Indian Patents. 203275:"FLAME-RETARDANT PLASTIC COMPOSITION"

Title of Invention	"FLAME-RETARDANT PLASTIC COMPOSITION"
Abstract	The present invention relates to a flame-retarded plastic composition comprising (A) a styrene-based plastic material, (B) a brominated aromatic compound having a melting point from 200oC to 260°C in which all bromine atoms are attached to the aromatic ring, (C) a bromine-containing organic compound having at least one 2,3-dibromopropyl group, and optionally antimony trioxide.

Full Text	"FLAME-RETARDANT PLASTIC COMPOSITION" [001] FIELD OF THE INVENTION The invention relates to a flame-retadant plastic composition and particularly to styrene-based plastic composition which has anexcellent flame retardancy and is self-extinguishable by melt-dripping. The composition comprises a plurality of flame retardants which exhibit when used in combination a synergistic effect on the flame retardancy. Since the combined flame retardants exhibit desired flame retardancy even in small amounts of addition and are highly heat stable and less detriorative to the appearance and mechanical properties of the plastics, a cost effective flame-retarded styrene-based plastic composition having an excellent moldability may be provided for use in fabricating housings and parts of household and office automation apparatus and equipments as well as other flame retarded articles of melt-dripping type. [002] BACKGROUND PRIOR ART Styrene-base plastics are widely used to fabricate housings and parts of household and office automation apparatus and equipments utilizing their excellent moldability, appearance and mechanical properties. For 1 these applications, the fabricated articles are required to be flame retarded to avoid dangerous firing and flame-retarded styrene-based plastic compositions containing a halogenated flame retardant have been used to date. In addition to the flame retardancy, the plastic compositions are required to have increased heat stability, heat resistance, melt-flowability, impact strength and other properties for such applications. [003] A typical example of cases where fabricated plastic products are required to be self-extinguishable by melt-dripping is to produce plastic articles meeting grade V-2 in the vertical burning test method according to UL-94 standard of Underwriters Laboratoires. JP-B-5904360 and JP-B-62034784 disclose a flame retarding technology to achieve the above requirement by incorporating hexabromocyclododecane known to be effective in small amounts of addition into plastics. Hexabromocyclododecane is, however, thermally decomposed at a relatively low temperature. Therefore, when compounding with plastics under heat it decreases the heat stability of the resulting composition and changes color thereof from bright to dark. [004] German Patent No. 2,150,700 discloses bis(2,3-dibromopropyl) ether of tetrabromobisphenol A as a flame 2 retardant having improved heat stability compared to hexabromocyclododecane. This flame retardant is still not satisfactory in heat stability and may produce. scorching when used for instance, in the hot runner molding technique to shorten the molding cycle time and improve the efficiency of molding operations. [005] JP-A-05 140389 discloses use of certain heat stabilizers in combination with bis(2, 3-dibromopropyl) ether of tetrabromobisphenol A to remedy the above defect. The heat stability of the above flame retardant was found to be not entirely satisfactory in practice by this approach. [006] Use of another flame retardant in combination with tetrabromobisphenol A bis(2, 3-dibromopropyl)ether has been proposed. JP-A-0 42 39 5 48 and JP-A-04292646 disclose a bromine-containing organic phosphorus compound and a bromine-containing epoxy polymer, respectively as a flame retardant to be combined. These proposals are proven, however, to be not entirely effective to increase the heat stability or deteriorative to the heat resistance, impact strength and other properties of plastics because a relatively large amount must be added. [007] JP-A-08208939 discloses a styrene-based plastic 3 composition having well-balanced heat resistance, impact strength and heat stability containing a polyhalogenated diphenylalkane and an organopolysiloxane. Polvhalogenated diphenylalkane itself is, however, not uniformly dispersible in the plastics and the composition are often not stable in properties among different batches and also exhibit poor flowability. [008] SUMMARY OF THE INVENTION The object of the present invention is to eliminate or ameliorate various problems associated with prior art. [009] The present invention provides an economically effective, flame-retarded styrene-based plastic composition having well-balanced properties including heat stability, heat resistance, melt-flowability and impact strength. [010] The composition comprises: (A) a styrene-based plastic material; (B) a brominated aromatic compound having a melting point from 200oC to 260oC in which all bromine atoms are attached to the aromatic ring; (C) an organic compound having at least one 2,3- dibromopropyl group; and optionally 4 (D) antimony trioxide; the proportions of components (B),(C) and (D) per 100 part by weight of the styrene-based plastic material (A) being such that the sum of (B) + (C) is 3 to 10 parts by weight in which (B) occupies 20 to 80 % by weight of the sum, and (D) is 0 to 3 part by weight. [011] DESCRIPTION OF PREFERRED EMBODIMENTS The term "styrene-based plastic material" as used herein refers to polystyrene, styrene- -methylstyrene copolymer and otter copolymera of styrene with minor proportions of comonomers such as butadiene, methyl