JP2002060612A - Flame-retardant aromatic polycarbonate resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a flame-retardant aromatic polycarbonate resin composition excellent in mold release properties and also excellent in flame retardancy in a thin-walled portion. SOLUTION: The flame-retardant aromatic polycarbonate resin composition comprises 94-99.979 wt.% of an aromatic polycarbonate resin (component (a)), 0.001-1 wt.% of at least one compound (component (b)) selected from an organic alkali metal salt and an organic alkaline earth metal salt, 0.01-2 wt.% of a fluorine-containing polymer (component (c)) having fibril-forming ability and 0.01-3 wt.% of a specific silicone compound (component (d)) bearing an Si-H bond and having a viscosity of 150 mm2/sec or lower at 25 deg.C in 100 wt.% of the total of the components (a), (b), (c) and (d).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flame-retardant aromatic polycarbonate resin composition having excellent release properties and excellent flame retardancy in a thin portion.

[0002]

2. Description of the Related Art Aromatic polycarbonate resins are formed into various molded products by a simple and excellent productivity processing method such as injection molding, and are used in a wide range of industrial fields. Also,
A flame-retardant aromatic polycarbonate resin composition obtained by adding a halogen-based compound or a phosphorus-based compound to an aromatic polycarbonate resin has been used for OA equipment, home electric appliances, and the like, for which there is a strong demand for flame retardancy. However, on the other hand, flame-retardant aromatic polycarbonate resin compositions replacing these flame retardants have been developed and are being used in the above-mentioned products and the like. The purpose of such a change in the flame retardant is to suppress the generation of corrosive gas during molding or to improve the recyclability of products.

[0003] As a flame retardant in place of the flame retardant mentioned above, for example, a silicone compound can be mentioned. In recent years, flame-retardant resin compositions in which a silicone compound is blended with an aromatic polycarbonate resin have been energetically studied, and various proposals have been made.

For example, a method of blending an alkali (earth) metal salt of perfluoroalkanesulfonic acid with an organic siloxane having an alkoxy group, a vinyl group and a phenyl group in a polycarbonate resin (Japanese Patent Laid-Open No. 6-306265); A method of blending an alkali metal salt or an alkaline earth metal salt of perfluoroalkanesulfonic acid with an organopolysiloxane containing an organooxysilyl group bonded to a silicon atom through a divalent hydrocarbon group (Japanese Patent Laid-Open No. 6-336546) Gazette) has been proposed.

[0005] Further, a method of blending a silicone compound with a specific petroleum heavy oil or pitch in a resin component (JP-A-9-169914), and a method in which a non-silicone resin having an aromatic ring has the formula R ₂ SiO _1.0 Units and RS
It has a unit represented by iO _1.5 and has a weight average molecular weight of 1
A method of compounding a silicone resin having a molecular weight of from 000 to 270,000 (JP-A-10-139964)
And so on.

On the other hand, the polycarbonate resin has a relatively high affinity for the mold and a relatively low molding shrinkage, so that the releasability from the mold is not sufficient. Therefore, in a polycarbonate resin or a composition thereof, a release agent such as a saturated fatty acid ester or an olefin wax is generally blended.

However, when such a flame-retardant resin composition is blended with such a release agent for the purpose of improving the releasability from a mold at the time of molding, a thickness of 1.0 mm
Flame retardancy in thin parts such as the following tended to decrease.

[0008] JP-A-6-306265, JP-A-6-306265
The silicone compounds proposed in JP-A-333647, JP-A-9-169914, JP-A-10-139964 and the like have not yet obtained a sufficient releasing effect.

[0009]

SUMMARY OF THE INVENTION An object of the present invention is to provide a flame-retardant aromatic polycarbonate resin composition which is excellent in releasability and flame retardancy in a thin portion.

The present inventors have conducted intensive studies in order to achieve the above object, and as a result, have found that at least one compound selected from aromatic polycarbonate resins, organic alkali metal salts and organic alkaline earth metal salts, and fibril-forming ability. The present inventors have found that a desired flame-retardant aromatic polycarbonate resin having excellent releasability can be obtained by combining a specific amount of a fluorine-containing polymer and a specific silicone compound.

[0011]

Means for Solving the Problems The present invention provides the following component a:
94 to 99.979% by weight of an aromatic polycarbonate resin in a total of 100% by weight of the components b, c and d
(A component), at least one compound selected from organic alkali metal salts and organic alkaline earth metal salts (b
Component) 0.001 to 1% by weight, a fluoropolymer having fibril-forming ability (Component c) 0.01 to 1% by weight, and a viscosity at 25 ° C represented by the following general formulas (1) and (2) of 150 mm ² The present invention relates to a flame-retardant aromatic polycarbonate resin composition containing 0.01 to 0.8% by weight of a silicone compound (component (d)) of not more than / sec.

[0012]

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[0013]

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(In the formulas (1) and (2), Z ^{1 to} Z ⁶ each independently represent a hydrogen atom, a monovalent organic residue having 1 to 20 carbon atoms, or the following general formula (3) Α1 to α6 each independently represent 0 or 1. R ^{1 to} R ⁴ each independently represent a monovalent organic residue having 1 to 20 carbon atoms, and m1 represents an integer of 0 or more. , M2 is 3
Represents the above integer. Furthermore, the compounds of the formulas (1) and (2) each have at least one or more Si—H bond, and in the formula (1), when m1 is 2 or more, the repeating units are different from each other. You can take units. The repeating unit in the formula (2) can take a plurality of different repeating units. )

[0015]

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(In the formula (3), Z ^{7 to} Z ⁹ each independently represent a hydrogen atom or a monovalent organic residue having 1 to 20 carbon atoms. Α
7 to α9 each independently represent 0 or 1. Also R
⁵ and R ⁶ each independently represent a monovalent organic residue having 1 to 20 carbon atoms. m3 represents an integer of 0 or more. Further, in formula (3), when m3 is 2 or more, the repeating unit can take a plurality of different repeating units. )

The aromatic polycarbonate resin used as the component (a) in the present invention is usually obtained by reacting a dihydric phenol with a carbonate precursor by an interfacial polycondensation method or a melt transesterification method. 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 here 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, haloformate and the like are 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 an interfacial polycondensation method or a melt transesterification method, if necessary, a catalyst, a terminal stopper and an oxidation of the dihydric phenol may be carried out. Antioxidants or the like may be used to prevent the occurrence of oxidization. Further, even if the polycarbonate resin is a branched polycarbonate resin obtained by copolymerizing a trifunctional or higher polyfunctional aromatic compound,
A polyester carbonate resin obtained by copolymerizing an aromatic or aliphatic bifunctional carboxylic acid may be used,
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 a polyfunctional compound which produces such a branched polycarbonate resin is contained, 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 addition, particularly in the case of the melt transesterification method, a branched structure may be generated as a side reaction, and the amount of such a branched structure is also 0.001 to 1 mol%, preferably 0.005 to 5 mol%, of the total amount of the aromatic polycarbonate.
0.5 mol%, particularly preferably 0.01 to 0.3 mol%
Is preferred. The ratio is ¹ H
-It can be calculated by 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. Examples of the acid binder include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide and amine compounds such as pyridine.
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 tertiary amine such as triethylamine, tetra-n-butylammonium bromide and tetra-n-butylphosphonium bromide, a quaternary ammonium compound, and 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, and such monofunctional phenols are generally phenols or lower alkyl substituted phenols,
Monofunctional phenols represented by the following general formula (4) can be shown.

