WO2006072952A2 - Ignifuges halogenes de dimension nanometrique - Google Patents

Ignifuges halogenes de dimension nanometrique Download PDF

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Publication number
WO2006072952A2
WO2006072952A2 PCT/IL2006/000022 IL2006000022W WO2006072952A2 WO 2006072952 A2 WO2006072952 A2 WO 2006072952A2 IL 2006000022 W IL2006000022 W IL 2006000022W WO 2006072952 A2 WO2006072952 A2 WO 2006072952A2
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flame retardant
formulation
particles
composition
manufacture
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WO2006072952A3 (fr
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Itzhak Shalev
Royi Mazor
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Bromine Compounds Ltd
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Bromine Compounds Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/06—Ethers; Acetals; Ketals; Ortho-esters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/02—Halogenated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives

Definitions

  • the present invention relates to the field of flame retardants and, more particularly, to novel aqueous dispersions of nano-sized flame retardants.
  • Textiles are an essential part of everyday life and are found, for example, in draperies, cloths, furniture and vehicle upholsteries, toys, packaging material and many more applications. Consequently, textile flammability is a serious industrial concern.
  • the flammability of textile fabrics is typically determined by the type of fiber of which the fabric is made.
  • some synthetic fibers such as melamine, polyaramides, carbonized acrylic, and glass, are inherently flame resistant, whereas others, such as cotton, polyester and linen, can readily ignite.
  • Fabric flammability also depends on fabric characteristics such as thickness and/or looseness.
  • the term "fiber” as used herein refers to a natural or synthetic filament capable of being spun into a yam or made into a fabric.
  • fabric fabric
  • textile and “textile fabric” are used herein interchangeably hereinafter to describe a sheet structure made from fibers.
  • One approach involves fiber copolymerization.
  • this technique several fiber monomers are mixed and copolymerized, thus improving the properties of a certain fiber (e.g., a flammable fiber) through the enhanced properties of another fiber (e.g., a fire resistant fiber).
  • This technique is limited by the number of existing fire resistant fibers and their properties, and cannot be tailor-made for any substrate or requirements.
  • fiber t) ⁇ es e.g. flammable fiber versus fire resistant fiber
  • An additional disadvantage of this approach is the high cost of the fire resistant fibers.
  • Another approach includes introduction of flame retardants (FR) in or on the fabric. Thus, flame retardants can be incorporated in the fabric either topically or as a part of the fabric.
  • an applied flame retardant when used in textiles, has to be: (a) compatible with the fabric, (b) non-damaging to the aesthetical and textural properties of the fabric, (c) transparent, (d) light stable, (e) resistant to extensive washing and cleaning, (f) environmentally and physiologically safe, (g) of low toxic gas emittance, and (h) inexpensive.
  • a flame retardant or smoldering suppressant agent should pass the standard flammability and smoldering tests in the field.
  • Inorganic flame retardants such as aluminum oxide, magnesium hydroxide and ammonium polyphosphate
  • Halogenated flame retardants primarily based on bromine and chlorine
  • Organophosphorous flame retardants which are primarily phosphate esters
  • Bromine-containing compounds have been long established as flame retardants.
  • U. S. Patent Nos. 3,955,032 and 4,600,606; and Mischutin teach flame retardation of textiles using formulations containing aromatic bromine compounds which are adhered to the substrates by means of binders.
  • bromine-containing compounds as FRs for textiles, however, suffers major disadvantages including, for example, high bromine content demand, high binder content demand, which together result in a relatively high add-on.
  • the thickness of the coating layer determines the textural properties of the fabric. Thinner coating layer results in more flexible and softer fabric. The thickness of the layer evidently depends on the amount of the add-on.
  • dry add-on relates to the total amount of dry additives (mainly flame retardants, binders and synergists) which is left on the fabric after being coated.
  • bromine-containing FR formulations Using existing bromine-containing FR formulations, a dry add-on of 60 % or higher (compared to the dry fabric weight) is often required to obtain satisfactory flame retardation. This high add-on is due in part to the large amount of binder needed to affix the FR agents to the textile.
  • the binder used in bromine-containing formulations typically constitutes about 50 % by weight of the total FR formulation [Toxicological Risks of Selected Flame-Retardant Chemicals, page 506-507, V. Mischutin, Nontoxic Flame Retardant for Textiles, J. Coated Fabrics, Vol. 7, 1978, p. 315].
  • the substantial presence of the binder is further disadvantageous since the binder often contributes in itself to flammability and dripping, thus requiring even higher loading of bromine and creating an inefficient cycle.
  • Using existing bromine-containing FR formulations is further disadvantageous since the addition of additives such as flame retardant synergists and thickeners (thickening agents) is often required.
  • Thickening agents are often added to flame retardant formulations in order to increase their viscosity and facilitate the application of the FR formulations on substrates such as textiles.
  • the thickening agents are often flammable compounds themselves, and therefore an additional amount of FR agent and/or synergist in necessary to overcome this adverse effect.
  • antimony-based compounds have been used as flame- retardants, including Sb 2 O 3 , Sb 2 O 5 and Na 3 SbO 4 [Touval, L, (1993) "Antimony and other inorganic Flame Retardants” in Kirk Othmer's Encyclopedia of Chemical Technology, Vol. 10, p. 936-954, 4 th Edition, John Wiley and Sons, N. Y.].
  • Antimony based compounds are very expensive and are therefore not used on their own, but are used as synergists with other flame retardants.
  • the addition of antimony oxide to halogenated flame retardants increases their efficiency and reduces the amount of additives and/or halogenated FR agent to be used.
  • the addition of such synergist is costly and further contributes to the high add-on of the formulation.
  • Nano-sized powders are known to those skilled in the art to adhere better to surfaces than coarser powders, due to increased surface area and better spreading, and are also known to have improved transparency compared to dispersions of coarser powders. For example, the transparency of liquid dispersions is maintained when the particle size is smaller than about 400 nanometers (0.4 micron).
  • nano sized powders are known to those skilled in the art to form stable dispersions, with an increased viscosity compared to dispersions containing coarser powders.
  • the increased viscosity of nano-sized powders is also attributed to the high surface area of the powder.
  • nano- sized dispersions of halogenated FRs would result in a FR formulation with the desired improved performance. More specifically, it was envisioned that such a formulation would lead to a decrease in the amount of binder and/or synergist to be used and to improved textural and aesthetical properties of a textile substrate. Furthermore, it was envisioned that using nano-sized dispersions of halogenated FRs would facilitate the application of the FR formulation on substrates such as textiles, while decreasing the amount of thickening agent to be used.
  • the nano-sized decabromodiphenylether particles have an average volumetric length of 0.25 micron and a size cut-off of 2.7 microns. While U.S. Patent No. 5,948,323 suggests the advantageous use of the compositions taught therein as FR formulations, U.S. Patent No. 5,948,323 fails to teach the actual application of these compositions to substrates such as textiles and further fails to characterize the FR properties of these compositions.
  • a flame retardant composition comprising a plurality of halogenated flame retardant particles having an average size ranging from about 100 nanometers to about 250 nanometers.
  • a flame retardant composition comprising a plurality of halogenated flame retardant particles, wherein at least 90 % of the particles in the composition have a particle size smaller than 500 nanometers.
  • a flame retardant composition comprising a plurality of halogenated flame retardant particles wherein at least 10 % of the particles in the composition have a particle size smaller than 90 nanometers.
  • each of the compositions described herein further comprises a carrier.
  • the carrier is an aqueous carrier.
  • the aqueous carrier is water.
  • the halogenated flame retardant is a brominated flame retardant.
  • the brominated flame retardant is Decabromodiphenylether (FR-1210).
  • the brominated flame retardant is l,2-Bis(2,3,4,5,6-pentabromophenyl)ethane (Saytex 8010).
  • the brominated flame retardant is pentabromobenzyl acrylate (PBB-MA).
  • an amount of the halogenated flame retardant ranges from about 1 weight percentage to about 70 weight percentages of the total weight of the composition.
  • the composition further comprises at least one additional ingredient selected from the group consisting of a surface active agent, a wetting agent, a dispersing agent, a suspending agent, a pH buffer and any mixture thereof.
