KR100989908B1 - Flame retardant resin composition of polycarbonate with low gloss and molding articles using the same - Google Patents

Abstract

In the present invention, (A) 50 to 99 parts by weight of aromatic polycarbonate; (B) 1 to 50 parts by weight of a rubber-modified vinyl graft copolymer comprising a rubbery polymer having an average particle diameter of 0.2 to 10 µm; (C) 0 to 45 parts by weight of the vinyl copolymer; (D) 1 to 30 parts by weight of the phosphate ester compound; 0.05 to 5 parts by weight of (E) fluorinated polyolefin; And (F) 0.1 to 10 parts by weight of a terpolymer containing ethylene, methyl acrylate and glycidyl methacrylate as monomers. It provides a low gloss flame retardant polycarbonate resin composition comprising a molded article prepared using the same.

Polycarbonate, rubber modified vinyl graft copolymer, low gloss, flame retardant, phosphate ester compound, fluorinated polyolefin

Description

Low gloss flame retardant polycarbonate resin composition and molded article using the same {FLAME RETARDANT RESIN COMPOSITION OF POLYCARBONATE WITH LOW GLOSS AND MOLDING ARTICLES USING THE SAME}

The present invention relates to a low gloss flame retardant polycarbonate resin composition and a molded article using the same.

Generally, the resin composition of the polycarbonate / vinyl copolymer is a resin composition having improved processability while maintaining excellent impact resistance, heat resistance, and mechanical strength, and is generally used in a housing of automobile parts, computer housing, or other office equipment.

The resin composition of the polycarbonate / vinyl copolymer shows high surface gloss. This high gloss property may be an advantage of plastic molded parts, but in certain applications, it may be disadvantageous, such as excessive glossiness, which causes eye fatigue or visual impairment. Sometimes. For example, in applications such as automobile interiors, computers, office equipment, and housings of electronic products, a low gloss surface is required in order to eliminate the visual impairment effect and give a luxurious atmosphere.

However, in order to make the high gloss surface low gloss, it is necessary to go through the painting process, which increases the cost and also causes the environmental pollution problem. Is increasing.

In order to meet such demands, to reduce the surface gloss of a resin molded article, a method of adding an inorganic filler such as silica, silicate or alumina to a polycarbonate / vinyl copolymer resin composition is known (US Pat. Nos. 4,460,733 and 4,987,174). number)

However, the method of adding the inorganic filler as described above has a slight matting effect. In addition, when increasing the content of the additive to increase the matting effect, there is a disadvantage that the mechanical properties such as impact strength is lowered and the fluidity is also sharply reduced.

In order to solve the problem of such an inorganic filler, a method of adding a high molecular weight organic quencher to a polycarbonate / vinyl copolymer resin composition has been proposed.

However, the method of adding the high molecular weight organic matting agent has a problem of causing not only impact strength but also deterioration of other physical properties such as heat deformation temperature and light stability.

As a method for reducing the surface gloss, a technique for increasing melt flow characteristics by mixing a polystyrene resin with a polycarbonate resin is common.

However, polycarbonate resins do not have compatibility with polystyrene resins and thus do not exhibit good physical properties. In particular, polycarbonate resins exhibit a layered peeling phenomenon caused by shear force during injection molding, and have a low impact strength. In order to solve such a problem, there is an example in which a low molecular weight organic additive such as a siloxane binder is used, but when the polystyrene-based resin content is increased, its addition effect is low.

On the other hand, U.S. Patent No. 3,825,393 describes a resin composition in which flame retardance is imparted by mixing an appropriate amount of a halogen compound and an antimony compound in a mixture of a polycarbonate / ABS resin.

However, the use of halogen-based flame retardants has recently increased the demand for resins containing no halogen-based flame retardants due to the human hazards of toxic gases generated during combustion.

Currently, the most popular technique for imparting flame retardancy without using a halogen-based flame retardant is to use a phosphate ester flame retardant.

Among them, there are flame retardant resin compositions using monomeric phosphate esters (US Pat. Nos. 4,692,488 and 5,061,745). In such resin compositions, a so-called plate-out phenomenon occurs in which a flame retardant moves to the surface of a molded product and is deposited during molding. there is a problem.

Resin compositions using an oligomeric phosphate ester as a flame retardant are also known (Japanese Patent Laid-Open No. 59-202,240 and U.S. Patent No. 5,204,394). In this composition, there is a problem in that the resin molded article exhibits a high gloss surface.

An object of the present invention is to provide a polycarbonate resin composition excellent in flame retardancy and low gloss and a molded article using the same.

Another object of the present invention is to provide a polycarbonate resin composition and a molded article using the same, which are excellent in flame retardancy and low gloss, and excellent in physical properties such as impact resistance, mechanical strength, fluidity, heat resistance, and workability. will be.

In the present invention, the aromatic polycarbonate resin composition comprising a phosphate ester compound, (B) rubber-modified vinyl graft copolymer containing a rubbery polymer having an average particle diameter of 0.2 ~ 10㎛; And (F) terpolymers containing ethylene, methyl acrylate and glycidyl methacrylate as monomers, thereby providing a low gloss flame retardant polycarbonate resin composition having improved low glossiness with flame retardancy. Here, the low gloss flame retardant polycarbonate resin composition (A) 50 to 99 parts by weight of an aromatic polycarbonate as an embodiment; (B) 1 to 50 parts by weight of a rubber-modified vinyl graft copolymer comprising a rubbery polymer having an average particle diameter of 0.2 to 10 µm; (C) 0 to 45 parts by weight of the vinyl copolymer; (D) 1 to 30 parts by weight of the phosphate ester compound; 0.05 to 5 parts by weight of (E) fluorinated polyolefin; And (F) 0.1 to 10 parts by weight of terpolymer containing ethylene, methyl acrylate and glycidyl methacrylate as monomers.

