JP2002047428A - Flame-retardant thermoplastic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a thermoplastic resin composition which contains an excellently flame-retardant metal or metal-coated filler. SOLUTION: This flame-retardant thermoplastic resin composition comprises at least one thermoplastic resin (component A) selected from (a) a polycarbonate resin, an aromatic polyester resin, a polyarylate resin, a polyester carbonate resin, a styrene resin, a polyphenylene ether resin and a polyamide resin; at least one filler component B) selected from (b) metals belonging to the 3-16 groups of Periodic Table and/or their metal compounds (component B-1) and fillers surface-coated with the metals belonging to the 3-16 groups of Periodic Table and/or their metal compounds (component B-2); and (c) an organic siloxane compound (component C), wherein the content of the B component is 0.001-55 wt.% and that of the C component is 0.05-10 wt.% relative to 100 wt.% of the sum of the component B, the component B and the component C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a thermoplastic resin composition containing a specific metal or a metal-coated filler and having excellent flame retardancy. More specifically, a resin composition containing an organic siloxane and other flame retardants in a resin composition in which a specific metal or a metal-coated filler is mixed with a thermoplastic resin, the thermoplastic resin having excellent flame retardancy Composition.

[0002]

2. Description of the Related Art Metal fillers or fillers whose surfaces are coated with metal (hereinafter referred to as "metal-based fillers")
) Is conventionally known. The purpose of such a resin composition is mainly as follows.

[0003] First, there is a design property utilizing metallic luster. In particular, metal flakes and flakes obtained by coating a surface of a plate-like filler such as glass flakes or mica with a metal are widely known as those which impart a metallic appearance to a resin molded product. Secondly, it is widely known and used to impart antistatic, conductive, or EMI shielding properties to a resin molded product by utilizing the conductivity of a metal. In such a case, various shapes such as a particle shape, a plate shape, and a fibrous shape have been proposed, and in particular, a fibrous shape is widely used.

[0004] Since such resin molded products are used mainly for housings of electronic and electric equipment, flame retardancy is often required at the same time. Therefore, engineering plastics such as polycarbonate resin and polyphenylene ether resin and ABS resin satisfy the strength required for housings of electronic and electrical equipment, etc., and are excellent in flame retardancy as resins containing metallic fillers. Are widely used.

However, when the above-mentioned metal-based filler is blended, there arises a problem that the flame retardancy tends to be inferior to other fillers. This is considered to be because the metal-based filler also has excellent thermal conductivity, so that the apparently unburned portion tends to be heated to a high temperature during combustion, thereby facilitating the thermal decomposition of the resin. Therefore, when a flame retardant is added to a resin composition containing such a metal-based filler, it is usual that more flame retardancy is required as compared with other fillers such as a glass filler. More flame retardants are not preferred because they often cause poor thermal stability and poor mechanical properties. Therefore, there has been a demand for a resin composition having a small decrease in flame retardancy even when such a metal-based filler is contained.

Several proposals have been made for improving the flame retardancy of polyorganosiloxanes. JP 5
JP-A-7-195757 describes a rubber composition comprising a polyolefin-based rubber containing a polyorganosiloxane, a silica-based fine powder and a nickel compound. JP-A-2-16136 describes a flame-retardant resin composition comprising a polyolefin and a specific selenium compound, a silicone having a specific viscosity or more, and an inorganic hydrate.

[0007] However, the invention described in the above publication does not sufficiently provide knowledge on improving the flame retardancy or suppressing the addition amount of the flame retardant in a resin composition containing a polycarbonate resin or the like and a metal-based filler. .

On the other hand, many proposals have been made to increase the flame retardancy by blending an organic siloxane compound with a polycarbonate resin. JP-A-50-77457
And JP-A-50-78643 propose a flame-retardant polycarbonate resin composition containing a polyorganosiloxane. Japanese Patent Application Laid-Open No. H11-263903 proposes a method in which a silicone varnish having a specific viscosity or less and a metal sulfonic acid salt are used in combination. In addition, Japanese Unexamined Patent Publication
JP 100785 and JP-A-8-295796 propose a method in which a silicone resin and an organic phosphorus-based flame retardant are used in combination with a polyphenylene ether resin or a polycarbonate resin. However, none of these methods provides sufficient knowledge on improving the flame retardancy of a resin composition containing a metal-based filler in a polycarbonate resin or the like, or suppressing the addition amount of a flame retardant.

Therefore, there is a demand for a flame-retardant resin composition which can improve the flame retardancy even when it contains a metal-based filler and can suppress the amount of the flame retardant to be added.

[0010]

SUMMARY OF THE INVENTION An object of the present invention is to provide a thermoplastic resin composition containing a metal or a metal-coated filler excellent in flame retardancy. The present inventors have conducted intensive studies to achieve the above object, and as a result, a thermoplastic resin such as a polycarbonate resin, a metal-based filler,
It has been found that the flame retardant resin composition comprising an organic siloxane has improved flame retardancy in a metallic filler, contrary to the case where no organic siloxane is used. Therefore, even when used in combination with another flame retardant, it is possible to obtain a flame-retardant resin composition capable of suppressing an unnecessary increase in the flame retardant and suppressing the heat stability and mechanical properties caused by the flame retardant. As a result, the present invention has been completed.

[0011]

SUMMARY OF THE INVENTION The present invention provides a polycarbonate resin, an aromatic polyester resin, a polyarylate resin, a polyester carbonate resin, a styrene resin,
At least one thermoplastic resin (component A) selected from a polyphenylene ether resin and a polyamide resin, (b) a metal of Group 3 to 16 of the periodic table and / or a metal compound thereof (component B-1) and a period Ritsu Table 3 ~
At least one filler (component B) selected from a filler (component B-2) having a surface coated with a Group 16 metal and / or a metal compound thereof; and (c) an organic siloxane compound (C) Component B) in a total of 100% by weight of Component A, Component B and Component C in an amount of 0.00
The present invention relates to a flame-retardant thermoplastic resin composition containing 1 to 55% by weight and C to 0.05 to 10% by weight.

The thermoplastic resin used as the component A in the present invention is at least one selected from a polycarbonate resin, an aromatic polyester resin, a polyarylate resin, a polyester carbonate resin, a styrene resin, a polyphenylene ether resin, and a polyamide resin. Is a thermoplastic resin. These resins or polymer alloys composed of two or more of these resins have good flame retardancy and strength, and are suitable and widely used in fields such as housings of electronic and electric devices.

[0013] The polycarbonate resin used 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. It is obtained by polymerizing by a method or by ring-opening polymerization 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.

Among them, 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. Further, bisphenol A homopolymer, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, bisphenol A, 2,2-bis {(4-hydroxy-3-methyl) Phenyl｝ propane and α, α '
A copolymer with one or more monomers selected from -bis (4-hydroxyphenyl) -m-diisopropylbenzene is preferably used, and particularly, a homopolymer of bisphenol A or 1,1-bis (4-hydroxy Phenyl) -3,3,5-trimethylcyclohexane and α,
A copolymer with α'-bis (4-hydroxyphenyl) -m-diisopropylbenzene is preferred.

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

In producing the polycarbonate resin by reacting the above-mentioned dihydric phenol with the carbonate precursor by 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. An inhibitor or the like may be used. Further, the polycarbonate resin may be a branched polycarbonate resin obtained by copolymerizing a trifunctional or higher polyfunctional aromatic compound, or a polyester carbonate resin obtained by copolymerizing an aromatic or aliphatic bifunctional carboxylic acid, Further, a mixture of two or more of the obtained polycarbonate resins may be used.

Examples of the trifunctional or higher polyfunctional aromatic compound include phloroglucin, phloroglucid, and 4,6-
Dimethyl-2,4,6-tris (4-hydroxydiphenyl) heptene-2,2,4,6-trimethyl-2,4
6-tris (4-hydroxyphenyl) heptane, 1,
3,5-tris (4-hydroxyphenyl) benzene,
1,1,1-tris (4-hydroxyphenyl) ethane, 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane, 2,6-bis (2-hydroxy-5-methylbenzyl) ) -4-Methylphenol, 4
-{4- [1,1-bis (4-hydroxyphenyl) ethyl] benzene} -trisphenol such as α, α-dimethylbenzylphenol, tetra (4-hydroxyphenyl) methane, bis (2,4-dihydroxyphenyl) ) Ketone, 1,4-bis (4,4-dihydroxytriphenylmethyl) benzene, or trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid and acid chlorides thereof.
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 preferably from 0.001 to 1 mol%, more preferably from 0.005 to 0.5 mol%, particularly preferably from 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 occur 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. As the acid binder, for example, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide or an amine compound such as pyridine is used. As the organic solvent, for example, halogenated hydrocarbons such as methylene chloride and chlorobenzene are used. Also,
To promote the reaction, for example, triethylamine, tetra-n
Catalysts such as tertiary amines such as -butylammonium bromide and tetra-n-butylphosphonium bromide, quaternary ammonium compounds and quaternary phosphonium compounds can also be used. At that time, the reaction temperature is usually 0 to
40 ° C., reaction time is about 10 minutes to 5 hours, 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 the resulting polycarbonate resins are capped by groups based on monofunctional phenols, so that Excellent heat stability. Such a monofunctional phenol is generally a phenol or a lower alkyl-substituted phenol, and may be a monofunctional phenol represented by the following general formula (1).

