboxylic acid anhydride-containing unsaturated vinyl monomer and the unsaturated vinyl monomer containing the carboxylic acid anhydride-containing unsaturated vinyl monomer; Copolymer, epoxy compound, polyurethane resin, homopolymer of acrylic acid, copolymers of acrylic acid and other copolymerizable monomers, and primary, secondary and tertiary amines thereof And a copolymer containing a carboxylic acid anhydride-containing unsaturated vinyl monomer and an unsaturated vinyl monomer excluding the carboxylic acid anhydride-containing unsaturated vinyl monomer. These may be used individually by 1 type and may be used in combination of 2 or more type.

  Among these, from the viewpoint of the mechanical strength of the obtained welded molded article, it comprises a carboxylic acid anhydride-containing unsaturated vinyl monomer and an unsaturated vinyl monomer excluding the carboxylic acid anhydride-containing unsaturated vinyl monomer. Copolymers, epoxy compounds, polyurethane resins, and combinations thereof as units are preferred. More preferably, a copolymer and a polyurethane resin containing, as constituent units, a carboxylic acid anhydride-containing unsaturated vinyl monomer and an unsaturated vinyl monomer excluding the carboxylic acid anhydride-containing unsaturated vinyl monomer, and These are combinations.

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

Among these combinations, from the group consisting of a copolymer of maleic anhydride and butadiene, a copolymer of maleic anhydride and ethylene, a copolymer of maleic anhydride and styrene, and a mixture thereof. More preferably, it is at least one selected.
Further, the copolymer containing the above-mentioned carboxylic acid anhydride-containing unsaturated vinyl monomer and the unsaturated vinyl monomer excluding the carboxylic acid anhydride-containing unsaturated vinyl monomer as a constituent unit has a weight average molecular weight. Is preferably 2,000 or more. Moreover, from a viewpoint of improving the fluidity | liquidity of the fusion-molded article obtained, More preferably, it is 2,000-1,000,000, More preferably, it is 2,000-500,000. In addition, the weight average molecular weight in this specification is a gel.

It is a value measured by permeation chromatography (GPC).
Examples of the epoxy compound include, but are not limited to, ethylene oxide, propylene oxide, butene oxide, pentene oxide, hexene oxide, heptene oxide, octene oxide, nonene oxide, decene oxide, undecene oxide, dodecene oxide, penta Aliphatic epoxy compounds such as decene oxide and eicosene oxide, glycidol, epoxypentanol, 1-chloro-3,4-epoxybutane, 1-chloro-2-methyl-3,4-epoxybutane, 1 , 4-dichloro-2,3-epoxybutane, cyclopentene oxide, cyclohexene oxide, cycloheptene oxide, cyclooctene oxide, methylcyclohexene oxide, vinylcyclohexene oxide And alicyclic epoxy compounds such as epoxidized cyclohexene methyl alcohol, terpene epoxy compounds such as pinene oxide, aromatic epoxy compounds such as styrene oxide, p-chlorostyrene oxide and m-chlorostyrene oxide, epoxidized soybean oil, And epoxidized linseed oil.

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

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

  The polymer of acrylic acid may be a copolymer of acrylic acid and other copolymerizable monomers. Examples of the monomer that forms a copolymer with acrylic acid include, but are not limited to, for example, among monomers having a hydroxyl group and / or a carboxyl group, acrylic acid, maleic acid, methacrylic acid, vinyl acetic acid, crotonic acid, and isocrotone. One or more selected from the group consisting of acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid are included (except for the case of acrylic acid only). Preferably, it has 1 or more types of ester monomers among the above-mentioned monomers.

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

  The weight average molecular weight of the acrylic acid polymer forming the salt is not limited to the following, but is preferably in the range of 3,000 to 50,000. That is, 3,000 or more is preferable from the viewpoint of improving the converging property of glass fiber or carbon fiber, and 50,000 or less is preferable from the viewpoint of improving the mechanical properties of the obtained welded molded product.

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

  Inorganic fillers other than glass fiber and carbon fiber include wollastonite, kaolin, mica, talc, calcium carbonate, magnesium carbonate, potassium titanate, aluminum borate from the viewpoint of improving the strength and surface appearance of the welded molded product. Clay is preferred. These average particle diameters are preferably 0.01 to 38 μm from the viewpoint of improving toughness and surface appearance. 0.03-30 micrometers is more preferable, 0.05-25 micrometers is more preferable, 0.10-20 micrometers is still more preferable, 0.15-15 micrometers is the most preferable.

