JP2002317110A - Colored flame-retardant polycarbonate composition and production method therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a colored flame-retardant polycarbonate composition showing, when molded into a thin article, excellent flame retardance, melt flowing characteristics, impact resistance, heat resistance on wetting, and very low mold staining properties. SOLUTION: This colored flame-retardant polycarbonate composition comprises 50-95 pts.wt. of an aromatic polycarbonate resin (A), 50-5 pts.wt. of a rubber-modified styrene resin (B), 5-30 pts.wt. of at least one type of organophosphorus compound oligomer (C), 0.05-1 pt.wt. of a fluoropolymer (D), and 0.0001-10 pts.wt. of a coloring agent (E), wherein the total amount of slip agents (F) contained in the composition is 3,000 ppm by weight.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polycarbonate-based colored flame-retardant resin composition having excellent flame retardancy, melt flowability, impact resistance, low mold contamination and wet heat resistance in a thin-walled molded article, and a process for producing the same. About.

[0002]

2. Description of the Related Art A composition obtained by blending an acrylonitrile-butadiene-styrene resin (ABS) and an organic phosphorus compound-based flame retardant in a polycarbonate resin (PC) (hereinafter, referred to as "a").
It is referred to as "PC / ABS / phosphorus flame retardant composition". ) Is a non-bromine and non-chlorine flame-retardant resin material that has excellent properties such as melt fluidity, rigidity, impact resistance, heat resistance, and light discoloration resistance.
It is widely used as a housing material for notebook computers, printers, word processors, copiers and the like.

[0003] In recent years, in order to reduce the weight and thickness of equipment, the same material can be molded into a thin wall with good flowability of molten resin.
In a thin molded product, high flame retardancy corresponding to the flame retardant level of V-0 or 5V in UL94 is also required. However, in the PC / ABS / phosphorous flame retardant composition, the melt flowability can be improved by increasing the amount of the ABS resin in the composition, but the flame retardancy is reduced. further,
As the material becomes thinner, the flame drip tends to occur more easily in the UL94 vertical combustion test, and the thinner the molded product, the more difficult it is to maintain high flame retardancy. That is, it has not been easy to simultaneously improve the melt fluidity and the flame retardancy.

Recently, oligomer-type phosphorus-based flame retardants having a small amount of volatile components have attracted attention as flame retardants for PC / ABS / phosphorus-based flame retardant compositions in order to reduce mold contamination during molding. Among them, bisphenol A diphosphate (BDP) type oligomeric phosphorus compound flame retardants having excellent hydrolysis resistance can simultaneously improve the moist heat resistance of the PC / ABS / phosphorus flame retardant composition, and thus the use amount thereof is increasing. . However, while the use of an oligomeric phosphorus-based flame retardant can improve low mold contamination, it is thinner than a case of using a mono-type phosphorus compound flame retardant represented by triphenyl phosphate (TPP). However, there is a problem that the flame retardant performance of the rubber is reduced.

Further, the PC / ABS / phosphorous flame retardant composition is used as a molding material after being colored to a desired color by using a coloring agent (mainly a dye / pigment). The problem of reduced performance often occurred.

As described above, the PC / ABS / phosphorus-based flame retardant composition has excellent flame retardancy even in a thin molded product, and has excellent melt fluidity, impact resistance, and low mold contamination. Despite the strong demand for polycarbonate-based colored flame-retardant resin compositions as a molding material having both wet heat resistance, satisfactory performance has not been obtained at present.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide an excellent flame retardancy even in a thin-walled molded product, and at the same time, to have excellent melt fluidity, impact resistance, low mold contamination and wet heat resistance. An object of the present invention is to provide a polycarbonate-based colored flame-retardant resin composition having the same and a method for producing the same.

[0008]

SUMMARY OF THE INVENTION PC / ABS / phosphorous flame retardant compositions usually contain various "lubricants".
As used herein, the term “lubricant” refers to a resin which improves processing lubricity, dispersibility of a dye / pigment as a colorant for the resin, and further improves mold releasability from a mold. A compound having an effect, and refers to a compound selected from the group consisting of aliphatic hydrocarbons, polyolefin waxes, higher carboxylic acids, higher carboxylic acid metal salts, fatty acid amides, fatty acid esters, and higher alcohols.

The above-mentioned lubricant may be already contained in the resin raw material of the composition, or may be blended in processing such as compounding and coloring of the resin. For example, the raw material PC resin of the PC / ABS / phosphorus-based flame retardant composition may contain a lubricant component as a release agent or a processing aid. Similarly, the raw material ABS resin contains a fatty acid or a fatty acid derived from an emulsifier. Fatty acid metal salts, processing aids, release agents, and the like may be included.

The PC / ABS / phosphorus-based flame retardant composition is generally molded into various molded articles by injection molding like other thermoplastic resins. In injection molding, the molded article is separated from a molding die. PC / ABS to improve moldability
In some cases, a release agent is added to the phosphorus-based flame retardant composition.

For example, JP-A-8-48844 discloses (A) polycarbonate, (B) styrene resin,
(E) Average molecular weight of 1,000 to 50,000 based on 100 parts by weight of a resin composition comprising (C) a resorcinol polyphosphate compound and (D) polytetrafluoroethylene.
A flame-retardant resin composition comprising 0.1 to 2 parts by weight of a saturated fatty acid ester-based wax of 0.1 and 0.01 to 2 parts by weight of (F) a polyethylene wax having an average molecular weight of 1,000 to 3,000 is described. .

Japanese Patent Application Laid-Open No. 2000-63649 discloses (A) polycarbonate, (B) styrene resin,
A flame-retardant resin composition is described in which (C) a composition comprising an esterified product of pentaerythritol and a saturated aliphatic carboxylic acid is further mixed with a halogen-free phosphate ester.

Further, in the process of coloring the PC / ABS / phosphorus-based flame retardant composition with a coloring agent (mainly a dye / pigment), a colorant dispersing agent or a resin pellet surface is used to enhance the dispersibility of the coloring agent in the resin. A colorant spreading agent or the like may be used.

The PC thus used as a molding material
/ ABS / phosphorus flame retardant composition, especially colored PC /
The ABS / phosphorous flame retardant composition generally contains the above lubricant component. The above-mentioned lubricant component contained in the PC / ABS / phosphorus-based flame retardant composition is generally contained in the resin composition in the order of several thousand to several tens of thousands of ppm by weight as a total amount. However, since these lubricant components are trace components, the effects of these lubricant components on flame retardancy have not been strictly studied so far.

