JPH09221590A - Polyamide resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyamide resin compsn. excellent in sound-insulating properties. SOLUTION: This compsn. mainly comprises a copolyamide resin and a granular high-specific-gravity inorg. filler. The resin has amide bonds (X) which are formed from a 4-14C aliph. diamine and terephthalic acid and of which the ratios of the content observed to that calculated of amide bonds satisfy the relations: 0.9<=[XY]obs. /[XY]calcd. <=1.1 and 0.9<=[XX]obs. /[XX]calcd. <=1.1 (wherein Y is an amide bond other than X; [XY] is a content of adjacent X-Y bonds; calcd. means a value calculated; and obs. means a value observed). The half-crystallization time of the resin satisfies the relation: 4.4-0.1(Tm-T)<=logt1/2 <=5.5-0.1(Tm-T) [wherein t1/2 is the half-crystallization time (sec); Tm is the m.p. ( deg.C) of the resin; and T is the temp. ( deg.C) at which t1/2 is measured].

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, and in particular, it is a filler excellent in moldability, heat resistance, chemical resistance, mechanical properties and the like and excellent in sound insulation. The present invention relates to a reinforced polyamide resin composition.

[0002]

2. Description of the Related Art Polyamides are widely used in the fields of automobiles, electric / electronic fields, etc. by utilizing their excellent properties as engineering plastics. Along with weight reduction and miniaturization / complexity of parts in these fields, polyamide materials having excellent heat resistance, chemical resistance, mechanical strength, and moldability have been used as various parts materials. In particular, since the partially aromatic polyamide has excellent heat resistance and chemical resistance, its use for the above-mentioned parts is being promoted.

On the other hand, in recent years, measures against noise as an environmental problem,
The issue of noise reduction is important from the standpoint of quietness and comfort in terms of commerciality, and quietness and comfort are required not only in building materials but also in automobiles, home appliances, office automation equipment, etc. It is becoming important how to suppress the noise generated from the vehicle. Therefore, sound insulating materials are considered important, and inorganic and metallic materials are often used as such materials. However, these inorganic and metallic materials are inferior in moldability to resin materials, and as a result, the degree of freedom in design is limited. From such a situation and the characteristic which the above-mentioned partially aromatic polyamide essentially has,
A polyamide resin composition having high sound insulation has been demanded.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a polyamide resin composition having excellent heat resistance and chemical resistance and having excellent sound insulation.

[0005]

In view of the above circumstances, the inventors of the present invention have conducted extensive studies to solve the above problems, and as a result, have determined that a copolymerized polyamide resin having a specific composition and a chain distribution should have a specific gravity. The present invention has been achieved by paying attention to a polyamide resin composition containing the inorganic filler. That is, the present invention "(a) has an amide bond formed from an aliphatic diamine having 4 to 14 carbon atoms and terephthalic acid, and the chain distribution ratio of the amide bond satisfies (A) and (B). A polyamide resin composition, further comprising a copolyamide having a semi-crystallization time satisfying the formula (C), and (b) a particulate high specific gravity inorganic / inorganic filler.

[0006] _{0.9 ≦ [XY] obs. /} [XY] calcd. ≦ 1.1 (A) 0.9 ≦ [XX] obs. / [XX] calcd. ≦ 1.1 (B) [wherein , X is an amide bond formed from an aliphatic diamine having 14 to 14 carbon atoms and terephthalic acid, and Y means an amide bond other than X. [XY] is the ratio of X and Y adjacent to all amide bonds in the polymer structure, and [XX] is the ratio of X and X adjacent to all amide bonds in the polymer structure. Indicates a percentage. [XY] _{calcd. And} [XX] _{calcd. Are} the respective values of [XY] and [XX] in which the amide bonds of X and Y are calculated as a statistically random chain distribution, and [XY] _{obs. And} [XX] _obs. Is measured from the copolyamide [X]
It is each value of Y] and [XX]. ] 4.4-0.1 (Tm-T) ≤ logt _1/2 ≤ 5.5-
0.1 (Tm-T) (C) [where t _1/2 is the half-crystallization time (seconds), Tm is the melting point (° C.) of the copolyamide)
And T is the measurement temperature (° C.) of the half crystallization time. ] ”
It consists of

[0007]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The details of the present invention will be described below.

The copolyamide of the present invention has 4 carbon atoms.
It is a copolyamide having an amide bond consisting of an aliphatic diamine of No. 14 to terephthalic acid. The melting point of the copolyamide of the present invention is preferably 260 to 320.
C., more preferably 270 to 310.degree. This range is preferable, when the melting point is low, it is not possible to obtain a resin having heat resistance which is the object of the present invention, and when the melting point is too low, a high temperature is required for processing the resin, This is because problems such as foaming due to the thermal decomposition reaction occur.

Specific examples of the aliphatic diamine having 4 to 14 carbon atoms include 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,5-diamino-2-methylpentane, 1,7-diaminoheptane,
1,8-diaminooctane, 1,9-diaminononane,
It is an aliphatic alkylenediamine such as 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, 1,13-diaminotridecane and 1,14-diaminotetradecane. Of these aliphatic diamines, long-chain aliphatic diamines having a large number of carbon atoms are preferably used in order to reduce the water absorption of the obtained polyamide. These aliphatic diamines can be used alone or in combination of two or more. Particularly, as the aliphatic diamine component having 4 to 14 carbon atoms, that having 6 carbon atoms, that is, 1,6-diaminohexane and 1,5-diamino-2-methylpentane are heat-resistant of the copolymerized polyamide produced, It is preferably used because it has an excellent balance of crystallinity.

In the copolyamide of the present invention, the starting material for the amide structural unit forming the remaining portion of the terephthalamide structural unit is, for example, ε-caprolactam, ζ-enanetetractam, η-capryllactam,
Lactams such as ω-laurolactam, the above diamines, 1,15-diaminopentadecane, 1,16-diaminohexadecane, 1,17-diaminoheptadecane,
15 to 1 carbon atoms such as 1,18-diaminooctadecane
8 aromatic alkylenediamines, aromatic diamines such as phenylenediamine, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid , Pracilinic acid, tetradecanedioic acid, pentadecanedioic acid, octadecanedioic acid, and other aliphatic dicarboxylic acids having 2 to 18 carbon atoms, and aromatic dicarboxylic acids such as isophthalic acid. Among the amide structural units derived from these, caproamide, hexamethylene adipamide and hexamethylene isophthalamide are particularly preferably used alone or in combination in the present invention.

