KR100550261B1 - Flame Retardant Styrene Resin Composition - Google Patents

Abstract

The flame-retardant styrene-based thermoplastic resin composition of the present invention (A) 100 parts by weight of rubber-reinforced polystyrene resin prepared by mixing and polymerizing rubber and aromatic monoalkenyl monomer and / or alkyl ester monomer; (B) 5 to 20 parts by weight of 2,4,6-tri (2,4,6-tribromophenoxy) -1,3,5-triazine compound; And (C) 1 to 3 parts by weight of a flame retardant aid.

Flame retardant styrenic thermoplastics composition, 2,4,6-tri (2,4,6-tribromophenoxy) -1,3,5-triazine, flame retardant aid, antimony trioxide

Description

Flame Retardant Styrene Resin Composition

Field of invention

The present invention relates to a styrene resin composition having flame retardancy. More specifically, the present invention comprises a 2,4,6-tri (2,4,6-tribromophenoxy) -1,3,5-triazine compound and a flame retardant aid in a rubber-reinforced polystyrene resin copolymer, The present invention relates to a styrene resin composition having flame retardancy and excellent thermal stability.

Background of the Invention

In general, styrene-based resins have good processability and mechanical strength, and are mainly used as exterior materials for electrical and electronic products. However, the resin itself is not resistant to the flame, and when the spark is ignited by an external ignition source, the resin itself acts as an energy to assist combustion, thereby continuously spreading the fire. In recent years, in the case of televisions among electronic products, molded products are becoming larger and thinner, and colors are spreading from dark black to pale bright colors. Therefore, styrene-based resins applied in these fields have a problem in that not only flame retardancy but also injection molding moldability and thermal stability must be simultaneously met.

Generally, the method of imparting flame retardancy to a resin may be divided into an additional flame retardant method in which a flame retardant and a flame retardant aid are added, and a polymerized flame retardant method in which a resin is prepared using a special monomer containing a flame retardant atom during polymerization. Among them, polymerized flame retardation has been studied in a pilot scale stage, but commercialized products have not been released due to high cost and difficulty in achieving flame retardancy. Therefore, most commercialized flame retardant resins are prepared by an additive flame retardant method in which a flame retardant containing halogen or phosphorus, which is an inactive element, is added during compounding.

An additional flame retardant method in which a flame retardant is added to impart flame retardancy to a styrene resin is prepared by adding one or more components selected from halogen-containing organic compounds and antimony-containing inorganic compounds to the resin. By the way, the halogen-containing organic compound is mainly bromine or chlorine compound, when added to the styrene resin is very excellent in flame retardancy, but causes serious degradation in the overall physical properties. In addition, there is a problem that the thermal stability is lowered. Therefore, in manufacturing a flame retardant resin, a technique of minimizing physical properties and side effects while maintaining excellent flame retardancy is very important.

Conventional UL94 V-2 products are designed to cause drips of the resin in a short time during combustion by promoting decomposition of the resin by decomposition of the flame retardant. Due to this feature, the flame retardant is designed to cause thermal decomposition quickly, while this characteristic causes the decomposition of the flame retardant at the normal processing temperature of the resin, which lowers the thermal stability of the resin itself, thereby causing silver streak. There is a disadvantage, or heat discoloration from light to dark red color occurs. In addition, in order to maintain the flame retardancy of UL94 V-2 products, an important combination of a rubber-reinforced polystyrene resin copolymer, a flame retardant and a flame retardant aid is required.

On the other hand, the present inventors, in order to overcome the above problems, through the combination of halogen compounds, which are the main flame retardant in the rubber-reinforced polystyrene resin copolymer, and antimony trioxide as a flame retardant aid, the flame resistance of UL94 V-2 products and thermal stability during injection molding It has led to the development of a flame retardant thermoplastic resin composition suitable for injection molded articles of large products, in particular large televisions, by greatly improving the flow characteristics while maintaining the.

An object of the present invention is to provide a UL94 V-2 flame-retardant styrene resin composition excellent in injection molding molding properties to be applied to large thin-film molded article.

Another object of the present invention is to provide a flame retardant styrene-based resin composition which can be used for high temperature injection processing and improves the thermal stability of the resin to prevent thermal discoloration of the molded article and to make the molded article beautiful.

