JPH11343406A - Black colored polyamide resin composition excellent in weather resistance - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a black colored polyamide resin composition excellent in mechanical characteristics, appearance and weather resistance. SOLUTION: This back colored polyamide resin composition contains (A) 30-70 pts.wt. of a polyamide, (B) 70-30 pts.wt. of at least one kind of inorganic filler selected from glass fiber, mica, talc, kaolin and wollastonite, (C) a copper compound in an amount of 10-1,000 ppm based on copper in the copper compound and based on the component (A), (D) a carbon black in amount of 0.05-10 pts.wt. based on 100 pts.wt. of the total amount of the components (A) and (B) and (E) a copper phthalocyanine derivative of a specific structure in an amount of 5-100 pts.wt. based on 100 pts.wt. of the component (D).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention has an excellent initial appearance,
The present invention relates to a black-colored polyamide resin composition having mechanical properties capable of replacing metals, and capable of obtaining a molded article with little black discoloration even under use conditions outdoors, particularly under rainfall.

[0002]

2. Description of the Related Art Polyamide resins are widely used for parts such as automobiles and electric / 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 that parts made of conventional metals can be reduced in weight and streamlining processes. It is also possible to substitute for it, and in recent years, it has been actively studied.

[0003] In particular, when it is used for outdoor applications, it is often used in the form of a black colored molded product. Therefore, addition of carbon black has been performed as a means for improving weather resistance at the lowest cost and easily. However, the use of carbon black alone, particularly in the case of a polyamide resin in which an inorganic filler such as glass fiber is blended at a high concentration, has a disadvantage that the inorganic filler is likely to be exposed on the surface of a molded article obtained using the same. For this reason, the use of organic dyes such as azine dyes and copper phthalocyanine dyes alone or in combination with carbon black has been actively studied.

[0004] For example, a molding compound obtained by blending carbon black and nigrosine with a polyamide resin (Japanese Patent Publication No.
No. 43379) and examples of blackening a fiber reinforced polyamide resin to enhance the appearance of a molded product include a reinforced good appearance black polyamide resin composition comprising polyamide, glass fiber, carbon black, and nigrosine (JP-A-Hei. 4-370148) and the like have been proposed. However, when a black-colored molded article using an azine-based dye such as nigrosine is used outdoors, particularly when used under conditions exposed to rain, cracks are generated on the surface thereof, fading proceeds, and whitening is remarkable. There was a problem. In particular, when an inorganic filler such as glass fiber is blended in a high concentration, the emergence of the inorganic filler such as glass fiber becomes prominent, and when a molded article using a reinforced polyamide resin is used as a substitute for a metal product, It was a big problem.

Further, a method using a copper phthalocyanine dye and carbon black for the purpose of improving toughness is disclosed in JP-B-6-35541 and JP-B-6-35540. However, in the black coloring with these copper phthalocyanine dyes and carbon black, there is no suggestion for the improvement of the appearance and weatherability of the molded product in the polyamide resin composition reinforced with the inorganic filler, and the appearance of the molded product and The weather resistance was not simultaneously satisfied.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a polyamide resin composition which has little black discoloration and excellent appearance of a molded article even under use conditions outdoors, particularly under rainfall.

[0007]

Means for Solving the Problems As a result of intensive studies on the above problems, the present inventors have found that a specific amount of a copper compound and a phosphite type compound are blended in a black-colored polyamide resin reinforced with an inorganic filler, And by coloring black with carbon black and specific copper phthalocyanine derivative,
In particular, the present inventors have found a polyamide resin composition capable of obtaining a molded article having less appearance of black and having excellent appearance even under a use condition exposed to rainfall, and the present invention.