When 1,6-diaminohexane is used as the aliphatic diamine component of the terephthalic acid amide structural unit, the structural unit (I)

Embedded image (Hexamethylene terephthalamide unit (hereinafter referred to as 6T)), and at least one structural unit selected from Yuji structural units (II) to (IV),

[Chemical 6] (Hexamethylene adipamide unit (hereinafter referred to as 66)),

Embedded image (Hexamethylene isophthalamide unit (hereinafter referred to as 6I)),

Embedded image A 6T-containing copolyamide having a repeating unit consisting of (caproamide unit (hereinafter referred to as 6)) is preferable.

In the above 6T-containing copolyamide,
In the case of 6T / 6I, the two-component copolymer composition ratio is preferably 45 / 55-80 / 20 in terms of weight ratio in the raw material stage,
Preferably 55/45 to 80/20, more preferably 6
It is in the range of 0/40 to 75/25. When the copolymerization composition is 6T / 66, the copolymerization ratio is 20/80 to 80/20, preferably 30 by weight in the raw material stage.
/ 70 to 70/30, more preferably 30/70 to 60
The range is / 40. When the copolymer composition is 6T / 6, the copolymerization ratio in the raw material stage is 40/60 by weight.
To 90/10, preferably 55/45 to 85/15, and more preferably 60/40 to 80/20. The copolymerization ratio of these 6T-containing copolyamides is preferably selected to give a crystalline copolyamide with a polymer melting point in the range of 260 ° C to 320 ° C. 6T / 6I, 6T
/ 66, and 6T / 6 by weight have a copolymerization composition ratio of 45/55, 20/80, 4 in the raw material stage, respectively.
When the amount of 6T is smaller than 0/60, the sound insulation is not improved so much, the heat resistance such as the heat distortion temperature is lowered due to the decrease of the polymer melting point, and the water absorption is increased due to the decrease of the amount of 6T. Also, 6T / 6I, 6T / 66, and 6T
If the copolymerization composition ratio in the raw material stage by the weight of T / 6 is 6T more than 80/20, 80/20, 90/10, the sound insulation is greatly improved, the polymer melting point is increased, and the heat resistance is improved. However, the processing temperature becomes high and the polymer is thermally decomposed, which is not preferable. Of these copolyamides, 6T / 66 is particularly preferable from the viewpoint of crystallization characteristics, and the copolymerization ratio is 35/65 to 60/40 by weight.
Particularly, the copolyamide in the range of 37/63 to 50/50 can realize excellent properties.

The 6T-containing polyamide of the present invention may be a copolymer of three or more components, and specific examples of preferable copolymerization composition are 6T / 66 / 6I,
Mention may be made of compositions containing 6T / 66 such as 6T / 66/6. 6 in these copolyamides
The T / 66 component is preferably 50% by weight or more,
Further, it is preferably 60% by weight or more, particularly preferably 70% by weight or more, and further preferably 95% by weight or more.

Further, as the aliphatic diamine having a terephthalic acid amide structural unit, a diamine having 12 carbon atoms is also preferably used, and in that case (hereinafter, the bonding unit with terephthalic acid is 12).
12T-containing polyamide in which repeating units such as hexamethylene adipamide unit, dodecamethylene adipamide unit, hexamethylene isophthalamide unit, dodecamethylene isophthalamide unit, caproamide unit are copolymerized is preferably used To be

The copolymerized polyamide of the present invention is a substantially random copolymer, and the chain distribution abundance ratio of amide bonds satisfies the formulas (A) and (B). _{0.9 ≦ [XY] obs. /} [XY] calcd. ≦ 1.1 (A) 0.9 ≦ [XX] obs. / [XX] calcd. ≦ 1.1 (B) [wherein, X is An amide structural unit formed from an aliphatic diamine having 4 to 14 carbon atoms and terephthalic acid, and Y is X
Means an amide structural unit other than. When there are two or more kinds of amide structural units formed from an aliphatic diamine having 4 to 14 carbon atoms and terephthalic acid, the one serving as the main component is defined as X. For example, in the case of 6T / 12T / 66 = 50/5/45% by weight, the 6T component is X and 12T and 66 are Y. [XY] is the proportion of X and Y adjacent to each other in the polymer structure, and [XX] is the proportion of X and X adjacent to the total number of structural units in the polymer structure. [XY] _{calcd. And} [XX] _{calcd. Are} the respective values of [XY] and [XX] in which the structural units of X and Y are calculated as a statistically random chain distribution, and [XY] _{obs. And} [XX] _obs. Are respective values of [XY] and [XX] actually measured from the copolyamide. The chain distribution abundance ratio of structural units preferably satisfies the formulas (D) and (E). _{0.95 ≦ [XY] obs. /} [XY] calcd. ≦ 1.05 (D) 0.95 ≦ [XX] obs. / [XX] calcd. ≦ 1.05 (E)

When the chain distribution abundance ratio of the structural units is outside the ranges of the formulas (A) and (B), the block property is strong, so that the random copolymer has excellent mechanical properties, for example, balance between tensile strength and elongation, In addition, the characteristics such as heat distortion temperature are impaired.

The copolymerized polyamide of the present invention has a semi-crystallization time satisfying the formula (C). 4.4-0.1 (Tm-T) ≤ logt _1/2 ≤ 5.5-0.1 (Tm-T) (C) [where t _1/2 is the half crystallization time (seconds) and Tm is the copolyamide. It is a melting point (° C.), T is a measurement temperature (° C.) of the half-crystallization time, and means a range from a temperature 35 ° C. lower to a temperature 25 ° C. lower than the melting point of the copolyamide. Further, it is particularly preferable that the half-crystallization time of the copolyamide satisfies the formula (F). 4.6-0.1 (Tm-T) ≤ logt _1/2 ≤ 5.3-0.1 (Tm-T) (F) Where logt _1/2 is less than 4.4-0.1 (Tm-T) The toughness is insufficient and 5.5-0.
If it exceeds 1 (Tm-T), the crystallization time is long and molding in a fast molding cycle (particularly mold releasability during molding) becomes difficult, so the above range is used. As the temperature for measuring the half crystallization time, a temperature lower than the melting point of the copolyamide by 30 ° C. is preferably used.