[0022]

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

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

[0025]

Embedded image

[0026]

Embedded image

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

As such substituted phenols of the general formula (2), those having n of 10 to 30, especially 10 to 26 are preferred. Specific examples thereof include decylphenol, dodecylphenol, tetradecylphenol, hexadecylphenol and Octadecylphenol, eicosylphenol, docosylphenol, triacontylphenol and the like can be mentioned.

As the substituted phenols of the general formula (3), 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 terminal terminator is desirably introduced at least at 5 mol%, preferably at least 10 mol%, based on all terminals of the obtained polycarbonate resin. More preferably, the terminal terminator is introduced in an amount of 80 mol% or more with respect to all terminals, that is, the terminal hydroxyl group (OH group) derived from dihydric phenol is more preferably 20 mol% or less, and particularly preferably. This is the case when 90 mol% or more of the terminal terminator is introduced to all the terminals, that is, when the OH group is 10 mol% or less. 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 alcohol or phenol to be produced, but is usually 120 to 350 ° C.
Range. 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.

In order to increase the polymerization rate, a polymerization catalyst is used.
The polymerization catalyst can be used, for example, water
Sodium oxide, potassium hydroxide, dihydric phenol
Alkali metal compounds such as thorium and potassium salts, water
Calcium oxide, barium hydroxide, magnesium hydroxide
Alkaline earth metal compounds such as tetramethylammonium
Hydroxide, tetraethylammonium hydroxide
Nitrogen containing sid, trimethylamine, triethylamine, etc.
Basic compounds, alkali metals and alkaline earth metals
Lucoxides, organic alkali metals and alkaline earth metals
Acid salts, zinc compounds, boron compounds, aluminum
Compounds, silicon compounds, germanium compounds, organic
Tin compounds, lead compounds, osmium compounds, ann
Timon compounds, manganese compounds, titanium compounds, di
Normal esterification reactions such as ruconium compounds,
The catalyst used in the exchange reaction can be used. Touch
The medium may be used alone or in combination of two or more.
May be used. The amount of these polymerization catalysts used is
Preferably 1 × 10 ^-8~
1 × 10^-3Equivalent, more preferably 1 × 10^-7~ 5 × 10
^-FourIt is selected within the range of equivalents.

In such a polymerization reaction, to reduce the number of phenolic terminal groups, for example, bis (chlorophenyl) carbonate, bis (bromophenyl) carbonate, bis (nitrophenyl) carbonate is used later or after completion of the polycondensation reaction. , Bis (phenylphenyl)
Carbonate, chlorophenylphenyl carbonate,
It is preferable to add compounds such as bromophenylphenyl carbonate, nitrophenylphenyl carbonate, phenylphenyl carbonate, methoxycarbonylphenylphenyl carbonate, and ethoxycarbonylphenylphenyl carbonate. Above all, 2-
Chlorophenyl phenyl carbonate, 2-methoxycarbonyl phenyl phenyl carbonate and 2-ethoxycarbonyl phenyl phenyl carbonate are preferred, and 2-methoxy carbonyl phenyl phenyl carbonate is particularly preferred.

Further, it is preferable to use a deactivator for neutralizing the activity of the catalyst in such a polymerization reaction. Specific examples of this deactivator include, for example, benzenesulfonic acid, p-toluenesulfonic acid, methylbenzenebenzenesulfonic acid, ethylbenzenebenzenesulfonic acid, butylbenzenesulfonic acid, octylbenzenesulfonic acid, phenylbenzenebenzenesulfonic acid, p-toluenesulfonic acid. 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, octylsulfonic acid tetrabutylphosphonium salt, decylsulfonic acid tetrabutylphosphonium salt, benzenesulfonic acid tetrabutylphosphonium salt, dodecylbenzenesulfonic acid tetraethylphosphonium salt, dodecylbenzenesulfonic acid tetrabutylphosphonium salt, dodecylbenzenesulfone 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 per 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. It is used at a rate of 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 40,000, the moldability will be reduced. 10,00
It is preferably from 0 to 40,000, and from 12,000 to 3
000 is more preferable, and further preferably 11
5,000 to 25,000, particularly preferably 16,50
0 to 23,500. 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 preferable because it has a high drip preventing 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 was determined by using an Ostwald viscometer to determine the specific viscosity calculated by the following equation from a solution of 0.7 g of a polycarbonate resin dissolved in 100 ml of methylene chloride at 20 ° C. The viscosity average molecular weight M is determined by inserting the specific viscosity by the following equation. 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 polyester resin of the present invention is a polymer or copolymer obtained by a condensation reaction containing an aromatic dicarboxylic acid and a diol or an ester derivative thereof as main components.

The aromatic dicarboxylic acids mentioned here include terephthalic acid, isophthalic acid, orthophthalic acid, 1,5-
Naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 4,4'-
Biphenyl ether dicarboxylic acid, 4,4'-biphenylmethane dicarboxylic acid, 4,4'-biphenyl sulfone dicarboxylic acid, 4,4'-biphenyl isopropylidene dicarboxylic acid, 1,2-bis (phenoxy) ethane-
4,4′-dicarboxylic acid, 2,5-anthracenedicarboxylic acid, 2,6-anthracenedicarboxylic acid, 4,4 ′
Aromatic dicarboxylic acids such as -p-terphenylenedicarboxylic acid and 2,5-pyridinedicarboxylic acid are preferably used, and terephthalic acid and 2,6-naphthalenedicarboxylic acid are particularly preferably used.

The aromatic dicarboxylic acids may be used as a mixture of two or more kinds. In addition, if it is a small amount, dicarboxylic acids other than aromatic dicarboxylic acids typified by aliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid and dodecane diacid, and alicyclic dicarboxylic acids such as cyclohexane dicarboxylic acid together with the dicarboxylic acid. It is also possible to use a mixture of one or more acids.

The diol which is a component of the aromatic polyester resin of the present invention includes ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, neopentyl glycol, 2-methyl-1,2
Examples thereof include aliphatic diols such as 3-propanediol, diethylene glycol and triethylene glycol, alicyclic diols such as 1,4-cyclohexanedimethanol, and mixtures thereof.

Specific aromatic polyester resins include polyethylene terephthalate (PET), polypropylene terephthalate, polybutylene terephthalate (PBT), polyhexylene terephthalate, polyethylene naphthalate (PEN), polybutylene naphthalate (PBN), polyethylene In addition to -1,2-bis (phenoxy) ethane-4,4'-dicarboxylate,
Copolymerized polyesters such as polyethylene isophthalate / terephthalate, polybutylene terephthalate / isophthalate, and the like. Of these, polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, and polybutylene naphthalate, which have well-balanced mechanical properties and the like, can be preferably used.

According to a method for producing such an aromatic polyester resin, a dicarboxylic acid component and the diol component are polymerized while heating in the presence of a polycondensation catalyst containing titanium, germanium, antimony, etc., according to a conventional method. It is performed by discharging water or lower alcohol produced as a by-product outside the system. The reaction may be a batch system or a continuous polymerization system.

With respect to the molecular weight of the aromatic polyester resin, the intrinsic viscosity measured at 35 ° C. using o-chlorophenol as a solvent is 0.6 to 1.3, preferably 0.7.
5 to 1.15.

The polyarylate resin of the present invention refers to a wholly aromatic polyester resin as a whole. The term polyarylate resin may refer only to an amorphous wholly aromatic polyester resin, but in the present invention, includes a type of crystalline polyester resin called a so-called liquid crystal polymer.

The amorphous wholly aromatic polyester resin used in the present invention includes dihydric phenol, or dihydric phenol and hydroquinone and / or resorcinol as a diol component, and terephthalic acid and / or isophthalic acid as a dicarboxylic acid component. Is referred to as a wholly aromatic polyester resin. As such a dihydric phenol component, the bis (4-hydroxyphenyl) alkane described in the polycarbonate resin of the present invention can be preferably used, and bisphenol A is particularly preferable. The use of hydroquinone and / or resorcinol can be preferably used from the viewpoint of improving the chemical resistance of the resin composition of the present invention. In such a case, the use of hydroquinone is particularly preferred.

One of the preferred embodiments for improving the moldability and chemical resistance of the amorphous wholly aromatic polyester resin of the present invention is to use hydroquinone and bisphenol A as a diol component and isophthalic acid as an acid component. The ratio of hydroquinone to bisphenol A is 5
One in which 0/50 to 70/30 equivalent% is used.
Further, as an embodiment useful for increasing the heat resistance temperature of the resin composition of the present invention, bisphenol A as a diol component,
There is a case where terephthalic acid is used as an acid component.

