JP2001115017A - Polyamide resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyamide resin composition having high strength and elastic modulus and excellent moldability, rigidity retention at high temperature, durability at high temperature and mechanical property retention in water- absorbed state and usable as a substitute for metals. SOLUTION: The objective polyamide resin composition is produced by compounding 10-150 pts.wt. of an inorganic filler to 100 pts.wt. of a mixed resin composed of (A) 70-100 wt.% polyamide resin produced by the polycondensation of a diamine component containing >=70 mol% mixture composed of 60-100 mol% cis-1,3-bis(aminomethyl)cyclohexane and 40-0 mol% trans-1,3-bis(aminomethyl)cyclohexane and a dicarboxylic acid component containing >=70 mol% 4-20C α,ω-straight-chain aliphatic dicarboxylic acid and (B) 30-0 wt.% (A+B is 100 wt.%) thermoplastic resin other than the polyamide resin A.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyamide resin composition which can be replaced with a metal, that is, it has high strength, high elastic modulus, moldability, rigidity retention at high temperature, and high temperature. The present invention relates to a polyamide resin composition having excellent durability and mechanical performance retention when absorbing water.

[0002]

2. Description of the Related Art Molded articles made of polyamide resins such as polyamide 6 and polyamide 66 are excellent in toughness, chemical resistance, electric properties, and the like. Widely used for equipment parts. Depending on the application of these metal substitute materials, not only the mechanical strength such as the strength and elastic modulus of the molded product, but also the rigidity retention at high temperatures and the mechanical performance retention at water absorption, Some of them require durability.

Conventionally, a polyamide resin obtained by polycondensation of 1,3-bis (aminomethyl) cyclohexane and adipic acid (hereinafter sometimes referred to as “polyamide BAC6”) is disclosed in Japanese Patent Application Laid-Open No. 48-48548, JP-A-50-
JP-A-145492 and JP-B-50-37717 each disclose films and fibers made of polyamide BAC6.

Accordingly, a polyamide BAC6 having high strength and a high elastic modulus, moldability, rigidity retention at high temperature, durability at high temperature, and mechanical performance retention at the time of water absorption have been used. Polyamide resin compositions having excellent properties have not been specifically disclosed and have not been used industrially.

[0005]

SUMMARY OF THE INVENTION The present invention has high strength, high elastic modulus, moldability, rigidity retention under high temperature,
An object of the present invention is to provide a resin composition comprising polyamide BAC6 which is excellent in durability at high temperatures and retention of mechanical performance when absorbing water.

[0006]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to achieve the above object, and as a result, the use of a specific polyamide resin has improved moldability, and the resin composition has the above-mentioned properties. The inventors have found that they have excellent performance, and have completed the present invention.

That is, the present invention relates to a method for preparing cis-1,3-bis (aminomethyl) cyclohexane 60 in a diamine component.
A diamine containing at least 70 mol% of a mixture of -100 mol% and 40-0 mol% of trans-1,3-bis (aminomethyl) cyclohexane (the total of the mol% is 100 mol%); Α, ω with 4-20 carbon atoms
A polyamide resin (A) 7 obtained by polycondensing a dicarboxylic acid containing at least 70 mol% of a linear aliphatic dicarboxylic acid
0 to 100% by mass, and 30 to 0% by mass of the thermoplastic resin (B) other than the polyamide resin (A) (the total
The present invention relates to a polyamide resin composition obtained by blending 10 to 150 parts by mass of an inorganic filler with respect to 100 parts by mass of a mixed resin (C) which is 100% by mass.

[0008] The polyamide resin (A) used in the present invention refers to 60 to 100 mol% of cis-1,3-bis (aminomethyl) cyclohexane and trans-1,3-bis (aminomethyl) in the starting diamine component. Cyclohexane 40-
A polyamine obtained by polycondensation of a diamine containing at least 70 mol% of a mixture of 0 mol% and a dicarboxylic acid containing at least 70 mol% of an α, ω-linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms in a raw material dicarboxylic acid component. Polyamide resin. The polyamide resin is practically a crystalline polyamide resin.

