KR20030087492A - Flame Retardant Styrenic Resin Composition - Google Patents

Abstract

PURPOSE: Provided is a fire-retardant styrene-based resin composition, which is excellent in fire retardancy, weather resistance, and heat stability and can be used at high temperature. CONSTITUTION: The fire-retardant styrene-based resin composition comprises 100pts.wt. of a rubber-reinforced polystyrene resin produced by polymerizing a rubber and an aromatic monoalkenyl monomer and/or an alkyl ester monomer, wherein the rubber is selected from the group consisting of a butadiene rubber, an isoprene rubber, a copolymer of butadiene and styrene, and an alkylacrylated rubber; 1-5pts.wt. of 2,2-bis(4-2-3-dibromopropoxy)'-3,5-dibromophenyl propane(formula I); 5-10pts.wt. of 2,4,6-tri(2,4,6-tribromophenoxy)-1,3,5-triazine(formula II); and 0.5-5pts.wt. of a fire-retardant selected from the group consisting of antimony trioxide, chlorinated paraffin, potassium sulfone sulfate, and a mixture thereof.

Description

Flame retardant styrene resin composition {Flame Retardant Styrenic Resin Composition}

Field of invention

The present invention relates to a styrene resin composition having flame retardancy. More specifically, the present invention provides a rubber-reinforced polystyrene resin copolymer, 2,2-bis (4-2-3-dibromopropoxy) '-3,5-dibromophenyl propane, 2,4,6-tri A flame retardant styrene resin composition having excellent weather resistance composed of (2,4,6-tribromophenoxy) -1,3,5-triazine and a flame retardant aid.

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, styrene-based resins do not have flame resistance in themselves, and when the spark is ignited by an external ignition source, the resin itself acts as an energy to help burn and continuously burns. Will spread. Therefore, in view of the above point, in order to ensure the stability of fire of electronic products, in the United States, Europe, etc., only the flame-retardant resin is legalized to be used in the manufacture of molded articles of electronic product exterior materials.

The method of imparting flame retardancy to a resin can 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 by using a special monomer containing a flame retardant atom during polymerization. Among them, polymerized flame retardant methods have been studied in a pilot scale, but commercialized products have not been released due to high cost and difficulty in achieving flame retardancy. Therefore, most commercialized flame retardant resins have been prepared by the addition flame retardant method of adding a flame retardant containing halogen or phosphorus, which is an inert element 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 styrenic resin, while the flame retardancy is very excellent, causing a serious deterioration in the overall physical properties, especially thermal stability is deteriorated. Therefore, in manufacturing a flame retardant resin, a technique of minimizing physical properties and side effects while maintaining excellent flame retardancy is very important.

In addition, in recent years, the market of TVs among electronic products has been formed due to the trend toward larger and thinner films, and the color has also been widened from dark to light colors. Therefore, styrene resins applied in these fields must satisfy not only flame retardancy but also moldability and thermal stability at the same time.

Conventional UL94 V-2 products are designed to cause drips of resins in a short time during combustion by promoting decomposition of resins by decomposition of flame retardants. Due to these characteristics, the flame retardant is designed to cause thermal decomposition quickly, while the decomposition of the flame retardant occurs at the normal processing temperature of the resin, and the thermal stability of the resin itself is degraded, resulting in poor silver streak, or There is a disadvantage that the heat discoloration from light color to dark red color occurs.

On the contrary, the present inventors added halogen compounds and flame retardant aids as main flame retardants to rubber-reinforced polystyrene resin copolymers to reinforce thermal stability while maintaining the flame retardancy of UL94 V-2 products. The application is of course to develop a flame retardant thermoplastic resin composition suitable for injection molding of large products.

An object of the present invention is to provide a UL94 V-2 styrene resin composition excellent in flame retardancy.

Another object of the present invention is to provide a flame-retardant styrene-based resin composition that can be used at a high temperature, and excellent in heat stability in which thermal discoloration is prevented.

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 flame retardant styrenic thermoplastic resin composition of the present invention comprises (A) 100 parts by weight of rubber-reinforced polystyrene resin prepared by mixing and polymerizing rubber with an aromatic monoalkenyl monomer and / or an alkyl ester monomer; (B) 1 to 5 parts by weight of 2,2-bis (4-2-3-dibromopropoxy) '-3,5-dibromophenyl propane; (C) 5 to 10 parts by weight of 2,4,6-tri (2,4,6-tribromophenoxy) -1,3,5-triazine; And (D) 0.5 to 5 parts by weight of flame retardant auxiliaries, the details of each of which are as follows.

