ANTIMONY FREE BROMINATED FLAME RETARDANT SYSTEM FOR TEXTILES

Abstract

The present invention teaches an antimony free brominated flame retardant composition, comprising a brominated flame retardant, an organic phosphorus-containing flame retardant which is an organic phosphate that is either an amorphous solid or a liquid, and a flame retardant which is a source of nitrogen and inorganic phosphorus, this source being amorphous compound. The invention further teaches textile coating formulations comprising these compositions, a process for applying them on textile fabrics, and the flame retarded fabrics coated by these compositions and formulations.

Claims

1.-26. (canceled)

27. A flame retardant composition, comprising: a. A brominated flame retardant, b. An organic phosphorus-containing flame retardant, said organic phosphorus-containing flame retardant being an organic phosphate that is either an amorphous solid or a liquid, c. A flame retardant which is a source of nitrogen and inorganic phosphorus, said source being an amorphous inorganic phosphate salt, wherein said inorganic phosphate salt is Aluminum Ammonium superphosphate; wherein said composition is substantially antimony-free.

28. The composition of claim 27, wherein said organic phosphate is selected from the group comprising of Resorcinol-bis(diphenylphosphate), Tris (2-chloroisopropyl) phosphate, 2-Ethylhexyl Diphenyl Phosphate, and Butylated triphenyl phosphate ester.

29. The composition of claim 27 wherein said brominated flame retardant ranges from 35% to 90% of the total weight of said flame retardant composition.

30. The composition of claim 27 wherein said organic phosphate ranges from 15% to 50% of the total weight of said flame retardant composition.

31. The composition of claim 27 wherein said source of nitrogen and inorganic phosphorus ranges from 10% to 30% of the total weight of said flame retardant composition.

32. The composition of claim 27, being a durable flame retardant composition, wherein said amorphous inorganic phosphate salt is further: non-water soluble at room temperature, and non-hydrolyzable.

33. The composition of claim 27, which is antimony-free.

34. A flame retardant composition, comprising: I. A brominated phosphate ester, II. A flame retardant which is a source of nitrogen and inorganic phosphorus, said source being an amorphous inorganic phosphate salt, wherein said inorganic phosphate salt is Aluminum Ammonium superphosphate, wherein said composition is substantially antimony-free .

35. A substantially antimony-free flame retardant formulation comprising the composition of claim 27, and an aqueous carrier.

36. The flame retardant formulation of claim 35, further comprising one or more additives selected from the group consisting of a flame retardant synergist, a smoldering suppressant agent, a surface active agent, an antifoaming agent, a preservative, a stabilizing agent, a binding agent, a thickening agent, a wetting agent, a suspending agent, a pH buffer, an anti creasing agent, a sequestering agent, a detergent, a dye, a pigment and any mixture thereof.

37. The formulation of claim 35, being in the form of an aqueous dispersion.

38. The formulation of claim 35, which is antimony-free.

39. A textile coated by the formulation of claim 35.

40. A textile flame retarded by the composition of claim 27.

41. A durable textile flame retarded by the composition of claim 32.

42. The textile of claim 39, wherein said textile is a fabric selected from nylon, cotton, polyester, and combinations thereof.

43. The textile of claim 42 which is substantially antimony-free.

44. The textile of claim 43 which is antimony-free.

45. A process of applying the flame retardant formulation of claim 35 onto a flammable textile fabric, the process comprising: a. Contacting the flammable textile fabric with the flame retardant formulation; and b. heating said flammable textile fabric, thereby obtaining a flame retarded textile fabric.

46. The process of claim 45, wherein said heating is conducted at between 140 C. and 180 C.

47. The process of claim 45, wherein said contacting is effected by exhaustion, spreading, coating, padding, dipping, printing, foaming and/or spraying.

Description

EXAMPLES

[0218] Reference is now made to the following examples, which together with the above descriptions, illustrate the invention in a non limiting fashion.

Materials and Analytical Methods

[0219] Materials:

The Following Brominated Polymers Were Obtained From ICL-IP:

[0220] TexFRon 4001 (Tetrabromobisphenol A diglycidyl ether copolymer, CAS Number 68928-70-1) [0221] TexFRon 4002 (2,2-[(1-Methylethylidene)bis[(2,6-dibromo-4,1-phenylene)oxymethylene]]bisoxirane polymer with 2,2,6,6-tetrabromo-4,4-isopropylidenediphenol and 2,4,6-tribromophenol, CAS# 135229-48-0) [0222] TexFRon 9001 (Tetrabromobisphenol A bis (2,3 dibromopropyl ether) CAS# 21850-44-2) [0223] TexFRon P (proprietary polymeric brominated flame retardant) [0224] FR 1410 (Decabromodiphenyl Ethane, CAS# 84852-53-9) [0225] FR 370 (TexFRon 3000, Tris(tribromoneopentyl) phosphate, CAS# 19186-97-1) [0226] SAYTEX BT-93 brominated flame retardant (Ethylenebistetrabromophthalimide, CAS 32588-76-4) was obtained from ALBEMARLE Corp. [0227] Emerald Innovation 1000 brominated flame retardant (Brominated proprietary polymeric) was obtained from Chemtura.

Organic Phosphates Were Obtained From ICL-IP:

[0228] Resorcinol-bis(diphenylphosphate) (RDP, or High Purity RDP, RDP-HP, CAS# 125997-21-9). [0229] Fyrol PCF (Tris (2-chloroisopropyl) phosphate, CAS 13674-84-5). [0230] Phosflex 362 (2-Ethylhexyl Diphenly Phosphate, CAS: 2-ethlhexyl diphenyl phosphate 1241-94-7, Triphenyl phosphate 115-86-6) [0231] Phosflex 71B (Butylated triphenyl phosphate ester, CAS: t-butylphenyl diphenyl phosphate 56803-37-3, bis(t-butylphenyl) phenyl phosphate 65652-41-7, Tri (t-butylphenyl) phosphate 78-33-1, Triphenyl phosphate 115-86-6) [0232] Sol-DP (hydroquinone bis diphenyl phosphate, CAS# 51732-57-1) was obtained from ICL-IP

Source of Nitrogen and Inorganic Phosphorus:

[0233] TexFRon AG (proprietary Aluminum Ammonium Super polyphosphate) was obtained from ICL-IP, and its preparation is described in U.S. Pat. No. 8,524,125. [0234] Ammonium polyphosphate (APP, CAS# 68333-79-9) was obtained from ICL-PPLP. [0235] MPP (Melamine poly phosphate , CAS# 20208-95-1) was obtained from Ciba PLEASE COMPLETE

[0236] Other Materials: [0237] Disperbyk 2010 (dispersing agent) was obtained from BYK Addtives and Instrument. [0238] Supragil WP (wetting agent) was obtained from Rhodia. [0239] CELLOSIZE HEC QP-100MH (thickener) was obtained from DOW. [0240] AC-178 binder and GP acrylic thickening agent were obtained from B. G. Polymers.

