CN115703926A - Flame-retardant aromatic polycarbonate resin composition and molded product thereof - Google Patents

Abstract

The present invention provides a flame-retardant aromatic polycarbonate resin composition which has an aromatic structure-containing organophosphorus flame retardant as a flame retardant, and which can improve the flame retardancy of an aromatic polycarbonate resin and maintain good impact resistance by adding a siloxane compound having an Si-H group and an aryl structure.

Description

Flame-retardant aromatic polycarbonate resin composition and molded product thereof

Technical Field

The invention belongs to the field of high polymer materials, and particularly relates to a flame-retardant aromatic polycarbonate resin composition and a molded product thereof.

Background

An alloy of an aromatic polycarbonate resin (PC) and a styrene resin represented by ABS and the like is a plastic having excellent moldability and impact resistance, and is widely used. In the fields of office automation equipment such as office computers, notebook computers, projectors and the like, electronic equipment and the like, the requirements on flame retardance and formability are high, and the demand on flame-retardant PC/ABS is large. In recent years, for the purpose of weight reduction and cost reduction, further reduction in the thickness of a product is required, and therefore, a material having excellent impact resistance and flame retardancy while maintaining high fluidity is required.

In order to achieve flame retardant properties of PC and styrene resins represented by ABS and the like, there are known in the art methods of: adding phosphorus flame retardant, metal salt, halogen flame retardant and silicone flame retardant.

A method in which a phosphorus-based flame retardant is added is widely used in view of fluidity, flame retardancy, and cost. However, when a phosphorus flame retardant is used, the impact resistance and heat resistance are greatly reduced, and the strength of a thin-walled product is reduced. The combination of both phosphate and silicone flame retardants also shows a method for improving flame retardancy and chemical resistance, but in the case of thin-walled molded articles (1.0 mm or less), the flame retardancy of the material is further deteriorated due to the poor flammability of silicone itself.

Disclosure of Invention

In order to overcome the problem that the impact resistance of the aromatic polycarbonate resin alloy is deteriorated after the phosphorus flame retardant is used in the prior art, the specific embodiment of the invention provides a flame-retardant aromatic polycarbonate resin composition and a molded product thereof, wherein the flame-retardant aromatic polycarbonate resin composition comprises the following components:

a flame retardant aromatic polycarbonate resin composition comprising:

100 parts by weight of a resin component, the resin component comprising:

100 to 1wt% of an aromatic polycarbonate resin as the component A,

And 0 to 99wt% of an impact modifier resin as component B;

0.1 to 25 parts by weight of a phosphorus flame retardant as a component C, wherein the phosphorus flame retardant is an organic phosphorus flame retardant having an aromatic structure;

0.1 to 15 parts by weight of a siloxane compound as component D;

the siloxane compound contains Si-H group and aryl group represented by general formula (1) in the molecule,

in the general formula (1), X ¹ 、X ² 、X ³ 、X ⁴ And X ⁵ Each independently selected from a hydrogen atom, an OH group, or an organic group having 1 to 20 carbon atoms.

Optionally, the organic group is a hydrocarbyl group.

Optionally, the molecule of the siloxane compound contains at least one of the structural units shown in the general formulas (2) and (3),

in the general formulae (2) and (3), Z ¹ 、Z ² And Z ³ Each independently selected from a hydrogen atom, an organic group having 1 to 20 carbon atoms, or a compound group represented by the general formula (4), α 1, α 2, and α 3 are each independently selected from 0 or 1, and m1 is an integer of 0 or 1 or more; in the general formula (2), when m1 is 2 or more, Z in the repeating unit ¹ And alpha 1 are each the same or different,

in the general formula (4), Z ⁴ 、Z ⁵ 、Z ⁶ 、Z ⁷ And Z ⁸ Each independently selected from a hydrogen atom or an organic group having 1 to 20 carbon atoms, [ alpha ] 4, [ alpha ] 5, [ alpha ] 6, [ alpha ] 7 and [ alpha ] 8 independently selected from 0 or 1, and m2 is an integer of 0 or 1 or more; in the general formula (4), when m2 is 2 or more, Z in the repeating unit ⁴ 、Z ⁵ α 4 and α 5 are the same or different, respectively.

Optionally, the molecule of the siloxane compound is composed of 1 or 2 or more structural units represented by general formula (2) and 2 or more structural units represented by general formula (3); when the number of the structural units represented by the general formula (2) is 2 or more, Z in each structural unit ¹ α 1 and m1 are the same or different; when the number of the structural units represented by the general formula (3) is 2 or more, Z in each structural unit ² 、Z ³ Alpha 2 and alpha 3 phasesThe same or different.

Optionally, the organic group is a hydrocarbyl group.

Optionally, based on the weight of the siloxane compound, the content of the Si-H group is 0.1-1.2 mol/100g, and the content of the aryl group is 10-70 wt%.

Optionally, the siloxane compound has an average degree of polymerization of 3 to 80 and a kinematic viscosity of 1 to 1000mm at 25 ℃ ² /s。

Optionally, the content of the component D is 0.05 to 7 parts by weight.

Optionally, the component A accounts for 70-99.5 wt% and the component B accounts for 30-0.5 wt% of the weight of the resin component.

Optionally, the component B is a polymer resin containing a rubber unit.

Optionally, the component B comprises at least one of a component B1 and a component B2;

wherein the component B1 is a copolymer resin containing a vinyl cyanide monomer unit, an aromatic vinyl monomer unit and a rubber unit;

the component B2 is core-shell rubber graft copolymer resin.

Optionally, the rubber unit of the component B1 has at least one of a butadiene monomer unit and a methyl acrylate monomer unit, wherein the butadiene monomer unit and the methyl acrylate monomer unit together account for 1 to 70wt% of the total weight of the component B1.

Optionally, the component B1 is acrylonitrile-styrene-butadiene copolymer resin.

Optionally, in the component B2, the rubber unit is selected from at least one of unsaturated olefin rubber, silicone rubber or acrylate rubber, and the grafted compound monomer includes at least one of acrylate and methacrylate.

Optionally, the organophosphorus flame retardant is a phosphazene flame retardant or an organophosphorus flame retardant with a structure shown in a general formula (5),

in the general formula (5), X ² Is arylene, n2 is an integer of 0 to 5, R ¹ 、R ² 、R ³ And R ⁴ Each independently selected from aryl groups.

Optionally, the arylene group is derived from a dihydroxy compound of hydroquinone, resorcinol, bis (4-hydroxydiphenyl) methane, bisphenol a, dihydroxybiphenyl, dihydroxynaphthalene, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) ketone, or bis (4-hydroxyphenyl) sulfide; the aryl group is derived from phenol, cresol, xylenol, isopropylphenol, butylphenol, or p-cumylphenol.

