Brominated epoxy polymers as textile-finishing flame retardant formulations

Abstract

The present invention discloses novel flame retardant aqueous formulations comprising micronized particles of brominated epoxy polymers having a predetermined molecular weight and glass transition temperature, their use as flame retardants for textile applications, their preparation and flame-retarded textile fabrics prepared by using them.

Claims

1. A flame retardant textile fabric having a homogeneous flame retardant film thereon or therein, said film comprising at least one brominated epoxy polymer, crosslinked on or in said textile fabric, wherein: a) said brominated epoxy polymer has a molecular weight ranging from 1,000 to 5,000 grams/mol; and b) said brominated epoxy polymer has a glass transition initiation temperature (Tg) that is lower than about 130 C.; c) said fabric comprises a flame retardant synergist and a binding agent, and optionally further comprises at least one additive selected from the group consisting of a smoldering suppressant agent, a surface active agent, an antifoaming agent, a preservative, a stabilizing agent, a thickening agent, a dispersing agent, a wetting agent, a suspending agent, a pH buffer, an anti creasing agent, a hardener, a curing agent, a sequestering agent, a detergent, a dye, a pigment and any mixture thereof, wherein said textile fabric is selected from the group consisting of garments, linen, decorative or technical textiles, draperies, carpets, tents, sleeping bags, toys, wall fabrics, decorative fabrics, mattresses and upholsteries, further wherein said textile fabric is composed of fibres selected from the group consisting of: wool, silk, cotton, linen, hemp, ramie, jute, acetate, lyocell, acrylic, polyolefin, polyamide, polylactic acid, polyester, rayon, viscose, spandex, metallic composite, ceramic, glass, carbon or carbonized composite, and any combination thereof, wherein said flame retardant textile fabric has an add-on ranging from 4% to 40%.

2. The flame retardant textile fabric of claim 1, having an after flame flame ranging from 0 seconds to 5 seconds and/or a char length ranging from 10 to 17 cm before laundry.

3. The flame retardant textile fabric of claim 2, having a washing fastness of at least 5 laundry cycles.

4. The flame retardant textile fabric of claim 3, having a washing fastness of at least 25 laundry cycles.

5. The flame retardant textile fabric of claim 1, wherein said film is transparent.

6. The flame retardant textile fabric of claim 1, wherein said textile fabric is composed of cotton, polyester or combinations thereof.

7. The flame retardant textile fabric of claim 1, wherein at least one aesthetical or textural property which is substantially the same as that of said textile fabric per se.

8. The flame retardant textile fabric of claim 1, being free of a flame retardant synergist and free of a binding agent, having an add-on lower than 12%.

9. The flame retardant textile fabric of claim 8, being composed of a hydrophobic fiber.

10. The flame retardant textile fabric of claim 9, wherein said hydrophobic fiber is selected from polypropylene, polyester and nylon.

11. A flame retarded textile fabric having a homogeneous flame retardant film thereon or therein, said film comprising said at least one brominated epoxy polymer, crosslinked on or in said textile fabric, wherein: a) said brominated epoxy polymer has a molecular weight ranging from 1,000 to 5,000 grams/mol; and b) said brominated epoxy polymer has a glass transition initiation temperature (Tg) that is lower than about 130 C.; and c) said fabric is free of a flame retardant synergist and free of a binding agent, wherein said fabric is obtained by exhaustion.

12. The flame retardant textile fabric of claim 11 being free of a flame retardant synergist and free of a binding agent, having an add-on lower than 12%, said flame retardant textile fabric being composed of a hydrophobic fibre selected from polypropylene, polyester and nylon.

Description

DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 shows test results for an ignition test for F-3020 and F-2016 and samples as well as Deca ethane and a blank.

(2) FIG. 2 shows a transparent and clear extraction medium for F-2016 and a milky medium for Deca ethane medium as obtained from the durability test of the treated fabrics after 8 hours in boiling water.

(3) FIG. 3 shows a SEM micrograph of the 50/50 polyester/cotton surface after curing and 15 laundry cycles according to Example 4.

(4) FIG. 4 is a SEM micrograph of the polyester surface coated by the 2016 FR before curing according to Example 4.

(5) FIG. 5 is a SEM micrograph of the polyester surface coated by the 2016 FR after curing, showing penetration of the particles into the fiber according to Example 4.

(6) FIG. 6 is a SEM micrograph of a cross section of the polyester fabric after thermal curing of F-2016 coating, showing penetration of the bromine into the fiber according to Example 4.

EXAMPLES

(7) Reference is now made to the following examples, which together with the above descriptions, illustrate the invention in a non limiting fashion.

(8) Throughout the examples, the terms polyester fabric, cotton fabric etc. refer to fabrics composed of polyester fibers, cotton fibers, respectively.

Materials and Analytical Methods

(9) Materials: Brominated epoxy polymers of the F-series: F-2100, F-2100L, F-2016, F-2400, F-3020 and F-3516 (as detailed in Table 1) were obtained from ICL-IP. Disperbyk 2010 dispersing agent (Structured acrylate copolymer with pigment affinic groups) was obtained from BYK Additives and Instrument Tersperse 2735 dispersing agent (2-Propenoic acid, 2-methyl-, polymer with ethenylbenzene) was obtained from Huntsman Supragil WP wetting agent (a sodium alkylnaphthalenesulfonic acid-formaldehyde condensate) was obtained from Rhodia Morwet EFW wetting agent (diisobutyl naphthalene sulfonate) was obtained from AkzoNobel CELLOSIZE HEC QP-100MH thickener (hydroxyethylcellulose) was obtained from DOW. Antimony trioxide (ATO, CAS No. 1309-64-4) was obtained from Campine Belgium. AC-170 binder (Diazenedicarboxamide) and GP acrylic thickening agent were obtained from B. G. Polymers. The acrylic binders are typically supplied as 50% solids emulsions. TexFRon AG (Aluminum ammonium polyphosphate) 90% solid, was obtained from ICL-IP, Beer Sheva Israel.
Light Scattering Particle Size Measurement:

(10) This method was used to determine the particle size distribution of liquid particles, using a Malvern Mastersizer (Hydrogel 2000G), manufactured by Malvern Instruments. The instrument uses the principle of MIE scattering, has an accuracy of 1%, and is set to measure particles in the size range 0.02-2000 microns. A spherical (general) model was used. The surface mean particle size (d.sub.50) or 50 percentile, the 99 percentile (d.sub.99) and the 90 percentile (d.sub.90) are directly obtained from the data generated by the instrument.