methacrylate,acrylonitrile maleic anhydride or a derivative thereof or itaconic acid. [012] Examples of brominated aromatic compounds having a melting point from 200oC to 260 oC (B) include . tris(tribromophenoxy) triazine (m.p.about 230oC), a mixture thereof with dibromophenoxy-bis(tribromophenoxy) triazine and/or bis(dibromophenoxy)-tribromophenoxytriazine, bis(tribromophenoxy)ethane (m.p. about 225oC ) and brominated trimethylphenylindane (m.p. 235-255oC ). Because all bromine atoms are directly attached to the aromatic ring, component (B) itaelf is thermally stable. In contrast, similar compounds having a melting point lower 5 than 200°C adversely affects the heat resistance of the resulting plastic composition while those compounds having a melting point higher than 260oC are not homogeneously dispersible in the plastic material because it does not melt at the process temperature of the plastic material. [013] Organic compounds having at least one 2,3-dibromopropyl group (C) include 2, 3-dibromopropyl ethers of chlorinated or brominated phenols and tris(2,3 dibromopropyl)isocyanurate. Specific examples thereof include the following: [014] l-(2,3-dibromopropoxy)-2,4,6-tribromobenzene; l-(2,3-dibromopropoxy)-2,4-dibromobenzene; 4,4'-bis(2,3-dibromopropoxy)-3,3',5,5'-tetrabromobiphenyl; bis[4-(2,3-dibromopropoxy)-3,5-dibromophenyl] methane; 1, l-bis[4-(2,3-dibromopropoxy)-3,5-dibromophenyl] ethane; 2,2-bis[4-(2,3-dibromopropoxy)-3,5-dibromophenyl] propane; bis[4-(2,3-dibromopropoxy)-3,5-dichlorophenyl] methane; l,l-bis[4-(2,3-dibromopropoxy)-3,5-dichlorophenyl] 6 ethane; 2,2-bis[4-(2,3-dibromopropoxy)-3,5-dichlorophenyl] propane; bis[4-(2,3-dibromopropoxy)-3,5-dibromophenyl] s u1fide; bis[4-(2,3-dibromopropyl)-3,5-dibromophenyl] sulfoxide; bis[4-(2,3-dibromopropyl)-3,5'dibromophenyl] sulfone; and tris(2,3-dibromopropyl) isocyanurate. [015] Antimony trioxide (D) which is known to be a flame retardancy enhancer may optionally added. Particles having an average diameter of 0.4 to 1.2 m are preferred for ease of dispersion in the plastic material. The sum of proportions of component (B) and component (C) is 3 to 10 parts by weight per 100 parts by weight of the plastic material (A). The desired flame retardancy level will not be obtained with a proportion less than the above range while a proportion higher than the above range is not only uneconomical but also adversely affects the strength properties and impact strength in particular ofthe resulting composition. [016] The proportion of antimony trioxide (D) is, if used, 7 should be up to 3 parts by weight per 100 parts by weight of the plastic material (A). Excessive addition thereof does not further enhance the flame retardancy and adversely affects the thermal stability, impact strength melt-flowability and other properties of the resulting composition. [017] It is important for the present invention that the weight ratio B/(B + C) lies between 0.2 to 0.8. In other words, the bromine-containing flame retardant combination consists of 20 to 80 % by weight of component (B) and the balance of component (C). When departing from the above range, the balance between the flame retardancy and other properties of the resulting plastic composition will be lost and these properties will not be significantly different compared to the addition of respective components separately. [018] The temperature at which all components of the flame retarded plastic composition of the present invention are blended together preferably lies between 180oC and 260oC . Since it is important for component (B) to be blended in molten state with the styrene-based plastic material (A), the blending process is advantageously carried out at a temperature close the melting point of component (B). Component (C) normally has a melting point below 150oC 8 and decreases the melting point of component (B) when mixed. The blending process may, therefore, be carried out at a temperature slightly lower than the melting point of component (B). However, a blending temperature higher than 260oC should be avoided since component (C) will be thermally decomposed at such temperatures to darken the plastic material. [019] The flame retarded plastic composition of the present invention may be processed into fabricated articles at the conventional fabricating temperature for styrene-based plastic materials. Once blended homogeneously, no concern is needed about the melting point of component (B). [020] The flame retarded styrene-based plastic composition of the present invention may comprise a variety of other conventional additives provided that the beneficial properties of the composition are not compromised. Examples thereof include melt-dripping enhancers, heat stabilizers, antioxidants, UV absorbers, UV stabilizers, fillers, pigments, lubricants, mold release agents and antistatic agents. [021] EXAMPLES The following examples are o f f ered to specifically 9 illustrate the flame retarded plastic composition of the present invention without limiting the invention thereto. [022] Examples 1-13 and Comparative Examples 1-14. Formulations of the compositions of Examples and Comparative Examples are shown in Tables 1-5. [023] Component (B), component (C), antimony trioxide and antioxidant were initially mixed together in a vertical mixer for 3 minutes. Thereafter styrene-based plastic material (A) was added to the same mixer to obtain a dry blend. The blend was fed to a twin screw extruder provided with a barrel having an inner diameter of 20 mm and extruded through a die having an orifice diameter of 3 mm at a barrel temperature of 230oC. The extruded strand was cooled and solidified by passing through a water