Optionally, the phosphazene cyclotriphosphazene content of the phosphazene flame retardant is more than 60 mol%.

Optionally, the phosphazene cyclotriphosphazene content of the phosphazene flame retardant is more than 98.5 mol%.

Optionally, the content of the component C is 2-20 parts by weight.

Optionally, the flame retardant property of the composition reaches the V-0 grade requirement of the UL94 standard flame retardant level, and the Charpy notch impact strength is 20KJ/m ² The above.

Optionally, the composition further comprises an anti-drip agent, an inorganic filler material, and an acid-modified olefin wax comprising a copolymer of maleic anhydride and an alpha-olefin.

A molded article obtained by processing the flame-retardant aromatic polycarbonate resin composition as described above.

The flame retardant aromatic polycarbonate resin composition according to the embodiment of the present invention can effectively improve the impact resistance by adding the siloxane compound having a specific structure to an aromatic polycarbonate resin containing a phosphorus flame retardant.

Detailed Description

The present inventors have found that the flame retardancy of an aromatic polycarbonate resin (PC) can be improved and good impact resistance can be maintained by adding a siloxane compound having an Si-H group and an aryl structure in a molecule to the aromatic polycarbonate resin composition, using an organophosphorus flame retardant having an aromatic structure as a flame retardant.

Specifically, an embodiment of the present invention provides a flame retardant aromatic polycarbonate resin composition comprising:

100 parts by weight of a resin component, the resin component comprising:

100 to 1wt% of an aromatic polycarbonate resin as the component A,

And 0 to 99wt% of an impact modifier resin as component B;

0.1 to 25 parts by weight of a phosphorus flame retardant as a component C, wherein the phosphorus flame retardant is an organic phosphorus flame retardant having an aromatic structure;

0.1 to 15 parts by weight of a siloxane compound as component D;

the siloxane compound contains Si-H group and aryl group shown in the general formula (1) in the molecule,

in the general formula (1), X ¹ 、X ² 、X ³ 、X ⁴ And X ⁵ Each independently selected from a hydrogen atom, an OH group, or an organic group having 1 to 20 carbon atoms.

The flame retardant aromatic polycarbonate resin composition according to the embodiments of the present invention is prepared by reacting a dihydric phenol with a carbonate precursor, and specific reaction preparation methods include, for example, an interfacial polymerization method, a melt transesterification method, a solid-phase transesterification method of a carbonate prepolymer, a ring-opening polymerization method of a cyclic carbonate compound, and the like. Examples of the dihydric phenols include hydroquinone, resorcinol, 4,4' -dihydroxydiphenyl-biphenyl, 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, 3584-bis { (4-hydroxy-3-phenyl) phenyl } propane, 2,2-bis { (4-hydroxy-3-phenyl) phenyl } propane, 3584-bis { (3-hydroxy-phenyl) phenyl } propane, 3525-bis (3-hydroxy-phenyl) -4225-bis (3-phenyl) -4225-hydroxy-phenyl) -butane, 3525-bis { (3-hydroxy-phenyl) -3225-hydroxy-phenyl) -2-bis (3-phenyl) -4225, bis (3-phenyl) -4225-methyl) butane, and the like, 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) 3264 zxft 64-dimethyladamantane, 3782 zxft 3282 ' -dihydroxydiphenylsulfone, 4,4' -dihydroxydiphenylsulfoxide, 4,4' -dihydroxydiphenylsulfide, 3638 zxft 3238 ' -dihydroxydiphenylketone, 3724 zxft 3224 ' -dihalodiphenylether, 4924 ' -dihydroxydiphenylether, 4924, and the like, and the above-polycarbonate can be used as a binary carbonate or a carbonate, and the above-carbonate can be used as a carbonate, and the above-carbonate can be used in a carbonate, and the like.

In some embodiments, the aromatic polycarbonate resin is a copolymer of a dihydric phenol with a carbonate precursor and another monomer or polymer, for example, a branched polycarbonate resin obtained by copolymerizing a polyfunctional aromatic compound having at least three functions, a polyester carbonate resin obtained by copolymerizing an aliphatic (including alicyclic) bifunctional carboxylic acid, a copolymerized polycarbonate resin obtained by copolymerizing a bifunctional alcohol (including alicyclic), a polyester carbonate resin obtained by copolymerizing the bifunctional carboxylic acid and the bifunctional alcohol together, or a polycarbonate-polyorganosiloxane copolymer obtained by copolymerizing a polyorganosiloxane with the bifunctional carboxylic acid and the bifunctional alcohol. In addition, in some embodiments, it may be a mixture of 2 or more of the aromatic polycarbonate resins.

The flame-retardant aromatic polycarbonate resin composition according to the embodiment of the present invention can be given anti-dripping properties or the like to the resin composition of the present invention by way of example, a trifunctional or higher polyfunctional aromatic compound used in the branched polycarbonate resin such as phloroglucinol, phloroglucinol or 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 (65 zxft 3265-dimethyl-4-hydroxyphenyl) ethane, 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenol, 4- {4- [ 3525 zxft 3225-bis (4-hydroxyphenyl) ethyl) ethane, 3525-bis (2-hydroxy-5-hydroxyphenyl) ethyl]Triphenols such as benzene } -alpha, alpha-dimethylbenzylphenol, tetrakis (4-hydroxyphenyl) methane, bis (2,4-dihydroxyphenyl) ketone, 1,4-bis (4,4-dihydroxytriphenylmethyl) benzene, trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid, and acid chlorides thereof. The structural unit derived from the polyfunctional aromatic compound in the branched polycarbonate is 0.01 to 1mol%, or 0.05 to 0.9 mol%, or 0.05 to 0.8 mol% in some embodiments, of the total 100 mol% of the structural unit derived from the dihydric phenol and the structural unit derived from the polyfunctional aromatic compound. In some embodiments, particularly in the case of the melt transesterification method, a branched structural unit may be generated as a side reaction, and the amount of the branched structural unit is 0.001 to 1mol%, or 0.005 to 0.9 mol%, or 0.01 to 0.8 mol% of the total 100 mol% of structural units derived from the dihydric phenol. The ratio of the branched structure can be determined by ¹ H-NMR measurement.

