JP2002302597A - Flame retardant polycarbonate resin composition and molded article comprising the same - Google Patents

Abstract

(57) [Summary] (Modified) [PROBLEMS] To provide a flame-retardant polycarbonate resin composition excellent in impact resistance and a molded article excellent in surface appearance obtained by melt-molding the same. SOLUTION: Aromatic polycarbonate resin (a component)
1-80 weight% of polytetrafluoroethylene particles (component c1) having a particle diameter of 10 μm or less based on 100 weight parts of a resin composition comprising 70-99 weight% and 1-30 weight% of a crosslinked phosphazene-based flame retardant (component b) Flame retardant polycarbonate resin composition comprising 0.1 to 10 parts by weight of a mixture (component (c)) comprising a total of 100% by weight of the organic polymer (component (c2)) and 20 to 99% by weight of the organic polymer (component (c2)). Molded products.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flame-retardant polycarbonate resin composition having excellent impact resistance and thermal stability, and a molded article having an excellent surface appearance obtained by melt-molding the same.

[0002]

2. Description of the Related Art Aromatic polycarbonate resins are excellent in mechanical properties, dimensional accuracy, electrical properties, thermal properties, etc., and are widely used as engineer plastics in various fields such as electric, electronic equipment, automobile, OA, etc. Have been. Among these applications, there is a strong demand for flame retardancy of the resin material used, especially for applications such as OA equipment and home electric appliances. In order to meet these demands, study the flame retardancy of aromatic polycarbonate resin. There have been many. Heretofore, a flame-retardant polycarbonate resin composition has been proposed in which a halogen-based flame retardant, a phosphorus-based flame retardant, or the like is added in order to impart flame retardancy to an aromatic polycarbonate resin.

[0003] Halogen-based flame retardants containing halogen elements such as bromine and chlorine are flame retardants having excellent flame-retardant effects. However, they are thermally decomposed during molding to generate hydrogen halide and corrode molds. There is a problem that the thermal stability of the resin composition is lowered. There is also a problem that harmful substances are generated during combustion. Examples of the phosphorus-based flame retardant include a phosphoric ester-based compound, red phosphorus, and a phosphazene-based compound. Phosphate ester compounds are widely used because of their relatively good flame retardant effects. However, in order to obtain a high flame retardant effect, it is necessary to add a large amount of a flame retardant, and there is a problem that the heat resistance of the composition is reduced or the impact strength is reduced. Further, when flame retardation is achieved by using red phosphorus, a high flame retardant effect can be obtained by adding a small amount, but there are problems such as coloring of the composition and odor during molding.

[0004] On the other hand, phosphazene-based compounds have attracted attention recently because they do not relatively adversely affect mechanical properties, thermal properties, and moldability in comparison with phosphate-based compounds and red phosphorus. . Examples of the resin composition flame-retarded using a phosphazene-based compound include a method of blending a specific amount of a phosphazene compound with a polycarbonate resin (JP-A-51-37149), Flame-retardant resin composition containing fluorine-based resin (JP-A-7-292)
No. 233), a phosphazene compound having a specific structure in a polycarbonate resin, a polytetrafluoroethylene resin,
A flame-retardant polycarbonate resin composition containing an impact modifier and an ultraviolet absorber (JP-A-2000-351893) is disclosed.

[0005] Resin compositions containing these phosphazene compounds exhibit excellent flame retardancy and high heat resistance. Further, JP-A-2001-2908 discloses a resin composition comprising a polycarbonate resin, a copolymer obtained by graft polymerizing an acrylate monomer component to a rubbery polymer, a phosphazene compound, and polytetrafluoroethylene,
A description that the Izod impact strength is maintained even at relatively high molding temperatures compared to typical commercial products of phosphate ester oligomers, and that the decrease in Izod impact value under high temperature and high humidity resistance is small. Has been made. However, in some cases, further improvement is required even in a resin composition containing such a phosphazene compound. One is that it is difficult to obtain a good color tone as compared with conventional phosphate ester compounds and the like. Secondly, there is a demand for better impact resistance and less decrease even when exposed to high temperatures. That is, the resin composition containing the phosphazene-based compound is required to be improved with respect to hue, appearance, impact resistance, and especially these properties when the resin composition is retained in a cylinder during molding.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a flame-retardant polycarbonate resin composition having excellent impact resistance and hue, and a molded article having an excellent surface appearance obtained by melt-molding the same. is there. The present inventors have conducted intensive studies to achieve the above object, and as a result, a resin composition comprising an aromatic polycarbonate resin and a specific crosslinked phosphazene-based flame retardant has a polytetrafluoroethylene particle having a specific particle size and an organic polymer. By blending a polytetrafluoroethylene-containing mixture consisting of the following, a flame-retardant polycarbonate resin composition having excellent impact resistance and heat stability, and a molded article having an excellent surface appearance obtained by melt-molding the same. The inventors have found that the present invention can be obtained, and arrived at the present invention.

[0007]

According to the present invention, 100 parts by weight of a resin composition comprising 70 to 99% by weight of an aromatic polycarbonate resin (component (a)) and 1 to 30% by weight of a crosslinked phosphazene flame retardant (component (b)) is used. On the other hand, polytetrafluoroethylene particles having a particle diameter of 10 μm or less (component c1) 1 to 80
% By weight and 20 to 99% by weight of an organic polymer (c2 component)
A mixture (component (c)) consisting of 100% by weight of
A crosslinked phosphazene-based flame retardant comprising the following general formula (1):

[0008]

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Wherein m represents an integer of 3 to 25. Ph represents a phenyl group. A phenoxyphosphazene represented by the general formula (2):

[0010]

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Wherein X ¹ represents a group —N ＝ P (OPh) ₃ or —N ＝ P (O) OPh, and Y ¹ represents a group —P (OPh).
h) ₄ or the radical -P (O) (OPh) ₂ . n is 3 ~
Indicates an integer of 10,000. Ph is the same as above. At least one phosphazene compound selected from the group consisting of linear phenoxyphosphazenes represented by the following formulas: o-phenylene group, m-phenylene group, p-phenylene group and general formula (3)

[0012]

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Wherein A is —C (CH ₃ ) ₂ —, —SO
_{It represents 2-} , -S- or -O-. a represents 0 or 1. A compound cross-linked by at least one type of cross-linking group selected from the group consisting of bisphenylene groups represented by the formula (a): Interposed between atoms, (b)
The phosphazene compound (1) having a phenyl group content of
And / or 50 to 99.9% based on the total number of all phenyl groups in (2), and (c) a crosslinked phenoxyphosphazene compound having no free hydroxyl group in the molecule. The present invention relates to a molded article obtained by melt-molding a flame-retardant polycarbonate resin composition.

The aromatic polycarbonate resin in the component a of the present invention refers to a polycarbonate resin obtained by reacting a dihydric phenol with a carbonate precursor, that is, an aromatic polycarbonate resin. Representative examples of the dihydric phenol used here include 2,2-bis (4-hydroxyphenyl) propane (hereinafter referred to as bisphenol A), 1,1-bis (4-hydroxyphenyl) ethane, and 1,1-bis ( 4-hydroxyphenyl) cyclohexane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2- Bis (4-hydroxy-3-methylphenyl) propane, bis (4-hydroxyphenyl) sulfide, bis (4
-Hydroxyphenyl) sulfone and the like. Preferred dihydric phenols are 2,2-bis (4-hydroxyphenyl) alkanes, and bisphenol A is particularly preferred. Examples of the carbonate precursor include carbonyl halide, carbonic acid diester, bishaloformate, and the like.Specifically, phosgene, diphenyl carbonate,
And dibischloroformate of dihydric phenol. In producing the aromatic polycarbonate resin by reacting the dihydric phenol with the carbonate precursor, the dihydric phenol may be used alone or in combination of two or more. It may be a mixture of two or more aromatic polycarbonate resins.

The molecular weight of the aromatic polycarbonate resin is
Usually 10,000 to 40,000 expressed in terms of viscosity average molecular weight
And 12,000 to 30,000 is preferred. The viscosity average molecular weight (M) is determined by inserting the specific viscosity (ηsp) obtained from a solution obtained by dissolving 0.7 g of an aromatic polycarbonate resin in 100 ml of methylene chloride at 20 ° C. into the following equation. ηsp / C = [η] + 0.45 × [η] ² C [η] = 1.23 × 10 ^-4 M ^0.83 (where [η] is the intrinsic viscosity and C is the polymer concentration of 0.7)

An interfacial polymerization method for producing an aromatic polycarbonate resin will be briefly described. In the interfacial polymerization method using phosgene as a carbonate precursor, the reaction is usually performed in the presence of an acid binder and an organic solvent. As the acid binder, for example, a hydroxide of an alkali metal such as sodium hydroxide or potassium hydroxide, or an amine compound such as pyridine is used. As the organic solvent, for example, halogenated hydrocarbons such as methylene chloride and chlorobenzene are used. For promoting the reaction, a catalyst such as a tertiary amine or a quaternary ammonium salt can be used. As the molecular weight regulator, for example, an alkyl-substituted phenol such as phenol or p-tert-butylphenol and 4- (2 It is desirable to use a terminal stopper such as an aralkyl-substituted phenol such as (-phenylisopropyl) phenol. The reaction temperature is usually 0 to 40 ° C., the reaction time is preferably several minutes to 5 hours, and the pH during the reaction is preferably maintained at 10 or more. It is not necessary that all of the resulting molecular chain ends have a structure derived from the terminator.