Here, the crystalline polyamide is a crystalline polymer having a melting point, such as polyamide 6 or polyamide 66, and has a crystallinity, a crystallinity distribution, and a size of a spherulite which is an aggregate of crystals. , And its distribution affect the physical properties, specific gravity, dimensional stability and the like of the polyamide resin molded article. For example, molded articles made of these crystalline polyamides can be obtained by injection molding from a molten state into a mold, and by sufficiently solidifying and crystallizing in the mold, molding from the mold is possible. The product can be easily taken out, and the strength and the rigidity retention under high temperature can be enhanced.

In the present invention, the starting diamine of the polyamide (A) is composed of 60 to 100 mol% of cis-1,3-bis (aminomethyl) cyclohexane and trans-1,3-bis (aminomethyl) cyclohexane in the diamine component. 4
It contains at least 70 mol% of a mixture of 0 to 0 mol% (the total of the mol% is 100 mol%). 1,3-bis (aminomethyl) cyclohexane includes a cis form and a trans form. In the present invention, the isomer molar ratio (cis / trans) is 100/0 to 60/40, preferably 100/0 to 60/40. 0-80 / 20, more preferably 100 /
0 to 90/10. By molding a polyamide using 1,3-bis (aminomethyl) cyclohexane containing a cis-form of 60 mol% or more, a molded article having sufficiently solidified and crystallized in a mold can be obtained. Has strength, high modulus, and rigidity retention under high temperature,
It is useful as a resin composition for molded article materials having excellent durability at high temperatures and excellent mechanical performance retention when absorbing water.

In the present invention, other diamines in bis (aminomethyl) cyclohexane include aliphatic diamines such as tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, octamethylenediamine, nonamethylenediamine, and paraphenylenediamine. And diamines having an aromatic ring such as meta-xylylenediamine and para-xylylenediamine can be used in a range of less than 30 mol% in the total diamine component.

In the present invention, as the dicarboxylic acid component of the raw material of the polyamide (A), examples of the α, ω-linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms include succinic acid, glutaric acid, adipic acid, pimelic acid, Examples thereof include aliphatic dicarboxylic acids such as suberic acid, azelaic acid, sebacic acid, undecandioic acid, and dodecandioic acid. Terephthalic acid, isophthalic acid, α-ω-linear aliphatic dicarboxylic acid
Aromatic rings such as aromatic dicarboxylic acids such as 2,6-naphthalenedicarboxylic acid and 4,4'-biphenyldicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, decalindicarboxylic acid and tetralindicarboxylic acid Those containing less than 30 mol% of group dicarboxylic acids in the total dicarboxylic acid component can also be used.

The polyamide resin (A) contains 60 to 100 mol% of cis-1,3-bis (aminomethyl) cyclohexane and 40 to 0 mol% of trans-1,3-bis (aminomethyl) cyclohexane in the starting diamine component. Mix 7
0 mol% or more, and 4 carbon atoms in the starting dicarboxylic acid component
70 mol% of α, ω-linear aliphatic dicarboxylic acid of from 20 to 20
When obtained by polycondensation from the raw material containing the above, high strength when finally formed into a molded product, high elastic modulus, and rigidity retention at high temperatures, durability at high temperatures, Characteristics such as mechanical performance retention during water absorption can be maintained.

The polyamide resin composition used in the present invention may contain a thermoplastic resin (B) other than the above-mentioned polyamide resin (A). As the other thermoplastic resin (B), various thermoplastic resins can be used. Specifically, polyamide MXD6 obtained by polycondensation of metaxylylenediamine and adipic acid, and metaxylylenediamine and paraxylylene Polyamide MP6 obtained by polycondensation of diamine and adipic acid, polyamide MP6 obtained by polycondensation of metaxylylenediamine and paraxylylenediamine and adipic acid and terephthalic acid
T, polyamide 6, polyamide 66, polyamide 46,
Polyamide 6/66 (copolymer of polyamide 6 component and polyamide 66 component), polyamide 610, polyamide 612, polyamide 11, polyamide 12, and mixtures thereof, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate,
Polybutylene naphthalate and the like can be exemplified, but in the present invention, polyamide MXD6, polyamide MP6, polyamide 6, polyamide 66, polyamide 46, polyethylene terephthalate, and polybutylene terephthalate can be preferably used. By using these resins, crystallization during the molding process is promoted, and the molding time can be easily reduced.

