JP3228639B2 - Flame retardant polycarbonate resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention is the combination of certain compounds, namely, resorcinol polyphosphate compounds, polytetrafluoroethylene and a metal salt flame retardant polycarbonate resin composition without comprising a containing colored sulfide It is about.

[0002]

2. Description of the Related Art Polycarbonate is produced by a phosgene method in which a divalent hydroxy compound and phosgene are interfacially polycondensed or reacted, or an ester in which a divalent hydroxy compound and a diester carbonate are reacted in a molten state. Exchange methods and the like are generally known.

A typical example of the transesterification method is to add a transesterification catalyst to a dihydric phenol and a carbonic acid diester, synthesize a prepolymer while distilling off the phenol under heating and reduced pressure, and finally produce a high vacuum. And heating to 290 ° C. or higher to distill phenol to obtain a high molecular weight polycarbonate (US Pat. No. 4,345,062).

In the transesterification method, in order to advance the reaction efficiently, in the initial stage of the reaction, a prepolymer is synthesized in a tank-type reactor having ordinary stirring blades, and then a device such as a horizontal extruder with a vent is used. It is known to carry out a polycondensation reaction to produce a high molecular weight polycarbonate.

However, since high molecular weight polycarbonates have extremely high melt viscosities unlike other engineering plastics, they require high temperatures of 280 ° C. or higher as reaction conditions and distill off monohydric hydroxy compounds having a high boiling point. Therefore, a high vacuum (1 to 10 ^-2 torr) is required, which has a problem of adversely affecting the physical properties of the produced polycarbonate.

[0006] "Polycarbonate resin", 3rd edition, Nikkan Kogyo Shimbun P.64, describes that bisphenol A, which is a monomer, is decomposed when an alkaline catalyst is used to produce a colored substance or a resinous substance. In addition, the produced polycarbonate is subjected to the action of alkali at high temperature, and Kolbe-
It is also described that a side reaction similar to the Schmitt reaction produces branching and crosslinking.

However, conventionally used aromatic polycarbonates are aromatic polycarbonates produced by the phosgene method, and bisphenol A is reacted with phosgene to produce a polycarbonate. By adding, the polymer terminal is sealed with phenol. By adding the amount of phenol added at this time in excess of the expected concentration of the terminal chloroformate group, the terminal hydroxyl group concentration is sealed to less than about 5 mol%.

Since the polycarbonate thus produced has excellent physical properties, it is used for various purposes such as automobile parts, electric equipment, interior decorations, building materials, and various other molded products. However, since polycarbonate is flammable, it is subject to various legal regulations depending on the application, and a high degree of flame retardancy is required even when a flame retardant material is mixed.

[0009] In response to the requirement of the flame retardancy of polycarbonate, various polychlorinated organic compounds, polybrominated organic compounds,
A method of adding a flame retardant such as antimony trioxide and a phosphorus compound has been proposed.

However, halogen-containing flame retardants are unstable at high temperatures and are easily decomposed, so that synthetic resins containing halogen-containing flame retardants are colored during processing, especially during high-temperature processing. Is remarkable.

The phosphorus compounds include aromatic phosphate compounds (JP-B-48-38768), bisphenol A polyphosphate, hydroquinone bisphosphate compounds (JP-A-55-118957), and resorcinol polyphosphate compounds (JP-B-55-118957). Publication No. 63-65109, Tokuhei 2-
No. 25381). However,
In order to enable flame retardation with these phosphorus compounds, a relatively large amount of addition is required, which has the drawbacks that not only the heat distortion temperature is remarkably lowered but also dripping phenomenon often occurs.

Furthermore, it has been disclosed that a specific resorcinol polyphosphate compound and a zinc salt of an inorganic acid are added to a synthetic resin (Japanese Patent Application Laid-Open No. 5-230281). I can't say.

[0013]

Means for Solving the Problems The present inventors have added a resorcinol polyphosphate compound, polytetrafluoroethylene and a metal salt of a specific sulfide to a polycarbonate resin as a specific compound combination. The present inventors have found a flame-retardant polycarbonate resin composition which not only exhibits a remarkable flame-retardant effect but also can remarkably improve the dripping phenomenon, and has completed the present invention.

That is, the present invention relates to a resorcinol polyphosphate compound represented by the following general formula (I), polytetrafluoroethylene and zinc sulfide:
The present invention relates to a flame-retardant polycarbonate resin composition containing tin sulfide or titanium sulfide .