That is, the first of the present invention is that (A) 30 to 70 parts by weight of polyamide, (B) glass fiber, mica,
Talc, kaolin, 70-30 parts by weight of at least one inorganic filler selected from wollastonite,
(C) The copper compound is defined as (A) based on the copper in the copper compound.
(D) 0.05 to 10 parts by weight based on 100 parts by weight of the total amount of (A) and (B), and (E) carbon black of (I) and / or (II). The present invention relates to a black-colored polyamide resin composition comprising the copper phthalocyanine derivative represented by the formula (5) in an amount of 5 to 100 parts by weight per 100 parts by weight of (D). ^{CuPc - (- X-NR 1} R 2) n (I) CuPc - (- SO 2 -NR 3 R 4) n (II) [ wherein, copper phthalocyanine residue of CuPc is substituted or unsubstituted, X is - _{CH 2 -, - CH 2 -CH} 2 -COO-
C ₂ H ₄ — or —CH ₂ —CH ₂ —COO—C ₃ H ₆
-, R ¹ , R ² and R ³ each independently represent a hydrogen atom,
Unsubstituted alkyl group, substituted alkyl group, cycloalkyl group, alkylaryl group, aryl group, alkoxyalkyl group or heterocyclic residue, R ⁴ is an alkylaryl group,
It represents an aryl group, an alkoxyalkyl group or a heterocyclic residue, and R ¹ and R ² , or R ³ and R ⁴ may be mutually bonded to form a substituted or unsubstituted heterocyclic ring. n is 1 to
4 (average value). ]

A second aspect of the present invention is that the polyamide (A) comprises (a)
1) 85 to 100% by weight of a semi-aromatic polyamide having a crystallization temperature of 210 ° C. or less and containing an aromatic ring in its monomer structural unit, and (a2) an aliphatic polyamide 0 to 15 having a crystallization temperature of 210 ° C. or less. The present invention relates to the black-colored polyamide resin composition according to the first aspect of the present invention, which is a polyamide comprising 100% by weight. A third aspect of the present invention is that the semi-aromatic polyamide (a1) has a hexamethylene adipamide unit 70 to 9 obtained from adipic acid and hexamethylene diamine.
Black coloring according to the second aspect of the present invention, which is a semi-aromatic polyamide composed of 5% by weight and 5 to 30% by weight of hexamethylene isophthalamide units obtained from isophthalic acid and hexamethylene diamine. The present invention relates to a polyamide resin composition.

Hereinafter, the present invention will be described in detail. The polyamide (A) used in the present invention is not particularly limited, and examples thereof include polyamide 6, polyamide 66, and polyamide 61.
0, polyamide 612, polyamide 11, polyamide 1
2. A homopolymer such as polyamide 46, polyamide MXD6, a polyamide obtained by polymerizing terephthalic acid and hexamethylenediamine (hereinafter referred to as polyamide 6T), and a polyamide obtained by polymerizing hexamethylenediamine and isophthalic acid (hereinafter referred to as polyamide 6I) alone or And blends thereof. Further, a copolymer alone containing the polyamide as a component or a blend of the copolymers,
A blend of a copolymer and a homopolymer can be used.

More preferably, the polyamide (A) comprises (a1)
85-100% by weight of a semi-aromatic polyamide having a crystallization temperature of 210 ° C. or less and an aromatic ring in the monomer structural unit, and (a2) a crystallization temperature of 210 ° C. or less and an aromatic ring in the monomer structural unit Is a polyamide comprising 0 to 15% by weight of an aliphatic polyamide containing no. The polyamide, especially when the blending amount of the inorganic filler is large,
A molded article having a good appearance can be obtained. The crystallization temperature of the polyamide used in the present invention is JIS-K-712.
Refers to the crystallization peak top temperature measured at a temperature lowering rate of 20 ° C./min after holding at a temperature of melting point + 20 ° C. for 5 minutes using DSC according to 1. (A1) The crystallization temperature of the present invention is 21
The semiaromatic polyamide at 0 ° C. or lower and containing an aromatic ring in its monomer structural unit will be described in more detail below.

