KR101510407B1 - A polysiloxane-polycarbonate resin composition having excellent flame retardance and impact resistance simultaneously and a molded article thereof - Google Patents

Abstract

The present invention relates to a polysiloxane-polycarbonate resin composition having excellent flame retardancy and impact resistance at the same time, and a molded article thereof, and more particularly to a polysiloxane-polycarbonate resin composition containing a polysiloxane-polycarbonate resin, a polyethylene terephthalate resin and a polycarbonate resin, To a polysiloxane-polycarbonate resin composition having improved mechanical strength and flame retardancy, and to molded articles thereof.

Description

TECHNICAL FIELD [0001] The present invention relates to a polysiloxane-polycarbonate resin composition having excellent flame retardancy and impact resistance at the same time, and to a molded article thereof. BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polysiloxane-

The present invention relates to a polysiloxane-polycarbonate resin composition having excellent flame retardancy and impact resistance at the same time, and a molded article thereof, and more particularly to a polysiloxane-polycarbonate resin composition containing a polysiloxane-polycarbonate resin, a polyethylene terephthalate resin and a polycarbonate resin, To a polysiloxane-polycarbonate resin composition having improved mechanical strength and flame retardancy, and to molded articles thereof.

The polycarbonate / vinyl copolymer resin composition is widely used in automobile parts, computer housings or other office equipment housings because it exhibits improved workability while maintaining excellent impact resistance, heat resistance and mechanical strength. Flame retardancy is also required due to its characteristics.

In general, the flame retarding system for PET and PC resin alloys, in which a polycarbonate (PC) resin having self-extinguishing properties is incorporated in a polyethylene terephthalate (PET) resin, includes a phenoxy compound of tetrabisphenol A A fluorinated olefin based resin is used as a phenoxy-terminated carbonate oligomer of Tetrabromobisphenol A or triphenylphosphate as a phosphorus compound and an anti-dripping agent.

U.S. Patent No. 4,692,488 and U.S. Patent No. 5,061,745 disclose a flame retardant resin composition prepared by mixing a diphenol-based aromatic polycarbonate resin with a monomer-type phosphate ester flame retardant.

However, halogen-based flame retardants and phosphorus-based flame retardants used in such resin compositions are required to minimize their use as harmful components to the human body. Further, the use of such a low-molecular-weight flame retardant agent has a problem in that the physical properties (for example, impact strength, etc.) of the article are lowered and the so-called "plate-out" phenomenon occurs in which the added flame retardant agent migrates to the surface of the molded article It is also said.

Accordingly, there is a demand for development of a flame retardant resin composition capable of remarkably improving the flame retardancy while minimizing the use of the halogen-based flame retardant and phosphorus flame retardant, and at the same time having excellent physical properties such as impact resistance, flowability and workability.

Disclosure of Invention Technical Problem [8] Accordingly, the present invention has been made keeping in mind the above problems occurring in the prior art, and it is an object of the present invention to provide a flame- A polysiloxane-polycarbonate resin composition excellent in physical properties and a molded article thereof.

The present invention provides a flame retardant polysiloxane-polycarbonate resin composition comprising (A) a polysiloxane-polycarbonate resin, (B) a polyethylene terephthalate resin, and (C) a polycarbonate resin.

According to another aspect of the present invention, there is provided a molded article of the flame retardant polysiloxane-polycarbonate resin composition.

The polysiloxane-polycarbonate resin composition according to the present invention can remarkably improve flame retardancy while minimizing the use or use of a halogen-based flame retardant and a phosphorus-based flame retardant, and at the same time has excellent properties such as impact resistance, flowability, Such as office equipment and housings of electrical and electronic products, which require the use of the above-mentioned components.

Hereinafter, the present invention will be described in more detail.

(A) Polysiloxane - Polycarbonate resin ( Si - PC  Suzy)

The flame retardant resin composition of the present invention comprises a polysiloxane-polycarbonate resin. The content of the polysiloxane-polycarbonate resin is preferably 5 to 80 parts by weight, more preferably 10 to 70 parts by weight, per 100 parts by weight of the total composition. If the content of the polysiloxane-polycarbonate resin in the resin composition of the present invention is less than 5 parts by weight per 100 parts by weight of the total composition, sufficient flame retardancy can not be exhibited and low-temperature impact strength may be lowered. On the contrary, if it exceeds 80 parts by weight, transparency, The physical properties such as impact strength at room temperature may be lowered.

According to one preferred embodiment of the present invention, the polysiloxane-polycarbonate resin included in the resin composition of the present invention comprises a hydroxyl-terminated siloxane of the following formula (1) and a polycarbonate block of the following formula (3) as repeating units.

