JP2001270983A - Flame retardant polycarbonate resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide flame retardant polycarbonate resin compositions which excel in flame retardance at thin parts, particularly flame retardance at thin parts having a thickness of <=1.2 mm and possess high impart resistance, wet heat resistance, and heat stability. SOLUTION: The flame retardant polycarbonate resin compositions comprise 99.90-88.97 wt.% aromatic polycarbonate resin substantially containing no halogen atom [component (a)], 0.01-10 wt.% aromatic group-containing organosiloxane having a weight average molecular weight, measured by the gel permeation chromatography(GPC) described in the specification, of 300-2,000 and an aromatic group [component (b)], 0.05-1 wt.% fluorine containing polymer capable of forming fibrils [component (c)], and 0.0005-0.03 wt.% at least one metal salt selected from an alkali metal salt and an alkaline earth metal salt [component (d)] with a total of component (b), component (c), and component (d) of at least >=0.1 wt.% and a total of component (a) to component (d) of 100 wt.%.

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 which is thin and excellent in flame retardancy, furthermore excellent in impact resistance and wet heat resistance, and has high heat stability at the time of melting and kneading.

[0002]

2. Description of the Related Art Aromatic polycarbonate resins are excellent in mechanical properties, dimensional accuracy, electric properties and the like, and are widely used as engineering plastics in various fields such as electric, electronic equipment, automobile, and office automation. And among these applications, the OA field,
In the field of electronics and electronics, there is a strong demand for flame retardant OA equipment and home appliances. In recent years, as products have become thinner and lighter, flame resistance has become thinner, mechanical strength such as high impact strength, and wet heat resistance. , And high fluidity for molding thin-walled products, or thermal stability that can withstand high-temperature molding is required.

[0003] In recent years, demands for thinner and lighter weight and higher flame retardancy are increasing more and more, for example, it is required to achieve UL standard 94V-0 at a thickness of 1.0 mm.

[0004] In order to meet these demands, flame-retardant polycarbonate resin compositions to which halogen-based compounds and phosphorus-based compounds have been added have been proposed. However, in these flame-retardant polycarbonate resin compositions, the halogen-based compound and the phosphorus-based compound may cause a problem of gas generation during molding, and the polycarbonate resin can always sufficiently maintain impact strength, wet heat resistance and the like of the polycarbonate resin. Not something. Further, in the case of a phosphorus compound, the heat resistance of the polycarbonate resin is reduced, and while maintaining the original characteristics of the polycarbonate resin, for example, at a thickness of 1.0 mm, UL standard 94V-
It was not enough to achieve zero.

On the other hand, in polycarbonate resin,
It is widely known that various studies have been made on other flame retardants.

For example, JP-A-8-31320 discloses a polycarbonate resin containing a salt-based flame retardant in an amount corresponding to an alkali metal and / or alkaline earth metal content of 5 to 1000 ppm and a phosphorus-containing compound having a specific structure. Have been. However, the polycarbonate resin composition specifically described in this publication does not sufficiently satisfy flame retardancy.

JP-A-6-306265 discloses that an alkali (earth) metal salt of perfluoroalkanesulfonic acid has 0.03 to 0.3 parts by weight, an alkoxy group, a vinyl group and a phenyl group per 100 parts by weight of a polycarbonate resin. A method of incorporating 0.05 to 2 parts by weight of an organic siloxane is disclosed. However, the polycarbonate resin composition specifically described in this publication also did not satisfy sufficient flame retardancy.

JP-A-6-33647 discloses a flame-retardant polycarbonate resin composition in which an alkali metal salt and / or an alkaline earth metal salt of perfluoroalkanesulfonic acid and a specific organopolysiloxane are mixed with a polycarbonate resin. It has been disclosed. However, the resin compositions specifically exemplified in this publication are not sufficiently satisfactory in flame retardancy, long-term wet heat properties, and the like.

JP-A-11-263903 describes a polycarbonate resin composition comprising a polycarbonate resin and a silicone varnish having a specific viscosity and a metal salt of an organic sulfonic acid. However, the resin compositions specifically exemplified in this publication have a high content of an organic sulfonic acid metal salt, and are not sufficiently satisfactory in properties inherent to the polycarbonate resin, particularly, impact resistance and wet heat resistance. .

JP-A-11-217494 describes a silicone compound having a branched main chain and an aromatic group in a polycarbonate resin, a metal salt of an aromatic sulfur compound, and a fiber-forming fluoropolymer. Have been. However, the composition specifically exemplified in this publication achieves a flame-retardant polycarbonate resin composition capable of maintaining the inherent properties of a polycarbonate resin while achieving UL standard 94V-0 at a thickness of 1.0 mm. Was not.

[0011]

SUMMARY OF THE INVENTION An object of the present invention is to provide a flame-retardant polycarbonate resin composition which is excellent in thin-walled flame retardancy, furthermore excellent in impact resistance and wet heat resistance, and has high thermal stability at the time of melting and kneading. To provide things.

The present inventors have conducted intensive studies to achieve the above object, and as a result, have found that an aromatic polycarbonate resin containing substantially no halogen atom, an organic siloxane having an aromatic group having a specific molecular weight, and a fibril-forming ability are obtained. The combination of the fluorine-containing polymer having, and the alkali metal salt and / or alkaline earth metal salt whose addition amount is significantly reduced is excellent in flame retardancy at a target extremely thin wall, and further has impact resistance, wet heat resistance, The present inventors have found that a flame-retardant polycarbonate resin composition capable of maintaining characteristics inherent to an aromatic polycarbonate resin such as thermal stability during melt-kneading can be obtained, and have reached the present invention.

[0013]

According to the present invention, there is provided an aromatic polycarbonate resin (component (a)) substantially containing no halogen atom in an amount of 99.90 to 88.97% by weight;
Organosiloxane having an aromatic group having a weight average molecular weight of 300 to 2,000 measured by a PC (gel permeation chromatography) method (component b) 0.0
1 to 10% by weight, 0.05 to 1% by weight of a fluorine-containing polymer having fibril-forming ability (component (c)), and at least one metal salt selected from alkali metal salts and alkaline earth metal salts (component (d)) A flame-retardant polycarbonate comprising 0.0005 to 0.03% by weight, wherein the sum of components b, c and d is at least 0.1% by weight and the sum of components a to d is 100% by weight The present invention relates to a resin composition.

The aromatic polycarbonate resin used as the component (a) in the present invention is generally obtained by reacting a dihydric phenol with a carbonate precursor by an interfacial polycondensation method or a melt transesterification method, and also comprises a carbonate prepolymer. Is obtained by polymerizing the compound by a solid phase transesterification method, or obtained by polymerizing the compound by a ring opening polymerization method of a cyclic carbonate compound.