[0026]

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(Wherein A is a hydrogen atom or a carbon number of 1 to 9)
Wherein 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, 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 set at 1.33 × 10 ³ -1.
The distillation of alcohol or phenol generated by reducing the pressure to about 3.3 Pa is facilitated. 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 these polymerization catalysts used is preferably 1 × 10 ⁻⁸ to 1 × with ^respect to 1 mol of the starting dihydric phenol.
It is selected in the range of 10 ⁻³ equivalents, more preferably 1 × 10 ^{−7 to} 5 × 10 ⁻⁴ equivalents.

In order to reduce the number of phenolic terminal groups in the polymerization reaction, for example, bis (chlorophenyl) carbonate, bis (bromophenyl) carbonate, bis (nitrophenyl) carbonate may be used later or after completion of the polycondensation reaction. , Bis (phenylphenyl)
Carbonate, chlorophenylphenyl carbonate,
Compounds such as bromophenyl phenyl carbonate, nitro phenyl phenyl carbonate, phenyl phenyl carbonate, methoxy carbonyl phenyl phenyl carbonate and ethoxy carbonyl phenyl phenyl 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
It is preferably from 0 to 50,000, and from 14,000 to 3
000 is more preferable, and 1 is more preferable.
4,000 to 24,000. Also, two or more polycarbonate resins may be mixed. In this case, it is of course possible to mix with a polycarbonate resin having a viscosity average molecular weight outside the above range.

In particular, a mixture with a polycarbonate resin having a viscosity average molecular weight of more than 50,000 is preferred because it has a high drip prevention ability and more effectively exerts the effects of the present invention. More preferably, the viscosity average molecular weight is 80,
A mixture with 2,000 or more polycarbonate resins,
More preferably, it is a mixture with a polycarbonate resin having a viscosity average molecular weight of 100,000 or more. GPC (gel permeation chromatography)
Those having a molecular weight distribution of two or more peaks by such a method can be preferably used.

The viscosity-average molecular weight referred to in the present invention is determined by using an Ostwald viscometer from a solution obtained by dissolving 0.7 g of a polycarbonate resin in 100 ml of methylene chloride at 20 ° C. η _SP ) = (t−t ₀ ) / t ₀ [t ₀ is the number of seconds of falling methylene chloride, t is the number of seconds of falling of the sample solution] 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

As the organic alkali metal salt and organic alkaline earth metal salt used as the component b in the present invention, various metal salts conventionally used for making polycarbonate resins flame-retardant can be used. And especially 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.

The metal salt of the organic sulfonic acid of the present invention includes an alkali metal salt of an aliphatic sulfonic acid, an alkaline earth metal salt of an aliphatic sulfonic acid, an alkali metal salt of an aromatic sulfonic acid, and an alkali metal salt of an aromatic sulfonic acid. Earth metal salts and the like. Preferred examples of such an aliphatic sulfonic acid metal salt include an alkali (earth) metal alkanesulfonate and an alkali sulfonic acid in which a part of the alkyl group of the alkali (earth) metal alkanesulfonate is substituted with a fluorine atom. (Earth) metal salts, and alkali (earth) metal salts of perfluoroalkanesulfonic acid, and these can be used alone or in combination of two or more. Classification) The term metal salt is used to mean both alkali metal salts and alkaline earth metal salts.

Preferred examples of the alkanesulfonic acid used in the alkali (earth) alkanesulfonic acid metal salt 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 alkanesulfonate, sodium ethanesulfonate is exemplified by alkali (earth) perfluoroalkanesulfonate.
As the metal salt, potassium perfluorobutanesulfonate can be preferably mentioned.

The aromatic sulfonic acid used for the alkali (earth) metal salt of an aromatic sulfonic acid may be a monomeric or polymeric sulfonic acid of aromatic sulfide, a sulfonic acid of aromatic carboxylic acid and ester, a monomeric or sulfonic acid of ester. 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) sulfonic acid 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 salt of sulfonic acid of aromatic carboxylic acid and ester, JP-A-50-9
No. 8540, and examples thereof include potassium 5-sulfoisophthalate, sodium 5-sulfoisophthalate, and polysodium polyethylene terephthalate polysulfonate.

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

As a monomeric or polymeric alkali (earth) metal salt of an aromatic sulfonate, Japanese Patent Application Laid-Open No.
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 (salt) metal salts of aromatic sulfone sulfonates are described in JP-A-52-54746, and include, for example, sodium diphenylsulfonate-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) metal sulfonate metal salt of an aromatic ketone is described in JP-A-50-98547, for example, sodium α, α, α-trifluoroacetophenone-4-sulfonate, Benzophenone-3,3'-dipotassium dipotassium and the like can be mentioned.

The heterocyclic sulfonate alkali (earth) metal salt 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 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 naphthalene sulfonate 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 organic alkali (earth) metal salts include alkali (earth) metal salts of aromatic sulfonamides, such as saccharin, N- (p-tolylsulfonyl) -p-toluene. Sulfoimide, N-
(N'-benzylaminocarbonyl) sulfanylimide, and alkali (earth) metal salts of N- (phenylcarboxyl) sulfanylimide.

Of the above-mentioned organic alkali (earth) metal salts, alkali (earth) metal salts of aromatic sulfonsulfonic acid and alkali (earth) metal salt of perfluoroalkanesulfonic acid are more preferable components. Can be mentioned.

Examples of the fluorine-containing polymer having fibril-forming ability used as the component c in the present invention include polytetrafluoroethylene, tetrafluoroethylene copolymers (for example, 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.

The polytetrafluoroethylene having a fibril-forming ability is a powder obtained by coagulating and drying a latex obtained by emulsion polymerization of tetrafluoroethylene (a so-called fine powder of polytetrafluoroethylene, which is classified into type 3 in the ASTM standard). Classified). Alternatively, an aqueous dispersion (a so-called polytetrafluoroethylene dispersion) produced by adding a surfactant to the latex and concentrating and stabilizing the latex may be mentioned.

The molecular weight of the polytetrafluoroethylene having the ability to form fibrils is 1,000,000 to 10,000,000, more preferably 2,000,000 to 9,000,000 in terms of the number average molecular weight determined from the standard specific gravity.

Further, the polytetrafluoroethylene having a fibril-forming ability has a primary particle diameter of 0.05 to
It is preferably in the range of 1.0 μm, more preferably 0.1 to 0.5 μm. When fine powder is used, the secondary particle diameter can be 1 to 1000 μm, more preferably 10 to 500 μm.

