KR100496708B1 - Thermoplastic Flameproof Resin Composition - Google Patents

Abstract

The thermoplastic resin composition having flame retardancy of the present invention comprises (A) 40 to 95 parts by weight of rubber-modified styrene resin; (B) 5 to 60 parts by weight of polyphenylene ether resin; (C) 10 to 40 parts by weight of styrene resin; (D) 2 to 30 parts by weight of a styrene-acrylonitrile copolymer resin having an acrylonitrile content of 5 to 18% by weight based on 100 parts by weight of the base resin (A) + (B) + (C); (E) 0.5 to 30 parts by weight of the cyclic alkyl phosphonic acid compound based on 100 parts by weight of the base resin (A) + (B) + (C); And optionally (F) 0 to 20 parts by weight of an aromatic phosphate ester compound based on 100 parts by weight of the base resin (A) + (B) + (C).

Description

Thermoplastic Flameproof Resin Composition

Field of invention

The present invention relates to a thermoplastic flame retardant resin composition. More specifically, the present invention is a ring as a flame retardant in a resin blend composed of a rubber modified styrene resin, a polyphenylene ether resin, a styrene resin and a styrene-acrylonitrile copolymer resin having an acrylonitrile content of 5-18% by weight. The present invention relates to a thermoplastic resin composition in which an aromatic phosphate ester compound is optionally applied together with a type alkyl phosphonic acid compound.

Background of the Invention

Rubber-modified styrene resins, especially acrylonitrile-butadiene-styrene copolymer resins (hereinafter referred to as 'ABS resins') have good processability, excellent physical properties, particularly impact strength, and good appearance, so that electrical appliances, office equipment, etc. Has been applied to many different uses. However, it has been manufactured by applying a flame-retardant resin because of the disadvantage that it is generally combustible in application to heat-dissipating products such as personal computers or fax machines.

The most widely known flame retardant method is to provide a flame retardant properties by applying a halogen compound and an antimony compound in combination to the rubber-modified styrene resin. However, halogen-containing compounds can damage the mold due to hydrogen halide gas generated during processing and can have a fatal effect on the human body. 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.

Although a method of imparting flame retardancy to a resin composition by adding a compound containing phosphorus or nitrogen as a compound containing no halogen has been studied, the phosphorus compound alone lowers the heat resistance of rubber-modified styrene-based resin and lacks flame retardancy. There is a limit to the application.

In general, rubber-modified styrene-based resin has a disadvantage in that it is difficult to expect a flame retardant effect in a solid phase because there is little char remaining during combustion (Journal of Applied Polymer Science, 1998, vol 68, p1067). Therefore, by adding an additional char forming agent so that the char can be produced smoothly to obtain the desired flame retardancy.

Japanese Patent Application Laid-Open No. 7-48491 discloses a thermoplastic flame retardant resin prepared by applying a phosphate ester as a flame retardant to a thermoplastic copolymer resin such as a high-molecular polymer and an aromatic vinyl monomer, and adding a novolak-type phenol resin as a char forming agent. A method is disclosed. However, phenolic resins not only lower the heat resistance of styrene resins, but also have insufficient char forming ability, so that a relatively large amount of phosphate ester and novolak resin must be added to obtain desired flame retardancy, and thus mechanical strength such as heat resistance and impact strength is required. Has the disadvantage of further lowering.

In order to solve the above problems, the present inventors use a rubber-modified styrene copolymer, a polyphenylene ether resin and a styrene resin blend as a base resin, without using a phenol resin, and improve compatibility between them to improve thermal stability and flame retardancy. In order to improve the degree, a styrene-acrylonitrile copolymer having an acrylonitrile content of 5-18% by weight as a compatibilizer is applied to develop a thermoplastic resin having excellent mechanical properties and has already applied for a patent.

The present inventors have developed a resin composition having excellent flame retardancy, excellent heat resistance and mechanical properties by using a cyclic alkyl phosphonic acid compound as a flame retardant and optionally using an aromatic phosphate ester compound together.

An object of the present invention is to provide a thermoplastic resin composition having flame retardancy without fear of environmental pollution by using a non-halogen flame retardant.