Representative examples of the dihydric phenol used herein include hydroquinone, resorcinol, 4,4
4'-dihydroxydiphenyl, bis (4-hydroxyphenyl) methane, bis {(4-hydroxy-3,5-
Dimethyl) phenyl @ methane, 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 2,2-bis (4
-Hydroxyphenyl) propane (commonly known as bisphenol A), 2,2-bis} (4-hydroxy-3-methyl)
Phenyl {propane, 2,2-bis {(4-hydroxy-3,5-dimethyl) phenyl} propane, 2,2-bis {(3-isopropyl-4-hydroxy) phenyl}
Propane, 2,2-bis {(4-hydroxy-3-phenyl) phenyl} propane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) -3-methylbutane, 2,2-bis (4-hydroxyphenyl) -3,3-dimethylbutane, 2,4
-Bis (4-hydroxyphenyl) -2-methylbutane, 2,2-bis (4-hydroxyphenyl) pentane, 2,2-bis (4-hydroxyphenyl) -4-methylpentane, 1,1-bis (4 -Hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -4-isopropylcyclohexane, 1,1-
Bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis {(4-hydroxy-3-methyl) phenyl} fluorene, α , Α'-bis (4-hydroxyphenyl) -o-diisopropylbenzene, α, α'-bis (4-hydroxyphenyl) -m
-Diisopropylbenzene, α, α'-bis (4-hydroxyphenyl) -p-diisopropylbenzene, 1,
3-bis (4-hydroxyphenyl) -5,7-dimethyladamantane, 4,4′-dihydroxydiphenylsulfone, 4,4′-dihydroxydiphenylsulfoxide, 4,4′-dihydroxydiphenylsulfide,
4,4'-dihydroxydiphenyl ketone, 4,4'-
Examples thereof include dihydroxydiphenyl ether and 4,4′-dihydroxydiphenyl ester, and these can be used alone or as a mixture of two or more.

Bisphenol A, 2,2-bis {(4-hydroxy-3-methyl) phenyl} propane, 2,2-bis (4-hydroxyphenyl) butane,
2,2-bis (4-hydroxyphenyl) -3-methylbutane, 2,2-bis (4-hydroxyphenyl)-
3,3-dimethylbutane, 2,2-bis (4-hydroxyphenyl) -4-methylpentane, 1,1-bis (4
A homopolymer obtained from at least one bisphenol selected from the group consisting of -hydroxyphenyl) -3,3,5-trimethylcyclohexane and α, α'-bis (4-hydroxyphenyl) -m-diisopropylbenzene, or Copolymers are preferred. In particular, bisphenol A homopolymer and 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane and bisphenol A, 2,2-bis {(4-hydroxy- Copolymers with 3-methyl) phenyl} propane or α, α′-bis (4-hydroxyphenyl) -m-diisopropylbenzene are preferably used.

As the carbonate precursor, carbonyl halide, carbonate ester or haloformate is used, and specific examples include phosgene, diphenyl carbonate and dihaloformate of dihydric phenol.

In producing the polycarbonate resin by reacting the above-mentioned dihydric phenol with the carbonate precursor by the interfacial polycondensation method or the melt transesterification method, if necessary, a catalyst, a terminal stopper and the oxidation of the dihydric phenol may be used. An inhibitor or the like may be used. Further, the polycarbonate resin may be a branched polycarbonate resin obtained by copolymerizing a trifunctional or higher polyfunctional aromatic compound, or a polyester carbonate resin obtained by copolymerizing an aromatic or aliphatic bifunctional carboxylic acid, Further, a mixture of two or more of the obtained polycarbonate resins may be used.

Examples of the trifunctional or higher polyfunctional aromatic compound include phloroglucin, phloroglucid, and 4,6-
Dimethyl-2,4,6-tris (4-hydroxydiphenyl) heptene-2,2,4,6-trimethyl-2,4
6-tris (4-hydroxyphenyl) heptane, 1,
3,5-tris (4-hydroxyphenyl) benzene,
1,1,1-tris (4-hydroxyphenyl) ethane, 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane, 2,6-bis (2-hydroxy-5-methylbenzyl) ) -4-Methylphenol, 4
-{4- [1,1-bis (4-hydroxyphenyl) ethyl] benzene} -α, α-dimethylbenzylphenol and other trisphenols, tetra (4-hydroxyphenyl) methane, bis (2,4-dihydroxyphenyl) )
Examples thereof include ketone, 1,4-bis (4,4-dihydroxytriphenylmethyl) benzene, trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid, and acid chlorides thereof, among which 1,1,1-tris (4-hydroxyphenyl) ethane, 1,1,1-
Tris (3,5-dimethyl-4-hydroxyphenyl)
Ethane is preferred, and 1,1,1-tris (4-hydroxyphenyl) ethane is particularly preferred.

When the composition contains a polyfunctional compound capable of producing such a branched polycarbonate resin, the proportion is 0.001 to 1 mol%, preferably 0.005 to 0.5 mol%, particularly preferably 0.001 to 1 mol%, based on the total amount of the aromatic polycarbonate. 0.01
~ 0.3 mol%. In particular, in the case of the melt transesterification method, a branched structure may occur as a side reaction, and the amount of such a branched structure is also 3;
It is preferably from 0.5 to 0.5 mol%, particularly preferably from 0.01 to 0.3 mol%. The ratio is ¹
It can be calculated by 1 H-NMR measurement.

The reaction by the interfacial polycondensation method is usually a reaction between dihydric phenol and phosgene, and is carried out in the presence of an acid binder and an organic solvent. As the acid binder, for example, an alkali metal hydroxide 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. Further, for promoting the reaction, for example, a catalyst such as a tertiary amine such as triethylamine, tetra-n-butylammonium bromide, or tetra-n-butylphosphonium bromide, a quaternary ammonium compound, or a quaternary phosphonium compound may be used. it can. At that time, the reaction temperature is usually 0 to 40 ° C., the reaction time is preferably about 10 minutes to 5 hours, and the pH during the reaction is preferably maintained at 9 or more.

In such a polymerization reaction, a terminal stopper is usually used. Monofunctional phenols can be used as such a terminal stopper. Monofunctional phenols are commonly used as molecular terminators for molecular weight control, such monofunctional phenols are generally phenols or lower alkyl substituted phenols,
Monofunctional phenols represented by the following general formula (1) can be shown.

[0023]

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(Wherein A is a hydrogen atom or a group having 1 to 9 carbon atoms)
Is a linear or branched alkyl group or a phenyl group-substituted alkyl group, and r is an integer of 1 to 5, preferably 1 to 3. Specific examples of the above monofunctional phenols include, for example, phenol, p-tert-butylphenol, p-cumylphenol and isooctylphenol.

Further, other monofunctional phenols include:
Phenols or benzoic acid chlorides having a long-chain alkyl group or aliphatic polyester group as a substituent, or long-chain alkylcarboxylic acid chlorides can also be used. Among these, phenols having a long-chain alkyl group represented by the following general formulas (2) and (3) as a substituent are preferably used.