The copolyamide used in the present invention is
It can be manufactured by the following method. For example, it is a two-stage polymerization method in which a primary condensate is formed under specific conditions and then melt-extruded by a twin-screw extruder having a specific screw segment to increase the degree of polymerization. First, the method for forming the primary condensate will be described.

The primary condensate is prepared by charging an aqueous solution of a salt containing a monomer, a diamine and a dicarboxylic acid, which gives the above-mentioned copolymerization composition, into a pressure polymerization tank or the like, and polymerizing the solution using water as a solvent under stirring conditions. Obtained by reacting. The concentration of the raw material charged in the solution is 5% by weight or more, preferably 15% by weight or more and 90% by weight or less, preferably 85% by weight or less.

The primary condensate is formed by raising the temperature and pressure under stirring conditions. The polymerization temperature is raised and controlled within a range from the temperature after the charging or after the concentration step described below, which is performed as necessary, to the highest reached temperature. Further, the polymerization pressure is controlled below the maximum ultimate pressure according to the progress of polymerization. The highest temperature and the highest pressure do not have to be at the end of the polymerization and may be at any time until the completion of the polymerization.

In the polymerization of the above primary condensate, the maximum ultimate pressure is 5 kg / cm ² (493.4615 kPa) -G.
23 kg / cm ² (2269.9229 kPa)-
It may be less than G, but is preferably 10 kg / cm.
² (986.923 kPa) -G or more, 22 kg / cm
² (2171.2306 kPa) -G or less, preferably 20 kg / cm ² (1973.846 kPa) -G or less. When it is 23 kg / cm ² -G or more, the water content in the reaction system becomes high, so that there is a problem that the increase in the degree of polymerization is poor and the reaction rate to the primary condensate is insufficient. If the maximum ultimate pressure is less than 5 kg / cm ² -G, there is a risk that the primary condensate will precipitate in the polymerization tank.

The maximum temperature reached at the time of forming the primary condensate is more than 260 ° C. and 330 ° C. or less, but 260 ° C. when the melting point of the target copolyamide is less than 280 ° C.
The temperature is generally higher than 300 ° C and lower than 300 ° C, preferably lower than 290 ° C. The melting point of polyamide is 280 to 320 ° C.
In such a case, the melting point of the copolyamide is less than minus 20 ° C, preferably not less than minus 15 ° C and not more than plus 10 ° C, preferably not more than plus 5 ° C. If the maximum temperature reached is 260 ° C. or lower, not only is it insufficient to increase the degree of polymerization of the primary condensate,
Due to the difference in the reactivity of each of the copolymerization components, a primary condensate having an extremely high chain distribution of chain distribution is obtained, and even if the degree of polymerization of this is increased, the obtained polymer still has the block property. On the other hand, if the maximum temperature reached exceeds 330 ° C., the thermal history of the copolyamide becomes too large and various properties are deteriorated, which is not preferable.

Further, after the primary condensate is formed, the discharge is carried out, but the discharge is preferably carried out under the pressure of steam. The steam pressure may be equal to or lower than the maximum ultimate pressure in the formation of the primary condensate, but the maximum ultimate pressure minus 10 k.
It is preferably g / cm ² (986.923 kPa) -G or more and not more than the ultimate pressure. The steam pressure is preferably maintained during discharge, and it is preferable to supply water or steam into the polymerization tank and maintain a constant steam pressure during discharge, or discharge while increasing the pressure. When water, preferably ion-exchanged water, is supplied from the outside of the system to the polymerization tank by a metering pump, it is preferable to preheat and supply the water via a heat exchanger. The heating temperature is preferably 100
℃ or more, more preferably 150 ℃ or more. It is more preferable that the heating temperature is the saturated steam temperature of the pressure in the polymerization tank in order to maintain the stability of the polymerization state. When steam is supplied into the polymerization tank from outside the system, the pressure of the steam generating boiler must be higher than the pressure in the polymerization tank. The maximum temperature reached during discharge is -10.
It is preferable that the temperature is maintained at not less than 0 ° C and not more than the highest reached temperature.

The formation and discharge of the primary condensate according to the present invention may be within the ranges of the highest temperature and the highest pressure shown above. As shown in Japanese Patent Application Laid-Open No. 5-170895, it is known that there exists a region where a primary condensate precipitates and solidifies under conditions of high temperature and low pressure. It is difficult for the reaction to proceed sufficiently when polymerization is performed at high pressure and low temperature while avoiding such a precipitation-solidified region. In the present invention, the primary condensate can be obtained under higher temperature and lower pressure than in the past by terminating the reaction before the primary condensate is precipitated even under the condition that it may precipitate and solidify. The temperature and pressure regions of precipitation and solidification are determined by the composition of polyamide, temperature, pressure and time. For example, in the formation of the primary condensate at 66 / 6T = 50/50% by weight, room temperature, atmospheric pressure to 265 ° C., 27
If the temperature is rapidly raised to a condition of kg / cm ² (2664.6921 kPa) -G and the condition is maintained, it will be about 5
After a lapse of time, it begins to precipitate and solidify. Also, 265 ° C, 2
If the temperature is rapidly raised up to the condition of ² kg / cm ² (2171.2306 kPa) -G and the condition is maintained, it will be about 2
After a lapse of time, it begins to precipitate and solidify. Even under such conditions, if the polymerization is completed and discharged in less than 2 hours from the start of holding the conditions, precipitation solidification does not become a problem. As described above, even in the precipitation-solidified region, the reaction can be performed if the time required for precipitation is not reached. The time in the region of precipitation solidification is preferably 0.1 hours shorter than the time it takes to start precipitation, further 0.2 hours shorter, or even 0.5 hours shorter. Further, the total polymerization time (polymerization and discharge) is 10 hours or less, preferably 7 hours or less, more preferably 5 hours or less, and particularly preferably 4 hours or less.

Further, as a method for avoiding precipitation and solidification during polymerization, it is effective to stir the side surface of the polymerization tank efficiently. The distance between the stirring blade and the polymerization tank is preferably 10% or less, and more preferably 5% or less, with respect to the radius of the polymerization tank. Where the distance between the stirring blade and the polymerization tank is 10% or less with respect to the radius of the polymerization tank, it is preferable that the blade is rotating and occupy 70% or more of the side surface below the liquid surface of the polymerization tank. It is preferably 80% or more and less than 100%. Precipitation and solidification can be delayed by efficiently stirring the side surface of the polymerization tank, which easily reacts by heating.

