JP2002080709A - Frame-retarded polycarbonate resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polycarbonate resin composition containing an inorganic filler having excellent flame retardancy. SOLUTION: This aromatic polycarbonate resin composition comprises (A) 96.8999-24.95 wt.% aromatic polycarbonate resin, (B) 3-55 wt.% inorganic filler, (C) 0.1-20 wt.% organic phosphorus compound and (D) 0.0001-0.05 wt.% at least one kind of a metal salt selected from an alkali metal salt and/or an alkaline earth metal salt when the total of the components A, B, C and D is 100 wt.%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an aromatic polycarbonate resin composition containing an inorganic filler having excellent flame retardancy. More specifically, a resin composition in which an inorganic filler is blended with an aromatic polycarbonate resin contains an organic phosphorus compound and a very small amount of at least one metal salt selected from alkali metal salts and / or alkaline earth metal salts. The present invention relates to a resin composition, which is an aromatic polycarbonate resin composition having excellent flame retardancy at a thin portion.

[0002]

2. Description of the Related Art Aromatic polycarbonate resins are known as engineering plastics having excellent mechanical properties such as impact resistance and also excellent flame retardancy and heat resistance. However, the aromatic polycarbonate resin reinforced with the filler has a problem that although the strength and the rigidity are improved, the flame retardancy and the impact resistance are significantly inferior to those of the non-reinforced aromatic polycarbonate resin composition. Particularly, in the case of a notebook personal computer casing, a portable computer casing, and a molded product for a thin casing such as a portable terminal device, the molded article has sufficient strength, rigidity and thin moldability, and further has impact resistance. There has been a strong demand for the appearance of a resin composition having a good balance of flame retardancy. Various proposals have been made for improving the flame retardancy of the aromatic polycarbonate resin. For example, JP-A-64-22958
Japanese Patent Application Laid-Open Publication No. H11-139,086 discloses a method of adding an organic halogen compound as a flame retardant and antimony trioxide as a flame retardant aid. However, these flame-retardant resin compositions thermally decompose during combustion and molding to generate harmful hydrogen halides, which corrode the mold, degrade or color the resin itself, and further reduce the working environment. There is a drawback that it worsens. Resin compositions containing halogen compounds are also a social problem because they emit highly toxic dioxins when burned, and there is a growing demand for halogen-free flame retardants. Therefore, a method of blending red phosphorus which does not contain halogen and has a high flame retardant effect (Japanese Patent Laid-Open No.
JP-A-85642) and a method of blending microencapsulated red phosphorus (JP-A-6-116473), wherein red phosphorus or microencapsulated red phosphorus is used in a resin composition. The system has disadvantages such as generation of harmful phosphine gas upon combustion and limitation of coloring property. As the phosphorus-based flame retardant alone, aromatic phosphate compounds (JP-B-48-38768),
Bisphenol A polyphosphate, hydroquinone bisphosphate compound (JP-A-55-118957), resorcinol polyphosphate compound (Japanese Patent Publication No.
No. 3-65109, Japanese Patent Publication No. 2-25381, etc.) are disclosed. However, in order to make these phosphorus compounds flame-retardant in thin-walled parts, a large amount of addition is required, which causes not only a drop in impact resistance and a remarkable drop in heat distortion temperature, but also often causes a dripping phenomenon. There are drawbacks such as. Furthermore, it is known that a silicone resin or a metal salt-based flame retardant is blended as a method of imparting flame retardancy without generating harmful gas during combustion.
However, with a silicone resin and a metal salt-based flame retardant alone, in an aromatic polycarbonate resin composition reinforced with an inorganic filler, high flame retardancy at a thin portion cannot be obtained, and when a large amount is added, poor appearance, Problems such as a decrease in thermal stability and a decrease in impact resistance occur. Therefore, as a method of reducing the amount of the flame retardant to be added, a method in which a silicone resin and a metal salt-based flame retardant are used in combination (Japanese Patent No. 2719486, Japanese Patent Application Laid-Open No. 11-217494, etc.) is disclosed. In a polycarbonate resin composition reinforced with a chemical agent, when left in a high-temperature and high-humidity environment for a long time, the metal salt-based flame retardant has high hygroscopicity. There is a disadvantage that the properties are significantly reduced. Furthermore, compared to the unreinforced polycarbonate resin composition, it is difficult to obtain high flame retardancy, and the high flame retardancy required for molded articles for thin-walled housings with the polycarbonate resin composition reinforced with an inorganic filler is increased. To be satisfactory, such compositions are not yet satisfactory. Next, a method in which a metal salt-based flame retardant and a phosphorus-based flame retardant are used in combination (JP-A-2-92961, JP-A-10-306208, etc.) is disclosed. The polycarbonate resin composition specifically exemplified in the former publication does not sufficiently satisfy the high flame retardancy in the thin portion, and furthermore, the polycarbonate resin causes decomposition at the time of high-temperature molding, so that the mechanical strength, There is a disadvantage that the impact resistance is significantly reduced. Further, the polycarbonate resin composition specifically exemplified in the latter publication has a large amount of an organic sulfonic acid metal salt, and is not sufficiently satisfactory in impact resistance and wet heat resistance. As for those satisfying the high flame retardancy required for molded articles for thin-walled housings with a polycarbonate resin composition reinforced with an inorganic filler, which is difficult to obtain high flame retardancy compared to the resin composition, Such compositions are not yet satisfactory. For this reason, there is a demand for an excellent resin composition which has an excellent flame-retarding effect with a small amount of a flame retardant and has a small generation of harmful gas during combustion in order to have excellent mechanical properties, especially impact resistance. .