  By setting the average particle size to 38 μm or less, a welded molded article having excellent toughness and surface appearance can be obtained. On the other hand, when the thickness is 0.1 μm or more, a welded molded article having an excellent balance between cost and powder handling surface and mechanical properties (strength, toughness, weldability, etc.) can be obtained.

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

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

  The measurement of needle-like fibers (wollastonite, etc.) in this specification is performed using a scanning electron microscope (SEM) (manufactured by JEOL Ltd., JSM-6700F). A fiber image of a needle-like fiber was taken at a magnification of 1,000 to 50,000 times, and an average particle size (average value of the major axis of the cross section if the cross section was not a circle) from arbitrarily selected 500 inorganic fillers ).

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

  The content of the (B) inorganic filler is preferably 1 to 300 parts by mass, more preferably 10 to 200 parts by mass, and further preferably 15 to 180 parts by mass with respect to 100 parts by mass of the (A) polyamide. Part, even more preferably 20 to 160 parts by weight, and most preferably 30 to 150 parts by weight.

By setting the content to 1 part by mass or more, the effect of improving the strength of the obtained welded molded product is sufficiently exhibited. On the other hand, by setting the content to 300 parts by mass or less, a welded molded product having excellent extrudability, moldability, and surface appearance 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]
In the polyamide resin composition of the present embodiment, the (A) polyamide copolymer contains the above-described (B) various additives such as the inorganic filler, deterioration inhibitor, moldability improver, colorant, and other resins. It can produce by mix | blending.
It does not specifically limit as a compounding method, A well-known extrusion technique can be used. At that time, the blending, kneading method and kneading order are not particularly limited, and they can be mixed using a commonly used mixer such as a Henschel mixer, a tumbler, and a ribbon blender.
As the kneader, a single-screw or multi-screw extruder is usually used. Among these, a twin-screw extruder equipped with a pressure reducing device is preferable from the viewpoint of productivity.

[Molded product of polyamide resin composition]
The molded article of the polyamide resin composition of the present embodiment is obtained by molding the above-described polyamide resin composition of the present embodiment by a predetermined method.

  The molding method is not particularly limited as long as it is a method capable of obtaining a molded product from the polyamide resin composition of the present embodiment, 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 product containing the polyamide resin composition of the present embodiment has good heat resistance and moldability and is excellent in the welding strength and appearance of the welded joint, it can be used for applications of welded molded products.

  Although it does not specifically limit as a polyamide welding molded product, For example, it can use suitably in a motor vehicle part, an electrical component, an electronic component, a portable equipment part, a machine / industrial part, an office equipment part, an aerospace part.

  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 welded 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 of polyamide (Mn))
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 its glass transition temperature (Tg (° C.)) was measured.

[Production of welded molded product for weld strength evaluation]
Using the injection molding machine [SE130D manufactured by Sumitomo Heavy Industries, Ltd.], the polyamide composition pellets obtained in the examples and comparative examples were used to form two types of flat plate plate pieces (12 cm × 8 cm, thickness 10 mm). , 12 cm × 8 cm, thickness 3 mm). The injection conditions (3 mm thickness) were set to injection pressure 105 MPa, injection time 0.4 seconds, pressure holding time 12 seconds, cooling time 18 seconds, and screw rotation speed 100 rpm. The injection conditions (10 mm thickness) were set to an injection pressure of 55 MPa, an injection time of 0.2 seconds, a pressure holding time of 30 seconds, a cooling time of 60 seconds, and a screw rotation speed of 100 rpm. The mold temperature was set to Tg + 20 ° C., cylinder temperature = (Tm2 + 10) ° C. to (Tm2 + 30) ° C., the obtained flat plate was cut, and two types of flat plate test pieces (4 cm × 12 cm, thickness 10 mm, 4 cm) × 12 cm, thickness 3 mm).

  The side surfaces (12 cm × 10 mm surface and 12 cm × 3 mm surface) of the two types of flat plates obtained are aligned as shown in FIG. 1, using a BRANSON MICRO PPL vibration welding machine, frequency 233 Hz, welding pressure 10 Welding was performed under the conditions of 0.2 kgf / cm 2, amplitude 1.5 mm (thickness direction), and welding allowance 2 mm.

The weld-molded pieces were cut at intervals of 2 cm in the direction perpendicular to the weld surface to prepare weld test pieces having a width of 2 cm.
The created welding test piece was subjected to a tensile test at a tensile speed of 5 mm / min, and the strength at break was measured to obtain the welding strength.

