KR0182357B1 - Styrenic antiflammable resin composition having high impact strength and flowability - Google Patents

Abstract

The present invention is to provide a styrene-based flame retardant resin composition excellent in impact resistance, processability and beautiful appearance, the composition of the present invention is (a) an alkyl ester of an aromatic monoalkenyl monomer, vinyl cyanated monomer, acrylic acid or methacrylic acid An average rubber particle obtained by mass, suspension or emulsion polymerization of one or more monomers selected from monomers with a diene rubber component or alkyl acrylate rubber component of high concentration cis (HIGH-CIS) type having a cis content of 90% or more. 0.5 to 1.0 μm in diameter and having a gloss of 70 or more, 100 parts by weight of a gypsum copolymer HIPS resin and (b) an aliphatic compound such as an aliphatic compound such as brominated epoxy resin or chlorinated polyethylene resin or an aromatic compound such as vinyl chloride resin, from 0.5 to 1.0 30 parts by weight (c) decabromodiphenyl ether, octabromodiphenyl ether, decabromod Characterized butadiene block copolymer with 0-3 parts by weight that is configured - carbonyl secondary flame retardant 1-20 parts by weight (d) selected from the group consisting of ethane, antimony trioxide, 1 to 10 parts by weight (e) styrene as an impact modifier.

Description

Styrene-based flame retardant resin composition excellent in impact resistance and processability

The present invention relates to a styrene flame retardant resin composition, and more particularly, to a styrene flame retardant resin composition having excellent impact resistance, processability, and beautiful appearance.

In general, styrene-based plastics have excellent processability and mechanical strength, and are mainly used as exterior materials for electrical and electronic products.In countries such as the US and Europe, only resins having flame retardance are used to increase the stability of electronic products to fire. It is legal to use. The plastic itself has no resistance to flame, so when the spark is ignited by an external ignition factor, the resin itself acts as an energy to help burn and continuously burns the fire. Diffused. Examples of the method of imparting flame retardancy to a plastic having such characteristics include an additive flame retardant method in which a flame retardant and an auxiliary flame retardant are added, and a polymer flame retardant method in which a resin is prepared using a special monomer containing a flame retardant atom during polymerization. Can be. Among them, many studies have been conducted in the pilot scale stage, but commercialized products have not yet 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 additive flame retardant method in which a flame retardant is added to impart flame retardancy to a styrene resin is prepared by adding at least one component selected from halogen-containing organic compounds and antimony-containing inorganic compounds to the resin. Halogen-containing organic compounds, mainly bromine or chlorine compounds, are highly flame retardant when added to styrene-based resins, but seriously deteriorate in overall physical properties such as impact strength, UV stability, heat resistance and processability of the resin itself. Therefore, in producing a flame retardant resin, a technique of imparting excellent flame retardancy while minimizing a decrease in physical properties of the resin is very important.

In recent years, as household appliances such as TV, which is the main use of flame retardant resins, have been gradually enlarged, high-flow flame-retardant resins having excellent moldability and workability have been required. In order to increase the flowability of the resin, a flame retardant having excellent flowability should be used. In the styrene resin, a melt flame retardant having a low melting point is mainly used. However, molten flame retardants do not have superior flame retardance compared to filler flame retardants, so that excessive addition is inevitable to show flame retardancy that meets the US UL (Underwriters Laboratories) standard. It is not good because it causes degradation.

In order to solve the above problems, styrene-butadiene block copolymer (SBR Block Copolymer), which is mainly an impact modifier, is used in an excessive amount. In this case, the impact modifier has poor thermal stability during injection molding. (Silver streak) has a problem that adversely affect the appearance of the molded product by acting as a cause of molding failure.

In addition, due to the advancement of resin manufacturing technology and cost reduction efforts by resin users, resins with low price and physical properties are replacing relatively expensive high-functional resins. For example, in case of styrene resin, HIPS resin is ABS. ABS market is rapidly encroaching on NORYL or PC / ABS resin market. Therefore, the lower products are rapidly progressing in their high functionalization and high quality, which are the advantages of the upper product group, and especially in the case of HIPS resin, establishing a beautiful appearance and excellent impact resistance, which is an advantage of the ABS resin, has emerged as a major technology. However, there are many difficulties with this technology.

The present invention is to solve the above problems, to establish a technique for minimizing the physical properties of the resin and the molding defect rate, to provide a styrene-based flame retardant resin composition having excellent impact resistance and workability and has a beautiful appearance. .

The present inventors earnestly researched in order to achieve the above object, and by using a resin having excellent impact resistance and appearance, which is made by specially modifying the rubber component in the base resin, the impact modifier is drastically reduced and fluidity and When the main flame retardant having excellent thermal stability and secondary flame retardant having excellent impact resistance and flame retardancy are used in combination, it has been found that the above object can be achieved.