In the transesterification reaction (melting method) using carbonic acid diester as a carbonate precursor, a predetermined ratio of a dihydric phenol component and, if necessary, a branching agent and the like are stirred with the carbonic acid diester under an inert gas atmosphere while heating. This is carried out by a method of distilling off alcohols or phenols produced. The reaction temperature varies depending on the boiling point of the alcohol or phenol to be formed, but is usually 1
It is in the range of 20 to 300 ° C. The reaction is completed under reduced pressure from the beginning while distilling off alcohol or phenols produced. Further, in order to accelerate the reaction, it is possible to use a catalyst which is currently used in a transesterification reaction such as an alkali metal compound or a nitrogen-containing basic compound. Examples of the carbonic acid diester used in the transesterification reaction include diphenyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate and the like. Of these, diphenyl carbonate is particularly preferred. Further, diphenyl carbonate, methyl (2-phenyloxycarbonyloxy) benzene carboxylate, or the like is added as a terminal terminator at the initial stage of the reaction or during the middle of the reaction. It is also preferable to add an agent. In the present invention, b
The crosslinked phosphazene compound used as a component has the general formula (1)

[0018]

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Wherein m represents an integer of 3 to 25. Ph represents a phenyl group. A phenoxyphosphazene represented by the general formula (2):

[0020]

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Wherein X ¹ represents a group —N 基 P (OPh) ₃ or —N−P (O) OPh, and Y ¹ represents a group —P (OPh).
h) ₄ or the radical -P (O) (OPh) ₂ . n is 3 ~
Indicates an integer of 10,000. Ph is the same as above. At least one phosphazene compound selected from the group consisting of linear phenoxyphosphazenes represented by the following formulas: o-phenylene group, m-phenylene group, p-phenylene group and general formula (3)

[0022]

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Wherein A is —C (CH ₃ ) ₂ —, —SO
_{It represents 2-} , -S- or -O-. a represents 0 or 1. A compound cross-linked by at least one type of cross-linking group selected from the group consisting of bisphenylene groups represented by the formula (a): Interposed between atoms, (b)
The phosphazene compound (1) having a phenyl group content of
And / or 50 to 99.9% of the total number of phenyl groups in (2), and (c) a crosslinked phenoxyphosphazene compound having no free hydroxyl group in the molecule.

The terminal group X in the general formula (2)¹You
And Y¹Varies depending on the reaction conditions, etc.
For example, when a mild reaction is performed in a non-aqueous system, X
¹Is -N = P (OPh)_Three, Y¹Is -P (OPh)_FourStructure
And the moisture or alkali metal hydroxide in the reaction system
Reaction conditions or transfer reactions occur
When the reaction is performed under such severe reaction conditions, X¹But
-N = P (OPh)_Three, Y ¹Is -P (OPh)_FourOf the structure
Besides, X¹Is -N = P (O) OPh, Y¹Is -P (O)
(OPh)_TwoIt is in a state where those having the structure of are mixed.

Further, in the present specification, "having no free hydroxyl group in the molecule" means "Analytical Chemistry Handbook (3rd revised edition, edited by The Japan Society for Analytical Chemistry, Maruzen Co., Ltd., 1981)"
When quantified according to the acetylation method using acetic anhydride and pyridine described on page 353, it means that the amount of free hydroxyl groups is below the detection limit. Here, the detection limit is
Sample (crosslinked phenoxyphosphazene compound of the present invention) 1
It is a detection limit as a hydroxyl equivalent per g, more specifically, 1 × 10 ⁻⁶ hydroxyl equivalent / g or less. In addition,
When the crosslinked phenoxyphosphazene compound of the present invention is analyzed by the above acetylation method, the amount of the remaining hydroxyl groups of the raw phenol is also added.However, since the raw phenol can be quantified by high performance liquid chromatography, the free phenol in the crosslinked phenoxyphosphazene compound can be determined. Only the hydroxyl group of can be determined. The crosslinked phenoxyphosphazene compound of the present invention has the following general formula (4)

[0026]

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[Where m is the same as above. A cyclic dichlorophosphazene represented by the general formula (5):

[0028]

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Wherein X ² represents a group —N−PCl ₃ or a group —N
= P (O) Cl, and Y ² represents a group -PCl ₄ or a group -P
(O) Cl ₂ is shown. n is the same as above. At least one dichlorophosphazene compound selected from the group consisting of linear dichlorophosphazenes represented by the general formula (6):

[0030]

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[Wherein M represents an alkali metal. An alkali metal phenolate represented by the general formula (7):

[0032]

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Wherein M is the same as above. An alkali metal diphenolate represented by the general formula (8):

[0034]

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Wherein A, a and M are as defined above. And a mixture with at least one diphenolate selected from the group consisting of alkali metal diphenolates represented by the formula (1) and then further reacting the obtained compound with the above-mentioned alkali metal phenolate (2)
It is manufactured by

In the method for producing a crosslinked phenoxyphosphazene compound of the present invention, the dichlorophosphazene compounds represented by the general formulas (4) and (5) used as raw materials are described in, for example, JP-A-57-87427. JP, JP-B-58-19604, JP-B-61-13
No. 63, Japanese Patent Publication No. 62-20124 and the like. As an example, first, in chlorobenzene, ammonium chloride and phosphorus pentachloride (or ammonium chloride, phosphorus trichloride, and chlorine) are used.
It can be produced by reacting at about 120 to 130 ° C. and dehydrochlorinating.

As the alkali metal phenolate represented by the general formula (6), conventionally known alkali metal phenolates can be widely used, for example, sodium phenolate, potassium phenolate,
Lithium phenolate and the like can be mentioned. These alkali metal phenolates can be used alone or in combination of two or more.

In the alkali metal diphenolate represented by the general formula (7), the two groups —OM (M is the same as above) may be in any of the ortho, meta and para positional relationships. Specific examples of the alkali metal diphenolate include, for example, resorcinol, hydroquinone,
Examples thereof include alkali metal salts such as catechol.
Among these, sodium salts and lithium salts are preferred. As the alkali metal diphenolate, one type can be used alone, or two or more types can be used in combination.

As the alkali metal diphenolate represented by the general formula (8), for example, 4,4′-isopropylidene diphenol (bisphenol-A), 4,4′-
Sulfonyldiphenol (bisphenol-S), 4,
Examples thereof include alkali metal salts such as 4'-thiodiphenol, 4,4'-oxydiphenol, and 4,4'-diphenol. Among these, sodium salts and lithium salts are preferred. As the alkali metal diphenolate, one type can be used alone, or two or more types can be used in combination.

In the present invention, the alkali metal diphenolate represented by the general formula (7) and the alkali metal diphenolate represented by the general formula (8) may be used alone or in combination. You may. According to the present invention, a specific reaction of reacting a mixture of an alkali metal phenolate and an alkali metal diphenolate with a dichlorophosphazene compound (first step), and then further reacting the obtained compound with an alkali metal phenolate (second step). By adopting the configuration, M of both OM groups of the alkali metal diphenolate is eliminated without leaving a free hydroxyl group in the molecule, and two oxygen atoms are bonded to a phosphorus atom in the dichlorophosphazene compound, Crosslinked (ie, increased molecular weight) phenoxyphosphazene compounds are produced.

In the process for producing the crosslinked phenoxyphosphazene compound of the present invention, the first step is to prevent all of the chlorine atoms in the dichlorophosphazene compound from being consumed by the reaction with the alkali metal phenolate and the alkali metal diphenolate, that is, dichlorophenol. It is desirable to control the amount of alkali metal phenolate and alkali metal diphenolate used so that the chlorine atom in the phosphazene compound still remains after the reaction with the alkali metal phenolate and alkali metal diphenolate. Thereby, both -O of the alkali metal diphenolate can be obtained.
An M group (M is as defined above) is attached to the phosphorus atom of the dichlorophosphazene compound. In the first step, the amount of the alkali metal phenolate and the alkali metal diphenolate to be used is generally about 0.05 to 0.9 equivalent, preferably about 0.9 equivalent, in terms of the total amount of both phenolates, based on the chlorine amount of the dichlorophosphazene compound. It may be about 1 to 0.8 equivalent.

