KR100478438B1 - Flame Retardant Thermoplastic Resin Composition Having Excellent Flowability - Google Patents

Abstract

The flame-retardant thermoplastic resin composition excellent in fluidity of the present invention comprises (A) a SAN resin composed of 70 to 80% by weight of styrene and 20 to 30% by weight of acrylonitrile and having a weight average molecular weight of 80,000 to 120,000, and acrylonitrile 5 100 parts by weight of acrylonitrile-butadiene-styrene copolymer resin consisting of 30 to 30% by weight, 5 to 30% by weight of butadiene rubber and 40 to 90% by weight of styrene; (B) 5 to 30 parts by weight of a halogen compound having a weight average molecular weight in the range of 500 to 2,000; (C) 1 to 15 parts by weight of antimony oxide; And (D) 0.05 to 10 parts by weight of the aluminosilicate inorganic compound.

Description

Flame Retardant Thermoplastic Resin Composition Having Excellent Flowability

Field of invention

The present invention relates to a flame retardant thermoplastic resin composition excellent in fluidity. More specifically, the present invention is composed of an acrylonitrile-butadiene-styrene copolymer resin, a low molecular weight halogen compound, an antimony oxide compound, and an aluminosilicate inorganic compound, and a flame retardant thermoplastic resin composition having excellent fluidity. It is about.

Background of the Invention

In general, the thermoplastic acrylonitrile-butadiene-styrene copolymer (ABS) resin has good processability and mechanical strength, and thus is widely used for the manufacture of interior and exterior parts such as electrical / electronic products and office automation equipment. However, the ABS copolymer resin itself is not resistant to combustion, and when the spark is ignited by an external ignition factor, there is a problem in that the resin itself acts as an energy to help the combustion to continuously spread the fire. For this reason, in order to secure stability against fires in electric and electronic products, the United States, Europe, and other countries have legalized to use only flame-retardant resins for the production of molded parts of internal and external parts of electrical and electronic products.

There are various methods for imparting flame retardancy to the ABS copolymer resin, and an additive flame retardant method of adding a flame retardant and a flame retardant aid is a commercialized method. In other words, an acrylonitrile-butadiene-styrene copolymer resin is prepared by adding an organic compound containing halogen such as bromine and an inorganic compound containing antimony oxide to the resin.

However, when the halogen-containing organic compound is added to the acrylonitrile-butadiene-styrene copolymer resin, the flame retardancy is very good, but the overall physical properties such as impact strength, weather resistance, heat resistance, and workability of the resin itself are seriously deteriorated. There is this.

In addition, the flame retardant ABS resin is widely used in various applications because of its excellent workability and physical properties, but the resin itself has a lack of fluidity compared to polystyrene resins, so the structure is complicated and large in size such as TV and audio enclosures. Another problem is that its use is limited.

Therefore, the development of acrylonitrile-butadiene-styrene copolymer resins having excellent fluidity, while minimizing side effects such as lowering of physical properties and workability, lowering of weather stability, particularly lowering of heat resistance and thermal stability while maintaining excellent flame retardancy, It is emerging as an important task.

In order to solve the above problems, the present inventors use a SAN resin having a low molecular weight and a low acrylonitrile content as a matrix, and using a halogen compound having a relatively low molecular weight as a flame retardant to improve fluidity, and By using an aluminosilicate inorganic compound composed of (Al), silicon (Si) and sodium (Na) or calcium (Ca), that is, a zeolite inorganic material, it has good flame retardancy and mechanical properties and has excellent fluidity. It is early to develop a thermoplastic resin composition.

An object of the present invention is to provide a thermoplastic resin composition excellent in flame retardancy and thermal stability.

Another object of the present invention is to provide a thermoplastic resin composition having excellent mechanical properties.

It is still another object of the present invention to provide a thermoplastic resin composition having excellent fluidity, which is very useful for manufacturing interior and exterior parts such as various electric and electronic products and office automation equipment.