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide an aromatic polycarbonate resin composition containing an inorganic filler excellent in flame retardancy, which generates little harmful gas during combustion. The present inventors have conducted intensive studies to achieve the above object, and as a result, in an aromatic polycarbonate resin composition reinforced with an inorganic filler whose flame retardancy is reduced as compared with an unreinforced polycarbonate resin composition, an organic By combining a phosphorus compound with an alkali metal salt and / or an alkaline earth metal salt whose addition amount is significantly reduced, the flame retardancy and mechanical properties, particularly the impact resistance, are improved, and the intended thin portion (thickness 0.8 mm or less) ) Was found to be excellent in flame retardancy and impact resistance, and reached the present invention.

[0004]

According to the present invention, when the total of component A, component B, component C and component D is 100% by weight,
Aromatic polycarbonate resin (component A) 96.8999
-24.95 wt%, inorganic filler (component B) 3-55 wt%, organic phosphorus compound (component C) 0.1-20 wt%,
At least one metal salt (D component) selected from alkali metal salts and / or alkaline earth metal salts 0.00
The present invention relates to an aromatic polycarbonate resin composition and a molded article in an amount of from 0.01 to 0.05% by weight.

The aromatic polycarbonate resin used as the component A in the present invention is usually obtained by reacting a dihydric phenol with a carbonate precursor by an interfacial polycondensation method or a melt transesterification method. It is obtained by polymerizing by a solid phase transesterification method or obtained by polymerizing by a ring opening polymerization method of a cyclic carbonate compound.

Typical 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 in combination 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, and furthermore, bisphenol A homopolymer and 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane and bisphenol A, 2,2-bis {(4-hydroxy- Copolymers with 3-methyl) phenyl} propane or α, α′-bis (4-hydroxyphenyl) -m-diisopropylbenzene are preferably used. In particular, a homopolymer of bisphenol A 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 aromatic polycarbonate resin by reacting the dihydric phenol with the carbonate precursor by an interfacial polycondensation method or a melt transesterification method, if necessary, a catalyst, a terminal stopper, a dihydric phenol may be used. May be used. The aromatic 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. Alternatively, a mixture of two or more of the obtained aromatic polycarbonate resins may be used.

[0010] 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 0.001 to 1 mol%, preferably 0.005 to 0.5 mol%, particularly preferably 0.001 to 1 mol%, based on the total amount of the aromatic polycarbonate. 0.01
~ 0.3 mol%. In addition, particularly in the case of the melt transesterification method, a branched structure may be generated as a side reaction, and the amount of such a branched structure is also 0.001 to 1 mol%, preferably 0.005 to 5 mol%, of the total amount of the aromatic polycarbonate.
0.5 mol%, particularly preferably 0.01 to 0.3 mol%
Is preferred. The ratio is ¹ H
-It can be calculated by NMR measurement.

The reaction by the interfacial polycondensation method is usually a reaction between dihydric phenol and phosgene, and is carried out in the presence of an acid binder and an organic solvent. 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 aromatic polycarbonate resins are not terminated because the ends are blocked by groups based on monofunctional phenols. Excellent in thermal 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).

[0014]

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

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. Of these, phenols having a long-chain alkyl group represented by the following general formulas (2) and (3) as a substituent are preferably used.