[0015] However, the present inventors have proposed PC / AB
As a result of intensive studies on the improvement of the flame retardancy of the S / phosphorus-based flame retardant composition in a thin-walled molded product, it was found that a slight amount of the lubricant component contained in the resin composition has a great effect on the flame retardancy of the resin composition. I found it. Surprisingly, by controlling the total amount of the lubricant component contained in the PC / ABS / phosphorus-based flame retardant composition to a certain level or less, high flame retardancy in thin-walled molded articles and excellent melt fluidity are obtained. The present inventors have found that a polycarbonate-based colored flame-retardant resin composition having both impact resistance, low mold contamination, and wet heat resistance can be obtained, and have completed the present invention.

That is, the present invention provides: [1] 50 to 95 parts by weight of an aromatic polycarbonate resin (A), 50 to 5 parts by weight of a rubber-modified styrene resin (B),
At least one type of organophosphorus compound oligomer (C)
A polycarbonate-based colored flame-retardant resin composition containing 30 parts by weight, 0.05 to 1 part by weight of a fluoropolymer (D), and 0.0001 to 10 parts by weight of a colorant (E), which is contained in the composition. 3,000 weight p
pm or less, a polycarbonate-based colored flame-retardant resin composition,

[2] When the lubricant (F) is an aliphatic hydrocarbon, a polyolefin wax, a higher carboxylic acid, a higher carboxylic acid metal salt, a higher fatty acid amide, a higher fatty acid ester,
Wherein the polycarbonate-based colored flame-retardant resin composition according to the above [1], wherein at least one kind of the organic phosphorus compound oligomer (C) is represented by the following formula (1): :

[0018]

Embedded image The polycarbonate-based colored flame-retardant resin composition according to the above [1] or [2], which is selected from a compound group represented by the following formula:

[4] Aromatic polycarbonate resin (A)
50 to 95 parts by weight, rubber-modified styrene resin (B) 50
To 5 parts by weight, at least one kind of the organic phosphorus compound oligomer (C) 5 to 30 parts by weight, and the fluoropolymer (D) 0.
A method for producing a polycarbonate-based flame-retardant resin composition containing 0.05 to 1 part by weight and a colorant (E) in an amount of 0.0001 to 10 parts by weight using a melt-kneading apparatus, wherein a lubricant (F) contained in the composition is used. A) a method for producing a polycarbonate-based colored flame-retardant resin composition, wherein the total amount of

[5] The lubricant (F) is a compound selected from aliphatic hydrocarbons, polyolefin waxes, higher carboxylic acids, metal salts of higher carboxylic acids, fatty acid amides, fatty acid esters, and higher alcohols. [4] The method for producing a polycarbonate-based colored flame-retardant resin composition according to the above [4], [6] wherein at least one kind of the organic phosphorus compound oligomer (C) is represented by the following formula (1)

[0021]

Embedded image The method for producing a polycarbonate-based colored flame-retardant resin composition according to the above [4] or [5], which is selected from the group of compounds represented by the following formulas:

[7] The method for producing a polycarbonate-based colored flame-retardant resin composition according to [4], [5] or [6], wherein the melt-kneading apparatus is a twin-screw extruder.

The present invention will be specifically described below.
The aromatic polycarbonate resin (A) preferably used as the component (A) of the composition of the present invention has a main chain composed of a repeating unit represented by the following formula (2).

[0024]

Embedded image (In the formula, Ar is a divalent aromatic residue, for example, phenylene, naphthylene, biphenylene, pyridylene,
One represented by the following formula (3) is given. )

[0025]

Embedded image (In the formula, Ar ¹ and Ar ² are each an arylene group. For example, they represent groups such as phenylene, naphthylene, biphenylene, and pyridylene, and Y is an alkylene group or a substituted alkylene group represented by the formula (4). )

[0026]

Embedded image (Wherein R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom, a C 1-6 lower alkyl group, a C 5-10 cycloalkyl group, a C 6-30 aryl group, a carbon number 7 ~
31 aralkyl groups, optionally a halogen atom,
It may be substituted with an alkoxy group having 1 to 10 carbon atoms,
k is an integer of 3 to 11, R ⁵ and R ⁶ are individually selected for each X, and each independently represents a hydrogen atom, or a lower alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 30 carbon atoms. Then, it may be optionally substituted by a halogen atom or a C1 to C10 alkoxy group, and X represents a carbon atom. ) Further, a divalent aromatic residue represented by the following formula (5) may be contained as a copolymer component.

[0027]

Embedded image (In the formula, Ar ¹ and Ar ² are the same as those in the formula (3). Z is a mere bond or —O—, —CO—, —S—, —SO ₂ —,
_{-CO 2 -, - CON (R} 1) - (R 1 is as defined in the formula (4)) is a divalent group such as. Examples of these divalent aromatic residues include those shown below.

[0028]

Embedded image

[0029]

Embedded image (Wherein R ⁷ and R ⁸ are each independently hydrogen, halogen, a C 1-10 alkyl group, a C 1-10 alkoxy group, a C 5-10 cycloalkyl group or a C 6-30 aryl M and n are integers of 1 to 4, and when m is 2 to 4, each R ⁷ may be the same or different, and when n is 2 to 4, each R 7 ⁸
May be the same or different. Among them, one represented by the following formula (6) is a preferable example.

[0030]

Embedded image

In particular, the one represented by the above formula (6) is represented by A
A polycarbonate containing 85 mol% or more (based on all monomer units in the polycarbonate) of a repeating unit represented by r is particularly preferred.

The polycarbonate which can be used in the present invention may contain a trivalent or higher aromatic residue as a copolymer component. Although the molecular structure of the polymer terminal is not particularly limited, one or more terminal groups selected from a phenolic hydroxyl group, an aryl carbonate group, and an alkyl carbonate group can be bonded. The aryl carbonate terminal group is represented by the following formula (7).

[0033]

Embedded image (In the formula, Ar ³ is a monovalent aromatic residue, and the aromatic ring may be substituted.) Specific examples of the aryl carbonate terminal group include those represented by the following formula, for example. .

[0034]

Embedded image The alkyl carbonate terminal group is represented by the following formula (8).

[0035]

Embedded image (In the formula, R ⁹ represents a linear or branched alkyl group having 1 to 20 carbon atoms.) Specific examples of the alkyl carbonate terminal group include, for example, those represented by the following formula.