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

The resin composition of the present invention comprises (A) SAN resin having 70 to 80% by weight of styrene and 20 to 30% by weight of acrylonitrile and having a weight average molecular weight of 80,000 to 120,000, 5 to 30% by weight of acrylonitrile, (B) Halogenated compounds having a weight average molecular weight in the range of 500 to 2,000 with respect to 100 parts by weight of acrylonitrile-butadiene-styrene copolymer resin composed of 5 to 30% by weight of butadiene rubber and 40 to 90% by weight of styrene. 30 parts by weight, (C) 1 to 15 parts by weight of antimony oxide and (D) 0.05 to 10 parts by weight of the aluminosilicate inorganic compound, optionally (E) 0.05 to 5 parts by weight of the tin maleate compound or (F) It may further comprise 1 to 10 parts by weight of the chlorine compound. Detailed description of each of these components is as follows.

(A) Acrylonitrile-butadiene-styrene copolymer resin

The acrylonitrile-butadiene-styrene copolymer resin (A) used in the present invention is composed of 5 to 30% by weight of acrylonitrile, 5 to 30% by weight of butadiene rubber and 40 to 90% by weight of styrene.

The acrylonitrile-butadiene-styrene copolymer resin includes a SAN resin having a low molecular weight and acrylonitrile content as 50 to 80% by weight of the total acrylonitrile-butadiene-styrene copolymer resin (A).

The SAN resin having a low molecular weight and acrylonitrile content is composed of 70 to 80% by weight of styrene and 20 to 30% by weight of acrylonitrile, and the weight average molecular weight is preferably in the range of 80,000 to 120,000. If the weight average molecular weight is 80,000 or less, there is a problem that the heat resistance and impact resistance is significantly lowered, and if the weight average molecular weight is 120,000 or more, the high-fluidity expression, which is the object of the present invention, is lowered, so that unmolded and GAS are generated during the injection molding of a large complex structure. It may cause a defect or the like.

SAN resins having a low molecular weight and acrylonitrile content of the present invention are well known to those skilled in the art to which the present invention belongs, and may be polymerized by suspension polymerization or bulk polymerization. It is more preferable to use SAN resin manufactured by the bulk polymerization method with little additive content added to a polymerization manufacturing process, and few gel generation. If the additive content is high during the polymerization manufacturing process, it is easy to cause appearance defects such as GAS defects in the molded products during injection molding, and when gel is included in the SAN resin, it protrudes on the surface of the final molded product to improve the quality of the molded products. There is a problem of deterioration.

(B) a halogen compound having a weight average molecular weight of 500 to 2,000

In the present invention, the halogen-based compound is used as a flame retardant, and is a product currently commercialized and commonly used. Examples of the halogen-based compound usable in the present invention include tetra-bromobisphenol-A, bis (tribromophenoxy) ethane, and brominated epoxy resins. Or a brominated epoxy resin terminated with tribromophenol having an epoxy terminal substituted with tribromophenol.

The halogen-based compound is used 5 to 30 parts by weight based on 100 parts by weight of the base resin (A) of the present invention. When 5 parts by weight or less is added, the flame retardant effect is insufficient, and when 30 parts by weight or more is used, deterioration of workability and mechanical strength occurs, which is not preferable because the balance of physical properties is lost.

In addition, the halogen-based compound is used in the weight average molecular weight range of 500 to 2,000. If the weight average molecular weight is 500 or less, there is a problem that the heat resistance is significantly lowered. If the weight average molecular weight is 2,000 or more, the fluidity is lowered, which may cause unmolding, poor GAS generation, etc. during injection molding of a complicated structure, as well as impact resistance. It is also significantly reduced.

(C) antimony oxide

The antimony oxide of the present invention acts as a flame retardant adjuvant that synergizes with the halogen-based compound used as the flame retardant and imparts proper flame retardancy to the thermoplastic acrylonitrile-butadiene-styrene copolymer resin.

