Halogen-containing flame retardant polyamide compositions

Abstract

Flame retardant thermoplastic polyamide compositions are described that provide a superior combination of glow wire ignition and elongation/toughness properties, comprising a polyamide resin; a bromine-containing flame retardant; a hindered phenolic heat stabilizer; and optionally at least one of a flame retardant synergist, a plasticizer, a lubricant, a mold release agent, an acid scavenger and a colorant.

Claims

1. A flame retardant polyamide composition consisting of: at least 65% by weight of PA6,6 or PA6,6/6 or a combination thereof: a bromine-containing flame retardant; a hindered phenolic heat stabilizer; 1-8% by weight of a flame retardant synergist; 0-5% by weight of a colorant; 0-5% by weight of a lubricant; 0-5% by weight of a mold release agent; 0-5% by weight of an acid scavenger; 0-5% by weight of a plasticizer; wherein the percentages are based on the total weight of the polyamide composition; wherein the polyamide composition exhibits a glow wire ignition temperature greater than 850° C. and an elongation at break greater than 13%.

2. The polyamide composition according to claim 1, wherein the polyamide resin is PA-6,6.

3. The polyamide composition according to claim 1, wherein the bromine-containing flame retardant is bis(pentabromophenyl)ethane.

4. The polyamide composition according to claim 1, wherein the hindered phenolic heat stabilizer is N,N′-hexamethylenebis(3,5-di-tert-butyl-4-hydroxy-hydrocinnamamide).

5. The polyamide composition according to claim 1, wherein the flame retardant synergist is diantimony trioxide.

6. The polyamide composition according to claim 1, wherein a plasticizer is present.

7. The polyamide composition according to claim 6, wherein the plasticizer is diundecyl phthalate.

8. The polyamide composition according to claim 1, wherein a lubricant or a mold release agent or a combination thereof is present.

9. The polyamide composition according to claim 1, wherein a colorant is present.

10. The polyamide composition according to claim 1, wherein the composition consists of: 65-85% by weight of the PA6,6 or PA6,6/6 or a combination thereof; 5-35% by weight of the bromine-containing flame retardant; and 0.01-5% by weight of the hindered phenolic heat stabilizer.

11. An article obtained from the polyamide composition according to claim 10.

12. The article according to claim 11, where the article is an electrical or electronic part.

13. An article obtained from the polyamide composition according to claim 1.

14. The article according to claim 13, where the article is an electrical or electronic part.

Description

DETAILED DESCRIPTION OF THE INVENTION

(1) The flame retardant polyamide compositions of the present invention are superior to conventional flame retardant compositions in their consistently elevated high glow wire ignition temperatures (such as 800° C. or higher, such as 850° C. or higher) combined with high RTI values and desirable mechanical properties, such as increased processability (superior elongation) and ductility.

(2) The polyamide resin component of the flame retardant composition of the invention is not particularly limited. In an exemplary embodiment, the polyamide resin is selected from the group consisting of PA-6; PA-6,6; PA-6,10; PA-4,6; PA-11; PA-12; PA-12,12; PA-6, I; PA-6,T; PA-6,T/6,6-copolyamide; PA-6,T/6-copolyamide; PA-6/6,6-copolyamide; PA-6,6/6,T/6,1-copolyamide; PA-6,T/2-MPMDT-copolyamide; PA-9,T; PA-4,6/6-copolyamide; and mixtures and copolyamides of the aforementioned polyamides. In a particular embodiment, the polyamide resin is selected from the group consisting of PA-4,6; PA-6,I; PA-6,T; PA-6,6; PA-6/6,6; and a mixture or copolyamide thereof. In an exemplary embodiment, the polyamide resin is one or more selected from the group consisting of a high viscosity polyamide resin, a medium viscosity polyamide resin and a low viscosity polyamide resin. In a particular embodiment, the polyamide resin is high viscosity PA-6,6. In another particular embodiment, the polyamide resin is medium viscosity PA-6,6. In another particular embodiment, the polyamide resin is low viscosity PA-6,6. In another particular embodiment, the polyamide resin is a mixture of high viscosity PA-6,6 and low viscosity PA-6,6. In another particular embodiment, the polyamide resin is a copolymer of PA-6,6 and PA-6. In another particular embodiment, the polyamide resin is PA-6,6 in the form of a fine powder.