  • the dispersing agent is selected from the group comprising of Dispergator WA, AMP-95, Clorocontin NGD and Triton X-IOO.
  • the wetting agent is Clorocontin NGD.
  • the surface active agent is an anionic surface active agent.
  • the composition is in a form of a dispersion, preferably an aqueous dispersion.
  • the composition is characterized by a viscosity that ranges from about 100 centipoises to about 2000 centipoises.
  • a process of preparing an aqueous dispersion of each of the flame retardant compositions described herein comprising: milling a dispersion which comprises a halogenated flame retardant and an aqueous carrier until particles smaller than about 1 microns are obtained.
  • the dispersion which comprises a halogenated flame retardant and an aqueous carrier further comprises at least one ingredient selected from the group consisting of a surface active agent, a wetting agent, a dispersing agent, a suspending agent, a pH buffer and any mixture thereof, as described herein.
  • the milling is conducted for at least 2 hours.
  • the process is conducted under basic conditions.
  • a flame retardant fonnulation comprising any of the compositions described herein and a carrier.
  • the flame retardant formulation further comprises at least one additive selected from the group consisting of an antifoaming agent, a preservative, a stabilizing agent, a binding agent, a thickening agent and any mixture thereof.
  • the binding agent is selected from the group consisting of an acrylate, a polyurethane, a vinyl acetate, or a polyvinyl chloride (PVC). More preferably, the binding agent is an acrylate. Further preferably, an amount of the binding agent is lower than 40 weight percentages of the total weight of the formulation, more preferably lower than 30 weight percentages, and most preferably lower than 25 weight percentages of the total weight of the formulation.
  • a flame retardant formulation comprising a carrier, a plurality of halogenated flame retardant particles having an average size smaller than about 1 micron dispersed in the carrier, and a binding agent, wherein an amount of the binding agent is lower than 40 weight percents of the total weight of the formulation.
  • the carrier in each of the formulations described herein is an aqueous earner.
  • any of the above-described flame retardant formulations further comprises a flame retardant synergist.
  • the synergist is antimony oxide (ATO). More preferably, a molar ratio between an elemental antimony of the ATO and an elemental halogen of the halogenated flame retardant ranges from about 1 :1 to about 1:6.
  • an amount of the flame retardant synergist is lower than 30 weight percentages of the total weight of the composition, more preferably ranging from about 10 weight percentages to about 30 weight percentages.
  • an amount of the thickening agent is lower than 5 weight percentages of the total weight of the formulation.
  • any of the above-described flame retardant formulations is stable for at least three months upon storage at room temperature.
  • any of the above-described flame retardant formulations is stable for at least six months.
  • any of the above-described flame retardant formulations is stable for at least 12 weeks upon storage at elevated temperatures.
  • any of the above-described flame retardant formulations have a viscosity that ranges from about 100 to about 2,000 centipoises.
  • an article-of-manufacture comprising a flammable substrate and any of the above- described flame retardant formulations being applied thereon.
  • the flammable substrate comprises a flammable textile fabric. More preferably, the flammable textile fabric is selected from the group consisting of a synthetic textile fabric, a natural textile fabric and blends thereof.
  • the flammable textile fabric is selected from the group consisting of wool, silk, cotton, linen, hemp, ramie, jute, acetate fabric, acrylic fabric, latex, nylon, polyester, rayon, viscose, spandex, metallic composite, carbon or carbonized composite, and any combination thereof.
  • the textile fabric is selected from the group consisting of cotton, polyester, and any combination thereof.
  • the substrate is selected from the group consisting of a drapery, a garment, linen, a mattress, a carpet, a tent, a sleeping bag, a toy, a decorative fabric, an upholstery, a wall fabric, and any other technical textile.
  • the above-described article-of-manufacture is characterized by an after flame time, as defined by ASTM D-6413 12 seconds ignition test, of less than 5 seconds.
  • the after flame time of less than 5 seconds remains substantially unchanged upon subjecting the article-of-manufacture to at least 1 washing cycle.
  • the after flame time of less than 5 seconds remains substantially unchanged upon subjecting the article-of-manufacture to at least 5 washing cycles.
  • the above-described article-of-manufacture is characterized by an after glow time, as defined by ASTM D-6413 12 seconds ignition test, of less than 200 seconds.
  • the after glow time of less than 200 seconds remains substantially unchanged upon subjecting the article-of-manufacture to at least 1 washing cycle.
  • the after glow time of less than 200 seconds remains substantially unchanged upon subjecting the article-of-manufacture to at least 5 washing cycles.
  • the above-described article-of-manufacture is characterized by a char length, as defined by ASTM D-6413 12 seconds ignition test, of less than 15 centimeters.
  • the char length of less than 15 centimeters remains substantially unchanged upon subjecting the article-of-manufacture to at least 1 washing cycle.
  • the char length of less than 15 centimeters remains substantially unchanged upon subjecting the article-of-manufacture to at least 5 washing cycles.
  • any of the above-described articles-of-manufacture is characterized by at least one aesthetical or textural property which is substantially the same as that of the flammable substrate per se.
  • the at least one aesthetical or textural property is selected from the group consisting of flexibility, smoothness, streakiness and color vivacity.
  • the property remains substantially unchanged upon subjecting the article-of-manufacture to at least 1 washing cycle. More preferably, the property remains substantially unchanged upon subjecting the article- of-manufacture to at least 5 washing cycles.
  • the present invention successfully addresses the shortcomings of the presently known configurations by providing nano-sized halogen-containing flame retardant compositions and formulations containing same which are far superior to the presently known halogen-containing (particularly bromine-containing) flame retardant formulations for application on a substrates such as textile substrates.
  • halogen-containing flame retardant compositions and formulations containing same which are far superior to the presently known halogen-containing (particularly bromine-containing) flame retardant formulations for application on a substrates such as textile substrates.
  • FIGs. IA-B present plots showing the particle size distributions of a micron- sized milling-base of FR-1210 (before grinding, as the surface area versus particle size, Figure IA) and of a nano-sized FR-1210 dispersion (as the volume versus particle size, Figure IB), obtained by a Malvern Mastersizer 2002;
  • FIG. 2 presents a Cryogenic Tunneling Electron Microscopy (Cryo-TEM) image of a nano-sized FR-1210 dispersion, according to the present embodiments;
  • FIGs. 3A-E present scanning electron microscopy (SEM) images of a cotton fabric treated with a nano-sized FR-1210 dispersion, according to the present embodiments (x 43 resolution, Figure 3 A; x 2,200 resolution, Figure 3B; at the edge of the sample, at x 60 resolution, Figure 3 C; at fibers at inner side of yam in the sample, at x 430 resolution, Figure 3D; at fibers at inner side of yarn in the sample, at x 7,000 resolution, Figure 3E);
  • SEM scanning electron microscopy
  • FIGs. 4A-D present a SEM image of a cotton fabric treated with a nano-sized FR-1210 dispersion, according to the present embodiments (x 2300 resolution, Figure 4A), and Energy Dispersive X-ray Spectra (EDS) of points 1, 2 and 3 on the surface displayed in Figure 5A ( Figures 4B, 4C and 4D, respectively); and
  • FIGs. 5A-F present comparative Optical Microscope Micrograph images of untreated polyester fabric (Figure 5A), a polyester fabric treated with a micron-sized FR-1210 formulation (Figure 5B), a polyester fabric treated with a nano-sized FR- 1210 formulation according to the present embodiments ( Figure 5C), untreated cotton fabric (Figure 5D), a cotton fabric treated with a micron-sized FR-1210 formulation (Figure 5E) and a cotton fabric treated with a nano-sized FR-1210 dispersion according to the present embodiments ( Figure 5F).
  • DESCRIPTION QF THE PREFERRED EMBODIMENTS DESCRIPTION QF THE PREFERRED EMBODIMENTS
  • the present invention is of novel nano-sized halogenated flame retardant compositions and of flame retardant formulations containing same, which can be efficiently applied on flammable substrates such as textile fabrics.
  • the present invention is further of articles-of-manufacture having these nano-sized flame retardant formulations applied thereon.