In the present invention, 1 to 15 parts by weight, preferably 2 to 10 parts by weight, of the antimony oxide is used based on 100 parts by weight of the base resin (A).

Antimony oxide which may be used in the present invention includes antimony trioxide or antimony pentoxide. In the case where antimony oxide is used in an amount less than 1 part by weight, sufficient flame retardant effect may not be obtained, and when an excess amount is used in excess of 15 parts by weight, the balance of physical properties of the resin composition is not good.

(D) Aluminosilicate Inorganic Compound

Aluminosilicate inorganic compounds composed of aluminum (Al), silicon (Si) and sodium (Na) or calcium (Ca) are commonly referred to as zeolites and are used as thermal stabilizers in the present invention.

In the aluminosilicate inorganic compound, aluminum oxide (Al ₂ O ₃ ) and silicon oxide (SiO ₂ ) form a three-dimensional basic skeleton, and sodium oxide (Na ₂ O) or calcium oxide (CaO) is electronically It is added to achieve neutrality. The aluminosilicate inorganic compound is composed of 10 to 60% Al ₂ O ₃ , 10 to 60% SiO ₂ and 5 to 30% Na ₂ O or CaO, the average particle size of 0.5 to 5 μm.

In the present invention, the aluminosilicate inorganic compound is added to improve the thermal stability of the flame retardant acrylonitrile-butadiene-styrene copolymer resin using a halogen-based compound as a flame retardant. The aluminosilicate inorganic compound may be used alone in an amount of 0.05 to 10 parts by weight with respect to 100 parts by weight of the base resin (A), or synergistic effect may be obtained by using in combination with the following tin maleate compound (E). When the aluminosilicate inorganic compound (D) is added in an amount of 0.05 parts by weight or less, the effect of improving thermal stability is small, and when used in an amount of 10 parts by weight or more, it is not preferable because it impairs the physical properties of the resin.

Therefore, the thermal stability of the acrylonitrile-butadiene-styrene copolymer resin is improved by the addition of the aluminosilicate inorganic compound, which is generated by heat or high shear stress applied to the resin during extrusion and injection molding of the resin. Decomposition of the flame retardant due to the frictional heat can be suppressed, and the effect of suppressing the gas silver can be increased by collecting decomposition gas to minimize discoloration and black streaks of the resin.

(E) Tin Maleate Compound

The tin maleate compound is used as an auxiliary heat stabilizer in the present invention. In this invention, it is preferable to use the tin maleate type compound which is a tin compound normally. It is more synergistic to use in combination with the above-mentioned aluminosilicate inorganic compound (D) than to use it alone. Therefore, the effect of suppressing discoloration of the resin, black streaks and gas silver is greatly increased during injection molding, in particular, even in the injection molding machine, compared to the resin composition using the tinmalate-based and hydrotalcite-based compounds as heat stabilizers.

In the present invention, the tin maleate compound is preferably used in an amount of 0.05 to 5 parts by weight based on 100 parts by weight of the base resin (A) of the present invention. When it is used at 0.05 parts by weight or less, the effect of improving the thermal stability is small, and when it is added at 5 parts by weight or more, there is no obvious improvement of the thermal stability, and the physical property balance of the flame retardant resin may be lowered, in particular, the fluidity decrease.

(F) chlorine compound

The chlorine compound is added to improve the impact strength of the flame retardant acrylonitrile-butadiene-styrene resin in the present invention. In the present invention, chlorinated polyethylene (CPE) and the like are used as the chlorine compound.

A preferred amount of the chlorine compound of the present invention is 1 to 10 parts by weight based on 100 parts by weight of the base resin (A).

In addition to the above components, the flame retardant thermoplastic resin composition of the present invention may further add inorganic additives, antioxidants, other light stabilizers, metal lubricants, wax pigments, and / or dyes in required amounts according to their respective uses.