[0015]

Embedded image

(In the formula, R represents a hydrogen atom or a methyl group, and n represents an integer of 1 to 5.) As the polycarbonate resin, a polycarbonate resin obtained by polymerizing with phosgene, or a divalent hydroxy compound And a carbonic acid diester in the presence of a transesterification catalyst to obtain a terminal hydroxyl group concentration of 5 obtained by melt polycondensation.
6060 mol% of polycarbonate resin is used.

As the resorcinol polyphosphate compound, phenylcresylresorcinol polyphosphate is preferable, and its addition amount is preferably in the range of 1 to 25 parts by weight based on 100 parts by weight of the polycarbonate resin. Addition amount is 1
When the amount is less than 25 parts by weight, there is no effect of improving the flame retardancy.

The amount of polytetrafluoroethylene is 0.1 to 100 parts by weight of the polycarbonate resin.
A range of 10 parts by weight is preferred. If the added amount is less than 0.1 part by weight, there is no effect of suppressing the dripping phenomenon at the time of combustion. If the added amount exceeds 10 parts by weight, not only does the fluidity during molding processing be impaired, but also the heat deformation temperature decreases.

Further , the addition amount of zinc sulfide, tin sulfide or titanium sulfide is based on 100 parts by weight of the polycarbonate resin.
A range of 0.1 to 15 parts by weight is preferred. If the amount is less than 0.1 part by weight, there is no effect of suppressing the dripping phenomenon at the time of combustion.

Hereinafter, in the presence of a general transesterification catalyst,
A method for producing a polycarbonate resin obtained by melt polycondensation will be specifically described.

Representative examples of the divalent hydroxy compound include:
Examples include compounds selected from the compounds represented by the following general formulas (1) to (4).

[0022]

Embedded image

As bisphenols classified into the general formula (1), 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) -4-methylpentane, 2,2-bis (4-hydroxyphenyl) octane, 4,4′-dihydroxy-2,2,2-
Triphenylethane, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane and the like.

As bisphenols classified into the general formula (2), 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxy-3-
Isopropylphenyl) propane, 2,2-bis (4-
(Hydroxy-3-sec-butylphenyl) propane, 2,
2-bis (4-hydroxy-3-tert-butylphenyl) propane and the like.

As bisphenols classified into the general formula (3), 1,1'-bis (4-hydroxyphenyl) -p
-Diisopropylbenzene, 1,1'-bis (4-hydroxyphenyl) -m-diisopropylbenzene, and the like.

Examples of bisphenols classified into the general formula (4) include 1,1'-bis (4-hydroxyphenyl) cyclohexane.

Among these, in particular, 2,2-bis (4-
(Hydroxyphenyl) propane is preferred.

Furthermore, it is also possible to produce a copolymerized polycarbonate in which two or three or more divalent hydroxy compounds selected from the compounds represented by the above general formulas (1) to (4) are combined. is there.

As typical examples of the carbonic acid diester,
Diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate, diethyl carbonate, dimethyl carbonate, dibutyl carbonate,
Dicyclohexyl carbonate and the like are used. Of these, diphenyl carbonate is particularly preferred.

In producing the polycarbonate in the present invention, the above-mentioned carbonic acid diester is required to be equimolar to the divalent hydroxy compound present in the reaction system. Generally, in order to produce a high molecular weight polycarbonate, one mole of a carbonate compound and one mole of a divalent hydroxy compound must react. When diphenyl carbonate is used, 2 moles of phenol are formed by the reaction. These two moles of phenol are distilled out of the reaction system. The viscosity [η] of the polycarbonate thus obtained is 0.2 to 0.8 dl / g.

However, when distilling out the produced monovalent hydroxy compound out of the system in order to proceed with the reaction, the diester carbonate used as a monomer may be simultaneously distilled off. 1.01 to 1.5 mol, preferably 1 mol, per mol of the hydroxy compound
Preferably, it is used in an amount of 1.015 to 1.45 mol.

The transesterification catalyst that can be used in the present invention includes an electron-donating amine compound, an alkali metal compound and an alkaline earth metal compound, and a borate. And Na, K, Be, Ca, Sr, Ba, Zn, C
d, Al, Cr, Mo, Fe, Co, Ni, Ag, A
Metals such as u, Sn, Sb, Pb, Pt, and Pd and alcoholates, oxides, carbonates, acetates, hydrides, and the like can also be used.