[0036]

Embedded image Among them, phenolic hydroxyl group, phenyl carbonate group, pt-butylphenyl carbonate group, p-
Cumyl phenyl carbonate and the like are preferably used.

In the present application, the ratio of the phenolic hydroxyl group terminal to the other terminal is not particularly limited, but from the viewpoint of obtaining excellent strength in any of various mechanical strength tests, the ratio of the phenolic hydroxyl group terminal is considered to be excellent. The ratio is preferably 20% or more of the total number of terminal groups, more preferably 20 to 80%. When the ratio of the phenolic terminal group exceeds 80% of the total number of terminal groups, the thermal stability at the time of melting tends to slightly decrease.

The method for measuring the phenolic hydroxyl group terminal amount is as follows.
Generally, a method using NMR (NMR method), a method using titanium (titanium method), and a method using UV or IR (UV method or IR method)
Can be obtained by

The weight average molecular weight (Mw) of the polycarbonate resin (A) used in the present invention is generally 5,000.
~ 50,000, more preferably from 10,000 to 40,000, further preferably from 15,000 to 30,000, particularly preferably from 18,000 to 25,000. . If it is less than 5,000, the impact resistance tends to be insufficient.
If it exceeds 000, the melt fluidity tends to be insufficient.

In the present invention, the weight average molecular weight (Mw) of the polycarbonate is measured by using gel permeation chromatography (GPC), and the measurement conditions are as follows. That is, it can be determined by using a polystyrene gel using tetrahydrofuran as a solvent, and using a reduced molecular weight calibration curve according to the following equation from a configuration curve of standard monodisperse polystyrene. ^{_{M PC = 0.3591M PS 1.0388 (M}} PC is the weight average molecular weight of the polycarbonate, M _PS weight average molecular weight of polystyrene)

As the aromatic polycarbonate resin (A) in the composition of the present invention, those produced by a known method can be used. Specifically, for example, a known method of reacting an aromatic dihydroxy compound with a carbonate precursor, for example, reacting an aromatic dihydroxy compound with a carbonate precursor (eg, phosgene) in the presence of an aqueous sodium hydroxide solution and a methylene chloride solvent The crystallization carbonate prepolymer obtained by the interfacial polymerization method (for example, phosgene method), the transesterification method of reacting an aromatic dihydroxy compound with a carbonic acid diester (for example, diphenyl carbonate), the phosgene method or the melting method is used to solidify Phase polymerization method (Japanese Patent Application Laid-Open No. 1-158033 (corresponding to U.S. Pat. No. 4,948,871);
1426, JP-A-3-68627 (U.S. Pat.
No. 204,377))).

Preferred polycarbonate resins include:
A polycarbonate resin containing substantially no chlorine atom, which is produced from a dihydric phenol (aromatic dihydroxy compound) and a carbonic acid diester by a transesterification method, may be mentioned. In the present invention, two or more different polycarbonates having different structures and molecular weights can be used in combination as the component (A).

The amount of the component (A) in the composition of the present invention is 50 to 95 parts by weight, preferably 60 to 90 parts by weight, per 100 parts by weight of the total of the components (A) and (B). More preferably, it is 70 to 85 parts by weight. If the amount of the component (A) is less than 50 parts by weight, the heat resistance and the flame retardancy of the thin molded article will be insufficient, while if it exceeds 95 parts by weight, the melt fluidity will be insufficient.

The component (B) used in the present invention is a rubber-modified styrenic resin. Here, the rubber-modified styrenic resin means a rubbery polymer and all rubber-modified styrenic resins containing one or more vinyl compounds as components.

As the rubbery polymer of the rubber-modified styrenic resin, those having a glass transition temperature of 0 ° C. or less can be used. Specifically, polybutadiene, styrene / butadiene copolymer rubber, butadiene / butyl acrylate copolymer rubber, diene rubber such as acrylonitrile / butadiene copolymer rubber, acrylic rubber such as polybutyl acrylate, silicon / acryl composite rubber , Polyisoprene, polychloroprene, ethylene-propylene rubber,
Block copolymers such as ethylene / propylene / diene terpolymer rubber, styrene / butadiene block copolymer rubber, styrene / isoprene block copolymer rubber, and hydrogenated products thereof can be used. Among these polymers, preferred are polybutadiene, styrene / butadiene copolymer rubber, acrylonitrile / butadiene copolymer rubber, polybutyl acrylate, and the like.

The proportion of the rubbery polymer in the rubber-modified styrenic resin is used in the range of 1 to 95% by weight, and is determined according to the required mechanical strength, rigidity and moldability. Preferably, it is 5-45% by weight, more preferably 10-40% by weight.

Examples of the vinyl compound used in the rubber-modified styrene resin include aromatic vinyl compounds such as styrene, α-methylstyrene and paramethylstyrene, and alkyl (meth) acrylates such as methyl methacrylate, methyl acrylate, butyl acrylate and ethyl acrylate. A) acrylates, (meth) acrylic acids such as acrylic acid and methacrylic acid, vinyl cyanide monomers such as acrylonitrile and methacrylonitrile, and α and β such as maleic anhydride.
-Unsaturated carboxylic acids, N-phenylmaleimide, N-methylmaleimide, maleimide-based monomers such as N-cyclohexylmaleimide, and glycidyl group-containing monomers such as glycidyl methacrylate. , Alkyl (meth) acrylates, vinyl cyanide monomers, and maleimide monomers, more preferably styrene, acrylonitrile, N-phenylmaleimide, and butyl acrylate.

These vinyl compounds can be used alone or in combination of two or more. Preferably,
It is a combination of an aromatic vinyl compound and a non-aromatic vinyl compound. In this case, the aromatic vinyl compound and the non-aromatic vinyl compound are used in an arbitrary ratio, but the preferable ratio of the non-aromatic vinyl compound is 5 to 80% by weight based on the total amount of the vinyl compound alone. Range.

As rubber-modified styrene resins, ABS resins (acrylonitrile-butadiene-styrene resins),
AAS resin (acrylonitrile / butyl acrylate /
Styrene resin), HIPS (high impact polystyrene resin) and the like.

The method for producing the rubber-modified styrenic resin is not particularly limited, and bulk polymerization, solution polymerization, suspension polymerization,
A generally known production method such as emulsion polymerization can be used. Among them, rubber-modified styrenic resin produced by bulk polymerization or solution polymerization can obtain rubber-modified styrenic resin without using an emulsifier, so that fatty acid or fatty acid metal salt derived from emulsifier is rubber-modified. Since it is not substantially contained in the styrene-based resin, it can be particularly preferably used as the component (B).