[0026]

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[0027]

Embedded image

(Wherein X is -RO-, -R-CO-O
— Or —RO—CO—, wherein R represents a single bond or a divalent aliphatic hydrocarbon group having 1 to 10, preferably 1 to 5 carbon atoms, and n represents an integer of 10 to 50. Show. )

As the substituted phenols of the general formula (2), those having n of 10 to 30, especially 10 to 26 are preferred. Specific examples thereof include decyl phenol, dodecyl phenol, tetradecyl phenol, hexadecyl phenol and Octadecylphenol, eicosylphenol, docosylphenol, triacontylphenol and the like can be mentioned.

As the substituted phenols of the general formula (3), compounds wherein X is -R-CO-O- and R is a single bond are suitable, and n is 10-30, especially 10-26.
Are preferred, and specific examples thereof include, for example, decyl hydroxybenzoate, dodecyl hydroxybenzoate,
Examples include tetradecyl hydroxybenzoate, hexadecyl hydroxybenzoate, eicosyl hydroxybenzoate, docosyl hydroxybenzoate and triacontyl hydroxybenzoate. Further, the terminal stoppers may be used alone or in combination of two or more.

The reaction by the melt transesterification method is usually a transesterification reaction between a dihydric phenol and a carbonate ester, and is produced by mixing the dihydric phenol with the carbonate ester while heating in the presence of an inert gas. It is performed by a method of distilling alcohol or phenol. The reaction temperature varies depending on the boiling point of the produced alcohol or phenol, but is usually in the range of 120 to 350 ° C. In the late stage of the reaction, the system was adjusted to 1.33 × 10 ³ -1.
The alcohol or phenol produced by reducing the pressure to about 3.3 Pa is easily distilled. Reaction time is usually 1-4
About an hour.

Examples of the carbonate ester include an optionally substituted ester such as an aryl group having 6 to 10 carbon atoms, an aralkyl group or an alkyl group having 1 to 4 carbon atoms. Specifically, diphenyl carbonate, bis (chlorophenyl) carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate and the like can be mentioned, with diphenyl carbonate being preferred.

A polymerization catalyst may be used to increase the polymerization rate. Examples of the polymerization catalyst include sodium hydroxide, potassium hydroxide, alkali metal compounds such as sodium and potassium salts of dihydric phenol, and water. Alkaline earth metal compounds such as calcium oxide, barium hydroxide and magnesium hydroxide; nitrogen-containing basic compounds such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, trimethylamine and triethylamine; alkoxides of alkali metals and alkaline earth metals Manganese, organic acid salts of alkali metals and alkaline earth metals, zinc compounds, boron compounds, aluminum compounds, silicon compounds, germanium compounds, organic tin compounds, lead compounds, osmium compounds, antimony compounds Compounds, titanium compounds, usually the esterification reaction, such as zirconium compounds, there can be used a catalyst used in the transesterification reaction. The catalyst may be used alone or in combination of two or more. The amount of the polymerization catalyst used is preferably 1 × 10 ⁻⁸ to 1 ×, based on 1 mol of the dihydric phenol used as the raw material.
It is selected in the range of 10 ⁻³ equivalents, more preferably 1 × 10 ^{−7 to} 5 × 10 ⁻⁴ equivalents.

In such a polymerization reaction, to reduce the number of phenolic terminal groups, for example, bis (chlorophenyl) carbonate, bis (bromophenyl) carbonate, bis (nitrophenyl) carbonate is used later or after completion of the polycondensation reaction. , Bis (phenylphenyl)
Carbonate, chlorophenylphenyl carbonate,
Compounds such as bromophenylphenyl carbonate, nitrophenylphenyl carbonate, phenylphenyl carbonate, methoxycarbonylphenylphenyl carbonate and ethoxycarbonylphenylphenyl carbonate can be added. Among them, 2-chlorophenylphenyl carbonate, 2-methoxycarbonylphenylphenyl carbonate and 2-ethoxycarbonylphenylphenyl carbonate are preferred,
Particularly, 2-methoxycarbonylphenylphenyl carbonate is preferably used.

Further, it is preferable to use a deactivator for neutralizing the activity of the catalyst in such a polymerization reaction. Specific examples of the deactivator include, for example, benzenesulfonic acid, p-toluenesulfonic acid, methylbenzenebenzenesulfonate, ethylbenzenebenzenesulfonate, butylbenzenesulfonate, octylbenzenesulfonate, phenylbenzenesulfonate, and p-toluenesulfone. Sulfonates such as methyl acrylate, ethyl p-toluenesulfonate, butyl p-toluenesulfonate, octyl p-toluenesulfonate, and phenyl p-toluenesulfonate; further, trifluoromethanesulfonic acid, naphthalenesulfonic acid, and sulfonated polystyrene , Methyl acrylate-sulfonated styrene copolymer, 2-phenyl-2-propyl dodecylbenzenesulfonic acid, dodecylbenzenesulfonic acid-2-
Phenyl-2-butyl, tetrabutylphosphonium octylsulfonate, tetrabutylphosphonium decylsulfonate, tetrabutylphosphonium benzenesulfonate, tetraethylphosphonium dodecylbenzenesulfonate, tetrabutylphosphonium dodecylbenzenesulfonate, dodecylbenzenesulfonate Acid tetrahexyl phosphonium salt, dodecyl benzene sulfonic acid tetraoctyl phosphonium salt, decyl ammonium butyl sulfate, decyl ammonium decyl sulfate, dodecyl ammonium methyl sulfate, dodecyl ammonium ethyl sulfate, dodecyl methyl ammonium methyl sulfate, dodecyl dimethyl ammonium tetradecyl sulfate, tetradecyl Dimethyl ammonium Chill sulfate, tetramethylammonium hexyl sulfate, decyltrimethylammonium hexadecyl sulfate, tetrabutylammonium dodecylbenzyl sulfate, tetraethylammonium dodecylbenzyl sulfate, there may be mentioned compounds such as tetramethylammonium dodecylbenzyl sulfate, and the like. Two or more of these compounds can be used in combination.

Among the deactivators, those of the phosphonium salt or ammonium salt type are preferred. The amount of such a catalyst is preferably 0.5 to 50 mol based on 1 mol of the remaining catalyst, and 0.01 to 500 ppm, more preferably 0 to 500 ppm, based on the polycarbonate resin after polymerization. 0.01 to 300 ppm, particularly preferably 0.01 to 100 ppm.

Although the molecular weight of the polycarbonate resin is not specified, if the molecular weight is less than 10,000, the high-temperature properties and the like will be reduced, and if it exceeds 50,000, the moldability will be reduced. 10,00
0 to 50,000 are preferred, and 14,000 to 3
Particularly preferred are those having a molecular weight of 0000. Also, two or more polycarbonate resins may be mixed. In the present invention, the viscosity average molecular weight is determined by first calculating the specific viscosity calculated by the following equation using 100 ml of methylene chloride and 0.1% of polycarbonate resin.
Using a Ostwald viscometer from a solution prepared by dissolving 7 g at 20 ° C., specific viscosity (η _SP ) = (t−t ₀ ) / t ₀ [t ₀ is the number of seconds during which methylene chloride falls, and t is the drop of the sample solution. Seconds] The obtained specific viscosity is inserted by the following equation to obtain the viscosity average molecular weight M
Ask for. η _SP /c=[η]+0.45×[η] ² c (where [η]
Is the intrinsic viscosity) [η] = 1.23 × 10 ⁻⁴ M ^0.83 c = 0.7

The aromatic polycarbonate of the component (a) of the present invention is the above-mentioned aromatic polycarbonate resin and contains substantially no halogen atom. Substantially not containing a halogen atom means that it does not contain a halogen-substituted dihydric phenol or the like, and is intended to include trace amounts of chlorine-based solvents remaining in the above-mentioned method for producing an aromatic polycarbonate, even carbonate precursors and the like. is not.

