JP2020111668A - Flame-retardant polycarbonate resin composition and molded article - Google Patents

Abstract

To provide a flame-retardant polycarbonate resin composition excellent in heat resistance and thermal discoloration resistance.SOLUTION: The flame-retardant polycarbonate resin composition contains, based on 100 pts.mass of an aromatic polycarbonate resin (A), 3-20 pts.mass of a condensed phosphate ester (B) of a specific structural formula, 1-10 pts.mass of a core-shell type graft copolymer (C), and 0.005-1 pt.mass of a fluorinated polyolefin (D).SELECTED DRAWING: None

Description

The present invention relates to a flame-retardant polycarbonate resin composition and a molded article, and more particularly to a flame-retardant polycarbonate resin composition excellent in heat resistance and heat discoloration resistance and a molded article thereof.

Polycarbonate resin is a resin having excellent heat resistance, mechanical properties, and electrical properties, and is widely used as a material for manufacturing parts such as automobile materials, electric/electronic device materials, housing materials, and other industrial fields. There is. In particular, the flame-retarded polycarbonate resin composition is suitable as a member for information/mobile devices such as computers, notebook computers, tablet terminals, smartphones, mobile phones, and OA/information devices such as printers and copying machines. It is used.
In recent years, the thickness of the product tends to be thinner for the purpose of weight reduction. Therefore, there is a demand for a flame-retardant polycarbonate resin composition having excellent flame retardancy, impact resistance, heat resistance, moist heat resistance, and melt stability.

As a means for imparting flame retardancy to a polycarbonate resin, a halogen-based flame retardant has conventionally been blended with the polycarbonate resin. However, a polycarbonate resin composition containing a halogen-based flame retardant containing chlorine or bromine may cause a decrease in thermal stability or may cause corrosion of a molding machine screw or a molding die during molding. there were.

As a method of imparting flame retardancy to a thermoplastic resin without using a halogen-based compound, there is a method of using a phosphoric acid-based flame retardant. For example, Patent Document 1 discloses divalent compounds represented by phosphorus oxychloride and HOArOH. Of polyphenols obtained by the reaction with the phenols and monovalent phenols represented by ArOH have been proposed.
However, in the case of adding a phosphate ester to make it flame-retardant, it is necessary to add a relatively large amount of the phosphate ester. However, if the amount of the phosphate ester is increased, the impact resistance and the heat distortion temperature (DTUL) are increased. The typical heat resistance, and further the moist heat resistance, tend to be significantly reduced.

JP-A-59-202240

The present invention was devised in view of such problems, while having excellent flame retardancy, impact resistance, heat resistance, flame retardant polycarbonate resin composition excellent in moist heat resistance, etc., and this composition The object is to provide a molded product using the product.

MEANS TO SOLVE THE PROBLEM As a result of earnestly studying, in order to solve the said subject, as a result, the condensed phosphoric acid ester which has a specific structural formula, a core-shell type graft copolymer, and a fluorinated polyolefin are each combined with a specific amount. It was found that a flame-retardant polycarbonate resin composition having a high degree of flame retardancy, heat resistance and moist heat resistance can be obtained in this way, and the present invention was completed.
The present invention provides the following flame-retardant polycarbonate resin composition and molded articles.

[1] With respect to 100 parts by mass of the aromatic polycarbonate resin (A), 3 to 20 parts by mass of the condensed phosphate ester (B) represented by the following general formula (1) and the core-shell type graft copolymer (C) are added. 1-10 mass parts, 0.005-1 mass part of fluorinated polyolefin (D) are contained, The flame-retardant polycarbonate resin composition characterized by the above-mentioned.
(In the formula, R represents an alkyl group having 1 to 4 carbon atoms, l represents an integer of 3 to 11, m represents an integer of 0 to 22, and n represents a number of 1 to 10.)
[2] The flame-retardant polycarbonate resin composition according to the above [1], wherein the condensed phosphoric acid ester (B) is a phosphoric acid ester represented by the following general formula (2).
(In formula, n shows the number of 1-10.)
[3] The flame-retardant polycarbonate resin composition according to the above [1] or [2], wherein the core-shell type graft copolymer (C) is a core-shell type graft copolymer having a butadiene rubber as a core.
[4] A molded product comprising the flame-retardant polycarbonate resin composition according to any one of [1] to [3].

The flame-retardant polycarbonate resin composition of the present invention has high heat resistance and high moist heat resistance, and exhibits a high degree of flame resistance.

Hereinafter, the present invention will be described in detail with reference to embodiments and exemplifications, but the present invention should not be construed as being limited to the embodiments and exemplifications shown below.

The flame-retardant polycarbonate resin composition of the present invention contains 3 to 20 parts by mass of the condensed phosphoric acid ester (B) represented by the following general formula (1), and 100% by mass of the aromatic polycarbonate resin (A), and a core shell. It is characterized by containing 1 to 10 parts by mass of the type graft copolymer (C) and 0.005 to 1 part by mass of the fluorinated polyolefin (D).
(In the formula, R represents an alkyl group having 1 to 4 carbon atoms, l represents an integer of 3 to 11, m represents an integer of 0 to 22, and n represents a number of 1 to 10.)

[Aromatic Polycarbonate Resin (A)]
The aromatic polycarbonate resin (A) used in the polycarbonate resin composition of the present invention is not limited in its type, and may be used in one kind alone, in two or more kinds in any combination and in any ratio, You may use together.
The aromatic polycarbonate resin is a polymer having a basic structure having a carbonic acid bond, which is represented by the general formula: -[-O-X-O-C(=O)-]-. In the formula, X is an aromatic hydrocarbon, but X having a hetero atom or a hetero bond introduced may be used to impart various characteristics.

The aromatic polycarbonate resin is not particularly limited in specific type, and examples thereof include an aromatic polycarbonate polymer obtained by reacting an aromatic dihydroxy compound and a carbonate precursor. At this time, in addition to the aromatic dihydroxy compound and the carbonate precursor, a polyhydroxy compound or the like may be reacted. A method of reacting a cyclic ether with carbon dioxide as a carbonate precursor may also be used. The aromatic polycarbonate polymer may be linear or branched. Further, the aromatic polycarbonate polymer may be a homopolymer composed of one type of repeating unit or a copolymer having two or more types of repeating units. At this time, as the copolymer, various copolymerization forms such as a random copolymer and a block copolymer can be selected. In addition, such an aromatic polycarbonate polymer is usually a thermoplastic resin.