Further, in the present invention, it is also effective to use two or more different rubber-modified styrene resins having different structures and molecular weights in combination as the component (B). For example, by using an ABS resin and an MBS resin (methyl methacrylate / butadiene / styrene resin) in combination as the component (B), it is possible to simultaneously improve excellent melt fluidity and impact resistance.

As a specific example of such an MBS, “METABLEN C-MN” manufactured by Mitsubishi Rayon Co., Ltd.
223A "and" METABLEN C-323A ", manufactured by Kanegabuchi Chemical Industry Co., Ltd.
511 "and" Kane Ace B-564 ", and" M-51 "manufactured by Taiwan Plastics Company, Taiwan.

The amount of the component (B) in the composition of the present invention is 50 to 5 parts by weight, preferably 40 to 10 parts by weight, per 100 parts by weight of the total of the components (A) and (B). More preferably, it is 30 to 15 parts by weight. If the component (B) exceeds 50 parts by weight, the heat resistance and the flame retardancy of the thin molded article become insufficient, while if it exceeds 5 parts by weight, the melt fluidity becomes insufficient.

The component (C) used in the present invention is at least one kind of organic phosphorus compound, and is an organic phosphorus compound oligomer which is a compound having two or more phosphorus atoms in its structure. Particularly preferred examples of the organic phosphorus compound oligomer used in the present invention include those selected from the group of compounds represented by the following formula (1).

[0055]

Embedded image

The substituents R ^a , R ^b and R in the above formula (1)
^c and R ^d each independently represent an aryl group having 6 to 12 carbon atoms, and one or more hydrogen atoms thereof may or may not be substituted. When one or more hydrogen atoms are substituted, the substituent may be an alkyl group, an alkoxy group,
Examples thereof include an alkylthio group, a halogen, an aryl group, an aryloxy group, an arylthio group, and a halogenated aryl group. A group obtained by combining these substituents (for example, an arylalkoxyalkyl group) or these substituents are represented by an oxygen atom, A group (for example, an arylsulfonylaryl group) combined by combining with a sulfur atom, a nitrogen atom or the like may be used as a substituent.

Particularly preferred aryl groups as the substituents R ^a , R ^b , R ^c and R ^d are phenyl, cresyl, xylyl, propylphenyl and butylphenyl. Substituents R ^a , R ^b and R in the compound of the above formula (1)
^{When c} and R ^d are an alkyl group or a cycloalkyl group, thermal stability is generally insufficient, and decomposition is likely to occur during melt kneading.

X in the above formula (1) representing a group of compounds as examples of the organic phosphorus compound is a diphenyloldimethylmethane group as described above. Many of the commonly used oligomeric phosphate esters are those in which X is a resorcinol group or a hydroquinone group. Compared to these, (X is a diphenyloldimethylmethane group)
When a compound selected from the group of compounds represented by the above formula (1) is used as the organic phosphorus compound, the hydrolysis resistance and thermal stability of the organic phosphorus compound are improved, which is preferable.

The organophosphorus compound oligomer represented by the formula (1) is usually used as a mixture of a plurality of different organophosphorus compound oligomers having different values of n (n is a natural number) in the formula (1). Many. At this time, it is preferable that the weight average degree of condensation (N) of the plurality of different organic phosphorus compound oligomers is 1 to less than 1.2. For N, the weight fraction (A _n ) of each component having a different n is determined by gel permeation chromatography or liquid chromatography, and the weight average of n, N = Σ (n · A _n ) / Σ (A _n ).

Here, in _order to obtain An, a UV detector or an RI detector is usually used as a detector. However, in the calculation of N, when the compound having a structure in which n in the above formula (1) is 0 is used or included (that is, when an organic phosphorus compound having only one phosphorus atom in one molecule is used or included). ) Excludes compounds where n is 0 from the calculation of N. The weight average condensation degree N is
It is usually 1 or more and 5 or less, preferably 1 or more and 2 or less, and 1
The value is more preferably from 1.5 to 1.5, and particularly preferably from 1 to less than 1.2.

The smaller the N, the better the compatibility with the resin, the better the melt fluidity, and the higher the flame retardancy. In particular, the compound of N = 1 has particularly excellent balance between flame retardancy and melt fluidity in the resin composition. When the N of the compound of the formula (1) as the organic phosphorus compound is 5 or more, the viscosity of the compound is increased, and the melt fluidity particularly in a high shear rate region tends to be reduced. Properties tend to decrease.

Further, the organic phosphorus compound used in the present invention preferably has an acid value of not more than 0.1 mgKOH / g, more preferably not more than 0.08 mgKOH / g, and still more preferably not more than 0.05 mgKOH / g. g or less. By using an organic phosphorus compound having a low acid value, it is possible to obtain a polycarbonate-based flame-retardant resin composition that is more excellent in wet heat resistance.

The organic phosphorus compounds represented by the above general formula (1) are disclosed in US Pat. No. 2,520,090, JP-B-62-25706, and JP-A-63-22763.
No. 2, publication No. 2 etc., by reacting phosphorus oxychloride with bisphenol A and monohydric phenols in the presence of a Lewis acid catalyst such as magnesium chloride or aluminum chloride, and then synthesizing a crude organic phosphorus compound Can be made into a product by washing, purifying and drying.

However, in the organophosphorus compound used in the present invention, an aqueous solution containing mainly magnesium or aluminum derived from the catalyst contained in the organophosphorus compound or a metal ion such as alkali or alkaline earth for washing and purification is used. The total amount of metals, such as sodium, potassium, calcium, etc., which may be introduced in the case, is preferably 30 p
pm or less, more preferably 20 ppm or less, still more preferably 10 ppm or less, particularly preferably 5 ppm or less, in order to obtain a polycarbonate-based flame-retardant resin composition having more excellent wet heat resistance.

Further, the chlorine concentration contained in the organic phosphorus compound is preferably 20 ppm or less, more preferably 1 ppm or less.
It is preferably 0 ppm or less, more preferably 5 ppm or less, particularly preferably 1 ppm or less, in order to obtain a polycarbonate-based flame-retardant resin composition having better resistance to moist heat.

The amount of component (C) in the composition of the present invention is 5 to 30 parts by weight, preferably 8 to 20 parts by weight, per 100 parts by weight of the total of components (A) and (B). More preferably, it is 10 to 17 parts by weight. When the amount of the component (C) is less than 5 parts by weight, the flame retardancy of the thin molded article becomes insufficient. On the other hand, when the amount exceeds 30 parts by weight, the impact resistance of the resin composition becomes insufficient.