Another object of the present invention is to provide a styrene-based thermoplastic resin composition having excellent flame resistance and excellent heat resistance, tensile strength and impact strength.

The above and other objects of the present invention can be achieved by the present invention described below. Hereinafter, the content of the present invention will be described in detail.

The thermoplastic resin composition having flame retardancy of the present invention comprises (A) 40 to 95 parts by weight of rubber-modified styrene resin; (B) 5 to 60 parts by weight of polyphenylene ether resin; (C) 10 to 40 parts by weight of styrene resin; (D) 2 to 30 parts by weight of a styrene-acrylonitrile copolymer resin having an acrylonitrile content of 5 to 18% by weight based on 100 parts by weight of the base resin (A) + (B) + (C); (E) 0.5 to 30 parts by weight of the cyclic alkyl phosphonic acid compound based on 100 parts by weight of the base resin (A) + (B) + (C); And (F) 0 to 20 parts by weight of the aromatic phosphate ester compound based on 100 parts by weight of the base resin (A) + (B) + (C). Hereinafter, each component of the present invention will be described in detail.

(A) Rubber modified styrene resin (ABS resin)

Rubber modified resin refers to a polymer in which a rubber polymer is dispersed in a particulate form in a matrix (continuous phase) made of a vinyl aromatic polymer, and an aromatic vinyl monomer and a vinyl monomer copolymerizable with an aromatic vinyl monomer in the presence of a rubber polymer are present. It is prepared by addition and polymerization. Such rubber-modified styrene resins can be prepared by known polymerization methods such as emulsion polymerization, suspension polymerization, and bulk polymerization, and are usually produced by mixing and extruding graft copolymer resin and copolymer resin. In the case of bulk polymerization, rubber modified styrene resins are produced by only one step reaction without graft copolymer resin and copolymer resin, but in all cases, the rubber content of the final rubber modified styrene resin components It is preferably 5 to 30% by weight relative to.

Examples of such resins include acrylonitrile-butadiene-styrene copolymer resins (ABS), acrylonitrile-acryl rubber-styrene copolymer resins (AAS), acrylonitrile-ethylenepropylene rubber-styrene copolymer resins, and the like. .

As the rubber-modified styrene-based resin (A) of the present invention, the graft resin can be applied alone or in combination with the copolymer resin, and it is preferable to mix the graft resin in consideration of each compatibility.

(a ₁ ) Styrene-acrylonitrile-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 which are hydrogenated with the diene rubber, isoprene rubber, Although acrylic rubbers, such as a chloroprene rubber and polybutylacrylic acid, and an ethylene-propylene-diene monomer terpolymer (EPDM), etc. can be mentioned, Among these, diene rubber is preferable, and butadiene rubber is used. It is more preferable. The content of rubber is preferably 10 to 60% by weight of the graft copolymer resin.

Among the graft polymerizable monomer mixtures, an aromatic vinyl monomer may include styrene, α-methylstyrene, p-methylstyrene, and the like, of which styrene is most preferred, and a monomer copolymerizable with the aromatic vinyl monomer may be added thereto. Apply at least one of them. As a monomer which can be introduced, vinyl cyanide-based compounds such as acrylonitrile and unsaturated nitrile-based compounds such as methacrylonitrile are preferable.

The graft copolymer is prepared by graft copolymerization of 90 to 40 wt% of monomers in 10 to 60 wt% of rubber. The component of the monomer grafted to the rubber is composed of 50 to 82% by weight of an aromatic vinyl monomer such as styrene and 18 to 50% by weight of an unsaturated nitrile monomer.

Further, in order to impart properties such as workability and heat resistance, monomers such as acrylic acid, methacrylic acid, maleic anhydride and N-substituted maleimide may be added and graft polymerization. The monomer is preferably added in an amount of 0 to 40 parts by weight based on 100 parts by weight of the graft resin.

In the production of the graft copolymer, in consideration of impact strength and appearance, the average size of the rubber particles is preferably in the range of 0.1 to 4 μm.

