JP2002294069A - Polyamide resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a continuously moldable polyamide resin composition having high rigidity and gloss of the molded article and free from the tearing trouble of sprue and provide a molded article of the composition. SOLUTION: The polyamide resin composition contains (A) 30-70 pts.wt. of a polyamide containing an aromatic ring-containing polymer unit and 30-70 pts.wt. in total of (B) glass fiber and (C) wollastonite (the sum of A, B and C is 100 pts.wt. and the C/B weight ratio is 0.2-3), (D) carbon black, (E) a copper compound, (F) 0.01-5 pts.wt. (based on 100 pts.wt. of the component A) of calcium salt, lithium salt or sodium salt of a >=28C fatty acid and (G) an azine dye. The present invention further provides a molded article of the resin composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyamide resin composition which has high rigidity, is excellent in gloss of a molded product, has no sprue tearing, and can be continuously molded, and a molded product thereof.

[0002]

2. Description of the Related Art Polyamide resins are widely used for parts such as automobiles, electric and electronic products because of their excellent mechanical and thermal properties and oil resistance. In addition, the reinforced polyamide resin in which glass fiber is blended with polyamide greatly improves the mechanical properties, heat resistance, chemical resistance, etc., so parts that were conventionally made of metal can be replaced from the viewpoint of weight reduction and streamlining of processes. It is also possible to use a reinforced polyamide resin, which has been actively studied in recent years. In particular, a reinforced polyamide material that is mixed with glass fiber alone or in combination with glass fiber and other wollastonite and has a high concentration, not only does the obtained molded article have high rigidity, but also the combination of the molded article and It is used in a wide range of applications because it enhances the surface smoothness and provides a material with excellent vibration characteristics.

[0003] In order to achieve high rigidity and good molded product appearance, it is necessary to incorporate a reinforcing agent such as glass fiber or other mineral filler in a high concentration. It is advantageous to use a polyamide having excellent properties. Examples of such polyamides include copolymers of an amorphous aromatic polyamide and a crystalline aliphatic polyamide, but such copolymers generally have lower crystallinity than homopolymers, When the molding shrinkage decreases or the crystallization speed decreases, moldability, particularly mold release, tends to deteriorate. Particularly, in the case of a material reinforced with a reinforcing material such as glass fiber at a high concentration, sprue breakage occurs frequently during injection molding, and there is a problem that continuous molding cannot be performed.

It has been proposed to add a fatty acid metal salt, a fatty acid ester, a bisamide compound, etc. in order to improve the releasability of a non-reinforced and highly crystalline polyamide resin. For example, Japanese Patent Publication No. 54-4742 proposes that by adding an aliphatic carboxylic acid salt having 10 to 20 carbon atoms and an aliphatic carboxylic acid having 22 or more carbon atoms or a derivative thereof, the pushing force of a molded article can be improved. Have been. In Japanese Patent Publication No. 23448/1995, phosphonic acid or phosphinic acid or a metal salt thereof is used in combination with
It is described that by adding the above-mentioned sodium salt of an aliphatic carboxylic acid, the protruding force of a molded article can be reduced, and at the same time, plasticity and bubbles generated in the molded article can be reduced. These proposals are all based on the principle of increasing the crystallization rate and improving the pushing force of the molded article.

On the other hand, Japanese Patent Laid-Open No. 11-79372 discloses a polyamide resin composition having high rigidity and good appearance relating to a copolymer of an amorphous polyamide and a crystalline polyamide. Combinations have been proposed. However, there is no description regarding the releasability, and no description of a specific method or the like for improving this is described. As described above, a polyamide resin having a low crystallization rate, such as a copolymer of an amorphous aromatic polyamide and a crystalline aliphatic polyamide, has a high rigidity, a good molded product appearance, and a sprue tear with respect to a polyamide resin having a small molding shrinkage. There was no known material capable of continuous molding.

[0006]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a polyamide resin composition which has high rigidity, is excellent in gloss of a molded product, has no sprue tearing, and can be continuously molded, and a molded product thereof. .

[0007]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that a polyamide resin having a specific amount of aromatic ring-containing polymer units in combination with glass fiber and wollastonite has carbon atoms. It has been found that a composition comprising a specific amount of 28 or more fatty acids and a metal salt composed of a calcium salt, a lithium salt or a sodium salt and a copper compound and a molded product thereof can achieve the object of the present invention. Was completed.