Examples of the aromatic dihydroxy compound as a raw material monomer of the aromatic polycarbonate resin are as follows.
Dihydroxybenzenes such as 1,2-dihydroxybenzene, 1,3-dihydroxybenzene (that is, resorcinol) and 1,4-dihydroxybenzene;
Dihydroxybiphenyls such as 2,5-dihydroxybiphenyl, 2,2′-dihydroxybiphenyl, 4,4′-dihydroxybiphenyl;

2,2'-dihydroxy-1,1'-binaphthyl, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 1 Dihydroxynaphthalenes such as 7,7-dihydroxynaphthalene and 2,7-dihydroxynaphthalene;

2,2'-dihydroxydiphenyl ether, 3,3'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dimethyldiphenyl ether, 1,4-bis(3-hydroxyphenoxy) Dihydroxydiaryl ethers such as benzene and 1,3-bis(4-hydroxyphenoxy)benzene;

2,2-bis(4-hydroxyphenyl)propane (ie, bisphenol A),
1,1-bis(4-hydroxyphenyl)propane,
2,2-bis(3-methyl-4-hydroxyphenyl)propane,
2,2-bis(3-methoxy-4-hydroxyphenyl)propane,
2-(4-hydroxyphenyl)-2-(3-methoxy-4-hydroxyphenyl)propane,
1,1-bis(3-tert-butyl-4-hydroxyphenyl)propane,
2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane,
2,2-bis(3-cyclohexyl-4-hydroxyphenyl)propane,
2-(4-hydroxyphenyl)-2-(3-cyclohexyl-4-hydroxyphenyl)propane,
α,α′-bis(4-hydroxyphenyl)-1,4-diisopropylbenzene,
1,3-bis[2-(4-hydroxyphenyl)-2-propyl]benzene,
Bis(4-hydroxyphenyl)methane,
Bis(4-hydroxyphenyl)cyclohexylmethane,
Bis(4-hydroxyphenyl)phenylmethane,
Bis(4-hydroxyphenyl)(4-propenylphenyl)methane,
Bis(4-hydroxyphenyl)diphenylmethane,
Bis(4-hydroxyphenyl)naphthylmethane,
1,1-bis(4-hydroxyphenyl)ethane,
1,2-bis(4-hydroxyphenyl)ethane,
1,1-bis(4-hydroxyphenyl)-1-phenylethane,
1,1-bis(4-hydroxyphenyl)-1-naphthylethane,
1,1-bis(4-hydroxyphenyl)butane,
2,2-bis(4-hydroxyphenyl)butane,
2,2-bis(4-hydroxyphenyl)pentane,
1,1-bis(4-hydroxyphenyl)hexane,
2,2-bis(4-hydroxyphenyl)hexane,
1,1-bis(4-hydroxyphenyl)octane,
2,2-bis(4-hydroxyphenyl)octane,
4,4-bis(4-hydroxyphenyl)heptane,
2,2-bis(4-hydroxyphenyl)nonane,
1,10-bis(4-hydroxyphenyl)decane,
1,1-bis(4-hydroxyphenyl)dodecane,
Bis(hydroxyaryl)alkanes such as;

1,1-bis(4-hydroxyphenyl)cyclopentane,
1,1-bis(4-hydroxyphenyl)cyclohexane,
1,4-bis(4-hydroxyphenyl)cyclohexane,
1,1-bis(4-hydroxyphenyl)-3,3-dimethylcyclohexane,
1,1-bis(4-hydroxyphenyl)-3,4-dimethylcyclohexane,
1,1-bis(4-hydroxyphenyl)-3,5-dimethylcyclohexane,
1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane,
1,1-bis(4-hydroxy-3,5-dimethylphenyl)-3,3,5-trimethylcyclohexane,
1,1-bis(4-hydroxyphenyl)-3-propyl-5-methylcyclohexane,
1,1-bis(4-hydroxyphenyl)-3-tert-butyl-cyclohexane,
1,1-bis(4-hydroxyphenyl)-4-tert-butyl-cyclohexane,
1,1-bis(4-hydroxyphenyl)-3-phenylcyclohexane,
1,1-bis(4-hydroxyphenyl)-4-phenylcyclohexane,
Bis(hydroxyaryl)cycloalkanes such as;

Cardo structure-containing bisphenols such as 9,9-bis(4-hydroxyphenyl)fluorene and 9,9-bis(4-hydroxy-3-methylphenyl)fluorene;
Dihydroxydiarylsulfides such as 4,4'-dihydroxydiphenylsulfide and 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfide;
Dihydroxydiaryl sulfoxides such as 4,4′-dihydroxydiphenyl sulfoxide and 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfoxide;
Dihydroxy diaryl sulfones such as 4,4′-dihydroxydiphenyl sulfone and 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfone; and the like.

Among these, bis(hydroxyaryl)alkanes are preferable, bis(4-hydroxyphenyl)alkanes are more preferable, and 2,2-bis(4-hydroxyphenyl)propane (that is, from the viewpoint of impact resistance and heat resistance) , Bisphenol A) are preferred.
The aromatic dihydroxy compounds may be used alone or in any combination of two or more at any ratio.

Among the monomers as the raw material of the aromatic polycarbonate resin, examples of the carbonate precursor include carbonyl halide and carbonate ester. The carbonate precursor may be used alone or in any combination of two or more at any ratio.

Specific examples of the carbonyl halide include phosgene; haloformates such as bischloroformate of dihydroxy compound and monochloroformate of dihydroxy compound.

Specific examples of the carbonate ester include diphenyl carbonates such as diphenyl carbonate and ditolyl carbonate; dialkyl carbonates such as dimethyl carbonate and diethyl carbonate; biscarbonates of dihydroxy compounds, monocarbonates of dihydroxy compounds, and cyclic carbonates. Examples thereof include carbonates of dihydroxy compounds.

-Method for producing polycarbonate resin The method for producing the polycarbonate resin is not particularly limited, and any method can be adopted. Examples thereof include an interfacial polymerization method, a melt transesterification method, a pyridine method, a ring-opening polymerization method of a cyclic carbonate compound, and a solid-state transesterification method of a prepolymer.
Of these methods, particularly preferable ones will be specifically described below.

Interfacial Polymerization Method First, the case of producing a polycarbonate resin by the interfacial polymerization method will be described.
In the interfacial polymerization method, the pH is usually maintained at 9 or more in the presence of an organic solvent and an alkaline aqueous solution which are inert to the reaction, the dihydroxy compound and the carbonate precursor (preferably phosgene) are reacted, and then the polymerization catalyst A polycarbonate resin is obtained by performing interfacial polymerization in the presence. If necessary, a molecular weight modifier (end terminator) may be added to the reaction system, or an antioxidant may be added to prevent oxidation of the dihydroxy compound.

The dihydroxy compound and the carbonate precursor are as described above. It is preferable to use phosgene among the carbonate precursors, and the method using phosgene is particularly called the phosgene method.

