KR100654534B1 - Flame Retardant Thermoplastic Composition - Google Patents

Abstract

The present invention relates to a flame retardant thermoplastic resin composition, and more particularly, to an acrylic graft polymer, a diene graft polymer, a vinyl cyanide compound-aromatic vinyl compound copolymer, and a halogen-based compound as a flame retardant and an antimony oxide type. A flame retardant thermoplastic resin composition having excellent weather resistance containing a compound as a flame retardant aid and a chlorine-based organic compound as an impact reinforcing material.

The flame retardant thermoplastic resin composition according to the present invention has the advantage of having excellent weather resistance and excellent flame retardancy by using a halogen-based flame retardant and antimony oxide in combination with ASA resin.

Description

Flame Retardant Thermoplastic Resin Composition

The present invention relates to a flame retardant thermoplastic resin composition, and more particularly, to an acrylic graft polymer, a diene graft polymer, a vinyl cyanide compound-aromatic vinyl compound copolymer, and a halogen-based compound as a flame retardant and an antimony oxide type. A flame retardant thermoplastic resin composition having excellent weather resistance containing a compound as a flame retardant aid and a chlorine-based organic compound as an impact reinforcing material.

Generally, acrylonitrile-butadiene-styrene resin (hereinafter referred to as 'ABS resin') is widely used in electric / electronic products, automobile parts, and general merchandise because of its excellent impact resistance, mechanical strength, surface properties, and workability. Resin. However, the ABS resin contains a chemically unstable double bond in the rubber component of the resin due to the characteristics of the resin, so that the rubber component can be easily aged by ultraviolet rays, so the weather resistance and light resistance are not good, and when it is left outdoors for a long time However, over time, discoloration and physical property deterioration are relatively large, which makes it unsuitable for outdoor use exposed to sunlight.

Therefore, in order to compensate for this problem, a post-processing such as painting or plating is applied to the ABS resin molded article or a method of adding a large amount of UV stabilizer during extrusion processing of the ABS resin, but the former has a disadvantage in that the process is complicated and the defect rate is high. However, the latter has the disadvantage of failing to obtain a rise in manufacturing cost and satisfactory long-term weather resistance.

In order to overcome the limitations of the use of ABS resins, various resins are known to have excellent weather resistance instead of ABS resins. Of these, acrylate-styrene-acrylonitrile resins (hereinafter referred to as 'ASA resins') are used. Most widely used.

ASA resins are generally vinyl cyanide compounds-aromatic vinyl compounds obtained by copolymerizing an acrylic graft polymer, a vinyl cyanide compound, and an aromatic vinyl compound graft-polymerized with an acrylic synthetic rubber by an emulsion graft polymerization method. The copolymer is prepared by mixing and extruding. At this time, by controlling the physical properties and content of the acrylic synthetic rubber and acrylic graft polymer, and the matrix polymer, the vinyl cyanide compound-aromatic vinyl compound copolymer, and selectively adding a reinforcing material of a specific role, the desired physical resin can be obtained. have.

Thus prepared ASA resin is excellent in weather resistance, light resistance, chemical resistance, heat resistance, etc., so it is suitable for use in outdoor exterior parts with high exposure to sunlight, such as outdoor electrical / electronic products, automotive exterior parts, building materials. On the other hand, ASA resin itself is not resistant to combustion, and when a spark is ignited by an external ignition factor, there is a problem in that the resin itself acts as an energy to assist combustion and continuously spreads fire.

Therefore, in the United States, Europe, etc., in order to secure stability against fires of electric and electronic products, a resin having flame retardancy is used to manufacture molded articles of internal and external parts of electric and electronic products.

As a method for producing ASA resin, a method of copolymerizing acrylonitrile and styrene using an acrylic rubber (US Pat. Nos. 4,753,988, 4,801,646, and Japanese Patent Application Laid-Open No. 60-3350, Special Publication 59-15331), poly A method of copolymerizing acrylonitrile and styrene on rubber mixed with butadiene rubber and acrylic rubber (Japanese Patent Laid-Open Nos. 57-212215, 58-187411 and 57-167308) is disclosed. In the prior art, a method of imparting flame retardancy of ASA resin is not disclosed.

In order to solve the problems of the prior art, the present inventors use ASA resin instead of ABS resin to improve the weather resistance of the ABS resin, and to improve the flame retardancy, an organic compound containing halogen as a flame retardant, antimony oxide The present invention was completed by adding an inorganic compound containing a flame retardant aid.