If necessary, a salt adjusting step and / or a concentrating step may be carried out before the polymerization of the primary condensate. The salt tone is a step of producing a salt from a dicarboxylic acid component and a diamine component, and is in the range of the pH of the neutralization point of the salt of ± 0.5, and further, of the pH of the neutralization point of the salt of ± 0.3. It is preferable to adjust the range. Concentration is the value of the concentration of the raw material charging solution plus 2 to 90% by weight, more preferably plus 5
It is preferred to concentrate to a concentration of ~ 80% by weight. The temperature of the concentration step is preferably 90 to 220 ° C, more preferably 100 to 210 ° C, and 130 to 20 ° C.
0 ° C. is particularly preferred. Pressure in the concentration step is 0 to 20 kg /
cm ² (0 to 1973.846 kPa) -G, preferably 1 to 10 kg / cm ² (9.86923 to 98.69).
23 kPa) -G. Usually, the concentration pressure is controlled below the pressure for forming the primary condensate. Further, in order to accelerate the concentration, it is possible to perform the forced discharge of the solvent by, for example, a nitrogen stream. The concentration step is effective in shortening the polymerization time.

The relative viscosity of a 1% sulfuric acid solution of the primary condensate at 25 ° C. (JIS-K6810 method) is 1.15.
Is preferably 2.5 to 2.5, more preferably 1.2 or more, preferably 1.3 or more, more preferably 1.4 or more, 2.3 or less, preferably 2.0 or less, more preferably 1. It is 8 or less. When the relative viscosity is less than 1.15,
A primary condensate having an extremely high blocking property is likely to be formed, and it is necessary to prolong the polymerization time for increasing the degree of polymerization and to raise the temperature, so that the thermal history given to the copolyamide becomes large. On the other hand, if the relative viscosity exceeds 2.5, the melt viscosity of the primary condensate becomes too high, which causes ejection failure during ejection after the formation of the primary condensate, which is not preferable. The water content of the primary condensate is 20% by weight or less, preferably 10% by weight or less, and more preferably 5% by weight or less. If it exceeds 20% by weight, it becomes difficult to increase the degree of polymerization. The water content can be controlled by discharging the primary condensate into water and then drying it, or by cooling the discharged high temperature primary condensate with cooling water and evaporating it using the heat of the primary condensate. It is generally controlled. In addition, the primary condensate is preferably crushed to an appropriate size before increasing the degree of polymerization.

As an example of a suitable apparatus for producing the primary condensate, a batch reaction tank or a batch reaction apparatus of 1 to 3 tank type in series can be mentioned.

Next, a method of melt-extruding the primary condensate to increase the degree of polymerization will be described.

The extruder used in the step of increasing the degree of polymerization of the primary condensate in the present invention is a twin-screw extruder including a screw segment having L / D of 2 or less. Here, L represents the length of the screw segment, and D represents the outer diameter, that is, the outermost diameter when the screw segment is rotated. By using a short screw segment having L / D of 2 or less, the state of the polymer in the cylinder can be finely controlled, and a high quality copolyamide can be obtained. In particular, for the purpose of making the copolyamide a random structure without undergoing thermal deterioration, it is sufficiently kneaded while controlling the state in the cylinder with a short L / D screw segment, and vacuum degassing is carried out to quickly achieve high polymerization. It is necessary to be refined. L
The ratio of the screw segment having / D of 2 or less is preferably 5% or more and 100% or less, further 30% or more, and further preferably 50% or more with respect to the entire length of the screw.

The screw segments constituting the screw of the twin-screw extruder include a resin feeding segment and a mixing segment, and a forward full flight segment is preferably used as the resin feeding segment. Mixing segments include rotor, notched rotor, forward kneading, orthogonal kneading, reverse kneading, kneading neutral, gear kneading, pineapple kneading, twist kneading, reverse full flight, and notch flight. It is preferable to use one kind or a combination of two or more kinds. Further, as other segments, there are a seal ring, a torpedo ring, etc., and it is effective to use them appropriately. The forward full flight segment includes all of the forward full flight structures, and for example, those having different flight pitches, those having a sharp flight or those having a wide flight can also be used. Further, from the viewpoint of controlling the polymerization reaction, it is effective to use one or more, preferably two or more reverse full flight segments. The segments other than the forward full flight may be arranged in one part or divided into some parts. By using a segment other than the normal full flight, the polymerization reaction can be effectively promoted. The L / D of the forward full flight and the segment other than the forward full flight are selected so as to match the ratio of the screw segment having the L / D of 2 or less described above, but the L / D of the segment other than the forward full flight is 2 The following segments are preferably included, and L / D is 0.2 or more.
It is even more preferred that it contains 8 or less.

The total length of the segments other than the forward full flight is 0% or more, further 3% or more, further 5% or more, while 70% or less, further 50% or less, or further, with respect to the entire length of the screw. Is preferably used in the range of 45% or less. The number of threads of the screw may be any, but 1, 2, 3 threads are preferable, and 2 threads are particularly preferable.
The groove type may be either a shallow groove or a deep groove, but a deep groove is more preferable.

The twin-screw extruder according to the present invention may rotate either in the same direction or in different directions, but it is preferable that the twin-screw extruder rotates in the same direction from the viewpoint of easy control of polymerization conditions.
The rotation speed is 50 rpm or more, preferably 70 rpm or more,
It is 800 rpm or less, preferably 500 rpm or less. A larger rotation number is better for shearing and stirring, and further for renewing the resin surface for degassing the condensation water, but if it is too large, the shear heat generation will become too large and the resin will be deteriorated. It is preferable to select the number of rotations.

The L / D of the entire screw of the twin-screw extruder used in the present invention is not particularly limited, but is usually set to 10 or more, preferably 15 or more and 100 or less, preferably 70 or less. . If it is smaller than 10 or larger than 100, it becomes difficult to proceed the polymerization stably.

Next, the extrusion conditions for increasing the degree of polymerization by the extruder in the present invention will be shown.