Such polytetrafluoroethylene is UL
Polytetrafluoroethylene having a fibril-forming ability and having a fibril-forming ability in a standard vertical combustion test has a drip-preventing performance at the time of a combustion test of a test piece. For example, Mitsui-DuPont Fluorochemical Co., Ltd.
Teflon 6J and Teflon 30J manufactured by Daikin Chemical Industries, Ltd., polyflon MPA FA-500, polyflon F-201L and polyflon D-1 and CD076 manufactured by Asahi ICI Fluoropolymers Co., Ltd. .

As such polytetrafluoroethylene, fine powder that has been subjected to various treatments in order to prevent secondary agglomeration is more preferably used. As such a treatment, the surface of polytetrafluoroethylene may be calcined. In addition, as such a treatment, the surface of polytetrafluoroethylene having a fibril-forming ability may be coated with polytetrafluorotetrafluoroethylene having a non-fibril-forming ability.
More preferred in the present invention is polytetrafluoroethylene subjected to the latter treatment. In the former case, the intended fibril-forming ability tends to decrease. In such a case, the content of polytetrafluoroethylene having a fibril-forming ability is preferably in the range of 70 to 95% by weight of the total amount. The non-fibril-forming polytetrafluoroethylene has a molecular weight of 10,000 to 1,000,000, more preferably 1 to 10,000 in number average molecular weight determined from the standard specific gravity.
10,000 to 800,000.

Such polytetrafluoroethylene (hereinafter sometimes referred to as PTFE) may be in the form of an aqueous dispersion in addition to the solid as described above. Further, PTFE having such fibril-forming ability can use a PTFE mixture of the following forms in order to improve the dispersibility in a resin and 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 is described in which a PTFE dispersion of 5 to 5 μm is mixed with a dispersion of a vinyl polymer, PTFE particles larger than 30 μm are coagulated without purification, and the coagulated product is dried to obtain a PTFE mixture. The use of such mixtures is possible.

Secondly, a mixture obtained by mixing a PTFE dispersion and dried polymer particles can be mentioned. As such polymer particles, various types can be used, and more preferably, polycarbonate resin powder or ABS resin powder is used. It was done. For such a mixture, JP-A-4-272957 discloses a PTFE dispersion and ABS.
A mixture with a resin powder is described, 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.

Fourth, a PTFE mixture obtained by polymerizing another vinyl monomer in a PTFE dispersion can be mentioned.
Japanese Patent No. 5583 specifically describes a method for 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 exemplified. 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 1.0 μm.
In a dispersion obtained by mixing a m-PTFE dispersion and a polymer particle dispersion, a monomer having an ethylenically unsaturated bond is emulsion-polymerized, and then a PTFE mixture pulverized by coagulation or spray drying is preferable. It can be mentioned as.

Here, the polymer particles include a block copolymer composed of polypropylene, polyethylene, polystyrene, HIPS, AS resin, ABS resin, MBS resin, MABS resin, ASA resin, polyalkyl (meth) acrylate, styrene and butadiene. The hydrogenated copolymer, a block copolymer composed of styrene and isoprene, and the hydrogenated copolymer, an acrylonitrile-butadiene copolymer, a random copolymer and a block copolymer of ethylene-propylene, and a copolymer of ethylene-butene Random copolymer and block copolymer, copolymer of ethylene and α-olefin, copolymer of ethylene-unsaturated carboxylic acid ester such as ethylene-butyl acrylate, acrylate-butadiene copolymer, polyorgano Shiroki Rubber and a copolymer obtained by grafting a vinyl-based monomer such as styrene, acrylonitrile, or polyalkyl methacrylate onto such a composite rubber. (Meth) acrylate, polystyrene, AS resin, ABS resin and ASA resin are preferred.

On the other hand, monomers having an ethylenically unsaturated bond include styrene, p-methylstyrene, o-methylstyrene, p-methoxystyrene, o-methoxystyrene, 2,4-dimethylstyrene and α-methylstyrene. Styrene monomers such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, acrylic acid-2-
Ethylhexyl, 2-ethylhexyl methacrylate,
Acrylic ester monomers such as dodecyl acrylate, dodecyl methacrylate, cyclohexyl acrylate and cyclohexyl methacrylate; vinyl cyanide monomers such as acrylonitrile and methacrylonitrile; vinyl ethers such as vinyl methyl ether and vinyl ethyl ether Vinyl monomers such as vinyl acetate and vinyl butyrate; olefin monomers such as ethylene, propylene and isobutylene; and diene monomers such as butadiene, isoprene and dimethylbutadiene. can do. These monomers can be used alone or in combination of two or more.

As the PTFE mixture of the fifth embodiment, “METABLEN A3000” from Mitsubishi Rayon Co., Ltd.
(Trade name) is commercially available, easily available, and can be preferably used in the present invention.

The ratio of PTFE in the PTFE mixture was 1% by weight in 100% by weight of the PTFE mixture.
-60% by weight, more preferably 3-40% by weight, even more preferably 5-30% by weight. When the proportion of PTFE is in such a range, good dispersibility of PTFE can be achieved.

At least one silicone compound selected from silicone compounds having a viscosity at 25 ° C. of 150 mm ² / sec or less represented by the following general formulas (1) and (2) used as the component d of the present invention. It is.

[0073]

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[0074]

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(In the formulas (1) and (2), Z ^{1 to} Z ⁶ each independently represent a hydrogen atom, a monovalent organic residue having 1 to 20 carbon atoms, or the following general formula (3) Α1 to α6 each independently represent 0 or 1. R ^{1 to} R ⁴ each independently represent a monovalent organic residue having 1 to 20 carbon atoms, and m1 represents an integer of 0 or more. , M2 is 3
Represents the above integer. Furthermore, the compounds of the formulas (1) and (2) each have at least one or more Si—H bond, and in the formula (1), when m1 is 2 or more, the repeating units are different from each other. You can take units. The repeating unit in the formula (2) can take a plurality of different repeating units. )

[0076]

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(In the formula (3), Z ^{7 to} Z ⁹ each independently represent a hydrogen atom or a monovalent organic residue having 1 to 20 carbon atoms. Α
7 to α9 each independently represent 0 or 1. Also R ⁵
And R ⁶ each independently represent a monovalent organic residue having 1 to 20 carbon atoms. m3 represents an integer of 0 or more. Further, in formula (3), when m3 is 2 or more, the repeating unit can take a plurality of different repeating units. )

As the monovalent organic residue having 1 to 20 carbon atoms in R ^{1 to} R ⁶ and Z ^{1 to} Z ⁹ in the general formulas (1) and (2), preferably an alkyl group, a vinyl group, a cycloalkyl Groups may be mentioned, and these groups may further include various functional groups such as an epoxy group, a carboxyl group, a carboxylic anhydride group, an amino group, and a mercapto group. More preferably, it is an alkyl group or vinyl group having 1 to 8 carbon atoms, and particularly preferably an alkyl group or vinyl group having 1 to 4 carbon atoms.

In the above general formulas (1) to (3), when a plurality of repeating units of a siloxane bond are present, they can take any form of random copolymerization, block copolymerization and tapered copolymerization. It is. In the case of a mixture of a plurality of polysiloxanes having different repeating units, the values of the above general formulas (1) to (3) represent their average values.