Accordingly, an object of the present invention is to provide a flame retardant thermoplastic resin composition having excellent weather resistance by adding a halogen flame retardant and antimony oxide to an ASA resin.

The present invention is a base resin (A) having a weight ratio of (A) + (B) :( C) of 20 to 60:40 to 80, and a weight ratio of (A) to (B) of 50 to 90:10 to 50. A flame retardant thermoplastic resin composition comprising 5 to 30 parts by weight of a halogen compound, 1 to 15 parts by weight of antimony oxide, and 1 to 10 parts by weight of chlorine organic compound, based on 100 parts by weight of + (B) + (C).

(A) Acrylic graft polymer which consists of 30-60 weight% of acrylic synthetic rubbers and 40-70 weight% of a vinyl cyanide compound-aromatic vinyl compound copolymer;

(B) a diene graft polymer composed of 30 to 60 wt% of a diene synthetic rubber and 40 to 70 wt% of a vinyl cyanide compound-aromatic vinyl compound copolymer;

(C) Vinyl cyanide compound-aromatic vinyl compound copolymer which consists of 20-40 weight% of vinyl cyanide compounds and 60-80 weight% of aromatic vinyl compounds.

Hereinafter, the present invention will be described in detail.

(A) Acrylic Graft Polymer

The acrylic graft polymer used in the thermoplastic resin composition according to the present invention is prepared by a conventional emulsion graft polymerization method by mixing a monomer mixture of a vinyl cyanide compound and an aromatic vinyl compound in an acrylic synthetic rubber.

As the monomer mixture of the vinyl cyanide compound and the aromatic vinyl compound, 20 to 30% by weight of a vinyl cyanide compound and 70 to 80% by weight of an aromatic vinyl compound are used, and the vinyl cyanide compound grafted on the acrylic synthetic rubber- The aromatic vinyl compound copolymer is preferably 40 to 70% by weight based on the total acrylic graft polymer.

In addition, the acrylic synthetic rubber for producing the acrylic graft polymer is preferably synthesized from an alkyl acrylate having 2 to 8 carbon atoms, the average particle diameter of the acrylic synthetic rubber particles may be in the range of 0.05 to 0.5 ㎛, 0.1 ~ The range of 0.3 micrometer is preferable.

Vinyl cyanide compounds for preparing the acrylic graft polymer used in the resin composition according to the present invention include acrylonitrile, methacrylonitrile, and the like, and these may be used alone or in combination. Aromatic vinyl compounds for preparation include styrene, alpha-methylstyrene, pt-butylstyrene, 2,4-dimethylstyrene, vinyltoluene and the like, which may be used alone or in combination.

(B) diene graft polymer

The diene graft polymer used in the resin composition according to the present invention is prepared by a conventional emulsion graft polymerization method by mixing a diene-based synthetic rubber with a monomer mixture of a vinyl cyanide compound and an aromatic vinyl compound.

The monomer mixture of the vinyl cyanide compound and the aromatic vinyl compound is composed of 20 to 30% by weight of vinyl cyanide compound and 80 to 70% by weight of aromatic vinyl compound on the basis of solid content, and vinyl cyanide compound grafted on the diene-based synthetic rubber. The aromatic vinyl compound copolymer is preferably 40 to 70% by weight based on the total diene graft polymer.

In addition, the diene-based synthetic rubber for preparing the diene-based graft polymer may include polybutadiene, polyisoprene, polychloroprene, butadiene-styrene copolymer, butadiene-acrylonitrile copolymer, and the like, and polybutadiene, butadiene- Styrene copolymers and butadiene-acrylonitrile copolymers are preferred, and the average particle diameter of the diene-based synthetic rubber particles is preferably in the range of 0.1 to 0.6 mu m, more preferably in the range of 0.2 to 0.5 mu m.

Vinyl cyanide compounds for producing the diene graft polymer used in the flame retardant thermoplastic resin composition according to the present invention include acrylonitrile, methacrylonitrile, and the like. Aromatic vinyl compounds for the production of the polymers include styrene, alpha-methylstyrene, pt-butylstyrene, 2,4-dimethylstyrene, vinyltoluene, and the like, which may be used alone or in combination.

