WO2014098341A1

WO2014098341A1 - Flame retardant thermoplastic resin composition, and articles molded therefrom

Info

Publication number: WO2014098341A1
Application number: PCT/KR2013/006944
Authority: WO
Inventors: 배수학; 주민정; 박동민; 신승식; 최동길
Original assignee: 제일모직 주식회사
Priority date: 2012-12-17
Filing date: 2013-08-01
Publication date: 2014-06-26
Also published as: KR20140090290A

Abstract

The present invention relates to a flame retardant thermoplastic resin composition which is characterized by comprising: (A) about 10 to 49 wt% of aromatic vinyl-based resin; (B) 100 parts by weight of base resin comprising about 51 to 90 wt% of polyphenylene ether based resin; and (C) about 0.1 to 30 parts by weight of polyphosphonates comprising units expressed by chemical formula 1 of claim 1. The flame retardant thermoplastic resin has excellent flame retardancy, thermal stability, long-term durability, and is environmentally-friendly.

Description

Flame retardant thermoplastic resin composition and molded article formed therefrom

The present invention relates to a flame retardant thermoplastic resin composition and a molded article formed therefrom. More specifically, the present invention relates to a flame-retardant thermoplastic resin composition having excellent flame retardancy, thermal stability and long-term durability and environmentally friendly flame retardant thermoplastic resin composition and molded articles formed by applying a polymerized phosphorus compound having a specific structure as a flame retardant.

Styrene-based resins, which are used as exterior materials for electronic products, are applied to almost all electronic products due to their excellent processability and mechanical properties. However, the styrene resin itself has a property that combustion can easily occur and is not resistant to fire. Therefore, the styrene-based resin can be easily burned by the external ignition source, and may serve to further spread the fire. Accordingly, in order to guarantee the safety of fire of electronic products, the United States, Japan, Europe and the like regulate the law to use only polymer resin satisfying the flame retardant standard as an exterior material.

Known flame retardant methods are most commonly applied to impart flame retardancy by applying a halogen-based compound and an antimony-based compound to the resin. However, halogen-containing compounds may damage the mold and have a fatal effect on the human body due to the hydrogen halide gas generated during processing. In addition, since polybrominated diphenyl ethers, which are mainly halogen-based flame retardants, are highly likely to generate very toxic gases such as dioxins and furans during combustion, attention has been focused on flame-retardant methods that do not apply halogen-based compounds.

As the compound containing no halogen, a method of imparting flame retardance to a resin composition by adding a compound containing phosphorus or nitrogen has been studied. In particular, blends that can be flame retarded using a phosphorus compound include a blend of polycarbonate and acrylonitrile-butadiene-styrene copolymer, a blend of rubber-reinforced styrene resin and polyphenylene ether resin, and the like.

Korean Patent No. 2002-007813 discloses a method of using a mixture of carboxy phosphonic acid and phosphoric acid or a derivative compound as a flame retardant in a polystyrene resin or the like, and studies similar to the present patent have been actively conducted. The patent and the like have excellent flame retardancy when using a halogen-based flame retardant or a phosphate ester flame retardant, but may not bond to a material that requires long-term durability such as a solar material.

In order to solve the problems of the conventional flame-retardant thermoplastic resin, the present inventors apply a polymeric phosphonate flame retardant to the thermoplastic resin, while excellent in environmental stability and fire safety, excellent heat resistance and excellent long-term durability compared to existing products It is early to develop a thermoplastic resin composition.

It is an object of the present invention to provide a flame retardant thermoplastic resin composition excellent in flame retardancy, thermal stability and long-term durability and a molded article formed therefrom.

Another object of the present invention is to provide an environmentally friendly flame retardant thermoplastic resin composition and a molded article formed therefrom without using a halogen-based flame retardant.

Still another object of the present invention is to provide a flame retardant thermoplastic resin composition and a molded article formed therefrom which can be used as an internal / exterior material such as electronic products due to relatively excellent thermal stability, mechanical strength and fluidity.

The above and other objects of the present invention can be achieved by the present invention described below.