Weight Percentage Calculations and Definitions:

[0241] 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, after drying of the formulation on the fabric (deviation of 1%). The weight of the formulation includes the flame retardant weight (% FR) as well as the weight of any other additives, such as surfactants and binder.

[0242] The percentage of total flame retardant in the FR composition (% FR): was calculated by adding the weight percentages of the three FR components: the brominated FR(s) (component 1), the organic phosphate(s) (component 2) and the source of nitrogen and inorganic phosphorus (component 3). For example, in sample 2349-34-02 hereinbelow, the brominated FR (component 1) is BT-93 which is present in an amount of 21.49% by weight; the organic phosphate (component 2) is RDP which is present in an amount of 10.74% by weight; and the source of nitrogen and inorganic phosphorus (component 3) is TexFRon AG which is present in an amount of 3.58% by weight. Thus, the total % FR is 35.81% by weight.

[0243] The difference between % add-on and % FR: In all of the examples, there is a few percentage difference between the % add-on and the % FR. This difference reflects the total weight of the any other additives, such as surfactants and binder. For example, in the previous example, the % add-on was 40.71%, while the total % FR was 35.81%. Thus, the 4.9% difference reflects the weight of the surfactant and binder within the dry formulation.

[0244] The bromine content on the fabric (% Br) was calculated using the % FR, and knowing the weight ratio of bromine atoms for each brominated FR. For example, if the brominated FR is TexFRon 4002 (2,2-[(1-Methylethylidene)bis[(2,6-dibromo-4,1-phenylene)oxymethylene]]bisoxirane polymer with 2,2,6,6-tetrabromo-4,4-isopropylidenediphenol and 2,4,6-tribromophenol), the weight % of bromine within the FR molecule is 56%. Therefore, in sample 2349-03-08, the FR-4002 FR content was 30.77% weight, and hence the % bromine was calculated by multiplying this number by 0.56 to obtain 17.2% bromine.

[0245] The bromine % of several commonly used FRs is provided in the table below:

TABLE-US-00001 FR % bromine (weight) BT-93 67 TexFRon 4002 56 TexFRon 4001 50 TexFRon 9001 68 TexFRon P 19 TexFRon 3000 (FR 370) 70 FR 1410 82 Emerald Innovation 1000 78 FR-122P 65 FR 803 66 FR 1025 71

[0246] The organic Phosphorus content on the fabric (% OP) was calculated using the % of the organic phosphate as part of the % FR, and knowing the weight ratio of phosphorus atoms for each organic phosphate. For example, if the organic phosphate is Resorcinol-bis(diphenylphosphate) (RDP), the weight % of phosphorus within the organic phosphate molecule is 10.8%. Therefore, in sample 2349-03-08, the RDP content was 15.03% weight, and hence the % organic phosphate was calculated by multiplying this number by 0.108 to obtain 1.61% organic phosphate.

[0247] The organic phosphorus % of several commonly used organic phosphates is provided in the table below:

TABLE-US-00002 FR % OP (weight) RDP 10.8 Fyrol PCF 9.5 Phosflex 362 8.5 Phosflex 71B 8.5

[0248] The inorganic Phosphorus content on the fabric (% INP) was calculated using the % of the inorganic phosphorus as part of the % FR, and knowing the weight ratio of phosphorus atoms for each inorganic phosphorus component. For example, if the source of nitrogen and inorganic phosphorus is TexFRon AG, the weight % of phosphorus within the TexFRon AG molecule is 21%. Therefore, in sample 2349-03-08, the TexFRon AG content was 6.26% weight, and hence the % source of nitrogen and inorganic phosphorus was calculated by multiplying this number by 0.21 to obtain 1.31% source of nitrogen and inorganic phosphorus.

[0249] The inorganic phosphorus % (% IPN) of several suitable sources of nitrogen and inorganic phosphorus is provided in the table below:

TABLE-US-00003 FR % IPN (weight) TexFRon AG 21 MPP 30 APP 31-32

Textile Flammability Tests:

[0250] 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, and its after glow time is less than 150 seconds, so as to render the sample applicable even in the stricter children's nightwear flammability standards.

Textile Washing Fastness Tests:

[0251] Samples treated with formulations described herein were subjected to 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).

[0252] 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 a TexFRon 4002 Dispersion

[0253] TexFRon 4002 (100 grams) having a size distribution of d.sub.50<5 micron d.sub.90<15 micron d.sub.99<35 micron, was added to a mixed solution of deionized water (104 grams), dispersing agent Disperbyk 2010 (4 grams) and wetting agent Supragil WP (0.4 grams). The dispersion was allowed to mix for fifteen minutes and an acrylic binder AC-178 (25 grams) was added to the mixed dispersion and the dispersion was allowed to mix for fifteen minutes and thickened by adding a small amount of hydroxyethylcellulose (0.3 grams). The composition of the dispersion is detailed in Table 1 below:

[0254] Formulation quantities are provided for 100gr TexFRon 4002, at 50% solids content by weight:

TABLE-US-00004 TABLE 1 Component Amount [grams] Remarks Water 104.0 Dispersion agent 4.0 4% relative to active (surfactant) ingredient (FR) Wetting agent 0.40 10% relative to surfactant TexFRon 4002 100.0 (brominated FR) AC-178 binder 25.0 25% relative to active ingredient (FR)

