KR100576326B1 - Flame Ratardant Thermoplastic Resin Composition - Google Patents

Abstract

The flame retardant thermoplastic resin composition according to the present invention is 100 parts by weight of a polyphenylene ether resin comprising (A) 60 to 95 parts by weight of (a ₁ ) polyphenylene ether resin and 5 to 40 parts by weight of (a ₂ ) vinyl aromatic polymer resin. (B) 1 to 30 parts by weight of the phosphate ester compound represented by the following formula (1), (C) 0.05 to 5 parts by weight of the fluorinated polyolefin resin, and (D) 1 to 20 parts by weight of the rubber-modified styrene resin. do.

[Formula 1]

(In Formula 1, R ₃ , R ₄ , R ₆ and R ₇ are each C ₆ -C ₂₀ aryl or alkyl substituted C ₆ -C ₂₀ , and R ₅ is C ₆ -C ₂₀ aryl or alkyl substituted C _6. -C ₂₀ aryl group derivative, l is the number average degree of polymerization, the average value of l is 0 to 3.)

Polyphenylene ether resin, organophosphorus compound, fluorinated polyolefin resin, rubber modified styrene resin, flame retardancy, impact strength

Description

Flame Retardant Thermoplastic Resin Composition

Field of invention

The present invention relates to a flame retardant thermoplastic polyphenylene ether resin composition. More specifically, the present invention provides a thermoplastic resin composition having excellent flame retardancy and impact strength by blending a thermoplastic polyphenylene ether resin, a phosphate ester flame retardant, a fluorinated polyolefin resin, and a rubber modified styrene resin having a specific acrylonitrile content. It is about.

Background of the Invention

In general, polyphenylene ether resin (PPE or PPO) is excellent in heat resistance and mechanical strength, and excellent in dimensional stability. However, polyphenylene ether resin has a disadvantage that it is difficult to process the resin alone. Therefore, it is blended with polystyrene resin having good compatibility and is mainly used as interior and exterior materials of electronic products.

The blend of the polyphenylene ether resin and polystyrene occurs while the workability is improved while the impact strength is reduced. As a known technique for compensating for this, there is a method of applying rubber-reinforced polystyrene resin including rubber. By this method, the impact strength of the resin can be greatly improved. Due to these characteristics, the mixture of polyphenylene ether and vinyl aromatic polymer (MPPO resin) has excellent electrical properties as well as mechanical properties, and thus has been widely applied in various industrial fields such as automobile parts, electrical parts, and electronic parts.

However, polyphenylene ether-based resin tends to increase the heat resistance as the content of the polyphenylene ether resin increases, but the impact strength tends to decrease significantly, so that the styrene-based impact reinforcing material is applied to the polyphenylene ether-based resin. There is a need.

Accordingly, the present inventors have developed a thermoplastic resin composition which is excellent in impact strength and flame retardancy but does not deteriorate in other physical properties by blending a rubber modified styrene resin having a specific acrylonitrile content with a polyphenylene ether resin as an impact modifier. will be.

An object of the present invention is to provide a thermoplastic resin composition having excellent flame retardancy by blending a rubber modified styrene resin having a specific acrylonitrile content with a polyphenylene ether resin.                         

Another object of the present invention is to provide a thermoplastic resin composition which is excellent in impact strength but does not lower in heat deformation temperature and melt flow index.

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

The flame retardant thermoplastic resin composition according to the present invention is 100 parts by weight of a polyphenylene ether resin comprising (A) 60 to 95 parts by weight of (a ₁ ) polyphenylene ether resin and 5 to 40 parts by weight of (a ₂ ) vinyl aromatic polymer resin. (B) 1-30 parts by weight of a phosphate ester compound represented by the following formula (1), (C) 0.05-5 parts by weight of a fluorinated polyolefin resin, and (D) 1-20 parts by weight of a rubber-modified styrene resin. It features.

[Formula 1]

(In Formula 1, R ₃ , R ₄ , R ₆ and R ₇ are each C ₆ -C ₂₀ aryl or alkyl substituted C ₆ -C ₂₀ , and R ₅ is C ₆ -C ₂₀ aryl or alkyl substituted C _6. -C ₂₀ aryl group derivative, l is the number average degree of polymerization, the average value of l is 0 to 3.)

