KR100583170B1 - Flame Retardant Thermoplastic Acrylonitrile-Butadiene-StyreneABS Copolymer Resin Composition with Good UV-Resistance and Good Heat-stability - Google Patents

Abstract

The present invention relates to a brominated epoxy oligomer and 2,4,6-tri (2,4,6-tribromophenoxy) -1,3 in acrylonitrile-butadiene-styrene copolymers. Flame-retardant acrylic furnace having excellent weather stability and thermal stability, which is produced by using 5-triazine as flame retardant, antimony oxide compound as flame retardant, tin maleate compound as heat stabilizer, and chlorine compound as impact modifier. A nitrile-butadiene-styrene-based copolymer resin composition.

Acrylonitrile-butadiene-styrene-based copolymer, brominated epoxy oligomer, 2,4,6-tri (2,4,6-tribromophenoxy) -1,3,5-tri Azine, antimony oxide, tin maleate, weathering stability, thermal stability, flame retardant

Description

Flame Retardant Thermoplastic Acrylonitrile-Butadiene-Styrene (ABS) Copolymer Resin Composition with Good UV-Resistance and Good Heat-stability}

Field of invention

The present invention relates to a thermoplastic acrylonitrile-butadiene-styrene copolymer (ABS) flame-retardant resin composition having excellent weather stability and thermal stability. More specifically, the present invention relates to a brominated epoxy oligomer and 2,4,6-tri (2,4,6-tribromophenoxy) -1 in acrylonitrile-butadiene-styrene copolymers. It has excellent weather stability and thermal stability, which is produced by using 3,5-triazine as flame retardant, antimony oxide compound as flame retardant, tin maleate compound as heat stabilizer, and chlorine compound as impact modifier. A flame retardant acrylonitrile-butadiene-styrene copolymer resin composition.

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, 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. Although there are various methods for imparting flame retardancy to ABS copolymer resin having such characteristics, an additional 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 a halogen such as bromine and an inorganic compound containing antimony oxide to the resin. Halogen-containing organic compounds are mainly bromine or chlorine compounds, and when added to acrylonitrile-butadiene-styrene copolymer resins, the flame retardancy is very good, whereas the resin itself has an impact strength, weather resistance, thermal stability, heat resistance, processability, and the like. This will cause serious degradation of the overall physical properties.

Therefore, in manufacturing a flame retardant resin, a technique for minimizing incidental effects such as deterioration in physical properties and workability, in particular weather resistance deterioration and thermal stability deterioration, while maintaining excellent flame retardancy is very important. To prevent degradation of the thermal stability of these products, additives, commonly referred to as thermal stabilizers, are added to the flame retardant resin. Commonly used thermal stabilizers in flame retardant acrylonitrile-butadiene-styrene copolymer resins include tinmalate compounds.

In recent years, the market of TVs among electronic products is becoming larger and thinner, and the color is also expanding from dark to light colors. Therefore, the styrene-based resins applied in these fields have a problem in that not only flame retardancy but also moldability and thermal stability must be simultaneously satisfied.

The flame retardant is designed to cause thermal decomposition quickly, but this characteristic causes the decomposition of the flame retardant at the normal processing temperature of the resin, which lowers the thermal stability of the resin itself, resulting in poor silver streak or brightness. There is a disadvantage that the heat discoloration from color to dark red color occurs.

 Therefore, in order to overcome the above problems, it is to develop a flame retardant thermoplastic resin composition suitable for injection molding of a large product as well as a light product by maintaining thermal stability while maintaining flame retardancy.

The present inventors brominated the acrylonitrile-butadiene-styrene copolymer resin in order to improve the weather resistance and thermal stability of the thermoplastic acrylonitrile-butadiene-styrene copolymer resin to which flame retardancy was added as described above. Brominated epoxy oligomer and 2,4,6-tri (2,4,6-tribromophenoxy) -1,3,5-triazine are added as flame retardant, and antimony trioxide as a flame retardant aid Flame retardant acrylonitrile-butadiene-styrene copolymer resin having good flame retardancy and mechanical properties and excellent weather resistance and thermal stability by using chlorine compound as impact modifier and tin maleate compound as heat stabilizer. It is very suitable for the manufacture of interior and exterior parts such as electric and electronic products and office automation equipments that require flame retardancy due to the manufacture and injection molding processing. Useful resin compositions have been invented.

An object of the present invention is to provide a flame-retardant acrylonitrile-butadiene-styrene-based copolymer resin composition having good flame retardancy and excellent weather resistance.