One aspect of the invention relates to a flame retardant thermoplastic resin composition. The flame retardant thermoplastic resin composition may include 100 parts by weight of a basic resin comprising (A) about 10 to about 49% by weight of an aromatic vinyl resin and (B) about 51 to about 90% by weight of a polyphenylene ether resin; And (C) about 0.1 to about 30 parts by weight of a polyphosphonate comprising a unit represented by Formula 1 below:

[Formula 1]

In Formula 1, A is a single bond, C1-C5 alkylene group, C2-C5 alkylidene group, C5-C6 cycloalkylidene group, -S- or -SO _2- , R ₁ is substituted or unsubstituted A substituted C1-C6 alkyl group, a substituted or unsubstituted C6-C20 aryl group, or a C6-C20 substituted or unsubstituted aryloxy group, R ₂ and R ₃ are each independently substituted or unsubstituted C1- An alkyl group of C6, a substituted or unsubstituted cycloalkyl group of C3-C6, a substituted or unsubstituted C6-C12 aryl group or a halogen atom, a and b are each independently an integer of 0 to 4, n is 1 to It is an integer of 500.

In embodiments, the polyphosphonate (C) may include at least one polyphosphonate including a unit represented by the following formula (2).

[Formula 2]

In Formula 2, A and B are each independently a single bond, an alkylene group of C1-C5, an alkylidene group of C2-C5, a cycloalkylidene group of C5-C6, -S- or -SO _2- , A and B are not the same as each other, R ₁ and R ₄ are each independently a substituted or unsubstituted C1-C6 alkyl group, a substituted or unsubstituted C6-C20 aryl group or C6-C20 substituted or unsubstituted Is an aryloxy group, R ₂ , R ₃ , R ₅ and R ₆ are each independently a substituted or unsubstituted C1-C6 alkyl group, a substituted or unsubstituted C3-C6 cycloalkyl group, a substituted or unsubstituted C6 -C12 is an aryl group or a halogen atom, a, b, c and d are each independently an integer of 0 to 4, m is an integer of 0 to 500, n is an integer of 1 to 500.

Preferably, the sum of m and n may be 3 to 600.

In an embodiment, the aromatic vinyl-based resin (A) comprises a monomer mixture comprising about 1 to about 30 weight percent of a rubbery polymer having an average particle diameter of about 0.1 to about 3 μm and about 70 to about 99 weight percent of an aromatic vinyl monomer. It may be a polymer.

In an embodiment, the polyphenylene ether resin (B) may be poly (2,6-dimethyl-1,4-phenylene) ether, poly (2,6-diethyl-1,4-phenylene) ether, Poly (2,6-dipropyl-1,4-phenylene) ether, poly (2-methyl-6-ethyl-1,4-phenylene) ether, poly (2-methyl-6-propyl-1,4 -Phenylene) ether, poly (2-ethyl-6-propyl-1,4-phenylene) ether, poly (2,6-diphenyl-1,4-phenylene) ether, poly (2,6-dimethyl Copolymer of -1,4-phenylene) ether and poly (2,3,6-trimethyl-1,4-phenylene) ether, and poly (2,6-dimethyl-1,4-phenylene) ether It may contain one or more of the copolymers of poly (2,3,6-triethyl-1,4-phenylene) ether.

In embodiments, the flame retardant thermoplastic resin composition has a tensile strength of about 610 to about 800 kgf / according to ASTM D-638 after exposure at a temperature of about 135 ° C. for about 3,000 hours. may be ² mm.

In embodiments, the flame retardant thermoplastic resin composition may further comprise an additive comprising at least one flame retardant, lubricant, plasticizer, heat stabilizer, anti-drip agent, antioxidant, compatibilizer, light stabilizer, pigment, dye and inorganic additives. have.

Another aspect of the invention relates to a molded article. The molded article is formed from the flame retardant thermoplastic resin composition.

The present invention is excellent in flame retardancy, thermal stability and long-term durability, environmentally friendly by not using a halogen-based flame retardant, relative to thermal stability, mechanical strength and fluidity, flame retardant thermoplastic resin that can be used as an interior / exterior material such as electronic products It has the effect of providing the composition and the molded article formed therefrom.

Hereinafter, the present invention will be described in detail.

The flame retardant thermoplastic resin composition according to the present invention comprises 100 parts by weight of a base resin comprising about 10 to about 49 wt% of an aromatic vinyl resin and about 51 to about 90 wt% of a polyphenylene ether resin; And about 0.1 to about 30 parts by weight of a polyphosphonate including a unit represented by Formula 1 below.

(A) Aromatic vinyl resin

The aromatic vinyl resin (A) used in the present invention is a polymer of an aromatic vinyl monomer (monomer), a copolymer with another monomer copolymerizable with an aromatic vinyl monomer, or a polymer of a monomer mixture containing the aromatic vinyl monomer and a rubbery polymer. Phosphorus rubber-modified aromatic vinyl resin.