The method for producing such an amorphous wholly aromatic polyester is not particularly limited. For example, a method in which terephthalic acid chloride or isophthalic acid chloride is used as an acid component, and a method in which the diol component is reacted with a catalyst such as an alkali component by an interfacial polymerization method or a solution polymerization method, may be mentioned. Further, using an aryl terephthalate or a diaryl isophthalate as an acid component, in addition to a titanium compound such as titanium tetrabutoxide, a germanium compound already known as a melt polycondensation catalyst for a polyester polymer, an antimony compound and a tin compound A melt polymerization method in which a diol component is reacted with a catalyst is used. Further, terephthalic acid or isophthalic acid is used as an acid component, p-diacetoxybenzene or 2,2'-bis (4-acetoxyphenyl) propane is used as a diol component, and the reaction is performed using the above-mentioned molten polycondensation catalyst. A polymerization method and the like can also be mentioned. These production methods can be appropriately used according to the purpose.

The amorphous wholly aromatic polyester resin of the present invention has an intrinsic viscosity measured at 35 ° C. in a phenol / tetrachloroethane mixed solvent (weight ratio of 60/40) which is different from the viewpoint of heat resistance and moldability. From 0.3 to 1.2, and particularly preferably from 0.4 to 0.9.

The crystalline wholly aromatic polyester resin used in the present invention includes at least one dihydric phenol containing no alkylene group, at least one aromatic dicarboxylic acid and / or at least one aromatic dihydroxy acid. It is obtained from a carboxylic acid. More specifically, a method of using such a dihydric phenol that does not contain an alkylene group as a derivative such as acetate and increasing the activity of the dihydric phenol, or using such an aromatic dicarboxylic acid as an acid chloride and a phenyl ester It is obtained from a method of using a derivative having an increased activity of a carboxylic acid as a derivative thereof. Furthermore, using aromatic dicarboxylic acid directly,
Those obtained by a method of increasing the activity of a carboxylic acid with a condensing agent such as p-toluenesulfonyl chloride can be used.

Preferred among such dihydric phenols containing no alkylene group are 1,4-dihydroxybenzene, 4,4'-dihydroxydiphenyl,
Examples include 2,6-dihydroxynaphthalene, and those containing an aromatic ring containing one or more non-reactive functional groups such as a lower alkyl group, a halogeno group, and a phenyl group.

The aromatic dicarboxylic acid used in the crystalline wholly aromatic polyester resin of the present invention includes terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid,
4,4′-diphenyldicarboxylic acid, and those having an aromatic ring containing one or more non-reactive functional groups such as a lower alkyl group, a halogeno group, and a phenyl group.

Further, as the aromatic hydroxycarboxylic acid, 1-carboxy-4-hydroxybenzene, 1-carboxy-3-hydroxybenzene, 2-carboxy-
6-Hydroxynaphthalene and its aromatic ring containing one or more non-reactive functional groups such as a lower alkyl group, a halogeno group, and a phenyl group.

One preferred embodiment of the crystalline wholly aromatic polyester resin of the present invention is 1-carboxy-4-
One in which hydroxybenzene and 2-carboxy-6-hydroxynaphthalene are used in an amount of 70/30 to 85/15 equivalent%. In addition, 1-carboxy-4-hydroxybenzene, 4,4'-dihydroxydiphenyl and terephthalic acid were used in a ratio of 40/30/30 to 60/20/2.
And 0 equivalent%.

The polyester carbonate resin of the present invention is a resin obtained by reacting a dihydric phenol with an aromatic dicarboxylic acid, an aromatic hydroxycarboxylic acid, an aliphatic dicarboxylic acid and the like with a carbonate precursor. As the dihydric phenol, aromatic dicarboxylic acid, aromatic hydroxycarboxylic acid, and the like, those similar to the above can be used. Examples of the aliphatic dicarboxylic acid include, for example, those having 4 carbon atoms.
To 20, preferably 8 to 12 aliphatic dicarboxylic acids. Such aliphatic dicarboxylic acids may be linear, branched, or cyclic. Further, α, ω-dicarboxylic acid is preferred. Examples of preferred aliphatic dicarboxylic acids include decane dicarboxylic acid, dodecane dicarboxylic acid,
Examples include linear saturated aliphatic dicarboxylic acids such as tetradecanedicarboxylic acid, octadecanedicarboxylic acid, and eicosanedicarboxylic acid, and sebacic acid and dodecanedicarboxylic acid are particularly preferred.

The styrenic resin of the present invention comprises
A resin containing 20% by weight or more, preferably 25% by weight, of a component derived from a styrene-based monomer such as styrene, α-methylstyrene and vinyltoluene per 0% by weight. Therefore, as the styrene resin, homopolymers of such styrene monomers or mutual copolymers of these monomers and other vinyl monomers copolymerizable with these styrene monomers, for example, copolymers with acrylonitrile, methyl methacrylate, etc. No. Further, diene rubbers such as polybutadiene, ethylene / propylene rubbers, acrylic rubbers, and composite rubbers having a structure in which a polyorganosiloxane component and a poly (meth) alkyl acrylate component are entangled with each other so that they cannot be separated. The rubber component may be obtained by graft-polymerizing a styrene-based monomer or a styrene-based monomer and another copolymerizable vinyl monomer.

Specific examples of the styrene resin include polystyrene, high impact polystyrene (HIPS), acrylonitrile / styrene copolymer (AS resin), acrylonitrile / butadiene / styrene copolymer (ABS resin), and methyl methacrylate / butadiene.・ Styrene copolymer (MBS resin), methyl methacrylate, acrylonitrile, butadiene, styrene copolymer (MABS)
Resins), resins such as acrylonitrile / acrylic rubber / styrene copolymer (AAS resin), acrylonitrile / ethylene propylene rubber / styrene copolymer (AES resin), and mixtures thereof. In these copolymers and mixtures, a component derived from a styrene monomer is contained in an amount of 20% by weight or more based on 100% by weight of the resin.

The method for producing such various polymers is not particularly limited. For example, those produced by various polymerization methods such as bulk polymerization, suspension polymerization, emulsion polymerization and bulk suspension polymerization can be used. In addition, any one of a method of copolymerizing in one step and a method of copolymerizing in multiple steps in the method of copolymerization can be selected.

Among the styrenic resins of the present invention, among them, polystyrene and high impact polystyrene (HIP)
S), an acrylonitrile-styrene copolymer (AS resin), and an acrylonitrile-butadiene-styrene copolymer (ABS resin) are preferred, and among them, the ABS resin is most preferred from the viewpoint of impact resistance. The styrene resin may be used alone or in combination of two or more.

The ABS resin of the present invention is a thermoplastic graft copolymer obtained by graft-polymerizing a vinyl cyanide compound and an aromatic vinyl compound on a diene rubber component.
It forms a mixture with another polymer by-produced during graft polymerization of a resin or the like. Further ABS
A mixture of a resin and a separately polymerized AS resin is widely used industrially.

In the present invention, as the B component, the periodic table 3 to 16
Group B and / or their metal compounds (component B-1) and fillers (B-
At least one filler selected from two components) is used. Here, the metal includes a simple metal and an alloy containing the metal as a main component. A more preferable filler as the component B is one having a volume resistivity value of 1 Ω · m or less. More preferably, the volume resistivity is 10 ^-1 Ω · m or less.

From the viewpoint of synergistic action with the organic siloxane compound, it is more preferable that the component B-1 be represented by the periodic table 8 to 1
Group 1 metals and / or their metal compounds are mentioned, and as the B-2 component, fillers formed by coating the surfaces of the metals of Groups 8 to 11 of the periodic table and / or their metal compounds are mentioned.

For the same reason, more preferably, the component B-1 is iron, cobalt, nickel, copper, palladium,
And at least one metal selected from platinum and / or a metal compound thereof, and the B-2 component includes at least one metal selected from iron, cobalt, nickel, copper, palladium, and platinum; And / or a filler obtained by coating the surface with a metal compound thereof.

The metal or metal compound of component B-1 may be of various shapes as appropriate for the purpose. Examples of such a shape include a granular shape, a plate shape, a fibrous shape, and a needle shape. Examples of the metal compound include oxides, hydroxides, and various chelate compounds. These are generally commercially available as conductive fillers, conductive fibers, conductive whiskers, heat ray reflectors / absorbers, or coloring agents for imparting a metallic tone, and are readily available.

A filler obtained by coating the surface of a metal or metal compound of the component B-2 can be more preferably used in the present invention. That is, the design, heat ray reflection properties, conductivity, and the like generally expected of the metal-based filler are largely contributed by the surface portion. Therefore, if the surface of another filler is coated with a metal or the like, these properties can be further imparted while fully utilizing the properties of the filler serving as the base.

In the component B-2, the method of coating the surface of the filler with a metal or a metal compound is not particularly limited. For example, various known plating methods (for example, electrolytic plating, electroless plating, hot-dip plating, and the like), vacuum deposition, ion plating, and CVD (for example, thermal CV)
D, MOCVD, plasma CVD, etc.), PVD method, and sputtering method.

As the component B-2, specifically, a metal core
Carbon fiber, metal-coated glass fiber, metal-coated glass flake, and the like. In particular, metal-coated carbon fibers can be preferably used because they have excellent electrical conductivity and a high reinforcing effect of the resin composition. Such a metal-coated carbon fiber is obtained by coating a carbon fiber with a metal such as nickel, copper, silver, or an alloy thereof by the above-described plating method or vapor deposition method. As the carbon fibers, both pitch-based and PAN-based carbon fibers can be used. Further, carbon fibers produced by a vapor growth method and carbon fibers produced from a formalin condensate of a naphthalene sulfonate can also be used.

