US3877974A - Flame retardants for blends of natural and synthetic fibers - Google Patents

Flame retardants for blends of natural and synthetic fibers Download PDF

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US3877974A
US3877974A US33073172A US3877974A US 3877974 A US3877974 A US 3877974A US 33073172 A US33073172 A US 33073172A US 3877974 A US3877974 A US 3877974A
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flame
polybrominated
parts
dispersion
retardant
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Vladimir Mischutin
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White Chemical Corp
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    • D06M13/00Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/325Amines
    • D06M13/338Organic hydrazines; Hydrazinium compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUSE OF INORGANIC OR NON-MACROMOLECULAR ORGANIC SUBSTANCES AS COMPOUNDING INGREDIENTS
    • C08K13/00Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
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    • D06M11/00Treating 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
    • D06M11/07Treating 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
    • D06M11/11Treating 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
    • D06M11/20Halides of elements of Groups 4 or 14 of the Periodic System, e.g. zirconyl chloride
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    • D06M11/32Treating 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
    • D06M11/36Treating 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
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    • D06M11/36Treating 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
    • D06M11/47Oxides or hydroxides of elements of Groups 5 or 15 of the Periodic System; Vanadates; Niobates; Tantalates; Arsenates; Antimonates; Bismuthates
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    • D06M11/00Treating 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
    • D06M11/77Treating 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 silicon or compounds thereof
    • D06M11/79Treating 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 silicon or compounds thereof with silicon dioxide, silicic acids or their salts
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    • D06M13/00Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/02Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with hydrocarbons
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    • D06M13/00Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/08Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with halogenated hydrocarbons
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    • D06M13/00Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/152Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen having a hydroxy group bound to a carbon atom of a six-membered aromatic ring
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    • D06M13/00Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/184Carboxylic acids; Anhydrides, halides or salts thereof
    • D06M13/207Substituted carboxylic acids, e.g. by hydroxy or keto groups; Anhydrides, halides or salts thereof
    • D06M13/21Halogenated carboxylic acids; Anhydrides, halides or salts thereof
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    • D06M13/00Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/244Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
    • D06M13/282Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing phosphorus
    • D06M13/292Mono-, di- or triesters of phosphoric or phosphorous acids; Salts thereof
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    • D06M15/00Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/263Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
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    • D06M15/00Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/693Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural or synthetic rubber, or derivatives thereof
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    • D06M2101/00Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/02Natural fibres, other than mineral fibres
    • D06M2101/04Vegetal fibres
    • D06M2101/06Vegetal fibres cellulosic
    • DTEXTILES; PAPER
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    • D06M2101/00Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16Synthetic fibres, other than mineral fibres
    • D06M2101/30Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/32Polyesters
    • DTEXTILES; PAPER
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    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS, OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/30Flame or heat resistance, fire retardancy properties
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00Stock material or miscellaneous articles
    • Y10S428/92Fire or heat protection feature
    • Y10S428/921Fire or flameproofing
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/20Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
    • Y10T442/2631Coating or impregnation provides heat or fire protection
    • Y10T442/2713Halogen containing

Abstract

A process for rendering synthetic materials, of synthetic fibers or mixtures of the same flame resistant which entails employing water insoluble flame retardant agents which are treated as colorless pigments, reduced to extremely finely divided condition, suspended in latex medium and applied as such or as part of a dispersed dye paste to the fabric, dried and set in place. The active flame retardant agents are brominated organic chemical compounds, and reduced to a fine state of subdivision, preferably under two microns, average particle diameter, which compound is supported in an aqueous suspension with a colloidal protective agent, and thus, is in a form for blending in a binder, plastic resin latex, so that when the composition is dried and cured in place on the fabric, a very useful retardant effect is obtained which is durable to laundering and dry cleaning, and the hand of the fabric is preserved.

Description

United States Patent [191 Mischutin [451 Apr. 15, 1975 FLAME RETARDANTS FOR BLENDS OF NATURAL AND SYNTHETIC FIBERS 75 Inventor; Vladimir Mischutin, Union City,

[73] Assignee: White Chemical Corporation,

Bayonne, NJ.

[22] Filed: Oct. 25, 1972 21 Appl. No.: 330,731

[52] US. Cl. 428/290; 252/81; 427/290; 427/428; 427/358; 428/921 [51] Int. Cl. C09k 3/28; C09d 5/18 [58] Field of Search 117/137, 136,111 F,l21; 106/15 FP; 252/81 [56] References Cited UNITED STATES PATENTS 2,668,294 2/1954 Gilpin 117/155 UA 2,912,392 11/1959 Stilbert et al. 117/137 X 3,047,425 7/1962 Hirshfeld et a1. 117/136 X 3,093,599 6/1963 Mueller-Tamm et al. 117/136 UX 3,658,634 4/1972 Yanagi 106/15 FP 3,668,155 6/1972 Raley 252/8.1 X 3,715,310 2/1973 Butcher 252/8.l 3,770,577 11/1973 Humphrey 117/137 X FOREIGN PATENTS OR APPLICATIONS 1,191,569 3/1968 Germany 117/136 Primary Examiner-Harry .l. Gwinnell Attorney, Agent, or Firm-Thomas B. Graham [57] ABSTRACT A process for rendering synthetic materials, of synthetic fibers or mixtures of the same flame resistant which entails employing water insoluble flame retardant agents which are treated as colorless pigments, reduced to extremely finely divided condition, suspended in latex medium and applied as such or as part of a dispersed dye paste to the fabric, dried and set in place.