The aromatic vinyl monomers may include styrene, α-methylstyrene, β-methylstyrene, p-methylstyrene, para t-butylstyrene, ethyl styrene, and the like. These can be used individually or in mixture of 2 or more types.

The other copolymerizable monomer may be acrylonitrile, acrylic acid, methacrylic acid, maleic anhydride, N-substituted maleimide, or the like. These can be used individually or in mixture of 2 or more types.

The rubbery polymers include butadiene type rubbers, copolymers of butadiene and styrene, diene rubbers such as poly (acrylonitrile-butadiene) and saturated rubbers hydrogenated with the diene rubber, isoprene rubber, acrylic rubber and ethylene-propylene- Diene terpolymer (EPDM) and the like can be used. For example, polybutadiene, a copolymer of butadiene and styrene, isoprene rubber, alkyl acrylate rubbers, and the like can be used.

As the aromatic vinyl resin (A), when the rubber modified aromatic vinyl resin is used, the content of the rubbery polymer may be about 1 to about 30% by weight, for example, about 5 to about 15% by weight of the monomer mixture. And the content of the aromatic vinyl monomer may be about 70 to about 99% by weight, for example about 85 to about 95% by weight of the monomer mixture. It is possible to obtain a good balance of physical properties of the impact strength and mechanical properties in the above range.

In addition, the average particle diameter of the rubbery polymer may be about 0.1 to about 3 μm, for example, about 0.25 to about 2.5 μm in Z-average. When the rubber-modified aromatic vinyl resin and the polyphenylene ether resin blend in the above range can exhibit appropriate physical properties.

In an embodiment, examples of the aromatic vinyl resin (A) include polystyrene (PS), high impact polystyrene (HIPS), acrylonitrile-butadiene-styrene copolymer resin (ABS), acrylonitrile-styrene copolymer resin ( SAN), acrylonitrile-styrene-acrylate copolymer resin (ASA), etc. can be illustrated. These can be used individually or in mixture of 2 or more types. For example, rubber modified aromatic vinyl resins such as high impact polystyrene (HIPS) may be used, and these may be excellent in compatibility with polyphenylene ether resins.

The method for producing the aromatic vinyl resin (A) is well known by those skilled in the art to which the present invention pertains, and is easy to purchase commercially.

For example, the aromatic vinyl resin (A) may be polymerized by thermal polymerization without an initiator or polymerized in the presence of an initiator. As the polymerization initiator, at least one of peroxide initiators such as benzoyl peroxide, t-butyl hydroperoxide, acetyl peroxide, cumene hydroperoxide, and azo initiators such as azobis isobutyronitrile may be selected and used. However, it is not limited thereto.

The aromatic vinyl resin (A) may be prepared using a bulk polymerization, suspension polymerization, emulsion polymerization or a mixture thereof, and among these polymerization methods, a bulk polymerization method may be preferably used.

The aromatic vinyl resin (A) may have a weight average molecular weight of about 50,000 to about 200,000 g / mol, for example, about 100,000 to about 200,000 g / mol, measured by gel permeation chromatography (GPC), but is not limited thereto. .

The aromatic vinyl resin (A) constitutes a base resin in the flame retardant thermoplastic resin composition of the present invention, and is about 10 to about 49 wt% of the base resin consisting of (A) + (B), for example, about 15 to about 45 weight percent, specifically about 20 to about 40 weight percent. If the content of the aromatic vinyl-based resin (A) is less than about 10% by weight of the base resin, there is a risk that the impact strength, fluidity, etc. may be lowered, and when it exceeds 49% by weight, long-term durability may be lowered. .

(B) polyphenylene ether resin

The polyphenylene ether resin (B) used in the present invention is for increasing flame retardancy and heat resistance. As the polyphenylene ether resin (B), a common polyphenylene ether resin used in a flame retardant thermoplastic resin composition can be used, for example, poly (2,6-dimethyl-1,4-phenylene) Ether, poly (2,6-diethyl-1,4-phenylene) ether, poly (2,6-dipropyl-1,4-phenylene) ether, poly (2-methyl-6-ethyl-1, 4-phenylene) ether, poly (2-methyl-6-propyl-1,4-phenylene) ether, poly (2-ethyl-6-propyl-1,4-phenylene) ether, poly (2,6 -Diphenyl-1,4-phenylene) ether, poly (2,6-dimethyl-1,4-phenylene) ether and poly (2,3,6-trimethyl-1,4-phenylene) ether Copolymers, copolymers of poly (2,6-dimethyl-1,4-phenylene) ether and poly (2,3,6-triethyl-1,4-phenylene) ether and the like can be used. Specifically, poly (2,6-dimethyl-1,4-phenylene) ether or poly (2,6-dimethyl-1,4-phenylene) ether and poly (2,3,6-trimethyl-1, Copolymers of 4-phenylene) ether may be used, and specifically, poly (2,6-dimethyl-1,4-phenylene) ether may be used.