As the component b of the present invention, the following GPC
(Organic siloxane having an aromatic group and having a weight average molecular weight of 300 to 2,000 measured by a (gel permeation chromatography) method is used. More preferably, the weight average molecular weight is from 400 to 1,000, and still more preferably from 400 to 800. The present invention relates to such b
By using the component, a synergistic action with the component c and the component d, which cannot be obtained with other organosiloxane compounds, is exhibited.
The object of the present invention is achieved by enabling the amount of components to be reduced.

The G used for the measurement of the component b of the present invention
The PC method is based on the following conditions. That is, temperature 2
Using a GPC measuring device placed in a clean air environment at 3 ° C. and a relative humidity of 50%, MIXED-C (length 300 mm, inner diameter 7.5 mm) manufactured by Polymer Laboratories as a column, chloroform as a mobile phase, standard Easycal P manufactured by Polymer Laboratories
Using a differential refractometer as a detector and chloroform as a developing solvent, 100 μl of a solution obtained by dissolving 1 mg of a sample per 1 ml of the chloroform was injected into a GPC measuring apparatus by 100 μl, and a column temperature of 35 ° C. and a flow rate were measured. GPC measurement is performed under the condition of 1 ml / min, and the weight average molecular weight of the component b is calculated.

Examples of the aromatic group contained in the component b include a phenyl group, a biphenyl group, a naphthalene group, and derivatives thereof, with a phenyl group being preferred. The content of the aromatic group is preferably at least 10 mol%, more preferably at least 20 mol% and at most 75 mol%, of the organic functional groups contained in the component b. The organic group other than the aromatic group is preferably a methyl group, and the terminal group is at least one selected from a methyl group, a phenyl group, a hydroxyl group, and an alkoxy group.
It is preferable that the number of species is two or more. More preferably, it contains an alkoxy group, especially a methoxy group. Further, the organosiloxane that is the component b of the present invention may be one in which a functional group such as an epoxy group, a carboxyl group, or a vinyl group is substituted. One or more of these organosiloxanes can be used in combination.

Examples of the fluorine-containing polymer having a fibril-forming ability used as the component c in the present invention include polytetrafluoroethylene, tetrafluoroethylene copolymers (eg, tetrafluoroethylene / hexafluoropropylene copolymer, etc.). ), U.S. Pat.
Examples include partially fluorinated polymers and polycarbonate resins produced from fluorinated diphenols as described in JP-A No. 0, preferably polytetrafluoroethylene.

Polytetrafluoroethylene having a fibril-forming ability is classified into Type 3 in the ASTM standard. Further, polytetrafluoroethylene having such a fibril-forming ability has a primary particle size of 0.1.
Those having a secondary particle diameter of 50 to 700 μm are preferred. Such a polytetrafluoroethylene has a drip-preventing performance at the time of a combustion test of a test piece in a vertical combustion test of UL standard, and such a polytetrafluoroethylene having a fibril-forming ability is, for example, Mitsui-Dupont Fluorochemical Co., Ltd. It is commercially available as Teflon 6J or as Polyflon from Daikin Chemical Industries, Ltd. and can be easily obtained.

In the case where such polytetrafluoroethylene (hereinafter sometimes referred to as PTFE) is blended, not only a usual solid form but also an aqueous dispersion form can be used. PT having such fibril-forming ability
FE improves the dispersibility in the resin, and it is also possible to use a PTFE mixture of the following forms in order to obtain better flame retardancy and mechanical properties.

First, a coagulated mixture of a PTFE dispersion and a dispersion of a vinyl polymer can be given. Specifically, JP-A-60-258263 discloses an average particle size of 0.0
A method of mixing a PTFE dispersion of 5 to 5 μm and a dispersion of a vinyl polymer, coagulating PTFE particles larger than 30 μm without purification, and drying the coagulated product to obtain a PTFE mixture is described. The use of such mixtures is possible.

Secondly, there can be mentioned a mixture obtained by mixing a PTFE dispersion and dried polymer particles, and various kinds of such polymer particles can be used, and more preferably, a polycarbonate resin powder is used. . Such a mixture is disclosed in JP-A-4-272957.
Japanese Patent Application Laid-Open Publication No. HEI 9-125114 describes a mixture of a PTFE dispersion and an ABS resin powder, and such a method can be used.

Third, a PTFE mixture obtained by simultaneously removing the respective media from the mixture of the PTFE dispersion and the thermoplastic resin solution can be mentioned. Specifically, the media can be obtained by using a spray drier. The removed mixture can be mentioned, and such a mixture is described in JP-A-08-188653. In particular, the use of an aromatic polycarbonate resin as the thermoplastic resin is preferred.

Fourth, a PTFE mixture obtained by polymerizing another vinyl monomer in a PTFE dispersion can be mentioned.
No. 5583 specifically describes a method of obtaining a PTFE mixture by supplying styrene and acrylonitrile into a PTFE latex, and such a mixture can be used.

Fifth, a method of mixing a PTFE dispersion and a polymer particle dispersion and then polymerizing a vinyl monomer in the mixed dispersion can be cited. Can be cited as a preferred PTFE mixture in terms of achieving both fine dispersion. The details of such a mixture are described in JP-A-11-29679, that is, a particle size of 0.05 to 1.
After emulsifying and polymerizing a monomer having an ethylenically unsaturated bond in a dispersion obtained by mixing a 0-μm PTFE dispersion and a polymer particle dispersion, a PTFE mixture pulverized by coagulation or spray drying may be mentioned. Can be. As the PTFE mixture of the fifth embodiment, METABLEN “A3000” (trade name) is commercially available from Mitsubishi Rayon Co., Ltd., and is easily available.

The at least one metal salt selected from the alkali metal salts and alkaline earth metal salts used as the component d in the present invention includes various kinds of metal salts conventionally used for flame retarding polycarbonate resins. Although metal salts can be used, mention may be made in particular of metal salts of organic sulfonic acids or metal salts of sulfates. These can be used alone or in combination of two or more. Incidentally, as the alkali metal of the present invention, lithium, sodium, potassium, rubidium, cesium may be mentioned, and as the alkaline earth metal, beryllium, magnesium, calcium, strontium, barium may be mentioned, and particularly preferably lithium, sodium, Potassium.