In addition, the present invention provides a molded article manufactured using the low-gloss flame retardant polycarbonate resin composition.

The low gloss flame retardant polycarbonate resin composition of the present invention is excellent in flame retardancy and matting effect. In addition, the low-gloss flame retardant polycarbonate resin composition of the present invention is excellent in balance with various physical properties such as mechanical strength, fluidity, heat resistance and workability such as impact resistance, as well as flame retardancy and matting effect.

Hereinafter, the components of the low gloss flame retardant polycarbonate resin composition according to the embodiment of the present invention will be described in detail.

(A) Aromatic Polycarbonate Component

The aromatic polycarbonate resin (A) is at least one selected from the group consisting of linear polycarbonate resins, branched polycarbonate resins, polyester-carbonate resins, and copolycarbonates copolymerized with silicone resins.

Specifically, aromatic polycarbonate resin (A) is manufactured from divalent phenols, a carbonate precursor, a molecular weight modifier, etc., for example.

The dihydric phenols may be any substance derived from the structure of the following [Formula 1].

[Formula 1]

Wherein X represents no alkyl group or functional group, or represents functional groups such as sulfide, ether, sulfoxide, sulfone and ketone or a straight, branched or cyclic alkyl group, preferably X represents 1 to 10 carbons And R ₁ and R ₂ represent hydrogen, a halogen atom, a linear, branched or cyclic alkyl group, n and m may each independently select an integer from 0 to 4. )

Specifically, the dihydric phenols include bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) phenylmethane, bis (4-hydroxyphenyl) naphthylmethane, bis (4-hydroxyphenyl)- (4-isobutylphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 1-ethyl-1,1-bis (4-hydroxyphenyl) propane, 1-phenyl-1,1-bis (4-hydroxyphenyl) ethane, 1-naphthyl-1,1-bis (4-hydroxyphenyl) ethane, 1,2-bis (4-hydroxyphenyl) ethane, 1,10-bis (4- Hydroxyphenyl) decane, 2-methyl-1,1-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), and the like. Bisphenol A.

As the carbonate precursor, it is preferable to apply phosgene (carbonyl chloride) as another monomer of the polycarbonate resin, and carbonyl bromide, bis halo formate, diphenyl carbonate or dimethyl carbonate may be used.

The molecular weight modifier may use a monofunctional compound similar to a known material, that is, a monomer used to prepare a polycarbonate resin. For example, derivatives (e.g., para-isopropylphenol, para-tert-butylphenol, para-cumylphenol, para-isooctylphenol, para-isononylphenol, etc.) based on phenol can be used. In addition, various kinds of substances such as aliphatic alcohols can be used, and among them, para-tert-butylphenol (PTBP) is most preferably applied.

The aromatic polycarbonate resin (A) used in the present invention preferably has a viscosity average molecular weight (M _v ) measured in a methylene chloride solution of 17,000 to 40,000, more preferably 20,000 to 30,000. .

If the average molecular weight is less than 20,000, mechanical properties such as impact strength and tensile strength are lowered. If the average molecular weight is less than 17,000, mechanical properties such as impact strength and tensile strength are significantly lowered.

If the average molecular weight exceeds 30,000, there may be a problem in the processing of the resin due to the rise of the melt viscosity, if it exceeds 40,000, processing of the resin is very difficult.

As the aromatic polycarbonate resin (A) used in the present invention, both homopolymers, copolymers, or blends thereof may be used.

In addition, the above aromatic polycarbonate resin (A) is partially or entirely replaced by a copolycarbonate copolymerized with an aromatic polyester-carbonate resin or a silicone-based resin obtained by polymerization in the presence of an ester precursor, such as a bifunctional carboxylic acid. It is also possible.

(B) Rubber modified vinyl graft copolymer component

The rubber-modified vinyl-based graft copolymer (B) is a rubber-modified vinyl-based graft copolymer including a rubbery polymer having an average particle diameter of 0.2 μm to 10 μm, preferably a rubbery polymer having an average particle diameter of 1 μm to 10 μm. It includes a large particle size rubber modified vinyl graft copolymer (B.1) comprising a.

For reference, in the present invention, the average particle diameter is (d ₅₀ ), and refers to the diameter in which 50% of the particles exist above and below the value. This can be determined by ultracentrifuge measurement.

The rubber-modified vinyl-based graft copolymer (B) is more preferably, in combination with a large-diameter rubber-modified vinyl polymer (B.1) comprising a rubbery polymer having the average particle diameter of 1 μm to 10 μm. A medium particle size rubber-modified vinyl graft copolymer (B.2) containing a rubbery polymer having a particle size of 0.2 μm to 0.6 μm is included.

Here, the rubber-modified vinyl-based graft copolymer (B) is (B.1) 10 to 100% by weight of a large-diameter rubber-modified vinyl-based graft copolymer containing a rubbery polymer having an average particle diameter of 1 to 10 µm and ( B.2) It is preferable to consist of 0-90 weight% of particle size rubber modified vinyl type graft copolymers containing the rubbery polymer whose average particle diameter is 0.2-0.6 micrometer.