Representative examples of the electron donating amine compound include 4-dimethylaminopyridine, 4-diethylaminopyridine, 4-pyrrolidinopyridine, 4-aminopyridine, 2-hydroxypyridine, 4-hydroxypyridine, and 2-methoxypyridine. , 4-methoxypyridine, 2
-Methoxyimidazole, 1-methylimidazole, imidazole, aminoquinoline, 4-methylimidazole, diazabicyclooctane (DABCO) and the like.

Representative examples of the alkali metal compound and the alkaline earth metal compound include sodium hydroxide, lithium hydroxide, potassium hydroxide, sodium hydrogen carbonate, lithium hydrogen carbonate, potassium hydrogen carbonate, sodium carbonate, lithium carbonate, and potassium carbonate. , Sodium acetate, lithium acetate, potassium acetate, sodium stearate, lithium stearate, potassium stearate, sodium borohydride, lithium borohydride, potassium borohydride, sodium benzoate, lithium benzoate, potassium benzoate, water Barium oxide, calcium hydroxide, magnesium hydroxide, barium hydrogen carbonate, calcium hydrogen carbonate, magnesium hydrogen carbonate, barium carbonate, calcium carbonate, magnesium carbonate, barium acetate, calcium acetate, magnesium acetate , Barium stearate, calcium stearate, magnesium stearate, and the like.

Representative examples of borates include sodium diborate, sodium tetraborate, sodium pentaborate, sodium hexaborate, sodium octaborate, lithium metaborate, lithium tetraborate, lithium pentaborate , Potassium metaborate, potassium tetraborate, potassium pentaborate,
Potassium hexaborate, potassium octaborate, ammonium metaborate, ammonium tetraborate, ammonium pentaborate, ammonium octaborate, ammonium borate, tetramethylammonium borate, aluminum potassium borate, cadmium borate, boric acid Examples include silver, copper borate, lead borate, nickel borate, magnesium borate, and manganese borate.

These transesterification catalysts may be used alone or in combination of two or more. When a plurality of catalysts are used in combination, the catalyst may be added at the same time as the monomer is charged, or may be added stepwise during the reaction.

The amount of the transesterification catalyst used is from 10 ^-1 mol to 10 ^-8 mol, preferably from 10 ^-2 mol to 10 ^-8 mol, per 1 mol of the divalent hydroxy compound present in the reaction system.
^-7 mol. When the amount is less than 10 ^-8 mol, the catalytic action is small and the polymerization rate of the polycarbonate is slowed. When the amount is 10 ^-1 mol or more, the rate of remaining in the produced polycarbonate is increased, so that the physical properties of the polycarbonate are deteriorated.

Further, boric acid added to the reaction mixture and / or
Or typical examples of borate esters, boric acid, triphenyl borate, trimethyl borate, triethyl borate,
Examples thereof include butyl borate and tolyl borate.
These boric acids and / or boric esters may be added at the beginning of the reaction, or during or after the reaction. These boric acids and / or borate esters have the effect of deactivating the basic polymerization catalyst and increasing the thermal stability of the polymer. The amount of the boric acid and / or boric ester used is based on 1 mol of the basic group and / or the alkali metal atom and the alkaline earth metal atom of the catalyst used.
It is preferably from 0.01 to 500 mol. If it is less than 0.01 mol, there is no effect on heat stabilization, and if it exceeds 500 mol, the degree of polymerization cannot be increased, which is not preferable.

The polycarbonate synthesized by the above production method has a terminal hydroxyl group concentration of 5 to 60 mol%. The molar ratio of the raw material carbonic acid diester to the divalent hydroxy compound (carbonic acid diester / divalent hydroxy compound) is
If it exceeds 1.5, the concentration of terminal hydroxyl groups of the resulting polycarbonate will be less than 5 mol%, but the diester carbonate will remain too much, the molecular weight will not increase and the color will be adversely affected. When the molar ratio of the raw material carbonic acid diester to the divalent hydroxy compound is less than 1.01, the concentration of terminal hydroxyl groups of the resulting polycarbonate exceeds 60 mol%, but adversely affects the physical properties after the heat stability test, especially the number of cuts. It is not preferable.

Next, as a typical method of adding the additive, an extruder having a feeder capable of feeding the additive is used, and the additive is continuously added to the molten resin through a feeder. There is a method of kneading with an extruder.