Semi-aromatic polyamides having a crystallization temperature of 210 ° C. or lower and containing an aromatic ring in its monomer structural unit include:
For example, hexamethylene terephthalamide units obtained from terephthalic acid and hexamethylene diamine (hereinafter referred to as 6T component), hexamethylene isophthalamide units obtained from isophthalic acid and hexamethylene diamine (hereinafter referred to as 6I component), adipic acid And a semi-aromatic polyamide containing at least one selected from meta-xylylene adipamide units (hereinafter referred to as MXD6 components) obtained from methacrylate and metaxylylenediamine, and selected from the 6T component, the 6I component, and the MXD6 component. And a hexamethylene adipamide unit (hereinafter referred to as 66 component) obtained from adipic acid and hexamethylene diamine, and a homopolymer of each unit and / or
Alternatively, it may be a blend with a copolymer.

The semiaromatic polyamide (a1) particularly preferred in the present invention is a polyamide 66 / 6I copolymer in which the 66 component is in the range of 70 to 95% by weight and the 6I component is in the range of 5 to 30% by weight, Particularly preferred are copolymers in which the 66 component is in the range of 72 to 93% by weight and the 6I component is in the range of 7 to 28% by weight. If the 6I component is less than 5% by weight, the strength and rigidity are reduced in actual use after water absorption, and the molding shrinkage during molding is large, causing problems such as warpage. In particular, as the size of a molded article increases, the molded article as a whole becomes significantly warped due to a slight difference in the molding shrinkage of the resin, and the problem becomes greater. If the 6I component is more than 30% by weight, the inorganic filler is likely to float on the surface of the molded product, for example, when molded using a mold at a temperature of 100 ° C. or less, which is temperature-controlled by water, and has a sufficient surface gloss. Cannot be obtained. Furthermore, if a sufficient cooling time is not taken in the mold, the molded product will not be released from the mold, resulting in poor productivity.

Next, the aliphatic polyamide (a2) having a crystallization temperature of 210 ° C. or lower will be described. Examples of these are polyamide 6, polyamide 610, polyamide 61
2, GA such as polyamide 66/6 copolymer or a blend thereof. The polyamide (A) used in the present invention contains the aliphatic polyamide (a2) in an amount of 0 to 1;
5% by weight can be contained. If it exceeds 15% by weight, the mechanical properties deteriorate, and furthermore, black discoloration due to weather resistance accompanied by rainfall is extremely undesirable.

As a method for producing the polyamide used in the present invention, for example, a melt polymerization method, a solid phase polymerization method, a bulk polymerization method, a solution polymerization method, or a combination thereof, from a salt of adipic acid, isophthalic acid and hexamethylenediamine. Various methods capable of performing polycondensation, such as a method, can be used. It can also be obtained from adipic acid chloride, isophthalic acid chloride and hexamethylenediamine by a method such as solution polymerization or interfacial polymerization. Among these, a method based on melt polymerization or a combination of melt polymerization and solid phase polymerization is preferably economically preferable.

The polyamide used in the present invention has a molecular weight of 1.5 to 3.5, preferably 1.8 to 3.0 as a sulfuric acid solution viscosity ηr (100 ml of 95.5% sulfuric acid per 1 g of polymer, measured at 25 ° C.). 0, and more preferably in the range of 2.0 to 2.8. If ηr is less than 1.5, the resin composition becomes brittle, and furthermore, drawing during the molding from the nozzle tip of the cylinder becomes severe, making molding impossible. On the other hand, if ηr is higher than 3.5, the melt viscosity of the resin becomes too high, and depending on the design of the mold at the time of molding, floating of the inorganic filler is partially observed, and the surface gloss is undesirably lowered.
The compounding amount of the polyamide (A) is in the range of 30 to 70 parts by weight, preferably 35 to 67 parts by weight. 30
If the compounding amount is less than the weight part, not only the fluidity of the resin becomes poor, but also it becomes difficult to fill the resin into the thin part,
It is difficult to obtain a molded product having good surface gloss. or,
If the amount is more than 70 parts by weight, the strength and rigidity are insufficient as an exterior material that can be replaced with metal.