Another object of the present invention is to provide a flame retardant ABS copolymer resin composition which can be used at a high temperature and improves thermal stability to prevent thermal discoloration.

It is still another object of the present invention to provide an ABS copolymer resin composition which is very useful for the manufacture of interior and exterior parts such as various electrical and electronic products and office automation equipment.

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

Summary of the Invention

ABS copolymer resin composition according to the present invention is 2 to 20 parts by weight of brominated epoxy oligomer (B) with respect to 100 parts by weight of acrylonitrile-butadiene-styrene copolymer resin (A) 2 to 20 parts by weight of 4,6-tri (2,4,6-tribromophenoxy) -1,3,5-triazine (C) as a flame retardant to increase the weather resistance and thermal stability of the resin itself. , 1 to 15 parts by weight of antimony trioxide (D) is used as a flame retardant adjuvant, and has excellent thermal stability by using 0.05 to 5 parts by weight of tin maleate compound (E), and 1 to 1 chlorine compound (F) as an impact modifier. It is prepared using 10 parts by weight. Inorganic fillers, waxes, metal lubricants, antioxidants, other light stabilizers, pigments and / or dyes may be added in the required amounts, depending on the use and needs of the resin composition, the details of each of which are as follows.

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

Detailed Description of the Invention

(A) Acrylonitrile-butadiene-styrene copolymer resin

The acrylonitrile-butadiene-styrene copolymer resin used in the present invention is a graphene resin containing a styrene monomer and an acrylonitrile monomer in a rubber selected from butadiene rubbers, isoprene rubbers, copolymers of butadiene and styrene or alkylacrylate rubbers. It is a resin which consists of a copolymer manufactured by copolymerizing the graft copolymer obtained by the superposition | polymerization polymerization, a styrene monomer, and an acrylonitrile monomer. The rubber content of the ABS resin is 5 to 25%, the styrene-acrylonitrile copolymer content is 75 to 95%, the acrylonitrile content in the styrene-acrylonitrile copolymer is comprised in the range of 20 to 40%.

(B) brominated epoxy oligomers

In the present invention, a melt halogen flame retardant, particularly a bromine flame retardant, is used to maintain flame retardancy, weather resistance, and thermal stability. The brominated flame retardant is preferably a brominated epoxy oligomer terminated with tribromophenol in which one epoxy terminal is substituted with tribromophenol.

The brominated epoxy oligomer is represented by the following formula (I):

[Formula I]

Where n is a natural number.

The molecular weight of the brominated epoxy resin is 500 to 3000, preferably 700 to 2000 range. If the molecular weight is less than 500, sufficient heat resistance cannot be obtained. If the molecular weight exceeds 3000, impact resistance and fluidity decrease occur.

The melt halogenated flame retardant (B) is used 2 to 20 parts by weight, preferably 10 to 20 parts by weight based on 100 parts by weight of acrylonitrile-butadiene-styrene copolymer resin (A). If 2 parts by weight or less is added, the flame retardancy decreases, and a flame retardant timeout occurs during the evaluation of flame retardancy, and when 20 parts by weight or more is used, the weather resistance and thermal stability are deteriorated. 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, since the aliphatic halogenated flame retardant (B) has a problem in thermal stability, in order to improve thermal stability, 2,4,6-tri (2,4,6-tribromophenoxy) -1,3,5- Triazine is used as the main flame retardant. By adding the 2,4,6-tri (2,4,6-tribromophenoxy) -1,3,5-triazine flame retardant, it is possible to reinforce the thermal stability while maintaining the flame resistance of the product and the weather resistance of the resin. In addition to improving, it is possible to prepare a flame retardant thermoplastic resin composition having excellent 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):

[Formula II]

The 2,4,6-tri (2,4,6-tribromophenoxy) -1,3,5-triazine compound (C) is acrylonitrile-butadiene-styrene copolymer resin (A) 100 2 to 20 parts by weight is used with respect to parts by weight, preferably 5 to 10 parts by weight. If the addition of 2 parts by weight or less is insufficient flame retardant effect, when using more than 20 parts by weight is not preferable because it impairs the balance of weather resistance and physical properties.

(D) antimony trioxide

The antimony oxide added as a flame retardant aid in order to synergize with the halogen-based compound used as the flame retardant in the present invention to impart proper flame retardancy to the thermoplastic acrylonitrile-butadiene-styrene copolymer resin is the basic resin (A) of the present invention. It is preferable to use 1 to 10 parts by weight based on 100 parts by weight. When antimony trioxide is used below 1 part by weight, a sufficient flame retardant effect cannot be obtained, and when used in excess of 10 parts by weight, the balance of the physical properties of the resin composition is not good.