The component (D) used in the present invention is a fluoropolymer, and is used for the purpose of preventing the dripping of a combustion product. In the present invention, it is possible to use a fluoropolymer having a fibril-forming ability, such as a fine powder-type fluoropolymer, an aqueous dispersion of a fluoropolymer, and a powdery mixture with a second resin such as AS or PMMA. Any form of fluoropolymer can be used.

In the present invention, an aqueous dispersion of a fluoropolymer can be suitably used as the component (D). With the aqueous dispersion of the fluoropolymer,
Polytetrafluoroethylene, a tetrafluoroethylene polymer such as a tetrafluoroethylene-propylene copolymer, a perfluoroalkane polymer other than polytetrafluoroethylene, preferably a tetrafluoroethylene polymer, particularly preferably polytetrafluoroethylene is, for example, As described in "Fluorine Resin Handbook" (published by Nikkan Kogyo Shimbun, 1990), those produced by suspension polymerization or emulsion polymerization and used as a form of an aqueous dispersion are shown.

That is, a milky white aqueous dispersion obtained by concentrating a dispersion of fluoropolymer fine particles obtained by suspension polymerization or emulsion polymerization to a certain concentration and then stabilizing the dispersion with a surfactant is shown. The solid concentration of the fluoropolymer in the aqueous dispersion of the fluoropolymer may be any concentration at which the dispersion state is stable, but is preferably 5 to 70 wt%, more preferably 20 to 65 wt%, and particularly preferably 30 to 60 wt%. .

The average primary particle size of the fluoropolymer in the aqueous dispersion is. It is preferably from 1 to 0.6 μm, more preferably from 0.5 to 0.4 μm, particularly preferably from 0.18 to 0.3 μm. As the surfactant for stabilizing the aqueous dispersion of the fluoropolymer, a nonionic surfactant such as an ethoxylated alkylphenol or an ethoxylated higher alcohol is preferably used, and the amount thereof is usually 1 wt% to 15 wt%. %, Preferably 2 wt% to 10 wt%, more preferably 3 wt% to 7 wt%.

Further, an aqueous dispersion of the fluoropolymer whose pH value is usually adjusted to 9 to 10 is preferably used. When the fluoropolymer has a solid content of 60 wt%, the liquid specific gravity is about 1.5, and the viscosity (25 ° C.) is in the range of 15 to 30 cp.
As aqueous dispersions of fluoropolymers that can be preferably used in the present invention, "Teflon (R) 30J" manufactured by Mitsui Dupont Fluorochemicals Co., Ltd., "Polyflon D-1", "Polyflon D-" manufactured by Daikin Industries, Ltd.
2 "," Polyflon D-2C "," Polyflon D-2C "
E "can be exemplified.

Further, in the present invention, as component (D), JP-A-9-95583, JP-A-11-49912, JP-A-2000-143966, and JP-A-2000-143966
AS and PMM disclosed in JP-297189A
A fluoropolymer in the form of a powdery mixture with a second resin such as A can also be suitably used. Examples of these which can be preferably used in the present invention include "Blendex 449" manufactured by GE Specialty Chemicals and "Metabrene A-3000" manufactured by Mitsubishi Rayon Co., Ltd.

In the present invention, the compounding amount of the component (D) is 0.1 part by weight based on 100 parts by weight of the total of the component (A) and the component (B).
It is 0.5 to 1 part by weight. The compounding amount of the component (D) is 0.1 part by weight based on 100 parts by weight of the total of the component (A) and the component (B).
It is preferably in the range of 1 to 0.8 part by weight, more preferably 0.15 to 0.6 part, and even more preferably 0.2 to 0.6 part by weight.
0.5 part. The amount of the fluoropolymer is 0.0
When the amount is less than 5 parts by weight, the effect of preventing the dripping of the burned material is insufficient, and it becomes difficult to maintain high flame retardancy particularly in a thin-walled molded product. In addition, the compounding amount of the fluoropolymer is 1
When the amount exceeds the weight part, the melt fluidity and impact resistance tend to decrease.

The component (E) used in the present invention is a coloring agent. Examples of the coloring agent include inorganic pigments such as titanium white (titanium oxide), titanium yellow, red iron oxide, ultramarine, and spinel green; condensed azo organic pigments; quinacridone organic pigments; isoindolinone organic pigments; perylene organic pigments; Organic pigments such as quinone-based organic pigments and phthalocyanine-based organic pigments, carbon black, perylene-based dyes, perinone-based dyes, anthraquinone-based dyes, and heterocyclic-based dyes can be given.

Among the coloring agents, titanium oxide is not limited by the production method and crystal structure, but titanium oxide produced by a chlorine method and having a rutile crystal structure is preferable. Further, the average particle diameter of the titanium oxide used is not particularly limited, but is 0.01 to 0.1.
Those having a diameter of 5 μm are preferred, and those having a diameter of 0.1 to 0.3 μm are particularly preferred. In addition, as long as the object of the present invention is not impaired, the titanium oxide may be previously treated with a treating agent usually used as a surface treating agent for titanium oxide. Such treating agents include, for example, alumina and silica,
Each of them may be used alone or in combination.
In addition, these surface treatment agents may contain an organic dispersant, a stabilizer and the like in an amount not to impair the present invention.

The component (E) in the present invention is often used in combination of a plurality of colorants in order to produce a desired color, but the compounding amount is the total amount of the component (E). ) And the component (B) in a total amount of 0.0001 to 10 parts by weight based on 100 parts by weight. If it is less than 0.0001 parts by weight, it becomes difficult to keep the product color tone constant,
On the other hand, if it exceeds 10 parts by weight, the mechanical properties of the resin composition may be reduced, or the flame retardancy may be reduced, which is not preferable. The amount of the component (E) varies depending on the desired color tone and the color tone of the base resin, and the total amount thereof is usually preferably in the range of 0.1 to 3 parts by weight.

The lubricant (F) in the present invention includes aliphatic hydrocarbons, polyolefin waxes, higher carboxylic acids,
Shown are compounds selected from the group of compounds such as higher carboxylic acid metal salts, fatty acid amides, fatty acid esters, and higher alcohols.

These lubricants (F) may already be contained in the resin raw material, but as a processing aid for the resin, as a dispersant or a spreading agent for a dye or pigment for coloring a resin, and further as a molding agent. In some cases, it is blended as a release agent for improving the releasability of the body from the mold.