(11) Fabric Characterization Methods:

(12) Scanning electron microscope (SEM) equipped with an energy dispersive x-ray spectrometer (EDS; hereinafter SEM/EDS) was performed on a JEOL JSM-7400F ultrahigh resolution cold FEG-SEM. In this method a piece of fabric is coated with 10 nanometer of gold layer.

(13) The percentage of bromine on the fabric was determined by adding tetrahydrofuran (THF) and extracting the coating from fabric specimens weighing 0.5 grams each. Each specimen is reacted with a sodium biphenyl complex reagent, to produce NaBr in an amount equivalent to the amount of bromine in the sample. The access reagent is treated with isopropanol and acidified with acetic acid. Finally, the amount of bromine is determined using a titration with AgNO.sub.3.

(14) Extraction Experiments to Demonstrate Durability

(15) In order to demonstrate the durability of the brominated epoxy formulations of the present invention, treated fabric samples were extracted in boiling water in a Soxhlet apparatus for 8 hours. The resultant extract was evaluated visually and analytically, both for the samples of the present invention and in comparison with a Deca Ethane reference.

(16) The percentage of additives on the fabric (Add-on) was determined by the difference between sample weight before and after application of the FR formulation and drying thereof (deviation of 1%).

(17) Flammability Tests:

(18) ASTM D 6413 12 seconds ignition test: In this method, samples are cut from the fabric to be tested, and are mounted in a frame that hangs vertically from inside the flame chamber. A controlled flame is exposed to the sample for a specified period of time (in this case for 12 seconds, one of the strictest flammability tests), and the after-flame time and the after-glow time are both recorded. Finally, the sample is torn by use of weights and the char length is measured. To pass, the average char length of five samples cannot exceed 7 inches (17.8 cm). In addition, none of the individual specimens can have a char length of 10 inches (25.4 cm). The sample is further classified as passing the test if its after-flame time is less than 5 seconds.

(19) For some applications, an after-glow time of less than 200 seconds, and even less than 150 seconds, is advantageous so as to render the sample applicable even in the stricter children's nightwear flammability standards.

(20) Fabrics are tested in both directions (warp and fill) i.e. 5 samples are cut along the length and 5 samples are tested along their width.

(21) Test Results are displayed in FIG. 1. Deca Ethane was used as reference and blank show significant dripping.

(22) Washing Fastness Tests:

(23) Samples treated with formulations described herein were subjected to at least 5 successive washing cycles in accordance with the washing procedure set forth below, followed by one drying cycle in accordance with commonly used drying procedure, based on the Standard Laboratory Practice for Home Laundering (AATCC technical manual/2001).

(24) In all washing cycles, the temperature of the washing water is maintained between 58 C. and 62 C., for automatic washing machines, the washing cycle is set for normal washing cycle, and a synthetic detergent that conforms to Standard Laboratory Practice for Home Laundering (AATCC technical manual/2001) is used.

Example 1

Preparation of Micronized F-2016, F-2100, F-3020 and F-3516

(25) Coarse F-2016, F-2100, F-3020 and F-3516 were micronized by a Micronizer Jet Mill (wet milling) or by a ball mill (dry milling). The particle size distribution before and after the milling was measured using Malvern Mastersizer 2000 in water (3 minutes ultrasonic treatment, 500 psi, 1250 rpm).

(26) For F-2400 and F-3100 milling was impossible due to hardness of the material and therefore no size reduction was obtained.

Example 2

Preparation of F-2016, F-2100, F-3020 and F-3516 Aqueous Dispersions

(27) F-2100 (96 grams) having a size distribution of d.sub.50<3.5 micron d.sub.90<7.5 micron d.sub.99<15 micron was added to a mixed solution of deionized water (443.8 grams), dispersing agent Tersperse 2735 (5 grams) and wetting agent Morwet EFW (0.5 grams). The dispersion was allowed to mix for thirty minutes. Sb.sub.2O.sub.3 (30.4 grams) and acrylic binder AC-170 (75.8 grams) were added to the mixed dispersion and the dispersion was allowed to mix for fifteen minutes and thickened by adding a small amount of hydroxyethylcellulose (1.7 grams).

(28) The same process was repeated for F-2016, F-3020 and F-3516, whereas the dispersing agent was Disperbyk 2010 and the wetting agent was Supragil WP. The compositions of the different aqueous dispersions are detailed in Table 2 below:

(29) TABLE-US-00003 TABLE 2 Composition F-2100 F-2016 F-3020 F-3516 Properties (wt %) in deionized water Dry solids 26 27 27 28 FR 14.7 16.1 15.6 16.88 Br 7.7 8.1 8.7 9.1 Acrylic binder 5.8 5.25 5.25 5.6 AC-170 Sb.sub.2O.sub.3 4.7 4.9 5.3 5.12 Dispersion agent 1 1 1 1 Tersperse Disperbyk Disperbyk Disperbyk 2735 2010 2010 2010 Wetting Agent 0.1 0.1 0.1 0.1 Morwet EFW Supragil Supragil WP Supragil WP?? Thickener: 0.15-0.2 0.15-0.2 0.15-0.2 0.15-0.2 Hydroxyethyl- cellulose

Example 3

Application of F-2100 Formulation on Fabrics (Padding)

(30) 3A) Application on a 50%/50% Cotton Polyester Fabric

(31) A 50%/50% cotton/polyester fabric weighing 205 grams per square meter was treated by padding with the F-2100 dispersion prepared in Example 2. Fabrics were cured at 160 C. for 4 minutes, laundered 5 times according to AATCC Standard Practice for Home Laundry at 60 C., bone dried and tested according to ASTM D 6413-08 vertical flame, 12 seconds ignition. i) Results for high shear wet milled F-2100 samples at about 32-34% dry add-on and at a 3:1 Br:Sb molar ratio are provided in Table 3:

(32) TABLE-US-00004 TABLE 3 flammability test % After After Char Sam- Add- % % % flame Glow Length Laundry ple # on FR Br ATO sec sec cm Cycles 2103- 32.9 19 12.9 6 2 90 16 5 52-02 2103- 34.4 19.9 13.5 6.3 2 67 15 5 52-03 2103- 26.6 15.3 10.4 4.8 0 95 15 Before 52-04 laundry 2 95 15 5 2103- 35.0 20.2 13.7 6 2 70 16 5 52-06 ii) Results for dry-milled F-2100 samples having an add-on ranging from 24-34% at a Br:Sb molar ratio of 3:1 are provided in Table 4:

(33) TABLE-US-00005 TABLE 4 flammability test % After After Char Sam- Add- % % % flame Glow Length Laundry ple # on FR Br ATO sec sec cm Cycles 2103- 26.1 14.8 10.1 4.7 1 128 15 Before 64-02 laundry 2 56 15 5 2103- 24 13.6 9.3 4.3 0 134 15.5 Before 64-03 laundry 2 50 16 5 2103- 26.5 15.1 10.2 4.8 0 70 15 Before 64-04 laundry 1 65 15 5 2103- 29.4 16.7 11.3 5.3 1 143 15.5 Before 64-05 laundry 1 40 15 5 2103- 25.7 14.6 9.9 4.6 0 88 14 Before 64-06 laundry 1 60 15 5 2103- 25.7 14.6 9.9 4.6 0 110 15 Before 64-07 laundry 0 60 14 5 2103- 30.5 17.3 11.8 5.5 0 90 15 Before 64-08 laundry 1 75 15 5 2103- 33.8 19.2 13 6.1 0 134 16 Before 64-09 laundry 1 65 15 5
3B) Application on a 100% Cotton Fabric

(34) A 100% cotton knit 220 grams/m.sup.2 fabric was padded with the F-2100 dispersion of Example 2, having a 39-47% dry add-on at a Br:Sb molar ratio of 3:1. Fabrics were cured at 160 C. for 4 minutes, laundered 5 times according to AATCC Standard Practice for Home Laundry at 60 C., bone dried and tested according to ASTM D 6413-08 vertical flame, 12 seconds ignition. As can be seen in Table 5, it passed the flammability tests but failed the laundry durability test (flammability after laundry):

(35) TABLE-US-00006 TABLE 5 flammability test % After After Char Sam- Add- % % % flame Glow Length Laundry ple # on FR Br ATO sec sec cm cycles 2103- 39.7 22.5 11.7 7.1 0 162 9 Before 72-07 laundry BEL 5 2103- 41.5 23.5 12.2 7.4 0 160 7.5 Before 72-08 laundry BEL 5 2103- 46.7 26.5 13.8 8.4 0 160 7.5 Before 72-09 laundry BEL 5 2103- 44.5 25.2 13.1 8 0 158 8.5 Before 72-10 laundry BEL 5 2103- 45.1 25.6 13.3 8.1 0 120 6.5 Before 72-11 laundry BEL 5 BEL = burnt entire length
3C) Application on a 100% Polyester Fabric

(36) A 100% polyester fabric weighing 200 treated by padding with the dispersion of Example 2, 30-47% dry add-on at a 3:1 Br:Sb molar ratio. Fabrics were cured at 160 C. for 4 minutes, laundered 5 times according to AATCC Standard Practice for Home Laundry at 60 C., bone dried and tested according to ASTM D 6413-08 vertical flame, 12 seconds ignition. As can be seen in Table 6, it passed the flammability tests and also passed the laundry durability test (flammability after laundry) above 8.8% Br:

(37) TABLE-US-00007 TABLE 6 flammability test % After After Char Sam- Add- % % % flame Glow Length Laundry ple # on FR Br ATO sec sec cm cycles 2103- 45 25 13.3 8.1 0 8 12 Before 72-02 laundry 0 0 11 5 2103- 40 22.8 11.8 7.2 0 5 13.5 Before 72-03 laundry 0 0 9 5 2103- 30.9 17.5 9.1 5.5 0 5 13.5 Before 72-04 laundry 0 0 14 5 2103- 29.7 16.8 8.8 5.3 0 9 13 Before 72-05 laundry 0 0 11 5 2103- 47.1 26.7 13.9 8.4 0 8 11.1 Before 72-06 laundry 0 0 11 5

Example 4

Application of F-2016 Formulation on Fabrics (Padding)

(38) 4A) Application on a 50%/50% Cotton/Polyester Fabric

(39) 50%/50% cotton polyester fabric weighing 205 grams per square meter was treated by padding with the F-2016 dispersion prepared according to Example 2. Fabrics were cured at 160 C. for 4 minutes, laundered 5 times according to AATCC Standard Practice for Home Laundry at 60 C., bone dried and tested according to ASTM D 6413-08 vertical flame, 12 seconds ignition. i) Results for high shear wet milled samples, at 32-34% dry add-on and at a 3:1 Br:Sb molar ratio, are provided in Table 7:

(40) TABLE-US-00008 TABLE 7 flammability test % After After Char Sam- Add- % % % flame Glow Length Laundry ple # on FR Br ATO sec sec cm Cycles 1979- 34.92 20.76 10.4 6.30 0 53 17 Before 74-03 laundry 2 30 17 5 1979- 32 19.03 9.52 5.78 0 74 17 Before 74-04 laundry 5 20 22 5 1979- 32.88 19.55 9.78 5.94 1 58 16 Before 74-05 laundry 2 31 18 5 ii) Results for dry milled samples, at 25-36% dry add-on and at a 3:1 Br:Sb molar ratio, are provided in Table 8:

(41) TABLE-US-00009 TABLE 8 flammability test % After After Char Sam- Add- % % % flame Glow Length Laundry ple # on FR Br ATO sec sec cm Cycles 1979- 31.5 19.2 9.6 5.8 0 38 14 Before 81-10 laundry 0 58 13 5 1979- 35.8 21.9 10.9 6.6 0 42 15.5 Before 81-11 laundry 0 42 10.5 5 1979- 25.2 15.4 7.7 4.7 0 33 13.5 Before 81-12 laundry 0 68 10 5 1979- 33.8 20.6 10.3 6.3 0 30 14 Before 81-13 laundry 0 83 10 5

(42) Sample 1979-81-13, having a 33.8% add-on, 20.6% FR, 10.3% Br, 6.3% ATO and at a Br:Sb molar ratio of 3:1, was then further tested after up to 30 laundry cycles according to AATCC Standard Practice for Home Laundry at 60 C. Results are presented in Table 9:

(43) TABLE-US-00010 TABLE 9 flammability test After flame After Glow Char Length Laundry Sample # sec sec cm Cycles 1979-81-13 0 30 14 Before laundry 2169-36-13 0 36 13.5 5 2169-36-01 0 28 13 10 2169-36-16 0 30 11 15 2169-36-10 2 34 13 25 2169-36-15 2 35 14 30

(44) FIG. 3 is a SEM micrograph of the 50/50 polyester/cotton surface after curing and 15 laundry cycles. White specs are identified as ATO by XRD. F-2016 shows as an invisible clear film on the cotton fibers and penetrates into the polyester fiber.

(45) 4B) Application on a 100% Cotton Fabric, with and without TexFRon AG Smoldering Suppressant

(46) A 100% cotton knit 220 grams/m.sup.2 fabric was padded with the F-2016 dispersion of Example 2. Fabrics were cured at 160 C. for 4 minutes, laundered 5 times according to AATCC Standard Practice for Home Laundry at 60 C., bone dried and tested according to ASTM D 6413-08 vertical flame, 12 seconds ignition. i) Results for the F-2016 dispersion of Example 2 (no TexFRon AG) at 23-26% dry add-on and at a 3:1 Br:Sb molar ratio, are provided in Table 10:

(47) TABLE-US-00011 TABLE 10 flammability test % After After Char Sam- Add- % % % flame Glow Length Laundry ple # on FR Br ATO sec sec cm Cycles 1979- 23.2 14.2 7.1 4.3 0 544 12 Before 81-14 laundry 0 561 11.5 5 1979- 25.3 15.5 7.7 4.7 0 459 13.5 Before 81-15 laundry 0 359 11 5 1979- 26.4 16.1 8.1 4.9 0 520 12.5 Before 81-16 laundry 0 523 10 5 ii) Results for the F-2016 dispersion of Example 2 after combining it with TexFRon AG (50%-50% wt) at a 3:1 Br:Sb molar ratio, whereby the add-on increased to 48-65%, are provided in Table 11:

(48) TABLE-US-00012 TABLE 11 flammability test % Br:Sb After After Char Sam- Add- % % % Molar flame Glow Length ple # on FR Br ATO ratio sec sec cm 2103- 65.1 26.7 13.4 8.1 3:1 0 12 10 89-02 2103- 56.2 23.1 11.5 7 3:1 0 18 12 89-01 2103- 48.6 19.9 10.0 6.1 3:1 0 12 12.5 89-05

(49) % FR as appears throughout the specification refers to the % wt of the brominated FRs of the present invention on the fabric.

(50) 4C) Application on a 100% Polyester Fabric

(51) A 100% polyester fabric weighing 200 treated by padding with the F-2016 dispersion of Example 2, at a 22-35% dry add-on and a 3:1 Br:Sb molar ratio. Fabrics were cured at 160 C. for 4 minutes, laundered 5 times according to AATCC Standard Practice for Home Laundry at 60 C., bone dried and tested according to ASTM D 6413-08 vertical flame, 12 seconds ignition. Results are provided in Table 12:

(52) TABLE-US-00013 TABLE 12 flammability test % After After Char Sam- Add- % % % flame Glow Length Laundry ple # on FR Br ATO sec sec cm Cycles 1979- 21.8 13.3 6.7 4.0 0 0 10.5 Before 81-17 laundry 0 0 10.5 5 1979- 32.9 20.1 10.1 6.1 0 0 11.5 Before 81-18 laundry 0 0 10 5 1979- 35.1 21.5 10.7 6.5 0 0 11 Before 81-19 laundry 0 0 11 5

(53) Sample 1979-81-18 having a 32.9% add-on, 20.1% FR, 10.1% Br, 6.1% ATO and at a 3:1 Br:Sb molar ratio was then further tested after up to 25 laundry cycles according to AATCC Standard Practice for Home Laundry at 60 C. Results are presented in Table 13:

(54) TABLE-US-00014 TABLE 13 flammability test After flame After-glow Char Length laundry Sample # sec sec cm cycles 1979-81-18 0 0 11.5 Before laundry 1979-81-18 0 0 10 5 2169-38-01 0 0 9 10 2169-38-05 0 0 7.5 15 2169-38-08 0 0 10 20 2169-38-07 0* 0 10 25 *dripping

(55) FIG. 4 is a SEM micrograph of the polyester surface coated by the 2016 FR before curing, while FIG. 5 is a SEM micrograph of the polyester surface coated by the 2016 FR after curing, showing penetration of the particles into the fiber. The white spots in the micrographs indicate ATO particles.

(56) FIG. 6 is a SEM micrograph of a cross section of the polyester fabric after thermal curing of F-2016 coating, showing penetration of the Bromine into the fiber.

(57) In a soxhlet extraction experiment on an F-2016 sample, it was observed that while before the extraction the after-flame was 0 seconds, the after-glow was 63 seconds, and the char length was 14 cm, after the 8-hr extraction in boiling water, the after-flame was still 0 seconds, the after-glow was 36 seconds, and the char length was 13.5 cm. Furthermore, the Br content in the extraction medium was below detection level and the medium was clear and transparent.

