JP2003041114A - Polycarbonate-based flame-retardant resin composition excellent in impact resistance - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polycarbonate-based flame retardant resin composition. SOLUTION: This polycarbonate-based flame-retardant composition comprises 50-95 pts.wt. aromatic polycarbonate resin (A), 49-0 pts.wt. copolymer (B) containing an aromatic vinyl monomer unit (b-1) and a vinyl cyanide monomer unit (b-2), 49-1 pts.wt. cyanide-containing graft copolymer (C) obtained by copolymerizing an aromatic vinyl compound (c-1) and a vinyl cyanide compound (c-2) in the presence of a rubbery polymer (c-3), 49-0.1 pts.wt. (meth)acrylate- containing graft copolymer (D) obtained by copolymerizing an aromatic vinyl compound (d-1) and an alkyl (meth)acrylate (d-2) in the presence of a rubbery butadiene polymer (d-3), hereafter 5-30 pts.wt. at least 1 species of organophosphorus compound oligomers (E) and 0.1-20 pts.wt. talc (F) based on 100 pts.wt. sum total of the components (A), (B), (C) and (D).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a polycarbonate-based flame-retardant resin composition having excellent impact resistance, melt flowability, flame retardancy, and rigidity with an extremely thin wall. More specifically, the aromatic polycarbonate resin (A), the copolymer (B) containing the aromatic vinyl monomer unit and the vinyl cyanide monomer unit, the aromatic vinyl compound and the vinyl cyanide compound are rubbers. Cyanide-containing graft copolymer (C) obtained by copolymerization in the presence of a rubbery polymer, and an aromatic vinyl compound and an alkyl (meth) acrylate are obtained in the presence of a rubbery butadiene polymer. (Meth) acrylate-containing graft copolymer (D), at least one organic phosphorus compound oligomer (E), and talc (F)
And a polycarbonate-based flame-retardant resin composition containing

The resin composition of the present invention has excellent impact resistance, melt flowability, flame retardancy, and rigidity in a thin wall, and also has low mold contamination and heat resistance. INDUSTRIAL APPLICABILITY The resin composition of the present invention can be suitably used for housings of OA equipment and electric / electronic equipment, and various other molded articles,
In particular, it can be suitably used for an extremely thin molded body having a portion having a wall thickness of 1.2 mm or less.

[0003]

2. Description of the Related Art A composition obtained by blending a polycarbonate resin (PC) with an acrylonitrile / butadiene / styrene resin (ABS) and an organic phosphorus compound flame retardant (hereinafter referred to as
It is referred to as "PC / ABS / phosphorus flame retardant composition". ) Is used as a non-bromine and non-chlorine flame-retardant resin material as a housing material for computer monitors, notebook computers, printers, word processors, copiers, etc.

In recent years, the housing of the equipment has been designed to simplify the structure so as to be easily disassembled and sorted, to improve the recyclability, and to reduce the thickness by reducing the thickness, and at the same time, to reduce the cost and the cost. In particular, portable OA equipment housings such as notebook personal computers are required to be ultra-thin housings with a wall thickness of 1.2 mm or less for the purpose of further weight reduction. From such a flow of housing design, the material used therewith has excellent fluidity of molten resin that enables ultra-thin molding, high flame retardancy in ultra-thin molded products,
In addition, rigidity, impact resistance, and heat resistance for preventing deformation and breakage in an ultrathin molded body are being demanded at the same time, and a resin composition having a high balance of physical properties is demanded.

In order to enable molding of an extremely thin molded body having a wall thickness of 1.2 mm or less among the above problems, it is general to use a resin composition having excellent melt fluidity. PC /
The ABS / phosphorus flame retardant composition has better melt flowability than PC alone because ABS and phosphorus flame retardant are mixed with PC, but in order to easily process thin-walled molded products, Further improvement of fluidity is required. Therefore, in the conventional techniques, a method of increasing the blending amount of ABS resin having a lower melt viscosity than PC, a method of using a low molecular weight PC, and the like have been used. However, in this method, if the ABS resin content is increased, there is a problem that flame retardancy and rigidity tend to decrease, and if a low molecular weight PC is used, impact resistance tends to decrease, so melt flow It was not easy to improve flame resistance, rigidity, and impact resistance at the same time as improving the properties.

Therefore, as a method for increasing the melt fluidity by increasing the amount of ABS compounded and improving flame retardancy and rigidity, a technique of compounding talc is disclosed in JP-A-13-49106, JP-A-13-72852, and JP-A-12-. 191896, JP-A-11-199768 and the like. However, although the technique is effective in improving flame retardancy and rigidity, the impact resistance tends to be lowered by blending talc, and particularly, the impact resistance is sufficient for an extremely thin molded body having a wall thickness of 1.2 mm or less. It was difficult to give the sex.

Generally, when a powder obtained by crushing an ore such as talc is blended with a resin composition as a reinforcing agent, it is better to blend a powder having a smaller particle size than a large particle size to lower the impact resistance. The percentage tends to be small. Therefore, the average particle size is 2
Japanese Patent Application Laid-Open No. 7-316411 describes a method of blending talc having a small particle size of not more than μm to suppress the deterioration of impact resistance. However, even this technique is not sufficient as a method for suppressing the impact resistance deterioration due to talc blending, and particularly when a low molecular weight PC is used for improving melt fluidity, the impact resistance is apt to be significantly decreased. was there. Therefore, in the conventional technique of blending talc with the conventional PC / ABS / phosphorus flame retardant composition, the melt flowability and flame retardancy of the molded ultra-thin molded product having a wall thickness of 1.2 mm or less are sufficient. It has been extremely difficult to simultaneously impart rigidity, rigidity, and impact resistance.

On the other hand, recently, as a flame retardant to be added to a PC / ABS / phosphorus flame retardant composition in order to reduce mold contamination during molding, an oligomeric phosphorus flame retardant having a small amount of volatile components has been attracting attention. ing. Among them, a bisphenol A diphosphate (BDP) type oligomeric phosphorus compound flame retardant having excellent heat resistance is a flame retardant capable of reducing mold contamination of a PC / ABS / phosphorus flame retardant composition and improving heat resistance at the same time. Is being used as. However, while oligomer-based phosphorus flame retardants can reduce mold contamination, triphenyl phosphate (TPP)
There is a problem that the flame retardant performance is inferior to that of the mono-type phosphorus compound flame retardant represented by. Therefore PC / AB
When an oligomeric phosphorus compound is used as the phosphorus-based flame retardant of the S / phosphorus-based flame retardant composition, low mold stainability and heat resistance are satisfied, but the wall thickness of the composition is 1.2.
It was difficult to impart a high flame retardancy level equivalent to V-0 of UL94 to the ultra-thin mm molded product.

As described above, the PC / ABS / phosphorus flame retardant composition has excellent impact resistance, melt flowability and rigidity, even in an extremely thin molded body having a wall thickness of 1.2 mm or less. Despite the strong demand for a polycarbonate-based flame-retardant resin composition having excellent flame retardancy, low mold contamination, and heat resistance, it is the current situation that satisfactory performance has not been obtained.

[0010]

The object of the present invention is to provide excellent impact resistance, melt flowability, and rigidity, and at the same time, excellent flame retardancy, even for an ultrathin molded product having a wall thickness of 1.2 mm or less. Another object of the present invention is to provide a polycarbonate-based flame-retardant resin composition having low mold contamination and heat resistance.

[0011]

The inventors of the present invention have found that PC / A
The BS / phosphorus flame retardant composition has improved impact resistance while being blended with talc for the purpose of improving rigidity and flame retardancy, and at the same time, an ultra-thin molded body having a wall thickness of 1.2 mm or less can be easily formed. As a result of diligent examination of a method of obtaining a PC / ABS / phosphorus flame retardant composition which is moldable and has excellent melt fluidity, by incorporating a specific graft copolymer, impact resistance is remarkably improved, It has also been found that a resin composition having a good flow can be obtained. That is, the present inventors have surprisingly found that P
A (meth) acrylate-containing graft copolymer obtained by copolymerizing an aromatic vinyl compound and an alkyl (meth) acrylate in a C / ABS / phosphorus flame retardant composition in the presence of a rubbery butadiene polymer is blended. It has excellent impact resistance, melt flowability, and rigidity, and is extremely difficult to form an ultrathin molded product with a wall thickness of 1.2 mm or less even when an oligomer phosphorus-based flame retardant is used. The inventors have found that flammability is exhibited and have completed the present invention.