Hereinafter, each component of the present invention will be described in detail below.

(A) polyphenylene ether resin

The polyphenylene ether resin used in the preparation of the resin composition according to the present invention comprises (a ₁ ) 60 to 95 parts by weight of the polyphenylene ether resin and (a ₂ ) 40 to 5 parts by weight of the vinyl aromatic polymer resin.

The polyphenylene ether resin (a ₁ ) 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-dimethyl-1,4 -Phenylene) ether and a copolymer of poly (2,3,6-trimethyl-1,4-phenylene) ether and poly (2,6-dimethyl-1,4-phenylene) ether and poly (2, A mixture of one or two or more selected from the group consisting of copolymers of 3,6-triethyl-1,4-phenylene) ether is used. Among these, copolymers of poly (2,6-dimethyl-1,4-phenylene) ether and poly (2,3,6-trimethyl-1,4-phenylene) ether or poly (2,6-dimethyl- Preference is given to using 1,4-phenylene) ether, in particular poly (2,6-dimethyl-1,4-phenylene) ether. These polyphenylene ether resins may be used alone or in combination of two or more thereof.

The degree of polymerization of the polyphenylene ether resin used in the preparation of the resin composition of the present invention 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 0.2 It is preferable that it is -0.8.

As the vinyl aromatic polymer resin (a ₂ ) used in the present invention, polystyrene, high-impact polystyrene (HIPS), polychlorostyrene, polyα-methylstyrene, poly-butylstyrene, and the like and copolymers thereof alone or two kinds thereof are used. The above can be mixed and used. Of these, it is preferable to use polystyrene or high impact polystyrene.

The molecular weight of the vinyl aromatic copolymer is not particularly limited, but the weight average molecular weight is preferably 20,000 to 50,000 in consideration of thermal stability, workability, and the like of the resin composition.

The resin composition according to the present invention is prepared by adding other components based on 100 parts by weight of the polyphenylene ether resin.

(B) phosphate ester compound

The phosphate ester compound (B), which is an organic phosphorus compound flame retardant used in the present invention, uses a phosphate ester compound or a mixture of phosphate ester compounds represented by the following formula.

[Formula 1]

(In Formula 1, R ₃ , R ₄ , R ₆ and R ₇ are each C ₆ -C ₂₀ aryl or alkyl substituted C ₆ -C ₂₀ , and R ₅ is C ₆ -C ₂₀ aryl or alkyl substituted C _6. -C ₂₀ aryl group derivative, l is the number average degree of polymerization, the average value of l is 0 to 3.)

In the formula, R ₃ , R ₄ , R ₆ and R ₇ are preferably a phenyl group or a phenyl group substituted with an alkyl group such as methyl, ethyl, isopropyl, t-butyl, isobutyl, isoamyl and t-amyl, among which More preferred is a phenyl group substituted with a phenyl group, methyl, ethyl, isopropyl or t-butyl group.

The phosphate ester compound (B) represented by Formula 1 is an oligomeric phosphate ester compound derived from a C ₆ -C ₃₀ aryl or alkyl substituted C ₆ -C ₃₀ aryl group. Preferred examples thereof include those derived from resorcinol, hydroquinone or bisphenol-A.

Phosphoric acid ester compound (B) of this invention is a monomer type or oligomer type aryl derived phosphate ester whose average value of l is 0-3. In the present invention, phosphate ester compounds having an average value of l of 0, 1, 2 and 3 may be used alone or in a mixed form. Here, in the case of a mixture of phosphate ester compounds, when the components are prepared in the polymerization process, those components may be mixed or may be used separately by mixing phosphate ester compounds having different l values.

Among the phosphate esters used in the present invention, the phosphate ester having an l value of 0 is selected from the group consisting of tri (alkylphenyl) phosphate, di (alkylphenyl) monophenylphosphate, diphenylmono (alkylphenyl) phosphate and triphenylphosphate Preference is given to using one or a mixture of two or more.