Examples of the additives include a heat stabilizer, a light stabilizer, an ultraviolet absorber, a release agent, a colorant, and a moldability improver. Examples of the heat stabilizer include organic phosphorus compounds and hindered phenol compounds. Examples of the light stabilizer include a hindered amine compound, and examples of the ultraviolet absorber include a benzotriazole compound.

Representative examples of the phosphorus compound which can be used in the present invention include triethyl phosphite, triisopropyl phosphite, triisodecyl phosphite, tridodecyl phosphite, phenyl diisodecyl phosphite,
Diphenylisodecyl phosphite, triphenyl phosphite, tris-tolyl phosphite, phenyl-bis (4-nonylphenyl) phosphite, tris (4-
Octylphenyl) phosphite, tris (4- (1-
Phenylethyl) phenyl) phosphite, tris (2,4-di-t-butylphenyl) phosphite, tetrakis (2,4-di-t-butylphenyl) -4,4′-biphenyl represented by the following formula: Range phosphonite,

[0043]

Embedded image

Pentaerythritol represented by the following formula:
Di [(2,6-di-t-butyl-4-methylphenyl)
Phosphite),

[0045]

Embedded image

Pentaerythritol represented by the following formula:
Di [(2,4-di-t-butylphenyl) phosphite],

[0047]

Embedded image

Tetrakis (2,4-di-t-butylphenyl) -4,4 ′-(2,2-diphenylpropane) phosphonite represented by the following formula:

[0049]

Embedded image

The dialkoxyphosphoric acid phenyl ester represented by the following formula

[0051]

Embedded image

(R ₆ and R _{7 each} represent a linear or branched alkyl group having 1 to 20 carbon atoms, and Ph represents a phenyl group.). The amount of the phosphorus compound to be added is preferably 10 to 1000 ppm based on the divalent hydroxy compound. If it is less than 10 ppm, there is no effect on heat stabilization, and if it exceeds 1000 ppm, physical properties are adversely affected.

Representative examples of the hindered phenol compound that can be used in the present invention include octadecylpropionate-3- (3,5-di-tert-butyl-4-hydroxyphenyl), N, N'-hexamethylene Bis (3,5-di-
t-butyl-4-hydroxy-hydrocinnamamide),
Triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5
-Di-t-butyl-4-hydroxyphenyl) propionate], pentaerythrityl-tetrakis [3-
(3,5-di-t-butyl-4-hydroxyphenyl)
Propionate], 3,5-di-t-butyl-4-hydroxybenzylphosphonate-diethyl ester, and compounds represented by the following formulas (A) to (C).

[0054]

Embedded image

The amount of the hindered phenol compound to be added is preferably 10 to 2000 ppm based on the divalent hydroxy compound. Less than 10 ppm has no effect on thermal stabilization,
If it exceeds 00 ppm, the properties are adversely affected, which is not preferable.

Representative examples of the hindered amine compound that can be used in the present invention include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate and bis-succinic acid
(2,2,6,6-tetramethyl-4-piperidinyl) ester, 2- (3,5-di-t-butyl-4-hydroxybenzyl) -2-n-butylmalonic acid bis (1,2,
2,6,6-ventamethyl-4-piperidyl) and the like.

Representative examples of the benzotriazole compound that can be used in the present invention include 2- (5-methyl-2-hydroxyphenyl) benzotriazole and 2- (3,5-di-t-butyl-2-hydroxyphenyl). ) Benzotriazole, 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole,
-(2'-hydroxy-5'-t-octylphenyl)
Benzotriazole and the like.

The release agent used in the present invention may be a general release agent, and is not particularly limited. Examples of the hydrocarbon release agent include natural and synthetic paraffins, polyethylene waxes, and the like. And fluorocarbons.

As the fatty acid-based release agent, stearic acid,
Higher fatty acids such as hydroxystearic acid, oxy fatty acids and the like can be mentioned.

Examples of the fatty acid amide release agent include fatty acid amides such as stearic acid amide and ethylenebisstearamide, and alkylenebisfatty acid amides.

Examples of the alcohol-based release agent include aliphatic alcohols such as stearyl alcohol and cetyl alcohol, polyhydric alcohols, polyglycols, and polyglycerols.

Examples of the fatty acid ester release agents include lower fatty acid esters such as butyl stearate and pentaerythritol tetrastearate, fatty acid polyhydric alcohol esters, and fatty acid polyglycol esters.