The degree of polymerization of the polyphenylene ether resin (B) is not particularly limited, but considering the thermal stability and workability of the resin composition, the intrinsic viscosity when measured in a chloroform solvent at 25 ° C. is about 0.2 to about 0.8 dl. / g may be used.

The polyphenylene ether-based resin (B) constitutes a base resin in the flame retardant thermoplastic resin composition of the present invention, and is about 51 to about 90% by weight of the base resin consisting of (A) + (B), for example, about 55 To about 85% by weight, specifically about 60 to about 80% by weight. If the content of the polyphenylene ether resin (B) is less than about 51% by weight of the basic resin, there is a fear that long-term durability, flame retardancy and heat resistance is lowered, and when it exceeds about 90% by weight, impact strength and the like There is a risk of deterioration.

(C) polyphosphonates

Polyphosphonate (C) used in the present invention includes a unit represented by the following formula (1).

[Formula 1]

In Formula 1, A is a single bond, C1-C5 alkylene group, C2-C5 alkylidene group, C5-C6 cycloalkylidene group, -S- or -SO _2- , R ₁ is substituted or unsubstituted A substituted C1-C6 alkyl group, a substituted or unsubstituted C6-C20 aryl group, or a C6-C20 substituted or unsubstituted aryloxy group, R ₂ and R ₃ are each independently substituted or unsubstituted C1- An alkyl group of C6, a substituted or unsubstituted cycloalkyl group of C3-C6, a substituted or unsubstituted C6-C12 aryl group or a halogen atom, a and b are each independently an integer of 0 to 4, n is 1 to 500, for example, an integer from 4 to 500.

[Formula 2]

In Formula 2, A and B are each independently a single bond, an alkylene group of C1-C5, an alkylidene group of C2-C5, a cycloalkylidene group of C5-C6, -S- or -SO _2- , A and B are not the same as each other, R ₁ and R ₄ are each independently a substituted or unsubstituted C1-C6 alkyl group, a substituted or unsubstituted C6-C20 aryl group or C6-C20 substituted or unsubstituted Is an aryloxy group, R ₂ , R ₃ , R ₅ and R ₆ are each independently a substituted or unsubstituted C1-C6 alkyl group, a substituted or unsubstituted C3-C6 cycloalkyl group, a substituted or unsubstituted C6 -C12 is an aryl group or halogen atom, a, b, c and d are each independently an integer of 0 to 4, m is an integer of 0 to 500, for example 1 to 500, n is 1 to 500, For example, it is an integer of 4-500.

In embodiments, the sum of m and n may be 3 to 600. More excellent flame retardancy can be provided in the above range.

The polyphosphonates (C) are, for example, polyphosphonates in the form of homopolymers, polyphosphonates in the form of copolymers, respectively, or polyphosphonates in the form of homopolymers and polyphosphes in the form of copolymers. Phonates may be used together, but are not limited thereto.

The polyphosphonate (C) is prepared by reacting a diol including one or more of a diol represented by the following Chemical Formula 3 and a diol represented by the following Chemical Formula 4 and a phosphonic dichloride represented by the following Chemical Formula 5. can do.

[Formula 3]

[Formula 4]

In Formulas 3 and 4, A, B, R ₂ , R ₃ , R ₅ , R ₆ , a, b, c and d are as defined in Formula 2 above.

Specific examples of the diol include 4,4'-dihydroxybiphenyl, 2,2-bis- (4-hydroxyphenyl) -propane, 2,4-bis- (4-hydroxyphenyl) -2- Methylbutane, 1,1-bis- (4-hydroxyphenyl) -cyclohexane, 2,2-bis- (3-chloro-4-hydroxyphenyl) -propane, 2,2-bis- (3,5 -Dichloro-4-hydroxyphenyl) -propane and the like, and may be used alone or in combination of two or more thereof. In an embodiment, 4,4'-dihydroxybiphenyl alone or 4,4'-dihydroxybiphenyl and 2,2-bis- (4-hydroxyphenyl) -propane may be applied. When using two diols, the ratio between diols may be appropriately adjusted according to the physical properties to be expressed. In an embodiment, the molar ratio of 4,4′-dihydroxybiphenyl and 2,2-bis- (4-hydroxyphenyl) -propane may be from about 5 to about 95: about 95 to about 5. More excellent flame retardancy can be provided in the above range.