Example 5

Application of F-3020 Formulation on Fabrics (Padding)

(58) 5A) Application on a 50%/50% Cotton Polyester Fabric

(59) A 50%/50% cotton polyester fabric weighing 205 grams per square meter was treated by padding with the F-3020 dispersion of Example 2. Fabrics were cured at 160 C. for 4 minutes, laundered 5 times according to AATCC Standard Practice for Home Laundry at 60 C., bone dried and tested according to ASTM D 6413-08 vertical flame, 12 seconds ignition. i) Results for high shear wet milled samples, at 29-32% dry add-on at a 3:1 Br:Sb molar ratio, are provided in Table 14:

(60) TABLE-US-00015 TABLE 14 flammability test % After After Char Sam- Add- % % % flame Glow Length Laundry ple # on FR Br ATO sec sec cm Cycles 1979- 31.71 18.35 10.3 6.24 1 68 15 Before 73-13 laundry 3 42 17 5 1979- 31.89 18.68 10.44 6.35 1 58 16 Before 74-04 laundry 2 47 15 5 1979- 29.44 17.33 9.64 5.89 1 74 16 Before 74-05 laundry 2 75 15 5 ii) Results for dry milled samples, at 27-33% dry add-on and at a 3:1 Br:Sb molar ratio, are provided in Table 15:

(61) TABLE-US-00016 TABLE 15 flammability test % After After Char Sam- Add- % % % flame Glow Length Laundry ple # on FR Br ATO sec sec cm Cycles 1979- 28.0 16.7 9.3 5.7 0 94 16 Before 81-01 laundry 0 80 13.5 5 1979- 33.2 19.7 11.1 6.7 0 56 13 Before 81-02 laundry 0 66 15 5 1979- 27.4 16.3 9.1 5.5 0 68 14.0 Before 81-03 laundry 0 58 13.5 5 1979- 32.1 19.1 10.7 6.5 0 63 14.5 Before 81-04 laundry 0 71 14.5 5

(62) Sample 2169-41-02, having a 31.5% add-on, 18.2% FR, 10.2% Br, 6.2% ATO and a 3:1 Br:Sb molar ration, was then further tested after up to 30 laundry cycles according to AATCC Standard Practice for Home Laundry at 60 C. Results are provided in Table 16:

(63) TABLE-US-00017 TABLE 16 flammability test After flame After-glow Char Length Laundry Sample # sec sec cm Cycles 2169-41-05 0 44 12 5 2169-41-04 0 32 11 10 2169-41-03 0 46 15 15 2169-41-06 1 54 16 20 2169-41-07 0 47 15 30
5B) Application on a 100% Cotton Fabric

(64) A 100% cotton knit 220 grams/m.sup.2 fabric was padded with the dispersion of F-3020 prepared in Example 2 at about 22-23% dry add-on and at a 3:1 Br:Sb molar ratio. Fabrics were cured at 160 C. for 4 minutes, laundered 5 times according to AATCC Standard Practice for Home Laundry at 60 C., bone dried and tested according to ASTM D 6413-08 vertical flame, 12 seconds ignition. Results are shown in Table 17:

(65) TABLE-US-00018 TABLE 17 flammability test % After After Char Sam- Add- % % % flame Glow Length Laundry ple # on FR Br ATO sec sec cm Cycles 1797- 23.1 13.7 7.7 4.7 0 601 16.5 Before 81-05 laundry 0 473 13 5 1979- 22.1 13.2 7.4 4.5 0 534 17 Before 81-06 laundry 0 581 12.5 5

(66) TextFron AG was added as in Example 4B to successfully overcome the smoldering effect.

(67) 5C) Application on a 100% Polyester Fabric

(68) A 100% polyester fabric weighing 200 treated by padding with the D-3020 dispersion of Example 2, at a 34% dry add-on and at a 3:1 Br:Sb molar ratio. Fabrics were cured at 160 C. for 4 minutes, laundered 5 times according to AATCC Standard Practice for Home Laundry at 60 C., bone dried and tested according to ASTM D 6413-08 vertical flame, 12 seconds ignition. Results are provided in Table 18:

(69) TABLE-US-00019 TABLE 18 flammability test % After After Char Sam- Add- % % % flame Glow Length Laundry ple # on FR Br ATO sec sec cm cycles 1979- 26.5 15.8 8.8 5.4 0 0 16 Before 81-07 laundry 0 0 12 5 1979- 17.3 10.3 5.8 3.5 0 0 13.5 Before 81-08 laundry 0 0 15 5 1979- 29.5 17.5 9.8 6.0 0 0 13.5 Before 81-09 laundry 0 0 15.5 5

(70) In a soxhlet extraction experiment on an F-3020 sample, it was observed that while before the extraction the after-flame was 0 seconds, the after-glow was 42 seconds, and the char length was 15 cm, after the 8-hr extraction in boiling water, the after-flame was still 0 seconds, the after-glow was 32 seconds, and the char length was 13.5 cm. Furthermore, the Br content in the extraction medium was below detection level and the medium was clear and transparent.

Example 6

Application of F-3516 Formulation on Fabrics

(71) 6A) Application on a 50%/50% Cotton Polyester Fabric

(72) A 50%/50% cotton polyester fabric weighing 205 grams per square meter was treated by padding with the F-3516 dispersion of Example 2. Fabrics were cured at 160 C. for 4 minutes, laundered 5 times according to AATCC Standard Practice for Home Laundry at 60 C., bone dried and tested according to ASTM D 6413-08 vertical flame, 12 seconds ignition. Results for high shear wet milled samples, at 27-38% dry add-on at a 3:1 Br:Sb molar ratio, are provided in Table 19:

(73) TABLE-US-00020 TABLE 19 flammability test % After After Char Sam- Add- % % % flame Glow Length Laundry ple # on FR Br ATO sec sec cm cycles 2169- 35.7 20.8 10.4 6.8 0 103 11 Before 32-01 laundry 0 100 12.5 5 2169- 38.2 22.3 11.2 7.3 0 74 13 Before 32-02 laundry 0 68 13 5 2169- 27.2 15.9 7.9 5.2 0 130 13.5 Before 32-04 laundry 3 150 18 5 2169- 35.9 21 10.5 6.9 0 62 11 Before 32-05 laundry 0 70 12 5
6B) Application on a 100% Polyester Fabric