The flame-retardant aromatic polycarbonate resin composition according to the embodiment of the present invention is exemplified by aliphatic difunctional carboxylic acids such as straight-chain saturated aliphatic dicarboxylic acids including sebacic acid (decanedioic acid), dodecanedioic acid, tetradecanedioic acid, octadecanedioic acid, eicosanedioic acid and the like, and alicyclic dicarboxylic acids including cyclohexanedicarboxylic acid and the like; examples of the difunctional alcohol include aliphatic diols such as ethylene glycol, butanediol, decanediol, dodecanediol, octadecanediol and eicosanediol, and alicyclic diols such as cyclohexanedimethanol, cyclohexanediol and tricyclodecanedimethanol.

The aromatic polycarbonate resin composition of the embodiment of the present invention further comprises an auxiliary component or unit such as a catalyst, a chain terminator, an antioxidant for preventing oxidation of the dihydric phenol, or a deactivator for neutralizing the activity of the catalyst, which is introduced during the synthesis. Examples of the catalyst include those used in ordinary esterification and transesterification reactions such as sodium hydroxide, potassium hydroxide, alkali metal compounds such as sodium salts and potassium salts of dihydric phenols, alkaline earth metal compounds such as calcium hydroxide, barium hydroxide and magnesium hydrochloride, nitrogen-containing basic compounds such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, trimethylamine and triethylamine, alkoxides of alkali metals and alkaline earth metals, organic acid salts of alkali metals and alkaline earth metals, zinc compounds, boron compounds, aluminum compounds, silicon compounds, germanium compounds and organotin compounds, lead compounds, osmium compounds, antimony compounds, manganese compounds, titanium compounds and zirconium compounds. One kind of catalyst may be used alone, or two or more kinds of catalysts may be used in combination. By way of example, the chain terminator is a monofunctional phenol such as phenol, p-tert-butylphenol, p-cumylphenol, and isooctylphenol. By way of example, the antioxidant for preventing oxidation of dihydric phenol is pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-laurylthiopropionate), glycerol-3-stearylthiopropionate, triethylene glycol bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate ], 1,6-hexanediol bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate ], pentaerythritol-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate ], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, N, N-hexamethylenebis (3,5-di-tert-butyl-4-hydroxyhydrocinnamamide), 3,5-di-tert-butyl-4-hydroxy-benzylphosphonic acid diethyl ester, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, and 3,9-bis {1,1-dimethyl-2- [ beta- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy ] ethyl } -2,4,8,10-tetraoxaspiro (5,5) undecane, and the like. Examples of the deactivator for neutralizing the catalyst activity include benzene sulfonic acid esters such as benzene sulfonic acid, p-toluene sulfonic acid, methyl benzene sulfonate, ethyl benzene sulfonate, butyl benzene sulfonate, octyl benzene sulfonate, phenyl benzene sulfonate, methyl p-toluene sulfonate, ethyl p-toluene sulfonate, butyl p-toluene sulfonate, octyl p-toluene sulfonate, phenyl p-toluene sulfonate and the like, and also include compounds such as trifluoromethanesulfonic acid, naphthalene sulfonic acid, sulfonated polystyrene, methyl acrylate-sulfonated styrene copolymer, 2-phenyl-2-propyl dodecylbenzene sulfonate, 2-phenyl-2-butyl dodecylbenzene sulfonate, tetrabutylphosphonium octylsulfonate, tetrabutylphosphonium decylsulfonate, tetrabutylphosphonium benzenesulfonate, tetraethylphosphonium dodecylbenzene sulfonate, tetrabutylphosphonium dodecylbenzene sulfonate, tetrahexylphosphonium dodecylbenzene sulfonate, tetraoctylphosphonium dodecylbenzene sulfonate, decylammonium decylsulfate, dodecylammonium methylsulfate, dodecylammonium ethylsulfate, dodecylmethylammonium methylsulfate, dodecyldimethyl tetradecyldimethylammonium methylsulfate, tetramethylammonium hexylammonium, hexadecylbenzylammonium, dodecylbenzylammonium, tetrabutylammonium, and the like.

The flame retardant aromatic polycarbonate resin composition according to an embodiment of the present invention is not particularly limited in molecular weight, and in some embodiments, the aromatic polycarbonate resin has a viscosity average molecular weight of 10,000 to 50,000, further 14,000 to 30,000, and further 14,000 to 24,000, considering that when it is less than 10,000, the high temperature characteristics of the resin are lowered, and when it exceeds 50,000, the molding processability of the resin is lowered. In addition, in some embodiments, it may be a mixture of 2 kinds of the aromatic polycarbonates having different viscosity average molecular weights.

The flame retardant aromatic polycarbonate resin composition according to an embodiment of the present invention has a viscosity average molecular weight as follows: first, a specific viscosity (. Eta.) calculated by the following formula was determined from a solution obtained by dissolving 0.7g of the aromatic polycarbonate in 100mL of methylene chloride at 20 ℃ using an Ostwald viscometer _SP )，

Specific viscosity (. Eta.) _SP )＝(t-t ₀ )/t ₀

[t ₀ The number of seconds of dropping the methylene chloride, and t is the number of seconds of dropping the sample solution]

From the determined specific viscosity (. Eta.) _SP ) The viscosity average molecular weight M was calculated by the following equation.

η _SP /c＝[η]+0.45×[η] ² c (wherein, [ eta. ])]To limit viscosity)

[η]＝1.23×10 ^-4 M ^0.83

c＝0.7。

The flame-retardant aromatic polycarbonate resin composition according to the embodiment of the present invention is a flame-retardant aromatic polycarbonate resin composition in which an impact modifier resin as a component B is used for improving the impact resistance of an aromatic polycarbonate resin, and in some embodiments, the impact modifier resin is a resin having a rubber unit with high elasticity or high toughness, such as, for example, a butadiene-based rubber, a butadiene-acrylic composite rubber, an acrylic rubber, a silicone-acrylic composite rubber, an isobutylene-silicone composite rubber, an isoprene rubber, a styrene-butadiene rubber, a chloroprene rubber, an ethylene-propylene rubber, a nitrile rubber, an ethylene-acrylic rubber, a silicone rubber, an epichlorohydrin rubber, a fluorine rubber, and a rubber unit obtained by adding hydrogen to an unsaturated bond portion thereof, and in some embodiments, the rubber unit does not contain a halogen atom from the viewpoint of fear of generating a harmful substance at the time of combustion. In view of the toughening effect, in some embodiments, the glass transition temperature of the rubber unit is-10 ℃ or lower, further-30 ℃ or lower, specifically, for example, butadiene-based rubber, acrylic silicone-acrylic composite rubber. The composite rubber is a rubber obtained by copolymerizing 2 kinds of rubber components or a rubber obtained by polymerizing a rubber so as to obtain an IPN structure which is entangled with each other so as not to be separated.