bath and cut into pellets. Test pieces were produced by injection molding the pellets using an injection molding machine at a mold temperature of 200°C and tested for flame retardancy, HDT, ball impact strength, Izod impact strength and thermal stability according to the test methods described below. Melt flow rate (MFR) was determined using the pellets before injection molding. The results obtained are shown in Tables 1-4. [024] 10 The materials used in the formulations shown in Tables 1-5 and the test methods are as follows. [025] Materials 1. Styrene-based plastic material (A) A#l: HI-PS, available from Toyo Styrene Co., Ltd. under the name of TOYO STYROL H650. A#2: ABS, available from Ube Cycon Ltd. under the name of CYCOLAC T . A#3: HI-PS, available from Toyo Styrene Co., Ltd. under the name of TOYO STYROL H450. A#4: HI-PS, available from Toyo Styrene Co., Ltd. under the name of TOYO STYROL H400. 2. Component (B) B#l: 2,4,6-tris(2,4,6-tribromophenoxy)-l,3,5-triazine, m.p. 231°C, available from Dai-Ichi Kogyo Seiyaku Co., Ltd. under the name of PYROGUARD SR-245. B#2: Brominated 1, l,3-trimethyl-3-phenylindane, m.p. 234-2531: , available from DSBG under the name of FR-1808. 3. Component (C) C#l: 2,2-bis[4-(2,3-dibromopropoxy)-3,5- dibromophenyl]propane, availble from Teijin Kasei Co., Ltd. under the name of FIRE GUARD FG-3100. C#2: Bis[4-(2,3-dibromopropoxy)-3,5- dibromophenyl]sulfone, available from Marubishi Yuka Co., 11 Ltd. under the name of NONNEN PR-2. C#3: Tris(2,3-dibromopropyl)isocyanurate, available from Nippon Kasei Co., Ltd. under the name of TAIC-6B. 4. Reference compound (A) Decabromodiphenylethane, m.p. >300°C , available from Albemarle Corp. under the name of SAYTEX 8010. 5. Reference compound (B) Tribromophenol modified brominated epoxy oligomer, m.p. 6. Antimony trioxide Sb2O3 available from Dai-Ichi Kogyo Seiyaku Co., Ltd. under the name of PYROGUARD AN-800(T). 7. Antioxidant IRGANOX 1010, available from Ciba Specialty Chemicals, Ltd. 8. Filler Zinc borate, available from US BORAX under the name of FIRE BRAKE 297. 9. Pigment Titanium dioxide, available from Ishihara Sangyo Kaisha Ltd. under the name of PF711. [026] Test methods 1. Flame retardancy 12 The vertial burning method according to UL-94 standard was followed. The thickness of the test piece was 3.2 mm. 2. MFR A melt flow index tester, Model 120-FWP available from Yasuda Seiki Seisakusho, Ltd. was used. Test conditions for the formulations in the tables are as follows. a) Formulations containing plastic material A#l Temperature 200oC, load 5 kgf, displacement distance 4 mm. b) Formulation containing plastic material A#2 Temperature 220oC, load 10 kgf, displacement distance 4 mm. 3. HDT heat distorsion temperature JIS K-6871 was followed using a test piece having a width of 3.2 mm and a height of 12.7 mm. The temperature at which the deformation amount of the test piece reached 0.26 mm at a load of 8.4 kg was determined. 4. Izod impact strength JIS K-6871 was followed at a notch length of 3.2 mm. 5. DuPont type ball impact tester was used. A 1/4 inch radius steel ball was placed on a test piece having a thickness of 3.2 mm and a 500 g weight was dropped on the ball. The maximum height of drop distance at which the back of test piece remained uncracked was determined. 13 6. Thermal stability The test compositions was allowed to stay in molten state at 230oC for 30 minutes in the injection molding machine and then injection molded. A control speciment was produced by repeating the above process without subjecting the composition to preheating in the machine for 30 minutes. The degree of coloring was evaluated as color difference between the test specimen and the control specimen according to the follow schedule. E E = 3-20, noticable coloring E>20, remarkable coloring 14 Table 1 Material Example (parts by weight) 1 2 3 4 5 Component A#l,HI-PS 100.0 100.0 100 .0 100 .0 100.0 Component B#l 2.0 5.0 4. 0 6. 0 - Component B#2 - - 3.5 Component C#l 5.0 2.0 - - 4.5 Component C#2 - - 3. 5 - Component C#3 - - 2 .5 - Total flame retardants 7.0 7.0 7 .5 8 .5 8.0 B/(B + C) 0.29 0.71 0. 57 0. 71 0.44 Sb2O3 2.5 2.5 2 .5 3 .0 2.0 Antioxidant 0.2 0.2 0 .2 0 .2 0.2 15 Table 1 (continued) Example Test item 1 2 3 4 5 UL-94,V-2 Pass Pass Pass Pass Pass Dripping Yes Yes Yes Yes Ye s MFR,g/10min. 5.7 5.6 5.7 5.5 5.8 HDT, oC 80 81 81 80 80 Izod impact,J/m 67 70 68 66 69 Ball impact,mm 850 800 850 750 850 Thermal stability, E 16 Table 2 Material Comparative Examples (parts by weight) 12 3 4 5 Component A# 1,HI-PS 100.0 100.0 100.0 100.0 100.0 Component B#l 8.0 11.0 - - - Ref.Compound A - - - 3.0 - 6.0 - - 6.0 6.0 4.0 8.0 11.0 6.0 9.0 10. C 2.5 3.0 2.0 3.0 3.0 0.2 0.2 0.2 0.2 0.2 Ref. Compound B Component C#l Total flame retardants Sb2O3 Antioxidant Remarks: Comparative Example 4 additional contains 0.01 parts of organopolysiloxane TSF451-100 available from Toshiba Silicone Co. 17 Table 2 (continued) Comparative Example Test item 1 2 3 4 5 UL-94,V-2 Not pass Not pass Pass Pass Pass Dripping Yes No Yes Yes Yes MFR,g/10min. 5.3 5.0 5.9 4.5 6.2 HDT oC 80 81 77 79 75 Izod impact,J/m 65 62 64 62 58 Ball impact,mm. 500 400 800 500 250 Theraml stability 18 Table 3 Material Example (Darts bv weight) 6 7 8 9 Component A#2,ABS 100.0 100.0 100.0 100.0 Component B#l 5.5 2.0 6.0 - Component B#2 - - - 3.0 Component C#l 3.5 - - - Component C#2 - 5.0 - 4.0 Component C#3 - - 2.0 - Total flame retardants 9.0 7.0 8.0 7.0 B/(B + C) 0.61 0.29 0.75 0.43 Sb2O3 2.0 1.5 2.5 2.5 Antioxidant 0.3 0.3 0.3 0.3 19 Table 3 (continued) Material Comparative Example (part by weight) 6 7 8 9 Component A#2,ABS 100.0 100.0 100.0 100.0 Component B#l 9.0 12.0 - - Component B#2 - - - 11.0 