In the present invention, in the above formula, 1
Compounds having two or more Si-H bonds in the molecule are preferred. Having a plurality of Si—H bonds facilitates formation of a silicone structure during combustion. More preferably, it is a compound having three or more Si-H bonds in one molecule. . The structure of silicone here is
A network structure formed by the reaction between silicone compounds or the reaction between a resin and silicone.

For the above-mentioned reasons, more preferred as the d component in the present invention is a case where all the repeating units in the above general formula (1) or (2) have a Si—H bond. This is the case where the repeating unit is a methylhydrogensiloxane unit (that is, in formula (1), Z ³ is a hydrogen atom, α3 is 0, Z ⁴ is a methyl group, and α4 is 0. In formula (2), Z is ^Five
Is a hydrogen atom, α5 is 0, Z ⁶ is a methyl group, and α 6 is 0. ).

On the other hand, in order for the silicone compound (b) to efficiently exhibit the flame retardant effect, its dispersed state is important. This is because if the silicone compound is unevenly distributed, it becomes difficult to form a uniform silicone structure during combustion. An important factor that determines such a dispersion state is a molecular weight.

From this viewpoint, the component (b) of the present invention is more preferably a silicone compound represented by the general formula (1) or (2) and having a viscosity at 25 ° C. of 150 mm ² / sec or less. More preferably, the viscosity at 25 ° C. is 5 to 100 mm ² / sec,
More preferably, it is 10 to 80 mm ² / sec. In such a case, as the repeating units m1, m2, and m3 in the above formulas (1) to (3), the total of these repeating units is preferably 3 to 100, more preferably 5 to 80, and still more preferably 10 to 70. It is.

Specific examples of the silicone compound represented by the general formula (1) include methyl hydrogen polysiloxane, methyl hydrogen polysiloxane-dimethyl polysiloxane copolymer, and the like. Examples of the methyl hydrogen polysiloxane include SH1107 manufactured by Dow Corning Toray Silicone Co., Ltd., KF99 manufactured by Shin-Etsu Chemical Co., Ltd., and T manufactured by GE Toshiba Silicone Co., Ltd.
SF484, TSF483, etc., which are readily available on the market. Examples of methyl hydrogen polysiloxane-dimethyl polysiloxane copolymer include SiH-modified silicone oil L-3 manufactured by Nippon Unicar Co., Ltd.
1, FZ-3702, FZ-3797, FZ-3805
And these are easily available on the market.

Other silicone compounds represented by the general formula (1) include pentamethyldisiloxane, 1,1,
1,3,5,5,5-heptamethyltrisiloxane, tris (trimethylsiloxy) silane, 1,1,3,3-
Tetramethyldisiloxane, 1,1,3,3,5,5-
Hexamethyltrisiloxane, 1,1,1,3,5
7,7,7-octamethyltetrasiloxane and the like can be mentioned.

Examples of the silicone compound represented by the general formula (2) include 1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7,9-pentamethylcyclopentasiloxane, and pentamethylcyclopentasiloxane. Examples include tetrasiloxane.

Next, the composition ratio of each component will be described. The composition ratio of at least one compound selected from the organic alkali metal salts and the organic alkaline earth metal salts which are the component b of the present invention is 0.001 to 1% by weight in a total of 100% by weight of the components a to d. %, Preferably 0.01 to 0.8% by weight, more preferably 0.05 to 0.5% by weight. If the composition ratio of the component b is less than 0.001% by weight, the flame retardancy may be insufficient, and if it exceeds 1% by weight, the flame retardancy is insufficient due to a decrease in thermal stability. Occurs.

The composition ratio of the fluorine-containing polymer having the fibril-forming ability as the component c is 0.01 to 2% by weight, preferably 0.05 to 1%, of the total 100% by weight of the components a to d. %, More preferably 0.1% by weight.
1 to 0.8% by weight, particularly preferably 0.1 to 0.1% by weight.
6% by weight. If the amount of the component c is less than 0.01% by weight, the flame retardancy may be insufficient, and if it exceeds 2% by weight, the impact resistance and the like may be reduced, which is not preferable.

The composition ratio of the silicone compound, which is the component d, is 0.1% in the total 100% by weight of the components a to d.
0.01 to 1% by weight, preferably 0.01 to 1% by weight
, More preferably 0.01 to 0.8% by weight, still more preferably 0.05 to 0.6% by weight, and particularly preferably 0.05 to 0.5% by weight. Such c
If the composition ratio of the component is less than 0.01% by weight, the flame retardancy and the releasability may be insufficient, and if it exceeds 3% by weight, appearance problems such as peeling may occur.

The flame-retardant aromatic polycarbonate resin composition of the present invention may contain various thermoplastic resins and additives as long as the effects of the present invention are exhibited.

The thermoplastic resin other than the polycarbonate resin includes, for example, polyethylene resin, polypropylene resin, polystyrene resin, HIPS resin, polyacrylstyrene resin, ABS resin, AS resin, AES resin, ASA resin, SMA resin, and polystyrene resin. General-purpose plastics represented by alkyl methacrylate resins, polyphenylene ether resins, polyacetal resins, aromatic polyester resins, polyamide resins, cyclic polyolefin resins, polyarylate resins (amorphous polyarylate, liquid crystalline polyarylate), etc. So-called super engineering such as engineering plastics, polyetheretherketone, polyetherimide, polysulfone, polyethersulfone, polyphenylenesulfide, etc. Mention may be made of what is referred to as a Rasuchikkusu. Further, thermoplastic elastomers such as styrene-based thermoplastic elastomer, olefin-based thermoplastic elastomer, polyamide-based thermoplastic elastomer, polyester-based thermoplastic elastomer, and polyurethane-based thermoplastic elastomer can also be used.

Examples of other various additives include 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,
Flame retardants other than ceramic particles, ceramic fibers, aramid particles, aramid fibers, polyarylate fibers, graphite, conductive carbon black, various whiskers, etc., organic alkali metal salts and organic alkaline earth metal salts (halogens, phosphate esters) System, metal salt system, red phosphorus,
Metal hydrates), heat stabilizers, ultraviolet absorbers, light stabilizers, release agents, lubricants, sliding agents (PTFE particles, etc.), coloring agents (inorganic pigments such as carbon black and titanium oxide, organic dyes) , Organic pigments), light diffusing agents (acrylic crosslinked particles,
Silicon cross-linked particles, ultra-thin glass flakes, calcium carbonate particles, etc.), fluorescent whitening agents, luminous pigments, fluorescent dyes, antistatic agents, flow modifiers, crystal 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.

The flame-retardant aromatic polycarbonate resin composition of the present invention preferably contains a phosphorus-based stabilizer as a heat stabilizer. As the phosphorus-based stabilizer, any of phosphite-based, phosphonite-based, and phosphate-based stabilizers can be used.

Various phosphite-based stabilizers in the present invention can be used. Specifically, for example, the general formula (5)

[0095]

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[Wherein R ⁸ is hydrogen or C 1-20
An alkyl group, an aryl group or alkaryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, or a halo or alkylthio (the alkyl group has 1 to 3 carbon atoms)
0) or a hydroxy substituent, and the three R ^{8 s} can be selected whether they are the same or different from each other,
Further, a cyclic structure can be selected by being derived from a dihydric phenol. ] It is a phosphite compound represented by these.

