JP2002294063A - Flame-retardant aromatic polycarbonate resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a flame-retardant aromatic polycarbonate resin composition having excellent flame-retardance in the form of thin wall and high thermal stability in molding, giving little load on the environment and producible without compounding a halogen-based flame-retardant or a phosphoric acid ester flame- retardant. SOLUTION: The flame-retardant aromatic polycarbonate resin composition contains 100 pts.wt. of an aromatic polycarbonate resin (component A), 0.001-1 pt.wt. of at least one kind of metal salt selected from alkali metal salt and alkaline earth metal salt (component B), 0.05-5 pts.wt. of an alkoxysilane compound (component C) and 0.01-1 pt.wt. of a fluorine-containing polymer (component D) having fibril-forming capability.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention has a low environmental load without blending a halogen-based flame retardant and a phosphate ester-based flame retardant, has excellent thin-walled flame retardancy, and has high thermal stability during molding. The present invention relates to a flame-retardant aromatic polycarbonate resin composition.

[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 order to meet these demands, flame retardant polycarbonate resin compositions containing various flame retardants such as halogen compounds and phosphorus compounds have been generally proposed. (For example, it is introduced in a polycarbonate resin handbook (published by Nikkan Kogyo Shimbun, edited by Seiichi Honma, 1992).) However, when a halogen compound is used, toxic gas such as dioxin can be generated during combustion. There is. In addition, when a phosphorus compound is used, there is some concern that phosphorus will be eluted into soil during landfill. In particular, in recent years, with increasing interest in environmental issues, a flame-retardant aromatic polycarbonate resin material using a flame retardant having a smaller environmental load has been desired.

[0004] On the other hand, a flame-retardant aromatic polycarbonate resin composition using a silicone compound or a metal salt compound as a flame retardant having a small environmental load has been proposed.

JP-A-51-45159 discloses a flame-retardant polycarbonate resin composition in which an organic alkali (earth) metal salt and a fluorinated polyolefin are blended with an aromatic polycarbonate resin. JP-A-11-
JP-A-263903 describes a flame-retardant polycarbonate resin composition comprising a polycarbonate resin containing a silicone varnish having a specific viscosity and a metal salt of an organic sulfonic acid. JP-A-11-217494 discloses that
A flame-retardant polycarbonate resin composition comprising a silicone compound having a branched main chain and an aromatic group in a polycarbonate resin, and a metal salt of an aromatic sulfur compound, and further containing a fiber-forming fluoropolymer. I have.

However, when the metal salt compounds specifically disclosed in these publications are incorporated in large amounts, the thermal stability, mechanical properties, and impact resistance of the resin composition decrease, and conversely, flame retardancy occurs. In some cases, problems such as a decrease in performance occur. Therefore, the addition amount is limited, and the flame retardant effect is also limited.

On the other hand, in recent years, products are becoming thinner and lighter in the OA field and the electronic / electric field, and flame-retardant polycarbonate resin materials are also required to have high rigidity and high strength. Is desired. However, the flame retardant resin composition containing the metal salt compound has a problem that the flame retardancy is greatly reduced when an inorganic filler is further combined.

JP-A-53-50261 discloses an aromatic carbonate polymer, an organic alkali (earth) metal salt,
A resin composition comprising a halogen compound and further containing a fluorinated polyolefin, glass fiber, silicone fluid, or the like as an anti-drip agent is described. However, this publication did not sufficiently consider flame retardancy when a halogen compound was not contained.

Japanese Patent Application Laid-Open No. Hei 6-329894 discloses that
A resin composition comprising a polycarbonate resin, an alkali (earth) metal salt of perfluoroalkanesulfonic acid, a specific polyorganosiloxane, and an inorganic filler is described. However, such organopolysiloxanes are not general and some are not practical.

On the other hand, it is widely known that alkoxysilane compounds having various functional groups are useful as silane coupling agents for improving the adhesion between an inorganic filler and a resin.

[0011]

SUMMARY OF THE INVENTION An object of the present invention is to reduce the environmental load without blending a halogen-based flame retardant and a phosphoric ester-based flame retardant, to provide a thin-walled flame-retardant material, and to provide a heat-stable material during molding. An object of the present invention is to provide a flame-retardant aromatic polycarbonate resin composition having high heat resistance.

That is, as described above, it is difficult to make the metal salt compound (i) flame-retardant with a thin wall due to problems such as thermal stability of the composition. It is an object of the present invention to provide an aromatic polycarbonate resin composition having improved thermal stability when containing such a metal salt compound and further having improved flame retardancy. In particular, (i
i) There is a limit to the flame retardant effect, and furthermore, the combination with an inorganic filler greatly reduces the flame retardancy, so that the addition of an inorganic filler or the like is restricted. An object of the present invention is to provide an aromatic polycarbonate resin composition having good flame retardancy by suppressing a decrease in flame retardancy even in combination with such an inorganic filler.

The present inventor has conducted intensive studies to achieve the above object. As a result, an aromatic (earth) metal salt, a specific alkoxysilane compound,
It has been found that the above problems can be solved by combining and blending a fluorine-containing polymer having fibril-forming ability, and the present invention has been completed.

[0014]

That is, the present invention provides at least one metal salt (B) selected from an alkali metal salt and an alkaline earth metal salt with respect to 100 parts by weight of an aromatic polycarbonate resin (A component). Component) 0.001
1 part by weight, 0.05 to 5 parts by weight of an alkoxysilane compound (component C) represented by the following formula (1), and 0.01 to 1 part by weight of a fluoropolymer having fibril-forming ability (component D). The present invention relates to a flame-retardant aromatic polycarbonate resin composition.

[0015]

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(In the formula, R ¹ is a monovalent organic group having 1 to 8 carbon atoms, which may be the same or different, and R ² is a monovalent organic group having 1 to 10 carbon atoms.) And n may be any of the same or different from each other, and n is 2, 3 or 4.)

The aromatic polycarbonate resin as the component A of the present invention is obtained by reacting a dihydric phenol with a carbonate precursor. Examples of the reaction method include an interfacial polycondensation method, a melt transesterification method, a solid-phase transesterification method of a carbonate prepolymer, and 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, a homopolymer of bisphenol A is preferably used. Such an aromatic polycarbonate resin is preferable in that it has excellent impact resistance.

As the carbonate precursor, carbonyl halide, carbonate ester or haloformate is used, and specific examples thereof 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 a dihydric phenol are oxidized. For example, an antioxidant or the like may be used to prevent the oxidation.
Further, the aromatic polycarbonate resin may be a polyester carbonate resin obtained by copolymerizing an aromatic or aliphatic bifunctional carboxylic acid, or a mixture obtained by mixing two or more kinds of the obtained aromatic polycarbonate resins. Is also good.

The aliphatic difunctional carboxylic acid includes, for example, an aliphatic difunctional carboxylic acid having 8 to 20, preferably 10 to 12 carbon atoms. Such an aliphatic bifunctional carboxylic acid may be linear, branched or cyclic. Aliphatic bifunctional carboxylic acids have α, ω
-Dicarboxylic acids are preferred.

In the polymerization reaction of the aromatic polycarbonate resin, 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, such monofunctional phenols are generally phenols or lower alkyl substituted phenols,
Monofunctional phenols represented by the following general formula (2) can be shown.

[0026]

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(Wherein A is a hydrogen atom or a carbon number of 1 to 9)
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 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 alkyl carboxylic acid chlorides can also be used. Among them, phenols having a long-chain alkyl group represented by the following general formulas (3) and (4) as a substituent are preferably used.

[0030]

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[0031]

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(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 (3), 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 (4), a compound in which X is -R-CO-O- and R is a single bond is suitable, and n is 10 to 30, especially 10 to 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.