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

Summary of the Invention

The flame-retardant styrene-based thermoplastic resin composition of the present invention (A) 100 parts by weight of rubber-reinforced polystyrene resin prepared by mixing and polymerizing rubber and aromatic monoalkenyl monomer and / or alkyl ester monomer; (B) 5 to 20 parts by weight of 2,4,6-tri (2,4,6-tribromophenoxy) -1,3,5-triazine compound; And (C) 1 to 3 parts by weight of a flame retardant aid.

Hereinafter, the detailed description of each component of the flame-retardant styrene resin composition of the present invention is as follows.

Detailed Description of the Invention

(A) Rubber reinforced polystyrene resin

The rubber-reinforced polystyrene resin according to the present invention is prepared by mixing a rubber with an aromatic monoalkenyl monomer and / or an alkyl ester monomer and polymerizing it using a polymerization initiator.

The rubber is preferably used in 5 to 15 parts by weight of a rubber selected from the group consisting of butadiene rubbers, isoprene rubbers, copolymers of butadiene and styrene, alkyl acrylate rubbers and the like.

In addition, the monomer is preferably 85 to 95 parts by weight of one or more monomers selected from the group consisting of aromatic monoalkenyl monomers and alkyl ester monomers of acrylic acid or methacrylic acid.

The polymerization initiator may be prepared by bulk polymerization using one or more polymerization initiators selected from the group consisting of benzoyl peroxide, t-butyl hydroperoxide, acetyl peroxide, and cumene hydroperoxide. have.

The rubber-reinforced polystyrene resin may be prepared using a bulk polymerization, suspension polymerization, emulsion polymerization or a mixture thereof, in the embodiment of the polymerization method used a rubber-reinforced polystyrene resin produced by the bulk polymerization method.

(B) 2,4,6-tri (2,4,6-tribromophenoxy) -1,3,5-triazine

In the present invention, since the melt type aliphatic halogenated flame retardant has a problem in thermal stability, it is an aromatic halogenated flame retardant to improve thermal stability. 2,4,6-tri (2,4,6-tribromophenoxy) -1,3,5-triazine (B) is used as the main flame retardant. By using the flame retardant to improve the thermal stability and improve the weather resistance of the resin while maintaining the flame retardancy of the UL94 V-2 product, it is possible to manufacture a flame retardant thermoplastic resin composition that is excellent in formability as well as applied to a bright color product will be.

The 2,4,6-tri (2,4,6-tribromophenoxy) -1,3,5-triazine compound (B) is a substance represented by the following formula (1).

[Formula 1]

The 2,4,6-tri (2,4,6-tribromophenoxy) -1,3,5-triazine compound (B) is 5 to 20 based on 100 parts by weight of rubber-reinforced polystyrene resin (A) Preference is given to using parts by weight. If less than 5 parts by weight of the flame retardant effect is insufficient, and when used in excess of 20 parts by weight is not preferable because it impairs the balance of mechanical properties.

(C) flame retardant supplements

The flame retardant adjuvant is a combination selected from antimony trioxide, paraffin chloride, and potassium sulfone sulfate, It is added to further improve the flame retardancy of the bromine flame retardant. The antimony trioxide is preferably used 1 to 3 parts by weight based on 100 parts by weight of the base resin (A) of the present invention. If the amount is less than 1 part by weight, a sufficient flame retardant effect cannot be obtained. If the content is more than 3 parts by weight, the balance of the physical properties of the resin composition is impaired.

In addition to the above components, the flame retardant thermoplastic resin composition of the present invention may add inorganic additives, antioxidants, other light stabilizers, pigments, and dyes in required amounts depending on their respective uses.

The resin composition of the present invention can be used for molding a variety of products, in particular, because of the thermal stability and UL94 V-2 flame retardancy, injection of the high temperature of the housing of all V-2 electrical and electronic products that require flame retardancy and thermal stability Suitable for manufacture

The invention can be better understood by the following examples, which are intended for the purpose of illustration of the invention and are not intended to limit the scope of protection defined by the appended claims.

Example

In Examples 1 to 3 and Comparative Examples 1 to 3 of the present invention, (A) rubber-reinforced polystyrene resin was used as HR-1360 of Cheil Industries, and (B) 2, which is an aromatic halogen flame retardant represented by Chemical Formula 1, 4,6-tri (2,4,6-tribromophenoxy) -1,3,5-triazine was used, and (B ') tetrabromo bisphenol represented by the following formula (2') as an aliphatic halogen flame retardant A bis (2,3-dibromopropylether) compound was used, and (C) antimony trioxide was used as a flame retardant aid.