That is, the present invention provides (1) the following (A) to
A polyamide resin composition comprising (G), wherein A and B
(A) is 30 when the total of C and C is 100 parts by mass.
To 70 parts by mass, and 30 to 70 parts in total of (B) and (C).
Parts by mass, and the mass ratio of (C) to (B) is 0.2 to
3, and (D) is 0 to 10 parts by mass relative to 100 parts by mass of the total amount of (A), (B), and (C).
(E) is 0 relative to (A) based on copper in the copper compound.
-5000 ppm, (F) 0.01 to 5 parts by mass with respect to 100 parts by mass of (A), and (G) 0 to 2 parts by mass with respect to 100 parts by mass of (A). Resin composition.

(A) (a1) hexamethylene adipamide unit 60 obtained from adipic acid and hexamethylene diamine
50% to 100% by weight of a semi-aromatic polyamide composed of 0 to 95% by weight, 0 to 10% by weight of capramide units obtained from caprolactam, and 5 to 30% by weight of hexamethylene isophthalamide units obtained from isophthalic acid and hexamethylene diamine. ) Aliphatic polyamide 0-50w
(B) Glass fiber (C) Wollastonite (D) Carbon black (E) Copper compound (A) F) Calcium salt, lithium salt or sodium salt of fatty acid having 28 or more carbon atoms (G) Azine dye

(2) 0.05 to 10 parts by mass of carbon black (D) based on 100 parts by mass of (A), (B) and (C), and copper compound (E) in the copper compound 10 to 5000 with respect to (A) on the basis of copper
The polyamide resin composition according to (1), wherein the polyamide resin composition contains 0.1 ppm. (3) A molded article obtained by molding the polyamide resin composition according to the above (1) or (2). (4) The molded body is an outer handle, outer door handle, wheel cap, roof rail, door mirror base, room mirror arm, sunroof deflector,
Radiator fan, radiator grill, bearing retainer, console box, sun visor arm, spoiler, sliding door rail cover, desk and chair legs, seat, armrest, wheelchair parts, door handle,
The molded article according to (3), which is any of a handrail, a grip bar for a bathroom or the like, and a knob for a window. (1) ~
(4) The present invention relates to the polyamide resin composition described in (4) and a molded article thereof. In the present invention, (D),
The capramide units in (E), (G), (a2) and (a1) are optional components.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The (a1) semi-aromatic polyamide used in the present invention is described in more detail below. The semi-aromatic polyamide includes hexamethylene adipamide units (hereinafter referred to as 66 components) obtained from adipic acid and hexamethylene diamine, and hexamethylene isophthalamide units (hereinafter referred to as 6I components) obtained from isophthalic acid and hexamethylene diamine. And / or capramide units derived from caprolactam or aminocaproic acid (hereinafter referred to as 6). These copolymers may be terpolymers such as copolymers with adipic acid, isophthalic acid, hexamethylenediamine and caprolactam.

In the present invention, the semi-aromatic polyamide (a1)
Is 60 to 95 wt% of 66 components and 0 to 10 w of 6 components.
Polyamide 66/6 / 6I copolymer with t% and 6I components in the range of 5-30 wt%. The 6I component is 5 wt% or more from the viewpoint of the appearance of the molded product, and is 30 watts from the viewpoint of the cooling time in the mold, the releasability from the mold, and the productivity.
t% or less. The six components are 10 wt% or less from the viewpoint of mechanical properties and rigidity.

Next, the aliphatic polyamide (a2) will be described. Examples of these are polyamide 6, polyamide 6
6, polyamide 610, polyamide 612, polyamide 11, polyamide 12, polyamide 66/6 copolymer,
Or, a blend thereof or the like may be used. Preferably polyamide 6, polyamide 610, polyamide 612,
Polyamide 12, polyamide 66/6 copolymer and the like. By using these polyamides, even when the blending amount of glass fiber and wollastonite is large,
A molded article having a good appearance can be obtained.

The polyamide (A) used in the present invention comprises:
A polyamide comprising (a1) 50 to 100 wt% of a semi-aromatic polyamide and (a2) 0 to 50 wt% of an aliphatic polyamide, wherein the aromatic ring-containing polymer unit concentration in the polyamide (A) is 3 to 90 mol%. When used in combination with (a2) an aliphatic polyamide, the unit concentration of the aromatic ring-containing polymer of (a1) the semi-aromatic polyamide is 90 mol% or more, and
Those having a range of mol% or less are preferred.

The aromatic ring-containing polymer unit used in the present invention means a repeating unit containing one acid amide (-CONH-) and one aromatic ring. Specifically, the polymer unit is obtained from isophthalic acid and hexamethylenediamine. Hexamethylene isophthalamide unit. The aromatic ring-containing polymer unit is at least 3 mol% from the viewpoint of the appearance of the molded article. As a method for measuring the unit concentration of the aromatic ring-containing polymer, for example, a method of dissolving and measuring a polyamide as a sample using NMR using bisulfuric acid, deuterated trifluoroacetic acid or the like as a solvent can be used.