In the case of a fiber, the following are preferable as the fiber diameter. That is, the metal fiber has a diameter of 1 to 8
It is preferably 0 μm, particularly preferably 1 to 60 μm. The metal-coated carbon fiber and the metal-coated glass fiber each having a diameter of 1 to 20 μm are particularly preferable.

As the component B of the present invention, those which have been surface-treated with a silane coupling agent, a titanate coupling agent, an aluminate coupling agent or the like can be used. A filler which has been surface-treated or bundle-treated with an olefin resin, a styrene resin, a polyester resin, an epoxy resin, a urethane resin, a polyamide resin, or the like can also be used. In particular, when the shape is fibrous or plate-like, it is preferable that such surface treatment or convergence treatment has been performed since dispersion in the resin can be favorably maintained.

The flame-retardant thermoplastic resin composition of the present invention comprises an organic siloxane as the component C. In order for organic siloxanes to exhibit better flame retardancy, it is believed that it is important to form a siloxane structure upon combustion. There are two main concepts to facilitate the formation of such siloxane structures. Here, the structure of siloxane refers to a network structure formed by a reaction between siloxanes or a reaction between a resin and siloxane.

First, there is a method of blending an organic siloxane which easily forms a siloxane structure during combustion. Second, there is a method of blending an organic siloxane in which a branched structure of siloxane has already been developed to some extent.

In the first method, the following factors (i) to (iii) are important. That is, (i) it contains a highly reactive component that easily forms a siloxane structure upon combustion, (ii) it has good dispersibility in the resin, and (iii) the component in the organic siloxane forms char or It is to include those that contribute to the formation of the siloxane structure. It can be said that whether or not good flame retardancy can be imparted is determined depending on the degree to which these factors are totally satisfied.

In order to satisfy the above condition (i),
(I) -1. Contains a group that easily forms a siloxane structure; and (i) -2. A method of introducing a branched structure into the organosiloxane can be used. (I) -3. Moderate molecular weight conditions that allow transfer to the surface during combustion are also important.

The above (i) -1. Is preferably a hydrogen atom, a halogen atom, a hydroxyl group, an alkoxy group and a vinyl group when represented in the form of Si-α. More preferred are a hydrogen atom and an alkoxy group. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. Among these, a methoxy group is most preferable because reactivity and the overall molecular weight can be reduced.

The group represented by α is 10 to 5 of the organic functional groups (including a hydrogen atom, a halogen atom, and a hydroxyl group; the same applies hereinafter) contained in the organosiloxane.
The content is preferably in the range of 0 mol%, more preferably 15 to 45 mol%, and particularly preferably 15 to 40 mol%.

When the compound has the group represented by α, the reaction between the organic siloxane and the reaction with the component A such as a polycarbonate resin easily occurs during combustion. Therefore, the formation of the siloxane structure is facilitated,
Good flame retardancy can be achieved. Especially Si-
When the compound has an H group, it has high reactivity and exhibits preferable characteristics. On the other hand, when the reactivity is high, it is necessary to consider the reaction with other additives.

(I) -2. When the organosiloxane is represented by the following general formula (4), a method in which at least the sum of at least c and d is not 0 is used. A more preferred range is 0.2 ≦ c ≦ 0.
5, and 0 ≦ d ≦ 0.2, more preferably 0.2
≦ c ≦ 0.4 and 0 ≦ d ≦ 0.2. The value of a in the following general formula (4) is preferably 0.5 ≦ a ≦ 0.75 when any one of R ⁵ is an alkoxy group.

[0080]

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(Here, in the general formula (4), R ⁵ ,
R ⁶ and R ⁷ each represent a hydrogen group, a hydroxyl group, a halogen atom, an alkoxy group having 1 to 12 carbon atoms, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms,
An aryl group having 12 to 12 carbon atoms and an aralkyl group having 7 to 12 carbon atoms. The substituents of R ⁵ and R ⁶ may be the same or different. )

In order to satisfy the above condition (ii),
(Ii) -1. Optimization of molecular weight, (ii) -2. Introduction of a functional group or copolymerization of a component A with a thermoplastic resin, (i
i) -3. Examples of the method include introduction of an aryl group. In particular, (ii) -1. The molecular weight condition is extremely important, including the above (i) -3, and is the most easily controlled condition. Basically, the component A of the present invention and the organosiloxane have inherently low affinity. Therefore, the higher the molecular weight, the lower the compatibility tends to be. Therefore, it is preferable that the molecular weight is low to some extent. A somewhat lower molecular weight also facilitates the transfer of the organosiloxane to the surface during combustion. Thereby, the structure of the siloxane effectively contributes to the flame retardancy. On the other hand, if the molecular weight is too low, volatilization is likely to occur with migration to the surface, and the flame retardant effect will decrease.

The control of the molecular weight of the organosiloxane can be controlled in consideration of the following factors. For example, the molecular weight can be controlled by controlling the amount of siloxane chains (the molecular weight increases as the chain weight increases). Further, the introduction of a substituent having a large molecular weight can increase the molecular weight. Furthermore, the cross-linking ratio can be controlled by adjusting the amount of water when the organic siloxane is produced by hydrolysis from the monomer component (the molecular weight increases as the cross-linking ratio increases).

(Ii) -1. Examples of suitable molecular weights include those having a weight average molecular weight of 200 to 10,000 measured by GPC (gel permeation chromatography) described below. More preferably, the weight average molecular weight is 200 to
It is 9,000, more preferably 400 to 1,000. In particular, when the component A is a polycarbonate resin, it is desirable to satisfy such conditions.

The GPC method used for measuring the organosiloxane of the present invention is based on the following conditions. That is, using a GPC measuring device placed in a clean air environment at a temperature of 23 ° C. and a relative humidity of 50%, as a column, MIXED-C manufactured by Polymer Laboratories (300 mm length,
7.5 mm in inner diameter), chloroform as a mobile phase, Easycal P manufactured by Polymer Laboratories as a standard substance
S-2, and using a differential refractometer as a detector, chloroform as a solvent,
100 μl of a solution in which 1 mg of a sample was dissolved per liter was injected into a GPC measuring apparatus, and the column temperature was 35 ° C. and the flow rate was
GPC measurement is performed under the condition of ml / min, and the weight average molecular weight of the component c is calculated.

(Ii) -2. Is a method in which various functional groups are reacted with the thermoplastic resin of the component A. Good dispersibility can be achieved by bonding to the main resin. Even when no reaction occurs, the affinity of the component A with the thermoplastic resin is improved, so that the dispersibility can be improved. A more preferable method is a method using an organic siloxane copolymerized with a thermoplastic resin of the component A and / or a resin having a high affinity for the thermoplastic resin of the component A. Known methods can be used for producing such a copolymer. Here, as the functional group, for example, an alcoholic hydroxyl group, a phenolic hydroxyl group, an epoxy group, a carboxylic acid group, a carboxylic anhydride group,
Examples include an amino group, an oxazoline group, and a mercapto group.

The above (ii) -3. Is to improve the affinity with the thermoplastic resin of the component A, particularly a styrene resin, or a resin having an aromatic group in the main chain by introducing an aryl group. Such a method is simple and is one of the methods for achieving the following condition (iii), and is therefore a preferable method. The content of the aryl group is preferably at least 10 mol% of the organic functional groups contained in the organic siloxane,
More preferably, it is at least 20 mol%. On the other hand, the upper limit is preferably 95 mol% or less, more preferably 70 mol% or less.

In order to satisfy the above (iii), (i)
ii) -1. Examples include a method containing a cyclic compound such as an aryl group. In addition to the aryl group as the cyclic compound,
Examples thereof include a nitrogen-containing heterocyclic compound and a sulfur-containing heterocyclic compound. Examples of the aryl group contained in the organic siloxane include a phenyl group, a biphenyl group, a naphthalene group, and derivatives thereof, and among them, a phenyl group is preferable.

On the other hand, the second method mentioned above, that is, a method of blending an organic siloxane already constituting a siloxane structure to some extent, mainly comprises the following method (i).
Factors v) to (vi) are important. That is, (iv)
(V) good dispersibility in the resin; and (vi) components in the organosiloxane that contribute to char formation or formation of the siloxane structure. It is that you are. That is, the basic idea is the same as in the first method.

In order to satisfy the above condition (iv),
When expressed by the general formula (4), at least c
And the sum of d and d is not 0. As a more preferable range, 0.2 ≦ c ≦ 0.5,
And 0 ≦ d ≦ 0.2, more preferably 0.2 ≦ c
≦ 0.4 and 0 ≦ d ≦ 0.2.

In order to satisfy the above condition (v), the molecular weight is preferably in a specific range. Therefore, the weight average molecular weight measured by the above-mentioned GPC method was 10,0.
It is preferably in the range of 00 to 80,000. More preferably, it is in the range of 10,000 to 70,000.

From the above, a method satisfying the condition (v) is as follows.
(Ii) -2. And (ii) -3. It is preferable to use the same method as in the above method. In particular, the introduction of an aryl group is effective, and the content of the aryl group is preferably at least 10 mol%, more preferably at least 20 mol%, of the organic functional groups contained in the organic siloxane. . On the other hand, the upper limit is preferably 95 mol% or less, more preferably 70 mol% or less.