Among the components (F), examples of the aliphatic hydrocarbon include liquid paraffin. Examples of the polyolefin wax include paraffin wax, polyethylene wax, polypropylene wax, ethylene / vinyl acetate copolymer wax, and polyolefin ionomer wax.

The higher carboxylic acids include long-chain fatty acids having 8 or more carbon atoms, such as stearic acid, valeric acid, and the like.
Examples thereof include caproic acid, capric acid, lauric acid, arachiic acid, behenic acid, lignoceric acid, cerotic acid, melicic acid, tetratricontanic acid, glutaric acid, adipic acid, azelaic acid, and rosin acid.

The metal salts of higher carboxylic acids include alkali metal salts of the compounds exemplified as the above-mentioned higher carboxylic acids,
Examples thereof include calcium stearate, zinc stearate, magnesium stearate, and lead stearate. Examples of the fatty acid amide include stearic acid amide, oleic acid amide, erucic acid amide, ethylenebisstearic acid amide, methylenebisstearic acid amide, ethylenebisoleic acid amide, and the like.
Aliphatic amide compounds having the above long-chain fatty acid structural units can be exemplified.

Examples of the fatty acid ester include an ester of a higher carboxylic acid having 8 or more carbon atoms such as butyl stearate and a monohydric alcohol, and an ester of a polyhydric alcohol and a long chain fatty acid having 8 or more carbon atoms, for example, ethylene. Glycol monostearate, glycerin monostearate, trimethylolpropane monostearate, pentaerythritol monostearate, pentaerythritol monolaurate, pentaerythritol distearate, glycerin dilaurate, glycerin tristearate, trimethylolpropane distearate, Glycerin distearate, glycerin tribehenate, pentaerythritol tristearate, trimethylolpropane tricaplate, trimethylolpropanediolate, pentaerythritol It is possible to increase the tetrastearate and the like. Examples of the higher alcohol include a long-chain alcohol having 8 or more carbon atoms, for example, stearyl alcohol.

In the present invention, the total amount of the lubricant (F) contained in the polycarbonate-based colored flame-retardant resin composition is 3,000.
Weight ppm or less, preferably 0.1 to 2,000
ppm, more preferably 1-1500 ppm,
Particularly preferably, when the content is 10 to 1,000 ppm, high flame retardancy can be achieved even in the case of a thin-walled molded product.

The content of the component (F) in the polycarbonate-based colored flame-retardant resin composition according to the present invention is determined by separating or extracting these components from the composition,
Quantification can be performed by a combination of analytical methods such as GC / MS and LC / MS.

In the polycarbonate-based colored flame-retardant resin composition of the present invention, for the purpose of modifying the resin composition as required, inorganic materials such as glass fibers, glass flakes, glass beads, calcium carbonate, talc, mica, etc. Fillers, reinforcing materials such as carbon fiber and charcoal, or other thermoplastic resins can also be added. In the polycarbonate-based colored flame-retardant resin composition of the present invention, a heat stabilizer, an antioxidant, an ultraviolet absorber and the like can be added as required.

Next, a method for producing the polycarbonate-based colored flame-retardant resin composition of the present invention will be described. The resin composition of the present invention can be obtained by melt-kneading the above components (A) to (E), and if necessary, the lubricant (F) and other components at the composition ratio described in the present specification. In the present invention, the total amount of the lubricant (F) contained in the polycarbonate-based colored flame-retardant resin composition is 3,000 ppm by weight or less, preferably 2,000 ppm or less, more preferably 1,50 ppm or less.
The melt-kneading is carried out so as to be 0 ppm or less, particularly preferably 1,000 ppm or less.

The compounding and melt kneading at this time are performed by using a generally used apparatus, for example, a premixing apparatus such as a tumbler or a ribbon blender, or a melt kneading apparatus such as a single-screw extruder, a twin-screw extruder, or a co-kneader. Can be done.

As a method for obtaining a polycarbonate-based colored flame-retardant resin composition, first, components (A) to (D) are melt-kneaded to produce pellets of an uncolored flame-retardant resin composition. A method of obtaining a colored flame-retardant resin composition by further melt-kneading E) or a desired colored flame-retardant resin composition by simultaneously melt-kneading the components (A) to (E). A method of obtaining an object may be used.

At this time, the lubricant (F) can be blended at any stage of melt-kneading as long as it is within the range described in the present invention. In addition, the raw materials can be supplied to the melt kneading apparatus after the respective components are mixed in advance, but it is also possible to supply the respective components to the melt kneading apparatus independently.

An extruder, preferably a twin-screw extruder, is usually used as a melt kneading apparatus. When the component (C) is in a liquid state, the component (C) is directly fed to the extruder to perform melt kneading. It is also possible to do. When an aqueous dispersion of a fluoropolymer is used as the component (D), the component (D) can be mixed with other raw materials in advance and then fed to an extruder. Then, melt kneading can be performed.

In the melt kneading, the cylinder set temperature of the extruder is usually set at 200 to 300 ° C., preferably 220 to 270 ° C.
And the screw speed of the extruder 100 to 700 rpm,
Preferably, it can be appropriately selected in the range of 200 to 500 rpm, but care is taken not to give excessive heat generation during melt kneading. Furthermore, it is also effective to reduce the total amount of the lubricant component in the colored flame-retardant resin composition by providing an opening in the latter part of the extruder or performing devolatilization under reduced pressure as necessary.

The residence time of the molten resin in the extruder is usually appropriately selected within the range of 10 to 60 seconds. The shorter the residence time of the molten resin in the extruder, the more excellent the resin composition in wet heat resistance. Is preferred.

A pellet of the uncolored flame-retardant resin composition comprising the components (A) to (D) is prepared in advance, and the pellet is mixed with the component (E). In the method of obtaining a colored flame-retardant resin composition by melt-kneading with a mixer, a component (F) as a colorant dispersant or a colorant spreading agent is used in order to improve the dispersibility and color uniformity of the component (E). ) Can be used, but in the present invention, the component (F) including these colorant dispersants and colorant spreaders is used.
Is 3,000 weight parts with respect to the colored flame-retardant resin composition.
It is necessary to consider the range below pm.

In this case, if a twin-screw extruder is used as the melt-kneading apparatus, the colorant can be added to the resin composition without reducing or using the amount of the colorant dispersant or the colorant spreader. It is preferable because it can be dispersed well. The use of a twin-screw extruder is also preferable in that the coloring uniformity of the colored resin composition can be improved. When a single screw extruder is used, it has a screw configuration with enhanced kneading and dispersing function, for example, 3 to
It is preferred to use a single screw extruder with six dalmage screw parts.

