JPH08134208A - Crystalline copolyamide and polyamide resin composition containing it - Google Patents

Abstract

PURPOSE: To obtain a crystalline copolyamide which is tough and excellent in dimensional stability etc., by producing a copolyamide consisting of ε- capronamide units, ε-carboxamide units and hexamethyleneterephthalamide units at a specified molar ratio. CONSTITUTION: This copolyamide consists of ε-capronamide units (A), ε- carboxamide units (B) of the formula (wherein n is 10 or 11) and hexamethyleneterephthalamide units (C), wherein the proportions of these units are adjusted so as to provide a composition represented by any point within the circumference defined by the points (57,3,40), (32,27,40), (25,27,48) and (25,3,72) on a triangular diagram (A,B,C) showing the proportions (mol%) to thereby produce a crystalline copolyamide. The obtained resin gives a molding having high deflection temperature under load and high rigidity and excellent in tensile strength, impact strength, etc.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a crystalline copolyamide having specific components and compositions, and a polyamide resin composition containing the same in a specific amount. More specifically, it has excellent heat resistance, rigidity, impact resistance, low water absorption, and crystalline copolyamide excellent in melt moldability, and a filler and a crystalline copolyamide. And a polyamide resin composition having improved flexural temperature under load and improved rigidity.

[0002]

2. Description of the Related Art Polyamides are structurally heterogeneous in that they have a main chain skeleton composed of a carbon-carbon bond such as a methylene group or a phenylene group and an amide bond, and an amide-amide intermolecular hydrogen bond. It is a material with a structure and has characteristic physical properties based on the orientation, crystallinity, etc. of the molecule due to this structure. Typical examples thereof are crystalline aliphatic polyamides such as polyamide 6 and polyamide 66. These are mechanical properties such as rigidity, toughness, impact resistance, and wear resistance, thermal properties such as deflection temperature under load, electrical properties such as high insulation, optical properties such as weather resistance, and oil resistance and solvent resistance. It is a core material of engineering plastics in the fields of automobiles and electric and electronic parts, as a well-balanced material that has excellent chemical properties such as resistance and chemical resistance as well as excellent melt moldability.

However, in order to cope with the recent trend toward higher performance and higher output of engines in the field of automobiles and SMT (surface mounting) in the fields of electric and electronic parts, higher thermal and mechanical properties are required. Materials having these are required, and the above aliphatic polyamides are no longer sufficient. In addition, since the above aliphatic polyamide has high water absorption, molded articles made of such aliphatic polyamide have drawbacks that physical properties are deteriorated and dimensional change is large due to water absorption. Furthermore, the above-mentioned aliphatic polyamide is associated with high water absorption, and thus has insufficient resistance to metal halides such as calcium chloride and zinc chloride, and has drawbacks such as cracking on contact with these metal salts. Have.

Polyamides having an aromatic ring in the main chain skeleton are known as materials that meet the market demand for such polyamides having high heat resistance, high rigidity and low water absorption. Specifically, a melt-processable crystalline semi-aromatic polyamide containing an aromatic dicarboxylic acid such as terephthalic acid or isophthalic acid and / or an aromatic diamine such as metaxylylenediamine as a component, and a composition thereof Is. For example, JP-A-59-53536 discloses a semi-aromatic compound in which an aromatic dicarboxylic acid such as terephthalic acid and isophthalic acid or naphthalene dicarboxylic acid is used as the dicarboxylic acid component, and a linear aliphatic alkylenediamine is used as the diamine component. A molding polyamide composition comprising a polyamide and a filler is disclosed in JP-A-60-158220.
Japanese Patent Laid-Open Publication No. 1989-96359 discloses molding for a sliding material made of a semi-aromatic polyamide using an aromatic dicarboxylic acid such as terephthalic acid and isophthalic acid or naphthalene dicarboxylic acid as a dicarboxylic acid component and a linear aliphatic alkylenediamine as a diamine component. As for the material, and JP-A-3-72
JP-A 565 discloses that terephthalic acid and an aromatic dicarboxylic acid other than terephthalic acid are used as the dicarboxylic acid component, and an aliphatic alkylenediamine and / or an alicyclic alkylenediamine is used as the diamine component. Infrared reflow compositions comprising a polyamide and a white pigment have been proposed. Further, in JP-A-3-143957, a semi-aromatic compound using terephthalic acid or an aromatic dicarboxylic acid other than terephthalic acid or an aliphatic dicarboxylic acid as a dicarboxylic acid component and a linear aliphatic alkylenediamine as a diamine component is disclosed. A cage for rolling bearings made of polyamide and glass fiber is disclosed in Japanese Patent Laid-Open No. 3-188700 as terephthalic acid as a dicarboxylic acid component and an aliphatic dicarboxylic acid or an aliphatic dicarboxylic acid other than terephthalic acid, and an aliphatic diamine component as an aliphatic dicarboxylic acid. Electromagnetic wave shield members in which a conductive layer is provided on the surface of a resin formed of semi-aromatic polyamide using alkylenediamine have been proposed, respectively. Furthermore, JP-A-3-20
In 1375, terephthalic acid as a dicarboxylic acid component and an aromatic dicarboxylic acid other than terephthalic acid or an aliphatic dicarboxylic acid, and a semiaromatic using an aliphatic alkylenediamine and / or an alicyclic alkylenediamine as a diamine component. A resin composition for a connector obtained from polyamide has been proposed.

The crystalline semi-aromatic polyamides and compositions thereof described in the above publications have excellent heat resistance and high rigidity which are not present in the crystalline aliphatic polyamides such as conventional polyamide 6 and polyamide 66. It is a material with. However, there is a problem that the characteristic properties of the aliphatic polyamide such as tensile elongation and impact strength, which are excellent in toughness, are lost.

Therefore, in order to solve these problems,
Crystalline semi-aromatic polyamide with aliphatic polyamide and /
Alternatively, a composition in which a polyolefin is blended or copolymerized has been tried. Regarding a composition obtained by blending or copolymerizing an aliphatic polyamide, for example, Japanese Patent Publication No.
Japanese Unexamined Patent Publication No. 2-9617 discloses an underhood component for an automobile obtained by blending an amorphous polyamide containing an aromatic amino acid and / or an aromatic dicarboxylic acid as a main constituent with an aliphatic polyamide. 57458
Japanese Patent Laid-Open Publication No. 2000-242242 discloses that terephthalic acid and an aromatic dicarboxylic acid other than terephthalic acid or an aliphatic dicarboxylic acid as a dicarboxylic acid component, and a semi-aromatic polyamide and an aliphatic polyamide using an aliphatic alkylenediamine as a diamine component are melt-blended. The polyamide composition thus obtained is described in JP-A-62-156130.
A terephthalic acid as a dicarboxylic acid component and an aromatic dicarboxylic acid or an aliphatic dicarboxylic acid other than terephthalic acid, and a multi-component copolymerized polyamide comprising a semi-aromatic polyamide unit and an aliphatic polyamide unit using an aliphatic alkylenediamine as a diamine component, JP-A-3-7256
No. 4 discloses semi-aromatic using terephthalic acid and an aromatic dicarboxylic acid other than terephthalic acid or an aliphatic dicarboxylic acid as a dicarboxylic acid component and an aliphatic alkylenediamine and / or an alicyclic alkylenediamine as a diamine component. A polyamide resin composition for engine head covers, which is obtained by melt-blending polyamide, linear polyamide and inorganic fiber, is disclosed in JP-A-4-370116.
In the publication, there is disclosed a crystalline polyamide comprising a hexamethylene adipamide unit, a hexamethylene terephthalamide unit, a hexamethylene isophthalamide unit and a cyclic lactam having 6 to 12 carbon atoms or a polyamide unit obtained from an aminocarboxylic acid. Japanese Patent Laid-Open No. 5-23020
No. 9 discloses terephthalic acid as a dicarboxylic acid component,
An aliphatic dicarboxylic acid and / or isophthalic acid,
A polyamide composition comprising a semi-aromatic polyamide unit obtained from an aliphatic alkylenediamine as a diamine component, an aliphatic polyamide unit and a ω-aminocarboxylic acid unit, which has excellent impact resistance and tensile elongation, has been proposed.

