Masterbatch for resin coloring, polyamide resin composition, molded article, and method for producing the same

Abstract

To provide: a resin coloring masterbatch which contains a polyamide resin and carbon black and can provide a polyamide resin composition and a molded article having an original black hue; a polyamide resin composition; a molded article thereof: and production methods of these.SOLUTION: Provided is a resin coloring masterbatch formed by mixing a polyamide resin (A), carbon black (B), and a metal phthalocyanine derivative (C) forming a complex with copper or zinc. The metal phthalocyanine derivative (C) has a functional group represented by the following general formula (1) or the following general formula (2). Relative to 100 pts.mass of the polyamide resin (A), a content of the carbon black (B) is in a range of 15 pts.mass to 100 pts.mass and a content of the metal phthalocyanine derivative (C) is in a range of 3 pts.mass to 50 pts.mass: -(X-NR1R2)n1 (1); and -(SO2-NR3R4)n2 (2).SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a masterbatch for resin coloring, a polyamide resin composition, a molded article, and methods for producing them.

Background Art

[0002] Polyamide resins have excellent mechanical properties, particularly toughness, and excellent chemical properties. Therefore, the demand for polyamide resins is increasing in various fields such as fibers, films, and parts for automobiles, electric and electronic products, etc.

[0003] Coloring of polyamide resins is carried out for purposes such as decorative effects, color separation effects, improvement of the light resistance of molded articles, protection and concealment of contents, etc. Among these, black coloring is the most important in the industry. Conventionally, coloring of polyamide resins with carbon black has been mainly attempted.

[0004] However, although carbon black has excellent physical properties, polyamide resins colored with carbon black have a specific reddish-black hue, which gives an inexpensive impression to products. Therefore, improvement of this reddish-black hue has been desired.

[0005] For example, Patent Document 1 below discloses a molded article comprising a molding composition colored with carbon black and nigrosine in a polyamide resin. However, with the technique disclosed in Patent Document 1, the reddish hue could not be eliminated.

[0006] Further, for example, Patent Document 2 below discloses a molded article made of a molding composition colored with carbon black and copper phthalocyanine pigment in a polyamide resin. However, when passing through a masterbatch, a masterbatch is produced by blending a high concentration of carbon black and copper phthalocyanine pigment in a polyamide resin, and then diluted with a thermoplastic resin to produce a colored resin composition. However, since the melt viscosity of the masterbatch is high and the difference in melt viscosity from the thermoplastic resin is large, the dispersibility during dilution of the coloring components of carbon black and copper phthalocyanine pigment is poor, and the original black color hue cannot be obtained.

Prior Art Documents

Patent Documents

[0007]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0008] Therefore, the problem to be solved by the present invention is to provide a resin coloring masterbatch, a polyamide resin composition, a molded article thereof, and a method for producing them, which contain a polyamide resin and carbon black and can obtain a polyamide resin composition and a molded article having an original black color hue.

Means for Solving the Problems

[0009] The present inventors conducted intensive studies to solve the above problems. As a result, they found that by blending a specific metal phthalocyanine derivative and making the conductivity below a certain level, the above problems can be solved, and thus the present invention was completed.

[0010] That is, the present invention is a resin coloring masterbatch comprising a polyamide resin (A), carbon black (B), and a metal phthalocyanine derivative (C) that forms a complex with copper or zinc, wherein the metal phthalocyanine derivative (C) has a functional group represented by the following general formula (1) or a functional group represented by the following general formula (2), and with respect to 100 parts by mass of the polyamide resin (A), the carbon black (B) is in the range of 15 parts by mass or more to 100 parts by mass or less, and the metal phthalocyanine derivative (C) is in the range of 3 parts by mass or more to 50 parts by mass or less. -(X-NR 1 R 2 ) n1 (1) -(SO2-NR 3 R 4 ) n2 (2) (In the general formula (1), X is -CH2-, -CH2-CH2-COO-C2H4- or -CH2-CH2-COO-C3H6-, R 1 and R 2 each independently represent a hydrogen atom, an unsubstituted alkyl group, a substituted alkyl group, a cycloalkyl group, an alkylaryl group, an aryl group, an alkoxyalkyl group or a heterocyclic residue, and R 1 and R 2 may be bonded to each other to form a substituted or unsubstituted heterocyclic ring, and n1 is an integer in the range of 1 or more to 4 or less. In the general formula (2), R 3 is a hydrogen atom, an unsubstituted alkyl group, a substituted alkyl group, a cycloalkyl group, an alkylaryl group, an aryl group, an alkoxyalkyl group or a heterocyclic residue, R 4 represents an alkylaryl group, an aryl group, an alkoxyalkyl group or a heterocyclic residue, and R 3 and R 4 may be bonded to each other to form a substituted or unsubstituted heterocyclic ring, and n2 is an integer in the range of 1 or more to 4 or less.)

[0011] The present invention also relates to a polyamide resin composition obtained by blending the masterbatch for resin coloring and further a thermoplastic resin (D), wherein, based on 100 parts by mass in total of the polyamide resin (A) and the thermoplastic resin (D), the carbon black (B) is in the range of 0.3 parts by mass or more to 17 parts by mass or less, the metal phthalocyanine derivative (C) is in the range of 0.05 parts by mass or more to 10 parts by mass or less, and the total proportion of the polyamide resin (A), the carbon black (B), the metal phthalocyanine derivative (C) and the thermoplastic resin (D) in the polyamide resin composition is in the range of more than 72% by mass.

[0012] The present invention also relates to a molded article obtained by melt-molding the polyamide resin composition.

[0013] The present invention also relates to a method for producing a masterbatch for resin coloring, which comprises a step 1 of blending and melt-kneading a polyamide resin (A), a carbon black (B), and a metal phthalocyanine derivative (C) that forms a complex with copper or zinc, wherein the metal phthalocyanine derivative (C) has a functional group represented by the following general formula (1) or a functional group represented by the following general formula (2), and the blending ratios of the polyamide resin (A), the carbon black (B), and the metal phthalocyanine derivative (C) are such that, based on 100 parts by mass of the polyamide resin (A), the carbon black (B) is in the range of 15 parts by mass or more to 100 parts by mass or less, and the metal phthalocyanine derivative (C) is in the range of 3 parts by mass or more to 50 parts by mass or less. -(X-NR 1 R 2 ) n1 (1) -(SO2-NR 3 R 4 ) n2 (2) (In the general formula (1), X is -CH2-, -CH2-CH2-COO-C2H4- or -CH2-CH2-COO-C3H6-, R 1 and R 2each independently represents a hydrogen atom, an unsubstituted alkyl group, a substituted alkyl group, a cycloalkyl group, an alkylaryl group, an aryl group, an alkoxyalkyl group, or a heterocyclic residue, R 1 and R 2 may be bonded to each other to form a substituted or unsubstituted heterocyclic ring, and n1 is an integer in the range from 1 or more to 4 or less. In the general formula (2), R 3 is a hydrogen atom, an unsubstituted alkyl group, a substituted alkyl group, a cycloalkyl group, an alkylaryl group, an aryl group, an alkoxyalkyl group, or a heterocyclic residue, R 4 represents an alkylaryl group, an aryl group, an alkoxyalkyl group, or a heterocyclic residue, R 3 and R 4 may be bonded to each other to form a substituted or unsubstituted heterocyclic ring, and n2 is an integer in the range from 1 or more to 4 or less.)