In some embodiments of the flame retardant aromatic polycarbonate resin composition of the present invention, the component B comprises a copolymer resin containing a vinyl cyanide monomer unit, an aromatic vinyl monomer unit and the above rubber unit as the component B1. In some embodiments, the monomeric source of the vinyl cyanide monomer units is at least one of acrylonitrile or methacrylonitrile, and the like. In some embodiments, the monomeric source of the aromatic vinyl monomer units is at least one of styrene, alpha-methylstyrene, o-methylstyrene, p-methylstyrene, vinylxylene, ethylstyrene, dimethylstyrene, p-tert-butylstyrene, vinylnaphthalene, methoxystyrene, and the like. In some embodiments, the rubber units have at least one of butadiene monomer units and methyl acrylate monomer units, wherein the butadiene monomer units and the methyl acrylate monomer units together constitute 1 to 70wt%, specifically, for example, 1wt%, 5wt%, 10wt%, 15wt%, 20wt%, 25wt%, 30wt%, 35wt%, 40wt%, 45wt%, 50wt%, 55wt%, 60wt%, 65wt%, 70wt%, and the like, of the total weight of the B1 component. In some embodiments, the B1 component is an acrylonitrile-styrene-butadiene copolymer resin.

In the flame retardant aromatic polycarbonate resin composition according to the embodiments of the present invention, the component B may include a core-shell type rubber graft copolymer resin as the component B2. In some embodiments, the core-shell type graft polymer is a graft copolymer in which a rubber component having a glass transition temperature of 10 ℃ or less is used as a core and at least one monomer selected from the group consisting of aromatic vinyl, vinyl cyanide, acrylate, methacrylate and a vinyl compound copolymerizable therewith is used as a shell. In some embodiments, the rubber unit in the core-shell rubber graft copolymer resin is as described above, and in some embodiments, the rubber is selected from at least one of unsaturated olefin rubber, silicone rubber, or acrylate rubber. In some embodiments, the grafted compound monomer includes at least one of an acrylate such as, by way of example, methyl acrylate, ethyl acrylate, butyl acrylate, cyclohexyl acrylate, octyl acrylate, and the like, and a methacrylate such as, by way of example, methyl methacrylate, ethyl methacrylate, butyl methacrylate, cyclohexyl methacrylate, octyl methacrylate, and the like. In some embodiments, the vinyl compound copolymerized as the shell of the core-shell type graft polymer in the rubber component is aromatic vinyl, such as at least one of styrene, α -methylstyrene, o-methylstyrene, p-methylstyrene, vinylxylene, ethylstyrene, dimethylstyrene, p-tert-butylstyrene, vinylnaphthalene, methoxystyrene, and the like, by way of example. In some embodiments, the B2 component is a methylmethacrylate-butadiene-styrene graft copolymer (MBS).

The flame retardant aromatic polycarbonate resin composition according to embodiments of the present invention, in some embodiments, the B component includes B1 component and B2 component, and in some embodiments, the weight ratio of the B1 component to the B2 component is 1:10 to 10:1, specifically such as 1: 10. 2: 10. 3: 10. 4: 10. 5: 10. 6: 10. 7: 10. 8: 10. 9: 10. 10: 10. 10: 9. 10: 8. 10: 7. 10: 6. 10: 5. 10: 4. 10: 3. 10: 2. 10:1, etc.

The flame retardant aromatic polycarbonate resin composition according to the embodiment of the present invention may contain, in some embodiments, the component A in an amount of 70 to 99.5wt%, specifically, for example, 70wt%, 75wt%, 80wt%, 85wt%, 90wt%, 95wt%, etc., and the component B in an amount of 30 to 0.5wt%, specifically, for example, 30wt%, 25wt%, 20wt%, 15wt%, 10wt%, 5wt%, etc., based on the weight of the resin component.

In some embodiments, the flame retardant aromatic polycarbonate resin composition of the present invention may contain other resins and elastomers in a small proportion within the range in which the effects of the present invention are exhibited. Examples of the other resin include resins such as polyamide resin, polyimide resin, polyetherimide resin, polyurethane resin, silicone resin, polyphenylene ether resin, polyphenylene sulfide resin, polysulfone resin, polymethacrylate resin, phenol resin, and epoxy resin. Examples of the elastomer include isobutylene/isoprene rubber, ethylene/propylene rubber, acrylic elastomer, polyester elastomer, and polyamide elastomer.

In the flame-retardant aromatic polycarbonate resin composition according to the embodiment of the present invention, the phosphorus-based flame retardant as the component C is an organophosphorus flame retardant having an aromatic structure, and in some embodiments, the organophosphorus flame retardant is a phosphazene flame retardant or an organophosphorus flame retardant having a structure represented by the general formula (5),

in the general formula (5), X ² Is arylene, n2 is an integer of 0 to 5, R ¹ 、R ² 、R ³ And R ⁴ Each independently selected from aryl groups. In some embodiments, the arylene group is derived from a dihydroxy compound of hydroquinone, resorcinol, bis (4-hydroxydiphenyl) methane, bisphenol a, dihydroxydiphenyl, dihydroxynaphthalene, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) ketone, or bis (4-hydroxyphenyl) sulfide; the aryl group is derived from phenol, cresol, xylenol, isopropylphenol, butylphenol, or p-cumylphenol. Examples of the organophosphorus flame retardant represented by the general formula (5) include monophosphate compounds such as triphenyl phosphate and tris (2,6-xylyl) phosphate, and phosphate oligomers mainly composed of resorcinol bis (di (2,6-xylyl) phosphate), 4,4-dihydroxydiphenyl bis (diphenyl phosphate) and bisphenol A bis (diphenyl phosphate) (the term "predominantly" means a compound capable of forming a flame retardantThe other components having different polymerization degrees, for example, the component with n2=1 in the above general formula (5) is contained in a small amount of 80 parts by weight or more, 85 parts by weight or more, or 90 parts by weight or more). In some embodiments, the aryl group is substituted with a halogen atom, and as specific examples of the phosphate ester compound having a group derived therefrom, for example, tris (2,4,6-tribromophenyl) phosphate, tris (2,4-dibromophenyl) phosphate, tris (4-bromophenyl) phosphate, and the like can be given.

In the flame retardant aromatic polycarbonate resin composition according to an embodiment of the present invention, the organophosphorus flame retardant represented by the general formula (5) may be a mixture of compounds having different n2 numbers, and in the case of the mixture, the average n2 number is in the range of 0.5 to 1.5 in some embodiments, the n2 number is in the range of 0.8 to 1.2 in some embodiments, the n2 number is in the range of 0.95 to 1.15 in some embodiments, and the n2 number is in the range of 1 to 1.14 in some embodiments.