(C) Vinyl Cyanide Compound-Aromatic Vinyl Compound Copolymer

The vinyl cyanide compound-aromatic vinyl compound copolymer used in the resin composition according to the present invention is prepared by a conventional polymerization method using 20 to 40% by weight of a vinyl cyanide compound and 60 to 80% by weight of an aromatic vinyl compound on a solids basis. It is preferable that the weight average molecular weight is in the range of 80,000 to 400,000. When the weight average molecular weight of the vinyl cyanide compound-aromatic vinyl compound copolymer (C) is lower than 80,000, impact resistance is significantly lowered, and when higher than 400,000, fluidity is low. Difficulties in processing the molded article.

As the vinyl cyanide compound constituting the vinyl cyanide compound-aromatic vinyl compound copolymer used in the resin composition of the present invention, an acrylonitrile, methacrylonitrile or the like or a mixture thereof may be used. As the aromatic vinyl compound, styrene, alpha-methyl styrene, pt-butyl styrene, 2,4-dimethyl styrene, vinyl toluene or the like or a mixture thereof may be used, and these and N-phenylmaleimide, N Cyclohexyl maleade, maleic anhydride, and the like may be copolymerized, and as the production method, an emulsion polymerization method, suspension polymerization method, solution polymerization method, or bulk polymerization method may be applied.

(D) halogen-based compound

The halogen-based compound used in the resin composition according to the present invention may be used as a flame retardant, and a halogen-based compound commercially used and generally used may be used. Specific examples include tetrabromoobisphenol A, bibro (tribromophenoxy) ethane, brominated epoxy resin, or brominated epoxy in which the epoxy terminal is substituted with tribromophenol. Brominated epoxy resin terminated with tribromophenol, 2,4,6-tri (2,4,6-tribromophenoxy) -1,3,5-triazine can be used.

 The halogen-based compound is used in an amount of 5 to 30 parts by weight based on 100 parts by weight of the base resin (A) + (B) + (C), but when used less than 5 parts by weight, the flame retardant effect is reduced, and 30 parts by weight When used in excess, the problem occurs that the workability and mechanical strength are deteriorated and the balance of physical properties is lost, which is not preferable.

(E) antimony oxide

The antimony oxide used in the resin composition according to the present invention is used as a flame retardant aid to synergize with the halogen-based compound used as a flame retardant to impart proper flame retardancy to the ASA resin, and examples thereof include antimony trioxide or antimony pentoxide. .

The content of the antimony oxide is preferably used 1 to 15 parts by weight based on 100 parts by weight of the base resin (A) + (B) + (C), when the antimony oxide is used in less than 1 part by weight sufficient flame retardant effect It cannot be obtained, and when it is used in excess of 15 parts by weight, it is not preferable because the balance of physical properties of the resin composition is lost.

(F) chlorine organic compounds

The chlorine organic compound used in the resin composition according to the present invention may be used as a flame retardant adjuvant and an impact modifier. In the present invention, the chlorine organic compound refers to an organic compound containing chlorine due to substitution or addition of chlorine. Examples include chlorinated polyethylene (CPE) and polyvinyl chloride (PVC), of which chlorinated polyethylene (CPE) is particularly preferred.

The content of the chlorine organic compound is 1 to 10 parts by weight based on 100 parts by weight of the base resin (A) + (B) + (C), but when used less than 1 part by weight, sufficient flame retardant auxiliary effect and impact strength cannot be obtained. If it exceeds 10 parts by weight, thermal stability is significantly lower.

The flame retardant thermoplastic resin composition according to the present invention has a weight ratio of (A) + (B) :( C) to 100 parts by weight of the base resin (A) + (B) + (C) in the range of 60:40 to 20:80 When the weight of (A) + (B) exceeds 60 parts by weight with respect to the base resin, the fluidity is significantly lowered, and when it is less than 20 parts by weight, the impact strength is lowered, which is not practical.

In addition, the weight ratio of (A) :( B) is preferably in the range of 90:10 to 50:50, but when the weight ratio of (A) is greater than 90, the impact strength is lowered and is not practical, and the weight ratio of (A) When is less than 50, weather resistance is not enough and the value as a weathering resin falls.

The flame-retardant thermoplastic resin composition according to the present invention may be prepared by further adding a specific antioxidant, lubricant, impact modifier, light stabilizer, filler, inorganic additive, pigment and / or dye, etc. according to each use. That is, the resin composition according to the present invention is a tin maleate compound or an aluminosilicate inorganic compound, a wax, a metal lubricant, an antioxidant, according to the use and need thereof in the resin composition comprising the above (A) to (F). It may further comprise one or more materials selected from the group consisting of light stabilizers, pigments and dyes.