(74) A 100% polyester fabric weighing 200 treated by padding with the F-3516 dispersion of Example 2, at 28-46% dry add-on and at a 3:1 Br:Sb molar ratio. Fabrics were cured at 160 C. for 4 minutes, laundered 5 times according to AATCC Standard Practice for Home Laundry at 60 C., bone dried and tested according to ASTM D 6413-08 vertical flame, 12 seconds ignition. Results are provided in Table 20:

(75) TABLE-US-00021 TABLE 20 flammability test % After After Char Add- % % % flame Glow Length Laundry Sample # on FR Br ATO sec sec cm cycles 2169-33- 38 22.2 11.1 7.3 0 0 10 Before 01 laundry 1 1 11 5 2169-33- 41.3 24.1 12.1 7.9 1 1 11.5 Before 02 laundry 0 0 11 5 2169-33- 28.5 16.6 8.3 5.4 1 1 11 Before 03 laundry 0 0 11 5 2169-33- 37.7 22 11 7.2 0 0 11 Before 04 laundry 0 0 10.5 5 2169-33- 45.9 26.8 13.4 8.8 2 2 11.5 Before 05 laundry 1 1 11.5 5

Example 7

Preparation of Reduced Antimony F-2016 Formulations

(76) F-2016 formulations were prepared as described above in Example 2, having a solid content of about 25-40%, while lowering the Sb:Br molar ratio from 1:3 to 1:18. The various formulations are provided in Table 21:

(77) TABLE-US-00022 TABLE 21 Composition 1979- 2195- 2169- 2195- 2195- 2195- Properties 73 63 91 03 09 10 Dry solids (wt %) 28 27 38.2 34 32 32 FR (wt %) 16.88 18.17 26.6 24.4 23.33 23.55 Br (wt %) 9.1 9.08 13.3 12.2 11.7 11.8 Sb.sub.2O.sub.3 (wt %) 5.12 2.76 2.7 1.8 1.4 1.2 Sb:Br (molar) 1:3 1:6 1:9 1:12 1:15 1:18 Dispersion Agent 0.83 0.83 1.2 1.0 0.98 0.98 (wt %)

(78) Additional F-2016 formulations were prepared by adding TexFRon AG (50% F-2016+50% TexFRon AG).

(79) TABLE-US-00023 TABLE 22 Composition 2120- 2120- 2120- Properties 07 08 12 (wt %) 38 38 40 FR (wt %) 12.3 13.2 14.2 Br (wt %) 6.15 6.6 7.2 % TexFRon AG 12.3 12.3 14.2 Sb.sub.2O.sub.3 (wt %) 3.7 2 1.43 Sb:Br (molar) 1:3 1:6 1:9

Example 8

Application of Reduced Antimony F-2016 Formulations on a 50/50 Polyester/Cotton Fabric (Padding)

(80) The F-2016 reduced-antimony aqueous dispersions prepared according to Example 7 were applied to 50/50 Polyester/Cotton 200 gr/m.sup.2 by padding. Fabrics were cured at 160 C. for 4 minutes, bone dried and tested. Several replications were tested for the various combinations. Treated fabrics were tested according to ASTM D 6413-08 vertical flame, 12 seconds ignition. At least 3 samples were burned for each test/formulation. Results are provided in Tables 23-28 below: A) For a Br:Sb molar ratio is 3:1 i) without TexFRon AG, at an add-on of 25-36%, results are presented in Table 23i:

(81) TABLE-US-00024 TABLE 23i flammability test % After After Char Add- % % % flame Glow Length Laundry Sample # on FR Br ATO sec sec cm cycles 1979-81- 31.5 19.2 9.6 5.8 0 38 14 Before 10 laundry 0 58 13 5 1979-81- 35.8 21.9 10.9 6.6 0 42 15.5 Before 11 laundry 0 42 10.5 5 1979-81- 25.2 15.4 7.7 4.7 0 33 13.5 Before 12 laundry 0 68 10 5 1979-81- 33.8 20.6 10.3 6.3 0 30 14 Before 13 Laundry 0 36 13.5 5 ii) with TexFRon AG (50%+50%), at an add-on of 50-61% results are provided in Table 23ii:

(82) TABLE-US-00025 TABLE 23ii flammability test % After After Char Add- % % % flame Glow Length Laundry Sample # on FR Br ATO sec sec cm cycles 2120-07-10 60.7 19.7 9.8 6.0 0 2 6 Before laundry 2120-07-10 60.7 19.7 9.8 6.0 0 2 6.5 5 2120-07-11 58.1 18.8 9.4 5.7 0 2 11 Before laundry 2120-07-11 58.1 18.8 9.4 5.7 0 3 10 5 2120-07-12 49.8 16.1 8.1 4.9 0 3 11 Before laundry 2120-07-12 49.8 16.1 8.1 4.9 0 4 17 5 2120-07-13 51.1 16.1 8.3 5.0 0 3 13 Before laundry 2120-07-13 51.1 16.1 8.3 5.0 0 3 13 5 B) For a Br:Sb molar ratio of 6:1 i) without TexFRon AG, at an add-on of 23-36%, results are presented in Table 24i:

(83) TABLE-US-00026 TABLE 24i flammability test % After After Char Add- % % % flame Glow Length Laundry Sample # on FR Br ATO sec sec cm cycles 2195-63- 33 22.2 11.1 3.4 0 25 12 Before 02 laundry 0 20 13.5 5 2195-63- 26.2 17.7 8.8 2.7 0 26 13.5 Before 02 laundry 2 34 15 5 2195-63- 32.2 21.7 10.8 3.3 0 40 11 Before 03 laundry 0 32 11 5 2195-63- 23.7 15.9 8.0 2.4 0 22 11.5 Before 04 laundry 2 23 11.5 5 2195-63- 27.3 18.4 9.2 2.8 0 28 12 Before 05 laundry 0 21 12.5 5 2195-63- 35.6 24 12 3.6 0 24 11 Before 06 laundry 0 24 12.5 5 ii) with TexFRon AG (50%+50%), at an add-on of 57-62% results are provided in Table 24ii:

(84) TABLE-US-00027 TABLE 24ii flammability test % After After Char Add- % % % flame Glow Length Laundry Sample # on FR Br ATO sec sec cm cycles 2120-08- 59.74 20.6 10.3 3.1 0 3 12 Before 08 laundry 0 4 14 5 2120-08- 60.7 21.0 10.5 3.2 0 1 14 Before 11 laundry 0 2 10 5 2120-08- 62.6 21.7 10.9 3.3 0 0 7 Before 12 laundry 0 1 6.5 5 2120-08- 56.8 19.7 9.9 3.0 0 2 14 Before 10 laundry 0 2 13 5 C) For a Br:Sb molar ratio of 9:1 i) without TexFRon AG, at an add-on of 28-35%, results are presented in Table 25i:

(85) TABLE-US-00028 TABLE 25i flammability test % After After Char Add- % % % flame Glow Length Laundry Sample # on FR Br ATO sec sec cm cycles 2195-64- 30.2 21.2 10.6 2.1 0 24 13.5 Before 01 laundry 1 20 14.5 5 2195-64- 35.1 24.0 12.0 2.4 0 26 13.5 Before 02 laundry 1 25 15 5 2195-64- 31.9 22.4 11.2 2.3 0 30 12 Before 03 laundry 4 27 17.5 5 2195-64- 27.8 19.6 9.8 2 0 32 13.5 Before 4 laundry 2 24 14 5 2195-64- 32.9 23.2 11.6 2.3 0 26 11.5 Before 05 laundry 1 26 15 5 2195-64- 33.4 23.5 11.8 2.4 0 28 12.5 Before 6 laundry 0 25 15.5 5 ii) with TexFRon AG (50%+50%), at an add-on of 59-69% results are provided in Table 25ii:

(86) TABLE-US-00029 TABLE 25ii flammability test % After After Char Add- % % % flame Glow Length Laundry Sample # on FR Br ATO sec sec cm cycles 2120-12- 59.0 21.0 10.5 2.1 0 2 12 Before 02 laundry 0 2 12.5 5 2120-12- 56.2 20.0 10.0 2.0 0 3 7 Before 03 laundry 0 3 7 5 2120-12- 64.9 23.0 11.5 2.3 0 2 9 Before 07 laundry 0 2 11.5 5 2120-12- 68.9 24.5 12.2 2.5 0 2 11 Before 01 laundry 0 5 15 5 D) For a Br:Sb molar ratio of 12:1 at an add-on of 37-42%, results are presented in Table 26:

(87) TABLE-US-00030 TABLE 26 flammability test % After After Char Add- % % % flame Glow Length Laundry Sample # on FR Br ATO sec sec cm cycles 2195-03- 38.9 28.0 14.0 2.1 0 33 14 Before 02 laundry 2195-03- 38.9 28.0 14.0 2.1 0 24 12.5 5 02 2195-03- 36.8 26.5 13.3 2.0 0 30 13 Before 03 laundry 2195-03- 36.8 26.5 13.3 2.0 0 24 15 5 03 2195-01- 42.2 30.4 15.2 2.3 0 34 15 Before 01 laundry 2195-01- 42.2 30.4 15.2 2.3 0 22 12 5 01 2195-01- 40.1 28.9 14.4 2.2 0 31 13 Before 04 laundry 2195-01- 40.1 28.9 14.4 2.2 0 21 10 5 04 E) For a Br:Sb molar ratio of 15:1 at an add-on of 37-43%, results are presented in Table 27:

(88) TABLE-US-00031 TABLE 27 flammability test % After After Char Add- % % % flame Glow Length Laundry Sample # on FR Br ATO sec sec cm cycles 2195-09- 38.5 28.1 14.1 1.7 0 25 15 Before 01 laundry 2195-09- 38.5 28.1 14.1 1.7 2 15 14 5 01 2195-09- 42.6 31.2 15.6 1.9 0 20 8 Before 02 laundry 2195-09- 42.6 31.2 15.6 1.9 2 14 15 5 02 2195-09- 37.1 27.1 13.5 1.6 0 21 15.5 Before 04 laundry 2195-09- 37.1 27.1 13.5 1.6 BEL 5 04 BEL = burnt entire length F) For a Br:Sb molar ratio of 18:1 at an add-on of 34-42%, results are presented in Table 28:

(89) TABLE-US-00032 TABLE 28 flammability test % After After Char Add- % % % flame Glow Length Laundry Sample # on FR Br ATO sec sec cm cycles 2195-10- 33.8 24.9 12.5 1.3 1 26 16 Before 02 laundry 2195-10- 33.8 24.9 12.5 1.3 BEL 5 02 2195-10- 42.1 31.0 15.5 1.6 3 22 17 Before 03 laundry 2195-10- 42.1 31.0 15.5 1.6 8 28 13 5 03 2195-10- 41 30.2 15.1 1.5 Before 05 laundry 2195-10- 41 30.2 15.1 1.5 6 26 16 5 05 2195-10- 36.1 26.6 13.3 1.3 BEL Before 06 laundry

Example 9

Preparation of Reduced Antimony F-3020 Formulations

(90) F-3020 formulations were prepared as described above in Example 2, having a solid content of about 25-40%, while lowering the Sb:Br molar ratio from 1:3 to 1:9. The various formulations are provided in Table 29:

(91) TABLE-US-00033 TABLE 29 Composition Sample Sample Sample Properties 1 2 3 Dry solids (wt %) 27 27 27 FR (wt %) 15.61 17.9 19.3 Br (wt %) 8.74 10.01 10.9 Sb.sub.2O.sub.3 (wt %) 5.31 3.04 1.6 Sb:Br (molar) 1:3 1:6 1:9 Binder (wt %) 5.25 5.23 5.27 Dispersion Agent 0.83 0.83 0.83 (wt %)