Example 2

Preparation of a TexFRon AG Dispersion (Source of Nitrogen and Inorganic Phosphorus)

[0255] TexFRon AG (100 grams) having a size distribution of d50<5 micron d90<15 micron d99<35 micron, was added to a mixed solution of deionized water (104 grams), dispersing agent Disperbyk 2010 (4 grams) and wetting agent Supragil WP (0.4 grams). The dispersion was allowed to mix for fifteen minutes and an acrylic binder AC-178 (25 grams) was added to the mixed dispersion and the dispersion was allowed to mix for fifteen minutes and thickened by adding a small amount of hydroxyethylcellulose (0.3 grams). The composition of the dispersion is detailed in Table 2 below:

[0256] Formulation quantities are provided for 100gr TexFRon AG, at 50% solids content by weight:

TABLE-US-00005 TABLE 2 Component Amount [gr] Remarks Water 104.0 Dispersion agent 4.0 4% relative to active (surfactant) ingredient (FR) Wetting agent 0.40 10% relative to surfactant TexFRon AG (source 100.0 of nitrogen and inorganic phosphorus) Binder AC-178 25.0 25% relative to active ingredient (TexFRon AG)
The same process was repeated for preparing the other tested source of nitrogen and inorganic phosphorus, such as ammonium polyphosphate (APP) and melamine polyphosphate (MPP).

Example 3

Preparation of RDP Dispersion (Organic Phosphate)

[0257] Resorcinol-bis(diphenylphosphate) (RDP, 100 grams) was added to a mixed solution of deionized water (104 grams), dispersing agent Disperbyk 2010 (4 grams) and wetting agent Supragil WP (0.4 grams). The dispersion was allowed to mix for fifteen minutes and an acrylic binder AC-178 (25 grams) was added to the mixed dispersion and the dispersion was allowed to mix for fifteen minutes and thickened by adding a small amount of hydroxyethylcellulose (0.3 grams). The composition of the dispersion is detailed in Table 3 below:

[0258] Formulation quantities are provided for 100gr of RDP-HP, at 50% solids content by weight:

TABLE-US-00006 TABLE 3 Component Amount [gr] Remarks Water 104.0 Dispersion agent 4.0 4% relative to active (surfactant) ingredient (FR) Wetting agent 0.40 10% relative to surfactant RDP (organic 100.0 phosphate) Binder AC-178 25.0 25% relative to active ingredient (RDP FR)
The same process was repeated for preparing the other organic phosphates, such as Fyrol PCF (Tris (2-chloroisopropyl) phosphate, CAS 13674-84-5), Phosflex 362 (2-Ethylhexyl Diphenly Phosphate, CAS: 2-ethlhexyl diphenyl phosphate 1241-94-7, Triphenyl phosphate 115-86-6), Phosflex 71B (Butylated triphenyl phosphate ester, CAS: t-butylphenyl diphenyl phosphate 56803-37-3, bis(t-butylphenyl) phenyl phosphate 65652-41-7, Tri (t-butylphenyl) phosphate 78-33-1, Triphenyl phosphate 115-86-6) and Sol-DP (hydroquinone bis diphenyl phosphate).

Example 4

Preparation of a Brominated FR Dispersions

[0259] TexFRon 9001 or any of the other brominated FRs listed in table 5 below (100 grams) having a size distribution of d.sub.50<5 micron d.sub.90<15 micron d.sub.99<35 micron, was added to a mixed solution of deionized water (104 grams), dispersing agent Disperbyk 2010 (4 grams) and wetting agent Supragil WP (0.4 grams). The dispersion was allowed to mix for fifteen minutes and an acrylic binder AC-178 (25 grams) was added to the mixed dispersion and the dispersion was allowed to mix for fifteen minutes and thickened by adding a small amount of hydroxyethylcellulose (0.3 grams). NOTE: TexFRon P was used as received. The composition of the dispersion is detailed in Table 4 below:

[0260] Quantities are provided for a 100gr formulation, at 50% solids content by weight.

TABLE-US-00007 TABLE 4 Component Amount [gr] Remarks Water 104.0 Dispersion agent 4.0 4% relative to active ingredient (FR) Wetting agent 0.40 10% relative to surfactant Brominated FR 100.0 binder 25.0 25% relative to active ingredient (FR)

Example 5

Preparation of Combined FR Formulations

[0261] TexFRon 4002 and other Brominated Flame Retardant (BFRs) were combined with an organic phosphate, such as RDP-HP and an source of nitrogen and inorganic phosphorus, such as TexFRon AG at different weight ratios and the dispersion was allowed to mix for fifteen minutes and thickened by adding a small amount of hydroxyethylcellulose (0.3 grams). The formulations were all stable, flowed smoothly and did not settle.

[0262] The various formulations that were prepared are summarized in Table 5:

TABLE-US-00008 TABLE 5 Organic Inorganic Brominated % Phosphate % P & N source % Formulation FR (BFR) BFR (OP) OP (IPN) IPN #1a 4002 80% RDP 20% 0 comparative #1b 0 RDP 50% TexFRon AG 50% comparative #1c 4001 50% 0 TexFRon AG 50% Comparative Incl. ATO #1d 3000 100% * * 0 comparative #1e 4002 60% Sol-DP 30% TexFRon AG 10% comparative #2 4002 60% RDP 30% TexFRon AG 10% #3 9001 60% RDP 30% TexFRon AG 10% #4 1410 60% RDP 30% TexFRon AG 10% #5 4002 50% RDP 30% TexFRon AG 20% #6 4002 38% RDP 38% TexFRon AG 24% #7 4002 35% RDP 42% TexFRon AG 23% #8 4002 75% RDP 15% TexFRon AG 10% #9 TexFRon P 60% RDP 30% TexFRon AG 10% #10 4001 60% RDP 30% TexFRon AG 10% #11 BT-93 60% RDP 30% TexFRon AG 10% #12 Emerald 1000 60% RDP 30% TexFRon AG 10% #13 4002 60% Phosflex 362 30% TexFRon AG 10% #14 4002 60% Phosflex 71B 30% TexFRon AG 10% #16 4002 60% RDP 30% APP 10% #17 4002 60% RDP 30% MPP 10% #18 3000 .sup.90% * * * TexFRon AG 10% * includes both brominated FR and Organic phosphate in the same molecule