9 Claims, No Drawings FLAME RETARDANTS FOR BLENDS OF NATURAL AND SYNTHETIC FIBERS RELATED APPLICATION This application is related to my copending application, Ser. No. 300,732, filed of even date herewith, incorporated herein fully.

BACKGROUND OF THE INVENTION Purely for safety purposes, flame retardance or flame resistance of a fabric is a highly desirable characteristic. Of many methods available for developing various levels of flame retardancy all possess a variety of disadvantages, the principal ones being the inability of the flame retardant material, or treatment, to last through laundering or dry cleaning operations. Another principal disadvantage of treatments of fabrics to develop this characteristic of flame retardance is the loss of hand in the substrate. The problem is greatly aggravated in some areas of handling, particularly where it is necessary to meet statutory requirements for flame retardance in garments. Their physical condition being in the form of a bundle of fine fibers invites and encourages the sustenance of a flame if one gets started in the fabric. That is, a large area of oxidation is presented to any flame which gets started.

It is accordingly a basic object of this invention to provide a method employing familiar techniques in the textile industry for the application of flame retardant materials to textile fibers, whether the fibers be in the form of woven cloth, knitted cloth or in the form of balls of the thread prior to being woven into cloth.

Other objects and advantages of the invention will be in part be obvious and in part appear hereinafter.

DESCRIPTION OF THE INVENTION Flame retardants for textiles and related materials of the durable type have been found to possess a multitude of side effects which would either render the flame retarded substrate unusuable or reduce its useful life. In addition, most commonly used methods will be effective on one particular substrate while completely ineffective on others or blends of the same.

The present invention relates to a new method of flame retarding textile and related materials using a commonly employed method in pigment printing and dyeng, that is, through the use of a primary binder which serves as an adhesive to fasten the flame retardant to a given substrate. In addition this technique can also be employed to flame retard the said binders, which normally are emulsions of synthetic polymeric materials which are highly flammable and contribute to the flammability of flame retarded substrates.

The subject of the present invention consists of two basic elements, the flame retardant element and a binding element.

The flame retarding element is a colorless highly halobrominated, organic compound, solid at room temperature, possessing high melting and decomposition points, which is easily reduced to an extremely small particle size by conventional means of grinding. The solid flame retardant material is reduced to a submicron or micron particle size and suspended in water in a fashion similar to the preparation of pigment disper sions. In some cases, especially when extremely heat stable materials are used, a synergist which will contribute to render the halobrominated solids more heat unstable must be-employed. This synergist must possess similar characteristics to the halobrominated flame retardant, that is, it is a micropulverized solid possessing good heat stability, finely dispersed in water. In addition it must react with the halobrominated flame retarder at combustion temperatures to form a gaseous non-flammable gas which will prevent oxygen from reaching the flaming substrate, thus impeding the oxidation process.

The second element used in this invention is an emulsion of a high molecular weight polymer, commonly referred to as latex. The polymer employed can be the result of polymerizing acrylic acid, methacrylic acid, acrylamide, methacrylamide, acrylonitrile, esters of acrylic and methacrylicacids, vinyl chloride, vinylidene chloride, styrene, butadiene, maleic or fumaric acids and esters of same and the like. The polymer can be homopolymers or copolymers of the above described monomers. These emulsion polymers are commercially available in differing grades depending on the ultimate properties desired. They have in common the fact that they form films at room or elevated temperatures, alone or in the presence of plasticizers. The properties of the film depend on the chemical composition of the same.

Due to the fact that the latexes possess extremely good adhesive properties, they are normally used for bonding purposes. They are used for bonding of pigments to hard to dye substrates, to bond fibers with fibers to obtain non woven fabrics, to bond fibers to fabrics to produce flocked fabrics and to bond fabrics to fabrics, fabrics to foams, fabrics to films, to non wovens, etc., to obtain laminated fabrics. They are also used for fabric backcoating to achieve various effects such as dimensional stability, to prevent ravelling, to give fabrics non-slipping characteristics, with a filler, to impart opacity to the same, etc., and for finishing to achieve dimensional stability, to increase strength, decreasae air permeability, impart waste repellency, etc.

This invention relates to two uses of these materials:

a. To bond the flame retardant to non-reactive substrates by the use of latex adhesives; and

b. To use the flame retardant to make the latex films non-combustible or self extinguishing when they are applied to flame retarded substrates.

In this application the solid flame retardant is the predominant ingredient and the latex is the minor ingredient.