Further, regarding a composition having improved toughness by blending or copolymerizing a polyolefin with a crystalline semi-aromatic polyamide, for example, JP-A-2-229855 discloses terephthalate as a dicarboxylic acid component. Acid and an aromatic dicarboxylic acid other than terephthalic acid or an aliphatic dicarboxylic acid, a semi-aromatic polyamide using an aliphatic alkylenediamine and / or an alicyclic alkylenediamine as a diamine component and an α-olefin component unit and α, β- A composition having excellent heat resistance, impact strength, water resistance, chemical resistance and melt flowability, which comprises an olefin-based copolymer composed of a glycidyl ester component unit of an unsaturated acid, and JP-A-5-983.
In JP-A No. 2 (1994) -1989, terephthalic acid and an aromatic dicarboxylic acid other than terephthalic acid or an aliphatic dicarboxylic acid as a dicarboxylic acid component, and an aliphatic alkylenediamine and / or an alicyclic alkylenediamine as a diamine component are used. A connector comprising a polyamide, a graft-modified α-olefin random copolymer and / or a graft-modified aromatic vinyl hydrocarbon / conjugated diene copolymer or a hydride thereof and an aliphatic polyamide,
Each has been proposed.

However, the compositions described in these publications also have various problems as described below, and have excellent physical properties (stiffness, toughness, impact resistance, abrasion resistance, deflection temperature under load) inherent in polyamide resins. , High insulation, weather resistance, oil resistance, solvent resistance, chemical resistance, etc.) and melt moldability, while at the same time fundamentally obtaining a material with improved high heat resistance, high rigidity and low water absorption It has not been resolved. That is, a semi-aromatic polyamide obtained by blending or copolymerizing an aliphatic polyamide has improved impact resistance and tensile elongation, but since most of the polyamides used are polyamide 6 or polyamide 66, the water absorption becomes large. ,
The low water absorption characteristic of semi-aromatic polyamide is reduced,
There is a problem that it causes deterioration of physical properties during actual use. In addition, dimensional stability also decreases with water absorption. A composition obtained by blending or graft-copolymerizing a polyolefin with a crystalline semi-aromatic polyamide has a low specific gravity,
Although it has low water absorption and a small dimensional change, it has a problem that the high heat resistance and high rigidity inherent in the semi-aromatic polyamide are significantly reduced.

[0009]

SUMMARY OF THE INVENTION An object of the present invention is to provide a crystalline copolyamide having excellent heat resistance, rigidity, impact resistance and low water absorption, and excellent melt moldability, and the crystalline property thereof. Composed of a copolyamide and a filler, while maintaining the excellent physical properties of the crystalline copolyamide,
Another object of the present invention is to provide a polyamide resin composition having improved deflection temperature under load and rigidity.

[0010]

Therefore, the present inventors have proposed a crystalline polyamide which is excellent in high heat resistance, high rigidity, low specific gravity, low water absorption and toughness, and also excellent in melt moldability, and the same. As a result of repeated studies on a polyamide resin composition containing, a crystalline copolyamide having a specific composition comprising specific components, and a polyamide resin composition having a specific composition comprising the crystalline copolyamide and a filler are conventionally The present inventors have found that the polyamide resin or the polyamide resin composition has extremely excellent physical properties and moldability that are not found in the art, and have reached the present invention.

That is, the first aspect of the present invention is
(A) ε-caproic acid amide unit, (B) general formula [OC
(CH ₂ ) nNH] (where n in the formula represents 10 to 11) is a copolyamide formed from an ω-carboxylic acid amide unit and (C) hexamethylene terephthalamide unit. The composition of each component unit is a triangular coordinate [(A), which indicates the composition ratio (mol%),
(B), (C)] points [57, 3, 40], [32,
27, 40], [25, 27, 48] and [25,
3, 72] can be achieved by providing a crystalline copolyamide having a composition within the range surrounded by straight lines. The second invention can be achieved by providing a polyamide resin composition comprising 100 parts by weight of the crystalline copolyamide according to the first invention and 1 to 200 parts by weight of a filler.

The present invention will be described in detail below. The polyamide obtained and used in the present invention has (A) ε-caproic acid amide unit of 25 to 57 mol%, (B) a general formula [OC (CH ₂ ) nNH] (however,
Where n in the formula represents 10 to 11)
3 to 27 mol% of carboxylic acid amide units and 40 to 72 (C) hexamethylene terephthalamide units.
It is a copolyamide prepared in the range of mol% (however, the total of the component units of (A), (B) and (C) is 100 mol%). That is, the composition of each of these component units is shown by the hatched portion in FIG. 1, that is,
Points [57, 3, 4 on triangular coordinates [(A), (B), (C)] indicating the composition ratio (mol%) of each component unit
0], [32, 27, 40], [25, 27, 48] and [25, 3, 72] are sequentially connected by a straight line and are crystalline copolyamides having a composition within the range.

When the content of (A) ε-caproic acid amide unit is less than 25 mol%, the crystallinity becomes small and 57 mol%
If it exceeds, the water absorbency becomes large, the physical properties at the time of actual use are lowered due to the water absorption, and the dimensional stability of the molded product is deteriorated. On the other hand, (B) general formula [OC (CH ₂ ) nNH] (where n in the formula is
When the ω-carboxylic acid amide unit represented by (10 to 11) is less than 3 mol%, the toughness such as tensile elongation and impact strength is low, and when it exceeds 27 mol%, the rigidity is lowered and the crystal is melted. In any case, the temperature becomes 270 ° C. or lower and the heat resistance becomes low, which is not preferable. When the (C) hexamethylene terephthalamide unit is less than 40 mol%, the rigidity becomes low, and when it exceeds 72 mol%, the crystal melting temperature becomes 330 ° C. or higher,
There is a problem that thermal decomposition during melting becomes remarkable.

