WO1991009093A1 - Flame retardant impregnation solution and the use of the solution - Google Patents

Flame retardant impregnation solution and the use of the solution Download PDF

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Publication number
WO1991009093A1
WO1991009093A1 PCT/SE1990/000832 SE9000832W WO9109093A1 WO 1991009093 A1 WO1991009093 A1 WO 1991009093A1 SE 9000832 W SE9000832 W SE 9000832W WO 9109093 A1 WO9109093 A1 WO 9109093A1
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WO
WIPO (PCT)
Prior art keywords
magnesium
composition
acid
zinc
calcium
Prior art date
Application number
PCT/SE1990/000832
Other languages
French (fr)
Inventor
Thomas Falkman
Original Assignee
Pyrotite Corporation
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Filing date
Publication date
Application filed by Pyrotite Corporation filed Critical Pyrotite Corporation
Publication of WO1991009093A1 publication Critical patent/WO1991009093A1/en

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Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/73—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof
    • D06M11/76—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof with carbon oxides or carbonates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D15/00—Woodstains
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/18—Fireproof paints including high temperature resistant paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K21/00—Fireproofing materials
    • C09K21/02—Inorganic materials
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/07—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof
    • D06M11/11—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof with halogen acids or salts thereof
    • D06M11/155—Halides of elements of Groups 2 or 12 of the Periodic Table
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/44—Oxides or hydroxides of elements of Groups 2 or 12 of the Periodic Table; Zincates; Cadmates
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/51—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with sulfur, selenium, tellurium, polonium or compounds thereof
    • D06M11/55—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with sulfur, selenium, tellurium, polonium or compounds thereof with sulfur trioxide; with sulfuric acid or thiosulfuric acid or their salts
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/68—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with phosphorus or compounds thereof, e.g. with chlorophosphonic acid or salts thereof
    • D06M11/70—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with phosphorus or compounds thereof, e.g. with chlorophosphonic acid or salts thereof with oxides of phosphorus; with hypophosphorous, phosphorous or phosphoric acids or their salts
    • D06M11/71—Salts of phosphoric acids
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/34—Ignifugeants
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K2240/00—Purpose of the treatment
    • B27K2240/30—Fireproofing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
    • B27K3/16—Inorganic impregnating agents
    • B27K3/18—Compounds of alkaline earth metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
    • B27K3/16—Inorganic impregnating agents
    • B27K3/22—Compounds of zinc or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
    • B27K3/34—Organic impregnating agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
    • B27K3/52—Impregnating agents containing mixtures of inorganic and organic compounds

