KR100907082B1 - Flame retardant rubber modified aromatic vinyl resin composition - Google Patents

Abstract

The flame-retardant rubber-modified aromatic vinyl resin composition of the present invention comprises (A) 100 parts by weight of rubber-modified aromatic vinyl resin, (B) 0.001 to 30 parts by weight of bromine compound, (C) 0.001 to 30 parts by weight, (D) It is characterized by providing a flame-retardant rubber-modified aromatic vinyl resin composition composed of 0.001 to 10 parts by weight of antimony trioxide has excellent flame retardancy, low specific gravity and economic advantages.

Chlorine, Bromine, Flame Retardant, Heat Stabilizer, Flame Retardant, Flame Retardant

Description

Flame retardant rubber modified aromatic vinyl resin composition {FLAME-RETARDANT RUBBER-MODIFIED AROMATIC VINYL-BASED RESIN COMPOSITION}

Field of invention

The present invention relates to a flame retardant rubber modified aromatic vinyl resin composition. More specifically, the present invention relates to a flame-retardant rubber-modified aromatic vinyl resin composition having a high flame retardancy, low specific gravity, and economic advantages by adding a bromine compound and a chlorine compound to a thermoplastic resin at the same time.

Background of the Invention

In general, styrene-based resins are used as interior and exterior materials of electrical and electronic products because of their excellent mechanical strength and extrusion and injection processability. However, the resin itself is not resistant to sparks, and when the spark is ignited by an external ignition factor, the resin itself decomposes and serves to expand or sustain combustion by providing a raw material. As social interest in fire safety has increased recently and standards have been strengthened, the necessity of flame retardation of exterior materials of electrical and electronic products has increased.

In addition, since the industry prefers a light resin having a lower mass than the same volume, development of a rubber-modified aromatic vinyl resin having a low specific gravity is required.

In general, a method of imparting flame retardancy to a resin includes an additional flame retardant method in which a flame retardant and a flame retardant aid are added. The flame retardant used to impart flame retardancy to the styrene resin is prepared by mixing a halogen-containing organic compound and an antimony-containing inorganic compound.

In general, the total amount of halogen compounds and antimony trioxide added to flame-retardant rubber-modified aromatic vinyl resins to obtain UL 94 V-0 characteristics is 15 to 40 parts by weight based on 100 parts by weight of styrene resin, thereby ensuring high flame retardancy. However, the excessive weight of the flame retardant causes a problem of increasing the specific gravity. In addition, among the halogen-based flame retardant bromine-based flame retardant has a high specific gravity, there is a problem to increase the specific gravity of the composition. However, when the content of the flame retardant or flame retardant, particularly antimony trioxide, is reduced to reduce the specific gravity, the flame retardancy is reduced, which makes it difficult to secure flame retardancy, which is the purpose of the original flame retardant resin.

Accordingly, the present inventors have simultaneously added a chlorine-based flame retardant and a bromine-based flame retardant among halogen-based flame retardants to develop a flame-retardant resin composition having not only excellent flame retardancy but also low specific gravity.

An object of the present invention is to provide a flame retardant rubber-modified aromatic vinyl resin composition.

Another object of the present invention is to provide a flame retardant rubber-modified aromatic vinyl resin composition having excellent flame retardancy and low specific gravity of the composition.

Still another object of the present invention is to provide a flame retardant rubber-modified aromatic vinyl resin composition having excellent flame retardancy, low specific gravity of the composition, and economic advantages.

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

Summary of the Invention

The flame retardant rubber modified aromatic vinyl resin composition of the present invention comprises 100 parts by weight of rubber modified aromatic vinyl resin; 0.001 to 10 parts by weight of a thermally stable compound; 0.001-30 parts by weight of bromine compound; 0.001 to 30 parts by weight of a chlorine compound; It is characterized by consisting of 0.001 to 10 parts by weight of antimony trioxide.