(3) Conventional bromine-containing flame retardants are generally suitable for use in the compositions of the present invention. In a particular embodiment, the bromine-containing flame retardant is a bis(pentabromophenyl)ethane, such as commercially available SAYTEX® 8010 (Albemarle).

(4) Historically, preferred heat stabilizers for polyamides have been copper iodide or copper acetate because of their excellent resistance to heat aging. However, due to their negative effect on electrical properties such as dielectric strength, surface and volume resistivity, and comparative tracking index (CTI), these copper salts are not typically suitable for use in electrical/electronic applications. In an exemplary embodiment of the present invention, the heat stabilizer is a hindered phenolic complex. Examples of hindered phenolic stabilizers include, but are not limited to, N,N′-hexane-1,6-diylbis[3-(3,5-di-tert-butyl-4-hydroxyphenylpropionamide)]; pentaerythrityl-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]; N,N′-hexamethylenebis(3,5-di-tert-butyl-4-hydroxy-hydrocinnamamide); triethyleneglycol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate]; 3,9-bis{2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl}-2,4,8,10-tetraoxaspiro[5,5]undecane; 3,5-di-tert-butyl-4-hydroxybenzylphosphonate diethyl ester; 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene; and 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate. In a particular embodiment, the heat stabilizer is N,N′-hexamethylenebis(3,5-di-tert-butyl-4-hydroxy-hydrocinnamamide), which is commercially available under several names, such as, Irganox® 1098 (BASF), Lowinox® HD98 (Addivant), Songnox® 1098 (Songwon).

(5) In an exemplary embodiment, the polyamide compositions of the invention contain a plasticizer. Plasticizers assist in increasing the flow of the compositions and provide toughness/increased elongation at break. Examples of suitable plasticizers include those commonly used in polyamides, such as, but not limited to, diundecyl phthalate, dioctyl phthalate, dibenzyl phthalate, butyl benzyl phthalate, hydrocarbon oils, N-(n-butyl)benzenesulphonamide. In an exemplary embodiment, the plasticizer is diundecyl phthalate which is commercially available under several names, such as, Jayflex™ L11P (Exxon Mobil) and Palatinol® 111P (BASF).

(6) In an exemplary embodiment, the compositions of the invention contain a lubricant/mold release agent. Suitable lubricant/mold release agents for use in the present invention include, but are not limited to, long-chain fatty acids (e.g., stearic acid or behenic acid), their salts (e.g., Ca stearate or Zn stearate) or their ester or amide derivatives (e.g., N,N′ ethylene bisstearylamide), montan waxes (mixtures composed of straight-chain, saturated carboxylic acids having chain lengths of from 28 to 32 carbon atoms) or low-molecular weight polyethylene waxes or low-molecular weight polypropylene waxes. In an exemplary embodiment, the lubricant/mold release agent is N,N′ ethylene bisstearylamide, which is commercially available as Acrawax®.

(7) In an exemplary embodiment, the polyamide compositions of the invention contain an acid scavenger for stabilization. In a particular embodiment, the acid scavenger is a zeolite, which includes modified zeolites. In a particular embodiment, the zeolite has a mean particle diameter in the range of about 0.25 to about 1.5 μm, a less than 90% value particle diameter (i.e., 90% by weight of the particles have a particle diameter below the range) of about 0.30 to about 3 μm, and a water content of less than 10 weight percent. In a particular embodiment, the zeolite is an aluminosilicate zeolite and may have a general formula of M.sub.2/nO:[Al.sub.2O.sub.3].sub.x:[SiO.sub.2].sub.y:[H.sub.2O].sub.z, where M represents a metal, n represents the valence of the metal and x, y and z vary depending on the specific aluminosilicate zeolite. In a particular embodiment, the zeolite is one or more selected from the group consisting of zeolite A (U.S. Pat. No. 2,822,243); zeolite X (U.S. Pat. No. 2,822,244); zeolite Y (U.S. Pat. No. 3,130,007); zeolite L (Belgian Patent 575,117); zeolite F (U.S. Pat. No. 2,996,358) zeolite B (U.S. Pat. No. 3,008,803); zeolite M (U.S. Pat. No. 2,995,423); zeolite H (U.S. Pat. No. 3,010,789); zeolite L (U.S. Pat. No. 3,011,869); and zeolite W (U.S. Pat. No. 3,102,853). In another exemplary embodiment, the acid scavenger is an alkaline-earth-containing aluminum hydroxide carbonate, which includes naturally occurring hydrotalcites (magnesium-containing aluminum hydroxide carbonates), synthetic hydrotalcites and anionic clays, in both their hydrated and dehydrated states. Hydrotalcites suitable for use in the present invention include, but are not limited to, Stabiace HT-9 (Sakai Chemical), DHT-4C (Kisuma Chemicals) and the hydrotalcites described in U.S. Pat. Nos. 3,879,523; 4,351,814; 4,656,156; 4,904,457; 5,348,725; 5,246,899; 5,116,587; 5,437,720; and 5,578,286.