[0014] Further, the present invention is a method for producing a polyamide resin composition, which includes step 2 of melt-kneading the resin masterbatch for coloring obtained by the method for producing the resin masterbatch for coloring and further a thermoplastic resin (D).

[0015] Further, the present invention is a method for producing a molded article, which includes step 3 of melt-molding the polyamide resin composition obtained by the method for producing the polyamide resin composition. [Effect of the Invention]

[0016] According to the present invention, it is possible to provide a resin masterbatch for coloring, a polyamide resin composition, a molded article thereof, and methods for producing them, which contain a polyamide resin and carbon black and can obtain a polyamide resin composition and a molded article having an original black color tone. [Embodiments for Carrying Out the Invention]

[0017] Hereinafter, embodiments for carrying out the present invention will be described in detail.

[0018] In one embodiment of the present invention, the masterbatch for resin coloring is a masterbatch for resin coloring obtained by blending a polyamide resin (A), carbon black (B), and a metal phthalocyanine derivative (C) that forms a complex with copper or zinc, wherein the metal phthalocyanine derivative (C) has a functional group represented by the following general formula (1) or a functional group represented by the following general formula (2), and with respect to 100 parts by mass of the polyamide resin (A), the carbon black (B) is in the range of 15 parts by mass or more to 100 parts by mass or less, and the metal phthalocyanine derivative (C) is in the range of 3 parts by mass or more to 50 parts by mass or less. -(X-NR 1 R 2 ) n1 (1) -(SO2-NR 3 R 4 ) n2 (2) (In the general formula (1), X is -CH2-, -CH2-CH2-COO-C2H4- or -CH2-CH2-COO-C3H6-, R 1 and R 2 each independently represent a hydrogen atom, an unsubstituted alkyl group, a substituted alkyl group, a cycloalkyl group, an alkylaryl group, an aryl group, an alkoxyalkyl group or a heterocyclic residue, and R 1 and R 2 may be bonded to each other to form a substituted or unsubstituted heterocyclic ring, and n1 is an integer in the range of 1 or more to 4 or less. In the general formula (2), R 3 is a hydrogen atom, an unsubstituted alkyl group, a substituted alkyl group, a cycloalkyl group, an alkylaryl group, an aryl group, an alkoxyalkyl group or a heterocyclic residue, R 4 represents an alkylaryl group, an aryl group, an alkoxyalkyl group or a heterocyclic residue, and R 3 and R 4 may be bonded to each other to form a substituted or unsubstituted heterocyclic ring, and n2 is an integer in the range of 1 or more to 4 or less.)

[0019] According to the masterbatch for resin coloring, a masterbatch for resin coloring, a polyamide resin composition, and a molded article thereof that contain a polyamide resin and carbon black and can obtain a polyamide resin composition and a molded article having an original black hue can be provided. The reason for obtaining such an effect is not necessarily clear, but it is presumed to be due to the following mechanism.

[0020] As described above, when a molded article made of a molding composition colored with carbon black and a copper phthalocyanine pigment is manufactured via a masterbatch in a polyamide resin, the melt viscosity of the masterbatch increases. The inventors of the present invention have found that there is a correlation between the melt viscosity and the conductivity of the masterbatch for resin coloring, and based on this correlation, they hypothesized that carbon black and the copper phthalocyanine pigment interact and adsorb to each other to form aggregates, resulting in an increase in melt viscosity. It is considered that there is a correlation between the melt viscosity and the conductivity of the masterbatch because the aggregates serve as conductive paths, increasing the conductivity of the masterbatch. The masterbatch for resin coloring of the present invention sets the respective contents of the polyamide resin (A), carbon black (B), and metal phthalocyanine derivative (C) within a specific range, so that steric hindrance occurs due to the functional group of the metal phthalocyanine derivative (C), reducing the formation of aggregates of the carbon black (B) and the metal phthalocyanine derivative (C) and suppressing the conductivity below a certain level, thus it is considered that the above problems can be solved.

[0021] The polyamide resin (A) is a polymer having an acid amide bond (-CONH-) in the main chain. Examples of such polyamide resins (A) include nylon 6 (also referred to as "poly(caprolactam)"), nylon 11 (also referred to as "poly(11-aminoundecanoic acid)"), nylon 12 (also referred to as "poly(lauryllactam)" or "poly(12-aminododecanoic acid)"), nylon 6.6 (also referred to as "poly(hexamethylene adipamide)"), nylon 6.9 (also referred to as "poly(hexamethylene azelamide) or poly(hexamethylene nonanediamide)"), nylon 6.10 (also referred to as "poly(hexamethylene sebacamide)" or "poly(hexamethylene decanediamide)"), nylon 6.12 (also referred to as "poly(hexamethylene dodecanediamide)"), nylon 4 (also referred to as "poly(δ-butyrolactam)"), nylon 7 (also referred to as "poly(7-aminoheptanoic acid)" or "poly(7-aminocaprylic acid)"), nylon 8 (also referred to as "poly(8-aminocaprylic acid)" or "poly(8-aminooctanoic acid)"), nylon 10,6 (also referred to as "poly(decamethylene adipamide)"), partially aromatic nylon (PARNS), and the like.

[0022] The carbon black (B) can be carbon black used as a pigment, which is produced by methods such as the known contact method, furnace method, thermal method, etc. without particular limitation. For example, the #2600 series, #2300 series, #1000 series, #900 series, MA series manufactured by Mitsubishi Chemical Corporation, the COLOR-BLACK series, SPESIAL-BLACK series, PRINTEX series, HIBLACK series, NEROX series, NIPex series manufactured by Orion Engineered Carbons, the SUNBLACK series, #70 series, #80 series manufactured by Asahi Carbon Co., Ltd., the Tokablack #7000 series, #8000 series manufactured by Tokai Carbon Co., Ltd., and the like.

[0023] The average particle size of the carbon black (B) contained in the resin coloring masterbatch is not particularly limited, but since it can exhibit a black color phase with an improved red hue, it is preferably 500 nm or less, more preferably 100 nm or less. The lower limit is not particularly limited, but is preferably 10 nm or more, more preferably 15 nm or more. In this specification, the average particle size is measured by the method described in the examples.