In the present invention, the polyamide component is dissolved using deuterated trifluoroacetic acid as a solvent so that the concentration of the polyamide resin composition becomes 2 wt%, and ¹ H-NMR is performed using AC-300P manufactured by Brucker. It was measured. In determining the chemical shift value, tetramethylsilane was used as a reference substance. In the polyamide (A) in the present invention, the aliphatic polyamide (a2) can be contained in an amount of 0 to 50 wt% as long as the aromatic ring-containing polymer unit concentration in all the polyamides is in the range of 3 to 90 mol%. .
The content of the aliphatic polyamide (a2) is 50 wt% or less from the viewpoint of mechanical properties and appearance of a molded product.

In the present invention, the polyamide is produced by, for example, a melt polymerization method from a salt of adipic acid, isophthalic acid and hexamethylenediamine, a solid-phase polymerization method, a bulk polymerization method, a solution polymerization method, or a combination thereof. Can be used. Further, for example, a method such as solution polymerization or interfacial polymerization of adipic acid chloride, isophthalic acid chloride and hexamethylenediamine may be used. Among these, a method based on melt polymerization or a combination of melt polymerization and solid phase polymerization is more preferably used in the present invention from an economic viewpoint.

The molecular weight of the polyamide used in the present invention is as follows: sulfuric acid solution viscosity ηr (100 ml of 95.5% sulfuric acid per 1 g of polymer, 25% using an Oswald viscometer).
Measure in ° C. )), From the viewpoint of brittleness of the resin composition and drawing from the tip of the cylinder nozzle at the time of molding, it is preferably 1.5 or more, and from the viewpoint of melt viscosity and surface glossiness of the resin, it is preferably 3.5 or less. More preferably 1.8
To 3.0, more preferably 2.0 to 2.8.

The preferred amount of the terminal group of the polyamide (A) used in the present invention is such that the amino group is 10 per kg of the polyamide.
８０80 meq, the carboxyl group is preferably 60-150 meq, more preferably the amino group is 20-6.
0 meq, 70-120 meq carboxyl groups. As the glass fiber as the component (B) of the present invention, those commonly used for thermoplastic resins can be used, and the fiber diameter and length are not particularly limited.
30 μm chopped strand, roving, milled fiber and the like. When using chopped strands, the length is preferably in the range of 0.1 to 6 mm.

In the glass fiber used in the present invention, a glass fiber having an average fiber diameter in the range of 6 to 15 μm is particularly preferably used. A composition using glass fibers having an average fiber diameter in this range is preferable because it has excellent mechanical properties and can reduce abrasion of a processing device. It is preferable to use a glass fiber having a surface to which a known sizing agent or silane coupling agent is adhered. Examples of the sizing agent include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-
β (aminoethyl) -γ-aminopropyltrimethoxysilane, vinyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane and the like.

The wollastonite which is the component (C) of the present invention has a chemical name of calcium metasilicate and is a mineral having white needle-like crystals. Normally, the SiO ₂ 40~60wt%,
CaO is contained in an amount of 40 to 55 wt%, and Fe ₂ O ₃ ,
It contains components such as Al ₂ O ₃ , MgO, Na ₂ O, and K ₂ O. Wollastonite used in the present invention, oil absorption 20 to 50 cm ^3/100 g, a bulk specific gravity of 0.1
1.0, a fiber length of 0.1 to 1000 μm, and a fiber diameter of 0.1.
Those having a thickness of 1 to 50 μm are preferred.

The average particle size of wollastonite in the present invention is preferably 50 μm or less, more preferably 5 to 50 μm.
30 μm. If the average particle diameter exceeds 50 μm, it may happen that particles embedded on the surface or in the vicinity thereof can be visually confirmed when the molded article is formed. Here,
The average particle size is derived by using a laser diffraction / scattering type particle size distribution device to extract wollastonite dispersed in pure water which has been stirred and, if necessary, further irradiated with ultrasonic waves so that the transmittance becomes 85%. 50% of the particle size distribution accumulation
Is shown. The maximum diameter of the particles is preferably 100 μm or less from the viewpoint of the appearance of the molded article.

Incidentally, these wollastonites may be obtained by pulverizing and classifying naturally occurring substances,
Synthetic products can also be used. In addition, in the sense that the Hunter whiteness is 60 or more and the weather resistance to polyamide is not deteriorated, the pH value of the slurry when the slurry is 10% in high-purity water is 6%.
To 8 are more preferable. Further, the wollastonite in the present invention may use a conventionally known surface treatment agent for the purpose of improving the adhesiveness to the polyamide. Examples of the type of the surface treatment agent include a silane coupling agent and a titanate coupling agent containing an amino group or an epoxy group. Such a surface treatment agent may be previously applied to the wollastonite surface, or may be added when the polyamide and wollastonite are mixed.