Examples of the silicone-based release agent include silicone oils.

These release agents can be used alone or in combination of two or more. The use amount of these release agents is preferably 10 to 10,000 ppm based on 1 mol of the divalent hydroxy compound.

The colorant used in the present invention may be a pigment or a dye. The coloring agent includes an inorganic coloring agent and an organic coloring agent, and either one may be used or a combination thereof may be used.

Specific examples of the inorganic colorant include oxides such as titanium dioxide and red iron oxide, hydroxides such as alumina white, sulfides such as zinc sulfide, selenides, ferrocyanides such as navy blue, and zinc chromate. , Chromates such as molybdenum red, sulfates such as barium sulfate, carbonates such as calcium carbonate, silicates such as ultramarine blue,
Phosphates such as manganese violet; carbon such as carbon black; and metallic powder coloring agents such as bronze powder and aluminum powder.

Specific examples of the organic colorant include nitroso compounds such as naphthol green B, nitro compounds such as naphthol yellow S, lithol red and Bordeaux 10B.
Examples include azo-based coloring agents such as naphthol red and chromophtal yellow, phthalocyanine-based coloring agents such as phthalocyanine blue and fast sky blue, and condensed polycyclic coloring agents such as indanthrone blue, quinazodone violet, and dioxazine violet.

These colorants can be used alone or in combination of two or more. The amount of these colorants to be used is usually 1 × 10 ^{−6 to} 5 parts by weight, preferably 1 × 10 ^{−5 to} 3 parts by weight, more preferably 1 × 10 ⁻⁵ to 1 part by weight, per 100 parts by weight of the polycarbonate. It is about parts by weight.

As the moldability improver, a phthalate compound is used.

All of the additives described herein may be used alone or in combination.

[0071]

EXAMPLES The present invention will be described below in more detail with reference to Examples, but the present invention is not limited to these Examples.

Next, methods for measuring and evaluating the viscosity average molecular weight (Mv), hue (YI) and terminal hydroxyl group concentration ([OH]) will be described.

Viscosity average molecular weight (Mv): The intrinsic viscosity [η] of a methylene chloride solution of the polymer was measured at 20 ° C. using an Ubbelohde viscometer and calculated from the following equation. [Η] = 1.11 × 10 ^-4 (Mv) ^0.82 hue (YI): A 2 mm thick sheet was prepared from the polymer by a hot press quenching method, and the color and color of Nippon Denshoku Industries Co., Ltd.
Using a Color Defference Meter ND-1001 DP, X, Y, and Z were measured by a transmission method, and yellowness (YI) was measured. YI = 100 (1.28X-1.06Z) / Y-terminal hydroxyl group concentration ([OH]): A chloroform solution of the polymer was added to chloroform at 40 ° C. by UV-9 (manufactured by JASCO Corporation).
It was measured by GPC using a 70 detector, and the terminal hydroxyl group concentration ([OH]) was determined from the peak intensity ratio.

Synthesis Example 1 In a nickel-plated tank reactor, 4560 g (20 mol) of 2,2-bis (4-hydroxyphenyl) propane, 4434.4 g (20.7 mol) of diphenyl carbonate and 489 mg (4 mol) of 4-dimethylaminopyridine were added. × 10 ^-3 mol), 1.2366 g of boric acid (2 ×
10 ^-2 mol) was added, after thawing under nitrogen at 160 ° C., and stirred for 1 hour, allowed to warm slowly reducing the pressure, finally 1 Torr,
Polycondensation was performed at 270 ° C. for 4 hours to remove the formed phenol, and the mixture was further reacted in a vertical twin-screw self-cleaning reactor for 50 minutes to obtain a colorless and transparent polycarbonate. As a result of the measurement, the viscosity average molecular weight (Mv) of the obtained polycarbonate was 26,000, the hue (YI) was 1.5, and the terminal hydroxyl group concentration was 12 mol%.

