KR0149450B1 - Inflammable resin composition - Google Patents

Abstract

The present invention is to provide a thermoplastic resin composition excellent in flame retardancy and impact resistance, 10 to 90 parts by weight of polycarbonate resin, 10 to 90 parts by weight of polyester resin, 1 to 30 parts by weight of styrene-based copolymer resin, 0.5 polyfunctional compound -10 parts by weight, phosphorus compounds 0.01-2 parts by weight, phenol compounds 0.01-2 parts by weight, brominated bisphenol-A carbonate oligomer 5-25 parts by weight and antimony oxide 1-10 parts by weight, flame retardant, impact resistance As well as the improvement in processability during molding processing.

Description

Flame Retardant Resin Composition

The present invention relates to a thermoplastic resin composition excellent in flame retardancy and impact resistance. More specifically, polycarbonate resin, polyester resin, styrene copolymer polyfunctional compound, phosphorus compound and phenolic stabilizer, brominated bisphenol-acarbonate oligomer and antimony trioxide while maintaining a high impact strength while maintaining The present invention relates to a thermoplastic resin composition having excellent flame retardancy.

In general, polycarbonate resins are widely used in various fields because of their excellent impact resistance, heat resistance, transparency, and electrical properties, and good dimensional stability. On the other hand, polycarbonate resins have high melt viscosity during molding, resulting in poor flowability during molding and impact strength. It has the disadvantage of showing dependency and temperature dependence.

In addition, thermoplastic polyester resins represented by polyalkylene terephthalates such as polybutylene terephthalate and polyethylene terephthalate, when used by reinforcement such as glass fiber and inorganic filler, have higher mechanical strength, heat resistance and chemical resistance than other thermoplastic resins. While excellent in electrical insulation and molding processability, when used in a non-reinforced state, its rigidity, heat resistance, impact strength, etc. are limited and its use is limited, or handling difficulties occur. A method of adding is proposed.

For example, the addition of polyalkylacrylates and aromatic polycarbonate resins has been proposed in US Pat. No. 4,425,377, and in US Pat. Nos. 3,444,8 and 4040473, polybutylene terephthalate alone or in mixtures with other polyesters. A method of adding a monomer-grafted conjugated dienevinylaromatic copolymer and an aromatic polycarbonate has been disclosed.

In addition, US Pat. No. 4,804,94 has proposed the addition of core-shell resins and aromatic polycarbonates having butadiene core to polybutylene terephthalate, and US Pat. No. 4280948 describes dienes conjugated to polybutylene terephthalate copolymers. Either alone or in combination with a polyaromatic grafted vinylaromatic mixture, acrylic or methacrylate monomer.

However, in the case of simple melt mixing of polycarbonate and polyester, the two components may form copolymers due to undesirable phenomena such as transesterification reactions, and thus not only interfere with proper physical balance, but also rely on hydrolysis. Insufficient and difficult to determine optimum processing conditions. Therefore, in order to solve such a problem, a method of adding various stabilizers has been proposed. In Japanese Patent Laid-Open No. 52-11956, di-n-octadecyl phosphite, triphenol phosphite, and the like are added, US Patent No. 4560772 In the arc, boric acid is added, and in Japanese Patent Laid-Open No. 53-65355, a polymer having an amide group is added. However, di-n-octadecyl phosphite has a good effect of preventing the exchange of esters, but does not have excellent hydrolysis stability, and triphenyl phosphite, boric acid, and an amide group-containing polymer have insufficient effects as a transesterification inhibitor. In addition, the above-described prior arts have a problem in that the impact strength is improved only at a specific temperature and a specific thickness, and in particular, the thermal stability is not satisfactory.

As a specific example, the US Patent No. 4257937, in which acrylate is added as an impact reinforcing material, has an excellent impact strength at room temperature, but at a low temperature, the impact strength drops sharply and lacks thermal stability. In addition, U.S. Pat. Nos. 3,854,28 and 4280948 have excellent impact strength at room temperature and low temperature, but have a thickness dependence of impact strength, which is a disadvantage of polycarbonate resin, and exhibit high value at thin thickness (1/8 inch) and thick. At the time (1/4 inch), the strength decreased and the heat resistance was also poor.