The flame retardant rubber-modified aromatic vinyl resin composition of the present invention is a surfactant, a nucleating agent, a coupling agent, a filler, a plasticizer, an impact modifier, a lubricant, an antibacterial agent, a mold release agent, a heat stabilizer, an oxidation inhibitor, a light stabilizer, a compatibilizer, an inorganic additive, a coloring agent. It may further comprise an additive selected from the group consisting of stabilizers, lubricants, antistatic agents, pigments, dyes, flame retardants and mixtures thereof.

The flame retardant rubber-modified aromatic vinyl resin composition of the present invention can be produced as a molded article extruded the composition.

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

Detailed Description of the Invention

The flame-retardant rubber-modified aromatic vinyl resin composition of the present invention includes (A) rubber-modified aromatic vinyl resin; (B) bromine compounds; (C) a chlorine compound and (D) antimony trioxide.

(A) Rubber modified aromatic vinyl resin

The rubber-modified aromatic vinyl resin according to the present invention is prepared by mixing a rubber, an aromatic monoalkenyl monomer or an alkyl ester monomer, and acrylonitrile and polymerizing it using a polymerization initiator.

In one embodiment of the present invention, the rubber-modified aromatic vinyl-based resin is a polymer of 85 to 95% by weight of the monomer containing an aromatic vinyl monomer in 5 to 15% by weight of the rubber.

In another embodiment, the (meth) acrylic acid alkyl ester monomer and / or acrylonitrile may be mixed with the aromatic vinyl monomer.

The rubber is preferably used at 5 to 15% 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. However, it is not necessarily limited thereto.

The aromatic vinyl monomers include styrene, pt-butylstyrene, alpha-methylstyrene, beta-methylstyrene, vinyl xylene, monochlorostyrene, dichlorostyrene, dibromostyrene, chlorostyrene, ethyl styrene, vinyl naphthalene, and divinyl. Benzene and the like can be used. These can be used individually or in mixture of 2 or more types.

As the (meth) acrylic acid alkyl ester monomer, methacrylic acid methyl ester, methacrylic acid ethyl ester, methacrylic acid propyl ester, methacrylic acid 2-ethyl hexyl ester, methacrylic acid decyl ester, methacrylic acid lauryl ester, and butyl acrylate , Ethyl acrylate, methyl acrylate and methyl methacrylate monomers and the like can be used. These can be used individually or in mixture of 2 or more types.

The monomer is preferably 85 to 95% by weight of one or more monomers selected from the group consisting of aromatic monoalkenyl monomers, alkyl ester monomers of acrylic acid or methacrylic acid, and acrylonitrile. However, it is not necessarily limited thereto.

The rubber-modified aromatic vinyl resin of the present invention may be prepared by polymerizing a monomer including a rubber and an aromatic monoalkenyl monomer in the presence of a polymerization initiator.

As the polymerization initiator, benzoyl peroxide, t-butyl high peroxide, acetyl peroxide, cumene hydroperoxide, etc. may be used, but are not necessarily limited thereto. These can be used individually or in mixture of 2 or more types.

The polymerization method may be prepared using bulk polymerization, suspension polymerization, emulsion polymerization or a mixture thereof, but is not necessarily limited thereto. Preferably, block polymerization may be applied.

(B) bromine compound

The bromine compound of the present invention has a structure of Formula 1 below.

[Formula 1]

Wherein n and m are each 1 to 5, R is a linear alkyl group having 1 to 10 carbon atoms, a cyclic alkyl group having 3 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, and CH ₂ CH (OH) CH ₂ or triazine form)

Examples of the bromine compounds include decabromo diphenyl ethane, 2,4,6-tris (2,4,6-tribromophenoxy) -1,3,5-triazine, brominated epoxy oligomers, and the like. There is this. The compounds are preferably 50% or more of bromine in consideration of mechanical properties and flame retardancy, and may be mixed or used alone, depending on the end use.

The bromine compound is used in an amount of 0.001 to 30 parts by weight, preferably 1 to 25 parts by weight, more preferably 5 to 20 parts by weight, most preferably 100 parts by weight of the rubber-modified aromatic vinyl resin (A). It is used at 7-18 parts by weight. When the content of the bromine compound is less than 0.001 parts by weight, it is difficult to expect the flame retardant effect occurs, and if it exceeds 30 parts by weight, the physical property balance may be lowered.