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 to 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 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 the polymerization reaction, in order 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 the deactivator is preferably 0.5 to 50 mol per 1 mol of the remaining catalyst, and 0.01 to 500 ppm, more preferably, to the polycarbonate resin after polymerization. Is used at a ratio of 0.01 to 300 ppm, particularly preferably 0.01 to 100 ppm.

The molecular weight of the polycarbonate resin is not specified, but if the molecular weight is less than 10,000, the strength and the like will be reduced, and if it is more than 50,000, the moldability will be reduced. 10,000
~ 50,000, preferably 14,000 to 3
000 is more preferable, and 1 is more preferable.
6,000-25,000.

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 an aromatic polycarbonate resin in 100 ml of methylene chloride at 20 ° C. Viscosity (η _SP ) = (t−t ₀ ) / t ₀ [t ₀ is the number of seconds of falling of 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

The aromatic polycarbonate resins include those having different dihydric phenols, those with and without terminal stoppers, those with linear and branched chains, those with different production methods, and those with terminal stoppers. , Two or more having different structures and properties such as polycarbonate and polyester carbonate may be mixed.
In this case, it is naturally possible to mix with an aromatic polycarbonate resin having a viscosity average molecular weight outside the above range.

In the present invention, as one of the component A, the aromatic polycarbonate resin (A) contains 0.05 to 0.3 mol% of a repeating unit having a branched structure in 100 mol% of the repeating unit. 2 component) can also be used (hereinafter sometimes referred to as "branched aromatic polycarbonate resin"). By using such a branched aromatic polycarbonate resin, it is possible to suppress melt dripping (so-called drip) when the resin is burned, and to achieve higher flame retardancy. In order to produce such a branched aromatic polycarbonate resin, a method of copolymerizing a trifunctional or higher polyfunctional aromatic compound is usually 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.

In the branched aromatic polycarbonate resin suitable as the component A, the proportion of the polyfunctional compound is such that the repeating unit having a branched structure is 0.05 to 0.05 mol% of the repeating unit in the aromatic polycarbonate resin.
It is 0.3 mol%, more preferably 0.05 to 0.2 mol%, and still more preferably 0.05 to 0.15 mol%.

In particular, in the case of the melt transesterification method, a branched structure may occur as a side reaction. That is, even when the polyfunctional aromatic compound is not contained, a branched structure is generated due to an isomerization reaction of a monomer component during the polymerization reaction. The component A of the present invention also includes such a branched aromatic polycarbonate resin. The ratio can be calculated by ¹ H-NMR measurement.

Further, a repeating unit having the above branched structure is represented by A
The aromatic polycarbonate resin (component A-2) comprising 0.05 to 0.3 mol% in 100 mol% of the repeating unit of the component is an aromatic polycarbonate resin containing a higher concentration of a branch component, and a branched component. It is also possible to use a mixture of an aromatic polycarbonate resin having a low content of or containing substantially no branched component.

In the present invention, as one of the components A, A
Aromatic polycarbonate resin having a viscosity average molecular weight of 70,000 to 300,000 (A-3-1 component) and aromatic polycarbonate resin having a viscosity average molecular weight of 10,000 to 30,000 (A-3-2 component) And an aromatic polycarbonate resin (A3 component) having a viscosity average molecular weight of 16,000 to 35,000 (hereinafter sometimes referred to as an "aromatic polycarbonate resin containing a high molecular weight component").

The aromatic polycarbonate resin containing the high molecular weight component (A3 component) increases the entropy elasticity of the resin due to the presence of the A-3-1 component, and has draw-down properties in blow molding and the like, and anti-drip properties in combustion. And functions such as jetting prevention in injection molding. On the other hand, by containing the low molecular weight component of the A-3-2 component, the overall melt viscosity is significantly reduced, and the practicality in various molding methods such as injection molding is sufficiently satisfied. That is, while achieving a higher degree of flame retardancy as in the case of the above-mentioned branched aromatic polycarbonate resin, it simultaneously has the above various functions.

In the aromatic polycarbonate resin containing a high molecular weight component (A3 component), the molecular weight of the A-3-1 component is preferably from 70,000 to 200,000, more preferably from 80,000 to 200,000, and still more preferably. 1
00,000 to 200,000, particularly preferably 10
It is between 000 and 160,000. Further, the molecular weight of the A-3-2 component is preferably 10,000 to 25,000,
More preferably, 11,000 to 24,000, further preferably 12,000 to 24,000, particularly preferably 1 to 24,000.
2,000 to 23,000.

The high molecular weight component-containing aromatic polycarbonate resin (A3 component) is obtained by mixing the above-mentioned A-3-1 component and A-3-2 component at various ratios and adjusting the mixture so as to satisfy a predetermined molecular weight range. be able to. Preferably, the amount of the A-3-1 component is 2 to 40% by weight in 100% by weight of the A3 component, more preferably the A-3-1 component is 3 to 30% by weight, and still more preferably A- 3-1 component is 4 to 20
% By weight, particularly preferably 5 to 2% of the A-3-1 component.
0% by weight.

The method for adjusting the component A-3 is as follows.
(1) a method of independently polymerizing the A-3-1 component and the A-3-2 component and mixing them;
GP, represented by the method disclosed in JP-A-306336
A method for producing an aromatic polycarbonate resin exhibiting a plurality of polymer peaks in a molecular weight distribution chart by the method C in the same system, and producing such an aromatic polycarbonate resin so as to satisfy the condition of the component A-1 of the present invention. And (3) an aromatic polycarbonate resin obtained by the production method (the production method of (2));
A-3-1 component and / or A-3- produced separately
A method of mixing two components can be used.

The component B used in the present invention is at least one kind of metal salt compound selected from alkali metal salts and alkaline earth metal salts, and various components conventionally used for flame retarding polycarbonate resins. Can be used. For example, a metal salt of an organic sulfonic acid, a metal salt of a sulfate ester, a metal salt of a phosphate ester, and a metal salt of a carboxylic acid can be exemplified. As the metal forming the metal salt, an alkali metal and an alkaline earth metal are preferable. The alkali metals of the invention include lithium, sodium, potassium, rubidium, and cesium, and the alkaline earth metals include beryllium, magnesium, calcium, strontium, and barium.

The metal salts of the organic sulfonic acids of the present invention include alkali metal salts of aliphatic sulfonic acids, alkaline earth metal salts of aliphatic sulfonic acids, alkali metal salts of aromatic sulfonic acids, and alkali metal salts of aromatic sulfonic acids. 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) 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 salt of ethanesulfonic acid is exemplified by an alkali (earth) of perfluoroalkanesulfonic acid.
As the metal salt, potassium perfluorobutanesulfonate can be particularly preferably mentioned.

As the aromatic sulfonic acid used in the alkali (earth) metal salt of aromatic sulfonic acid, sulfonic acid of monomeric or polymeric 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.

The alkali (earth) metal sulfonates of aromatic carboxylic acids and esters are described in JP-A-50-9.
No. 8540, and examples thereof include potassium 5-sulfoisophthalate, sodium 5-sulfoisophthalate, and polysodium polyethylene terephthalate polysulfonate.

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

As monomeric or polymeric alkali (earth) metal salts of aromatic sulfonates, 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 (earth) metal salts of aromatic sulfone sulfonates are described in JP-A-52-54746. Such a metal salt can be represented by the following formula (5).

[0066]

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(Where A and B are an alkali metal or an alkaline earth metal, q and r are any integers selected from 0, 1, and 2; and q + r is an integer of 1 to 4) A and B may be the same or different from each other.)

Examples of such metal salts include sodium diphenylsulfon-3-sulfonate, potassium diphenylsulfon-3-sulfonate, and diphenylsulfone-3-sulfonate.
Examples thereof include dipotassium 3,3'-disulfonate and dipotassium diphenylsulfone-3,4'-disulfonate.