(8) In an exemplary embodiment, the polyamide compositions of the invention contain a colorant for the purpose of satisfying the aesthetic requirements of the final application of the composition. Examples of suitable colorants include those commonly used in polyamides, such as, but not limited to, inorganic pigments (such as titanium dioxide, ultramarine blue, iron oxide, zinc sulphide and carbon black) and also organic pigments (such as phthalocyanines, quinacridones and perylenes) and dyes (such as nigrosine and anthraquinones). In an exemplary embodiment, the colorant is carbon black.

(9) In an exemplary embodiment, the thermoplastic polyamide composition comprises 60-90% by weight of the polyamide resin, such as 60-85% by weight, such as 60-80% by weight, such as 60-75% by weight, such as 60-70% by weight, such as 65-85% by weight, such as 65-80% by weight, such as 65-75% by weight, such as 60-70% by weight.

(10) In an exemplary embodiment, the thermoplastic polyamide composition comprises 5-35% by weight of a bromine-containing flame retardant, such as 5-30% by weight, such as 10-25% by weight, such as 10-20% by weight, such as 15-25% by weight, such as 15-20% by weight.

(11) In an exemplary embodiment, the thermoplastic polyamide composition comprises 0.01-5% by weight of a hindered phenolic heat stabilizer, such as 0.05-5% by weight, such as 0.05-3% by weight, such as 0.1-3% by weight, such as 0.1-2% by weight.

(12) In an exemplary embodiment, the thermoplastic polyamide composition comprises 1-10% by weight of a flame retardant synergist, such as 1-8% by weight, such as 1-6% by weight, such as 1-5% by weight, such as 2-8% by weight, such as 2-6% by weight.

(13) In an exemplary embodiment, the thermoplastic polyamide composition comprises 0.5-5% by weight of a plasticizer, such as 1-5% by weight, such as 1-3% by weight, such as 0.5-3% by weight.

(14) In an exemplary embodiment, the thermoplastic polyamide composition independently comprises 0-5% by weight of each of a lubricant, a mold release agent and an acid scavenger, such as independently 0.05-5% by weight of a lubricant, a mold release agent and an acid scavenger, such as independently 0.05-3% by weight, such as 0.05-1% by weight, such as 0.1-5% by weight, such as 0.1-3% by weight, such as 0.1-1% by weight, such as 1-5% by weight, such as 1-3% by weight.

(15) In an exemplary embodiment, the thermoplastic polyamide composition comprises 65-80% by weight of high viscosity PA-6,6 as the polyamide resin; 15-25% by weight bis(pentabromophenyl)ethane as the flame retardant; 1-5% by weight diantimony trioxide as the flame retardant synergist; 1-5% by weight diundecyl phthalate as the plasticizer; 0.05-3% by weight N,N′-hexamethylenebis(3,5-di-tert-butyl-4-hydroxy-hydrocinnamamide) as the heat stabilizer; and 0.05-3% by weight of N,N′ ethylene bisstearylamide as the lubricant/mold release agent.

(16) In an exemplary embodiment, the thermoplastic polyamide composition comprises 65-80% by weight of medium viscosity PA-6,6 as the polyamide resin; 15-25% by weight bis(pentabromophenyl)ethane as the flame retardant; 1-5% by weight diantimony trioxide as the flame retardant synergist; 1-5% by weight diundecyl phthalate as the plasticizer; 0.05-3% by weight N,N′-hexamethylenebis(3,5-di-tert-butyl-4-hydroxy-hydrocinnamamide) as the heat stabilizer; and 0.05-3% by weight of N,N′ ethylene bisstearylamide as the lubricant/mold release agent.