The micropulverized solid flame retardant is first dispersed in water containing a wetting agent by adding it slowly to the aqueous phase under strong agitation, with a high speed, high shear mixer. After addition of the solid has been completed, the resulting dispersion is stabilized by adding small quantities of a protective colloid (commonly called thickener) such as carboxy methyl cellulose, methoxy or ethoxycellulose of selected molecular weight to achieve an optimum viscosity and prevent the particles from settling.

The FR (flame retardant) is now diluted with water to a predetermined strength and sufficient amount of latex to achieve adhesion is added. This solution is now applied to the substrate by dipping it into this solution and removing the excess by squeezing between two rollers. The w'et substrate is now air dried at any convenient temperature and baked at C. to C. for to 90 seconds.

The resulting material is flame retardant when tested by commonly used flammabililty tests and the flame retardant is not lost after multiple launderings and/or dry cleanings. The feel or hand of the flame retarded material is unchanged, but can be made stiff, if desirable, by selecting a harder latex.

The FR dispersion prepared as described above, is diluted in water, the latex is added and the viscosity adjusted by the use of a thickener.

This treating batch is now applied by different techniques depending on the final effect desired. It can be padded, knife coated, roller coated, sprayed, roller printed, screen printed, applied by saturation and the like. The substrates are now air dried at any convenient temperature, and baked as above.

This technique is usually employed when the substrate to which the latex is applied is either intrinsically flame retardant or has been flame proofed in a separate operation. It can be used to flame retard latices, which will be employed as flocking adhesives, for fabric backcoating, pigment dyeing or printing, bonding or non woven fabric lamination and the like.

The process of this invention is applicable to textile materials, in staple, tow, yarn, fiber, woven fabrics, non-woven fabrics, circular and flat knits, carpets and the like, to paper, to films, to foams, etc.

The substrate can be of natural origin such as cotton, linen, jute, coco fiber, wool, silk and the like, man made such as regenerated cellulose, cellulose diand triacetates, fiberglass and the like or synthetic polymeric materials such as nylon, polyester, acrylics, polypropylene and the like.

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention utilizes brominated aromatic compounds, preferably brominated as flame retarding materials. The preferred aromatic compounds employed are derivatives of Benzene Where A through N are the same can be H, Br, CH C I'I Ca 7,

. or different and CH and the like; and X, Y, Z can be the same or different and can be H, CH C H C 1, s s

Bis (hexachlorocyclopentadieno)-cycl00ctane 01 V Bl Dibromohexachloroeyclopentadienocyclooctaue N lN -ethylbis (dibromonorbornene) -dicarb0xamide The preferred entities are: 1. Polybrominated benzenes of the general formula:

I E I where A to F are the same or different and may be H, Br, with at least one Br present on the benzene ring.

2. Polybromo monoalkyl benzene of the general formula:

where R may be alkyl, preferably of 1-5 carbons such as methyl, ethyl, propyl, butyl, pentyl, isopropyl, tertbutyl; unsaturated alkyls, haloalkyl or polyhaloalkyl wherein the moiety may include up to four bromine atoms where the halogens are chlorine and/or bromine and A, B, C, D, E, are as above.

3. Polybromo dialkyl benzene of the general formula:

where R, and R are the same or different and are similar to R in (2).

4. Polybrominated phenols 0f the general formula:

where R and R are the same or different and can be H, alkyl preferably of 1-5 carbon atoms, bromoalkyl, polybromoalkyl and the like; aryl, phenyl, bromoaryl, bromophenyl, polybromoaryl, polybromopenyl, NH NH Na, K, Li, Ca, Ba, Sb, Ti and the like;

O Ra.

5. Polybrominated biphenyls of the general formula:

where A to J are the same or different and can be H, Br, lower alkyl C to C aryl,

O OHLX,

X being OH, NH,, ONH Na, K and the like.

6. Polybrominated terphenyls of the general formula:

B A N M L K D E F G H I where A to N are the same as in 5.

7. Polybrominated aniline of the general formula:

XNY

where A to E are the same as in 5, and X and Y are H, lower alkyl C to C aryl, bromoalkyl, polybromoalkyl, bromoaryl, polybromoaryl, phenyl bromophenyl, polybromophenyl and the like.

8. Polybrominated aromatic mono and polyacids, anhydrides or esters of the same or the general formula:

9. Polybrominated bisphenol A of the general formula:

In the process of preparing the flame proofing agent of the present invention, there is also utilized a synergist which reacts with the halobrominated organic material at the flame temperatures inducing its decomposition and liberating a nonflammable gas which forms a blanket around the flaming substrate, displacing the oxygen from the vicinity of the same thus impeding the oxidation process of the combustion.

The synergists are normally metallic oxides of the general formula:

where Me can be Al, Ga, Si, Ge, As, Sb, Bi, Ti, Zr, and the like and n is the valence of the metal in its oxidized state. Especially are the oxides of aluminum, germanium, antimony and titanium useful.