The polyamide resin composition of the present invention must contain the polyamide resin (A) in the mixed resin (C) in an amount of 70% by mass or more, preferably 80% by mass or more. When the mixing ratio of the polyamide resin (A) is 70% by mass or more, the polyamide BAC6 has high strength, high elastic modulus, rigidity retention at high temperature, mechanical performance retention at water absorption, and high temperature. Properties such as durability can be reflected in the physical properties of the resulting molded article. Therefore, the blending ratio of the thermoplastic resin (B) in the polyamide molded article of the present invention needs to be less than 30% by mass in the resin.

The amount of the inorganic filler used in the present invention is 10 to 150 parts by mass, preferably 15 to 100 parts by mass, per 100 parts by mass of the mixed resin (C). The inorganic filler,
There is no particular limitation as long as it is generally used in this type of composition, but inorganic fillers such as powdery fillers, fibrous fillers, granular and flake-like fillers, or a combination thereof are preferably used.

As the powdery filler, preferably 100
having a particle size of not more than 80 μm, more preferably not more than 80 μm, such as carbonates such as kaolinite, silica, calcium carbonate and magnesium carbonate, sulfates such as calcium sulfate and magnesium sulfate, sulfides and metal oxides and the like. Can be exemplified. Examples of the fibrous filler include glass fibers, whiskers of potassium titanate and calcium sulfate, carbon fibers, and alumina fibers. Examples of the flake-like filler include kaolinite, halloysite, chrysotile, smectites (eg, montmorillonite, hectorite, beidellite, savonite, etc.), mica (eg, muscobite, phlogovite, etc.), pyrophyllite, vermiculite, chlorite, etc. it can. Furthermore, those obtained by subjecting these flake-shaped fillers to surface treatment with a polymer compound, an organic compound, an inorganic compound, or the like can also be used. In addition, if necessary, one or more additives such as a flame retardant, an antistatic agent, a lubricant, a plasticizer, a stabilizer against oxidation, deterioration by heat and ultraviolet rays, and a colorant can be used.

In the present invention, it is preferable to use talc powder in order to further promote crystallization. The talc used is preferably 100 μm or less, more preferably 8 μm or less.
It has a particle size of 0 μm or less, and is blended at a ratio of 30 parts by mass or less to 100 parts by mass of the polyamide resin. When the blending ratio of talc is 30 parts by mass or less with respect to 100 parts by mass of the polyamide resin, it is possible to prevent adverse effects such as a decrease in the fluidity of the resin at the time of molding and a decrease in mechanical performance of the obtained molded product.

[0019]

The present invention will be specifically described below with reference to production examples, examples and the like. In the examples and the like, the following method was used to evaluate a polyamide molded product. Moldability: It was determined whether a molded product could be easily obtained by injection molding. Tensile test: ASTM D638 Bending test: ASTM D790 100 ° C. bending performance retention Bending strength and elastic modulus in a 100 ° C. atmosphere were measured using a bending tester equipped with a thermostat (Autograph manufactured by Shimadzu Corporation). Heat aging resistance A test piece for a tensile test was treated in a gear oven at 180 ° C. for 1000 hours, and then the tensile strength was measured. Retention of mechanical performance when absorbing water A test piece for tensile test was put in boiling water at 100 ° C for 100
After treating for 0 hours, the tensile strength was measured.

Production Example 1 A reaction vessel having an inner volume of 50 liters equipped with a stirrer, a decomposer, a thermometer, a dropping funnel and a nitrogen gas inlet tube was charged with 10.000 kg of precisely weighed adipic acid, and sufficiently purged with nitrogen. ,
Further, adipic acid was dissolved at 170 ° C. in a small amount of nitrogen stream to make a uniform fluid state. To this, 1,3-bis (aminomethyl) cyclohexane (cis-form / trans-
(Formula: 97/3, hereinafter, 1,3-bis (aminomethyl) cyclohexane is sometimes referred to as "1,3-BAC") 8.370 kg was added dropwise with stirring over 119 minutes. During this time, the internal temperature was continuously raised to 240 ° C. Subsequently, 1.365 kg of the 1,3-BAC was added dropwise with stirring over 72 minutes. During this time, the internal temperature was continuously raised to 250 ° C. Water distilled off along with the dropping of 1,3-BAC was removed from the system through a decompressor and a cooler. After the completion of the dropping of 1,3-BAC, the internal temperature was continuously raised to 26.
The temperature was raised to 5 ° C., and the reaction was continued for 25 minutes. Thereafter, the internal pressure of the reaction system was continuously reduced to 80 kPa for 10 minutes,
Thereafter, the reaction was continued for 42 minutes. During this time, the reaction temperature was continuously raised to 270 ° C. Obtained polyamide BAC6 (hereinafter sometimes referred to as “PA-BAC6”)
Has a relative viscosity of 1 g / 100 mL of a 96% sulfuric acid solution.
2.5, melting point 257 ° C.

