KR0142204B1 - High impact polystyrene resin composition - Google Patents

Abstract

The present invention is a decabromodiphenyl-based brominated flame retardant HIPS (High Impact polystyrene) copolymer and non-PBDE. The present invention relates to a non-PBDE thermoplastic resin composition composed of a bromide epoxy and a phosphate flame retardant plasticizer.

The present invention provides a HIPS resin composition which is inexpensive in manufacturing cost, does not reduce heat resistance even when a large amount is added, and thermal aging does not occur during molding processing, that is, weather resistance, flowability, and thermal stability are simultaneously improved. It aims to do it.

The present invention is characterized in that 100 parts by weight of HIPS resin is added 5-11 parts by weight of decabromodiphenyl-based non-PBDE brominated flame retardant, 13-7 parts by weight of brominate epoxy, 3-6 parts by weight of phosphate-based flame retardant plasticizer The composition prepared in this way exhibits the effect of improving weather resistance, flowability and thermal stability at the same time.

Description

HIPS resin composition with excellent weatherability, flowability and thermal stability

The present invention relates to a thermoplastic resin composition excellent in weatherability, flowability and thermal stability, and more particularly, non-PBDE composed of HIPS (High Impact Polystyrene) copolymer, two non-PBDE brominated flame retardants, and a flame retardant plasticizer. It relates to a thermoplastic resin composition.

Conventional techniques for increasing flame retardancy in HIPS include the use of brominated flame retardants such as bromine flame retardants and antimony trioxide in HIPS, but due to recent toxicity, non-PBDE bromine flame retardants and chlorine flame retardants The application of light is diversified.

Among the brominated flame retardants, decaromophenyl oxide is the most widely used in HIPS because of its excellent thermal stability and flame retardancy, but it is a PBDE product that has been controversial as polybromodiphenyl. In order to improve this, it is required to add a large amount of UV stabilizer, but there is a problem that the cost is increased.

In addition, decabromodiphenyl, a non-PBDE bromine-based flame retardant, has excellent weather resistance and thermal stability, but has low flowability and is required to be applied to large products and complex moldings. As a technique for solving this problem, there is a method of adding a lubricant, but there are many problems such as heat resistance, flame retardancy reduction, and gas generation during injection.

Brominted-EPOXY flame retardant is non-PBDE, which has the advantages of weather resistance and flowability, but requires much addition due to its low bromine content compared to decabromodiphenyl oxide flame retardant. Problems such as discoloration due to thermal aging occur.

In the case of increasing thermal stability by mixing brominated epoxy in HIPS, various stabilizers may be used as thermal stabilizers, but there is a problem in that manufacturing costs are increased.

The present invention is to solve the above problems, the manufacturing cost is low, there is no decrease in the heat resistance even when a large amount is added, the heat aging phenomenon does not occur during the molding process, that is weather resistance and flowability, and thermal stability At the same time, it is an object to provide an improved HIPS resin composition.

The present inventors have studied in order to achieve the above object, the bromine flame retardant bromide flame retardant and bromide epoxy (hereinafter referred to as Br-EPOXY) flame retardant, phosphate flame retardant plasticizer, and flame retardant aid It has been found that the proper use of antimony trioxide in combination improves heat stability, weather resistance and flowability.

That is, according to the present invention, 5-11 parts by weight of decabromodiphenyl-based bromine-based flame retardant and 13-8 parts by weight of bromide epoxy are added to 100 parts by weight of HIPS resin, and 3-6 parts by weight of a phosphate flame retardant plasticizer is added thereto. The addition is further characterized in that it is added.

The present invention is described in detail as follows.

Examples of HIPS resins that can be used in the present invention are butadiene-styrene copolymers, acrylonitrile-butadiene-styrene copolymers, acrylonitrile-butadiene-isoprene-styrene copolymers, and the like. Appropriate amount of flame retardant decabromodiphenyl and Br-EPOXY is 5-11: 13-8 parts with respect to 100 parts by weight of HIPS resin (hereinafter abbreviated as parts), 5-8 parts of antimony trioxide, phosphate flame retardant plasticizer The system is 3-6 parts.

The decabromodiphenyl bromine flame retardant is a non-PBDE Br-based flame retardant, which has a slightly higher price than the existing decabromo phenyl oxide, but has excellent weather resistance at 2.5 times to 3 times at 1/16 and V-0 levels. The heat resistance is equivalent, but the flow rate is 1.5-2 times lower, which requires improvement. In addition, Br-EPOXY has better weather resistance than decabromodiphenyl series, and shows an increase in flowability as the content increases, but thermal stability decreases.

As a result, non-PBDE products can complement each other's strengths and weaknesses when mixed flame retardants are used at the proper amount to maintain 1/16 and V-0 levels. At this time, the proper use of content is important. If the amount of decabromodiphenyl-based and Br-EPOXY is 5-11: 13-8 parts, 1/16, V-0 level is maintained, and the product has good weather resistance, flowability and thermal stability. You can expect.