[0024] The carbon black (B) may have its surface physically or chemically treated. The surface area of the carbon black (B) is not particularly limited, but preferably the BET specific surface area [m 2 / g] is in the range of 30 or more, more preferably 50 or more, still more preferably 80 or more to preferably 500 or less, more preferably 400 or less, still more preferably 350 or less.

[0025] The metal phthalocyanine derivative (C) is a coloring material that exhibits a color from blue to green. The metal phthalocyanine derivative (C) has a phthalocyanine skeleton having a functional group represented by the general formula (1) or a functional group represented by the general formula (2), and copper or zinc is coordinated as a central metal element to form a complex.

[0026] Examples of the metal phthalocyanine derivative (C) include, for example, (alkyl) phthalimidomethyl copper phthalocyanine, dialkylaminomethyl copper phthalocyanine, (alkyl) anilinylsulfamoyl copper phthalocyanine, alkoxypropylsulfonamide copper phthalocyanine, dialkylaminopropylsulfonamide copper phthalocyanine, (alkyl) phthalimidomethyl zinc phthalocyanine, dialkylaminomethyl zinc phthalocyanine, (alkyl) anilinylsulfamoyl zinc phthalocyanine, alkoxypropylsulfonamide zinc phthalocyanine, dialkylaminopropylsulfonamide zinc phthalocyanine, and the like. Among them, copper phthalocyanine sulfonamide derivatives such as (alkyl) anilinylsulfamoyl copper phthalocyanine, alkoxypropylsulfonamide copper phthalocyanine, and dialkylaminopropylsulfonamide copper phthalocyanine are preferred because they exhibit a black color phase with improved redness.

[0027] As a method for producing the metal phthalocyanine derivative (C), it can be produced by a conventionally known method using copper phthalocyanine substituted with a chlorine atom, bromine atom, sulfone group, etc., or unsubstituted copper phthalocyanine, or zinc phthalocyanine substituted with a chlorine atom, bromine atom, sulfone group, etc., or unsubstituted zinc phthalocyanine. For example, as a method for producing sulfonamide-substituted copper phthalocyanine, it can be obtained by a known method, for example, dissolving copper phthalocyanine in chlorosulfonic acid, then treating it with thionyl chloride to obtain copper phthalocyanine sulfochloride, and reacting this copper phthalocyanine sulfochloride with various amines.

[0028] The average particle size of the metal phthalocyanine derivative (C) contained in the resin coloring masterbatch is not particularly limited, but since it can exhibit a black color phase with improved redness, it is preferably in the range of 400 nm or less, more preferably in the range of 300 nm or less. The lower limit value is not particularly limited, but it is preferably in the range of 5 nm or more, more preferably in the range of 15 nm or more.

[0029] The maximum particle sizes of the carbon black (B) and the metal phthalocyanine derivative (C) contained in the masterbatch for resin coloring are not particularly limited. However, since a black color phase with an improved red hue is exhibited, it is preferable that 99% by mass of the particles of the carbon black (B) and the metal phthalocyanine derivative (C) are in the range of less than 40 μm, more preferably in the range of 20 μm or less, and even more preferably 100% by mass of the particles are in the range of 20 μm or less.

[0030] In the masterbatch for resin coloring, the compounding ratios of the polyamide resin (A), the carbon black (B), and the metal phthalocyanine derivative (C) are such that, based on 100 parts by mass of the polyamide resin (A), the carbon black (B) is in the range of 15 parts by mass or more, preferably 30 parts by mass or more, more preferably 40 parts by mass or more to 100 parts by mass or less, preferably 80 parts by mass or less, and the metal phthalocyanine derivative (C) is in the range of 3 parts by mass or more, preferably 4 parts by mass or more to 50 parts by mass or less, preferably 20 parts by mass or less. When the compounding ratios of the carbon black (B) and the metal phthalocyanine derivative (C) are each below the lower limit, the addition amount of the masterbatch to the final molded product increases, and the thermal history during processing increases, resulting in a stronger yellowish-red color of the product. When the compounding ratios of the carbon black (B) and the metal phthalocyanine derivative (C) each exceed the upper limit, the processability deteriorates and the color development property decreases.

[0031] The compounding ratio of the carbon black (B) and the metal phthalocyanine derivative (C) in the masterbatch for resin coloring is not particularly limited. However, from the viewpoint of obtaining a black color phase with an improved red hue, based on 100 parts by mass of the carbon black (B), the metal phthalocyanine derivative (C) is preferably in the range of 3 parts by mass or more, more preferably 4 parts by mass or more to 333 parts by mass or less, more preferably 30 parts by mass or less.

[0032] In the masterbatch for resin coloring, known additives other than the polyamide resin (A), the carbon black (B), and the metal phthalocyanine derivative (C) can also be used as optional raw material components. Such known additives include halogen-based flame retardants, nitrogen-based flame retardants, phosphate ester-based flame retardants, inorganic flame retardants such as metal hydroxides and oxides, silicone-based flame retardants, flame retardants such as organic metal phosphates, antioxidants such as hindered phenol-based compounds, hydroquinone-based compounds, phosphite-based compounds and their substituents, weathering agents such as resorcinol-based compounds, salicylate-based compounds, benzotriazole-based compounds, benzophenone-based compounds, hindered amine-based compounds, mold release agents or lubricants such as aliphatic alcohols, aliphatic amides, aliphatic bisamides, bisurea compounds, polyethylene wax, crystal nucleating agents such as talc, silica, kaolin, clay, plasticizers such as octyl p -oxybenzoate, N -butylbenzenesulfonamide, antistatic agents such as alkyl sulfate type anionic antistatic agents, quaternary ammonium salt type cationic antistatic agents, nonionic antistatic agents such as polyoxyethylene sorbitan monostearate, betaine type amphoteric antistatic agents, particulate, acicular, plate-like various fillers such as graphite, barium sulfate, magnesium sulfate, calcium carbonate, magnesium carbonate, antimony oxide, titanium oxide, aluminum oxide, zinc oxide, iron oxide, zinc sulfide, zinc, lead, nickel, aluminum, copper, iron, stainless steel, bentonite, montmorillonite, synthetic mica, reinforcing materials such as glass fiber, glass flake, carbon fiber, boron nitride, potassium titanate, aluminum borate, etc. When these additives are used as optional components, the blending ratio in the masterbatch for resin coloring is in the range of 25% by mass or less because a black color phase with an improved red hue can be exhibited. In other words, the total ratio of the polyamide resin (A), the carbon black (B), and the metal phthalocyanine derivative (C) in the masterbatch for resin coloring is preferably more than 72% by mass, more preferably more than 75% by mass.