In the present invention, the degree of polymerization is increased by the extruder by using the above-mentioned twin-screw extruder while performing vacuum deaeration using the formula (G).
It is preferable to carry out within the range of the residence time that satisfies t ≦ 5000 × Δηr / (TR −280) (G) (t: residence time (seconds)) (Δηr: amount of change in relative viscosity due to high polymerization degree) (TR: maximum arrival of resin at high polymerization degree) Temperature (° C.) Further, it is preferable to increase the degree of polymerization within the range of the residence time that satisfies the formula (H). 20.ltoreq.t.ltoreq.4000.times..DELTA..eta.r / (TR.sub.-280) (H) Generally, the residence time of the extruder has a distribution, but here it means the shortest residence time in the extruder. It is preferable that the residence time is within the above range, because if excessive heat is applied at the time of increasing the polymerization degree, the physical properties are deteriorated due to thermal deterioration, and if it is too short, the polymerization degree does not increase. The amount of change in relative viscosity (Δηr) due to the increase in the degree of polymerization is preferably 0.2 or more, more preferably 0.5 or more. When the polymerization degree is high, the maximum temperature the resin reaches is higher than the melting point, preferably the melting point plus 1.
The temperature is 0 ° C or higher and 350 ° C or lower, preferably 340 ° C or lower. If the maximum temperature is too high, the thermal load is large even if the residence time is short, which is not preferable. In particular, it is important to keep the temperature at 350 ° C. or lower in order to prevent thermal decomposition and thermal deterioration of the polymer.

In the present invention, vacuum deaeration at the time of increasing the degree of polymerization by the extruder is carried out from one or more vents,
The shape of the vent may be any. The vacuum deaeration is for shifting the chemical equilibrium by removing the water generated by the polymerization, and it is important to perform it efficiently so as to increase the degree of polymerization within a certain residence time. Therefore, the degree of vacuum of the vent is -500 mmHg (-66.6).
61 kPa) or less, preferably -600 mmHg (-7
9.9932 kPa) or less. Further, in addition to the above-described vent having the degree of vacuum, a vent having a low degree of vacuum or an atmosphere vent may be used in combination.

The degree of polymerization of the copolyamide used in the present invention is not particularly limited and is usually 2% of that of a 1% sulfuric acid solution.
Those having a relative viscosity (ηr) at 5 ° C. in the range of 1.8 to 5.0 are practical, and those having a relative viscosity in the range of 2.0 to 3.5 are preferable.

In ordinary polyamide polymerization, it is common to charge the raw materials so that the total amount of carboxyl groups and the total amount of amino groups contained in the monomer and the dicarboxylic acid / diamine salt are equal. It is also possible to prepare a polyamide having a large amount of terminal carboxyl groups or terminal amino groups by adding an excess of dicarboxylic acid component or diamine component when charging the raw materials. Further, in the polymerization reaction of the present invention, a polymerization degree adjusting agent can be added in order to facilitate the adjustment of the polymerization degree of the polyamide and the adjustment of the polymerization degree when the polymerization degree is increased. As the polymerization degree regulator, usually, a monoamine compound and a monocarboxylic acid compound are used, preferably acetic acid,
Benzoic acid, stearic acid, particularly preferably acetic acid,
Benzoic acid.

A phosphorus-based catalyst can be used for the polymerization of the copolyamide used in the present invention. For example, hypophosphite, phosphate, hypophosphorous acid, phosphoric acid, phosphoric acid ester, polymetaphosphoric acid, polyphosphoric acid, phosphine oxides, phosphonium halogen compounds and the like are preferable, hypophosphite, phosphate , Hypophosphorous acid and phosphoric acid are particularly preferably used. Specific examples of the hypophosphite, for example, sodium hypophosphite, potassium hypophosphite, calcium hypophosphite, magnesium hypophosphite, aluminum hypophosphite, vanadium hypophosphite,
Manganese hypophosphite, zinc hypophosphite, lead hypophosphite,
Nickel hypophosphite, cobalt hypophosphite, ammonium hypophosphite and the like are preferred, sodium hypophosphite,
Particularly preferred are potassium hypophosphite, calcium hypophosphite and magnesium hypophosphite. Examples of the phosphate include sodium phosphate, potassium phosphate, potassium dihydrogen phosphate, calcium phosphate, vanadium phosphate,
Magnesium phosphate, manganese phosphate, lead phosphate, nickel phosphate, cobalt phosphate, ammonium phosphate, diammonium hydrogen phosphate and the like are preferable. Examples of the phosphoric acid ester include ethyl octadecyl phosphate. As the polymetaphosphoric acids, for example,
Examples include sodium trimetaphosphate, sodium pentametaphosphate, sodium hexametaphosphate, polymetaphosphoric acid, and the like. Examples of polyphosphoric acids include sodium tetrapolyphosphate and the like. Examples of the phosphine oxides include hexamethylphosphoramide. The amount of the phosphorus-based catalyst added is 0.0001 to 100 parts by weight of the polyamide.
5 parts by weight is preferable, and 0.001 to 1 part by weight is more preferable. Further, the addition time may be any time until the completion of the high degree of polymerization, but it is preferably from the time of charging the raw materials to the completion of the polymerization of the primary condensate. Moreover, you may add many times. Further, different phosphorus-based catalysts may be added in combination.

The polyamide resin composition of the present invention contains a particulate high specific gravity inorganic filler as the component (b). The copolymerized polyamide, that is, the particulate high specific gravity inorganic filler which is the component (b) with respect to 100 parts by weight of the component (a) is 0.1
It is preferably not less than 5 parts by weight, more preferably not less than 5 parts by weight, especially not less than 10 parts by weight, while not more than 200 parts by weight, more preferably not more than 100 parts by weight, particularly preferably not more than 50 parts by weight. When the content of the filler is small, the sound insulation is not improved, and when the content of the filler is too large, moldability is deteriorated. The specific gravity of the particulate high specific gravity inorganic filler is preferably 2.0 or more,
Further, it is preferably 4.0 or more. If the specific gravity of the filler is small, the effect on the sound insulation is small even if the content is increased, and it is important to use the filler having a specific gravity to a certain degree in order to improve the sound insulation. As the particulate high specific gravity inorganic filler, graphite, barium sulfate, magnesium sulfate, calcium carbonate, magnesium carbonate, antimony oxide, titanium oxide, aluminum oxide, zinc oxide, iron oxide, zinc sulfide, zinc, lead, nickel, aluminum,
Examples thereof include powdery substances such as copper, iron and stainless steel (the fine structure may be plate-like or needle-like), among which antimony trioxide, iron, copper, zinc, lead and the like can be preferably used. These particulate high specific gravity inorganic fillers may be used alone or in combination with different fillers.