The alkali (earth) 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 sulfonate (earth) 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 metal salt of an aromatic sulfonate (earth) 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 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.

Among the above-mentioned alkali (earth) metal salts, the alkali (earth) metal salt of aromatic sulfonesulfonic acid represented by the above formula (5) and the alkali (earth) metal of perfluoroalkanesulfonic acid A metal salt can be mentioned as a more preferable B component.

The phosphate metal salts of the present invention include:
For example, compounds represented by the following general formulas (6), (8) and (9) can be exemplified.

[0077]

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(In the formula (6), M is a group 1 of the periodic table, 2
Group 3, Group 8, Group 11, Group 11, or Group 12 metals.
Z ¹ and Z ² each represent a monovalent organic group having 1 to 20 carbon atoms. Further, when Z ¹ and Z ² are both aryl groups, Z ¹ and Z ² are combined to include a group represented by the following general formula (7). )

[0079]

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[0080] (In the formula (7), R ³ and R ⁴ each represent a monovalent organic group having 1 to 9 carbon atoms. The m ³ and m ⁴ .R ³ representing integers of 0-3 And R ⁴ may be the same or different from each other, a plurality of R ³ and R ⁴ may be the same or different from each other, and Y represents a single bond or CR ⁵ R ⁶ ( Wherein C represents a carbon atom, R ⁵ represents a hydrogen atom or a methyl group bonded to C, and R ⁵ represents
⁶ represents a hydrogen atom bonded to C or a monovalent organic group having 1 to 9 carbon atoms). )

[0081]

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(In the formula (8), M is a group 1 of the periodic table, 2
Group 3, Group 8, Group 11, Group 11, or Group 12 metals. )

[0083]

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(In the formula (9), M is a group 1 of the periodic table, 2
Group 3, Group 8, Group 11, Group 11, or Group 12 metals.
Z ³ and Z ⁴ each represent a monovalent organic group having 1 to 20 carbon atoms. )

In the above general formulas (6), (8) and (9), M is preferably an alkali metal of Group 1 of the periodic table or an alkaline earth metal of Group 2 of the periodic table.
More preferably, it is at least one atom selected from Na, K, Ca and Mg. Particularly, Na and K are preferable in the general formula (6), and Ca and Mg are preferable in the general formula (8).

Further, specific examples of Z ¹ and Z ² in the general formula (6) and Z ³ and Z ⁴ in the general formula (9) include a methyl group, an ethyl group,
Propyl, isopropyl, n-butyl, s-butyl, isobutyl, t-butyl, neopentyl,
n-pentyl group, isopentyl group, s-pentyl group, n
-Hexyl group, n-octyl group and n-nonyl group.

The cycloalkyl group includes a cyclohexyl group.

Examples of the aryl group include a phenyl group, a 1-naphthyl group and a 2-naphthyl group.

The aryl group having an alkyl substituent includes a 2-methylphenyl group, a 3-methylphenyl group,
-Methylphenyl group, 2,4-xylyl group, 2,6-xylyl group, 2-tert-butyl-4-methylphenyl group, 2,6-di-tert-butylphenyl group, 2,4
-Di-tert-butylphenyl group, 2,4-dimethyl-6-tert-butylphenyl group, 2,4,6-tri-tert-butylphenyl group, 2,6-di-tert
-Butyl-4-methylphenyl group, 2,6-di-ter
t-butyl-4-ethylphenyl group, 4-tert-butyl-2,6-dimethylphenyl group, 2,6-di-te
rt-butyl-4-s-butylphenyl group, 4-isopropylphenyl group, 4-tert-butylphenyl group,
4-isobutylphenyl group, 4-n-butylphenyl group, 4-neopentylphenyl group, 4-n-octylphenyl group, 4-n-heptylphenyl group, 4-hexylphenyl group, and 4-n-nonylphenyl And the like.

Examples of the aryl group having an aralkyl substituent include a 4- (2-phenylisopropyl) phenyl group.

Examples of the aryl group having an aryl substituent include a 2-phenylphenyl group, a 3-phenylphenyl group,
And a 4-phenylphenyl group. Organic phosphoric acid ester metal salts having the groups specifically exemplified above can be preferably used.

Of the above, organophosphate metal salts having an aryl group are preferred. In particular, an organic metal phosphate salt having an aryl group having an alkyl substituent, an aralkyl substituent and an aryl substituent is preferred.

On the other hand, when the compound has a substituent represented by the general formula (7), such an organic metal phosphate salt can be produced by a known method. In this case, as a raw material, the following general formula (1)
The bisphenol compound shown in 0) or a reactive derivative thereof is used.

[0094]

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(In the formula (10), R^ThreeAnd R^FourAre each
It represents a monovalent organic group having 1 to 9 carbon atoms. Also m^ThreeAnd m^Four
Represents an integer of 0 to 3, respectively. R^ThreeAnd R^FourAre each other
The same or different cases can be selected. More
Number R^ThreeAnd R^FourAre the same or different from each other
In the case of deviation, it can be selected. Y is a single bond or CR
^FiveR⁶Wherein C represents a carbon atom and R^FiveIs in C
Denote a bonded hydrogen atom or a methyl group;⁶Is
A hydrogen atom bonded to C or an organic group having 1 to 9 carbon atoms
Shown). )

Specific examples of the compound represented by formula (10) 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, and they can be preferably used.

The compound of the general formula (10) 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).

As the organophosphate metal salt represented by the general formula (6), a commercially available product such as ADK STAB NA-1 represented by the following formula (11) manufactured by Asahi Denka Kogyo KK
0 and NA-11 represented by the following formula (12). These are readily available.

[0099]

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[0100]

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The cyclic phosphate metal salts represented by the general formula (8) include sodium-2,4,8,1
0-tetraoxa-3,9-diphosphaspiro [5.
5] Undecane 3,9-dihydroxy-3,9-dioxide, potassium-2,4,8,10-tetraoxa-
3,9-diphosphaspiro [5.5] undecane 3,9
-Dihydroxy-3,9-dioxide, calcium-
2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane 3,9-dihydroxy-
3,9-dioxide, magnesium-2,4,8,1
0-tetraoxa-3,9-diphosphaspiro [5.
5] undecane 3,9-dihydroxy-3,9-dioxide, aluminum-2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane 3,9-dihydroxy-3,9-di Oxide, barium-2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane 3,9-dihydroxy-3,9-dioxide, zinc-2,4,8,10-tetraoxa- 3,9-diphosphaspiro [5.5] undecane 3,9-dihydroxy-3,9-dioxide,
Or tin-2,4,8,10-tetraoxa-3,9
-Diphosphaspiro [5.5] undecane 3,9-dihydroxy-3,9-dioxide; Of these, calcium-2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane 3,9-dihydroxy-3,9-dioxide is particularly preferred.

The alkoxysilane compound (component C) used in the present invention is represented by the above formula (1).