In the second step of the production method of the present invention,
It is desirable to adjust the amount of the alkali metal phenolate used so that all the chlorine atoms and free hydroxyl groups in the compound formed in the first step are consumed by the reaction with the alkali metal phenolate. In the present invention, the amount of the alkali metal phenolate used is usually about 1 to 1.5 equivalents, preferably about 1 to 1.2 equivalents, based on the chlorine amount of the dichlorophosphazene compound. In the present invention, the ratio of the alkali metal phenolate (total amount used in the first step and the second step) to the alkali metal diphenolate (alkali metal diphenolate / alkali metal phenolate, molar ratio) is usually from 1/2000 to 1/2000.
It may be about 1/4, preferably 1/20 to 1/6.

The reactions of the first step and the second step are each usually carried out at a temperature of about room temperature to about 150 ° C., preferably about 80 to 140 ° C., usually for about 1 to 12 hours, preferably for about 3 to 7 hours. Ends with The reactions of the first step and the second step are usually carried out in an organic solvent such as aromatic hydrocarbons such as benzene, toluene and xylene, and halogenated aromatic hydrocarbons such as monochlorobenzene and dichlorobenzene. Will be The crosslinked phenoxyphosphazene compound of the present invention produced by the above reaction can be easily isolated and purified from the reaction mixture according to a usual isolation method such as washing, filtration, and drying. The content ratio of the phenyl group in the crosslinked phenoxyphosphazene compound in the present invention is based on the total number of all phenyl groups in the cyclic phenoxyphosphazene of the general formula (1) and / or the chain phenoxyphosphazene of the general formula (2). It is 50 to 99.9%, preferably 70 to 90%.

The component c of the present invention comprises polytetrafluoroethylene particles having a particle diameter of 10 μm or less (component c1) 1 to 80.
% Of the organic polymer (component (c2)) and 20 to 99% by weight of the organic polymer (c2 component). The component c improves the dispersibility of the polytetrafluoroethylene particles in the aromatic polycarbonate resin, and makes it possible to obtain an excellent surface appearance and a high level of combustibility. The polytetrafluoroethylene (hereinafter sometimes abbreviated as “PTFE”) which is the c1 component of the present invention includes P having fibril-forming ability.
TFE has an extremely high molecular weight, and has a tendency to form a fibrous state by bonding PTFE together by an external action such as shearing force. Its molecular weight is 1,000,000 to 1000 in number average molecular weight determined from standard specific gravity.
10,000, more preferably 2,000,000 to 9,000,000.

The component c1 has a particle diameter of 10 μm or less, and preferably has a particle diameter of 0.05 to 1 μm. Such PTFE particles are dispersed in water containing an emulsifier and the like, and the aqueous dispersion containing the PTFE particles is obtained by polymerizing tetrafluoroethylene monomer by emulsion polymerization using a fluorine-containing surfactant. . PTF
In the emulsion polymerization of the E particles, other components can be copolymerized as long as the properties of PTFE are not impaired. As the copolymerization component, a fluorinated olefin such as hexafluoropropylene, chlorotrifluoroethylene, fluoroalkylethylene, or perfluoroalkylvinyl ether, or a fluorinated alkyl (meth) acrylate such as perfluoroalkyl (meth) acrylate may be used. it can. The content of the copolymer component is preferably 10% by weight or less based on tetrafluoroethylene.

Commercially available PTFE aqueous dispersions include:
Fluon A manufactured by Asahi IC Fluoropolymers Co., Ltd.
Representative examples include D-1, AD-936, Fluon D-1, D-2 manufactured by Daikin Industries, Ltd., and Teflon (registered trademark) 30J manufactured by DuPont-Mitsui Fluorochemicals Co., Ltd.

On the other hand, the organic polymer particles used as the component c2 are not particularly limited, and various organic polymers can be used. Specifically, for example, polycarbonate, polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate,
Aromatic polyesters such as polyethylene naphthalate,
6-nylon, 6,6-nylon, polyamide such as MXD nylon, wholly aromatic polyester such as polyarylate, polyarylene ether such as polyphenylene ether, polyarylene sulfide such as polyphenylene sulfide, polysulfone, polyether sulfone,
Block copolymer composed of polyetherimide, polyamideimide, polypropylene, polyethylene, polystyrene, HIPS, AS resin, ABS resin, MBS resin, MABS resin, ASA resin, polymethyl (meth) acrylate, styrene and butadiene, and hydrogenated copolymer thereof Polymer, block copolymer comprising styrene and isoprene, and hydrogenated copolymer thereof, acrylonitrile-
Butadiene copolymer, random copolymer and block copolymer of ethylene-propylene, random copolymer and block copolymer of ethylene-butene, copolymer of ethylene and α-olefin, ethylene such as ethylene-butyl acrylate -Copolymer with unsaturated carboxylic acid ester, acrylate such as butyl acrylate-butadiene-butadiene copolymer, polyalkyl (meth)
A rubbery polymer such as acrylate, a composite rubber containing polyorganosiloxane and polyalkyl (meth) acrylate, and a copolymer obtained by grafting a vinyl-based monomer such as styrene, acrylonitrile, and polyalkyl methacrylate to the composite rubber. Can be mentioned. Various methods can be mentioned as a method for producing the mixture composed of the components c1 and c2.

First, an aqueous dispersion of PTFE and an aqueous dispersion or solution of organic polymer particles are mixed to form a uniform aqueous dispersion by various mixing methods, and coprecipitation is performed to obtain a coaggregated mixture. Methods can be mentioned. As a mixing method, in addition to a method using a stirring blade such as a mixer and a homogenizer, a static mixing means such as a static mixer or a porous glass body can be used. More specifically,
JP-A-258263 discloses a PT having an average particle size of 0.05 to 5 μm.
Mixing an aqueous dispersion of FE and a dispersion of vinyl polymer,
The PTFE particles larger than 30 μm are coagulated without purification, and the coagulated material is dried to obtain PTFE.
A method for obtaining the mixture is described. Also, JP-A-63-
JP-A-154744 describes a method of mixing an aqueous dispersion of PTFE in an aromatic polycarbonate resin solution, stirring and homogenizing the mixture, and then obtaining a mixture by coprecipitation. As a mixture of the c1 component and the c2 component of the present invention, a mixture obtained by these production methods can be used.

Second, a method of mixing the aqueous dispersion of PTFE with the dried organic polymer particles can be mentioned.
With respect to such a method, JP-A-4-272957 describes a mixture of an aqueous dispersion of PTFE and an ABS resin powder.

Third, there is a method in which an aqueous dispersion of PTFE and an organic polymer particle solution are uniformly mixed, and the respective media are simultaneously removed from the mixture. Specifically, a method such as supplying the mixture under a high-temperature steam atmosphere by a method such as a spray drier can be used. The c1 component and c by the production method
A mixture comprising two components is described in JP-A-06-220210 and JP-A-08-188653.

Fourth, there is a method of obtaining a mixture comprising the c1 component and the c2 component by polymerizing a monomer which forms an organic polymer in an aqueous dispersion of PTFE. As for such a method, JP-A-9-95583 specifically describes a method for obtaining a mixture by supplying styrene and acrylonitrile into an aqueous dispersion of PTFE.

Fifth, there can be mentioned a method of uniformly mixing an aqueous dispersion of PTFE and an organic polymer dispersion, further polymerizing a vinyl monomer in the mixed dispersion, and then obtaining a mixture. . The mixture is described in JP-A-11-2.
No. 9679 describes the details. That is, in a dispersion obtained by uniformly mixing an aqueous dispersion of PTFE having a particle size of 0.05 to 1.0 μm and a dispersion of organic polymer particles,
After emulsion polymerization of a monomer having an ethylenically unsaturated bond, a method of obtaining a powder by coagulation or spray drying can be used.

Among the above-mentioned various methods, the above-mentioned fourth method and fifth method can be cited in that finer dispersion of PTFE particles can be achieved. That is, PT
It is more preferable that the FE is produced by polymerizing a monomer forming an organic polymer in an aqueous dispersion state of FE. According to the fourth method and the fifth method, c
As a mixture of one component and c2 component, "BLENDEX" manufactured by GE Specialty Chemicals Co., Ltd. was used.
449 "(trade name) and METABLEN" A3000 "(trade name) are commercially available from Mitsubishi Rayon Co., Ltd. and can be easily obtained.

From this viewpoint, the c2 component of the present invention is preferably a vinyl polymer which can be subjected to emulsion polymerization and the like among the various organic polymers mentioned above. Further, from the viewpoint of compatibility with the aromatic polycarbonate resin and flame retardancy, the following organic polymers can be preferably cited as the c2 component. That is, polyalkyl (meth) acrylate,
Polystyrene, AS resin, ABS resin, ASA resin can be preferably mentioned, and more preferably AS resin,
Polyalkyl (meth) acrylate.