Example 6

Application of FR Formulations to 35%/65% Cotton/Polyester Woven Fabric

[0263] Fabrics were treated using a pad-squeeze-cure process. A 35%/65% cotton polyester woven 192 grams/m.sup.2 fabric was padded with the formulations of Example 5, achieving a 35-60% dry add-on. 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. [0264] A) 60% TexFRon 4002+30% RDP+10% TexFRon AG (formulation # 2, Table 5)

TABLE-US-00009 TABLE 6 flammability test After After Char flame Glow Length Sample # % add-on % FR % Br % OP % IPN sec sec cm 2349-03-07 48.05 RDP-12.2% 14.2 1.31 1.07 0 0 15 4002-24.98% AG-5.08% 2349-03-08 59.17 RDP-15.03% 17.2 1.61 1.31 0 0 14.5 4002-30.77% AG-6.26% 2349-03-09 54.75 RDP %-13.9 15.9 1.49 1.22 0 0 14 4002-28.46% AG-5.79% 2349-03-10 48.93 RDP %-12.43 14.2 1.33 1.09 0 0 15.5 4002 25.44% AG 5.17% 2346-84-09 35.66 RDP-10.23% 10.3 1.09 0.57 0 0 15.5 4002-18.41% AG-2.73% 2346-84-10 37.93 RDP10.-88% 10.9 1.16 0.61 0 0 15.5 4002-19.58% AG-2.90% 2346-84-11 37.17 RDP-10.66% 10.7 1.14 0.60 0 0 16 4002-19.19% AG-2.84% [0265] B) 60% FR 1410+30%RDP+10% TexFRon AG (formulation # 4, Table 5)

TABLE-US-00010 TABLE 7 flammability test After After Char flame Glow Length Sample # % add-on % FR % Br % OP % IPN sec sec cm 2349-18-08 35.91% 1410-18.54% 15.20% 1.10% 0.58% 0 0 10 RDP-10.30% AG-2.75% 2349-18-09 39.07% 1410-20.17% 16.54% 1.20% 0.63% 0 0 15 RDP-11.21% AG-2.99% 2349-18-10 38.25% 1410-19.75% 16.19% 1.17% 0.61% 0 0 10.5 RDP-10.97% AG-2.93% 2349-18-11 40.33% 1410-20.82% 17.07% 1.24% 0.65% 0 0 18 RDP-11.75% AG-3.08% 2349-18-12 38.12% 1410-19.68% 16.14% 1.17% 0.61% 0 0 12 RDP-10.93% AG-2.92% 2349-18-13 39.07% 1410-20.17% 16.54% 1.20% 0.63% 0 0 12 RDP-11.21% AG-2.99% 2349-18-14 37.17% 1410-19.19% 15.74% 1.14% 0.60% 0 0 10 RDP-10.66% AG-2.84% [0266] C) 60% TexFRon 9001+30%RDP+10% TexFRon AG (formulation # 3, Table 5)

TABLE-US-00011 TABLE 8 flammability test After After Char flame Glow Length Sample # % Add-on % FR % Br % OP % IPN sec sec cm 2349-14-06 41.41% 9001-21.38% 14.54% 1.27% 0.67% 0 0 12 RDP-11.88% AG-3.17% 2349-14-07 41.79% 9001-21.57% 14.67% 1.28% 0.67% 0 0 11.5 RDP-11.98% AG-3.20% 2349-08-05 44.38 RDP-12.73% 15.5 1.36 0.71 0 0 14.5 9001-22.85% AG-3.39% 2349-08-06 45.08 RDP-12.93% 15.8 1.38 0.72 0 0 15 9001-23.21% AG-3.45% 2349-08-07 45.52 RDP-13.05% 15.9 1.40 0.73 0 0 14.5 9001-23.44% AG-3.48% 2349-08-08 46.09 RDP-13.22% 11.2 1.41 0.74 0 0 14 9001-23.73% AG-3.52% [0267] D) 60% TexFRon P+30% RDP+10% TexFRon AG (formulation 9, Table 5)

TABLE-US-00012 TABLE 9 Flammability Test After After Char Flame Glow Length Sample # % Add-on % FR % Br % OP % IPN (sec) (sec) (cm) 2349-23-05 43.50 P-26.10% 4.41 1.23 0.80 0 0 15.5 RDP-11.48% AG-3.83% 2349-23-06 42.80 P-25.68% 4.34 1.21 0.79 0 0 9.5 RDP-11.29% AG-3.76% 2349-23-07 40.90 P-24.54% 4.14 1.15 0.76 0 0 10.4 RDP-10.79% AG-3.60% 2349-23-08 42.10 P-25.26% 4.27 0.19 0.78 0 0 17.5 RDP-11.11% AG-3.70% [0268] E) 60% BT-93+30% RDP+10% TexFRon AG (formulation 11 in Table 5)

TABLE-US-00013 TABLE 10 Flammability Test After After Char Flame Glow Length Sample # % add-on % FR % Br % OP % IPN (sec) (sec) (cm) 2349-34-01 41.73 BT-93-22.02% 16.7 1.18 0.77 0 0 13 RDP-11.01% AG-3.67% 2349-34-02 40.71 BT-93-21.49% 15.68 1.15 0.75 0 0 13.5 RDP-10.74% AG-3.58% 2349-34-03 40.59 BT-93-21.42% 15.64 1.15 0.75 0 0 14 RDP-10.71% AG-3.57% 2349-34-04 42.74 BT-93-22.55% 16.46 1.21 0.79 0 0 14 RDP-11.28% AG-3.76% [0269] F) 60% Emerald 1000+30% RDP+10% TexFRon AG (formulation 12 in Table 5)