Specific examples of the alkoxysilane compound of the component C include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, tetraisobutoxysilane, tetraacetosilane and the like. (N = 4 in the formula (1)), methyltrimethoxysilane,
Methyltriethoxysilane, methyltrimethoxyethoxysilane, methyltriacetoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, isobutyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxyethoxy Silane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriacetoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-amino Propyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, N-β (aminoethyl)-
γ-aminopropyltrimethoxysilane, N-β (aminoethyl) -γ-aminopropyltriethoxysilane,
β-cyanoethyltriethoxysilane, methyltriphenoxysilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, α-glycidoxyethyltrimethoxysilane, α-glycidoxyethyltriethoxysilane, β- Glycidoxyethyltrimethoxysilane, β-glycidoxyethyltriethoxysilane, α-glycidoxypropyltrimethoxysilane, α-glycidoxypropyltriethoxysilane, β
-Glycidoxypropyltrimethoxysilane, β-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltripropoxysilane, γ -Glycidoxypropyltributoxysilane, γ-glycidoxypropyltrimethoxyethoxysilane, γ-glycidoxypropyltriphenoxysilane, α-glycidoxybutyltrimethoxysilane, α-glycidoxybutyltriethoxysilane, β-
Glycidoxybutyltrimethoxysilane, β-glycidoxybutyltriethoxysilane, γ-glycidoxybutyltrimethoxysilane, γ-glycidoxybutyltriethoxysilane, δ-glycidoxybutyltrimethoxysilane, δ- Glycidoxybutyltriethoxysilane,
(3,4-epoxycyclohexyl) methyltrimethoxysilane, (3,4-epoxycyclohexyl) methyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ) Ethyltriethoxysilane, β
-(3,4-epoxycyclohexyl) ethyltripropoxysilane, β- (3,4-epoxycyclohexyl) ethyltributoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β-
(3,4-epoxycyclohexyl) ethyltriphenoxysilane, γ- (3,4-epoxycyclohexyl)
Propyltrimethoxysilane, γ- (3,4-epoxycyclohexyl) propyltriethoxysilane, δ-
Trialkoxy, triacyloxy or triphenoxysilanes (n = 3 in the formula (1)) such as (3,4-epoxycyclohexyl) butyltrimethoxysilane and δ- (3,4-epoxycyclohexyl) butyltriethoxysilane; And dimethyldimethoxysilane, phenylmethyldimethoxysilane, dimethyldiethoxysilane, phenylmethyldiethoxysilane, dimethyldiacetoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-mercaptopropylmethyl Dimethyldimethoxysilane, γ-mercaptopropyldiethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, vinylmethyldimethoxysila , Vinylmethyldiethoxysilane, glycidoxymethyldimethoxysilane, glycidoxymethyldiethoxysilane, α-glycidoxyethylmethyldimethoxysilane, α-glycidoxyethyldiethoxysilane, β-glycidoxyethylmethyldimethoxy Silane, β-glycidoxyethylmethyldiethoxysilane, α-glycidoxypropylmethyldimethoxysilane, α-glycidoxypropylmethyldiethoxysilane, β-glycidoxypropylmethyldimethoxysilane, β-glycidoxypropyl Methyldiethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldipropoxysilane, γ-glycidoxypropylmethyldibutoxysilane, γ- G Sidoxypropylmethyldimethoxyethoxysilane, γ-glycidoxypropylmethyldiphenoxysilane, γ-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylethyldiethoxysilane, γ-glycidoxypropylethyldipropoxysilane Alkoxysilanes or diacyloxysilanes such as γ-glycidoxypropylvinyldimethoxysilane, γ-glycidoxypropylvinyldiethoxysilane, γ-glycidoxypropylphenyldimethoxysilane, γ-glycidoxypropylphenyldiethoxysilane (N = 2 in the formula (1)). These organic siloxanes can be used alone or in combination of two or more.

More preferably, n = 3 or 4 in the above formula (1). R ¹ is an alkyl group having 1 to 4 carbon atoms, and R ² is a group consisting of an alkyl group having 1 to 4 carbon atoms, a vinyl group, a methacryloxy group, an amino group, a glycidoxy group, and a 3,4-epoxycyclohexyl group. More preferably, it is an alkyl group having 1 to 3 carbon atoms substituted with one or more groups selected from Specifically, for example, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, tetraisobutoxysilane, methyltrimethoxysilane, methyltriethoxysilane,
Ethyltrimethoxysilane, isobutyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyl Trimethoxysilane, γ-aminopropyltrimethoxysilane,
γ-aminopropyltriethoxysilane, N-β (aminoethyl) -γ-aminopropyltrimethoxysilane,
N-β (aminoethyl) -γ-aminopropyltriethoxysilane, dimethyldimethoxysilane, vinylmethyldimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-aminopropylmethyldi Ethoxysilane and the like are mentioned, and among them, methyltrimethoxysilane, vinyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, and N-β (aminoethyl) -γ-aminopropyltriethoxysilane are preferable. These can be used alone or in combination.

Examples of the fluorine-containing polymer having a fibril-forming ability used in the present invention include polytetrafluoroethylene, tetrafluoroethylene copolymers (eg, tetrafluoroethylene / hexafluoropropylene copolymer), and US Pat. No. 4,379,910. Japanese Patent Application Publication No. JP-A-2005-64131 discloses a partially fluorinated polymer, a polycarbonate resin produced from a fluorinated diphenol, and the like, preferably polytetrafluoroethylene (hereinafter sometimes referred to as PTFE).

The molecular weight of PTFE having a fibril-forming ability is extremely high, and tends to form a fibrous state by bonding PTFE together by an external action such as shearing force. Its molecular weight is 1,000,000 to 10,000,000, more preferably 2,000,000 to 9,000,000, in number average molecular weight determined from the standard specific gravity. As the PTFE, not only a solid form but also an aqueous dispersion form can be used. Further, PTFE having such a fibril-forming ability can improve the dispersibility in a resin, and a PTFE mixture in a mixed form with another resin can be used in order to obtain better flame retardancy and mechanical properties. is there.

PTFE having such fibril-forming ability
Examples of commercially available products include Teflon 6J manufactured by DuPont-Mitsui Fluorochemicals Co., Ltd., and Polyflon MPA FA500 and F-201L manufactured by Daikin Chemical Industries, Ltd. Commercially available PTFE aqueous dispersions include Fluon AD-1, AD-936 manufactured by Asahi ICI Fluoropolymers Co., Ltd., Fluon D-1, D-2 manufactured by Daikin Industries, Ltd., and Mitsui-Dupont Fluoro. Teflon 30J manufactured by Chemical Co., Ltd. can be mentioned as a representative.

The mixed form of PTFE includes (1) PT
A method in which an aqueous dispersion of FE and an aqueous dispersion or solution of an organic polymer are mixed and coprecipitated to obtain a coaggregated mixture (JP-A-60-258263, JP-A-63-15474).
4, a method of mixing an aqueous dispersion of PTFE and dried organic polymer particles (a method described in JP-A-4-272957),
(3) A method of uniformly mixing an aqueous dispersion of PTFE and an organic polymer particle solution and simultaneously removing the respective media from the mixture (described in JP-A-06-220210, JP-A-08-188655, and the like) Method),
(4) a method of polymerizing a monomer that forms an organic polymer in an aqueous dispersion of PTFE (method described in JP-A-9-95583), and (5) an aqueous dispersion of PTFE and an organic polymer. After uniformly mixing the coalesced dispersion, a vinyl-based monomer is further polymerized in the mixed dispersion, and then a mixture obtained by a method of obtaining a mixture (a method described in JP-A-11-29679, etc.) is used. Can be used. PT of these mixed forms
Commercially available FEs include “METABLEN A3000” (trade name) manufactured by Mitsubishi Rayon Co., Ltd., and “BLENDEX449” (trade name) manufactured by GE Specialty Chemicals.

The proportion of PTFE in the mixed form was as follows: PTFE was 1 to 6 in 100% by weight of the PTFE mixture.
It is preferably in the range of 0% by weight, more preferably in the range of 5 to 55% by weight. When the proportion of PTFE is in such a range, good dispersibility of PTFE can be achieved.

