TWI450930B - Carbonate-based polymer composition and products made from said carbonate-based polymer composition - Google Patents

Description

Carbonate-based polymer composition and molded article formed therefrom

The present invention relates to a material suitable for preparing a plastic molded article for use in electrical equipment, office equipment, automobile parts, household articles, and the like, and more particularly to a carbonate-based polymer composition containing a rubber-based polymer component. The present invention also provides a molded article formed from the composition.

In recent years, carbonate polymers have been widely used in the optoelectronic industry, biotechnology industry or information electronics industry due to their impact resistance, light weight per unit volume, easy processing, and strong insulation. . However, the carbonate-based polymer is a flammable substance, and in order to enhance the flame retardancy of the carbonate-based polymer, a phosphorus-based flame retardant is usually added to enhance the flame retardancy, but a phosphorus-based flame retardant is added. The physical properties of the carbonate-based polymer are affected, and the carbonate-based polymer has disadvantages such as embrittlement, poor impact resistance, and poor moldability.

In order to improve the impact resistance, it has been upgraded by adding a rubber-modified styrene resin to make it both flame retardant and impact resistant. However, as the molding processing conditions become more stringent, for example, large molded articles such as televisions and computers, and thin-shell molded articles require physical properties such as better appearance, high impact resistance, and high rigidity. Then, by adding a styrene-diene-(meth)acrylate-based resin, the compatibility between the carbonate-based polymer and the rubber-modified styrene-based resin is improved, so that the molded article formed therefrom can be improved. More in line with the needs. However, although there is some slight improvement in compatibility, this method does not have a large improvement in fluidity during molding processing, and the formed bonding line of the molded article formed is not good in appearance.

In order to improve the disadvantage of the poor appearance of the processing bond line of the molded article formed by kneading the carbonate-based polymer and the rubber-modified styrene-based resin, it is still required to develop a carbonate polymer having better fluidity and compatibility. The composition, and after subsequent processing to form a molded article, can make the molded article have better flame retardancy and a processed bond line appearance to meet the needs of the industry.

Accordingly, a first object of the present invention is to provide a carbonate polymer composition which is preferably fluid and compatible.

Thus, the carbonate-based polymer composition of the present invention comprises: 100 parts by weight of the polymer mixture (A), and comprises 50 parts by weight to 98 parts by weight of the carbonate-based polymer component (A ₁ ) and 2 parts by weight to ～ 50 parts by weight of the rubber-based polymer component (A ₂ ); 5 parts by weight to 30 parts by weight of the phosphorus-based flame retardant (B); and 0.1 part by weight to 2.0 parts by weight of the fluorine-based polymer (C), wherein The rubber-based polymer component (A ₂ ) includes a styrene-acrylonitrile-diene copolymer (A ₂₁ ) and a styrene-acrylonitrile copolymer (A ₂₂ ), and the rubber-based polymer component The water content of (A ₂ ) is in the range of less than 3% by weight, and the weight average molecular weight of the styrene-acrylonitrile-based copolymer (A ₂₂ ) ( The range is 20,000 to 80,000.

A second object of the present invention is to provide a molded article of a carbonate-based polymer composition having a preferred flame retardancy and a processed bond line appearance.

Then, the molded article of the carbonate-based polymer composition of the present invention is formed from a carbonate-based polymer composition as described above.

The effect of the present invention is to control the water content of the rubber-based polymer component (A ₂ ) and the weight average molecular weight of the styrene-acrylonitrile-based copolymer (A ₂₂ ) ( The composition is made to have better fluidity, and the compatibility of the components in the composition is improved, and the molded article formed from the composition has better flame retardancy and a processed bond line appearance.

As used herein, "(meth)acrylic acid" refers to acrylic acid or methacrylic acid, and "(meth)acrylate" refers to acrylate or methacrylate.

The carbonate-based polymer composition of the present invention comprises: 100 parts by weight of the polymer mixture (A), comprising 50 parts by weight to 98 parts by weight of the carbonate-based polymer component (A ₁ ) and 2 parts by weight to 50 parts by weight. Parts of the rubber-based polymer component (A ₂ ); 5 parts by weight to 30 parts by weight of the phosphorus-based flame retardant (B); and 0.1 parts by weight to 2.0 parts by weight of the fluorine-based polymer (C), wherein The rubber-based polymer component (A ₂ ) includes a styrene-acrylonitrile-diene copolymer (A ₂₁ ) and a styrene-acrylonitrile copolymer (A ₂₂ ), and the rubber-based polymer component (A) ₂ ) a water content in the range of less than 3% by weight, and a weight average molecular weight of the styrene-acrylonitrile-based copolymer ( _A22 ) ( The range is 20,000 to 80,000.