These oxides must also be present in a fine particle state of the same size as the halobrominated compound or smaller.

The synergist is blended with the halobrominated compound during the preparation of the FR dispersion, the ratio of halobrominated compound to synergist depending on the stability of the halobrominated material and the reactivity of the particular metallic oxide employed. It was found that normally 3 to 7 parts halobrominated flame retarder for each part of metallic oxide, preferably 4-6 parts to 1 part, give the best results.

The emulsion polymers, commonly referred to as synthetic latices, are commercially available materials, obtained by emulsion homoor co-polymerization of monomers of the general class:

where R and R can be the same or different and can be selected among 1-1, Cl, Br, CH C H where n is 1 to 5 and m 2n 1, COOH, CONH CN, CH =CH C H and the like.

The preferred monomers are alkyl esters of acrylic and methacrylic acids, acryland methacryl amides, acrylonitrile, acrylic and methacrylic acids, maleic or fumaric acids and alkyl esters of the same vinyl and vinylidene chlorides, styrene and butadiene.

Due to the infinite number of possible combinations we will class the polymers in the following group:

a. Acrylic latices, mainly homoor co-polymers of alkyl esters of acrylic or methacrylic acids which can also contain acrylic or methacrylic acid, acrylonitrile, acrylamide, n-methylol acrylamide, vinyl and vinylidiene chlorides and the like. The alkyl group of the esters can also contain hydroxyl groups. The presence of reactive groups, such as HO, CONH COOH,

suggests the possibility of further crosslinkage by the effect of heat leading to a higher molecular weight and thus much more stable polymers. These types of polymers are referred to as cross-linking, self-cross linking 0r thermosetting latices.

b. Acrylonitrile Latices: where the major ingredient is acrylonitrile which can be found as homo polymers or copolymers as in (a).

. c. Vinylchloride Latices: where the major constituent is this monomer homo-polymerized or copolymerized asin (a).

d. Vinylidine chloride latices;

e. ABS (acrylonitrile butadiene styrene) latices:

where these three monomers are the principal ingredients and can also be copolymerized with other monomers as in (a).

f. SBR (styrene butadiene rubber) latices.

g. Also there are employed emulsion polymers obtained by the reaction of a polyisocyanate and an aliphatic polyol which can be a polyether, a polyester, or a polycaprolactone, the preferred polyisocyanate being a mixture of isomers of toluene diisocyanate and the preferred polyol being a polyethylene glycol condensate having a molecular weight in excess of 3,000, commonly referred to as a polyurethane latex.

The reason for blending these various monomers is to achieve polymers with varying film properties, such as:

1. Feel or hand of film. This can vary from soft to hard and from tacky to dry. This parameter is measured by the glass transition temperature (T.G.) or in some cases by T (temperature at which the torsional modulus of an air dried film is 300 Kg/CM Both are measured in C and can range from l00C to +100C. As a general rule, the lower the T6 or T the softer the film, the film becoming harder with increasing temperatures.

2. Solvent swelling resistance. Latices are known to swell when wetted with organic, especially chlorinated solvents, resulting in lack of durability to dry cleaning. This property is improved by introducing cross-linkable sites into the molecule of the polymer.

3. Film strength. The strength of the film is also improved by increasaing the molecular weight of the polymer through the introduction of crosslinkable sites which are made to react by heat and/or catalysts.

4. Adhesion of film. This property is very important since the durability of the flame retarder will greatly depend on it.

In the process of preparing the flame retardant dispersion 1 to 4 parts, preferably 2 to 3 parts, of a finely divided powdered halobrominated organic material is dispersed in 1 part of water containing 0.1 to 1% of anionic wetting agent by the use of a high shear mixer. After addition is completed 0.1 to 1 part, preferably 0.2

to 0.4 part, based on the weight of the halobrominated.

organic compound of a metallic oxide is slowly added. After addition is complete the dispersion is stabilized by adding 0.1 to 0.5%, preferably 0.2 to 0.3%, on the weight of the dispersion of a protective colloid such as ethoxy cellulose.

In the case when it is necessary to flame retard a given substrate 0.5 to 1.5 parts, preferably 0.8 to 1.2 parts, of FR dispersion are dissolved in 1 part of water with mild agitation. To this solution 0.05 to 0.4, preferably 0.1 to 0.3 part of a latex containing 35 to preferably 45 to 55%, of a polymer is added. In treating hydrophobic substrates, 0.5.to 1.5%, preferably 0.8 to 1.2% of a wetting agent is added.

The'substrate to be treated is dipped in this solution and the excess removed by squeezing between two rollers. The wet material is air dried in an oven at C to C, preferably 100C to 1 10C, and baked at C 9 to 18C, preferably 150C to 170C for /2 to minutes,

' preferably 1 /2 to3'minutes.