As a method for further improving the dispersibility,
It is preferable to adopt a method of pre-kneading or preparing an organosiloxane master agent. For example, a method of dissolving and mixing a polycarbonate resin and an organic siloxane in an organic solvent such as methylene chloride and then removing the solvent can be cited as one of the methods for preparing the master agent.

In the method satisfying the above condition (vi), it is preferable to introduce an aryl group as in the case of (v), and the amount of the aryl group is preferably in the above range.

Of the above-mentioned concepts of flame retardancy by blending an organic siloxane, the first method can preferably be used because it can achieve better flame retardancy than the second method. The cause of the difference in flame retardancy is expected to be due to the mobility of molecules during combustion due to molecular weight. That is, because the transferability to the surface is inferior to those having a low molecular weight,
It is expected that the efficiency of the siloxane structure contributing to the flame retardancy is somewhat inferior.

Accordingly, particularly preferred organosiloxanes include those satisfying any of the following conditions. That is, (I) the weight average molecular weight measured by GPC shown above is 200 to 10,000,
The alkoxy group is contained in the range of 10 to 50 mol% of the organic functional groups contained in the organic siloxane, and the content of the aryl group is at least 10 mol% of the organic functional groups contained in the organic siloxane. An organosiloxane, or (I
I) An organosiloxane having a Si-H bond having a considerable weight average molecular weight. More preferably, in the above general formula (4), 0.2 ≦ c ≦ 0.5 and 0 ≦
d ≦ 0.2, more preferably 0.2 ≦ c ≦ 0.
4, and 0 ≦ d ≦ 0.2.

Specific structures of the organosiloxane satisfying the above condition (I) include the following general formulas (5) and (6).
Can be mentioned.

[0098]

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[0099] (.γ ¹ shown in the formula, beta ¹ is a vinyl group, an alkyl group having 1 to 6 carbon atoms, cycloalkyl group having 3 to 6 carbon atoms, and an aryl group and aralkyl group having 6 to 12 carbon atoms, 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.
δ ¹ , δ ² and δ ³ each represent an alkoxy group having 1 to 4 carbon atoms. )

[0100]

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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. In the above general formulas (5) and (6), β ¹ , β ² and β ³ are preferably any one of a methyl group, a phenyl group and a vinyl group. In addition, the above general formula (5)
In (6) and (6), γ ^{1 to} γ ¹⁴ are preferably any one of a methyl group and a phenyl group;
It is preferable that there are three or more phenyl groups. Further δ ¹
More preferably a methoxy group in ~δ ^7.

These can be used alone or in combination of two or more. In addition to the case where the respective compounds are individually synthesized and then mixed according to the purpose, various compounds may be mixed and produced depending on the raw materials at the time of synthesis.

The organic siloxanes represented by the above general formulas (5) and (6) are more specifically represented by the following formulas (7) to (7).
Examples shown in (15) can be given.

[0104]

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[0105]

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[0106]

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[0107]

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[0108]

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[0109]

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[0110]

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[0111]

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[0112]

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(In the formulas (7) to (15), Me is a methyl group,
Ph represents a phenyl group, Vi represents a vinyl group, and Bu represents a butyl group. )

On the other hand, (II) the organosiloxane having a Si—H bond has a viscosity at 25 ° C. of 150 mm
Various polymethylhydrogen siloxanes of ² / sec or less can be mentioned, and more preferably 5 to 100 mm ² / sec.
sec, more preferably from 10 to 80
It has a viscosity of mm ² / sec.

In the case of (I), it can be said that the main factor satisfying the condition (i) is an alkoxy group. The activity of such a group is somewhat low but stable, and is therefore practically preferable. On the other hand, other conditions must be sufficiently satisfied in order to sufficiently exhibit the flame retardant function. On the other hand, in the case of (II), since the main factor satisfying the condition (i) is a Si—H bond, the activity is high, and a sufficient effect is exhibited even when other conditions are not sufficiently satisfied. However, since the activity is extremely strong, it is necessary to consider side effects with other additives contained in the resin composition. Taking these characteristics into account,
The type and amount of the organosiloxane used as appropriate according to the purpose and the composition ratio when two or more types are used are determined.

It is not clear why organosiloxane compounds have different properties from other flame retardants. That is, in a resin composition having a metal-based filler in which organosiloxane is usually disadvantageous in flame retardancy, the reason for the property that the flame retardancy is improved is unclear. However, the following are conceivable as predictions of the present inventors. That is, the dehydrating effect and the radical scavenging effect of the metal promote the char formation of the thermoplastic resin as the component A of the present invention, and the same effect is required in the formation of the siloxane structure by the organic siloxane. It is considered that the char and siloxane structure of the thermoplastic resin are rapidly and simultaneously generated due to the presence of the agent, and flame retardancy is obtained by forming these structures.

Here, the ratio of the A component, the B component and the C component in the resin composition is 0.001 to 100% by weight of the total of the A component, the B component and the C component.
55% by weight, and 0.05 to 10% by weight of the C component. Component B is more preferably 0.01 to 35% by weight, and even more preferably 0.1 to 30% by weight. Component C is more preferably 0.1 to 5% by weight, and even more preferably 0.2 to 3% by weight.

When the content of the component B is less than 0.001% by weight, the synergistic effect with the component C is not sufficiently exhibited, and the flame retardancy becomes insufficient. On the other hand, if it exceeds 55% by weight, molding becomes difficult. If the content of the C component is less than 0.1% by weight, the flame retardancy is insufficient.
On the other hand, if it is more than 10% by weight, the flame retardancy decreases and the mechanical properties decrease. It is also not preferable in that the appearance is deteriorated.

The flame-retardant thermoplastic resin composition of the present invention comprises
Further, other flame retardants (D component) can be included for the purpose of enhancing flame retardancy. That is, since the mechanism of developing flame retardancy by the organosiloxane compound is different from the mechanism of developing flame retardancy by another flame retardant, the blending of another flame retardant can provide better flame retardancy. .

The other flame retardants are not particularly limited, but are typically represented by red phosphorus or stabilized red phosphorus in which the surface of red phosphorus is microencapsulated with a known thermosetting resin and / or inorganic material. Red phosphorus flame retardants used: tetrabromobisphenol A, oligomers of tetrabromobisphenol A, brominated bisphenol epoxy resin, brominated bisphenol phenoxy resin, brominated bisphenol polycarbonate, brominated polystyrene, brominated cross-linked polystyrene, bromide Halogenated flame retardants represented by polyphenylene ether, polydibromophenylene ether, decabromodiphenyl oxide bisphenol condensate and halogenated phosphoric acid ester; triphenyl phosphate as a monophosphate compound Such as phosphate ester oligomers such as resorcinol bis (dixylenyl phosphate) and bisphenol A bis (diphenyl phosphate); and pentaerythritol diphenyl diphosphate and pentaerythritol di (2,6-dimethyl-phenyl) as a phosphate having a spiro ring skeleton. 6-oxo-6-phenoxy-12H-dibenzo (d, g) (1,3,2) -dioxaphosphine, 2,10-dimethyl-phosphate, such as diphosphate, and a phosphate having a cyclic skeleton containing an aromatic ring 6-oxo-6
-Phenoxy-12H-dibenzo (d, g) (1,3,
2) -dioxaphosphosine and 6-oxo-6
Organophosphate flame retardants represented by (2,6-dimethylphenoxy) -12H-dibenzo (d, g) (1,3,2) -dioxaphosphine; ammonium polyphosphate, aluminum phosphate Inorganic phosphates such as zirconium phosphate, hydrates of inorganic metal compounds such as aluminum hydroxide and magnesium hydroxide, zinc borate, zinc metaborate, magnesium oxide, molybdenum oxide, zirconium oxide, tin oxide, oxide Inorganic flame retardants represented by antimony; potassium perfluorobutanesulfonate, calcium perfluorobutanesulfonate, cesium perfluorobutanesulfonate, potassium diphenylsulfon-3-sulfonate, diphenylsulfone-3,3'-disulfone Alkali (earth) gold such as potassium silicate A genus salt-based flame retardant; examples thereof include phosphazene-based flame retardants represented by phenoxyphosphazene oligomers and cyclic phenoxyphosphazene oligomers.

Among the above flame retardants, red phosphorus, halogen flame retardants, and organic phosphorus flame retardants are particularly preferred in the present invention. Above all, in the case of red phosphorus or an organic phosphorus flame retardant, the impact resistance is apt to be reduced by increasing the amount of the flame retardant, so that the effect of the present invention can be effectively utilized and it is preferably used together. Particularly, the case of a phosphoric ester-based flame retardant can be said to be a suitable flame retardant since the effects of the present invention are recognized.

The proportion of the D component in the resin composition is 0.001 to 30 parts by weight based on 100 parts by weight of the total of the A, B and C components. In particular, the phosphate ester flame retardant suitable as the component D is preferably 1 to 20 parts by weight, more preferably 2 to 15 parts by weight. If the amount is more than 30 parts by weight, mechanical properties may be insufficient.