[0017]

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[0018]

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

The substituted phenols of the general formula (2) are preferably those having n of 10 to 30, especially 10 to 26, and specific examples thereof include, for example, decylphenol, dodecylphenol, tetradecylphenol, hexadecylphenol, 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 5 mol%, preferably at least 10 mol%, based on all terminals of the obtained aromatic 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. 90 mol% or more of a terminator is introduced to all terminals, that is, O
This is the case when the H 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 the polymerization reaction, in order to reduce the number of phenolic terminal groups, for example, bis (chlorophenyl) carbonate, bis (bromophenyl) carbonate, bis (nitrophenyl) carbonate is used later or after completion of the polycondensation reaction. , Bis (phenylphenyl)
Carbonate, chlorophenylphenyl carbonate,
It is preferable to add a compound 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.

Although the molecular weight of the aromatic 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. 1
It is preferably from 4,000 to 40,000,
More preferably, the number is from 00 to 30,000, particularly preferably from 14,000 to 23,000. Further, two or more aromatic polycarbonate resins may be mixed. The viscosity average molecular weight referred to in the present invention is 100 ml of methylene chloride and 0.7 part of an aromatic polycarbonate resin.
The specific viscosity (η _SP ) obtained from a solution of g dissolved at 20 ° C. is inserted into 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

Here, the ratio of the component A in the resin composition is 10 times the sum of the components A, B, C and D.
96.8999 to 24.95% by weight when 0% by weight
It is. If the amount is less than 24.95% by weight, the flame retardancy decreases, and if it is more than 96.8999% by weight, molding becomes difficult.

Next, the inorganic filler used as the component B is as follows:
There is no particular limitation as long as it is generally used for reinforcing an aromatic polycarbonate resin. Mineral fibers such as wollastonite, zonotolite, and attapulgite; glass fibers such as glass fiber, milled fiber, and metal-coated glass fiber Types; carbon fibers such as carbon fiber, carbon milled fiber and metal-coated carbon fiber; metal fibers such as stainless steel wire, copper wire, aluminum wire and tungsten wire; alumina fiber, zirconia fiber, silicon carbide fiber, boron fiber, etc. Fillers such as ceramic fibers, aluminum borate whiskers, potassium titanate whiskers, basic magnesium sulfate whiskers, various kinds of whiskers such as needle-like titanium oxide and needle-like calcium carbonate, talc, mica, glass flakes and graphite Plates such as flakes Fillers, glass beads, glass balloons, ceramic balloons, carbon beads, silica particles, titania particles, alumina particles, kaolin, clay,
Examples include various particulate fillers such as calcium carbonate, titanium oxide, cerium oxide, and zinc oxide, and two or more of these can be used in combination.

Among these, preferred inorganic fillers include fibrous fillers such as glass fibers, carbon fibers, metal fibers, and ceramic fibers. Among them, the effects of the present invention are remarkable and preferred. Are glass fibers and carbon fibers, and among them, carbon fibers are particularly preferable. The reason for this is that while carbon fibers can achieve high rigidity and high strength with a small amount, good impact resistance is hardly achieved, and especially when flame retardancy is required, the properties of carbon fibers It requires more flame retardant than the above, and the impact resistance in such a case is significantly reduced.

As the carbon fiber in the present invention, any of cellulose type, polyacrylonitrile type, pitch type and the like can be used, and a raw material comprising a polymer of aromatic sulfonic acids or their salts by a methylene type bond and a solvent. It is also possible to use a composition obtained by a method of performing spinning without going through an infusibilization step typified by spinning or molding the composition and then carbonizing. Further, those manufactured by a manufacturing method that does not go through a spinning step represented by a vapor phase growth method can also be used.

Further, any of a so-called general-purpose type, a medium elasticity type and a high elasticity type can be used, and a polyacrylonitrile-based high elasticity type is particularly preferable.
The shape is a chopped strand, a roving strand or the like. In addition, for the production method, either melt spinning or solvent spinning can be used,
Further, for solvent spinning, either wet spinning or dry spinning can be used.

Regarding the fiber diameter, the diameter is 0.5 to 20 μm.
m is preferable, and 1 to 10 μm is particularly preferable. If it is less than 0.5 μm, the fibers are easily entangled with each other, and the fiber is severely bent in the step of dispersing the fiber in the aromatic polycarbonate, and the efficiency of rigidity improvement is reduced. The reinforcing efficiency of the steel decreases. These carbon fibers oxidize the surface of the carbon fibers by a method such as gas-phase oxidation in which the fibers are heated in an oxidizing gas, liquid-phase oxidation using a solution of an oxidizing agent, or anodizing the carbon fibers in an electrolytic bath. It is desirable. The carbon fiber is usually cut as a chopped strand by a sizing agent into a fiber length of about 1 to 10 mm with thousands to tens of thousands of fibers as one unit, and these can be used as appropriate.