That is, the present invention relates to [1] aromatic polycarbonate resin (A) 50 to 95
49 to 0 parts by weight of a copolymer (B) containing, by weight, an aromatic vinyl monomer unit (b-1) and a vinyl cyanide monomer unit (b-2), an aromatic vinyl compound (c- 1)
49 to 1 part by weight of a cyanide-containing graft copolymer (C) obtained by copolymerizing a vinyl cyanide compound (c-2) with a rubbery polymer (c-3), an aromatic vinyl compound (Meth) acrylate-containing graft copolymer (D) obtained by copolymerizing (d-1) with an alkyl (meth) acrylate (d-2) in the presence of a rubbery butadiene polymer (d-3). 49 to 0.1 parts by weight, and the following components (A), components (B), components (C), and components (D)
A total of 100 parts by weight of at least one organic phosphorus compound oligomer (E) 5 to 30 parts by weight, and a talc (F) 0.1 to 20 parts by weight of a flame retardant resin composition, [2] The polycarbonate-based flame retardant according to the above [1], wherein the talc (F) has an average particle size of 1 to 50 μm, and 1 to 80% of all talc particles are particles having a particle size of 7 μm or more. Resin composition,

[3] At least one organic phosphorus compound oligomer (E) is represented by the following formula (1):

[Chemical 3] Selected from the group of compounds represented by the above [1] and [2], the polycarbonate-based flame-retardant resin composition,

[4] At least one organic phosphorus compound oligomer (E) is represented by the following formula (2):

[Chemical 4] Selected from the group of compounds represented by the above [1] and [2], the polycarbonate-based flame-retardant resin composition,

[5] A molded article molded from the polycarbonate resin composition described in [1], [2], [3], and [4], and having a thickness of 1.2 mm or less. Is a thin-walled molded product having at least one of

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be specifically described below. The aromatic polycarbonate resin (A) of the present invention has a main chain composed of a repeating unit represented by the following formula (3).

[0017]

[Chemical 5]

(In the formula, Ar is a divalent aromatic residue, for example, phenylene, naphthylene, biphenylene,
Examples include pyridylene and those represented by the following formula (4). )

[0019]

[Chemical 6]

(In the formula, Ar ¹ and Ar ² are each an arylene group. For example, a group such as phenylene, naphthylene, biphenylene, and pyridylene is represented, and Y is an alkylene group represented by the formula (5) or a substituted alkylene group. It is.)

[0021]

[Chemical 7]

(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 C7-31 aralkyl group, which may be optionally substituted with a halogen atom or a C1-10 alkoxy group, k is an integer of 3-11, and R ⁵ and R ⁶
Are independently selected for each X and independently of each other a hydrogen atom, or a lower alkyl group having 1 to 6 carbon atoms, or a lower alkyl group having 6 to 6 carbon atoms.
A 30 aryl group, which may be optionally substituted with a halogen atom or an alkoxy group having 1 to 10 carbon atoms;
Represents a carbon atom. ) Further, a divalent aromatic residue represented by the following formula (6) may be contained as a copolymer component.

[0023]

[Chemical 8]

(In the formula, Ar ¹ and Ar ² are the same as in the formula (4).
Z is a mere bond, or -O-, -CO-, -S-,
_{-SO 2 -, - CO 2 -} , - CON (R 1) - (R 1 is as defined in the formula (5)) is a divalent group such as. ) Examples of these divalent aromatic residues include those represented below.

[0025]

[Chemical 9]

[0026]

[Chemical 10]

(In the formula, R ⁷ and R ⁸ are each independently
Hydrogen, halogen, C1-10 alkyl group, C1
It is a C-10 alkoxy group, a C5-C10 cycloalkyl group, or a C6-C30 aryl group. m and n are 1
In to 4 integer, m is may be different in each of R ⁷ is the same in the case of 2-4, there is n is different in each of the same each R ⁸ in the case of 2-4 May be. Among these, one represented by the following formula (7) is a preferable example.

[0028]

[Chemical 11]

Particularly, A represented by the above formula (7) is
A polycarbonate containing 85 mol% or more (based on all monomer units in the polycarbonate) of a repeating unit represented by r is particularly preferable. The polycarbonate that can be used in the present invention may have a branched structure having a trivalent or higher valent aromatic residue as a branch point. The molecular structure of the polymer terminal is not particularly limited, but 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 (8).

[0030]

[Chemical 12]

(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, for example, those represented by the following formula. Is mentioned.

[0032]

[Chemical 13]

The alkyl carbonate end group is represented by the following formula (9).

[0034]

[Chemical 14]

(In the formula, R ⁹ represents a straight-chain or branched alkyl group having 1 to 20 carbon atoms.) Specific examples of the alkyl carbonate terminal group include those represented by the following formula.

[0036]

[Chemical 15]

Of these, phenolic hydroxyl group, phenyl carbonate group, pt-butylphenyl carbonate group, p-cumylphenyl carbonate and the like are preferably used. In the present invention, the ratio of the phenolic hydroxyl group terminal to the other terminal is not particularly limited, but from the viewpoint of obtaining excellent mechanical strength and heat stability, the ratio of the phenolic hydroxyl group terminal is 20% of the total number of terminal groups. The above is preferable, and the range of 20 to 80% is more preferable. The ratio of phenolic end groups is 80% of the total number of end groups
If it exceeds, the thermal stability during melting tends to be slightly lowered.

The method for measuring the amount of terminal phenolic hydroxyl groups is as follows:
Generally, a method using NMR (NMR method), a method using titanium (titanium method), a method using UV or IR (UV method or IR method)
Can be found at. The weight average molecular weight (Mw) of the polycarbonate resin (A) used in the present invention is generally preferably in the range of 5,000 to 50,000, more preferably 10,000 to 40,000, and further preferably Is 15,000 to 30,000, particularly preferably 18,000 to 25,000. If it is less than 5,000, impact resistance tends to be insufficient, and if it exceeds 50,000, melt fluidity tends to be insufficient.

In the present invention, the weight average molecular weight (Mw) of the polycarbonate is measured by gel permeation chromatography (GPC), and the measurement conditions are as follows. That is, using tetrahydrofuran as a solvent and polystyrene gel, the conversion molecular weight calibration curve according to the following equation is used to determine from the constitutional 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)

The aromatic polycarbonate resin (A) used in the composition of the present invention may be one produced by a known method. Specifically, for example, a known method of reacting an aromatic dihydroxy compound and a carbonate precursor, for example, reacting an aromatic dihydroxy compound and a carbonate precursor (for example, phosgene) in the presence of an aqueous sodium hydroxide solution and a methylene chloride solvent. The crystallized carbonate prepolymer obtained by the interfacial polymerization method (eg, phosgene method), the transesterification method (melting method) in which an aromatic dihydroxy compound is reacted with a carbonic acid diester (eg, diphenyl carbonate), or the phosgene method or the melting method is solidified. Phase polymerization method (Japanese Patent Laid-Open No. 1-158033
(Corresponding to U.S. Pat. No. 4,948,871), Japanese Patent Laid-Open No. 1-271426, Japanese Laid-Open Patent No. 3-68627.
(Corresponding to US Pat. No. 5,204,377)) and the like are used.

The preferred polycarbonate resin is
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 can be used. In the present invention, two or more different polycarbonates having different structures and molecular weights may be combined and used as the component (A). The amount of component (A) in the composition of the present invention is as follows: component (A), component (B), component (C),
And 50 to 95 relative to 100 parts by weight of the total of the component (D).
The amount is preferably 60 to 90 parts by weight, more preferably 65 to 85 parts by weight. When the amount of the component (A) is less than 50 parts by weight, it becomes difficult to satisfy the heat resistance and the flame retardancy in a thin molded product, while when it exceeds 95 parts by weight, it becomes difficult to satisfy the melt fluidity, which is preferable. Absent.

The component (B) used in the present invention is a copolymer containing an aromatic vinyl monomer unit (b-1) and a vinyl cyanide monomer unit (b-2). Examples of the aromatic vinyl monomer unit (b-1) in the component (B) include styrene, α-methylstyrene, paramethylstyrene, vinylxylene, p-tertiarybutylstyrene, ethylstyrene, vinylnaphthalene and the like. And one or more of them may be used.
Styrene and α-methylstyrene are preferred, and styrene is most preferred.

As the vinyl cyanide monomer unit (b-2) in the component (B), for example, acrylonitrile, methacrylonitrile and the like can be mentioned, and one or more of them are used. Of these, acrylonitrile is preferred. (B-1) / (b-2) in the component (B)
The composition ratio of (b-1) and (b-
With respect to 100 parts by weight in total of 2), preferably (b-
1) 95 to 50% by weight, (b-2) 5 to 50% by weight
More preferably, (b-1) is 90 to 60% by weight, (b-2) is 10 to 40% by weight, and more preferably (b-1) is 85 to 65% by weight, -2) is 15
~ 35% by weight.