The components A, B, C and D of the present invention
The composition ratio of the components is 0.001 to 1 part by weight of the component B, 0.05 to 5 parts by weight of the component C, and 0.01 to 1 part by weight of the component D based on 100 parts by weight of the component A. A preferred ratio is 100 parts by weight of the component A, and 0.0% of the component B.
0.01 to 0.7 parts by weight, 0.1 to 4 parts by weight of the C component, and 0.03 to 0.7 parts by weight of the D component. A more preferable ratio is 100 parts by weight of the component A,
Component B is 0.005 to 0.5 parts by weight, and component C is 0.5 to 0.5 parts by weight.
3 parts by weight and the D component may be 0.05 to 0.5 parts by weight.

If the B component is less than 0.001 part by weight, the flame retardancy may be insufficient, and if it exceeds 1 part by weight, problems such as a decrease in thermal stability and metal corrosion may occur. If the amount of the component C is less than 0.05 part by weight, the flammability and the thermal stability may be insufficient. D component is 0.0
If the amount is less than 1 part by weight, the drip prevention effect is insufficient, and if it exceeds 1 part by weight, the impact value decreases, which is not preferable. When PTFE in a mixed form is used as the D component, the amount of the PTFE contained in the mixture is the amount of the D component.

The flame-retardant aromatic polycarbonate resin composition of the present invention may further comprise an inorganic filler 1 to 3 as an E component.
50 parts by weight can be blended. In a conventional flame retardant formulation using a metal salt compound, when an inorganic filler is combined, the flame retardancy is significantly reduced, and a high-rigidity, high-strength material having such a flame retardant formulation cannot be obtained. On the other hand, in the flame-retardant aromatic polycarbonate resin composition of the present invention, not only the thermal stability of the metal salt compound is improved, but also a good flame-retardant effect can be obtained in combination with an inorganic filler having poor compatibility. It is possible to demonstrate.

Inorganic filler (E component) used in the present invention
May be in any form of plate, granule, needle, or fiber, and is generally used as a resin filler. For example, alumina, zinc oxide, titanium oxide, cerium oxide,
Metal oxides such as calcium oxide and magnesium oxide;
Metal hydroxides such as calcium hydroxide, magnesium hydroxide and aluminum hydroxide; basic magnesium carbonate;
Carbonates such as calcium carbonate, magnesium carbonate, zinc carbonate, barium carbonate, dawsonite, and hydrotalcite; sulfates such as calcium sulfate, barium sulfate, magnesium sulfate, and gypsum fiber; calcium silicate (wollastonite, zonotolite, etc.), talc Silicate compounds such as clay, mica, montmorillonite, bentonite, activated clay, sepiolite, imogolite, palygorskite (attapulgite), sericite, kaolin, vermiculite, smectite; glass fiber;
Glass-based fillers such as milled glass fibers, glass beads, glass flakes, and glass balloons; silicate compounds such as silica (such as white carbon) and silica sand; and ferrites. Other inorganic fillers include red phosphorus, carbon black (acetylene black, oil furnace black, lamp black, etc.), graphite, graphite whiskers, carbon nanotubes, fullerenes, carbon fibers, metal fibers, various metal-coated fibers, titanate. Potassium whiskers and aluminum borate whiskers can also be used.

Of these, silicate compounds and glass-based fillers are preferably used from the viewpoint of characteristics. For example, talc, wollastonite, mica, and glass fiber are preferred. More preferably, it is a silicate compound.
Better flame retardancy is achieved than with silicate compounds. Among them, talc and wollastonite are more preferable, and wollastonite is particularly preferable. Further, the above-mentioned inorganic fillers may be used alone or in combination of two or more.

When the composition contains the component E, its composition ratio is as follows:
The amount is preferably 1 to 50 parts by weight based on 100 parts by weight of the aromatic polycarbonate resin (A component). Preferably, it is 2 to 30 parts by weight, more preferably 3 to 20 parts by weight, per 100 parts by weight of the aromatic polycarbonate resin (A component). In the range of 1 to 50 parts by weight, a flame-retardant aromatic polycarbonate resin composition having high rigidity and a flame-retardant formulation using a metal salt compound is achieved.

On the other hand, the alkoxysilane compound as the component C of the present invention is considered to have some effect on the inorganic filler as the component E of the present invention. Therefore, their composition ratio is also important. is there. The ratio of the C component to the E component is such that the C component is 3 to 5 parts per 100 parts by weight of the E component.
The range is preferably 0 parts by weight, more preferably 5 to 40 parts by weight, and still more preferably 7 to 35 parts by weight.

The flame-retardant aromatic polycarbonate resin composition of the present invention may further contain an organic siloxane having an aromatic group as the F component. When the organic siloxane is contained, the composition ratio is preferably from 0.1 to 5 parts by weight, more preferably from 0.3 to 3 parts by weight, per 100 parts by weight of the component A. As a result, even higher levels of flame retardancy can be achieved without impairing properties such as thermal stability.

The organic siloxane having an aromatic group (component F) used in the present invention is an organic siloxane having a phenyl group, a biphenyl group, a naphthalene group, or a derivative thereof as an aromatic group, and among them, a phenyl group. Organic siloxanes are preferred. The content of the aromatic group is preferably at least 10 mol%, more preferably at least 20 mol% and at most 95 mol%, of the organic functional groups contained in the component F. As the organic group other than the aromatic group, a methyl group is preferable. Further, the organic siloxane which is the component F 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. Such an organic siloxane may be used alone or in combination.

Further, the component F of the present invention has a weight average molecular weight of 300 to 10,000 as measured by the following GPC (gel permeation chromatography) method.
0, more preferably a weight average molecular weight of 400 to 5,000, even more preferably 400 to 1,000.
0. The GP used for the measurement of the F component of the present invention
Method C is as follows: device: Gulliver series (manufactured by JASCO), column: MIXED-C (manufactured by PL), mobile phase: chloroform, standard substance: EasyCal (PS-2), detector:
Using a differential refractometer at a flow rate of 1 ml / min, a concentration of 0.1
100 μl of the mg / ml sample was injected, and the column temperature was 35 ° C.
It was measured at.

Preferred examples of the component F include at least one compound selected from the compounds represented by the general formulas (13) and (14).

[0121]

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(Wherein β ¹ represents a vinyl group, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, and an aryl group and an aralkyl group having 6 to 12 carbon atoms. Γ ¹ , γ ² , γ ³ , γ ⁴ , γ ⁵ , and γ ⁶ have 1 to 1 carbon atoms
6 represents an alkyl group and a cycloalkyl group, and an aryl group and an aralkyl group having 6 to 12 carbon atoms, and at least one group is an aryl group or an aralkyl group. δ ¹ , δ ² and δ ³ each represent an alkoxy group having 1 to 4 carbon atoms. )

[0123]

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(Wherein β ² and β ³ represent a vinyl group, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, and an aryl group and an aralkyl group having 6 to 12 carbon atoms. ^{γ 7, γ 8, γ 9} , γ 10, γ 11, γ 12, γ 13
And γ ¹⁴ are an alkyl group having 1 to 6 carbon atoms, 3 to 6 carbon atoms.
And an aryl group and an aralkyl group having 6 to 12 carbon atoms, wherein at least one group is an aryl group or an aralkyl. δ ⁴ , δ ⁵ , δ ⁶ , and δ ⁷ each represent an alkoxy group having 1 to 4 carbon atoms. ) When the component F is contained, the composition ratio is 0.1 to 5 parts by weight based on 100 parts by weight of the aromatic polycarbonate resin (component A).
Parts by weight, preferably 0.5 to 4 parts by weight, more preferably 1 to 3% by weight, based on 100 parts by weight of the aromatic polycarbonate resin (A component).