In addition, when the resin composition according to the related art is used as a basic composition and the flame retardant is blended, the impact resistance is sharply lowered due to the hard properties of the flame retardant, which leads to the same problem as described above.

The present inventors have completed the present invention as a result of studying a method of improving the workability during molding processing, increasing impact resistance and imparting flame retardancy at the same time.

That is, the present invention is 10 to 90 parts by weight of polycarbonate resin, 10 to 90 parts by weight of polyester resin, 1 to 30 parts by weight of styrene copolymer resin, 0.5 to 10 parts by weight of polyfunctional compound, 0.01 to 2 parts by weight of phosphorus compound, A flame retardant resin composition comprising 0.01 to 2 parts by weight of a phenol compound, 5 to 25 parts by weight of bromate bisphenol-a carbonate oligomer, and 1 to 10 parts by weight of antimony oxide.

In the present invention, the polycarbonate resin may be used in an amount of 10 to 90 parts by weight and may be selected from an aromatic polycarbonate, an aliphatic polycarbonate, or an aliphatic-aromatic polycarbonate resin, and more preferably, a polypolymer polymerized by bisphenol-A and phosgene ( Bisphenol-A carbonate) having an average molecular weight of 10,000 to 80,000, preferably 20,000 to 60,000.

In the present invention, the polyester resin is used in 10 to 90 parts by weight and derivatives capable of forming dicarboxylic acid or esters thereof, 1,4-butanediol, 2,3-butanediol, 2,4-butanediol, ethylene glycol, propylene glycol and It is a polymer obtained through direct esterification or transesterification with the same diol or a derivative capable of esterification thereof as a main component. Examples of such polyester resins include polyethylene terephthalate and polybutylene terephthalate, but in the present invention, polybutylene terephthalate, which has a fast crystallization rate and does not require the addition of a nucleating agent, has an extreme viscosity (60% phenol in tetraphenol at 25 ° C. by weight). Preferably in a solvent of 40% ethane).

In the present invention, the styrenic copolymer resin is used in an amount of 1 to 30 parts by weight and a copolymerized site of styrene and olefin is used. Olefin monomers include diblocks and triblocks such as ethylene, propylene, 1-butene, 4-methyl-1-pentene, butadiene, and isoprene, and diblocks include styrene-butadiene-styrene (SBS), styrene-isoprene-styrene ( SIS) and triblock include styrene-ethylene / butylene-styrene (S-EB-S), and various composition ratios of styrene and olefins. Since the diblock contains unsaturated olefins and the heat resistance and processability are slightly inferior to those of the triblocks containing saturated olefins, it is preferable to use a triblock copolymer resin in the present invention.

In the present invention, the polyfunctional compound is used in an amount of 0.5 to 10 parts by weight, and a ternary copolymer of olefin-unsaturated carboxylic acid alkyl ester-maleic anhydride is used as the main chain, and polymethyl methacrylate, polystyrene or polyacrylonitrile styrene is added thereto. The back is grafted. The olefin monomer is ethylene, propylene, 1-butene, 4-methyl-1-pentene and the like, and the unsaturated carboxylic acid alkyl ester monomer is methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, methyl methacrylate. Elate, ethyl methacrylate, butyl methacrylate, hydroxyethyl acrylate, hydroxypropyl methacrylate, etc. are mentioned. Preferred polyfunctional compounds are those in which ethylene-ethylacrylate-maleic anhydride is the main chain and polystyrene is grafted at a weight ratio of 7: 3.

In the present invention, the phosphorus compound is 0.01 to 2 parts by weight and has the structure of the following general formula (I) or (II) as a phosphate in the form of a monoester or a diester, and it is preferable to use one or two of them. .