Further, the component (B) is a component (b-1) and a component (b-2) as long as the gist of the present invention is not impaired.
In addition, a monomer copolymerizable with these components can be used. As such a copolymerizable monomer,
Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth)
Acrylate, 2-ethyl (meth) acrylate, 2-
Alkyl (meth) acrylate monomers such as ethylhexyl methacrylate, (meth) acrylic acids such as acrylic acid and methacrylic acid, α, β-unsaturated carboxylic acids such as maleic anhydride, N-phenylmaleimide, N-methylmaleimide, Examples thereof include maleimide-based monomers such as N-cyclohexylmaleimide and glycidyl group-containing monomers such as glycidyl methacrylate. These monomers may be used alone or in combination of two or more within the range not impeding the gist of the present invention.

Preferred examples of the component (B) include styrene / acrylonitrile copolymer resin (SAN) and butyl acrylate / styrene / acrylonitrile copolymer resin (BAAS). In this
S is preferable for improving the impact resistance and fluidity of the resin composition, and particularly, the above BAAS preferably contains 2 to 20% by weight of a butyl acrylate monomer component in the component (B). The most preferable component (B) is SAN.

As the method for producing the component (B), there may be mentioned generally known production methods such as bulk polymerization, solution polymerization, suspension polymerization and emulsion polymerization. The weight average molecular weight (Mw) of the component (B) is usually in the range of 20,000 to 200,000. Preferably 60,000 to 180,000
And more preferably 70,000 to 150,000.
0, particularly preferably 80,000 to 140,00
It is 0. If it is less than 20,000, it becomes difficult to maintain the impact resistance, and if it exceeds 200,000, it becomes difficult to obtain a composition having a high fluidity.

The proportion of the component (B) is 49 parts by weight to 0 parts by weight, preferably 100 parts by weight of the components (A), (B), (C) and (D). Is 3
The amount is 0 to 1 part by weight, more preferably 20 to 3 parts by weight. The component (B) is not an essential component for achieving the purpose of the present invention, but it is preferable to mix it because it can improve the fluidity. In this case, if the blending amount exceeds 49 parts by weight, it becomes difficult to maintain the heat resistance, impact resistance and flame retardancy of the resin composition, which is not preferable. Further, the component (B) may be a combination of two or more components (B) having different structures and molecular weights.

Component (C) is an aromatic vinyl compound (c
It is a cyanide-containing graft copolymer obtained by copolymerizing -1) with a vinyl cyanide compound (c-2) in the presence of a rubbery polymer (c-3). Rubbery polymer (c-
As 3), those having a glass transition temperature of 0 ° C. or lower can be used, and preferably the glass transition temperature is −1.
A rubber-like polymer having a temperature of 0 ° C. or lower, more preferably a glass transition temperature of −30 ° C. or lower, and most preferably a glass transition temperature of −50 ° C. or lower.

Specific examples of the rubber-like polymer as the component (c-3) include polybutadiene, styrene / butadiene copolymer rubber, butadiene / butyl acrylate copolymer rubber, acrylonitrile / butadiene copolymer rubber and the like diene rubbers. Rubber, acrylic rubber such as polybutyl acrylate,
Block copolymers such as silicone / acrylic composite rubber, polyisoprene, polychloroprene, ethylene / propylene rubber, ethylene / propylene / diene terpolymer rubber, styrene / butadiene block copolymer rubber, styrene / isoprene block copolymer rubber, And those hydrogenated products etc. can be used. Among these polymers, polybutadiene, styrene / butadiene copolymer rubber, acrylonitrile / butadiene copolymer rubber, polybutyl acrylate and the like are preferable, and polybutadiene is most preferable.

The average particle size of the component (c-3) is 0.1-1.
5 μm is preferable, and more preferably 0.15 to 1.0 μm.
m, more preferably 0.2 to 0.8 μm, and most preferably 0.25 to 0.7 μm. If it is less than 0.1 μm or exceeds 1.5 μm, it becomes difficult to maintain the impact resistance of the resin composition, which is not preferable. The proportion of the rubber-like polymer (c-3) in the component (C) is used within the range not deviating from the gist of the present invention, and is determined according to the required flame retardancy, mechanical strength, rigidity and molding processability. To be The preferred range is 5 to 45% by weight, more preferably 8 to 40% by weight, still more preferably 10 to 30% by weight, and most preferably 12 to 25% by weight, relative to 100 parts by weight of the component (C). is there. If the amount of component (c-3) is too large, the flame retardancy, rigidity, and fluidity deteriorate, which is not preferable, and if it is too small, it becomes difficult to maintain the impact resistance of the resin composition, which is not preferable.

As the aromatic vinyl compound (c-1) used as the component (C), styrene, α-methylstyrene, paramethylstyrene, vinylxylene, p-tert-butylstyrene, ethylstyrene, vinylnaphthalene, etc. Is mentioned. Of these, styrene is particularly preferable. Vinyl cyanide compound (c
-2) includes, for example, acrylonitrile, methacrylonitrile and the like.
Use more than one seed. Of these, acrylonitrile is preferred.

The composition ratio of (c-1) / (c-2) in the component (C) is not particularly limited, but is preferably 100 parts by weight in total of (c-1) and (c-2). (C-1) is 9
5 to 50% by weight, (c-2) is 5 to 50% by weight,
More preferably, (c-1) is 90 to 60% by weight, (c-1)
-2) is 10 to 40% by weight, more preferably (c-1).
Is 85 to 65% by weight, and (c-2) is 15 to 35% by weight.

Further, the component (C) is a component (c-1) and a component (c-2) as long as they do not impair the gist of the present invention.
In addition, a monomer copolymerizable with these components can be used. As such a copolymerizable monomer,
Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth)
Acrylate, 2-ethyl (meth) acrylate, 2-
Alkyl (meth) acrylate monomers such as ethylhexyl methacrylate, (meth) acrylic acids such as acrylic acid and methacrylic acid, α, β-unsaturated carboxylic acids such as maleic anhydride, N-phenylmaleimide, N-methylmaleimide, Examples thereof include maleimide-based monomers such as N-cyclohexylmaleimide and glycidyl group-containing monomers such as glycidyl methacrylate. These monomers may be used alone or in combination of two or more within the range not impeding the gist of the present invention.

Preferred examples of the component (C) are ABS resin (acrylonitrile-butadiene-styrene resin),
AAS resin (acrylonitrile / butyl acrylate /
Styrene resin) and the like. Among them, ABS resin is preferable. Examples of the method for producing the component (C) include generally known production methods such as bulk polymerization, solution polymerization, suspension polymerization and emulsion polymerization. Among them, the component (C) produced by bulk polymerization or solution polymerization is
Since the component (C) can be obtained without using an emulsifier, the fatty acid or the fatty acid metal salt derived from the emulsifier is not substantially contained in the component (C), and thus it is particularly preferably used as the component (C). it can.

The component (D) used in the present invention includes an aromatic vinyl compound (d-1) and an alkyl (meth) acrylate (d-2), which is a rubber-like butadiene polymer (d-3).
Is a (meth) acrylate-containing graft copolymer obtained by copolymerization in the presence of As the rubber-like butadiene polymer (d-3), those having a glass transition temperature of 0 ° C. or lower can be used, preferably a rubber-like butadiene polymer having a glass transition temperature of −10 ° C. or lower, and more preferably A rubbery butadiene polymer having a glass transition temperature of -30 ° C or lower, more preferably a rubbery butadiene polymer having a glass transition temperature of -50 ° C or lower, and most preferably a rubbery butadiene having a glass transition temperature of -80 ° C or lower. It is a polymer.

Specific examples of the component (d-3) include dibutadiene rubbers such as polybutadiene, styrene / butadiene copolymer rubber, butadiene / butyl acrylate copolymer rubber, acrylonitrile / butadiene copolymer rubber, and hydrogen thereof. An additive etc. can be mentioned. Among these rubbery butadiene polymers, polybutadiene, styrene / butadiene copolymer rubber, butadiene / butyl acrylate copolymer rubber, acrylonitrile / butadiene copolymer rubber, and other diene rubbers are preferable, and the most preferable one is glass transition temperature- It is polybutadiene having a temperature of 80 ° C or lower. Further, in the present invention, a styrene / butadiene block copolymer rubber having a glass transition temperature in the range of −50 to −60 ° C. is not preferable because the effect of improving impact resistance is not satisfied.