Synthesis Example 2 4,560 g (20 mol) of 2,2-bis (4-hydroxyphenyl) propane, 4305.8 g (20.1 mol) of diphenyl carbonate, lithium borate 1 were placed in a nickel-plated tank reactor.
7.2 mg (2 × 10 ^-4 mol), boric acid 197.9 mg (3.2 × 10 ^-3 mol)
After melting at 200 ° C. under nitrogen, the mixture was stirred for 1 hour, and the temperature was raised while gradually reducing the pressure.
Polycondensation was carried out for a period of time, and the resulting phenol was distilled off. The mixture was further reacted in a vertical twin-screw self-cleaning reactor for 50 minutes to obtain a colorless and transparent polycarbonate. As a result of the measurement, the viscosity average molecular weight of the obtained polycarbonate (Mv)
Is 31,000, hue (YI) is 1.8, terminal hydroxyl group concentration is 60 mol%
Met.

Synthesis Example 3 4,560 g (20 mol) of 2,2-bis (4-hydroxyphenyl) propane, 6450 g (30.1 mol) of diphenyl carbonate, 17.2 mol of lithium borate were placed in a nickel-plated tank reactor.
mg (2 × 10 ^-4 mol) and 197.9 mg (3.2 × 10 ^-3 mol) of boric acid were added, and the mixture was melted at 200 ° C. under nitrogen, stirred for 1 hour, and gradually heated under reduced pressure. Polycondensation was carried out at 1 Torr and 265 ° C. for 4 hours to remove the formed phenol, and the mixture was reacted in a vertical twin-screw self-cleaning reactor for 50 minutes to obtain a slightly pale yellow transparent polycarbonate.
As a result of the measurement, the viscosity average molecular weight (Mv) of the obtained polycarbonate was 14,000, the hue (YI) was 3.0, and the terminal hydroxyl group concentration was 2
Mol%.

Synthesis Example 4 394 parts by weight of a 12.3% aqueous NaOH solution in which 114 parts by weight of 2,2-bis (4-hydroxyphenyl) propane were dissolved and methylene chloride were placed in a reaction vessel equipped with a phosgene blowing tube, a thermometer and a stirrer. Add 291 parts by weight and stir for 20
At 2525 ° C., 69.3 parts by weight of phosgene were introduced over 40 minutes to produce the oligomer. To this, 9 parts by weight of a 10% aqueous solution of NaOH in which 4.0 parts by weight of p-tert-butylphenol were dissolved was added, followed by stirring for 5 minutes. Then, 0.23 parts by weight of triethylamine was added, followed by stirring for 10 minutes to react. After a while, 2,2
237 parts by weight of a 4% aqueous solution of NaOH in which 22.8 parts by weight of -bis (4-hydroxyphenyl) propane were dissolved was added, and stirring was continued for about 40 minutes to complete the reaction. The methylene chloride phase is separated from the reaction mixture, washed with water, acidified with hydrochloric acid, and washed with water until the conductivity of the aqueous phase becomes almost the same as that of ion-exchanged water.The methylene chloride phase is separated, and the methylene chloride is evaporated to obtain a polymer. I got As a result of the measurement, the viscosity average molecular weight (Mv) of the obtained polycarbonate was 25,000, the hue (YI) was 1.4,
The terminal hydroxyl group concentration was 8 mol%.

Example 1 Phenylcresyl resorcinol polyphosphate (n = 1.8) was added to 100 parts by weight of the polycarbonate resin obtained in Synthesis Example 1.
After dry blending 8 parts by weight, 3 parts by weight of polytetrafluoroethylene and 4 parts by weight of zinc sulfide, the mixture was dried at 90 ° C. for 6 hours. Next, cylinder temperature 240 ° C, rotation speed 200r
Pellet using a twin screw extruder at pm
For 6 hours. Using the pellets, a test piece having a thickness of 2 mm was prepared using an injection molding machine at 260 ° C. Using the five test pieces, the oxygen index, the dropping property, and the bleeding of the surface state after being taken out were observed by the test method of JIS K-7201. Table 1 shows the results.

Comparative Example 1 Phenylcresyl resorcinol polyphosphate (n = 1.8) was added to 100 parts by weight of the polycarbonate resin obtained in Synthesis Example 3.
8 parts by weight, 5 parts by weight of polytetrafluoroethylene and 5 parts by weight of titanium sulfide were added in the same manner as in Example 1, a test piece was prepared, and the same observation was performed. Table 1 shows the results.

Example 2 The same operation and the same observation as in Example 1 were performed using 10 parts by weight of tin sulfide instead of zinc sulfide. Table 1 shows the results.