Further, in the present invention, various rubber-like elastic materials can be further compounded for the purpose of improving impact resistance. Examples of the rubber-like elastic material of the E component which can be used in the present invention include a rubber component having a glass transition temperature of 10 ° C. or less, an aromatic vinyl, a vinyl cyanide, an acrylate, a methacrylate, and a copolymer thereof. One or two of monomers selected from polymerizable vinyl compounds
Graft copolymers in which at least one species is copolymerized can be given. On the other hand, it is also possible to use various types of thermoplastic elastomers having no cross-linked structure, such as polyurethane elastomers, polyester elastomers, styrene-ethylene propylene-styrene elastomers, and polyetheramide elastomers.

The rubber component having a glass transition temperature of 10 ° C. or less includes butadiene rubber, butadiene-acryl composite rubber, acrylic rubber, acryl-silicon composite rubber, isobutylene-silicon composite rubber, isoprene rubber, styrene-butadiene rubber. , Chloroprene rubber, ethylene-propylene rubber, nitrile rubber, ethylene-acrylic rubber, silicone rubber, epichlorohydrin rubber,
Examples thereof include fluororubbers and those obtained by adding hydrogen to the unsaturated bond portions thereof.

Among them, a rubber-like elastic body containing a rubber component having a glass transition temperature of 10 ° C. or less is preferable, and a rubber-like elastic body using butadiene rubber, butadiene-acryl composite rubber, acrylic rubber, or acrylic-silicon composite rubber is particularly preferable. preferable. Butadiene-acrylic composite rubber is a rubber obtained by polymerizing a component of butadiene rubber and a component of acrylic rubber so as to have an IPN structure entangled with each other so as not to be copolymerized or separated. An acrylic rubber component and a silicone rubber component have an IPN structure entangled with each other so as to be inseparable or copolymerized with a functional group in the silicone rubber.

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

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

Such rubber-like elastic bodies are commercially available and can be easily obtained. For example, as a rubber component having a glass transition temperature of 10 ° C. or less, butadiene rubber or butadiene-acrylic composite rubber is mainly used, for example, Kaneace B series of Kanebuchi Chemical Industry Co., Ltd., and Metablen C of Mitsubishi Rayon Co. Series, EXL series, KIA series, BTA series, KCA series of Kureha Chemical Industry Co., Ltd.
Examples of the rubber component having a temperature of 0 ° C. or lower that are mainly composed of acryl-silicon composite rubber include those commercially available from Mitsubishi Rayon Co., Ltd. under the trade name of Metablen S-2001 or SRK-200.

Commercially available styrene-based thermoplastic elastomers include “Septon” and “Hibler” manufactured by Kuraray Co., Ltd.
And the like. Examples of the olefin-based thermoplastic elastomer include those marketed by Mitsui Chemicals, Inc. under the trade name “Mirastomer”. Examples of commercially available polyamide-based thermoplastic elastomers include "Pebax" manufactured by Toray Industries, Inc. Examples of commercially available polyester-based thermoplastic elastomers include "Nouvellen" manufactured by Teijin Limited.
Examples include "Perprene" manufactured by Toyobo Co., Ltd. and "Hytrel" manufactured by Toray Industries. Commercially available polyurethane thermoplastic elastomers include "Kuramilon U" manufactured by Kuraray Co., Ltd., and Takeda Birdish Urethane ( Co., Ltd., "Elastolane", etc., each of which is easily available.

The proportion of the E component is as follows:
1 to 20 parts by weight is preferable based on 100 parts by weight of the total components. When the content is in such a range, more favorable compatibility between flame retardancy and impact resistance can be achieved.

In the present invention, a lubricant having at least one functional group selected from a carboxyl group, a carboxylic anhydride group, an epoxy group, and an oxazoline group can be blended as the F component. The lubricant having such a functional group has a high affinity with the surface of the metal-based filler of the B component,
In the flame retardant resin composition of the present invention, it exists so as to cover the periphery of the component B. Thereby, when manufacturing the flame-retardant thermoplastic resin composition of the present invention or when melt-molding the flame-retardant thermoplastic resin composition of the present invention, it is suppressed that excessive stress is applied to the B component, Has the effect of minimizing breakage of By such an effect, it is possible to further maintain the desired conductivity and design properties. In addition, since the filler does not restrict the component A serving as the resin matrix, the toughness of the component A can be further utilized.

Examples of the lubricant referred to as the component F include mineral oil, synthetic oil, higher fatty acid ester, higher fatty acid amide, paraffin wax, polyolefin wax, polyalkylene glycol, fluorinated fatty acid ester, trifluorochloroethylene, and polyhexafluoropropylene glycol. And other fluorine oils. Therefore F
The component is obtained by modifying these lubricants with at least one functional group selected from a carboxyl group, a carboxylic anhydride group, an epoxy group, and an oxazoline group.

Examples of the higher fatty acid ester referred to as the component F include glycerin fatty acid ester, sorbitan fatty acid ester, polyglycerin fatty acid ester, propylene glycol fatty acid ester, ethylene glycol fatty acid ester, and polyoxyethylene fatty acid ester.

Among the lubricants mentioned above, polyolefin waxes are preferred. As the polyolefin wax, use of a polyethylene wax and / or a 1-alkene polymer is particularly preferable. As the polyethylene wax, those generally widely used at present can be used, and examples thereof include those obtained by polymerizing ethylene under high temperature and high pressure, those obtained by thermally decomposing polyethylene, and those obtained by separating and purifying a low molecular weight component from a polyethylene polymer. The molecular weight and the degree of branching are not particularly limited, but the molecular weight is preferably 500 to 20,000 in terms of weight average molecular weight.
More preferably, it is 1,000 to 15,000.

As the functional group, at least one functional group selected from a carboxyl group, a carboxylic anhydride group and an epoxy group is more preferable, and in particular, at least one functional group selected from a carboxyl group and a carboxylic anhydride group is preferred. Certain functional groups are preferred.

As a method for bonding these lubricants with at least one functional group selected from a carboxyl group, a carboxylic anhydride group, an epoxy group, and an oxazoline group, the above-mentioned specific functional group and the above-mentioned lubricant are combined with the lubricant. A method of reacting a compound having a reactive functional group, a method of copolymerizing a compound having the above specific functional group during synthesis of a lubricant, a method of mixing a lubricant, a compound having a functional group and a radical generator under heating Etc., and any method can be used.

Particularly preferred as the F component in the present invention are:
It is a polyolefin wax having at least one functional group selected from a carboxyl group and a carboxylic anhydride group. The carboxyl group or the carboxylic acid anhydride group can be contained in the polyolefin wax by various methods. For example, maleic acid or maleic anhydride and polyethylene, 1-
A method of mixing a polymer of an alkene, a polymer such as a copolymer of 1-alkene and ethylene with heating, in the presence or absence of a radical generator, includes a main chain, a side chain or a bonding atom. These functional groups can be introduced along with the cleavage. An even more preferred method is to introduce a functional group by copolymerizing maleic acid, preferably maleic anhydride, when polymerizing or copolymerizing ethylene, propylene, 1-alkene having 4 or more carbon atoms, and the like. is there. Such a method is a more preferable method because unnecessary heat load is not generated and the amount of the functional group can be easily controlled. The amount of such functional groups is preferably in the range of 0.1 to 6 meq / g per g of polyolefin wax.

Examples of the polyolefin wax include diamond carna PA30 and PA30M (trade names of Mitsubishi Chemical Corporation), and these can be used alone or as a mixture of two or more.

The proportion of the component F in the composition is 0.05 to 5 parts by weight based on 100 parts by weight of the total of the components A to C. Within such a range, both suppression of the intended damage of the B component and maintenance of the flame retardancy can be achieved.

Further, in order to further improve the flame retardancy, the composition of the present invention may contain an anti-dripping agent during combustion as a G component. Examples of the anti-dripping agent include a fluorine-containing polymer having a fibril-forming ability. Examples of such a polymer include polytetrafluoroethylene and a tetrafluoroethylene-based copolymer (eg, a tetrafluoroethylene / hexafluoropropylene copolymer, etc.). ), A partially fluorinated polymer as shown in U.S. Pat. No. 4,379,910, a polycarbonate resin produced from fluorinated diphenol, and the like, and preferably polytetrafluoroethylene.

As polytetrafluoroethylene having a fibril-forming ability, 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, and more preferably 10 to 500 μm.

The polytetrafluoroethylene is UL
Polytetrafluoroethylene having a fibril-forming ability and having a fibril-forming ability in a standard vertical combustion test during a combustion test of a test piece, specifically, for example, a product of Mitsui DuPont Fluorochemical Co., Ltd. Examples include Teflon 6J and Teflon 30J, polyflon MPA FA-500, polyflon F-201L and polyflon D-1 manufactured by Daikin Chemical Industry Co., Ltd., and CD076 manufactured by Asahi ICI Fluoropolymers Co., Ltd.

As such polytetrafluoroethylene, fine powder which 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.

As such polytetrafluoroethylene (hereinafter sometimes referred to as PTFE), in addition to the solid form as described above, an aqueous dispersion form can be used. 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 mentioned. 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.

Thirdly, a PTFE mixture obtained by simultaneously removing each medium from a mixture of a PTFE dispersion and a thermoplastic resin solution can be mentioned. Specifically, the medium is 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 mentioned. 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. was used.
(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.

