KR100866588B1 - A flame retardant composite - Google Patents

Abstract

A nonpoisonous and lead free ABS flame retardant resin composition can substitute the preexisting ABS flame retardant resin by reducing the generation of smoke in firing. A nonpoisonous and lead free ABS flame retardant resin composition comprises 50~70 parts by weight of a flame retardant additive based on 100 parts by weight of ABS resin. The flame retardant additive comprises 100 parts by weight of chlorinated poly ethylene resin; 20 parts by weight of a fire retardant booster which is a zinc borate; 5 parts by weight of a thermal stabilizer which is an epoxy resin; 2 parts by weight of a lubricant which is an ethylene bis stearic amide; and 1 part by weight of a dispersing agent which is the barium stearic acid.

Description

Non-toxic, non-flammable ABS flame retardant resin composition {A flame retardant composite}

The present invention relates to a non-toxic, non-flammable ABS flame retardant resin composition, and more particularly to a flame retardant resin composition which does not generate any carcinogens, and does not generate toxic gas when the plastic is burned, acrylonitrile-butadiene It relates to a non-toxic, non-flammable, excellent flame retardant resin composition comprising a polymeric chlorinated polystyrene, inorganic aluminum hydroxide and zinc borate which impart flame retardancy and flame retardancy.

Generally, acrylonitrile-butadiene-styrene (hereinafter referred to as "ABS") flame retardant resins are used in the field of electric appliances, batteries, chargers, It is widely used in construction materials, and these ABS flame retardant resins are conventional organic brominated flame retardants such as tetrabromobisphenol, decabromodiphenyl oxide, octabromodiphenyl oxide, pentabromodiphenyl oxide, and polydibromodie. It has been proposed to add low molecular weight organic bromine flame retardants such as phenyl oxide or brominated epoxy resins which are thermosetting resins. These flame retardants have been used until now to add the flame retardant enhancer Sb203 (antimony trioxide) in order to pass the US safety standards UL combustion standards.

However, the flame retardant used has a problem that globally produced carcinogens such as dioxin and difuran are produced from the appearance of molded products made of the final product, and the World Health Organization regulates anti-reflective dose (LD50). Use Prohibited use through PBBs / PBDEs.

Therefore, only tetrabromo bisphenol and brominated epoxy resin are used at present, and these flame retardants are limited to temporary use because toxic gases are generated due to the composition of bromine during combustion, that is, inevitable generation of carcinogens during combustion.

In addition, Sb203 (antimony trioxide), a flame retardant synergist that is necessarily added to bromine flame retardants, is classified as a poison that is harmful to humans. It is a substance that generates a large amount of carcinogens and is currently limited because there is no replacement item.

Therefore, in order to solve the problem of the occurrence of carcinogens, development of chlorine flame retardants and inorganic flame retardants instead of the low molecular weight bromine flame retardant has been actively made, for example, phosphorus, aluminum hydroxide, magnesium hydroxide and the like have been proposed.

However, chlorine-based, phosphorus-based, magnesium hydroxide and aluminum hydroxide flame retardant has a low flame retardant effect so that the flame retardant effect is not comparable to bromine flame retardant, so it has not been applied to ABS resin until now.

In addition, aluminum hydroxide hydroxide has a hydrate in the flame retardant itself, and when added to the ABS resin, the hygroscopicity of the ABS resin caused a non-uniform flame retardant effect and a fatal problem in the appearance of the plastic molding, and thus it was proved impossible to use the flame retardant. Flame retardants are only used to impart flame retardancy of polyethylene and polypropylene resins.

The chlorine-based flame retardant may include chlorinated polyethylene, but US Pat. Nos. 4067930, 5,376,718 and 5,395,875 show that when 5 parts by weight or 10 parts by weight or more of chlorinated polyethylene is used with respect to the ABS resin, the heat resistance, light resistance, and weather resistance of the final resin composition. It is described that a significant degradation is caused.

In other words, chlorinated polyethylene resins have been used as impact modifiers to compensate for the decrease in plastic strength caused by adding bromine flame retardants to ABS resins, rather than imparting flame retardancy to ABS resins.

Therefore, an object of the present invention is to solve the problems of the prior art as described above, the existing low-molecular-weight organic compound flame retardants and inorganic antimony trioxide occurs in the process of the generation of carcinogenic substances harmful to the human body and the plastic burning in the event of fire. It does not use carcinogenic substances, and inorganic aluminum hydroxide or magnesium hydroxide, which minimizes the amount of carcinogens and smoke generated when burning plastics, which is harmless to humans and plastics, is used as a flame retardant.In particular, antimony trioxide is used as an inorganic zinc borate. As a replacement, a new composition is to provide an ABS flame retardant resin.

The present invention also removes moisture by first mixing and processing the hydrate (H2O) contained in the magnesium hydroxide, aluminum and zinc borate flame retardant itself applied to the chlorinated polyethylene resin, and then removing the water secondly. Another object of the present invention is to provide a method for preparing a non-toxic, non-flammable ABS flame retardant resin composition in which a flame retardant is mixed with an ABS resin and extruded.