In view of the influence of thermal stability during molding, the flame-retardant aromatic polycarbonate resin composition according to an embodiment of the present invention has an acid value of the organophosphorus flame retardant compound represented by the general formula (5) of 0.2mgKOH/g, or less than 0.15mgKOH/g, or less than 0.1mgKOH/g, or less than 0.05 mgKOH/g. The lower limit of the acid value may be substantially 0, and in some embodiments, it is 0.01mgKOH/g or more.

In some embodiments, the phosphazene flame retardant is represented by the general formula (6), and R in the general formula (6) ₅ And R ₆ Each independently is an aryl or aryloxy group, such as phenyl or phenoxy, and k is an integer from 3 to 10.

The flame retardant aromatic polycarbonate resin composition according to an embodiment of the present invention may have a phosphazene cyclotrisome (k = 3) content of 90mol% or more, and may have a phosphazene cyclotrisome (k = 3) content of 98.5mol% or more.

The flame-retardant aromatic polycarbonate resin composition according to the embodiment of the present invention contains as the component C a phosphorus-based flame retardant

In some embodiments, the phosphorus-based flame retardant is

And (3) parts by weight, specifically, for example, 15 parts by weight, 16 parts by weight, 17 parts by weight, 18 parts by weight, 19 parts by weight, 20 parts by weight, and the like.

A flame-retardant aromatic polycarbonate resin composition according to an embodiment of the present invention is a flame-retardant aromatic polycarbonate resin composition comprising a siloxane compound having an Si-H group and an aryl group represented by the general formula (1) in the molecule,

in the general formula (1), X ¹ 、X ² 、X ³ 、X ⁴ And X ⁵ Each independently selected from a hydrogen atom, an OH group, or an organic group having 1 to 20 carbon atoms. In some embodiments, the organic group is a hydrocarbon group, which may or may not have a substituent, such as an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, a decyl group, a cycloalkyl group such as a cyclohexyl group, an alkenyl group such as a vinyl group, an allyl group, an aryl group such as a phenyl group, a tolyl group, or the like, or the above-mentioned alkyl, cycloalkyl, alkenyl, or aryl groups, which may have various functional substituents such as an epoxy group, a carboxyl group, a carboxylic anhydride group, an amino group, and a mercapto group, or the like; in some embodiments, the organic group is an alkyl, alkenyl, or aryl group having 1 to 8 carbon atomsIn some embodiments, the organic group is an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, or the like, a vinyl group, or a phenyl group.

The flame-retardant aromatic polycarbonate resin composition according to the embodiment of the present invention, in some embodiments, comprises at least one of the structural units represented by the general formulae (2) and (3) in the molecule of the siloxane compound,

in the general formulae (2) and (3), Z ¹ 、Z ² And Z ³ Each independently selected from a hydrogen atom, an organic group having 1 to 20 carbon atoms, or a compound group represented by the general formula (4), α 1, α 2, and α 3 are each independently selected from 0 or 1, and m1 is an integer of 0 or 1 or more; in the general formula (2), when m1 is 2 or more, Z in the repeating unit ¹ And alpha 1 are each the same or different,

in the general formula (4), Z ⁴ 、Z ⁵ 、Z ⁶ 、Z ⁷ And Z ⁸ Each independently selected from a hydrogen atom or an organic group having 1 to 20 carbon atoms, each of α 4, α 5, α 6, α 7 and α 8 independently selected from 0 or 1, and m2 is an integer of 0 or 1 or more; in the general formula (4), when m2 is 2 or more, Z in the repeating unit ⁴ 、Z ⁵ α 4 and α 5 are the same or different, respectively. In some embodiments, the organic group is a hydrocarbon group, which may or may not have a substituent, such as an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, a decyl group, a cycloalkyl group such as a cyclohexyl group, an alkenyl group such as a vinyl group, an allyl group, an aryl group such as a phenyl group, a tolyl group, or the like, or the above-mentioned alkyl, cycloalkyl, alkenyl, or aryl groups, which may have various functional substituents such as an epoxy group, a carboxyl group, a carboxylic anhydride group, an amino group, and a mercapto group, or the like; in some embodiments, the organic group has 1E to C atoms8, and in some embodiments, the organic group is an alkyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, a propyl group, or the like, a vinyl group, or a phenyl group.

The flame-retardant aromatic polycarbonate resin composition according to the embodiment of the present invention may be a siloxane compound containing at least one or more of the structural units represented by the general formulae (2) and (3), and when the siloxane compound has a plurality of siloxane bond repeating units, random copolymerization, block copolymerization, or the like may be selected.

The flame-retardant aromatic polycarbonate resin composition according to the embodiment of the present invention is, in some embodiments, a composition comprising 1 or 2 or more structural units represented by the general formula (2) and 2 or more structural units represented by the general formula (3) as molecules of the siloxane compound; when the number of the structural units represented by the general formula (2) is 2 or more, Z1, α 1 and m1 in each structural unit are the same or different; when the number of the structural units represented by the general formula (3) is 2 or more, Z2, Z3, α 2 and α 3 in each structural unit may be the same or different.

The flame retardant aromatic polycarbonate resin composition according to embodiments of the present invention may have an Si-H content in the siloxane compound in the range of 0.1 to 1.2mol/100g, in some embodiments, in the range of 0.2 to 1.0mol/100g, based on the weight of the siloxane compound. The Si-H amount means the number of moles of the Si-H structure contained per 100g of the siloxane compound. It can be determined by measuring the volume of hydrogen gas generated per unit weight of the siloxane compound by the alkali decomposition method. For example, when 122ml of hydrogen gas is generated at 25 ℃ from 1g of the siloxane compound, the Si-H amount is 0.5mol/100g as determined by the following calculation formula.

The flame retardant aromatic polycarbonate resin composition according to the embodiment of the present invention may contain the aromatic group in a proportion of 10 to 70wt% in some embodiments, and 15 to 60wt% in some embodiments, based on the weight of the siloxane compound, in view of the dispersibility of the siloxane compound.