Examples of the organic solvent inert to the reaction include chlorinated hydrocarbons such as dichloromethane, 1,2-dichloroethane, chloroform, monochlorobenzene and dichlorobenzene; aromatic hydrocarbons such as benzene, toluene and xylene; and the like. To be In addition, as the organic solvent, one kind may be used, and two kinds or more may be used in optional combination and ratio.

Examples of the alkaline compound contained in the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, lithium hydroxide, alkali metal compounds such as sodium hydrogen carbonate and alkaline earth metal compounds, among which sodium hydroxide and water Potassium oxide is preferred. The alkaline compounds may be used alone or in any combination of two or more at any ratio.

There is no limitation on the concentration of the alkaline compound in the alkaline aqueous solution, but it is usually used at 5 to 10% by mass in order to control the pH of the alkaline aqueous solution in the reaction to 10 to 12. Further, for example, when blowing phosgene, in order to control the pH of the aqueous phase to be 10 to 12, preferably 10 to 11, the molar ratio of the bisphenol compound to the alkali compound is usually 1:1.9 or more. Above all, it is preferably 1:2.0 or more, usually 1:3.2 or less, and particularly preferably 1:2.5 or less.

Examples of the polymerization catalyst include aliphatic tertiary amines such as trimethylamine, triethylamine, tributylamine, tripropylamine and trihexylamine; alicyclic rings such as N,N′-dimethylcyclohexylamine and N,N′-diethylcyclohexylamine. Formula tertiary amine; aromatic tertiary amine such as N,N'-dimethylaniline, N,N'-diethylaniline; quaternary ammonium salt such as trimethylbenzylammonium chloride, tetramethylammonium chloride, triethylbenzylammonium chloride, etc. Pyridine; a salt of guanidine; and the like. The polymerization catalyst may be used alone or in any combination of two or more in any ratio.

Examples of the molecular weight modifier include aromatic phenols having a monovalent phenolic hydroxyl group; aliphatic alcohols such as methanol and butanol; mercaptans; phthalic acid imides and the like. Among them, aromatic phenols are preferable. Specific examples of such an aromatic phenol include alkyl groups such as m-methylphenol, p-methylphenol, m-propylphenol, p-propylphenol, p-tert-butylphenol, and p-long-chain alkyl-substituted phenol. Substituted phenols; vinyl group-containing phenols such as isopropenylphenol; epoxy group-containing phenols; carboxyl group-containing phenols such as o-hydroxybenzoic acid and 2-methyl-6-hydroxyphenylacetic acid;
The molecular weight modifier may be used alone or in any combination of two or more at any ratio.

The amount of the molecular weight modifier used is usually 0.5 mol or more, preferably 1 mol or more, and usually 50 mol or less, preferably 30 mol or less, relative to 100 mol of the dihydroxy compound. By setting the amount of the molecular weight modifier used in this range, the thermal stability and hydrolysis resistance of the resin composition can be improved.

In the reaction, the order of mixing the reaction substrate, the reaction medium, the catalyst, the additives and the like is arbitrary as long as the desired polycarbonate resin can be obtained, and an appropriate order may be set arbitrarily. For example, when phosgene is used as the carbonate precursor, the molecular weight modifier can be mixed at any time between the reaction of the dihydroxy compound and phosgene (phosgenation) and the start of the polymerization reaction.
The reaction temperature is usually 0 to 40° C., and the reaction time is usually several minutes (for example, 10 minutes) to several hours (for example, 6 hours).

Melt Transesterification Method Next, the case of producing a polycarbonate resin by the melt transesterification method will be described.
In the melt transesterification method, for example, a transesterification reaction between a carbonic acid diester and a dihydroxy compound is performed.

The dihydroxy compound is as described above.
On the other hand, examples of carbonic acid diesters include dialkyl carbonate compounds such as dimethyl carbonate, diethyl carbonate, and di-tert-butyl carbonate; diphenyl carbonate; and substituted diphenyl carbonates such as ditolyl carbonate. Among them, diphenyl carbonate and substituted diphenyl carbonate are preferable, and diphenyl carbonate is particularly preferable. One kind of carbonic acid diester may be used, or two or more kinds thereof may be used in optional combination and ratio.

The ratio of the dihydroxy compound and the carbonic acid diester is arbitrary as long as a desired polycarbonate resin can be obtained, but it is preferable to use the carbonic acid diester in an equimolar amount or more with respect to 1 mol of the dihydroxy compound, and in particular 1.01 mol or more is used. Is more preferable. The upper limit is usually 1.30 mol or less. With such a range, the amount of terminal hydroxyl groups can be adjusted to a suitable range.

In a polycarbonate resin, the amount of terminal hydroxyl groups tends to have a great influence on thermal stability, hydrolysis stability, color tone and the like. Therefore, the amount of terminal hydroxyl groups may be adjusted as necessary by any known method. In the transesterification reaction, usually, a polycarbonate resin having an adjusted amount of terminal hydroxyl groups can be obtained by adjusting the mixing ratio of a carbonic acid diester and an aromatic dihydroxy compound; the degree of pressure reduction during the transesterification reaction. By this operation, the molecular weight of the polycarbonate resin usually obtained can also be adjusted.

When the mixing ratio of the carbonic acid diester and the dihydroxy compound is adjusted to adjust the amount of terminal hydroxyl groups, the mixing ratio is as described above.
Further, as a more positive adjustment method, a method of separately mixing a terminal stopper during the reaction can be mentioned. Examples of the terminal terminator at this time include monohydric phenols, monohydric carboxylic acids, carbonic acid diesters and the like. The end terminator may be used alone or in any combination of two or more in any ratio.

When producing a polycarbonate resin by the melt transesterification method, a transesterification catalyst is usually used. Any transesterification catalyst can be used. Among them, it is preferable to use, for example, an alkali metal compound and/or an alkaline earth metal compound. In addition, a basic compound such as a basic boron compound, a basic phosphorus compound, a basic ammonium compound, or an amine compound may be used in combination as a supplement. The transesterification catalyst may be used alone or in any combination of two or more at any ratio.

In the melt transesterification method, the reaction temperature is usually 100 to 320°C. The pressure during the reaction is usually a reduced pressure condition of 2 mmHg or less. As a specific operation, the melt polycondensation reaction may be carried out under the above conditions while removing by-products such as aromatic hydroxy compounds.

The melt polycondensation reaction can be performed by either a batch method or a continuous method. When performing in a batch system, the order of mixing the reaction substrate, the reaction medium, the catalyst, the additive and the like is arbitrary as long as the desired aromatic polycarbonate resin can be obtained, and an appropriate order may be set arbitrarily. However, among them, it is preferable to carry out the melt polycondensation reaction continuously in consideration of the stability of the polycarbonate resin.