[Formula 5]

In Formula 5, each R is independently a substituted or unsubstituted C1-C6 alkyl group, a substituted or unsubstituted C6-C20 aryl group, or a C6-C20 substituted or unsubstituted aryloxy group. Here, the phosphonic dichloride represented by Formula 5 may use two kinds of compounds in which R is not the same, and R in Formula 5 corresponds to R ₁ and R ₄ in Formulas 1 and 2.

In an embodiment, the phosphonic dichloride can be reacted dropwise with a solution containing a diol, a catalyst, and an end capping agent, and about 1 equivalent of the total diol can be reacted with about 1 equivalent of the phosphonic dichloride. .

The reaction of the diol and phosphonic dichloride can be carried out by a conventional polymerization method under a Lewis acid catalyst. For the polymerization, for example, solution polymerization may be used. As the Lewis acid catalyst, aluminum chloride, magnesium chloride, or the like may be used, but is not limited thereto. The catalyst may be applied in an amount of about 0.01 to about 10 equivalents, such as about 0.01 to about 1 equivalents, specifically about 0.01 to about 0.1 equivalents, based on about 1 equivalent of the total diol.

In addition, the reaction may be carried out in the presence of an end capping agent. As the end capping agent, C1-C5 alkyl group-containing phenol may be preferably applied. For example, phenol, 4-t-butylphenol, or 2-t-butylphenol may be used. The end capping agent may be used in an amount of about 1 equivalent or less, such as about 0.01 to about 0.5 equivalents, based on about 1 equivalent of the total diol.

In an embodiment, the reaction may be completed and then washed with an acid solution. Phosphoric acid, hydrochloric acid, nitric acid, sulfuric acid, etc. may be applied as the acid solution, for example, phosphoric acid or hydrochloric acid. At this time, the acid solution may be in a concentration of about 0.1 to about 10%, for example about 1 to about 5%. Thereafter, washing and filtration may give a polyphosphonate in the form of a white solid.

The polyphosphonate (C) may have a weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of about 1,000 to about 50,000 g / mol. For example, about 1,000 to about 20,000 g / mol, specifically about 1,000 to about 10,000 g / mol. More excellent flame retardancy can be provided in the above range.

The polyphosphonate may have an acid value of about 0.005 to about 4 KOH mg / g, for example, about 0.01 to about 1 KOH mg / g. Decomposition of the thermoplastic resin does not occur in the above range.

The polyphosphonate may have a polydispersity index (PDI) of about 1 to about 3.5, for example about 1.5 to about 2.5. In the above range, physical properties such as flame retardancy and fluidity, impact strength, heat resistance, and the like may be excellent.

The polyphosphonate may have a glass transition temperature of about 75 to about 90 ℃, for example about 78 to about 87 ℃. The processability of the resin composition may be excellent in the above range.

The polyphosphonate (C) may have an acid value change rate of about 0.005 to about 6, for example, about 0.01 to about 5, by the following Formula 1. In the above range, decomposition of the thermoplastic resin may not occur. In embodiments, the rate of change of the acid value of the polyphosphonate (C) may be about 0.05 to about 1.

[Equation 1]

In Formula 1, ΔAV represents an acid value change rate, AVa represents an acid value after about 10 g of polyphosphonate is left at about 280 ° C. for about 1 hour, and AVb represents an initial acid value of polyphosphonate.

The polyphosphonate (C) is about 0.1 to about 30 parts by weight, for example about 1 to about 25 parts by weight, specifically about 10 to about 100 parts by weight of the base resin consisting of (A) + (B) About 25 parts by weight. If the content of the polyphosphonate (C) is less than about 0.1 part by weight based on 100 parts by weight of the base resin, there is a risk that the flame resistance, heat resistance, and the like may be lowered. When the content of the polyphosphonate (C) exceeds about 30 parts by weight, fluidity, impact strength, Physical properties such as flame retardancy and heat resistance, and long-term durability may be lowered.

The flame-retardant thermoplastic resin composition according to the present invention has a tensile strength of about 610 to about 800 kgf / mm measured under the condition of about 5 mm / min after exposure to about 3,000 hours at a temperature of about 135 ℃ according to ASTM D-638 ² , for example, about 620 to about 750 kgf / mm ² , the tensile strength change rate according to the following formula 2 is about 10% or less, the long-term durability is particularly excellent.