Component C#l - - 8.0 - Component C#2 - - - - Component C#3 - - - - Total flame retardants 9.0 12.0 8.0 11.0 Sb2O3 2.5 2.0 3.0 2.5 Antioxidant 0.3 0.3 0.3 0.3 20 Table 3 (continued) Example Test item 6 7 8 9 UL-94,V-2 Pass Pass Pass Pass Dripping Yes Yes Yes Yes MFR.g/l0min. 28 29 26 27 HDT oC 82 80 83 82 Izod impact,J/m 211 207 214 204 Thermal stability, AE Comparative Example Test item 6 7 8 9 UL-94,V-2 Not Pass Pass Pass Pass Dripping Yes Ye s Ye s Ye s MFR,g/10min. 25 23 28 22 HDT oC 78 77 76 78 Izod impact,J/m 195 192 210 190 Thermal stability, E 20 21 Table 4 Material Example Camp. Exam (parts by weight) 10 11 12 10 11 12 Component A#3,HI-PS 100.0 100.0 100.0 100.0 100.0 100.0 Component B#l 4.5 3.5 4.5 12.0 - - Component C#l 3.0 3.5 2.0 - 7.5 9.0 Total flame retardant 7.5 7.0 6.5 12.0 7.5 9.0 B/(B + C) 0.60 0.50 0.69 - - - Sb2O3 - - 1.0 - - - Antioxidant 0.2 0.2 0.2 0.2 0.2 0.2 Filler - 1 .0 - - - 3.0 Pigment 1.0 0.5 0.5 1.0 1.0 - 22 Table 4 (continued) Example Comp. Example Test item 10 11 12 10 11 12 UL-94,V-2 Pass Pass Pass Not pass Not pass Pass Dripping Ye s Yes Ye s No Yes Ye s MFR/g/l0min. 10.5 10.0 10.2 10.0 10.8 9.6 HDT oC 77 80 78 76 75 76 Izod impact, J/m 67 67 68 62 64 58 Ball impact,mm 900 850 850 650 800 400 Thermal stability, A E 23 Table 5 Material (parts by weight) Ex.13 Comp.Ex.13 Comp.Ex.14 Component A#l,HI-PS 70.0 70.0 70.0 Component A#4,HI-PS 30.0 30.0 30.0 Component B#l 2.6 8.0 - Component C#l 1.4 - 4.0 Total flame retardant 4.0 8.0 4.0 B/(B + C) 0.65 1.00 - Sb2O3 0.5 1.0 0.5 Antioxidant 0.2 0.2 0.2 Test item UL-94,V-2 Pass Pass Pass Dripping Yes Yes Yes MFR.g/10min. 8.8 7.8 9.0 HDT,oC 76 78 7.4 Izod impact,J/m 65 58 62 Ball impact, mm 850 600 800 Thermal stability, E 20 24 [027] From the above test results, it will be appreciated that the flame retarded compositions of Examples are excellent in impact strength to the compositions of Comparative Examples containing component (B) alone and in thermal stability relative to compositions of Comparative Examples containing component (C) alone. [028] The composition of Comparative Example 4 containing Reference flame retard-ant compound (A) in combination with component (C) exhibits the desired level of flame retardancy but is inferior to the compositions of Examples in MFR and . impact strength. [029] The composition of Comparative Example 5 containing an amount of Reference flame retardant compound B sufficient to exhibit the desired level of flame retardancy in combination with component (C) is inferior to the compositions of Examples in thermal deformation temperature and impact strength. [030] Table 5 demonstrates that the combined use component (B) and component (C) in Example 13 results in higher impact strengh than the use component (B) alone in Comparative Example 13 and also in higher thermal 25 stability than the use of component (C) alone in Comparative Example 14. [031] Table 4 demonstrates that component (B) or component (C) alone is not effective to impart the composition with the desired level of flame retardancy unless antimony trioxide is used but the desired level of flame retardancy may be achieved without antimony trioxide when component (B) and component (C) are used in combination. 26 CLAIMS: 1. A flame-retarded plastic composition comprising : (A) a styrene-based plastic material such as herein described; (B) a brominated aromatic compound having a melting point from 200oC to 260oC in which all bromine atomsphare attached to the aromatic ring; (C) an organic compound such as herein described having at least one 2,3-dibromopropyl group; and optionally (D) antimony trioxide; the proportions of components (B), (C) and (D) per 100 parts of the srtyrene-based plastic material (A) being such that the sum of (B) + (C) is 3 to 10 parts by weight in which (B) occupies 20 to 80 % by weight of the sum, and (D) is 0 to 3 parts by weight. 2. The composition according to claim 1 wherein said component (B) is : selected from the group consisting of tris(tribromophenoxy)triazine, a mixture thereof with dibromophenoxy-bis(tribromophenoxy)triazine and/or bis(dibromophenoxy)-tribromophenoxytriazine, bis (tribromophenoxy) ethane and brominated trimethyl phenylindane 3. The composition according to claim 1 or 2 wherein said component (C) is 2,3-dibromopropyl ether of a chlorinated or brominated phenol, or tris(2,3- dibromopropyl)isocyanurate. 27 4. The composition according to claim 1 or 2 wherein said component (C) is selected from the group consisting of 1-(2,3-dibromopropoxy)-2,4,6-tribromobenzene ; l-(2,3-,dibromopropoxy)-2,4-dibromobenzene; 4,4'-bis(2, 3-dibromopropoxy)-3, 3', 5, 5'-tetrabromobiphenyl; bis[4-(2,3-dibromopropoxy)-3,5-dibromophenyl] methane; l,l-bis[4-(2,3-dibromopropoxy)-3,5-dibromophenyl] ethane; 2,2-bis[4-(2,3-dibromopropoxy)-3,5-dibromophenyl] propane; bis[4-(2,3-dibromopropoxy)-3,5-dichlorophenyl] methane; l,l-bis[4-(2,3-dibromopropoxy)-3,5-dichlorophenyl] ethane; 2,2-bis[4-(2,3-dibromopropoxy)-3,5-dichlorophenyl] propane; bis[4-(2,3-dibromopropoxy)-3,5-dibromophenyl] sulfide; bis[4-(2,3-dibromopropyl)-3,5-dibromophenyl] sulfoxide; bis[4-(2,3-dibromopropyl)-3,5-dibromophenyl] sulfone; and tris(2,3-dibromopropyl)isocyanurate. 28 5. A flame-retarded plastic articles fabricated from the composition of one of claims 1 to 4. 29 The present invention relates to a flame-retarded plastic composition comprising (A) a styrene-based plastic material, (B) a brominated aromatic compound having a melting point from 200oC to 260°C in which all bromine atoms are attached to the aromatic ring, (C) a bromine-containing organic compound having at least one 2,3-dibromopropyl group, and optionally antimony trioxide.