The general formula (6)

[0098]

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[Wherein R ⁹ and R ¹⁰ are each hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group or an alkylaryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, 20 cycloalkyl groups, having 15 to 15 carbon atoms
And represents 25 2- (4-oxyphenyl) propyl-substituted aryl groups. The cycloalkyl group and the aryl group can be selected from those not substituted with an alkyl group and those substituted with an alkyl group. And a phosphite compound represented by the following formula:

The general formula (7)

[0101]

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[Wherein R ¹¹ and R ¹² are alkyl groups having 12 to 15 carbon atoms. Note that R ¹¹ and R ¹² may be the same or different from each other. And a phosphite compound represented by the following formula:

Examples of the phosphonite stabilizer include a phosphonite compound represented by the following general formula (8) and a phosphonite compound represented by the following general formula (9).

[0104]

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[0105]

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[Wherein, Ar ¹ and Ar ^{2 each} represent an aryl group or an alkylaryl group having 6 to 20 carbon atoms, or
It represents 5 to 25 2- (4-oxyphenyl) propyl-substituted aryl groups, and the four Ar ^{1 s} can be the same or different. Alternatively, ^two Ar ² may be the same or different. ]

Preferred specific examples of the phosphite compound corresponding to the above general formula (5) include diphenylisooctyl phosphite, 2,2′-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, Examples include diphenyl mono (tridecyl) phosphite, phenyl diisodecyl phosphite, and phenyl di (tridecyl) phosphite.

Preferred specific examples of the phosphite compound corresponding to the above general formula (6) include distearyl pentaerythritol diphosphite, bis (2,4-
Di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, dicyclohexylpentaerythritol diphosphite And distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-ter
(tert-butyl-4-methylphenyl) pentaerythritol diphosphite. Such phosphite compounds can be used alone or in combination of two or more.

Preferred specific examples of the phosphite compound corresponding to the general formula (7) include 4,4′-isopropylidenediphenol tetratridecyl phosphite.

Preferred specific examples of the phosphonite compound corresponding to the above general formula (8) include tetrakis (2,4-di-iso-propylphenyl) -4,4 ′
-Biphenylenediphosphonite, tetrakis (2,4-
Di-n-butylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,4-di- tert-butylphenyl) -4,3′-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -3,
3'-biphenylenediphosphonite, tetrakis (2,
6-di-iso-propylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,6-di-n
-Butylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,6-di-tert-butyl) Phenyl)-
4,3′-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -3,3 ′
-Biphenylenediphosphonite; tetrakis (di-tert-butylphenyl) -biphenylenediphosphonite is preferred; tetrakis (2,4-di-t
(tert-butylphenyl) -biphenylenediphosphonite is more preferred. This tetrakis (2,4-di-te
(rt-butylphenyl) -biphenylenediphosphonite is preferably a mixture of two or more, specifically, tetrakis (2,4-di-tert-butylphenyl) -4,
4'-biphenylenediphosphonite (E2-1 component),
Tetrakis (2,4-di-tert-butylphenyl)
One kind of -4,3'-biphenylenediphosphonite (E2-2 component) and tetrakis (2,4-di-tert-butylphenyl) -3,3'-biphenylenediphosphonite (E2-3 component) Alternatively, two or more of them can be used in combination, but a mixture of these three is preferred. In the case of three kinds of mixtures, the mixing ratio is E2-1.
Component, E2-2 component and E2-3 component in a weight ratio of 10
The range of 0:37 to 64: 4 to 14 is preferable, and 100:
The range of 40-60: 5-11 is more preferable.

Preferred specific examples of the phosphonite compound corresponding to the general formula (9) include bis (2,4-di-
iso-propylphenyl) -4-phenyl-phenylphosphonite, bis (2,4-di-n-butylphenyl) -3-phenyl-phenylphosphonite, bis (2,4-di-tert-butylphenyl)- 4-phenyl-phenylphosphonite, bis (2,4-di-te
rt-butylphenyl) -3-phenyl-phenylphosphonite bis (2,6-di-iso-propylphenyl) -4-phenyl-phenylphosphonite, bis (2,6-di-n-butylphenyl) -3 -Phenyl-
Phenylphosphonite, bis (2,6-di-tert-
Butylphenyl) -4-phenyl-phenylphosphonite, bis (2,6-di-tert-butylphenyl)-
3-phenyl-phenylphosphonite and the like, and bis (di-tert-butylphenyl) -phenyl-phenylphosphonite is preferable, and bis (2,4-di-te
(rt-butylphenyl) -phenyl-phenylphosphonite is more preferred. This screw (2,4-di-tert)
-Butylphenyl) -phenyl-phenylphosphonite is preferably a mixture of two or more, specifically, bis (2,4-di-tert-butylphenyl) -4-phenyl-phenylphosphonite and bis (2 , 4-di-tert-butylphenyl) -3-phenyl-phenylphosphonite may be used alone or in combination, and preferably a mixture of the two. In the case of two kinds of mixtures, the mixing ratio is 5: 1 by weight.
-4 is preferable, and 5: 2-3 is more preferable.

On the other hand, examples of the phosphate-based stabilizers include tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, triethyl phosphate, diphenylcresyl phosphate, diphenyl monoorthoxenyl phosphate, tributoxyethyl phosphate, and the like. Examples thereof include dibutyl phosphate, dioctyl phosphate, and diisopropyl phosphate, and preferred is trimethyl phosphate.

More preferred phosphorus stabilizers for the above phosphorus stabilizers include compounds represented by the following formulas (10) and (11).

[0114]

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(In the formula (10), R ¹³ and R ¹⁴ each represent an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group.)

[0116]

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(In the formula (11), R ¹⁵ , R ¹⁶ , R ¹⁷ ,
^{R 18, R 21, R 22} , and R ²³ are each a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group, R ¹⁹ is 1 to hydrogen or carbon atoms 4 represents an alkyl group, and R ²⁰
Represents a hydrogen atom or a methyl group. )

In the formula (10), preferably, R ¹³ and R ¹⁴
Is an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms. Equation (12)
Specific examples of the compound of (1) include tris (dimethylphenyl) phosphite, tris (diethylphenyl) phosphite, tris (di-iso-propylphenyl) phosphite, tris (di-n-butylphenyl) phosphite, and tris ( 2,4-di-tert-butylphenyl) phosphite, tris (2,6-di-tert-butylphenyl) phosphite, tris (2,6-di-t
tert-butylphenyl) phosphite and the like, and particularly preferred is tris (2,4-di-tert-butylphenyl) phosphite.

On the other hand, the phosphorus compound of the formula (11) can be produced by a known method. For example, a bisphenol compound represented by the following general formula (12) is reacted with phosphorus trichloride to obtain a corresponding phosphoric acid chloride, which is then reacted with the following general formula (1)
There is a method of reacting with phenol shown in 5).

[0120]

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(In the formula (12), R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ each represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group; ¹² represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ¹³ represents a hydrogen atom or a methyl group.)