When the water content of the rubber-based polymer component (A ₂ ) is in the range of 3% by weight or more and is mixed with the phosphorus-based flame retardant (B), the phosphorus-based flame retardant (B) is easily cleaved. On the other hand, the molded article formed of the composition is deteriorated in flame retardancy, and the appearance of the processed bonding wire of the molded article is extremely poor. Preferably, the rubber-based polymer component (A ₂ ) has a water content in the range of less than 2% by weight. More preferably, the rubber-based polymer component (A ₂ ) has a water content in the range of less than 1% by weight.

The method for preparing the rubber-based polymer component (A ₂ ) and having a water content of less than 3% by weight may be subjected to a coagulation step after the polymerization of the rubber-based polymer component (A ₂ ), followed by a dehydration and drying step. And finished. In the dehydration step, dehydration may be performed using a dehydrator or the like; in the drying step, drying may be performed using an auto oven or the like; or an extruding device having both dehydration and drying functions may be used.

The particle size of the rubber-based polymer component (A ₂ ) is not particularly limited, and preferably, the rubber-based polymer component (A ₂ ) has a particle diameter ranging from less than 1,500 μm; more preferably, The rubber-based polymer component (A ₂ ) has a particle diameter in the range of 1,000 μm or less.

Hereinafter, the carbonate polymer component (A ₁ ), the rubber polymer component (A ₂ ), the phosphorus flame retardant (B), and the fluorine polymer (C) will be described in detail one by one:

[Carbonate polymer component (A ₁ )]

The method and type of synthesis of the carbonate-based polymer component (A ₁ ) are not particularly limited, and can be used conventionally in the art. The synthesis method includes, for example, a phosgene method, a transesterification method, a ring-opening polymerization method, a carbon dioxide polymerization method, etc., wherein the phosgene method is a dihydroxy aryl compound dissolved in an alkali solution in a homogeneous system or a heterogeneous system. The polymerization is carried out under phosgene with phosgene dissolved in a solvent such as dichloromethane. The transesterification method is a transesterification reaction of a dihydroxyaryl compound with a carbonate compound such as diphenyl carbonate or dimethyl carbonate in a molten state. Further, for example, the disclosures of U.S. Patent Nos. 2,964,974, 2,970,137, 2,999,835, 3,999,846, 3,028,365, 3,153,008, 3,187,065, 3,215,668, 3,258,414 and 5,010,162. Further, in the method of the Japanese Patent Application Laid-Open No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei. In the solid state polymerization, a carbonate-based polymer component (A ₁ ) can be obtained.

Preferably, the carbonate-based polymer component (A ₁ ) is optionally produced by transesterification of a dihydroxy aryl compound with a carbonate-based compound.

The dihydroxyaryl compound is selected from the group consisting of dihydroxybiphenyls, bis-(hydroxyphenyl)alkanes, bis-(hydroxyphenyl)bisalkanes, bis-(hydroxyphenyl)-vulcanization. , bis-(hydroxyphenyl)ethers, bis-(hydroxyphenyl) ketones, bis-(hydroxyphenyl)anthracene compounds, bis-(hydroxyphenyl)anthracene compounds, alkyl rings A hexamethylene bisphenol compound, a bis-(hydroxyphenyl)-diisopropylbenzene compound, an alkylated derivative of the above compound, a halogenated derivative of the above compound, or a combination thereof.

The dihydroxyaryl compound is specifically, for example, 4,4'-dihydroxybiphenyl, 2,2'-bis-(4-hydroxyphenyl)-propane, 2,4'-bis-(4-hydroxyphenyl) -2-methylbutane, 1,1-bis-(4-hydroxyphenyl)-cyclohexane, α,α-bis-(4-hydroxyphenyl)-diisopropylbenzene, 2,2- Bis-(3-methyl-4-hydroxyphenyl)-propane, 2,2-bis-(3-chloro-4-hydroxyphenyl)-propane, bis-(3,5-dimethyl-4- Hydroxyphenyl)-methane, 2,2-bis-(3,5-dimethyl-4-hydroxyphenyl)-propane, bis-(3,5-dimethyl-4-hydroxyphenyl)-indole 2,4-bis-(3,5-dimethyl-4-hydroxyphenyl)-2-methylbutane, 1,1-bis-(3,5-dimethyl-4-hydroxyphenyl )-cyclohexane, α,α-bis-(3,5-dimethyl-4-hydroxyphenyl)-p-diisopropylbenzene, 2,2-bis-(3,5-dichloro- 4-Hydroxyphenyl)-propane, 2,2-bis-(3,5-dibromo-4-hydroxyphenyl)-propane, and the like. Preferably, the dihydroxyaryl compound is 2,2'-bis-(4-hydroxyphenyl)-propane [commonly known as bisphenol A].