(E) Tin Maleate Compound

The auxiliary heat stabilizer used in the present invention is a tin maleate compound, which is usually a tin compound. It is synergistic when used in combination with the inorganic thermal stabilizer (D) rather than used alone, and stays in the injection molding machine, especially for a long time, compared to the resin composition using the tinmalate-based and hydrotalcite-based compounds as the thermal stabilizer. Even so, the effect of suppressing discoloration of the resin, black streaks and gas silver is greatly increased.

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 basic 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

In the present invention, the additive used to improve the impact strength of the flame retardant acrylonitrile-butadiene-styrene resin is a chlorine compound such as chlorinated polyethylene (CPE) and the like, and the amount is 1 based on 100 parts by weight of the base resin (A). To 10 parts by weight.

In addition, according to the use of the resin composition, an additive selected from the group consisting of inorganic fillers, antioxidants, light stabilizers, metal lubricants, waxes, pigments and dyes may be added in a required amount.

The flame retardant acrylonitrile-butadiene-styrene resin composition of the present invention uses a halogen compound as a flame retardant, adds antimony trioxide as a flame retardant adjuvant, uses a chlorine compound as an impact modifier, adds a tin maleate compound in combination , And other antioxidants, metal lubricants and waxes titanium dioxide, benzotriazole and hindered amine light stabilizers are added, then mixed in a conventional mixer and the mixture is made into a resin composition in pellet form through an extruder.

The present invention will be further illustrated by the following examples, which are only described for the purpose of illustrating the present invention and are not intended to limit the protection scope of the present invention.

Example

(A) Acrylonitrile-butadiene-styrene copolymer resin, (B) Brominated epoxy oligomer, (C) 2,4,6-tree used in the following Examples and Comparative Examples The specifications of (2,4,6-tribromophenoxy) -1,3,5-triazine, (D) antimony trioxide, (E) tinmalate type compound, and (F) chlorine type compound are as follows. ABS resin was used by Cheil Industries, Inc., and other additives such as flame retardants were purchased on the market and used as they were without further purification.

(A) Acrylonitrile-butadiene-styrene copolymer resin

ABS resin (PBD CONTENT: 58%) prepared by graft polymerization using a rubber having an average particle diameter of 0.32 μm and a SAN resin having a weight average molecular weight of 120,000, consisting of 28% by weight of acrylonitrile and 72% by weight of styrene ABS resin (made by Cheil Industries Co., Ltd.) manufactured by processing was used.

(B) brominated epoxy oligomers

Brominated epoxy resin EPC-15 (brominated epoxy oligomer in which one epoxy end is replaced with tribromophenol) and EC-14 (both epoxy ends are tribromophenol) Substituted brominated epoxy oligomer), EP-13 (both epoxy terminated unsubstituted epoxy oligomers) were used.

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

FR-245 manufactured by DSBG, Israel, was used.

(D) antimony trioxide

Antimony trioxide manufactured by Ilsung Antimony Co., Ltd. was used.

(E) Tin Maleate Compound

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

(F) chlorine compound

 US DDE company cloned polyethylene (CPE) Tyrin 3245P was used.

Example 1-3

0.3 parts by weight of Irganox1076, a hindered phenol antioxidant, manufactured by Songwon Industrial Co., Ltd., and SONGSTAB Ca-ST, a stearic acid-based metal lubricant, are added to the components as shown in Table 1 below. 0.4 parts by weight and 1 part by weight of wax were added and mixed uniformly with a mixer, followed by extrusion with a twin screw extruder to prepare pellets.

Comparative Example 1-4

When the content of the flame retardant of the resin composition of the present invention was used outside the range of the above examples, the resin composition was prepared in the same manner as in the above examples.

Example Comparative Example One 2 3 One 2 3 4 (A) ABS resin 100 100 100 100 100 100 100 (B) Brominated epoxy oligomers with one epoxy end substituted with tribromophenol 10 15 20 20 - - - (C) 2,4,6-tri (2,4,6-tribromophenoxy) -1,3,5-triazine 10 10 5 - 20 - - (B ') Brominated epoxy oligomers with both epoxy ends substituted with tribromophenols - - - - - 20 - (B ″) Brominated epoxy oligomers in which both epoxy ends are unsubstituted - - - - - - 20 (D) antimony trioxide 6 5 5 6 6 6 6 (E) Tin Maleate Compound One One One One One One One (F) chlorine compound 6 6 6 6 6 6 6

From the pellets prepared according to the ingredients and the amount of the additives described in Table 1, the specimens for physical properties and flame retardancy test were prepared by injection molding, and the measurement method for each property item was experimentally evaluated based on the following test analysis criteria.