[0034] After the carbon fiber is cut, the carbon milled fiber is further pulverized by a ball mill or the like.
The length is adjusted to less than the length of a normal chopped strand. In such a case, the carbon fibers mentioned above can be used as the base carbon fibers.

The metal-coated carbon fiber has a diameter of 1 to 1.
Those having a thickness of 20 μm are particularly preferred. If it is less than 1 μm, the mechanical properties will be insufficient, and if it exceeds 20 μm, the conductivity will also be insufficient due to the decrease in the number of fibers. Metal-coated carbon fibers and metal-coated glass fibers are more susceptible to breakage than metal fibers, so that the decrease in conductivity due to the fiber diameter tends to be remarkable. These conductive fibers are preferably surface-treated with a silane coupling agent, a titanate coupling agent, an alumina coupling agent, or the like. Further, it is preferable to use a resin that has been subjected to a bunching treatment with an olefin resin, a styrene resin, a polyester resin, an epoxy resin, a urethane resin, a polyamide resin, or the like. Here, the ratio of the component B in the resin composition is 3 to 55% by weight, preferably 8 to 30% by weight when the total of the components A, B, C and D is 100% by weight. It is. 3% by weight
If the amount is less than the above, the strength is insufficient. If the amount is more than 55% by weight, the flame retardancy is reduced or the molding becomes difficult.

As the organic phosphorus compound used as the component C in the present invention, a phosphonium salt, a phosphinate, a phosphate, a phosphite and the like can be mentioned. More specifically, triphenyl phosphate, methyl neopentyl phosphite, pentaerythritol diethyl diphosphite, methyl neopentyl phosphate, phenyl neopentyl phosphate, pentaerythritol diphenyl diphosphate, dicyclopentyl high positive phosphate, dineopentyl hypophosphate Phosphite, phenylpyrocatechol phosphite, ethyl pyrocatechol phosphate, dipyrocatechol hypoxic phosphate and the like can be mentioned.

Here, in particular, 1 represented by the following general formula (4)
Species or two or more phosphoric ester compounds can be mentioned.

[0038]

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(Where X in the above formula is hydroquinone,
Derived from resorcinol, bis (4-hydroxydiphenyl) methane, bisphenol A, dihydroxydiphenyl, dihydroxynaphthalene, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) ketone, bis (4-hydroxyphenyl) sulfide J, k, l, and m are each independently 0 or 1, n is an integer of 0 to 5,
Or 0 in the case of a mixture of n different phosphate esters.
And R ₁ , R ₂ , R ₃ , and R ₄ are each independently phenol, cresol, xylenol, isopropylphenol, butylphenol substituted or unsubstituted with one or more halogen atoms. p-
It is derived from cumylphenol. )

Of these, X in the above formula preferably includes those derived from hydroquinone, resorcinol and bisphenol A, wherein j, k, l and m are each 1 and n is 0 to 3 Is an integer or an average of 0 to 3 in the case of a blend of n different phosphate esters, wherein R ₁ , R ₂ , R ₃ , and R ₄ are each independently 1
It is derived from phenol, cresol, or xylenol with or without substitution of at least two halogen atoms.

Among such phosphate ester-based flame retardants,
Triphenyl phosphate is used as the monophosphate compound, and resorcinol bis (dixylenyl phosphate) and bisphenol A are used as the condensed phosphate.
Bis (diphenyl phosphate) is most preferably used because it has good flame retardancy and good fluidity during molding.

It is also possible to use a phosphazene compound represented by a phenoxyphosphazene oligomer or a cyclic phenoxyphosphazene oligomer.

Regarding the amount of the organic phosphorus compound, the component A,
When the total of the components B, C and D is 100% by weight, it is 0.1 to 20% by weight, preferably 3 to 15% by weight. If it is less than 0.1% by weight, the flame retardancy is insufficient,
If it exceeds 20% by weight, mechanical properties and heat resistance are insufficient, which is not preferable.