Weight average molecular weight of the carbonate-based polymer component (A ₁ ) The range is 10,000 to 100,000. Preferably, the carbonate-based polymer component (A ₁ ) has a weight average molecular weight ranging from 20,000 to 100,000. When two carbonate polymers having different weight average molecular weights are used in the carbonate polymer component (A ₁ ), preferably a carbonate polymer having a weight average molecular weight of 20,000 to 100,000 and a weight average A carbonate-based polymer having a molecular weight of 3,000 to 20,000 is used in combination; more preferably, a carbonate-based polymer having a weight average molecular weight of 21,000 to 50,000 and a carbonate-based polymer having a weight average molecular weight of 10,000 to 19,000 are used in combination.

When the amount of the carbonate-based polymer component (A ₁ ) used is more than 98 parts by weight, the fluidity of the carbonate-based polymer composition is poor, and the amount of the carbonate-based polymer component (A ₁ ) is less than When the amount is 50 parts by weight, the molded article formed from the carbonate-based polymer composition has poor impact strength. Preferably, the carbonate-based polymer component (A ₁ ) is used in an amount ranging from 60 parts by weight to 97 parts by weight, based on 100 parts by weight of the total of the polymer mixture (A); more preferably, the carbonic acid The ester polymer component (A ₁ ) is used in an amount ranging from 70 parts by weight to 96 parts by weight.

[Rubber-based polymer component (A ₂ )]

The rubber-based polymer component (A ₂ ) is obtained by graft polymerization of a rubber emulsion (solid content) containing 40% by weight to 90% by weight and 10% by weight to 60% by weight of the monomer component. The monomer component contains 50% by weight to 90% by weight of a styrene-based monomer and 10% by weight to 50% by weight of an acrylonitrile-based monomer. In the graft polymerization reaction, an emulsifier, a polymerization initiator, a chain transfer agent or the like may be optionally added. Further, after the graft polymerization reaction, it is optional to carry out the steps of coagulation, dehydration, drying, and the like. Preferably, the graft polymerization reaction has an operating temperature in the range of 90 ° C or less; more preferably, the graft polymerization has an operating temperature in the range of 30 ° C to 80 ° C.

The rubber emulsion is obtained by an emulsion polymerization method from a rubber component, and optionally, another copolymerizable monomer is added to the emulsion polymerization reaction, and is further subjected to a hypertrophy treatment after the emulsion polymerization reaction. The other copolymerizable monomers include, but are not limited to, styrene, acrylonitrile, (meth) acrylate, and the like. The rubber component is selected from a diene rubber, a polyacrylate rubber, or a polyoxyalkylene rubber.

Preferably, the diene rubber is obtained by anionic polymerization of a diene monomer, and has a glass transition temperature of -20 ° C or lower. Preferably, the diene monomer includes, but is not limited to, butadiene, isoprene, chloroprene, and the like. The diene rubber may be used singly or in combination, and the diene rubber includes, but is not limited to, butadiene rubber, isoprene rubber, chloroprene rubber, styrene-diene rubber, acrylonitrile rubber. Wait. The butadiene rubber includes, but is not limited to, a high cis (Hi-Cis) content of butadiene rubber and a low cis (Low-Cis) content of butadiene rubber. The typical weight composition of cis (Cis)/vinyl (Vinyl) in the high cis content butadiene rubber is (94 to 98 wt%) / (1 to 5 wt%), and the rest of the composition is trans. (Trans) structure, and Mooney viscosity is between 20 and 120, and the molecular weight range is preferably from 100,000 to 800,000. The typical weight composition of cis/vinyl in the low cis content butadiene rubber ranges from (20 to 40 wt%) / (1 to 20 wt%), the balance is trans structure, and the Mooney viscosity is 20 to 120 rooms.

The styrene-diene rubber includes, but is not limited to, styrene-butadiene rubber (SBR). The structure of the styrene-diene rubber may be a di-block copolymerization, a tri-block copolymerization, a random copolymerization or a star type. . Preferably, the weight ratio of the styrene monomer unit to the butadiene monomer unit in the styrene-butadiene rubber ranges from 5/95 to 80/20. Preferably, the styrene-butadiene rubber has a molecular weight in the range of 50,000 to 600,000. The rubber component is selected from butadiene rubber, styrene-butadiene rubber, or a combination thereof. Preferably, the rubber component is a styrene-butadiene rubber.