[0033] Since the conductivity of the masterbatch for resin coloring can exhibit a black color phase with improved red hue, it is preferably 10 -1 Scm -1 or less, more preferably 10 -2 Scm -1 or less, and within the following range.

[0034] The range of the melt flow rate of the masterbatch for resin coloring is such that at 280 °C and a load of 2.16 kg, the lower limit value is 1 g / 10 min or more, preferably 5 g / 10 min or more. On the other hand, the upper limit value is not particularly limited, but is preferably equal to or less than the value measured for the polyamide resin (A) used under the same conditions, and more preferably 50 g / 10 min or less.

[0035] In one embodiment of the present invention, the polyamide resin composition is the polyamide resin composition obtained by blending the masterbatch for resin coloring and further a thermoplastic resin (D). With respect to a total of 100 parts by mass of the polyamide resin (A) and the thermoplastic resin (D), the carbon black (B) is in the range of 0.3 part by mass or more to 17 parts by mass or less, and the metal phthalocyanine derivative (C) is in the range of 0.05 part by mass or more to 10 parts by mass or less. The total proportion of the polyamide resin (A), the carbon black (B), the metal phthalocyanine derivative (C), and the thermoplastic resin (D) in the polyamide resin composition is in the range of more than 72% by mass.

[0036] The average particle diameter of the carbon black (B) in the polyamide resin composition is not particularly limited, but since it can exhibit a black color phase with improved red hue, it is preferably in the range of 30 nm or less, more preferably in the range of 28 nm or less. The lower limit value is not particularly limited, but is preferably in the range of 10 nm or more, more preferably in the range of 15 nm or more.

[0037] The average particle size of the metal phthalocyanine derivative (C) in the polyamide resin composition is not particularly limited, but since it can exhibit a black color phase with an improved red color phase, it is preferably in the range of 800 nm or less, more preferably in the range of 500 nm or less. The lower limit value is not particularly limited, but is preferably in the range of 10 nm or more, more preferably in the range of 30 nm or more.

[0038] The maximum particle size of the carbon black (B) and the metal phthalocyanine derivative (C) in the polyamide resin composition is not particularly limited, but since it can exhibit a black color phase with an improved red color phase, it is preferable that 99% by mass of the particles of the carbon black (B) and the metal phthalocyanine derivative (C) is in the range of less than 40 μm, more preferably in the range of 20 μm or less, and even more preferably 100% by mass of the particles is in the range of 20 μm or less.

[0039] The blending ratios of the polyamide resin (A), the carbon black (B) and the metal phthalocyanine derivative (C) in the polyamide resin composition are not particularly limited as long as the effects of the present invention are not impaired, but based on 100 parts by mass of the polyamide resin (A), the carbon black (B) is preferably in the range of 15 parts by mass or more, more preferably 30 parts by mass or more, even more preferably 40 parts by mass or more to preferably 100 parts by mass or less, more preferably 80 parts by mass or less, and the metal phthalocyanine derivative (C) is preferably in the range of 3 parts by mass or more, more preferably 4 parts by mass or more to preferably 50 parts by mass or less, more preferably 20 parts by mass or less.

[0040] The blending ratio of the carbon black (B) and the metal phthalocyanine derivative (C) in the polyamide resin composition is not particularly limited, but from the viewpoint of obtaining a black color phase with an improved red color phase, based on 100 parts by mass of the carbon black (B), the metal phthalocyanine derivative (C) is preferably in the range of 3 parts by mass or more, more preferably 4 parts by mass or more to preferably 333 parts by mass or less, more preferably 30 parts by mass or less.

[0041] The thermoplastic resin (D) is not particularly limited as long as the effects of the present invention are not impaired. For example, polyamide resin, polycarbonate resin, rubber-reinforced styrene resin, polyester resin, polyether ketone resin, polyether resin, polyimide resin, polyarylene sulfide resin, polyarylene ether resin, silicone compound, etc. may be mentioned. Among these, polyamide resin is preferably mentioned. When using a polyamide resin as the thermoplastic resin (D), depending on the purpose, the same type of resin may be used, or a different type of polyamide resin from that used as the polyamide resin (A) may be used. However, from the viewpoint of compatibility, it is preferable to use the same type of polyamide resin as the polyamide resin (A).

[0042] In the polyamide resin composition, the blending ratio of the polyamide resin (A), the carbon black (B), the metal phthalocyanine derivative (C), and the thermoplastic resin (D) is such that, based on a total of 100 parts by mass of the polyamide resin (A) and the thermoplastic resin (D), the carbon black (B) is in the range of 0.3 parts by mass or more, preferably 0.5 parts by mass or more, to 17 parts by mass or less, preferably 12 parts by mass or less, and the metal phthalocyanine derivative (C) is in the range of 0.05 parts by mass or more, preferably 0.08 parts by mass or more, to 10 parts by mass or less, preferably 5 parts by mass or less.

[0043] In the polyamide resin composition, the total ratio of the polyamide resin (A), the carbon black (B), the metal phthalocyanine derivative (C), and the thermoplastic resin (D) is in the range of more than 72% by mass, preferably 75% by mass or more.

[0044] The range of the melt flow rate of the polyamide resin composition is not particularly limited, but at 280 °C and a load of 2.16 kg, the lower limit is 1 g / 10 min or more, preferably 5 g / 10 min or more. On the other hand, the upper limit is not particularly set, but is preferably the same as or less than the value measured for the polyamide resin (A) under the same conditions. Although it is difficult to uniformly define specific numerical values because they depend on the type of polyamide resin (A) used, it is preferably 300 g / 10 min or less.

[0045] The form of the polyamide resin composition is not particularly limited as long as the effects of the present invention are not impaired. After the melt kneading, it can also be extruded into a strand shape and then cut into granular forms such as pellet shape and chip shape.

[0046] In one embodiment of the present invention, the method for producing the resin coloring masterbatch includes step 1 of blending and melt kneading the polyamide resin (A), the carbon black (B), and the metal phthalocyanine derivative (C), and the blending ratios of the polyamide resin (A), the carbon black (B), and the metal phthalocyanine derivative (C) are in the range of 15 parts by mass or more to 100 parts by mass or less of the carbon black (B) and 3 parts by mass or more to 50 parts by mass or less of the metal phthalocyanine derivative (C) with respect to 100 parts by mass of the polyamide resin (A).

[0047] In step 1, the shape of the carbon black (B) is preferably particulate. The average particle size is in the range of 30 nm or less, more preferably 28 nm or less, and even more preferably 25 nm or less, from the viewpoint of obtaining a deep black color hue. The lower limit of the average particle size range is not particularly set, but is preferably 10 nm or more, more preferably 15 nm or more, and even more preferably 18 nm or more.