When the content of the large-diameter rubber-modified vinyl-based graft copolymer (B.1) is less than 10% by weight, it is difficult to exhibit a low gloss property more than a predetermined level required by the present invention.

Hereinafter, the components of (B.1) and (B.2) will be described in more detail as follows.

(B.1) large particle size rubber modified vinyl graft copolymer

The large particle size rubber-modified vinyl-based graft copolymer (B.1) is preferably (B.1.1) a glass transition temperature of less than 10 ° C of 5-20% by weight of a rubbery polymer having an average particle diameter of 1 to 10 µm, preferably Is a monomer compound 80 to 95 consisting of 50 to 95 parts by weight of an aromatic vinyl compound and 5 to 50 parts by weight of a vinyl cyanide compound on one or more graft bases of less than 0 ° C and more preferably less than -10 ° C. The weight percent is preferably prepared by graft polymerization in bulk, solution or bulk-suspension polymerization process.

The graft base (B.1.1) of the rubbery polymer is a polybutadiene rubber, acrylic rubber, ethylene / propylene rubber, styrene / butadiene rubber, acrylonitrile / butadiene rubber, isoprene rubber, acrylic rubber, ethylene-propylene-diene Copolymer (EPDM), polyorganosiloxane / polyalkyl (meth) acrylate rubber composites, and may be used alone or in a mixture thereof.

The graft base (B.1.1) of the rubbery polymer has a glass transition temperature of less than 10 ° C, preferably less than 0 ° C, more preferably less than -10 ° C, and the gel content (measured in toluene) is 5 Or more, preferably 10% or more by weight.

It is preferable that the average particle diameter of the said large particle size rubbery polymer is 1-10 micrometers. If the average particle diameter is less than 1 µm, a sufficient low gloss effect cannot be exhibited. If the average particle diameter is 10 µm or more, there is a problem that the impact strength is lowered.

As the monomer compound (B.1.2) capable of polymerizing with the graft base (B.1.1) of the rubbery polymer, aromatic vinyl compounds include styrene, a-methylstyrene, halogen or alkyl-substituted styrene, and the like. Ronitrile, methacrylonitrile and the like. Styrene is preferable in the said aromatic vinyl compound, and acrylonitrile is preferable in a vinyl cyanide compound.

Further, the graft base (B.1.1) of the rubbery polymer may further include graft polymerization by adding monomers such as C ₁ -C ₈ methacrylic acid alkyl esters, C ₁ -C ₈ acrylic acid alkyl esters, maleic anhydride, and the like. Can be. At this time, the amount added is 0 to 40% by weight based on the graft copolymer total resin.

The C ₁ -C ₈ methacrylic acid alkyl esters or C ₁ -C ₈ acrylic acid alkyl esters are esters obtained from monohydryl alcohols containing 1 to 8 carbon atoms as alkyl esters of methacrylic acid or acrylic acid, respectively. to be. Specific examples thereof include methacrylic acid methyl ester, methacrylic acid ethyl ester, methacrylic acid propyl ester, acrylic acid ethyl ester or acrylic acid methyl ester.

Preferred examples of the large particle size rubber-modified vinyl graft copolymer (B.1) used in the present invention include styrene and acrylonitrile and optionally (meth) acrylic acid in polybutadiene rubber, acrylic rubber, or styrene / butadiene rubber. And graft copolymerized ester monomers in the form of a mixture. In addition, examples of other preferred large-diameter rubber-modified vinyl-based graft copolymers (B.1) include those obtained by graft copolymerization of a monomer of (meth) acrylic acid methyl ester to polybutadiene rubber, acrylic rubber, or styrene / butadiene rubber. Can be. An example of the most preferred large-diameter rubber modified graft copolymer (B.1) is an ABS graft copolymer, which is preferably prepared by graft polymerization of the monomer compound described above by bulk, solution or bulk-suspension polymerization. .

(B.2) Medium Grain Rubber Modified Vinyl Graft Copolymer

The medium-diameter rubber-modified vinyl-based graft copolymer (B.2) is preferably (B.2.1) a glass transition temperature of less than 10 ° C of 40-70% by weight of a rubbery polymer having an average particle diameter of 0.2 to 0.6 µm, preferably The monomer compound 60-30 which consists of 50-95 weight part of aromatic vinyl compounds and 5-50 weight part of vinyl cyanide compounds on one or more graft bases below 0 degreeC, More preferably, less than -10 degreeC The weight% is preferably produced by graft polymerization by an emulsion polymerization method.

The graft base of the rubbery polymer (B.2.1) is a polybutadiene rubber, acrylic rubber, ethylene / propylene rubber, styrene / butadiene rubber, acrylonitrile / butadiene rubber, isoprene rubber, acrylic rubber, ethylene-propylene-diene Copolymer (EPDM), polyorganosiloxane / polyalkyl (meth) acrylate rubber composites are selected from the group consisting of, either alone or mixtures thereof may be used.

The graft base (B.2.1) of the rubbery polymer has a glass transition temperature of less than 10 ° C, preferably less than 0 ° C, more preferably less than -10 ° C, and the gel content (as measured in toluene) is 40% by weight. % Or more, preferably 50% by weight or more.

It is preferable that the average particle diameter of a particle size rubbery polymer is 0.2-0.6 micrometer among said. If the average particle diameter is less than 0.2 μm, a sufficient low gloss effect cannot be exhibited, and impact strength is lowered. If the average particle diameter is more than 0.6 μm, rubber manufacturing time is long.