The molding method for obtaining a molded article comprising the polycarbonate-based colored flame-retardant resin composition of the present invention is not particularly limited. Examples thereof include injection molding, gas assist molding, extrusion molding, and compression molding. In particular, injection molding is preferably used.

Examples of molded articles using the resin composition of the present invention include OA equipment housings such as monitors, notebook computers, copiers, and printers, OA equipment chassis, and mobile phone housings.

[0097]

Embodiments of the present invention will be specifically described below with reference to Examples and Comparative Examples. In Examples and Comparative Examples, the following components (A), (B),
A polycarbonate colored resin composition was produced using (C), (D), (E) and, if necessary, component (F). However, some of the components (C) used in the comparative examples do not satisfy the requirements of the component (C) in the present invention, but for convenience, these components were also classified as (C).

1. Component (A): Aromatic polycarbonate (PC1) A bisphenol A-based polycarbonate produced from bisphenol A and diphenyl carbonate by a melt transesterification method and containing no lubricant component. Weight average molecular weight (Mw) = 21,800 Phenolic terminal group ratio (ratio of phenolic terminal groups to all terminal groups) = 28 mol%

(PC2) A commercially available bisphenol A-based polycarbonate obtained by the phosgene method, containing 2,500 ppm of a lubricant component as a release agent. Weight average molecular weight (Mw) = 28,000 Monoglycerin release agent content = 2,500 ppm

(PC3) A commercially available bisphenol A-based polycarbonate obtained by the phosgene method, containing 500 ppm of a lubricant component as a release agent. Weight average molecular weight (Mw) = 15,000 Paraffin-based release agent content = 500 ppm

2. Component (B): rubber-modified styrenic resin (ABS1) An ABS graft copolymer obtained by an emulsion polymerization method was prepared by mixing ABS having a weight average molecular weight (Mw) of 130,000.
Butadiene rubber content obtained by diluting and kneading with S resin (styrene / acrylonitrile resin) is 25 wt%,
An emulsion-polymerized acrylonitrile-butadiene-styrene resin having a rubber weight average particle diameter of 0.26 μm, acrylonitrile units of 27 wt%, and styrene units of 73 wt%, containing 1,200 ppm of a lubricant component as an emulsifier residue. Potassium rosinate content = 1,200 ppm

(ABS2) The butadiene rubber content obtained by the solution polymerization method is 12% by weight, the styrene unit is 66% by weight, the acrylonitrile unit is 22% by weight, the weight average particle diameter of the rubber is 0.7 μm, A solution-polymerized acrylonitrile-butadiene-styrene resin having a graft copolymer component having a weight average molecular weight (Mw) of 110,000 and containing no lubricant component.

(MBS) Methyl methacrylate / butadiene / styrene copolymer (manufactured by Taiwan Plastics Co., Ltd. (Trade name: M-51))

3. Component (C): Organic phosphorus compound oligomer (phosphate 1) An organic phosphorus compound oligomer represented by the formula (1), wherein the substituents R ^a , R ^b , R ^c , and R ^d are all phenyl groups, Weight average degree of condensation (N) is 1.1
5, the magnesium content is 4.5 ppm,
The chlorine content is 1 ppm or less, and the acid value is 0.02 mg.
KOH / g.

(Phosphate 2) Resorcinol diphosphate (CR733S) manufactured by Daihachi Chemical Co., Ltd. The weight average condensation degree (N) is 1.41, the magnesium content is 5.2 ppm, and the chlorine content is 1 ppm. The following, having an acid value of 0.053 mg / KOH.

(Phosphate 3) Triphenyl phosphate (TP) manufactured by Daihachi Chemical Co., Ltd.
P) Monophosphate compound

4. Component (D): Fluoropolymer (PTFE1) Aqueous PTFE dispersion of polytetrafluoroethylene (trade name: Teflon (R) 30J) manufactured by DuPont-Mitsui Fluorochemicals Co., Ltd. Solid content = 60 wt%

(PTFE2) 50/50 (w / w) powdery mixture of polytetrafluoroethylene and acrylonitrile / styrene copolymer manufactured by GE Specialty Chemicals (trade name B)
lensex 449)

5. Ingredient (E): Colorant (white) Titanium oxide manufactured by DuPont (trade name: Ti-Ture®)
103-08) (Black) Carbon black manufactured by Tokai Carbon Co., Ltd. (trade name: carbon black 7550F) (yellow) Titanium yellow manufactured by Shephard Company (trade name: Yellow)
w 29)

6. Component (F): Lubricant (Release agent 1) Pentaerythritol tetrastearate release agent manufactured by NOF Corporation (trade name: Unistar H476) (Release agent 2) Stearic acid monoglyceride release agent manufactured by Kao Corporation Agent (trade name EXCEL T-95)

(Dispersant 1) Ethylene / vinyl acetate copolymer manufactured by Allied Signal Co. (trade name: AC400A) (Dispersant 2) Ethylene bisstearyl amide manufactured by Kao Corporation (trade name: Kao Wax EB-P) (Exhibition) Adhesive) Paraffin oil manufactured by Esso Oil Co., Ltd. (trade name: Christol J-352)

[0112]

EXAMPLES Examples 1 to 10 and Comparative Examples 1 to 3 The components (A), (B), (C), (D), (E) and (F) in the amounts shown in Table 1 (units are weights) Part) to obtain a polycarbonate-based colored flame-retardant resin composition. The melt kneading device is a twin screw extruder (ZSK-25, L / D = 3
7, Werner & Pfleiderer), cylinder temperature 250 ° C, screw rotation speed 25
Melt kneading was performed under the conditions of 0 rpm and a discharge speed of the kneaded resin of 23 kg / Hr, and the temperature of the molten resin was set to 260 to 270 ° C.

The raw materials were charged into the twin-screw extruder by pre-blending components (A), (B), (D), (E) and component (F) in advance using a weight feeder. The phosphorus compound oligomer (C) is previously 80
The mixture was preheated to ° C. and compounded by press-fitting through an injection nozzle from the middle of the extruder with a gear pump. In addition, an opening was provided in the latter part of the extruder, and atmospheric pressure release devolatilization was performed. The obtained pellets were dried and molded by an injection molding machine (Autoshot 50D, manufactured by FANUC), and the following tests were performed.