In the melt transesterification method, a catalyst deactivator may be used if necessary. As the catalyst deactivator, any compound that neutralizes the transesterification catalyst can be used. Examples thereof include sulfur-containing acidic compounds and their derivatives. The catalyst deactivator may be used alone or in any combination of two or more at any ratio.

The amount of the catalyst deactivator used is usually 0.5 equivalents or more, preferably 1 equivalent or more, and usually 10 equivalents or less with respect to the alkali metal or alkaline earth metal contained in the transesterification catalyst. It is preferably 5 equivalents or less. Further, it is usually 1 ppm or more, and usually 100 ppm or less, and preferably 20 ppm or less with respect to the polycarbonate resin.

The molecular weight of the aromatic polycarbonate resin (A) is preferably 15,000 to 30,000 in terms of viscosity average molecular weight (Mv) calculated from the solution viscosity measured at a temperature of 25° C. using methylene chloride as a solvent. , More preferably 18,000 or more, still more preferably 19,000 or more, more preferably 27,000 or less, further preferably 26,000 or less, more preferably 25,000 or less. By setting the viscosity average molecular weight to the lower limit or more of the above range, it is possible to further improve the mechanical strength of the polycarbonate resin composition of the present invention, and by making the viscosity average molecular weight not more than the upper limit of the above range, the resin The fluidity of the composition can be suppressed and improved, and the molding processability can be improved to facilitate the molding process.
It should be noted that two or more types of polycarbonate resins having different viscosity average molecular weights may be mixed and used, and in this case, polycarbonate resins having a viscosity average molecular weight outside the preferred range may be mixed.

The viscosity average molecular weight [Mv] means the intrinsic viscosity [η] (unit dl/g) at a temperature of 25° C. using methylene chloride as a solvent and a Ubbelohde viscometer, and the Schnell's viscosity formula, that is, , Η=1.23×10 ⁻⁴ Mv ^0.83 . Further, the intrinsic viscosity [η] is a value calculated by measuring the specific viscosity [η _sp ] at each solution concentration [C] (g/dl) and using the following formula.

The concentration of terminal hydroxyl groups of the polycarbonate resin is arbitrary and may be appropriately selected and determined, but is usually 1000 ppm or less, preferably 800 ppm or less, more preferably 600 ppm or less. This makes it possible to further improve the retention heat stability and color tone of the polycarbonate resin. In addition, the lower limit is usually 10 ppm or more, preferably 30 ppm or more, and more preferably 40 ppm or more, especially for the polycarbonate resin produced by the melt transesterification method. This makes it possible to suppress the decrease in the molecular weight and further improve the mechanical properties of the resin composition.

The unit of the terminal hydroxyl group concentration is the mass of the terminal hydroxyl group expressed in ppm with respect to the mass of the polycarbonate resin. The measuring method is a colorimetric determination by the titanium tetrachloride/acetic acid method (method described in Macromol. Chem. 88 215 (1965)).

Polycarbonate resin is not limited to a polycarbonate resin alone (a polycarbonate resin alone is not limited to an embodiment containing only one kind of polycarbonate resin, and is used in the sense of including an embodiment containing plural kinds of polycarbonate resins having mutually different monomer compositions and molecular weights). .) or an alloy (mixture) of a polycarbonate resin and another thermoplastic resin may be used in combination. Further, for example, for the purpose of further improving flame retardancy and impact resistance, a polycarbonate resin is a copolymer with an oligomer or polymer having a siloxane structure; a phosphorus atom for the purpose of further improving thermal oxidation stability and flame retardancy. Copolymer with a monomer, oligomer or polymer having: a copolymer with a monomer, oligomer or polymer having a dihydroxyanthraquinone structure for the purpose of improving thermooxidative stability; polystyrene for improving optical properties A copolymer mainly composed of a polycarbonate resin, such as a copolymer with an oligomer or polymer having an olefinic structure; a copolymer with a polyester resin oligomer or polymer for the purpose of improving chemical resistance; Good.

The polycarbonate resin may contain a polycarbonate oligomer in order to improve the appearance and fluidity of the molded product. The viscosity average molecular weight [Mv] of this polycarbonate oligomer is usually 1,500 or more, preferably 2,000 or more, and usually 9,500 or less, preferably 9,000 or less. Further, the content of the polycarbonate ligomer is preferably 30% by mass or less of the polycarbonate resin (including the polycarbonate oligomer).

Furthermore, the polycarbonate resin may be not only a virgin raw material but also a polycarbonate resin recycled from a used product (so-called material-recycled polycarbonate resin).
However, the recycled polycarbonate resin is preferably 80% by mass or less, and more preferably 50% by mass or less, of the polycarbonate resin. Recycled polycarbonate resin is likely to have undergone deterioration such as heat deterioration and aging deterioration, so using more than this range of polycarbonate resin may reduce hue and mechanical properties. Because there is a nature.

[Condensed phosphoric acid ester (B)]
The polycarbonate resin composition of the present invention contains a condensed phosphoric acid ester (B) represented by the following general formula (1) as a flame retardant. By containing the condensed phosphoric ester (B) in combination with the core-shell type graft copolymer (C) and the fluorinated polyolefin (D), the flame retardancy of the polycarbonate resin composition can be further increased, and It can be made to have an excellent balance of flame retardancy, heat resistance, and moist heat resistance.
(In the formula, R represents an alkyl group having 1 to 4 carbon atoms, l represents an integer of 3 to 11, m represents an integer of 0 to 22, and n represents a number of 1 to 10.)

L in the general formula (1) is an integer of 3 to 11 and forms a cyclic alkyl group. Preferable examples of cyclic alkyl include cyclohexane, cyclooctane, cyclodecane, cyclododecane and the like.
R in the general formula (1) is an alkyl group having 1 to 4 carbon atoms, preferably a methyl group, an ethyl group, a propyl group or a butyl group, and particularly preferably a methyl group. m is 0 to 22, preferably 0 to 10, more preferably 0, 1, 2, 3 and particularly preferably 0, 2, 3.
N in the general formula (1) is the number of units shown in [], and is 1 to 10, preferably 1 to 5, more preferably 1 to 3, and further preferably 1 or 2.

As the condensed phosphoric acid ester (B), the phosphoric acid ester represented by the following general formula (2) is preferable among the general formula (1).
In the formula, n is a number of 1 to 10, and n is preferably 1 to 3.

As the condensed phosphoric acid ester (B), a commercially available product may be used. For example, as the one represented by the above general formula (2), a product name of “SR-3000” manufactured by Daihachi Chemical Industry Co., Ltd. Can be mentioned.