  • Halogen-containing compounds and particularly bromine-containing compounds, are commonly-used flame retardants (FRs).
  • FRs flame retardants
  • application of flame retardant formulations that incorporate halogenated FRs on textiles is limited due to excessive dripping during combustion, a relatively high level of smoldering and a general instability of the flame retardant formulation.
  • these formulations do not adhere well to the textile, and therefore have a low washing fastness, further demanding large amounts of these FRs, as well as of binders and other additives, such as flame retardant synergists, to achieve the desired flame retardant properties.
  • Thickening agents are also often added due to a low viscosity of these FR formulations, in order to facilitate application on the fabric.
  • a textile having a high binder content and/or a high add-on is adversely characterized by undesirable texrural and/or aesthetical properties, such as streak marks on dark fabrics and a non-uniform application thereof on the fabric.
  • undesirable texrural and/or aesthetical properties such as streak marks on dark fabrics and a non-uniform application thereof on the fabric.
  • the use of the presently available halogen-containing FR formulations in textiles often results in a coated substrate characterized by rigidness, uneven surfaces, faded colors and other undesirable textural and/or aesthetical properties.
  • the coated textiles are typically characterized by a low washing fastness, which renders the fabric flammable once the FR has been washed-off (usually after just a few washing cycles).
  • FR compositions While colloidal (smaller than about 1 micron) FR compositions have been suggested in U.S. Patent No. 5,948,323, to McLaughlin, the exemplary compositions taught in this patent are characterized by an average volumetric length in the range of 0.07 to 0.25 micron and a size cut-off of between 0.3 to 2.7 microns.
  • U.S. Patent No. 5,948,323 teaches a decabromodiphenylether (referred to herein as FR-1210) composition which has an average volumetric length of 0.25 micron and a size cut-off of 2.7 microns. Such a composition is therefore characterized by particles having a relatively high average size at a nano scale and a size cut-off in the micron-size and not the nano-size scale.
  • U.S. Patent No. 5,948,323 further fails to teach the actual application of the compositions taught therein to substrates such as textiles and to characterize the FR properties of these compositions.
  • nano-sized halogenated FR compositions could be prepared and efficiently incorporated in stable formulations, which can be utilized as efficient flame retardant formulations for application onto fabrics.
  • such formulations when applied onto various fabrics, allow for smooth application thereof and are characterized by improved adherence to the fabric and yet good flame retardancy, even when relatively low amounts of a binder, a FR synergist and/or a thickener are used.
  • fabrics treated by such formulations are non-flammable, exhibit an improved washing fastness and further maintain the textural and aesthetical properties thereof.
  • a flame retardant composition which comprises a plurality of halogenated flame retardant particles.
  • flame retardant which is also referred to herein, interchangeably, as “fire retardant”, “flame resistant” and “fire resistant”, describes a compound, a composition or a formulation which is capable of reducing or eliminating the tendency of a substance to ignite when exposed to a low-energy flame.
  • halogenated flame retardants that can be utilized within the context of the present invention are also known to act as smoldering suppressants, exhibiting smoldering suppression.
  • meltdering also known in the art as “after flame burning” refers to a burning which continues after the open flame has been extinguished.
  • smoldering suppressant which is also referred to herein interchangeably as “smoldering suppressing agent” or “SS”, therefore describes a compound or a composition which reduces or eliminates the tendency of a substance to bum after no longer being exposed to a flame.
  • flame retardant as used herein, also encompasses compounds, compositions and formulations that may further exhibit smoldering suppression.
  • halogenated flame retardant describes a flame retardant compound that includes one or more halides (also referred to herein as halogens), namely, one or more of fluoride, chloride, bromide and iodide. While most of the presently known FRs are bromides, preferred halogenated flame retardants according to the present embodiments include brominated flame retardants.
  • brominated flame retardants include, without limitation, bromides of aliphatic or alicyclic hydrocarbons such as hexabromocyclododecane; bromides of aromatic compounds such as decabromodiphenyloxide, hexabromobenzene, 1,2- bis(2,3,4,5,6-pentabromophenyl)ethane, ethylene bis(pentabromodiphenyl), pentabromobenzyl acrylate, tetradecabromodiphenoxy benzene, octabromodiphenyl ether, 2,3-dibromopropyl pentabromophenyl ether and the like; brominated bisphenols and their derivatives such as tetrabromobisphenol A, tetrabromobisphenol A bis(2,3- dibromopropyl ether), tetrabromobisphenol A (2-bromoeth
  • Preferred brominated FR agents are decabromodiphenylether (FR-1210, also referred to herein and in the art as decabromodiphenyloxide, and also known as DECA), 1,2-Bis(2,3,4,5,6- pentabromophenyl)ethane (also referred to herein and in the art as decabromodiphenylethane, and also referred to herein as Saytex-8010) and pentabromobenzyl acrylate (FR-1025M, also known as PBB-MA).
  • composition as used herein in the context of a "flame retardant composition” refers to any compound and/or a combination of compounds that have flame retardant properties.
  • Flame retardant compositions may optionally include a carrier and additional, non-FR ingredients, which are typically used to stabilize the composition.
  • formulation refers to a composition, as defined hereinabove, which is formulated so as to facilitate and/or enable its application on a substrate.
  • a flame retardant formulation typically includes a flame retardant composition as defined hereinabove, a carrier and optionally additives such a binder, a FR synergist, additional FRs, as well as non-FR additives.
  • the FR compositions described herein comprise halogenated FR particles having an average size that ranges from about 100 nanometers to about 250 nanometers.
  • average particle size represents the average particle radius of the particles of a given FR, and is typically determined by conventional analytical techniques such as, for example, microscopic determination utilizing a scanning electron microscope or by means of a laser granulometer (such as a small angle scattering, for example, a Malvern).
  • d 50 represents the particle size which 50 % of the particles do not exceed.
  • the volumetric distribution of the sample relates to the weight distribution. While the average particle radius is derived from a volumetric average particle size or length and expresses the same values, this phrase is also referred to interchangeably herein and in the art as "volumetric average particle size", “volumetric average particle length” and “average particle length”.
  • nanoscale all refer to a range of from about 1 nanometer to about 1000 nanometers (from about 1 x 10 "9 meters to about 1 x 10 'b meters).
  • a “nanoscale” therefore describes a scale in the above cited range and “nano-sized” describe particles and/or a composition or a formulation containing the particles, whereby the particles size is within the above cited range.
  • micro refers to a range of from about 1 micron to about 1000 microns (from about 1 x 10 "6 meters to about 1 x 10 "3 meters).
  • a “microscale” therefore describes a scale in the above cited range and “micro-sized” describes particles and/or a composition or a formulation containing the particles, whereby the particles size is within the above cited range.
  • the te ⁇ n "nano-sized" preferably relates to particles and/or a composition or a formulation containing the particles, whereby the average particles size is in the lower range of a nanoscale, namely, is 500 nanometers or less, and more preferably 250 nanometers or less.
  • nano-sized compositions and “micro-sized compositions” refer to compositions, as these are defined hereinabove, comprising “nano-sized particles” and “micro-sized particles”, respectively.
  • nano-sized formulations and “micro-sized formulations” refer to formulations comprising “nano-sized compositions” and “micro-sized compositions”, respectively.
  • nano-sized dispersions and “micro-sized dispersions” refer to “nano-sized compositions” or “nano-sized formulations” and to “micro-sized compositions” or “micro-sized formulations”, as those have been defined hereinabove, which are in a form of a dispersion.
  • the halogenated flame retardant particles incorporated hi the composition presented herein have an average size ranging from about 1 nanometer to about 450 nanometers, and are preferably in the range of from about 50 nanometers to about 450 nanometers. More preferably, the halogenated flame retardant particles incorporated in the composition presented herein have an average size (d 50 ) that ranges from about 100 nanometers to about 250 nanometers.
  • Such an average size (100-250 ran) is highly advantageous in the context of the present invention, particularly as compared with compositions that contain particulate FRs having higher average particle size, since the lower the average particle size is, the better is the adhesion of the particles to the substrate, due to improved penetration of the particles to the substrate.