The hypertrophy treatment can be carried out by a general method of freezing fertilizer, additive hypertrophy or mechanical hypertrophy. The additives used in the additive hypertrophy method include, but are not limited to, (1) acidic substances: acetic anhydride, hydrogen chloride, sulfuric acid, etc.; (2) salt-based substances: sodium chloride, potassium chloride, calcium chloride, etc.; A polymer aggregating agent containing a carboxylic acid group: a (meth)acrylic acid-(meth)acrylate copolymer (such as a methacrylic acid-butyl acrylate copolymer, a methacrylic acid-ethyl acrylate copolymer) or the like. For example, the method for producing a diene rubber emulsion can be polymerized by an emulsion polymerization method using a diene monomer (for example, butadiene), or 50% by weight to 100% by weight of a diene monomer and 0% by weight. 50% by weight of a monomer such as styrene and/or acrylonitrile is polymerized by an emulsion polymerization method to obtain a small particle size diene rubber emulsion having a weight average particle diameter of 0.05 μm to 0.15 μm, and then subjected to a fertilizer treatment. The small particle size diene rubber emulsion is grown into a large particle size diene rubber emulsion having a weight average particle diameter of 0.15 μm to 0.45 μm.

The styrene monomer may be used singly or in combination, and the styrene monomer includes, but is not limited to, styrene, α-methylstyrene, α-chlorostyrene, p-tert-butylstyrene, p- Methylstyrene, o-chlorostyrene, p-chlorostyrene, 2,5-dichlorostyrene, 3,4-dichlorostyrene, 2,4,6-trichlorostyrene, 2,5- Dibromostyrene, and the like. Preferably, the styrenic monomer is selected from the group consisting of styrene, alpha-methylstyrene, or a combination thereof. Preferably, the content of the styrene-based monomer ranges from 50% by weight to 85% by weight based on 100% by weight of the total of the monomer components.

The acrylonitrile-based monomer may be used singly or in combination, and the acrylonitrile-based monomer includes, but not limited to, acrylonitrile, α-methacrylonitrile, and the like. Preferably, the acrylonitrile-based monomer is acrylonitrile. Preferably, the content of the acrylonitrile-based monomer ranges from 15% by weight to 50% by weight based on 100% by weight of the total of the monomer components.

In the graft polymerization, a polymerization initiator may be optionally added. The polymerization initiator may be used singly or in combination, and the polymerization initiator includes, but is not limited to, benzoyl peroxide, dicumyl hydroperoxide, and tributyl peroxide. T-butyl peroxide, cumene peroxide, potassium persulfate, and the like. Among them, organic hydrogen peroxide is preferred.

In the graft polymerization, a chain transfer agent may be selectively added. The chain transfer agent may be used singly or in combination, and the chain transfer agent includes, but is not limited to, n-dodecyl mercaptan (NDM), and tri-dodecyl mercaptan (t-dodecyl). Mercaptan (abbreviated as TDM), n-butyl mercaptan, n-octyl mercaptan, and the like.

The rubber-based polymer component (A ₂ ) includes a styrene-acrylonitrile-diene copolymer (A ₂₁ ) and a styrene-acrylonitrile copolymer (A ₂₂ ). The styrene-acrylonitrile-diene copolymer (A ₂₁ ) is selected from the first styrene-acrylonitrile-diene copolymer (A ₂₁₁ ) and the second styrene-acrylonitrile-diene copolymer. (A ₂₁₂ ), or a combination of these. The styrene-acrylonitrile-diene copolymer (A ₂₁ ) has a weight average particle diameter ranging from 0.2 μm to 0.5 μm.

The first styrene-acrylonitrile-diene copolymer (A ₂₁₁ ) is a first rubber body comprising one or several styrene copolymers, coated with a styrene copolymer, and grafted to the first a first graft copolymer on a rubber body; and the second styrene-acrylonitrile-diene copolymer (A ₂₁₂ ) comprises a second rubber body and the graft onto the second rubber body The second graft copolymer is composed of. The first rubber body and the second rubber body may be the same or different, and the first graft copolymer and the second graft copolymer may be the same or different. The styrene-based copolymer, the first graft copolymer or the second graft copolymer are each formed by polymerization of one of the above monomer components. The first rubber body or the second rubber body is formed of the above rubber component, respectively.

a first rubber body or a second styrene-acrylonitrile-diene copolymer of the first styrene-acrylonitrile-diene copolymer (A ₂₁₁ ) of the rubber-based polymer component (A ₂ ) The graft ratio of the second rubber body of ₂₁₂ ) can be controlled by polymerization conditions, for example, polymerization temperature, polymerization initiator, emulsifier, amount and type of chain transfer agent, and addition method of monomer component. control. The method of adding the monomer component refers to each monomer which can be added to the monomer component at one time, or may be added in portions, or may be continuously added or the monomers may be added in stages.