[0122]

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(In the formula (13), R ¹⁴ , R ¹⁵ and R ¹⁶
Represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group, respectively. )

Specific examples of the compound represented by the general formula (12) include 2,2'-methylenebisphenol and 2,2'-
Methylenebis (4-methylphenol), 2,2′-methylenebis (6-methylphenol), 2,2′-methylenebis (4,6-dimethylphenol), 2,2′-
Ethylidenebisphenol, 2,2′-ethylidenebis (4-methylphenol), 2,2′-isopropylidenebisphenol, 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), 2,2′-methylenebis (4,6-di-ter
t-butylphenol), 2,2′-methylenebis (4
-Methyl-6-cyclohexylphenol), 2,2 ′
-Dihydroxy-3,3'-di (α-methylcyclohexyl) -5,5'-dimethylphenylmethane, 2,2 '
-Methylenebis (6-α-methyl-benzyl-p-cresol), 2,2′-ethylidene-bis (4,6-di-
tert-butylphenol) and 2,2-butylidene-bis (4-methyl-6-tert-butylphenol) and the like can be preferably used.

The compound of the general formula (12) is more preferably 2,2'-methylenebis (4-methyl-6-te
rt-butylphenol), 2,2′-methylenebis (4-ethyl-6-tert-butylphenol),
2,2′-methylenebis (4,6-di-tert-butylphenol), 2,2′-ethylidene-bis (4,6
-Di-tert-butylphenol), and 2,2-
Butylidene-bis (4-methyl-6-tert-butylphenol) can be mentioned.

On the other hand, specific examples of the compound of the general formula (13) include phenol, 2-methylphenol, 3-methylphenol, 4-methylphenol, 2,4-dimethylphenol, 2,6-dimethylphenol, −te
rt-butyl-4-methylphenol, 2,4-di-t
tert-butylphenol, 2,6-di-tert-butylphenol, 2,6-di-tert-butyl-4-
Methylphenol, 2,4-dimethyl-6-tert-
Butylphenol, 2,6-di-tert-butyl-4
-Ethylphenol, 2,4,6-tri-tert-butylphenol, and 2,6-di-tert-butyl-4-s-butylphenol, and the like can be preferably used. A more preferred specific example of the compound of the general formula (13) is a case having two or more alkyl substituents.

The flame-retardant aromatic polycarbonate resin composition of the present invention may contain a phenolic antioxidant. The phenolic antioxidant suppresses discoloration during heat exposure, and also exhibits some effect in improving flame retardancy. Various phenolic antioxidants can be used.

Specific examples of such phenolic antioxidants include, for example, vitamin E, n-octadecyl-β-
(4'-hydroxy-3 ', 5'-di-tert-butylphenyl) propionate, 2-tert-butyl-
6- (3'-tert-butyl-5'-methyl-2'-
(Hydroxybenzyl) -4-methylphenyl acrylate, 2,6-di-tert-butyl-4- (N, N-dimethylaminomethyl) phenol, 3,5-di-ter
t-butyl-4-hydroxybenzylphosphonate diethyl ester, 2,2'-methylenebis (4-methyl-
6-tert-butylphenol), 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), 4,4′-methylenebis (2,6-di-tert)
-Butylphenol), 2,2'-methylenebis (4-
Methyl-6-cyclohexylphenol), 2,2′-
Dimethylene-bis (6-α-methyl-benzyl-p-cresol), 2,2′-ethylidene-bis (4,6-di-tert-butylphenol), 2,2′-butylidene-bis (4-methyl- 6-tert-butylphenol), 4,4′-butylidenebis (3-methyl-6-t
tert-butylphenol), triethylene glycol-N-bis-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, 1,6-
Hexanediol bis [3- (3,5-di-tert-
Butyl-4-hydroxyphenyl) propionate, bis [2-tert-butyl-4-methyl 6- (3-te
rt-butyl-5-methyl-2-hydroxybenzyl)
Phenyl] terephthalate, 3,9-bis {2- [3-
(3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1, -dimethylethyl {-2,4,8,10-tetraoxaspiro [5,5] undecane, 4,4 -Thiobis (6-ter
t-butyl-m-cresol), 4,4′-thiobis (3-methyl-6-tert-butylphenol),
2,2′-thiobis (4-methyl-6-tert-butylphenol), bis (3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, 4,4′-di-thiobis (2,6- Di-tert-butylphenol), 4,4′-tri-thiobis (2,6-di-ter
t-butylphenol), 2,4-bis (n-octylthio) -6- (4-hydroxy-3 ′, 5′-di-te
rt-butylanilino) -1,3,5-triazine,
N, N'-hexamethylenebis- (3,5-di-ter
t-butyl-4-hydroxyhydrocinnamide), N,
N'-bis [3- (3,5-di-tert-butyl-4
-Hydroxyphenyl) propionyl] hydrazine,
1,1,3-tris (2-methyl-4-hydroxy-5
-Tert-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert)
-Butyl-4-hydroxybenzyl) benzene, tris (3,5-di-tert-butyl-4-hydroxyphenyl) isocyanurate, tris (3,5-di-ter
t-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (4-tert-butyl-3-
Hydroxy-2,6-dimethylbenzyl) isocyanurate, 1,3,5-tris 2 [3 (3,5-di-ter
t-butyl-4-hydroxyphenyl) propionyloxy] ethyl isocyanurate, tetrakis [methylene-3- (3 ′, 5′-di-tert-butyl-4-hydroxyphenyl) propionate] methane and the like, It can be used preferably.

More preferably, n-octadecyl-β-
(4'-hydroxy-3 ', 5'-di-tert-butylphenyl) propionate, 2-tert-butyl-
6- (3'-tert-butyl-5'-methyl-2'-
(Hydroxybenzyl) -4-methylphenyl acrylate, 3,9-bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1, -dimethylethyl}- 2,4,8,
10-tetraoxaspiro [5,5] undecane and tetrakis [methylene-3- (3 ′, 5′-di-te
rt-butyl-4-hydroxyphenyl) propionate] methane, and furthermore n-octadecyl-β- (4 ′
-Hydroxy-3 ', 5'-di-tert-butylphenyl) propionate is preferred.

The flame-retardant aromatic polycarbonate resin composition of the present invention can contain a sulfur-based antioxidant. It is particularly suitable when molding is used for rotational molding or compression molding. Specific examples of such sulfur-based antioxidants include:
Dilauryl-3,3'-thiodipropionate,
Ditridecyl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate, laurylstearyl-3,3'-thiodiester Propionate, pentaerythritol tetra (β-laurylthiopropionate) ester, bis [2-methyl-4- (3-laurylthiopropionyloxy) -5
-Tert-butylphenyl] sulfide, octadecyl disulfide, mercaptobenzimidazole, 2-
Mercapto-6-methylbenzimidazole, 1,1 ′
-Thiobis (2-naphthol) and the like. More preferably, pentaerythritol tetra (β
-Lauryl thiopropionate) ester.

The phosphorus-based stabilizer, phenolic antioxidant, and sulfur-based antioxidant described above can be used alone or in combination of two or more. The case where a phosphorus-based stabilizer is essential is more preferable, and it is particularly preferable that the compound of the general formula (10) is contained as the phosphorus-based stabilizer.