(C) chlorine compound

The chlorine compound of the present invention has a structure of formula (2).

[Formula 2]

Wherein n and m are each 1 to 5, R is a linear alkyl group having 1 to 10 carbon atoms, a cyclic alkyl group having 3 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, and CH ₂ CH (OH) CH ₂ or triazine form)

Chlorinated compounds that can be used in the present invention are 1,2,3,4,7,8,9,10,13,13,14-dodecachloro-1, 4, 4a, 5, 6, 6a, 7, 10 , 10a, 11, 12, 12a-dodecahydro-1, 4, 7, 10-dimethanodibenzo (a, e) cyclooctene, cloned polyethylene wax, and the like. In view of mechanical properties and flame retardancy, the compounds may have a chlorine content of 50% or more and may be mixed or used alone, depending on the end use.

The chlorine compound is used in an amount of 0.001 to 30 parts by weight, preferably 1 to 25 parts by weight, more preferably 5 to 20 parts by weight, most preferably 7 to 100 parts by weight of the rubber-modified aromatic vinyl resin (A). It is used at -16 parts by weight. If the content of the chlorine-based compound is less than 0.001 parts by weight, it is difficult to expect a flame retardant effect occurs, and if it exceeds 30 parts by weight, the physical property balance may be lowered.

(D) antimony trioxide

Antimony trioxide of the present invention is used as a flame retardant adjuvant for improving the flame retardancy of the bromine compound and chlorine compound.

The antimony trioxide is used in an amount of 0.001 to 30 parts by weight based on 100 parts by weight of the rubber-modified aromatic vinyl resin (A), preferably 0.1 to 20 parts by weight, more preferably 1 to 10 parts by weight, most preferably 2 It is used at -6 parts by weight. If the content of the antimony trioxide is less than 0.001 parts by weight, it is difficult to expect a synergistic effect of flame retardancy, and if it exceeds 30 parts by weight, the physical property balance may be lowered.

The resin composition of the present invention can significantly lower the specific gravity of the final resin composition by applying the bromine flame retardant and the chlorine flame retardant together. In one embodiment, the resin composition has a specific gravity of 1.125 to 1.135. In addition, UL94 flame retardance for thickness 2.0mm has V-0.

The resin composition of the present invention may be a surfactant, a nucleating agent, a coupling agent, a filler, a plasticizer, an impact modifier, a lubricant, an antibacterial agent, a mold release agent, a heat stabilizer, an antioxidant, a light stabilizer, a compatibilizer, an inorganic additive, a colorant, a stabilizer, It may further include additives such as lubricants, antistatic agents, pigments, dyes, flame retardants. The additives may be applied alone or by mixing two or more kinds.

The resin composition of this invention can be manufactured by a well-known method. For example, the components of the present invention and other additives may be manufactured into various molded articles after mixing by a known mixing method using an extruder, a kneader, a mixer, or the like. In one embodiment of the present invention, the components were melt extruded in an extruder and prepared in pellet form, and the prepared pellets were injected into an injection machine. In one embodiment of the present invention, the molded article may be used for applications such as electrical and electronic parts, office equipment such as computers, or sundries. In particular, the present invention can be preferably applied to housings of electric and electronic products such as televisions, computers, printers, washing machines, cassette players, audio, mobile phones, game machines, and the like.

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

Example

The specification of the material used in the Example and comparative example of this invention is as follows.

(A) Rubber modified aromatic vinyl resin

Rubber modified aromatic vinyl-based resin is the impact polystyrene (HIPS) resin of Cheil Industries, high gloss resin was used HIPS-1, high impact resin was used HIPS-2.

(B) bromine compound

Bromine compounds are decabromo diphenyl ethane (HB-1), 2,4,6-tris (2,4,6-tribromophenoxy) -1,3,5-triazine (HB-2) , Brominated epoxy oligomer (HB-3) was used.