That is, according to the present invention, the a component 9
9.90 to 88.97% by weight, the above-mentioned component b 0.01 to 1
0% by weight, 0.05 to 1% by weight of the component c, and alkali metal salts of organic sulfonic acids, alkaline earth metal salts of organic sulfonic acids, alkali metal salts of sulfates, and alkaline earth salts of sulfates as the components d. At least one metal salt selected from the group consisting of metal salts 0.0005 to 0.03
A flame-retardant polycarbonate resin composition comprising at least 0.1% by weight of the components b, c and d, and 100% by weight of the total of the components a to d. .

According to the present invention, more preferably, the a component 9
9.70 to 93.9% by weight, 0.1% to 5% by weight of component b, 0.1% to 1% by weight of component c, and alkali metal salts of organic sulfonic acids and alkaline earth metals of organic sulfonic acids as component d At least one metal salt selected from the group consisting of a salt, an alkali metal salt of a sulfate ester, and an alkaline earth metal salt of a sulfate ester. Is 0.3% by weight
As described above, there is provided a flame-retardant polycarbonate resin composition in which the total of the components a to d is 100% by weight.

As the metal salt of the organic sulfonic acid of the present invention,
Examples thereof include alkali metal salts of aliphatic sulfonic acids, alkaline earth metal salts of aliphatic sulfonic acids, alkali metal salts of aromatic sulfonic acids, and alkaline earth metal salts of aromatic sulfonic acids. Preferred examples of such a metal salt of an aliphatic sulfonic acid include an alkali (earth) metal salt of an alkanesulfonic acid,
The alkali (earth) metal sulphonate in which a part of the alkyl group of the alkali (earth) metal alkanesulfonate is substituted with a fluorine atom, and the alkali (earth) metal perfluoroalkanesulfonate may be mentioned. These can be used alone or in combination of two or more. (Here, the notation of an alkali (earth) metal salt is used to mean both an alkali metal salt and an alkaline earth metal salt.) Do).

Preferred examples of the alkanesulfonic acid used for the alkali (earth) metal salt of the alkanesulfonic acid include methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, methylbutanesulfonic acid, hexanesulfonic acid, Heptanesulfonic acid, octanesulfonic acid and the like can be mentioned, and these can be used alone or in combination of two or more. Further, a metal salt in which a part of such an alkyl group is substituted with a fluorine atom can also be mentioned.

On the other hand, preferred examples of perfluoroalkanesulfonic acid include perfluoromethanesulfonic acid,
Perfluoroethanesulfonic acid, perfluoropropanesulfonic acid, perfluorobutanesulfonic acid, perfluoromethylbutanesulfonic acid, perfluorohexanesulfonic acid, perfluoroheptanesulfonic acid, perfluorooctanesulfonic acid, etc. Is 1
To 8 are preferred. These can be used alone or in combination of two or more.

As such an alkali (earth) metal salt of an alkanesulfonic acid, sodium ethanesulfonate is exemplified by an alkali (earth) perfluoroalkanesulfonic acid.
As the metal salt, potassium perfluorobutanesulfonate can be preferably mentioned.

The aromatic sulfonic acid used in the alkali (earth) metal salt of an aromatic sulfonic acid includes monomeric or polymeric sulfonic acid of aromatic sulfide, sulfonic acid of aromatic carboxylic acid and ester, monomeric or Polymeric aromatic ether sulfonic acid, aromatic sulfonate sulfonic acid, monomeric or polymeric aromatic sulfonic acid, monomeric or polymeric aromatic sulfonic sulfonic acid, aromatic ketone sulfonic acid, heterocyclic At least one acid selected from the group consisting of sulfonic acids, sulfonic acids of aromatic sulfoxides, and condensates of aromatic sulfonic acids by methylene-type bonds can be given, and these can be used alone or in combination of two or more. Can be used.

The alkali (earth) metal sulfonate metal salt of a monomeric or polymeric aromatic sulfide is described in JP-A-50-98539.
For example, disodium diphenylsulfide-4,4'-disulfonate, diphenylsulfide-4,4 '
-Dipotassium disulfonate.

As the alkali (earth) metal sulfonic acid salts of aromatic carboxylic acids and esters, JP-A-50-9
No. 8540, and examples thereof include potassium 5-sulfoisophthalate, sodium 5-sulfoisophthalate, and polysodium polyethylene terephthalate polysulfonate.

The alkali (earth) metal sulfonate of a monomeric or polymeric aromatic ether is described in JP-A-50-98542, for example, calcium 1-methoxynaphthalene-4-sulfonate. ,
Disodium 4-dodecylphenyl ether disulfonate, poly (2,6-dimethylphenylene oxide) polysodium sulfonate, poly (1,3-phenylene oxide) polysodium sulfonate, poly (1,1
4- (phenylene oxide) polysodium polysulfonate, poly (2,6-diphenylphenylene oxide) polypotassium polysulfonate, poly (2-fluoro-6-
Butylphenylene oxide) lithium polysulfonate and the like.

The alkali (earth) sulfonate metal salt of an aromatic sulfonate is described in JP-A-50-98544, and examples thereof include potassium sulfonate of benzene sulfonate.

The monomeric or polymeric alkali (earth) metal salts of aromatic sulfonic acids are disclosed in
No. 98546, for example, sodium benzenesulfonate, strontium benzenesulfonate, magnesium benzenesulfonate, dipotassium p-benzenedisulfonate, dipotassium naphthalene-2,6-disulfonate, biphenyl-3,3′-disulfone Calcium acid and the like can be mentioned.

The monomeric or polymeric alkali (earth) metal salts of aromatic sulfone sulfonates are described in JP-A-52-54746, and include, for example, sodium diphenylsulfon-3-sulfonate, diphenylsulfone Potassium-3-sulfonate, dipotassium diphenylsulfone-3,3'-disulfonate, dipotassium diphenylsulfon-3,4'-disulfonate, and the like can be given.

The alkali (earth) sulfonate metal salt of an aromatic ketone is described in JP-A-50-98547, and includes, for example, sodium α, α, α-trifluoroacetophenone-4-sulfonate, Benzophenone-3,3'-dipotassium dipotassium and the like can be mentioned.

The alkali (earth) metal salt of a heterocyclic sulfonic acid is described in JP-A-50-116542. For example, disodium thiophene-2,5-disulfonate, thiophene-2,5- Dipotassium disulfonate, calcium thiophene-2,5-disulfonate,
Examples thereof include sodium benzothiophene sulfonate.

The alkali (earth) metal sulfonate metal salt of aromatic sulfoxide is described in JP-A-52-54545, and examples thereof include potassium diphenylsulfoxide-4-sulfonate. .

Examples of the condensate of an alkali (earth) metal aromatic sulfonate by a methylene type bond include a formalin condensate of sodium naphthalenesulfonate and a formalin condensate of sodium anthracene sulfonate.

On the other hand, examples of the alkali (earth) metal salts of sulfates include alkali (earth) metal salts of sulfates of monohydric and / or polyhydric alcohols. Or, as sulfates of polyhydric alcohols, methyl sulfate, ethyl sulfate, lauryl sulfate, hexadecyl sulfate, polyoxyethylene alkyl phenyl ether sulfate, pentaerythritol mono,
Examples thereof include di, tri, tetrasulfate, sulfate of monoglyceride laurate, sulfate of monoglyceride palmitate, and sulfate of monoglyceride stearate. Preferred examples of the alkali (earth) metal salt of these sulfates include alkali (earth) metal salts of lauryl sulfate.