In the present invention, the total amount of the glass fiber (B) and the wollastonite (C) is 30 to 70 parts by mass, and (B)
It is important to set the ratio of (C) to 0.2 to 3. The total of the glass fiber (B) and the wollastonite (C) is 30 parts by mass or more from the viewpoint of strength and rigidity, and the glass fiber floats when exposed outdoors, the resin fluidity,
70 mass parts or less are preferable from a viewpoint of surface glossiness. The mass ratio of wollastonite (C) to glass fiber (B) is 0.2 or more from the viewpoint of suppressing floating of the glass fiber when exposed outdoors, and 3 from the viewpoint of strength and rigidity.
It is as follows.

The carbon black which is the component (D) of the present invention is not always necessary, but when weather resistance is required,
Addition can improve gloss retention and black fading. As the carbon black used in the present invention, those produced by any of an oil furnace method, a gas furnace method, a channel method and a thermal method can be used and are not particularly limited.

In the present invention, the average primary particle diameter is defined as the number average diameter of the primary particles measured by an electron microscope, and the use of carbon black having an average primary particle diameter of 20 nm or less is defined as a glossy flat plate or grain. It is preferable from the viewpoint of excellent weather resistance of the flat plate, and the more preferable range of the primary particle diameter is 1
5 nm or less. Carbon black has a weight loss (volatile content) of 0.5 to 5% when heated at 950 ° C. for 7 minutes specified in Japanese Industrial Standard K6221 and an oil absorption (measured value using dibutyl phthalate) of 50 to 50%. 150cm ^3/1
Those having a range of 00 g are preferred.

The preferable addition amount of carbon black in the present invention is 100 parts by mass of the total amount of polyamide (A), glass fiber (B) and wollastonite (C).
The amount is 0 to 10 parts by mass, more preferably 0.1 to 7 parts by mass, from the viewpoint of the mechanical strength, rigidity and the like of the molded product. The copper compound, which is the component (E) of the present invention, has an effect of improving weather resistance by being added when weather resistance is required.

Examples of the copper compound of the present invention include copper chloride, copper bromide, copper fluoride, copper iodide, copper thiocyanate, copper nitrate, copper acetate, naphthenic copper, copper caprate, copper laurate, stearin Examples thereof include copper oxide, copper acetylacetone, copper oxide (I), and copper oxide (II). Particularly preferred in the present invention are copper halides such as copper iodide, and copper acetate. The amount of the copper compound added to the polyamide (A) is based on the copper in the copper compound as a reference. Corrosion of metal in polymerization reactors, extruders, molding machines, etc., corrosion of metal inserted in molded products, etc. 0-5000 ppm from the viewpoint of
It is. Preferably it is 10 to 2000 ppm. still,
The copper compound may be added to either (a1) the semi-aromatic polyamide or (a2) the aliphatic polyamide constituting the polyamide (A), or may be added to only one of them.

In the present invention, the copper compound (E) is
It is more preferable to use it in combination with an iodine compound. Examples of the iodine compound include potassium iodide, magnesium iodide, ammonium iodide, and the like, and iodine alone may be used. More preferably, it is potassium iodide. The preferred compounding amount of the iodine compound is such that the gram atomic ratio of the iodine element and the copper element to the polyamide resin ([iodine] / [copper]) is 5 or more from the viewpoint of a sufficient weather resistance improving effect. From the viewpoint of corrosion of metals such as extruders and molding machines, and corrosion of metals inserted into molded products. More preferably, it is 10 to 25.

The calcium salt, lithium salt or sodium salt of a fatty acid having 28 or more carbon atoms, which is the component (F) of the present invention, has a low molding shrinkage and a low solidification material, as in the present invention, exerts a pushing force on the material. Has no specific effect, but exhibits a very specific effect on sprue tearing. The calcium salt, lithium salt or sodium salt of a fatty acid having 28 or more carbon atoms which is the component (F) of the present invention includes, for example, sodium salt, lithium salt and calcium salt of a fatty acid having 28 or more carbon atoms such as montanic acid and melicic acid. However, calcium montanate and sodium montanate are preferably used as those having a high effect.

These fatty acid metal salts preferably have an acid value of 5 to 15 mg KOH / g and a volatility of 2% or less (at 105 ° C.,
4 hours), and those having a bulk density of 100 to 1000 g / l can be used. Further, two or more of these fatty acid metal salts may be used in combination. The present invention has found that sprue tearing, which is slow in crystallization and is likely to occur only in a polyamide resin having a small molding shrinkage, can be eliminated by adding a specific fatty acid metal salt, and the releasability of the prior art is known. The effect of reducing the release force described in the improvement is not seen in the present invention.