The content of the condensed phosphoric acid ester (B) is 3 to 20 parts by mass with respect to 100 parts by mass of the aromatic polycarbonate resin (A), but preferably 4 parts by mass or more, more preferably 5 parts by mass or more, and It is preferably 6 parts by mass or more, especially 7 parts by mass or more, particularly preferably 8 parts by mass or more, and preferably 19 parts by mass or less, more preferably 18 parts by mass or less, and further 17 parts by mass or less. It is preferable to have. When the content is less than 3 parts by mass, it is difficult to obtain sufficient flame retardancy, and when the content is more than 20 parts by mass, thermal stability and hydrolysis resistance are likely to decrease.

[Core-shell type graft copolymer (C)]
As the core-shell type graft copolymer (C) used in the present invention, a rubber polymer is used as a core layer and a monomer component such as an acrylic ester, a methacrylic ester or an aromatic vinyl compound is copolymerized around the core layer. It is a core-shell type graft copolymer comprising a shell layer formed by the above process.

As the core layer of the rubber polymer, at least one rubber polymer selected from a butadiene-containing rubber, a butyl acrylate-containing rubber, a 2-ethylhexyl acrylate-containing rubber, and a silicone rubber is used as a core layer. Those are preferable.
The rubber polymer component has a glass transition temperature of usually 0°C or lower, preferably -20°C or lower, and more preferably -30°C or lower.

The core-shell type graft copolymer (C) is preferably a graft copolymer obtained by graft-polymerizing a diene rubber component with a monomer component copolymerizable therewith. The method for producing such a graft copolymer may be any of production methods such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization, and the method of copolymerization may be a single-stage graft or a multi-stage graft. Good.

Specific examples of the diene rubber component include polybutadiene rubber, butadiene-acrylic composite rubber, styrene-butadiene rubber, ethylene-propylene-butadiene rubber and the like. You may use these individually or in mixture of 2 or more types.

Specific examples of the monomer component that can be graft-copolymerized with the rubber component include aromatic vinyl compounds, vinyl cyanide compounds, (meth)acrylic acid ester compounds, (meth)acrylic acid compounds, and glycidyl (meth)acrylate. Epoxy group-containing (meth)acrylic acid ester compound; Maleimide compounds such as maleimide, N-methylmaleimide, N-phenylmaleimide; α,β-unsaturated carboxylic acid compounds such as maleic acid, phthalic acid and itaconic acid, and their anhydrides (For example, maleic anhydride, etc.) and the like. These monomer components may be used alone or in combination of two or more.
Among these, aromatic vinyl compounds, vinyl cyanide compounds, (meth)acrylic acid ester compounds, and (meth)acrylic acid compounds are preferable from the viewpoint of mechanical properties and surface appearance, and more preferably (meth)acrylic acid esters. It is a compound. Specific examples of the (meth)acrylate compound include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, cyclohexyl (meth)acrylate, and octyl (meth)acrylate. be able to.
Here, “(meth)acrylic” refers to one or both of “acrylic” and “methacrylic”. The same applies to "(meth)acrylate".

The core-shell type graft copolymer (C) is preferably a butadiene-based elastomer. Above all, a core-shell type graft copolymer comprising a core layer made of a polybutadiene-containing rubber component and a shell layer formed by copolymerizing a (meth)acrylate ester around the core layer is particularly preferable. In the above core-shell type graft copolymer, one containing 40% by mass or more of a butadiene rubber component is preferable, and one containing 60% by mass or more is more preferable. Further, the (meth)acrylic acid component preferably contains 10% by mass or more.

Specific preferred examples of these core-shell type graft copolymers include methyl methacrylate-butadiene-styrene copolymer (MBS), methyl methacrylate-acrylonitrile-butadiene-styrene copolymer (MABS), methyl methacrylate-butadiene copolymer ( MB), methyl methacrylate-acrylic/butadiene rubber copolymer, methyl methacrylate-acrylic/butadiene rubber-styrene copolymer and the like. Such rubbery polymers may be used alone or in combination of two or more.

The content of the core-shell type graft copolymer (C) is in the range of 1 to 10 parts by mass, preferably 2 parts by mass or more, and more preferably 3 parts by mass with respect to 100 parts by mass of the aromatic polycarbonate resin (A). Parts or more, more preferably 4 parts by mass or more, preferably 9 parts by mass or less, more preferably 8 parts by mass or less, still more preferably 7 parts by mass or less. If it is less than 1 part by mass, the effect of improving the impact resistance, which is the object of the present invention, cannot be obtained, and if it exceeds 10 parts by mass, the heat resistance is lowered and the flame retardancy of the polycarbonate resin composition is deteriorated. ..

[Fluorinated polyolefin (D)]
The polycarbonate resin composition of the present invention contains the fluorinated polyolefin (D) in an amount of 0.005 to 1 part by mass based on 100 parts by mass of the aromatic polycarbonate resin (A). As the fluorinated polyolefin, one type may be used, or two or more types may be used in any combination at any ratio. By thus containing the fluorinated polyolefin, the melting characteristics of the resin composition can be improved, and the dropping prevention property at the time of combustion can be improved.
When the content of the fluorinated polyolefin is less than 0.005 parts by mass, the flame retardancy improving effect is insufficient, and when it exceeds 1 part by mass, the appearance of the molded product molded from the resin composition is poor and the mechanical strength is low. Occurs. The content of the fluorinated polyolefin is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, still more preferably 0.15 parts by mass or more, with respect to 100 parts by mass of the aromatic polycarbonate resin (A). It is particularly preferably 0.2 parts by mass or more, preferably 0.8 parts by mass or less, more preferably 0.6 parts by mass or less, and particularly preferably 0.5 parts by mass or less.

As the fluorinated polyolefin, a fluoroolefin resin is preferable. The fluoroolefin resin is usually a polymer or copolymer containing a fluoroethylene structure, and specific examples thereof include difluoroethylene resin, tetrafluoroethylene resin, and tetrafluoroethylene/hexafluoropropylene copolymer resin. Of these, tetrafluoroethylene resin is preferable.
Further, the fluorinated polyolefin is preferably one having a fibril forming ability, and specific examples thereof include a fluoroolefin resin having a fibril forming ability. As described above, the ability to form fibrils tends to significantly improve the drip prevention property during combustion.