[0048] In the above step 1, the shape of the metal phthalocyanine derivative (C) is preferably particulate. The average particle size is not particularly limited, but from the viewpoint of obtaining a black color phase with an improved red hue, it is preferably 10 nm or more, more preferably 30 nm or more, still more preferably 40 nm or more, and preferably 800 nm or less, more preferably 500 nm or less, still more preferably in the range of 300 nm or less.

[0049] In the above step 1, the polyamide resin (A), the carbon black (B), the metal phthalocyanine derivative (C), and, if necessary, the other colorants and the other additives which are optional raw material components (hereinafter simply referred to as "optional raw material components") are pre-mixed in various forms such as bulk, pellet, chip, etc. as required, and then charged into a melt kneader and heated to a temperature equal to or higher than the melting point of the polyamide resin (A) for melt kneading. The form of the melt kneaded product is not particularly limited as long as the effects of the present invention are not impaired, and it can be fed to the subsequent step 2 in a molten state, but it is preferably extruded into strands once and then cut into granules such as pellets and chips.

[0050] In the above step 1, the blending ratio of the polyamide resin (A), the carbon black (B), and the metal phthalocyanine derivative (C) is such that, based on 100 parts by mass of the polyamide resin (A), the carbon black (B) is in the range of 15 parts by mass or more, preferably 30 parts by mass or more, more preferably 40 parts by mass or more, and 100 parts by mass or less, preferably 80 parts by mass or less, and the metal phthalocyanine derivative (C) is in the range of 3 parts by mass or more, preferably 4 parts by mass or more, and 50 parts by mass or less, preferably 20 parts by mass or less.

[0051] In the step 1, from the viewpoint of obtaining a black hue with improved red hue, the compounding ratio of the carbon black (B) and the metal phthalocyanine derivative (C) is preferably 3 parts by mass or more, more preferably 4 parts by mass or more, and preferably 333 parts by mass or less, more preferably 30 parts by mass or less, based on 100 parts by mass of the carbon black (B).

[0052] In the step 1, the preliminary mixing is not particularly limited as long as the effects of the present invention are not impaired, and examples thereof include dry blending using a ribbon blender, a Henschel mixer, a V blender, etc. Further, the melt kneader is not particularly limited as long as the effects of the present invention are not impaired, and examples thereof include a melt kneader equipped with a heating mechanism such as a Banbury mixer, a mixing roll, a single-screw or twin-screw extruder, and a kneader. In addition, the melt kneader in the step 1 may be loaded with a filter having an opening size in the range of preferably 100 μm or less, more preferably 50 μm or less, and further preferably 30 μm or less in the apparatus.

[0053] In one embodiment of the present invention, the method for producing the polyamide resin composition includes a step 2 of blending and melt kneading the resin coloring masterbatch, the thermoplastic resin (D), and, if necessary, the optional raw material components.

[0054] In the step 2, the resin coloring masterbatch, the thermoplastic resin (D), and, if necessary, the optional raw material components are preliminarily mixed in various forms such as powder, pellet, and chip, if necessary, and then charged into a melt kneader and heated to a temperature equal to or higher than the melting points of the polyamide resin (A) and the thermoplastic resin (D) for melt kneading.

[0055] In the step 2, the blending ratio of the thermoplastic resin (D) with respect to the masterbatch for resin coloring is not particularly limited, but the blending conditions of the polyamide resin (A), the carbon black (B), the metal phthalocyanine derivative (C), and the thermoplastic resin (D) are such that, with respect to a total of 100 parts by mass of the polyamide resin (A) and the thermoplastic resin (D), the carbon black (B) is preferably in the range of 0.3 parts by mass or more, more preferably 0.5 parts by mass or more, and preferably 17 parts by mass or less, more preferably 12 parts by mass or less, or the metal phthalocyanine derivative (C) is preferably in the range of 0.05 parts by mass or more, more preferably 0.08 parts by mass or more, and preferably 10 parts by mass or less, more preferably 5 parts by mass or less. The thermoplastic resin (D) may be blended so as to preferably satisfy either one, preferably both of the conditions.

[0056] In the step 2, the preliminary mixing is not particularly limited as long as the effects of the present invention are not impaired, but the same one as that used in the step 1 can be used. In the step 2, it is particularly preferable to preliminarily mix the masterbatch for resin coloring processed into granules, the granular thermoplastic resin (D), and, if necessary, the optional raw material components in a solid phase state, because the dispersibility of the carbon black (B) and the metal phthalocyanine derivative (C), which are coloring components, is improved.

[0057] Also, in the step 2, the melt kneader is not particularly limited as long as the effects of the present invention are not impaired, but the same one as that used in the step 1 can be used. Note that the melt kneader used in the step 2 may be loaded with a filter having an aperture in the range of preferably 100 μm or less, more preferably 50 μm or less, and even more preferably 30 μm or less in the apparatus.

[0058] Incidentally, as described above, the polyamide resin composition is preferably produced by blending and melt-kneading a resin coloring masterbatch composed of the polyamide resin (A), the carbon black (B), and the metal phthalocyanine derivative (C) with the thermoplastic resin (D). This is because the carbon black (B) and the metal phthalocyanine derivative (C), which are coloring components, can be stably and uniformly dispersed, and can be added at a high concentration, thereby imparting an excellent black color tone to the molded article, that is, a black color tone with an improved red hue.

[0059] In one embodiment of the present invention, the molded article is formed by melt-molding the polyamide resin composition. Also, in one embodiment of the present invention, the method for producing the molded article includes a step 3 of melt-molding the polyamide resin composition.

[0060] The step 3 is not particularly limited as long as the effects of the present invention are not impaired. After the melt-kneading in the step 2, the granular polyamide resin composition is directly or melt-mixed, and then subjected to various melt-molding methods such as injection molding, compression molding, composite molding, sheet molding, pipe extrusion molding, drawing molding, blow molding, and transfer molding to obtain a molded article. Particularly, in the case of fibers, after the melt-kneading, the granular material is directly or melt-spun and appropriately drawn to form fibers. In the case of sheets or films, after the melt-kneading, the granular material is directly or melted to form a sheet or film, and then appropriately drawn to form a sheet or film.

[0061] In the present invention, the shape of the fiber is not particularly limited, and it may be a so-called filament (long fiber) with a long fiber length or a so-called staple (short fiber) with a short fiber length. The fiber diameter (diameter) of the fiber varies depending on the application and can be of any thickness. Usually, the average diameter is preferably 0.01 μm or more, more preferably 0.05 μm or more, still more preferably 0.1 μm or more, most preferably 0.5 μm or more, and preferably 100 μm or less, more preferably 50 μm or less, still more preferably 30 μm or less, particularly preferably 8 μm or less, particularly more preferably 3 μm or less, and most preferably 1 μm or less. Among these, in the case of extremely fine fibers such as fibers in the range of 8 μm or less (referred to as microfibers in the present invention), conventionally, the appearance tends to become whitish due to irregular reflection of light, and it has been difficult to obtain a dark color. However, the fibers of the present invention are particularly preferable because a black color phase with an improved reddish hue can be obtained and the improvement effect is significant.