The composition ratio in the mixture comprising the c1 component and the c2 component is as follows:
1-80% by weight of one component, 20-99% by weight of c2 component
It is. Less than 1% by weight of c1 component or 99% of c2 component
If the amount is more than 10% by weight, it is difficult to obtain a sufficient drip-preventing performance, which is not appropriate. When the c2 component is less than 20% by weight or the c2 component exceeds 80% by weight, the P1 of the c1 component
The dispersibility of the TFE particles tends to be insufficient, and the appearance may be deteriorated.

The proportions of the above-mentioned c1 component and c2 component are preferably 1 to 60% by weight of the c1 component and 40 to 99% of the c2 component.
% By weight, more preferably 3 to 60% by weight of the c1 component,
The two components are 40 to 97% by weight, more preferably the c1 component is 5 to 55% by weight, and the c2 component is 45 to 95% by weight. In addition, various forms of the mixture comprising the c1 component and the c2 component can be used, for example, a form in which an organic polymer is surrounded around polytetrafluoroethylene particles, and a polytetrafluoroethylene is formed around an organic polymer. Examples include a form in which ethylene is surrounded, and a form in which several particles are aggregated with respect to one particle.

Next, the mixing ratio of each component in the resin composition of the present invention will be described. The mixing ratio of the component a and the component b in the resin composition is represented based on the total weight of the two.
The component a is in the range of 70 to 99% by weight, preferably 80 to 99% by weight, and the component b is in the range of 1 to 30% by weight, preferably 1 to 20% by weight based on 100% by weight of both. When the component a is less than 70% by weight or the component b exceeds 30% by weight, heat resistance (particularly, deflection temperature under load) and mechanical strength are reduced. The component a is 99
If the content is more than 1% by weight or the content of the component b is less than 1% by weight, sufficient flame retardancy cannot be obtained. The compounding ratio of the component c is
0.1 to 10 per 100 parts by weight of the total of the components a and b
It is in the range of parts by weight. If the compounding ratio of the component c is less than 0.1 part by weight, it is difficult to obtain sufficient melt dripping prevention performance,
If it exceeds 10 parts by weight, the appearance, hue and impact resistance may be deteriorated. The proportion of the component c is particularly preferably 0.1 to 5 parts by weight.

In the present invention, it is also possible to add a flame retardant other than the component b, which has a flame retardant effect, as long as the characteristics of the present invention are not impaired. At least one selected from a red phosphorus flame retardant, an organic phosphorus flame retardant, an inorganic phosphate, a hydrate of an inorganic metal compound, an organic alkali (earth) metal salt flame retardant, and a silicone flame retardant Flame retardants can also be added.

As the red phosphorus-based flame retardant, red phosphorus in which the surface of red phosphorus is microencapsulated with a thermosetting resin and / or an inorganic material can be used in addition to general red phosphorus. In addition, the use of such microencapsulated red phosphorus is preferably used in the form of a master pellet in order to improve safety and workability. Examples of the inorganic material used for such microencapsulation include magnesium hydroxide, aluminum hydroxide, titanium hydroxide, tin hydroxide, cerium hydroxide, and the like.
Phenol-formalin, urea
Formalin-based resins, melamine-formalin-based resins, and the like are included. Further, red phosphorus or the like obtained by forming a coating using a thermosetting resin on a material coated with such an inorganic material and performing a double coating treatment can also be preferably used. Also, the red phosphorus used may be an electroless plated one, and as the electroless plating film, nickel, cobalt, copper,
A metal plating film selected from iron, manganese, zinc or an alloy thereof can be used. In addition, red phosphorus coated with the inorganic material and the thermosetting resin described above can be used for the electroless plated red phosphorus. The amount of the inorganic material, thermosetting resin, and component used for microencapsulation such as electroless plating is desirably 20% by weight or less, more preferably 5 to 15% in 100% by weight of the red phosphorus-based flame retardant. % By weight.
When the content is 20% by weight or less, workability and dispersibility in a resin are excellent. The average particle size of the red phosphorus flame retardant is 1
１００100 μm, preferably 1-40 μm is used.
Commercial products of such microencapsulated red phosphorus flame retardants include Nova Excel 140 and Nova Excel F-
5 (manufactured by Rin Chemical Co., Ltd .: trade name).

As the organic phosphorus-based flame retardant, an organic phosphate ester-based flame retardant is preferable, and as the organic phosphate ester-based flame retardant, one or two of the following general formula (9) are particularly preferred.
More than one phosphate ester compound can be mentioned.

[0061]

Embedded image

(Where X in the above formula (9) is hydroquinone, resorcinol, bis (4-hydroxydiphenyl) methane, bisphenol A, dihydroxydiphenyl, dihydroxynaphthalene, bis (4-hydroxyphenyl) sulfone, bis (4- Hydroxyphenyl) ketone, and those derived from bis (4-hydroxyphenyl) sulfide, wherein j, k, l, and m are each independently 0 or 1, n is an integer of 0 to 5, Alternatively, in the case of a mixture of phosphate esters having different n numbers, the average value is from 0 to 5, and R ₁ , R ₂ , R ₃ , and R ₄ are each independently substituted or substituted with one or more halogen atoms. Not phenol, cresol, xylenol, isopropylphenol, butylphenol,
It is derived from p-cumylphenol. Preferably, X in the above formula (9) includes those derived from hydroquinone, resorcinol and bisphenol A, j, k, l and m are each 1 and n is 0 to 3 Or an average of 0 to 3 for a blend of n different phosphate esters;
R ₁ , R ₂ , R ₃ , and R ₄ are each independently derived from phenol, cresol, or xylenol with or without one or more halogen atoms.

Furthermore, particularly preferably, X is derived from resorcinol, j, k, l, m are each 1, n is 0 or 1, and R ₁ , R ₂ ,
R ₃ and R ₄ are each independently derived from phenol or xylenol. Among these organic phosphate ester flame retardants, triphenyl phosphate is used as a monophosphate compound, and resorcinol bis (dixylenyl phosphate) and bisphenol A bis (diphenyl phosphate) are used as condensed phosphate esters. It can be preferably used because it has good fluidity during molding. Examples of the inorganic phosphate include ammonium polyphosphate.

Examples of the hydrate of the inorganic metal compound include aluminum hydroxide, magnesium hydroxide, dolomite, hydrotalcite, calcium hydroxide, barium hydroxide,
Basic magnesium carbonate, zirconium hydroxide, tin oxide hydrate and the like can be used. Examples of the inorganic or organic alkali (earth) metal salt-based flame retardant include alkali metal or alkaline earth metal salts of organic acids or inorganic acids, and halogen-containing compounds. here,
Preferred inorganic alkali metal salts include sodium salts,
Potassium salts, lithium salts, cesium salts and the like can be mentioned. In addition, examples of the inorganic alkaline earth metal salt include a calcium salt and a magnesium salt. Examples of the inorganic acid used for obtaining the inorganic alkali metal salt or the inorganic alkaline earth metal salt include H ₃ AlF ₆ , H ₃ BF ₆ , and H ₃
SbF ₆ , H ₂ TiF ₆ , H ₂ SiF ₆ , H ₃ PO, H ₂ Zr
F ₆ , H ₂ WF ₆ , HBF _{4 and the} like. Preferred inorganic alkali metal salts or inorganic alkaline earth metal salts include Na ₃ AlF ₆ and Ca ₃ (AlF ₆ ) ₂ .

Preferred organic acids used for obtaining the organic alkali metal salt or the organic alkaline earth metal salt include aliphatic sulfonic acids, aromatic sulfonic acids, aromatic carboxylic acids and aliphatic carboxylic acids. Specific examples include mono- or disulfone such as methyl sulfonic acid, lauryl sulfonic acid, hexadecyl sulfonic acid, polyoxyethylene alkyl ether sulfonic acid, polyoxyethylene alkyl phenyl ether sulfonic acid, ethylene glycol, propylene glycol, and butanediol. Acid, pentaerythritol mono, di, tri or tetrasulfonic acid, stearic acid monoglyceride monosulfonic acid, 1,3-bis (2-ethylhexyl) glycerin ether monosulfonic acid, trifluoromethanesulfonic acid, perfluoroethanesulfonic acid, perfluoroethanesulfonic acid Fluoropropanesulfonic acid, perfluorobutanesulfonic acid, perfluoromethylbutanesulfonic acid, perfluorohexanesulfonic acid, perfluoroheptanesulfonic acid, perfume Fluorooctanesulfonic acid, dodecanesulfonic acid, benzenesulfonic acid, 2,5-dichlorobenzenesulfonic acid, 2,4,6-trichlorobenzenesulfonic acid, 2,4,5-trichlorobenzenesulfonic acid, diphenylsulfone-3- Sulfonic acid, diphenyl sulfone-
3,3′-disulfonic acid, naphthalene trisulfonic acid,
Examples include caprylic acid, lauric acid, benzoic acid, naphthol carboxylic acid, and 2,4,6-tribromobenzoic acid. Preferred organic alkali metal salts or organic alkaline earth metal salts include potassium perfluorobutanesulfonate, calcium perfluorobutanesulfonate, cesium perfluorobutanesulfonate, potassium diphenylsulfon-3-sulfonate, diphenylsulfone-
Potassium 3,3'-disulfonate is mentioned.