As the fluoroolefin resin having a fibril forming ability, a fluoroethylene resin having a fibril forming ability is preferable, and for example, "Teflon (registered trademark) 6J" manufactured by Mitsui-Du Pont Fluorochemical Co., Ltd., "Polyflon (registered trademark) manufactured by Daikin Chemical Industries, Ltd. ) F201L", "Polyflon (registered trademark) F103", "Polyflon (registered trademark) FA500C" and the like. Further, as commercially available products of an aqueous dispersion of fluoroethylene resin, for example, “Teflon (registered trademark) 30J”, “Teflon (registered trademark) 31-JR” manufactured by Mitsui DuPont Fluorochemicals, and “Fluon (manufactured by Daikin Chemical Industry Co., Ltd. Registered trademark) D-1" and the like.
Furthermore, a fluoroethylene polymer having a multilayer structure formed by polymerizing a vinyl-based monomer can also be used, and examples of such a fluoroethylene polymer include polystyrene-fluoroethylene composite and polystyrene-acrylonitrile-fluoroethylene. Examples thereof include composites, polymethylmethacrylate-fluoroethylene composites, polybutylmethacrylate-fluoroethylene composites, and specific examples include "Metabrene (registered trademark) A-3800" manufactured by Mitsubishi Chemical Corporation, GE Specialty Chemicals. For example, "Blendex (registered trademark) 449" manufactured by the company is mentioned.

In addition, 1 type may be contained and 2 or more types may be contained in the fluorinated polyolefin (D) in arbitrary combinations and ratios.

[Phosphorus stabilizer]
The polycarbonate resin composition of the present invention preferably contains a phosphorus-based stabilizer. Any known phosphorous stabilizer can be used. Specific examples thereof include phosphorous oxo acids such as phosphoric acid, phosphonic acid, phosphorous acid, phosphinic acid, and polyphosphoric acid; metal acid pyrophosphate salts such as sodium acid pyrophosphate, potassium acid pyrophosphate, and calcium acid pyrophosphate; phosphoric acid Phosphates of Group 1 or Group 2C metals such as potassium, sodium phosphate, cesium phosphate, and zinc phosphate; organic phosphate compounds, organic phosphite compounds, organic phosphonite compounds, and the like. Particularly preferred.

Examples of the organic phosphite compound include triphenyl phosphite, tris(monononylphenyl)phosphite, tris(monononyl/dinonylphenyl)phosphite, tris(2,4-di-tert-butylphenyl)phosphite, monooctyl. Diphenyl phosphite, dioctyl monophenyl phosphite, monodecyl diphenyl phosphite, didecyl monophenyl phosphite, tridecyl phosphite, trilauryl phosphite, tristearyl phosphite, 2,2-methylenebis(4,6-di- tert-butylphenyl)octyl phosphite and the like. As such an organic phosphite compound, specifically, for example, "ADEKA STAB 1178", "ADEKA STAB 2112", "ADEKA STAB HP-10" manufactured by ADEKA, "JP-351" manufactured by Johoku Chemical Industry Co., Ltd., JP-360", "JP-3CP", "Irgafos 168" by BASF, etc. are mentioned.
In addition, 1 type may be contained and 2 or more types may be contained in the phosphorus stabilizer in arbitrary combinations and ratios.

The content of the phosphorus-based stabilizer is usually 3 parts by mass or more, preferably 0.01 parts by mass or more, and more preferably 0.03 parts by mass or more with respect to 100 parts by mass of the aromatic polycarbonate resin (A), The amount is usually 1 part by mass or less, preferably 0.7 part by mass or less, and more preferably 0.5 part by mass or less. When the content of the phosphorus-based stabilizer is less than the lower limit of the above range, the heat stabilizing effect may be insufficient, and when the content of the phosphorus-based stabilizer exceeds the upper limit of the above range, the effect is May reach a ceiling and become uneconomical.

[Phenolic stabilizer]
The polycarbonate resin composition of the present invention also preferably contains a phenolic stabilizer. Examples of phenolic stabilizers include hindered phenolic antioxidants. Specific examples thereof include pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] and octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl). ) Propionate, thiodiethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], N,N'-hexane-1,6-diylbis[3-(3,5-di- tert-butyl-4-hydroxyphenylpropionamide), 2,4-dimethyl-6-(1-methylpentadecyl)phenol, diethyl [[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl] ] Methyl]phosphate, 3,3',3",5,5',5"-hexa-tert-butyl-a,a',a"-(mesitylene-2,4,6-triyl)tri-p- Cresol, 4,6-bis(octylthiomethyl)-o-cresol, ethylenebis(oxyethylene)bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate], hexamethylenebis[3 -(3,5-Di-tert-butyl-4-hydroxyphenyl)propionate], 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5- Triazine-2,4,6(1H,3H,5H)-trione,2,6-di-tert-butyl-4-(4,6-bis(octylthio)-1,3,5-triazin-2-ylamino ) Phenol, 2-[1-(2-hydroxy-3,5-di-tert-pentylphenyl)ethyl]-4,6-di-tert-pentylphenyl acrylate, and the like.

Among them, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] and octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate are preferable. .. Specific examples of such a phenolic antioxidant include "Irganox 1010", "Irganox 1076" manufactured by BASF, "Adeka Stab AO-50", and "Adeka Stub AO-60" manufactured by ADEKA. Are listed.
In addition, 1 type may be contained and 2 or more types may be contained in the phenolic stabilizer in arbitrary combinations and ratios.

The content of the phenolic stabilizer is usually 0.001 part by mass or more, preferably 0.01 part by mass or more, and usually 1 part by mass or less, relative to 100 parts by mass of the aromatic polycarbonate resin (A). It is preferably 0.5 part by mass or less. When the content of the phenolic stabilizer is less than the lower limit value of the above range, the effect as the phenolic stabilizer may be insufficient, and the content of the phenolic stabilizer exceeds the upper limit value of the above range. In that case, the effect may peak and become less economical.

[Release agent]
The polycarbonate resin composition of the present invention also preferably contains a release agent. Examples of the release agent include aliphatic carboxylic acids, esters of aliphatic carboxylic acids and alcohols, aliphatic hydrocarbon compounds having a number average molecular weight of 200 to 15,000, and polysiloxane silicone oil.

Examples of the aliphatic carboxylic acid include saturated or unsaturated aliphatic monovalent, divalent or trivalent carboxylic acid. Here, the aliphatic carboxylic acid also includes an alicyclic carboxylic acid. Among these, preferable aliphatic carboxylic acids are monovalent or divalent carboxylic acids having 6 to 36 carbon atoms, and aliphatic saturated monovalent carboxylic acids having 6 to 36 carbon atoms are more preferable. Specific examples of such aliphatic carboxylic acids include palmitic acid, stearic acid, caproic acid, capric acid, lauric acid, arachidic acid, behenic acid, lignoceric acid, cerotic acid, melissic acid, tetrariacontanoic acid, montanic acid, adipic acid. Acid, azelaic acid and the like can be mentioned.