[0062] In the present invention, the thickness of the sheet or film varies depending on its application and can be of any thickness. Usually, it is preferably 0.01 μm or more, more preferably 0.05 μm or more, still more preferably 0.1 μm or more, particularly preferably 0.3 μm or more, most preferably 0.5 μm or more, and preferably 1 mm or less, more preferably 500 μm or less, still more preferably 150 μm or less, particularly preferably 100 μm or less, and most preferably 70 μm or less.

[0063] In the present invention, the terms "sheet" or "film" are not particularly used to strictly distinguish between a sheet and a film, but are used to clearly include both. As long as it has the characteristics of the present invention, the sheet and the film can be interpreted as widely as possible. The term "sheet" includes what is called a plate or a board as long as it has the characteristics of the present invention. When it is necessary to distinguish between a sheet and a film, among the above thickness ranges of the sheet or film, the term "sheet" is used for those with a thickness of 0.5 mm or more, and the term "film" is used for those with a thickness of less than 500 μm.

[0064] The masterbatch for resin coloring obtained by the production method of the present invention can finely, stably and highly concentratedly disperse the carbon black (B) as the coloring component and the metal phthalocyanine derivative (C) with good uniformity. Therefore, when diluting with the thermoplastic resin (D) to produce the polyamide resin composition, the molded article, preferably a fiber, particularly a fiber for original dyeing, or the molded article such as a sheet or a film, it not only has a black color phase with an improved red hue, but also has excellent hue stability, surface appearance, and surface smoothness. Furthermore, it can suppress film or sheet breakage and thread breakage, suppress clogging of the filter loaded in the melt kneader, and improve productivity and product yield.

Example

[0065] Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited by these examples.

[0066] (Example 1) Production of masterbatch for resin coloring (1) 100 parts by mass of 6-nylon (「UBE NYLON 1013B」manufactured by Ube Industries, Ltd., MFR 200 [g / 10 min]), 44.8 parts by mass of carbon black (B1) (「SUNBLACK320」manufactured by Asahi Carbon Co., Ltd., average particle size 20 nm), and 4.5 parts by mass of a metal phthalocyanine derivative (C1) represented by the following general formula (3) (manufactured by DIC Corporation, average particle size 50 nm) were preliminarily mixed with a tumbler mixer, and then melt-kneaded in a 30 mmφ twin-screw vent extruder (set temperature 280 °C, mesh filter with a supplementary particle size of 45 μm), and then pelletized to produce a masterbatch for resin coloring (1).

[0067]

Chemical formula

[0068] (Example 2) Production of masterbatch for resin coloring (2) 100 parts by mass of 6-nylon (“UBE NYLON 1013B” manufactured by Ube Industries, Ltd., MFR 200 [g / 10 min]), 44.8 parts by mass of carbon black (B1) (“SUNBLACK 320” manufactured by Asahi Carbon Co., Ltd., average particle diameter 20 nm), and 4.5 parts by mass of a metal phthalocyanine derivative (C2) represented by the following general formula (4) (manufactured by DIC Corporation, average particle diameter 55 nm) were premixed in a tumbler mixer and then melt-kneaded in a 30 mmφ twin-screw vent extruder (set temperature 280°C, mesh filter with a supplementary particle diameter of 45 μm), and then pelletized to produce a masterbatch (2) for resin coloring.

[0069] [Chemical formula] (In the general formula (4), CuPc represents a copper phthalocyanine residue.)

[0070] (Example 3) Production of masterbatch (3) for resin coloring 100 parts by mass of 6-nylon (“UBE NYLON 1013B” manufactured by Ube Industries, Ltd., MFR 200 [g / 10 min]), 44.8 parts by mass of carbon black (B1) (“SUNBLACK 320” manufactured by Asahi Carbon Co., Ltd., average particle diameter 20 nm), and 4.5 parts by mass of a metal phthalocyanine derivative (C3) represented by the following general formula (5) (manufactured by DIC Corporation, average particle diameter 45 nm) were premixed in a tumbler mixer and then melt-kneaded in a 30 mmφ twin-screw vent extruder (set temperature 280°C, mesh filter with a supplementary particle diameter of 45 μm), and then pelletized to produce a masterbatch (3) for resin coloring.

[0071] [Chemical formula]

[0072] (Example 4) Production of masterbatch (4) for resin coloring 100 parts by mass of 6-nylon (“UBE NYLON 1013B” manufactured by Ube Industries, Ltd., MFR 200 [g / 10 min]), 44.8 parts by mass of carbon black (B2) (“SUNBLACK 930” manufactured by Asahi Carbon Co., Ltd., average particle diameter 13 nm), and 4.5 parts by mass of a metal phthalocyanine derivative (C1) represented by the following general formula (3) (manufactured by DIC Corporation, average particle diameter 50 nm) were preliminarily mixed with a tumbler mixer and then melt-kneaded in a 30 mmφ twin-screw vented extruder (set temperature 280 °C, mesh filter with a supplementary particle diameter of 45 μm), and then pelletized to produce a masterbatch (4) for resin coloring.

[0073] (Example 5) Production of masterbatch (5) for resin coloring 100 parts by mass of 6-nylon (“UBE NYLON 1013B” manufactured by Ube Industries, Ltd., MFR 200 [g / 10 min]), 33.4 parts by mass of carbon black (B1) (“SUNBLACK 320” manufactured by Asahi Carbon Co., Ltd., average particle diameter 20 nm), and 20 parts by mass of a metal phthalocyanine derivative (C1) represented by the following general formula (3) (manufactured by DIC Corporation, average particle diameter 50 nm) were preliminarily mixed with a tumbler mixer and then melt-kneaded in a 30 mmφ twin-screw vented extruder (set temperature 280 °C, mesh filter with a supplementary particle diameter of 45 μm), and then pelletized to produce a masterbatch (5) for resin coloring.

[0074] (Comparative Example 1) Production of masterbatch (6) for resin coloring 100 parts by mass of 6-nylon (“UBE NYLON 1013B” manufactured by Ube Industries, Ltd., MFR 200 [g / 10 min]), 44.8 parts by mass of carbon black (B1) (“SUNBLACK 320” manufactured by Asahi Carbon Co., Ltd., average particle diameter 20 nm), and 4.5 parts by mass of copper phthalocyanine (C1) (“FASTOGEN BLUE PDB50” manufactured by DIC Corporation, average particle diameter 50 μm) were preliminarily mixed with a tumbler mixer and then melt-kneaded in a 30 mmφ twin-screw vented extruder (set temperature 280 °C, mesh filter with a supplementary particle diameter of 45 μm), and then pelletized to produce a masterbatch (6) for resin coloring.