The amount of the calcium salt or sodium salt of the fatty acid having 28 or more carbon atoms is determined by the polyamide (A) 1
With respect to 00 parts by mass, the amount is 0.01 part by mass or more from the viewpoint of the effect of improving sprue tearing when the molded product is released from the mold, and 5 parts by mass from the viewpoint of bleed-out, appearance of the molded product, and weather resistance. Not more than parts by mass. Preferably it is 0.1 to 2 parts by mass. Further, from the viewpoint of the effect of improving sprue tearing, the fatty acid metal salt has 28 or more carbon atoms.

The glossiness of a molded article can be further improved by using the azine dye as the component (G) of the present invention in combination with carbon black as a black colorant.
The azine-based dye is a mixture of azine-based compounds such as triphenazine osadine and phenazine azine obtained by using aniline, nitrobenzene, and hydrochloric acid as main raw materials and using ferric oxide or the like as a catalyst, and includes plastics, leather, and the like. Is well known as a black colorant.

Such azine dyes include Nigro
sine Base EXBP, Nubian Com
plex Black G-02, Nubian Bl
ack PA-0800, Nubian Black
PA-0801, Nubian Black PA-0
850, Nubian Black PA-2800,
Nubian Black PA-2801, Nubi
an Black PA-9800, Nubian B
black PA-9801, Nubian Black
PA-9811, Nubian Black PA-
9802, Nubian Black PA-980
3, Nubian Black EP-3, Nigro
sineBase EE, NigrosineBase
EX, Special Black EB, Nigr
osineBase SA, NigrosineBas
e SAP and NigrosinBase N
B, Orient Spirit BlackSB (all manufactured by Orient Chemical Co., Ltd.), Spirit Blac
k No. 850 (Sumitomo Chemical), Nigrosin
e Base LK (manufactured by BASF), NYB2762
A commercially available product such as OB (manufactured by Sanyo Kako) can be used.

The amount of the azine dye is from 0 to 2 parts by mass, preferably from 0.1 to 2 parts by mass, based on 100 parts by mass of the polyamide (A) from the viewpoint of suppression of sprue tearing and gloss of the molded product. 1 part by mass, more preferably 0.2 to
0.7 parts by mass. In addition, such azine-based dyes often exhibit acidity, but the azine-based dye used in the present invention having a pH of 5 or more is preferable in that the decomposition of the polymer is not promoted.

The polyamide resin composition and the molded article of the present invention can be produced, for example, by mixing and kneading the above-mentioned components (A) to (G) and various additives used as required. At this time, the method of blending, mixing, and kneading and the order thereof are not particularly limited, and they may be mixed with a commonly used mixer, for example, a Henschel mixer, a tumbler, a ribbon blender, or the like. As the kneader, a single-screw or twin-screw extruder is usually used. The molded article according to the present invention
An extruder is usually obtained by first producing a pellet comprising the resin composition of the present invention, and then molding the pellet into an arbitrary shape by compression molding, injection molding, extrusion molding, or the like to obtain a desired resin product. .

In the present invention, the injection molding conditions are not particularly limited, but it is preferable to perform molding at a molding temperature of 250 ° C. to 310 ° C. and a mold temperature of 40 ° C. to 120 ° C. Also,
The composition of the present invention is not particularly limited in the order of mixing to obtain it, and for example, (A), (B), (C), (D),
A method of kneading (E), (F) and (G) together;
A method in which (A), (B), (E), (F), and (G) are melt-kneaded, and then kneading (C) and (D) is performed. The pellet blend is obtained by kneading a part of (A) with (B), (E), (F) and (G), and kneading the rest of (A) with (C) and (D). For example, a method of pellet blending and subjecting it to processing can be exemplified. In addition, polyamide
A master pellet containing a high concentration of carbon black (D) and an azine dye (G) in (A) is prepared, and this is mixed with (A), (B), (C), (E) and (F).
May be re-kneaded or pellet-blended for use. (F) is replaced with (A), (B),
After kneading (C), (D), and (E) to form pellets, the mixture may be dusted on the pellet surface together with an additive such as polyethylene glycol.