  • Such a low average size is further advantageous since it beneficially results in increased viscosity of a composition containing same, due to large surface area thereof, as is discussed in detail herein.
  • the flame retardant composition comprises a plurality of halogenated flame retardant particles characterized in that at least 90 % of these particles have a particle size smaller than 500 nanometers.
  • the cut-off size of the particles is less than 500 nanometers.
  • such compositions preferably do not Include more than 10 % of particles larger than 500 nanometers, more preferably do not include more than 5 % of particles larger than 500 nanometers, and even more preferably do not include any particles larger than 500 nanometers.
  • an exemplary nano-sized composition according to the present embodiments which contains FR- 1210 as the nano-sized flame retardant, was found to have a top cut-off of 360 nanometers.
  • Such a top cut-off is highly advantageous, particularly as compared with compositions that contain halogenated (e.g., brominated) FRs having a higher top cutoff, particularly in the microscale range, since a composition having a combination of small (e.g., 100-400 nm) particles and large (above 450 manometers) particles loses its uniformity and may lead to non-uniform application of such a composition on a substrate. In such a composition, the larger particles will not penetrate into the substrate at the same level as the smaller particles, will thus clog on the surface and may therefore result in an uneven coating on the substrate.
  • halogenated e.g., brominated
  • the FR compositions presented herein by having 90 % of the particles that have a size lower than 1 micron and even lower than 500 nm (namely a size cutoff lower than 500 nanometers), are highly advantageous as compared, for example, with compositions having a size cut-off of about 2.7 microns, such as the compositions taught in U.S. Patent No. 5,948,323.
  • the flame retardant composition comprises a plurality of halogenated flame retardant particles characterized in that at least 10 % of these particles have a particle size smaller than 90 nanometers.
  • Having a portion of the particles as small as 90 nanometers and even less (e.g., 50 nanometers) is highly advantageous, and in fact, has never been disclosed in the art for halogen-containing and particularly bromine-containing FR compositions.
  • Such an extremely small particle size further improves the adhesion of the FR particles to the substrate and further increases the viscosity of the composition.
  • the FR particles incorporated in the composition described herein further have a narrow size distribution, as is shown, for example, in Figure 1 B and in Table 2 in the Examples section that follows. Such a narrow size distribution further provides for a uniform incorporation of the composition on a substrate.
  • each of the compositions described herein further comprises a carrier.
  • carrier describes an inert material with which the composition is mixed or formulated to facilitate its application, or its storage, transport and/or handling. Since the flame retardant compositions described herein are particularly useful for the treatment of textiles, the carrier is preferably a textile acceptable carrier.
  • textile acceptable carrier refers to an inert, environmentally acceptable carrier, which is not harmful to the textile.
  • the carrier is an aqueous carrier and more preferably the carrier is water, as is further discussed hereinbelow.
  • the amount of the flame retardant can range from about 1 weight percentage to about 70 weight percentages of the total weight of the composition.
  • the amount of the halogenated flame retardant ranges from about 10 weight percentages to about 70 weight percentages, more preferably from about 20 weight percentages to about 70 weight percentages, more preferably from about 30 weight percentages to about 70 weight percentages, more preferably from about 40 weight percentages to about 60 weight percentages of the total weight of the composition, whereby in the presently most preferred composition that amount of the halogenated FR is about 50 weight percentages of the total weight of the composition.
  • halogenated flame retardant compositions described herein can further comprise additional ingredients that may stabilize the composition, prolong its shelf- life and/or provide it with other desired properties such as certain viscosity, homogeneity, and adherence to the substrate.
  • additional ingredients include, for example, one or more of a surface active agent, a wetting agent, a dispersing agent, a suspending agent and a pH buffer and any mixture thereof.
  • the surface active agent and/or wetting agent can be nonionic or anionic agents.
  • nonionic agents that are suitable for use in the context of the present invention include, but are not limited to, polyoxyethylene (POE) alkyl ethers, preferably NP-6 (Nonylphenol ethoxylate, 6 ethyieneoxide units) such as DisperByk 101®.
  • POE polyoxyethylene
  • anionic agents that are suitable for use in the context of the present invention include, but are not limited to, free acids or organic phosphate esters or the dioctyl ester of sodium sulfosuccinic acid.
  • dispersing agents and/or suspending agents that are suitable for use in the context of the present invention include, but are not limited to, acrylic acids, acrylic acids ester copolymer neutralized sodium polycarboxyl such as naphthalene sulfonic acid-formaldehyde condensate sodium salt, alginates, cellulose derivatives and xanthan.
  • FR-1210 nano-sized dispersions were found to be more viscous by an order of magnitude than micron- sized FR-1210 dispersions having the same FR concentration (amount) (see, Examples 1 and 2), facilitating further processing of these compositions.
  • compositions according to the present embodiments are characterized by a viscosity that ranges from about 100 centipoises to about 2,000 centipoises.
  • exemplary compositions were shown to have a viscosity in the range of from about 100 centipoises to about 800 centipoises.
  • Compositions characterized by such a viscosity are highly advantageous since the relatively high viscosity circumvents the need to use large amounts of thickening agents when applying a formulation that contains the
  • compositions containing brominated FRs form stable compositions. It has further been surprisingly uncovered that such compositions are stable even during long-term shelving. It was therefore demonstrated that the instability of compositions containing brominated FRs can be circumvented by using a nano-sized aqueous dispersion of the flame retardant.
  • a nano- sized halogenated flame retardant e.g., brominated
  • the halogenated (e.g., brominated) flame retardant is utilized in a form of a dispersion, which comprises a plurality of halogenated flame retardant particles dispersed in the carrier.
  • a preferred carrier according to the present embodiments is an aqueous carrier and more preferably it is water.
  • preferred compositions according to the present embodiments include an aqueous dispersion of halogenated flame retardant nanoparticles.
  • a process for preparing aqueous dispersions of the nano-sized halogenated FRs has been designed and successfully practiced.
  • a process of preparing flame retardant compositions comprising a plurality of halogenated flame retardant particles, as described herein, dispersed within an aqueous carrier.
  • the process is effected by milling a dispersion which comprises a halogenated flame retardant and an aqueous carrier until particles smaller than about 1 microns are obtained.
  • composition further comprises additional ingredients, as described hereinabove, such agents are added to the initial dispersion, prior to the milling.
  • exemplary dispersing agents which were found suitable for use in this context of the present invention (in the preparation of aqueous dispersions of nano- sized halogenated flame retardant) include dispergator WA, AMP-95, Clorocontin NGD and Triton X-IOO (see, for example, Examples 1 and 2 in the Examples section that follows).
  • an exemplary wetting agent which was found suitable for use in this context of the present invention (in the preparation of aqueous dispersions of nano- sized halogenated flame retardant) is Clorocontin NGD.
  • the milling procedure can be conducted according to any of the known wet milling practices.
  • the milling is conducted during a time period of at least 2 hours. More preferably, the milling is conducted for a time period that ranges from three to four hours, so as to achieve the desired FR average particle size and particle size distribution.
  • comparing the particles size distribution before and after the milling of FR-1210 particles shows that after milling, the size distribution is narrower and has a higher ratio of nano-sized particles: while before milling 90 % of the particles are 8.42 microns (8420 nanometers) or larger, after milling- 90 % of the particles are 205 nanometers (about 2.5 % of the original size) or smaller, and about 10 % of the particles are 71 nanometers (about 0.8 % of the original size) or larger.
  • the size distribution of the nano-sized dispersions is very different that the size distribution obtained for the colloidal FR-1210 compositions taught in U.S.
  • Patent No. 5,948,323 As discussed above, the compositions taught in U.S. Patent No. 5,948,323. As discussed above, the compositions taught in U.S. Patent No. 5,948,323. As discussed above, the compositions taught in U.S. Patent No. 5,948,323. As discussed above, the compositions taught in U.S. Patent No. 5,948,323. As discussed above, the compositions taught in U.S. Patent No. 5,948,323. As discussed above, the compositions taught in U.S. Patent No. 5,948,323.