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

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

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

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

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

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

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

As the alkali (earth) metal salt of a sulfonate of an aromatic carboxylic acid or an ester, JP-A-50-9
No. 8540, and examples thereof include potassium 5-sulfoisophthalate, sodium 5-sulfoisophthalate, and polysodium polyethylene terephthalate polysulfonate.

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

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

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

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

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

The heterocyclic sulfonate alkali (earth) metal salts are described in JP-A-50-116542. For example, disodium thiophene-2,5-disulfonate, thiophene-2,5- Dipotassium disulfonate, calcium thiophene-2,5-disulfonate,
Examples thereof include sodium benzothiophene sulfonate.

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

Examples of the condensate of an alkali (earth) metal salt of an aromatic sulfonic acid by a methylene type bond include a formalin condensate of naphthalene sulfonic acid and a formalin condensate of anthracene sulfonic acid.

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

Examples of other alkali (earth) metal salts include alkali (earth) metal salts of aromatic sulfonamides, such as saccharin, N- (p-tolylsulfonyl) -p-toluenesulfonate. Imide, N-
(N'-benzylaminocarbonyl) sulfanylimide, and alkali (earth) metal salts of N- (phenylcarboxyl) sulfanylimide. Of the above-mentioned D components, more preferred alkali (earth) metal salts include alkali (earth) metal salts of aromatic sulfonic acids and alkali (earth) metal salts of perfluoroalkanesulfonic acids. it can.

Regarding the amount of the D component, the A component, the B component,
When the total of the C component and the D component is 100% by weight, 0.1%.
0001-0.05% by weight, preferably 0.0001-
0.01% by weight. If it is less than 0.0001% by weight,
Flame retardancy is insufficient, and if it exceeds 0.05% by weight, mechanical properties and wet heat resistance are insufficient, which is not preferable.

Further, in the present invention, the polyorganosiloxane rubber component and the polyalkyl (meth) acrylate rubber component are not separated so as not to be separated from each other for the purpose of improving impact resistance as an E component within a range not to impair the flame retardancy. It is also possible to add a composite rubber-based graft polymer obtained by graft-polymerizing one or more vinyl monomers to a composite rubber having a structure entangled with It is obtained and can be preferably used. In order to obtain the composite rubber-based graft copolymer used in the present invention, first, various cyclic organosiloxanes having three or more ring members, for example, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and the like. And a latex of the polyorganosiloxane rubber is prepared by emulsion polymerization using a crosslinking agent and / or a graft crosslinking agent, and then an alkyl (meth) acrylate monomer, a crosslinking agent and a graft crosslinking agent are combined with the polyorganosiloxane rubber. It is obtained by impregnating latex and then polymerizing. Examples of the alkyl (meth) acrylate monomer used here include alkyl acrylates such as methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate and 2-ethylhexyl acrylate, and alkyls such as hexyl methacrylate and 2-ethylhexyl methacrylate. Methacrylate is mentioned, and especially n-
Preferably, butyl acrylate is used.

Examples of the vinyl monomer to be graft-polymerized to the composite rubber include aromatic vinyl compounds such as styrene and α-methylstyrene, vinyl cyanide compounds such as acrylonitrile and methacrylonitrile, methyl methacrylate, and 2-ethylhexyl methacrylate. And acrylates such as methyl acrylate, ethyl acrylate and butyl acrylate. These may be used alone or in combination of two or more. Among such composite rubber-based graft copolymers, particularly preferred are those marketed by Mitsubishi Rayon Co., Ltd. under the trade name of Metablen S-2001 or SRK-200.

The amount of the composite rubber-based graft polymer is preferably 1 to 20 parts by weight based on 100 parts by weight of the composition comprising the components A and D.

The olefin wax containing a carboxyl group and / or a carboxylic anhydride group used as the component F in the present invention is a olefin wax containing a carboxyl group and / or a carboxylic anhydride group by post-treatment of an olefin wax. Compounds, preferably those modified with maleic acid and / or maleic anhydride. Further, when polymerizing or copolymerizing ethylene and / or 1-alkene, a compound containing a carboxyl group and / or a carboxylic anhydride group copolymerizable with such monomers, preferably maleic acid and / or maleic anhydride is used. Copolymers may also be mentioned, and those obtained by copolymerization include carboxyl groups and / or
Alternatively, a carboxylic acid anhydride group is preferably contained at a high concentration and stably. By blending such a wax,
It is considered that the conductive fibers are prevented from being damaged by shearing during the molding process, the original aspect ratio is maintained, and a higher electromagnetic wave shielding effect is exhibited. The carboxyl group or carboxylic anhydride group may be bonded to any part of the olefin wax, and the concentration thereof is not particularly limited, but 0.1 to 6 m / g of the olefin wax.
The range of eq / g is preferred. If less than 0.1 meq / g, the effect of improving rigidity and impact resistance becomes insufficient,
If it exceeds 6 meq / g, the thermal stability of the olefin-based wax itself deteriorates, which is not preferable. Commercially available olefin waxes include, for example, Diacarna-PA30 (trade name of Mitsubishi Chemical Corporation), 2203A and 1105A of high wax acid treatment type (trade names of Mitsui Petrochemical Co., Ltd.) and the like. Are used alone or as a mixture of two or more thereof,
With respect to 100 parts by weight of the composition comprising the component and the D component,
0.005 to 5 parts by weight.