The styrene-acrylonitrile-based copolymer (A ₂₂ ) contains a copolymer which is not grafted onto the first rubber body or which is not grafted onto the second rubber body.

The content of the styrene-acrylonitrile-diene copolymer (A ₂₁ ) is in the range of 15% by weight to 85% by weight based on the total amount of the rubber-based polymer component (A ₂ ) of 100% by weight, and The content of the styrene-acrylonitrile-based copolymer (A ₂₂ ) ranges from 15% by weight to 85% by weight. Weight average molecular weight of the styrene-acrylonitrile copolymer (A ₂₂ ) The range is 20,000 to 80,000. Preferably, the weight average molecular weight of the styrene-acrylonitrile copolymer (A ₂₂ ) ( The range is from 25,000 to 70,000. More preferably, the weight average molecular weight of the styrene-acrylonitrile copolymer (A ₂₂ ) ( The range is 30,000 to 60,000. When the weight average molecular weight of the styrene-acrylonitrile copolymer (A ₂₂ ) ( When the range is more than 80,000, the processing bond line of the molded article formed of the carbonate-based polymer composition is extremely poor in appearance; when the weight average molecular weight of the styrene-acrylonitrile-based copolymer (A ₂₂ ) ( When the range is less than 20,000, the molded article formed of the carbonate-based polymer composition has poor impact strength properties.

[Phosphorus-based flame retardant (B)]

The phosphorus-based flame retardant (B) may be used singly or in combination, and the phosphorus-based flame retardant (B) includes, but is not limited to, an aromatic phosphate ester or an aromatic phosphate ester polymer. The aromatic phosphate ester may be used singly or in combination, and the aromatic phosphate ester is specifically, for example, triphenyl phosphate (TPP), tricresyl phosphate (TCP), and tris(dimethyl) phosphate. Trixylyl phosphate, cresyldiphenyl phosphate (CDP), tri(isopropylphenyl)phosphate (TIPP), tris(2,6-dimethyl) phosphate Phenyl ester, phosphoric acid-bis(2,6-dimethylphenyl)phenyl ester, phosphoric acid-(2,6-dimethylphenyl)diphenyl ester, resorcinol bis (diphenyl phosphate) [resorcinol bis diphenylphosphate] , referred to as RDP], bisphenol A bis-diphenylphosphate (BDP). Preferably, the phosphorus-based flame retardant (B) is used in an amount ranging from 10 parts by weight to 25 parts by weight based on 100 parts by weight of the total of the polymer mixture (A).

[Fluoropolymer (C)]

The type of the fluorine-based polymer (C) is not particularly limited, and it can be used conventionally in the prior art. Preferably, the fluorine-based polymer (C) is a powdery fluorine having a water content of 3% by weight or less. Is a polymer. The fluorine-based polymer (C) may be used singly or in combination, and the fluorine-based polymer (C) includes, but is not limited to, polytetrafluoroethylene (PTFE). The fluorine-based polymer (C) has an average particle diameter ranging from 60 μm to 2,000 μm. When the amount of the fluorine-based polymer (C) used is more than 2 parts by weight, the surface of the molded article formed of the carbonate-based polymer composition is poor in appearance; the amount of the fluorine-based polymer (C) used is less than 0.1. When the parts are parts by weight, the molded article formed from the carbonate-based polymer composition is poor in flame retardancy. Preferably, the fluorine-based polymer (C) is used in an amount ranging from 0.5 part by weight to 1.5 parts by weight based on 100 parts by weight of the total of the polymer mixture (A).

[Additive (D)]

Various additives (D) may be added as necessary within the range which does not impair the effect of the carbonate-based polymer composition of the present invention. The additive may be used singly or in combination, and the additive includes, but is not limited to, a lubricant, a release agent, a flame retardant, a plasticizer, a tackifier, a charge inhibitor, an antioxidant, a conductive agent, a colorant, a filler, and a reinforcement. Agents and flame retardant additives. Preferably, the additive (D) is used in an amount ranging from 0.02 part by weight to 2.0 parts by weight based on 100 parts by weight of the total amount of the polymer mixture (A).