The proportion of these stabilizers in the composition is such that the phosphorus-based stabilizer, phenolic antioxidant, or sulfur-based antioxidant is based on 100 parts by weight of the total of components a to d of the present invention. It is preferably 0.0001 to 1 part by weight. More preferably, the amount is 0.0005 to 0.5 part by weight per 100 parts by weight of the total of the components a to d. More preferably, it is 0.001 to 0.2 parts by weight.

Since the flame-retardant aromatic polycarbonate resin composition of the present invention is often used for the housing of OA equipment and the like, it preferably contains an ultraviolet absorber. Examples of the ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-n-dodecyloxybenzophenone, and 2-hydroxy -4-benzyloxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxybenzophenone, 2,2 '-Dihydroxy-4,4'-dimethoxybenzophenone, 2,
2 ′, 4,4′-tetrahydroxybenzophenone,
2,2'-dihydroxy-4,4'-dimethoxy-5
Benzophenone-based ultraviolet absorbers represented by sodium sulfoxybenzophenone, bis (5-benzoyl-4-hydroxy-2-methoxyphenyl) methane and the like can be mentioned.

As the ultraviolet absorber, for example, 2-
(2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-5′-tert)
-Butylphenyl) benzotriazole, 2- (2'-
Hydroxy-5'-tert-octylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'
-Di-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-ter
t-amylphenyl) benzotriazole, 2- (2 ′
-Hydroxy-3'-dodecyl-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-
3 ′, 5′-bis (α, α′-dimethylbenzyl) phenylbenzotriazole, 2- [2′-hydroxy-
3 '-(3 ", 4", 5 ", 6" -tetraphthalimidomethyl) -5'-methylphenyl] benzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl ) -5-chlorobenzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-te)
rt-butylphenyl) -5-chlorobenzotriazole, 2,2 ′ methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol], methyl -3- [3-ter
Benzotriazole ultraviolet absorbers represented by condensates with t-butyl-5- (2H-benzotriazol-2-yl) -4-hydroxyphenylpropionate-polyethylene glycol can be mentioned.

Further, as an ultraviolet absorber, for example, 2-
(4,6-diphenyl-1,3,5-triazine-2-
Yl) -5-hexyloxyphenol, 2- (4,6
And hydroxyphenyltriazine-based compounds such as -bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl) -5-hexyloxyphenol.

Bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,2)
6,6-pentamethyl-4-piperidyl) sebacate,
Bis (1,2,2,6,6-pentamethyl-4-piperidyl) -2- (3,5-di-tert-butyl-4-hydroxybenzyl) -2n-butylmalonate,
Condensate of 2,3,4-butanecarboxylic acid with 2,2,6,6-tetramethyl-4-piperidinol and tridecyl alcohol, 1,2,3,4-butanedicarboxylic acid with 1,2,2 Condensation product of 6,6,6-pentamethyl-4-piperidinol and tridecyl alcohol, tetrakis (2,2,6,6-tetramethyl-4-piperidyl)-
1,2,3,4-butanetetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, poly {[6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl] [(2,2,6,6-tetramethylpiperidyl) imino] hexamethylene [(2 , 2,6,6-tetramethylpiperidyl) imino]}, poly {[6-morpholino-s-triazine-2,4-diyl] [(2,2,6
6-tetramethylpiperidyl) imino] hexamethylene [(2,2,6,6-tetramethylpiperidyl) imino]}, 1,2,3,4-butanetetracarboxylic acid and 2,2,6,6-tetra Methyl-4-piperidinol and β, β, β ′, β′-tetramethyl-3,9- (2,
Condensation product with 4,8,10-tetraoxaspiro [5,5] undecane) diethanol, N, N′-bis (3-aminopropyl) ethylenediamine and 2,4-bis [N-
Butyl-N- (1,2,2,6,6-pentamethyl-4
-Piperidyl) amino] -chloro-1,3,5-triazine, 1,2,3,4-butanetetracarboxylic acid, 1,2,2,6,6-pentamethyl-4-piperidinol and β , Β, β ', β'-tetramethyl-3,9
-(2,4,8,10-tetraoxaspiro [5,5]
A condensate with undecane) diethanol and a hindered amine-based light stabilizer represented by polymethylpropyl 3-oxy- [4- (2,2,6,6-tetramethyl) piperidinyl] siloxane can also be blended.

The ratio of the ultraviolet absorber and the light stabilizer is as follows:
The amount of 0.1 to 100 parts by weight in total of the components a to d of the present invention.
It is from 0.01 to 5 parts by weight, more preferably from 0.02 to 1 part by weight.

For producing the thermoplastic resin composition of the present invention, any method is employed. For example, pre-mixing the components a to d and optionally other components, followed by melt kneading,
Examples of the method include pelletization. As means for pre-mixing, V-blender, Henschel mixer,
Examples include a mechanochemical device and an extrusion mixer. In the pre-mixing, granulation can also be carried out by an extrusion granulator or a briquetting machine in some cases. After the premixing, the mixture is melt-kneaded by a melt-kneader typified by a vented twin-screw rudder, and pelletized by a device such as a pelletizer.

In addition, it is also possible to adopt a method in which the components a to d and optionally other components are independently supplied to a melt kneader represented by a twin-screw ruder without premixing. Further, a method is also possible in which after premixing some of the components a to d and any other components, the mixture is supplied to the melt kneader independently of the remaining components. Premixing means and granulation are the same as described above.

The components b and d are diluted and mixed with water or an organic solvent and then supplied to a melt kneader, or the diluted mixture is preliminarily mixed with other components and then supplied to the melt kneader. . Further, when a dispersion component is used as the component c, it is also appropriate to adopt a method of mixing the component c and the component b. 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 aromatic polycarbonate resin composition of the present invention can be used to produce various products by injection molding such pellets to obtain molded products. In such injection molding, not only a normal cold runner type molding method but also a hot runner that enables runnerless can be manufactured. In addition, in 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 aromatic polycarbonate resin composition of the present invention can be obtained by extrusion molding of various shaped extrusion molded articles.
It can be used in the form of a sheet, a film and the like. Further, a fine flation method, a casting method, or the like can be used for forming a sheet or a film. Furthermore, it is also possible to form a heat-shrinkable tube by performing a specific stretching operation. Further, the flame-retardant aromatic polycarbonate resin composition of the present invention can be formed into a molded product by rotational molding without melt-kneading. Furthermore, various hollow molded articles can be obtained by blow molding.