The polyamide resin composition of the present invention may contain, if necessary, an antioxidant, an ultraviolet absorber, an antioxidant, and the like, which are added to a usual polyamide resin within a range not to impair the object of the present invention.
Heat stabilizers, light deterioration inhibitors, plasticizers, lubricants, release agents, nucleating agents, flame retardants, coloring dyes such as copper phthalocyanine derivatives, etc. can also be added, and other thermoplastic resins can be blended. Is also good. The composition according to the present invention includes, for example, an outer door handle, a wheel cap, a roof rail, a door mirror base, a room mirror arm, a sunroof deflector, a radiator fan, a radiator grill,
Molded products for automotive parts such as bearing retainers, console boxes, sun visor arms, spoilers, sliding door rail covers, and legs and seats for desks and chairs,
It can be particularly preferably used for various office parts such as armrests, wheelchair parts, door handles, handrails, grip bars for bathrooms, etc., window knobs, industrial molded articles such as grating materials and molded articles for miscellaneous goods.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. In addition, the evaluation method is as follows. [Determination of unit concentration of aromatic ring-containing polymer in polyamide]
The unit concentration of the aromatic ring-containing polymer is determined by dissolving the polyamide component using deuterated trifluoroacetic acid as a solvent so that the concentration of the polyamide resin composition becomes 2 wt%.
¹ H-NMR was measured using AC-300P manufactured by R Co., Ltd., and the aromatic ring-containing polymer unit concentration was calculated from the integral value of the proton peak. The measurement conditions are described below. Measurement temperature: 30 ° C. Pulse width: 4.4 μsec Pulse repetition time: 3.0 sec Integration number: 128 In determining the chemical shift value, tetramethylsilane was used as a reference substance.

[Surface gloss] IS1 manufactured by Toshiba Machine Co., Ltd.
Using a 50E injection molding machine, cylinder temperature 290 ° C,
At a mold temperature of 120 ° C., the injection pressure and speed are appropriately adjusted so that the filling time is about 1.5 seconds, and 100 × 90 × 3
mm injection molded plate was obtained. Using this flat plate, a gloss meter (H
JIS-K7150 using ORIBA IG320)
The gloss was measured at 60 degrees according to.

[Release Force and Sprue Torn] Using a mold equipped with a release force measuring device shown in FIG. 1, a cylinder temperature of 290 ° C. was obtained using a Nissei Plastic FN3000 injection molding machine.
Molding was performed under the conditions of an injection pressure of 40 MPa, and a projecting stress when the molded product was ejected from the mold was measured as a mold release force. Further, when 30 shots were formed by the same method and sprue tearing occurred in 3 or more shots, the evaluation was x, and 2 shots or less was evaluated as ○.

[Mechanical properties] IS-5 manufactured by Toshiba Machine Co., Ltd.
Using a 0EP injection molding machine, screw rotation speed 200r
Under the molding conditions of pm and resin temperature of 290 ° C., an ASTM type 1 having a thickness of 3 mm was molded, and this molded piece was used as a sample for measuring physical properties. Tensile breaking strength and flexural modulus were measured in accordance with ASTM D638 and D790, respectively. did.

[Weather Resistance (Glossiness Change and Glass Fiber Floating)] Using an FN3000 injection molding machine manufactured by Nissei Plastics Co., Ltd., a grain flat plate (60 mm × 90 mm × 3 mm) and a gloss flat plate (60 mm × 90 mm × 3 mm). ) An injection molded plate was obtained using a mold.

This injection molded plate was manufactured by WE manufactured by Suga Test Instruments Co., Ltd.
Exposure was carried out for 500 hours using a L-SUN-DCH type sunshine carbon arc lamp type weather resistance tester under the conditions of a black panel temperature of 83 ° C. and a cycle of water spraying for 12 minutes during irradiation for 60 minutes. As an evaluation method after the weather resistance test, the gloss change rate of the grained flat plate before and after the exposure was measured by a gloss meter (I manufactured by HORIBA).
G320) was used to measure the gloss at 60 degrees according to JIS-K7150, and the gloss value after exposure was defined assuming that the gloss value before exposure was 100%.

Regarding the float of the glass fiber on the grain plate, the grain plate after the exposure was visually evaluated with a 50-fold loupe.
Those in which glass fibers could not be confirmed were evaluated as 、, those in which glass fibers could be confirmed in a range of less than 20% of the visual field, and those in which glass fibers could be confirmed in 20% or more of the visual field were evaluated as ×. The raw materials used in the examples of the present invention are shown below. (A) Polyamide a1: Polyamide 66/6 obtained in Polymerization Example 1 described below
I copolymer a2: polyamide 66/6 obtained in Polymerization Example 2 described below
I / 6 copolymer a3: polyamide 66, manufactured by Asahi Kasei Corporation; trade name
Leona 1300

(B) Glass fiber b1: Glass fiber manufactured by NEC Corporation CS03T275H Average fiber diameter 10 μm
m (C) Wollastonite c1: Wollastonite manufactured by Nyco Corp. Product name Nyglos8 Average particle diameter = 8 μm (D) Carbon black d1: Carbon black manufactured by Mitsubishi Chemical Corporation # 980 Average primary particle size 16 nm