Example 3 Phenylcresyl resorcinol polyphosphate (n = 1.8) was added to 100 parts by weight of the polycarbonate resin obtained in Synthesis Example 2.
8 parts by weight, 5 parts by weight of polytetrafluoroethylene and 5 parts by weight of titanium sulfide were added in the same manner as in Example 1, a test piece was prepared, and the same observation was performed. Table 1 shows the results.

Comparative Example 2 5 parts by weight of polytetrafluoroethylene and 5 parts by weight of zinc sulfide were added to 100 parts by weight of the polycarbonate resin obtained in Synthesis Example 1.
A part by weight was added in the same manner as in Example 1, a test piece was prepared, and the same observation was performed. Table 1 shows the results.

Comparative Example 3 Phenylcresyl resorcinol polyphosphate (n = 1.8) was added to 100 parts by weight of the polycarbonate resin obtained in Synthesis Example 1.
8 parts by weight and 4 parts by weight of zinc sulfide were added in the same manner as in Example 1, a test piece was prepared, and the same observation was performed. Table 1 shows the results.

Comparative Example 4 Phenylcresyl resorcinol polyphosphate (n = 1.8) was added to 100 parts by weight of the polycarbonate resin obtained in Synthesis Example 1.
8 parts by weight and 3 parts by weight of polytetrafluoroethylene were added in the same manner as in Example 1, a test piece was prepared, and the same observation was performed. Table 1 shows the results.

Example 4 Phenylcresyl resorcinol polyphosphate (n = 1.8) was added to 100 parts by weight of the polycarbonate resin obtained in Synthesis Example 4.
8 parts by weight, 3 parts by weight of polytetrafluoroethylene and 4 parts by weight of zinc sulfide were added in the same manner as in Example 1, a test piece was prepared, and the same observation was performed. Table 1 shows the results.

[0086]

[Table 1]

Claims (11)

(57) [Claims] 1. A polycarbonate resin having the following general formula
Resorcinol polyphosphate compound represented by (I), polytetrafluoroethylene and zinc sulfide, tin sulfide or sulfur
Flame-retardant polycarbonate resin composition characterized by containing titanium. Embedded image (Wherein, R represents a hydrogen atom or a methyl group, and n represents 1 to 5
Indicates an integer. ) 2. The flame-retardant polycarbonate resin composition according to claim 1, wherein the polycarbonate resin is a polycarbonate resin obtained by polymerizing with phosgene. 3. The polycarbonate resin according to claim 1, wherein the polycarbonate resin is obtained by melt polycondensation of a divalent hydroxy compound and a carbonic acid diester in the presence of a transesterification catalyst and has a terminal hydroxyl group concentration of 5 to 60 mol%. Flame retardant polycarbonate resin composition. 4. The flame-retardant polycarbonate resin composition according to claim 1, wherein the resorcinol polyphosphate compound is phenylcresyl resorcinol polyphosphate. 5. A resorcinol polyphosphate compound in an amount of 1 to 25 parts by weight, based on 100 parts by weight of a polycarbonate resin.
The flame retardant polycarbonate resin composition according to any one of claims 1 to 4 , comprising 0.1 to 10 parts by weight of polytetrafluoroethylene and 0.1 to 15 parts by weight of a sulfide metal salt. 6. A transesterification catalyst, an electron-donating amine compound and / or an alkali metal compound or flame retardant polycarbonate resin composition according to any one of claims 3-5 is an alkaline earth metal compound . 7. A transesterification catalyst, flame retardant polycarbonate resin composition according to any one of claims 3-5 is borate. 8. The flame-retardant polycarbonate resin composition according to any one of claims 3-7, characterized in that it contains boric acid in the polycarbonate resin. 9. The flame-retardant polycarbonate resin composition according to any one of claims 3 to 7 , wherein the polycarbonate resin contains a borate ester. 10. A divalent hydroxy compound represented by the following general formula:
The flame-retardant polycarbonate resin composition according to any one of claims 3 to 9 , which is selected from the compounds represented by (1) to (4). Embedded image (In the formula, R ₁ , R ₂ , R ₃ , R ₄ , and R ₅ are hydrogen, an alkyl group having 1 to 8 carbon atoms containing a straight or branched chain, or a phenyl group, X represents a halogen atom, and n = 0 to 4, m = 1 to 4.) 11. A method comprising using two or three or more kinds selected from the divalent hydroxy compounds according to claim 10.
10. The flame-retardant copolymerized polycarbonate resin composition according to any one of claims 9 to 9 .