(Wherein R ₁ , R ₂ , R ₃ are the same or different aliphatic alkyl groups of 1 to 30 carbon atoms)

Specific examples include methyl dihydrogen phosphate, ethyl dihydrogen phosphate, 2-ethylnucleosil dihydrogen phosphate, decyl dihydrogen phosphate, dodecyl dihydrogen phosphate, tridecyl dihydrogen phosphate, stearyl dihydrogen phosphate Mono esters such as dimethylhydrogen phosphate, diethylhydrogen phosphate, dibutylhydrogen phosphate, diisoamylhydrogen phosphite, dioctylhydrogen phosphite, diisooctylhydrogen phosphite, bis (2-ethyl For example, diesters such as hexyl) hydrogen phosphite, didodecylhydrogen phosphite and dioctadecylhydrogen phosphite are examples.

In the present invention, a phenolic compound is used in an amount of 0.02 to 2 parts by weight, and as a hindered phenolic compound, 2,2′-methylenebis (4-ethyl-6-t-butylphenol) and tris (4-t-butyl-3 -Hydroxy-2,6-dimethylbenzyl) -1,3,5-triazine-2,4,6-trione, 2,2'-ethylenebis (4-methyl-6-t-butylphenol), Triethyleneglycol-bis-3- (3-t-butyl-4-hydroxy-5-methyl-phenyl) -propinate, 1,6-hexane-diol-bis-3- (3,5-di-t -Butyl-4-hydroxy-phenyl) -propinate, 2,4-bis- (n-octylthio) -6- (4`-hydroxy-3`, 5`-di-t-butylanirio) -1,3,5-triazine, tetrakis (methylene-3,5-di-t-butyl-4-hydroxy-phenyl-propinate) methane, 2,2'-thiodiethyl-bis [3- (3,5-di-t-butyl-4-hydroxy-phenyl)]-propinate, an octadecyl-3- (3,5-di-t-hydroxy-phenyl) -propinate, etc. are mentioned. .

In the present invention, the bromate bisphenol-A carbonate oligomer and the antimony trioxide are used as the flame retardant component, and the ratio of the bromate bisphenol-A carbonate oligomer and the antimony trioxide is preferably in a ratio of 1: 1 to 5: 1. The bromate bisphenol-A carbonate oligomer used in the present invention is preferably free of toxic by-products during molding at high temperatures. Particularly preferred examples thereof include the following general formula (III), and the amount used is 5 to 25 weight. The addition is good and the antimony trioxide is preferably 1 to 10 parts by weight.

Wherein X ₁ and X ₂ are hydrogen, methyl, ethyl, methyl, ethyl with cancellation or cancellation;

X ₃ is hydrogen, methyl, ethyl or cancellation, with at least half of the cancellations substituted;

n is an integer of 5 to 10.)

In preparing the flame retardant resin composition of the present invention, after mixing the composition in a super mixer, a single screw extruder or a twin screw extruder may be used, and the temperature during extrusion may be 220 ° C. to 270 ° C., preferably 230 ° C. to 250 ° C. .

Hereinafter, the present invention will be described in detail in Examples and Comparative Examples.

Example 1

Extreme viscosity (measured at 25 ° C. in a solvent having phenol: tetrachloroethane = 6: 4) 22.7 parts by weight of polybutylene terephthalate (PBT) of 0.9, 71.3 parts by weight of polycarbonate (PC) having an average molecular weight of 25,000 5 parts by weight of Chemical's Kraton G-1657 (styrene-ethylene / butylene-styrene) and polystyrene grafted with A-8100 (ethylene-ethyl acrylate-maleic anhydride hydride) from Nippon Oil Apparel. 7: 3) 2 parts by weight, Mark AX-710.5 part by Asahi Denka Co., Ltd., < RTI ID = 0.0 > Iganox 1010 < / RTI > (Detrakis (methylene-3,5-di-t-butyl-4-hydroxy-phenylpropy) Nate) methane) 0.3 parts by weight, Cray Lake Chemical's BC-58 (phenoxyternate tetrabromobisphenol-A carbonate oligomer) 15.0 parts by weight, Cheil Retardant Co., Ltd. After mixing using a twin screw extruder 230 The pellet was extruded at a temperature of 250C to 250C. In order to measure the physical properties, pellets were sufficiently dried at 100 ° C. for at least 4 hours, and then injected at a temperature of 220 ° C. to 240 ° C. using an ENGEL injection machine to obtain injection specimens for measurement of ASTM standards. The specimen thus prepared was measured for impact strength according to ASTM D256, tensile yield strength and elongation at break according to ASTM D638, flexural strength according to ASTM D790, and flame retardancy was measured according to the UL94 standard (1/6 inch thickness of the test specimen). Table 1 shows.