The inorganic filler (B) used in the present invention comprises:
Glass fiber, carbon fiber, mica, talc, kaolin, at least one inorganic filler selected from wollastonite, glass fiber and mica, glass fiber and kaolin or calcined kaolin, glass fiber and wollastonite It can also be used in combination as described above. Among them, glass fibers are preferred. As the glass fiber, those commonly used for thermoplastic resins can be used, and there is no particular limitation on the fiber diameter or length.For example, any of chopped strands having a diameter of 5 to 25 μm, roving, and milled fibers can be used. May be. When using chopped strands,
The length can be appropriately selected and used within a range of 0.1 to 6 mm.

As the inorganic filler, those having a generally known silane coupling agent adhered to the surface thereof may be used.
For example, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β (aminoethyl) -γ-aminopropyltrimethoxysilane, vinyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane and the like are used. it can. The amount of the inorganic filler is 30 to 70 parts by weight, preferably 33 to 65 parts by weight.
Parts by weight. If the compounding amount is less than 30 parts by weight, the strength and rigidity are insufficient as a material that can be substituted for metal. Also, 7
If the amount is more than 0 parts by weight, the fluidity of the resin deteriorates, and it becomes difficult not only to fill the thin portion with the resin, but also to obtain a molded product having good surface gloss.

The copper compound (C) used in the present invention includes:
Copper chloride, copper bromide, copper fluoride, copper iodide, copper thiocyanate, copper nitrate, copper acetate, copper naphthenate, copper caprate, copper laurate, copper stearate, copper acetylacetone, copper oxide (I), And copper (II) oxide, among which copper halide and copper acetate are particularly preferred. The amount of the copper compound added is 10 to 10 with respect to the polyamide based on the copper in the copper compound.
00 ppm, preferably 50 to 800 ppm. When the addition amount is less than 10 ppm, the effect of improving the weather resistance is not sufficiently obtained, and when the addition amount is more than 1000 ppm, the effect of improving the weather resistance is saturated and corrosion to the metal, for example, in a polymerization reactor Corrosion of metals in extruders, molding machines, etc., and of metals inserted into molded products are likely to occur.

In the present invention, the copper compound (C) is
It is 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. Preferably, it is potassium iodide. As the compounding amount of the iodine compound, the gram atomic ratio of the iodine element and the copper element to the polyamide ([iodine] /
[Copper]) is in the range of 5 to 30, preferably 10 to 25. If it is smaller than 5, sufficient weather resistance improvement effect cannot be obtained, and if it is larger than 30, corrosion on metals, for example, corrosion of metals in polymerization reactors, extruders, molding machines, etc., and corrosion of metals inserted in molded articles occurs. It will be easier.

The carbon black (D) used in the present invention
Is not particularly limited, for example, the average particle size is in the range of 10 μm to 40 μm, the specific surface area is 50 to 300
m ² / g (BET adsorption method), oil absorption (measured value using dibutyl phthalate) is 50 cc / 100 g to 15
Those having a range of 0 cc / 100 g can be used. In the present invention, the addition amount of carbon black is 0.05 to 10 parts by weight, preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the total of (A) and (B). If the amount is less than 0.05 parts by weight, the effect of improving weather resistance is not sufficiently exhibited, and if the amount exceeds 10 parts by weight, strength, rigidity and the like are impaired.

The copper phthalocyanine derivative (E) used in the present invention is a copper phthalocyanine derivative represented by the following general formula (I) or (II). ^{CuPc - (- X-NR 1} R 2) n (I) CuPc - (- SO 2 -NR 3 R 4) n (II) [ wherein, copper phthalocyanine residue of CuPc is substituted or unsubstituted, X is - _{CH 2 -, - CH 2 -CH} 2 -COO-
C ₂ H ₄ — or —CH ₂ —CH ₂ —COO—C ₃ H ₆
-, R ¹ , R ² and R ³ each independently represent a hydrogen atom,
Unsubstituted alkyl group, substituted alkyl group, cycloalkyl group, alkylaryl group, aryl group, alkoxyalkyl group or heterocyclic residue, R ⁴ is an alkylaryl group,
It represents an aryl group, an alkoxyalkyl group or a heterocyclic residue, and R ¹ and R ² , or R ³ and R ⁴ may be mutually bonded to form a substituted or unsubstituted heterocyclic ring. n is 1 to
4 (average value). ]