Definitions

  • This invention relates to a substantially clear, stable, aqueous solution of an inorganic oxygen-con ⁇ taining metal compound, such as MgO, a metal chloride, such as MgCl,, and an anhydride or an organic acid, such as acetic acid.
  • an inorganic oxygen-con ⁇ taining metal compound such as MgO
  • a metal chloride such as MgCl
  • an anhydride or an organic acid such as acetic acid.
  • This invention also relates to the use of the solution for rendering porous materials, such as wood and textiles, flame retardant.
  • inflam ⁇ mable barrier between the object and the fire.
  • these barriers often take the form of a fire protective coating surrounding the object to be protec- ted.
  • the coating is often comprised of inorganic mate ⁇ rials, such as Portland cement, gypsum, calcium alumi- nate cement, phosphate-bonded cement, metal-pigment loaded silicate coatings, high temperature silicone, as well as magnesium oxychloride and magnesium oxysulfate cements.
  • coatings provide a significant measure of fire protection, there are many instances where the presence of a distinct layer of fireproofing material on the surface of an object is not desired.
  • the coatings are often viscous reactive cements that are not entirely suitable for some applications. For example, the fireproofing of textiles, wooden beams, and paper products with cements presents practical and aesthetic problems. Therefore, there exists a need in the art to utilize the fireproofing properties of such cements in an alternative form.
  • a commonly used fireproofing coating is derived from a magnesium oxychloride cement. This cement is made by mixing magnesium chloride and magnesium oxide with other materials to form a viscous, cementitious mixture that can be applied to the material to be fireproofed.
  • magnesium oxychloride coatings as well as fireproofing coatings derived from other.oxy- salt cements, have some shortcomings. For example, these cements tend to be brittle, rigid, and suscep ⁇ tible to spalling or decrepitating under heat. The coatings exhibit poor aging and weatherability charac- teristics. In addition, there is a loss of tensile strength and cohesiveness after exposure to flame.
  • DE-B-27 10 498 shows a flame retardant comprising a fire protecting paint containing a metal salt, e.g. a magnesium salt and phosphor carboxylic acids.
  • a metal salt e.g. a magnesium salt and phosphor carboxylic acids.
  • DE-C-592402 shows a coating material for flame protec ⁇ tion of wood comprising a lye of magnesium chloride and magnesite, appropriate fillers, dyestuff together with a small amount of an aromatic acid, e.g. salicylic acid.
  • GB-A-932 546 shows a method of rendering inflammable substances flame-resistant, by treating the material with an aliphatic carboxylic acid containing at least three carbon atoms and 50% chemically bound bromine.
  • the aqueous solution consists essentially of at least one inorganic oxygen-containing metal compound selected from the group consisting of magnesium oxide, zinc oxide, zinc hydroxide, calcium-magnesium oxide, calcium-magnesium carbonate, magnesium carbonate, magnesium hydroxide, strontium oxide, strontium hydroxide and strontium carbonate; at least one metal salt selected from the group consisting of magnesium chloride, zinc chloride, calcium chloride, magnesium sulfate, calcium sulfate, zinc sulfate, magnesium phosphate, zinc phosphate, calcium phosphate, and strontium chloride, sulfate or phosphate, and an organic acid.
  • inorganic oxygen-containing metal compound selected from the group consisting of magnesium oxide, zinc oxide, zinc hydroxide, calcium-magnesium oxide, calcium-magnesium carbonate, magnesium carbonate, magnesium hydroxide, strontium oxide, strontium hydroxide and strontium carbonate
  • at least one metal salt selected from the group consisting of magnesium chloride, zinc chloride
  • the inorganic oxygen- containing metal compound and the metal salt are pre ⁇ sent at a concentration sufficient to impart flame retardant properties to the porous material when the composition is incorporated in the porous material.
  • the organic acid is present in an amount sufficient to provide a homogenous and stable solution at room tempe ⁇ rature.
  • the concen ⁇ tration of organic acid is such that carboxyl groups in the acid are present in a molar quantity of about 1.5 times to about 3 times the molar quantity of oxygen- containing metal compound that is present.
  • the metal salt is present in an amount of about 0.2 times to about 5 times the molar quantity of the oxygen-containing metal compound.
  • an organic anhydride can be employed.
  • the organic anhydride is present in the composition of the invention such that the molar quan ⁇ tity of carboxyl groups derived from hydrolysis of the anhydride is about 1.5 times to about 3 times the molar quantity of oxygen-containing metal compound that is present.
  • the oxygen-containing metal compounds are magnesium oxide and zinc oxide in a ratio of about 3 parts to about 1 part, respectively, by weight.
  • the metal salts are magnesium chloride and zinc chloride in a ratio of about 3 parts to about 1 part, respectively, by weight.
  • This invention also provides a method for rendering porous metals flame retardant comprising incorporating the composition of the invention into the porous mate ⁇ rial in an amount sufficient to render the porous material flame retardant, and drying the material.
  • one embodiment of this invention relates to a solution with the same proportions between Mg 2+ and Cl- as in magnesium oxychloride, as distinct from a magnesium oxychloride cement, that is capable of impregnating material with a small pore size rendering such material flame retardant.
  • a key aspect of this invention is an organic acid which solubilizes the mixture that is present in supra-stoichiometric amounts relative to the magnesium chloride.
  • the "magnesium oxychloride" solution can be easily incorporated into many porous materials by absorption followed by drying.
  • an evacuation/impregnation method can be used to incorporate the fireproofing solution into the porous material, followed by drying.
  • the solution can be incorporated into a porous flammable material in an amount sufficient to render the porous material flame retardant.
  • DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT This invention is useful for rendering a porous mate ⁇ rial flame retardant by incorporating a substantially clear fireproofing solution into a flammable porous substrate.
  • the term "clear aqueous solution” designates a water solution that appears substantially clear to the unaided eye.
  • flame retardant material is used to indicate a material designated Class A or B using an ASTM E-84 surface Flame Spread test procedure or a material designated Class 1 or Class 2 using Nordtest NT Fire 004 or a material designated V-O, V-l or V-2 using the Bunsen burner vertical burn test procedure UL-94 or equivalent test.
  • room temperature refers to a temperature range of about 18°C to about 27°C.
  • the composition of this invention is a stable, homoge ⁇ nous, clear, aqueous solution at room temperature.
  • the solution contains a dissolved inorganic oxygen-contain ⁇ ing metal compound and a metal salt reactive therewith.
  • the dissolution obtained with an organic acid or an organic anhydride which can be volatilized when the solution is incorporated in a porous material to be fireproofed and the material is dried.
  • the solution is ' capable of uniformly penetrating the porous material to fireproof the material.
  • the fire- proofing solution is a stable homogeneous "magnesium oxychloride” solution, which is prepared by solubiliz- ing magnesium chloride and magnesium oxide with an acidic component.
  • the terms "magnesium chloride” and “magnesium oxide” are used to refer to MgCl_.nH 2 0 arid MgO, respectively, in any standard water soluble crystalline form and in any hydration state.
  • the term “magnesium chloride” encompasses both the unhydrated form (MgCl_) and the hexahydrate form (MgCl 2 -6H 2 0) .
  • the term “magnesium oxychloride” is used in a conventional sense to refer to the products formed upon mixing magnesium chloride, magnesium oxide, and water.
  • magnesium oxide is a preferred component for use in this invention
  • this invention includes solutions where a compound exhibiting similar chemical and solu ⁇ bility properties is substituted in part or in total for magnesium oxide in the fireproofing solution.
  • zinc oxide, zinc hydroxide, magnesium hydroxi- de, calcium-magnesium oxide, calcium-magnesium car- . bonate, magnesium carbonate, strontium oxide or stron ⁇ tium carbonate can be employed as a substitute, in part or in total, for magnesium oxide.
  • zinc oxide As used herein the terms “zinc oxide”, “zinc hydroxide”, “magnesium hydro- xide”, “magnesium carbonate”, “calcium-magnesium oxide”, and “calcium-magnesium carbonate” include these compounds in any standard water soluble crystalline form or hydration state. It should be noted that under conditions where the imparting of antimicrobial proper- ties to the substrate would be especially desired, zinc ' containing compounds are preferred components of the fireproofing solution.
  • Magnesium chloride is a preferred component of the fireproofing solution of this invention. Nevertheless, the invention includes solutions where an alternative compound exhibiting similar chemical and solubility properties is substituted in part or in total for magnesium chloride.
  • zinc chloride, calcium chloride, magnesium sulfate, zinc sulfate, calcium sulfate, zinc phosphate, magnesium phosphate, strontium chloride, and calcium phosphate can be employed in lieu of or in admixture with magnesium chloride.
  • the acidic component of the fireproofing solution is selected from any of a variety of organic acids includ ⁇ ing, but not limited to, monocarboxylic acids, dicar- boxylic acids, tricarboxylic acids, and tetracarboxylic acids.
  • Typical of the acids that can be employed are formic acid, acetic acid, propionic acid, valeric acid, adipic acid, citric acid, glutaric acid, succinic acid, trimellitic acid, fumaric acid, maleic acid, malonic acid, oxalic acid, cyclohexanecarboxylic acid, benzoic acid, toluic acid, phthalic acid, pyromellitic acid, and the like.
  • the acidic component is present in the solution in an amount sufficient to solubilize the other components.