(a ₂ ) Styrene-acrylonitrile-containing copolymer resin

The copolymer resin is prepared according to the monomer ratio and compatibility of the graft copolymer prepared in the above composition except for rubber, and the components thereof are as follows.

As the aromatic vinyl monomer to be copolymerized, styrene, α-methyl styrene, p-methyl styrene, and the like may be added, of which styrene is most preferred, and the content of the aromatic vinyl monomer in the entire copolymer resin is 50 to 82. Weight percent. One or more monomers copolymerizable with the aromatic vinyl monomers may be introduced and applied thereto. As the monomer to be introduced, unsaturated nitrile compounds such as acrylonitrile and methacrylonitrile are preferable, and are introduced in an amount of 18 to 50% by weight in the components of the entire copolymer. Further, monomers such as acrylic acid, methacrylic acid, maleic anhydride, N-substituted maleimide and the like can be copolymerized by adding 0 to 40 parts by weight based on 100 parts by weight of the copolymer resin.

Rubber modified styrene resin (A) of the present invention is 20 to 100% by weight of the styrene-acrylonitrile-containing graft copolymer resin (a ₁ ) and the styrene-acrylonitrile-containing copolymer resin (a ₂ ) 0 to 80 wt%.

(B) polyphenylene ether resin

Rubber-modified styrene-based resin itself is used as a base resin by adding a polyphenylene ether-based resin because of its low flame retardancy and low rigidity and heat resistance. Polyphenylene ether resins usable in the present invention include poly (2,6-dimethyl-1,4-phenylene) ether, poly (2,6-diethyl-1,4-phenylene) ether, and 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, Copolymer of 4-phenylene) ether and poly (2,3,6-trimethyl-1,4-phenylene) ether and poly (2,6-dimethyl-1,4-phenylene) ether and poly (2, Copolymers of 3,5-triethyl-1,4-phenylene) ether. Of these, copolymers of poly (2,6-dimethyl-1,4-phenylene) ether with poly (2,3,6-trimethyl-1,4-phenylene) ether and poly (2,6-dimethyl- Preference is given to using 1,4-phenylene) ether, most preferably poly (2,6-dimethyl-1,4-phenylene) ether.

Although the degree of polymerization of the polyphenylene ether is not particularly limited, it is preferable that the intrinsic viscosity measured in the chloroform solvent at 25 ° C. is 0.2 to 0.8 in consideration of thermal stability and workability of the resin composition.

(C) styrene resin

It can be prepared using a bulk polymerization, suspension polymerization, emulsion polymerization, or a mixture thereof, and described as a bulk polymerization method of these polymerization methods as an example.

1 type selected from aromatic monoalkenyl monomers, alkyl ester monomers of acrylic acid or methacrylic acid with respect to 0 to 20 parts by weight of rubber selected from butadiene rubbers, isoprene rubbers, copolymers of butadiene and styrene or alkyl acrylate rubbers or the like The resin may be prepared by adding 80 to 100 parts by weight of one or more monomers and bulk polymerization using one or more initiators selected from benzoyl peroxide, t-butyl hydroperoxide, acetyl peroxide, and cumene hydroperoxide. . The above resin may be used alone or mixed with each other, a resin having a rubber content of 0 and a resin containing a rubber content.

(D) SAN resin having an acrylonitrile content of 5 to 18% by weight

The styrene-acrylonitrile copolymer resin is added to improve the compatibility of the ABS resin with the polyphenylene ether resin.

The styrene-acrylonitrile copolymer consists of 82 to 95% by weight of styrene and 5 to 18% by weight of acrylonitrile. The polymerization method of the styrene acrylonitrile copolymer may be prepared by applying emulsification, suspension, bulk polymerization, etc., and the weight average molecular weight is preferably in the range of 50,000 to 200,000. Monomers further copolymerizable to the styrene-acrylonitrile include methacrylate, phenylmaleimide, and the like, and styrene may be replaced with α-methylstyrene to improve heat resistance. If the styrene-acrylonitrile copolymer is not added, the compatibility of the blend of the rubber-modified styrene-based resin and the polyphenylene ether resin cannot be improved, and thus the mechanical strength is drastically lowered, making it difficult to apply the actual product.