[0075] (Comparative Example 2) Production of Masterbatch (7) for Resin Coloring 100 parts by mass of 6-nylon (UBE NYLON 1013B manufactured by Ube Industries, Ltd., MFR 200 [g / 10 min]), 14.0 parts by mass of carbon black (B1) (SUNBLACK 320 manufactured by Asahi Carbon Co., Ltd., average particle diameter 20 nm), and 2.8 parts by mass of the metal phthalocyanine derivative (C1) (manufactured by DIC Corporation, average particle diameter 50 nm) were preliminarily mixed in a tumbler mixer and then melt-kneaded in a 30 mmφ twin-screw vent extruder (set temperature 280°C, mesh filter with a supplementary particle diameter of 45 μm). Thereafter, it was pelletized to produce masterbatch (7) for resin coloring.

[0076] The evaluation results of each obtained masterbatch for resin coloring are shown in Table 1.

[0077] [Table 1]

[0078] (Examples 6 to 10, Comparative Examples 3 and 4) Production of Polyamide Molded Products (Filaments) 4 parts by mass of each of the obtained masterbatches (1) to (4), (6), and (7) for resin coloring were melt-kneaded with 96 parts by mass of 6-nylon (UBE NYLON 1013B manufactured by Ube Industries, Ltd.) in a 30 mmφ twin-screw vent extruder (set temperature 280°C), and then pelletized to produce polyamide resin compositions <1> to <4>, <6>, and <7>. Similarly, polyamide resin composition <5> was produced using 8 parts by mass of masterbatch (5) for resin coloring and 92 parts by mass of 6-nylon. The evaluation results of each measurement of the obtained polyamide resin compositions are shown in Table 2 (Evaluation Result 1).

[0079] Similarly, the colorant masterbatches (1) to (7) for each resin and 6-nylon were mixed at the same ratio as the ratio of the colorant masterbatches (1) to (7) for each resin and 6-nylon in the above polyamide resin compositions <1> to <7>, vacuum dried at 105°C for 12 hours, and then melt spun using a spinning machine under the conditions of a spinning temperature of 280°C, a spinning speed of 1250 m / min, and a nozzle diameter of 0.24 mm - 24H (holes). Filament samples "1" to "7" (average fiber diameter 20 μm) of 3 dtex were each produced by 3-fold drawing. The evaluation results of each measurement are shown in Table 2 (Evaluation Results 2).

[0080]

Table 2

[0081] (Example 11, Comparative Examples 5 and 6) Production of Colored Resin Composition and Molded Product (Microfiber) 16 parts by mass of each of the obtained masterbatches (1), (6), and (7) for resin coloring were each mixed with 42 parts by mass of 6-nylon ("UBE NYLON 1013B" manufactured by Ube Industries, Ltd., MFR 200 [g / 10 min]) and 42 parts by mass of low-density polyethylene ("Petrosen 203" manufactured by Tosoh Corporation), vacuum dried at 105°C for 12 hours, and then melt spun using a spinning machine under the conditions of a spinning temperature of 280°C, a spinning speed of 1250 m / min, and a nozzle diameter of 0.24 mm - 24H (holes). A 5 dtex filament was obtained by 3-fold drawing. The polyethylene component was eluted from the obtained filament sample using toluene to produce microfiber samples {1} to {3} (average fiber diameter 1 μm). The evaluation results of each measurement are shown in Table 3 (Evaluation Results 3 and 4).

[0082]

Table 3

[0083] The above evaluation results were obtained by the following measurement examples.

[0084] (Measurement Example 1) Measurement of the Average Particle Size of Carbon Black and Metal Phthalocyanine Derivatives The carbon black or metal phthalocyanine derivative to be measured was observed by transmission electron microscopy (TEM) (magnification: 30,000 times) to obtain particle images of the carbon black or metal phthalocyanine derivative. The particle diameters (equivalent circle diameters) were measured for at least 200 randomly selected particles (which may be primary particles or may further contain secondary particles), and the average value was calculated.

[0085] (Measurement Example 2) Measurement of the Particle Size Range of Aggregated Particles after Melt Kneading The obtained resin coloring masterbatches (1) to (7) diluted 20-fold with polyamide resin (A), polyamide resin compositions <1> to <7>, or microfiber samples {1} to {3} were pressed into a film shape using a preparate and then observed by optical microscopy (magnification: 200 times) to obtain particle images of carbon black and metal phthalocyanine derivatives. The particle diameters (equivalent circle diameters) were measured for at least 200 randomly selected particles (which may be primary particles or may further contain secondary particles).

[0086] (Measurement Example 3) Measurement of Melt Flowability (Melt Flow Rate) The obtained resin coloring masterbatches (1) to (7) were each put into a melt indexer (cylinder temperature: 280 °C, orifice diameter: 2 mm), a load of 2.16 kg was applied, and after preheating for 5 minutes, the melt flow rate (MFR) was measured.

[0087] (Measurement Example 4) Measurement of Hue For filament samples "1" to "7" or microfiber samples {1} to {3}, L*, a*, and b* were measured using a spectrophotometer (CM-700d manufactured by Konica Minolta, Inc.).

[0088] (Measurement Example 5) Conductivity Using the obtained masterbatches (1) to (7) for resin coloring, test pieces were compression molded into a size of 10×20×1 mm at a temperature of 240°C, a pressure of 10 MPa, a melting time of 90 seconds, and a compression time of 90 seconds, and then rapidly cooled at 20°C. The conductivity was measured using the four-terminal method with a 2110 51 / 2 DIGIT MULTMETER (manufactured by KEITHLEY).