  • acetic acid is employed as the acidic component in an amount sufficient to solubilize the other com- ponents of the solution.
  • the oxygen-containing metal compound and the metal salt can be solubilized with an organic anhydride.
  • the anhydride is employed in the solution in an amount sufficient to solubilize the other compo-
  • acetic anhydride is employed in an amount suffi ⁇ cient to solubilize the other components of the solu ⁇ tion.
  • the amount of magnesium salt or other metal salt pre ⁇ sent in the solution of this invention is related to the quantity of magnesium oxide or other oxygen-con ⁇ taining metal compound present in the solution.
  • the magnesium salt or other metal salt will generally be present at a level of about 0.2 times to about 5 times the molar quantity of the oxygen-containing metal compound, and preferably about 1 to about 2.5 times the molar quantity.
  • the molar ratio of the metal salt to the oxygen-containing metal compound to acid is as follows. If a monocarboxylic acid is employed, the acid is present in the solution in a molar quantity in excess of about one and one-half times, preferably about two times, the molar quantity of the oxygen-containing metal compound present. A large excess of acid over about three times the molar quantity of the oxygen containing metal is to be avoi- ded, because the presence of residual acid has been found to have a detrimental effect on the substrate to be fireproofed. If the acid employed has greater than one carboxyl group, the molar amount of acid can be decreased such that about two carboxyl groups are provided for each molecule of the oxygen-containing 'metal compound. For example, the molar ratio of a dicarboxylic acid, such as adipic acid, to magnesium oxide is about 1:1.
  • the molar ratio of the metal salt to the oxygen-containing metal compound to anhydride is as follows. If upon hydrolysis, 1 mole of anhydride yields 1 mole of car- boxyl groups, the anhydride is present in solution at about two times the molar quantity of the oxygen-con ⁇ taining metal compound present. However, if an anhyd ⁇ ride yields more than 1 mole of carboxyl groups per mole of anhydride hydrolyzed, the molar amount of anhydride is decreased such that about two carboxyl groups are provided for each oxygen-containing metal compound upon hydrolysis of the anhydride.
  • the oxygen-con ⁇ taining metal compound, the metal salt, and the acid or anhydride are present in the fireproofing solution such that the aggregate weight of these materials comprises about 1% to about 50% by weight of the aqueous solu- tion, with the preferred range being about 5% to about 20% by weight.
  • the clear solution according to the present application can also be obtained by just dissolving a salt of the used organic acid together with a chloride sulphate or phosphate salt of magnesium, one or more of the metals calcium and zinc. This can e.g. be done to obtain a solution of 1300-2500 mole m —3 metal ions 700.3600 mole m -3 of chloride, sulphate or phosphate ions and 1300- 2000 mole m -3 carboxyli.c or organi.c aci.d ani.ons.
  • Porous " materials suitable for fireproofing within the scope of this invention are solid, flammable materials. They include, but are not limited to, natural or syn- thetic fibers, such as cotton, rayon, nylon, polyester, wool, and silk, and fabrics made therefrom.
  • Other porous materials suitable for use in this invention include paper, pulp, cardboard, and some agricultural products, such as sugar cane bygasse, rice hulls, hay, hemp, wood, wood chips, wood fibers and products manu- factured from these materials. Examples of such manu ⁇ factured products are wood beams, trusses, pallets, cardboard boxes, paper tubes and pipes, chip board, rope, canopies, drapes, carpeting, furniture, up- holstery, and wallcoverings.
  • the manufactured materials can be treated with the fireproofing solution of this invention prior to, during, or after the manufacturing process.
  • additives can be incorporated into the composition of the invention to further affect the properties of the porous, flammable material.
  • boric acid, boric oxide, or ix- tures thereof can be added to reduce after-glowing of the textile.
  • other finishing additives can be employed to improve properties of the fire retardant textile. These include, but are not limited to, addi ⁇ tives for improving fabric drape and water or soil resistance.
  • antimicrobial compounds can be added to the composition to reduce rotting.
  • suitable antimicrobial agents are tin, arsenic, zinc, chromium, and copper compounds.
  • Hydro- phobic weather-proofing additives can also be added to the wooden substrates during or after the impregnation process. It is also possible to add surfactants or other modifiers which aid penetration of the fire retardant solution into the porous substrate.
  • the process by which the fireproofing composition of this invention is employed to treat the various porous, flammable materials is dependent on the nature of the material and dimensions of the article from which the material is made.
  • Typical application methods include brushing, spraying, dipping, and roller coating.
  • an evacuation-impregnation procedure which is well-known in the art for preserving wood against rot, is the most effective method.
  • This method involves placing the wood in a chamber, which is eva ⁇ cuated prior to the introduction of pressure to force the fireproofing solution into interstices of the material.
  • a typical applied vacuum is about -0.95 kg/cm 2 to about -0.75 kg/cm2, which can be followed by a typical posi .ti.ve pressure of about 2 kg/cm2 to about
  • the material After treatment of the material with the fireproofing solution, the material is dried.
  • the conditions of the drying process depend on the nature of the porous material and the fireproofing solution employed.
  • the fire retarding solution of the invention is incor ⁇ porated in a porous flammable material in an amount sufficient to render the porous material a flame retar ⁇ dant material.
  • the quantity of the composition incor- porated in the material will depend upon the concentra ⁇ tion of ingredients in the composition, the flamma- bility of the material, and the degree of flame ex ⁇ posure to which the material will be subjected.
  • the amount of the composition incorporated in the porous material is typically about 1% to about 100%, and preferably about 20% to about 85% by weight (after drying) when compared to the initial weight of the article to be impregnated).
  • the composition is incorporated in the material at a level of about 20% to about 45% by weight in order to obtain a class A fire rating by ASTM E-84.
  • loadings of about 5% to about 15% by weight generally suffice for an equivalent rating.
  • flame retardant wood was prepared in accordance with the method of the invention.
  • Magnesium oxide (30 kg) obtained from Natural Magnesia Company under the tradename Mag Plus 30 was added portionwise to 600 liters of 15% aqueous acetic acid over 45 minu ⁇ tes, such that the solution temperature did not exceed 50°C.
  • 600 liters of 28% aqueous magnesium chloride with a specific gravity of 1.26 was added.
  • the resulting solution was employed to vacuum impregnate 1 cubic meter of mixed European fir and pine using an evacuation cycle of 40 minutes at -0.9 kg/cm 2 followed by a pressure cycle of 60 minutes at 9.0
  • the impregnated wood exhibited a wet absorption of between 40 and 125% depending on the type and geo ⁇ metry of the wood (see Table 1).
  • the wood was dried in a kiln at 50°C for five days.
  • flame retardant textiles were prepared in accordance with the method of this invention.
  • Aqueous solutions containing a mixture of magnesium oxide, magnesium chloride, and acetic acid, at two times the molar concentration of magnesium oxide, were prepared according to the concentrations indicated in Table 2.
  • Cotton fabric was dipped into the solution and squeezed free of excess solution using a two roll textile damper. The fabric pieces were dried in an oven at 100°C for 20 minutes and then allowed to equilibrate to ambient room conditions over a period of 24 hours.
  • the flame retardant behaviour of the treated fabrics was evaluated by a Bunsen burner vertical burn test, procedure UL-94. This test demonstrated that good fire performance required the presence of both magnesium oxide and magnesium chloride.
  • a 50 cm x 50 cm piece of untreated cotton cloth was immersed for 30 seconds in a 1 liter solution contai- ning 1.16 mole/liter magnesium oxide, 2.32 mole/liter acetic acid, and 1.35 mole/liter calcium chloride.
  • the cloth was passed between two rollers with applied pressure to remove excess impregnation solution.
  • the cloth was dried at 50°C for 8 hours and allowed to equillibrate at 65°C, 50% relative humidity before testing according to the SIS 650082 procedure where it was observed not to burn and produced an afterglow of 3 seconds.
  • Wood Chip Board In this example, flame retardant wood chip board was prepared in accordance with the method of this inven ⁇ tion. Wood chips were soaked at 80°C for 14 hours in excess fireproofing solution with the same composition
  • Example 4 Preparation of Flame Retardant Wood
  • Chip Board flame retardant wood chip board was prepared using an alternate procedure in accordance with the method of this invention.
  • Standard untreated wood chip board (5/8 inch thickness) was heated in an oven to 80"C and then was quenched while still hot in an impregnating solution of the same composition as in Example 1. After the chip board was immersed in the solution for five minutes, it was removed and dried in an oven at 50 ⁇ C for 72 hours.
  • the treated chip board did not burn through after a 45 minute exposure to a propane torch, whereas burn through occurred in the untreated board after 7 minutes.
  • This invention offers distinct advantages over fire ⁇ proofing techniques that have been previously employed.
  • fireproofing cements have been used to encase the object being fireproofed, the object itself is not rendered flame retardant, but rather is protected by the flame retardant coating.
  • the flame retardant property of the composition is imparted to the object as a whole by incorporating the fire ⁇ proofing composition into the interstices of the sub- strate.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Fireproofing Substances (AREA)
  • Chemical And Physical Treatments For Wood And The Like (AREA)