[Chemical Formula 1]

In Formula 1,

R ₁ independently represents a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group or an aryl group. For example, the halogen atom may be Cl or Br, and the alkyl group may be an alkyl group having 1 to 13 carbon atoms, such as methyl, ethyl or propyl, and the alkoxy group may be an alkoxy group having 1 to 13 carbon atoms such as methoxy, Ethoxy or propoxy, and the aryl group may be an aryl group having 6 to 10 carbon atoms, such as phenyl, chlorophenyl or tolyl.

R ₂ independently represents a hydrocarbon group or a hydroxy group having 1 to 13 carbon atoms. For example, R ₂ is an alkyl group or alkoxy group having 1 to 13 carbon atoms, an alkenyl group or alkenyloxy group having 2 to 13 carbon atoms, a cycloalkyl group or cycloalkoxy group having 3 to 6 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, An aralkyl group or an aralkoxy group having 7 to 13 carbon atoms, or an alkaryl group or an alkaryloxy group having 7 to 13 carbon atoms.

R ₃ independently represents an alkylene group having 2 to 8 carbon atoms.

A is X or NH-X-NH wherein X is a linear or branched aliphatic group having 1 to 20 carbon atoms, a cycloalkylene group (e.g., a cycloalkylene group having 3 to 6 carbon atoms), or a halogen atom, an alkyl group, Or an unsubstituted mono- or polycyclic arylene group having 6 to 30 carbon atoms, which is substituted with an aryl group or a carboxyl group. For example, X may be an aliphatic group substituted with a halogen atom or an unsubstituted aliphatic group, an aliphatic group containing an oxygen, nitrogen or sulfur atom in the main chain, or an aryl group which may be derived from bisphenol A, resorcinol, hydroquinone or diphenyl phenol And may be represented, for example, by the following formulas (2a) to (2h).

(2a)

(2b)

[Chemical Formula 2c]

(2d)

[Formula 2e]

(2f)

[Chemical Formula 2g]

[Chemical Formula 2h]

m is independently an integer of 0 to 10, preferably an integer of 0 to 4.

n independently represents an integer of 2 to 1,000, preferably an integer of 2 to 500, more preferably an integer of 5 to 100.

In one embodiment, the hydroxy-terminated siloxane of Formula 1 may be the reaction product of a hydroxy-terminated siloxane of Formula 1a with an acyl compound (i.e., a hydroxy-terminated siloxane having an ester linkage).

[Formula 1a]

R ₁ , R ₂ , R ₃ , m and n are as defined in the above formula (1).

The hydroxy-terminated siloxane of formula (1a) can be prepared, for example, by synthesizing a compound of formula (1b) having a double bond with a hydroxyl group and a compound of formula (1c) containing silicon at a molar ratio of 2: 1 .

[Chemical Formula 1b]

In Formula 1b, R < _{1 >} And m are the same as defined in the formula (1), and k represents an integer of 1 to 7.

[Chemical Formula 1c]

In the above formula (1c), R ₂ and n are the same as defined in the above formula (1).

)를 사용할 수 있으나, 반드시 이에 한정되는 것은 아니다. 또한 상기 화학식 1a의 히드록시 말단 실록산의 제조와 관련하여 미국특허 US 6,072,011호를 참조할 수 있다.Specifically, the hydroxyl-terminated siloxane of formula (1a) is a siloxane monomer of Dow Corning Corporation

) May be used, but the present invention is not limited thereto. Reference may also be made to U.S. Patent No. 6,072,011 for the preparation of the hydroxy-terminated siloxane of Formula 1a above.

The acyl compound used in the preparation of the hydroxy-terminated siloxane of the above formula (1) may have a mixed structure including, for example, aromatic, aliphatic, aromatic and aliphatic groups. When the acyl compound is aromatic or mixed, it may have 6 to 30 carbon atoms. When the acyl compound is aliphatic, it may have 1 to 20 carbon atoms. The acyl compound may further contain a halogen, an oxygen, a nitrogen or a sulfur atom.

In another embodiment, the hydroxy-terminated siloxane of Formula 1 may be the reaction product of the hydroxy-terminated siloxane of Formula 1a with a diisocyanate compound (i.e., a hydroxy-terminated siloxane having a urethane bond).

Here, the diisocyanate compound may be, for example, 1,4-phenylenediisocyanate, 1,3-phenylenediisocyanate or 4,4'-methylenediphenyl diisocyanate. (4,4'-methylenediphenyl diisocyanate).

The polysiloxane-polycarbonate resin included in the resin composition according to the present invention includes a polycarbonate block represented by the following formula (3) as a repeating unit in addition to the hydroxyl-terminated siloxane of the above-mentioned formula (1).