  • No. 5,948,323 have an average size of about 0.25 micron (250 nanometers) and a size cut-off of about 2.7 microns (2700 nanometers). According to the present embodiments, 50 % of the nano-sized particles obtained by the process described herein are in the size range of 100-250 nanometers, and the top cut-off was found to be as small as 350-450 nanometers, about 17 % of the top cut-off displayed according to the teachings of U.S. Patent No. 5,948,323. Furthermore, while the compositions obtained by the process described herein include at least 10 % of the particles wliich have a particle size smaller than 90 nanometers, such compositions are not obtained using the process described in U.S. Patent No. 5,948,323.
  • the process is conducted under basic pH conditions. It has been shown that under these conditions, stable dispersions of the nano-sized brominated FRs are obtained.
  • the flame retardant compositions described herein are preferably incorporated in flame retardant formulations.
  • a flame retardant formulation as defined herein, which comprises any of the compositions described herein and a carrier.
  • FR formulations preferably further comprise additional ingredients that may stabilize the formulation, prolong its shelf-life and/or provide it with other desired properties such as certain viscosity, homogeneity, stability and adherence to the substrate.
  • Exemplary additives include, but are not limited to, one or more of an antifoaming agent, a defoaming agent, a preservative, a stabilizing agent, a binding agent, a thickening agent and any mixture thereof.
  • defoaming and/or antifoaming agents that are suitable for use in the context of the present invention, include, but are not limited to, mineral oil emulsions, natural oil emulsions, and preferably are silicon oil emulsions, such as AF- 52.
  • preserving or stabilizing agents examples include, but are not limited to, formaldehyde and alkyl hydroxy benzoates; preferably the preserving or stabilizing agents is a mixture of methyl and propyl hydroxy benzoates.
  • the binding agent (also termed herein interchangeably as a "binder”) is necessary to adhere the molecules of a flame retardant, herein a brominated flame retardant, to a substrate.
  • brominated FRs are known as typically requiring a large amount of a binder, which may reach about 50 % by weight of the total FR formulation, to affix them to a textile substrate [Mischutin (1978) supra].
  • a large amount of a binder results is high add-on, which, as is further discussed in detail hereinabove, is undesirable since it causes a deterioration of the textile properties by, for example, stiffening the fabrics or fading of fabric shades, and may further lower the tear strength and abrasion properties of the fabric.
  • the high binder content also contributes in itself to flammability and dripping. Therefore when the binder is added in large amounts, yet higher amounts of the FR are needed, and as a result, more binder is needed to attach the extra FR to the substrate, thereby creating an endless cycle.
  • the formulation described herein can be effectively applied on various substrates in the presence of relatively low concentrations of a binder. While the exact amount of binder used depends on the flame retardant type and concentration, as well as on the fabric type onto which the formulation is applied, it has been shown herein that an efficient application of the formulations described herein on, can be effected in cases where the concentration of the binding agent in the formulations described herein is lower than 40 weight percentages of the total weight of the formulation, lower than 30 weight percentages of the total weight of the formulation and even equal to or lower than 25 weight percentages.
  • nano-sized brominated flame retardant formulations containing 20 weight percentages of a binder were well adhered to the substrates, and remained such even upon subjecting the substrate to several washing cycles, while maintaining the flame resistance properties.
  • a 100 % Rib knitted cotton fabric having a nano-sized brominated flame retardant formulation that contains 20 % by weight of a binder applied thereon passed a 12 seconds ignition test (ASTM D-6413) with an after flame time of 2 seconds, an after glow time of 151.5 seconds, and a char length of 15.3 centimeters, even after 5 cycles of washing (see, Example 12).
  • nano-sized halogenated (e.g., brominated) FR formulations have an improved adhesion to the fabric (evident from the lower amount of binder required to achieve wash-fastness).
  • the binder concentrations are considerably lower as compared to traditional (e.g., micron-sized) brominated FR formulations (50 weight percent).
  • nano-sized halogenated (e.g., brominated) FR formulations can contain higher amounts of the halogen (e.g., bromine) at the same total add-on, as compared to conventional nano-sized brominated FR presently known.
  • a flame retardant formulation comprising a carrier, a plurality of halogenated flame retardant particles having an average size smaller than about 1 micron dispersed in the carrier, and a binding agent, wherein the amount of the binding agent is less than 40 weight percents of the total weight of the formulation.
  • the binder used in the formulations described herein is selected depending on the specific application.
  • different binders may be suitable to attach the FR formulation described herein to wood, plastic or textile.
  • the binder can thus be selected from a large variety of suitable materials, such as, but not limited to, synthetic polymers, such as styrene-butadiene (SBR) copolymers, carboxylated-SBR copolymers, melamine resins, phenol-aldehyde resins, polyesters, polyamides, polyureas, polyvinylidene chloride, polyvinyl chloride (PVC), acrylic acid- methylmethacrylate copolymers, acetal copolymers, polyurethanes, and mixtures and cross-linked versions thereof.
  • SBR styrene-butadiene
  • PVC polyvinyl chloride
  • acrylic acid- methylmethacrylate copolymers acetal copolymers
  • polyurethanes and mixtures and cross-
  • the binder is selected suitable for use on textiles, and is therefore selected to be both non- damaging to the aesthetical and textural properties of the fabric, and durable (to washing, drying, UV light etc.), and should further be compatible with the flame retardants and the additional additives in the formulation.
  • the binder is an aery late, a polyurethane, or PVC. More preferably, the binder is an acrylate.
  • the formulations described herein may further comprise additional ingredients which may improve the flame retardancy performance of the formulation.
  • An exemplary ingredient is a flame retardant synergist, which acts in synergy with the nano-sized halogenated flame retardant or with any other FR that is incorporated in the formulation described herein and thus enhances the flame resistance properties of the formulation.
  • the formulation described herein further comprises at least one fire retardant synergist.
  • An exemplary fire retardant synergist which is suitable for use in this context of the present invention is antimony oxide (ATO).
  • FR synergist e.g., ATO
  • the FR synergist (e.g., ATO) incorporated in the FR formulations presented herein can be either nano-sized or non nano-sized (e.g., micron-sized or of higher particles size)
  • the molar ratio between the fire retardant synergist and nano-sized halogenated flame retardant in the formulations described herein preferably ranges from about 1:1 to about 1:6 of the active atoms in each compound (antimony and the halogen, respectively).
  • the amount of the flame retardant synergist is lower than 30 weight percentages of the total weight of the composition, preferably ranging from about 10 weight percentages to about 30 weight percentages of the total weight of the composition.
  • the formulations described herein may further comprise additional flame retardants and/or smoldering suppressants.
  • additional flame retardants and/or smoldering suppressants can be utilized in this respect, whereby preferably no more than 10 different FR and/or SS agents are incorporated in the formulation.
  • FR formulations described herein were smoother flowing, did not require stirring, and were easier to apply onto fabrics, as compared with corresponding micron-sized halogenated FR formulations (see Examples 6-9).
  • these FR formulations were found to have a relatively high viscosity, which is highly suitable for easily applying the formulations onto fabrics.
  • lower amounts of thickening agents are required, further decreasing the add-on of the treated fabric, and resulting in a coated textile with improved textural and aesthetical properties.
  • the above-described flame retardant formulations have a viscosity that ranges from about 100 to about 2,000 centipoises. It has thus been demonstrated that nano-sized halogenated FR formulations as described herein can be efficiently applied on textiles while circumventing the need to use high concentrations of binders, thickening agents and synergists, and further while maintaining the desirable aesthetical, textural properties and flame retardancy properties of the fabric, even after extensive washing.
  • the flame retardant formulations described herein can be applied to a substrate by simply contacting the substrate with the flame retardant formulation, whereby the contacting can be effected by any industrially acceptable manner. Optionally, subsequent to contacting the FR formulation, the substrate is heated.
  • the industrially acceptable manner in which the contacting is effected includes, for example, spreading, padding, foaming and/or spraying the FR formulation onto the substrate.
  • Padding is a process that is typically used for applying the formulation on a textile substrate and is defined as a process in which the fabric is first passed through a padder containing the FR formulation, and is then squeezed between heavy rollers to remove any excess formulation.
  • the process described herein can be effected, for example, either during the dyeing or the finishing stages of the substrate manufacture.