[Equation 2]

ΔTS = (TS ₀ -TS _3,000 ) × 100 / TS ₀

In Equation 1, TS ₀ is tensile strength before high temperature exposure, and TS _3,000 is tensile strength after about 3,000 hours of exposure at high temperature.

The flame retardant thermoplastic resin composition of the present invention may further include additives such as flame retardant aids, lubricants, plasticizers, heat stabilizers, anti-drip agents, antioxidants, compatibilizers, light stabilizers, pigments, dyes, inorganic additives, and the like, if necessary. These can be used individually or in mixture of 2 or more types. For example, the additive may include about 0.1 to about 10 parts by weight based on 100 parts by weight of the base resin, but is not limited thereto.

The flame retardant thermoplastic resin composition may be prepared by pelletizing after melt-extrusion in an extruder after mixing the components and other additives at the same time. The prepared pellets may be manufactured into various molded articles through various molding methods such as injection molding, extrusion molding, vacuum molding, and casting molding.

Another aspect of the present invention provides a molded article formed from the thermoplastic resin composition. The molded article is excellent in impact resistance, fluidity, flame retardancy, etc. can be widely applied to parts, exterior materials, automobile parts, sundries, structural materials of electrical and electronic products.

Hereinafter, the configuration and operation of the present invention through the preferred embodiment of the present invention will be described in more detail. However, this is presented as a preferred example of the present invention and in no sense can be construed as limiting the present invention.

실시예 Example

The specifications of each component used in the following Examples and Comparative Examples are as follows:

(A) Aromatic vinyl resin

Cheil Industries Ltd. rubber-reinforced styrene resin HG-1760S was used. The average particle diameter of the butadiene rubber (rubber polymer) used is 1.5 μm, and the content of the rubber is 6.5% by weight.

(B) polyphenylene ether resin

Poly (2,6-dimethyl-phenylether) (trade name: LXR-035C) from China Buluta Chemical was used. The resin is in the form of a pale yellow powder having an average particle diameter of several tens of micrometers to several mm.

(C-1) polyphosphonate

As the flame retardant, biphenyl polyphosphonate represented by Chemical Formula 1a manufactured by Cheil Industries was used.

[Formula 1a]

In Formula 1a, n is 4.

(C-2) polyphosphonate

As the flame retardant, polyphosphonate represented by Chemical Formula 2a manufactured by Cheil Industries was used.

[Formula 2a]

In Formula 2a, m and n are each 2.

(C-3) Aromatic Phosphate Ester Compounds

Bis (dimethylphenyl) phosphate bisphenol A (trade name: CR741S) of Nippon-Dhalf Chemical was used as a flame retardant.

실시예 1~7 및 비교예 1~6Examples 1-7 and Comparative Examples 1-6

After adding each of the components in the content as described in Tables 1 and 2, 0.1 parts by weight of a hindered phenol-based heat stabilizer was added, melted, kneaded and extruded to prepare a pellet. At this time, the extrusion was used a twin screw extruder having a diameter of L / D = 29, 45 mm, the prepared pellet was dried for 6 hours at 80 ℃, and injected into a 6 Oz injection machine to prepare a specimen. The physical properties of the prepared specimens were evaluated by the following method, and the results are shown in Tables 1 and 2 below.

After mixing the components in the amounts of Tables 1 and 2, the pellets were prepared by extruding in a temperature range of 200 to 280 ℃ in a conventional twin screw extruder. The prepared pellet was dried at 80 ° C. for 3 hours, and then injected into a mold at a temperature of 180 to 280 ° C. and a mold temperature of 40 to 80 ° C. in a 6 Oz injection machine to prepare a flame retardant specimen. The physical properties of the prepared specimens were evaluated by the following method.

Property measurement method

(1) Flame retardancy: A specimen of 1/10 "thickness was prepared and the flame retardance was measured according to UL94 VB flame retardancy regulations.

(2) Izod impact strength (unit: kgf · cm / cm): Notch was evaluated by making an Izod specimen having a thickness of 1/8 "by the evaluation method specified in ASTM D256.

(3) Heat resistance (VST, unit: ℃): measured at 5 kgf load in accordance with ASTM D1525.