That is, in the present invention, the polyamide 66 component, the polyamide 11 or 12 component, and the polyamide 6T are used.
A crystalline copolyamide having a specific composition comprising a component (T represents a terephthalic acid component unit; the same applies below), and a polyamide resin composition having a specific composition comprising the crystalline copolyamide and a filler, Rigidity, toughness, impact resistance, heat resistance, oil resistance and chemical resistance, toughness of polyamide 11 and / or 12, low water absorption and impact resistance, high rigidity of polyamide 6T, high heat resistance and low water absorption It is based on a design concept aiming at the creation of a new polyamide resin and a polyamide resin composition that make the best use of the advantages of each polyamide.

The crystallinity of the polyamide in the present invention can be judged by the presence or absence of an endothermic or exothermic peak obtained when the temperature is raised or lowered at a rate of 10 ° C./min using a differential scanning calorimeter (DSC).

The starting material for the crystalline copolyamide of the present invention is ε-aminocaproic acid or caprolactam as the component (A), and 11-aminoundecanoic acid, 12-aminododecanoic acid or lauro as the component (B). As the lactam and the component (C), equimolar amounts of terephthalic acid and hexamethylenediamine or equimolar salts obtained from them can be preferably used.

In the present invention, there is no particular limitation on the method of polymerizing the above raw materials. Any of melt polymerization, solid phase polymerization, solution polymerization and the like is possible, and these methods may be used alone or in an appropriate combination. Generally, a method of melt polymerization or a combination of melt polymerization and solid phase polymerization is adopted. Specifically, the above raw materials and water are charged into a pressure polymerization tank, an oligomer is produced under pressure, and then the oligomer is melted and / or solid-phase polymerized under normal pressure or reduced pressure to obtain a desired crystallinity. A copolyamide is obtained.

For example, the powdery raw materials of the above-mentioned components (A), (B) and (C) are dry-blended or mixed in the form of an aqueous solution of salts and / or monomers or an aqueous slurry. , These raw materials mixed in a predetermined ratio in advance, and a predetermined amount of water are charged into a polymerization tank and stirred at 230 to 280 ° C. and 15 to 50 kg.
An oligomer can be obtained by polymerizing at f / cm ² G. The polymerization is preferably carried out in an atmosphere of an inert gas such as nitrogen for the purpose of preventing deterioration and decomposition of the oligomer due to oxygen. The polymerization temperature is 230 to 280.
It is necessary to control the temperature to 240C, preferably 240 to 275C, and more preferably 240 to 270C. Polymerization temperature is 2
If it is lower than 30 ° C., aromatic components are precipitated, uniform polymerization cannot be carried out, or the polymerization time becomes long, which is not preferable. Further, if the polymerization temperature is higher than 280 ° C., undesirable side reactions or thermal decomposition reactions occur in the physical properties of the polymer, the polymer is colored, and the physical properties of the obtained copolymer are deteriorated, which is not preferable. . In order to surely suppress the occurrence of these unfavorable phenomena, the polymerization temperature should be in the above-mentioned preferable range, and particularly in the preferable range.
Here, the pressure at the time of producing the oligomer is the pressure in the polymerization tank at that time, and is mainly the steam pressure at the polymerization equilibrium shown by the mixture of the oligomer and water. Therefore,
This pressure can be appropriately adjusted to a pressure within the saturated steam pressure depending on the temperature and the amount of water, but is preferably 15 to 50 kgf / cm ² G. This pressure can be adjusted by, for example, a pressure control valve provided in a steam discharge line directly connected to the polymerization tank. When the pressure is less than 15 kgf / cm ² G, it becomes difficult to discharge the oligomer from the polymerization tank in a uniform state,
When it exceeds 50 kgf / cm ² G, the degree of polymerization of the obtained oligomer becomes extremely low, which is not preferable in any case.

When the oligomer is produced in the present invention, as described above, the raw material is heated and pressurized to the above temperature and pressure in the presence of water. The method of supplying water to the polymerization tank is not particularly limited, and it may be supplied in the form of an aqueous solution of the salt and / or monomer of the raw material or a water slurry, or alternatively, a predetermined amount of ion-exchanged water or the like. Pure water or distilled water may be supplied separately. The amount of water present in the polymerization tank is determined by the amount of the raw material charged to the polymerization tank and the temperature / pressure conditions of the polymerization tank. It is desirable that the total amount is 1 to 200 parts by weight, preferably 5 to 150 parts by weight, per 100 parts by weight. When the amount of water is less than 1 part by weight per 100 parts by weight of the total amount of the raw materials, it is necessary to raise the polymerization temperature in order to maintain the molten state of the oligomer, and therefore, the oligomer is thermally decomposed or vapor pressure is increased. It is not preferable that the concentration balance of the acid / amine in the polymerization tank is lost due to the evaporation of the hexamethylenediamine component having a high temperature. Further, when the amount of water is more than 200 parts by weight per 100 parts by weight of the raw material, the degree of polymerization of the obtained oligomer becomes small, and the hexamethylenediamine component is evaporated during the polymerization of the oligomer under normal pressure or reduced pressure. Becomes noticeable,
The end group concentration balance of the copolyamide finally obtained is disturbed and the degree of polymerization does not increase, which is not preferable. In addition,
If the amount of water present in the polymerization vessel deviates from the preferable range described above, the above-mentioned undesirable phenomenon may occur.

In the present invention, the degree of polymerization of the oligomer is determined by the relative viscosity (η) of a 1% sulfuric acid solution at 25 ° C.
When represented by r), it is preferably 1.50 or less,
It is more preferably 1.12 to 1.40. By adjusting the ηr of the oligomer to such a range,
The oligomer can be easily handled and the polymerization in the next step can be facilitated. If the relative viscosity is higher than 1.50, the melt viscosity of the oligomer becomes too high and ejection failure occurs, which is not preferable.

The oligomer obtained as described above is
Subsequently, the melting point of the finally obtained polyamide + 10 ° C
The final copolyamide is obtained by melt-polymerizing at a temperature in the range of 340 ° C., solid-phase polymerization at a temperature in the range of 200 ° C. to the melting point of the polyamide finally obtained, or a combination thereof. To get Polymerization temperature during melt polymerization is the melting point of the final polyamide +
If it is lower than 10 ° C., the polymer may not be completely melted, and there is a possibility that stable production cannot be achieved due to partial solidification during production. Further, when the polymerization temperature is higher than 340 ° C., it is not preferable because it causes coloration and deterioration of mechanical properties due to thermal deterioration. On the other hand, the solid phase polymerization temperature is 200
When the temperature is lower than 0 ° C, the polymerization rate is remarkably reduced and the polymerization is substantially not progressed, which is not preferable.

Since the crystalline copolyamide finally obtained by the above polymerization method has a high melting point of 270 ° C. or higher, there is a risk that the physical properties will be deteriorated by thermal decomposition unless polycondensation is completed in a short time. . Therefore, a kneading extruder having an excellent surface renewal property is preferably used for the melt polymerization of the oligomer. The kneading extruder used is a single-screw kneading extruder, a single-screw kneading extruder such as a special single-screw kneading extruder, or a twin-screw kneading extruder (meshing type, co-rotating type, meshing type). -Biaxial kneading extruders such as different direction rotating type, non-meshing type / same direction rotating type, non-meshing type / different direction rotating type, etc. can be used. Especially, the twin-screw kneading extruder is suitable.