Examples of other alkali (earth) metal salts include alkali (earth) metal salts of aromatic sulfonamides, such as saccharin, N- (p-tolylsulfonyl) -p-toluenesulfonate. Imide, N-
(N'-benzylaminocarbonyl) sulfanylimide, and alkali (earth) metal salts of N- (phenylcarboxyl) sulfanylimide.

Of the above-mentioned d components, more preferred alkali (earth) metal salts include alkali (earth) metal salts of aromatic sulfonic acids and alkali (earth) metal salts of perfluoroalkanesulfonic acids. Can be mentioned.

That is, in a preferred embodiment of the present invention, 99.90 to 88.97% by weight of the component a, 0.01 to 10% by weight of the component b, 0.05 to 1% by weight of the component c,
And an alkali metal salt of an aromatic sulfonic acid as the d component,
At least one metal salt selected from the group consisting of alkaline earth metal salts of aromatic sulfonic acids, alkali metal salts of perfluoroalkanesulfonic acids, and alkaline earth metal salts of perfluoroalkanesulfonic acids 0.0005 to 0.03
A flame-retardant polycarbonate resin composition comprising at least 0.1% by weight of the components b, c and d, and 100% by weight of the total of the components a to d. .

More preferably, according to the present invention, 99.70 to 93.9% by weight of the above-mentioned component a and 0.1 to 93.9% by weight of the above-mentioned component b.
5% by weight, 0.1 to 1% by weight of component c, and alkali metal salt of aromatic sulfonic acid, alkaline earth metal salt of aromatic sulfonic acid, alkali metal salt of perfluoroalkanesulfonic acid, and B. At least one metal salt selected from the group consisting of alkaline earth metal salts of fluoroalkanesulfonic acids, in an amount of 0.001 to 0.01% by weight;
A flame-retardant polycarbonate resin composition is provided in which the sum of components, c and d is 0.3% by weight or more, and the sum of components a to d is 100% by weight.

Next, the composition ratio of each component will be described. The blending ratio of the aromatic polycarbonate resin used as the component a in the present invention is such that the proportion of the aromatic group-containing organic siloxane having a specific molecular weight, which is the component b of the present invention, in the total of 100% by weight of the components a to d. as,
0.01 to 10 in a total of 100% by weight of the components a to d
%, Preferably 0.1 to 5% by weight. More preferably, it is 0.5 to 3% by weight. When the proportion of the component b is less than 0.01% by weight, the flame retardancy is insufficient,
If it exceeds 10% by weight, the strength such as heat resistance and impact resistance will be reduced.

The proportion of the fluorine-containing polymer having fibril-forming ability as the component c is 1 in total of the components a to d.
0.05 to 1% by weight, preferably 0.1 to
It is 0.7% by weight, more preferably 0.1 to 0.5% by weight. When the blending ratio of the component c is less than 0.05% by weight, the flame retardancy is insufficient, and when it exceeds 1% by weight, no improvement in the flame retardancy is observed, and a decrease in the impact resistance and the like is observed. large.

The proportion of the d component is 0.0005 to 0.03% by weight, preferably 0.001 to 0.02% by weight, more preferably 0.001 to 0.03% by weight based on 100% by weight of the total of the components a to d. 0.01% by weight. If the added amount of the metal salt is less than 0.0005% by weight (5 ppm), the flame retardancy is not sufficient, and if it exceeds 0.03% by weight, the wet heat property is greatly reduced and the heat stability is low. The decomposition reaction easily proceeds during melt-kneading, and the appearance and strength are significantly reduced.

The total amount of the component (b), component (c) and component (d) must be at least 0.1% by weight based on 100% by weight of the total of the components (a) to (d). 0.3% by weight or more, particularly preferably 0.35%
% By weight or more and 2% by weight or less. When the total amount of the components b to d is less than 0.1% by weight, the flame retardancy becomes insufficient.

The flame-retardant polycarbonate resin composition of the present invention may contain polyethylene, polypropylene,
It is also possible to mix other thermoplastic resins such as polystyrene, ABS resin, polyethylene terephthalate, polybutylene terephthalate, polyamide, acrylic resin, and polyarylate.

The flame-retardant polycarbonate resin composition of the present invention may optionally contain a release agent.
Since the present invention has good flame retardancy, good flame retardancy can be achieved even when a release agent that usually has a bad influence on flame retardancy is added. Such release agents include saturated fatty acid esters, for example, monoglycerides such as stearic acid monoglyceride, decaglycerin decastearate, polyglycerin fatty acid esters such as tetraglycerin pentastearate,
Lower fatty acid esters such as stearic acid stearate,
Higher fatty acid esters such as sebacic acid behenate and erythritol esters such as pentaerythritol tetrastearate can be used. Other release agents include olefin waxes, silicone oils other than the component b, silicone varnishes other than the component b, fluorine oil, paraffin wax, beeswax, etc. Among these, saturated fatty acid esters, b Silicone oil other than the component, silicone varnish other than the component b, and fluorine oil can be exemplified. As the silicone oil other than the component b and the silicone varnish other than the component b, those containing an aromatic group, particularly 20 mol% or more, preferably 40 mol% or more and 95 mol% of the organic group.
Hereinafter, those having an aromatic group are preferable, and those having a phenyl group are particularly preferable. In addition, examples of the fluorine oil include perfluoroalkyl ether. Such a release agent is preferably used in an amount of 0.01 to 0.3 parts by weight based on 100 parts by weight of the total of the components a to d.

Further, a phosphorus-based heat stabilizer can be added to the flame-retardant polycarbonate resin composition of the present invention, if necessary. As the phosphorus-based heat stabilizer, a phosphite compound and a phosphate compound are preferably used.
Examples of the phosphite compound include triphenyl phosphite, trisnonylphenyl phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, and dioctadecyl phosphite. Decyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, bis (2,6-di-tert-butyl-4-) Methylphenyl) pentaerythritol diphosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl)
Octyl phosphite, bis (nonylphenyl) pentaerythritol diphosphite, bis (2,4-di-t
phosphite compounds such as tert-butylphenyl) pentaerythritol diphosphite. Of these, tris (2,4-di-tert-butylphenyl) phosphite is preferably used from the viewpoint of flame retardancy and wet heat resistance.

On the other hand, examples of the phosphate compound used as a heat stabilizer include tributyl phosphate,
Trimethyl phosphate, tricresyl phosphate,
Triphenyl phosphate, trichlorophenyl phosphate, triethyl phosphate, diphenylcresyl phosphate, diphenyl monoorthoxenyl phosphate, tributoxyethyl phosphate, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate and the like, among which triphenyl phosphate, trimethyl phosphate preferable.