In order to further improve the flame retardancy, it is possible to add polytetrafluoroethylene having fibril-forming ability as a G component to the composition of the present invention. Polytetrafluoroethylene having such a fibril-forming ability is classified into Type 3 in the ASTM standard. Further, the polytetrafluoroethylene having a fibril-forming ability preferably has a primary particle diameter in the range of 0.05 to 10 μm, and more preferably has a secondary particle diameter of 50 to 700 μm. Such a polytetrafluoroethylene has a drip-preventing performance at the time of a combustion test of a test piece in a UL standard vertical combustion test, and such a polytetrafluoroethylene having a fibril-forming ability is, for example, Mitsui-Dupont Fluorochemical Co., Ltd. It is commercially available as Teflon 6J or as Polyflon from Daikin Chemical Industries, Ltd. and can be easily obtained.

As the polytetrafluoroethylene (hereinafter sometimes simply referred to as “PTFE”), not only a usual solid form but also 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 given. Specifically, JP-A-60-258263 discloses an average particle size of 0.0
A method is described in which a PTFE dispersion of 5 to 5 μm is mixed with a dispersion of a vinyl polymer, PTFE particles larger than 30 μm are coagulated without purification, and the coagulated product is dried to obtain a PTFE mixture. The use of such mixtures is possible.

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

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

Fourth, a PTFE mixture obtained by polymerizing another vinyl-based 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, there is a method of mixing the PTFE dispersion and the polymer particle dispersion, and further polymerizing the ethylenically unsaturated monomer in the mixed dispersion. And a fine PTFE mixture in terms of achieving both of fine dispersion of PTFE. The details of such a mixture are described in JP-A-11-29679, that is, a particle diameter of 0.05.
PTFE mixture pulverized by coagulation or spray drying after emulsion polymerization of a monomer having an ethylenically unsaturated bond in a dispersion obtained by mixing a PTFE dispersion of about 1.0 μm and a polymer particle dispersion. Are preferred.

Here, the polymer particles include a block copolymer comprising 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, the ethylenically unsaturated monomers include styrene, p-methylstyrene, o-methylstyrene and p-methylstyrene.
-Methoxystyrene, o-methoxystyrene, 2,4-
Styrene-based monomers such as dimethylstyrene and α-methylstyrene; methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, methacrylic acid-2 -Acrylate monomers such as ethylhexyl, dodecyl acrylate, dodecyl methacrylate, cyclohexyl acrylate and cyclohexyl methacrylate; vinyl cyanide monomers such as acrylonitrile and methacrylonitrile; vinyl methyl ether and vinyl ethyl ether Vinyl ether monomers such as vinyl acetate and vinyl butyrate; olefin monomers such as ethylene, propylene and isobutylene; diene monomers such as butadiene, isoprene and dimethylbutadiene. It can be selected from among. These monomers can be used alone or in combination of two or more.

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

The proportion of polytetrafluoroethylene having fibril-forming ability is preferably 3 parts by weight or less, more preferably 0.05 to 1.5 parts by weight, per 100 parts by weight of the aromatic polycarbonate resin composition of the present invention. Parts, particularly preferably 0.1 to 1.0 part by weight. When the amount is in the range of 3 parts by weight, it is possible to obtain a sufficient melting dripping prevention performance.

In the present invention, a char-forming resin can be added for the purpose of further improving the flame retardancy. As a char forming resin, novolak type phenol resin,
Cresol-modified phenolic resin, poly (2,6-dimethyl-1,4-phenylene ether), allylated poly (2,6-dimethyl-1,4-phenylene ether),
2,6-diphenyl polyphenylene ether, polyphenyl, polyether sulfone, polyarylate, polyphenylene sulfide, polysulfone, polyether sulfone, and the like, and one or a combination of two or more selected from these. Can be. Among these, particularly preferred char-forming resins include novolak-type phenol resins, poly (2,6-dimethyl-1,4-phenylene ether), and polyphenylene sulfide.