That is, the resin composition of the present invention comprises (a) one or more monomers selected from aromatic monoalkenyl monomers, vinyl cyanide monomers, alkyl ester monomers of acrylic acid or methacrylic acid, and a highly concentrated sheath having a cis content of 90% or more. It is obtained by mass, suspension or emulsion polymerization with a diene rubber component or an alkyl acrylate rubber component in the form of HIGH-CIS), and has an average rubber particle diameter of 0.5-1.0 µm and a gloss of 70 or more. Part and (b) main flame retardant selected from aliphatic compounds such as brominated epoxy resin or chlorinated polyethylene resin or aromatic compounds such as vinyl chloride resin, which are diglycidyl ether polymers of tetrabromobisphenol a or tetrabromobisphenol a (C) decabromodiphenyl ether, octabromodiphenyl ether, decabromodiphenyl ethane 1 to 20 parts by weight of the selected auxiliary flame retardant (d) 1 to 10 parts by weight of antimony trioxide (e) It is characterized by consisting of 0 to 3 parts by weight of styrene-butadiene block copolymer (SBR Block Copolymer) as an impact modifier.

Hereinafter, the present invention will be described in detail.

The graft copolymer HIPS resin (a), which is a basic resin component of the styrene-based flame retardant resin composition according to the present invention, may be prepared using a bulk polymerization, suspension polymerization, emulsion polymerization, or a mixture thereof. For example, the bulk polymerization method is described below.

That is, aromatic monoalkenyl monomers and vinyl cyanated monomers are used for 3-30 parts by weight, preferably 5-15 parts by weight of rubber selected from butadiene rubbers, isoprene rubbers, copolymers of butadiene and styrene or alkylacrylate rubbers. 70-97 parts by weight, preferably 85-95 parts by weight of one or more monomers selected from alkyl ester monomers of acrylic acid or methacrylic acid, benzoyl peroxide, t-butylhydro peroxide, acetyl peroxide The graft copolymer HIPS resin (a) may be prepared by bulk polymerization using at least one initiator selected from cumene hydroperoxide and the like.

The rubber used for polymerization is a highly concentrated cis diene rubber or alkyl acrylate rubber component having a cis content of 90% or more, and when it is massed, suspended or emulsion-polymerized with a monomer, the average rubber particle diameter of HIPS resin is 0.5-1.0 μm. The glossiness becomes 70 or more, which is an appropriate range for exhibiting excellent impact resistance and beautiful appearance.

If the sheath content in the rubber is less than 90%, it is difficult to obtain excellent impact strength, and if the glossiness is less than 70, it is difficult to exhibit a beautiful appearance during injection molding.

In addition, the main flame retardant (b) used to improve the fluidity in the present invention is a brominated epoxy bromide which is a diglycidyl ether polymer of tetrabromobisphenol a or tetra bromobisphenol a as an organic compound containing chlorine or bromine among halogen elements. Aliphatic compounds, such as resin or chlorinated polyethylene resin, or aromatic compounds, such as vinyl chloride resin, can be used. In particular, brominated epoxy resins, which are diglycidyl ether polymers of tetrabromobisphenol a, have a molecular weight of 500-3000, preferably 700-2500, and are represented by the following general formula (I) or (II): to be.

In the above general formula, n is an integer of 0 or more, and R1 is Br (X) (an integer of X = 1 to 5).

If the molecular weight is less than 500, the heat deflection temperature of the composition is lowered, and if it exceeds 3000, the impact strength and fluidity are lowered. The main flame retardant (b) is preferably used 0.5-30 parts by weight based on 100 parts by weight of the basic resin (a) of the present invention. If the excess amount exceeds 30 parts by weight, the physical properties may not be balanced due to the impact strength of the resin composition, the workability and the lowering of the heat deformation temperature.

In the present invention, the auxiliary flame retardant (c) used to increase the flame retardancy may be a flame retardant selected from decabromodiphenyl ether, octabromodiphenyl ether, and decabromodiphenyl ethane having excellent flame retardant as a bromine-based flame retardant. (c) is preferably 1 to 20 parts by weight, preferably 2 to 10 parts by weight based on 100 parts by weight of the base resin (a) of the present invention. In the case where the auxiliary flame retardant (c) is used in an amount of less than 1 part by weight, an excessive amount of the main flame retardant (b) must be used in order to obtain the same flame retardancy, resulting in a decrease in impact strength and heat resistance, and in excess of 20 parts by weight. Even when used in excess, the balance of physical properties is impaired due to the decrease in processability and impact strength of the resin composition.