The tin maleate compound or aluminosilicate inorganic compound acts as a flame retardant heat stabilizer to prevent discoloration of the resin composition by acting as a halogen capture when using a halogen-based flame retardant, the amount of the other additives is used as the base resin (A) It may further include up to 30 parts by weight based on 100 parts by weight of + (B) + (C).

The method for producing a flame retardant thermoplastic resin composition according to the present invention is already known in the art to which the present invention pertains, and the thermoplastic resin composition of the present invention may also be prepared by the conventional method. However, for one embodiment,

(A) The ASA resin (A) + (B) + (C) is mixed with a halogen compound (D), which is a flame retardant, and the mixture is a flame retardant, antimony oxide (E), an impact modifier, a chlorine organic compound (F). And optionally adding at least one material selected from the group consisting of inorganic additives, waxes, metal lubricants, antioxidants, light stabilizers, pigments and dyes;

(B) mixing the added ingredients in a mixer; And

(C) can be prepared by a method comprising the step of extruding the mixture, more specifically a tin maleate-based compound or aluminosilicate-based compound as a halogen capture to each component of the above (A) to (F) After adding an inorganic compound, an antioxidant, a metal lubricant, a wax, titanium dioxide, benzotriazole and a hindered amine light stabilizer, they are mixed in a conventional mixer, and the mixture is extruded through an extruder to form a resin composition in pellet form. It can be prepared as.

The resin composition according to the present invention may be better understood by the following examples, but the following examples are not intended to limit the protection scope of the present invention for the purpose of illustrating the present invention.

Example

(A) acrylic graft polymer, (B) diene graft polymer, (C) vinyl cyanide compound-aromatic vinyl compound copolymer, (D) halogen compound, (E) used in the following Examples and Comparative Examples The specifications of antimony oxide and (F) chlorine organic compounds are as follows. Halogen-based compounds, antimony oxide, chlorine organic compounds and other additives were used as such without commercially available products.

(A) Acrylic Graft Polymer

100 parts by weight of a monomer mixture composed of 25% by weight of acrylonitrile and 75% by weight of styrene acrylate rubber was used as a core-shell graft ASA resin having a rubber particle diameter of about 0.2 μm. .

(B) diene graft polymer

A core-shell graft ABS resin having a rubber particle size of about 0.3 μm of a graft emulsion-polymerized rubber was used in 58 parts by weight of butadiene rubber in an amount of 100 parts by weight of a monomer mixture composed of 25% by weight of acrylonitrile and 75% by weight of styrene.

(C) Vinyl Cyanide Compound-Aromatic Vinyl Compound Copolymer

A styrene-acrylonitrile copolymer resin (hereinafter referred to as 'SAN resin') having an acrylonitrile content of 28% by weight, a styrene content of 72% by weight, and a weight average molecular weight of about 120,000 was used.

(D) halogen-based compound

SAYTEX RB 100, a flame retardant of the TBBA system manufactured by ALBERMALE, USA having a weight average molecular weight of 550 was used.

(E) antimony oxide

As antimony oxide contained in the thermoplastic resin composition according to the present invention, antimony trioxide (manufactured by Ilsung Antimony Co., Ltd.) was used.

(F) chlorine organic compounds

As the chlorine organic compound contained in the thermoplastic resin composition according to the present invention, US DDE's Chlorinated Polyethylene (CPE) Tyrin 3245P was used.

Example  1 to Example  4

Each component is added in an amount as shown in Table 1 below, 1.0 parts by weight of tin maleate compound TM-600P (Songwon Industrial Co., Korea) as a halogen capture, Irganox1076 (Songwon, a hindered phenolic antioxidant as an antioxidant) Industries, Korea) 0.3 parts by weight, 0.4 parts by weight of SONGSTAB Ca-ST (Songwon Industry Co., Korea), a stearic acid-based metal lubricant, and 1 part by weight of wax are mixed uniformly with a mixer, and then extruded with a twin screw extruder to form pellets. A flame retardant thermoplastic resin composition was prepared.

Comparative example  One

A flame-retardant thermoplastic resin composition was prepared in the same manner as in Example 1 except that (A) graft ASA resin was not used and only (B) graft ABS resin was used.

Comparative example  2

A flame-retardant thermoplastic resin composition was prepared in the same manner as in Example 1 except that (B) graft ABS resin was not used and only (A) graft ASA resin was used.

Comparative example  3

A flame retardant thermoplastic resin composition was prepared in the same manner as in Example 2 except that a halogen-based compound as a flame retardant and an antimony oxide as a flame retardant were not used.