The lubricant may be used singly or in combination, and the lubricant includes, but is not limited to, metal stearate such as calcium stearate, magnesium stearate, zinc stearate, and ethylene bis stearyl amide. , referred to as EBA), methine bis-lipidamine, palmitic acid amide, butyl stearate, palmitate stearate, glyceryl monostearate, n-docosic acid, stearic acid , polyethylene wax, montan wax, etc.

The antioxidant may be used singly or in combination, and the antioxidant includes, but is not limited to, 2,6-di-tert-butyl-4-methylphenol (2,6-di-tert-butyl-4-methylphenol), Tri-(nonyl phenyl) phosphate, 3-(3,5-di-t-butyl-4-hydroxyphenyl)-propanoic acid octadecyl ester [octadecyl- 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], bis(3,5-di-t-butyl-4-hydroxy-β-phenylpropionic acid) thio-secondary Ester [thio diethylene bis(3,5-di-t-butyl-4-hydroxy hydrocinnamate)], tetra[(3,5-di-t-butyl-4-hydroxy-β-phenylpropionate methine) Methane {tetrakis[methylene(3,5-di-butyl-4-hydroxy-hydrocinnamate)]methane}, 2,4-bis[(thiooctyl)methyl]o-cresol {2,4-bis [(octyl thio)methyl]O-cresol}, tris(2,4-di-tert-butyl)phenyl phosphite [tris(2,4-di-tert-butyl-phenyl)phosphite], thiodi Dilauryl thio dipropionate, distearyl thio dipropionate, bis-3-(3-tert-butyl-4-hydroxy-5-methylphenyl) Triethylene glycol-bis-3-(3-t-butyl-4-hydroxy-5-met Hylphenyl)propionate], 1,1-bis(2-methyl-4-hydroxy-5-t-butylphenyl)butane [1,1-bis(2-methyl-4-hydroxy-5-t- Butylphenyl)butane] and so on.

The carbonate-based polymer composition can be produced by a general mixing method, and the carbonate-based polymer component (A ₁ ), the rubber-based polymer component (A ₂ ), and the phosphorus-based flame retardant (B). The fluorine-based polymer (C) is placed in a stirrer to be stirred, uniformly mixed, and if necessary, the additive (D) can be added to obtain the carbonate-based polymer composition of the present invention.

The molded article of the carbonate-based polymer composition of the present invention is formed from a carbonate-based polymer composition as described above. The formation method can be carried out by a kneading method, a processing molding method, or a combination thereof. The kneading method and the forming method can be carried out in a conventional manner, and therefore will not be described again.

The invention is further described in the following examples, but it should be understood that these examples are for illustrative purposes only and are not to be construed as limiting.

<Example> real Test materials: 1. Carbonate polymer component (A ₁ ):

Made by Chi Mei Industrial Co., Ltd., model number is WONDERLITE PC-110.

2. Rubber polymer component (A ₂ ):

A ₂ -a: styrene-acrylonitrile-butadiene copolymer (A ₂₁ ) and styrene-acrylonitrile copolymer (A ₂₂ ), manufactured by Guoqiao, product type 60P, water content 0.67 wt%, Appearance is powder;

A ₂ -b: styrene-acrylonitrile-butadiene copolymer (A ₂₁ ) and styrene-acrylonitrile copolymer (A ₂₂ ), manufactured by Kumho, model number HR-181, water content 0.36 by weight %, the appearance is powder;

A ₂ -c: styrene-acrylonitrile-butadiene copolymer (A ₂₁ ) and styrene-acrylonitrile copolymer (A ₂₂ ), manufactured by Changzhou Xinhu Company, product type B-338, water content 0.74 % by weight, the appearance is powder;

A ₂ -d: styrene-acrylonitrile-butadiene copolymer (A ₂₁ ) and styrene-acrylonitrile copolymer (A ₂₂ ), manufactured by Chimei, product type 60R (dehydrated), water content 0.43 % by weight, the appearance is powder;

A ₂ -e: second styrene-acrylonitrile-butadiene copolymer (A ₂₁₂ ) and styrene-acrylonitrile copolymer (A ₂₂ ), manufactured by Chi Mei, product type 60R (not dehydrated), water content 3.8 wt%;