Full Text

"FLAME-RETARDANT PLASTIC COMPOSITION"
[001]
FIELD OF THE INVENTION
The invention relates to a flame-retadant plastic composition and particularly to styrene-based plastic
composition which has anexcellent flame retardancy and is self-extinguishable by melt-dripping. The composition comprises a plurality of flame retardants which exhibit when used in combination a synergistic effect on the flame retardancy. Since the combined flame retardants exhibit desired flame retardancy even in small amounts of addition and are highly heat stable and less detriorative to the appearance and mechanical properties of the plastics, a cost effective flame-retarded styrene-based plastic composition having an excellent moldability may be provided for use in fabricating housings and parts of household and office automation apparatus and equipments as well as other flame retarded articles of melt-dripping type. [002] BACKGROUND PRIOR ART
Styrene-base plastics are widely used to fabricate housings and parts of household and office automation apparatus and equipments utilizing their excellent moldability, appearance and mechanical properties. For
1

these applications, the fabricated articles are required to be flame retarded to avoid dangerous firing and flame-retarded styrene-based plastic compositions containing a halogenated flame retardant have been used to date. In addition to the flame retardancy, the plastic compositions are required to have increased heat stability, heat resistance, melt-flowability, impact strength and other properties for such applications. [003]
A typical example of cases where fabricated plastic products are required to be self-extinguishable by melt-dripping is to produce plastic articles meeting grade V-2 in the vertical burning test method according to UL-94 standard of Underwriters Laboratoires. JP-B-5904360 and JP-B-62034784 disclose a flame retarding technology to achieve the above requirement by incorporating hexabromocyclododecane known to be effective in small amounts of addition into plastics. Hexabromocyclododecane is, however, thermally decomposed at a relatively low temperature. Therefore, when compounding with plastics under heat it decreases the heat stability of the resulting composition and changes color thereof from bright to dark. [004]
German Patent No. 2,150,700 discloses bis(2,3-dibromopropyl) ether of tetrabromobisphenol A as a flame
2

retardant having improved heat stability compared to hexabromocyclododecane. This flame retardant is still not satisfactory in heat stability and may produce. scorching when used for instance, in the hot runner molding technique to shorten the molding cycle time and improve the efficiency of molding operations. [005]
JP-A-05 140389 discloses use of certain heat stabilizers in combination with bis(2, 3-dibromopropyl) ether of tetrabromobisphenol A to remedy the above defect. The heat stability of the above flame retardant was found to be not entirely satisfactory in practice by this approach. [006]
Use of another flame retardant in combination with tetrabromobisphenol A bis(2, 3-dibromopropyl)ether has been proposed. JP-A-0 42 39 5 48 and JP-A-04292646 disclose a bromine-containing organic phosphorus compound and a bromine-containing epoxy polymer, respectively as a flame retardant to be combined. These proposals are proven, however, to be not entirely effective to increase the heat stability or deteriorative to the heat resistance, impact strength and other properties of plastics because a relatively large amount must be added. [007]
JP-A-08208939 discloses a styrene-based plastic
3

composition having well-balanced heat resistance, impact
strength and heat stability containing a polyhalogenated
diphenylalkane and an organopolysiloxane. Polvhalogenated
diphenylalkane itself is, however, not uniformly dispersible
in the plastics and the composition are often not stable in
properties among different batches and also exhibit poor
flowability.
[008]
SUMMARY OF THE INVENTION
The object of the present invention is to eliminate or ameliorate various problems associated with prior art. [009]
The present invention provides an economically effective, flame-retarded styrene-based plastic composition having well-balanced properties including heat stability, heat resistance, melt-flowability and impact strength. [010]
The composition comprises:
(A) a styrene-based plastic material;
(B) a brominated aromatic compound having a melting
point from 200oC to 260oC in which all bromine atoms are
attached to the aromatic ring;
(C) an organic compound having at least one 2,3-
dibromopropyl group;
and optionally
4

(D) antimony trioxide;
the proportions of components (B),(C) and (D) per 100 part by weight of the styrene-based plastic material (A) being such that the sum of (B) + (C) is 3 to 10 parts by weight in which (B) occupies 20 to 80 % by weight of the sum, and (D) is 0 to 3 part by weight. [011] DESCRIPTION OF PREFERRED EMBODIMENTS
The term "styrene-based plastic material" as used herein refers to polystyrene, styrene- -methylstyrene copolymer and otter copolymera of styrene with minor proportions of comonomers such as butadiene, methyl methacrylate,acrylonitrile maleic anhydride or a derivative
thereof or itaconic acid.
[012]
Examples of brominated aromatic compounds having a
melting point from 200oC to 260 oC (B) include .
tris(tribromophenoxy) triazine (m.p.about 230oC), a mixture
thereof with dibromophenoxy-bis(tribromophenoxy) triazine
and/or bis(dibromophenoxy)-tribromophenoxytriazine,
bis(tribromophenoxy)ethane (m.p. about 225oC ) and brominated trimethylphenylindane (m.p. 235-255oC ). Because all bromine atoms are directly attached to the aromatic ring, component (B) itaelf is thermally stable. In contrast, similar compounds having a melting point lower
5

than 200°C adversely affects the heat resistance of the resulting plastic composition while those compounds having a melting point higher than 260oC are not homogeneously dispersible in the plastic material because it does not melt at the process temperature of the plastic material. [013]
Organic compounds having at least one 2,3-dibromopropyl group (C) include 2, 3-dibromopropyl ethers of chlorinated or brominated phenols and tris(2,3 dibromopropyl)isocyanurate. Specific examples thereof include the following: [014]
l-(2,3-dibromopropoxy)-2,4,6-tribromobenzene;
l-(2,3-dibromopropoxy)-2,4-dibromobenzene;
4,4'-bis(2,3-dibromopropoxy)-3,3',5,5'-tetrabromobiphenyl;
bis[4-(2,3-dibromopropoxy)-3,5-dibromophenyl]
methane;
1, l-bis[4-(2,3-dibromopropoxy)-3,5-dibromophenyl]
ethane;
2,2-bis[4-(2,3-dibromopropoxy)-3,5-dibromophenyl]
propane;
bis[4-(2,3-dibromopropoxy)-3,5-dichlorophenyl] methane;
l,l-bis[4-(2,3-dibromopropoxy)-3,5-dichlorophenyl]
6