As the monomer compound (B.2.2) capable of polymerizing with the graft base (B.2.1) of the rubbery polymer, aromatic vinyl compounds include styrene, a-methylstyrene, halogen or alkyl-substituted styrene, and the like. Ronitrile, methacrylonitrile and the like. Styrene is preferable in the said aromatic vinyl compound, and acrylonitrile is preferable in a vinyl cyanide compound.

Further, graft polymerization may be performed by further adding monomers such as C ₁ -C ₈ methacrylic acid alkyl esters, C ₁ -C ₈ acrylic acid alkyl esters and maleic anhydride to the graft base (B.2.1) of the rubbery polymer. Can be. Here, the amount added is 0-40 weight% with respect to the graft copolymer total resin.

The C ₁ -C ₈ methacrylic acid alkyl esters or C ₁ -C ₈ acrylic acid alkyl esters are esters obtained from monohydryl alcohols containing 1 to 8 carbon atoms as alkyl esters of methacrylic acid or acrylic acid, respectively. to be. Specific examples thereof include methacrylic acid methyl ester, methacrylic acid ethyl ester, methacrylic acid propyl ester, acrylic acid ethyl ester or acrylic acid methyl ester.

Preferred examples of the medium-size rubber-modified vinyl-based graft copolymer (B.2) used in the present invention include styrene and acrylonitrile and optionally alkyl (meth) acrylates in polybutadiene rubber, acrylic rubber, or styrene / butadiene rubber. And graft copolymerized ester monomers in the form of a mixture. In addition, examples of the other preferred particle size rubber-modified vinyl-based graft copolymer (B.2) include those obtained by graft copolymerization of a monomer of (meth) acrylic acid methyl ester to polybutadiene rubber, acrylic rubber, or styrene / butadiene rubber. Can be. An example of the most preferable medium-diameter rubber modified graft copolymer (B.2) is an ABS graft copolymer, which is preferably prepared by graft polymerization of the monomer compound and the emulsion polymerization method.

On the other hand, the rubber-modified vinyl-based graft copolymer (B) used in the present invention is preferably used in 1 to 50 parts by weight based on the total resin composition, less than 1 part by weight sufficient impact resistance and low gloss required by the present invention It is difficult to show the property, and if it exceeds 50 parts by weight, the rigidity is lowered, which adversely affects the mechanical properties and the fluidity is worsened, which causes problems in processing of the resin.

(C) vinyl copolymer component

The vinyl copolymer (C) is preferably (C.1) styrene, a-methylstyrene, halogen or alkyl substituted styrene, C ₁ -C ₈ methacrylic acid alkyl ester, C ₁ -C ₈ acrylic acid ester or these and mixture 50 to 95% by weight of, (C.2) acrylonitrile, methacrylonitrile, C ₁ -C ₈ methacrylic acid alkyl esters, C ₁ -C ₈ acrylic acid alkyl esters, maleimide anhydride acid, C ₁ -C ₄ is a mixture of alkyl or phenyl nucleus-substituted maleimide or a vinyl copolymer, or their copolymer obtained by copolymerizing a mixture of 5 to 50% by weight thereof.

The C ₁ -C ₈ methacrylic acid alkyl esters or C ₁ -C ₈ acrylic acid alkyl esters are esters obtained from monohydryl alcohols containing 1-8 carbon atoms as esters of methacrylic acid or acrylic acid, respectively. . Specific examples thereof include methacrylic acid methyl ester, methacrylic acid ethyl ester, acrylic acid ethyl ester or methacrylic acid propyl ester, of which methacrylic acid methyl ester is particularly preferred.

The vinyl copolymer (C) may be produced as a by-product in the preparation of the rubber-modified vinyl-based graft copolymer (B), and in particular, in the case of grafting an excess monomer mixture to a small amount of rubbery polymer or as a molecular weight regulator. It is more likely to occur in the case of using an excessive amount of the chain transfer agent used.

However, the content of the vinyl copolymer (C) is not shown including the by-product of the rubber-modified vinyl-based graft copolymer (B).

The vinyl copolymer (C) used in the present invention is a monomer mixture of styrene and acrylonitrile and optionally methacrylic acid methyl ester, a monomer mixture or styrene of a-methylstyrene and acrylonitrile and optionally methacrylic acid methyl ester. Preference is given to preparing from a monomer mixture of a-methylstyrene and acrylonitrile and optionally methacrylic acid methylester. The styrene-acrylonitrile copolymer may be prepared by emulsion polymerization, suspension polymerization, solution polymerization or bulk polymerization, and it is preferable to use a weight average molecular weight of 15,000 to 300,000.

Further preferred vinyl copolymers (C) include those prepared from monomeric mixtures of methacrylic acid methyl ester monomers and optionally acrylic acid methyl esters. The methacrylic acid methyl ester polymer may be prepared by emulsion polymerization, suspension polymerization, solution polymerization, or bulk polymerization, and a weight average molecular weight of 20,000 to 250,000 is preferably used.

Another preferred vinyl copolymer (C) is a copolymer of styrene and maleic anhydride, which can be produced using continuous bulk polymerization and solution polymerization. The composition ratio of the two monomer components can be varied in a wide range, it is preferable that the content of maleic anhydride is 5 to 50% by weight. The molecular weight of the styrene-maleic anhydride copolymer may also be used in a wide range, but it is preferable to use a weight average molecular weight of 20,000 to 200,000.

In particular, the preferred vinyl copolymer (C) is a styrene-acrylonitrile copolymer.

The vinyl copolymer (C) is also used alone or in the form of a mixture of two or more thereof, and the content thereof is used in the range of 0 to 45 parts by weight based on the total resin composition.