Further, as the silicone-based flame retardant, mainly a bifunctional unit [R ₂ SiO] and a trifunctional unit [RS
iO _1.5 ], and a relatively low-molecular-weight solution-type silicone resin which can contain a monofunctional unit [R ₃ SiO _0.5 ] and / or a tetrafunctional unit [SiO ₂ ]. Here, R is a hydrocarbon group having 1 to 12 carbon atoms or a hydrocarbon group having 1 to 12 carbon atoms substituted with one or more substituents, and the substituent is an epoxy group, an amino group,
Examples include a hydroxyl group and a vinyl group. It is possible to improve the compatibility with the matrix resin by changing the structure of R.

Examples of the silicone flame retardant include a solvent-free silicone flame retardant and a solvent-containing silicone flame retardant, and a solvent-free silicone flame retardant is preferred. The viscosity of the silicone-based flame retardant is preferably 300 centistokes or less. If it exceeds 300 centistokes, the flame retardancy becomes insufficient. The viscosity of the silicone flame retardant is preferably 250 centistokes or less, more preferably 200 centistokes or less. It is also possible to add a char-forming compound to the flame-retardant polycarbonate resin composition of the present invention for the purpose of further improving the flame retardancy. The char forming compounds include the following.

First, a condensate of formaldehyde with a hydroxybenzene compound, a hydroxynaphthalene compound, a hydroxyanthracene compound, or the like can be given. For example, a novolak-type phenol resin and a cresol-modified phenol resin can be mentioned. Further, compounds having a sulfonic acid group or a sulfonic acid group are easily available and can be preferably used. For example, a formaldehyde condensate of sodium naphthalene sulfonate can be mentioned.

Secondly, condensates of heavy oils or pitches with formaldehyde can be mentioned. Such heavy oils or pitches have an aromatic hydrocarbon fraction fa value of 0.40 to 0.40.
0.95, and the aromatic ring hydrogen content Ha value is preferably 20 to 80%. For example, a condensate of paraformaldehyde and a bottom oil obtained in a fluid catalytic cracking step of vacuum gas oil can be mentioned.

Thirdly, the above heavy oils or pitches themselves can be mentioned. Fourth, as thermoplastic resin types, poly (2,6-dimethyl-1,4-phenylene ether) and allylated poly (2,6-dimethyl-1,4)
-Phenylene ether), 2,6-diphenylpolyphenylene ether, polyparaphenylene, polyethersulfone, polyarylate, polyphenylene sulfide, polysulfone, polyethersulfone and the like. In addition, polyparaphenylene oligomer,
1,1′-thiobis (2-naphthol) and the like can be mentioned.

One or more selected from these can be used. Of these, particularly preferred char-forming resins include novolak-type phenol resins, poly (2,6-dimethyl-1,4-phenylene ether), and polyphenylene sulfide. In order to further improve the impact strength and the like of the flame-retardant polycarbonate resin composition obtained in the present invention, an elastic polymer can be used. Examples of the elastic polymer that can be used in the present invention include a rubber component having a glass transition temperature of 10 ° C. or less, an aromatic vinyl, a vinyl cyanide, an acrylate, a methacrylate, and a vinyl copolymerizable with these. One of the monomers selected from the compounds
Examples thereof include a graft copolymer in which one or two or more species are copolymerized.

Further, a block copolymer of such a rubber component and the above monomer may also be used. Specific examples of the block copolymer include styrene / ethylene propylene / styrene elastomer (hydrogenated styrene / isoprene / styrene elastomer) and hydrogenated styrene / butadiene / styrene.
Examples include thermoplastic elastomers such as styrene elastomers. Further, it is also possible to use various elastic polymers known as other thermoplastic elastomers, for example, polyurethane elastomers, polyester elastomers, polyetheramide elastomers and the like.

The rubber component having a glass transition temperature of 10 ° C. or lower includes butadiene rubber, butadiene-acryl composite rubber, acrylic rubber, acryl-silicon composite rubber, isobutylene-silicon composite rubber, isoprene rubber, styrene-butadiene rubber. , Chloroprene rubber, ethylene-propylene rubber, nitrile rubber, ethylene-acrylic rubber, silicone rubber, epichlorohydrin rubber,
Examples thereof include fluororubbers and those obtained by adding hydrogen to the unsaturated bond portions thereof. Among them, an elastic polymer containing a rubber component having a glass transition temperature of −10 ° C. or lower, more preferably −30 ° C. or lower is preferable, butadiene rubber, butadiene-acryl composite rubber, acrylic rubber,
Elastic polymers using acrylic-silicon composite rubber are preferred. The composite rubber refers to a rubber obtained by copolymerizing two types of rubber components or a rubber obtained by polymerizing so as to have an IPN structure entangled with each other so as not to be separated.

Examples of the aromatic vinyl include styrene, α-methylstyrene, p-methylstyrene, alkoxystyrene, and halogenated styrene. Styrene is particularly preferred. Also, as acrylates,
Examples thereof include methyl acrylate, ethyl acrylate, butyl acrylate, cyclohexyl acrylate, octyl acrylate, and the like. Examples of methacrylates include methyl methacrylate, ethyl methacrylate, butyl methacrylate, cyclohexyl methacrylate, and methacryl. Examples thereof include octyl acid, and methyl methacrylate is particularly preferable.

The elastic polymer containing a rubber component having a glass transition temperature of 10 ° C. or less may be produced by any of bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization. May be a single-stage graft or a multi-stage graft. Further, it may be a mixture with a copolymer of only a graft component produced as a by-product at the time of production. In addition to the general emulsion polymerization method,
Examples thereof include a soap-free polymerization method using an initiator such as potassium persulfate, a seed polymerization method, and a two-step swelling polymerization method. In the suspension polymerization method, a method in which an aqueous phase and a monomer phase are separately held, and both are accurately supplied to a continuous disperser, and the particle diameter is controlled by the number of revolutions of the disperser. In the method, a method may be employed in which the monomer phase is supplied to an aqueous liquid having dispersibility by passing it through a small-diameter orifice having a diameter of several to several tens of μm or a porous filter to control the particle size.

Such an elastic polymer is commercially available and can be easily obtained. For example, if the glass transition temperature is 1
As a rubber component having a temperature of 0 ° C. or less, butadiene rubber, acrylic rubber or butadiene-acrylic composite rubber is mainly used. Kaneace B series of Kanebuchi Chemical Industry Co., Ltd., Metablen C series of Mitsubishi Rayon Co., Ltd., W
Series, Kureha Chemical Industry's EXL Series, HI
A series, BTA series, KCA series and UCL Modifier resin series of Ube Saikon Co., Ltd. are listed. As a rubber component having a glass transition temperature of 10 ° C. or less, an acrylic-silicon composite rubber is mainly used as Mitsubishi Rayon ( Co., Ltd. under the trade name of Metablen S-2001 or SRK-200.

Further, the flame retardant polycarbonate resin composition of the present invention may contain a heat stabilizer. Such heat stabilizers include phosphorous acid, phosphoric acid, phosphonous acid,
Examples thereof include phosphonic acid and esters thereof, and specific examples thereof include triphenyl phosphite, tris (nonylphenyl) phosphite, and tris (2,4-di-tert).
-Butylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl Phosphite, monooctyldiphenyl phosphite, bis (2,6-di-ter
t-butyl-4-methylphenyl) pentaerythritol diphosphite, 2,2-methylenebis (4,6-di-
tert-butylphenyl) octyl phosphite, bis (nonylphenyl) pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl)
Pentaerythritol diphosphate, distearyl pentaerythritol diphosphate, tributyl phosphate, triethyl phosphate, trimethyl phosphate, triphenyl phosphate, diphenyl monoorthoxenyl phosphate, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate,
Tetrakis (4,4′-biphenylenediphosphosphinate) (2,4-di-tert-butylphenyl), dimethyl benzenephosphonate, diethyl benzenephosphonate, dipropyl benzenephosphonate and the like can be mentioned. Among them, tris nonylphenyl phosphite, trimethyl phosphate, tris (2,4-di-tert-butylphenyl) phosphite and dimethyl benzenephosphonate are preferably used. These heat stabilizers may be used alone or in combination of two or more. The compounding amount of such a heat stabilizer is preferably 0.0001 to 1 part by weight, preferably 0.00001 to 1 part by weight, based on 100 parts by weight in total of the component a and the component b of the present invention.
005 to 0.5 part by weight is more preferable, and 0.001 to 0.5 part by weight.
One part by weight is more preferred.