Weather Stability: According to ASTM D4459 test method, the color difference (dE) between the standard specimen of natural color without pigment or dye and irradiated with xenon arc for 300 hours was measured using a colorimeter.

Thermal Stability: The number of molded articles which showed defects (black streaks) on the surface of the molded articles injected by continuous injection of 20 molded articles at a high temperature (injector cylinder temperature 250 ° C.) was measured and used as a standard of thermal stability.

Flame retardancy measurement: Determined by testing for 1/10 inch thickness according to the UL-94 flame retardance determination test method.

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

Test Items Example Comparative Example One 2 3 One 2 3 4 Weatherability (dE) 2.2 2.5 2.8 3.8 10.8 4.0 3.5 Thermal Stability (Black Line Water) One 2 3 5 One 4 5 Flame retardant V-0 V-0 V-0 V-0 V-0 V-0 V-0

As shown in Table 2, a brominated epoxy oligomer and 2,4,6-tri (2,4,6-tribromophenoxy) -1,3, which are melt halogen flame retardants, In Example 1-3, in which 5-triazine was used at the same time, weather resistance, thermal stability, and flame retardancy were excellent. Comparative Examples 1, 3, and 4 using brominated epoxy oligomers alone showed relatively low weathering stability and thermal stability, and 2,4,6-tree (2,4) as a flame retardant. In the case of Comparative Example 2 using, 6-tribromophenoxy) -1,3,5-triazine alone, the weather resistance was lowered. Therefore, excellent weather stability by using a combination of brominated epoxy oligomer, 2,4,6-tri (2,4,6-tribromophenoxy) -1,3,5-triazine And it can be seen that it is possible to prepare a flame-retardant acrylonitrile-butadiene-styrene copolymer resin having thermal stability.

The present invention is a brominated flame retardant brominated epoxy oligomer, 2,4,6-tri (2,4,6-tribromophenoxy) -1,3,5-triazine, and trioxide By using antimony in combination, it has good flame retardancy and mechanical properties, as well as excellent weather stability and thermal stability, and is very useful for the production of interior and exterior parts such as various electrical and electronic products and office automation equipment, and is very useful for flame retardant acrylonitrile-butadiene. It has the effect of providing an styrene-based copolymer resin composition.

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) Graft copolymer obtained by graft polymerization of styrene monomer and acrylonitrile monomer in butadiene rubber, isoprene rubber, copolymer of butadiene and styrene or alkyl acrylate rubber, and styrene monomer and acryl In the ABS resin made of a copolymer prepared by copolymerizing nitrile monomer, the rubber content is 5 to 25% by weight, the styrene-acrylonitrile copolymer content is 75 to 95% by weight, and the acrylonitrile content in the styrene-acrylonitrile copolymer. 100 parts by weight of the thermoplastic acrylonitrile-butadiene-styrene-based copolymer resin composed of 20 to 40% by weight of silver; (B) 2 to 20 parts by weight of a brominated epoxy oligomer represented by the following formula (I); [Formula I]

Where n is a natural number. (C) 2 to 20 parts by weight of 2,4,6-tri (2,4,6-tribromophenoxy) -1,3,5-triazine represented by the following formula (II); And [Formula II]

(D) 3 to 10 parts by weight of antimony trioxide; A thermoplastic acrylonitrile-butadiene-styrene-based copolymer flame retardant resin composition having excellent weather stability and thermal stability. The thermoplastic acrylonitrile-butadiene-styrene copolymer flame retardant resin composition of claim 1, further comprising 0.05 to 5 parts by weight of the tin maleate compound (E). The thermoplastic acrylonitrile-butadiene-styrene-based copolymer flame retardant resin composition according to claim 1 or 2, further comprising 1 to 10 parts by weight of a chlorine-based compound (F). The thermoplastic acrylonitrile having excellent weather resistance and thermal stability according to claim 3, further comprising an additive selected from the group consisting of inorganic fillers, antioxidants, light stabilizers, metal lubricants, waxes, pigments and dyes. Butadiene-styrene copolymer flame retardant resin composition.