The styrene-acrylonitrile copolymer resin (D) having an acrylonitrile content of 5 to 18% by weight is used in an amount of 2 to 30 parts by weight based on 100 parts by weight of the base resin (A) + (B) + (C). do.

(E) Cyclic Alkyl Phosphonic Acid Compounds

The cyclic alkyl phosphonic acid compound (E) used as the flame retardant in the present invention is represented by the following formula (I):

In formula (I), R ₁ , R ₂ are each independently an alkyl group of C ₁ -C ₄ , and x is 0 or 1.

Examples of the cyclic alkyl phosphonic acid compound represented by formula (I) include methyl-bis (5-ethyl-2-methyl-1,3,2, -dioxaphosphorin-5yl) methyl methyl phosphonic acid Ester P oxide, methyl-bis (5-ethyl-2-methyl-1,3,2, -dioxaphosphorinan-5yl) phosphonic acid ester P, P'-dioxide.

The cyclic alkyl phosphonic acid compound (E) is used in an amount of 0.5 to 30 parts by weight based on 100 parts by weight of the base resin (A) + (B) + (C).

(F) Aromatic Phosphate Ester Compounds

In the present invention, in addition to the cyclic alkyl phosphonic acid compound (E), an aromatic phosphate ester compound may be optionally added as a flame retardant. The aromatic phosphate ester compound (F) used in the present invention is represented by the following formula (II):

In formula (II), R ₃ , R ₄ , and R ₅ are each independently hydrogen or an alkyl group of C ₁ -C ₄ , and X is a C ₆ -C ₂₀ substituted with an aryl group or alkyl group of C ₆ -C ₂₀ . As an aryl group, it is derived from dialcohols, such as resorcinol, hydroquinol, bisphenol-A, and bisphenol-S, and m ranges from 0 to 4.

Examples of the aromatic phosphate ester compound represented by the formula (II) include triphenyl phosphate, tricresyl phosphate, trigyrenyl phosphate, tri (2,6-dimethylphenyl) phosphate, and tri (2,4, 6-trimethylphenyl) phosphate, tri (2,4-dibutylbutylphenyl) phosphate, tri (2,6-dibutylbutylphenyl) phosphate, and the like, when m is 1, resorcinol bis (diphenyl) Phosphate, resorcinolbis (2,6-dimethylphenyl) phosphate, resorcinolbis (2,4-dibutylbutylphenyl) phosphate, hydroquinolbis (2,6-dimethylphenyl) phosphate, hydroquinolbis (2 , 4-dibutylbutylphenyl) phosphate and the like are typical examples. These phosphoric acid ester compounds may be applied alone or in combination with each other.

The aromatic phosphate ester compound (F) is used in an amount of 0 to 20 parts by weight based on 100 parts by weight of the base resin (A) + (B) + (C).

In the preparation of the thermoplastic resin composition of the present invention, an antidripping agent, an impact modifier, an inorganic additive, a heat stabilizer, an antioxidant, a light stabilizer, a pigment, and a dye may be added according to each use. The inorganic additives to be added include asbestos, glass fibers, talc, ceramics, sulfates, and the like, which may be used within a range of 50 parts by weight based on 100 parts by weight of the base resin of the present invention.

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

Preparation and specifications of the base resin, compatibilizer and flame retardant additive used in the following Examples and Comparative Examples are as follows.

(A) Rubber modified styrene resin (ABS resin)

(a ₁ ) Graft ABS Resin

A monomer to be grafted to 50 parts by weight of butadiene rubber latex solid, 36 parts by weight of styrene, 14 parts by weight of acrylonitrile and 150 parts by weight of deionized water were added, and 1.0 parts by weight of potassium oleate and 0.4 parts by weight of cumene hydroperoxide based on the total solids. , 0.2 parts by weight of mercaptan-based chain transfer agent, 0.4 parts by weight of glucose, 0.01 parts by weight of iron sulfate hydrate, 0.3 parts by weight of sodium pyrophosphate, and maintained at 75 ° C. for 5 hours to complete the reaction to prepare graft ABS latex, 0.4 parts by weight of sulfuric acid was added to the solid content of the resin and solidified to prepare a graft copolymer resin (g-ABS) powder.