The flame retardant aromatic polycarbonate resin composition according to the embodiment of the present invention has a structure in which the siloxane compound is formed by arbitrarily combining four siloxane units (CH) ₃ ) ₃ SiO _1/2 、H(CH ₃ ) ₂ SiO _1/2 、H ₂ (CH ₃ )SiO _1/2 、(CH ₃ ) ₂ (CH ₂ ＝CH)SiO _1/2 、(CH ₃ ) ₂ (C ₆ H ₆ )SiO _1/2 、(CH ₃ )(C ₆ H ₅ )(CH ₂ ＝CH)SiO _1/2 Isofunctional siloxane units, (CH) ₃ ) ₂ SiO、H(CH ₃ )SiO、H ₂ SiO、H(C ₆ H ₅ )SiO、(CH ₃ )(CH ₂ ＝CH)SiO、(C ₆ H ₅ ) ₂ Difunctional siloxane units of SiO, etc., (CH) ₃ )SiO _3/2 、(C ₃ H ₇ )SiO _3/2 、HSiO _3/2 、(CH ₂ ＝CH)SiO _3/2 、(C ₆ H ₅ )SiO _3/2 Iso-trifunctional siloxane units, siO ₂ Tetrafunctional siloxane units are shown.

The flame retardant aromatic polycarbonate resin composition according to an embodiment of the present invention has an average degree of polymerization of the siloxane compound of 3 to 80 in some embodiments, an average degree of polymerization of the siloxane compound of 3 to 60 in some embodiments, an average degree of polymerization of the siloxane compound of 4 to 40 in some embodiments, and an average degree of polymerization of the siloxane compound of 4 to 20 in some embodiments.

In the flame-retardant aromatic polycarbonate resin composition according to an embodiment of the present invention, the siloxane compound has a kinematic viscosity at 25 ℃ of 1 to 1000mm ² In some embodiments, the siloxane compound has a kinematic viscosity at 25 ℃ of 5 to 500mm ² In some embodiments, the siloxane compound has a kinematic viscosity at 25 ℃ of 10 to 100mm ² /s。

The flame-retardant aromatic polycarbonate resin composition according to the embodiment of the present invention may be used alone or in combination of two or more kinds of the above siloxane compounds.

The flame-retardant aromatic polycarbonate resin composition according to the embodiment of the present invention can be obtained by a method known per se, for example, hydrolyzing the corresponding organochlorosilanes in accordance with the structure of the desired siloxane compound by bringing them together to remove hydrochloric acid and low boiling components produced as by-products. Further, the desired silicone compound can be obtained by using a silicone (oxy) oil, a cyclic siloxane and an alkoxysilane containing an Si-H bond and an aryl group represented by the general formula (1) and other organic groups in the molecule as starting materials, adding water for hydrolysis, and then removing the acid catalyst and low boiling point components used in the same manner.

The flame retardant aromatic polycarbonate resin composition according to an embodiment of the present invention may contain 0.1 to 25 parts by weight of the component C, and 2 to 20 parts by weight of the component C.

The flame retardant aromatic polycarbonate resin composition according to an embodiment of the present invention may contain the component D in an amount of 0.1 to 15 parts by weight, and in an amount of 0.05 to 7 parts by weight.

In some embodiments, the flame retardant properties of the flame retardant aromatic polycarbonate resin compositions of embodiments of the present invention meet the UL94 Standard flame retardant level V-0 requirement with a Charpy notched impact strength of 20KJ/m ² As above, specific examples are 25KJ/m ² 、30KJ/m ² 、35KJ/m ² Or 40KJ/m ² And so on.

The flame retardant aromatic polycarbonate resin composition according to embodiments of the present invention may further comprise an anti-dripping agent, an inorganic filler, and an acid-modified olefin wax comprising a copolymer of maleic anhydride and an α -olefin.

The flame-retardant aromatic polycarbonate resin composition according to the embodiment of the present invention may be, for example, polytetrafluoroethylene, a tetrafluoroethylene copolymer (e.g., tetrafluoroethylene/hexafluoropropylene copolymer), a partially fluorinated polymer such as that shown in U.S. Pat. No. 4379910, a polycarbonate resin produced from a fluorinated diphenol, or the like. Wherein, in some embodiments, the anti-drip agent is Polytetrafluoroethylene (PTFE). The content of the anti-dripping agent is 0.05 to 2 parts by weight, 0.1 to 1.5 parts by weight, and 0.2 to 1 part by weight in some embodiments, per 100 parts by weight of the resin component, and in the case where the anti-dripping agent is in the above range, sufficient flame retardancy is obtained, poor appearance due to precipitation of PTFE on the surface of a molded article is avoided, and the cost of the resin composition is reduced.

The flame-retardant aromatic polycarbonate resin composition according to the embodiment of the present invention may contain an inorganic filler such as calcium carbonate, talc, glass fiber, glass beads, glass hollow spheres, glass milled fiber, glass flakes, carbon fiber, carbon flakes, carbon beads, carbon fiber, milled carbon fiber, graphite, vapor grown ultrafine carbon fiber (fiber diameter less than 0.1 μm), carbon nanotubes (fiber diameter less than 0.1 μm and hollow), fullerene, metal flakes, metal fiber, metal-coated glass fiber, metal-coated carbon fiber, metal-coated glass flakes, silica, metal oxide particles, metal oxide fiber, metal oxide hollow spheres, and various whiskers (potassium titanate whisker, aluminum borate whisker, basic magnesium sulfate, etc.). These inorganic fillers may contain 1 kind or 2 or more kinds in combination. The inorganic filler is contained in an amount of 0.1 to 60 parts by weight, in some embodiments, 0.5 to 50 parts by weight, based on 100 parts by weight of the resin component.

The flame-retardant aromatic polycarbonate resin composition according to the embodiment of the present invention may contain a small amount of additives which are known per se, and these additives may be contained in a general amount as long as the purpose of the present invention is not impaired, in order to impart various functions to the product and improve the properties. Examples of the additive include a sliding agent (e.g., PTFE particles), a colorant (e.g., pigments such as carbon black and titanium oxide, dyes), a light diffusing agent (e.g., acrylic crosslinked particles, silicone crosslinked particles, ultra-thin glass flakes, and calcium carbonate particles), a fluorescent dye, an inorganic phosphor (e.g., a phosphor having aluminate as a mother crystal), an antistatic agent, a nucleating agent, an inorganic or organic antibacterial agent, a photocatalyst-based antiscratch agent (e.g., fine-particle titanium oxide and fine-particle zinc oxide), a radical generator, an infrared absorber (a heat ray absorber), and a photochromic agent.

The flame-retardant aromatic polycarbonate resin composition according to the embodiment of the present invention can be produced by any method, for example, a method comprising thoroughly mixing the above-mentioned component A, component B, component C, component D and any other components by a premixing method such as a V-type mixer, henschel mixer, chemical power plant and extrusion mixer, granulating the mixture by an extrusion granulator, a granulator and the like as necessary, melt-kneading the mixture by a melt-kneading machine typified by a vented twin-screw extruder, and granulating the mixture by a granulator and the like.