The flame-retardant aromatic polycarbonate resin composition of the present invention may contain various additives as long as the effects of the present invention are not impaired. Heat stabilizer, UV absorber,
Light stabilizers, mold release agents, lubricants, sliding agents, colorants (pigments and dyes such as carbon black and titanium oxide), polymer crosslinked particles, high heat-resistant polymer particles, fluorescent brighteners, phosphorescent pigments, fluorescent dyes And antistatic agents, flow modifiers, crystal nucleating agents, inorganic and organic antibacterial agents, photocatalytic antifouling agents (fine particle titanium oxide, fine particle zinc oxide, etc.), infrared absorbers, photochromic agents, and the like. In order to prevent the deterioration of the resin composition, it is preferable that a heat stabilizer, an ultraviolet absorber, a light stabilizer and the like are contained in the resin composition. In particular, it is preferable to include a heat stabilizer.

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

As the phosphite-based stabilizer, a phosphite compound having an aryl group in which two or more alkyl groups are substituted is preferable. For example, tris (diethylphenyl) phosphite, tris (di-iso-propylphenyl) phosphite, tris (di-n-butylphenyl) phosphite, tris (2,4-di-tert)
-Butylphenyl) phosphite, tris (2,6-di-tert-butylphenyl) phosphite, tris (2,6-di-tert-butylphenyl) phosphite and the like, and particularly tris (2,4- J-tert
-Butylphenyl) phosphite is preferred.

Further, a phosphite compound having an aryl group in which a part of the aryl group has a cyclic structure can also be used. For example, 2,2'-methylenebis (4,6-di-te
rt-butylphenyl) (2,4-di-tert-butylphenyl) phosphite, 2,2′-methylenebis (4,6-di-tert-butylphenyl) (2-te
rt-butyl-4-methylphenyl) phosphite,
2,2′-methylenebis (4-methyl-6-tert-
Butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite, 2,2′-ethylidenebis
(4-methyl-6-tert-butylphenyl) (2-
tert-butyl-4-methylphenyl) phosphite and the like.

Other examples of the phosphorus-based heat stabilizer other than those described above include the following. As the phosphite compound, distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) Pentaerythritol diphosphite, phenylbisphenol A
Examples thereof include pentaerythritol diphosphite, dicyclohexylpentaerythritol diphosphite, and the like. Preferably, distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, 4,4′-
Isopropylidene diphenol ditridecyl phosphite.

Examples of the phosphate compound include tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, triethyl phosphate, diphenylcresyl phosphate, diphenyl monoorthoxenyl phosphate, tributoxyethyl phosphate, dibutyl phosphate, and tributyl phosphate. Dioctyl phosphate,
Diisopropyl phosphate and the like,
Preferred are triphenyl phosphate and trimethyl phosphate.

As the phosphonite compound, tetrakis (2,4-di-tert-butylphenyl) -4,4 ′
-Biphenylenediphosphonite, tetrakis (2,4-
Di-tert-butylphenyl) -4,3'-biphenylenediphosphonite, tetrakis (2,4-di-ter
t-butylphenyl) -3,3′-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite,
Tetrakis (2,6-di-tert-butylphenyl)
-4,3'-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -3,3 '
-Biphenylenediphosphonite, bis (2,4-di-t
tert-butylphenyl) -4-phenyl-phenylphosphonite, bis (2,4-di-tert-butylphenyl) -3-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 tetrakis (di-tert-butylphenyl) -biphenylenediphosphonite and bis (di-tert-butylphenyl) -phenyl-phenylphosphonite are preferred,
Tetrakis (2,4-di-tert-butylphenyl)
-Biphenylenediphosphonite, bis (2,4-di-t
(tert-butylphenyl) -phenyl-phenylphosphonite is more preferred. Such a phosphonite compound can be preferably used in combination with the phosphite compound having an aryl group in which two or more alkyl groups are substituted.

The flame-retardant aromatic polycarbonate resin composition of the present invention can contain various stabilizers. Examples of the antioxidant include a phenol-based antioxidant and a sulfur-based antioxidant. Various phenolic antioxidants can be used.

Specific examples of the phenolic antioxidant include, for example, n-octadecyl-β- (4′-hydroxy-3 ′, 5′-di-tert-butylphenyl) propionate, 2-tert-butyl-6- (3'-ter
t-butyl-5'-methyl-2'-hydroxybenzyl) -4-methylphenyl acrylate, 3,9-bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyl Oxy] -1,
1, -dimethylethyl {-2,4,8,10-tetraoxaspiro [5,5] undecane and tetrakis [methylene-3- (3 ', 5'-di-tert-butyl-4-hydroxyphenyl) Propionate] methane and the like, and n-octadecyl-β
More preferred is-(4'-hydroxy-3 ', 5'-di-tert-butylphenyl) propionate.

Specific examples of the sulfur-based antioxidant of the present invention include dilauryl-3,3'-thiodipropionate, ditridecyl-3,3'-thiodipropionate, and dimyristyl-3,3'-. Thiodipropionate, distearyl-3,3'-thiodipropionate, laurylstearyl-3,3'-thiodipropionate, 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 can be mentioned. More preferably, pentaerythritol tetra (β-laurylthiopropionate) ester can be mentioned.

The flame-retardant aromatic polycarbonate resin composition of the present invention may contain an ultraviolet absorber. Examples of the ultraviolet absorber include 2-hydroxy-4-n-dodecyloxybenzophenone and 2,2′-dihydroxy-
Benzophenone ultraviolet absorbers represented by 4,4'-dimethoxybenzophenone, 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-3 ′, 5′-di-tert-amylphenyl) benzotriazole,
-(2'-hydroxy-3 ', 5'-bis (α, α'-
Dimethylbenzyl) phenylbenzotriazole, 2,
2 ′ methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol], methyl-3- [3-tert-butyl-5- (2H -Benzotriazol-2-yl) -4
And benzotriazole-based ultraviolet absorbers represented by condensates with -hydroxyphenylpropionate-polyethylene glycol.

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

Further, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,2)
6,6-pentamethyl-4-piperidyl) sebacate,
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]} and hindered amine light stabilizers represented by polymethylpropyl 3-oxy- [4- (2,2,6,6-tetramethyl) piperidinyl] siloxane and the like. Such light stabilizers exhibit better performance in terms of weather resistance and the like when used in combination with the above-mentioned ultraviolet absorbers and various antioxidants.

The above-mentioned phosphorus-based stabilizers, phenolic antioxidants, and sulfur-based antioxidants can be used alone or in combination of two or more.

The ratio of these stabilizers in the composition is as follows:
Flame-retardant aromatic polycarbonate resin composition 10 of the present invention
0% by weight, phosphorus stabilizer, phenolic antioxidant,
Or the sulfur-based antioxidants are 0.0001 to 1 respectively.
% By weight. More preferably, 0.0% in 100% by weight of the flame retardant aromatic polycarbonate resin composition.
005 to 0.5% by weight. More preferably 0.00
1 to 0.2% by weight.

The proportions of the ultraviolet absorber and the light stabilizer are determined according to the flame retardant aromatic polycarbonate resin composition 100 of the present invention.
0.01 to 5% by weight, more preferably 0.02% by weight
１1% by weight.

The flame-retardant aromatic polycarbonate resin composition of the present invention can contain a release agent. Known release agents can be used. For example, saturated fatty acid ester, unsaturated fatty acid ester, polyolefin wax (polyethylene wax, 1-alkene polymer, etc .; those modified with a functional group-containing compound such as acid modification can also be used), fluorine compound (polyfluoroalkyl) Fluorine oil represented by ether), paraffin wax, beeswax, and the like.