The proportion of the rubber-like butadiene polymer (d-3) in the component (D) is used in the range of 1 to 95% by weight based on 100 parts by weight of the component (D). Properties, mechanical strength, rigidity, and moldability. It is preferably 10 to 95% by weight, more preferably 30 to 95% by weight, further preferably 50 to 90% by weight, and most preferably 70 to 90% by weight. When the component (C) in which the ratio of the component (c-3) is not large is used, the ratio of the component (d-3) is specifically the component (C) 100.
In the case of using the component (C) in which the ratio of the component (c-3) is 30% by weight or less based on parts by weight, the component (d-3) is particularly a component in the range of 70 to 90% by weight. It is preferable to use (D).

As the aromatic vinyl compound (d-1) used as the component (D), styrene, α-methylstyrene, paramethylstyrene, vinylxylene, p-tertiarybutylstyrene, ethylstyrene, vinylnaphthalene, etc. These may be used alone or in combination of two or more, and styrene is particularly preferable. Examples of the alkyl (meth) acrylate (d-2) used in the component (D) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and 2-ethyl (meth). ) Acrylate, 2-ethylhexyl methacrylate and the like can be mentioned, and these can be used alone or in combination of two or more, and methyl (meth) acrylate is particularly preferable.

The composition ratio of (d-1) / (d-2) in the component (D) is not particularly limited, but preferably the component (d-
(D) with respect to 100 parts by weight of the total of component (d-2) and (d).
-1) is 0.1 to 80% by weight, and (d-2) is 99.9 to.
20% by weight, more preferably (d-1) is 10
~ 75 wt%, (d-2) is 90-25 wt%,
More preferably, (d-1) is 20 to 70% by weight, (d-
2) is 80 to 30% by weight, most preferably (d-1)
Is 35 to 65% by weight, and (d-2) is 65 to 35% by weight. When the content of the component (d-1) is less than 0.1% by weight, particularly 0% by weight, it becomes difficult to maintain the impact resistance of the resin composition, which is not preferable. In addition, the component (d-2) is 2
If it is less than 0% by weight, especially 0% by weight, the compatibility with the resin composition decreases, and it becomes difficult to maintain the impact resistance of the resin composition, which is not preferable.

The component (D) is a component (d-1) and a component (d-2) as long as they do not impair the gist of the present invention.
In addition, a monomer copolymerizable with these components can be used. As such a copolymerizable monomer,
(Meth) acrylic acids such as acrylic acid and methacrylic acid, α, β-unsaturated carboxylic acids such as maleic anhydride, N
Examples include maleimide-based monomers such as phenylmaleimide, N-methylmaleimide, and N-cyclohexylmaleimide, and glycidyl group-containing monomers such as glycidyl methacrylate. These monomers may be used alone or in combination of two or more within the range not impeding the gist of the present invention.

As a specific example of the preferred component (D) in the present invention, MBS in which the component (d-1) is styrene, the component (d-2) is methyl (meth) acrylate, and the component (d-3) is polybutadiene. Resin (methyl (meth) acrylate /
Butadiene / styrene resin) and the like. Examples of the method for producing the component (D) include generally known production methods such as bulk polymerization, solution polymerization, suspension polymerization and emulsion polymerization.

In the present invention, the resin composition having excellent impact resistance, melt flowability, flame retardancy and rigidity at the same time can be obtained for the first time by using the component (C) and the component (D) together. . In particular, when the component (C) in which the ratio of the component (c-3) is not large is used, specifically, the component (C) 100
When the component (C) in which the ratio of the component (c-3) is 30% by weight or less based on parts by weight and MBS as the component (D) are used in combination, it is suitable for satisfying the gist of the present invention. Is. A specific example of such an MBS is "METABLEN C-2 manufactured by Mitsubishi Rayon Co., Ltd. of Japan.
23A "and" Metablene C-323A "," Kane Ace "manufactured by Kanegafuchi Chemical Industry Co., Ltd. of Japan.
M-511 ”and“ Kaneace B-564 ”, Kureha Chemical Industry Co., Ltd.“ Kureha BTA751 ”,“ M-51 ”manufactured by Taiwan Plastics Co., Ltd., and the like.

The component (E) used in the present invention is at least one 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 organophosphorus compound oligomer used in the present invention include those selected from the group of compounds represented by the following formula (1).

[0064]

[Chemical 16]

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 is an alkyl group having 1 to 30 carbon atoms, an alkoxy group, an alkylthio group, a halogen, an aryl group, an aryloxy group, an arylthio group, a halogenated aryl group, etc. Or a group in which these substituents are combined (for example, an arylalkoxyalkyl group or the like) or a group in which these substituents are bonded by an oxygen atom, a sulfur atom, a nitrogen atom or the like (for example, an arylsulfonylaryl group). Etc.) may be used as a substituent.

Particularly preferred aryl groups as the substituents R ^a , R ^b , R ^c and R ^d are a phenyl group, a cresyl group, a xylyl group, a propylphenyl group and a butylphenyl group. 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, which is not preferable. X in the above formula (1), which represents a group of compounds as an example of the organophosphorus compound, is an aromatic group derived from a divalent phenol, and catechol, resorcinol, hydroquinol, 4-t-butylcatechol, 2 Examples of aromatic groups derived from -t-butylhydroquinone, bisphenol A, bisphenol S sulfide, bisphenol F, bis (4-hydroxyphenyl) sulfone, bis (3,5dimethyl-4-hydroxyphenyl) sulfone and the like. However, in the present invention, in particular, the formula (2)

[0067]

[Chemical 17]

X is a diphenylol dimethyl methane group (aromatic group derived from bisphenol A) represented by
By using the oligomeric organophosphorus compound which is, the hydrolysis resistance is improved, the retention stability of the resin composition is improved, and the mold deposit (MD) that adheres to the mold surface during molding is generated. Is preferable and the mold contamination property can be 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 plurality of different organophosphorus compound oligomers have a weight average condensation degree (N) of 1 to less than 1.2. N is a gel permeation chromatography or liquid chromatography to obtain the weight fraction (A _n ) of each component having different n, and the weight average of n is N = Σ (n · A _n ) / Σ (A _n ) is calculated.

Here, a UV detector or an RI detector is usually used as a detector for obtaining A _n . However, in the calculation of N, a compound having a structure in which n in the above formula (1) is 0 is used in combination or included (that is, an organic phosphorus compound having only one phosphorus atom in one molecule is used or included). In the case), a compound in which n is 0 is excluded 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
It is more preferably 1.5 or more and 1.5 or less, and particularly preferably 1 or more and less than 1.2. The smaller N is, the better the compatibility with the resin is, the better the melt fluidity is, and the higher the flame retardancy is. In particular, the compound of N = 1 has a particularly excellent balance between flame retardancy and melt fluidity in the resin composition. When N of the compound of the formula (1) as the organic phosphorus compound is 5 or more, the viscosity of the compound becomes large, and the melt fluidity tends to be lowered particularly in a high shear rate region, and the flame retardancy is high. Sex tends to decrease.

The acid value of the organic phosphorus compound used in the present invention is preferably 0.1 mgKOH / g or less, more preferably 0.05 mgKOH / g or less, and further preferably 0.01 mgKOH / g. g or less. By using an organic phosphorus compound having a low acid value, it is possible to obtain a polycarbonate flame-retardant resin composition having more excellent resistance to moist heat.

Further, the organic phosphorus compound represented by the above general formula (1) is a compound of US Pat. No. 2,520,090, JP-B-62-25706, and JP-A-63-22763.
According to the method described in Japanese Patent Publication No. 2, etc., phosphorus oxychloride is reacted with bisphenol A and monohydric phenol in the presence of a Lewis acid catalyst such as magnesium chloride or aluminum chloride to synthesize, and thereafter, a crude organophosphorus compound The product can be obtained by washing, purifying, and drying, but in the organophosphorus compound used in the present invention, mainly catalyst-derived magnesium and aluminum contained in the organophosphorus compound, alkali for washing and purifying, and alkali When using an aqueous solution containing a metal ion such as earth, the total amount of metal components such as sodium, potassium and calcium that may be introduced is preferably 30 ppm or less, more preferably 20 ppm or less, further preferably 10 ppm or less, It is particularly preferable that the content of the polycarbonate is 5 ppm or less, which is more excellent in moist heat resistance. Desirable in order to obtain a sulfonate-based flame retardant resin composition.