(D) phosphate ester compound component

The phosphate ester compound (D) is preferably a phosphate ester compound of the following [Formula 2].

[Formula 2]

Wherein R ₁ , R ₂ , R ₃ and R ₄ are each independently of one another, optionally halogenated C ₁ -C ₈ alkyl, or alkyl, preferably C ₁ -C ₄ alkyl or halogen, preferably chlorine Or C ₅ -C ₆ cycloalkyl, C ₆ -C ₂₀ aryl or C ₇ -C ₂₀ aralkyl, which may each be optionally substituted with bromine, particularly preferred aryl groups are cresyl, phenyl, xenyl, propylfetyl or butyl Phenyl, and the corresponding brominated and chlorinated derivatives thereof, n may independently of one another be 0 or 1, preferably 1. N is 0-10, preferably 0.3-8, more preferably Preferably 0.5 to 5. X is a mononuclear aromatic or polynuclear aromatic group having 6 to 30 carbon atoms, preferably derived from diphenylphenol, bisphenol A, resorcinol or hydroquinone, or chlorinated or brominated derivatives thereof.)

The phosphate ester compound (D) is also preferably a phosphate ester compound of the following [Formula 3].

(3)

Wherein R ₁ , R ₂ , R ₃ and R ₄ are each independently of one another, optionally halogenated C ₁ -C ₈ alkyl, or alkyl, preferably C ₁ -C ₄ alkyl or halogen, preferably chlorine Or C ₅ -C ₆ cycloalkyl, C ₆ -C ₂₀ aryl or C ₇ -C ₂₀ aralkyl, which may each be optionally substituted with bromine, particularly preferred aryl groups are cresyl, phenyl, xenyl, propylfetyl or butyl Phenyl, and the corresponding brominated and chlorinated derivatives thereof, n may independently of one another be 0 or 1, preferably 1. N is 0-10, preferably 0.3-8, more preferably Preferably 0.5 to 5. R ₅ and R ₆ independently of _one another are C ₁ -C ₄ alkyl, preferably methyl, or halogen of chlorine or bromine Y is C ₁ -C ₇ alkylidene, C ₁ -C ₇ alkylene, C ₅ -C ₁₂ cycloalkylene, C ₅ -C ₁₂ cycloalkylidene, -O-, -S-, -SO-, -SO 2 - or denotes a -CO-, a Represents an integer of 0 to 2. Preferably, Y is a vinylidene C ₁ -C ₇ alkyl, more preferably isopropylidene or methylene.)

As the phosphate ester compound (D) used in the present invention, monophosphate (N = 0), oligophosphate (N = 1 to 10) or a mixture of monophosphate and oligophosphate can be used.

The phosphate ester compound (D) used in the present invention is used in the range of 1 to 30 parts by weight based on the total resin composition, and preferably in the range of 8 to 20 parts by weight.

(E) fluorinated polyolefin component

Fluorinated polyolefins (E) include polytetrafluoroethylene, polyvinylidene fluoride, tetrafluoroethylene / vinylidene fluoride copolymer tetrafluoroethylene / hexafluoropropylene copolymer and ethylene / tetrafluoroethylene And copolymers. These may be used independently from each other, or two or more different types may be used in combination.

The fluorinated polyolefin (E) used in the present invention preferably contains 66 to 76% by weight of fluorine, and good flame retardancy can be obtained when using a fluorinated polyolefin containing 70 to 76% by weight of fluorine. It is especially preferable because it is.

The fluorinated polyolefin (E) forms a fibrous network in the resin when mixed and extruded together with the other component resins of the present invention, thereby lowering the melt viscosity of the resin during combustion and increasing the shrinkage rate, thereby causing dripping. Prevents and improves flame retardancy.

The fluorinated polyolefin (E) may be prepared using a known polymerization method, for example, sodium at a pressure of 7 to 71 kg / cm ² and a temperature of 0 to 200 ° C., preferably 0 to 100 ° C. It can be prepared in an aqueous medium containing a free radical forming catalyst such as potassium or ammonium peroxydisulfate.

The fluorinated polyolefin (E) may be used in an emulsion state or in a powder state. The fluorinated polyolefin (E) in the emulsion state has good dispersibility in the entire resin composition, but the manufacturing process is complicated and the physical properties of the resin composition may be reduced by the remaining medium. Therefore, even if it is a powder state, if it can disperse | distribute suitably in a resin composition and can form a fibrous network structure, it is preferable to use in powder state.

The fluorinated polyolefin (E) of the present invention can also be used in the form prepared by emulsion polymerization of one or more monoethylenically unsaturated monomers in the presence of an aqueous dispersion of fluorinated polyolefin. Preferred monomer components are styrene, acrylonitrile, methyl methacrylate, and mixtures thereof, and are used as powder dried after precipitation of the polymer with acid. In addition, these powders usually contain 5 to 95% by weight, preferably 7 to 80% by weight, of fluorinated polyolefin as solid content.

The fluorinated polyolefin resin (E) which can be preferably used in the resin composition of the present invention is a fluorinated polyolefin resin having a particle size of 0.05 to 1,000 mm and a specific gravity of 1.2 to 2.3 g / cm ³ .

In the resin composition of the present invention, the fluorinated polyolefin (E) is used in the range of 0.05 to 5 parts by weight, preferably in the range of 0.1 to 1 part by weight.