(17) In an exemplary embodiment, the thermoplastic polyamide composition comprises 65-80% by weight of low viscosity PA-6,6 as the polyamide resin; 15-25% by weight bis(pentabromophenyl)ethane as the flame retardant; 1-5% by weight diantimony trioxide as the flame retardant synergist; 1-5% by weight diundecyl phthalate as the plasticizer; 0.05-3% by weight N,N′-hexamethylenebis(3,5-di-tert-butyl-4-hydroxy-hydrocinnamamide) as the heat stabilizer; and 0.05-3% by weight of N,N′ ethylene bisstearylamide as the lubricant/mold release agent.

(18) In an exemplary embodiment, the thermoplastic polyamide composition comprises 65-80% by weight of a mixture of high viscosity and medium viscosity PA-6,6 as the polyamide resin; 15-25% by weight bis(pentabromophenyl)ethane as the flame retardant; 1-5% by weight diantimony trioxide as the flame retardant synergist; 1-5% by weight diundecyl phthalate as the plasticizer; 0.05-3% by weight N,N′-hexamethylenebis(3,5-di-tert-butyl-4-hydroxy-hydrocinnamamide) as the heat stabilizer; and 0.05-3% by weight of N,N′ ethylene bisstearylamide as the lubricant/mold release agent.

EXAMPLES

Example 1. General Preparation of an Exemplary Halogen-Containing Flame Retardant Polyamide Composition of the Invention

(19) A polyamide feedstock and a plasticizer were placed in a drum and tumbled for 10-15 minutes. A halogen-containing flame retardant, a flame retardant synergist, a phenolic heat stabilizer, a lubricant/mold release agent, and a colorant were added to the drum and blended for an additional 10-15 minutes. The final blend was then placed in a hopper and added at the feed throat of a ZSK 40 mm twin screw extruder with extruder barrel temperatures ranging from 220-285° C., a screw speed of 400 rpm, and a throughput of 100 kg/hr to provide the desired polyamide composition.

(20) Molded articles containing the polyamide composition were produced on a Van Dorn 50-ton injection molding machine with cylinder temperatures of 250-285° C. (from hopper to nozzle) and a mold temperature of 95° C. for determining mechanical and thermal material properties.

(21) The following internationally recognized standardized tests were employed for measuring various properties of the polyamide compositions of the invention and the articles prepared therefrom.

(22) Tensile properties, stress, strain, and modulus were measured according to ISO 527-2.

(23) Flexural properties, strength and modulus were measured according to ISO 178.

(24) Charpy Notched Impact Strength at 23° C. was measured according to ISO 179/1eA.

(25) Charpy Unnotched Impact Strength at 23° C. was measured according to ISO 179/1eU.

(26) Izod Notched Impact Strength at +23° C. was measured according to ISO 180.

(27) Heat Deflection Temperature (HDT) with an applied load of 1.80 MPa was performed according to ISO 75-2/A.

(28) Polyamide composition melting points were determined according to ISO 11357-3.

(29) Relative Viscosity (RV) values were measured according to ASTM D789.

(30) Flammability testing was conducted on samples at various thicknesses (0.4 mm, 0.75 mm, 1.5 mm, and 3.0 mm) according to the UL94 standard.

(31) Glow Wire Flammability Index (GWFI) was performed on samples at various thicknesses (0.4 mm, 0.75 mm, 1.5 mm, and 3.0 mm) according to IEC 60695-2-12.

(32) Glow Wire Ignition Temperature (GWIT) was performed on samples at various thicknesses (0.4 mm, 0.75 mm, 1.5 mm, and 3.0 mm) according to IEC 60695-2-13.

(33) Volume Resistivity was measured according to IEC 60093.

(34) Dielectric Strength was measured according to IEC 60243.

(35) Arc Resistance was measured according to ASTM D495.

(36) Comparative Tracking Index (CTI) was measured according to both IEC 60112 and ASTM D3638.

(37) High Amp Arc Ignition (HAI) was performed on samples at various thicknesses (0.4, 0.75, 1.5, and 3.0 mm) according to UL 746.

(38) Hot Wire Ignition (HWI) was performed on samples at various thicknesses (0.4, 0.75, 1.5, and 3.0 mm) according to UL 746.

(39) High Voltage Arc Tracking Rate (HVTR) was measured according to UL 746.

(40) Relative Thermal Index (RTI) values were obtained at various thicknesses (0.4, 0.75, 1.5, and 3.0 mm) for Electrical, Impact, and Strength criteria according to UL 746.