A ₂ -f: a second styrene-acrylonitrile-butadiene copolymer (A ₂₁₂ ) and a styrene-acrylonitrile copolymer (A ₂₂ ), manufactured by Chi Mei, under the trade name Polylac PA-709M, water content 0.1% by weight;

A ₂ -g: first styrene-acrylonitrile-butadiene copolymer (A ₂₁₁ ) and styrene-acrylonitrile copolymer (A ₂₂ ), manufactured by Chi Mei, under the trade name Polylac PA-705N, water content 0.6% by weight;

A ₂ -h: 4.7 parts by weight of A ₂ -f and 3 parts by weight of a styrene-butadiene-methyl methacrylate graft copolymer (MBS, manufactured by Taihua Co., Ltd., trade name M-51), The water content is 0.8% by weight;

A ₂ -i: 2 parts by weight of A ₂ -g and 3 parts by weight of a styrene-butadiene-methyl methacrylate graft copolymer (MBS, manufactured by Taihua Co., Ltd., trade name M-51), The water content was 0.1% by weight.

3. Phosphorus-based flame retardant (B):

Tetraphenyl bisphenol A diphosphate, which is manufactured by ADEKA Chemical Co., Ltd., model FP-700.

4. Fluorine-based polymer (C):

A powdery polytetrafluoroethylene resin having an average particle diameter of 500 μm, which is manufactured by Mitsubishi Corporation and model number A-3750.

[Example 1] Carbonate-based polymer composition and molded article thereof

90 parts by weight of the carbonate-based polymer component (A ₁ ) and 10 parts by weight of the rubber-based polymer component (A ₂ ) of A ₂ -a are mixed to form a polymer mixture (A), followed by addition 0.7 parts by weight of the fluorine-based polymer (C), and fed by a one-weight screw feeder to a two-axis extruder with a plurality of exhaust ports (German W&PZSK-25), and the twin-shaft extruder The barrel temperature is set between 210 ° C and 240 ° C. Thereafter, 19 parts by weight of a phosphorus-based flame retardant (B) is added to the middle portion of the biaxial extruder and kneaded together to obtain a carbonate-based polymer composition of the present invention. The evaluation results are shown in Table 1.

[Examples 2 to 4 and Comparative Examples 1 to 5]

In Examples 2 to 4 and Comparative Examples 1 to 5, the carbonate-based polymer composition was prepared in the same manner as in Example 1, except that the rubber-based polymer component (A ₂ ) was changed and Its usage. The types and amounts of the rubber-based polymer component (A ₂ ) are shown in Table 1, and the evaluation results are shown in Table 1.

【Test items】 1. Impact strength evaluation (Izod) measurement:

The carbonate-based polymer compositions of Examples 1 to 4 and Comparative Examples 1 to 5 were injected, and standard test pieces were prepared in accordance with the standard method of ASTM D-256, and then tested in accordance with ASTM D-256 (unit: Kg-cm/cm).

2. Melting coefficient (representing fluidity, melt index, 220 ° C, 10 kg; referred to as MI) evaluation and determination:

The carbonate polymer compositions of Examples 1 to 4 and Comparative Examples 1 to 5 were tested in accordance with ASTM Standard D-1238, and the unit was g/10 minutes.

3. Determination of flame retardancy:

The carbonate polymer compositions of Examples 1 to 4 and Comparative Examples 1 to 5 were tested according to the vertical flame measurement specifications specified by Underwriter Laboratory (UL) (UL 94), and the thickness was 1.5 mm, wherein ◎ and ○ indicates measurement by V-0 combustion; x indicates that measurement by V-0 combustion cannot be performed.

4. Determination of the appearance of the processing bond line:

The carbonate-based polymer compositions of Examples 1 to 4 and Comparative Examples 1 to 5 were injection molded to produce a frame for a display surface of a liquid crystal television, and the white fog defects and bonding lines on the frame surface were visually observed. The evaluation results were as follows. Figure 1 to Figure 2;

◎ indicates that the processing bonding line has a good appearance;

XX indicates that the processing bond line has a poor appearance, as shown in Figure 1;

XXX indicates that the processing bond line has a very poor appearance, as shown in Figure 2.

As is apparent from the data of Table 1, the rubber-based polymer component (A ₂ ) in the carbonate-based polymer compositions of Examples 1 to 4 had a water content of 0.36% by weight to 0.74% by weight, and the rubber-based polymer group. The weight average molecular weight of the styrene-acrylonitrile copolymer (A ₂₂ ) in the portion (A ₂ ) is from 37,200 to 51,200, so that the carbonate polymer composition has better fluidity (melting coefficient is 50 g/10 min). ～59 g/10 min), and the molded article formed of the carbonate-based polymer composition has better flame retardancy and a processed bond line appearance.