(1) Flame retardancy test The obtained pellets were dried, and the cylinder temperature was 260 ° C.
Molding was performed with an injection molding machine set at a mold temperature of 60 ° C., and strip-shaped molded articles (thickness: 2.0 mm, 1.5 mm and 1.4 mm) for a combustion test were prepared, and a UL94 standard 20 MM vertical combustion test was performed It was classified into V-0, V-1 or V-2.
Note that the symbol NC in the table cannot be classified (non-classi
fiction). (Degree of flame retardancy: V-
0>V-1>V-2> NC)

(2) MFR Measured at 220 ° C. under a load of 10 kg according to ASTM D1238. (Unit: g / 10 min) (3) Izod (Izod) impact test The obtained pellets were dried, and the cylinder temperature was 240 ° C.
A 1/8 inch thick strip was molded using an injection molding machine set at a mold temperature of 60 ° C., and the Izod impact strength was measured with a 1/8 inch thick notch according to ASTM D256.
The measurement temperature is 23 ° C. (Unit: kgf · cm / c
m)

(4) Evaluation of mold contamination The injection molding machine (NIIGATA CN75, manufactured by Niigata Iron Works) set at a cylinder temperature of 260 ° C. and a mold temperature of 40 ° C.
Using an injection pressure of 905 kgf / cm ² and an injection time of 3
Specimen weight 4 g under the conditions of seconds, cooling time 1.2 seconds, mold opening / closing time 2.1 seconds, rest time 2 seconds, and molding cycle 8.3 seconds.
Continuously molded, and 100, 500, 1,000,
And the surface condition of the mold after 2,000 shots was visually observed. ◎: No MD was observed at 2,000 shots. ：: MD is observed at 101 to 2,000 shots. ×: MD is observed in 100 shots or less. Here, the MD includes both solid and liquid deposits attached to the mold surface.

(5) Moisture and heat resistance The obtained pellets were dried, and the cylinder temperature was 240 ° C.
Then, a 1/8 inch thick strip was molded by an injection molding machine set at a mold temperature of 60 ° C. 60 ° C, 85
After holding for 168 hours in an environment of RH% (relative humidity), the sample was taken out, and the Izod impact strength was measured with a notch according to ASTM D256. The measurement temperature of the Izod impact strength is 23 ° C. (Unit: kgf · cm / cm) The results are shown in Tables 1 and 2.

[0118]

[Table 1]

[0119]

[Table 2]

The total amount of the lubricant components in the compositions shown in Tables 1 and 2 is a calculated value, including the lubricant component contained in the raw material PC resin and the raw material ABS resin. Example 1
10 is the result of the composition of the present invention, which shows that the composition is excellent in thin-walled flame retardancy, melt fluidity, impact resistance, low mold contamination, and wet heat resistance. Comparative Examples 1 and 2 are the results when the total amount of the lubricant component in the composition exceeds the range of the present invention, and it is understood that the flame retardancy, particularly the flame retardancy of a thin molded article, is inferior. Comparative Example 3 is the result of using TPP, which is a mono-based phosphorus compound flame retardant, instead of the organic phosphorus compound oligomer, but the mold contamination is remarkable.

[0121]

Industrial Applicability The polycarbonate-based colored flame-retardant resin composition of the present invention is a polycarbonate-based colored flame-retardant excellent in flame retardancy, melt fluidity, impact resistance, low mold contamination and wet heat resistance in a thin molded article. Since it is a fuel resin composition, it is extremely useful as a housing material for computer monitors, notebook computers, printers, word processors, copiers and the like.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 27:12) (72) Inventor Hideki Nasu 3-1-1, Utsudori, Kurashiki-shi, Okayama Prefecture Asahi Kasei Corporation Of which F-term (reference) 4F070 AA07 AA08 AA18 AA50 AB08 AB09 AC32 AC36 AC40 AC43 AC47 AC55 AC79 AE04 AE07 AE09 FA03 FA17 FB06 FC06 4J002 BD123 BN12X BN14X BN15X BN16X CG00W CG01W CG02 E 018 CG02 018

Claims (7)

[Claims] 1. An aromatic polycarbonate resin (A) 50
To 95 parts by weight, rubber-modified styrene resin (B) 50 to 5
Parts by weight, 5 to 30 parts by weight of at least one kind of an organic phosphorus compound oligomer (C), 0.0 of a fluoropolymer (D)
A polycarbonate-based colored flame-retardant resin composition containing 5 to 1 part by weight and a colorant (E) 0.0001 to 10 parts by weight, wherein the total amount of the lubricant (F) contained in the composition is 3,0.
A polycarbonate-based colored flame-retardant resin composition having a content of not more than 00 ppm by weight. 2. The lubricant (F) is a compound selected from aliphatic hydrocarbons, polyolefin waxes, higher carboxylic acids, higher carboxylic acid metal salts, higher fatty acid amides, higher fatty acid esters, and higher alcohols. The polycarbonate-based colored flame-retardant resin composition according to claim 1. 3. At least one kind of the organic phosphorus compound oligomer (C) has the following formula (1): The polycarbonate-based colored flame-retardant resin composition according to claim 1, wherein the composition is selected from the group consisting of compounds represented by the formula: 4. An aromatic polycarbonate resin (A) 50
To 95 parts by weight, rubber-modified styrene resin (B) 50 to 5
Parts by weight, 5 to 30 parts by weight of at least one kind of an organic phosphorus compound oligomer (C), 0.0 of a fluoropolymer (D)
A method for producing a polycarbonate-based flame-retardant resin composition containing 5 to 1 part by weight and a colorant (E) in an amount of 0.0001 to 10 parts by weight using a melt-kneading apparatus, wherein a lubricant (F) contained in the composition is used. ) Is not more than 3,000 ppm by weight. 5. The lubricant (F) is a compound selected from aliphatic hydrocarbons, polyolefin waxes, higher carboxylic acids, metal salts of higher carboxylic acids, fatty acid amides, fatty acid esters, and higher alcohols. A method for producing the polycarbonate-based colored flame-retardant resin composition according to claim 4. 6. The at least one organic phosphorus compound oligomer (C) has the following formula (1): The method for producing a polycarbonate-based colored flame-retardant resin composition according to claim 4, wherein the composition is selected from the group consisting of compounds represented by the formula: 7. The method for producing a polycarbonate-based colored flame-retardant resin composition according to claim 4, wherein the melt-kneading apparatus is a twin-screw extruder.