The resin composition according to the present invention contains 1 to 30 parts by weight of the phosphate ester compound (B) based on 100 parts by weight of the polyphenylene ether resin.

(C) fluorinated polyolefin resin

Examples of the fluorinated polyolefin resin (C) used in the flame retardant thermoplastic resin composition according to the present invention include copolymers of polytetrafluoroethylene, polyvinylidene fluoride, tetrafluoroethylene and vinylidene fluoride, tetrafluoro Copolymers of ethylene and hexafluoropropylene, copolymers of ethylene and tetrafluoroethylene, and the like. These may be used independently from each other, and two or more different types may be used together.

When the fluorinated polyolefin resin is mixed and extruded together with the other component resins of the present invention, a fibrillar network is formed in the resin to reduce the flow viscosity of the resin during combustion and increase the shrinkage rate to increase the shrinkage of the resin. To prevent.

The fluorinated polyolefin resin (C) used in the resin composition of the present invention can be prepared using a known polymerization method. For example, in an aqueous medium containing a free radical forming catalyst such as sodium, potassium or ammonium peroxydisulfate under a pressure of 7 to 71 kgf / cm 2 and a temperature of 0 to 200 ° C., preferably at 20 to 100 ° C. It can be prepared by polymerization in.

The fluorinated polyolefin-based resin (C) may be used in an emulsion state or a powder state. If the fluorinated polyolefin resin in an emulsion state is used, the dispersibility in the entire resin composition is good, but the manufacturing process is complicated. Therefore, it is preferable to use it in powder state as long as it can disperse | distribute suitably in all the resin compositions and can form a fibrous network.

The fluorinated polyolefin resin (C) has a particle size of 0.05 to 1,000 µm and a density of 1.2 to 2.3 g / cm 3. Examples thereof include polytetrafluoroethylene.

The content of the fluorinated polyolefin resin (C) used in the production of the resin composition of the present invention is 0.05 to 5 parts by weight based on 100 parts by weight of the phenylene ether resin (A).

(D) Rubber modified styrene resin

The rubber modified styrene resin (D) having a specific acrylonitrile content used in the present invention is a styrene-containing graft copolymer resin. Examples of the rubber used for the graft copolymer resin include diene rubbers such as polybutadiene, poly (styrene-butadiene) and poly (acrylonitrile-butadiene), saturated rubbers hydrogenated with the diene rubber, isoprene rubber, And acrylic rubbers such as chloroprene rubber and butyl polyacrylate, and ethylene-propylene-diene monomer terpolymer (EPDM). Among these, diene rubber is preferable, butadiene rubber is more preferable. The average size of the rubber particles is preferably in the range of 0.1 to 0.5 μm in consideration of impact strength and appearance.

As the aromatic vinyl monomer in the graft polymerizable monomer mixture together with the rubber, styrene, α-methylstyrene, p-methylstyrene, and the like may be added, and styrene is most preferred. Here, one or more monomers copolymerizable with an aromatic vinyl monomer are introduced, and as the monomer to be introduced, vinyl cyanide-based compounds such as acrylonitrile and unsaturated nitrile-based compounds such as methacrylonitrile are preferable.

The weight ratio of rubber in all the components of the graft copolymer (D) used for this invention is 10-60 weight part. The monomer grafted with rubber is applied by graft copolymerization by adding 90 to 99.5 parts by weight of an aromatic vinyl monomer such as styrene and 0.5 to 10 parts by weight of an unsaturated nitrile monomer. In addition, in order to impart properties such as workability and heat resistance, monomers such as acrylic acid, methacrylic acid, maleic anhydride and N-substituted maleimide can be added and graft polymerization. The amount added is 0-40 weight part with respect to the whole graft resin. The acrylonitrile content in the portion of the rubber-modified styrene resin (D) except for the rubber component is 0.5 to 10% by weight.

In the present invention, 1 to 20 parts by weight of the rubber-modified styrene resin (D) which is the graft copolymer resin thus prepared is used based on 100 parts by weight of the polyphenylene ether resin (A).