Preparation Example 2 Into the same reaction vessel as in Preparation Example 1, precisely weighed adipic acid 10.0
After adding 100 kg, the atmosphere was sufficiently purged with nitrogen, and adipic acid was dissolved at 170 ° C. in a small amount of nitrogen stream to obtain a uniform fluid state. To this, 8.370 kg of 1,3-BAC (cis-form / trans-form: 85/15) was added dropwise with stirring over 120 minutes. During this time, the internal temperature was continuously raised to 235 ° C. Subsequently, the 1,3-BAC 1.36
5 kg was added dropwise with stirring over 72 minutes. During this time, the internal temperature was continuously raised to 245 ° C. 1,3-BAC
The water distilled off along with the dropwise addition was removed from the system through a condensing device and a cooler. After the completion of the dropping of 1,3-BAC, the internal temperature was continuously raised to 260 ° C., and the reaction was continued for 25 minutes.
Thereafter, the internal pressure of the reaction system was continuously reduced to 80 kPa for 10 minutes, and then the reaction was continued for 42 minutes. During this time,
The reaction temperature was continuously raised to 265 ° C. The relative viscosity of the obtained polyamide BAC6 (1 g / 96% sulfuric acid solution)
100 mL) was 2.5 and the melting point was 245 ° C.

Preparation Example 3 Adipic acid 10.0 was precisely weighed in the same reaction vessel as in Preparation Example 1.
After adding 100 kg, the atmosphere was sufficiently purged with nitrogen, and adipic acid was dissolved at 170 ° C. in a small amount of nitrogen stream to obtain a uniform fluid state. To this, 8.370 kg of 1,3-BAC (cis- / trans-form: 73/27) was added dropwise with stirring over 119 minutes. During this time, the internal temperature was continuously raised to 223 ° C. Subsequently, the 1,3-BAC 1.36
5 kg was added dropwise with stirring over 72 minutes. During this time, the internal temperature was continuously raised to 234 ° C. 1,3-BAC
The water distilled off along with the dropwise addition was removed from the system through a condensing device and a cooler. After the completion of the dropping of 1,3-BAC, the internal temperature was continuously raised to 250 ° C., and the reaction was continued for 25 minutes.
Thereafter, the internal pressure of the reaction system was continuously reduced to 80 kPa for 10 minutes, and then the reaction was continued for 42 minutes. During this time,
The reaction temperature was continuously raised to 260 ° C. The relative viscosity of the obtained polyamide BAC6 (1 g / 96% sulfuric acid solution)
100 mL) was 2.5 and the melting point was 230 ° C.

Production Example 4 Adipic acid 10.0, which was precisely weighed, was placed in the same reaction vessel as in Production Example 1.
After adding 100 kg, the atmosphere was sufficiently purged with nitrogen, and adipic acid was dissolved at 170 ° C. in a small amount of nitrogen stream to obtain a uniform fluid state. To this, 8.370 kg of 1,3-BAC (cis-form / trans-form: 50/50) was added dropwise with stirring over 119 minutes. During this time, the internal temperature was continuously raised to 210 ° C. Subsequently, the 1,3-BAC 1.36
5 kg was added dropwise with stirring over 72 minutes. During this time, the internal temperature was continuously raised to 220 ° C. 1,3-BAC
The water distilled off along with the dropwise addition was removed from the system through a condensing device and a cooler. After the completion of the dropping of 1,3-BAC, the internal temperature was continuously raised to 250 ° C., and the reaction was continued for 25 minutes.
Thereafter, the internal pressure of the reaction system was continuously reduced to 80 kPa for 10 minutes, and then the reaction was continued for 42 minutes. During this time,
The reaction temperature was continuously raised to 260 ° C. The relative viscosity of the obtained polyamide BAC6 (1 g / 96% sulfuric acid solution)
100 mL), 2.5, melting point not detected.