(41) Table 1 lists the results of standard test methods on an exemplary polyamide composition of the invention where the polyamide resin was PA-6,6; the flame retardant was bis(pentabromophenyl)ethane; the flame retardant synergist was diantimony trioxide; the plasticizer was diundecyl phthalate; the heat stabilizer was N,N′-hexamethylenebis(3,5-di-tert-butyl-4-hydroxy-hydrocinnamamide); and the lubricant/mold release agent was N,N′ ethylene bisstearylamide (hereinafter referred to as Example 1).

(42) TABLE-US-00001 TABLE 1 Value Unit Test Method Physical Property Relative Viscosity  47 ASTM D789 Mechanical Property Tensile Modulus (23° C.) 3200 MPa ISO 527-2 Tensile Stress (Yield, 23° C.)  70 MPa ISO 527-2 Tensile Strain (Break, 23° C.)  15 % ISO 527-2 Flexural Modulus (23° C.) 3200 MPa ISO 178 Flexural Strength (23° C.)  90 MPa ISO 178 Impact Property Charpy Notched Impact Strength   4.3 kJ/m2 ISO 179/1eA (23° C.) Charpy Unnotched Impact  65 kJ/m2 ISO 179/1eU Strength (23° C.) Notched Izod Impact Strength   4.1 kJ/m2 ISO 180 (23° C.) Thermal Property Heat Deflection Temperature  80 ° C. ISO 75-2/A (1.8 MPa, Unannealed) Melting Temperature  265 ° C. ISO 11357-3 RTI Elec (0.400 mm)  130 ° C. UL 746 RTI Elec (0.750 mm)  130 ° C. UL 746 RTI Elec (1.50 mm)  130 ° C. UL 746 RTI Elec (3.00 mm)  130 ° C. UL 746 RTI Imp (0.400 mm) N.A. ° C. UL 746 RTI Imp (0.750 mm) N.A. ° C. UL 746 RTI Imp (1.50 mm) N.A. ° C. UL 746 RTI Imp (3.00 mm) N.A. ° C. UL 746 RTI Str (0.400 mm)  110 ° C. UL 746 RTI Str (0.750 mm)  110 ° C. UL 746 RTI Str (1.50 mm)  110 ° C. UL 746 RTI Str (3.00 mm)  110 ° C. UL 746 Electrical Property Volume Resistivity (0.750 mm) 1.00E+18 ohm .Math. m IEC 60093 Dielectric Strength (1.00 mm)  17 kV/mm IEC 60243 Comparative Tracking Index  300 V IEC 60112 (3.00 mm) Comparative Tracking Index   2 PLC ASTM D3638 (3.00 mm) High Amp Arc Ignition (HAI)   0 PLC US 746 (0.200 mm) High Amp Arc Ignition   0 PLC UL 746 (0.400 mm) High Amp Arc Ignition   0 PLC UL 746 (0.750 mm) High Amp Arc Ignition   0 PLC UL 746 (1.50 mm) High Amp Arc Ignition   0 PLC UL 746 (3.00 mm) High Voltage Arc Tracking Rate   0 PLC UL 746 (HVTR) Hot-wire Ignition (HWI)   0 PLC UL 746 (0.200 mm) Hot-wire Ignition (0.400 mm)   0 PLC UL 746 Hot-wire Ignition (0.750 mm)   0 PLC UL 746 Hot-wire Ignition (1.50 mm)   0 PLC UL 746 Hot-wire Ignition (3.00 mm)   0 PLC UL 746 Flammability Property Flammability (UL Rating) V-0 UL 94 (0.200 mm) Flammability (UL Rating) V-0 UL 94 (0.400 mm) Flammability (UL Rating) V-0 UL 94 (0.750 mm) Flammability (UL Rating) V-0 UL 94 (1.50 mm) Flammability (UL Rating) V-0 UL 94 (3.00 mm) Glow Wire Flammability Index  960 ° C. IEC 60695-2-12 (0.200 mm) Glow Wire Flammability Index  960 ° C. IEC 60695-2-12 (0.400 mm) Glow Wire Flammability Index  960 ° C. IEC 60695-2-12 (0.750 mm) Glow Wire Flammability Index  960 ° C. IEC 60695-2-12 (1.50 mm) Glow Wire Flammability Index  960 ° C. IEC 60695-2-12 (3.00 mm) Glow Wire Ignition Temperature  960 ° C. IEC 60695-2-13 (0.200 mm) Glow Wire Ignition Temperature  960 ° C. IEC 60695-2-13 (0.400 mm) Glow Wire Ignition Temperature  960 ° C. IEC 60695-2-13 (0.750 mm) Glow Wire Ignition Temperature  960 ° C. IEC 60695-2-13 (1.50 mm) Glow Wire Ignition Temperature  960 ° C. IEC 60695-2-13 (3.00 mm)

(43) Tables 2 to 5 list exemplary polyamide compositions of the invention and an exemplary comparative example.