An embodiment of the present invention also provides a molded article processed from the above flame retardant aromatic polycarbonate resin composition. In some embodiments, the flame retardant aromatic polycarbonate resin composition is used for manufacturing various products by a method of obtaining a molded product by injection molding using pellets, and in the injection molding, a general cold runner type molding method may be used, a hot runner type without a material handle may be used, and in the injection molding, a general molding method may be used, and gas assist type injection molding, injection compression molding, ultra high speed injection molding, injection compression molding, two-color molding, sandwich molding, in-mold coating molding, insert molding, foam molding (including using a supercritical fluid), rapid heating and cooling mold molding, heat insulation mold molding, in-mold remelting molding, a combination use of these molding methods, and the like may be used. In some embodiments, various profiled extrusion molded articles are made by extrusion molding and used in the form of sheets, films, and the like. In the molding of sheets and films, the molding may be carried out by blowing, casting or the like, or a heat-shrinkable tube may be produced by performing a specific stretching operation, or a molded article may be produced by rotational molding without melting and kneading a resin.

In some embodiments, the molded article according to the embodiments of the present invention is used as an internal part or a housing of an OA device or a home electric appliance, and the OA device or the home electric appliance may be, for example, a personal computer, a notebook computer, a CRT display, a printer, a mobile terminal, a mobile phone, a copier, a facsimile machine, a recording medium (CD, CD-ROM, DVD, PD, FDD, or the like) drive, a parabolic antenna, an electric power tool, a VTR, a television, an iron, a hair dryer, an electric cooker, a microwave oven, an audio device such as a laser, a disc, or a disc, a lighting device, a refrigerator, an air conditioner, a typewriter, a word processor, or the like. In some embodiments, the molded article is a vehicle part such as a deflector part, a car navigation part, and a car audio part as another resin product.

The present invention is further illustrated by the following specific examples.

Examples

Description of Performance testing

1) Flame retardancy test

The flame retardancy was measured according to UL94 specification (V test) and the test specimens had a thickness of 0.7mm.

2) Charpy impact strength test

The measurement was carried out in accordance with ISO 179 standard, test specimens having dimensions of 80 mm. Times.10 mm. Times.4 mm were prepared, and Charpy notched impact strength was measured under ambient conditions of 23 ℃.

3) Evaluation of Productivity

And judging according to the difficulty of blanking the material from the cylinder, wherein the smooth blanking is judged as O, and the difficult blanking is judged as X.

Description of raw materials:

component A

PC: bisphenol A type, p-tert-butylphenol as a terminal agent, and phosgene were synthesized by an interfacial polycondensation method to obtain a linear aromatic polycarbonate resin powder (manufactured by Diko K.K.: panlite L-1250WP, viscosity molecular weight 23,500).

Component B

B1, component: ABS resin (manufactured by Nippon Dongli: 700-314);

b2, component (A): MBS: a core-shell graft copolymer (manufactured by Mitsubishi Yang, ltd.: C223A).

Component C

C-1: phosphoric acid esters containing bisphenol A-diphenylphosphoric acid as a main component (manufactured by Dai chemical industries, ltd.: CR-741);

c-2: the phosphazene having a structure represented by the following formula (7) contains a trimer (k = 3) in an amount of 98.5mol%, a tetramer (k = 4) in an amount of 1mol%, and a major amount of k =5 or more in an amount of 0.5mol%.

C-3 Triphenyl phosphate (manufactured by Daba chemical industries, ltd.: TPP)

C-4

Component D

D-1: a polymer having a structure represented by the following formula (8) and containing Si-H groups, methyl groups and aromatic groups, wherein the Si-H groups are present in an amount of 0.2mol/100g, the aromatic group content is 50wt%, the average degree of polymerization is 8, the molecular weight is 700, and the kinematic viscosity is 57mm ² A siloxane per second;

d-2: average polymerization degree of 800, molecular weight of about 59000 and kinematic viscosity of 1000mm ² Dimethyl silicone polymer of/sAn alkane.

Other ingredients

PTFE: polytetrafluoroethylene (manufactured by Dajin industries, ltd.: ポリフロン MPA FA 500H)

Talc: talcum powder (SKCE-26P manufactured by Shengguangshan institute)

DC30M: acidic modified olefin wax comprising a copolymer of maleic anhydride and an alpha-olefin (manufactured by Mitsubishi chemical corporation: ダイヤカルナ M)

Examples 1 to 13 and comparative examples 1 to 4

The resin compositions prepared by uniformly mixing the respective material ratios of examples 1 to 13 and comparative examples 1 to 4 in the following weight ratio of Table 1 were transferred from the barrels of the extruder to the extruder and pelletized, and the productivity was evaluated according to the ease of discharging the materials from the barrels, and the results are shown in Table 1 below. Wherein the extruder uses a screw having a diameter of

The vented twin-screw extruder (TEX-30. Alpha. Of Japan Steel works, ltd.). Extruding the strand under the conditions that the temperature of a machine barrel and the temperature of a machine head are 280 ℃ and the suction pressure of an exhaust port is 3000Pa, cooling in a water bath, and then cutting the strand into particles by using a material making machine to complete a granulation process.

The obtained pellets were dried at 80 ℃ for 5 hours by a hot air circulation type dryer, and then injected into test specimens by an injection molding machine [ Toshiba machine (strain) IS170GN-5Y ] for a flame retardancy test and a Charpy impact strength test, the test results being shown in the following Table 1, wherein the injection molding conditions are: barrel temperature: 260 ℃, mold temperature: at 60 deg.C.

As is clear from the results shown in Table 1 below, in examples 1 to 13, the siloxane having Si-H groups and aryl groups and the organophosphorus flame retardant having an aromatic structure improve the flame retardancy (evaluated as V-0 grade) of the aromatic polycarbonate resin while maintaining good impact resistance (Charpy's notch impact strength of 23 kJ/m) ² Above), however, when the siloxane content exceeds 10 parts by weight relative to 100 parts by weight of the resin component as in examples 12 and 13, the cylinder blanking is compared during the extrusion productionIt is difficult. In comparative example 1, when a siloxane having Si-H groups and aryl groups was not included, impact resistance was poor (Charpy notched impact strength of 16.5 kJ/m), although excellent flame retardancy was obtained (flame retardancy evaluation V-0 grade) ² ) In comparative examples 2 to 4, when the siloxane was a siloxane having no Si-H group and no aryl group, although it had excellent impact resistance (Charpy notched impact strength of 33 kJ/m) ² Above) but the flame retardancy was V-1 grade or below, and particularly comparative example 4 was poor in flame retardancy.