Furthermore, the chlorine concentration contained in the organic phosphorus compound is preferably 20 ppm or less, more preferably 1 ppm or less.
0 ppm or less, more preferably 5 ppm or less, and particularly preferably 1 ppm or less is desirable in order to obtain a polycarbonate-based flame retardant resin composition having excellent moist heat resistance. The amount of the component (E) in the composition of the present invention is 5 to 30 parts by weight, preferably 5 to 30 parts by weight, based on 100 parts by weight of the total of the components (A), (B), (C), and (D). 7
-20 parts by weight, more preferably 9-16 parts by weight. If the amount of the component (E) is less than 5 parts by weight, the flame retardancy of the thin-walled molded product becomes insufficient, which is not preferable, while if it exceeds 30 parts by weight, the impact resistance of the resin composition becomes insufficient, which is not preferable.

The component (F) used in the present invention is talc, which is used for the purpose of improving the flame retardancy and rigidity of the PC / ABS / phosphorus flame retardant composition. Talc is generally a hydrous silicate, which is a layered silicate having a layered structure. The layer structure is electrically neutral and has no interlayer material. The chemical formula is Mg ₃ Si ₄
The MgO layer represented by O ₁₀ (OH) ₂ is sandwiched between the SiO ₂ layers, and (OH) groups are present between the _two layers.
The O layer and the SiO ₂ layer have a three-layered plate-like structure in which they are chemically strongly bonded by sharing O. The main components are MgO and SiO ₂ , but there is a slight difference in the chemical composition depending on the ore used as the raw material of talc, and a small amount of Fe ²⁺ ,
It may contain Ni, Al or the like. In the present invention, talc produced from different rough stones and having slightly different chemical components may be used alone or in combination.
In addition, talc has various powder characteristics depending on the pulverization method and classification method, and for example, powders having different average particle size, particle size distribution, whiteness, bulk specific volume, specific surface area, water content, and oil absorption amount should be used. You can Therefore, when blended in the resin composition,
Each powder property may affect the physical properties of the resin composition, and particularly in the present invention, the average particle size of talc,
Also, since the particle size distribution affects the flame retardancy of the resin composition, caution is required when selecting a talc species.

The component (F) preferably used in the present invention has an average particle size of 1 to 50 μm, and particles having a particle size of 7 μm or more account for 1 to 80% of all the particles of the component (E). A more preferable average particle diameter is 1 to 20 μm, and further preferably 1 to 10 μm. When it is less than 1 μm, the thin-wall flame retardancy is lowered, which is not preferable, and when it exceeds 50 μm, the impact resistance is lowered, which is not preferable. The proportion of particles of 7 μm or more is preferably 3 to 75%, more preferably 5 to 70%, and further preferably 10 to 60%. If it is less than 1%, the flame retardance is lowered, which is not preferable.
When it exceeds 80%, it becomes difficult to maintain the impact resistance, which is not preferable.

In the present invention, talc having a different average particle size as the component (F) and a different ratio of particles having a particle size of 7 μm or more is mixed to have an average particle size of 1 to 50 μm and a particle size of 7 μm or more. Particle is 1 to 80 of the whole component (E) particle
It can also be prepared and used in the range of%. Specifically, monodisperse talc having a relatively uniform particle size and polydisperse talc having a relatively wide particle size range are singly or mixed to have an average particle size of 1 to 50 μm and a particle size of 7 μm or more. The particles can be prepared and used in the range of 1 to 80% of the whole particles of the component (F). Therefore, the particle size distribution width of the component (F) used in the present invention is not particularly limited, and particles having an average particle size of 1 to 50 μm and a particle size of 7 μm or more are 1 to If it is 80%, it can be used.

As the component (F) in the present invention, those which have not been surface-modified may be used, and in some cases, those which have been surface-modified to improve the compatibility with the resin may be used. The methods of use may be used alone or in combination. The surface modification here means a method of adsorbing a lipophilic organic compound in advance or coating a silane coupling agent on the surface to improve the affinity with a resin. The particle size distribution measuring method of the component (F) in the present invention is a sieving method, a microscope method, a coulter counter method,
There are sedimentation method, adsorption method, permeation method, laser diffraction method, etc.
In the present invention, Shimadzu SALD-2000 is used, the average particle size and the particle size distribution are measured by a laser diffraction method, and the ratio of particles having a particle size of 7 μm or more in the entire component (F) particles Was measured. Further, the definition of the average particle diameter of the component (F) includes median diameter, mode diameter, arithmetic average diameter, weight average diameter, etc., but the average particle diameter in the present invention corresponds to the median diameter.

The whiteness of the component (F) in the present invention is JI.
It carried out by the measuring method based on S.P8123, and it measured by Toyo Seiki Seisakusho Digital Hunter ST. The whiteness of the component (F) used in the present invention is not particularly limited,
It is preferably 86% or more, more preferably 90%.
% Or more, more preferably 94% or more. The specific surface area of the component (F) in the present invention is BE determined by the vapor phase adsorption method.
It was measured by the T method and was measured using a flow soap 2300 manufactured by Shimadzu Corporation. The specific surface area of the component (F) used in the present invention is not particularly limited, but it is preferably in the range of 0.5 to 40 m ² / g, more preferably 1 to 35 m ² / g.
It is preferably in the range of.

The water content of the component (F) in the present invention is JIS
The measurement was carried out according to the measurement method according to K5101, and the measurement was performed using STAC-5100 manufactured by Shimadzu Corporation. The water content of the component (F) used in the present invention is not particularly limited, but is 0.1 to 0.1.
It is preferably in the range of 1%, more preferably 0.
It is preferably in the range of 2 to 0.9%. The oil absorption of the component (F) in the present invention was measured by a measuring method according to JIS K5101. The oil absorption of the component (F) used in the present invention is not particularly limited, but is preferably in the range of 20 to 70 ml / 100 g, more preferably 30 to 70.
ml / 100 g, more preferably 40-65 ml / 10
It is preferably 0 g.

The bulk specific volume of the component (F) in the present invention is J
It was carried out by a measuring method based on IS / K5101. The bulk specific volume of the component (F) used in the present invention is not particularly limited, but is preferably in the range of 1 to 5 ml / g, more preferably 1 to
Range of 3 ml / g, more preferably 1.5-2.5 ml
It is preferably in the range of / g. The amount of the component (F) used in the present invention is 100 parts by weight of the total of the component (A), the component (B), the component (C), and the component (D).
The total amount of component (F) is in the range of 0.1 to 20 parts by weight, preferably 1 to 17 parts by weight, more preferably 3 to.
15 parts by weight, more preferably 5 to 12 parts by weight. When the amount of the component (F) is less than 0.1 parts by weight, the flame retardancy of the composition,
It is difficult to maintain rigidity, which is not preferable. on the other hand,
When the amount of component (F) used exceeds 20 parts by weight, it becomes difficult to maintain the impact resistance of the composition, which is not preferable.

The content of the component (F) in the polycarbonate-based flame-retardant resin composition according to the present invention is measured by burning and sintering the polycarbonate-based flame-retardant resin composition at a high temperature of 400 ° C. or higher, and then measuring the residual stress. Can be quantified. Alternatively, the content of the component (F) can be determined by quantitatively measuring the element content of Mg, Si, etc. in the polycarbonate-based flame retardant resin composition by fluorescent X-ray. Further, in the present invention, clay obtained by firing hydrous silica-alumina kaolin at a high temperature in place of the talc of the component (F), bentonite containing montmorillonite as a main component, and diatomaceous earth containing silicic acid (SiO ₂ ) as a main component, etc. The use of is not preferable because it may impair the gist of the present invention.

The molded article molded with the polycarbonate resin composition according to the present invention is a thin molded article having at least one portion having a wall thickness of 1.2 mm or less. The wall thickness has two facing surfaces extending at right angles to the thickness direction of the portion, and the wall thickness is defined as a distance between the facing surfaces. When the molded product has a hollow portion, such as when gas-assisted molding or a resin composition is mixed with a foaming agent, the wall thickness in the present invention means the wall thickness including the hollow portion.

The molding method for obtaining a molded product of the polycarbonate-based flame-retardant resin composition of the present invention is not particularly limited, and examples thereof include injection molding, gas assist molding, extrusion molding, compression molding and the like. Injection molding is preferably used. Examples of molded articles using the polycarbonate-based flame-retardant resin composition of the present invention include OA equipment casings such as monitors, notebook computers, copiers and printers.
Examples include OA equipment chassis and mobile phone housings.