The flame-retardant polycarbonate resin composition of the present invention may also contain a generally known antioxidant for the purpose of preventing oxidation. Examples of such antioxidants include pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-laurylthiopropionate), glycerol-3-stearylthiopropionate, and triethylene glycol-bis [3 -(3-tert-butyl-5-
Methyl-4-hydroxyphenyl) propionate],
1,6-hexanediol-bis [3- (3,5-di-t
tert-butyl-4-hydroxyphenyl) propionate], pentaerythritol-tetrakis [3-
(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5
-Di-tert-butyl-4-hydroxyphenyl) propionate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, N, N -Hexamethylenebis (3.5
-Di-tert-butyl-4-hydroxy-hydrocinnamide), 3,5-di-tert-butyl-4-hydroxy-benzylphosphonate-diethyl ester, tris (3,5-di-tert-butyl-4-) (Hydroxybenzyl) isocyanurate tetrakis (2,4-di-tert) 4,4′-biphenylenediphosphosphinate
-Butylphenyl), 3,9-bis {1,1-dimethyl-
2- [β- (3-tert-butyl-4-hydroxy-
5-methylphenyl) propionyloxy] ethyl}-
2,4,8,10-tetraoxaspiro (5,5) undecane and the like. The compounding amount of these antioxidants is 0.0 with respect to 100 parts by weight in total of the component a and the component b of the present invention.
001 to 0.5 parts by weight is preferred.

Further, in order to further improve the releasability from the mold at the time of melt molding, a release agent is added to the flame-retardant polycarbonate resin composition of the present invention within a range not to impair the object of the present invention. It is also possible. Such release agents include:
An olefin wax, an olefin wax containing a carboxyl group and / or a carboxylic anhydride group,
Examples include silicone oil, organopolysiloxane, higher fatty acid ester of monohydric or polyhydric alcohol, paraffin wax, beeswax and the like. The compounding amount of the release agent is preferably 0.01 to 5 parts by weight based on 100 parts by weight of the total of the component a and the component b of the present invention.

As the olefin wax, use of a polyethylene wax and / or a 1-alkene polymer is particularly preferred, and a very good releasing effect can be obtained. As the polyethylene wax, those generally widely known at present can be used, and examples thereof include those obtained by polymerizing ethylene under high temperature and high pressure, those obtained by thermally decomposing polyethylene, and those obtained by separating and purifying a low molecular weight component from a polyethylene polymer. The molecular weight and the degree of branching are not particularly limited, but the molecular weight is preferably 1,000 or more in number average molecular weight. The 1-alkene polymer has 5 to 40 carbon atoms.
Can be used. The molecular weight of the 1-alkene polymer is 1,000 in number average molecular weight.
The above is preferred.

An olefin wax containing a carboxyl group and / or a carboxylic anhydride group is a compound containing a carboxyl group and / or a carboxylic anhydride group by post-treatment of an olefin wax, preferably maleic acid. And / or those modified by post-treatment with maleic anhydride. Further, when polymerizing or copolymerizing ethylene and / or 1-alkene, a compound containing a carboxyl group and / or a carboxylic anhydride group copolymerizable with such monomers, preferably maleic acid and / or maleic anhydride is used. Copolymers are also preferred, and such copolymers are preferred because they contain carboxyl groups and / or carboxylic anhydride groups in a high concentration and stably. The carboxyl group or carboxylic anhydride group may be bonded to any part of the olefin wax, and the concentration thereof is not particularly limited, but is 0.1 to 6 m / g of the olefin wax.
The range of eq / g is preferred. Commercially available olefin-based olefin waxes containing a carboxyl group and / or a carboxylic anhydride group include, for example, Diacarna-PA30 (trade name of Mitsubishi Chemical Corporation), 2203A and 1105A of high wax acid treatment type. [Trade name of Mitsui Petrochemical Co., Ltd.] and the like, and these are used alone or as a mixture of two or more.

In the case where the inorganic filler is blended in the present invention, the addition of an olefin wax containing a carboxyl group and / or a carboxylic acid anhydride group can
It can be preferably used not only for improving the releasability from the mold at the time of melt molding, but also for exhibiting the effect of suppressing the decrease in impact strength due to the addition of the inorganic filler.

The higher fatty acid esters include monohydric or polyhydric alcohols having 1 to 20 carbon atoms and 10 carbon atoms.
Preference is given to partial or full esters with up to 30 saturated fatty acids. Examples of such a partial or total ester of a monohydric or polyhydric alcohol and a saturated fatty acid include stearic acid monoglyceride, stearic acid diglyceride, stearic acid triglyceride, stearic acid monosorbitate, behenic acid monoglyceride, pentaerythritol monostearate, and pentaerythritol Tetrastearate, pentaerythritol tetraperargonate, propylene glycol monostearate,
Stearyl stearate, palmityl palmitate, butyl stearate, methyl laurate, isopropyl palmitate, biphenyl biphenate, sorbitan monostearate, 2-ethylhexyl stearate and the like, among which stearic acid monoglyceride, stearin Acid triglyceride and pentaerythritol tetrastearate are preferably used.

A light stabilizer can be added to the flame-retardant polycarbonate resin composition of the present invention as long as the object of the present invention is not impaired. Such light stabilizers include, for example, 2- (2′-hydroxy-5′-tert-octylphenyl) benzotriazole, 2- (3-tert-
Butyl-5-methyl-2-hydroxyphenyl) -5
Chlorobenzotriazole, 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2,2 '-Methylenebis (4-cumyl-6-benzotriazolephenyl), 2,2'-p-phenylenebis (1,3-benzoxazin-4-one) and the like. The amount of the light stabilizer is preferably 0.01 to 2 parts by weight based on 100 parts by weight of the total of the component a and the component b of the present invention.

The flame-retardant polycarbonate resin composition of the present invention may contain an antistatic agent as long as the object of the present invention is not impaired. As such an antistatic agent,
For example, polyetheresteramide, glycerin monostearate, ammonium dodecylbenzenesulfonate, phosphonium dodecylbenzenesulfonate, sodium sulfonate, monoglyceride maleic anhydride, diglyceride maleic anhydride, and the like can be mentioned. The compounding amount of such an antistatic agent is the same as that of component a of the present invention and b.
The amount is preferably 0.5 to 20 parts by weight based on 100 parts by weight of the total components.

A filler can be added to the flame-retardant polycarbonate resin composition of the present invention as long as the object of the present invention is not impaired. Examples of such fillers include glass fillers such as glass chopped fiber, glass milled fiber, glass roving strand, glass flake, glass beads, and glass powder, and carbon filler such as carbon fiber, carbon milled fiber, carbon roving strand, and carbon flake. Filler, talc, mica, wollastonite, kaolin, montmorillonite, bentonite, sepiolite, zonotolite,
Examples include inorganic fillers such as clay and silica, organic fillers such as aramid fibers, inorganic pigments such as titanium oxide, and carbon black. These can be selected from these or a combination thereof. Among these, in the present invention, talc, wollastonite, and mica, which are inorganic fillers with little impact resistance and high reinforcing effect, can be mentioned as preferred fillers. Among them, talc and wollastonite are most preferable.

The flame-retardant polycarbonate resin composition of the present invention may contain other resins as long as the object of the present invention is not impaired. As such other resin, for example, polyethylene terephthalate, aromatic polyester resin such as polybutylene terephthalate, polyamide resin, polyimide resin, polyetherimide resin,
Polyurethane resin, polyphenylene ether resin, polyphenylene sulfide resin, polysulfone resin, polyolefin resin such as polyethylene and polypropylene, polystyrene resin, acrylonitrile / styrene copolymer (AS resin), acrylonitrile / butadiene / styrene copolymer (ABS resin), poly Methacrylate resin,
Resins such as phenolic resins and epoxy resins are exemplified.

For producing the flame-retardant thermoplastic resin composition of the present invention, any method is employed. For example, a component to c
After sufficiently mixing the components and other additives using a pre-mixing means such as a V-type blender, a Henschel mixer, a mechanochemical device, an extruder, and the like, the mixture is optionally formed using an extruder or a briquetting machine. Granulation is then performed, followed by melt kneading with a melt kneader typified by a vented twin-screw rudder, and pelletizing with a device such as a pelletizer.