The resin composition of the present invention may further contain a known fibrous filler for the purpose of improving mechanical strength. The amount of the fibrous filler is preferably 1 to 100 parts by weight, and more preferably 1 to 100 parts by weight of the copolyamide from the viewpoint of mechanical strength and molding processability.
0 to 70 parts by weight is preferable. Specific examples of the fibrous filler include glass fiber, carbon fiber, aramid fiber, potassium titanate fiber and the like. These fibrous fillers may be used alone or in combination with different fillers.

The method of blending the filler in the polyamide resin composition of the present invention is not particularly limited, and any known method can be used. Specific examples of the compounding method include a method of dry blending a filler to pellets of copolyamide and kneading with an extruder, or a method of directly melt kneading in a molding machine. In the step of increasing the degree of polymerization of the copolyamide by an extruder,
A method of adding the filler from the middle of the extruder is also possible.

The polyamide resin composition of the present invention contains a catalyst, a heat resistance stabilizer, a weather resistance stabilizer, a plasticizer, if necessary, at the stage of polymerization of primary condensate, high degree of polymerization of melt, compound or molding process. Agents, release agents, lubricants, crystal nucleating agents,
Pigments, dyes, other polymers and the like can be added.
These additives include heat-resistant stabilizers (hindered phenol-based, hydroquinone-based, phosphite-based and substitution products thereof, copper iodide, potassium iodide, etc.), weather-resistant stabilizers (resorcinol-based, salicylate-based, benzoic acid-based Triazole-based, benzophenone-based, hindered amine-based), release agents and lubricants (montanic acid and its metal salts, their esters, their half esters, stearyl alcohol, stearamide, various bisamides, bisurea and polyethylene wax, etc.), pigments (sulfurized) Cadmium, phthalocyanine, carbon black, etc.), and dyes (such as nigrosine), other polymers (other polyamides, polyesters, polycarbonates, polyphenylene ethers, polyphenylene sulfides, liquid crystal polymers,
Polyethersulfone, ABS resin, SAN resin, polystyrene, acrylic resin, polyethylene, polypropylene, ethylene / α-olefin copolymer, ionomer resin, SBS, SEBS, etc.).

[0045]

The present invention will be described in more detail with reference to the following examples. Various properties in the examples and comparative examples were measured by the following methods. 1) Melting point (Tm) Using DSC (PERKIN-ELMER7 type), samples 8 to 10
Let (T1) be the temperature at which the maximum value of the melting curve obtained by measuring mg at a temperature rising rate of 20 ° C./min. Sample 8
-10 mg is heated at a heating rate of 20 ° C / min to obtain T1 +2
Hold at 0 ° C. for 5 minutes, then cool to 30 ° C. at a cooling rate of 20 ° C./min, hold at 30 ° C. for 5 minutes, then repeat 2
Heat to T1 + 20 ° C. at a heating rate of 0 ° C./min.
The maximum value of the melting curve at this time was defined as the melting point (Tm). 2) Relative viscosity According to JIS K6810, 1 g of the sample was dissolved in 100 ml of 98% concentrated sulfuric acid, and the relative viscosity at 25 ° C was measured. Hereinafter, the relative viscosity is abbreviated as ηr. 3) Semi-crystallization time Using DSC (PERKIN-ELMER7 type), samples 8-10
melting point (Tm) plus 2 at a temperature rising rate of 20 ° C./min
After raising the temperature to 0 ° C and holding it for 5 minutes, it is rapidly cooled to the measurement temperature (T) of the half-crystallization time, and the time (seconds) to the endothermic peak
_Was measured as t _1/2 . 4) Chain distribution abundance ratio of structural units Using JNR-GSX400, FT-NMR (JEOL Ltd.), 100 mg of a sample was dissolved in 0.7 ml of a hexafluoroisopropanol / deuterated benzene mixed solution to obtain 13 C-NMR. Was measured. The measurement sensitivity was maximized, and the abundance ratio was quantified by converting from the intensity of the distribution of absorption due to the carbonyl carbon of each amide bond and, if necessary, the methylene carbon adjacent to the carbonyl carbon. For example, in the case of 6T / 66, the ratio of adjacent 6T and 6T (corresponding to [XX] _obs .) And the ratio of adjacent 6T and 66 (corresponding to [XY] _obs. ) _Were measured. [X
X] _{calcd. And} [XY] _{calcd. Are} statistically random chain distributions and calculate the ratios of adjoining each other, and from these values the chain distribution existence ratio [XX] _obs./[XX ]
_calcd. and _{[XY] obs. / [XY} ] calcd. was calculated.

Each embodiment will be described below. The reaction conditions and characteristics are shown in Tables 1 and 2, and the addition amount of monocarboxylic acid is shown therein. This amount means the amount (double mole) with respect to the number of moles of the monomer of the constituent component and the total number of moles of the dicarboxylic acid component unit and the diamine component unit of the salt.

5) Sound insulation The random noise generated from the sound source in the acoustic box was measured using a 2-channel FFT analyzer type 2034 and an acoustic intensity probe 3548 (both B & K). The acoustic intensities when the acoustic box opening is opened and when a sample molded piece (150 mm × 100 mm × 3 mm square plate) is set in the opening are measured outside the acoustic box, and the sound of the sample molded piece is measured from them. The transmission loss (dB) is calculated. The larger this sound transmission loss, the more difficult it is for sound to transmit.

Example 1 Hexamethylene ammonium adipate (66 salt), terephthalic acid, hexamethylene diamine, benzoic acid, ion-exchanged water and sodium hypophosphite were added in batches at the composition and concentration shown in Table 1. Charged in a pressure polymerization tank, concentration 85
Concentrated to wt%. Maximum temperature reached 2 with stirring
The temperature was raised to 90 ° C and the maximum polymerization pressure was 20 kg / cm ² (19
73.846 kPa) -G. For discharge, ion-exchanged water was supplied at a rate of 3 l / hr, and the steam pressure was 20 kg / c.
while keeping in m ² -G, it was carried out over a period of 0.1 hours. The viscosity of this primary condensate was ηr = 1.6, and the melting point was 297 ° C.