(4) Tensile strength and rate of change evaluation (long term durability evaluation): After the specimens were exposed to 0 hours, 1,000 hours, 2,000 hours and 3,000 hours under the condition that 80 ° C, 110 ° C and 135 ° C were kept constant, Based on D-638, tensile strength (tensile velocity: 5 mm / min, specimen thickness: 3.2 mm, unit: kgf / mm ² ) was measured, and tensile strength change rate (ΔTS, unit:%) was calculated according to the following Equation 2. Calculated.

[Equation 2]

ΔTS = (TS ₀ -TS _3,000 ) × 100 / TS ₀

In Equation 1, TS ₀ is tensile strength before high temperature exposure, and TS _3,000 is tensile strength after 3000 hours of exposure at high temperature.

Table 1

			Example
			One	2	3	4	5	6	7
(A)			49	45	35	30	20	35	35
(B)			51	55	65	70	80	65	65
(C-1)			21	20	15	15	12	-	7.5
(C-2)			-	-	-	-	-	15	7.5
UL94 flame retardant			V-0	V-0	V-0	V-0	V-0	V-0	V-0
Izod impact strength (kgfcm / cm)			11	12	12	13	15	11	12
VST heat resistance (℃)			131	135	138	141	150	140	139
Tensile strength (kgf / mm ² )	80 ℃	0hr	670	700	720	730	750	715	720
		1000hr	675	710	700	710	740	720	710
		2000hr	680	705	715	700	730	725	720
		3000hr	682	699	725	699	720	720	720
	110 ℃	0hr	670	700	720	730	750	715	720
		1000hr	660	705	700	710	730	700	700
		2000hr	651	680	695	695	700	695	700
		3000hr	644	660	690	680	690	690	690
	135 ℃	0hr	670	700	720	730	750	715	720
		1000hr	670	685	710	715	720	710	710
		2000hr	640	660	680	700	690	680	680
		3000hr	621	651	660	660	660	660	660
Tensile Strength Change Rate (%)		80 ℃	-1.79	0.14	-0.69	4.25	4	-0.7	0
		110 ℃	3.88	5.71	4.16	6.85	8	3.5	4.16
		135 ℃	7.31	7	8.33	9.59	12	8.0	8.3

TABLE 2

			Comparative example
			One	2	3	4	5	6
(A)			60	55	55	55	30	20
(B)			40	45	45	45	70	80
(C-1)			-	-	-	23	-	-
(C-3)			25	22	-	-	15	10
UL94 flame retardant			V-0	V-0	fail	V-0	V-0	V-0
Izod impact strength (kgfcm / cm)			7	8	16	9	12	12
VST heat resistance (℃)			85	89	137	110	132	145
Tensile strength (kgf / mm ² )	80 ℃	0hr	550	570	710	650	720	715
		1000hr	560	577	720	640	715	725
		2000hr	510	515	715	630	690	680
		3000hr	480	488	700	621	680	690
	110 ℃	0hr	※ Not measurable		710	650	720	715
		1000hr			700	620	715	700
		2000hr			690	590	610	615
		3000hr			690	480	545	595
	135 ℃	0hr	※ Not measurable		710	650	720	715
		1000hr			690	630	715	700
		2000hr			495	500	511	570
		3000hr			433	420	499	510
Tensile Strength Change Rate (%)		80 ℃	※ Not measurable		1.41	4.46	5.55	3.50
		110 ℃	※ Not measurable		2.82	26.15	24.31	16.78
		135 ℃	※ Not measurable		39.01	35.38	30.69	28.67

※: Low heat resistance (VST) of the specimen prevents measurement due to deformation of the specimen

From the results in Tables 1 and 2, it can be seen that when the polyphosphonate (C) of the present invention is used as a flame retardant (Examples 1 to 7), the flame retardancy, heat resistance, long-term heat resistance, impact strength and the like are excellent. On the other hand, Comparative Examples 1 and 2, in which the polyphenylene ether resin (B) content is low and the polyphosphonates (C-1, C-2, etc.) are not applied as a flame retardant, show that the heat resistance and mechanical strength sharply decrease. In addition, when the polyphenylene ether resin (B) content is low and a flame retardant is not used (Comparative Example 3), it can be seen that the long-term durability and flame retardancy at 135 ° C. are sharply reduced, as in Comparative Example 4 Even when the fonate (C-1) is applied, when the polyphenylene ether resin (B) content is low, it can be seen that long-term durability is lowered at 110 ° C or higher. Comparative Examples 5 and 6, in which the polyphosphonate (C) was not applied as the flame retardant, showed that the heat resistance and the flame retardancy were similar to those of the examples, but the long-term durability (long-term heat resistance) was significantly reduced.