When the substrate to be treated is either intrinsically flame resistant or has been flamed retarded in a separate operation and must be treated with a flammable latex to achieve some desirable effect on the substrate the treating solution is prepared as follows: To 1 part of water 0.5 to 1.5 parts, preferably 0.8 to 1.2 parts, of latex is added, and the solution is mixed until uniform. 0.05 to 0.2 part, preferably 0.1 to 0.15 part, based on the weight of the latex of FR dispersion is added and mixed to uniformity. At this point any other needed auxiliaries, such as pigments, thickeners, fillers, plasticizers, wetting agents, catalysts, and the like, are incorporated in any required proportion and the solution mixed.

The treating solution is now applied to the flame resistant substrate by any convenient way, such as padding, coating, printing, saturation and the like and the wet goods are dried and baked as above.

EXAMPLE I 70 parts of finely divided decabromo biphenyl possessing an average particle size between 1 and 2 microns was slowly added to 50 parts water containing 0.2% anionic wetting agent of the alkyl-aryl sulfonate type, under strong agitation with a high speed, high shear mixer. After completing the addition of the brominated compound 12 parts of finely divided antimony-trioxide possessing an average particle size between 1 and 2 microns were slowly added while agitation was continued. After all the antimony trioxide was added the resulting milky white dispersion was stabilized by addition of 5 parts of a 4% aqueous solution, having a viscosity of 300,000 centipoise, of ethoxycellulose. This dispersion, thus obtained, remained uniform after prolonged storage at room temperature and was designated dispersion I.

50 parts of dispersion I were now dissolved in 40 parts of water and parts of a 50% aqueous emulsion of a copolymer of ethyl acrylate and acrylamide having a T of -47C were added.

A woven fabric weighing 4 ozs. per square yard composed of 50% cotton 50% polyester was now treated with this solution by immersing it in the same and removing the excess by squeezing between two rollers. The wet pick-up was 90%. The fabric was now dried at 1 10C and baked at 150C for 3 minutes.

The fabric thus obtained was quite soft to the feel was further softened by padding it through a 10% emulsion of polyethylene softener in water.

The flame resistance of the fabric thus treated was evaluated by testing according to test method given in Standard for the Flammability of Childrens Sleepwear" DOC FF3-71 giving an initial average char length of 1 V2 inches and 2 inches after 50 launderings and tumble dryings.

EXAMPLE [1 70 parts of finely divided hexabromo benzene having an average particle size between 1 and 2 microns were dispersed in 50 parts of water in a similar fashion to dispersion l. parts of aluminum oxide were added to the dispersed brominated compound and this dispersion was stabilized as dispersion I. This material was designated dispersion ll.

40 parts of dispersion 11 were dissolved in 52 parts of water and 8 parts of a 50% emulsion of a styrene butadiene copolymer having a glass transition temperature of C were added.

A piece of cotton circular knit weighing 8 02s- /yd was immersed in this solution and the excess removed by squeezing between two rollers. The wet pickup was and the fabric was dried at 110C and baked at C for 3 minutes. The fabric was softened by padding through a 10% emulsion of a polyethylene softener and dried.

The fabric was judged flame retardant by using method outlined in DDC FF3-7 l giving an initial average char length of 1 inch and 2 /2 inches after 50 launderings and tumble dryings.

EXAMPLE III 70 parts of finely divided pentabromo toluene and 20 parts of titanium dioxide having an average particle size of between 1 and 2 microns were dispersed in 50 parts of water as in Example I. This dispersion was designated dispersion Ill.

50 parts of dispersion III were dissolved in 40 parts of water and 10 parts of a 50% acrylonitrile-styrenebutadiene latex having a glass transition temperature of 60C were added to this solution. The resulting mixture was padded onto a woven fabric composed of 80% rayon and 20% cellulose diacetate in a similar fashion as in Examples I and II. The fabric was dried at 1 10C, baked at 150C, top softened with a 10% emulsion of a polyethylene softener and redried.

The treated fabric gave an average char length of 3 inches initially, when treated according to AATCC Flammability Test 34-1967, an average char length of 4 inches after 5 launderings and tumble dryings and an average char length of 5 inches after 5 commercial dry cleanings.

EXAMPLE IV 70 parts of Tris dibromophenyl phosphate and 10 parts of antimony trioxide having an average particle size between 1 and 2 microns were dispersed in 40 parts of water as in Example 1. This dispersion was designated dispersion IV.

50 parts of a 50% emulsion of a butyl acrylate N methylol acrylamide acrylonitrile copolymer latex having a glass transition temperature of 0C were dispersed in 30 parts of water. To this solution 10 parts of a 50% aqueous dispersion of disperse blue 1 (color index No. 42025) and 10 parts of dispersion IV were added and the resulting mixture agitated until uniform.

A 100% woven fiberglass drapery fabric was immersed in this solution, the excess removed by squeezing between two rollers to obtain a wet pick-up of 50%, dried at 1 10C and baked at 150C for 3 minutes.