Claims (22)

1. A flame-retardant aromatic polycarbonate resin composition, comprising:

100 parts by weight of a resin component, the resin component comprising:

100 to 1wt% of an aromatic polycarbonate resin as the component A,

And 0 to 99wt% of an impact modifier resin as component B;

0.1 to 25 parts by weight of a phosphorus flame retardant as a component C, wherein the phosphorus flame retardant is an organic phosphorus flame retardant having an aromatic structure;

0.1 to 15 parts by weight of a siloxane compound as component D;

the siloxane compound contains Si-H group and aryl group represented by general formula (1) in the molecule,

in the general formula (1), X ¹ 、X ² 、X ³ 、X ⁴ And X ⁵ Each independently selected from a hydrogen atom, an OH group, or an organic group having 1 to 20 carbon atoms.

2. The flame-retardant aromatic polycarbonate resin composition according to claim 1, wherein the organic group is a hydrocarbon group.

3. The flame-retardant aromatic polycarbonate resin composition according to claim 1, wherein the siloxane compound has at least one of the structural units represented by the general formulae (2) and (3) in a molecule,

in the general formulae (2) and (3), Z ¹ 、Z ² And Z ³ Each independently selected from a hydrogen atom, an organic group having 1 to 20 carbon atoms, or a compound group represented by the general formula (4), α 1, α 2, and α 3 are each independently selected from 0 or 1, and m1 is an integer of 0 or 1 or more; in the general formula (2), when m1 is 2 or more, Z in the repeating unit ¹ And alpha 1 are each the same or different,

in the general formula (4), Z ⁴ 、Z ⁵ 、Z ⁶ 、Z ⁷ And Z ⁸ Each independently selected from a hydrogen atom or an organic group having 1 to 20 carbon atoms, [ alpha ] 4, [ alpha ] 5, [ alpha ] 6, [ alpha ] 7 and [ alpha ] 8 independently selected from 0 or 1, and m2 is an integer of 0 or 1 or more; in the general formula (4), when m2 is 2 or more, Z in the repeating unit ⁴ 、Z ⁵ α 4 and α 5 are the same or different, respectively.

4. The flame-retardant aromatic polycarbonate resin composition according to claim 3, wherein the molecule of the siloxane compound is composed of 1 or 2 or more structural units represented by the general formula (2) and 2 or more structural units represented by the general formula (3); when the number of the structural units represented by the general formula (2) is 2 or more, Z in each structural unit ¹ α 1 and m1 are the same or different; when the number of the structural units represented by the general formula (3) is 2 or more, Z in each structural unit ² 、Z ³ α 2 and α 3 are the same or different.

5. The flame-retardant aromatic polycarbonate resin composition according to claim 3, wherein the organic group is a hydrocarbon group.

6. The flame-retardant aromatic polycarbonate resin composition according to claim 1, wherein the Si-H group content is 0.1 to 1.2mol/100g and the aryl group content is 10 to 70wt% based on the weight of the siloxane compound.

7. The flame-retardant aromatic polycarbonate resin composition according to claim 1, wherein the siloxane compound has an average degree of polymerization of 3 to 80 and a kinematic viscosity at 25 ℃ of 1 to 1000mm ² /s。

8. The flame-retardant aromatic polycarbonate resin composition according to claim 1, wherein the component D is contained in an amount of 0.05 to 7 parts by weight.

9. The flame-retardant aromatic polycarbonate resin composition according to claim 1, wherein the component A is 70 to 99.5wt% and the component B is 30 to 0.5wt% based on the weight of the resin component.

10. The flame-retardant aromatic polycarbonate resin composition according to claim 1, wherein the component B is a polymer resin containing a rubber unit.

11. The flame-retardant aromatic polycarbonate resin composition according to claim 10, wherein the component B comprises at least one of a component B1 and a component B2;

wherein the component B1 is a copolymer resin containing a vinyl cyanide monomer unit, an aromatic vinyl monomer unit and a rubber unit;

the component B2 is core-shell rubber graft copolymer resin.

12. The flame-retardant aromatic polycarbonate resin composition of claim 11, wherein the rubber unit of the component B1 comprises at least one of a butadiene monomer unit and a methyl acrylate monomer unit, and the butadiene monomer unit and the methyl acrylate monomer unit together constitute 1 to 70wt% of the total weight of the component B1.

13. The flame-retardant aromatic polycarbonate resin composition according to claim 12, wherein the component B1 is an acrylonitrile-styrene-butadiene copolymer resin.

14. The flame-retardant aromatic polycarbonate resin composition according to claim 11, wherein the rubber unit in the component B2 is at least one selected from the group consisting of an unsaturated olefin rubber, a silicone rubber and an acrylate rubber, and the grafted compound monomer comprises at least one selected from the group consisting of an acrylate and a methacrylate.

15. The flame-retardant aromatic polycarbonate resin composition of claim 1, wherein the organophosphorus flame retardant is a phosphazene flame retardant or an organophosphorus flame retardant having a structure represented by general formula (5),

in the general formula (5), X ² Is arylene, n2 is an integer of 0 to 5, R ¹ 、R ² 、R ³ And R ⁴ Each independently selected from aryl groups.

16. The flame retardant aromatic polycarbonate resin composition of claim 15, wherein the arylene group is derived from a dihydroxy compound of hydroquinone, resorcinol, bis (4-hydroxydiphenyl) methane, bisphenol a, dihydroxybiphenyl, dihydroxynaphthalene, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) ketone, or bis (4-hydroxyphenyl) sulfide; the aryl group is derived from phenol, cresol, xylenol, isopropylphenol, butylphenol, or p-cumylphenol.

17. The flame-retardant aromatic polycarbonate resin composition according to claim 15, wherein the phosphazene cyclotrisaccharide content of the phosphazene flame retardant is 60mol% or more.

18. The flame-retardant aromatic polycarbonate resin composition according to claim 17, wherein the phosphazene cyclotrisaccharide content of the phosphazene flame retardant is 98.5mol% or more.

19. The flame-retardant aromatic polycarbonate resin composition according to claim 1, wherein the content of the component C is 2 to 20 parts by weight.

20. The flame-retardant aromatic polycarbonate resin composition of claim 1, wherein the flame retardancy of the composition meets the requirement of UL94 standard flame retardancy level V-0, and the Charpy notched impact strength is 20KJ/m ² The above.

21. The flame-retardant aromatic polycarbonate resin composition according to claim 1, further comprising an anti-dripping agent, an inorganic filler, and an acid-modified olefin wax comprising a copolymer of maleic anhydride and an α -olefin.

22. A molded article obtained by processing the flame-retardant aromatic polycarbonate resin composition according to any one of claims 1 to 21.