In addition, a method of independently supplying each component to a melt kneader typified by a vented twin-screw ruder,
A method in which a part of each component is preliminarily mixed and then supplied to a melt kneader independently of the remaining components is also included. As a method of pre-mixing, for example, a method of blending a part of an aromatic polycarbonate resin powder to be blended with a blending additive to prepare a master batch of an additive diluted with the aromatic polycarbonate resin powder can be mentioned. In addition, when there is a liquid component to be blended, a so-called liquid injection device or a liquid addition device can be used for supply to the melt kneader.

The flame-retardant polycarbonate resin composition of the present invention can be used to produce various products by injection molding such pellets to obtain molded products. In such injection molding, not only a normal cold runner type molding method but also a hot runner that enables runnerless can be manufactured. In addition, in injection molding, not only normal molding methods but also gas assist injection molding, injection compression molding, injection press molding, insert molding,
In-mold molding, local mold high-temperature molding (including heat-insulating mold molding), two-color molding, sandwich molding, ultra-high-speed injection molding, and the like can be used.

The flame-retardant polycarbonate resin composition of the present invention can be used in the form of various shaped extruded products, sheets, films, etc. by extrusion. For forming a sheet or film, an inflation method, a calendar method, a casting method, or the like can be used. Furthermore, it is also possible to form a heat-shrinkable tube by performing a specific stretching operation. Further, the flame-retardant thermoplastic resin composition of the present invention can be formed into a hollow molded article by rotational molding or blow molding.

The flame-retardant polycarbonate resin composition of the present invention is suitable for internal parts and housings of OA equipment and home electric appliances. Such applications include, for example, personal computer interior / exterior, notebook computer exterior, CRT display, printer, mobile terminal, mobile phone, copier, fax,
Recording media (CD, DVD, PD, FDD, etc.) drives, parabolic antennas, power tools, VTRs, TVs, irons, hair dryers, rice cookers, microwave ovens, audio equipment, audio laser disks (registered trademark), compact disks, etc. Audio equipment, lighting equipment, refrigerators,
Examples include air conditioners, typewriters, word processors, and the like.

Further, there may be mentioned vehicle parts such as lamp sockets, lamp reflectors, lamp housings, instrument panels, center console panels, deflector parts, car navigation parts and car stereo parts. It is also useful for various uses such as machine parts and miscellaneous goods.

[0094]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be further described below with reference to examples. "Parts" or "%" in the examples indicate parts by weight or% by weight, and the evaluation items and symbols of the components in the composition mean the following. (1) Flame retardancy: A combustion test was performed at a thickness of 1.6 mm according to UL standard 94V. (2) Impact resistance: according to ASTM D256, thickness 3.
The 2 mm Izod notch impact resistance was measured. (3) Thermal stability: At the time of molding, in normal injection molding, after the measurement is completed, the cylinder is retracted from the mold portion, and in that state, the resin is introduced into the cylinder at a cylinder temperature of 280 ° C. for 10 minutes.
Then, the test piece was prepared for evaluation of physical properties.
The Izod notched impact resistance value was measured using the test piece retained for 10 minutes. The retention rate represents the ratio of the impact resistance value after retention to the impact resistance value before retention in%.

(4) Appearance: A 50 mm × 80 mm × 2 mm square plate obtained simultaneously with the test piece for measuring the impact resistance was visually observed. The square plate used was 280 as above.
The one kept at 10 ° C. for 10 minutes was used. The appearance was evaluated according to the following evaluation criteria. ◎: uniform appearance without yellowish ○: relatively small appearance of yellowish ；: slightly yellowish ×: strong yellowish (component a) aromatic polycarbonate resin PC: bisphenol A and phosgene Polycarbonate resin having a viscosity average molecular weight of 22,500 [L-1225 manufactured by Teijin Chemicals Ltd.] (b component) cross-linked phenoxyphosphazene compound

FR-1 [Synthesis Example 1] Synthesis of phenoxyphosphazene compound having a crosslinked structure with paraphenylene 1.1 mol (103.5 g) of phenol, 1.1 mol (44.0 g) of sodium hydroxide, and water A mixture of 50 g and 500 mL of toluene was heated to reflux to remove only water from the system, thereby preparing a toluene solution of sodium phenolate.

In parallel with the above reaction, 0.15 mol (16.5 g) of hydroquinone, 1.0 mol (94.1 g) of phenol, 1.3 mol (31.1 g) were placed in a 2 L four-necked flask.
g) lithium hydroxide, water 52 g and toluene 600
A toluene solution of lithium salt of hydroquinone and phenol was prepared by adding a mixture of mL, heating and refluxing, and removing only water outside the system. 1.0 unit of dichlorophosphazene oligomer (a mixture of trimer 62%, tetramer 12%, pentamer and hexamer 11%, heptamer 3%, octamer or more 12%) was added to this toluene solution. Mole (115.9
After 580 g of a 20% chlorobenzene solution containing g) was added dropwise at 30 ° C. or lower with stirring, the mixture was stirred and reacted at 110 ° C. for 3 hours. Next, the toluene solution of sodium phenolate prepared above was added under stirring, and the reaction was continued at 110 ° C. for 4 hours.

After the completion of the reaction, the reaction mixture was washed three times with 1.0 L of a 3% aqueous sodium hydroxide solution and then three times with 1.0 L of water, and the organic layer was concentrated under reduced pressure. The obtained product is heated at 80 ° C. and 400 Pa (3 mmHg) or less at 11 ° C.
After heating and vacuum drying for 211 hours, 211 g of a slightly yellow powder was obtained.

The crosslinked phenoxyphosphazene compound obtained above had a hydrolytic chlorine content of 0.04% and a weight average molecular weight (Mw) of 1 in terms of polystyrene (by GPC analysis).
100, the composition of the phosphorus content and CHN final product elemental analysis values, [N = P (-O- C 6 H 4 -O-) 0.15
(-O-Ph) _1.7 ]. The TG / DTA analysis did not show a clear melting point, and the decomposition onset temperature was 306 ° C., 5%
The weight loss temperature was 311 ° C. In addition, as a result of quantifying the remaining hydroxy groups by the acetylation method, the detection limit (hydroxy equivalent per 1 g of sample: 1 × 1
0 ^-6 eq / g) were as follows.

FR-2 [Synthesis Example 2] Synthesis of a phenoxyphosphazene compound having a cross-linked structure with a 2,2-bis (p-oxyphenyl) isopropylidene group 0.7 mol (65.9 g) of phenol and 50 of toluene
0 mL was placed in a 1 L four-necked flask, and while stirring, the internal liquid temperature was maintained at 25 ° C., and 0.65 g atom (14.9 g) of metallic sodium was cut into small pieces and charged. After completion of the addition, stirring was continued at 77 to 113 ° C. for 8 hours until the sodium metal completely disappeared.

In parallel with the above reaction, bisphenol-A
0.25 mole (57.1 g), phenol 1.1 mole (1
33.5 g) and tetrahydrofuran (THF) 80
0 mL was placed in a 3 L four-necked flask, and while stirring, the internal liquid temperature was maintained at 25 ° C., and 1.6 g atom (1
1.1 g) was cut into small pieces and charged. After the end of loading, 6
Stirring was continued at 1-68 ° C. for 8 hours until the lithium metal completely disappeared. A dichlorophosphazene oligomer (concentration: 37%, chlorobenzene solution 3) was added to this slurry solution.
13 g, composition: 75% of trimer, 17% of tetramer, 6% of pentamer and hexamer, 1% of 7mer, 1% of octamer and 1% mixture) 1.0 mol (115.9 g) ) Was added dropwise with stirring over 1 hour while maintaining the internal liquid temperature at 20 ° C or lower.
The reaction was carried out at 2 ° C. for 2 hours. Then, while stirring, the internal liquid temperature was lowered to 20.
After maintaining the temperature at 0 ° C and adding a separately prepared sodium phenolate solution over 1 hour, the reaction was carried out at 80 ° C for 5 hours.

After completion of the reaction, the reaction mixture was concentrated to remove THF, and 1 L of toluene was newly added. The toluene solution was washed three times with 1 L of 2% NaOH and then three times with 1 L of water, and the organic layer was concentrated under reduced pressure. The obtained product is heated at 80 ° C. and 400 Pa (3 mmHg) or less at 11 ° C.
After heating and vacuum drying for an hour, 229 g of a white powder was obtained.

The crosslinked phenoxyphosphazene compound obtained above had a hydrolyzed chlorine content of 0.07%, and the composition of the final product was [N = P (-
_{O-C 6 H 4 -C (} CH 3) 2 -C 6 H 4 -O-) 0.25 (-O
-Ph) _1.50 ]. The weight average molecular weight (Mw) was 1130 in terms of polystyrene (by GPC analysis), no clear melting point was shown by TG / DTA analysis, the decomposition onset temperature was 308 ° C, and the 5% weight loss temperature was 313 ° C. Further, as a result of quantifying the residual hydroxyl group by the acetylation method, the residual hydroxyl group was below the detection limit (hydroxyl equivalent per gram of sample: 1 × 10 ⁻⁶ equivalent / g or less).