The flame-retardant aromatic polycarbonate resin composition of the present invention is suitable for internal parts and housings of OA equipment and home electric appliances because of its excellent thin-walled flame retardancy, and excellent impact resistance and wet heat resistance. It is something. Such applications include, for example, a relay case, a coil bobbin, an optical pickup chassis, a motor case, a notebook computer housing and internal parts, a CRT display housing and internal parts, a printer housing and internal parts, a mobile terminal housing and internal parts, a recording medium (CD, DVD,
(PD, FDD, etc.) Drive / housing and internal parts, copy machine housing / internal parts, electric / electronic parts typified by parabolic antennas and the like. Furthermore, VTR parts, TV parts, irons, hair dryers, rice cooker parts, microwave parts, audio parts, audio equipment parts such as audio / laser disc (registered trademark) / compact discs, lighting parts, refrigerator parts, air conditioner parts, Home and office electrical product parts such as typewriter parts and word processor parts. Vehicle parts such as lamp sockets, lamp reflectors, lamp housings, instrumental panels, center console panels, deflector parts, car navigation covers, car navigation parts, car stereo parts, and the like can also be mentioned. It is also useful for various uses such as machine parts and miscellaneous goods.

[0144]

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 properties (1-) Flame retardancy 1.6 mm and 1.0 m thickness prepared according to UL standard
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-) Release Property As shown in the figure, a cup-shaped molded product is molded using a release load measurement mold equipped with a load cell capable of detecting the load applied to the ejector pin at the time of release, and the release force of the release is measured. A measurement was made.
The releasability was evaluated based on the test results. (1-) Appearance peeling It evaluated visually using the test piece of thickness 1.0mm created according to UL standard. Either with or without peeling was evaluated based on the result of visual observation.

[Examples 1 to 16 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 and a cup-shaped molded product were formed at a cylinder temperature of 310 ° C. and a mold temperature of 70 ° C.

Raw materials used in Tables 1 to 3 are as follows. (A component) PC-1: linear polycarbonate resin (bisphenol A produced by the phosgene method and p as a terminal stopper)
-A polycarbonate resin comprising tert-butylphenol. Such a polycarbonate resin is produced without using an amine-based catalyst. In the polycarbonate resin terminal, the ratio of terminal hydroxyl groups is 10 mol%, and the viscosity average molecular weight is 2%.
PC-2: linear polycarbonate resin (polycarbonate resin made of bisphenol A produced by a melting method. In such polycarbonate resin, the proportion of terminal hydroxyl groups in the polycarbonate resin terminal is 34 mol%, (The viscosity average molecular weight was 19,500.)

(B) Metal salt 1: potassium perfluorobutanesulfonate (MegaFac F-1 manufactured by Dainippon Ink and Chemicals, Inc.)
14P) Metal salt 2: potassium diphenylsulfonate (KSS manufactured by UCB Japan)

(Component c) PTFE-1: Polytetrafluoroethylene having fibril-forming ability (Polyflon M manufactured by Daikin Industries, Ltd.)
PA FA500) PTFE-2: a mixture with an acrylic polymer containing about 20% by weight of polytetrafluoroethylene having a fibril-forming ability (METABLEN A- manufactured by Mitsubishi Rayon Co., Ltd.)
3000)

[0149] (d component) Si-1: viscosity at 25 ° C. of 20 mm ² / sec methylhydrogenpolysiloxane (Shin-Etsu Chemical Co., Ltd. KF99) Si-2: 25 Viscosity at ° C. of 20 mm ² / sec Methyl hydrogen polysiloxane-dimethyl polysiloxane copolymer (SiH-modified silicone oil L-31 manufactured by Nippon Unicar Co., Ltd.) (other than component d) Si-3: Silicone resin solid at 25 ° C (GE Toshiba Silicone Co., Ltd.) XC99-B5664) PEWAX: polyethylene wax (High wax HW405MP manufactured by Mitsui Chemicals, Inc.)

(Other Components) S-1: Phosphite antioxidant (IRGAFOS168 manufactured by Ciba-Geigy Japan) S-2: Phosphonite antioxidant (Sando)
z) Sandstab P-EPQ) CL-1: Colorant (titanium oxide, P from Ishihara Sangyo Co., Ltd.)
C-3) CL-2: Colorant (Yellow Dye, Plast Yellow 8050, manufactured by Arimoto Chemical Co., Ltd.) CL-3: Colorant (Blue Dye, Macrolex BLUE RR, manufactured by Bayer AG)

[0151]

[Table 1]

[0152]

[Table 2]

[0153]

[Table 3]

The following is clear from these tables. It can be seen that the flame-retardant aromatic polycarbonate resin composition comprising the components a to d of the present invention has good flame retardancy, release properties, and appearance. It can be seen that when the silicone compound is other than the above, there is one having insufficient releasability. It is also recognized that olefin waxes well known as release agents do not have sufficient flame retardancy.

Further, in the sample of Example 1 described above,
A molded product of a keyboard frame of a notebook personal computer was molded from such a sample, and all of the molded products had sufficient strength, and particularly the strength of a weld portion was good.

[0156]

As is clear from the above, the flame-retardant aromatic polycarbonate resin composition of the present invention is excellent in mold releasability and flame retardancy in a thin-walled part. It is extremely useful for various industrial uses such as the electric and electronic fields, and the industrial effects achieved are extremely large.

[Brief description of the drawings]

FIG. 1 is a view schematically showing an outline of a mold for measuring a release load.

FIG. 2 is a diagram schematically showing a load measurement at the time of mold release (an ejector pin and a load cell are pushed forward by an ejector rod; the load detected by the load cell when pushed out is recorded).

[Explanation of symbols]

 REFERENCE SIGNS LIST 1 load cell 2 fixed mold 3 movable mold 4 ejector pin 5 mold cavity 6 cup-shaped molded product

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (reference) C08L 83:04) C08L 83:04)

Claims (1)

[Claims] 1. An aromatic polycarbonate resin in an amount of 94 to 99.979% by weight (a component) in a total of 100% by weight of the following components a, b, c and d, an organic alkali metal salt and an organic alkaline earth metal 0.001 to 1% by weight of at least one compound selected from salts (component (b)), 0.01 to 2% by weight of a fluorine-containing polymer having fibril-forming ability (component (c)), the following general formulas (1) and (2) ) Is 150 mm ² /
sec or less silicone compound (d component) 0.01-3
Claims: 1. A flame-retardant aromatic polycarbonate resin composition, comprising: Embedded image Embedded image (In the formulas (1) and (2), Z ^{1 to} Z ⁶ each independently represent a hydrogen atom, a monovalent organic residue having 1 to 20 carbon atoms, or a compound represented by the following general formula (3). Α1 to α6
Represents 0 or 1 each independently. R ^{1 to} R ⁴ each independently represent a monovalent organic residue having 1 to 20 carbon atoms.
m1 represents an integer of 0 or more, and m2 represents an integer of 3 or more. Furthermore, the compounds of the formulas (1) and (2) each have at least one or more Si—H bond, and in the formula (1), when m1 is 2 or more, the repeating units are different from each other. You can take units. The repeating unit in the formula (2) can take a plurality of different repeating units. ) (In the formula (3), Z ⁷ ~Z ⁹ represents independently a hydrogen atom, a .α7~α9 each independently 0 or 1 indicating the monovalent organic residue having 1 to 20 carbon atoms. The R ⁵ And R ⁶ each independently represent a monovalent organic residue having 1 to 20 carbon atoms, m3 represents an integer of 0 or more, and in formula (3), when m3 is 2 or more, the repeating units are each other It can have multiple different repeating units.)