Preferred releasing agents include saturated fatty acid esters. In the case of such a release agent, good transparency can be maintained. For example, glycerin fatty acid esters such as monoglyceride, diglyceride and triglyceride of stearic acid, polyglycerin fatty acid esters such as decaglycerin decasterate and decaglycerin tetrastearate, lower fatty acid esters such as stearic acid stearate, sebacic acid behenate and the like Erythritol esters such as pentaerythritol tetrastearate. The release agent is preferably 0.01 to 2% by weight based on 100% by weight of the flame-retardant aromatic polycarbonate resin composition.

The flame-retardant aromatic polycarbonate resin composition of the present invention may contain a bluing agent in order to cancel the yellow tint due to an ultraviolet absorber or the like. Specific examples of the blueing agent include Macrolex Blue RR, Macrolex Violet B, and Terazol Blue RLS.

For producing the flame-retardant aromatic polycarbonate resin composition of the present invention, any method is employed. For example, the components A to D, and optionally the components E, F and other additives are mixed with a V-blender, a Henschel mixer,
After sufficient premixing using a premixing means such as a mechanochemical device or an extruder, a granulation is optionally performed by an extruder or a briquetting machine, and then represented by a vented twin-screw ruder. Examples thereof include a method of melt-kneading with a melt-kneading machine and a method of pelletizing with a device such as a pelletizer.

In addition, a method in which each component is independently supplied to a melt kneader typified by a vent type twin screw ruder,
A method in which a part of each component is preliminarily mixed and then supplied to a melt kneader independently of the remaining components is also included. As a method of pre-mixing, for example, a method of blending a part of the aromatic polycarbonate resin powder to be blended with the blended additive to form a master batch of the additive diluted with the aromatic polycarbonate resin powder can be mentioned. Further, a method in which the component E is independently supplied to the melt kneader from the side may be used. 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 injection molding, not only normal molding methods but also gas assist injection molding, injection compression molding, injection press molding, insert molding, in-mold molding, local high-temperature mold molding (including heat-insulating mold molding), and two-color molding. , Sandwich 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 extruded products,
It can be used in the form of a sheet, a film and the like. For forming a sheet or a film, an inflation method, a calendar method, a casting method, or the like can be used.
Furthermore, it is also possible to form a heat-shrinkable tube by performing a specific stretching operation. Further, the flame-retardant aromatic polycarbonate resin composition of the present invention can be formed into a hollow molded article by rotational molding or blow molding.

The flame-retardant aromatic polycarbonate resin composition of the present invention has a very small environmental load without blending a halogen-based flame retardant and a phosphate ester-based flame retardant, has excellent thin-walled flame retardancy, and has excellent moldability. Since it is excellent in thermal stability and flame retardancy at the time, it is suitable for internal components and housings of OA equipment and home electric appliances. Such products include, for example, desktop personal computers, notebook personal computers, displays, printers, mobile terminals, mobile phones, copiers, faxes, recording media (CD, DVD, PD, FDD, etc.) playback devices, parabolic antennas, power tools, VTRs,
Examples include a TV, an iron, a hair dryer, a rice cooker, a microwave oven, an audio device, an audio device such as an audio laser disk (registered trademark) and a compact disk, a lighting device, a refrigerator, an air conditioner, a typewriter, and a word processor.

In addition, portable precision devices such as cameras, digital cameras, video movies, telescopes, binoculars, portable telephones, portable information terminals, portable notebook computers, portable tape recorders, portable optical disk players, portable navigation devices, watches, and the like; Vehicle parts such as lamp sockets, lamp reflectors, lamp housings, instrument panels, center console panels, deflector parts, car navigation parts, car stereo parts and the like can be mentioned. It is also useful for various uses such as machine parts and miscellaneous goods.

[0151]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited thereto. The following items were evaluated. Flame retardancy 0.8mm thickness, 1.0 made according to UL94 standard
The test was performed using test specimens of mm and 1.2 mm.
UL-94V-0, V-1, V-
It was rated as either 2 or Not-V. Thermal stability during molding The thermal stability during molding was evaluated by retracting the cylinder from the mold after the end of weighing in normal molding of an injection molding machine.
In the case where the resin was retained in the cylinder for 10 minutes in this state, the evaluation was performed by the following evaluation method. -1 Impact resistance (Izod impact strength with notch) For the case of normal molding and the case of standing for 10 minutes,
A test piece having a thickness of 1/8 "was prepared in accordance with ASTM standard D-256, and a comparative evaluation was performed. -2 Silver generation status The silver generation when the test sample of -1 was retained for 10 minutes and molded was determined as follows. In such a case, 場合 indicates that silver was not generated, and X indicates that silver was generated.

[Examples 1 to 20 and Comparative Examples 1 to 9]
The raw materials described in Tables 1 to 3 were prepared by superposing 10 parts by weight of PC-1, B component, C component, and other components (that is, excluding the remainder of A component and the D component) in the proportions shown in the table. The mixture was mixed uniformly using a mixer. The mixture was placed in a polyethylene bag, and the D component was further added. The bag was shaken relatively gently so as not to cause agglomerates due to the fibrillated PTFE to obtain a uniform mixture. Further, the mixture and the remaining component A were charged into a tumbler and uniformly mixed. The obtained mixture was extruded at a cylinder temperature of 280 ° C. with a twin-screw extruder having a diameter of 30 mm [Kobe Steel Ltd. KTX-30] to obtain pellets. The obtained pellets were dried at 110 ° C. for 5 hours with a hot-air circulation dryer,
A test piece was molded at a cylinder temperature of 300 ° C. and a mold temperature of 70 ° C. using an injection molding machine [Fanac Corporation T-150D].

Raw materials used in Tables 1 to 3 are as follows. (A component) PC-1: Linear aromatic polycarbonate resin powder (Aromatic polycarbonate resin produced from bisphenol A and phosgene and having a viscosity average molecular weight of 22,500, "PANLITE L-1225WP" manufactured by Teijin Chemicals Ltd.) PC-2: polycarbonate resin pellets obtained by a melt transesterification reaction of bisphenol A and diphenyl carbonate and having a branched bond component of about 0.1 mol% in all the repeating units (viscosity average molecular weight 22,500; The proportion of the binding component was calculated from ¹ H-NMR measurement, and was 0 mol% (no corresponding peak) in the polycarbonate resin of PC-1 similarly measured. PC-3: Branched aromatic polycarbonate resin Pellets ("Taflon IB2500" manufactured by Idemitsu Petrochemical Co., Ltd.) PC-4: Bispheno A and p as a terminator
-Tert-butylphenol and linear aromatic polycarbonate resins synthesized from phosgene by the interfacial polycondensation method, those having a viscosity average molecular weight of 15,200 are 10
80 parts by weight with a viscosity average molecular weight of 23,700 and 10 with a viscosity average molecular weight of 120,000.
Parts by weight are melt-mixed and have a viscosity average molecular weight of 2
9,500 aromatic polycarbonate resin pellets

(Component B) F-114: Perfluorobutanesulfonic acid potassium salt (Megafac F-114 manufactured by Dainippon Ink and Chemicals, Inc.)
P) KSS: 2: 8 mixture of dipotassium diphenylsulfone-3,3'-disulfonic acid and potassium diphenylsulfon-3-monosulfonate (KSS manufactured by UCB Japan) P-Ca: The prepared phosphate calcium salt represented by the following formula (15)

Reference Example Method for producing calcium phosphate ester salt: 204.2 g of pentaerythritol was placed in a 5-liter three-necked flask equipped with a stirrer, a reflux condenser, a dropping funnel, and an oil bath.
(1.5 mol), 920.0 g of phosphorus oxychloride (6.
0 mol), 5.48 g of N, N-dimethylformamide
(0.075 mol), and reacted at a reaction temperature of 40 ° C. for 6 hours under a nitrogen stream. The generated hydrogen chloride was absorbed into a sodium hydroxide aqueous solution outside the reaction system through a reflux condenser. After the completion of the reaction, most of the excess phosphorus oxychloride was distilled off, and the remaining white product was washed with methylene chloride and dried to obtain 3,9-dichloro-2,2,3.
4,8,10-tetraoxa-3,9-diphosphaspiro [5,5] undecane 3,9-dioxide
4 g were obtained (80% yield).