(F) terpolymer component

Terpolymer (F) is a terpolymer containing ethylene, methyl acrylate and glycidyl methacrylate of the following [Formula 4] as monomers.

[Formula 4]

The terpolymer (F) consisting of ethylene, methyl acrylate and glycidyl methacrylate as monomers modifies the surface of the injection molded product of the resin composition of the present invention to increase the roughness and the diffuse reflectance of light, and the rubber of component (B) It is added together with the modified vinyl graft copolymer to exhibit a matting synergistic effect.

3-9 weight% is preferable with respect to 100 weight% of terpolymers (F), and, as for the ratio of the glycidyl methacrylate which is a functional group in the terpolymer (F) component, 5-7 weight% is more preferable. If the ratio is less than 3% by weight, the matting effect is insignificant, and if it exceeds 9% by weight, the flowability is greatly reduced due to the crosslinking reaction during processing.

In addition, the methyl acrylate ratio in the ethylene / methyl acrylate copolymer is preferably 20 to 50% by weight, more preferably 25 to 40% by weight relative to 100% by weight of the terpolymer (F). If the ratio is less than 20% by weight, the compatibility with polycarbonate may be lowered to cause a layered peeling phenomenon, the flowability is greatly lowered, and if the content is 50% by weight or more, the matting effect and impact strength may be lowered.

The terpolymer (F) may be added in the range of 0.1 to 10 parts by weight based on the total resin composition, and more preferably 0.5 to 5 parts by weight. If the amount is less than 0.1 part by weight, the matting effect is insignificant, and if it exceeds 10 parts by weight, flowability and flame retardancy are greatly reduced, and layer peeling may occur during injection molding.

In addition to the above (A) to (F) components, the following components may be further used in the resin composition of the present invention.

That is, in order to improve flame retardancy, generally well-known and commercially available flame retardants and flame retardant aids such as other organic phosphate ester compounds, phosphazene compounds, metal salt compounds, halogen-containing compounds and the like may be further used.

Metal salt compounds that can be used are generally known and are used in large quantities in compounds containing polycarbonates. All metal salt compounds suitable for the resin composition containing the polycarbonate can be used in the resin composition according to the present invention. Specifically, organic and inorganic sulfonates (eg sodium trichlorobenzene sulfonate), salts of sulfone sulfonate (eg potassium salt of diphenylsulfone sulfonate), salts of perfluorinated al sulfonic acid and Sodium aluminum hexa fluoride can be used.

Examples of suitable halogen-containing compounds are decabromodiphenylether, octabromodiphenyl, octabromodiphenylether and tetrabromobisphenol A or other oligomeric or polymeric bromine compounds derived from nucleobrominated polyphenylene ethers. .

In addition, the resin composition according to the present invention may further contain a metal compound (for example, antimony oxide, etc.) serving as a synergist. Such synergists are generally used with halogen containing compounds.

In addition, the resin composition of the present invention is an inorganic filler such as silica, silicate, alumina, glass fiber, glass beads, glass flakes, clay, talc, mica, calcium carbonate, etc. in order to further reduce surface gloss and increase heat resistance and dimensional stability. It may further contain, in this case it may be incorporated in 1 to 50 parts by weight based on 100 parts by weight of the total resin composition.

In addition, in order to increase the black color expression and conductivity of the resin composition, it may further contain an organic filler such as carbon fiber, carbon black, in this case, it may be incorporated in 1 to 30 parts by weight based on 100 parts by weight of the total resin.

In addition, the processing aid may further include an antioxidant, a heat stabilizer, a mold release agent, a lubricant, an ultraviolet stabilizer, etc., which may be used in an amount of 0.01 to 0.5 parts by weight based on 100 parts by weight of the total resin composition.

The resin composition according to the present invention is applied to molded parts for various interior materials and exterior materials that require flame retardancy and low gloss characteristics, and specifically includes, but is not limited to, housings for automobile parts, computer terminals, office equipment, and electrical and electronic products. Of course not.

Hereinafter, the present invention will be described in more detail with reference to Examples. However, the following specific examples are merely to illustrate the present invention, and the scope of the present invention is not limited to the following specific examples. In addition, the following comparative examples are only configured in order to contrast with the specific examples below, and should not be construed as being excluded from the scope of the present invention by the use of the name comparative example.

[ingredient]

(A) polycarbonate

Polycarbonate derived from bisphenol-A, intrinsic viscosity 0.55 dl / g (25 ° C., in methylene chloride)

(B) Rubber modified vinyl graft copolymer

(B.1) large particle size rubber modified vinyl graft copolymer

In the rubber-modified vinyl graft copolymer copolymerized through the bulk polymerization method, 23% by weight of acrylonitrile and 68% by weight of styrene were copolymerized to 9% by weight of polybutadiene having a particle diameter of 4 to 10 µm. The average particle diameter of rubber is 8 micrometers.

(B.2) Medium Grain Rubber Modified Vinyl Graft Copolymer

In the rubber-modified vinyl graft copolymer copolymerized through the emulsion polymerization method, 10% by weight of acrylonitrile and 30% by weight of styrene were copolymerized to 60% by weight of polybutadiene having a particle diameter of 0.1 to 0.5 µm. The average particle diameter of rubber is 0.3 micrometer.

(C) vinyl copolymer

And the weight ratio of acrylonitrile to styrene and acrylic 75: 25, weight average molecular weight (M _w) in the acrylonitrile copolymer of styrene acrylic 97,000.

(D) phosphate ester compound

(D.1) CR-733S from Daihachi, Japan, which was Resorcinol bis (diphenyl phosphate), was used.