In the present invention, it is preferable to use a fluoropolymer for the purpose of preventing dropping of combustion products of the resin composition. Specifically, in the present invention, it is preferable to use a fluoropolymer having a fibril forming ability in the resin composition, for example, a fine powder fluoropolymer, an aqueous dispersion of the fluoropolymer, and a second resin such as AS or PMMA. It is preferable to use a fluoropolymer such as a powdery mixture of

More specifically, in the present invention, it is preferable to suitably use an aqueous dispersion of a fluoropolymer, and the aqueous dispersion of the fluoropolymer is
Polytetrafluoroethylene, tetrafluoroethylene polymer such as tetrafluoroethylene propylene copolymer, perfluoroalkane polymer other than polytetrafluoroethylene, preferably tetrafluoroethylene polymer, particularly preferably polytetrafluoroethylene, for example, " As described in "Fluorocarbon Resin Handbook" (published by Nikkan Kogyo Shimbun Co., Ltd., 1990), those produced by suspension polymerization or emulsion polymerization and further used as a form of an aqueous dispersion are shown.

That is, the aqueous dispersion of the fluoropolymer preferably used in the present invention means that the dispersion liquid of the fluoropolymer fine particles obtained by suspension polymerization or emulsion polymerization is concentrated to a concentration of 40 to 70 wt% and 1 shows a milky white aqueous dispersion stabilized by an activator. The concentration of the fluoropolymer in the aqueous dispersion of the fluoropolymer can be diluted with water as long as it is a concentration at which the dispersion state is stable.
wt% is preferable, more preferably 20 to 65 wt%,
It is particularly preferably 30 to 60 wt%. The average primary particle diameter of the fluoropolymer in the aqueous dispersion is preferably 0.01 to 0.60 μm, more preferably 0.1 to 0.40 μm, and particularly preferably 0.18.
Is about 0.30 μm.

Further, as the surfactant for stabilizing the aqueous dispersion of the fluoropolymer, nonionic surfactants such as ethoxylated alkylphenol and ethoxylated higher alcohol are preferably used, and the compounding amount thereof is usually 1 -15 wt%, preferably 2-10
wt%, and more preferably 3 to 7 wt%. further,
The aqueous dispersion of the fluoropolymer has a pH
Those whose values are usually adjusted to 9 to 10 are preferably used.

The fluoropolymer concentration was 60 wt.
%, The aqueous dispersion has a liquid specific gravity of about 1.5 and a viscosity (25 ° C.) in the range of 15 to 30 cp. As an aqueous dispersion of a fluoropolymer that can be preferably used in the present invention, “Teflon 30J” manufactured by Mitsui DuPont Fluorochemical Co., Ltd., “Polyflon D-1” and “Polyflon D-” manufactured by Daikin Industries, Ltd.
2 "," Polyflon D-2C "," Polyflon D-2C
E ”can be illustrated.

Further, in the present invention, a fluoropolymer which is a powdery mixture with a second resin such as AS or PMMA can be preferably used as the fluoropolymer.
Techniques relating to fluoropolymers made into a powdery mixture with these second resins are disclosed in JP-A-9-95583, JP-A-11-49912, and JP-A-2000-1439.
No. 66, JP 2000-297189 A, and the like. As a fluoropolymer which can be preferably used in the present invention as a powdery mixture with these second resins, "Ble manufactured by GE Specialty Chemicals Co., Ltd.
Examples include "index 449" and "Metabrene A-3000" manufactured by Mitsubishi Rayon Co., Ltd.

The amount of the fluoropolymer used in the present invention is in the range of 0.01 to 2 parts by weight based on 100 parts by weight of the total of the components (A), (B), (C) and (D). Is preferred, and more preferably 0.1
1.8 parts by weight, more preferably 0.2 to 1.5 parts by weight,
It is particularly preferably 0.3 to 1.2 parts by weight. If the blending amount of the fluoropolymer is less than 0.01 part by weight, the effect of preventing the resin composition from dripping during combustion becomes insufficient, which is not preferable, and it becomes difficult to maintain high flame retardancy, especially in a thin molded product. Therefore, it is not preferable. On the other hand, if the blending amount of the fluoropolymer exceeds 2 parts by weight, melt flowability and impact resistance tend to be lowered, which is not preferable. Further, in the polycarbonate-based flame-retardant resin composition of the present invention, for the purpose of modifying the resin composition as necessary, glass fibers, glass flakes, glass beads, calcium carbonate, inorganic fillers such as mica and carbon fibers, It is also possible to add a reinforcing material such as charcoal or other thermoplastic resin.

Further, in the polycarbonate-based flame-retardant resin composition of the present invention, a release agent, a heat stabilizer, an antioxidant, an ultraviolet absorber, an epoxy compound, if necessary, within a range not impairing the gist of the present invention, Antistatic agents and the like can be added. In the present invention, the total amount of these releasing agent, heat stabilizer, antioxidant, ultraviolet absorber, epoxy compound, antistatic agent, etc. is 0 to 5,000 relative to 100 parts by weight of the resin composition.
It is preferably in the range of ppm by weight. When it exceeds 5,000 ppm by weight, the purpose of the present invention may be impaired, which is not preferable. Ingredient (A), ingredient (B), ingredient (C) and ingredient (D), which are raw materials of the polycarbonate-based flame-retardant resin composition according to the present invention, contain a release agent, a heat stabilizer, and an antioxidant. The amount is the same as that of a good solvent / poor solvent, but the same component is separated or extracted, and proton NMR
Method, GC / MS method, LC / MS method, and other analytical methods can be combined for quantification. Further, the contents of the release agent, the heat stabilizer, and the antioxidant in the polycarbonate-based flame retardant resin composition according to the present invention can be quantified by the same method.

Next, a method for producing the polycarbonate flame-retardant resin composition of the present invention will be described. The resin composition of the present invention contains the above-mentioned components (A) to (F) and, if necessary, other components in a composition ratio described in the present specification, and melt-kneaded using a melt-kneading device such as an extruder. Can be obtained by doing. For the blending and melt-kneading of the respective constituents at this time, a generally-used device, for example, a pre-mixing device such as a tumbler or a ribbon blender, a melt-kneading device such as a single-screw extruder or a twin-screw extruder, or a kneader is used. You can Further, the raw materials can be supplied to the melt-kneading device after mixing the respective components in advance, but it is also possible to supply the respective components independently to the melt-kneading device.

An extruder, preferably a twin-screw extruder is usually used as the melt-kneading device. When the component (E) is liquid, the component (E) is extruded using a gear pump or a plunger pump. It is also possible to carry out melt-kneading by directly feeding to a machine, and this method is generally preferred as a production method. Further, when the aqueous dispersion of the fluoropolymer is used as a drip prevention agent during the combustion of the resin composition, it is also possible to mix the aqueous dispersion of the fluoropolymer with other raw materials in advance and then feed the mixture to the extruder. However, it is also possible to directly feed it to the extruder for melt-kneading.

The melt kneading is usually carried out at a cylinder set temperature of the extruder of 200 to 300 ° C., preferably 220 to 270 ° C.
And the extruder screw rotation speed is 100 to 700 rpm,
Preferably, it can be appropriately selected within the range of 200 to 500 rpm, but it is necessary to take care not to give excessive heat during melt kneading. Furthermore, it is also effective to provide an opening in the latter part of the extruder or to perform devolatilization under reduced pressure if necessary. The residence time of the raw material resin in the extruder is usually
It is appropriately selected within a range of 10 to 60 seconds, but in the production of the polycarbonate-based flame-retardant resin composition of the present invention, the shorter the residence time of the raw material resin in the extruder, the better the mechanical properties and the moist heat resistance. It is preferable because a resin composition can be obtained.

Pellets of an uncolored polycarbonate-based flame-retardant resin composition comprising the components (A) to (F) are prepared in advance by melt-kneading, and then the pellets and the colorant are mixed to obtain a uniaxial or two-component resin. In the method of obtaining a polycarbonate-based flame-retardant resin composition that is melt-kneaded and colored by an axial extruder, in order to improve the dispersibility and color uniformity of the colorant, a colorant dispersant or a colorant spreader is used. However, in the present invention, the total amount of the components including the colorant dispersant and the colorant spreader is 0 to 3 with respect to the colored polycarbonate-based flame retardant resin composition. , 00
It is preferably in the range of 0 ppm by weight. in this case,
When a twin-screw extruder is used as the melt-kneading device, the amount of the colorant dispersant or the colorant spreader used can be reduced, or the colorant can be well dispersed in the resin composition without using them. ,preferable.