In the method for producing a flame retardant thermoplastic resin composition of the present invention, an antioxidant, a metal lubricant, a wax, titanium dioxide, benzotriazole, and a hindered amine light stabilizer are added to each of the above components, followed by mixing in a conventional mixer. The mixture may be prepared into a resin composition in pellet form through an extruder.

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

(A) Acrylonitrile-butadiene-styrene copolymer resin, (B) Halogen type compound, (C) Antimony oxide, (D) Aluminosilicate type inorganic compound used in the following Example and the comparative example, ( The specifications of E) tin maleate compound and (F) chlorine compound are as follows.

(A ₁ ) Acrylonitrile-butadiene-styrene copolymer resin

An ABS resin (manufactured by Cheil Industries Co., Ltd.) having a weight average molecular weight of 88,000 and manufactured by mixing and processing a SAN resin composed of 24% by weight of acrylonitrile and 76% by weight of styrene was used.

(A ₂ ) ABS resin

An ABS resin (manufactured by Cheil Industries Co., Ltd.) manufactured by mixing and processing a SAN resin composed of 32% by weight of acrylonitrile and 68% by weight of styrene with a weight average molecular weight of 180,000 was used.

(B ₁ ) 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.

(B ₂ ) halogen-based compound

A brominated epoxy resin ECX-30 manufactured by Japan DIC Corporation having a weight average molecular weight of 3,000 was used.

(C) antimony oxide

Antimony trioxide (manufactured by Ilsung Antimony Co., Ltd., Korea) was used.

(D) Aluminosilicate Inorganic Compound

Zeolite (APS30, manufactured by Aekyung Materials, Korea) was used.

(E) Tin Maleate Compound

TM-600P, a dibutyl tin maleate polymer manufactured by Songwon Industrial Co., Ltd., was used.

(F) chlorine compound

DDE's cloned polyethylene (CPE) 3611P was used.

Example 1-3

The components were added in the amounts shown in Table 1 below, 0.5 parts by weight of Irganox1076, a hindered phenol-based antioxidant manufactured by Korea Songwon Industries, and 0.5% by weight of SONGSTAB Ca-ST, a stearic acid-based metal lubricant, as other antioxidants. Part and 1 part by weight of wax were added and mixed uniformly with a mixer, and then extruded with a twin screw extruder to prepare pellets.

Comparative Example 1-4

In Comparative Example 1, instead of the acrylonitrile-butadiene-styrene copolymer resin (A) of the present invention, an ABS (A ₂ ) resin having a weight average molecular weight of 180,000 was used, and the weight average molecular weight was used as the halogen-based compound (B). The same procedure as in Example 1 was performed except that 3,000 halogen-based compound (B ₂ ) was used.

Comparative Example 2 was carried out in the same manner as in Example 1, except that the halogen-based compound (B ₂ ) having a weight average molecular weight of 3,000 was used as the halogen-based compound (B).

Comparative Example 3 was carried out in the same manner as in Example 1, except that ABS (A ₂ ) resin having a weight average molecular weight of 180,000 was used instead of the acrylonitrile-butadiene-styrene copolymer resin (A) of the present invention. .

In Comparative Example 4, instead of the acrylonitrile-butadiene-styrene copolymer resin (A) of the present invention, an ABS (A ₂ ) resin having a weight average molecular weight of 180,000 was used, and the aluminosilicate compound (D) was not used. Except that was carried out in the same manner as in Example 1.

Example Comparative Example One 2 3 One 2 3 4    (A) Acrylonitrile-butadiene-styrene copolymer resin (A ₁ ) 100 100 100 - 100 - - (A ₂ ) - - - 100 - 100 100  (B) halogen-based compound (B ₁ ) 22 22 21 - - 22 22 (B ₂ ) - - - 22 22 - -  (C) antimony trioxide 6 6 7 6 6 6 6  (D) Aluminosilicate Inorganic Compound 0.5 0.7 0.5 0.5 0.5 0.5 -  (E) Tin Maleate Compound 0.5 - 0.6 0.5 0.5 0.5 0.8  (F) chlorine compound 6 6 6 6 6 6 6

From the pellets prepared above, test specimens for physical properties and flame retardancy were prepared by injection molding, and the measurement method for each property item was experimentally evaluated based on the following test analysis criteria.