Abstract

A fireproofing solution and a method for obtaining fireproofed products using the fireproofing solution is described. In a preferred embodiment, the fireproofing solution comprises magnesium chloride and magnesium oxide, which are solubilized with an organic acid or an anhydride. The fireproofing solution can be incorporated in a porous material to render the entire material flame retardant.

Description

FLAME RETARDANT IMPREGNATION SOLUTION AND THE USE OF THE SOLUTION
BACKGROUND OF THE INVENTION
This invention relates to a substantially clear, stable, aqueous solution of an inorganic oxygen-con¬ taining metal compound, such as MgO, a metal chloride, such as MgCl,, and an anhydride or an organic acid, such as acetic acid. This invention also relates to the use of the solution for rendering porous materials, such as wood and textiles, flame retardant.
Numerous methods have been developed for protecting objects against fire. The rationale for each of these methods is found in the physics of combustion, the chemistry of flame, and the engineering of fire control systems.
One of the most successful ways in which the spread of fire can be contained is through the use of an inflam¬ mable barrier between the object and the fire. In practice, these barriers often take the form of a fire protective coating surrounding the object to be protec- ted. The coating is often comprised of inorganic mate¬ rials, such as Portland cement, gypsum, calcium alumi- nate cement, phosphate-bonded cement, metal-pigment loaded silicate coatings, high temperature silicone, as well as magnesium oxychloride and magnesium oxysulfate cements.
While coatings provide a significant measure of fire protection, there are many instances where the presence of a distinct layer of fireproofing material on the surface of an object is not desired. In addition, the coatings are often viscous reactive cements that are not entirely suitable for some applications. For example, the fireproofing of textiles, wooden beams, and paper products with cements presents practical and aesthetic problems. Therefore, there exists a need in the art to utilize the fireproofing properties of such cements in an alternative form.
A commonly used fireproofing coating is derived from a magnesium oxychloride cement. This cement is made by mixing magnesium chloride and magnesium oxide with other materials to form a viscous, cementitious mixture that can be applied to the material to be fireproofed. Unfortunately, some magnesium oxychloride coatings, as well as fireproofing coatings derived from other.oxy- salt cements, have some shortcomings. For example, these cements tend to be brittle, rigid, and suscep¬ tible to spalling or decrepitating under heat. The coatings exhibit poor aging and weatherability charac- teristics. In addition, there is a loss of tensile strength and cohesiveness after exposure to flame.
It has been found that many of these shortcomings can be overcome by cobonding the oxychloride cement with a high alumina calcium aluminate cement to form a cemen- 'titious mixture. However, there remains a distinct need in the art to utilize the fireproofing properties of oxysalt cements in an alternative form.
As these fireproofing cements are heterogeneous viscous mixtures, a process in which the components can be solubilized would represent a major advance. Such a soluble solution could be incorporated into a flammable object imparting an intrinsic fire resistance to the object being protected. Such a process would have the distinct advantage of endowing fire resistance proper¬ ties to the object as a whole, and not restricting such properties to a surface coating that could be compromi¬ sed.
DE-B-27 10 498 shows a flame retardant comprising a fire protecting paint containing a metal salt, e.g. a magnesium salt and phosphor carboxylic acids.
DE-C-592402 shows a coating material for flame protec¬ tion of wood comprising a lye of magnesium chloride and magnesite, appropriate fillers, dyestuff together with a small amount of an aromatic acid, e.g. salicylic acid.
GB-A-932 546 shows a method of rendering inflammable substances flame-resistant, by treating the material with an aliphatic carboxylic acid containing at least three carbon atoms and 50% chemically bound bromine.
In summary, there exists a need in the art to develop a fire protective or flame retardant solution that can easily be incorporated into porous materials rendering the entire object treated fire protected or flame retardant. Additionally, there exists a need in the art ' to develop a method in which such a fireproofing solu¬ tion can be incorporated into the porous material being fireproofed.
SUMMARY OF THE INVENTION
This invention aids in fulfilling these needs in the art by providing a composition comprising a substan¬ tially clear aqueous solution that can be used to render porous materials flame retardant. The aqueous solution consists essentially of at least one inorganic oxygen-containing metal compound selected from the group consisting of magnesium oxide, zinc oxide, zinc hydroxide, calcium-magnesium oxide, calcium-magnesium carbonate, magnesium carbonate, magnesium hydroxide, strontium oxide, strontium hydroxide and strontium carbonate; at least one metal salt selected from the group consisting of magnesium chloride, zinc chloride, calcium chloride, magnesium sulfate, calcium sulfate, zinc sulfate, magnesium phosphate, zinc phosphate, calcium phosphate, and strontium chloride, sulfate or phosphate, and an organic acid. The inorganic oxygen- containing metal compound and the metal salt are pre¬ sent at a concentration sufficient to impart flame retardant properties to the porous material when the composition is incorporated in the porous material. The organic acid is present in an amount sufficient to provide a homogenous and stable solution at room tempe¬ rature.
In specific embodiments of this invention the concen¬ tration of organic acid is such that carboxyl groups in the acid are present in a molar quantity of about 1.5 times to about 3 times the molar quantity of oxygen- containing metal compound that is present. In a prefer- red embodiment, the metal salt is present in an amount of about 0.2 times to about 5 times the molar quantity of the oxygen-containing metal compound.
In lieu of the organic acid, an organic anhydride can be employed. The organic anhydride is present in the composition of the invention such that the molar quan¬ tity of carboxyl groups derived from hydrolysis of the anhydride is about 1.5 times to about 3 times the molar quantity of oxygen-containing metal compound that is present. In another specific embodiment of this invention, the oxygen-containing metal compounds are magnesium oxide and zinc oxide in a ratio of about 3 parts to about 1 part, respectively, by weight. In a further specific embodiment the metal salts are magnesium chloride and zinc chloride in a ratio of about 3 parts to about 1 part, respectively, by weight.
This invention also provides a method for rendering porous metals flame retardant comprising incorporating the composition of the invention into the porous mate¬ rial in an amount sufficient to render the porous material flame retardant, and drying the material.
More specifically, one embodiment of this invention relates to a solution with the same proportions between Mg 2+ and Cl- as in magnesium oxychloride, as distinct from a magnesium oxychloride cement, that is capable of impregnating material with a small pore size rendering such material flame retardant. A key aspect of this invention is an organic acid which solubilizes the mixture that is present in supra-stoichiometric amounts relative to the magnesium chloride. The "magnesium oxychloride" solution can be easily incorporated into many porous materials by absorption followed by drying. Alternatively, in a specific embodiment of this inven¬ tion, an evacuation/impregnation method can be used to incorporate the fireproofing solution into the porous material, followed by drying. The solution can be incorporated into a porous flammable material in an amount sufficient to render the porous material flame retardant. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT This invention is useful for rendering a porous mate¬ rial flame retardant by incorporating a substantially clear fireproofing solution into a flammable porous substrate. As used herein, the term "clear aqueous solution" designates a water solution that appears substantially clear to the unaided eye. The term "flame retardant material" is used to indicate a material designated Class A or B using an ASTM E-84 surface Flame Spread test procedure or a material designated Class 1 or Class 2 using Nordtest NT Fire 004 or a material designated V-O, V-l or V-2 using the Bunsen burner vertical burn test procedure UL-94 or equivalent test. The term "room temperature" refers to a temperature range of about 18°C to about 27°C.
The composition of this invention is a stable, homoge¬ nous, clear, aqueous solution at room temperature. The solution contains a dissolved inorganic oxygen-contain¬ ing metal compound and a metal salt reactive therewith. The dissolution obtained with an organic acid or an organic anhydride which can be volatilized when the solution is incorporated in a porous material to be fireproofed and the material is dried. The solution is ' capable of uniformly penetrating the porous material to fireproof the material.