Next, a stirrer, a reflux condenser, a dropping funnel,
In a 5 liter three-necked flask equipped with an oil bath, N, N
-Dimethyl sulfoxide 904.2 g (11.6 mo
l) and cooled to 18 ° C. to give compound 3 obtained by the above method.
00.1 g (1.01 mol) was added little by little so as to keep the reaction temperature at 25 ° C. or lower, and the mixture was reacted for 1 hour. Chloroform was added to the white slurry after the reaction, and a white product was separated by filtration and further washed with chloroform. The obtained white product was dried to obtain 339.5 g of N, N-dimethylsulfoxonium salt of 2,4,8,10-tetraoxa-3,9-diphosphaspiro [5,5] undecanediphosphate ( Yield 100%).

Subsequently, in a 10-liter three-necked flask, 336.2 g (1.00 mol) of the compound obtained by the above method was dissolved in 5 liters of water, and 122.1 g of calcium carbonate was dissolved.
(1.22 mol) was added and reacted until the generation of bubbles ceased. After completion of the reaction, excess calcium carbonate was removed by a glass filter, and methanol was added to the filtrate to precipitate a white product. The precipitate is filtered off with suction filtration, dried and dried with 2,4,8,10-tetraoxa-
286.2 g (96% yield) of a calcium salt of 3,9-diphosphaspiro [5,5] undecane diphosphate was obtained.

[0158]

Embedded image

(Component C) C-1: γ-glycidoxypropyl-trimethoxysilane (“KBM-403” manufactured by Shin-Etsu Silicone Co., Ltd.) C-2: N-β (aminoethyl) γ-aminopropyl-
Trimethoxysilane (KBM manufactured by Shin-Etsu Silicone Co., Ltd.)
-603 ") C-3: Methyltrimethoxysilane (" KBM-13 "manufactured by Shin-Etsu Silicone Co., Ltd.) C-4: Vinyltrimethoxysilane (" KBM-1003 "manufactured by Shin-Etsu Silicone Co., Ltd.)

(D component) D-1: Polytetrafluoroethylene having fibril-forming ability (Polyflon MPA manufactured by Daikin Industries, Ltd.)
FA500) D-2: Mixture of polytetrafluoroethylene particles having fibril-forming ability and styrene-acrylonitrile copolymer particles (polytetrafluoroethylene content: 50% by weight) (manufactured by GE Specialty Chemicals)
BLENDEX449)

(E component) TALC: Talc (Upn HS manufactured by Hayashi Kasei Kogyo Co., Ltd.)
-T0.8) MICA: Mica (Micro Mica MK-100 manufactured by Corp Chemical) WSN: Wollastonite (NYGLOS manufactured by NYCO)
4) GF: Glass fiber (ECS 0 manufactured by NEC Corporation)
3T-511)

(Component F) Si-1: Substantially represented by the above formula (13) (partially there is a reaction between methoxy groups), and the ratio of vinyl group: methoxy group: phenyl group: methyl group (molar ratio) ) But about 2: 5: 7:
6, an organic siloxane having a weight average molecular weight of about 630 measured by a GPC method specified in the text (“X-40-9243” manufactured by Shin-Etsu Chemical Co., Ltd.) Si-2: phenyl group content Is an organic siloxane (organic siloxane not corresponding to the above formulas (13) and (14)) having a weight average molecular weight of 6,200 as measured by the GPC method defined in the text (GE Toshiba). "XC99-B566" manufactured by Silicone Corporation
4 ")

(Other Components) Antioxidant: Phosphorus antioxidant (Irgafos 168 manufactured by Nippon Ciba Geigy Co., Ltd.) Release agent: Saturated fatty acid ester-based release agent (Rikemar SL900 manufactured by Riken Vitamin Co., Ltd.)

[0164]

[Table 1]

[0165]

[Table 2]

[0166]

[Table 3]

As can be seen from Tables 1 to 3, the composition of the present invention has excellent thin-wall flame retardancy and excellent heat stability during molding without blending a halogen-based flame retardant and a phosphate-based flame retardant. It turns out that it is.

That is, flame retardancy and thermal stability are improved by combination with an alkoxysilane compound (for example, comparison between Example 1 and Comparative Examples 1 and 2). In addition, in the case of a flame-retardant polycarbonate resin composition formulated to be flame-retardant with a metal salt compound, the flame retardancy is greatly reduced by the addition of an inorganic filler (for example, comparison with Comparative Example 1 and Comparative Examples 6 and 7). On the other hand, in the case of the resin composition of the present invention, good flame retardancy is achieved (for example, comparison between Example 14 and Comparative Example 6,
Comparison between Example 17 and Comparative Example 7). From this comparison, it can be seen that the present invention achieves good flame retardancy even when compared with a resin composition in which an inorganic filler is simply added to a resin composition in which a conventionally known flame retardant component is combined.

It can be seen that higher flame retardancy can be achieved by further using the component F (for example, comparison of Examples 15 and 19 and Examples 17 and 20).

[0170]

EFFECT OF THE INVENTION The flame-retardant aromatic polycarbonate resin composition of the present invention has a small environmental load without blending a halogen-based flame retardant and a phosphoric ester-based flame retardant, has a thin-walled flame retardancy, and has good molding properties. Because of its excellent thermal stability, it is suitable for internal components and housings of OA equipment and home electric appliances. In particular, the present invention has achieved a polycarbonate resin composition having a higher rigidity by reducing the environmental load which has been conventionally difficult. Therefore, the industrial effect is enormous.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (reference) // (C08L 69/00 C08L 69/00 27:12) 27:12 (C08L 69/00 C08L 83:04 83:04 ) F term (reference) 4J002 BD152 CG001 CG032 CP033 DA028 DA038 DE078 DE088 DE098 DE108 DE138 DE148 DE188 DE238 DE268 DE288 DG048 DG058 DJ008 DL008 EG006 EV246 EV256 EX047 FD018 FD206 FD207 GM00 GN00 GQ00

Claims (5)

[Claims] 1. An aromatic polycarbonate resin (A component)
At least one metal salt selected from alkali metal salts and alkaline earth metal salts (B
Component) 0.001 to 1 part by weight, an alkoxysilane compound represented by the following formula (1) (C component) 0.05 to 5 parts by weight, a fluoropolymer having fibril-forming ability (D component) 0.01 to 1 A flame-retardant aromatic polycarbonate resin composition comprising parts by weight. Embedded image (Wherein, R ¹ is a monovalent organic group having 1 to 8 carbon atoms, and any of the same or different groups can be selected;
R ² is a monovalent organic group having 1 to 10 carbon atoms, which may be the same or different from each other, and n is 2,
3 or 4. ) 2. The flame-retardant aromatic polycarbonate resin composition according to claim 1, further comprising 1 to 50 parts by weight of an inorganic filler (E component). 3. The flame-retardant aromatic polycarbonate resin composition according to claim 1, wherein the inorganic filler (component E) is a silicate compound. 4. The composition ratio of the C component is 100% of the E component.
The flame-retardant aromatic polycarbonate resin composition according to any one of claims 2 to 3, wherein the amount is in the range of 3 to 50 parts by weight based on parts by weight. 5. An organic siloxane compound having an aromatic group (component F) in an amount of 0.1 to 5 parts by weight per 100 parts by weight of component A.
The flame-retardant aromatic polycarbonate resin composition according to any one of claims 1 to 4, comprising parts by weight.