TABLE 1

Test Example

From the resin composition of the pellet form prepared in Examples 1 to 4 and Comparative Examples 1 to 3 by the injection molding to test the physical properties and flame retardant test, etc. to measure the impact strength, fluidity, weather resistance and flame retardancy Bar, the measurement results for each property item are shown in Table 2 below.

Impact strength measurements were evaluated for 1/4 inch thickness by ASTM D-256 test method, unit was kgf · cm / cm, and fluidity was evaluated under conditions of 200 ° C and 5 kg load by ASTM D-1238 test method. The unit is g / 10 min.

In addition, the weather resistance was measured by the color difference meter (dE) between the standard specimen of natural color without the addition of pigments or dyes and the specimen irradiated with xenon arc for 300 hours according to ASTM D-4459 test method. It was determined by testing about 1/16 inch thickness according to the UL-94 flame retardancy determination test method.

TABLE 2

As can be seen from the physical property comparison results of Examples and Comparative Examples of Table 2, the flame-retardant thermoplastic resin composition of the present invention composed of an ASA resin, an ABS resin, and a halogen-based compound that is a flame retardant is composed only of an ABS resin to which no ASA resin is added Compared with the conventional resin composition, it can be seen that the physical properties of impact strength, fluidity, weather resistance, and flame retardancy are excellent overall. On the other hand, in the case of Comparative Example 1, the weather resistance is remarkably lowered, in the case of Comparative Example 2, the impact resistance is very low, and Comparative Example 3 was confirmed that the flame retardancy is lowered. As described above, it was confirmed that the flame retardant thermoplastic resin composition according to the present invention has an effect of improving the flame retardancy of the ASA resin by using a halogen-based compound and antimony oxide as a flame retardant.

The flame retardant thermoplastic resin composition according to the present invention has the advantage of using flame retardants and antimony oxide in combination with ASA resin, while maintaining mechanical properties and having excellent weather resistance and excellent flame retardancy.

Claims (7)

Basic resin (A) + (B) whose weight ratio of following (A) + (B) :( C) is 20-60: 40-80, and the weight ratio of (A) :( B) is 50-90: 10-50. ) 100 parts by weight (C), 5 to 30 parts by weight of a halogen compound; 1 to 15 parts by weight of antimony oxide; And A flame retardant thermoplastic resin composition comprising 1 to 10 parts by weight of a chlorine organic compound: (A) is an acrylic graft polymer composed of 30 to 60 wt% of acrylic synthetic rubber and 40 to 70 wt% of a vinyl cyanide compound-aromatic vinyl compound copolymer; (B) a diene graft polymer composed of 30 to 60 wt% of a diene synthetic rubber and 40 to 70 wt% of a vinyl cyanide compound-aromatic vinyl compound copolymer; (C) Vinyl cyanide compound-aromatic vinyl compound copolymer which consists of 20-40 weight% of vinyl cyanide compounds and 60-80 weight% of aromatic vinyl compounds. The flame retardant thermoplastic according to claim 1, wherein the vinyl cyanide compound-aromatic vinyl compound copolymer of (A) or (B) comprises 20 to 30% by weight of a vinyl cyanide compound and 70 to 80% by weight of an aromatic vinyl compound. Resin composition. The flame-retardant thermoplastic resin composition according to claim 1, wherein the weight average molecular weight of the vinyl cyanide compound-aromatic vinyl compound copolymer of (C) is 80,000 to 400,000. The flame retardant thermoplastic resin composition according to any one of claims 1 to 3, wherein the vinyl cyanide compound is one or two selected from the group consisting of acrylonitrile and methacrylonitrile. The method according to any one of claims 1 to 3, wherein the aromatic vinyl compound is one or two selected from the group consisting of styrene, alpha-methylstyrene, pt-butylstyrene, 2,4-dimethylstyrene and vinyltoluene. Flame retardant thermoplastic resin composition, characterized in that more than. The method of claim 1, wherein the halogen-based compound is tetrabromobisphenol A, bis (tribromophenoxy) ethane, brominated epoxy resin, a brominated epoxy resin substituted with tribromophenol epoxy terminal and 2,4,6 -Tri- (2,4,6-tribromophenoxy) -1,3,5 triazine, one or more selected from the group consisting of flame retardant thermoplastic resin composition. The flame retardant thermoplastic resin composition of claim 1, wherein the chlorine organic compound is one or two selected from the group consisting of chlorinated polyethylene (CPE) and polyvinyl chloride (PVC).