In a preferred embodiment of this invention, the fire- proofing solution is a stable homogeneous "magnesium oxychloride" solution, which is prepared by solubiliz- ing magnesium chloride and magnesium oxide with an acidic component. As used herein, the terms "magnesium chloride" and "magnesium oxide" are used to refer to MgCl_.nH20 arid MgO, respectively, in any standard water soluble crystalline form and in any hydration state. Thus, the term "magnesium chloride" encompasses both the unhydrated form (MgCl_) and the hexahydrate form (MgCl2-6H20) . The term "magnesium oxychloride" is used in a conventional sense to refer to the products formed upon mixing magnesium chloride, magnesium oxide, and water.
While magnesium oxide is a preferred component for use in this invention, this invention includes solutions where a compound exhibiting similar chemical and solu¬ bility properties is substituted in part or in total for magnesium oxide in the fireproofing solution. For example, zinc oxide, zinc hydroxide, magnesium hydroxi- de, calcium-magnesium oxide, calcium-magnesium car- . bonate, magnesium carbonate, strontium oxide or stron¬ tium carbonate can be employed as a substitute, in part or in total, for magnesium oxide. As used herein the terms "zinc oxide", "zinc hydroxide", "magnesium hydro- xide", "magnesium carbonate", "calcium-magnesium oxide", and "calcium-magnesium carbonate" include these compounds in any standard water soluble crystalline form or hydration state. It should be noted that under conditions where the imparting of antimicrobial proper- ties to the substrate would be especially desired, zinc ' containing compounds are preferred components of the fireproofing solution.
Magnesium chloride is a preferred component of the fireproofing solution of this invention. Nevertheless, the invention includes solutions where an alternative compound exhibiting similar chemical and solubility properties is substituted in part or in total for magnesium chloride. For example, zinc chloride, calcium chloride, magnesium sulfate, zinc sulfate, calcium sulfate, zinc phosphate, magnesium phosphate, strontium chloride, and calcium phosphate can be employed in lieu of or in admixture with magnesium chloride.
The acidic component of the fireproofing solution is selected from any of a variety of organic acids includ¬ ing, but not limited to, monocarboxylic acids, dicar- boxylic acids, tricarboxylic acids, and tetracarboxylic acids. Typical of the acids that can be employed are formic acid, acetic acid, propionic acid, valeric acid, adipic acid, citric acid, glutaric acid, succinic acid, trimellitic acid, fumaric acid, maleic acid, malonic acid, oxalic acid, cyclohexanecarboxylic acid, benzoic acid, toluic acid, phthalic acid, pyromellitic acid, and the like. The acidic component is present in the solution in an amount sufficient to solubilize the other components. In an especially preferred embodi¬ ment, acetic acid is employed as the acidic component in an amount sufficient to solubilize the other com- ponents of the solution.
Alternatively, the oxygen-containing metal compound and the metal salt can be solubilized with an organic anhydride. The anhydride is employed in the solution in an amount sufficient to solubilize the other compo-
'nents. Organic anhydrides that yield the organic acids described herein upon hydrolysis are typically employ¬ ed.
In an especially preferred embodiment of this inven¬ tion, acetic anhydride is employed in an amount suffi¬ cient to solubilize the other components of the solu¬ tion. The amount of magnesium salt or other metal salt pre¬ sent in the solution of this invention is related to the quantity of magnesium oxide or other oxygen-con¬ taining metal compound present in the solution. The magnesium salt or other metal salt will generally be present at a level of about 0.2 times to about 5 times the molar quantity of the oxygen-containing metal compound, and preferably about 1 to about 2.5 times the molar quantity.
In preferred embodiments of this invention, the molar ratio of the metal salt to the oxygen-containing metal compound to acid is as follows. If a monocarboxylic acid is employed, the acid is present in the solution in a molar quantity in excess of about one and one-half times, preferably about two times, the molar quantity of the oxygen-containing metal compound present. A large excess of acid over about three times the molar quantity of the oxygen containing metal is to be avoi- ded, because the presence of residual acid has been found to have a detrimental effect on the substrate to be fireproofed. If the acid employed has greater than one carboxyl group, the molar amount of acid can be decreased such that about two carboxyl groups are provided for each molecule of the oxygen-containing 'metal compound. For example, the molar ratio of a dicarboxylic acid, such as adipic acid, to magnesium oxide is about 1:1.
In preferred embodiments of this invention, where an organic anhydride is employed to solubilize the ingredients in the composition of the invention, the molar ratio of the metal salt to the oxygen-containing metal compound to anhydride is as follows. If upon hydrolysis, 1 mole of anhydride yields 1 mole of car- boxyl groups, the anhydride is present in solution at about two times the molar quantity of the oxygen-con¬ taining metal compound present. However, if an anhyd¬ ride yields more than 1 mole of carboxyl groups per mole of anhydride hydrolyzed, the molar amount of anhydride is decreased such that about two carboxyl groups are provided for each oxygen-containing metal compound upon hydrolysis of the anhydride.
Within the context of this invention, the oxygen-con¬ taining metal compound, the metal salt, and the acid or anhydride are present in the fireproofing solution such that the aggregate weight of these materials comprises about 1% to about 50% by weight of the aqueous solu- tion, with the preferred range being about 5% to about 20% by weight.
The clear solution according to the present application can also be obtained by just dissolving a salt of the used organic acid together with a chloride sulphate or phosphate salt of magnesium, one or more of the metals calcium and zinc. This can e.g. be done to obtain a solution of 1300-2500 mole m —3 metal ions 700.3600 mole m -3 of chloride, sulphate or phosphate ions and 1300- 2000 mole m -3 carboxyli.c or organi.c aci.d ani.ons.
/
Porous "materials suitable for fireproofing within the scope of this invention are solid, flammable materials. They include, but are not limited to, natural or syn- thetic fibers, such as cotton, rayon, nylon, polyester, wool, and silk, and fabrics made therefrom. Other porous materials suitable for use in this invention include paper, pulp, cardboard, and some agricultural products, such as sugar cane bygasse, rice hulls, hay, hemp, wood, wood chips, wood fibers and products manu- factured from these materials. Examples of such manu¬ factured products are wood beams, trusses, pallets, cardboard boxes, paper tubes and pipes, chip board, rope, canopies, drapes, carpeting, furniture, up- holstery, and wallcoverings. The manufactured materials can be treated with the fireproofing solution of this invention prior to, during, or after the manufacturing process.
In addition to the above components, additives can be incorporated into the composition of the invention to further affect the properties of the porous, flammable material. For example, for the preparation of fire retardant textiles, boric acid, boric oxide, or ix- tures thereof can be added to reduce after-glowing of the textile. Similarly, other finishing additives can be employed to improve properties of the fire retardant textile. These include, but are not limited to, addi¬ tives for improving fabric drape and water or soil resistance.
In the case of wooden substrates impregnated with the composition of this invention, antimicrobial compounds can be added to the composition to reduce rotting. Examples of suitable antimicrobial agents are tin, arsenic, zinc, chromium, and copper compounds. Hydro- phobic weather-proofing additives can also be added to the wooden substrates during or after the impregnation process. It is also possible to add surfactants or other modifiers which aid penetration of the fire retardant solution into the porous substrate.
The process by which the fireproofing composition of this invention is employed to treat the various porous, flammable materials is dependent on the nature of the material and dimensions of the article from which the material is made. Typical application methods include brushing, spraying, dipping, and roller coating. For example, it is sufficient to spray or dip textiles into a bath of the fireproofing solution to obtain an effec¬ tive loading of the material on a textile substrate. For materials having thick cross-sections, such as wooden beams, an evacuation-impregnation procedure, which is well-known in the art for preserving wood against rot, is the most effective method. This method involves placing the wood in a chamber, which is eva¬ cuated prior to the introduction of pressure to force the fireproofing solution into interstices of the material. A typical applied vacuum is about -0.95 kg/cm 2 to about -0.75 kg/cm2, which can be followed by a typical posi .ti.ve pressure of about 2 kg/cm2 to about