ethane;
2,2-bis[4-(2,3-dibromopropoxy)-3,5-dichlorophenyl] propane;
bis[4-(2,3-dibromopropoxy)-3,5-dibromophenyl] s u1fide;
bis[4-(2,3-dibromopropyl)-3,5-dibromophenyl] sulfoxide;
bis[4-(2,3-dibromopropyl)-3,5'dibromophenyl] sulfone; and
tris(2,3-dibromopropyl) isocyanurate. [015]
Antimony trioxide (D) which is known to be a flame retardancy enhancer may optionally added. Particles having an average diameter of 0.4 to 1.2 m are preferred for ease of dispersion in the plastic material. The sum of proportions of component (B) and component (C) is 3 to 10 parts by weight per 100 parts by weight of the plastic material (A). The desired flame retardancy level will not be obtained with a proportion less than the above range while a proportion higher than the above range is not only uneconomical but also adversely affects the strength properties and impact strength in particular ofthe resulting composition. [016]
The proportion of antimony trioxide (D) is, if used,
7

should be up to 3 parts by weight per 100 parts by weight of the plastic material (A). Excessive addition thereof does not further enhance the flame retardancy and adversely affects the thermal stability, impact strength melt-flowability and other properties of the resulting composition. [017]
It is important for the present invention that the weight ratio B/(B + C) lies between 0.2 to 0.8. In other words, the bromine-containing flame retardant combination consists of 20 to 80 % by weight of component (B) and the balance of component (C). When departing from the above range, the balance between the flame retardancy and other properties of the resulting plastic composition will be lost and these properties will not be significantly different compared to the addition of respective components separately. [018]
The temperature at which all components of the flame retarded plastic composition of the present invention are blended together preferably lies between 180oC and 260oC . Since it is important for component (B) to be blended in molten state with the styrene-based plastic material (A), the blending process is advantageously carried out at a temperature close the melting point of component (B). Component (C) normally has a melting point below 150oC
8

and decreases the melting point of component (B) when mixed. The blending process may, therefore, be carried out at a temperature slightly lower than the melting point of component (B). However, a blending temperature higher than 260oC should be avoided since component (C) will be thermally decomposed at such temperatures to darken the plastic material. [019]
The flame retarded plastic composition of the present invention may be processed into fabricated articles at the conventional fabricating temperature for styrene-based plastic materials. Once blended homogeneously, no concern is needed about the melting point of component (B). [020]
The flame retarded styrene-based plastic composition of the present invention may comprise a variety of other conventional additives provided that the beneficial properties of the composition are not compromised. Examples thereof include melt-dripping enhancers, heat stabilizers, antioxidants, UV absorbers, UV stabilizers, fillers, pigments, lubricants, mold release agents and antistatic agents. [021] EXAMPLES
The following examples are o f f ered to specifically
9

illustrate the flame retarded plastic composition of the
present invention without limiting the invention thereto.
[022]
Examples 1-13 and Comparative Examples 1-14.
Formulations of the compositions of Examples and
Comparative Examples are shown in Tables 1-5.
[023]
Component (B), component (C), antimony trioxide and
antioxidant were initially mixed together in a vertical mixer
for 3 minutes. Thereafter styrene-based plastic material (A) was added to the same mixer to obtain a dry blend. The blend was fed to a twin screw extruder provided with a barrel having an inner diameter of 20 mm and extruded through a die having an orifice diameter of 3 mm at a barrel temperature of 230oC. The extruded strand was cooled and solidified by passing through a water bath and cut into pellets. Test pieces were produced by injection molding the pellets using an injection molding machine at a mold temperature of 200°C and tested for flame retardancy, HDT, ball impact strength, Izod impact strength and thermal stability according to the test methods described below. Melt flow rate (MFR) was determined using the pellets before injection molding. The results obtained are shown in Tables 1-4. [024]
10

The materials used in the formulations shown in Tables 1-5 and the test methods are as follows. [025] Materials
1. Styrene-based plastic material (A)
A#l: HI-PS, available from Toyo Styrene Co., Ltd. under the name of TOYO STYROL H650.
A#2: ABS, available from Ube Cycon Ltd. under the name of CYCOLAC T .
A#3: HI-PS, available from Toyo Styrene Co., Ltd. under the name of TOYO STYROL H450.
A#4: HI-PS, available from Toyo Styrene Co., Ltd. under the name of TOYO STYROL H400.
2. Component (B)
B#l: 2,4,6-tris(2,4,6-tribromophenoxy)-l,3,5-triazine, m.p. 231°C, available from Dai-Ichi Kogyo Seiyaku Co., Ltd. under the name of PYROGUARD SR-245.
B#2: Brominated 1, l,3-trimethyl-3-phenylindane, m.p. 234-2531: , available from DSBG under the name of FR-1808.
3. Component (C)
C#l: 2,2-bis[4-(2,3-dibromopropoxy)-3,5-
dibromophenyl]propane, availble from Teijin Kasei Co., Ltd. under the name of FIRE GUARD FG-3100.
C#2: Bis[4-(2,3-dibromopropoxy)-3,5-
dibromophenyl]sulfone, available from Marubishi Yuka Co.,
11

Ltd. under the name of NONNEN PR-2.
C#3: Tris(2,3-dibromopropyl)isocyanurate, available from Nippon Kasei Co., Ltd. under the name of TAIC-6B.
4. Reference compound (A)
Decabromodiphenylethane, m.p. >300°C , available from
Albemarle Corp. under the name of SAYTEX 8010.
5. Reference compound (B)
Tribromophenol modified brominated epoxy oligomer, m.p. 6. Antimony trioxide
Sb2O3 available from Dai-Ichi Kogyo Seiyaku Co., Ltd. under the name of PYROGUARD AN-800(T).
7. Antioxidant
IRGANOX 1010, available from Ciba Specialty Chemicals, Ltd.
8. Filler
Zinc borate, available from US BORAX under the name of FIRE BRAKE 297.
9. Pigment
Titanium dioxide, available from Ishihara Sangyo Kaisha Ltd. under the name of PF711. [026] Test methods
1. Flame retardancy
12