  • the resulting substrate thus may have the formulation., as is, applied thereon, or, if subjected to the appropriate procedures, may have a dry formulation applied thereon.
  • the dry formulation typically includes the FRs, FR synergists, binders and any other solid substances present in the formulation. As is demonstrated in the Examples section that follows, the formulations and processes described herein were practiced so as to provide substrates having the FR formulation applied thereon.
  • an article-of-manufacture which comprises a flammable substrate and any of the flame retardant formulations described herein, being applied thereon.
  • the flame retardant formulations are being applied on the substrates as wet formulations comprising nano-sized particles.
  • other particles of a larger non-nano-size may be present in the formulation (for example the FR synergist).
  • the obtained articles-of-manufacture comprise the substrates coated by the dry ingredients of the flame retardant compositions, e.g., a flame retardant and/or a FR synergist and/or a binder.
  • the particles of the FR composition may exist either as nano-sized particles, or may agglomerate to form larger particles, together with any of the other larger particles which may exist in the FR formulation.
  • the favorable properties of the FR formulations of the present invention, and of the articles-of-manufacture obtained by applying these formulations upon the flammable substrates, are inherent to the existence of the nano-sized FR particles in the FR compositions comprised in these formulation, irrespective of the existence of other larger particles in the formulation, or on the dried FR coating on the substrate.
  • substrate describes an article which has a surface that can be beneficially coated (either wholly or partially) with a flame retardant formulation.
  • exemplary articles include, without limitation, textiles, wood, furniture, toys, bricks, electrical appliances, electrical cables, plastics and more.
  • Preferred substrates onto which the flame retardant formulations described herein can be beneficially applied are textile fabrics.
  • the textile fabrics can be synthetic, natural or a blend thereof.
  • Non-limiting examples of textile fabrics that can be beneficially used in the context of the present invention include wool, silk, cotton, linen, hemp, ramie, jute, acetate fabric, acrylic fabric, latex, nylon, polyester, rayon, viscose, spandex, metallic composite, carbon or carbonized composite, and any combination thereof.
  • Representative examples of textile fabrics which were shown to be suitable for use in the context of the present invention include, without limitation, cotton, polyester, and combinations thereof.
  • flammable substrate describes a substrate, as described hereinabove, that easily ignites when exposed to a low-energy flame.
  • the flammability of different articles-of-manufacture can be tested according to international standards.
  • ASTM D-1230 a standard test method for flammability of apparel textiles
  • ASTM D-4151 a standard test method for flammability of blankets
  • ASTM D-4723 a standard index of and descriptions of textile heat and flammability test methods and performance specifications
  • ASTM D- 4804 a standard test method for determining the flammability characteristics of non- rigid solid plastics
  • ASTM D-6545 a standard test method for flammability of textiles used in children's sleepwear
  • ASTM D-777 standard test methods for flammability of treated paper and paperboard
  • ASTM D- 1317 a standard test method for flammability of marine surface finishes
  • ASTM D-1955 a standard test method for flammability of sleeping bags
  • ASTM D-6413 a standard test method for flammability of apparel
  • the flame retardancy of the tested substrates was determined by methods acceptable in the industry, for example a 12 seconds ignition test, which is defined by ASTM D-6413, a test method used to measure the vertical flame resistance of textiles. According to this method a textile is classified on a pass/fail basis, according to predetermined criteria. More specifically, a textile is considered to have failed the 12 seconds ignition test, if its average "char length" exceeds 7 inches (17.8 cm) or an individual sample has a "char length" longer than 10 inches (25.4 cm).
  • the flammability of a substrate may be further defined by its "after flame time” and by its "after glow time".
  • a fabric is considered to have an excellent flame retardancy if either its "after flame time” is 10 seconds or less, or its “after glow time”, is 200 seconds or less.
  • a fabric is considered to have a superior flame retardancy if its "after flame time” is 5 seconds or less.
  • "After-flame time” is defined herein and in the art as the time period during which the sample continues to burn after removal of the burner.
  • After-glow time is defined herein and in the art as the time period during which the sample glows after the flame is extinguished.
  • Char length is defined herein and in the art as the distance from the edge of the fabric that was exposed to the flame to the end of the area affected by the flame.
  • a char is defined as a carbonaceous residue formed as the result of pyrolysis or incomplete combustion.
  • a bone-dry (as defined hereinafter the term "bone-dry” describes a substrate having zero percent moisture content) dyed knitted cotton fabric, which was padded with a nano-sized FR- 1210 formulation (Example 12), according to preferred embodiments of the present invention, passed ASTM D-6413 12 seconds ignition test with no dripping, having an after flame time of 2 seconds, an after glow time of 151.3 seconds, and a char length of 15.3 centimeters.
  • a cotton fabric padded with a nano-sized Saytex-8010 formulation (Example 14), according to preferred embodiments of the present invention, was subjected to 3 laundry cycles and passed an ASTM D-6413 12-seconds ignition test with an after flame time of 1 second, an after glow time of 75 seconds and a char length of 15 centimeters.
  • a woven polyester fabric padded with a nano-sized FR-1210 formulation (Example 13) and with a nano-sized Saytex- 8010 formulation (Example 14) passed ASTM D-6413 12-seconds ignition test, with no dripping.
  • the articles-of-manufacture described herein are therefore characterized by enhanced flame retardancy properties, which can be determined as described hereinabove.
  • the articles-of-manufacture according to the present embodiments are characterized by an after flame time of 2 seconds and less; an after glow time of 150 seconds or less and a char length of 15 centimeters or less.
  • the treated textile fabrics are characterized by enhanced washing fastness.
  • washing fastness which is also referred to herein interchangeably as “washing durability” or “laundry stability” refers to the ability of a substrate treated with the nano-sized halogenated FR formulations of the present invention, to maintain its characteristic flame resistance and/or textural and/or aesthetical properties, after being subjected to at least one washing cycle, as defined by Standard Laboratory Practice for Home Laundering (AATCC technical manual/2001).
  • a textile is considered “durable” if it withstands five washing cycles without having remarkable change of a property thereof, whereby a textile is considered “semi durable” if it similarly withstands at least 1 washing cycle.
  • the substrates treated with the formulations of the present embodiments were characterized by a washing fastness of three washing cycles, often exceeding 5 washing cycles.
  • the articles-of-manufacture described herein are characterized by washing fastness. This feature is particularly notable in view of the relatively low amount of the binder in the applied formulation.
  • the "after flame time”, “after glow time” and “char length” properties, as defined hereinabove, of an article-of-manufacture having the FR formulation described herein applied thereon remain substantially unchanged upon subjecting the article-of-manufacture to one or more washing cycles, and even upon subjecting the article-of-manufacture to 5 or more washing cycles.
  • substantially unchanged refers to a change of less than 30 %, preferably less than 20 %, and more preferably less than 10 % in the tested property.
  • the substrates upon applying the FR formulations described herein onto textile substrates, maintained textural and aesthetical properties.
  • These textile substrates were characterized by feel and appearance similar to those of a non-treated flammable substrate.
  • properties such as the flexibility, smoothness, color vivacity and streak-free look of a non-treated textile were maintained upon application of the FR formulation (see, for example, Examples 12-15).
  • FR-1210 and/or Saytex-8010 nano-sized formulations were applied to dark shade fabrics, the final shade was relatively close to the original shade.
  • these textural and aesthetical properties were maintained also upon subjecting the treated fabrics to several washing cycles.
  • the article- of-manufacture described herein is further characterized by at least one aesthetical or textural property which is substantially the same as that of the flammable substrate per se.
  • the textural and/or aesthetical properties of the substrate or article-of-manufacture include, but are not limited to flexibility, smoothness, streakiness and color vivacity.
  • each of these properties remains substantially unchanged upon subjecting the article-of-manufacture to one or more washing cycles, preferably to five or more washing cycles.
  • the substrates treated with the formulations of the present invention are characterized by a relatively low add-on, demonstrating the advantageous use of these formulations. It is suggested that for preferred formulations according to the present embodiments, which comprise an aqueous dispersion of nano-sized brominated FR, the low add-on is obtained since the nano-sized particles of the brominated FR adhere better to the substrate surface, thus strengthening the binding of the flame retardant to the fabric even at low binder concentration.