2 20 kg/cm . It should be noted that the levels of pres¬ sure and vacuum can be varied for optimum results depending on the type of equipment used and the nature of the substrate.
After treatment of the material with the fireproofing solution, the material is dried. The conditions of the drying process depend on the nature of the porous material and the fireproofing solution employed. The
'drying process removes water from the material treated with the aqueous solution and volatilizes or decomposes the acid. The residual water content of the material after drying is typically less than about 15% by weight. The material can be dried by exposure to an elevated temperature of typically about 15°C to about 150βC, and preferably about 45°C to about 120°C. Drying can be aided by a vacuum, the circulation of air, or a drying gas. The fire retarding solution of the invention is incor¬ porated in a porous flammable material in an amount sufficient to render the porous material a flame retar¬ dant material. The quantity of the composition incor- porated in the material will depend upon the concentra¬ tion of ingredients in the composition, the flamma- bility of the material, and the degree of flame ex¬ posure to which the material will be subjected. The amount of the composition incorporated in the porous material is typically about 1% to about 100%, and preferably about 20% to about 85% by weight (after drying) when compared to the initial weight of the article to be impregnated). For flammable materials, such as wood, the composition is incorporated in the material at a level of about 20% to about 45% by weight in order to obtain a class A fire rating by ASTM E-84. For less flammable materials, loadings of about 5% to about 15% by weight generally suffice for an equivalent rating.
This invention will be more fully understood by refe¬ rence to the following Examples in which all parts, proportions, and percentages are by weight unless otherwise indicated.
/ Example 1; Preparation of Flame Retardant Wood In this example, flame retardant wood was prepared in accordance with the method of the invention. Magnesium oxide (30 kg) obtained from Natural Magnesia Company under the tradename Mag Plus 30 was added portionwise to 600 liters of 15% aqueous acetic acid over 45 minu¬ tes, such that the solution temperature did not exceed 50°C. To this solution, 600 liters of 28% aqueous magnesium chloride with a specific gravity of 1.26 was added. The resulting solution was employed to vacuum impregnate 1 cubic meter of mixed European fir and pine using an evacuation cycle of 40 minutes at -0.9 kg/cm 2 followed by a pressure cycle of 60 minutes at 9.0
2 kg/cm . The impregnated wood exhibited a wet absorption of between 40 and 125% depending on the type and geo¬ metry of the wood (see Table 1). The wood was dried in a kiln at 50°C for five days. The wood was tested according to the ASTM E-84 surface flame spread test procedure and found to be Class A (Flame Spread Index = 15) compared to the non-impregnated control, which was found to be Class C (Flame Spread Index = 100).
/
Example 1A: Preparation and Testing of Flame Retardant Wood
20 liters of a solution containing 1.27 mole/L Mag¬ nesium Oxide, 2.54 mole/L Acetic Acid and 1.55 mole/L Magnesium Chloride was employed to impregnate 9 pieces
2 of 4" X 3/4" European Fir at a pressure of 4 Kg/Cm for a period of 4 hours. The impregnated wood was allowed to air dry over night and was then dried in a circula¬ ting air at 50°C for at period of 18 hours. The wood was then allowed to equillibrate at room temperature at 50% RH for 14 days and had an increase in mass of 78% compared with the starting, untreated wood. The equil- librated, treated sample was tested according to the NORDTEST NT004 Fire and found to be Class 1.
A similar experiment was conducted with 20 liters of a solution containing 1.62 mole/L MgO, 3.24 mole/L Acetic Acid and 0.99 mole/L Magnesium Chloride. The equilli- brated, treated sample had an increase in mass of 21% and was found to be Class 2 according to NORDTEST NT004.
According to ISO 5657 test no ignition was observed dduurriinngg tthhee wwhhoollee tteest period of 15 minutes at a heat radiation of 40 KWm -2
Example 2; Preparation of Flame Retardant Textiles
In this example, flame retardant textiles were prepared in accordance with the method of this invention. Aqueous solutions containing a mixture of magnesium oxide, magnesium chloride, and acetic acid, at two times the molar concentration of magnesium oxide, were prepared according to the concentrations indicated in Table 2. Cotton fabric was dipped into the solution and squeezed free of excess solution using a two roll textile damper. The fabric pieces were dried in an oven at 100°C for 20 minutes and then allowed to equilibrate to ambient room conditions over a period of 24 hours. The flame retardant behaviour of the treated fabrics was evaluated by a Bunsen burner vertical burn test, procedure UL-94. This test demonstrated that good fire performance required the presence of both magnesium oxide and magnesium chloride. The best combination of fire performance in fabric handling was with concentra- tions of magnesium oxide and magnesium chloride at 0.0406 grams/ml and 0.0450 grams/ml, respectively. Control samples, which omitted magnesium oxide and magnesium chloride, were found to be ineffective flame retardant.
/
Example 2A; Preparation of Flame Retardant Cotton Textiles
A 50 cm x 50 cm piece of untreated cotton cloth was immersed for 30 seconds in a 1 liter solution contai- ning 1.16 mole/liter magnesium oxide, 2.32 mole/liter acetic acid, and 1.35 mole/liter calcium chloride. The cloth was passed between two rollers with applied pressure to remove excess impregnation solution. The cloth was dried at 50°C for 8 hours and allowed to equillibrate at 65°C, 50% relative humidity before testing according to the SIS 650082 procedure where it was observed not to burn and produced an afterglow of 3 seconds.
A similar cotton sample was prepared except that stron¬ tium chloride at the same molar concentration was used in place of calcium chloride. The sample was observed not to burn under the SIS 650082 test conditions and produced an afterglow of 8 seconds. Example 3; Preparation of Flame Retardant
Wood Chip Board In this example, flame retardant wood chip board was prepared in accordance with the method of this inven¬ tion. Wood chips were soaked at 80°C for 14 hours in excess fireproofing solution with the same composition
' as in Example 1. The chips were isolated by filtration and allowed to air dry overnight. The dried chips were mixed with powdered melamine-type adhesive and pressed at 180°C for one hour at a pressure of 500 psi. Upon cooling, a wood chip board was obtained that was approximately one-half inch thick. The wood chip board showed no evidence of burnthrough after a one hour exposure to a propane torch. An identical sample made from untreated chips burned through in five minutes. Example 4: Preparation of Flame Retardant Wood
Chip Board In this example, flame retardant wood chip board was prepared using an alternate procedure in accordance with the method of this invention. Standard untreated wood chip board (5/8 inch thickness) was heated in an oven to 80"C and then was quenched while still hot in an impregnating solution of the same composition as in Example 1. After the chip board was immersed in the solution for five minutes, it was removed and dried in an oven at 50βC for 72 hours. The treated chip board did not burn through after a 45 minute exposure to a propane torch, whereas burn through occurred in the untreated board after 7 minutes.
This invention offers distinct advantages over fire¬ proofing techniques that have been previously employed. When fireproofing cements have been used to encase the object being fireproofed, the object itself is not rendered flame retardant, but rather is protected by the flame retardant coating. In this invention, the flame retardant property of the composition is imparted to the object as a whole by incorporating the fire¬ proofing composition into the interstices of the sub- strate.
In further experiments other acids than acetic acids were tested. Good results were obtained with hydro¬ chloric acid, formic acid and maleic acid. With these acids a good dissolution of MgO was obtained. A non- hygroscopic character and good fire protection was obtained. A somewhat lesser fire protection was ob¬ tained with propionic acid, malonic acid and glutaric acid. TABLE 2
EXPERIMENTS USING COTTON TEXTILES
MgO MgCl UL-94 (SECONDS) FABRIC HANDLING
SAMPLE /ml /ml *1 *2 NOTES
Good Drape, Slightly Damp
Poor Drape. Slightly Damp
Good Drape, Slightly Damp
Damp
Dry
Poor Drape, Not Damp
Good Drape, Not Damp
Good Drape, Not Damp
Figure imgf000021_0001
• N.G. = BURN GREATER THAN 20 SECONDS* * 1 = FIRST IGNITION
* 2 SECOND IGNITION