FR-3 [Synthesis Example 3] Synthesis of phenoxyphosphazene having a crosslinked structure with 4,4-sulfonyldiphenylene (bisphenol-S residue) 0.4 mol (37.6 g) of phenol and THF 50
0 mL was placed in a 1 L four-necked flask, and while stirring, the internal liquid temperature was maintained at 25 ° C., and 0.45 g atom (9.2 g) of sodium metal was cut into small pieces and charged. After loading is completed,
5 to 65 ° C to 72 ° C until metallic sodium is completely disappeared.
Stirring was continued for hours.

In parallel with the above reaction, 1.70 mol (160.0 g) of phenol and 0.05 mol (12.5 g) of bisphenol-S were dissolved in 500 ml of tetrahydrofuran (THF) in a 1 L four-necked flask. At 25 ° C. or less, 1.8 grams of metallic sodium (41.4 g) are charged,
After the completion of the charging, the temperature is raised to 61 ° C. over one hour, 61 ° C. to 68 ° C.
Stirring was continued at 6 ° C. for 6 hours to prepare a mixed solution of sodium phenolate. This solution is mixed with dichlorophosphazene oligomer (trimer 62%, tetramer 12%, pentamer and hexamer 11%, heptamer 3%, octamer or more 12%).
After dropwise adding to 580 g of a 20% chlorobenzene solution containing 1.0 unit mol (115.9 g) under cooling and stirring at 25 ° C. or lower, the mixture was reacted with stirring at 71 to 73 ° C. for 5 hours.

Next, after the sodium phenolate mixed solution prepared above was added dropwise, the reaction was continued at 71 to 73 ° C. for 3 hours. After completion of the reaction, the reaction mixture was concentrated, redissolved in 500 mL of chlorobenzene, washed 3 times with 5% aqueous NaOH, washed with 5% sulfuric acid, washed with 5% aqueous sodium bicarbonate, and washed 3 times with water, and concentrated to dryness. 218 g of a pale yellow wax were obtained.

The hydrolyzed chlorine of the crosslinked phenoxyphosphazene compound obtained above was 0.01% or less. From the phosphorus content and CHN elemental analysis, the composition of this product was [N
_{= P (-O-C 6 H} 4 -SO 2 -C 6 H 4 -O-) 0.05 (-
O-Ph) _1.90 ]. Weight average molecular weight (Mw)
Was 1080 in terms of polystyrene, the melting temperature (Tm) by TG / DTA analysis was 103 ° C, the decomposition onset temperature was 320 ° C, and the 5% weight loss temperature was 334 ° C. Further, as a result of quantifying the residual hydroxy group by the acetylation method, it was below the detection limit (hydroxy equivalent per 1 g of sample: 1 × 10 ⁻⁶ equivalent / g or less).

(Flame retardant other than component b) FR-4: A commercially available cyclic phenoxyphosphazene compound having no cross-linked structure [P-380 manufactured by Nippon Soda Co., Ltd.]
0] FR-5: triphenyl phosphate [TPP manufactured by Daihachi Chemical Industry Co., Ltd.] (c component) polytetrafluoroethylene mixture PTFE-1: polytetrafluoroethylene particles having fibril-forming ability and methyl methacrylate and dodecyl methacrylate Mixture of polymer particles (polytetrafluoroethylene content: 20% by weight) [METABLEN A-3000 manufactured by Mitsubishi Rayon Co., Ltd.] PTFE-2: Polytetrafluoroethylene particles having fibril-forming ability and styrene-acrylonitrile copolymer Mixture of particles (polytetrafluoroethylene content: 50% by weight) [BLENDEX449 manufactured by GE Specialty Chemical Co., Ltd.]

(Anti-dropping agent other than component c) PTFE-3: Polytetrafluoroethylene having fibril-forming ability [Polyflon MP manufactured by Daikin Industries, Ltd.]
A FA-500] <Other components> PMMA: Polymethyl methacrylate resin [Delpet 80N manufactured by Asahi Kasei Kogyo Co., Ltd.] SAN: Styrene-acrylonitrile copolymer resin [Styrac AS769 manufactured by Asahi Kasei Kogyo Co., Ltd.] ABS: Acrylonitrile -Butadiene-styrene copolymer resin [Santak UT-61 manufactured by Japan A & L Co., Ltd.] PET: polyethylene terephthalate resin [Teijin Co., Ltd.]
TR-8580, intrinsic viscosity 0.8 (o-chlorophenol solution, 25 ° C.)] Rubber: methyl methacrylate-based composite rubber graft copolymer [METABLEN S-2001 manufactured by Mitsubishi Rayon Co., Ltd.] Additive-1: Tris ( 2,4-di-tert-butylphenyl) phosphite [IRGAFOS168 manufactured by Nippon Ciba Geigy Co., Ltd.] Additive-2: fatty acid ester-based release agent [Rikemar SL-900 manufactured by Riken Vitamin Co., Ltd.]

Examples 1 to 6, Comparative Examples 1 to 9 The aromatic polycarbonate resin obtained above and Table 1
The components described were mixed in a V-type blender based on the amounts shown in the table, and then, with a 30 mmφ vented twin-screw extruder [KTX-30 manufactured by Kobe Steel Co., Ltd.] using a vacuum pump, 1.33 kPa ( Under a vacuum of 10 mmHg)
The mixture was melt-extruded at a cylinder temperature of 270 ° C. and pelletized. After drying the pellets at 110 ° C. for 5 hours, various test pieces were prepared and evaluated at a cylinder temperature of 280 ° C. and a mold temperature of 80 ° C. using an injection molding machine [T-150D manufactured by FANUC Corporation].

[0111]

[Table 1]

[0112]

[Table 2]

[0113]

Industrial Applicability The flame-retardant polycarbonate resin composition of the present invention is excellent in impact resistance and thermal stability, and is excellent in surface appearance of a molded product obtained by melt molding.
It is extremely useful for various industrial uses such as the equipment field and the electric and electronic equipment field.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (Reference) // (C08L 69/00 C08L 27:18 27:18 85:02 85:02 101: 00 101: 00) (72) Inventor Yuji Tada 3-2-2, Odori, Chuo-ku, Osaka City, Osaka Prefecture F-term in Otsuka Chemical Co., Ltd. 4F071 AA01 AA27 AA50 AA68 AC15 AE07 AF23 AF45 AH04 AH05 AH14 AH16 AH17 BA01 BB05 BB06 BC01 BC04 4H028 AA35 AA38 AA40 AA42 AA43 AA48 4J002 AA012 AA022 BD153 CG001 CG011 CG041 CQ014 EW156 FD019 FD049 FD069 FD079 FD133 FD134 FD136 FD139 FD169 GG01 GG02 GM00 GS01 GS01

Claims (2)

[Claims] 1. An aromatic polycarbonate resin (a component)
1-80 weight% of polytetrafluoroethylene particles (component c1) having a particle diameter of 10 μm or less based on 100 weight parts of a resin composition comprising 70-99 weight% and 1-30 weight% of a crosslinked phosphazene-based flame retardant (component b) %, And 0.1 to 10 parts by weight of a mixture (component (c)) consisting of 20% to 99% by weight of an organic polymer (component (c2)) and the crosslinked phosphazene-based resin. The flame retardant has the following general formula (1): [In the formula, m represents an integer of 3 to 25. Ph represents a phenyl group. A phenoxyphosphazene represented by the general formula (2): [Wherein X ¹ is a group -N = P (OPh) ₃ or a group -N = P
(O) OPh, and Y ¹ represents a group —P (OPh) ₄ or a group —P (O) (OPh) ₂ . n shows the integer of 3-10,000. Ph is the same as above. At least one phosphazene compound selected from the group consisting of linear phenoxyphosphazenes represented by the formula:
Phenylene group, p-phenylene group and general formula (3) Wherein A represents —C (CH ₃ ) ₂ —, —SO ₂ —, —S— or —O—. a represents 0 or 1. At least one selected from the group consisting of bisphenylene groups represented by
A compound cross-linked by a kind of cross-linking group,
(A) the cross-linking group is interposed between the two oxygen atoms from which the phenyl group of the phosphazene compound has been eliminated, and (b) the content of the phenyl group in the phosphazene compound (1) and / or (2) 50 to 99 based on the total number of phenyl groups.
A flame-retardant polycarbonate resin composition, which is 9% and (c) a crosslinked phenoxyphosphazene compound having no free hydroxyl group in the molecule. 2. A molded article obtained by melt-molding the flame-retardant polycarbonate resin composition according to claim 1.