(44) TABLE-US-00002 TABLE 2 Comparative Additive Ex 1 Ex 2 Ex 3 Ex 4 Ex 5 Ex 6 Ex 7 Ex 8 Ex 9 A 84.5 81 79.4 76.4 76.4 B 76.4 76.4 C 76.4 76.4 D 0.4 0.4 E 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 F 14.5 18 18 21 18 21 18 21 18 G 3 3 3 H 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 I 2 2 2 2 2 2 2 TOTAL (wt %) 100 100 100 100 100 100 100 100 100 A = PA66, low viscosity; B = PA66, high viscosity; C = PA66/6, copolymer; D = PA66, fine powder to assist compounding; E = Acrawax (lubricant); F = bis(pentabromophenyl)ethane (halogen, bromine-containing flame retardant); G = diantimony trioxide (synergist); H = phenolic organic heat stabilizer; I = diundecyl phthalate (plasticizer)

(45) TABLE-US-00003 TABLE 3 Additive Ex 10 Ex 11 Ex 12 Ex 13 Ex 14 Ex 15 Ex 16 Ex 17 A 75.9 71.4 71.4 71.4 71.4 69.4 76.4 74.4 B 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 C 18 18 18 18 18 20 18 18 D 3 3 3 3 3 3 E 3 3 F 0.5 0.5 0.5 0.5 0.5 0.5 G 0.5 H 2.5 I 2 2 2 2 2 2 2 2 J 0.5 K 5 L 5 M 5 N 5 5 TOTAL (wt %) 100 100 100 100 100 100 100 100 A = PA66, high viscosity; B = Acrawax (lubricant); C = bis(pentabromophenyl)ethane (halogen, bromine-containing flame retardant); D = diantimony trioxide (synergist); E = zinc borate (synergist); F = phenolic organic heat stabilizer; G = copper heat stabilizer; H = copper iodide heat stabilizer in PA66; I = diundecyl phthalate (plasticizer); J = DHT-4C (acid scavenger); K = Suzorite mica, untreated; L = Suzorite mica, treated; M = Wollastonite, treated; N = magnesium hydroxide

(46) TABLE-US-00004 TABLE 4 Ad- ditive Ex 18 Ex 19 Ex 20 Ex 21 Ex 22 Ex 23 Ex 24 Ex 25 Ex 26 A 75.4 75.4 74.4 72.4 74.4 72.4 73.4 71.4 71.4 B 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 C 22 18 18 20 18 20 18 20 18 D 2 E 3 5 5 3 3 3 F 5 5 3 3 5 G 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 H 2 1 2 2 2 2 2 2 2 TOTAL 100 100 100 100 100 100 100 100 100 (wt %) A = PA66, high viscosity; B = Acrawax (lubricant); C = bis(pentabromophenyl)ethane (halogen, bromine-containing flame retardant); D = diantimony trioxide (synergist); E = zinc borate (synergist); F = zinc stannate (synergist); G = phenolic organic heat stabilizer; H = diundecyl phthalate (plasticizer)

(47) TABLE-US-00005 TABLE 5 Additive Ex 27 Ex 28 Ex 29 Ex 30 A 76.4 76.4 74.5 73.9 B 0.1 0.1 C 0.1 D 0.1 E 18 18 18 18 F 3 3 3 3 G 0.5 0.5 0.5 0.5 H 2 2 2 2 I 1.875 2.5 TOTAL (wt %) 100 100 100 100 A = PA66, high viscosity; B = Acrawax (lubricant); C = stearyl eurcamide (lubricant); D = zinc stearate (lubricant); E = bis(pentabromophenyl)ethane (halogen, bromine-containing flame retardant); F = diantimony trioxide (synergist); G = phenolic organic heat stabilizer; H = diundecyl phthalate (plasticizer); I = carbon black in PA6 (colorant)

(48) Table 6 lists UL94 flammability testing data and mechanical testing data for the above-identified Examples 1-30.