The proportion of polytetrafluoroethylene having a fibril-forming ability is 1 in total of the components A to C of the present invention.
The amount is preferably 3 parts by weight, more preferably 0.01 to 1.5 parts by weight, even more preferably 0.05 to 1.0 part by weight with respect to 00 parts by weight. When the content is in the range of 3% by weight, it is possible to obtain a sufficient melting dripping prevention performance.

In the present invention, a char-forming compound can be added for the purpose of further improving the flame retardancy.
The char forming compounds include the following.

First, condensates of formaldehyde with a hydroxybenzene compound, a hydroxynaphthalene compound, a hydroxyanthracene compound, and the like can be given. For example, a novolak-type phenol resin and a cresol-modified phenol resin can be mentioned. Compounds in which such a hydroxy group is substituted with a sulfonic acid group or a sulfonic acid group are easily available and can be preferably used. For example, a formaldehyde condensate of sodium naphthalene sulfonate can be mentioned.

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

Third, the heavy oils or pitches themselves can be mentioned. Fourth, as thermoplastic resin types, poly (2,6-dimethyl-1,4-phenylene ether) and allylated poly (2,6-dimethyl-
1,4-phenylene ether), 2,6-diphenyl polyphenylene ether, polyparaphenylene, polyether sulfone, polyarylate, polyphenylene sulfide, polysulfone, polyether sulfone, and the like. Other examples include polyparaphenylene oligomers and 1,1′-thiobis (2-naphthol).

One or more selected from these can be used. Among these, particularly preferred char-forming resins include novolak-type phenol resins, poly (2,6-dimethyl-1,4-phenylene ether), and polyphenylene sulfide.

The flame-retardant thermoplastic resin composition of the present invention comprises
Various additives other than the above can be blended according to the purpose. Other various additives include, for example, reinforcing agents other than the B component (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, silica, ceramic particles, ceramic fiber,
Aramid particles, aramid fibers, polyarylate fibers, graphite, conductive carbon black, various whiskers, etc.), heat stabilizers, ultraviolet absorbers, light stabilizers, release agents,
Lubricants, coloring agents (pigments and dyes such as carbon black and titanium oxide), light diffusing agents (acrylic crosslinked particles, silicon crosslinked particles, ultrathin glass flakes, calcium carbonate particles, etc.), fluorescent brighteners, phosphorescent pigments, fluorescent dyes , Antistatic agent,
Examples include a flow modifier, a crystal nucleating agent, an inorganic and organic antibacterial agent, a photocatalytic antifouling agent (such as fine particle titanium oxide and fine particle zinc oxide), an infrared absorber, and a photochromic agent.

The heat stabilizer of the flame-retardant thermoplastic 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.

The phosphite-based stabilizer is preferably a phosphite compound having an aryl group in which two or more alkyl groups are substituted. 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 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 phosphorus-based heat stabilizers 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
Pentaerythritol diphosphite, dicyclohexylpentaerythritol diphosphite and the like are preferable, and 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 thermoplastic 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-butylfell) 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-tert-butyl-4-hydroxyphenyl) propionate] methane And n-octadecyl-β- (4 ′
-Hydroxy-3 ', 5'-di-tert-butylfell) propionate can more preferably be mentioned.

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 thermoplastic resin composition of the present invention can contain an ultraviolet absorber. As an ultraviolet absorber,
For example, benzophenone represented by 2-hydroxy-4-n-dodecyloxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, bis (5-benzoyl-4-hydroxy-2-methoxyphenyl) methane UV absorbers.

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-hexyloxy-phenol, 2- (4,
6-bis- (2,4-dimethylphenyl-1,3,5-
Examples thereof include hydroxyphenyltriazine compounds such as triazin-2-yl) -5-hexyloxy-phenol.

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 stabilizers, phenolic antioxidants and sulfur antioxidants can be used alone or in combination of two or more.

The proportion of these stabilizers in the composition is 100% by weight of the flame-retardant thermoplastic resin composition of the present invention.
Among them, the content of the phosphorus-based stabilizer, phenol-based antioxidant, or sulfur-based antioxidant is preferably 0.0001 to 1% by weight. More preferably, it is 0.0005 to 0.5% by weight in 100% by weight of the flame-retardant thermoplastic resin composition. More preferably, the content is 0.001 to 0.2% by weight.

The ratio of the ultraviolet absorber and the light stabilizer is 0.0% in 100% by weight of the flame-retardant thermoplastic resin composition of the present invention.
It is 1 to 5% by weight, more preferably 0.02 to 1% by weight.

The flame-retardant thermoplastic resin composition of the present invention can contain a release agent. Known release agents can be used. For example, saturated fatty acid esters, unsaturated fatty acid esters, polyolefin waxes (polyethylene wax, 1-alkene polymer, etc .; those modified with a functional group-containing compound such as acid modification can also be used), fluorine compounds (polyfluorocarbons) Fluorinated oil represented by alkyl ether), paraffin wax,
Beeswax and the like can be mentioned.

Preferred release agents include saturated fatty acid esters, for example, glycerin fatty acid esters such as glyceride stearate, polyglycerin fatty acid esters such as decaglycerin decastearate and decaglycerin tetrastearate, and stearate stearate. And lower fatty acid esters such as sebacic acid behenate and erythritol esters such as pentaerythritol tetrastearate. The release agent is a flame-retardant thermoplastic resin composition 10
It is preferably 0.01 to 2% by weight in 0% by weight.

The flame-retardant thermoplastic 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 blueing agents include, for example, Macrolex Blue R
R, Macrolex Violet B and Terazole Blue RLS.

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

In addition, a method of independently supplying the components A to C and optionally other components to a melt kneader represented by a vented twin-screw ruder, a method of supplying the components A to C and optionally other components Is preliminarily mixed and then supplied to the melt kneader independently of the remaining components. In particular, when the component B is fibrous, a method of supplying the component B to the molten resin in the middle of the extruder is preferable.

Further, a method of diluting and mixing the component C with water or an organic solvent and then supplying the diluted mixture to a melt kneader, or preliminarily mixing the diluted mixture with other components, and then supplying the mixture to the melt kneader may be mentioned.

When the components to be mixed include a liquid component, a so-called liquid injection device or a liquid adding device can be used for supplying to the melt kneader.

The flame-retardant thermoplastic resin composition of the present invention thus obtained has various properties at a high level.
That is, it has mechanical properties, flame retardancy, and various functions possessed by the metal-based filler, for example, design properties, antistatic properties, electrical conductivity, electromagnetic wave shielding properties, heat ray reflection properties, and the like. The flame-retardant thermoplastic resin composition of the present invention can be applied to extrusion molding, injection molding, compression molding, rotational molding, blow molding, vacuum molding, etc., and has a wide range of applications such as electronic / electric equipment, OA equipment, mechanical equipment, and vehicles. It can be used for In particular, notebook computers and portable computers that require electromagnetic shielding properties,
It is suitable for a housing of an electronic / electric device represented by a housing such as a portable information terminal and a wall-mounted display.

[0187]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be specifically described below with reference to examples. The present invention is not limited to this.

Reference Example 1 Preparation of Master Pelletized Red Phosphorus Flame Retardant Polycarbonate resin (L-122, manufactured by Teijin Chemicals Ltd.)
5WP, viscosity average molecular weight 22,500) 83.48 parts by weight and trimethyl phosphate 0.02 parts by weight
The mixture was uniformly mixed using a mold blender. Then 30m in diameter
mφ vent type twin screw extruder [TEX manufactured by Japan Steel Works, Ltd.]
30XSST] to remove the mixture from the last
Microencapsulated red phosphorus [NOVA EXCEL 140 manufactured by Rin Kagaku Kogyo KK, red phosphorus content 92% by weight, average particle diameter 35 μm] was measured from the second charging port of the side feed portion in the middle of the cylinder from the charging port. Container [CW made by Kubota Corporation]
F], 83.5 parts by weight of the mixture in the first input port was mixed with 1 micro-encapsulated red phosphorus in the second input port.
It was charged to 6.5 parts by weight. Each charging section was set to a nitrogen gas atmosphere by a nitrogen gas cylinder, and cylinder temperature 2
The temperature was set to 80 ° C., and a die having three circular holes each having a diameter of 4 mmφ was used. After extruding strands and cooling with a cooling bath, pellets were formed with a pelletizer. After uniformly mixing such pellets with a V-type blender,
The pellet was taken out, and the pellet was regarded as a cylinder. The diameter and length were measured with a digital caliper to calculate the surface area, and the weight was measured with an electronic balance to calculate the value of the specific surface area. As a result, a master-pelletized red phosphorus-based flame retardant (master 1) having a red phosphorus content of 15% by weight and a specific surface area of 15.5 cm ² / g was obtained.

Examples 1 to 20, Comparative Examples 1 to 5
The resin composition described in No. 4 was prepared in the following manner. The description will be made according to the symbols in the following table. First, when TMP or G-1 was contained in the components, premixing with PC shown below was performed. The amount of such PC is A component, B
The amount was equivalent to 10% by weight of the total of 100% by weight of the component and the component C. The mixture of these two or three components was uniformly mixed with a Henschel mixer.