The polymerization time of the oligomer should be selected so that the degree of polymerization is sufficiently increased and the polymer does not undergo thermal decomposition. In the melt polymerization, it is usually 0.5-1.
0 minutes, and usually 1 to 50 hours in solid phase polymerization. If the polymerization time is shorter than the above range, the increase of the molecular weight is not sufficient, and if the polymerization time is long, thermal deterioration occurs, and in any case, a copolyamide having desired mechanical properties cannot be obtained, which is not preferable.

The pressure during polymerization is preferably atmospheric pressure or reduced pressure, and a method of polymerization at 10 to 760 mmHg is adopted. If the pressure at the time of polymerization deviates from the above range too low, the molecular weight of the obtained copolyamide increases remarkably, and melt molding becomes difficult, which is not preferable. On the other hand, when the pressure during polymerization exceeds 760 mmHg, the increase in molecular weight is not sufficient, and a copolyamide having desired mechanical properties cannot be obtained, which is not preferable.

Therefore, the above-mentioned kneading extruder has at least one vent port, and the oligomer supplied to the kneading extruder in a molten state continuously or pulsatingly has the above-mentioned polymerization temperature. While being heated or melted by frictional heat due to kneading and simultaneously kneaded to obtain a crystalline copolyamide having a uniform degree of polymerization, water and heavy water contained in the oligomer are introduced from the vent port. A mixed vapor of water produced by the condensation reaction and residues such as unreacted monomers and oligomers is exhausted to the outside of the system.
In the present invention, it is necessary to positively evacuate from this vent port to advance the polycondensation reaction of the oligomer. For that purpose, the vent port is used as a decompression vent port or an atmosphere opening vent port, and the above kneading is performed. The inside of the extruder is maintained at the above pressure. The exhaust from the vent port when the vent port is a reduced pressure vent port can be performed by connecting the vent port to a known vacuum device such as a Nash pump.

The crystalline copolyamide of the present invention thus obtained has a relative viscosity (ηr) of a 1% sulfuric acid solution at 25 ° C. in the range of 2.0 to 5.0. η
When r is less than 2.0, a crystalline copolyamide having desired mechanical properties cannot be obtained, which is not preferable, and when it exceeds 5.0, viscosity at the time of melting becomes high and melt molding becomes difficult, which is not preferable. .

In the above polymerization, there is no problem if an inorganic phosphorus compound or the like is added as a polymerization accelerator if necessary.
As the inorganic phosphorus compound, phosphoric acid, phosphorous acid, hypophosphorous acid, pyrophosphoric acid, polyphosphoric acid, and their alkali metal salts and alkaline earth metal salts are preferable. The addition amount is usually 100 to 100 with respect to the oligomer or polymer.
It is 5000 ppm. The addition method is not particularly limited, and for example, a method of adding a phosphorus compound as it is or as an aqueous solution to copolyamide pellets or powders and mixing with a Henschel mixer is suitable. When the amount added is out of the above range, if it is less than 100 ppm, the effect of addition is hardly observed, and if it exceeds 5000 ppm, the polymerization rate remarkably increases, and it becomes difficult to control the polymerization, and the molecular weight increases. Both are not preferable because they may cause side reactions such as crosslinking.

The copolyamide obtained as described above may contain a heat-resistant agent, an antioxidant, and a heat-resistant agent, if necessary, during the production of the oligomer, the melt polymerization, or the solid-state polymerization.
It is also possible to add weathering agents, lubricants, crystal nucleating agents, antistatic agents, pigments, dyes and the like.

By the way, in the present invention, the crystalline copolyamide obtained as described above is mixed with a filler at a specific compounding ratio, and the excellent physical properties of the crystalline copolyamide are not impaired. It is also an object of the present invention to provide a polyamide resin composition having improved deflection temperature under load and rigidity.

The filler compounded in the polyamide resin composition of the present invention is an organic or inorganic compound having various forms such as powder, plate, fiber or cloth. Specifically, oxidation including silica, alumina, silica-alumina, titania, red iron oxide, zinc oxide, magnesia, calcia, potassium titanate, various ferrites and basic magnesium sulfate, basic magnesium carbonate and other complex oxides. Materials, talc, diatomaceous earth, clay, kaolin, quartz, mica, carbon black, graphite, activated carbon, glass beads, glass materials such as glass flakes, asbestos, silicates such as molybdenum disulfide, zinc silicate, and hydroxylation of various metals Compounds, carbonates, phosphates, borates, borosilicates, aluminosilicates, titanates, basic sulfates, basic carbonates and other basic salts, iron, copper, brass, nickel, titanium , Zinc, tin,
Metals such as lead, stainless steel, aluminum, magnesium, gold and silver, ceramics such as silicon carbide, silicon nitride, aluminum nitride, mullite and cordierite, and powdery and plate-like inorganic materials such as waste such as fly ash and micro silica. Compound, glass fiber, carbon fiber, boron fiber, ceramic fiber, silica fiber, alumina fiber, silica-alumina fiber, tyranno fiber (Si-Ti-C-O fiber),
Fiber form of asbestos fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber, basic magnesium sulfate fiber, stainless steel fiber and metal whiskers such as aluminum, iron, copper, titanium, brass, magnesium, gold and silver and metal fiber Inorganic compounds or secondary processed products such as cross products thereof, and polyparaphenylene terephthalamide, polymetaphenylene terephthalamide, polyparaphenylene isophthalamide, polymetaphenylene isophthalamide, diaminodiphenyl ether and terephthalic acid or isophthalic acid. Polycondensate with, p
-Or m-aminobenzoic acid polycondensate, etc., wholly aromatic polyamide, wholly aromatic polyamideimide, such as polycondensate of diaminodiphenyl ether and trimellitic anhydride or pyromellitic anhydride, wholly aromatic polyimide , Heterocyclic ring-containing compounds such as polybenzimidazole and polyimidazophenanthroline, powdery, plate-like, fibrous organic compounds such as polytetrafluoroethylene, polyester, polyacrylonitrile, and cellulose, or cross-like products thereof. Examples include secondary processed products. These fillers may be used alone or in combination of two or more. Also,
As these fillers, those surface-treated with a known silane coupling agent, titanate coupling agent or the like can also be used.

In the present invention, it is preferable to use a powdery or fibrous inorganic filler among the above-mentioned fillers. As the powdery inorganic filler, silica, alumina, silica
Alumina, titania, graphite, molybdenum disulfide, etc. are used to obtain a molded product obtained by molding the finally obtained polyamide resin composition, and the wear resistance such as dynamic friction coefficient, taper wear, and limit PV value, Tensile strength,
It is preferable from the viewpoint of improving mechanical properties such as bending strength and flexural modulus, and thermal properties such as deflection temperature under load. The average particle size of these fillers is usually in the range of 0.1 to 200 μm, and particularly in the range of 1 to 100 μm, because the above-mentioned wear resistance, mechanical properties, thermal properties, etc. are remarkably improved.