Examples of the copper phthalocyanine derivative in the present invention include, for example, (alkyl) phthalimidomethyl copper phthalocyanine, dialkylaminomethyl copper phthalocyanine, (alkyl) anilinosulfamoyl copper phthalocyanine, dialkylaminopropylsulfonamide copper phthalocyanine and the like. . Among them, copper phthalocyanine sulfonamide derivatives such as (alkyl) anilinosulfamoyl copper phthalocyanine, alkoxypropylsulfonamide copper phthalocyanine, and dialkylaminopropylsulfonamide copper phthalocyanine are preferable from the viewpoint of the appearance of molded articles.

The copper phthalocyanine derivative used in the present invention can be produced by a conventionally known method using copper phthalocyanine substituted with a chlorine atom, bromine atom, sulfone group or the like or unsubstituted copper phthalocyanine.
For example, as a method for producing a sulfonamide-substituted copper phthalocyanine, a known method, for example, dissolving copper phthalocyanine in chlorosulfonic acid, followed by treatment with thionyl chloride to obtain copper phthalocyanine sulfochloride, and using this copper phthalocyanine sulfochloride It can be obtained by reacting with various amines.

The amount of the copper phthalocyanine derivative (E) in the present invention is 5 to 100 parts by weight, preferably 10 to 50 parts by weight, per 100 parts by weight of the carbon black (D). If the amount of the copper phthalocyanine derivative added to the carbon black is less than 5 parts by weight, the glass fibers are exposed on the surface of the molded product, and the discoloration is large even when exposed outdoors. Further, even if the addition amount of the copper phthalocyanine derivative exceeds 100 parts by weight, the weather resistance is saturated and is not economical.

As a method for producing the black colored polyamide resin composition of the present invention, the above components (A) to (E) and various additives used as necessary may be mixed and kneaded. At this time, there is no particular limitation on the blending, kneading method and order, and mixing is performed by a commonly used mixer, for example, a Henschel mixer, a tumbler, a ribbon blender or the like. As a kneader, a single-screw or twin-screw extruder is generally used. By such an extruder, usually, first, a pellet made of the resin composition of the present invention is produced, and the pellet is formed into an arbitrary shape by compression molding, injection molding, extrusion molding, or the like to obtain a desired resin product. be able to.
The injection molding conditions are not particularly limited.
50 ° C to 310 ° C, mold temperature 40 ° C to 120 ° C
Can be exemplified.

The order of mixing for obtaining the composition of the present invention is not particularly limited, but (A), (B),
A method of kneading (C), (D) and (E) together;
After melt kneading (A), (B) and (C), (D)
And a method of kneading (E). In addition, as a method of so-called pellet blending without melt-kneading the whole, a part of (A) and (B) and (C) are melt-kneaded. And the rest of (A) and (D) and (F)
And a method of subjecting the mixture obtained by melt-kneading to pellet blending and subjecting it to processing. In addition, in advance, polyamide (a
In 2), a master pellet containing carbon black and a copper phthalocyanine derivative at a high concentration may be prepared in advance, and this and a polyamide resin containing an inorganic filler may be blended or re-kneaded.

The polyamide resin composition of the present invention may contain, if necessary, an antioxidant, an ultraviolet absorber, and the like, which are added to a usual polyamide resin within a range not to impair the object of the present invention.
A heat stabilizer, a photo-deterioration inhibitor, a plasticizer, a lubricant, a release agent, a nucleating agent, a flame retardant, and the like may be added, or another thermoplastic resin may be blended. By using the composition obtained according to the present invention, for example, automobile parts such as outer door handles, wheel caps, roof rails, door mirror bases, rearview mirror arms, sunroof deflectors, radiator fans, bearing retainers, and legs of desks and chairs, It can be used for various office parts such as seats and armrests, as well as wheelchair parts, door handles, handrails, grip bars in bathrooms, etc., window knobs, grating materials, and other industrial and miscellaneous goods.