Claims

WHAT IS CLAIMED IS:
1. A composition comprising a clear aqueous solution capable of rendering a porous material flame retardant, wherein the aqueous solution consists essentially of:
(a) a mixture of inorganic oxygen-containing metal compounds wherein said oxygen-containing metal com¬ pounds are selected from the group consisting of mag¬ nesium oxide, zinc oxide, zinc hydroxide, dalcium- magnesium oxide, calcium-magnesium carbonate, magnesium carbonate, and magnesium hydroxide;
(b) a mixture of metal salts wherein said metal salts are selected from the group consisting of magnesium chloride, zinc chloride, calcium chloride, magnesium sulfate, calcium sulfate, zinc sulfate, magnesium phosphate, zinc phosphate, and calcium phosphate; and
(c) an organic acid in an amount sufficient to provide a homogeneous and stable solution at room temperature; wherein the inorganic oxygen-containing metal compounds and metal salts are present in a concentration suffi¬ cient to impart flame retardant properties to the porous material when the composition is incorporated in the porous material.
2. A composition as claimed in Claim 1, wherein the
' mixture of inorganic oxygen-containing metal compounds consists essentially, of 3 parts magnesium oxide to 1 part zinc oxide by weight.
3. A composition as claimed in Claim 1, wherein the mixture of metal salts consists essentially of 3 parts magnesium chloride to 1 part zinc chloride by weight.
4. A composition comprising a clear aqueous solution capable of rendering a porous material flame retardant. wherein the aqueous solution consists essentially of:
(a) an inorganic oxygen-containing metal compound selected from the group consisting of magnesium oxide, zinc oxide, zinc hydroxide, calcium-magnesium oxide, calcium-magnesium carbonate, magnesium carbonate and magnesium hydroxide;
(b) a metal salt selected from the group consisting of magnesium chloride, zinc chloride, calcium chloride, magnesium sulfate, calcium sulfate, zinc sulfate, magnesium phosphate, zinc phosphate, and calcium phos¬ phate; and
(c) an organic acid in an amount sufficient to provide a homogeneous and stable solution at room temperature; wherein the inorganic oxygen-containing metal compound and the metal salt are present at a concentration sufficient to impart flame retardant properties to the porous material when the composition is incorporated in the porous material.
5. A composition as claimed in Claim 4, wherein the organic acid is a monocarboxylic acid.
6. A composition as claimed in Claim 5, wherein the monocarboxylic acid is selected from the gorup consist- ing of formic acid, acetic acid, propionic acid, vale- ' ric acid, cyclohexane carboxylic acid, benzoic acid and toluic acid.
7. A composition as claimed in Claim 5, wherein the monocarboxylic acid is acetic acid.
8. A composition as claimed in Claim 4, wherein the organic acid is dicarboxylic acid.
9. A composition as claimed in Claim 8, wherein the dicarboxylic acid is selected from the group consisting of adipic acid, maleic acid, malonic acid, glutaric acid, succinic acid, fμmaric acid, and oxalic acid.
10. A composition as claimed in Claim 4, wherein the organic acid is a tricarboxylic acid.
11. A composition as claimed in Claim 10, wherein the tricarbocylic acid is citric acid or trimellitic acid.
12. A composition as claimed in Claim 4, wherein the organic acid is tetracarboxcylic acid.
13. A composition as claimed in Claim 12, wherein the tetracarboxylic acid is pyromellitic acid.
14. A composition as claimed in Claim 4, wherein the inorganic oxygen-containing metal compound is magnesium oxide.
15. A composition as claimed in Claim 14, wherein the metal salt is magnesium chloride.
16. A composition comprising a clear aqueous solution capable of rendering porous material flame retardant, wherein the aqueous solution consists essentially of:
(a) a mixutre of inorganic oxygen-containing metal compounds wherein said oxygen-containing metal com- pounds are selected from the group consisting of mag¬ nesium oxide, zinc oxide, zinc hydroxide, calcium- magnesium oxide, calcium-magnesium carbonate, magnesium carbonate, and magnesium hydroxide;
(b) a mixture of metal salts wherein said metal salts are selected from the group consisting of magnesium chloride, zinc chloride, calcium chloride, magnesium sulfate, calcium sulfate, zinc sulfate, magnesium phosphate, zinc phosphate, and calcium phosphate; and (c) an organic anhydride in an amount sufficient to provide a homogeneous and stable solution at room temperature; wherein the inorganic oxygen-containing metal compounds and metal salts are present at a concentration suffi¬ cient to impart flame retardant properties to the porous material when the composition is incorporated in the porous material.
17. A composition as claimed in Claim 16, wherein the mixture of inorganic oxygen-containing metal compounds consists essentially of 3 parts magnesium oxide to 1 part zinc oxide by weight.
18. A composition as claimed in Claim 16, wherein the mixture of metal salts consists essentially of 3 parts magnesium chloride to 1 part zinc chloride by weight.
19. A composition comprising a clear aqueous solution capable of rendering a porous material flame retardant, wherein the aqueous solution consists essentially of: (a) an inorganic oxygen-containing metal compound
'selected from the group consisting of magnesium oxide, zinc oxide, zinc hydroxide, calcium-magnesium oxide, calcium-magnesium carbonate, and magnesium hydroxide;
(b) a metal salt selected from the group consisting of magnesium chloride, zinc chloride, calcium chloride, magnesium sulfate, calcium sulfate, zinc sulfate, magnesium phosphate, zinc phosphate, and calcium phos¬ phate; and
(c) an organic anhydride in an amount sufficient to provide a homogeneous and stable solution at room temperature; wherein the inorganic oxygen-containing metal compound and the metal salt are present at a concentration sufficient to impart flame retardant properties to the porous material when the composition is incorporated in the porous material.
20. A composition as claimed in Claim 19, wherein the organic anhydride is acetic anhydride.
21. A composition as claimed in Claim 19, wherein the inorganic oxygen-containing metal compound is magnesium oxide.
22. A composition as claimed in Claim 21, wherein the metal salt is magnesium chloride.
23. A composition comprising a substantially clear aqueous solution capable of rendering a porous material flame retardant, wherin the aqueous solution consists essentially of:
(a) at least one inorganic oxygen-containing metal compound selected from the group consisting of mag¬ nesium oxide, zinc oxide, zinc hydroxide, calcium- magnesium oxide, calcium-magnesium carbonate, magnesium ' carbonate and magnesium hydroxide;
(b) at least one metal salt selected from the group consisting of magnesium chloride, zinc chloride, cal¬ cium chloride, magnesium sulfate, calcium sulfate, zinc sulfate, magnesium phosphate, zinc phosphate, and calcium phosphate; and
(c) an organic acid, wherein the concentration of organic acid is such that carboxylic acid groups of the acid are present in a molar quantity of at least about 1.5 times to about 3 times the molar quantity of oxy- gen-containing metal present; and wherein the inorganic oxygen-containing metal compound and the metal salt are present at a concentration sufficient to make the porous material a flame retar- dant material when the composition is incorporated in the porous material.
24. A composition as claimed in Claim 23, wherein the metal salt is present in an amount of about 0.2 times to about 5 times the molar quantity of the metal oxide present.
25. A composition comprising a substantially clear aqueous solution capable of rendering a porous material flame retardant, wherein the aqueous solution consists essentially of:
(a) at least one inorganic oxygen-containing metal compound selected from the group consisting of mag¬ nesium oxide, zinc oxide, zinc hydroxide, calcium- magnesium oxide, calcium-magnesium carbonate, magnesium carbonate and magnesium hydroxide;
(b) at least one metal salt selected from the group consisting of magnesium chloride, zinc chloride, cal¬ cium chloride, magnesium sulfate, calcium sulfate, zinc sulfate, magnesium phosphate, zinc phosphate, and 'calcium phosphate; and
(c) an organic anhydride, wherein the concentration of organic anhydride is such that the molar quantity of carboxylic acid groups derived from hydrolysis of said anhydride is at least about 1.5 times to about 3 times the molar quantity of oxygen-containing metal present; and wherein the inorganic oxygen-containing metal compound and the metal salt are present at a concentration sufficient to make the porous material a flame retar- dant material when the composition is incorporated in the porous material.
26. A composition as claimed in Claim 19, wherein, the metal salt is present in an amount of about 0.2 times to about 5 times the molar quantity of metal oxide present.
27. A composition comprising a substantially clear aqueous solution capable of rendering a porous material flame retardant, wherein the aqueous solution compri¬ ses:
(a) at least one oxygen-containing metal compound selected from the group consisting of magnesium oxide, zinc oxide, zinc hydroxide, calcium-magnesium oxide, calcium-magnesium carbonate, magnesium carbonate, and magnesium hydroxide;
(b) at least one metal salt selected from the group consisting of magnesium chloride, zinc chloride, cal- cium chloride, magnesium sulfate, calcium sulfate, zinc sulfate, magnesium phosphate, zinc phosphate, and. calcium phosphate; and
(c) an organic acid in an amount sufficient to provide a homogeneous and stable solution at room temperature; wherein the metal salt is present in an amount of about '0.2 times to about 5 times the molar quantity of the oxygen-containing metal compound.
28. A composition as claimed in Claim 27, wherein the organic acid is a monocarboxylic acid.
29. A composition as claimed in Claim 28, wherein the monocarboxylic acid is acetic acid.
30. A composition as claimed in Claim 29, wherein the oxygen-containing metal compound is magnesium oxide and the metal salt is magnesium chloride.
31. A composition as claimed in Claim 27, wherein the oxygen-containing metal compounds are magnesium oxide and zinc oxide in a ratio of 3 parts to 1 part, respec¬ tively, by weight.
32. A composition as claimed in Claim 27, wherein the metal salts are chloride and zinc chloride in a ratio of 3 parts to 1 part, respectively, by weight.
33. A composition as claimed in Claim 1, wherein the solution capable of rendering a porous material flame retardant consists essentially of a water solution containing 1300-2500 mole m —3 Mg2+, 700 - 3600 mole m—3
Cl - and 1300-2000 mole m-3 cati.ons of an organic aci.d with the formula R 1COOH or R2(C00H)2 where R1 i.s hydro- gen or a saturated or unsaturated, branched or unbran- ched alkyl group with 1-4 carbon atoms, possibly sub¬ ssttiittuutteedd wwiitthh cchhlloorriinnee oorr bbrroommiinnee aann<d R 2 is an alkylene group with 1-3 carbon atoms; or HCI.
34. A method for rendering porous materials flame 'retardant, wherein the method comprises:
(a) incorporating the substantially clear aqueous solution as claimed in any one of the preceding claims into a porous material in an amount sufficient to render the porous material flame retardant; and
(b) drying the porous material.
35. A method as claimed in Claim 34, wherein the porous material is dried at a temperature of about 15"C to about 150°C.
36. A method as claimed in Claim 34, wherein the sub¬ stantially clear aqueous solution is incorporated into the porous material using an evacuation/impregnation process.
37. A method as claimed in Claim 34, wherein the mate¬ rial to be rendered flame retardant is selected from the group consisting of a textile or a textile fiber.
38. A method as claimed in Claim 34, wherein the porous material to be rendered flame retardant is selected from the group consisting of wood, paper, cardboard, and pulp.
PCT/SE1990/000832 1989-12-13 1990-12-13 Flame retardant impregnation solution and the use of the solution WO1991009093A1 (en)