On the other hand, examples of the fibrous inorganic filler include glass fiber, carbon fiber, boron fiber, alumina fiber,
Tyranno fiber (Si-Ti-C-O fiber), asbestos fiber, stainless steel fiber and the like can be preferably used. That is, by using these fibrous inorganic fillers, mechanical properties such as tensile strength, bending strength, and bending elastic modulus of the molded article obtained by molding the finally obtained polyamide resin composition, deflection temperature under load. Thermal properties such as, physical and chemical properties such as water resistance and organic solvent resistance, and dimensional stability are remarkably improved. Also,
These fibrous inorganic fillers have an average fiber diameter of 0.1 to 3
The use of those in the range of 0 μm improves the moldability of the finally obtained polyamide resin composition, and the molded article obtained from the composition has thermal properties such as deflection temperature under load and tensile strength. Mechanical properties such as strength, flexural strength and flexural modulus, low water absorption, physical and chemical properties such as resistance to organic solvents, and dimensional stability are improved, which is preferable.

The blending ratio of the filler must be 1 to 200 parts by weight, preferably 5 to 150 parts by weight, and particularly preferably 10 to 100 parts by weight, based on 100 parts by weight of the crystalline copolyamide. The range is parts by weight. When the blending ratio of the filler is more than 200 parts by weight with respect to 100 parts by weight of the crystalline copolyamide, the moldability of the finally obtained polyamide resin composition and the molding obtained by molding the polyamide resin composition This is not preferable because the flexibility of the body is significantly reduced. When the amount is less than 1 part by weight based on 100 parts by weight of the crystalline copolyamide, the molded article obtained from the finally obtained polyamide resin composition has thermal properties such as deflection temperature under load, tensile strength and bending strength. , Mechanical properties such as flexural modulus, dynamic friction coefficient, wear resistance such as taper wear, limit PV value, low water absorption, physical and chemical properties such as organic solvent resistance, dimensional stability, etc. Is not desirable because it cannot be expected.

As described above, the polyamide resin composition finally obtained in the present invention has the above-mentioned crystalline copolyamide and the above-mentioned filler as essential constituents, but it is composed of both of these essential constituents. It may be a composition, or may be a composition containing other components in addition to the both essential constituents. Examples of the components other than the both essential components that are optionally blended in the polyamide resin composition of the present invention include known stabilizers, plasticizers, release agents, lubricants, and the like. The polyamide resin composition can be blended within a range that does not impair the moldability and physical properties.

The method for preparing the polyamide resin composition is not particularly limited, and various known methods can be used, for example, while maintaining a predetermined amount of the crystalline copolyamide in a molten state. Examples thereof include a method of blending a predetermined amount of the filler. As a method for melt-kneading and blending, specifically, a conventional melt-kneading processing machine such as a single-screw or twin-screw extruder, a Banbury mixer, and a kneader is used to sufficiently melt the crystalline copolyamide. And, as the temperature that does not decompose,
At a temperature of 220 ° C or higher, preferably 240 to 300 ° C,
A method such as melt-kneading and blending can be applied. Further, the crystalline copolyamide and the filler, after pre-mixing at room temperature in the mixing ratio of the present invention as described above,
The method of melt kneading and blending described above can also be applied.
In this case, the premixing can be performed by using a high-speed rotary mixer such as a Henschel mixer and a low-speed rotary mixer such as a corn blender and a tumbler which are used for ordinary mixing. Furthermore, during the production of the oligomer or during the melt polymerization or the solid phase polymerization of the oligomer, the amount of the filler with respect to the crystalline copolyamide produced as an intermediate product is the above-mentioned weight ratio. The polyamide resin composition may be directly produced from the above-mentioned raw materials by adding a filler.

The polyamide resin composition of the present invention obtained as described above can be molded by ordinary melt molding such as compression molding, injection molding or extrusion molding.

[0037]

EXAMPLES The present invention will be described in more detail with reference to Examples and Comparative Examples below. However, the present invention is not limited to these Examples and Comparative Examples. Various properties of the oligomer and / or polymer in the following Examples and Comparative Examples were measured by the following methods. (1) Relative Viscosity (ηr) According to JIS K6810, 98% by weight sulfuric acid was used as a solvent and the concentration was measured at 25 ° C. at a concentration of 1% by weight / volume.

(2) Melting temperature (Tm) and crystallization temperature (Tc) Using a differential scanning calorimeter (DSC-50) manufactured by Shimadzu Corporation, the temperature was measured at 10 ° C./min in a nitrogen atmosphere. .

(3) Composition From a proton NMR spectrum measured at room temperature using a JNM-EX400 FT-NMR manufactured by JEOL Ltd. at a concentration of 5% by weight with 97% by weight bisulfuric acid as a solvent, a copolyamide was obtained. The composition of each component was determined.

(4) Tensile test (tensile strength and tensile elongation): ASTM D638 (5) Bending test (bending strength and flexural modulus): AST
MD790 (6) Impact strength (with Izod notch): ASTM D
256 (7) Deflection temperature under load: ASTM D468 (however,
(Copolyamide has a load of 4.6 kgf / cm ² and polyamide resin composition comprising copolyamide and a filler has a load of 18.6 kgf / cm ² ) (8) Water absorption: ASTM D570

Example 1 A pressure vessel having a capacity of 1 liter equipped with a stirrer, a thermometer, a pressure gauge, a reflux condenser, a nitrogen gas inlet and a pressure release port was used.
-Caprolactam 79.2 g (0.700 mol), 12
-Aminododecanoic acid 64.6 g (0.300 mol), an equimolar salt of terephthalic acid and hexamethylenediamine 282.4 g (1.000 mol), sodium hypophosphite monohydrate 1.06 g (0. 01 mol) and distilled water 6
0g was charged. After sufficiently replacing the inside of the pressure vessel with nitrogen, the temperature was raised from room temperature to 260 ° C. over 2.5 hours with stirring,
When the temperature reaches 260 ° C, increase the water vapor pressure in the pressure vessel to 25 kg.
After allowing the reaction to proceed for 4 hours while maintaining f / cm ² G, stirring was stopped, and the inside of the pressure vessel was 260 ° C. and 25 kgf / cm ²
While kept at G, the reaction mixture was removed from the bottom of the pressure vessel at atmospheric pressure. Then, this reaction mixture was vacuum dried at 80 ° C. for 48 hours to obtain a powdery oligomer composed of a nylon 6/12 / 6T copolymer. Ηr of the obtained oligomer is 1.28, Tm is 289 ° C., Tc is 249 ° C.
Met.

Subsequently, this oligomer was added to a twin-screw extruder (barrel inner diameter: 55 mm, L / D = 42, barrel temperature: 31).
(0 ° C.), the polycondensation reaction was further advanced, and a pellet-shaped polymer was obtained. Ηr of the obtained polymer is 2.6.
2, Tm 291 ° C, Tc 250 ° C, composition 6/12
/ 6T = 35/15/50 (mol%). After vacuum-drying the pellets at 80 ° C. for 48 hours, a test piece for measuring physical properties was prepared under the conditions of a cylinder temperature of 310 ° C. and a mold temperature of 40 ° C. by an injection molding machine. The physical properties of this polymer are shown in Table 1.