(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 the same using a polymerization initiator.

The rubber is preferably 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 aromatic monoalkenyl monomers, alkyl ester monomers of acrylic acid or methacrylic acid.

As the polymerization initiator, the resin may be prepared by bulk polymerization using one or more initiators selected from benzoyl peroxide, t-butyl hydroperoxide, acetyl peroxide, and cumene hydroperoxide.

The rubber-reinforced polystyrene resin may be prepared using a bulk polymerization, suspension polymerization, emulsion polymerization or a mixture thereof, and among the polymerization methods, a bulk polymerization method may be preferably used.

(B) 2,2-bis (4-2-3-dibromopropoxy) '-3,5-dibromophenyl propane

In order to maintain UL94 V-2 flame retardant in the present invention, an aliphatic halogen flame retardant, particularly a bromine flame retardant, is used. As the brominated flame retardant, 2,2-bis (4-2-3-dibromopropoxy) '-3,5-dibromophenyl propane is preferable.

The 2,2-bis (4-2-3-dibromopropoxy) '-3,5-dibromophenyl propane is represented by the following formula (I):

The aliphatic halogenated flame retardant (B) is preferably used 1 to 5 parts by weight based on 100 parts by weight of rubber-reinforced polystyrene resin (A). When 1 part by weight or less is added, a flame retardant timeout occurs, and when 5 parts by weight or more is used, a problem occurs in thermal stability. However, in the present invention, such problems by applying 2,4,6-tri (2,4,6-tribromophenoxy) -1,3,5-triazine (C) and antimony trioxide (D) together Solved.

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

In the present invention, when only the aliphatic halogenated flame retardant (B) is used, the thermal stability may be lowered. Therefore, in order to improve thermal stability, 2,4,6-tri (2,4,6-tribro) is used as an aromatic halogen flame retardant. Morfenoxy) -1,3,5-triazine is added. By adding the 2,4,6-tri (2,4,6-tribromophenoxy) -1,3,5-triazine flame retardant, the thermal stability is reinforced while maintaining the flame retardancy of the UL94 V-2 product, In addition to improving the weather resistance of the resin, it is possible to prepare a flame-retardant thermoplastic resin composition excellent in moldability as well as being applied to a light color product.

The 2,4,6-tri (2,4,6-tribromophenoxy) -1,3,5-triazine compound (C) is represented by the following formula (II):

The 2,4,6-tri (2,4,6-tribromophenoxy) -1,3,5-triazine compound (C) is 5 to 10 based on 100 parts by weight of rubber-reinforced polystyrene resin (A) Preference is given to using parts by weight. When 5 parts by weight or less is added, the flame retardant effect is insufficient, and when 10 parts by weight or more is used, it is not preferable because it impairs the balance of physical properties.

(D) flame retardant supplements

In the present invention, a flame retardant aid is further added to further improve the flame retardancy of the bromine flame retardant. The flame retardant aid (D) is preferably used in an amount of 0.5 to 5 parts by weight based on 100 parts by weight of the base resin (A). If the flame retardant aid is used less than 0.5 parts by weight, a sufficient flame retardant effect may not be obtained, and when used in excess of 5 parts by weight, the balance of the physical properties of the resin composition may be deteriorated.

The flame retardant aid (D) used in the present invention is selected from the group consisting of antimony trioxide, paraffin chloride, potassium sulfon sulfate and mixtures thereof.

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 necessary amounts depending on their respective uses.

The resin composition of the present invention can be used in the molding of various products, and particularly, because it has excellent thermal stability and UL94 V-2 flame retardancy, all V-2 flame-retardant grade electrical and electronics that require flame retardancy and thermal stability while being injected at high temperatures. Suitable for the manufacture of the housing of the product.

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 the following Examples and Comparative Examples, the rubber-reinforced polystyrene resin (A) used HR-1360 of Cheil Industries, Ltd., and the aliphatic halogen-based flame retardant (B) is represented by Chemical Formula (I). -Bis (4-2-3-dibromopropoxy) '-3,5-dibromophenyl propane was used, halogen-based flame retardant (C) is 2,4,6 represented by the formula (II) -Tri (2,4,6-tribromophenoxy) -1,3,5-triazine was used, and antimony trioxide was used as flame retardant aid (D).