This fabric gave an average char length of 3 inches when tested using AATCC flammability test 34-1967 initially, after 5 launderings and tumble drying and 5 commercial dry cleanings.

EXAMPLE V 70 parts of finely divided tribromoaniline and 15 parts of micropulverized aluminum trioxide having a particle size of between 1 and 2 microns were dispersed in 50 parts of water following procedure given in Example I. This dispersion was designated as dispersion V.

0.5 parts of tetrasodium pyrophosphate were dissolved in 14.5 parts of water. Under strong agitation 10 parts of a finely divided clay and parts of dispersion V were added. Upon completion of the addition 45 parts of a 50% aqueous emulsion of a polymer obtained by the copolymerization of ethyl acrylate, n-methylol acrylamide, acrylonitrile and acrylic acid having a glass transition temperature of 2C. were mixed in. The viscosity of this dispersion was adjusted to 35,000 centipoises by adding 24 parts of a 4% solution of methoxy cellulose. Finally, 1 part of a solution of oxalic acid (acid catalyst) were mixed into this dispersion. This dispersion was designated V-A.

A piece of the 80% rayon 20% cellulose diacetate fabric treated in Example III was coated on one side with dispersion V-A using a doctor blade to a loading of 70% on the weight of the fiber. The fabric was dried at 125C and cured at 160C for 2 minutes.

The fabric thus treated gave a char length of 3 inches when tested according to AATCC method 34-1967, initially after 5 launderings and 5 dry cleanings. The same fabric coated with the same composition, but without dispersion V was consumed entirely when tested by this flammability method.

EXAMPLE VI Parts By Weight Vl-A Vl-B Water 300 300 Anionic Dispersing Agent l l Hydroxyethyl Cellulose Thickener 5 5 Talc I25 125 Rutile Titanium Dioxide 225 225 50% Solids Vinylacetateethylacrylute copolymer 400 400 Dispersion VI 45 The dispersion were prepared by predissolving the ingredients in the given order in a tank equipped with a high-speed high-shear mixer and then transferring the resulting dispersion into the pebble mill and milling for 5 hours.

Two pieces of plywood were coated on both sides with dispersions VI-A and Vl-B using a paint brush and air dried at room temperature.

The flammability of both pieces of plywood was tested by applying to them a flame from a butane blow torch for seconds. The piece of plywood treated with dispersion VI-A immediately extinguished after removal of the blow torch giving a charred surface where the flame was in contact with the coating, whereas the plywood coated with dispersion VI-B continued burning until completely consumed.

EXAMPLE VII 70 parts of finely divided hexachlorocyclopentadienodibromocyclooctane and 10 parts of micropulverized antimony trioxide having a particle size between 1 and 2 microns were dispersed in 40 parts of water following procedure given in Example I. This dispersion was designated dispersion Ill.

parts of dispersion Vll were dispersed in 40 parts of water and 40 parts of a 50% aqueous emulsion of a 5 polymer obtained by reaction of a mixture of isomers of toluene diisocyanate and a condensation product of ethylene glycol having a molecular weight of approximately 4,000.

A piece of 100% nylon upholstery fabric was immersed in this solution and excess removed by squeezing between two rollers to achieve a 70% wet pickup and then dried at 125C.

The fabric thus treated was judged flame retardant when it gave a 3 inches char length when listed according to AATCC method 34-1969, whereas the untreated fabric burned the entire length when tested according to the same method.

Using and techniques and formulations of any of the examples given, namely, 1 through 7, the following compounds may be used for application to the various bases identified in the several examples:

pentabromo phenol tribromo aniline dibromo benzoic acid Polybrominated phenol Polybrominated aniline Polybrominated benzoic acid Tris phosphates of polybrominated phenols Polybrominated cyclopentane Polybrominated cyclohexane Polybrominated cyclooctane Polybrominated cyclodecane Polybrominated cyclododecane Hexachlorocyclopentadienodibromocyclooctane N,N'-ethyl-bis(dibromonorbornene-dicarboximide) Per chloro penta cyclodecane Polybrominated biphenyl hexabromo Polybrominated biphenyl oxide decabromo biphenoloxide Polybrominated benzene hexabromo Polybrominated toluene pentabromo toluene Polybrominated chlorotoluene tetrabromo tetrabromo cyclo hexabromo cyclo hexabromo cyclo hexabromo cyclo hexabromo cyclo hexabromo cyclo reduced to an average particle size below 2 microns, and being in weight ratio of 1:4 parts of brominated compound to 0. 1:1 part of metallic oxide,

said high molecular weight polymeric binder being present in amount sufficient to secure said brominated organic compound and metallic oxide flame retardant composition to said material, and drying and curing said treated material, wherein the total amount of flame retardant deposited on said material is effective to reduce the flammability of the textile and is durable to laundering and dry clean- 2. The method in accordance with claim 1 whereby drying is carried out at elevated temperatures of 100l75C.

3. The method in accordance with claim 1 in which the flame retardant is applied by'padding.

substantially totally insoluble in water, having been.