Next, with respect to the resin compositions shown in Tables 1, 2 and 3, except for the B component (and components other than the B component) in each of these components, the remaining components and the above-mentioned pre-mixture were V-shaped. The mixture was mixed with a blender to obtain a uniform mixture. The mixture was introduced from the first inlet at the end of the extruder. On the other hand, the component B (and components other than the component B) was charged from the second charging port in the middle of the cylinder using a side feeder. Each input amount is measured with a measuring instrument [KWota Co., Ltd. CW
F]. 30m diameter as an extruder
mφ vent type twin screw extruder (Nippon Steel Works TEX3)
0XSST). In the screw configuration, a first-stage kneading zone was provided before the side feeder position, and a second-stage kneading zone was provided after the side feeder. Cylinder temperature and die temperature of 280
The strand was extruded under the conditions of ℃ and vent suction degree of 3000 Pa, cooled in a water bath, and then cut with a pelletizer to form pellets.

On the other hand, with respect to the resin compositions shown in Table 3, pellets were produced in the same manner as above except for the following two points. That is, 1) PC, PBT and PET were dried at 120 ° C. for 5 hours and then subjected to the above-mentioned production. 2) ABS, AS, PBT, and PET as A components were independently supplied from the second inlet.

The pellets obtained above were dried at 100 ° C. for 5 hours, and then subjected to an injection molding machine (SG-SG, manufactured by Sumitomo Heavy Industries, Ltd.).
150U), cylinder temperature 280 ° C, mold temperature 8
Test pieces for evaluation were prepared at 0 ° C., and the evaluation results are shown in Tables 1 to 4.

The evaluation items are as follows. (A) Impact strength: Measured according to ASTM D-256 (with Izod notch, thickness 3.2 mm). (B) Deflection temperature under load: Measured under a load of 1.813 MPa according to JIS K-7207. (C) Flame retardancy: A combustion test was performed according to UL standard 94V.

The symbols indicating the components shown in Tables 1 to 4 are as follows. (A component) PC: polycarbonate resin (bisphenol A prepared by phosgene method and p-tert as a terminal stopper)
-A polycarbonate resin comprising butylphenol. Such a polycarbonate resin was produced without using an amine catalyst, and the terminal hydroxyl group ratio in the polycarbonate resin terminal was 10 mol%, and the viscosity average molecular weight of the polycarbonate resin was 22,500.) ABS: ABS resin (Santak UT-61 manufactured by A & L Japan Co., Ltd.) AS: AS resin (Light Tack A98 manufactured by Mitsui Chemicals, Inc.)
0PCU) PBT: PBT resin (TRB-J, manufactured by Teijin Limited) PET: PET resin (TR8580, manufactured by Teijin Limited)

(Component B) Ni-CF: Nickel coated carbon fiber (Vesfight MCHTA-C6-US manufactured by Toho Rayon Co., Ltd.)
(I)) Ni-GFL: Nickel-coated glass flake (Metashine RCFSX-5230N manufactured by Nippon Glass Fiber Co., Ltd.)
S) SUS: Stainless steel fiber (Sasmic 12-2700 manufactured by Tokyo Steel Co., Ltd.) Pt: 0.1% alumina particles having an average particle size of 5 μm as a carrier.
5% by weight of platinum supported (obtained by impregnating an alumina carrier with an aqueous solution of chloroplatinic acid and reducing the same)

(Component C) C-1: Organic siloxane (in 100 mol% of all organic groups,
The proportion of methoxy groups is 30 mol% and the proportion of phenyl groups is 3
5 mol%, the proportion of vinyl groups is 10 mol%, and the proportion of methyl groups is 25 mol%. In the general formula (4) in the text, R ⁵ has a methoxy group, R ⁷ is a vinyl group and a Is 0.75 and c is 0.25, and the weight average molecular weight measured by the GPC method is about 750. An organic siloxane (KR-2 manufactured by Shin-Etsu Chemical Co., Ltd.)
19) C-2: Organosiloxane (in 100 mol% of all organic groups,
The proportion of methoxy groups is 25 mol% and the proportion of phenyl groups is 3
5 mol%, the proportion of vinyl groups is 10 mol%, and the proportion of methyl groups is 30 mol%. In the general formula (4) in the text, R ⁵ has a methoxy group, R ⁷ is a vinyl group and a Is about 0.7 and c is about 0.3, and has a weight average molecular weight of about 630 measured by a GPC method defined in the text (X40- manufactured by Shin-Etsu Chemical Co., Ltd.).
9243)

(D component) FR-1: Phosphate ester oligomer type flame retardant (ADK STAB FP-500 manufactured by Asahi Denka Kogyo Co., Ltd.) FR-2: Phosphate ester oligomer type flame retardant (Daichi Chemical Industry Co., Ltd.) FR-7: Monophosphate ester type flame retardant (TPP manufactured by Daihachi Chemical Industry Co., Ltd.) FR-4: Halogen flame retardant (carbonate oligomer of tetrabromobisphenol A, fire manufactured by Teijin Chemicals Ltd.) Guard FG-7000) FR-5: Red phosphorus derived from the master pellet prepared in Reference Example 1 (a master pellet was used in such an amount that the amount of red phosphorus was applied).

(E component) E-1: Composite rubber-based graft copolymer (METABLEN S-2001 manufactured by Mitsubishi Rayon Co., Ltd.) E-2: Butadiene rubber reinforced-methyl methacrylate-ethyl acrylate copolymer (Kureha E-3: Butadiene-acrylate copolymer rubber reinforced-styrene-methyl methacrylate copolymer (HIA15 manufactured by Kureha Chemical Industry Co., Ltd.)

(F component): F-1: an olefin wax having a carboxylic acid anhydride group and a carboxyl group (Diacarna PA30M manufactured by Mitsubishi Chemical Corporation)

(G component) G-1: Polytetrafluoroethylene having a fibril-forming ability (Polyflon MPA manufactured by Daikin Industries, Ltd.)
FA-500)

(Others) TMP: Trimethyl phosphate (Daichi Chemical Industry Co., Ltd.)
TMP) L1: Saturated fatty acid ester-based release agent (Rikemar SL900 manufactured by Riken Vitamin Co., Ltd.)

[0202]

[Table 1]

[0203]

[Table 2]

[0204]

[Table 3]

[0205]

[Table 4]

As is clear from these tables, it is found that good flame retardancy can be obtained when an organic siloxane compound and a specific metal-based filler are used in combination. As can be seen from the reference example, the effect of the present invention can be said to be remarkable because the metal-based filler alone is inferior in flame-retardancy as compared with a glass-based filler or the like when used alone. Further, the above Examples 17 and 18
In the sample (1), a molded article of a front cover (a cover on the liquid crystal display side) of a notebook computer was molded from the sample. However, each of the molded articles had sufficient strength and was particularly excellent in surface impact strength. Was.

[0207]

Industrial Applicability The resin composition of the present invention has excellent flame retardancy and excellent mechanical properties, and thus is suitable for a wide range of industrial fields including housings for electronic equipment. The industrial effects of the resin composition obtained in the above are outstanding.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4J002 BC021 BC051 BC061 BN061 BN071 BN101 BN121 BN151 BP011 CF041 CF161 CG011 CG041 CH071 CL001 CL011 CL031 CP032 DA016 DL006 FA016 FA046 FB076 FD010 FD020 FD050 FD060 FD060 FD050 FD060

Claims (5)

[Claims] 1. (a) at least one thermoplastic resin selected from a polycarbonate resin, an aromatic polyester resin, a polyarylate resin, a polyester carbonate resin, a styrene resin, a polyphenylene ether resin, and a polyamide resin (component A) , (B) Periodic Table 3
Group 16 metals and / or their metal compounds (B
At least one filler (component B-2) selected from fillers (component B-2) having a surface coated with a metal of Group 3 to 16 of the periodic table and / or a metal compound thereof; And (c) an organic siloxane compound (component (C)), and the total of component A, component B and component C is 10
0% by weight, 0.001 to 55% by weight of the B component and C
A flame-retardant thermoplastic resin composition containing 0.05 to 10% by weight of a component. 2. A flame retardant (D component) is added in an amount of 0.001 to 2 based on 100 parts by weight of the total of the components A to C.
The flame-retardant resin composition according to claim 1, comprising 0 parts by weight. 3. The composition according to claim 1, wherein the component B comprises a metal of Group 8 to 11 of the periodic table and / or a metal compound thereof (component B-1) and a metal of Group 8 to 11 of the periodic table and / or a metal compound thereof on the surface. The flame-retardant thermoplastic resin composition according to claim 1, which is at least one kind of filler selected from fillers (B-2 component) formed by coating. 4. The component C has a weight average molecular weight of 200 to 10,000 as measured by GPC, and has an alkoxy group of 10 to 10 of the organic functional groups contained in the organic siloxane.
The content of the aryl group is within the range of 50 mol%, and the content of the aryl group is 10 mol% of the organic functional groups contained in the organosiloxane.
The flame-retardant thermoplastic resin composition according to any one of claims 1 to 3, which is an organosiloxane as described above. 5. The flame-retardant thermoplastic resin composition according to claim 1, wherein the component B has a fibrous or plate-like shape.