Claims

1. A masterbatch for resin coloring, which is prepared by blending a polyamide resin (A), carbon black (B), and a metal phthalocyanine derivative (C) that forms a complex with copper or zinc, wherein the metal phthalocyanine derivative (C) has a functional group represented by the following general formula (1) or a functional group represented by the following general formula (2), the particle size of 99% by mass of the carbon black (B) and the metal phthalocyanine derivative (C) is in the range of less than 40 μm, A masterbatch for resin coloring, wherein the carbon black (B) is in the range of 30 parts by mass or more to 100 parts by mass or less, and the metal phthalocyanine derivative (C) is in the range of 3 parts by mass or more to 50 parts by mass or less, based on 100 parts by mass of the polyamide resin (A). -(X-NR １ R ２ ) ｎ１ (1) -(SO ２ -NR ３ R ４ ) ｎ２ (2) (In the general formula (1), 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 and R ２ each independently represent a hydrogen atom, an unsubstituted alkyl group, a substituted alkyl group, a cycloalkyl group, an alkylaryl group, an aryl group, an alkoxyalkyl group or a heterocyclic residue, and R １ and R ２ may be bonded to each other to form a substituted or unsubstituted heterocyclic ring, and n1 is an integer in the range of 1 or more to 4 or less. In the general formula (2), R ３ is a hydrogen atom, an unsubstituted alkyl group, a substituted alkyl group, a cycloalkyl group, an alkylaryl group, an aryl group, an alkoxyalkyl group or a heterocyclic residue, R ４represents an unsubstituted alkyl group, an alkylaryl group, an aryl group, an alkoxyalkyl group or a heterocyclic residue, and R ３ and R ４ may be bonded to each other to form a substituted or unsubstituted heterocyclic ring, and n2 is an integer in the range from 1 or more to 4 or less. )

2. A resin coloring masterbatch comprising a polyamide resin (A), carbon black (B), and a metal phthalocyanine derivative (C) that forms a complex with copper or zinc, The metal phthalocyanine derivative (C) is one or more selected from the group consisting of (alkyl)phthalimidomethyl copper phthalocyanine, dialkylaminomethyl copper phthalocyanine, (alkyl)anilinylsulfamoyl copper phthalocyanine, alkoxypropylsulfonamide copper phthalocyanine, dialkylaminopropylsulfonamide copper phthalocyanine, (alkyl)phthalimidomethyl zinc phthalocyanine, dialkylaminomethyl zinc phthalocyanine, (alkyl)anilinylsulfamoyl zinc phthalocyanine, alkoxypropylsulfonamide zinc phthalocyanine, and dialkylaminopropylsulfonamide zinc phthalocyanine, The particle size of 99% by mass of the carbon black (B) and the metal phthalocyanine derivative (C) is in the range of less than 40 μm, A resin coloring masterbatch, wherein the carbon black (B) is in the range of 30 parts by mass or more to 100 parts by mass or less, and the metal phthalocyanine derivative (C) is in the range of 3 parts by mass or more to 50 parts by mass or less, based on 100 parts by mass of the polyamide resin (A).

3. The electrical conductivity is 10 －１ S cm －１ or less, the resin coloring masterbatch according to claim 1 or 2.

4. A polyamide resin composition comprising the resin coloring masterbatch according to any one of claims 1 to 3, and further a thermoplastic resin (D), With respect to a total of 100 parts by mass of the polyamide resin (A) and the thermoplastic resin (D), the carbon black (B) is in the range of 0.3 parts by mass or more to 17 parts by mass or less, and the metal phthalocyanine derivative (C) is in the range of 0.05 parts by mass or more to 10 parts by mass or less, A polyamide resin composition in which the total proportion of the polyamide resin (A), the carbon black (B), the metal phthalocyanine derivative (C), and the thermoplastic resin (D) in the polyamide resin composition is in the range of more than 72% by mass.

5. A molded article obtained by melt-molding the polyamide resin composition according to claim 4.

6. The molded article according to claim 5, wherein the molded article is a filament, staple, or microfiber.

7. It has step 1 of blending a polyamide resin (A), carbon black (B), and a metal phthalocyanine derivative (C) that forms a complex with copper or zinc and melt-kneading them with a melt-kneader, The melt-kneader is loaded with a filter having an opening in the range of 50 μm or less inside the apparatus, The metal phthalocyanine derivative (C) has a functional group represented by the following general formula (1) or a functional group represented by the following general formula (2), The blending ratio of the polyamide resin (A), the carbon black (B), and the metal phthalocyanine derivative (C) is such that, with respect to 100 parts by mass of the polyamide resin (A), the carbon black (B) is in the range of 30 parts by mass or more to 100 parts by mass or less, and the metal phthalocyanine derivative (C) is in the range of 3 parts by mass or more to 50 parts by mass or less. A method for producing a resin coloring masterbatch. -(X-NR １ R ２ ) ｎ１ (1) -(SO ２ -NR ３ R ４ ) ｎ２ (2) (In the general formula (1), X is -CH ２-1. -CH ２ -CH ２ -COO-C ２ H ４ -or -CH ２ -CH ２ -COO-C ３ H ６ -1., R １ and R ２ each independently represents a hydrogen atom, an unsubstituted alkyl group, a substituted alkyl group, a cycloalkyl group, an alkylaryl group, an aryl group, an alkoxyalkyl group or a heterocyclic residue, and R １ and R ２ may be bonded to each other to form a substituted or unsubstituted heterocyclic ring, and n1 is an integer in the range from 1 to 4. In the general formula (2), R ３ represents a hydrogen atom, an unsubstituted alkyl group, a substituted alkyl group, a cycloalkyl group, an alkylaryl group, an aryl group, an alkoxyalkyl group or a heterocyclic residue, R ４ represents an unsubstituted alkyl group, an alkylaryl group, an aryl group, an alkoxyalkyl group or a heterocyclic residue, and R ３ and R ４ may be bonded to each other to form a substituted or unsubstituted heterocyclic ring, and n2 is an integer in the range from 1 to 4. )

8. A step 1 of blending a polyamide resin (A), carbon black (B), and a metal phthalocyanine derivative (C) that forms a complex with copper or zinc and melt-kneading them in a melt-kneader, wherein the melt-kneader has a filter having an opening size in the range of 50 μm or less in the apparatus, The metal phthalocyanine derivative (C) is one or more selected from the group consisting of (alkyl) phthalimidomethyl copper phthalocyanine, dialkylaminomethyl copper phthalocyanine, (alkyl) anilinylsulfamoyl copper phthalocyanine, alkoxypropylsulfonamide copper phthalocyanine, dialkylaminopropylsulfonamide copper phthalocyanine, (alkyl) phthalimidomethyl zinc phthalocyanine, dialkylaminomethyl zinc phthalocyanine, (alkyl) anilinylsulfamoyl zinc phthalocyanine, alkoxypropylsulfonamide zinc phthalocyanine, and dialkylaminopropylsulfonamide zinc phthalocyanine, A method for producing a masterbatch for resin coloring, wherein the blending ratios of the polyamide resin (A), the carbon black (B), and the metal phthalocyanine derivative (C) are in the range of 30 parts by mass or more to 100 parts by mass or less of the carbon black (B) and 3 parts by mass or more to 50 parts by mass or less of the metal phthalocyanine derivative (C) with respect to 100 parts by mass of the polyamide resin (A).

9. A method for producing a polyamide resin composition, comprising a step 2 of melt-kneading the masterbatch for resin coloring obtained by the production method according to claim 7 or 8 and further a thermoplastic resin (D).

10. A method for producing a molded article, comprising a step 3 of melt-molding the polyamide resin composition obtained by the production method according to claim 9.

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