The obtained primary condensate was heated at 100 ° C. for 24 hours.
After vacuum drying, the degree of polymerization was increased by an extruder. The extruder used was a 30 mmφ vent type twin-screw extruder (L / D = 4
5.5), rotating in the same direction, deep groove type. Residence time 85 seconds, L / D = 5 long vent to vacuum -7
00 mmHg (-93.3254 kPa), L / D =
Vacuum degree of -700 mmHg from 1.8 short vent
The mixture was degassed at (-93.3254 kPa), melted to a high degree of polymerization at a screw rotation speed of 150 rpm and a maximum resin temperature of 325 ° C. to obtain white pellets having a relative viscosity ηr = 2.5 and a melting point of 305 ° C. The chain distribution abundance ratio of structural units is ¹³ C-NM
170.90ppm and 17 respectively obtained by high resolution measurement of R
[XX] obs./[XX] calculated by converting from the peak ratios of four peaks of 0.92ppm, 177.31ppm, and 177.33ppm _.
calcd. and _{[XY] obs. / [XY} ] calc d. were respectively 1.00 and 0.98.

The obtained copolyamide and iron powder were compounded at a preset temperature of 310 ° C. using a twin-screw extruder.
The obtained pellets were molded and the physical properties were measured. Table 1 shows the chain distribution ratio, crystallization characteristics and physical properties of the copolyamide.

Example 2 Table 1 shows salts of terephthalic acid and hexamethylenediamine, hexamethyleneammonium adipate (66 salts), salts of isophthalic acid and hexamethylenediamine, sodium hypophosphite and ion-exchanged water. The composition and concentration shown in (1) were charged into a batch pressure polymerization tank, nitrogen substitution was sufficiently performed, and then the temperature was raised to 290 ° C., which was the maximum temperature under stirring,
The maximum polymerization pressure was 20 kg / cm ² -G. The discharge was performed for 0.1 hour while supplying ion-exchanged water at a rate of 0.2 l / hr and maintaining the water vapor pressure at 20 kg / cm ² -G. The melting point of the obtained primary condensate is 302 ° C., ηr
Was a primary condensation product of 1.4.

The obtained primary condensate was heated at 100 ° C. for 24 hours.
After vacuum drying, 20 mmφ vent type twin-screw extruder (L
The degree of polymerization was increased by using / D = 25). Dwell time 75
Second, vacuum degree from the long vent of L / D = 5-700mm
Degassed with Hg, melted to a high degree of polymerization at a screw rotation speed of 150 rpm and a maximum resin temperature of 320 ° C., and a relative viscosity ηr =
A white pellet with a melting point of 2.6 and a melting point of 305 ° C. was obtained.

The obtained copolyamide, 1 glass fiber (diameter 9.5 μm) and iron powder were compounded at a preset temperature of 320 ° C. using a twin-screw extruder. The obtained pellets were molded and the physical properties were measured. Table 1 shows the chain distribution ratio, crystallization characteristics and physical properties of the copolyamide.

Example 3 Salt consisting of terephthalic acid and hexamethylenediamine, hexamethyleneammonium adipate (66 salt), ε-
Caprolactam, acetic acid, phosphoric acid and distilled water were charged at the composition and concentration shown in Table 1, and the maximum attainable temperature was 262 ° C. and the maximum polymerization pressure was 22 kg / cm ² -G (2 as in Example 2.
171.2306 kPa), water vapor pressure at discharge 22 kg /
The primary condensate was polymerized at cm ² -G.

The obtained primary condensate was heated at 100 ° C. for 24 hours.
After vacuum drying, the degree of polymerization was increased by an extruder. The extruder used was a 30 mmφ vent type twin-screw extruder (L / D = 4
5.5), rotating in the same direction, deep groove type. Vacuum time from a long vent with a residence time of 105 seconds and L / D = 5
Degassing from 700 mmHg and L / D = 1.8 short vent at vacuum level of -700 mmHg, screw rotation speed 2
The polymerization degree was melted to a high degree of polymerization at 00 rpm and a maximum resin temperature of 325 ° C. to obtain white pellets having a relative viscosity ηr = 2.5 and a melting point of 294 ° C. ^In the spectrum obtained by high resolution measurement of ¹³ C-NMR, 39.94 ppm, 40.16 pp
m, 40.58 ppm, 40.80 ppm, 170.2
1 ppm, 170.90 ppm, 170.92 ppm,
177.31Ppm, was obtained by conversion from nine peak ratio of _{177.33ppm, [XX] obs. /} [X
X] _calcd. And _{[XY] obs. / [XY} ] calcd. Were respectively 1.06 and 0.94.

The resulting copolyamide and iron powder were compounded at a preset temperature of 310 ° C. using a twin-screw extruder. The obtained pellets were molded and the physical properties were measured. Table 1 shows the chain distribution ratio, crystallization characteristics and physical properties of the copolyamide.

Example 4 Hexamethylene ammonium adipate (66 salt), a salt of terephthalic acid and hexamethylene diamine, benzoic acid and ion-exchanged water were placed in a batch pressure polymerization tank at the composition and concentration shown in Table 1. After the preparation, sodium hypophosphite was additionally added after the formation of the primary condensate, and the primary condensate was polymerized and the degree of polymerization was increased in the same manner as in Example 1.

The obtained copolyamide, glass fiber (diameter 9.5 μm) and iron powder were compounded at a preset temperature of 310 ° C. using a twin-screw extruder. The obtained pellets were molded and the physical properties were measured. Table 1 shows the chain distribution ratio, crystallization characteristics and physical properties of the copolyamide.

Example 5 Using hexamethylene ammonium adipate (66 salt), a salt of terephthalic acid and hexamethylene diamine as a raw material, and using a batch type pressure polymerization tank, a primary condensate was prepared in the same manner as in Example 1. Polymerization was carried out. Further, the degree of polymerization was increased in the same manner as in Example 1.

The obtained copolyamide and antimony trioxide were compounded at a preset temperature of 300 ° C. using a twin-screw extruder. The obtained pellets were molded and the physical properties were measured. Table 1 shows the chain distribution ratio, crystallization characteristics and physical properties of the copolyamide.

Example 6 The primary condensate was polymerized according to the method of Example 1 to give Example 1.
The degree of polymerization was increased using the same vent type twin-screw extruder.

The obtained copolymerized polyamide and iron powder were compounded at a preset temperature of 300 ° C. using a twin-screw extruder. The obtained pellets were molded and the physical properties were measured. Table 1 shows the chain distribution ratio, crystallization characteristics and physical properties of the copolyamide.