Production Example 5 In the same reaction vessel as in Production Example 1, 1,3-BAC (cis-form /
Trans-form: 97/3) and 1,3 consisting of adipic acid
15.000 kg of BAC6 salt, 6.500 k of distilled water
g, and sufficiently purged with nitrogen. After closing the reactor, the internal temperature was raised to 215 ° C. and the internal pressure was increased to 1.9 MPa, and the internal pressure was increased. The steam in the reactor was discharged for 90 minutes while maintaining the internal pressure at 1.9 MPa. Thereafter, the internal temperature was raised to 260 ° C. over a period of 150 minutes, and simultaneously, the internal pressure was reduced to 0.1 MPa, and the internal temperature was raised to 270 ° C. over a further 20 minutes. When the internal temperature reaches 270 ° C, the internal pressure of the reaction system is increased to 80k.
The pressure was continuously reduced to Pa for 10 minutes, and then the reaction temperature was continuously raised to 275 ° C., and the reaction was continued for 30 minutes. The relative viscosity of the obtained polyamide BAC6 (96%
(Sulfuric acid solution 1 g / 100 mL) 2.5, melting point 258
° C.

Production Example 6 8.01 adipic acid was precisely weighed in the same reaction vessel as in Production Example 1.
After adding 0 kg and 2.274 kg of terephthalic acid, the atmosphere was sufficiently purged with nitrogen, and adipic acid was dissolved at 170 ° C. in a small amount of nitrogen stream to obtain a uniform fluid state. In addition, 1,3-
BAC (cis- / trans-form: 97/3) 8.37
0 kg was added dropwise with stirring for 119 minutes. During this time,
The internal temperature was continuously raised to 240 ° C. Subsequently, 1.365 kg of the 1,3-BAC was added dropwise with stirring over 72 minutes. During this time, the internal temperature was continuously raised to 250 ° C. Water distilled off along with the dropping of 1,3-BAC was removed from the system through a decompressor and a cooler. 1,3-B
After the completion of AC dripping, the internal temperature was continuously raised to 265 ° C.
The reaction was continued for 25 minutes. After that, the internal pressure of the reaction
The pressure was continuously reduced to Pa for 10 minutes, and then the reaction was continued for 42 minutes. During this time, the reaction temperature was continuously raised to 270 ° C. The obtained copolymerized polyamide (hereinafter referred to as “P
A-BAC6T ”).
% Sulfuric acid solution 1g / 100mL) is 2.5, melting point is 25
4 ° C.

Example 1 5 parts by mass of polyamide 66 (manufactured by DuPont, trade name: Zytel 101) and 95 parts by mass of talc (manufactured by Hayashi Kasei Co., Ltd., 95 parts by mass of polyamide BAC6 obtained in Production Example 1) : Micron white 5000A) and 8 parts by mass of glass fiber (manufactured by Nippon Electric Glass Co., Ltd., size: 10 μmφ)
× 3 mmL) was blended in an amount of 100 parts by mass, melt-kneaded at a cylinder temperature of 290 ° C. using a vent type single screw extruder (manufactured by Nakatani Machinery Co., Ltd.), and then cooled with water and pelletized. Using the obtained resin composition, a test piece for a tensile test, a test piece for a bending test, and a test piece for a water absorption test were molded by an injection molding machine. Table 1 shows the evaluation results.

Example 2 Extrusion and molding were carried out in the same manner as in Example 1 except that the polyamide BAC6 obtained in Production Example 5 was used. Table 1 shows the evaluation results.

Example 3 To 100 parts by mass of the polyamide BAC6 obtained in Production Example 1, 8 parts by mass of talc (trade name: Micron White 5000A, manufactured by Hayashi Kasei Co., Ltd.) and glass fiber (Nippon Electric Glass) (Size: 10 μmφ × 3 mmL)
Was melt-kneaded at a cylinder temperature of 290 ° C. using a vent-type single screw extruder (manufactured by Nakatani Machinery Co., Ltd.), and then cooled with water to form pellets. The obtained resin composition was extruded and molded in the same manner as in Example 1. Table 1 shows the evaluation results.

Example 4 10 parts by mass of polyamide 66 (manufactured by DuPont, trade name: Zytel 101) was added to 90 parts by mass of polyamide BAC6T obtained in Production Example 6, and talc (manufactured by Hayashi Kasei Co., Ltd.) was used.
8 parts by mass of trade name: Micron White 5000A) and glass fiber (manufactured by Nippon Electric Glass Co., Ltd., size: 10 μm)
100 parts by mass of mφ × 3 mmL) were melt-kneaded at a cylinder temperature of 290 ° C. using a vent-type single screw extruder (manufactured by Nakatani Machinery Co., Ltd.), and then cooled with water and pelletized. The obtained resin composition was extruded and molded in the same manner as in Example 1. Table 1 shows the evaluation results.