As the aliphatic carboxylic acid in the ester of aliphatic carboxylic acid and alcohol, for example, the same aliphatic carboxylic acid as described above can be used. On the other hand, examples of the alcohol include saturated or unsaturated monohydric or polyhydric alcohols. These alcohols may have a substituent such as a fluorine atom or an aryl group. Among these, monohydric or polyhydric saturated alcohols having 30 or less carbon atoms are preferable, and aliphatic saturated monohydric alcohols or aliphatic saturated polyhydric alcohols having 30 or less carbon atoms are more preferable. In addition, an aliphatic is used here as a term including an alicyclic compound.

Specific examples of such alcohols include octanol, decanol, dodecanol, stearyl alcohol, behenyl alcohol, ethylene glycol, diethylene glycol, glycerin, pentaerythritol, 2,2-dihydroxyperfluoropropanol, neopentylene glycol, ditrimethylolpropane, dipentaerythritol and the like. Are listed.

The above ester may contain an aliphatic carboxylic acid and/or alcohol as impurities. The above-mentioned ester may be a pure substance or a mixture of a plurality of compounds. Furthermore, as the aliphatic carboxylic acid and alcohol which are combined to form one ester, one kind may be used, or two or more kinds may be used in optional combination and ratio.

Specific examples of the ester of an aliphatic carboxylic acid and an alcohol include beeswax (mixture containing myricyl palmitate as a main component), stearyl stearate, behenyl behenate, stearyl behenate, glycerin monopalmitate, glycerin monostear. Examples thereof include rate, glycerin distearate, glycerin tristearate, pentaerythritol monopalmitate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate, pentaerythritol tetrastearate and the like.

Examples of the aliphatic hydrocarbon having a number average molecular weight of 200 to 15,000 include liquid paraffin, paraffin wax, microwax, polyethylene wax, Fischer-Tropsch wax, and α-olefin oligomer having 3 to 12 carbon atoms. Here, alicyclic hydrocarbons are also included as the aliphatic hydrocarbons. Further, these hydrocarbons may be partially oxidized.

Among these, paraffin wax, polyethylene wax or a partial oxide of polyethylene wax is preferable, and paraffin wax and polyethylene wax are more preferable.
The number average molecular weight of the above aliphatic hydrocarbon is preferably 5,000 or less.
The aliphatic hydrocarbon may be a single substance, or may be a mixture of constituent components and various molecular weights as long as the main component is within the above range.

Examples of the polysiloxane-based silicone oil include dimethyl silicone oil, methylphenyl silicone oil, diphenyl silicone oil, and fluorinated alkyl silicone.

In addition, 1 type may be contained in the mold release agent mentioned above, and 2 or more types may be contained in arbitrary combinations and ratios.

The content of the release agent is usually 0.001 part by mass or more, preferably 0.01 part by mass or more, and usually 2 parts by mass or less, with respect to 100 parts by mass of the aromatic polycarbonate resin (A). Is 1 part by mass or less. If the content of the release agent is less than the lower limit of the range, the effect of releasability may not be sufficient, and if the content of the release agent exceeds the upper limit of the range, hydrolysis resistance Deterioration, and mold contamination during injection molding may occur.

[Other ingredients]
The polycarbonate resin composition of the present invention may contain other components in addition to those described above, if necessary, as long as desired physical properties are not significantly impaired. Examples of other components include resins other than polycarbonate resins and various resin additives. In addition, 1 type may be contained in other components and 2 or more types may be contained in arbitrary combinations and ratios.

-Other resins Examples of the other resins include thermoplastic polyester resins such as polyethylene terephthalate resin, polytrimethylene terephthalate, and polybutylene terephthalate resin;
Styrene resins such as polystyrene resin, high impact polystyrene resin (HIPS) and acrylonitrile-styrene copolymer (AS resin); polyolefin resins such as polyethylene resin and polypropylene resin; polyamide resin; polyimide resin; polyetherimide resin; polyurethane resin A polyphenylene ether resin; a polyphenylene sulfide resin; a polysulfone resin; a polymethacrylate resin.

In addition, 1 type may be contained in other resin and 2 or more types may be contained in arbitrary combinations and ratios.
However, when the other resin is contained, the content thereof is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, and further 5 parts by mass or less, with respect to 100 parts by mass of the polycarbonate resin (A). It is preferably 3 parts by mass or less, and particularly preferably 1 part by mass or less.

Resin additives Examples of resin additives include ultraviolet absorbers, dyes and pigments (including carbon black), antistatic agents, antifogging agents, antiblocking agents, fluidity improvers, plasticizers, dispersants, antibacterial agents. And so on. In addition, 1 type may be contained in the resin additive and 2 or more types may be contained in arbitrary combinations and ratios.

[Method for producing polycarbonate resin composition]
The method for producing the polycarbonate resin composition of the present invention is not limited, and known methods for producing a polycarbonate resin composition can be widely adopted.
Specific examples thereof include aromatic polycarbonate resin (A), condensed phosphoric acid ester (B), core-shell type graft copolymer (C) and fluorinated polyolefin (D), and other optional additives. A method in which the components are pre-mixed using various mixers such as a tumbler and a Henschel mixer, and then melt-kneaded with a mixer such as a Banbury mixer, roll, Brabender, single-screw kneading extruder, twin-screw kneading extruder, and kneader. Are listed.

Further, for example, without premixing the respective components, or premixing only some of the components, it is supplied to an extruder using a feeder and melt-kneaded to produce the polycarbonate resin composition of the present invention. You can also
Further, for example, a resin composition obtained by mixing some of the components in advance and supplying them to an extruder and melt-kneading the mixture is a master batch, and the master batch is mixed again with the remaining components and melt-kneaded. The polycarbonate resin composition of the present invention can also be manufactured.
Further, for example, when mixing a component that is difficult to disperse, the component that is difficult to disperse is dissolved or dispersed in a solvent such as water or an organic solvent in advance, and kneaded with the solution or the dispersion liquid to disperse the component. It can also enhance sex.

As a method for producing a molded article, any molding method generally used for polycarbonate resin compositions can be adopted. Examples include injection molding method, ultra-high speed injection molding method, injection compression molding method, two-color molding method, hollow molding method such as gas assist, molding method using heat insulating mold, and rapid heating mold. Molding method, foam molding (including supercritical fluid), insert molding, IMC (in-mold coating molding) molding method, extrusion molding method, sheet molding method, thermoforming method, rotational molding method, laminated molding method, press molding method, A blow molding method and the like can be mentioned, and a molding method using a hot runner method can also be used. Of these, injection molding methods such as the injection molding method, the ultra-high speed injection molding method and the injection compression molding method are preferable.