As is clear from the data of Comparative Example 1, the carbonate-based polymer composition used a rubber-based polymer component (A ₂ ) having a water content of 3.8% by weight to form a molded article composed of the carbonate-based polymer composition. The impact strength is poor, the flame retardancy is poor, and the processing bond line is extremely poor in appearance.

As is clear from the data of Comparative Examples 2 to 5, the rubber-based polymer component (A ₂ ) of the carbonate-based polymer composition used a styrene-acrylonitrile-based copolymer (A ₂₂ ) having a weight average molecular weight of 133,000 or 180,000. The processing bond line of the molded article formed from the carbonate-based polymer composition is extremely poor in appearance.

In summary, by adjusting the water content of the rubber-based polymer component (A ₂ ) and the molecular weight of the styrene-acrylonitrile-based copolymer (A ₂₂ ), the composition has better fluidity and enhances the composition. The compatibility of the components in the article and the molded article formed from the composition have better flame retardancy and a processed bond line appearance, so that the object of the present invention can be achieved.

The above is only the preferred embodiment of the present invention, and the scope of the invention is not limited thereto, that is, the simple equivalent changes and modifications made by the scope of the invention and the description of the invention are All remain within the scope of the invention patent.

Figure 1 is a schematic view showing the appearance of a processed bonding line of a molded article of a carbonate-based polymer composition of a comparative example;

Fig. 2 is a schematic view showing the appearance of a processed bonding line of a molded article of a carbonate-based polymer composition of a comparative example.

[Attachment Description]

Attachment 1 is a color diagram showing the appearance of a processed bonding line of a molded article of a carbonate-based polymer composition of a comparative example;

Attachment 2 is a color diagram showing the appearance of the processed bonding line of the molded article of the carbonate-based polymer composition of the comparative example.

Claims (8)

A carbonate-based polymer composition comprising: 100 parts by weight of a polymer mixture (A) comprising 50 parts by weight to 98 parts by weight of a carbonate-based polymer component (A ₁ ) and 2 parts by weight to 50 parts by weight Rubber-based polymer component (A ₂ ); 5 parts by weight to 30 parts by weight of a phosphorus-based flame retardant (B); and 0.1 part by weight to 2.0 parts by weight of a fluorine-based polymer (C), wherein the rubber The polymer component (A ₂ ) includes a styrene-acrylonitrile-diene copolymer (A ₂₁ ) and a styrene-acrylonitrile copolymer (A ₂₂ ), and the rubber-based polymer (A ₂ ) The water content is in the range of less than 3% by weight, and the weight average molecular weight of the styrene-acrylonitrile-based copolymer ( _A22 ) ranges from 20,000 to 80,000, and based on the total amount of the rubber-based polymer component (A ₂ ) 100% by weight, the content of the styrene-acrylonitrile-diene copolymer (A ₂₁ ) is in the range of more than 45.5 wt% to 83 wt%, and the content range of the styrene-acrylonitrile copolymer (A ₂₂ ) It is 17% by weight to less than 54.5% by weight. The carbonate-based polymer composition according to claim 1, wherein the rubber-based polymer component (A ₂ ) has a water content of less than 2% by weight. The carbonate-based polymer composition according to the above aspect of the invention, wherein the rubber-based polymer component (A ₂ ) has a water content of less than 1% by weight. The carbonate-based polymer composition according to claim 1, wherein the styrene-acrylonitrile-based copolymer (A ₂₂ ) has a weight average molecular weight ranging from 25,000 to 70,000. The carbonate-based polymer composition according to claim 1, wherein the styrene-acrylonitrile-based copolymer (A ₂₂ ) has a weight average molecular weight ranging from 30,000 to 60,000. The carbonate-based polymer composition according to the first aspect of the invention, wherein the styrene-acrylonitrile-diene system is 100% by weight based on the total amount of the rubber-based polymer component (A ₂ ). The content of the copolymer (A ₂₁ ) is in the range of 77% by weight to 83% by weight, and the content of the styrene-acrylonitrile-based copolymer (A ₂₂ ) is in the range of 17% by weight to 23% by weight. The carbonate-based polymer composition according to claim 1, wherein the styrene-acrylonitrile-based copolymer (A ₂₂ ) has a weight average molecular weight of more than 37,200 to 47,000. A molded article of a carbonate-based polymer composition, which is formed from a carbonate-based polymer composition as described in any one of claims 1 to 7.