Therefore, the present invention solves the problems of the flame retardants used in the invention through a primary processing method and secondly to provide a secondary composition by mixing a flame retardant additive in 100 parts by weight of ABS resin. .

The present invention to achieve the above object,

It provides a non-toxic, flame-retardant ABS flame retardant resin composition added 50-70 parts by weight of the flame retardant additive to 100 parts by weight of ABS resin. If the flame retardant additive is 50 parts by weight or less, the flame retardancy of the plastic is lowered to meet the UL94 combustion standard, and if more than 70 parts by weight of plastic flame retardancy is added because it is meaningless as above.

The flame retardant additives include flame retardants, flame retardants, heat stabilizers, lubricants or dispersants, and the flame retardants include chlorinated polyethylene resins; It is preferable to use at least one selected from aluminum hydroxide or magnesium hydroxide, and the content thereof is preferably 0.1 to 70 parts by weight based on 100 parts by weight of the ABS resin. More preferably, the chlorinated polyethylene resin is a commercial name Tyrin3611 manufactured by Dupont Dow Elastomer, aluminum hydroxide is alumina branded by Sumitomer Chemical of Japan, and magnesium hydroxide is bromine as a Japanese diuretic product. It can be used containing 83%. The flame retardant in the above is preferably containing 50 to 70 parts by weight of aluminum hydroxide or magnesium hydroxide relative to 100 parts by weight of chlorinated polyethylene resin, to satisfy the UL-94-V-O grade.

In addition, as a flame retardant enhancer, zinc borate (ZnO.3B205.5H ₂ O) may be used, but it may be preferable to use a trade name Firebreak ZB manufactured by Borex, USA, and the content thereof may be 100 parts by weight of ABS resin. 0.1 to 30 parts by weight with respect to the preferred, the most preferred content is 20 parts by weight.

In addition, epoxy resin is used as a heat stabilizer to prevent plastic from being decomposed by heat, and its content is 0.1 to 10 parts by weight based on 100 parts by weight of ABS resin, and is trade name YD-012 of Kukdo Chemical Co., Ltd. Can be used. The preferred content is 5 parts by weight.

In addition, lubricants used as lubricants for releasing plasticity, preventing atmospheric layer oxidation, and other dispersibility to mix well can use 0.1 to 5 parts by weight of ethylene bis stearic amide. EBS Wax may also be used, and as a dispersant, it is preferable to use 0.1-5 parts by weight of barium stearic acid, and the trade name Ba-st of Korea Songwon Industrial Co., Ltd. may be used. Of course, you can also use the product with.

As the ABS resin used in the present invention, a domestic Kumho Petrochemical product containing 20% of acrylonitrile, 20% of butadiene and 60% of styrene was used, but other same components and products may be used.

Hereinafter will be described in detail the manufacturing method of the present invention through a preferred embodiment.

Table 1 shows the actual composition ratio of the flame retardant additive of the present invention in parts by weight.

Table 1 Unit: parts by weight

Item matter Example 1. 2. 3. 4. 5. 6. Flame retardant Chlorinated Polyethylene Resin 100 100 100 100 100 100 Aluminum hydroxide 50 60 70 Magnesium hydroxide 50 60 70 Flame retardant Zinc borate 20 20 20 20 20 20 Heat stabilizer Epoxy resin 5 5 5 5 5 5 Lubricant (lubricant) Ethylenebis Stearamide 2 2 2 2 2 2 Dispersant Barium stearic acid One One One One One One

The materials according to Examples 1 to 6 each having a weight part of the composition as described above are placed in a blender, respectively, at a speed of 900 to 1100 rpm, preferably 1000 rpm, for 8 to 15 minutes, preferably for 10 minutes to 150 to 200 캜, preferably Preferably, the flame retardant additive is prepared by extrusion mixing at a temperature of 170 ° C. before the plastic itself is pyrolyzed.

The flame retardant additive prepared as described above is added to 100 parts by weight of the ABS resin in the content as shown in Table 2 below to make the nontoxic, flame retardant ABS flame retardant resin composition of the present invention.

TABLE 2

Item matter Composition ratio (part by weight) ABS resin Acrylonitrle Butadiene Styren 100 100 100 100 100 100 Flame retardant additive Example 1 Additive 50 Example 2 Additive 60 Example 3 Additives 70 Example 4 Additives 50 Example 5 Additives 60 Example 6 Additives 70

As shown in Table 2, 50 to 70 parts by weight of the flame retardant additives of Examples 1 to 6 made of the composition ratio in Table 1 were mixed with 100 parts by weight of ABS resin at a speed of 1000 rpm using a Henschel mixer, respectively, for 10 minutes or more. Compounding is carried out using a 40 mm diameter twin extruder, wherein the inside of the extruder cylinder is kept constant at about 200 ° C. The compounded resin is cooled and solidified again to prepare a physical specimen using a 6-ounce injection molding machine.