[Production of molded product for evaluation of molding appearance]
The polyamide composition pellets obtained in the examples and comparative examples were set using an injection molding machine [IS150E manufactured by Toshiba Machine Co., Ltd.], the mold temperature was set to 90 ° C., the injection time was 12 seconds, and the cooling time was 20 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 1 second. 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.

[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 internal 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 internal 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 internal 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 internal 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 obtained polyamide copolymer (A4) was evaluated for molecular weight, melting point, and glass transition temperature 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 internal 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 internal 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 internal 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 internal 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 internal 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.

[Inorganic filler (B)]
Glass fiber (B1) Congqing Polycomp International Corporation product name: ECS301HP Average fiber diameter: 10 μm, Cut length: 3 mm

[Polyamide resin composition]
<Example 1>
100 parts by mass of polyamide copolymer (A1) was manufactured by Toshiba Machine Co., Ltd., TEM 35 mm twin screw extruder (set temperature: temperature about 30 ° C. higher than the melting point of the polyamide copolymer determined according to the melting point measurement method, screw rotation speed) 300 rpm) from a feed hopper.
Furthermore, the glass fiber (B1) is supplied at a ratio of 100 parts by mass to 100 parts by mass of the polyamide copolymer (A) from the side feed port, and the melt-kneaded product extruded from the spinning port is cooled in a strand shape. And pelletizing to obtain a pellet-like polyamide resin composition.
By the method described above, the melting point, glass transition temperature, welding strength, and appearance of the resin composition described above were evaluated. The evaluation results are shown in Table 2 below.

<Example 2>
A polyamide resin composition was obtained in the same manner as in Example 1 except that the polyamide copolymer (A2) was used.
By the method described above, the melting point, glass transition temperature, welding strength, and appearance of the resin composition described above were evaluated. The evaluation results are shown in Table 2 below.

<Example 3>
A polyamide resin composition was obtained in the same manner as described in Example 1 except that the polyamide copolymer (A3) was used.
By the method described above, the melting point, glass transition temperature, welding strength, and appearance of the resin composition described above were evaluated. The evaluation results are shown in Table 2 below.

<Example 4>
100 parts by mass of a polyamide copolymer (A3), manufactured by Toshiba Machine Co., Ltd., TEM 35 mm twin screw extruder (set temperature: temperature about 30 ° C. higher than the melting point of the polyamide copolymer determined according to the melting point measurement method, screw rotation speed) 300 rpm) from a feed hopper.
Furthermore, the glass fiber (B1) is supplied at a ratio of 50 parts by mass with respect to 100 parts by mass of the polyamide copolymer (A) from the side feed port, and the melt-kneaded product extruded from the spinning port is cooled in a strand shape. And pelletizing to obtain a pellet-like polyamide resin composition.
By the method described above, the melting point, glass transition temperature, welding strength, and appearance of the resin composition described above were evaluated. The evaluation results are shown in Table 2 below.

<Example 5>
A polyamide resin composition was obtained in the same manner as in Example 1 except that the polyamide copolymer (A4) was used.
By the method described above, the melting point, glass transition temperature, welding strength, and appearance of the resin composition described above were evaluated. The evaluation results are shown in Table 2 below.

<Example 6>
A polyamide resin composition was obtained in the same manner as in Example 1 except that the polyamide copolymer (A5) was used.
By the method described above, the melting point, glass transition temperature, welding strength, and appearance of the resin composition described above were evaluated. The evaluation results are shown in Table 2 below.

<Example 7>
A polyamide resin composition was obtained in the same manner as in Example 1 except that the polyamide copolymer (A6) was used.
By the method described above, the melting point, glass transition temperature, welding strength, and appearance of the resin composition described above were evaluated. The evaluation results are shown in Table 2 below.

<Example 8>
A polyamide resin composition was obtained in the same manner as in Example 1 except that the polyamide copolymer (A7) was used.
By the method described above, the melting point, glass transition temperature, welding strength, and appearance of the resin composition described above were evaluated. The evaluation results are shown in Table 2 below.

<Example 9>
A polyamide resin composition was obtained in the same manner as in Example 1 except that the polyamide copolymer (A8) was used.
By the method described above, the melting point, glass transition temperature, welding strength, and appearance of the resin composition described above were evaluated. The evaluation results are shown in Table 2 below.