4. The method in accordance with claim 1 in which the flame retardant is applied by knife coating.

5. The method of claim 1 wherein the brominated solid organic material is selected from the group consisting of:

Polybrominated biphenyl Polybrominated biphenyl oxide Polybrominated benzene Polybrominated toluene Polybrominated chlorotoluene Polybrominated phenol Polybrominated aniline Polybrominated benzoic acid Tris phosphates of polybrominated phenols Polybrominated cyclopentane Polybrominated cyclohexane Polybrominated cyclooctane Polybrominated cyclodecane Polybrominated cyclododecane Hexachlorocyclopentadieno-dibromocyclooctan and N,N -ethyl-bis (dibromo-norbornenedicarboximide Y 6. The method of claim 1 wherein the metallic oxide is selected from the group consisting of: Al, Ga, Si, Ge, As, Sb, Bi, Ti and Zr oxides.

7. The method of claim 1 wherein the latexes are selected from the group consisting of:

Polymers of esters of acrylic acid Styrene butadiene copolymers Acrylonitrile-styrene-butadiene copolymers Copolymers of ethyl acrylic-N-methylol acrylamideacrylonitrile-acrylic acid Vinyl acetate-ethyl acrylate copolymers Butyl acrylate-Nmethylol acrylamideacr'ylonitrile,

and

Polyurethane polymers.

8. A textile material inherently flammable, rendered and, N,N -ethyl-bis (dibromo-norbornenedicarboximide the metallic oxide is selected from the group consisting of:

Al, Ga, Si, Ge, Sb, Bi, Ti, and Zr oxides,

and

the latex is selected from the group consisting of:

polymers of esters of acrylic acid styrene butadiene copolymers acrylonitrile-styrene-butadiene copolymers copolymers of ethyl acrylate-N-methylol acrylamideacrylonitrile-acrylic acid vinyl acetate-ethyl acrylate copolymers butyl acrylate-N-methylol acrylamide-acrylonitrile and polyurethane polymers.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No- 3,877,974 I D t April 15L 1975 1nventor(s) Vladimir Mischutin It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

In the Title Page, "[21] Appl. No. 330,731"

should read: [21] Appl. No. 300,731

Signed and sealed this 17th day of June 1975.

1 Arrest:

C. MARSHALL DAMN T791? 3. I"--;i3i-Z Co missi oner of Patents .tte tin Gfficer and Trademarks F ORM PO-1050 (10-69) USCOMMDC 60376-P89 w u.s. covenant"? PRINTING OFFICE Isis o-assqn.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No- 3 877,974 Dated April 1.5 1975 Inventor(s) Vladimir Mischutin It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

In the Title Page, "[21] Appl. No. 330,731"

.Signcci and sealer. this 17th day of June 1975.

C. ZZARSHALL DANE-3 Coflmissi oner of fate-tits and Trademarks .ktterttng C'fficer FORM PO-1050 (10-69) USCOMM-DC 60376-P69 i ".5. GOVERNMENT PRINTING OFFICE I9, 0-$5G'l34,

Claims (9)