After aging at 48 ° C. for 48 hours, the test specimens were tested for physical properties, flame retardancy, mechanical properties, thermal stability, weather resistance, gloss, antistatic effect and dioxin, difuran, etc. 3) is shown.

TABLE 3

Test Items Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Izod impact strength (kg.cm/cm) 10.3 9.5 8.7 12.1 10 9.6 Tensile strength (kg.cm/cm) 417 408 396 370 355 326 Heat deflection temperature (C) 83 80 77 85 82 79 Flame retardancy (UL94, specimen thickness 3.2mm) V-0 V-0 V-0 V-0 V-0 V-0 (UL94, specimen thickness 6.4mm) V-0 V-0 V-0 V-0 V-0 V-0 Weather resistance (300 hours) 0.8 0.9 1.1 1.5 1.8 2.2 Carcinogen generation Dioxin Not detected Not detected Not detected Not detected Not detected Not detected Difuran Not detected Not detected Not detected Not detected Not detected Not detected

Experimental Method

Izod Impact Strength: ASTM D-456

Tensile Strength: ASTM D-683

Heat Deflection Temperature: ASTM D-648

Flame retardant: UL-94

Weather Resistance: Device Name AATRAS WEATHER-O-METER

         Lamp Xenon Lamp 6500 watt

         Temperature 63 ± 2C

        Test Methods ; Irradiate for 102 minutes at this temperature or for 18 minutes

        Conducted under water jet conditions with light irradiation

Carcinogen detection: Gas chromatography-Mass spetrometer

As shown in the above results, it was confirmed that the molded article produced using the resin composition of the present invention is excellent in the Izod impact strength, tensile strength and heat resistance and flame retardancy, which is mechanical strength, and other physical properties. In addition, weather resistance was much better than the flame retardant resins developed to date.

As described above, the composition of the present invention exhibits excellent flame retardancy of V-0, respectively, even though the physical properties are excellent, even in the US UL94 combustion standard. In addition, the present invention shows the superiority of the present invention in that it is a nontoxic flame retardant resin composition which is harmless to humans due to the regulation of carcinogens.

In particular, the recent fire occurrence associated with the generation of a large amount of toxic gas is a very small amount of toxic gas generated by the present invention adds to the value of the invention.

The resin composition according to the present invention is toxic to the human body and extremely low smoke generation in the fire, it can be used as an alternative to the ABS flame retardant resin currently used.

Therefore, if the scope of application is applied to a wide range of electronic products such as TVs, computer monitors, laptops, photocopiers, refrigerators, washing machines, etc., including electrical constructions and switchboards, including construction materials requiring flame retardancy, the scope of use will be The use of material floors is expected to expand.

In addition, although the ABS flame retardant resin used in the past was very expensive, the flame retardant resin itself was expensive, but the use of the present invention is expected to be greatly increased by using a cheap inorganic flame retardant.

Although the present invention has been described by some embodiments, the present invention is not limited thereto, and various modifications and changes can be made without departing from the technical intent and scope of the present invention.

Claims (7)

In the non-toxic, non-flammable ABS flame retardant resin composition, 50 to 70 parts by weight of a flame retardant additive is included with respect to 100 parts by weight of ABS resin. The flame retardant is a flame retardant containing 50 to 70% by weight of aluminum hydroxide or magnesium, and 20 parts by weight of 100 parts by weight of chlorinated polyethylene resin, respectively. An ABS flame retardant resin composition comprising a zinc borate flame retardant, a 5 parts by weight heat stabilizer that is an epoxy resin, a 2 parts by weight ethylene bis stearamide lubricant, and a 1 part by weight barium stearic acid dispersant. delete delete delete As a method for producing a non-toxic, non-flammable, ABS flame retardant resin composition of claim 1, A flame retardant containing 50 to 70 parts by weight of aluminum hydroxide or magnesium hydroxide relative to 100 parts by weight of chlorinated polyethylene resin; Zinc borate, which is a 20 weight part flame retardant; 5 weight part of epoxy resin which is a heat stabilizer; Ethylenebis stearamide which is a 2 weight part lubricant; Mixing the 1 part by weight of barium stearic acid to make a flame retardant additive (S1), Method for producing an ABS flame retardant resin composition comprising the step (S2) of the additive (other than the chlorinated polyethylene resin in the step (S1) by mixing 50 to 70 parts by weight with respect to 100 parts by weight of ABS resin. 6. The method of claim 5, wherein the mixing in the step S1 is performed at a temperature of 150 to 200 ° C. for 8 to 15 minutes using a mixer having a speed of 900 to 1100 pm. According to claim 5, Extrusion camping in the step (S2), After mixing for 10 minutes with a mixer of 1000rpm speed, the compounding method of the ABS flame-retardant resin composition characterized in that the compounding in a twin screw extruder having an internal temperature of the extruder cylinder is 200 ℃.