TABLE-US-00014 TABLE 11 Flammability Test After After Char Flame Glow Length Sample # % add on % FR % Br % OP % IPN (sec) (sec) (cm) Remarks 2349-37-01 33.57 Emerald 1000-17.72% 14.53 0.95 0.62 0 0 12 smoke RDP-8.86% AG-2.95% 2349-37-02 36.16 Emerald 1000-19.08% 15.65 1.02 0.67 0 0 8 smoke RDP-9.54% AG-3.18% 2349-37-03 31.55 Emerald 1000-16.65% 13.65 0.89 0.58 0 0 15 smoke RDP-8.32% AG-2.77% 2349-37-04 32.75 Emerald 1000-17.28% 14.17 0.92 0.60 0 0 13.5 smoke RDP-8.64% AG-2.88% [0270] G) 60% TexFRon 4002+30% Phosflex 362+10% TexFRon AG (formulation 13 in Table 5)

TABLE-US-00015 TABLE 12 Flammability Test After After Char Flame Glow Length Sample # % add-on % FR % Br % OP % IPN (sec) (sec) (cm) 2349-40-12 40.97 4002-21.62% 12.11 0.92 0.76 0 0 6.5 Phosflex362-10.81% AG-3.60% 2349-40-13 39.70 4002-20.95% 11.73 0.89 0.73 0 0 12.5 Phosflex362-10.48% AG-3.49% 2349-40-14 40.97 4002-21.62% 12.11 0.92 0.76 2 0 13 Phosflex362-10.81% AG-3.60% [0271] H) 60% TexFRon 4002+30% Phosflex 71B+10% TexFRon AG (formulation 14 in Table 5)

TABLE-US-00016 TABLE 13 Flammability Test After After Char Flame Glow Length Sample # % add-on % FR % Br % OP % IPN (sec) (sec) (cm) 2349-43-01 39.64 4002-20.92% 11.71 0.89 0.73 0 0 15 71B-10.46% AG-3.49% 2349-43-02 39.39 4002-20.78% 11.64 0.88 0.73 0 0 12 71B -10.39% AG-3.46% 2349-43-03 34.58 4002-18.25% 10.22 0.78 0.64 0 0 14 71B -9.12% AG-3.04% [0272] I) 60% TexFRon 4001+30% RDP+10% TexFRon AG (formulation 10 in Table 5)

TABLE-US-00017 TABLE 14 Flammability Test After After Char Flame Glow Length Sample # % add-on % FR % Br % OP % IPN (sec) (sec) (cm) 2349-22-04 40.90 4001-21.59% 10.79 1.15 0.76 0 0 17.5 RDP-10.79% AG-3.60% 2349-22-05 42.67 4001-22.52% 11.26 1.20 0.79 0 0 13.5 RDP-11.26% AG-3.75% 2349-22-06 39.89 4001-21.05% 10.53 1.13 0.74 0 0 18.5 RDP-10.53% AG-3.51

Example 7

Application of FR Formulations to 50%/50% Cotton Polyester Knit Fabric

[0273] Fabrics were treated using a pad-squeeze-cure process. A 50%/50% cotton polyester knit 205 grams/m.sup.2 fabric was padded with the formulations of Example 5, achieving a 35-60% dry add-on. 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. [0274] A) 60% TexFRon 4002, 30% RDP, 10% TexFRon AG (formulation # 2, Table 5)

TABLE-US-00018 TABLE 16 flammability test After After Char flame Glow Length Sample # % add-on % FR % Br % OP % IPN sec sec cm 2346-81-02 43.7 RDP %11.36- 13.02 1.22 0.79 0 0 14 4002-%23.25 AG-3.78% 2346-81-03 45.5 RDP11.84-% 13.57 1.27 0.83 0 0 16 4002-%24.23 AG-3.94% 2346-81-04 49.6 RDP12.9%- 14.79 1.38 0.9 0 0 7.5 4002-%26.41 AG-4.30% 2346-81-05 41.1 RDP10.7%- 12.27 1.14 0.75 0 0 13 4002 %21.9 AG 3.56% 2346-81-06 49.7 RDP12.92%- 14.81 1.38 0.9 0 0 14 4002 %26.45 AG 4.3% 2346-84-01 32.85 RDP-%9.42 9.50 1.01 0.53 BEL 4002-%16.96 AG-2.51% 2346-84-02 32.31 RDP9.27-% 9.34 0.99 0.52 BEL 4002-%16.68 AG-2.47% 2346-84-03 33.95 RDP-9.74% 9.81 1.04 0.55 2 2 16 4002-17.52% AG-2.60% 2346-84-04 33.67 RDP-9.66% 9.74 1.03 0.54 BEL 4002 17.38% AG 2.58% 2346-84-05 36.47 RDP-10.46% 10.54 1.12 0.59 0 0 16 4002 18.83% AG-2.79% 2346-84-16 34.63 RDP-9.93% 10.01 1.06 0.56 0 0 16 4002 17.88% AG-2.65% 2346-84-17 40.57 RDP-11.64% 11.73 1.24 0.65 0 0 15 4002 20.94% AG-3.10% BEL = burnt entire length. [0275] B) 60% TexFRon P+30% RDP+10% TexFRon AG (formulation 9 in table 5)

TABLE-US-00019 TABLE 17 Flammability Test After After Char % add- Flame Glow Length Sample # on % Br % OP % IPN (sec) (sec) (cm) 2349-22-07 51.20 13.51 1.44 0.94 0 0 8 2349-22-08 45.94 12.12 1.29 0.84 0 0 11 2349-22-09 48.23 12.73 1.36 0.88 0 0 9.5 [0276] C) 60% TexFRon 4001+30% RDP+10% TexFRon AG (formulation 10 in Table 5)

TABLE-US-00020 TABLE 18 Flammability Test After After Char Flame Glow Length Sample # % add-on % FR % Br % OP % IPN (sec) (sec) (cm) 2349-22-07 51.20 4001-27.02 13.51 1.45 0.95 0 0 8 RDP-13.51% AG-4.5% 2349-22-08 45.94 4001-24.24% 12.12 1.30 0.85 0 0 11 RDP-12.12% AG-4.04% 2349-22-09 48.23 4001-25.24% 12.73 1.36 0.89 0 0 9.5 RDP-12.73% AG-4.24% [0277] D) Comparative example: 60% TexFRon 4002+30%RDP-HP, 10% ammonium polyphosphate (APP) (formulation 16 in Table 5). All samples before laundry.