(D.2) CR-741 from Daihachi, Japan, which was bisphenol-A bis (diphenyl phosphate) [Bisphenol-A bis (diphenyl phosphate)], was used.

(D.3) PX-200 from Daihachi, Japan, which was Lesocinol bis (di 2,6-dimethylphenyl phosphate) [Rescocinol bis (di 2,6-dimethylphenyl phosphate)], was used.

(E) fluorinated polyolefins

Teflon (trade name) 7AJ of DuPont, USA was used.

(F) terpolymers

IGETABOND 7M from Sumitomo Chemical, Japan, which is an ethylene / methylacrylate copolymer having 6% by weight of glycidyl methacrylate as a functional group and a methylacrylate content of 30% by weight based on 100% by weight of the total copolymer, was used.

[Measurement Method]

a) liquidity

It measured at 260 degreeC and 2.16 kg _f based on ASTMD1238.

b) impact strength

According to ASTM D256, the test piece was notched and evaluated. The final test result was calculated as the average of the test results of 10 test pieces.

c) glossiness

Measurement was made at 60 ^° angle according to ASTM D523.

d) heat deflection temperature

18.6kg _{f according} to ASTM D648 Measured at the load.

e) flame retardant

It was measured by the UL-94 flame retardant test method, defined by the United States Underwriter's Laboratories (UL), which burned after 10 seconds of sparking of the burner on a vertically fixed specimen of fixed size. It is a method of evaluating flame retardancy from drip properties.

Combustion time is the length of time that the specimen continues flame burning after the flame has been dropped away, and the flammability of the cotton by drips causes the flap of the flap to be about 300 mm below the bottom of the specimen, And the flame retardancy grades are divided according to Table 1 below.

division V-2 V-1 V-0 1st / 2nd combustion time of each sample 30 seconds or less 30 seconds or less 10 seconds or less Total combustion time of five samples 250 seconds or less 250 seconds or less 50 seconds or less Cotton ignition by drip has exist none none

[Examples 1-5 and Comparative Examples 1-3]

The composition shown in Table 2 was uniformly dispersed by mixing in a Henschel mixer and then extruded at a temperature of 240 to 270 ° C. in a twin screw melt mixing extruder having L / D = 40 and ф = 25 mm to form pellets, and 80 to 100 ° C. After drying for 4 hours or more in a hot air dryer, the specimen was injection molded at a temperature of 240 ~ 270 ℃.

 Example Comparative example One 2 3 4 5 One 2 3 Furtherance ( Parts by weight ) (A) polycarbonate 82 82 82 82 82 82 82 82 (B) Vinyl Graft Copolymer (B.1) 10 10 10 10 10 10 - 10 (B.2) 5 5 5 5 5 5 6.5 5 (C) vinyl copolymer 3 3 3 3 3 3 11.5 3 (D) phosphate ester compound (D.1) 16 - - - - - - - (D.2) - 16 - 16 8 16 16 25 (D.3) - - 16 - 8 - - - (E) fluorinated polyolefins 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 (F) terpolymers One One One 3 3 - One 12

The results of measuring physical properties according to the above method are shown in Table 3 below.

 Example Comparative example One 2 3 4 5 One 2 3 Properties Fluidity (g / 10min) 30 28 27 25 24 31 30 8 Impact Strength (1/8 "kg _f cm / cm) 50 54 55 52 52 56 41 32 Glossiness (%) 41 42 42 36 37 78 63 15 Heat Deflection Temperature (℃) 86 88 90 86 87 90 88 74 UL 94 flame retardant (2.0mm) V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-2 Total combustion time (seconds) 19 22 23 31 28 21 24 -

As shown in Table 3, Examples 1 to 5 were not only excellent in the matting effect and flame retardancy, but also excellent in all of fluidity, impact strength, and heat resistance.

On the other hand, in Comparative Example 1, in which the terpolymer (F) component was not applied, the glossiness was low as 78%.

In addition, Comparative Example 2, in which the large-diameter rubber-modified vinyl graft copolymer (B.1) was not applied, had a lower impact strength and a glossiness of 63%, which showed better low gloss characteristics than that of Comparative Example 1. However, it did not show sufficient low gloss compared to the examples.

On the other hand, Comparative Example 3 using more than 10 parts by weight of the terpolymer (F) component showed an effect of improving the low gloss, but fluidity and flame retardancy was sharply lowered.

Claims (17)