(C) chlorine compound

Chlorine compounds are 1,2,3,4,7,8,9,10,13,13,14-dodecachloro-1, 4, 4a, 5, 6, 6a, 7, 10, 10a, 11, 12 Octane (HC-1) was used as the 12a-dodecahydro-1, 4, 7, 10-dimethanodibenzo (a, e) cycle.

(D) antimony trioxide

Antimony trioxide was used as ANTIS N, antimony trioxide of Ilsung antimony.

Examples 1-9

The above-mentioned rubber-modified aromatic vinyl resin, bromine compound, chlorine compound, and antimony trioxide were mixed in the content of the following Table 1, and then extruded at a temperature of 190 to 230 ° C. in a conventional twin screw extruder to prepare pellets. The prepared pellets were dried for 3 hours at 70 ° C., and then injected in a 6 Oz injection machine under conditions of a molding temperature of 180 to 220 ° C. and a mold temperature of 30 to 50 ° C. to prepare physical properties and flame retardant specimens.

Flame retardancy of the prepared specimens was measured by UL94, specific gravity ASTM D792. The results are shown in Table 1.

Comparative Examples 1 to 3

Comparative Example 1 was carried out in the same manner as in Example 1 except that 15 parts by weight of a bromine compound (B) was used, and no chlorine compound (C) was used.

Comparative Example 2 was carried out in the same manner as in Example 4, except that 17 parts by weight of the bromine compound (B) was used and no chlorine compound (C) was used.

Comparative Example 3 was carried out in the same manner as in Example 7, except that 19 parts by weight of the bromine compound (B) was used and no chlorine compound (C) was used.

The results are shown in Table 2.

As shown in Tables 1 and 2, when a bromine compound and a low specific gravity chlorine compound are added to the rubber modified aromatic vinyl resin at the same time, a rubber modified aromatic vinyl compound having a lower specific gravity than the case where only a bromine compound is added as a flame retardant It was confirmed that a flame retardant resin composition was obtained.

The present invention provides a flame-retardant rubber-modified aromatic vinyl-based resin composition having excellent flame retardancy, low specific gravity, and economic advantages by adding bromine-based flame retardant, chlorine-based flame retardant, and antimony trioxide simultaneously to rubber-modified aromatic vinyl resin. 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) 100 parts by weight of rubber-modified aromatic vinyl resin; (B) 0.001 to 30 parts by weight of bromine compound; (C) 0.001 to 30 parts by weight of a chlorine compound; And (D) 0.001 to 10 parts by weight of antimony trioxide; A flame retardant rubber-modified aromatic vinyl resin composition comprising: The bromine compound (B) is decabromo diphenyl ethane, 2,4,6-tris (2,4,6-tribromophenoxy) -1,3,5-triazine, brominated epoxy oligomer And mixtures thereof, The chlorine compound (C) is 1,2,3,4,7,8,9,10,13,13,14-dodecachloro-1, 4, 4a, 5, 6, 6a, 7, 10, 10a , 11, 12, 12a-dodecahydro-1, 4, 7, 10-dimethanodibenzo (a, e) cyclooctene, chlorinated polyethylene wax and mixtures thereof A flame-retardant rubber modified aromatic vinyl resin composition. delete delete The flame retardant rubber-modified aromatic vinyl resin composition according to claim 1, wherein the resin composition has a specific gravity in the range of 1.125 to 1.135, and UL94 flame retardancy to a thickness of 2.0 mm is V-0. The method of claim 1, wherein the resin composition is a surfactant, nucleating agent, coupling agent, filler, plasticizer, impact modifier, lubricant, antibacterial agent, mold release agent, heat stabilizer, antioxidant, light stabilizer, compatibilizer, inorganic additives, colorants, stabilizers, A flame retardant rubber-modified aromatic vinyl resin composition further comprising an additive selected from the group consisting of lubricants, antistatic agents, pigments, dyes, flame retardants and mixtures thereof. The molded article which extruded the resin composition of Claim 1, 4 or 5.