TABLE-US-00021 TABLE 19 Flammability Test After After Char Flame Glow Length Sample # % add-on % FR % Br % OP % IPN (sec) (sec) (cm) 2233-19-04 41.89 4002-29.69% 16.6 1.77 1.32 0 3 9 RDP-16.5% APP-4.4% 2233-19-05 49.28 4002-34.93% 19.56 2.08 1.55 0 2 10 RDP-19.41% APP-5.18% 2233-19-06 31.54 4002-22.36% 12.52 1.33 0.99 0 2 11 RDP-12.42% APP-3.3% 2233-19-07 37.46 4002-26.65% 14.87 1.58 1.18 0 2 11 RDP- 14.75% AG-3.93% [0278] E) 60% TexFRon 4002+30%RDP-HP, 10% melamine polyphosphate (MPP) (formulation 17 in Table 5)

TABLE-US-00022 TABLE 20 Flammability Test After After Char Flame Glow Length Sample # % add-on % FR % Br % OP % IPN (sec) (sec) (cm) Remarks 2233-20-02 31.54 4002-22.3% 12.34 1.31 0.98 0 2 10 Before RDP-12.03% laundry MPP-3.2% 0 2 9 After 5 laundries 2233-20-03 42.38 4002-29.6% 16.58 1.76 1.32 0 2 10 Before RDP-16.45% laundry MPP-4.39 0 2 11 After 5 laundries 2233-20-04 55.93 4002-39% 21.8 2.32 1.74 0 2 10 Before RDP-21.7% laundry MPP-5.79% 0 2 9 After 5 laundries 2233-20-05 33.52 4002-23.4% 13.1 1.39 1.04 0 2 11 Before RDP- 13% laundry MPP-3.47% BEL After 5 laundries 2233-20-06 36.96 4002-25.82% 14.46 1.53 1.15 0 2 11 Before RDP-14.34% laundry MPP-3.82% 0 2 11 After 5 laundries

Example 8

Application of FR Formulations to a 50%/50% Cotton Polyester (Woven) Fabric

[0279] Fabrics were treated using a pad-squeeze-cure process. A 50%/50% cotton polyester woven 175 grams/m.sup.2 fabric was padded with the formulations of Example 5, achieving a 33-65% dry add-on. 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. [0280] A) 38% TexFRon 4002+38% RDP+24% TexFRon AG (formulation # 6, Table 5) before and after laundry

TABLE-US-00023 TABLE 21 Flammability Test After After Char Flame Glow Length Sample # % add-on % FR % Br % OP % IPN (sec) (sec) (cm) Remarks 2346-95-01 52.74 4002-20.47% 11.46 2.19 1.15 0 0 13 Before RDP-20.47% laundry AG-5.46% 0 0 13 After 5 laundries 2346-95-02 53.5 4002-20.75% 11.62 2.22 1.16 0 0 16.5 Before RDP-20.75% laundry AG-5.53% 0 0 12.8 After 5 laundries 2346-95-03 50.46 4002-19.58% 10.96 2.09 1.10 0 0 11 Before RDP-19.58% laundry AG-5.22% 1 0 10.6 After 5 laundries 2346-95-04 57.09 4002-22.15% 12.40 2.37 1.24 0 0 13 Before RDP-22.15% laundry AG-5.91% 1 0 9.8 After 5 laundries 2346-95-05 64.63 4002-25.08% 14.04 2.68 1.40 0 0 13 Before RDP-25.08% laundry AG-6.69% 1 0 12 After 5 laundries 2346-95-06 59.32 4002-23.02% 12.89 2.46 1.29 0 0 12 Before RDP-23.02% laundry AG-6.14% 2 0 11 After 5 laundries [0281] B) 60% FR 9001+30%RDP+10% TexFRon AG (formulation #3 in Table 5)

TABLE-US-00024 TABLE 22 flammability test After After Char flame Glow Length Sample # % add-on % FR % Br % OP % IPN sec sec cm 2349-14-03 35.93% 9001-18.35% 12.61% 1.10% 0.58% 0 0 16 RDP-10.30% AG-2.75% 2349-14-04 36.41% 9001-18.79% 12.78% 1.12% 0.58% 0 0 15 RDP-10.44% AG-2.78% 2349-18-05 36.20% 9001-18.69% 12.71% 1.11% 0.58% 0 0 14.5 RDP-10.38% AG-2.77% [0282] C) 60% FR 1410+30% RDP+10% TexFRon AG 50%/50% cotton polyester (woven) (formulation # 4, Table 5)

TABLE-US-00025 TABLE 23 flammability test After After Char flame Glow Length Sample # % add-on % FR % Br % OP % IPN sec sec cm 2349-18-01 36.34% 1410-18.76% 15.38% 1.12% 0.58% 0 0 13.5 RDP-10.42% AG-2.78% 2349-18-02 34.63% 1410-17.88% 14.66% 1.06% 0.56% 0 0 18.5 RDP-9.93% AG-2.65% 2349-18-03 34.15% 1410-17.63% 14.46% 1.05% 0.55% 0 0 16 RDP-9.79% AG-2.61% 2349-18-04 34.02% 1410-17.56% 14.40% 1.04% 0.55% 0 0 21.4 RDP-9.76% AG-2.60% 2349-18-05 36.06% 1410-18.62% 15.27% 1.11% 0.58% 0 0 13 RDP-10.34% AG-2.76% 2349-18-06 33.27% 1410-17.17% 14.08% 1.02% 0.53% 0 0 13 RDP-9.54% AG-2.54% 2349-18-07 33.02% 1410-17.14% 14.05% 1.02% 0.53% 0 0 18 RDP-9.52% AG-2.54% [0283] D) 60% TexFRon P+30% RDP+10% TexFRon AG (formulation 9 in Table 5) was tested and passed the flammability tests at an add-on of 40.9%. [0284] E) 60% TexFRon 4001+30% RDP+10% TexFRon AG (formulation 10 in Table 5) was tested and only succeeded at an add-on of 39%. [0285] F) 60% BT-93+30% RDP+10% TexFRon AG (formulation 11 in Table 5 was tested and only succeeded at an add-on of 34.6%. [0286] G) 60% Emerald 1000+30% RDP+10% TexFRon AG (formulation 12 in Table 5) was tested and only succeeded at an add-on of 31.5%. [0287] H) 60% TexFRon 4002+30% Phosflex 362+10% TexFRon AG (formulation 13 in Table 5)