In an aromatic polycarbonate resin composition containing a phosphate ester compound, (B) a rubber modified vinyl graft copolymer comprising a rubbery polymer having an average particle diameter of 0.2 to 10 µm; And (F) a terpolymer comprising ethylene, methyl acrylate and glycidyl methacrylate as monomers; low gloss flame retardant polycarbonate resin composition comprising a. (A) 50 to 99 parts by weight of aromatic polycarbonate; (B) 1 to 50 parts by weight of a rubber-modified vinyl graft copolymer comprising a rubbery polymer having an average particle diameter of 0.2 to 10 µm; (D) 1 to 30 parts by weight of the phosphate ester compound; 0.05 to 5 parts by weight of (E) fluorinated polyolefin; And (F) 0.1 to 10 parts by weight of terpolymer containing ethylene, methyl acrylate and glycidyl methacrylate as monomers; low gloss flame retardant polycarbonate resin composition comprising a. The method of claim 2, The resin composition further comprises a vinyl copolymer (C) in the range of more than 0 parts by weight and 45 parts by weight or less, low-gloss flame retardant polycarbonate resin composition. The method of claim 2, The aromatic polycarbonate (A) has a viscosity average molecular weight (M _v ) measured in methylene chloride solution is 20,000 to 30,000, low gloss flame retardant polycarbonate resin composition. The method of claim 2, The rubber-modified vinyl-based graft copolymer (B) comprises a rubber-modified vinyl-based graft copolymer comprising a rubbery polymer having a (B.1) average particle diameter of 1 to 10 µm. Carbonate resin composition. The method of claim 2, The rubber modified vinyl graft copolymer (B), (B.1) 10 wt% or more but less than 100 wt% of the rubber-modified vinyl-based graft copolymer comprising a rubbery polymer having an average particle diameter of 1 to 10 µm; And (B.2) A low-gloss flame retardant polycarbonate resin composition comprising a rubber-modified vinyl-based graft copolymer comprising a rubbery polymer having an average particle diameter of 0.2 to 0.6 µm in excess of 0% by weight to 90% by weight. The method of claim 5, The rubber-modified vinyl-based graft copolymer (B.1) is 50 to 95 parts by weight of an aromatic vinyl compound and 5 to 50 parts by weight of a vinyl cyanide compound to 5 to 20% by weight of a rubbery polymer having an average particle diameter of 1 to 10 µm. A low gloss flame retardant polycarbonate resin composition, which is prepared by graft polymerization of a monomer mixture of 80 to 95% by weight. The method of claim 7, wherein The rubber-modified vinyl-based graft copolymer (B.1) is a low gloss flame retardant polycarbonate resin composition, characterized in that prepared by bulk, solution or bulk-suspension polymerization. The method of claim 6, The rubber-modified vinyl-based graft copolymer (B.2) is composed of 50 to 95 parts by weight of an aromatic vinyl compound and 5 to 50 parts by weight of a vinyl cyanide compound in 40 to 70% by weight of a rubbery polymer having an average particle diameter of 0.2 to 0.6 µm. A low gloss flame retardant polycarbonate resin composition, which is prepared by graft polymerization of a monomer mixture of 60 to 30% by weight. The method of claim 9, The rubber-modified vinyl-based graft copolymer (B.2) is a low gloss flame retardant polycarbonate resin composition, characterized in that prepared by emulsion polymerization. The method of claim 3, wherein The vinyl copolymer (C) is, (C.1) 50 to 95% by weight of styrene, a-methylstyrene, halogen or alkyl substituted styrene, C ₁ -C ₈ methacrylic acid alkyl esters, C ₁ -C ₈ acrylic esters or mixtures thereof; And (C.2) Acrylonitrile, methacrylonitrile, C ₁ -C ₈ methacrylic acid alkyl esters, C ₁ -C ₈ acrylic acid alkyl esters, maleic anhydride, C ₁ -C ₄ alkyl or phenyl nuclear substitution Maleimide or a mixture of 5 to 50% by weight thereof; Low-gloss flame retardant polycarbonate resin composition characterized in that the copolymer obtained by copolymerizing or a copolymer of these copolymers. The method of claim 2, The phosphate ester compound (D) is a low gloss flame retardant polycarbonate resin composition, characterized in that the phosphate ester compound of the formula [2]. [Formula 2]

Wherein R ₁ , R ₂ , R ₃ and R ₄ are each, independently of one another, C ₅ -C ₆ cycloalkyl, which may be optionally halogenated C ₁ -C ₈ alkyl, or each optionally substituted with alkyl or halogen, C ₆ -C ₂₀ aryl or C ₇ -C ₂₀ aralkyl, n is independently of each other 0 or 1, N is 0-10, X is a mononuclear aromatic or polynuclear aromatic group having 6 to 30 carbon atoms.) The method of claim 2, The phosphate ester compound (D) is a low gloss flame retardant polycarbonate resin composition, characterized in that the phosphate ester compound of the formula [3]. (3)

Wherein R ₁ , R ₂ , R ₃ and R ₄ are each, independently of one another, C ₅ -C ₆ cycloalkyl, which may be optionally halogenated C ₁ -C ₈ alkyl, or each optionally substituted with alkyl or halogen, C ₆ -C ₂₀ aryl or C ₇ -C ₂₀ aralkyl, n is independently of each other 0 or 1, N is 0-10, R ₅ and R ₆ are independently of each other C ₁ -C ₄ alkyl or halogen And Y is C ₁ -C ₇ alkylidene, C ₁ -C ₇ alkylene, C ₅ -C ₁₂ cycloalkylene, C ₅ -C ₁₂ cycloalkylidene, -O-, -S-, -SO-, -SO ₂ -or -CO-, and a represents an integer of 0 to 2). The method of claim 2, Said phosphate ester compound (D) is a solely or a mixture of resorcinol bis (diphenyl phosphate), bisphenol-A bis (diphenyl phosphate) or resorcinol bis (di 2,6-dimethylphenyl phosphate). Low-gloss flame retardant polycarbonate resin composition, characterized in that. The method of claim 2, The terpolymer (F) is a low-gloss flame retardant polycarbonate resin composition, characterized in that the glycidyl methacrylate in the terpolymer is 3 to 9% by weight relative to 100% by weight of the terpolymer. The method of claim 2, The terpolymer (F) is a low gloss flame retardant polycarbonate resin composition, characterized in that the methyl acrylate in the terpolymer is 20 to 50% by weight relative to 100% by weight of the terpolymer. A molded article prepared using the polycarbonate resin composition according to any one of claims 1 to 16.