(a ₂ ) Styrene-containing copolymer resin (AN content: 25% by weight)

75 parts by weight of styrene, 25 parts by weight of acrylonitrile, 120 parts by weight of deionized water, 0.15 part by weight of azobisisobutyronitrile, 0.4 part by weight of tricalcium phosphate, 0.2 part by weight of mercaptan-based chain transfer agent, and the temperature from room temperature to 80 ° C. The copolymer resin (SAN) having an acrylonitrile content of 25% by weight was prepared by maintaining the temperature for 90 minutes and maintaining the temperature for 180 minutes at this temperature. This was washed with water, dehydrated and dried to prepare a SAN powder.

(B) polyphenylene ether resin (PPE)

As a poly (2,6-dimethyl-1,4-phenylene) ether (trade name: P-402) manufactured by Asahi Kasei Co., Ltd., a powder form having an average particle diameter of several tens of micrometers was used.

(C) styrene resin

(c ₁ ) General Purpose Polystyrene (GPPS)

Cheil Industries Co., Ltd. GPPS [trade name: HF-2680] used an average molecular weight of about 210,000.

(c ₂ ) Rubber reinforced Styrene resin (HIPS)

As the rubber-reinforced styrene resin (trade name: HG-1760S) of Cheil Industries, Ltd., a particle size of butadiene rubber was 0.4 µm and a rubber content of about 7% by weight was used.

(D) Styrene-acrylonitrile copolymer resin (AN content: 13 wt%)

Styrene 87 parts by weight, 13 parts by weight of acrylonitrile 120 parts by weight of deionized water, 0.1 part by weight of azobisisobutyronitrile, 1,1'di (tertiarybutylperoxy) 3,3 ', 5trimethylcyclohexane 0.2 Part by weight, 0.4 parts by weight of tricalcium phosphate and 0.2 parts by weight of mercaptan-based chain transfer agent were added, and the temperature was raised from room temperature to 80 ° C. for 90 minutes. The temperature was maintained at this temperature for 150 minutes, the temperature was raised to 95 ° C., and then maintained for 120 minutes. A copolymer resin (SAN) having an acrylonitrile content of 13% by weight was prepared. This was washed with water, dehydrated and dried to prepare a SAN powder.

(E) Cyclic Alkyl Phosphonic Acid Compounds

Rhodia cyclic alkyl phosphonic acid compound [trade name: Antiblaze 1045] methyl-bis (5-ethyl-2-methyl-1,3,2, -dioxaphosphorin-5yl) methyl methyl With 8% phosphonic acid ester P oxide and 85% methyl-bis (5-ethyl-2-methyl-1,3,2, -dioxaphosphorin-5yl) phosphonic acid ester P, P'-dioxide It was made and the phosphorus content was 20.8%.

(F) Aromatic Phosphate Ester Compounds

Triphenyl phosphate having a melting point of 48 ° C. was used.

Examples 1-3 and Comparative Examples 1-3

The components were added in the amounts shown in Table 1 and extruded at a temperature range of 200 to 280 ° C. in a conventional twin screw extruder to prepare pellets. The prepared pellets were dried at 80 ° C. for 3 hours, and then injected in a 6 Oz injection machine at a molding temperature of 220 to 280 ° C. and a mold temperature of 40 to 80 ° C. to prepare a physical specimen. The prepared specimens were measured for flame retardancy at a thickness of 2.0 mm according to UL 94 VB flame retardancy, measured for Izod impact strength according to ASTM D256, and melt flow index (g / 10min) at 220 ° C and 10 kg according to ASTM D-1238. Was measured and the heat deflection temperature was measured according to ASTM D1525.