(E) Azine dye e1: Nigrosine Orient Chemical Co., Ltd. Product name Nubian Black PA9801 (F) Fatty acid metal salt (release agent) f1: Calcium montanate Clariant Product name Recommont CaV102 f2: Calcium stearate Product name Calcium stearate f3: Ethylene bisstearylamide Product name Alflo H50S

[Polymerization Example 1] 2.00 kg of equimolar salt of adipic acid and hexamethylenediamine, 0.73 kg of equimolar salt of isophthalic acid and hexamethylenediamine, 18 g of adipic acid, 0.67 g of copper iodide, potassium iodide 11g
And 2.5 kg of pure water were charged into a 5 L autoclave and stirred well. After sufficiently purging with N _{2, the} temperature was raised from room temperature to 220 ° C. over about 1 hour with stirring. At this time, the internal pressure was 1.8 MPa due to the natural pressure of the steam in the autoclave, but the heating was further continued while removing water outside the reaction system so as not to reach a pressure of 1.8 MPa or more. After 2 hours, when the internal temperature reached 260 ° C., the heating was stopped, the discharge valve of the autoclave was closed, and the mixture was cooled to room temperature over about 8 hours. After cooling, the autoclave was opened and about 2 kg of the polymer was taken out and pulverized. The obtained pulverized polymer was placed in a 10 L evaporator and subjected to solid-state polymerization at 200 ° C. for 10 hours under a stream of N ₂ . The polyamide obtained by solid phase polymerization contains 27% by weight of hexamethylene isophthalamide unit and 73% by weight of hexamethylene adipamide unit, has a terminal carboxyl group concentration of 102.1 milliequivalents per kg of polymer, and has a terminal amino group. The base concentration was 44.1 meq / kg polymer. The polyamide contained 96 ppm of copper element, and the molar ratio of the copper-containing component to the iodine-containing component was 19.

[Polymerization Example 2] 2.10 kg of equimolar salt of adipic acid and hexamethylenediamine, 0.43 kg of equimolar salt of isophthalic acid and hexamethylenediamine, 0.16 kg of ε-caprolactam, 19 g of adipic acid, copper iodide 0.57 g, potassium iodide 11 g and pure water 2.5 kg
Was charged into a 5 L autoclave and stirred well. After sufficiently purging with N _{2, the} temperature was raised from room temperature to 220 with stirring.
The temperature was raised to about 1 hour over about 1 hour. At this time, the internal pressure was 1.8 MPa due to the natural pressure of the steam in the autoclave, but the heating was further continued while removing water outside the reaction system so as not to reach a pressure of 1.8 MPa or more. After 2 hours, when the internal temperature reached 260 ° C., the heating was stopped, the discharge valve of the autoclave was closed, and the mixture was cooled to room temperature over about 8 hours. After cooling, the autoclave was opened and about 2 kg of the polymer was taken out and pulverized. The obtained ground polymer is
Put in a 0 L evaporator under a stream of N ₂ at 200 ° C.
Solid phase polymerization was performed for 0 hours. The polyamide obtained by solid-state polymerization contained 78% by weight of hexamethylene adipamide unit, 15% by weight of hexamethylene isophthalamide unit, and 7% by weight of capramid unit. The polyamide contained 96 ppm of copper element, and the molar ratio of the copper-containing component to the iodine-containing component was 19.

[0050]

Examples 1 to 3 and Comparative Examples 1 to 4 Fatty acid metal salts (release agents) were added to a total of 100 parts by mass of the polyamide and wollastonite and the glass fiber, as shown in Table 1,
The mixture was mixed at a mass ratio, and a TEM35φ twin screw extruder manufactured by Toshiba Machine Co., Ltd. (set temperature: 290 ° C., screw rotation speed: 300 r)
pm) from the feed hopper, two side feed ports are further provided, wollastonite is supplied from the upstream side feed port at the mass ratio shown in Table 1, and glass fiber is supplied from the downstream side feed port. The melt-kneaded product supplied at the mass ratio described in 1, and extruded from the spinneret was cooled in a strand shape and pelletized to obtain a polyamide resin composition. Table 1 shows the evaluation results.

[0051]

[Table 1]

[0052]

Examples 4-6 and Comparative Examples 5-7 Fatty acid metal salts (mold release agents) were added to the types and weights shown in Table 2 with respect to 100 parts by weight of the total amount of polyamide and wollastonite and glass fiber. Mixed at the same ratio, TEM35φ manufactured by Toshiba Machine Co., Ltd.
Twin screw extruder (set temperature 290 ° C, screw rotation speed 30
0 rpm) from the feed hopper, two side feed ports are further provided, wollastonite is supplied from the upstream side feed port at a mass ratio shown in Table 2, and glass fiber is supplied from the downstream side feed port. The melt-kneaded product supplied at the mass ratio described in 2, and extruded from the spinneret was cooled in a strand shape and pelletized to obtain a polyamide resin composition. Table 2 shows the evaluation results.