TABLE-US-00026 TABLE 24 Flammability Test After After Char Flame Glow Length Sample # % add-on % FR % Br % OP % IPN (sec) (sec) (cm) 2349-40-09 34.49 4002-18.20% 10.19 0.77 0.64 0 0 13 Phosflex 362-9.10% AG-3.03% 2349-40-10 33.81 4002-17.84% 9.99 0.76 0.62 0 0 17 Phosflex 362-8.92% AG-2.97% 2349-40-11 35.11 4002-18.53% 10.38 0.79 0.65 0 0 19 Phosflex362-9.26% AG-3.09% [0288] I) 60% TexFRon 4002+30% Phosflex 71B+10% TexFRon AG (formulation 14 in Table 5)

TABLE-US-00027 TABLE 25 Flammability Test After After Char Flame Glow Length Sample # % add-on % FR % Br % OP % IPN (sec) (sec) (cm) 2349-43-04 37.16 4002-19.61% 10.98 0.83 0.69 0 0 15.5 71B -9.80% AG-3.27% 2349-43-05 32.45 4002-17.12% 9.59 0.73 0.60 3 0 19 71B -8.56% AG-2.85% 2349-43-06 34.49 4002-18.20% 10.19 0.77 0.64 0 0 13 71B -9.10% AG-3.03% [0289] J) 90% TexFRon 3000 (FR-370 containing an organic phosphate)+10% TexFRon AG (formulation 18 in Table 5)

TABLE-US-00028 TABLE 26 Flammability Test After After Char Flame Glow Length Sample # % add-on % FR % Br % OP (sec) (sec) (cm) Remarks 2143-61-01 61.7 28.73 20.11 0.86 0 46 9.5 Before laundry 0 49 12 After 5 laundry cycles 2143-61-02 53.17 24.74 17.32 0.74 0 22 7.0 Before laundry 2 30 14 After5 laundry cycles 2143-61-03 56.11 26.11 18.28 0.78 0 11 9.0 Before laundry 1 25 10 After 5 laundry cycles 2143-61-04 55.82 25.98 18.19 0.78 0 31 11.2 Before laundry 0 30 12 After 5 laundry cycles 2143-61-05 55.82 25.98 18.19 0.78 0 26 9 Before laundry 0 30 12 After 5 laundry cycles

Example 9

Application of Mixed Formulation to 100% Cotton Fabric (KNIT)

[0290] The mixed formulation # 7 prepared according to the process of Example 5, was applied on a 100% cotton fabric (KNIT). The results are presented in Table 27 below.

TABLE-US-00029 TABLE 27 Flammability Test After After Char Flame Glow Length Sample # % add-on % FR % Br % OP % IPN (sec) (sec) (cm) 2346-89-10 77.27% 4002-36.15% 20.25% 2.69% 1.41% 1 0 17 RDP-25.11% AG-6.70% 2346-89-11 80.05% 4002-37.45% 20.97% 2.78% 1.46% 1 0 12.5 RDP-26.01% AG-6.94% 2346-89-12 84.99% 4002-39.77% 22.27% 2.96% 1.55% 0 0 11.5 RDP-27.62% AG-7.36% 2346-96-05 54.57% 4002-19.21% 10.76% 2.47% 2.58% 0 0 15 RDP-23.06% AG-12.30% 2346-96-06 60.83% 4002-21.42% 11.99% 2.75% 1.83% 0 2 12.7 RDP-25.70% AG-13.71%

Example 10

Application of FR Formulations to a 50%/50% Cotton Nylon (NyCo Fabric, Woven)

[0291] Fabrics were treated using a pad-squeeze-cure process. A 50%/50% cotton nylon woven fabric (NyCo military fabric) was padded with some formulations of Table 5, achieving a range 40-50% dry add-on. In one case (see item A below) the fabric was pretreated with a first layer of 35% RDP to increase softness, and was then coated with the stated ratios of the ternary system as detailed in the table. In another case (see item B below) the fabric was treated with a single coating of the antimony free ternary system.

[0292] Fabrics were cured at 145 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. Fabrics passed flammability test before and after 30 laundries. [0293] A) 75% TexFRon 4002+15% RDP+10% TexFRon AG (formulation 8 in Table 5)

TABLE-US-00030 TABLE 28 Flammability Test After After Char Flame Glow Length Sample # % add-on % Br % IPN (sec) (sec) (cm) Remarks 2233-13-01 47.27 9.22 2.23 0 0 6 Before laundry 0 0 7 After 30 laundry cycles 2233-13-02 49 10.26 2.29 0 0 6 Before laundry 0 0 8 After 30 laundry cycles 2233-13-03 48.49 10 2.28 0 0 7 Before laundry 0 0 6 After 30 laundry cycles 2233-13-04 47.75 9.88 2.28 0 0 6 Before laundry 0 0 7 After 30 laundry cycles 2233-13-05 49.86 10.45 2.3 0 0 6 Before laundry 0 0 6 After 30 laundry cycles [0294] B)60% TexFRon 4002+30% RDP+10% TexFRon AG (formulation # 2, Table 5)

TABLE-US-00031 TABLE 29 Flammability Test After After Char Flame Glow Length Sample # % add-on % FR % Br % OP % IPN (sec) (sec) (cm) 2346-98-01 34.49% 4002-17.80% 9.77% 1.06% 0.55% 0 0 13 RDP-9.89% AG-2.64% 2346-98-02 34.99% 4002-18.06% 10.12% 1.07% 0.56% 0 0 12 RDP-10.04% AG-2.68% 2346-98-03 34.54% 4002-17.83% 9.99% 1.06% 0.55% 0 0 13 RDP-9.91% AG-2.64% 2346-98-04 33.70% 4002-17.40% 9.74% 1.03% 0.54% 0 0 11 RDP-9.66% AG-2.58% 2346-98-05 35.27% 4002-18.21% 10.20% 1.08% 0.57% 0 0 13 RDP-10.12% AG-2.70% 2346-98-06 34.71% 4002-17.92% 10.03% 1.07% 0.56% 0 0 13 RDP-9.95% AG-2.65%

Example 11

Multilayer Application of Ternary Antimony-Free FR Formulations on a 100% Nylon Fabric

[0295] A Mathis coating machine (knife over roll) was used to backcoat the test fabrics, weighting 330 grams/m.sup.2. Two or three passes on one side with intermediate curing at 160 C. in the Mathis forced air oven were required to obtain the desired add-on using a single layer or multiple layers.