  • articles of manufacture, and particularly substrates, treated by the formulation described herein have superior properties as compared with the presently known FR-treated products.
  • Exemplary articles-of-manufactures according to the present embodiments include any industrial product that comprises one or more flammable substrates and hence application of the FR formulation described herein thereon is beneficial.
  • Such articles-of-manufacture include, for example, textiles, wood, furniture, toys, bricks, electrical appliances, electrical cables, plastics and more.
  • bricks or wooden articles, which are often used in building or as home furniture can be easily coated with the FR formulation described herein, thus made flame resistant and applicable for home or industrial use.
  • the article-of-manufacture described herein comprises a flammable textile fabric.
  • articles-of-manufacture include, but are not limited to, textiles, wood, furniture, toys, bricks, electrical appliances, electrical cables, plastics and more.
  • the textile fabrics of this invention may be used as a single layer or as part of a multi-layer protective garment.
  • a textile substrate may be incorporated in various products, where it is desired to reduce the substrate flammability.
  • Such products include, for example, draperies, garments, linen, mattresses, carpets, tents, sleeping bags, toys, decorative fabrics, upholsteries, wall fabrics, and technical textiles.
  • textile flammability and textile smoldering are major concerns since textiles are used in all fields of life.
  • Some textile-based articles of manufacture, such as garments, linen and some decorative or technical textiles are subject to harsh usage (abrasion, exposure to various environmental conditions etc.) and therefore may need extensive, sometimes daily, cleaning and washing.
  • Alkyl alkanolamines dispersants (such as amino methylpropanol, AMP-95) were obtained from Dow.
  • Decabromodiphenylether decabromodiphenyloxide, DECA, CAS No. 1 163- 19-5, labeled as FR-1210
  • PBB-MA pentabromobenzyl acrylate
  • ICL-IP ICL-IP
  • Decabromodiphenylethane CAS No. 84852-53-9, labeled as Saytex-8010
  • the wetting agent CLOROCONTIN NGD was obtained from CHT.
  • the anionic surfactant LABS 100 (CAS No. 25155-30-0) was obtained from Zohar Dalia.
  • Dispergator WA was obtained from Avco-Chem.
  • AC-200 W binder and GP acrylic thickening agent were obtained from B. G. Polymers.
  • Ammonium hydroxide 22 % (CAS No. 1336-21-6) was obtained from Merck.
  • Antimony trioxide (ATO, CAS No. 1309-64-4) was obtained from Campine.
  • Viscosity was measured using a Brookf ⁇ eld viscometer (model DV-II).
  • Light scattering particle size measurement This method was used to determine the particle size distribution of liquid particles, using a Malvem 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 50 ) or 50 percentile, the 10 percentile (d 10 ) and the 90 percentile (dc >0 ) are directly obtained from the data generated by the instrument.
  • Ciyo-TEM Ciyo-TEM
  • Aqueous dispersion samples were characterized via direct imaging using cryo-TEM.
  • a drop of the solution was deposited on a TEM grid (300 mesh Cu grid) coated with a holey carbon film (Lacey substrate-Ted Pella Ltd).
  • the excess liquid was blotted and the specimen was vitrified by a rapid plunging into liquid ethane pre-cooled with liquid nitrogen, in a controlled environment vitrification system.
  • the samples were examined at -178 0 C using a FEI Tecnai 12 G TWIN TEM equipped with a Gatan 626 cold stage, and the images were recorded (Gatan model 794 CCD camera) at 12OkV in a low-dose mode.
  • Flainmability tests 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).
  • Washing Fastness Tests Samples treated with the flame retardant 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), unless otherwise noted.
  • the temperature of the washing water is maintained between 58 °C and 62 0 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.
  • Optical Microscope Micrographs Optical micrographs were obtained using a Nikon eclipse model ME600 with a Nikon optics X 100 lense.
  • Decabromodiphenylether (DECA, also known as decabromodiphenyl oxide, labeled bj' the inventors as FR-1210, 50 % by weight) was added to a mixture containing distilled water (46.2 % by weight), a dispersing agent (Dispergator WA, 2.5 % by weight), a wetting agent (CLOROCONTIN NGD, 0.4 % by weight) and an additional dispersant (AMP-95, 0.25 % by weight). The pH of the resulting mixture was adjusted to 7-8 using ammonium hydroxide and the mixture was thereafter stirred at 700 RPM for one hour, to afford a 1:1 (by weight) FR-1210:water milling base, containing approximately 41 % by weight bromine.
  • DECA decabromodiphenyl oxide
  • the obtained FR-1210 milling base was characterized by Malvem particle sizer, determining a Di 0 of 1.298 micron, a D 50 of 3.050 micron and a D 90 of 8.42 microns, and had a viscosity of about 160 centipoises (cP).
  • the size distribution of the obtained dispersion is presented in Table 1 below and in Figure IA.
  • the micron-sized FR-1210 milling base prepared as described in Example 1 above, was introduced into a milling unit. Samples were taken every hour and analyzed for particle size. Milling was conducted until the particles cut-off was below 1 micron, usually for about 3 hours.
  • the obtained nano-sized FR-1210 dispersions were characterized by a Malve ⁇ i particle sizer, determining a D 50 in the range of 100- 250 nanometers, and a top cut-off in the range of 350-450 nanometers.
  • a nano-sized FR-1210 dispersion prepared as described above was characterized by a D 10 of 71 nanometers, a D 50 of 120 nanometers and a D 90 of 205 nanometers.
  • the size distribution of the obtained dispersion is presented in Table 2 below and in Figure IB.
  • the dispersion was further characterized by Cryogenic Tunneling Electron Microscopy (Cryo-TEM), indicating that the particle size cut-off is well below 200 nanometers and that the particle size distribution is narrow.
  • the obtained image is presented in Figure 2, and displays nano FR-1210 particles having a variety of shapes and different orientations.
  • the particles size is in the range of 5 nanometers to 250 nanometers, with a size distribution typical to cryo-TEM, namely, the bigger structures are located close to the edges of the grid's original holes (where the vitrified ice is thicker) while the smaller ones are close to the middle of the holes.
  • Some overlap of structures could be found as well, as indicated by the strong contrast (white arrows).
  • FR-1210 nano-sized dispersions were found to be more viscous by an order of magnitude than the same concentration of micron- sized FR-1210 dispersions (see, Examples 1).
  • the pH of the resulting mixture was adjusted to 7-8 using ammonium hydroxide and the mixture was stirred at 700 RPM for one hour, to afford a Saytex-8010:water milling base, containing approximately 54 % of the Saytex-8010 FR, and a 50 % bromine content.
  • the micron-sized Saytex-8010 milling base prepared as described in Example 3 above, was milled according to the procedure described above for the FR- 1210 nano-sized dispersion (Example 2), to achieve a nano-sized Saytex-8010 dispersion (milling base). Particles size analysis showed that 99.95 % of the particles were under 1 micron and the largest particles (0.05 % of the particles) were 1.3 micron in size.
  • a milling base of pentabromobenzyl acrylate also labeled herein as FR-
  • Antimony trioxide (ATO, 14.5 grams) was added to micron-sized FR-1210 dispersion (56.8 grams) obtained in Example 1, and the resulting mixture was further diluted by water (33.0 grams). This mixture was then milled for about half an hour, so as to obtain a homogenous diluted mixture.
  • a polyacrylate thickening agent (17.1 grams) was added while stirring at 400 RPM. The pH was adjusted to 7-8 using ammonium hydroxide and a binder (AC-200 W, 13.3 grams, 50 % by weight) was added to obtain a dispersion containing about 14 % by weight total solids.
  • a typical formulation of the micron-sized FR-1210 dispersion sample contained 15 % solids, of which FR-1210 comprises 9.6 % and ATO comprises 4.8 %, with the total calculated bromine content at about 8 %.
  • the obtained micron-sized FR-1210 formulation was gritty, opaque, had a medium fluidity and required constant stirring to prevent partial settling.