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SE8904204-8 1989-12-13
SE8904204A SE465166B (en) 1989-12-13 1989-12-13 FIRE PROTECTIVE IMPROVEMENT SOLUTION AND USE OF ITS

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WO1995032930A1 (en) * 1994-05-30 1995-12-07 Baran Advanced Materials (94) Ltd. Improved foamed magnesite cement and articles made therewith
US5630861A (en) * 1994-07-07 1997-05-20 Baran Advanced Materials (94) Ltd. Controlled release fertilizers
US5645637A (en) * 1994-05-30 1997-07-08 Baran Advanced Materials 94 Ltd. Foamed magnesite cement and articles made therewith
WO2008031559A3 (en) * 2006-09-14 2008-11-06 Buma Advanced Technologies S L Flame retardant composition
CN103233356A (en) * 2013-05-09 2013-08-07 东华大学 Preparation method of inorganic flame-retardant fluorescent fabric
WO2015076842A1 (en) * 2013-11-25 2015-05-28 Nature Tech Llc Fire-resistant cellulose material
BE1022331B1 (en) * 2014-09-12 2016-03-16 Unilin, Bvba FIRE-RESISTANT PLATE AND METHOD FOR MANUFACTURING A FIRE-RESISTANT PLATE
WO2017014782A1 (en) * 2015-07-23 2017-01-26 Nature Tech Llc Fire-resistant cellulose material
CN109203154A (en) * 2018-09-08 2019-01-15 佛山市禅城区诺高环保科技有限公司 A kind of forest-friendly building timbers fire retardant
AU2019219810B1 (en) * 2019-08-02 2020-12-03 Zhejiang Yanmu Techonology Co., Ltd. Fire-proof wooden pressure board and the production method thereof
CN114654550A (en) * 2022-01-10 2022-06-24 东北林业大学 Flame-retardant wood, preparation method thereof and application of metal halide
CN115748004A (en) * 2023-01-04 2023-03-07 天津渤海伊丝特制衣有限公司 Flame-retardant antistatic polyester and preparation method thereof

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DE599402C (en) * 1932-08-03 1934-06-30 Bruno Ullrich Paints for making wood flame-proof, or the like.
US4083789A (en) * 1974-07-29 1978-04-11 Monsanto Company Composition containing halogenated polyphosphates
US4111885A (en) * 1977-07-25 1978-09-05 General Motors Corporation Synergistic fire retardant additives for plasticized polyvinyl chloride consisting essential of boric acid and zinc oxide or zinc phosphate
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Cited By (14)

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Publication number Priority date Publication date Assignee Title
WO1995032930A1 (en) * 1994-05-30 1995-12-07 Baran Advanced Materials (94) Ltd. Improved foamed magnesite cement and articles made therewith
US5645637A (en) * 1994-05-30 1997-07-08 Baran Advanced Materials 94 Ltd. Foamed magnesite cement and articles made therewith
US5630861A (en) * 1994-07-07 1997-05-20 Baran Advanced Materials (94) Ltd. Controlled release fertilizers
WO2008031559A3 (en) * 2006-09-14 2008-11-06 Buma Advanced Technologies S L Flame retardant composition
CN103233356A (en) * 2013-05-09 2013-08-07 东华大学 Preparation method of inorganic flame-retardant fluorescent fabric
WO2015076842A1 (en) * 2013-11-25 2015-05-28 Nature Tech Llc Fire-resistant cellulose material
BE1022331B1 (en) * 2014-09-12 2016-03-16 Unilin, Bvba FIRE-RESISTANT PLATE AND METHOD FOR MANUFACTURING A FIRE-RESISTANT PLATE
EP2995671A1 (en) 2014-09-12 2016-03-16 Unilin, BVBA Fire resistant board and method for manufacturing a fire resistant board
WO2017014782A1 (en) * 2015-07-23 2017-01-26 Nature Tech Llc Fire-resistant cellulose material
CN109203154A (en) * 2018-09-08 2019-01-15 佛山市禅城区诺高环保科技有限公司 A kind of forest-friendly building timbers fire retardant
AU2019219810B1 (en) * 2019-08-02 2020-12-03 Zhejiang Yanmu Techonology Co., Ltd. Fire-proof wooden pressure board and the production method thereof
CN114654550A (en) * 2022-01-10 2022-06-24 东北林业大学 Flame-retardant wood, preparation method thereof and application of metal halide
CN114654550B (en) * 2022-01-10 2023-09-26 东北林业大学 Flame-retardant wood, preparation method thereof and application of metal halide
CN115748004A (en) * 2023-01-04 2023-03-07 天津渤海伊丝特制衣有限公司 Flame-retardant antistatic polyester and preparation method thereof

Also Published As

Publication number Publication date
SE465166B (en) 1991-08-05
SE8904204D0 (en) 1989-12-13
AU6917391A (en) 1991-07-18
SE8904204L (en) 1991-06-14

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