The vertial burning method according to UL-94 standard was followed. The thickness of the test piece was 3.2 mm.
2. MFR
A melt flow index tester, Model 120-FWP available from Yasuda Seiki Seisakusho, Ltd. was used. Test conditions for the formulations in the tables are as follows.
a) Formulations containing plastic material A#l
Temperature 200oC, load 5 kgf, displacement distance 4
mm.
b) Formulation containing plastic material A#2
Temperature 220oC, load 10 kgf, displacement distance
4 mm.
3. HDT heat distorsion temperature
JIS K-6871 was followed using a test piece having a width of 3.2 mm and a height of 12.7 mm. The temperature at which the deformation amount of the test piece reached 0.26 mm at a load of 8.4 kg was determined.
4. Izod impact strength
JIS K-6871 was followed at a notch length of 3.2 mm.
5. DuPont type ball impact tester was used.
A 1/4 inch radius steel ball was placed on a test piece having a thickness of 3.2 mm and a 500 g weight was dropped on the ball. The maximum height of drop distance at which the back of test piece remained uncracked was determined.
13

6. Thermal stability
The test compositions was allowed to stay in molten state at 230oC for 30 minutes in the injection molding machine and then injection molded. A control speciment was produced by repeating the above process without subjecting the composition to preheating in the machine for 30 minutes. The degree of coloring was evaluated as color difference between the test specimen and the control specimen according to the follow schedule.
E E = 3-20, noticable coloring
E>20, remarkable coloring
14

Table 1

Material Example
(parts by weight) 1 2 3 4 5
Component A#l,HI-PS 100.0 100.0 100 .0 100 .0 100.0
Component B#l 2.0 5.0 4. 0 6. 0 -
Component B#2 - - 3.5
Component C#l 5.0 2.0 - - 4.5
Component C#2 - - 3. 5 -
Component C#3 - - 2 .5 -
Total flame retardants 7.0 7.0 7 .5 8 .5 8.0
B/(B + C) 0.29 0.71 0. 57 0. 71 0.44
Sb2O3 2.5 2.5 2 .5 3 .0 2.0
Antioxidant 0.2 0.2 0 .2 0 .2 0.2
15

Table 1 (continued)

Example
Test item 1 2 3 4 5
UL-94,V-2 Pass Pass Pass Pass Pass
Dripping Yes Yes Yes Yes Ye s
MFR,g/10min. 5.7 5.6 5.7 5.5 5.8
HDT, oC 80 81 81 80 80
Izod impact,J/m 67 70 68 66 69
Ball impact,mm 850 800 850 750 850
Thermal stability, E 16

Table 2

Material Comparative Examples
(parts by weight) 12 3 4 5
Component A# 1,HI-PS 100.0 100.0 100.0 100.0 100.0
Component B#l 8.0 11.0 - - -
Ref.Compound A - - - 3.0 -
6.0
- - 6.0 6.0 4.0
8.0 11.0 6.0 9.0 10. C
2.5 3.0 2.0 3.0 3.0
0.2 0.2 0.2 0.2 0.2
Ref. Compound B
Component C#l
Total flame retardants
Sb2O3
Antioxidant

Remarks: Comparative Example 4 additional contains 0.01 parts of organopolysiloxane TSF451-100 available from Toshiba Silicone Co.
17

Table 2 (continued)
Comparative Example

Test item 1 2 3 4 5 UL-94,V-2 Not pass Not pass Pass Pass Pass Dripping Yes No Yes Yes Yes MFR,g/10min. 5.3 5.0 5.9 4.5 6.2 HDT oC 80 81 77 79 75 Izod impact,J/m 65 62 64 62 58 Ball impact,mm. 500 400 800 500 250 Theraml stability 18

Table 3

Material Example (Darts bv weight) 6 7 8 9 Component A#2,ABS 100.0 100.0 100.0 100.0 Component B#l 5.5 2.0 6.0 - Component B#2 - - - 3.0 Component C#l 3.5 - - - Component C#2 - 5.0 - 4.0 Component C#3 - - 2.0 - Total flame retardants 9.0 7.0 8.0 7.0 B/(B + C) 0.61 0.29 0.75 0.43 Sb2O3 2.0 1.5 2.5 2.5 Antioxidant 0.3 0.3 0.3 0.3
19

Table 3 (continued)
Material Comparative Example
(part by weight) 6 7 8 9
Component A#2,ABS 100.0 100.0 100.0 100.0
Component B#l 9.0 12.0 - -
Component B#2 - - - 11.0
Component C#l - - 8.0 -
Component C#2 - - - -
Component C#3 - - - -
Total flame retardants 9.0 12.0 8.0 11.0
Sb2O3 2.5 2.0 3.0 2.5
Antioxidant 0.3 0.3 0.3 0.3
20

Table 3 (continued)
Example

Test item 6 7 8 9 UL-94,V-2 Pass Pass Pass Pass Dripping Yes Yes Yes Yes MFR.g/l0min. 28 29 26 27 HDT oC 82 80 83 82 Izod impact,J/m 211 207 214 204 Thermal stability, AE Comparative Example

Test item 6 7 8 9 UL-94,V-2 Not Pass Pass Pass Pass Dripping Yes Ye s Ye s Ye s MFR,g/10min. 25 23 28 22 HDT oC 78 77 76 78 Izod impact,J/m 195 192 210 190 Thermal stability, E 20 21

Table 4

Material Example Camp. Exam (parts by weight) 10 11 12 10 11 12 Component A#3,HI-PS 100.0 100.0 100.0 100.0 100.0 100.0 Component B#l 4.5 3.5 4.5 12.0 - - Component C#l 3.0 3.5 2.0 - 7.5 9.0 Total flame retardant 7.5 7.0 6.5 12.0 7.5 9.0 B/(B + C) 0.60 0.50 0.69 - - - Sb2O3 - - 1.0 - - - Antioxidant 0.2 0.2 0.2 0.2 0.2 0.2 Filler - 1 .0 - - - 3.0 Pigment 1.0 0.5 0.5 1.0 1.0 -
22

Table 4 (continued)

Example Comp. Example Test item 10 11 12 10 11 12 UL-94,V-2 Pass Pass Pass Not pass Not pass Pass Dripping Ye s Yes Ye s No Yes Ye s MFR/g/l0min. 10.5 10.0 10.2 10.0 10.8 9.6 HDT oC 77 80 78 76 75 76 Izod impact, J/m 67 67 68 62 64 58 Ball impact,mm 900 850 850 650 800 400 Thermal stability, A E 23