Example 2 105.9 g (0.936 mol) of ε-caprolactam, 12-
23.3 g (0.108 mol) of aminododecanoic acid, an equimolar salt of terephthalic acid and hexamethylenediamine 2
13.5 g (0.756 mol) and distilled water 91.5 g
Was charged. After sufficiently substituting the inside of the pressure vessel with nitrogen, polymerization was carried out under the same conditions as in Example 1 to obtain 260 in the pressure vessel.
The reaction mixture was taken out from the bottom of the pressure vessel under atmospheric pressure while maintaining the temperature at 25 ° C. and 25 kgf / cm ² G. Then, this reaction mixture was vacuum dried at 80 ° C. for 48 hours to obtain a powdered oligomer of nylon 6/12 / 6T. Ηr of the obtained oligomer is 1.31, Tm is 280 ° C.,
Tc was 243 ° C.

Next, this oligomer was processed into a twin-screw extruder (barrel inner diameter: 55 mm, L / D = 42, barrel temperature: 310).
C.) and the polycondensation reaction was further advanced to obtain a pelletized polymer. Ηr of the obtained polymer was 2.64.
Tm is 283 ° C, Tc is 240 ° C, composition is 6/12/6
It was T = 52/6/42 (mol%). After vacuum-drying the pellets at 80 ° C. for 48 hours, a test piece for measuring physical properties was prepared under the conditions of a cylinder temperature of 310 ° C. and a mold temperature of 40 ° C. by an injection molding machine. The physical properties of this polymer are shown in Table 1.

Example 3 In a pressure vessel having a capacity of 1 liter as in Example 1, 59.6 g (0.527 mol) of ε-caprolactam, 83.9 g (0.425 mol) of laurolactam, terephthalic acid and hexamethylene were used. 211.2 g equimolar salt consisting of diamine
(0.748 mol), sodium hypophosphite monohydrate 0.73 g (0.0069 mol) and distilled water 90.5
I charged g. After thoroughly replacing the inside of the pressure vessel with nitrogen, raise the temperature from room temperature to 260 ° C over 2.5 hours with stirring, and
When the temperature reaches 60 ° C, increase the water vapor pressure in the pressure vessel to 25 kgf.
/ Cm ² G, the reaction was allowed to proceed for 6 hours, stirring was stopped, and the inside of the pressure vessel was 260 ° C. and 25 kgf / cm ² G
The reaction mixture was withdrawn from the bottom of the pressure vessel at atmospheric pressure while maintaining Therefore, the reaction mixture was heated at 80 ° C. for 4 hours.
It was vacuum dried for 8 hours to obtain a powdered oligomer of nylon 6/12 / 6T. The obtained oligomer had ηr of 1.32, Tm of 278 ° C., and Tc of 235 ° C.

Next, this oligomer was processed into a twin-screw extruder (barrel inner diameter: 55 mm, L / D = 42, barrel temperature: 310).
C.) and the polycondensation reaction was further advanced to obtain a pelletized polymer. Ηr of the obtained polymer is 2.59,
Tm is 277 ° C, Tc is 234 ° C, composition is 6/12/6
It was T = 31/25/44 (mol%). After vacuum-drying the pellets at 80 ° C. for 48 hours, a test piece for measuring physical properties was prepared under the conditions of a cylinder temperature of 310 ° C. and a mold temperature of 40 ° C. by an injection molding machine. The physical properties of this polymer are shown in Table 1.
Shown in

Example 4 A pressure vessel having a capacity of 1 liter similar to that in Example 1 was charged with ε-capsule.
Prolactam 50.7 g (0.448 mol), 11-a
Minoundecanoic acid 16.1 g (0.080 mol), tele
Equimolar salt of phthalic acid and hexamethylenediamine 3
02.7 g (1.072 mol) and distilled water 75.8 g
Was charged. After thoroughly replacing the inside of the pressure vessel with nitrogen, stir
The temperature was raised from room temperature to 270 ° C. over 2.5 hours.
During heating, the pressure is 30 kgf / cm²Seems to exceed G
30 kgf / cm depending on pressure release²Adjust to G. 27
When the temperature reaches 0 ° C, the water vapor pressure in the pressure vessel is set to 30 kgf /
cm ²After continuing the reaction for 4 hours while maintaining at G, stop stirring.
Therefore, the inside of the pressure vessel is 270 ° C, 30 kgf / cm²To G
While maintaining the reaction mixture under atmospheric pressure from the bottom of the pressure vessel.
I took it out. Therefore, the reaction mixture was heated at 80 ° C. for 48 hours.
Powder that is vacuum dried for 6 hours and made of nylon 6/11 / 6T
An oligomer in the form of a solid was obtained. Ηr of the obtained oligomer is
The temperature was 1.37, Tm was 310 ° C, and Tc was 286 ° C.

Next, this oligomer was processed into a twin-screw extruder (barrel inner diameter: 55 mm, L / D = 42, barrel temperature: 330).
C.) and the polycondensation reaction was further advanced to obtain a pelletized polymer. Ηr of the obtained polymer is 2.71;
Tm is 310 ° C, Tc is 288 ° C, composition is 6/11/6
It was T = 28/5/67 (mol%). After vacuum-drying the pellets at 80 ° C. for 48 hours, a test piece for measuring physical properties was produced by an injection molding machine under the conditions of a cylinder temperature of 330 ° C. and a mold temperature of 40 ° C. The physical properties of this polymer are shown in Table 1.

Example 5 5.46 kg (48.24 mol) of ε-caprolactam,
3.24 kg (15.04 mol) of 12-aminododecanoic acid, 24.73 kg (87.58 mol) of an equimolar salt of terephthalic acid and hexamethylenediamine, and 79.92 g (0) of sodium hypophosphite monohydrate. 0.754 mol) was dry blended using a tumbler under a nitrogen atmosphere. 33 kg of this mixture and 8.25 kg of distilled water
Was charged into a pressure vessel having a capacity of 70 liters equipped with a stirrer, a thermometer, a pressure gauge, a reflux condenser, a nitrogen gas inlet and a pressure release port, and the inside of the pressure vessel was sufficiently replaced with nitrogen, and then the temperature was increased from room temperature with stirring. The temperature was raised to 260 ° C. over 3 hours. If the pressure exceeds 25 kgf / cm ² G during heating, the pressure is adjusted to 25 kgf / cm ² G. When the temperature reached 260 ° C in this way, the reaction was allowed to proceed for 3 hours while maintaining the water vapor pressure in the pressure vessel at 25 kgf / cm ² G, stirring was stopped, and the inside of the pressure vessel was kept at 260 ° C and 25 kg.
The reaction mixture was discharged under atmospheric pressure from the bottom of the pressure vessel while maintaining f / cm ² G. Therefore, this reaction mixture was vacuum dried at 80 ° C. for 48 hours to give nylon 6/12/6.
A powdered oligomer of T was obtained. Ηr of the obtained oligomer is 1.28, Tm is 302 ° C., and Tc is 271.
° C.