[0029]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples. In addition, the evaluation method is as follows. [Quantitative determination of copper element and iodine element] Regarding copper, the combustion residue of the sample was converted to an aqueous hydrochloric acid solution, and its concentration was determined by an ICP method. For iodine, its concentration was determined by an ion electrode method after extracting the sample with boiling water. [Crystallization temperature] 8 m sample according to JIS-K-7121
g was weighed accurately, and using PerkinElmer's DSC7,
After holding at a temperature of melting point + 20 ° C. for 5 minutes, a crystallization peak top temperature obtained at a measurement rate of 20 ° C./min was used.

[Surface gloss] IS1 manufactured by Toshiba Machine Co., Ltd.
Using a 50E injection molding machine, cylinder temperature 290 ° C,
At a mold temperature of 90 ° C. and 120 ° C., a filling time of about 1.5
Injection pressure and speed are adjusted appropriately so that
An injection molded plate of 00 × 90 × 3 mm was obtained. Using this flat plate, JI using a gloss meter (IG320 manufactured by HORIBA)
Gloss was measured at 60 degrees according to SK-7150. [Color difference (ΔE)] It was measured using a color difference meter ND-300A manufactured by Nippon Denshoku.

[Weather Resistance] In the same manner as used for the evaluation of the surface glossiness, an injection molded plate obtained at a mold temperature of 120 ° C. was subjected to a xenon arc accelerated weathering tester (XENOTE manufactured by Atlas Co., Ltd.).
(ST 1200 CPS), and exposed to water for 300 hours under a water spraying condition of 12 minutes per hour at a black panel temperature of 83 ° C. for evaluation. The surface gloss and color tone before and after exposure were measured, and the gloss retention and color difference were determined, respectively. The measuring method is as described above. The gloss retention is expressed as a percentage of the gloss after exposure to the gloss before exposure, and it can be determined that the higher the retention and the smaller the color difference (ΔE), the better the weather resistance.
The raw materials used in the examples of the present invention are shown below.

(A) Polyamide a1: Polyamide 66 / 6I copolymer obtained in Polymerization Example 1 described below Crystallization temperature 195 ° C. a2: Polyamide 66 / 6I / 6T copolymer obtained in Polymerization Example 2 described below Crystallization temperature 195 ° C a3: Polyamide MXD6 Made by Mitsubishi Engineering-Resin Co., Ltd .; Trade name Reny 6002 Crystallization temperature 205 ° C a4: Polyamide 66 Made by Asahi Kasei Corporation; Trade name Leona 1300 Crystallization temperature 225 ° C a5: Polyamide 6 Ube Industries, Ltd .; trade name SF1013A Crystallization temperature 162 ° C

(B) Inorganic filler b1: Glass fiber manufactured by Asahi Fiber Glass Co., Ltd. CS03JA416 b2: Glass fiber manufactured by Asahi Fiber Glass Co., Ltd. Product name CS03FT692 b3: Wallastonite Hayashi Kasei Co., Ltd. Product name VM-8N b4: Calcined kaolin Engelhard product name Translink 445

(E) Copper phthalocyanine derivative e1: Copper phthalocyanine sulfonamide derivative

Embedded image E2: Copper phthalocyanine imide methyl derivative manufactured by Dainippon Ink and Chemicals, Inc.

Embedded image Manufactured by Dainippon Ink and Chemicals, Inc.

[Polymerization Example 1] 5 l of 2.00 kg of equimolar salt of adipic acid and hexamethylenediamine, 0.50 kg of equimolar salt of isophthalic acid and hexamethylenediamine, 0.10 kg of adipic acid, and 2.5 kg of pure water Into an autoclave and stirred well. After the atmosphere is sufficiently purged with nitrogen, the temperature is raised from room temperature to 220 ° C. with stirring, for about 1 hour.
The temperature was raised over time. At this time, the internal pressure becomes 18 kg / cm ² -G 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 18 kg / cm ² -G 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. Open the autoclave after cooling, about 2kg
Was taken out and pulverized. The obtained pulverized polymer was put in a 10-liter evaporator, and was placed under a nitrogen stream for 200 hours.
Solid-state polymerization was performed at 10 ° C. for 10 hours. The polyamide obtained by solid phase polymerization had a terminal carboxyl group concentration of 102 and a terminal amino group concentration of 44.