Example 10

Application of Reduced Antimony F-3020 Formulations on a 50/50 Polyester/Cotton Fabric (Padding)

(92) The F-3020 reduced-antimony aqueous dispersions prepared according to Example 9 were applied to 50/50 Polyester/Cotton 200 gr/m.sup.2 by padding. Fabrics were cured at 160 C. for 4 minutes, bone dried and tested. Several replications were tested for the various combinations. Treated fabrics were tested according to ASTM D 6413-08 vertical flame, 12 seconds ignition. At least 3 samples were burned for each test/formulation. Results are provided in Tables 30-32 below: A) For a Br:Sb molar ratio of 3:1 at an add-on of 27-33%, results are presented in Table 30:

(93) TABLE-US-00034 TABLE 30 flammability test % After After Char Add- % % % flame Glow Length Laundry Sample # on FR Br ATO sec sec cm cycles 1979-81- 28.0 16.7 9.3 5.7 0 94 16 Before 01 laundry 0 80 13.5 5 1979-81- 33.2 19.7 11.1 6.7 0 56 13 Before 02 laundry 0 66 15 5 1979-81- 27.4 16.3 9.1 5.5 0 68 14.0 Before 03 laundry 0 58 13.5 5 1979-81- 32.1 19.1 10.7 6.5 0 63 14.5 Before 04 laundry 0 71 14.5 5 B) For a Br:Sb molar ratio of 6:1 at an add-on of 21-33%, results are presented in Table 31:

(94) TABLE-US-00035 TABLE 31 flammability test % After After Char Add- % % % flame Glow Length Laundry Sample # on FR Br ATO sec sec cm cycles 2120-42- 30.3 20.0 11.2 3.4 0 28 14.5 Before 02 laundry 0 10 16.5 5 2120-42- 31.1 20.6 11.5 3.5 0 28 13.5 Before 03 laundry 0 14 13 5 2120-42- 21.2 14.0 7.9 2.4 0 16 13.5 Before 04 laundry 0 13 15.5 5 2120-42- 29.3 19.4 10.9 3.3 0 26 15 Before 05 laundry 0 15 13.5 5 2120-42- 33.3 22.0 12.3 3.7 0 22 14 Before 06 laundry 0 22 14 5 2120-42- 27.4 18.1 10.2 3.1 0 22 17.5 Before 09 laundry 0 22 11.5 5 2120-42- 24.2 16.0 9.0 2.7 0 35 17.5 Before 12 laundry 0 20 17.0 5 C) For a Br:Sb molar ratio of 9:1 at an add-on of 27-33%, results are presented in Table 32:

(95) TABLE-US-00036 TABLE 32 flammability test % After After Char Add- % % % flame Glow Length Laundry Sample # on FR Br ATO sec sec cm cycles 2120-46- 27.1 18.8 10.6 2.1 0 20 14.5 Before 02 laundry 0 20 13 5 2120-46- 25.8 18.0 10.1 2.0 0 21 15.5 Before 03 laundry 0 23 20 5 2120-46- 22.2 15.4 8.6 1.8 0 21 17.5 Before 04 laundry BEL 5 2120-46- 24.6 17.1 9.6 1.9 0 23 17.5 Before 05 laundry 0 23 15 5 2120-46- 20.3 14.2 7.9 1.6 0 26 25 Before 06 laundry BEL 5 2120-46- 36.8 25.6 14.4 2.9 0 20 14 Before 08 laundry 0 22 13 5 2120-46- 28.3 19.7 11.0 2.2 0 18 12 Before 09 laundry 0 18 13 5 BEL = burnt entire length

Example 11

Preparation of ATO-Free and Binder-Free F-2016 or F-3020 Formulations

(96) F-2016 and F-3020 were prepared, similarly to Example 2, but without adding ATO or binder, having a total solid content of about 10-20%. The various formulations are provided in Table 33:

(97) TABLE-US-00037 TABLE 33 Composition Properties F-2016 F-2016 F-3020 F-3020 Dry solids (wt %) 10.42 20.84 10.42 20.84 FR (wt %) 10 20 10 20 Br (wt %) 5 10 5 10

Example 12

Application of MO-Free and Binder-Free F-2016 and F-3020 on a 100% Polyester Fabric (Exhaustion)

(98) 100% PET 229 gr/sqm fabric was padded with the formulation, dried and cured at different conditions to determine whether there is any difference between the reaction products: either 160 C. for 6 minutes, 160 C. for 8 minutes, 180 C. for 4 minutes or (as comparison) 205 C. for 2 minutes.

(99) Samples were examined under SEM with XRD for the cross section. The samples were laundered five times according to AATCC Standard Practice for Home Laundry at 60 C. Results are presented in Table 34 below:

(100) TABLE-US-00038 TABLE 34 % flammability test Dry After After Char Add- % % flame Glow Length Laundry Sample # Curing at: on FR Br sec Sec cm Cycles F- 1979-84-11 160 C. 6 min 7.08 6.8 3.4 0 0 13 Before 2016 laundry 0 0 8 5 1979-84-15 205 C. 2 min 9.55 9.17 4.6 0 0 13 Before laundry 0 0 8 5 F- 1979-84-03 180 C. 4 min 4.19 4.03 2.25 0 0 6 Before 3020 laundry 0 0 10 5 1979-84-07 160 C. 6 min 12.27 11.78 6.6 0 0 12 Before laundry 0 0 8 5

(101) Although the invention has been described in conjunction with specific embodiments thereof, it is evident that many alternatives, modifications and variations will be apparent to those skilled in the art. Accordingly, it is intended to embrace all such alternatives, modifications and variations that fall within the spirit and broad scope of the appended claims. All publications, patents and patent applications mentioned in this specification are herein incorporated in their entirety by reference into the specification, to the same extent as if each individual publication, patent or patent application was specifically and individually indicated to be incorporated herein by reference. In addition, citation or identification of any reference in this application shall not be construed as an admission that such reference is available as prior art to the present invention.