Example 1-5 and Comparative Example 1-3

The resin composition obtained by mixing the components in the amounts shown in Table 1 was uniformly mixed with a tumbler mixer, and then extruded in a twin screw extruder to prepare pellets, and produced by injection molding from 1/8 "by injection molding. Example 1-5 shows the use of a flame retardant and a flame retardant aid in the range according to the present invention, and Comparative Examples 1-3 is the case used outside the above range. .

The flame retardance of the resin composition prepared by the above method was evaluated according to the UL-94 judgment 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. Thermal stability evaluation was evaluated by measuring the number of black streaks appearing in the specimen during the injection molding after the resin stayed in the injection machine cylinder (10 minutes, 240 ℃), the results are shown in Table 1.

Example Comparative Example One 2 3 4 5 One 2 3 Composition (parts by weight) (A) Rubber reinforced polystyrene 100 100 100 100 100 100 100 100 (B) 2,2-bis (4-2-3-dibromopropoxy) '-3,5-dibromophenyl propane One 3 5 One 5 0.5 7 5 (C) 2,4,6-tri (2,4,6-tribromophenoxy) -1,3,5-triazine 10 7 5 10 5 10 5 3 (D) Flame retardant supplement 5 2 0.5 3 One 5 0.5 0.5 Properties Flame Retardant (1/8 ") V-2 V-2 V-2 V-2 V-2 Fail V-2 Fail Total combustion time (seconds) 190 150 130 175 125 268 115 254 Black line generation One 3 5 One 5 One 8 6

From the results in Table 1, 2,2-bis (4-2-3-dibromopropoxy) '-3,5-dibromophenyl propane (B) and 2,4, which are aliphatic halogen flame retardants In Example 1-5, where 6-tree (2,4,6-tribromophenoxy) -1,3,5-triazine (C) was used in the amounts of the present invention, flame retardancy and thermal stability were simultaneously It can be seen that it is excellent.

In the case of Comparative Example 1, 2,2-bis (4-2-3-dibromopropoxy) '-3,5-dibromophenyl propane (B) was used less than the reference amount, and the flame retardance fell. The degradation of the resin due to the decomposition of the flame retardant should be caused to cause drip of the resin within a short time during combustion. In Comparative Example 2, 2,2-bis (4-2-3-dibromopropoxy) '-3,5-dibromophenyl propane (B) was used more than the reference amount, and the flame retardancy was excellent. However, thermal stability was very low. In the case of Comparative Example 3, 2,4,6-tri (2,4,6-tribromophenoxy) -1,3,5-triazine (C) was used less than the reference amount, thereby reducing flame retardancy.

The present invention relates to 2,2-bis (4-2-3-dibromopropoxy) '-3,5-dibromophenyl propane, which is an aliphatic halogen flame retardant, in rubber-reinforced polystyrene resin copolymers. By simultaneously using 6-tri (2,4,6-tribromophenoxy) -1,3,5-triazine, it has the effect of providing a thermoplastic resin composition which is excellent in flame retardancy and excellent in thermal stability.

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 (4)

(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) 1 to 5 parts by weight of 2,2-bis (4-2-3-dibromopropoxy) '-3,5-dibromophenyl propane represented by the following formula (I); (C) 5 to 10 parts by weight of 2,4,6-tri (2,4,6-tribromophenoxy) -1,3,5-triazine represented by the following formula (II); And (D) 0.5 to 5 parts by weight of flame retardant aids: Flame-retardant styrene resin composition, characterized in that consisting of. The rubber of the rubber-reinforced polystyrene resin (A) is selected from the group consisting of butadiene rubbers, isoprene rubbers, copolymers of butadiene and styrene, alkyl acrylate rubbers, and the like. Resin composition. The flame retardant styrene resin composition according to claim 1, wherein the flame retardant aid (D) is selected from the group consisting of antimony trioxide, paraffin chloride, potassium sulfone sulfate and mixtures thereof. The flame retardant styrene resin composition according to claim 1, further comprising an inorganic additive, an antioxidant, other light stabilizers, pigments, and dyes.