[Polymerization Example 2] 1.75 kg of equimolar salt of adipic acid and hexamethylenediamine, 0.50 kg of equimolar salt of isophthalic acid and hexamethylenediamine, and 0.25 kg of equimolar salt of terephthalic acid and hexamethylenediamine
And adipic acid 0.10 kg, and pure water 2.5 kg
Was charged into a 5 L autoclave and stirred well. After sufficiently purging with nitrogen, 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 is 18 kg / cm ² −
The heating was continued while removing water from the reaction system so that the pressure did not reach 18 kg / cm ² -G. 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-liter evaporator and subjected to solid-state polymerization at 200 ° C. for 10 hours under a nitrogen stream. The polyamide obtained by solid-state polymerization had a terminal carboxyl group concentration of 105 and a terminal amino group concentration of 38.

[0037]

Example 1 A1 was mixed as polyamide, copper iodide, potassium iodide, carbon black (# 50, manufactured by Mitsubishi Chemical Corporation) as a copper compound, and e1 was mixed as a copper phthalocyanine derivative, and mixed with Toshiba Machine Co., Ltd. TEM35φ twin screw extruder (Set temperature 280 ° C, Screw rotation speed 300r
pm) from a feed hopper, and b1 as an inorganic filler from a side feed port so that the final composition has the composition shown in Table 1, respectively. The melt-kneaded product extruded from the spinneret is formed into a strand. The mixture was cooled and pelletized to obtain a black-colored polyamide resin composition. Table 1 shows the results of evaluating the obtained black-colored polyamide resin composition.

[0038]

Example 2 85.6 parts by weight of a4 as a polyamide,
12 parts by weight of carbon black (# 50, manufactured by Mitsubishi Chemical Corporation), and e1 as a copper phthalocyanine derivative.
4 parts by weight were mixed, and TEM35φ2 manufactured by Toshiba Machine Co., Ltd.
Screw extruder (set temperature 250 ° C, screw rotation speed 300
rpm) from a feed hopper to obtain a black coloring masterbatch. Then, a1 as a polyamide, copper iodide, potassium iodide and the masterbatch for black coloring were mixed, and a TEM35φ twin-screw extruder manufactured by Toshiba Machine Co., Ltd. (set temperature: 280 ° C., screw rotation speed: 300 rpm)
m) from the feed hopper, and b1 as an inorganic filler from the side feed port so that the final composition has the composition shown in Table 1, respectively. The melt-kneaded product extruded from the spinneret is supplied in the form of a strand. The mixture was cooled and pelletized to obtain a black-colored polyamide resin composition. Table 1 shows the results of evaluating the obtained black-colored polyamide resin composition.

[0039]

Examples 3 to 8 and 11 A black-colored polyamide resin composition was obtained in the same manner as in Example 1, except that the types and amounts of the polyamide and the inorganic filler were changed to the compositions shown in Tables 1 and 2, respectively. Was. Table 1 shows the results of evaluating the obtained black-colored polyamide resin composition.

Example 9 A black-colored polyamide resin composition was obtained in the same manner as in Example 1 except that the amount of the copper compound was changed as shown in Table 2. Table 2 shows the results of evaluating the obtained black-colored polyamide resin composition.

[0040]

Example 10 A black-colored polyamide resin composition was obtained in the same manner as in Example 1, except that the type of the copper phthalocyanine derivative was changed to e2. The compositions obtained in Examples 1 to 13 were:
In each case, excellent results were obtained in both surface gloss and weather resistance. Table 2 shows the results of evaluating the obtained black-colored polyamide resin composition.

[0041]

[Table 1]

[0042]

[Table 2]

[0043]

Comparative Example 1 A black-colored polyamide resin composition was obtained by the same composition and production method as in Example 1 except that no copper compound and no halogen compound were added. Table 3 shows the results of evaluating the obtained black-colored polyamide resin composition. The weather resistance is clearly inferior to Example 1.