Example Comparative Example One 2 3 One 2 3 Composition (part by weight) (A) ABS (a ₁ ) 30 30 30 30 30 30 (a ₂ ) 20 20 20 20 20 20 (B) PPE 30 30 30 30 30 30 (C) styrene resin (c ₁ ) 20 20 - 20 20 - (c ₂ ) - - 20 - - 20 (D) SAN 13 13 13 - 13 13 (E) cyclic alkyl phosphonic acids 12 8 4 12 - - (F) aromatic phosphate esters - 4 10 - 12 12 Properties Flame retardant (2.0mm) V-0 V-0 V-0 V-0 V-1 V-1 Izod impact strength (1/8 ") (kgcm / cm) 28 26 33 8 28 33 Melt Flow Index (g / 10min) 29 31 31 31 35 30 Heat Deflection Temperature (℃) 114 95 88 113 80 81

As shown in the table above, when a cyclic alkyl phosphonic acid compound is used as a flame retardant or when a cyclic phosphazene compound is used together with a phosphate ester compound (Examples 1 to 3), when a phosphate ester compound is applied alone ( It can be seen that flame retardancy is superior to Comparative Examples 1 to 3), and that heat resistance, tensile strength, and impact strength are excellent.

The present invention relates to a cyclic alkyl force as a flame retardant in a resin blend comprising a rubber modified styrene resin, a polyphenylene ether resin, a styrene resin and a styrene-acrylonitrile copolymer resin having an acrylonitrile content of 5-18% by weight. Invention to provide a styrene-based thermoplastic resin composition using a non-halogen-based flame retardant with a non-halogen-based flame retardant, optionally by applying an aromatic phosphate ester compound together with a phonic acid compound, excellent flame resistance and excellent heat resistance, tensile strength and impact strength Has the effect of.

Simple modifications or changes of the present invention can be easily carried out by those skilled in the art, and all such modifications or changes can be seen to be included in the scope of the present invention.

Claims (6)

(A) (a ₁₎ a rubber content of 10 to 60% by weight and, except for the rubber component, and an acrylonitrile content of 18 to 50% by weight of styrene-acrylonitrile graft copolymer resin, 20 to 100% by weight, and ( a ₂ ) 40 to 95 parts by weight of a rubber-modified styrene resin composed of 0 to 80% by weight of styrene-acrylonitrile copolymer resin having an acrylonitrile content of 18 to 50% by weight; (B) 5 to 60 parts by weight of a polyphenylene ether resin; (C) 10 to 40 parts by weight of styrene resin; (D) 2 to 30 parts by weight of a styrene-acrylonitrile copolymer resin having an acrylonitrile content of 5 to 18% by weight based on 100 parts by weight of the base resin (A) + (B) + (C); And (E) 0.5 to 30 parts by weight of the cyclic alkyl phosphonic acid compound based on 100 parts by weight of the base resin (A) + (B) + (C); Flame-retardant thermoplastic resin composition, characterized in that consisting of. The flame-retardant thermoplastic resin composition of claim 1, wherein the cyclic alkyl phosphonic acid compound (E) is a compound represented by the following formula (I) or a mixture thereof: In formula (I), R ₁ , R ₂ are independently of each other an alkyl group of C ₁ -C ₄ , x is 0 or 1. The flame-retardant thermoplastic resin according to claim 1, further comprising an aromatic phosphate ester compound (F) in an amount of 20 parts by weight or less based on 100 parts by weight of the base resin (A) + (B) + (C). Composition. The flame retardant thermoplastic resin composition according to claim 3, wherein the aromatic phosphate ester compound (F) is a compound represented by the following formula (II) or a mixture thereof: In formula (II), R ₃ , R ₄ , and R ₅ are each independently hydrogen or an alkyl group of C ₁ -C ₄ , and X is a C ₆ -C ₂₀ substituted with an aryl group or alkyl group of C ₆ -C ₂₀ . As an aryl group, it is derived from dialcohols such as resorcinol, hydroquinol, bisphenol-A, bisphenol-S, and m ranges from 0 to 4. The flame retardant thermoplastic resin composition of claim 1, further comprising an dripping inhibitor, an impact modifier, an inorganic additive, a heat stabilizer, an antioxidant, a light stabilizer, a pigment, and / or a dye. delete