[Molding]
Examples of molded articles include electric/electronic equipment, office automation equipment, information terminal equipment, machine parts, home appliances, vehicle parts, construction materials, various containers, leisure goods/miscellaneous goods, and lighting equipment. Among these, it is suitable for use in parts such as electric and electronic equipment, office automation equipment, information terminal equipment, home appliances, and lighting equipment. In particular, it is suitable for use as a member for a secondary battery device used indoors or outdoors, a member for a battery pack, a storage battery of an electric bicycle, a member for a housing used outdoors, and the like.

Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention should not be construed as being limited to the following examples.
In the following description, “parts” means “parts by mass” based on the mass standard unless otherwise specified.
The components used in Examples and Comparative Examples are shown in Table 1 below.

(Examples 1 to 6, Comparative Examples 1 to 3)
[Resin pellet production]
The components shown in Table 1 above were blended in the proportions (mass ratios) shown in Table 3 below, mixed for 20 minutes with a tumbler, and then twin-screw extruder (TEX30HSST) manufactured by Japan Steel Works, Ltd. equipped with one vent. ), kneading under the conditions of a screw rotation speed of 200 rpm, a discharge rate of 15 kg/hour, and a barrel temperature of 280° C., the molten resin extruded in the form of a strand is rapidly cooled in a water tank, pelletized using a pelletizer, and a polycarbonate resin. A pellet of composition was obtained.

[Q value of outflow per unit time (unit: ×10 ⁻² cm ³ /sec)]
The pellets obtained by the above method were dried at 80° C. for 5 to 7 hours by a hot air circulation dryer, and then, using an elevated flow tester, at a temperature of 280° C. and under a load of 1.6 kgf. The outflow amount Q value (unit: ×10 ⁻² cm ³ /sec) of the product per unit time was measured. The orifice used had a diameter of 1 mm and a length of 10 mm.

[Heat resistance DTUL (deflection temperature under load, unit: °C)]
After drying the pellets obtained by the above-mentioned method at 80° C. for 5 hours, using an injection molding machine (“NEX80III” manufactured by Nissei Plastic Industry Co., Ltd.), the cylinder temperature is 280° C., the mold temperature is 80° C., and the molding cycle is 45 seconds. Injection molding was carried out under the conditions of, and an ISO multipurpose test piece 4 mmt was molded.
According to ISO75-1&2, a constant bending load (1.8 MPa) is applied to the center of an ISO multipurpose test piece of 4 mm x 10 mm (flatwise direction), and the temperature is raised at a constant speed, and the strain in the center reaches 0.34 mm. The temperature (°C) was measured.

[Flame retardancy evaluation UL94 test]
The pellets obtained by the above method were dried at 80° C. for 5 hours, and then injection molded under the conditions of a cylinder temperature of 270° C. and a mold temperature of 80° C. using an SE100DU type injection molding machine manufactured by Sumitomo Heavy Industries, Ltd. Then, a test piece for UL test having a length of 125 mm, a width of 13 mm and a thickness of 1.5 mm was formed.
The flame retardancy of each polycarbonate resin composition was evaluated by subjecting the test pieces for UL test obtained above to humidity conditioning in a temperature-controlled room at a temperature of 23° C. and a humidity of 50% for 48 hours, and then using Underwriters Laboratories (US). It was conducted in accordance with UL94 test (combustion test of plastic material for parts of equipment) defined by UL).
UL94V is a method for evaluating flame retardancy from the afterflame time and drip property after indirectly burning a flame of a burner for 10 seconds on a test piece of a predetermined size held vertically, and V-0, V- In order to have flame retardancy of 1 and V-2, it is necessary to satisfy the criteria shown in Table 2 below.

Here, the afterflame time is the length of time for which the flammable combustion of the test piece is continued after the ignition source is moved away. The cotton ignition by drip is determined by whether or not the marking cotton, which is about 300 mm below the lower end of the test piece, is ignited by the drip from the test piece. Furthermore, when even one of the 5 samples did not satisfy the above criteria, it was evaluated as NR (Not Rated) as not satisfying V-2.

[Tensile fracture nominal strain (unit: %)]
After drying the pellets obtained by the above-mentioned method at 80° C. for 5 hours, using an injection molding machine (“NEX80III” manufactured by Nissei Plastic Industry Co., Ltd.), the cylinder temperature is 280° C., the mold temperature is 80° C., and the molding cycle is 45 seconds. Injection molding was carried out under the conditions of, and an ISO multipurpose test piece 4 mmt was molded.
Using an ISO multipurpose test piece (thickness: 4 mm), the nominal tensile fracture strain (unit: %) was measured according to the ISO527 standard.

[Moisture and heat resistance]
The pellets obtained by the above method are dried at 80° C. for 5 hours, and then injection molded with an injection molding machine (“NEX80III” manufactured by Nissei Plastic Co., Ltd.) under the conditions of a cylinder temperature of 280° C. and a mold temperature of 80° C. Then, an ISO multipurpose test piece 3 mmt was molded.
Using the obtained ISO multipurpose test piece (3 mmt), Charpy impact strength with notch (unit: kJ/m ² ) was measured according to ISO179.
Further, the ISO multipurpose test piece (3 mmt) was treated for 100 h under the conditions of a temperature of 80° C. and a relative humidity of 90% using a thermo-hygrostat, and the Charpy impact strength with notch (unit: kJ/m ² )) was measured. did. At this time, the Charpy impact strength retention rate before and after the moist heat treatment [Charpy impact strength after treatment/Charpy impact strength before treatment]×100] (unit: %) was obtained, and the moist heat resistance was evaluated. The larger this value, the better the resistance to moist heat.

INDUSTRIAL APPLICABILITY The flame-retardant polycarbonate resin composition of the present invention has excellent heat resistance and heat discoloration resistance, and thus can be widely and suitably used for parts such as electric and electronic devices, OA devices, information terminal devices, and home electric appliances, and has industrial applicability. Is very high.

Claims (4)

With respect to 100 parts by mass of the aromatic polycarbonate resin (A), 3 to 20 parts by mass of the condensed phosphoric acid ester (B) represented by the following general formula (1) and 1 to 10 parts of the core-shell type graft copolymer (C) are used. A flame-retardant polycarbonate resin composition comprising 0.005 to 1 part by mass of fluorinated polyolefin (D).
(In the formula, R represents an alkyl group having 1 to 4 carbon atoms, l represents an integer of 3 to 11, m represents an integer of 0 to 22, and n represents a number of 1 to 10.) The flame-retardant polycarbonate resin composition according to claim 1, wherein the condensed phosphoric acid ester (B) is a phosphoric acid ester represented by the following general formula (2).
(In formula, n shows the number of 1-10.) The flame-retardant polycarbonate resin composition according to claim 1, wherein the core-shell type graft copolymer (C) is a core-shell type graft copolymer having a butadiene rubber as a core. A molded article comprising the flame-retardant polycarbonate resin composition according to claim 1.