Subsequently, the supplied amount of this oligomer is 30 kg.
/ Hr, twin-screw extruder (barrel inner diameter: 55 mm, L / D
= 42, barrel temperature: 330 ° C.) to further advance the polycondensation reaction to obtain a polymer in pellet form. Ηr of the obtained polymer is 2.71, Tm is 300 ° C., Tc is 270 ° C., and the composition is 6/12 / 6T = 32/10/58.
(Mol%). After vacuum-drying the pellets at 80 ° C. for 48 hours, the temperature of the cylinder was 33
Test pieces for measuring physical properties were prepared under conditions of 0 ° C. and mold temperature of 40 ° C. The physical properties of this polymer are shown in Table 1.

[0051]

[Table 1]

Comparative Example 1 72.4 g (0.640 mol) of ε-caprolactam and an equimolar salt 27 of terephthalic acid and hexamethylenediamine were placed in a pressure vessel having a capacity of 1 liter as in Example 1.
1.2 g (0.960 mol) and 92.1 g of distilled water were charged. After sufficiently replacing the inside of the pressure vessel with nitrogen, Example 1
Polymerization is carried out under the same conditions as in,
The reaction mixture was taken out from the bottom of the pressure vessel under atmospheric pressure while maintaining the pressure at 25 kgf / cm ² G. Therefore, this reaction mixture was vacuum dried at 80 ° C. for 48 hours to give nylon 6 /
A powdered oligomer of 6T was obtained. The obtained oligomer has ηr of 1.34, Tm of 303 ° C., and Tc of 26.
5 ° C.

Subsequently, this oligomer was added to a twin-screw extruder (barrel inner diameter: 55 mm, L / D = 42, barrel temperature: 33).
(0 ° C.), the polycondensation reaction was further advanced, and a pellet-shaped polymer was obtained. Ηr of the obtained polymer is 2.6.
4, Tm is 305 ° C, Tc is 265 ° C, composition is 6 / 6T
= 40/60 (mol%). 80 this pellet
After vacuum drying at 48 ° C. for 48 hours, a test piece for measuring physical properties was prepared under the conditions of a cylinder temperature of 330 ° C. and a mold temperature of 40 ° C. by an injection molding machine. The physical properties of this polymer are shown in Table 2.
This polymer was a polyamide having low tensile elongation and poor toughness.

Comparative Example 2 152.1 g (1.344 mol) of ε-caprolactam and 12-
Equimolar salt 1 consisting of 36.2 g (0.168 mol) of aminododecanoic acid, terephthalic acid and hexamethylenediamine
66 g (0.588 mol) and 71.6 g of distilled water were charged. After sufficiently replacing the inside of the pressure vessel with nitrogen, polymerization was carried out under the same conditions as in Example 1, and the inside of the pressure vessel was set at 260 ° C.
The reaction mixture was taken out from the bottom of the pressure vessel under atmospheric pressure while maintaining the pressure at 5 kgf / cm ² G. Therefore, this reaction mixture was vacuum dried at 80 ° C. for 48 hours to give nylon 6/1.
A powdered oligomer of 2 / 6T was obtained. Ηr of the obtained oligomer was 1.32, Tm was 264 ° C., and Tc was 225 ° C.

Next, this oligomer was processed into a twin-screw extruder (barrel inner diameter: 55 mm, L / D = 42, barrel temperature: 300).
C.) and the polycondensation reaction was further advanced to obtain a pelletized polymer. Ηr of the obtained polymer is 2.59,
Tm is 265 ° C, Tc is 228 ° C, composition is 6/12/6
It was T = 64/8/28 (mol%). After vacuum-drying the pellets at 80 ° C. for 48 hours, a test piece for measuring physical properties was produced by an injection molding machine under the conditions of a cylinder temperature of 300 ° C. and a mold temperature of 40 ° C. The physical properties of this polymer are shown in Table 2. This polymer was a polyamide having a low deflection temperature under load and poor heat resistance. In addition, this polymer was a polyamide that has a high water absorption rate and is considered to have a large decrease in physical properties due to water absorption.

Comparative Example 3 45.3 g (0.400 mol) of ε-caprolactam, 120.6 g (0.560 mol) of 12-aminododecanoic acid and terephthalic acid were placed in the same pressure vessel having a capacity of 1 liter as in Example 1. Equimolar salt consisting of and hexamethylenediamine 1
80.7 g (0.640 mol) and distilled water 77.4 g
Was charged. After sufficiently substituting the inside of the pressure vessel with nitrogen, polymerization was carried out under the same conditions as in Example 1 to obtain 260 in the pressure vessel.
The reaction mixture was taken out from the bottom of the pressure vessel under atmospheric pressure while maintaining the temperature at 25 ° C. and 25 kgf / cm ² G. Then, this reaction mixture was vacuum dried at 80 ° C. for 48 hours to obtain a powdered oligomer of nylon 6/12 / 6T. The ηr of the obtained oligomer was 1.32, and Tm and Tc were
Had no clear peak.

Next, this oligomer was added to a twin-screw extruder (barrel inner diameter: 55 mm, L / D = 42, barrel temperature: 300).
C.) and further proceeded with polycondensation reaction to obtain a transparent pellet polymer. Ηr of the obtained polymer is 2.7.
It was 0, and no clear peak was observed for Tm and Tc. The composition is 6/12 / 6T = 25/35/4.
It was 0 (mol%). After vacuum-drying the pellets at 80 ° C for 48 hours, use an injection molding machine to set the cylinder temperature to 3
Test pieces for measuring physical properties were prepared under the conditions of 00 ° C. and mold temperature of 40 ° C. The physical properties of this polymer are shown in Table 2. This polymer was a highly amorphous polymer, which had a significantly low deflection temperature under load and was poor in heat resistance.

Comparative Example 4 35.1 g (0.310 mol) of ε-caprolactam, 10.0 g (0.046 mol) of 12-aminododecanoic acid and terephthalic acid were placed in a pressure vessel having a capacity of 1 liter as in Example 1. And equimolar salt of hexamethylenediamine 29
3.3 g (1.039 mol) and 73.3 g of distilled water were charged. After sufficiently replacing the pressure vessel with nitrogen, under stirring,
The temperature was raised from room temperature to 280 ° C. over 3 hours. During the temperature rise,
If the pressure exceeds 30 kgf / cm ² G, the pressure is adjusted to 30 kgf / cm ² G. When the temperature reaches 280 ° C, the water vapor pressure in the pressure vessel is set to 30 kgf / cm ² G
The reaction mixture was taken out from the bottom of the pressure vessel under atmospheric pressure while maintaining the inside of the pressure vessel at 280 ° C. and 30 kgf / cm ² G after the reaction was allowed to proceed for 4 hours while maintaining the temperature at 30 ° C. Then, this reaction mixture was vacuum dried at 80 ° C. for 48 hours to obtain a powdered oligomer of nylon 6/12 / 6T. Ηr of the obtained oligomer is 1.40,
The Tm was 320 ° C and the Tc was 288 ° C.