[0053]

Example 7 A total of 100 parts by mass of polyamide, wollastonite and glass fiber was mixed with a fatty acid metal salt, carbon black, and an azine-based dye in the types and mass ratios shown in Table 2 and mixed with each other. TEM35φ manufactured by Machine Co., Ltd.
Twin screw extruder (set temperature 290 ° C, screw rotation speed 30
0 rpm) from the feed hopper, two side feed ports are further provided, wollastonite is supplied from the upstream side feed port at a mass ratio shown in Table 2, and glass fiber is supplied from the downstream side feed port. The melt-kneaded product supplied at the mass ratio described in 2, and extruded from the spinneret was cooled in a strand shape and pelletized to obtain a polyamide resin composition. Table 2 shows the evaluation results.

[0054]

[Table 2]

[Brief description of the drawings]

FIG. 1 is a schematic diagram of a measuring device used for evaluating releasability and sprue tearing in Examples and Comparative Examples of the present invention.

[Explanation of symbols]

 Reference Signs List 1 sprue runner 2 cup-shaped molded product 3 ejector pin 4 ejector plate 5 pressure sensor 6 ejector rod 7 release force recorder

The polyamide resin composition of the present invention has excellent moldability and, when formed into a molded product, has excellent mechanical properties, appearance of the molded product, moldability and weatherability as compared with conventional ones. In particular, the exterior door handle, wheel cap, roof rail, door mirror base, room mirror arm, sunroof deflector, radiator fan, bearing retainer, etc. Since it has a high gloss resistance change and has no floating glass fiber, it can be suitably used in a wide range of fields.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (Reference) B62D 37/02 C08J 5/00 CFG C08J 5/00 CFG C08K 3/04 C08K 3/04 3/10 3/10 3 / 34 3/34 5/098 5/098 5/3462 5/3462 7/14 7/14 B60B 7/00 SF term (reference) 3D003 AA01 AA02 AA03 BB01 CA40 4F071 AA54 AB03 AB15 AB26 AB28 AC09 AD01 AE09 AH03 AH07 AH11 BA01 BB05 4J002 CL03X CL05W DA038 DD039 DD079 DD089 DE099 DG039 DJ007 DL006 EG029 EG039 EG049 EG089 FA046 FD099

Claims (4)

[Claims] 1. A polyamide resin composition comprising the following (A) to (G), wherein when A, B and C are combined to 100 parts by mass, (A) is 30 to 70 parts by mass, (B) ) And (C) in a total amount of 30 to 70 parts by mass, and the mass ratio of (C) to (B) is in the range of 0.2 to 3, and further (D) is (A), (B), And (C) 0 to 10 parts by mass with respect to 100 parts by mass in total, (E) 0 to 5000 ppm with respect to (A) based on copper in the copper compound, (F)
(A) 100 parts by mass of (A) 0.01 to 5 parts by mass, and (G) 100 parts by mass of (A) 0 to 2 parts by mass. (A) (a1) 60 to 95 wt% of hexamethylene adipamide units obtained from adipic acid and hexamethylene diamine
%, Capramide units obtained from caprolactam 0 to 1
0 wt%, and 5 to 3 hexamethylene isophthalamide units obtained from isophthalic acid and hexamethylene diamine
Semi-aromatic polyamide composed of 0 wt% 50 to 10
A polyamide comprising 0 wt% and (a2) an aliphatic polyamide of 0 to 50 wt%, wherein the polyamide has an aromatic ring-containing polymer unit concentration of 3 to 90 mol%. (B) Glass fiber (C) Warast Knight (D) Carbon black (E) Copper compound (F) Calcium salt, lithium salt or sodium salt of fatty acid having 28 or more carbon atoms (G) Azine dye 2. Carbon black (D) is (A),
0.0 to 100 parts by mass of the total amount of (B) and (C)
The polyamide resin composition according to claim 1, wherein the polyamide resin composition contains 5 to 10 parts by mass and 10 to 5000 ppm of the copper compound (E) with respect to (A) based on copper in the copper compound. 3. A molded article obtained by molding the polyamide resin composition according to claim 1 or 2. 4. The molded product is an outer handle, an outer door handle, a wheel cap, a roof rail, a door mirror base, a room mirror arm, a sunroof deflector, a radiator fan, a radiator grill, a bearing retainer, a console box, a sun visor arm, a spoiler, and a slide door rail. The molded article according to claim 3, which is any one of a cover, a leg of a desk and a chair, a seat, an armrest, a wheelchair part, a door handle, a handrail, a grip bar in a bathroom, and a knob for a window. .