(49) TABLE-US-00006 TABLE 6 GWIT UL94 UL94 UL94 UL94 at CTI Ex 3.2 mm 1.6 mm 0.8 mm 0.4 mm VN/RV TS TM Eb Fs Fm II C DTUL D 0.75 mm (V) C-1 V-2 V-2 V-0 V-0 138/51 75 5 103 3403 5.69 ± 0.45 4.4 ± 0.3 69.5 1.26 13 16 13 15 2 V-0 V-0 V-0 V-0 43 80 7 106 3591 6 3 4 2 3 V-2 V-2 V-2 V-2 38 69 24 95 3379 33 21 7 8 4 V-2 V-2- V-2 V-2 39 68 29 88 3210 26 19 9 9 5 V-0 V-0 V-0 V-0 37 72 21 92 3340 3 4 5 0 6 V-2 V-2 V-2 V-2 63 70 22 88 3190 50 33 4 1 7 V-0 V-0 V-0 V-0 53 71 19 90 3381 0 0 3 0 8 V-2 V-2 V-2 V-0 52 67 23 89 3231 10 7 9 1 9 V-0 V-0 V-0 V-0 48 69 19 89 3183 0 0 1 0 10 V-0 V-0 V-0 V-0 49 73 18 250 8 6 2 6 11 V-0 V-0 V-0 V-0 54 75 4 14 14 11 11 12 V-0 V-0 V-0 V-2 53 73 6 21 17 14 11 13 V-0 V-0 V-0 V-0 60 69 5 18 16 12 13 14 V-2 V-2 V-2 HB 50 74 5 70 144 39 53 15 V-0 HB V-2 HB 54 68 8 25 140 34 8 16 V-0 V-0 V-0 V-0 67 72 10 11 14 11 11 17 V-0 V-0 V-0 V-0 55 73 9 275 11 10 10 11 18 V-2 V-2 V-2 V-2 56 68 31 42 14 5 0 19 V-2 V-2 V-2 V-0 55 74 12 300 30 42 11 5 20 HB V-2 V-2 V-2 49 64 12 142 101 32 15 21 HB V-2 V-2 V-2 43 66 13 183 132 49 22 22 V-0 V-2 HB HB 54 74 23 6 64 75 90 23 V-0 HB V-2 HB 58 71 24 9 134 40 19 24 V-0 V-2 HB V-2 58 73 22 8 98 69 14 25 V-0 V-2 HB HB 56 73 20 10 27 46 31 26 V-0 V-0 HB V-2 56 71 21 2 14 37 20 27 V-0 V-0 V-0 V-0 48 70 2776 14 89 3421 3.9 3.3 77 1.32 930 0 0 0 0 28 V-0 V-0 V-0 V-0 48 73 2945 32 83 3360 3.9 2.8 1.32 960 0 0 0 0 29 V-0 V-0 V-0 V-0 53 75 9 95 3388 2.7 930 275 14 14 12 11 30 V-0 V-0 V-0 V-0 57 75.4 7 96 3400 2.9 275 13 16 14 12 C-1 = Comparative Example 1; VN = Viscosity Number; RV = Relative Viscosity; TS = Tensile Strength; TM = Tensile Modulus; Eb = Elongation at break; Fs = Flexural Strength; Fm = Flexural Modulus; II = Izod Impact-notched; C = Charpy Notched Impact Strength (23° C.); DTUL = Deflection Temperature under load; D = Density; GWIT = Glow Wire Ignition Temperature (° C.); CTI = Comparative Tracking Index (V)

(50) Table 7 lists several commercial (conventional) polyamide compositions that were tested against an exemplary composition of the present invention. Table 8 compares selected electrical properties of these compositions and Table 9 compares their elongation/impact properties.

(51) TABLE-US-00007 TABLE 7 Material Trademark Grade Code Type/Feature Example 1 HFR-PA66, unfilled Conventional 1 Vydyne ® M344 HFR-PA66, unfilled Conventional 2 Schulamid ® 6 MV 14 FR 4 HFR-PA6, unfilled, mel-cyanurate and K1681 Saytex 8010 Conventional 3 Durethan ® B 30 S F30 HFR-PA6, unfilled, aromatic Br compound with ATO Conventional 4 Durethan ® A 30 S F30 HFR-PA66, unfilled, aromatic Br compound with ATO Conventional 5 Latamid ® 66 H2PX-V0 HFR-PA66, unfilled, impact modified Conventional 6 Nilamid ® A FR C4 HFR-PA66, unfilled, ATO and PBDE Frianyl ® A3 V0-XI free Conventional 7 Technyl ® A 30G1 HFR-PA66, unfilled, heat stabilized Conventional 8 Technyl ® A 32G1 HFR-PA66, unfilled, heat stabilized Conventional 9 Glamide ® T-669VNR HFR-PA66, unfilled Conventional 10 BV2120 HFR-PA66, unfilled Conventional 11 Vampamid ® 66 0023 V0 H GW HFR-PA66, unfilled, heat stabilized