The composition of the present invention contains a phosphoric acid ester such as trimethyl phosphite or triphenyl phosphite, trisnonyl phenyl phosphite, distearyl pentaerythritol diphosphite, bis (2,6-di- By further adding 0.001 to 1% by weight of a phosphite such as (tert-butyl-4-methylphenyl) pentaerythritol diphosphite to the whole composition, the thermal stability is further improved. Is preferred. Further, various additives may be added as long as the object of the present invention is not impaired. 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, fluorescent whitening agents, luminous pigments, fluorescent dyes, antistatic agents, flow modifiers, crystal nucleating agents, inorganic and organic antibacterial agents, photocatalytic antifouling agents (fine particle titanium oxide,
Fine particle zinc oxide), an impact modifier represented by a graft rubber, an infrared absorber, and a photochromic agent within a range that does not impair the object of the present invention.

The aromatic polycarbonate resin composition of the present invention is obtained by mixing the above components simultaneously or in an arbitrary order by using a mixer such as a tumbler, a V-type blender, a Nauter mixer, a Banbury mixer, a kneading roll, an extruder and the like. Can be manufactured. Preferably, melt-kneading by a twin-screw extruder is preferable, and in that case, it is preferable that the component B is supplied into the other components that are melt-mixed from a second supply port by a side feeder or the like.

The resin composition thus obtained is extruded,
It can be easily molded by a method such as injection molding or compression molding, and can also be applied to blow molding, vacuum molding and the like. In particular, in injection molding and blow molding, it is preferable to use a mold having a heat insulating layer or a mold in which only the surface of the mold cavity is locally heated in advance. Molded products obtained by the above-mentioned various production methods are excellent in both rigidity and impact resistance, and are most suitable for fields such as thin-walled housings. Specific examples include the fields of portable communication devices, notebook computers, automobile internal parts, especially electric vehicle parts. Particularly, it is most suitable as a material in a field where high flame retardancy is required.

[0082]

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.

[Examples 1 to 10, Comparative Examples 1 to 6] Table 1,
After mixing each component described in 2 with a V-type blender at the mixing ratios shown in Tables 1 and 2, the mixture was mixed with a cylinder using a vented twin-screw extruder having a diameter of 30 mmφ (Tex30XSST, Japan Steel Works, Ltd.).
Pelletized at a temperature of 280 ° C. 100 pellets
After drying at 5 ℃ for 5 hours, injection molding machine (Sumitomo Heavy Industries, Ltd.)
SG-150U) to produce a test piece for evaluation at a cylinder temperature of 280 ° C. and a mold temperature of 80 ° C.
It was shown to. (A) Flame retardancy: A combustion test was performed according to UL standard 94V. (B) Impact strength: Measured according to ASTM D-256 (with Izod notch, thickness 3.2 mm). (C) Impact strength: Measured according to ASTM D-256 (with a reverse notch, thickness 3.2 mm). (D) Flexural modulus: measured according to ASTM D-790. (E) Deflection temperature under load: Measured under a load of 1.813 MPa according to JIS K-7207.

[0084]

[Table 1]

[0085]

[Table 2]

The symbols indicating the components shown in Tables 1 and 2 are as follows. (A component): PC: aromatic polycarbonate resin (L-1225, Teijin Chemicals Ltd., viscosity average molecular weight 22,50)
0) (Component B): B-1: Nickel coated carbon fiber (Vesfight MCHTA-C6-CS manufactured by Toho Rayon Co., Ltd.)
(I)): B-2: Carbon fiber (Vesfight HTA-C6-N manufactured by Toho Rayon Co., Ltd.): B-3: Glass fiber (ECS- manufactured by Nippon Electric Glass Co., Ltd.)
03T-511) (Component C): FR-1; Condensed phosphate ester flame retardant (ADK STAB FP-500 manufactured by Asahi Denka Kogyo Co., Ltd.): FR-2: Condensed phosphate ester flame retardant (Dahachi Chemical ( CR-741): FR-3: phosphazene compound (S. Otsuka Chemical Co., Ltd.)
(P-100) (D component): metal salt-1; potassium perfluorobutanesulfonate (MegaFac F-114 manufactured by Dainippon Ink and Chemicals, Inc.): metal salt-2; potassium diphenylsulfonate ( (KSS manufactured by UCB Japan) (E component): E-1: Composite rubber-based graft copolymer (METABLEN S-2001 manufactured by Mitsubishi Rayon Co., Ltd.): E-2: Composite rubber-based graft copolymer (Mitsubishi Rayon ( (Except E component): E-3: Methyl methacrylate-butadiene-styrene copolymer (METABLEN C-223A, manufactured by Mitsubishi Rayon Co., Ltd.) (F component): F-1: carboxyl Group-containing olefin wax (Diacarna-30 manufactured by Mitsubishi Kasei Co., Ltd.) (G component): G-1: PTFE fibril forming ability (Polyflon FA-500 manufactured by Daikin Industries, Ltd.) (Others): TMP: trimethyl phosphate (TMP manufactured by Daihachi Chemical Co., Ltd.)