  • Antimony trioxide (ATO, 175 grams) was added to the milled nano-sized FR-1210 dispersion (500 grams) obtained in Example 2, and the resulting mixture was further diluted by water (175 grams) so as to maintain a 50 % by weight of total solids. This mixture was then milled for an additional half an hour, so as to obtain a homogenous diluted mixture, containing approximately 30 % by weight FR-1210 (24.5 % bromine) and 20 % ATO. This mixture (350.7 grams) was yet further diluted with distilled water (176.3 grams), and a thickening agent (potyacrylate, 6.2 grams, 1.1 % by weight) was added while stirring at 400 RPM. The pH was adjusted to 7-8 using ammonium hydroxide and a binder (AC-200 W, 50 % by weight) was added to obtain a dispersion containing about 20 % by weight total solids.
  • ATO Antimony trioxide
  • a typical formulation of the nano-sized FR-1210 dispersion sample contained 17.5 % solids, of which FR-1210 comprises 11.3 % and ATO comprises 5.6 %, with the total calculated bromine content at about 9 %.
  • the obtained nano-sized FR-1210 formulation was smooth, translucent and had good fluidity, remaining stable for 6 months.
  • the micron-sized and nano-sized Saytex-8010 dispersions obtained in Examples 3 and 4 above were formulated according to the same procedure as described above for FR-1210 nano-sized formulations (see, Example 7).
  • the formulation contained 17.2 % solids, whereas the calculated flame retardant content is 1 1.3 %, the calculated bromine content is 9.3 % and the calculated ATO content is 5.6 %.
  • the viscosity of the formulation was measured and was determined to be in the range of 100-800 cP.
  • the formulation derived from the nano-sized Saytex-8010 dispersion was smooth, translucent and had good fluidity. It remained stable for 6 months.
  • Example 7 The micron-sized and nano-sized pentabromobenzyl acrylate dispersions obtained in Example 5 above were formulated according to the same procedure as described above for FR-1210 nano-sized formulations (Example 7).
  • a fabric comprising of 100% cotton fiber weighing 216 grams per square meter was padded with the micron-sized FR-1210 formulation, prepared as described in Example 6 above, using an SDL ATLAS lab padder at maximum pressure.
  • the fabric was air-dried and the formulation was then cured at 160 °C for 4 minutes.
  • the fabric was bone dried for 30 minutes at 105 °C and was thereafter washed with 1 gram per liter of a standard detergent at 60 °C for 30 minutes and dried. The process was repeated 5 times. The add-on was determined to be 38 %.
  • the treated fabric passed Flammability Tests (ASTM D-6413).
  • a polyester fabric weighing 164 grams per square meter was padded with the formulation of Example 7, using an SDL ATLAS lab padder at maximum pressure.
  • the fabric was air-dried and the formulation was then cured at 160 °C for 4 minutes.
  • the fabric was bone dried for 30 minutes at 105 °C.
  • the treated fabric passed flammability tests (ASTM D-6413).
  • a fabric composed of 100% cotton fiber weighing 216 grams per square meter was padded with the nano-sized FR-1210 formulation, prepared as described in Example 7 above and containing 20 % by weight of a binder, using same procedure as described in Example 10 above.
  • the add-on was determined to be 22 %, with the fabric containing 14.1 % of the FR-1210 flame retardant (or 11.7 % bromine) and 7 % of the ATO.
  • the treated cotton fabric was found to pass an ASTM D-6413 12-seconds ignition flammability test after 5 washing cycles, having an after flame time of 2.0 seconds, an after glow time of 151.5 seconds, and a char length of 15.3 centimeters.
  • the application of the nano-sized FR-1210 dispersion on a cotton fabric was further characterized by SEM pictures, after soaking a 100 % cotton fabric with the nano-sized FR-1210 dispersion of Example 2. SEM pictures of the soaked fabric upon drying are presented in Figure 3 and show that the fibers are smooth (figure 3A). Furthermore, at higher resolution (figure 3B) it is evident that the nano-sized FR-1210 dispersion either covered the fiber or agglomerated between the fibers.
  • Figures 3C-E which present the edge of the sample, also demonstrate the penetration of the nano- sized FR-1210 composition to the middle of the yarn (Figure 3 C presents the edge of the yarn, Figure 3D presents a cluster of fibers comprising the yarn, and at the highest resolution ( Figure 3E) presents a single fiber in the middle of the yarn).
  • Figure 3 C presents the edge of the yarn
  • Figure 3D presents a cluster of fibers comprising the yarn
  • Figure 3E presents a single fiber in the middle of the yarn.
  • X-Ray elemental analysis of different points on a SEM sample surface was conducted on the SEM/EDS device, confirming the bromine content in the material that covered the fibers and was between the fibers (see Figure 4 B-D which present the X-Ray elemental analysis of points 1 , 2 and 3 on the surface of the sample presented in Figure 4A).
  • a polyester fabric weighing 164 grams per square meter was padded with the formulation of Example 7, using the same procedure as described in Example 1 1 above.
  • the padded fabric passed ASTM D-6413 12-seconds ignition test, with no dripping.
  • FIGS. 5A-F present the comparative optical microscope micrograph images of untreated fabrics, and fabrics treated by the micro-sized FR-1210 formulation of Example 7, and by the nano-sized FR- 1210 formulation of Example 8.
  • the fabrics treated by the nano-sized FR-1210 formulation had a smooth and even coating (nano-FR-1210 treated polyester, Figure 5C and nano-FR-1210 treated cotton, Figure 5F), and appear quite similar to untreated fabrics (untreated polyester, Figure 5A and untreated cotton, Figure 5D), while fabrics treated by a micron-sized FR-1210 formulation display a gritty texture with large uneven particles visibly adhering to the fibers (micron-FR-1210 treated polyester, Figure 5B and nano-FR-1210 treated cotton, Figure5E).
  • a fabric comprising of 100% cotton fiber weighing 216 grams per square meter was padded with the nano-sized Saytex-8010 formulation, prepared as described in Example 8 above, using the same procedure as described in Example 10 above.
  • the add-on was determined to be 23.9 %, with the fabric containing 15.7 % of the Saytex-8010 flame retardant (or 12.9 % bromine) and 7.8 % of the ATO.
  • the treated fabric was subjected to 3 laundry cycles and passed an ASTM D- 6413 12-seconds ignition test with an after flame time of 1 second, an after glow time of 75 seconds and a char length of 15 centimeters.
  • Example 8 A polyester fabric weighing 164 grams per square meter was padded with the formulation of Example 8, using the same procedure as described in Example 11 above. The treated fabric passed an ASTM D-6413 12-seconds ignition test.

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Abstract

L'invention concerne de nouvelles compositions ignifuges contenant une pluralité de particules de dimension nanométrique d'ignifuges halogénés, en particulier bromés, ainsi que des procédés de préparation de celles-ci. L'invention concerne également des formulations contenant ces compositions et des articles dans lesquels sont appliquées lesdites formulations. Ces nouvelles formulations sont particulièrement efficaces comme ignifuges textiles, nécessitant une faible quantité de liant et se caractérisant par une rapidité de lavage élevée.
PCT/IL2006/000022 2005-01-05 2006-01-05 Ignifuges halogenes de dimension nanometrique Ceased WO2006072952A2 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120115381A1 (en) * 2006-02-23 2012-05-10 Bromine Compounds Ltd. Flame retardation of textiles

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3955032A (en) * 1972-10-25 1976-05-04 White Chemical Corporation Flame retardants for natural and synthetic materials
US4600606A (en) * 1979-04-18 1986-07-15 White Chemical Corporation Process for rendering non-thermoplastic fibrous materials flame resistant to molten materials by application thereto of a flame resistant composition, and related articles and compositions
IL118088A0 (en) * 1995-06-07 1996-08-04 Anzon Inc Colloidal particles of solid flame retardant and smoke suppressant compounds and methods for making them
US6610214B2 (en) * 2001-07-20 2003-08-26 Goldenguard Technologies Ltd. UVR attenuation of fabrics and finished textiles

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120115381A1 (en) * 2006-02-23 2012-05-10 Bromine Compounds Ltd. Flame retardation of textiles
EP2242882B1 (fr) * 2008-01-23 2016-11-02 Bromine Compounds Ltd. Ignifugation améliorée de textiles

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