The use of a twin-screw extruder is also preferable in that the coloring uniformity of the colored polycarbonate flame-retardant resin composition can be improved. When a single-screw extruder is used, it has a screw structure with an enhanced kneading and dispersing function, for example, 3 to
Preference is given to using a single-screw extruder with 6 stages of Dalmaged screw parts. Further, when a component other than the components (A) to (F), particularly a fluoropolymer, is blended, it is fed to the extruder at the same time as the components (A) to (F), and when it is not composed of the components (A) to (F). Although it may be fed when coloring the pellets of the colored polycarbonate-based flame-retardant resin composition, the components (A) to (F) are preferable.
At the same time, the method of feeding to the extruder is suitable for the present invention.

[0097]

EXAMPLES The present invention will be described in more detail with reference to Examples and Comparative Examples. In Examples or Comparative Examples, a polycarbonate-based flame retardant resin composition was produced using the following components (A), (B), (C), (D), (E), and (F).

1. Component (A) (PC1) A bisphenol A-based polycarbonate produced by a melt transesterification method from bisphenol A and diphenyl carbonate, which is octadecyl-3- (3,5-) as a hindered phenol-based antioxidant.
Those containing 300 ppm of di-t-butyl-4-hydroxyphenyl) propionate and 150 ppm of tris (2,4-di-t-butylphenyl) phosphite as a phosphite heat stabilizer. Weight average molecular weight (Mw) = 26,000 Phenolic end group ratio (ratio of phenolic end groups to the total number of end groups) = 34 mol%

(PC2) A bisphenol A type polycarbonate obtained by the phosgene method, containing 500 ppm of a paraffin type releasing agent as a releasing agent. Weight average molecular weight (Mw) = 20,500

2. Component (B) Acrylonitrile unit 3 obtained by solution polymerization method
Acrylonitrile-styrene resin having 0% by weight, 70% by weight of styrene unit, and a weight average molecular weight (Mw) of 85,000.

3. Component (C) (ABS1) obtained by a solution polymerization method, the butadiene rubber content is 12% by weight, the acrylonitrile unit is 21% by weight, the styrene unit is 67% by weight, the average particle size of the rubber is 0.65 μm, A solution polymerization acrylonitrile butadiene styrene resin having a weight average molecular weight (Mw) of the graft copolymer component of 110,000, containing no lubricant component, and octadecyl-3 as a hindered phenol antioxidant. 1- (3,5-di-t-butyl-4-hydroxyphenyl) propionate
000 ppm, and containing 500 ppm of tris (2,4-di-t-butylphenyl) phosphite as a phosphite heat stabilizer.

(ABS2) An ABS graft copolymer obtained by polymerization by emulsion polymerization, coagulation by sulfate salting out, washing and drying is used to obtain a weight average molecular weight (Mw).
Emulsification obtained by diluting and kneading with AS resin (styrene-acrylonitrile resin) of 110,000, butadiene rubber content 32 wt%, rubber average particle size 0.25 μm, acrylonitrile unit 20 wt%, styrene unit 48 wt% Polymerized acrylonitrile butadiene styrene resin, 1,100 ppm of lubricant component (rosin acid) as emulsifier residue, and hindered phenolic antioxidant (2,6-di-t-butyl-4-methylphenol) Containing 1,000 ppm.

(ABS3) The ABS graft copolymer obtained by polymerization by emulsion polymerization, coagulation by sulfate salting out, washing and drying was used to obtain a weight average molecular weight (Mw).
Emulsified by diluting and kneading with AS resin (styrene-acrylonitrile resin) of 110,000, having a butadiene rubber content of 22 wt%, rubber average particle size of 0.25 μm, acrylonitrile unit of 23 wt%, and styrene unit of 55 wt% Polymerized acrylonitrile butadiene styrene resin, 1,200 ppm of lubricant component (rosin acid) as emulsifier residue, and hindered phenolic antioxidant (2,6-di-t-butyl-4-methylphenol) Containing 1,000 ppm.

4. Component (D) (MBS1) Polymerized by an emulsion polymerization method, the content of butadiene rubber is 80 wt%, the average particle diameter of rubber is 0.22 μm, methyl (meth) acrylate unit is 2 wt%, and styrene unit is 1.
Emulsion polymerization type methyl (meth) acrylate-butadiene-styrene resin consisting of 8 wt%. (It has a glass transition temperature at −80.8 ° C.)

(MBS2) Polymerization was carried out by an emulsion polymerization method, the butadiene rubber content was 80% by weight, and the rubber average particle size was 0.1.
22 μm, methyl (meth) acrylate unit 10 wt%,
Emulsion polymerization type methyl (meth) acrylate-butadiene-styrene resin consisting of 10 wt% of styrene unit. (-8
It has a glass transition temperature at 0.8 ° C. )

5. Component (E): Organophosphorus compound oligomer (phosphate 1) An organophosphorus compound oligomer represented by the above formula (1), wherein the substituents R ^a , R ^b , R ^c and R ^d are all phenyl groups, Weight average condensation degree (N) is 1.1
4, the magnesium content is 3.5 ppm,
Chlorine content is less than 1ppm, acid value is 0.01mg
KOH / g or less.

(Phosphate 2) Resorcinol diphosphate (CR733S) manufactured by Daihachi Chemical Co., Ltd. Weight average condensation degree (N) is 1.43, magnesium content is 7.2 ppm, and chlorine content is 1 ppm. It is the following and has an acid value of 0.02 mg / KOH. (Phosphate 3) Triphenyl phosphate (TP manufactured by Daihachi Chemical Co., Ltd.)
P) Monophosphate compound

6. Ingredient (F) (talc 1) Average particle size = 3 μm 7 μm or more particle content = 14% Whiteness = 94% (talc 2) Average particle size = 5 μm 7 μm or more particle content = 23% Whiteness = 96% Bulk ratio Volume = 2.3 ml / g Specific surface area = 8.5 m ² / g Moisture = 0.2% Oil absorption = 51 ml / 100 g

(Talc 3) Average particle size = 7 μm Particle content of 7 μm or more = 54% Whiteness = 94% Bulk specific volume = 1.5 ml / g (Talc 4) Average particle size = 2.7 μm Particle content of 7 μm or more = 10% Whiteness = 96% Bulk specific volume = 2.1 ml / g Specific surface area = 34.8 m ² / g Moisture = 0.7% Oil absorption = 54 ml / 100 g

(Talc 5) Average particle size = 0.9 μm Particle content of 7 μm or more = 0% Whiteness = 96% Bulk specific volume = 3.0 ml / g Specific surface area = 36.6 m ² / g Water content = 1.0 % Oil absorption = 62 ml / 100 g (talc 6) Average particle size = 51.0 μm Particle content of 7 μm or more = 98.5% Whiteness = 85% Bulk specific volume = 5.0 ml / g Specific surface area = 0.7 m ² / g Moisture = 0.4% Oil absorption = 21 ml / 100g

7. Other components (MBA) methyl (meth) acrylate-butyl acrylate copolymer. Manufactured by Kanegafuchi Chemical Industry Co., Ltd. of Japan (Product name:
Kane Ace FM-21) (MB) Emulsion polymerization type methyl (meth) acrylate polymerized by emulsion polymerization method and having a butadiene rubber content of 80 wt%, a rubber average particle size of 0.22 μm, and a methyl (meth) acrylate unit of 20 wt%. -Butadiene resin. (-8
It has a glass transition temperature at 0.4 ° C. )

(SB) Polymerized by emulsion polymerization, the content of butadiene rubber is 80 wt%, and the average particle size of rubber is 0.22.
Emulsion polymerization type styrene-butadiene resin consisting of μm and styrene unit of 20 wt%. (It has a glass transition temperature at −80.4 ° C.) (MSBS) A copolymer having a styrene / butadiene block copolymer rubber content of 80 wt%, a styrene unit of 10 wt%, and a methyl (meth) acrylate unit of 10 wt%.
(It has a glass transition temperature at −58.3 ° C.)

(Clay) Made by English China Clay (trade name:
POLESTAR 450) (diatomaceous earth) made by Celite Corporation (trade name: Su
per Fine Super Floss)

(PTFE1) Mitsui DuPont Fluorochemical Co., Ltd. Polytetrafluoroethylene aqueous PTFE dispersion (trade name Teflon 30J) Solid content = 60 wt% (PTFE2) GE Specialty Chemicals Co., Ltd. Polytetra 50/50 (w / w) powdery mixture of fluoroethylene and acrylonitrile-styrene copolymer (trade name B
index 449)

[0115]

Examples 1 to 6 and Comparative Examples 1 to 24 Component (A),
(B), (C), (D), (E), (F), and other components were melt-kneaded using a twin-screw extruder in the amounts (units are parts by weight) shown in Tables 1 to 3. A polycarbonate-based flame-retardant resin composition was obtained. The melt-kneading device is a twin-screw extruder (ZSK-2
5, L / D = 37, manufactured by Werner & Pfleiderer), using a cylinder set temperature of 250 ° C. and a screw rotation speed of 2
Melt kneading was performed under the conditions of 50 rpm, a kneading resin discharge rate of 20 kg / Hr, and a raw material resin residence time in the extruder of 30 to 40 seconds. During the melt kneading, the temperature of the molten resin measured by thermocouple in the extruder die part was 255 to 265 ° C.