[Formula 2]

Examples 1 to 3

The resin composition obtained by mixing according to the composition of each component of the composition shown in Table 1 was uniformly mixed with a Tumbler mixer, then extruded with a twin screw extruder to produce pellets, and from the prepared pellets to injection molding 1/8 "thick flame retardant specimens, physical properties specimens and thermal stability test specimens were prepared and evaluated.

Comparative Examples 1 to 3

Comparative Examples 1 to 3 were prepared in the same manner as in Examples 1 to 3 except that the composition of each component was changed as described.

ingredient Example Comparative Example One 2 3 One 2 3 (A) Rubber reinforced styrene resin 2 types 100 100 100 100 100 100 (B) 2,4,6-tri (2,4,6-tribromophenoxy) -1,3,5-triazine compound 15 13 10 - 15 10 (B ') tetra bromo bisphenol A bis (2,3-dibromopropyl ether) compound - - - 15 - - (C) antimony trioxide 3 2 One 3 5 0.5

(Unit is by weight)

Measurement of the flame retardancy of the resin composition prepared by the above method was carried out according to the UL-94 determination test method. For reference, the V-2 grade is given to resins that extinguish a flame by dropping it on the specimen within a specified time when the specimen is ignited. In order to evaluate the mechanical properties, a notch was made in a 1/8 "IZOD specimen by the ASTM D256 evaluation method. The thermal stability evaluation was performed during injection molding after the resin stayed in the injection cylinder cylinder for 10 minutes. The degree of thermal stability appearing on the specimen was measured and evaluated.

Table 2 shows the physical properties of the resins prepared in Examples 1-3 and Comparative Examples 1-3. Examples 1-3 are the case where a flame retardant and a flame retardant adjuvant are used in the range by this invention, and comparative Examples 1-3 are the case where it used out of the said range.

ingredient Example Comparative Example One 2 3 One 2 3 (1) Flame retardant V-2 V-2 V-2 V-2 V-2 Fail (2) Total burning time (seconds) 140 150 160 145 125 200 (3) Injection stay result ○ ◎ ◎ × ○ ◎ (4) mechanical properties 9.8 10.0 10.5 9.0 8.9 10.7 (3) Indicates the thermal stability after injection retention at 250 ° C for 10 minutes-◎ (very good), ○ (good), × (bad-black lines / discoloration occur) (4) ASTM D256 Izod IZOD Impact Strength

From the results in Table 2 above, 2,4,6-tri (2,4,6-tribromophenoxy) -1,3,5-triazine compound (B) and an aromatic flame retardant as a flame retardant adjuvant In the embodiment in which antimony (C) was used in the composition range of the present invention, all of flame retardancy, thermal stability and mechanical properties were excellent. Comparative Example 1 using a large amount of tetra bromo bisphenol A bis (2,3-dibromopropyl ether) compound was excellent in flame retardancy, but the thermal stability was very low. In Comparative Example 2, the mechanical properties tended to be somewhat lowered due to the excessive effects of the flame retardant and antimony trioxide. In Comparative Example 3, the flame retardant problem occurred due to the lack of the flame retardant and antimony trioxide.

The present invention provides flame retardancy by using an appropriate amount of 2,4,6-tri (2,4,6-tribromophenoxy) -1,3,5-triazine compound and antimony trioxide in a rubber-reinforced polystyrene resin copolymer. This has the effect of providing a thermoplastic resin composition having excellent thermal stability and mechanical properties at the same time.

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 (3)

(A) 100 parts by weight of rubber-reinforced polystyrene resin prepared by mixing and polymerizing rubber with aromatic monoalkenyl monomer and / or alkyl ester monomer; (B) 5 to 20 parts by weight of 2,4,6-tri (2,4,6-tribromophenoxy) -1,3,5-triazine compound, which is an aromatic halogen flame retardant represented by the following formula (1); And [Formula 1]

(C) 1-3 parts by weight of flame retardant aids; Flame-retardant styrene resin composition, characterized in that consisting of. The rubber of claim 1, wherein the rubber of the rubber-reinforced polystyrene resin (A) comprises 5 to 15 parts by weight of rubber selected from the group consisting of butadiene rubber, isoprene rubber, copolymers of butadiene and styrene, and alkyl acrylate rubber Flame-retardant styrene resin composition, characterized in that. The flame retardant styrene resin composition according to claim 1, wherein the flame retardant auxiliary agent is one or more selected from the group consisting of antimony trioxide, paraffin chloride, and potassium sulfon sulfate.