(3)

In Formula 3,

R ₄ is (C 1 to 20) alkyl group (e.g., an alkyl group having a carbon number of 1 to 13), a cycloalkyl group (e.g., a cycloalkyl group having 3 to 6 carbon atoms), an alkenyl group (e.g., an alkenyl group having 2 to 13), An alkoxy group (e.g., an alkoxy group having 1 to 13 carbon atoms), a halogen atom, or an aromatic hydrocarbon group substituted or unsubstituted with nitro and having 6 to 30 carbon atoms.

Here, the aromatic hydrocarbon group may be derived from a compound having a structure represented by the following formula (3a).

[Chemical Formula 3]

In the above formula (3a)

X is an alkylene group, a linear, branched or cyclic alkylene group having no functional group, or a linear, branched or cyclic alkylene group containing a functional group such as sulfide, ether, sulfoxide, sulfone, ketone, naphthyl, Lt; / RTI > Preferably, X is a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms and 3 to 6 carbon atoms.

Each R ₆ independently represents a hydrogen atom, a halogen atom, or an alkyl group, for example, a linear, branched or cyclic alkyl group having from 1 to 20 carbon atoms and having from 3 to 20 (preferably from 3 to 6) carbon atoms.

n and m independently represent an integer of 0 to 4;

The compound of formula (3a) may be, for example, bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) phenylmethane, bis ) - (4-isobutylphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 1- Bis (4-hydroxyphenyl) ethane, 1-naphthyl-1,1-bis (4-hydroxyphenyl) (4-hydroxyphenyl) decane, 2-methyl-1,1-bis (4-hydroxyphenyl) propane, 2,2- Bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) pentane, Bis (4-hydroxyphenyl) propane, bis (3-methyl-4-hydroxyphenyl) propane, 2,2- , 4,4-bis (4-hydroxyphenyl) heptane, diphenyl-bis (4-hydroxyphenyl) Resorcinol, Hydroquine, 4,4'-dihydroxyphenyl ether [bis (4-hydroxyphenyl) ether], 4,4'-dihydroxy-2,5-di Dihydroxy-3,3'-dichlorodiphenyl ether, bis (3,5-dimethyl-4-hydroxyphenyl) ether, bis (3,5-dichloro- Hydroxyphenyl) ether, 1,4-dihydroxy-2,5-dichlorobenzene, 1,4-dihydroxy-3-methylbenzene, 4,4'-dihydroxydiphenol [p, Dihydroxyphenyl], 3,3'-dichloro-4,4'-dihydroxyphenyl, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1- (3,5-dimethyl-4-hydroxyphenyl) cyclohexane, 1,1-bis (3,5- (4-hydroxyphenyl) decane, 1,1-bis (4-hydroxyphenyl) decane, 1,1- Bis (4-hydroxyphenyl) propane, 1,4-bis (4- (4-hydroxyphenyl) butane, 2,2-bis (3-chloro-4-hydroxyphenyl) Bis (3,5-dimethyl-4-hydroxyphenyl) methane, bis (3,5-dichloro-4-hydroxyphenyl) methane, 2,2- Bis (3,5-dibromo-4-hydroxyphenyl) propane, 2,2-bis -Bis (4-hydroxyphenyl) sulfone], bis (3,5-dimethyl-4-hydroxyphenyl) Sulfone, bis (3-chloro-4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfide, bis , Bis (3,5-dimethyl-4-hydroxyphenyl) sulfide, bis (3,5-dibromo-4-hydroxyphenyl) sulfoxide, 4,4'-dihydroxybenzophenone, ', 5,5'-tetramethyl-4,4'-dihydroxybenzophe , 4,4'-dihydroxy-diphenyl, methyl may be a hydroquinone, 1,5-dihydroxynaphthalene, and 2,6-dihydroxy naphthalene, but is not limited thereto. Representative examples include 2,2-bis (4-hydroxyphenyl) propane (bisphenol A). Other functional dihydric phenols can be found in US Pat. Nos. US 2,999,835, US 3,028,365, US 3,153,008 and US 3,334,154, and the dihydric phenols may be used singly or in combination of two or more. Can be used.

In a preferred embodiment, the polysiloxane-polycarbonate copolymer has the structure of the following formula (4a) or (4b).

[Chemical Formula 4a]

(4b)

In the general formulas (4a) and (4b), R ₁ , R ₂ , R ₃ , m and n are the same as defined in the above formula (1), R ₄ is as defined in the above formula (3), and 1 represents an integer of 1 to 20.

In the polysiloxane-polycarbonate resin, the content ratio of the hydroxy-terminated siloxane: polycarbonate block is preferably 50 to 99: 50 to 1 as a weight ratio. If the relative content of the siloxane portion in the resin is less than the lower limit, the flame retardancy and the low-temperature impact strength may be lowered. On the other hand, if the relative content is less than the above range, the relative content of the polycarbonate portion in the resin is decreased to deteriorate the transparency, fluidity, heat resistance, The manufacturing cost may increase.