The flame retardant thermoplastic resin composition according to the present invention may include general additives such as flame retardant aids, lubricants, mold release agents, nucleating agents, antistatic agents, stabilizers, reinforcing agents, inorganic additives, pigments, dyes, etc. in addition to the above components. . The additive to be added is preferably 0 to 60 parts by weight, more preferably 0 to 40 parts by weight based on 100 parts by weight of the polyphenylene ether resin (A).

The resin composition according to the present invention can be produced by a general known method. For example, after mixing the components of the present invention and other additives simultaneously, they can be melt-extruded in an extruder and made into pellets.

The resin composition according to the present invention can be used for molding various products. In particular, it is suitable for the production of housings and interior materials for computers, electrical and electronic products that require flame resistance and high impact resistance while being injected at high temperatures.

The present invention will be further illustrated by the following examples, which are merely illustrative of the present invention and are not intended to limit or limit the scope of the present invention.

Example

Polyphenylene ether (PPE) resin (A), phosphate ester compound (B), fluorinated polyolefin resin (C), and rubber-modified styrene resin (D) used in Examples and Comparative Examples of the present invention. The specification is as follows.

(A) polyphenylene ether (PPE) resin

As the polyphenylene ether resin (a ₁ ) used in Examples and Comparative Examples of the present invention, polyphenylene ether resin P401 of Asahi Kasei, Japan, was used, and as the vinyl aromatic polymer resin (a ₂ ), Korea First Wool ( The high impact polystyrene HI-1190 of note) was used.

(B) Phosphoric Acid Ester Compound

Triphenylphosphate (TPP) manufactured by Daihachi, Japan, having a number average degree of polymerization l of 0, was used as a phosphate ester flame retardant.

(C) fluorinated polyolefin resin

Teflon 7AJ, DuPont, USA, was used.

(D) Rubber modified styrene resin

Rubber-modified styrene resin having a specific acrylonitrile content used in this embodiment was prepared by using a styrene-containing graft copolymer resin having an acrylonitrile content of 3% by weight in the copolymer as follows.

50 parts by weight of solid butadiene rubber latex, 47.5 parts by weight of styrene, 2.5 parts by weight of acrylonitrile and 150 parts of deionized water were added. 0.4 parts, 0.01 parts of iron sulfate hydrate, 0.3 parts of pyrophosphate sodium salt were added thereto, maintained at 75 ° C. for 5 hours, and the reaction was completed to prepare a graft latex. 0.4 parts by weight of sulfuric acid was added to the solids of the resin and solidified. A graft copolymer resin powder was prepared.

Examples 1-5

The resin composition was prepared by the composition shown in Table 1 below using the above components.

After adding the antioxidant and heat stabilizer to each component, they were mixed in a conventional mixer and extruded using a twin screw extruder having a screw L / D value of 35 and a Φ value of 45 mm. , The specimen for the measurement of physical properties and flame retardancy at the injection temperature 240 ℃ was prepared using a 10 oz injection machine. The specimens were allowed to stand for 48 hours at 23 ° C. and 50% relative humidity, and then physical properties were measured by the following method. The measurement results are shown in Table 1 together.

(1) flame retardant

Flame retardancy was evaluated using a 1.6 mm thick specimen in accordance with UL-94 regulations. The total combustion time is the sum of both primary and secondary combustion times when five specimens were evaluated.

(2) Izod impact strength

Izod notch impact strength was measured according to ASTM D-256, and the unit is kgf · cm / cm.

(3) flexural strength

Flexural strength was measured according to ASTM D-790 and the unit is kgf / cm 2.

(4) heat deflection temperature

The heat deflection temperature was measured at a load of 18.6 kgf in accordance with ASTM D-648. The unit is ° C.

(5) Melt Flow Index

Melt flow index was evaluated according to ASTM D-1238 with a load of 10 kgf at 250 ° C and the unit is g / 10min.