Next, this oligomer was mixed with a twin-screw extruder (barrel inner diameter: 55 mm, L / D = 42, barrel temperature: 355).
C.) and the polycondensation reaction was further advanced to obtain a pelletized polymer. Ηr of the obtained polymer is 2.60,
Tm is 320 ° C, Tc is 291 ° C, composition is 6/12/6
It was T = 20/3/77 (mol%). The polymer was colored yellow. After vacuum-drying the pellets at 80 ° C for 48 hours, use an injection molding machine to set the cylinder temperature to 3
Test pieces for measuring physical properties were prepared under the conditions of 50 ° C. and mold temperature of 40 ° C. The physical properties of this polymer are shown in Table 2. This polymer was a polyamide with poor toughness in which the tensile elongation was significantly reduced.

[0060]

[Table 2]

Example 6 Pellets of the nylon 6/12 / 6T copolymer obtained in Example 5 were dried under vacuum at 80 ° C. for 48 hours.
Parts by weight and 30 parts by weight of glass fiber having an average fiber diameter of 13 μm (manufactured by Nippon Electric Glass Co., Ltd., trade name: ECS T-24) were dry blended in a nitrogen atmosphere using a tumbler. Next, this mixture was subjected to a cylinder setting temperature of 330 using a twin-screw kneader PCM-45 manufactured by Ikegai Tekko KK
The mixture was kneaded at a temperature of 150 rpm and a discharge rate of 15 kg / hr to obtain a pelletized polyamide resin composition. Further, the obtained polyamide resin composition was vacuum-dried at 80 ° C. for 48 hours, and then the cylinder temperature was adjusted to 33 by an injection molding machine.
Injection molding was performed under the conditions of 0 ° C. and a mold temperature of 40 ° C. to prepare a test piece for measuring physical properties. Table 3 shows the physical properties of the obtained polyamide resin composition.

Example 7 Nylon 6/12 / 6T copolymer pellets obtained in Example 5 were vacuum dried at 80 ° C. for 48 hours to obtain 100.
Nylon 6/12 obtained in Example 3 in place of parts by weight
100 parts by weight of pellets of / 6T copolymer vacuum dried at 80 ° C. for 48 hours were used, 40 parts by weight of glass fiber similar to that used in Example 6 was used instead of 30 parts by weight, and Example 6 except that the cylinder setting temperature during kneading was changed to 330 ° C. to 310 ° C.
The treatment was carried out in exactly the same manner as above to obtain a pelletized polyamide resin composition. Next, 8 parts of the obtained polyamide resin composition
After vacuum drying at 0 ° C. for 48 hours, injection molding was performed by an injection molding machine under conditions of a cylinder temperature of 310 ° C. and a mold temperature of 40 ° C. to prepare a test piece for measuring physical properties. Table 3 shows the physical properties of the obtained polyamide resin composition.

Comparative Example 5 Pellets of the nylon 6/12 / 6T copolymer obtained in Example 5 were vacuum dried at 80 ° C. for 48 hours.
Nylon 6/12 obtained in Comparative Example 4 in place of parts by weight
Example 6 except that 100 parts by weight of pellets of / 6T copolymer vacuum dried at 80 ° C. for 48 hours were used, and that the cylinder temperature during kneading was changed to 330 ° C. to 350 ° C. The same treatment was carried out to obtain a pelletized polyamide resin composition. The obtained polyamide resin composition was colored yellow. Therefore, the obtained polyamide resin composition was vacuum dried at 80 ° C. for 48 hours and then injection-molded by an injection molding machine under the conditions of a cylinder temperature of 350 ° C. and a mold temperature of 40 ° C. to prepare a test piece for measuring physical properties. . Table 3 shows the physical properties of the obtained polyamide resin composition.
Shown in The polyamide resin composition had low tensile elongation and impact strength and was inferior in toughness.

Comparative Example 6 Pellets of the nylon 6/12 / 6T copolymer obtained in Example 5 were vacuum dried at 80 ° C. for 48 hours.
Nylon 6/12 obtained in Comparative Example 3 instead of parts by weight
100 parts by weight of pellets of / 6T copolymer vacuum dried at 80 ° C. for 48 hours were used, 40 parts by weight of glass fiber similar to that used in Example 6 was used instead of 30 parts by weight, and Example 6 except that the cylinder setting temperature during kneading was changed to 330 ° C. to 300 ° C.
The treatment was carried out in exactly the same manner as above to obtain a pelletized polyamide resin composition. Next, 8 parts of the obtained polyamide resin composition
After vacuum drying at 0 ° C. for 48 hours, injection molding was performed by an injection molding machine under the conditions of a cylinder temperature of 300 ° C. and a mold temperature of 40 ° C. to prepare a test piece for measuring physical properties. Table 3 shows the physical properties of the obtained polyamide resin composition. The polyamide resin composition had a low deflection temperature under load and was poor in heat resistance.

[0065]

[Table 3]

[0066]

Since the crystalline copolyamide obtained by the present invention is a semi-aromatic polyamide based on specific components and compositions, it has physical properties such as heat resistance, high rigidity and low water absorption inherent to polyamide resins. A polyamide that is tough and has excellent dimensional stability without sacrificing properties. Further, the polyamide resin composition obtained by the present invention, which is obtained by mixing the crystalline copolyamide and the filler in a specific ratio, in addition to the excellent physical properties of the crystalline copolyamide,
The resin composition has further improved physical properties such as deflection temperature under load and rigidity. Therefore, the molded product using the crystalline copolyamide of the present invention or the polyamide resin composition containing the same, as compared with molded products using the conventionally known polyamide or polyamide resin composition, high deflection temperature under load and Not only has high rigidity, it is tough and has excellent tensile elongation and impact strength, as well as dimensional stability.

[Brief description of drawings]

1 is a component unit of the crystalline copolyamide of the present invention, (A) ε-caproic acid amide unit, (B) the general formula [OC
(CH ₂ ) nNH] (where n in the formula represents 10 to 11) and the percentage composition (mol%) of the ω-carboxylic acid amide unit and (C) hexamethylene terephthalamide unit are triangular. Coordinates [(A), (B),
It is a graph represented by (C).

[Explanation of symbols]

A (A) ε-caproic acid amide unit in the crystalline copolyamide B (B) in the crystalline copolyamide General formula [OC (CH
₂ ) nNH] (wherein n represents 10 to 11) represented by ω-carboxylic acid amide unit C (C) hexamethylene terephthalamide unit in crystalline copolyamide

Claims (2)

[Claims] 1. (A) ε-caproic acid amide unit, (B)
General formula [OC (CH ₂ ) nNH] (where n in the formula
Is a copolyamide formed from an ω-carboxylic acid amide unit represented by 10 to 11) and (C) hexamethylene terephthalamide unit, and the composition of each of these component units is the composition ratio (mol%). ) Indicating triangular coordinates [(A), (B), (C)] on points [57, 3, 4
0], [32, 27, 40], [25, 27, 48] and [25, 3, 72] are sequentially connected by a straight line and have a composition within a range surrounded by the composition. 2. The crystalline copolyamide 10 according to claim 1.
A polyamide resin composition comprising 0 parts by weight and 1 to 200 parts by weight of a filler.