Feeding the raw materials into the twin-screw extruder was carried out by pre-blending components (A), (B), (C), (D), (F) and other components with a weight feeder. The organophosphorus compound oligomer (E) was added and preliminarily heated to 80 ° C. in advance, and the organophosphorus compound oligomer (E) was compounded by press-fitting through an injection nozzle from the middle of the extruder by a gear pump. Further, vacuum devolatization was performed in the latter part of the extruder. The obtained pellets were dried and molded with an injection molding machine (Autoshot 50D, manufactured by FANUC), and the following tests were carried out.

(1) Flame retardance The obtained pellets were dried and the cylinder temperature was 260 ° C.
Molded with an injection molding machine set at a mold temperature of 60 ° C, strip-shaped molded body for combustion test (thickness 1.2 mm, 2.0 mm)
And perform UL94 standard 20MM vertical combustion test
It was classified into -0, V-1 or V-2. (Degree of flame retardancy: V-0>V-1>V-2> NC) ◯: V-0 Δ: V-1 ×: V-2, or NC (NC means Non-Classification)

(2) Rigidity The obtained pellets are dried and the cylinder temperature is 240 ° C.
A 1/8 inch thick strip was molded with an injection molding machine set at a mold temperature of 60 ° C., and the flexural modulus was measured according to ASTM D790. The measurement temperature is 23 ° C. (Unit: kg
f / cm ² ) ○: 32,000 or more △: 30,000 or more and less than 32,000 ×: less than 30,000

(3) Melt fluidity The obtained pellets were dried and the cylinder temperature was 260 ° C.
Using an injection molding machine with the mold temperature set to 60 ° C, increase the injection pressure in increments of 10 kgf / cm ² when completely filling the strip-shaped molded product (thickness 1.2 mm) for combustion test. , 10kgf / c from fully filled injection pressure
m ² minus the value of the short shot point (SS
P) and used as a measure of melt fluidity. Melt fluidity is S
The lower the SP, the better. (Unit: kgf / cm ² ) ○: Less than 2,000 Δ: 2,000 or more and less than 2,500 ×: 2,500 or more

(4) Impact resistance The obtained pellets were dried and the cylinder temperature was 260 ° C.
1m gate diameter with injection molding machine with mold temperature set to 60 ℃
m, thickness 2 mm, length 100 mm, width 100 mm
Was molded, and a falling weight impact test was performed using the flat plate to measure the absorbed energy. The measured value was an average value of 5 sheets without distinguishing between ductile fracture and brittle fracture. Drop weight impact test is GRAPHIC IMP made by TOYOSEIKI
ACT TESTER B was used, and the drop height was 1 m, the load was 6.5 kg, and the weight diameter was 1 inch. The measurement temperature is 23 ° C. (Unit: J) ○: 35 or more △: 10 or more and less than 35 ×: less than 10

(5) Mold Contamination Injection molding machine (NIIGATA CN75, manufactured by Niigata Steel Co., Ltd.) with a cylinder temperature of 260 ° C. and a mold temperature of 40 ° C.
With an injection pressure of 905 kgf / cm ² and an injection time of 3
Seconds, cooling time 1.2 seconds, mold opening / closing time 2.1 seconds, dwell time 2 seconds, molding cycle 8.3 seconds, test piece weight 4 g
The continuous molding of 100, 500, 1,000,
And, the surface condition of the mold after 2,000 shots was visually observed. ◯: MD generation is not seen in 2,000 shots. Δ: Generation of MD is seen in 101 to 2,000 shots. X: MD generation is seen after 100 shots or less. Here, MD includes both solid and liquid deposits attached to the mold surface.

(6) Heat resistance The obtained pellets are dried and the cylinder temperature is 240 ° C.
Then, a 1/8 inch thick strip was molded with an injection molding machine set at a mold temperature of 60 ° C., and the heat distortion temperature was measured according to ASTM D648. (Unit: ° C.) ○: 85 or more Δ: 80 or more and less than 85 ×: less than 80 The results are shown in Tables 1 to 4.

[0123]

[Table 1]

[0124]

[Table 2]

[0125]

[Table 3]

[0126]

[Table 4]

Examples 1 to 6 are the results of the composition of the present invention, and it is understood that they are excellent in thin-wall flame retardancy, rigidity, melt flowability, impact resistance, mold stain resistance, and heat resistance. Comparative Example 1
No. 4 is a case where a graft copolymer outside the scope of the present invention was blended, but it is understood that the impact resistance is poor. Comparative Examples 5 to 7 are cases in which the graft copolymer of the component (D) was not included, but it can be seen that the impact resistance is inferior.

Comparative Examples 8 to 11 are cases in which the graft copolymer of the component (C) was not included, but none of them satisfy simultaneously impact resistance, flame retardancy, rigidity, melt flowability and heat resistance. I understand. Comparative Examples 12-18 are results outside the scope of the present invention. It can be seen that none of them satisfies the requirements of thin flame retardancy, rigidity, melt flowability, impact resistance, mold contamination, and heat resistance at the same time.

Comparative Examples 19 to 21 show the results when clay, bentonite and diatomaceous earth were used instead of talc.
It can be seen that none of them simultaneously satisfies flame retardancy, rigidity, impact resistance, mold contamination and heat resistance. Comparative Example 22 shows the results when a monophosphate compound was used as the component (E). It can be seen that not only mold contamination but also heat resistance is inferior. It can be seen that the talc species blended in Comparative Examples 23 and 24 cannot obtain sufficient flame retardancy and impact resistance.

[0130]

EFFECTS OF THE INVENTION The polycarbonate flame-retardant resin composition of the present invention has flame retardancy, rigidity, melt flowability, impact resistance, mold stain resistance, and heat resistance in an extremely thin molded body of 1.2 mm or less. Since it is an excellent polycarbonate-based flame-retardant resin composition,
It is extremely useful as a housing material for computer monitors, notebook computers, printers, word processors, copiers, etc.

Front page continuation (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08L 25:12 C08L 51:04 51:04) F-term (reference) 4F071 AA10X AA22 AA22X AA33X AA34X AA50 AA77 AB26 AC15 AD06 AF47 AH12 4J002 BC062 BN143 BN153 BN154 BN164 CG031 DJ007 DJ047 EW046 EW056 FA017 FD136 FD137 GT00

Claims (5)

[Claims] 1. Aromatic polycarbonate resin (A) 50
-95 parts by weight, a copolymer (B) containing an aromatic vinyl monomer unit (b-1) and a vinyl cyanide monomer unit (b-2) 49 to 0 parts by weight, an aromatic vinyl compound ( c-
49 to 1 part by weight of a cyanide-containing graft copolymer (C) obtained by copolymerizing 1) with a vinyl cyanide compound (c-2) in the presence of a rubbery polymer (c-3), aromatic A (meth) acrylate-containing graft copolymer ((a) obtained by copolymerizing a vinyl compound (d-1) and an alkyl (meth) acrylate (d-2) in the presence of a rubber-like butadiene polymer (d-3). D) 49 to 0.1 parts by weight, and the following components (A), (B), (C), and (D)
Polycarbonate flame-retardant resin composition containing 5 to 30 parts by weight of at least one organic phosphorus compound oligomer (E) and 0.1 to 20 parts by weight of talc (F) per 100 parts by weight of total. 2. Talc (F) has an average particle size of 1 to 50 μm.
And 1-80% of the total talc particles have a particle size of 7μ.
The polycarbonate-based flame-retardant resin composition according to claim 1, which is particles having a size of m or more. 3. At least one organophosphorus compound oligomer (E) is represented by the following formula (1): The polycarbonate-based flame retardant resin composition according to claim 1 or 2, which is selected from the group of compounds represented by: 4. At least one organic phosphorus compound oligomer (E) is represented by the following formula (2): The polycarbonate-based flame retardant resin composition according to claim 1 or 2, which is selected from the group of compounds represented by: 5. A molded product molded from the polycarbonate-based resin composition according to any one of claims 1, 2, 3, and 4, which has at least one portion having a wall thickness of 1.2 mm or less. .