(52) TABLE-US-00008 TABLE 8 RTI Flame GWFI GWIT Thickness [Elec/Imp/Str] Class (° C.) (° C.) Example 1 0.40 mm [130/65/110] V-0 960 960 0.75 mm [130/65/110] V-0 960 960  1.5 mm [130/65/110] V-0 960 960  3.0 mm [130/65/110] V-0 960 960 Conventional 1 0.43 mm [65/65/65] V-0 0.71 mm [130/65/95] V-0 960 700  1.5 mm [130/95/95] V-0 960 700  2.0 mm [130/95/95] V-0  3.0 mm [130/95/95] V-0 960 725 Conventional 2 0.38 mm [130/75/100] V-2 960 930 0.75 mm [130/90/110] V-2 930 930  1.5 mm [130/100/120] V-2 960 825  3.0 mm [130/100/120] V-2 960 825 Conventional 3 0.40 mm [150/100/100] V-0 960 960 0.75 mm [150/100/100] V-0 960 900  1.5 mm [150/105/105] V-0  2.0 mm [150/105/105] V-0  3.0 mm [150/105/105] V-0 960 850 Conventional 4 0.40 mm [65/65/65] V-0 960 825 0.75 mm [65/65/65] V-0 960 825  1.5 mm [65/65/65] V-0 960 825  3.0 mm [65/65/65] V-0 960 Conventional 5 0.40 mm [65/65/65] V-2 0.75 mm [65/65/110] V-0  1.0 mm [130/65/110] V-0  1.5 mm [130/65/110] V-0 960 775  3.0 mm [130/65/110] V-0 960 775 Conventional 6 0.45 mm [120/65/65] V-0 960 825 0.80 mm [130/65/65] V-0 960 800  1.6 mm [130/65/65] V-0 960 775  3.0 mm [130/65/65] V-0 960 775 Conventional 7 0.45 mm [65/65/65] V-0 0.75 mm [65/65/65] V-0 960 825  1.5 mm [65/65/65] V-0 960 775  3.0 mm [65/65/65] V-0 Conventional 8 0.75 mm [65/65/65] V-2 900 875  1.5 mm [65/65/65] V-2 900 900  3.0 mm [65/65/65] V-2 Conventional 9 0.77 mm [65/65/65] V-0 Conventional 10 0.75 mm [65/65/65] V-0 Conventional 11 0.40 mm [140/140/140] V-0 0.80 mm [140/140/140] V-0  1.5 mm [140/140/140] V-0 960 775  3.0 mm [140/140/140] V-0 960 775

(53) TABLE-US-00009 TABLE 9 Notched Tensile Tensile Charpy Strength Elongation Impact Yield/ Yield/ Tensile Flexural 23° C./ Break Break Modulus Modulus −30° C. (MPa) (%) (MPa) (MPa) (kj/m.sup.2) Example 1 −/70 −/17 3200 3200 4.5/− Conventional 1 60/−  5/35 3500 3000 5.5/5.2 Conventional 2 70/− 3.0/− 3800 4.0/3.0 Conventional 3 70/− 3.7/− 3600 3200 <10/<10 Conventional 4 −/6  3700 Conventional 5 55/50 2.5/10  2800   7/− Conventional 6 56/− 2.5/4   3000 Conventional 7 Conventional 8 −/50  15/− 2950   6/− Conventional 9 Conventional 10 −/77 −/3  3300 3200   3/− Conventional 11 50/− −/10 2600   7/−

(54) When compared to conventional polyamide compositions, the halogen-containing fire retardant polyamide compositions of the present invention were observed to unexpectedly (i) exhibit best in class Glow Wire Ignition Test performance (960° C. at all tested thicknesses) for an unfilled PA66 composition; (ii) exhibit excellent toughness by maintaining an ultimate elongation at a break minimum of 13%; (iii) provide high flow that allows the filling of thin-walled parts during injection molding at reduced cavity and injection pressures.

(55) All publications and patents cited herein are incorporated by reference in their entireties.