Comparative Example 2 A black-colored polyamide resin composition was obtained by the same composition and production method as in Example 1 except that no copper phthalocyanine derivative was added. Table 3 shows the results of evaluating the obtained black-colored polyamide resin composition. The surface glossiness and weather resistance are clearly inferior to those of Example 1.

[0044]

Comparative Example 3 A black colored polyamide resin composition was obtained in the same manner as in Example 1 except that the copper phthalocyanine derivative was added in an amount of 200 parts by weight based on 100 parts by weight of carbon black. Table 3 shows the results of evaluating the obtained black-colored polyamide resin composition. Compared with Example 1, there was no significant improvement in the surface gloss, weather resistance, and weather resistance, and the weather resistance was rather poor.

[0045]

[Table 3]

[0046]

Industrial Applicability The black-colored polyamide resin composition of the present invention has superior mechanical properties, molded article appearance, and weather resistance as compared with conventional ones. Wide range of automotive exterior parts such as door handles, wheel caps, roof rails, door mirror bases, rearview mirror arms, sunroof deflectors, radiator fans, bearing retainers, etc. because of their high fade resistance and gloss retention even under conditions including rainfall. It can be suitably used in the field.

[Procedure amendment]

[Submission date] November 4, 1998

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0041

[Correction method] Change

[Correction contents]

[0041]

[Table 1]

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0042

[Correction method] Change

[Correction contents]

[0042]

[Table 2]

[Procedure amendment 3]

[Document name to be amended] Statement

[Correction target item name] 0045

[Correction method] Change

[Correction contents]

[0045]

[Table 3]

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08K 7/14 C08K 7/14

Claims (3)

[Claims] 1. A polyamide resin composition comprising the following (A) to (E), wherein (A) is 30 to 70 parts by weight,
(B) 70 to 30 parts by weight, (C) 10 to 1000 ppm with respect to (A) based on copper in the copper compound,
(D) is 0.05 to 10 parts by weight based on 100 parts by weight of the total amount of (A) and (B), and (E) is 100 parts by weight of (D).
A black-colored polyamide resin composition comprising 5 to 100 parts by weight based on parts by weight. (A) Polyamide (B) At least one inorganic filler selected from glass fiber, mica, talc, kaolin, wollastonite (C) Copper compound (D) Carbon black (E) General formula (I) and / or (II) copper phthalocyanine derivative represented by ^{CuPc - (- X-NR 1} R 2) n (I) CuPc - (- SO 2 -NR 3 R 4) n (II) [ wherein, CuPc is substituted or unsubstituted copper phthalocyanine residue, X is _{-CH 2 -, - CH 2 -CH} 2 -COO-
C ₂ H ₄ — or —CH ₂ —CH ₂ —COO—C ₃ H ₆
-, R ¹ , R ² and R ³ each independently represent a hydrogen atom,
Unsubstituted alkyl group, substituted alkyl group, cycloalkyl group, alkylaryl group, aryl group, alkoxyalkyl group or heterocyclic residue, R ⁴ is an alkylaryl group,
It represents an aryl group, an alkoxyalkyl group or a heterocyclic residue, and R ¹ and R ² , or R ³ and R ⁴ may be mutually bonded to form a substituted or unsubstituted heterocyclic ring. n is 1 to
4 (average value). ] 2. A polyamide (A) comprising: (a1) 85 to 100% by weight of a semiaromatic polyamide having a crystallization temperature of 210 ° C. or lower and having an aromatic ring in its monomer structural unit;
2) Aliphatic polyamide 0 having a crystallization temperature of 210 ° C. or lower
The black-colored polyamide resin composition according to claim 1, which is a polyamide composed of from 15 to 15% by weight. 3. A semi-aromatic polyamide (a1) comprising 70 to 95% by weight of hexamethylene adipamide units obtained from adipic acid and hexamethylene diamine, and hexamethylene isophthalamide obtained from isophthalic acid and hexamethylene diamine. The black-colored polyamide resin composition according to claim 2, which is a semi-aromatic polyamide composed of 5 to 30% by weight of units.