The polysiloxane-polycarbonate resin, and has a measured in methylene chloride solution, preferably from 15,000 to 200,000, more preferably 15,000 to 70,000 viscosity-average molecular weight (M _v). If the viscosity average molecular weight of the polysiloxane-polycarbonate resin is less than 15,000, the mechanical properties may be significantly deteriorated. If the viscosity average molecular weight is more than 200,000, a problem may arise in processing the resin due to an increase in melt viscosity.

The polysiloxane-polycarbonate resin may be a homopolymer, a copolymer, or a blend thereof. The polysiloxane-polycarbonate resin may be partially or wholly substituted with an ester precursor, for example, an aromatic polyester-carbonate resin obtained by polymerization reaction in the presence of a bifunctional carboxylic acid, or a copolycarbonate copolymerized with a silicone resin .

(B) Polyethylene terephthalate  Suzy( PET  Suzy)

The flame retardant resin composition of the present invention includes a polyethylene terephthalate resin. The content of the polyethylene terephthalate resin is preferably 5 to 80 parts by weight, more preferably 10 to 70 parts by weight per 100 parts by weight of the total composition. If the content of the polyethylene terephthalate resin in the resin composition of the present invention is less than 5 parts by weight based on 100 parts by weight of the total composition, there may be a problem in processing depending on the flowability, and if it exceeds 80 parts by weight, flame retardancy and physical properties may be deteriorated.

According to a preferred embodiment of the present invention, as the polyethylene terephthalate resin, a polymer having a repeating unit represented by the following formula (5) may be used:

[Chemical Formula 5]

In the general formula (5), n represents an integer of 1 or more, and preferably represents an integer of 95 to 120.

The polyethylene terephthalate resin used in the flame retardant resin composition of the present invention is not particularly limited within the range defined by the above formula but preferably has a melting point of 255 to 265 DEG C and an intrinsic viscosity of 0.43 to 0.82 dl / It is more preferable since it is excellent in moldability.

(C) Polycarbonate resin ( PC  Suzy)

The flame retardant resin composition of the present invention comprises a polycarbonate resin. The content of the polycarbonate resin may preferably be 5 to 80 parts by weight, more preferably 10 to 70 parts by weight, per 100 parts by weight of the total composition. If the content of the polycarbonate resin in the resin composition of the present invention is less than 5 parts by weight based on 100 parts by weight of the total composition, the effect of improving properties such as transparency, fluidity, heat resistance and impact strength at room temperature may be insignificant. On the other hand, The strength may be lowered.

The polycarbonate resin that can be included in the resin composition of the present invention is preferably an aromatic polycarbonate resin, but the type thereof is not particularly limited, and thermoplastic aromatic polycarbonate resins commonly used in the art can be used.

In one embodiment, the aromatic polycarbonate resin may be prepared from a divalent phenol, a carbonate precursor, and a molecular weight modifier.

The dihydric phenol may be one of the monomers constituting the aromatic polycarbonate resin, and may be represented by the following formula (6).

[Chemical Formula 6]

In Formula 6,

X is an alkylene group, a linear, branched or cyclic alkylene group having no functional group, or a linear, branched or cyclic alkylene group containing a functional group such as sulfide, ether, sulfoxide, sulfone, ketone, naphthyl, Lt; / RTI > Preferably, X is a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms and 3 to 6 carbon atoms.

R ₁ And R ₂ independently represent a hydrogen atom, a halogen atom, or an alkyl group, for example, a linear, branched or cyclic alkyl group having 3 to 20 carbon atoms (preferably 3 to 6 carbon atoms) having 1 to 20 carbon atoms.

n and m independently represent an integer of 0 to 4;

Non-limiting examples of the dihydric phenols include bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) phenylmethane, bis (4- hydroxyphenyl) naphthylmethane, bis Ethyl-1,1-bis (4-hydroxyphenyl) propane, 1-phenyl-1, Bis (4-hydroxyphenyl) ethane, 1-naphthyl-1,1-bis (4-hydroxyphenyl) (4-hydroxyphenyl) decane, 2-methyl-1,1-bis (4-hydroxyphenyl) propane and 2,2-bis (4-hydroxyphenyl) propane (bisphenol A) Preferably, bisphenol A is used.

The carbonate precursor is another monomer constituting the aromatic polycarbonate resin, and examples thereof include carbonyl chloride (phosgene), carbonyl bromide, bishaloformate, diphenyl carbonate, dimethyl carbonate and the like . Preferably, carbonyl chloride (phosgene) is used.

As the molecular weight modifier, a monofunctional compound similar to the monomer used in the production of the thermoplastic aromatic polycarbonate resin may be used. Non-limiting examples of molecular weight regulators include phenol based derivatives such as para-isopropylphenol, para-tert-butylphenol (PTBP), para-cumylphenol, para- -Isononylphenol and the like), aliphatic alcohols and the like. Preferably, para-tert-butylphenol (PTBP) is used.