<Example 10>
A polyamide resin composition was obtained in the same manner as in the examples except that the polyamide copolymer (A13) was used.
By the method described above, the melting point, glass transition temperature, welding strength, and appearance of the resin composition described above were evaluated. The evaluation results are shown in Table 2 below.

<Comparative Example 1>
A polyamide resin composition was obtained in the same manner as in Example 1 except that the polyamide copolymer (A9) was used.
By the method described above, the melting point, glass transition temperature, welding strength, and appearance of the resin composition described above were evaluated. The evaluation results are shown in Table 2 below.

<Comparative example 2>
A polyamide resin composition was obtained in the same manner as in Example 1 except that the polyamide copolymer (A10) was used.
By the method described above, the melting point, glass transition temperature, welding strength, and appearance of the resin composition described above were evaluated. The evaluation results are shown in Table 2 below.

<Comparative Example 3>
A polyamide resin composition was obtained in the same manner as in Example 1 except that the polyamide copolymer (A11) was used.
By the method described above, the melting point, glass transition temperature, welding strength, and appearance of the resin composition described above were evaluated. The evaluation results are shown in Table 2 below.

<Comparative example 4>
A polyamide resin composition was obtained in the same manner as in Example 1 except that the polyamide copolymer (A12) was used.
By the method described above, the melting point, glass transition temperature, welding strength, and appearance of the resin composition described above were evaluated. The evaluation results are shown in Table 2 below.

<Comparative Example 5>
A polyamide resin composition was obtained in the same manner as in Example 1 except that the polyamide copolymer (A3) and the fiber reinforcement (B2) were used.
By the method described above, the melting point, glass transition temperature, welding strength, and appearance of the resin composition described above were evaluated. The evaluation results are shown in Table 2 below.

As shown in Table 2, it was confirmed that the weld-molded product obtained from the polyamide copolymer of each Example was excellent in weldability without impairing heat resistance and molding appearance.
On the other hand, as shown in Table 2, it was confirmed that the welded molded product obtained from the polyamide copolymer of each comparative example was deteriorated in any of weldability, heat resistance, and molded appearance.

  The welded molded article of the present invention can be industrially used as various parts in the automotive field, electrical / electronic field, portable device field, machine / industrial field, office equipment field, aviation / space field, daily / household field, etc. It has sex.

Claims (11)

(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%. A welded molded article containing 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) (A) 100 parts by mass of polyamide copolymer, (B) 1 to 300 parts by mass of inorganic filler,
The fusion-molded article according to claim 1, comprising a polyamide resin composition containing 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 content of the (cp) 1,4-cyclohexanedicarboxylic acid unit is 15 to 40 mol%,
The fusion-molded article according to any one of claims 1 and 2.   The fusion-molded article according to any one of claims 1 to 3, wherein the diamine component unit is an aliphatic diamine component unit.   The fusion-molded article according to claim 4, wherein the diamine component unit is a hexamethylenediamine unit. A polyamide copolymer obtained by copolymerizing a dicarboxylic acid component containing (am) adipic acid, (bm) isophthalic acid, and (cm) 1,4-cyclohexanedicarboxylic acid, and a diamine component. A polymer comprising:
In a total of 100 mol% of units derived from each of the dicarboxylic acid component including the (cm) 1,4-cyclodicarboxylic acid, the (am) adipic acid, and the (bm) isophthalic acid, The content (mol%) of units derived from (bp) isophthalic acid and the units of trans isomers of units derived from (c-1-p) 1,4-cyclodicarboxylic acid in the polyamide copolymer The fusion-molded article according to any one of claims 1 to 5, which contains (A) a polyamide copolymer whose relationship with the content (mol%) satisfies the following formula (2).
(C-1-p) Content of units of trans isomers of units derived from 1,4-cyclodicarboxylic acid> (bp) Content of units derived from isophthalic acid ≧ 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 fusion-molded article according to claim 6, wherein the final polymerization temperature in copolymerization is 270 ° C or higher.   The molar ratio of the trans isomer (c-1-m) to the cis isomer (c-2-m) in the (cm) 1,4-cyclodicarboxylic acid used as a raw material monomer for the copolymerization ( The fusion-molded article according to any one of claims 6 and 7, wherein (c-1-m) / (c-2-m)) is 50/50 to 10/90.   The welded molded article according to any one of claims 1 to 8, which is an automobile part.   The weld-molded product according to any one of claims 1 to 8, which is an electronic component.   The fusion-molded article according to any one of claims 1 to 8, which is a home appliance OA equipment part or a mobile equipment part.

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