As is clear from Tables 1 and 2, from the comparison between Example 1 and Comparative Example 1, high flame retardancy can be achieved without B component, but the flexural modulus is very low. . From Example 1 and Comparative Examples 2 and 3, C was used as a flame retardant.
High flame retardancy cannot be achieved by using only the component, and high flame retardancy and high impact resistance can be achieved when the content of the D component is large even when the C component and the D component are used in combination. Can not. Furthermore, from Comparative Example 4, when the content of the C component is large, high flame retardancy can be achieved, but heat resistance,
Impact resistance is greatly reduced. Furthermore, it is not possible to achieve high flame retardancy with components other than the E component from Comparative Example 6.

[0088]

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 (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08K 5/49 C08K 5/49 7/06 7/06 9/02 9/02 C08L 23/26 C08L 23 / 26 27/18 27/18 51/08 51/08 F term (reference) 4F071 AA27 AA33X AA50 AA67X AA77 AA78 AB03 AB23 AB24 AC15 AD01 AF47 BA01 BB03 BB05 BB06 BC04 BC07 4J002 BB21Y BD15Z BN21X CG00W DA016 EV188 FB 076 007 FD007 GQ00

Claims (11)

[Claims] When the total of the components A, B, C and D is 100% by weight, 96.8999 to 24.95% by weight of an aromatic polycarbonate resin (Component A) and inorganic filler (Component B) 3) to 55% by weight of an organic phosphorus compound (C
Component) Aromatic polycarbonate resin containing 0.1 to 20% by weight, and 0.0001 to 0.05% by weight of at least one metal salt (component (D)) selected from alkali metal salts and / or alkaline earth metal salts. Composition. 2. A composite rubber having a structure in which a polyorganosiloxane rubber component and a polyalkyl (meth) acrylate rubber component are entangled with each other so that they cannot be separated from each other. Component A, B
The aromatic polycarbonate resin composition according to claim 1, comprising 1 to 20 parts by weight based on 100 parts by weight of the composition comprising the component, the C component, and the D component. 3. A polyolefin wax having at least one functional group selected from a carboxyl group and / or a carboxylic anhydride group (component F), component A
The aromatic polycarbonate resin composition according to claim 1, comprising 0.05 to 5 parts by weight based on 100 parts by weight of the composition comprising the component, the component C, and the component D. 4. A polytetrafluoroethylene having a fibril-forming ability (component G) is added to 100 parts by weight of a composition comprising components A, B, C and D.
The aromatic polycarbonate resin composition according to claim 1, comprising 0.05 to 3 parts by weight. 5. The thermoplastic resin composition according to claim 1, wherein the component B is a carbon fiber or a metal-coated carbon fiber. 6. The aromatic polycarbonate resin composition according to claim 1, wherein the component B is a nickel-coated carbon fiber. 7. The method according to claim 1, wherein the amount of the component D is 0.0001 to 0.01% by weight.
Item 10. The aromatic polycarbonate resin composition according to item 1. 8. The aromatic polycarbonate resin composition according to claim 1, wherein the component D is a metal salt of an organic sulfonic acid. 9. The aromatic polycarbonate resin composition according to claim 1, wherein the component D is a metal salt of perfluoroalkane-sulfonic acid or a metal salt of aromatic sulfonesulfonic acid. . 10. The aromatic polycarbonate resin composition according to claim 1, wherein the component D is a perfluoroalkane-sulfonic acid metal salt. 11. A molded article formed from the aromatic polycarbonate resin composition according to any one of claims 1 to 10.