In the case of mixed use, when the decabromodiphenyl system exceeds 11 parts, the production cost is excessively increased due to the excessive flame retardant.

In addition, the flame retardant Br-EPOXY has a high possibility of thermal aging due to the molding process in the case of a large amount of mixed use, and therefore it is important to use an appropriate content. In the case of more than 13 parts, the flowability is increased due to the excessive flame retardant, but thermal aging is observed, and the addition of less than 8 parts results in the decrease of the flow effect and the reduction of the flame retardancy.

In addition, the addition of phosphate-based flame retardant plasticizers improves flowability and thermal stability of Br-EPOXY, which is relatively low in thermal stability compared to decabromodiphenyl, due to the decrease in viscosity of flame-retardant HIPS due to the plasticizer role. The most suitable addition amount is 3-6 parts, but heat stability and flowability are increased in the case of more than 6 parts, but the flame retardancy is decreased.

In the present invention, antimony trioxide, a flame retardant adjuvant, is added. In addition, a lubricant, an impact enhancer, and an antioxidant are used as additives, and a filler, an antistatic agent, a processing aid, and the like may be added as necessary. The method of adding the decabromodiphenyl type, Br-EPOXY, phosphate system, etc. used for this invention to HIPS is a conventional method. For example, HIPS and a flame retardant may be mixed using a Henschel mixer or a dumbler, or may be mixed with other additives after mixing the flame retardant and HIPS in advance.

Embodiments of the present invention are as follows.

Example 1

100 parts by weight of HIPS resin (Cheil Industries Co., Ltd., HR-1360) was used as a flame retardant, decabromodiphenyl (Ethyl SAYREX 8%) and bromide epoxy 0-20 parts ( The results of comparing and measuring weather resistance, flowability and thermal stability of decabromodiphenyl oxide (PBDE) and each flame retardant by participating in the eastern part YDB-406 are shown in Table 1 below.

At this time, 0.3 parts of an antioxidant (Ciba-Geige Iganox-24S) was added and 0.5 part of stearet, an internal lubricant, was added. Weather resistance was measured for 300hr using weather-o-Mether ATSAS, and the results of discoloration of each sample were compared. Flame retardance was measured by flame retardant using a flame retardant sample according to UL standard. . The thermal stability was compared for the color change of the injected sample after staying in the injection machine for 30 minutes (injection temperature 240 ℃, nozzle part). When comparing the measurement results, the color number of each sample was compared using sample No. 1 as a standard. (Measurement method is also the same below)

* 1. Antimony trioxide was added equally to 6 parts by weight of each sample.

* 2. Thermal stability, weather resistance evaluation legend

○: No color change. ○ ~: No color change than 0 (Triangle | delta): There is a little color change. △ ~: △ The color change is slightly larger. △ ~ ×: Color change is larger than △ ~ and smaller than ×. X: The color change is large. ××: The color change is quite large. ×××: Color change worst

* 3. Flow Assessment Legend

◎: Flow is very good. ◎ ~ ○: Better than ○, but lower than ◎ ○ ~: slightly better flow than ○: Good flow. △-: slightly better flow than △. (Triangle | delta): Flowability normal. X: The flow is poor. Δ ~ ×: Better than 으나 but not △.

* 4. Flame retardancy was carried out by UL test method.

As can be seen in the above examples, the thermal stability and flame retardancy are similar to those of decabromodiphenyl-based and DBDPO, and the flowability of the bromide epoxy is lower than that of DBDPO in terms of thermal stability and flame retardancy. The weather resistance was the best with bromide epoxy, followed by decabromodiphenyl-based and DBDPO, and it was found that non-PBDE products could compensate for the pros and cons of using decabromodiphenyl-based and bromo-epoxy. Able to know.

Example 2

This embodiment is to know the proper use amount of each when using the bromide epoxy and decabromodiphenyl-based at the same time. When 5-20 parts of bromineide epoxy and decabromodiphenyl series were added, the results are shown in Table 2 below.

As can be seen in the above examples, the appropriate content of decabromodiphenyl-based and bromide epoxy for improving weather resistance, flowability, and thermal stability in consideration of flame retardant V-0 is 5-11: 13-8 parts. .

Example 3

In this embodiment, to further improve thermal stability and flowability, decabromodiphenyl-based and bromate epoxy phosphate-based were added. Table 3 shows the results of evaluating the samples in which 0-8 parts of phosphate (AKZO, TTP) was added.

As shown in the above example, the addition of TPP to the decabromodiphenyl-based and bromide-epoxy epoxy resins resulted in an increase in flowability and thermal stability. There was no improvement in flowability when used less than a portion.

Claims (1)

5-11 parts by weight of decabromodiphenyl-based bromine-based flame retardant and 13-8 parts by weight of bromide epoxy are added to 100 parts by weight of HIPS resin, and 3-6 parts by weight of phosphate-based flame retardant is further added. HIPS resin composition, characterized in that.