Table 5
Material (parts by weight) Ex.13 Comp.Ex.13 Comp.Ex.14 Component A#l,HI-PS 70.0 70.0 70.0 Component A#4,HI-PS 30.0 30.0 30.0 Component B#l 2.6 8.0 - Component C#l 1.4 - 4.0 Total flame retardant 4.0 8.0 4.0 B/(B + C) 0.65 1.00 - Sb2O3 0.5 1.0 0.5 Antioxidant 0.2 0.2 0.2
Test item UL-94,V-2 Pass Pass Pass Dripping Yes Yes Yes
MFR.g/10min. 8.8 7.8 9.0 HDT,oC 76 78 7.4 Izod impact,J/m 65 58 62 Ball impact, mm 850 600 800 Thermal stability, E 20
24

[027]
From the above test results, it will be appreciated that the flame retarded compositions of Examples are excellent in impact strength to the compositions of Comparative Examples containing component (B) alone and in thermal stability relative to compositions of Comparative Examples containing component (C) alone. [028]
The composition of Comparative Example 4 containing Reference flame retard-ant compound (A) in combination with component (C) exhibits the desired level of flame retardancy but is inferior to the compositions of Examples in MFR and . impact strength. [029]
The composition of Comparative Example 5 containing an amount of Reference flame retardant compound B sufficient to exhibit the desired level of flame retardancy in combination with component (C) is inferior to the compositions of Examples in thermal deformation temperature and impact strength. [030]
Table 5 demonstrates that the combined use component (B) and component (C) in Example 13 results in higher impact strengh than the use component (B) alone in Comparative Example 13 and also in higher thermal
25

stability than the use of component (C) alone in Comparative
Example 14.
[031]
Table 4 demonstrates that component (B) or component
(C) alone is not effective to impart the composition with the desired level of flame retardancy unless antimony trioxide is used but the desired level of flame retardancy may be achieved without antimony trioxide when component (B) and component (C) are used in combination.
26

CLAIMS:
1. A flame-retarded plastic composition comprising :
(A) a styrene-based plastic material such as herein described;
(B) a brominated aromatic compound having a melting
point from 200oC to 260oC in which all bromine atomsphare
attached to the aromatic ring;
(C) an organic compound such as herein described
having at least one 2,3-dibromopropyl group; and optionally
(D) antimony trioxide;
the proportions of components (B), (C) and (D) per 100 parts of the srtyrene-based plastic material (A) being such that the sum of (B) + (C) is 3 to 10 parts by weight in which (B) occupies 20 to 80 % by weight of the sum, and (D) is 0 to 3 parts by weight.
2. The composition according to claim 1 wherein said
component (B) is : selected from the group consisting of
tris(tribromophenoxy)triazine, a mixture thereof with
dibromophenoxy-bis(tribromophenoxy)triazine and/or
bis(dibromophenoxy)-tribromophenoxytriazine,
bis (tribromophenoxy) ethane and brominated trimethyl phenylindane
3. The composition according to claim 1 or 2 wherein
said component (C) is 2,3-dibromopropyl ether of a
chlorinated or brominated phenol, or tris(2,3-
dibromopropyl)isocyanurate.
27

4. The composition according to claim 1 or 2 wherein said component (C) is selected from the group consisting of
1-(2,3-dibromopropoxy)-2,4,6-tribromobenzene ;
l-(2,3-,dibromopropoxy)-2,4-dibromobenzene;
4,4'-bis(2, 3-dibromopropoxy)-3, 3', 5, 5'-tetrabromobiphenyl;
bis[4-(2,3-dibromopropoxy)-3,5-dibromophenyl] methane;
l,l-bis[4-(2,3-dibromopropoxy)-3,5-dibromophenyl] ethane;
2,2-bis[4-(2,3-dibromopropoxy)-3,5-dibromophenyl] propane;
bis[4-(2,3-dibromopropoxy)-3,5-dichlorophenyl] methane;
l,l-bis[4-(2,3-dibromopropoxy)-3,5-dichlorophenyl] ethane;
2,2-bis[4-(2,3-dibromopropoxy)-3,5-dichlorophenyl] propane;
bis[4-(2,3-dibromopropoxy)-3,5-dibromophenyl] sulfide;
bis[4-(2,3-dibromopropyl)-3,5-dibromophenyl] sulfoxide;
bis[4-(2,3-dibromopropyl)-3,5-dibromophenyl] sulfone; and
tris(2,3-dibromopropyl)isocyanurate.
28
5. A flame-retarded plastic articles fabricated from the composition of one of claims 1 to 4.
29
The present invention relates to a flame-retarded plastic composition comprising (A) a styrene-based plastic material, (B) a brominated aromatic compound having a melting point from 200oC to 260°C in which all bromine atoms are attached to the aromatic ring, (C) a bromine-containing organic compound having at least one 2,3-dibromopropyl group, and optionally antimony trioxide.

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Patent Number

203275

Indian Patent Application Number

00787/KOLNP/2003

PG Journal Number

12/2007

Publication Date

23-Mar-2007

Grant Date

23-Mar-2007

Date of Filing

18-Jun-2003

Name of Patentee

DAI-ICHI KOGYO SEIYAKU CO LTD

Applicant Address

55, NISHISHICHIJO HIGASHIKUBO-CHO, SHIMOGYO-KU, KYOTO-SHI, KYOTO 600/8873,

Inventors:

#	Inventor's Name	Inventor's Address
1	ONISHI HIDEAKI	12-1-705, KOJOGAOKA OTSU-SHI, SHIGA 520-0821,
2	HIDETO KONDO	12-134,KOGANISHIDE-CHO,FUSHIMI-KU,KYOTO-SHI,KYOTO 612-8496

PCT International Classification Number

CO8L 25/04

PCT International Application Number

PCT/JP02/09001

PCT International Filing date

2001-10-24

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	2001-325993	2001-10-24	Japan
2	2002-068298	2002-03-13	Japan