Example One 2 3 4 5 (A) polyphenylene ether resin (a ₁ ) 75 75 75 75 75 (a ₂ ) 25 25 25 25 25 (B) phosphate ester compound 10 12 15 10 10 (C) fluorinated polyolefin resin 0.1 0.1 0.1 0.1 0.1 (D) Rubber modified styrene resin 3 3 3 5 10 UL 94 Flame Retardant (1/16 ") V-0 V-0 V-0 V-0 V-0 Total combustion time 31 29 27 27 32 Impact Strength (1/8 ") 24 25 23 32 37 Flexural strength 911 915 900 925 895 Heat deflection temperature 122 117 112 121 122 Melt flow index 5.2 6.1 7.0 5.4 4.8

Comparative Examples 1 to 6

By the composition shown in Table 2 below, a resin composition was prepared in the same manner as in Examples 1 to 5. In Comparative Example 1, the rubber modified styrene resin (D) used in Examples 1 to 5 was not used. In Comparative Examples 2 to 6, instead of using the rubber modified styrene resin (D) used in Examples 1 to 5, except that Kraton G 1651 (D '), which is an ABA triblock copolymer, was used as a styrene impact modifier, was used. Was measured in the same manner as in Examples 1 to 5. The measurement results are shown in Table 2 together.

Comparative Example One 2 3 4 5 6 (A) polyphenylene ether resin (a ₁ ) 75 75 75 75 75 75 (a ₂ ) 25 25 25 25 25 25 (B) phosphate ester compound 10 10 12 15 10 10 (C) fluorinated polyolefin resin 0.1 0.1 0.1 0.1 0.1 0.1 (D ') Styrene Shock Reinforcement - 3 3 3 5 10 UL 94 Flame Retardant (1/16 ") V-0 V-0 V-0 V-0 V-1 V-1 Total combustion time 28 40 29 27 54 61 Impact Strength (1/8 ") 17 22 23 25 30 33 Flexural strength 925 910 915 920 930 924 Heat deflection temperature 120 123 118 110 120 119 Melt flow index 4,5 5.1 6.5 7.8 5.1 5.2

From the results of Table 1 and Table 2, using rubber-modified styrene resin (D) having a specific acrylonitrile content of the present invention, thermal deformation and excellent flame retardancy and impact strength than when using a styrene-based impact reinforcing material It can be seen that a flame retardant thermoplastic resin composition can be obtained without a great change in temperature and melt flow index.

The present invention provides a thermoplastic resin composition which blends rubber modified styrene resin having a specific acrylonitrile content with a polyphenylene ether resin to provide excellent flame retardancy and impact strength while not lowering the heat deformation temperature and melt flow index. Has the effect of.

Simple modifications and variations of the present invention can be readily used by those skilled in the art, and all such variations or modifications can be considered to be included within the scope of the present invention.

Claims (3)

(A) 100 parts by weight of polyphenylene ether-based resin consisting of 60 to 95 parts by weight of (a ₁ ) polyphenylene ether resin and 5 to 40 parts by weight of (a ₂ ) vinyl aromatic polymer resin; (B) 1 to 30 parts by weight of the phosphate ester compound represented by the following formula (1); [Formula 1]

(In Formula 1, R ₃ , R ₄ , R ₆ and R ₇ are each C ₆ -C ₂₀ aryl or alkyl substituted C ₆ -C ₂₀ , and R ₅ is C ₆ -C ₂₀ aryl or alkyl substituted C ₆ -C ₂₀ aryl group derivative, l is the number average degree of polymerization, the average value of l is 0 to 3.) 0.05 to 5 parts by weight of (C) fluorinated polyolefin resin; And (D) 1 to 20 parts by weight of rubber-modified styrene resin; The rubber-modified styrene resin (D) is a flame-retardant thermoplastic resin composition, characterized in that the acrylonitrile content of the portion excluding the rubber component is 0.5 to 10% by weight. The method of claim 1, wherein the vinyl aromatic polymer resin is polystyrene, high impact polystyrene (HIPS), polychlorostyrene, polyα-methylstyrene, poly-butyl styrene is a mixture of one or more selected from the group consisting of Flame retardant thermoplastic resin composition. The flame retardant thermoplastic resin composition of claim 1, wherein the resin composition further comprises an additive selected from the group consisting of a plasticizer, a heat stabilizer, an antioxidant, a light stabilizer, a compatibilizer, a pigment, a dye, and an inorganic additive.