Further, other phosphorus-based heat stabilizers include tetrakis (2,4-di-tert-butylphenyl)-
4,4'-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,3 '
-Biphenylenediphosphonite, tetrakis (2,4-
Phosphonite compounds such as di-tert-butylphenyl) -3,3′-biphenylenediphosphonite and bis (2,4-di-tert-butylphenyl) -4-biphenylenediphosphonite are also flame-retardant and resistant to moist heat. It can be preferably used from the viewpoint of characteristics.

The phosphorus-based heat stabilizers may be used alone or in combination of two or more. The phosphorus-based heat stabilizer is used in an amount of 0.0001 to 0.0001 parts by weight based on a total of 100 parts by weight of the components a to d of the present invention.
0.5 parts by weight, more preferably 0.005 to 0.3 parts by weight.

The flame-retardant polycarbonate resin composition of the present invention may optionally contain a conventionally known antioxidant. Examples thereof include phenolic antioxidants, specifically, for example, triethylene glycol-bis (3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate),
1,6-hexanediol-bis (3- (3,5-di-
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, 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. The preferable range of the addition amount of these antioxidants is 0.0001 to 0.5 part by weight, more preferably 0.001 to 0.3 part by weight, based on 100 parts by weight of the total of the components a to d. is there.

The flame-retardant polycarbonate resin composition of the present invention may further contain, if necessary, an ultraviolet absorber or a light stabilizer. Examples of the ultraviolet absorber include a benzophenone-based ultraviolet absorber represented by, for example, 2,2′-dihydroxy-4-methoxybenzophenone, and, for example, 2- (3-tert-butyl-5-methyl-2)
-Hydroxyphenyl) -5-chlorobenzotriazole, 2- (3,5-di-tert-butyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2,
2'-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazole-2-
Yl) phenol], 2- [2-hydroxy-3,5-
Bis (α, α-dimethylbenzyl) phenyl] -2H-
Benzotriazole and 2- (3,5-di-tert)
Examples thereof include benzotriazole-based ultraviolet absorbers represented by (amyl-2-hydroxyphenyl) benzotriazole. Further, bis (2,2,6,6-tetramethyl-
4-piperidyl) sebacate, bis (1,2,2,6)
Hindered amine light stabilizers such as 6-pentamethyl-4-piperidyl) sebacate can also be used. These can be used alone or in combination of two or more. The preferable range of the addition amount of these ultraviolet absorbers and light stabilizers is 0.0001 to 1 part by weight, preferably 0.00 to 100 parts by weight of the total of the components a to d.
1 to 0.5 parts by weight.

The flame-retardant polycarbonate resin composition of the present invention may optionally contain a bluing agent for the purpose of improving color tone and the like. As a specific bluing agent, for example, a common name Solvent Violet
t13 [CA. No (color index No) 607
25; Trade name “Macrolex Violet B” manufactured by Bayer, “Diaresin Blue G” manufactured by Mitsubishi Chemical Corporation, “Sumiplast Violet B” manufactured by Sumitomo Chemical Co., Ltd.], and generic name Solvent Violet 31
[CA. No. 68210; Trade name “Diaresin Violet D” manufactured by Mitsubishi Chemical Corporation], generic name Solve
nt Violet 33 [CA. No. 60725; Trade name “Diaresin Blue J” manufactured by Mitsubishi Chemical Corporation], generic name Solvent Blue 94 [CA. No615
00; trade name “Diaresin Blue N” manufactured by Mitsubishi Chemical Corporation], generic name Solvent Violet 36 [C
A. No. 68210; brand name “Macrolex Violet 3R” manufactured by Bayer AG], generic name Solvent
Blue97 [trade name “Macrolex Blue RR” manufactured by Bayer AG] and generic name Solvent Blue
45 [CA. No. 61110; Trade name “Tetrazol Blue RLS” manufactured by Sando Co., Ltd.], Ciba Specialty
Examples include Macrolex Violet and Triazole Blue RLS of Chemicals.

If necessary, the flame-retardant polycarbonate resin composition of the present invention may further contain other conventional additives such as reinforcing agents (talc, mica, clay, wollastonite, calcium carbonate, glass fiber, glass beads). , Glass balloon, milled fiber, glass flake, carbon fiber, carbon flake, carbon beads, carbon milled fiber, metal flake, metal fiber, metal coated glass fiber,
Metal coated carbon fiber, metal coated glass flake, silica, ceramic particles, ceramic fiber, aramid particles,
Aramid fibers, polyarylate fibers, graphite, conductive carbon black, various whiskers, etc.), coloring agents (pigments and dyes such as carbon black and titanium oxide),
Light diffusing agents (crosslinked acrylic particles, crosslinked silicon particles, ultra-thin glass flakes, calcium carbonate particles, etc.), fluorescent brighteners, luminous pigments, fluorescent dyes, antistatic agents, flow modifiers, nucleating agents, inorganic and organic Antibacterial agents, photocatalytic antifouling agents (fine-particle titanium oxide, fine-particle zinc oxide, etc.), impact modifiers represented by graft rubber, infrared absorbers, and photochromic agents as long as the object of the present invention is not impaired. it can.

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

In addition, a method of independently supplying the components a to d and optionally other components to a melt kneader typified by a vented twin-screw ruder, wherein a part of the components a to d was premixed After that, a method of supplying the remaining components independently to the melt kneader, after diluting and mixing the components b and d with water or an organic solvent, supplying the melt kneader or premixing the diluted mixture with other components Thereafter, a method of supplying the mixture to a melt kneader may be used. Further, when a dispersion type component is used as the component c, it is appropriate to adopt a method of mixing the component c and the component d. In addition, when there is a liquid component to be blended, a so-called liquid injection device or liquid addition device can be used for supply to the melt kneader.

The flame-retardant polycarbonate resin composition of the present invention is generally prepared by a method generally used in industry, such as a method of producing a molded product by injection molding a pellet comprising the flame-retardant polycarbonate resin composition of the present invention. It can be manufactured by appropriately using it. 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 the injection molding, not only a normal molding method but also gas assist injection molding, injection compression 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 for various shaped extruded products, sheets, films and the like by extrusion. Further, for forming a sheet or a film, an inflation method or a casting method can be used. Furthermore, it is also possible to form a heat-shrinkable tube by performing a specific stretching operation. Further, the flame-retardant polycarbonate resin composition of the present invention can be formed into a molded product by rotational molding without melt-kneading.

[0091]

The present invention will be further described below with reference to examples, but the present invention is not limited thereto. The following items were evaluated. (1) Material characteristics (1-) Flame retardancy Thicknesses 1.2 mm and 1.0 m prepared according to UL standards
The test was performed using m test pieces. Based on the result of the test, it was rated as one of UL-94V-0, V-1 and V-2. (1-) Impact resistance (Izod impact strength with notch) Thickness 1 / according to ASTM standard D-256
The test was carried out using an 8 ″ test piece. (1-) Moisture / heat resistance (Izod impact strength with notch) Thickness 1 / made according to ASTM standard D-256
8 ”, the test piece after the notch cutting process was immersed in a hot water immersion tester at 93 ° C. for 48 hours, and the test piece was taken out.
After an hour, an Izod impact test was performed. The Izod impact strength retention was calculated according to the following equation.