EXAMPLES 2-6

Table 1 shows the results of measuring the physical properties of the same numerical value as in Example 1 by varying the content as shown in Table-1.

Comparative Example 1

Extreme viscosity (phenol: tetrachloroethane = 6: 4, measured at 25 ° C) 22.7 parts by weight of polybutylene terephthalate (PBT) of 0.9, 71.3 parts by weight of polycarbonate (PC) having an average molecular weight of 25,000, Kanega 5 parts by weight of B-56 (MBS) of Puchi Chemical Corporation, 0.5 parts by weight of Mart AX-71 of Asahi Denka Co., Ltd., ganoxox 1010 (detrakisu (methylene-3,5-di-t-butyl-4-) 0.3 parts by weight of hydroxy-phenylpropinate) methane), 15.0 parts by weight of BC58 (phenoxyternate tetrabromobisphenol-A carbonate oligomer) of Cray Lake Chemical, and 6.0 parts by weight of Cheil Flame Retardant Co., Ltd. After mixing in a supermix and extruded at a temperature of 230 ℃ to 250 ℃ using a JSW twin screw extruder to obtain a pellet. In order to measure physical properties, the pellets were sufficiently dried at 100 ° C. for at least 4 hours, and then injected at a temperature of 220 ° C. to 240 ° C. using an ENGEL injection machine to obtain injection specimens for measurement of ASTM standards. The specimens thus prepared were measured for impact strength according to ASTM D256, tensile yield strength and elongation at break according to ASTM D638, flexural strength according to ASTM D790, and flame retardancy was measured according to the UL94 standard (1/6 inch thickness of injection machine piece). -1 is shown.

Comparative Example 2-4

Table 1 shows the results of measuring the physical properties of the same resin as in Comparative Example 1 by varying the content as shown in Table-1.

Claims (7)

10 to 90 parts by weight of polycarbonate resin, 10 to 90 parts by weight of polyester resin, 1 to 30 parts by weight of styrene-based copolymer resin, 0.5 to 10 parts by weight of polyfunctional compound, 0.01 to 2 parts by weight of phosphorus compound, 0.01 to 0.01 parts by weight of phenol compound A flame-retardant resin composition comprising 2 parts by weight, 5-25 parts by weight of bromate bisphenol-A carbonate oligomer and 1-10 parts by weight of antimony oxide. The flame retardant resin composition according to claim 1, wherein the polycarbonate resin has an aromatic bisphenol-A unit and an average molecular weight of 10,000 to 80,000. The flame retardant resin composition according to claim 1, wherein the polyester resin is polybutylene terephthalate having an intrinsic viscosity of 0.4 to 1.2. The flame retardant resin composition according to claim 1, wherein the styrene copolymer resin is formed of diblock or triblock as a copolymer resin of styrene and olefin. The flame retardant resin composition according to claim 1, wherein the polyfunctional compound is made of ethylene-acrylate-maleic anhydride and grafted with polystyrene. The flame retardant resin composition according to claim 1, wherein the phosphorus compound is one or two phosphates in monoester or diester form. The flame retardant resin composition according to claim 1, wherein the phenolic compound is tetrakis (methylene-3,5-di-t-butyl-4-hydroxy-phenyl-propynate) methane.