Example 5 Extrusion and molding were carried out in the same manner as in Example 4 except that the polyamide BAC6 obtained in Production Example 2 was used. Table 2 shows the evaluation results.

Example 6 For 90 parts by mass of the polyamide BAC6 obtained in Production Example 3, 10 parts by mass of polyamide 66 (manufactured by Dupont, trade name: Zytel 101) and talc (manufactured by Hayashi Kasei Co., Ltd., trade name) : Micron white 5000A) and 8 parts by mass of glass fiber (manufactured by Nippon Electric Glass Co., Ltd., size: 10 μm)
100 parts by mass of (φ × 3 mmL) were blended and melt-kneaded at a cylinder temperature of 260 ° C. using a vented single-screw extruder (manufactured by Nakatani Machinery Co., Ltd.), followed by water cooling and pelletization. Using the obtained resin composition, a test piece for a tensile test, a test piece for a bending test, and a test piece for a water absorption test were molded by an injection molding machine. Table 2 shows the evaluation results.

Example 7 To 100 parts by mass of the polyamide BAC6 obtained in Production Example 1, 8 parts by mass of talc (trade name: Micron White 5000A, manufactured by Hayashi Kasei Co., Ltd.) and glass fiber (Nippon Electric Glass) (Size: 10 μmφ × 3 mmL)
Was melt-kneaded at a cylinder temperature of 290 ° C. using a vented single-screw extruder (manufactured by Nakatani Machinery Co., Ltd.), then cooled with water and pelletized. Using the obtained resin composition, an injection molding machine was extruded and molded in the same manner as in Example 1. Table 2 shows the evaluation results.

Example 8 For 100 parts by mass of the polyamide BAC6 obtained in Production Example 1, 8 parts by mass of talc (trade name: Micron White 5000A, manufactured by Hayashi Kasei Co., Ltd.) and glass fiber (Nippon Electric Glass) (Size: 10 μmφ × 3 mmL)
Was mixed and melt-kneaded at a cylinder temperature of 260 ° C. using a vented single-screw extruder (manufactured by Nakatani Machinery Co., Ltd.), followed by water cooling and pelletization. Using the obtained resin composition, an injection molding machine was extruded and molded in the same manner as in Example 1. Table 2 shows the evaluation results.

Example 9 To 100 parts by mass of the polyamide BAC6 obtained in Production Example 1, 8 parts by mass of talc, 10 parts by mass of glass fiber (manufactured by NEC Corporation, size: 10 μmφ × 3 mmL), And 5 parts by mass of montmorillonite (trade name: Orben, manufactured by Shiraishi Industry Co., Ltd.), and using a vented single-screw extruder (manufactured by Nakatani Machinery Co., Ltd.), the cylinder temperature was 2
After melt-kneading at 90 ° C., the mixture was cooled with water and pelletized. Using the obtained resin composition, an injection molding machine was extruded and molded in the same manner as in Example 1. Table 3 shows the evaluation results.

Comparative Example 1 Extrusion and molding were carried out in the same manner as in Example 6 except that the polyamide BAC6 obtained in Production Example 4 was used.
Solidification in the mold was insufficient, and the molded product could not be taken out.

Comparative Example 2 Polyamide 66 (manufactured by Ube Industries, Ltd., trade name: 2015)
B) 100 parts by mass of 100 parts of glass fiber (manufactured by NEC Corporation, size: 10 μmφ × 3 mmL)
The resulting mixture was melt-kneaded at a cylinder temperature of 290 ° C. using a vent-type single screw extruder (manufactured by Nakatani Machinery Co., Ltd.), and then cooled with water and pelletized. Using the obtained resin composition, a test piece for a tensile test using an injection molding machine,
A test piece for bending test and a test piece for water absorption test were formed. Table 3 shows the evaluation results.

[0037]

As described above, the resin composition of the present invention exhibits high strength and high elastic modulus, and has excellent rigidity retention at high temperatures, mechanical performance retention at water absorption, and durability at high temperatures. It is useful as a metal substitute material for automobile parts, mechanical parts, electric / electronic equipment parts and the like.