Antimony trioxide (d) is preferably used 1 to 10 parts by weight, preferably 2 to 7 parts by weight based on 100 parts by weight of the basic resin (a) component of the present invention. In this case, when the antimony trioxide (d) is used in less than 1 part by weight, sufficient flame retardant effect may not be obtained. On the other hand, when the excess amount is used in excess of 10 parts by weight, the impact strength of the resin composition is severely lowered, which is not preferable.

The impact modifier (e) is preferably used in an amount of 0-3 parts by weight, preferably 1.5 parts by weight or less, based on 100 parts by weight of the base resin (a) component of the present invention. In this case, when the impact modifier (e) is used in an amount of more than 3 parts by weight, it is not preferable because it does not exhibit a beautiful appearance, which is a target of the present invention, by causing a flow mark and silver streaks that are poor in molding during injection molding.

As described above, the styrene resin composition according to the present invention is characterized by excellent impact resistance and workability and exhibits a beautiful appearance.

Hereinafter, the present invention will be described based on Examples and Comparative Examples, and the present invention is not limited to these Examples.

First, the production and specifications of the materials used in Examples and the like are as follows.

(a) Basic resin

(a1) Special HIPS Resin

88 parts by weight of an aromatic monoalkenyl monomer was added to 12 parts by weight of butadiene rubber having a cis content of 90% or more, and prepared by mass polymerization using 0.4 parts by weight of t-butyl hydroperoxide. The average rubber particle diameter of the HIPS resin obtained in the polymerization was 0.7 µm and the glossiness was 75.

(a2) General HIPS resin: HR-1360 GRADE, Cheil Industries' product, was used.

(b) Brominated epoxy resin: TB-60 from Japan Toto Corporation was used.

(c) decabromodiphenylethane: US SAYTEX-8010 from ALBEMARE was used.

(d) Antimony trioxide. Cheil X-20 was used.

(e) Styrene-butadiene copolymer: 420P of Japanese ASAHI was used.

[Example 1-3 and Comparative Example 1-6]

In Example 1-3, a special HIPS resin, which is a resin composition of the present invention, was used. In Comparative Example 106, a general HIPS resin was used. In Comparative Example 4-6, an auxiliary flame retardant was not used, but a brominated epoxy resin, which is a main flame retardant, was used. Was used alone. The composition of each of the components used is shown in Table 1 below, and the resins used were uniformly mixed with a Henschel mixer and then extruded with a twin screw extruder to form pellets. Test specimens were prepared by injection molding the specimens obtained as described above, and the impact strength, flow index, flame retardancy, and appearance sensory evaluation were performed, and the results are shown in Table 2 below.

(1) Impact strength: measured according to ASTM D256.

(2) Flow index: measured according to ASTM D1238.

(3) Heat resistance: Measured according to ASTM D306.

(4) Flame retardant: Measured according to UL 94 VB.

(5) Appearance of molded article: Sensory evaluation after molding large injection molding in 400Z injection machine.

(◎: Very good, △: GAS SILVER occurs)

As shown in the above examples and comparative examples, by using a special HIPS in the present invention, the main flame retardant and auxiliary flame retardant is used in combination, the impact resistance and flame retardancy is significantly improved, the appearance is also very good results. In addition, the physical property deterioration by addition of the flame retardant is minimized to obtain excellent physical properties and fluidity.

Claims (2)

(a) a high-density cis-type diene rubber component or alkyl acryl having a cis content of 90% or more of one or more monomers selected from aromatic monoalkenyl monomers, vinyl cyanated monomers, alkyl ester monomers of acrylic acid or methacrylic acid 100 parts by weight of a graft copolymer HIPS resin having an average rubber particle diameter of 0.5-1.0 µm and a glossiness of 70 or more obtained by bulk rubber component and bulk, suspension or emulsion polymerization, and (b) tetrabromobisphenol a or tetrabromobis 0.5 to 30 parts by weight of a main flame retardant selected from aliphatic compounds such as brominated epoxy resins or chlorinated polyethylene resins, or phenol diglycidyl ether polymers of phenol a, or aromatic compounds such as vinyl chloride resins (c) decabromodiphenyl ether and octabromody 1 to 20 parts by weight of an auxiliary flame retardant selected from phenyl ether and decabromodiphenyl ethane (d) anti trioxide 1 to 10 parts by weight of (e) an impact modifier with a styrene-butadiene block copolymer having excellent impact resistance and processability 0 styrene as that feature is configured to 3 parts by weight based flame-retardant resin composition. The brominated epoxy resin according to claim 1, which is a diglycidyl ether polymer of tetrabromobisphenol a, has a molecular weight of 500-3000 and is represented by the following general formula (I) or (II). Styrene-based flame retardant resin composition. In the general formula, n is an integer of 0 or more, and R1 is (X = 1 to 5 integer).