Examples of the aromatic polycarbonate resin produced from such a dihydric phenol, a carbonate precursor and a molecular weight modifier include linear polycarbonate resin, branched polycarbonate resin, copolycarbonate resin and polyester carbonate resin , And these may be used alone or in combination of two or more.

The preferred aromatic polycarbonate having a viscosity average molecular weight of resin _(v M, as measured in methylene chloride solution) is from 15,000 to 40,000, more preferably 17,000 to 30,000, most preferably 20,000 to 30,000. If the viscosity average molecular weight of the aromatic polycarbonate resin is less than 15,000, mechanical properties such as impact strength and tensile strength may be significantly deteriorated. If the viscosity average molecular weight is more than 40,000, the melt viscosity may increase, which may cause problems in resin processing.

(D) Impact modifier

In addition to the above-mentioned components, the flame retardant resin composition of the present invention may further include an impact modifier in order to secure an appropriate impact strength required for electric and electronic parts. The impact modifier that can be used in the present invention is preferably an acrylic impact modifier, and more preferably a core-shell type acrylic impact modifier. Compared with a core-shell type MBS impact modifier generally used in the alloys of polycarbonate resin and polyester resin, the acrylic impact modifier has a core-butadiene rubber structure Has a relatively higher glass transition temperature and thermal stability than MBS type impact modifier, and has a short cycle time in injection molding. The acrylic material used as the core is not particularly limited, but is ethyl acryl rubber, butyl acryl rubber or a combination thereof, preferably butyl acryl rubber, and the preferred core diameter is 200 to 350 nm. The acrylic material used as the shell is not particularly limited, but styrene acrylonitrile, polymethyl methacrylate or a combination thereof, preferably polymethyl methacrylate.

When an impact modifier is used in the flame retardant resin composition of the present invention, the content of the impact modifier may preferably be 1 to 10 parts by weight, more preferably 1 to 5 parts by weight, per 100 parts by weight of the composition. If the amount of the impact modifier is less than 1 part by weight per 100 parts by weight of the total composition, the effect of improving the impact strength may be insignificant. If the amount is more than 10 parts by weight, the flame retardant property may be deteriorated.

(E) Halogen Flame retardant

The flame retardant resin composition of the present invention can remarkably improve the flame retardancy while minimizing the use or the use of the halogen-based flame retardant. However, this does not mean that the use of the halogen-based flame retardant is completely excluded in the flame-retardant resin composition of the present invention, and a halogen-based flame retardant suitably reduced in comparison with the conventional one can be used within the range of achieving the object of the present invention .

When a halogen-based flame retardant is used in the flame retardant resin composition of the present invention, a brominated epoxy-based flame retardant, which is a bromine-based compound, may be preferably used. The brominated epoxy flame retardant has excellent thermal stability and heat aging characteristics. The brominated epoxy flame retardant usable in the present invention is preferably a high molecular weight brominated epoxy flame retardant, more preferably an average molecular weight of 58,000 to 68,000, and more preferably an average molecular weight of 61,000 to 65,000.

The brominated epoxy flame retardant that can be used in the present invention includes, but is not limited to, polymers having repeating units of formula (7)

(7)

In formula (7), 1 represents an average degree of polymerization of 95 to 120, preferably an average degree of polymerization in the range of 105 to 115.

The brominated epoxy flame retardant of the formula (7) is a non-blooming type having a bromine content of 53% by weight and a specific gravity of 1.8. Also, it is different from polybrominated biphenyls (PBBs) and polybrominated diphenyl ethers (PBDEs) regulated by the Restriction of Hazardous Substances (RoHS) restriction. And can be widely applied to housings of electric / electronic parts.

When a halogen-based flame retardant is used in the flame retardant resin composition of the present invention, the content thereof may be preferably 1 to 15 parts by weight, more preferably 1 to 10 parts by weight, per 100 parts by weight of the total composition. If the amount of the halogen-based flame retardant is less than 1 part by weight per 100 parts by weight of the composition, the flame retardancy improvement effect may be insufficient. If the amount is more than 15 parts by weight, the rigidity of the material may increase and the tensile elongation may be rapidly lowered.

(F) Take over Flame retardant

The flame retardant resin composition of the present invention can remarkably improve the flame retardancy while minimizing the use of the phosphorus-based flame retardant or its use. However, this does not mean that the use of the phosphorus-based flame retardant is completely excluded in the flame-retardant resin composition of the present invention, and the amount of the phosphorus-based flame retardant suitably reduced compared with the conventional one can be used within the range of achieving the object of the present invention.