According to the methods of Examples 1 to 6, the primary condensates could be polymerized well, the chain distribution of the polymer after increasing the degree of polymerization supported a random structure, and the half crystallization time was also an appropriate value.
The moldability of the composition formed from this copolymerized polyamide and the particulate high specific gravity inorganic filler and the fibrous filler was good, and the polyamide resin composition was excellent in sound insulation.

Comparative Example 1 Using the copolyamide obtained in Example 1 and measuring the physical properties of the square plate and the molded product in exactly the same manner as in Example 1 except that no particulate high specific gravity inorganic filler was added. did. Table 1 shows the results
Shown in

Comparative Example 2 Using the copolyamide obtained in Example 4 and measuring the physical properties of the square plate and the molded article in exactly the same manner as in Example 4 except that the particulate high specific gravity inorganic filler was not added. did. Table 1 shows the results
Shown in

Comparative Example 3 Nylon 66 (Toray Nylon 66 CM3001 manufactured by Toray Industries, Inc.) was used as the polyamide instead of the copolyamide.
N) was used and the square plate was molded and the physical properties of the molded product were measured in exactly the same manner as in Example 1 except that the preset temperature of the molding machine was 280 ° C. The results are shown in Table 1.

Comparative Example 1 is a copolymerized polyamide simple substance containing no particulate high specific gravity inorganic filler, and Comparative Example 2 is a compounded glass fiber (diameter 9.5 μm) in the copolymerized polyamide. When these copolyamides and copolyamide compositions were molded, none of them contained a particulate high specific gravity inorganic filler, and thus were inferior in sound insulation compared to the examples. Comparative Example 3 is nylon 6
6 is a compound of iron powder, but it does not have the effect of improving the physical properties by controlling the chain distribution of the copolyamide bond and the crystallization behavior, so the sound insulation is inferior to the case of compounding iron powder with the copolyamide. You can see that

[0068]

[Table 1]

[0069]

The polyamide resin composition containing the copolyamide having the chain distribution and the crystallization property of the present invention and the particulate high specific gravity inorganic filler allows the moldability, mechanical strength, chemical resistance and heat distortion temperature to be improved. It is possible to obtain a product with improved sound insulation.

Claims (15)

[Claims] 1. A method comprising: (a) an amide bond formed from an aliphatic diamine having 4 to 14 carbon atoms and terephthalic acid, the chain distribution ratio of the amide bond satisfying (A) and (B);
Furthermore, a polyamide resin composition comprising a copolyamide having a semi-crystallization time satisfying the formula (C), and (b) a particulate high specific gravity inorganic filler. _{0.9 ≦ [XY] obs. /} [XY] calcd. ≦ 1.1 (A) 0.9 ≦ [XX] obs. / [XX] calcd. ≦ 1.1 (B) [wherein, X is It is an amide bond formed from an aliphatic diamine having a carbon number of 14 and terephthalic acid, and Y means an amide bond other than X. [XY] is the ratio of X and Y adjacent to all amide bonds in the polymer structure, and [XX] is the ratio of X and X adjacent to all amide bonds in the polymer structure. Indicates a percentage. [XY] _{calcd. And} [XX] _{calcd. Are} the respective values of [XY] and [XX] in which the amide bonds of X and Y are calculated as a statistically random chain distribution, and [XY] _{obs. And} [XX] _obs. Is measured from the copolyamide [X]
It is each value of Y] and [XX]. ] 4.4-0.1 (Tm-T) ≤ logt _1/2 ≤ 5.5-
0.1 (Tm-T) (C) [where t _1/2 is the half-crystallization time (seconds), Tm is the melting point (° C.) of the copolyamide)
And T is the measurement temperature (° C.) of the half crystallization time. ] 2. The melting point of the copolyamide is 260 to 32.
It is 0 degreeC, The polyamide resin composition of Claim 1 characterized by the above-mentioned. 3. From the temperature at which the measurement temperature T is lower than 35 ° C. below the melting point of the copolyamide during the half-crystallization time,
The polyamide resin composition according to claim 1 or 2, wherein the temperature is in the range of 5 ° C lower. 4. The polyamide resin composition according to claim 1, wherein the measurement temperature T is a temperature lower than 30 ° C. lower than the melting point of the copolyamide during the half crystallization time. 5. The polyamide resin composition according to claim 1, wherein the aliphatic diamine has 6 carbon atoms. 6. The copolymerized polyamide unit is (I): And at least one structural unit selected from structural units (II) to (IV): Embedded image Embedded image The polyamide resin composition according to any one of claims 1 to 5, which has a structural unit consisting of 7. The structural units (I) and (II) account for 50% by weight or more of the entire copolymer composition, and the weight ratio (I) / (II) is in the range of 80/20 to 20/80. A polyamide resin composition according to claim 6. 8. The chain distribution abundance ratios represented by the formulas (D) and (E).
The polyamide resin composition according to any one of claims 1 to 7, wherein _{0.95 ≦ [XY] obs. /} [XY] calcd. ≦ 1.05 (D) 0.95 ≦ [XY] obs. / [XY] calcd. ≦ 1.05 (E) 9. The polyamide resin composition according to claim 1, wherein the half-crystallization time satisfies the formula (F). 4.6-0.1 (Tm-T) ≤ logt _1/2 ≤ 5.3-0.1 (Tm-T) (F) 10. A maximum pressure reached is less than 5Kg / cm ² -G or 23 kg / cm ² -G, the maximum temperature is 2
After forming the primary condensate under the conditions of more than 60 ° C. and 330 ° C. or less, using a twin-screw extruder including a screw segment in which {screw length L} / {screw outermost diameter D} is 2 or less. The polyamide resin composition according to any one of claims 1 to 9, wherein a copolyamide produced by increasing the degree of polymerization is used. 11. The particulate high specific gravity inorganic filler as the component (b) is 0.1 to 200 parts by weight with respect to 100 parts by weight of the copolyamide as the component (a). The polyamide resin composition according to any one of 1 to 10. 12. The particulate high specific gravity inorganic filler has a specific gravity of 2.
It is an inorganic substance of 0 or more, It is characterized by the above-mentioned.
The polyamide resin composition according to any one of the above. 13. The polyamide resin composition according to claim 1, wherein the particulate high specific gravity inorganic filler is a metal compound. 14. The high-density inorganic filler in particulate form is at least one selected from iron powder, copper powder, zinc powder, lead powder and antimony oxide, according to claim 1. Polyamide resin composition. 15. The polyamide resin composition according to claim 1, further comprising a fibrous filler.