Table 1 Example No. Example 1 Example 2 Example 3 Example 4 Molding conditions Cylinder temperature (° C.) 290 290 290 290 Mold temperature (° C.) 140 140 150 150 Cooling time (second) 15 15 30 30 Moldability Good Good Good Good Tensile performance Tensile strength (MPa) 245 246 250 243 Elongation (%) 2.0 2.0 1.8 1.9 Flexural performance Flexural strength (MPa) 330 335 340 328 Elastic modulus (GPa) 17 .2 17.5 17.8 17.5 100 ° C. bending performance retention strength retention (%) 67.1 67.0 69.6 71.3 Modulus retention (%) 87.6 87.8 89. 2 96.6 Heat aging resistance (treated at 180 ° C. for 1000 hours) Tensile strength retention (%) 70.0 70.3 71.2 71.4 Mechanical performance retention when absorbing water (boiling) 1000 hours) tensile strength retention at medium (%) 49.8 50.0 50.6 65.0

Table 2 Example No. Example 5 Example 6 Example 7 Example 8 Molding conditions Cylinder temperature (° C.) 290 260 290 290 Mold temperature (° C.) 150 160 150 150 Cooling time (second) 30 55 30 30 Formability Good Good Good Good Tensile performance Tensile strength (MPa) 240 210 160 243 Elongation (%) 2.0 1.4 2.2 1.6 Bending performance Bending strength (MPa) 320 300 238 332 Elasticity (GPa) 16 8.8 16.5 9.3 20.4 100 ° C. Bending performance retention Strength retention (%) 66.9 64.6 67.0 70.2 Modulus retention (%) 87.1 73.8 87. 2 93.4 Heat aging resistance (treated at 180 ° C. for 1000 hours) Tensile strength retention (%) 69.8 70.3 71.4 72.0 Mechanical performance retention when absorbing water (boiling water) In 1000 hours) tensile strength retention (%) 49.0 49.2 49.5 51.7

[0040] Table 3 Example, Comparative Example No. Example 9 Comparative Example 1 Comparative Example 2 Molding conditions Cylinder temperature (° C.) 290 260 290 mold temperature (° C.) 0.99 160 100 Cooling time (sec) 30 120 15 formability good (Cannot be molded) Good Tensile performance Tensile strength (MPa) 165-200 Elongation (%) 2.1-3.0 Bending performance Bending strength (MPa) 256-310 Elastic modulus (GPa) 12.3-12.0 100 ° C bending performance retention rate Strength retention rate (%) 67.3-40.0 Modulus retention rate (%) 87.8-38.0 Heat aging resistance (treated at 180 ° C for 1000 hours) Tensile strength retention rate (%) 71.6-5.3 Mechanical Performance Retention During Water Absorption (Treatment in Boiling Water for 1000 Hours) Tensile Strength Retention (%) 50.7-35.0

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Claims (4)

[Claims] A mixture of 60 to 100 mol% of cis-1,3-bis (aminomethyl) cyclohexane and 40 to 0 mol% of trans-1,3-bis (aminomethyl) cyclohexane in a diamine component (molar%). (Total is 100 mol%) polycondensation with diamine containing 70 mol% or more of diamine and dicarboxylic acid containing 70 mol% or more of α, ω-linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms in dicarboxylic acid component. Resin (A) 70 to 100% by mass
And an inorganic filler with respect to 100 parts by mass of a mixed resin (C) composed of 30 to 0% by mass of the thermoplastic resin (B) other than the polyamide resin (A) (total of 100% by mass). A polyamide resin composition comprising 10 to 150 parts by mass of 2. The polyamide resin composition according to claim 1, wherein the inorganic filler is at least one of a fibrous filler, a powdery filler, and a flake-like filler. 3. The polyamide resin composition according to claim 2, wherein the fibrous filler is at least one of glass fiber, potassium titanate, carbon fiber and alumina fiber. 4. A polyamide M obtained by polycondensing a thermoplastic resin (B) with meta-xylylenediamine and adipic acid.
XD6, polyamide MP6, polyamide 6, polyamide 66, polyamide 4 obtained by polycondensing meta-xylylenediamine with para-xylylenediamine and adipic acid
6. The polyamide resin composition according to claim 1, which is a thermoplastic resin (B) containing at least one resin selected from polyethylene terephthalate and polybutylene terephthalate.