As mentioned above, embodiments of the present invention have been described with reference to the attached table, but the present invention is not limited to the above embodiments and can be manufactured in various forms, and the general knowledge in the art to which the present invention pertains. Those skilled in the art will appreciate that the present invention may be embodied in other specific forms without changing the technical spirit or essential features of the present invention. Therefore, it should be understood that the embodiments described above are exemplary in all respects and not restrictive.

Claims

100 parts by weight of a base resin comprising about 10% to about 49% by weight of an aromatic vinyl resin and about 51% to about 90% by weight of a polyphenylene ether resin; And

(C) a flame retardant thermoplastic resin composition comprising about 0.1 to about 30 parts by weight of a polyphosphonate comprising a unit represented by Formula 1 below:

[Formula 1]

In Formula 1, A is a single bond, C1-C5 alkylene group, C2-C5 alkylidene group, C5-C6 cycloalkylidene group, -S- or -SO 2- , R 1 is substituted or unsubstituted A substituted C1-C6 alkyl group, a substituted or unsubstituted C6-C20 aryl group, or a C6-C20 substituted or unsubstituted aryloxy group, R 2 and R 3 are each independently substituted or unsubstituted C1- An alkyl group of C6, a substituted or unsubstituted cycloalkyl group of C3-C6, a substituted or unsubstituted C6-C12 aryl group or a halogen atom, a and b are each independently an integer of 0 to 4, n is 1 to It is an integer of 500.
The flame retardant thermoplastic resin composition of claim 1, wherein the polyphosphonate (C) comprises at least one polyphosphonate comprising a unit represented by the following Chemical Formula 2:

[Formula 2]

In Formula 2, A and B are each independently a single bond, an alkylene group of C1-C5, an alkylidene group of C2-C5, a cycloalkylidene group of C5-C6, -S- or -SO 2- , A and B are not the same as each other, R 1 and R 4 are each independently a substituted or unsubstituted C1-C6 alkyl group, a substituted or unsubstituted C6-C20 aryl group or C6-C20 substituted or unsubstituted Is an aryloxy group, R 2 , R 3 , R 5 and R 6 are each independently a substituted or unsubstituted C1-C6 alkyl group, a substituted or unsubstituted C3-C6 cycloalkyl group, a substituted or unsubstituted C6 -C12 is an aryl group or a halogen atom, a, b, c and d are each independently an integer of 0 to 4, m is an integer of 0 to 500, n is an integer of 1 to 500.
The flame retardant thermoplastic resin composition of claim 2, wherein the sum of m and n is 3 to 600.
The monomer of claim 1, wherein the aromatic vinyl resin (A) comprises about 1 to about 30 wt% of a rubbery polymer having an average particle diameter of about 0.1 to about 3 μm and about 70 to about 99 wt% of an aromatic vinyl monomer. Flame retardant thermoplastic resin composition, characterized in that the polymer of the mixture.
The polyphenylene ether-based resin (B) is poly (2,6-dimethyl-1,4-phenylene) ether, poly (2,6-diethyl-1,4-phenylene). Ether, poly (2,6-dipropyl-1,4-phenylene) ether, poly (2-methyl-6-ethyl-1,4-phenylene) ether, poly (2-methyl-6-propyl-1 , 4-phenylene) ether, poly (2-ethyl-6-propyl-1,4-phenylene) ether, poly (2,6-diphenyl-1,4-phenylene) ether, poly (2,6 Copolymers of -dimethyl-1,4-phenylene) ether and poly (2,3,6-trimethyl-1,4-phenylene) ether, and poly (2,6-dimethyl-1,4-phenylene) A flame retardant thermoplastic resin composition comprising at least one of copolymers of ether and poly (2,3,6-triethyl-1,4-phenylene) ether.
The flame retardant thermoplastic resin composition of claim 1, wherein the flame retardant thermoplastic resin composition has a tensile strength of about 610 to about 800 measured at a condition of about 5 mm / min after exposure at a temperature of about 135 ° C. for about 3,000 hours according to ASTM D-638. The flame retardant thermoplastic resin composition, characterized in that kgf / mm 2 .
The method of claim 1, wherein the flame retardant thermoplastic resin composition further comprises an additive comprising at least one flame retardant aid, lubricant, plasticizer, heat stabilizer, anti-drip agent, antioxidant, compatibilizer, light stabilizer, pigment, dye, and inorganic additive. Flame retardant thermoplastic resin composition comprising a.
The molded article formed from the flame-retardant thermoplastic resin composition of any one of Claims 1-7.