(1) Impact strength measurement: The 1/4 inch thickness was evaluated by the ASTM D-256 test method, the unit is kgf · cm / cm.

(2) Fluidity: It was evaluated under the condition of 200 ℃ and 5 kg load by ASTM D-1238 test method, the unit is g / 10min.

(3) Thermal softening point temperature: The temperature was evaluated by the test method of ASTM D1525 under the condition of 50 ℃ / hr at 5 kg load, the unit is ℃.

(4) Flame retardancy measurement: According to the UL-94 flame retardancy determination test method, it was determined by testing about 1/12 inch thickness.

Physical properties of the resins prepared in Examples 1-3 and Comparative Examples 1-4 are shown in Table 2 below.

Test Items Example Comparative Example One 2 3 One 2 3 4 Notched Izod Impact Strength (kgfcm / cm, 1/4 ", 23 ℃) 13 12 14 17 13 15 15 Flow index (g / 10min, 10㎏, 220 ℃) 15 14 14 1.5 5 2 2.5 Thermal softening point temperature (℃, 5㎏, 50 ℃ / hr) 85 86 87 89 88 87 88 Flame retardant V-0 V-0 V-0 V-0 V-0 V-0 V-0

From the results in Table 2, the flow index is significantly increased in the case of using an ABS resin containing a low molecular weight and a low content of acrylonitrile in combination with a low molecular weight halogen-based compound compared to the comparative example Appeared to be. Therefore, by using the ABS resin including the SAN resin having a low molecular weight and low acrylonitrile content in combination with the halogen compound having a low molecular weight, not only does it ensure excellent flame retardancy and thermal stability, but also has excellent fluidity. Could know.

The present invention uses a ABS resin containing a SAN resin having a low molecular weight and a low acrylonitrile content and a halogen compound having a low molecular weight, so that a thermoplastic resin composition having good flame retardancy and mechanical properties and excellent fluidity can be obtained. Has the effect of providing.

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 (5)

(A) SAN resin consisting of 70 to 80% by weight of styrene and 20 to 30% by weight of acrylonitrile and having a weight average molecular weight of 80,000 to 120,000; 5 to 30% by weight of acrylonitrile and 5 to 30% by weight of butadiene rubber 100 parts by weight of acrylonitrile-butadiene-styrene-based copolymer resin consisting of% and 40 to 90% by weight of styrene; (B) 5 to 30 parts by weight of a halogen compound having a weight average molecular weight in the range of 500 to 2,000; (C) 1 to 15 parts by weight of antimony oxide; And (D) 0.05 to 10 parts by weight of the aluminosilicate inorganic compound; Flame-retardant thermoplastic resin composition, characterized in that consisting of. The flame retardant thermoplastic resin composition of claim 1, wherein the resin composition further comprises 0.05 to 5 parts by weight of the tin maleate compound (E). The flame retardant thermoplastic resin composition of claim 1, wherein the resin composition further comprises 1 to 10 parts by weight of a chlorine compound (F). The method of claim 1, wherein the halogen-based compound (B) is tetra bromobisphenol A, bis (tribromophenoxy) ethane (bis), brominated epoxy resin (brominated epoxy) A flame retardant thermoplastic resin composition characterized in that the resin or the epoxy terminal is a brominated epoxy resin terminated with tribromophenol substituted with tribromophenol. According to claim 1, wherein the aluminosilicate inorganic compound (D) is composed of 10 to 60% Al ₂ O ₃ , 10 to 60% SiO ₂ and 5 to 30% of Na ₂ O or CaO Flame retardant thermoplastic resin composition, characterized in that the average particle size is 0.5 to 5 ㎛ zeolite.