[0296] A) RDP as 1.sup.st Layer and Two Layers of Formulation 8: [0297] First layer was RDP, 50% solids dispersion alone and then 2 layers of the ternary system with ratio: RDP 15%, AG 10%, 4002 75% (formulation # 8). Add on was between 41-62%. Fabrics passed flammability test before and after 6 laundries cycles. Hand was good.

TABLE-US-00032 TABLE 30 Flammability Test After After Char Flame Glow Length Sample # % add-on % Br % OP % IPN (sec) (sec) (cm) Remarks 2349-79-01 50.48 10.4 1.35 0.52 2 2 9 Before laundry 0 0 7 After 6 laundry cycles 2349-79-02 62.05 14.49 2.55 0.72 0 0 6 Before laundry 0 0 6 After 6 laundry cycles 2349-79-03 41.45 8.27 1.26 0.41 2 2 9 Before laundry 0 0 6 After 6 laundry cycles [0298] B) Single layer of 90% TexFRon 3000(FR-370 containing an organic phosphate)+10% TexFRon AG (formulation 18 in Table 5)

TABLE-US-00033 TABLE 31 Flammability Test After After Char Flame Glow Length Sample # % Add-on % FR % Br % IPN (sec) (sec) (cm) Remarks 2143-61-01 61.7 28.73 20.11 0.86 0 46 9.5 Before laundry 0 49 12 After 5 laundry cycles 2143-61-02 53.17 24.74 17.32 0.74 0 22 7.0 Before laundry 2 30 14 After 5 laundry cycles 2143-61-03 56.11 26.11 18.28 0.78 0 11 9.0 Before laundry 1 25 10 After 5 laundry cycles 2143-61-04 55.82 25.98 18.19 0.78 0 31 11.2 Before laundry 0 30 12 After 5 laundry cycles 2143-61-05 55.82 25.98 18.19 0.78 0 26 9 Before laundry 0 30 12 After 5 laundry cycles

Comparative Example 12:

Application of Antimony-Free Binary Flame Retardant Systems on Various Fabrics

[0299] Antimony-free comparative formulations 1a, 1b, 1c and 1d were applied by padding on a variety of fabrics, including 100% cotton, 35-65% cotton/polyester and 50-50% cotton/polyester, as described in Examples XX-XX.

[0300] The results are summarized in Table 32 and some are also detailed in Tables 33-35:

TABLE-US-00034 TABLE 32 Flame Retardancy Formulation # BrFR OP IPN (before laundry) 1a failed (external organic phosphate) 1b failed 1c failed 1d failed (internal organic phosphate) [0301] A) Application of formulation 1a (80% TexFRon 4002+20% RDP) on 50%-50% cotton polyester (knit) fabric

TABLE-US-00035 TABLE 33 flammability test After After Char % % % % flame Glow Length Sample # add-on FR Br OP sec sec cm 2346-71- 43.9 RDP 6.93% 15.2 0.73 BEL 03-01 4002-27.2% 2346-71- 44.2 RDP 6.98% 15.3 0.74 BEL 03-02 4002-27.4% BEL = burnt entire length. [0302] B)Application of formulation 1d tris(tribromoneopentyl) phosphate (FR-370, TexFRon 3000) on a 50% cotton/50% polyester fabric

TABLE-US-00036 TABLE 34 Flammability Test After After Char Flame Glow Length Sample # % add-on % FR % Br % OP (sec) (sec) (cm) Remarks 1979-62-03 27.12 19.77 13.81 0.54 BEL Before laundry 1979-62-04 28.35 20.62 14.43 0.61 BEL Before laundry 1979-62-08 36.54 26.58 18.6 0.79 13 Before laundry FAIL 1979-62-09 43.37 31.54 22.08 0.94 15 Before laundry FAIL [0303] C)Application of formulation 1b (50% RDP-HP and 50% TexFRon AG) on a 35% cotton/65% polyester) fabric

TABLE-US-00037 TABLE 35 Flammability Test After After Char Flame Glow Length Sample # % add-on % FR % OP % IPN (sec) (sec) (cm) Remarks 1979-62-03 37.8 16.2 1.8 3.4 BEL Before laundry 1979-62-04 35.9 15.4 1.7 3.2 BEL Before laundry 1979-62-08 36.6 15.7 1.7 3.3 BEL Before laundry [0304] D) Application of formulation 1c (50% 4001 and 50% TexFRon AG) including ATO at a ratio of 1:9 Sb:Br, on a 50% 50% cotton polyester knit fabric

TABLE-US-00038 TABLE 36 flammability test Br:Sb After After Char % % % Molar flame Glow Length Sample # % Add-on FR Br ATO ratio sec sec cm remarks TexFRon 4001 + 2120-12-02 59.0 21.0 10.5 2.1 1:9 0 2 12 Before laundry TexFRon AG 2120-12-02 59.0 21.0 10.5 2.1 1:9 0 2 12.5 Five laundry (50% + 50%) 2120-12-03 56.2 20.0 10.0 2.0 1:9 0 3 7 Before laundry padding 2120-12-03 56.2 20.0 10.0 2.0 1:9 0 3 7 Five laundry 50%/50% 2120-12-07 64.9 23.0 11.5 2.3 1:9 0 2 9 Before laundry Cotton/ 2120-12-07 64.9 23.0 11.5 2.3 1:9 0 2 11.5 Five laundry polyester Knit 2120-12-01 68.9 24.5 12.2 2.5 1:9 0 2 11 Before laundry Br:Sb 2120-12-01 68.9 24.5 12.2 2.5 1:9 0 5 15 Five laundry Molar ratio 9:1

[0305] 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.

[0306] 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.