When a phosphorus-based flame retardant is used in the flame retardant resin composition of the present invention, it can be used without any particular limitation as long as it is a monomer-type phosphorus-based flame retardant. Preferred phosphorus flame retardants are triphenyl phosphate, tris (2,6-xylyl) phosphate, resorcinol bis (di xylenelyl phosphate), 4,4'-biphenyl- bis (di xylenelylphosphate), bisphenol A bis (Di-xylene ylphosphate) or hydroquinone bis (di-xylene yl phosphate), and more preferably triphenyl phosphate.

When a phosphorus-based flame retardant is used in the flame retardant resin composition of the present invention, its content may be preferably 0.1 to 1 part by weight, more preferably 0.1 to 0.5 part by weight per 100 parts by weight of the total composition. If the amount of the phosphorus-based flame retardant is less than 0.1 part by weight per 100 parts by weight of the total composition, the effect of improving the flame retardancy may be insufficient. If the amount is more than 1 part by weight, the thermal stability of the material may be deteriorated.

(G) Auxiliary Flame retardant

In addition to the above-mentioned components, the flame retardant resin composition of the present invention may further comprise an auxiliary flame retardant. In the case of using the flame retardant auxiliary in the flame retardant resin composition of the present invention, the use of the fluorinated polyolefin resin forms a fibrous network structure in the composition to suppress the flow of the base resin at the time of combustion and increase the shrinkage rate, Dripping can be prevented. The fluorinated polyolefin-based resins usable in the present invention include, but are not limited to, polytetrafluoroethylene (PTFE); Polyvinylidene fluoride; Copolymers of tetrafluoroethylene and vinylidene fluoride; Copolymers of tetrafluoroethylene and hexafluoropropylene; Styrene acrylonitrile-modified polytetrafluoroethylene, acrylic-modified polytetrafluoroethylene or a combination thereof, preferably acrylic-modified polytetrafluoroethylene. More preferably, the amount of polytetrafluoroethylene in the acrylic modified polytetrafluoroethylene is from 45 to 55% by weight, and the acrylic modified polytetrafluoroethylene is preferably a powder or granule type. The fluorinated polyolefin-based resins exemplified above may be used independently of each other, or a mixture of two different types may be used.

When an auxiliary flame retardant is used in the flame retardant resin composition of the present invention, its content may be preferably 0.1 to 2 parts by weight, more preferably 0.1 to 1 part by weight per 100 parts by weight of the composition. If the amount of the auxiliary flame retardant is less than 0.1 part by weight per 100 parts by weight of the composition, the effect of improving flame retardancy may be insufficient. If the amount is more than 2 parts by weight, there is a problem in extrusion processing, and flowability and impact resistance may be lowered.

In addition to the above-described components, the flame retardant resin composition of the present invention may further contain conventional additives such as heat stabilizers, antioxidants, nucleating agents, lubricants, pigments, dyes, light stabilizers or black master batches, May be further included.

But are not limited to, the thermal stabilizers that may be used in the present invention include bisphenol A epoxy resins, monocarbodiimides or polycarbodiimides; Antioxidants include tris (nonylphenyl) phosphite, (2,4,6-tri-tert-butylphenyl) (2-butyl- Bis (2,4-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite or bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, Organic antioxidants such as distearyl pentaerythritol diphosphite, antioxidants such as pentaerythritol tetrakis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate or octadecyl- A phenol-based antioxidant such as - (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, a thioester-based antioxidant such as pentaerythritol tetrakis (4,6-di-tert-butylphenyl) phosphate; the lubricant comprises a phenol, a silane, an ionomer, sodium 2,2'-methylene- (2'-hydroxyphenyl) -benzotriazole, 2-hydroxy-benzophenone, 2- (2'-hydroxyphenyl) benzothiophene, (1-methyl-1-phenylethyl) phenol, 2- (4,6-di Phenyl-1,3,5-triazin-2-yl) -5-hexyloxy-phenol, 2- (2H-benzotriazol- Methylbutyl) phenol or 2,2'-methylenebis (6- (2H-benzotriazol-2-yl)) - 4- (1,1,3,3-tetramethylbutyl) phenol; The amount of the additive that can be included in the flame retardant resin composition of the present invention can be selected without limitation within the range of usually used, but preferably the flame retardant resin composition of the present invention Are each independently from 0.2 to 3 parts by weight based on 100 parts by weight.

According to another aspect of the present invention, there is provided a molded article of the flame retardant polysiloxane-polycarbonate resin composition of the present invention as described above.

The method of molding the composition of the present invention into a molded article is not particularly limited, and a molded article can be manufactured by a method generally used in the plastic molding field.

The molded article produced from the flame retardant thermoplastic resin composition of the present invention can be usefully applied to interior materials and exterior materials that require flame retardancy, such as computer terminals, office equipment, housings of electrical and electronic products, and the like.

Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples. However, the scope of the present invention is not limited thereto.

[ Polysiloxane - Polycarbonate resin Manufacturing example ]

<Hydroxy terminal Siloxane  Manufacturing>

A condenser was attached to a 500 mL three-necked flask. 0.4 mol of monomer BY16-799 of Dow corning was dissolved in 300 mL of chloroform under nitrogen atmosphere, and 67 mL of triethylamine (TEA) catalyst was added. After 0.2 mol of terephthaloylchloride (TCL) was dissolved in 1,000 mL of chloroform while the solution was being refluxed, it was added slowly for 1 hour and refluxed for 12 hours. After the solvent of the reaction solution was removed, the solution was dissolved in acetone and washed with hot distilled water. And then dried in a vacuum oven for 24 hours to prepare a hydroxy-terminated siloxane having an ester bond represented by the following formula (7). The hydrogen peak of the methylene group of the polysiloxane observed at 2.6 ppm by H-NMR and the hydrogen peak of the benzene ring of TCL observed at 8.35 ppm and the hydrogen peak of the benzene ring of the polysiloxane observed at 6.75 to 7.35 ppm .

(7)

< Polysiloxane - Preparation of polycarbonate resin &gt;

Bisphenol A in an aqueous solution and phosgene gas were interfacially reacted in the presence of methylene chloride to prepare 400 mL of an oligomeric polycarbonate mixture having a viscosity average molecular weight of about 1,000. To the obtained oligomeric polycarbonate mixture were added 1.8 ml of a hydroxy-terminated siloxane having an ester bond (4.5% by weight), tetrabutyl ammonium chloride (TBACl) of the above formula (7) dissolved in methylene chloride, -Butylphenol (PTBP) and 275 트리 of triethylamine (TEA, 15 wt% aqueous solution) were mixed and reacted for 30 minutes. After the reaction, the oligomeric polycarbonate mixture was allowed to stand for separation. After the layer separation, only the organic phase was taken, and 170 g of aqueous sodium hydroxide solution, 360 g of methylene chloride and 300 μl of a 15% by weight aqueous solution of triethylamine were mixed and reacted for 2 hours. After separating the layers, the organic phase with increased viscosity was washed with alkali and separated. Subsequently, the organic phase was washed with 0.1 N hydrochloric acid solution and then washed with distilled water two to three times. After the washing was completed, the concentration of the organic phase was uniformly adjusted to 76 ° C using a predetermined amount of pure water. After the assembly was completed, it was dried at 110 ° C for 8 hours and then at 120 ° C for 10 hours. The peak of the methylene group of the polysiloxane observed at 2.6 ppm and 2.65 ppm by H-NMR and the hydrogen peak of the benzene ring of TCL observed at 8.35 ppm and the hydrogen peak of the benzene ring of the polysiloxane observed at 6.95 to 7.5 ppm ( M _v : 21,000).

At this time, 1 H-NMR data and viscosity average molecular weight (M _v ) were measured by the following method.

(a) H-NMR (nuclear magnetic resonance spectroscope): Measured using Avance DRX 300 from Bruker.

(b) a viscosity average molecular weight (M _v): to measure the viscosity of a methylene chloride solution at 20 ℃ using Ube load viscometer (Ubbelohde Viscometer) and an intrinsic viscosity from which the [η] was calculated from the equation below.

_{^{[η] = 1.23x10 -5 M v}} 0 .83

[ Example  1 to 3 and Comparative Example  1-6]

The components shown in the following Table 1 were mixed and dispersed uniformly in a Henschel mixer, and then extruded at a temperature of 240 to 270 ° C in a biaxial melt mixing extruder having L / D = 40 and? = 25 mm Pellet form.

The prepared pellets were dried in a hot air drier at 80 to 100 ° C. for 4 hours or more and then injection molded at 240 to 270 ° C. to prepare specimens. The properties of the prepared specimens were measured and evaluated in the following Table 2, and the results are shown in Table 2.

[Material Used]

- PET resin: Polyethylene terephthalate resin having an intrinsic viscosity of 0.64 dl / g

- Si-PC resin: Polysiloxane-polycarbonate resin prepared in the above preparation example, having an intrinsic viscosity of 0.55 dl / g (at 25 占 폚 in methylene chloride)

- PC resin: a linear polycarbonate resin derived from bisphenol A (trade name: TRIREX 3020PJ), viscosity-average molecular weight (M _v) 19,000

- Impact reinforcing agent: acrylic impact modifier (KANEACE M400, KANEKA)

- Halogen-based flame retardant: brominated epoxy polymer (F-2400H, DSBG)

- Phosphorous flame retardant: Aromatic polyphosphate (PX200, Daihachi)