[0092]

(Equation 1)

(1) Thermal Stability During molding, the resin was kept at a cylinder temperature of 290 ° C. for 15 minutes, and then the appearance of the molded product was evaluated by the following method to evaluate the thermal stability of the material. ：: No appearance defect such as silver occurred x: Appearance defect occurred such as silver

(2) Measurement of Molecular Weight of Organosiloxane A Gulliver series manufactured by JASCO Corporation was used as a measuring apparatus, and MIXE manufactured by Polymer Laboratories was used as a column under a clean air environment of a temperature of 23 ° C. and a relative humidity of 50%.
DC (length 300 mm, inner diameter 7.5 mm), chloroform as a mobile phase, Easycal PS-2 manufactured by Polymer Laboratories as a standard substance, and a differential refractometer as a detector, and chloroform as a developing solvent. Then, 100 μl of a solution in which 1 mg of a sample was dissolved per 1 ml of chloroform was injected into a GPC measuring apparatus, GPC measurement was performed under the conditions of a column temperature of 35 ° C. and a flow rate of 1 ml / min, the molecular weight of the organosiloxane was measured, and the weight average molecular weight was measured. Was calculated.

[Examples 1 to 15 and Comparative Examples 1 to 8] The raw materials shown in Tables 1, 2 and 3 were blended in a tumbler in an amount (expressed in% by weight) shown in Tables 1 to 3 to give a diameter. In a 30mm biaxial rudder [Kobe Steel, Ltd. KTX-30]
Extruded at a cylinder temperature of 280 ° C. to obtain pellets. The obtained pellets were dried at 110 ° C. for 5 hours with a hot air circulation type drier, and were injected with an injection molding machine [FANUC T-150 Co., Ltd.].
D], a test piece was formed at a cylinder temperature of 290 ° C. and a mold temperature of 70 ° C.

The raw materials and the like used in Tables 1 to 3 are as follows. (A component) PC-1: linear aromatic polycarbonate resin (viscosity average molecular weight 2 produced from bisphenol A and phosgene)
PC-2: Branched aromatic polycarbonate resin (Teflon IB2500 manufactured by Idemitsu Petrochemical Co., Ltd.)

(B component) Si-1: an organic siloxane having a phenyl group content of 30 mol% of the whole organic group and a weight average molecular weight of 750 measured by the GPC method of the above (2) (Shin-Etsu Chemical Co., Ltd.) (KR-219 manufactured by K.K.) Si-2: An organic siloxane having a phenyl group content of 37 mol% of the whole organic group and a weight average molecular weight of 630 measured by the GPC method in the above (2) (Shin-Etsu Chemical Co., Ltd.) Industrial Co., Ltd.
X-40-9243) (other than component b) Si-2: does not contain a phenyl group, and has the above-mentioned (2) GPC
Polydimethylsiloxane having a weight average molecular weight of 500 as measured by the method of Si-3: The content of the phenyl group is 65 mol% of the whole organic groups, and the weight average molecular weight as measured by the GPC method of the above (2) is 61200. An organic siloxane (XC99-B5664 manufactured by GE Toshiba Silicone Co., Ltd.)

(C component) PTFE: Polytetrafluoroethylene having fibril-forming ability (Polyflon FA manufactured by Daikin Industries, Ltd.)
-500)

(D component) Metal salt 1: Perfluorobutanesulfonic acid potassium salt (Megafac F-1 manufactured by Dainippon Ink and Chemicals, Inc.)
14) Metal salt 2: potassium diphenylsulfonate (KSS manufactured by UCB Japan)

(Other Components) S-1: Phosphite antioxidant (IRGAFOS168 manufactured by Ciba-Geigy Japan) S-2: Phosphonite antioxidant (Sands
oz) Sandstab P-EPQ) L-1: Saturated fatty acid ester release agent (Rikemar SL900, manufactured by RIKEN VITAMIN CO., LTD.) L-2: Silicone release agent (Dow Corning Toray)
L-3: Fluorine-based release agent (Demnam S-100, manufactured by Daikin Industries, Ltd.)

[0101]

[Table 1]

[0102]

[Table 2]

[0103]

[Table 3]

The following is clear from these tables. From the comparison between Example 1 and Comparative Example 1 and Comparative Example 8, and Example 5 and Comparative Example 2, the polycarbonate resin composition obtained by using an organic siloxane other than the component b of the present invention has a low flame retardancy. It turns out that they are not satisfied. Further, from the comparison between Example 4 and Comparative Example 4, it can be seen that extremely good flame retardancy is achieved when PTFE of the component c is added. From the comparison between Example 1 and Comparative Example 5, it can be seen that extremely good flame retardancy is achieved by adding an alkali metal salt or the like.

[0105]

As is clear from the above, the flame-retardant polycarbonate resin composition of the present invention is excellent in flame retardancy in a thin-walled molded product, and has high impact resistance, wet heat resistance and heat resistance inherent to the polycarbonate resin. Because it has stability,
It is extremely useful for various industrial uses such as the A-apparatus field and the electric / electronic field, and the industrial effects achieved are extremely large.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4J002 BD153 BD163 CG011 CG021 CP032 EV186 EV256 FD010 FD050 FD060 FD070 FD090 FD160

Claims (4)

[Claims] 1. An aromatic polycarbonate resin substantially free of halogen atoms (component (a)) 99.90 to 88.9.
7% by weight, an organic siloxane having an aromatic group having a weight average molecular weight of 300 to 2,000 measured by GPC (gel permeation chromatography) described in the text and having an aromatic group (component b) 0.01 to 10% by weight %, A fluorine-containing polymer having fibril-forming ability (component (c)) 0.05
And at least one metal salt selected from an alkali metal salt and an alkaline earth metal salt (component (d)) 0.0005 to 0.03% by weight;
the total amount of component c and component d is at least 0.1% by weight
The flame-retardant polycarbonate resin composition as described above, wherein the total of the components a to d is 100% by weight. 2. Component a, 99.70 to 93.9% by weight,
Component b is 0.1 to 5% by weight, component c is 0.1 to 1% by weight, and component d is 0.001 to 0.01% by weight, and the total amount of component b, component c and component d is 0.3. 2. The flame-retardant polycarbonate resin composition according to claim 1, wherein the total amount of the components a to d is 100% by weight or more. 3. 3. The component (d) is at least one selected from alkali metal salts of organic sulfonic acids, alkaline earth metal salts of organic sulfonic acids, alkali metal salts of sulfates, and alkaline earth metal salts of sulfates. The flame-retardant polycarbonate resin composition according to claim 1, which is a metal salt. 4. The component d is an alkali metal salt of an aromatic sulfonic acid, an alkaline earth metal salt of an aromatic sulfonic acid, an alkali metal salt of a perfluoroalkanesulfonic acid, or an alkaline earth metal of a perfluoroalkanesulfonic acid. 4. At least one metal salt selected from salts.
3. The flame-retardant polycarbonate resin composition according to item 1.