- Auxiliary flame retardant: Fluorinated polyolefin-based resin [Teflon 800J from DuPont)

[Measurement of physical properties]

- Flammability: It was measured by UL-94 flame retardant test method which is the method prescribed by Underwriters Laboratories (UL) of the United States. This is a method for evaluating the flame retardancy from the burning time and dripping property after attaching the flame of the burner to the specimen (thickness: 3 mm) of a fixed size fixed vertically for 10 seconds. The burning time is the length of time that the specimen continues to burn with flame after the flame has been removed and the burning of the cotton by the drip is carried out by a drop of cotton from a sample of cotton for about 300 mm below the bottom of the specimen And the degree of flame retardancy is determined as follows (NG: out of rating)

- Impact strength: Evaluated (23 ° C) by notching a specimen according to ASTM D256. The final test results are calculated as the average of the test results of 10 specimens.

As shown in Table 2, Examples 1 to 3 according to the present invention were able to achieve excellent flame retardancy and impact resistance at the same time. On the other hand, in Comparative Examples 1 to 6, when the flame retardancy is satisfactory, the impact resistance is insufficient (Comparative Examples 1, 2 and 6), when the impact resistance is satisfactory, the flame retardancy is insufficient (Comparative Example 4), or when both the impact resistance and flame retardancy (Comparative Examples 3 and 5).

Claims (10)

Per 100 parts by weight of total composition
(A) 10 to 70 parts by weight of a polysiloxane-polycarbonate resin,
(B) 10 to 70 parts by weight of a polyethylene terephthalate resin,
(C) 10 to 70 parts by weight of a polycarbonate resin,
(D) 0 to 10 parts by weight of an acrylic impact modifier,
(E) 0 to 15 parts by weight of a halogen-based flame retardant,
(F) 0 to 1 part by weight of phosphorus flame retardant, and
(G) 0 to 2 parts by weight of a fluorinated polyolefin-based auxiliary flame retardant
Wherein the flame retardant polysiloxane-polycarbonate resin composition is a thermoplastic resin composition. The flame-retardant polysiloxane-polycarbonate resin composition according to claim 1, wherein the polysiloxane-polycarbonate resin (A) comprises a hydroxyl-terminated siloxane of the following formula (1) and a polycarbonate block of the following formula
[Chemical Formula 1]

In Formula 1,
R ₁ independently represents a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group or an aryl group,
R ₂ independently represents a hydrocarbon group or a hydroxy group having 1 to 13 carbon atoms,
R ₃ independently represents an alkylene group having 2 to 8 carbon atoms,
A is X or NH-X-NH, wherein X is a linear or branched aliphatic group having 1 to 20 carbon atoms, a cycloalkylene group, or a substituted or unsubstituted alkylene group substituted with a halogen atom, an alkyl group, an alkoxy group, A monocyclic or polycyclic arylene group having 6 to 30 carbon atoms,
m is independently an integer of 0 to 10,
n independently represents an integer of 2 to 1,000;
(3)

In Formula 3,
R ₄ represents an aromatic hydrocarbon group substituted with an alkyl group, a cycloalkyl group, an alkenyl group, an alkoxy group, a halogen atom, or nitro, or an unsubstituted aromatic hydrocarbon group having 6 to 30 carbon atoms. The flame-retardant polysiloxane-polycarbonate resin composition according to claim 1, wherein the polysiloxane-polycarbonate resin (A) has a structure represented by the following formula (4a) or (4b)
[Chemical Formula 4a]

(4b)

In the above general formulas (4a) and (4b)
R ₁ independently represents a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group or an aryl group,
R ₂ independently represents a hydrocarbon group or a hydroxy group having 1 to 13 carbon atoms,
R ₃ independently represents an alkylene group having 2 to 8 carbon atoms,
R ₄ represents an aromatic hydrocarbon group substituted with an alkyl group, a cycloalkyl group, an alkenyl group, an alkoxy group, a halogen atom, or nitro, or an unsubstituted aromatic hydrocarbon group having 6 to 30 carbon atoms,
m is independently an integer of 0 to 10,
n independently represents an integer of 2 to 1,000,
l represents an integer of 1 to 20; The flame-retardant polysiloxane-polycarbonate resin composition according to claim 1, wherein the (B) polyethylene terephthalate resin is a polymer having a repeating unit represented by the following formula (5):
[Chemical Formula 5]

In Formula 5, n represents an integer of 1 or more. The flame-retardant polysiloxane-polycarbonate resin composition according to claim 1, wherein the polycarbonate resin (C) is an aromatic polycarbonate resin having a viscosity average molecular weight (measured in methylene chloride solution) of 15,000 to 40,000. A molded article of the flame-retardant polysiloxane-polycarbonate resin composition according to any one of claims 1 to 5. delete delete delete delete