1. A METHOD OF RENDERING FLAMMABLE TEXTILE MATERIALS FLAME RETARDANT WHICH COMPRISES: TREATING SAID MATERIALS WITH A FLAME RETARDANT COMPOSITION CONSISTING ESSENTIALLY OF ABROMINATED, ORGAIC AROMATIC OR CYCLIC COMPOUND AD A METALLIC OXIDE, IN AQUEOUS DISPERSION, IN ADMIXTURE WITH AN AQUEOUS EMULSION OF A SUITALEE HIGH MOLECULAR WEIGHT POLYMERIC ADHESIVE BIN BINDER, SAID BROMINATED COMPOUND AND SAID METALLIC OXIDE BEING SOLIDS AT ROOM TEMPERATURE, SUBSTANTIALLY TOTALLY INSOLUBLE IN WATER, HAVING BEEN REDUCED TO AN AVERAGE PARTICLE SIZE BELOW 2 MICRONS, AND BEING IN WEIGHT RATIO OF 1:4 PARTS OF BROMINATED COMPOUND OF 0.1:1 PART OF METALLIC OXIDE, SAID HIGH MOLECULAR WEIGHT POLYMERIC BINDER BEING PRESENT IN AMOUNT SUFFICIENT TO SECURE SAID BROMINATED ORGANIC COMPOUND AND METALLIC OXIDE FLAME RETARDANT COMPOSITION TO SAID MATERIAL, AND DRYING AND CURING SAID TREATED MATERIAL, WHEREIN THE TOTAL AMOUNT OF FLAME RETARDANT DEPOSITED ON SAID MATERIAL IS EFFECTIVE TO REDUCE THE FLAMMABILITY OF THE TEXTILE AND IS DURABLE TO LAUNDERING AND DRY CLEANING.
2. The method in accordance with claim 1 whereby drying is carried out at elevated temperatures of 100*-175*C.
3. The method in accordance with claim 1 in which the flame retardant is applied by padding.
4. The method in accordance with claim 1 in which the flame retardant is applied by knife coating.
5. The method of claim 1 wherein the brominated solid organic material is selected from the group consisting of: Polybrominated biphenyl Polybrominated biphenyl oxide Polybrominated benzene Polybrominated toluene Polybrominated chlorotoluene Polybrominated phenol Polybrominated aniline Polybrominated benzoic acid Tris phosphates of polybrominated phenols Polybrominated cyclopentane Polybrominated cyclohexane Polybrominated cyclooctane Polybrominated cyclodecane Polybrominated cyclododecane Hexachlorocyclopentadieno-dibromocyclooctane and N,N'' -ethyl-bis (dibromo-norbornene-dicarboximide).
6. The method of claim 1 wherein the metallic oxide is selected from the group consisting of: Al, Ga, Si, Ge, As, Sb, Bi, Ti and Zr oxides.
7. The method of claim 1 wherein the latexes are selected from the group consisting of: Polymers of esters of acrylic acid Styrene butadiene copolymers Acrylonitrile-styrene-butadiene copolymers Copolymers of ethyl acrylic-N-methylol acrylamideacrylonitrile-acrylic acid Vinyl acetate-ethyl acrylate copolymers Butyl acrylate-N-methylol acrylamide-acrylonitrile, and Polyurethane polymers.
8. A textile material inherently flammable, rendered flame resistant by the impregnation with a flame retardant composition in accordance with the process of claim 1.
9. The method of claim 1 wherein the brominated compound is selected from the group consisting of: Polybrominated biphenyl Polybrominated biphenyl oxide Polybrominated benzene Polybrominated toluene Polybrominated chlorotoluene Polybrominated phenol Polybrominated aniline Polybrominated benzoic acid Tris phosphates of polybrominated phenols Polybrominated cyclopentane Polybrominated cyclohexane Polybrominated cyclooctane Polybrominated cyclodecane Polybrominated cyclododecane Hexachlorocyclopentadieno-dibromocyclooctane, and, N,N'' -ethyl-bis (dibromo-norbornene-dicarboximide), the metallic oxide is selected from the group consisting of: Al, Ga, Si, Ge, Sb, Bi, Ti, and Zr oxides, and the latex is selected from the group consisting of: polymers of esters of acrylic acid styrene butadiene copolymers acrylonitrile-styrene-butadiene copolymers copolymers of ethyl acrylate-N-methylol acrylamide-acrylonitrile-acrylic acid vinyl acetate-ethyl acryLate copolymers butyl acrylate-N-methylol acrylamide-acrylonitrile and polyurethane polymers.
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US3974310A (en) * 1972-10-25 1976-08-10 White Chemical Corporation Flame retardants for synthetic materials (I)
US3955032A (en) * 1972-10-25 1976-05-04 White Chemical Corporation Flame retardants for natural and synthetic materials
US4087364A (en) * 1973-01-26 1978-05-02 American Cyanamid Company Liquid slurry of submicron particles of hexabromobenzene, and process of manufacture
US4116702A (en) * 1974-12-13 1978-09-26 Ciba-Geigy Corporation Agent for flame proofing synthetic fibrous material
US4113902A (en) * 1975-05-22 1978-09-12 White Chemical Corporation Flame retardants for natural and synthetic materials
US4054715A (en) * 1975-09-11 1977-10-18 Dixie Yarns, Inc. Sewing thread containing a flame retardant lubricant
US4046701A (en) * 1976-02-23 1977-09-06 Velsicol Chemical Corporation Durable flame retardant finishes for textile materials
US4154692A (en) * 1976-04-15 1979-05-15 Mcelveen John B Flame retardant process, solution and structures
US4279652A (en) * 1976-09-15 1981-07-21 Sniaviscosa Societa Nazionale Industria Applicazioni Viscosa, S.P.A. Self-extinguishing polymers
US4219605A (en) * 1976-09-29 1980-08-26 Ciba-Geigy Corporation Process for flameproofing synthetic fibre material and product
US4167603A (en) * 1976-12-13 1979-09-11 Ethyl Corporation Flame resistant cotton/polyester blend substrates
US4298509A (en) * 1977-10-05 1981-11-03 Antonio Fochesato Noninflammable olefin fibers and method of producing same
US4151316A (en) * 1977-11-09 1979-04-24 Chas. S. Tanner Co. Flameproofing of polyester fabrics using brominated cycloalkanes
US4178399A (en) * 1978-02-14 1979-12-11 Chemonic Industries, Inc. Flame retardant and process
US4237157A (en) * 1978-05-05 1980-12-02 Henry Hancock Process for making fire retardant polypropylene
EP0038899A1 (en) * 1980-04-30 1981-11-04 National Aeronautics And Space Administration Flame retardant elastomeric compositions, heat sealable, flame and abrasion resistant fabrics coated therewith, and process for making same
US4394413A (en) * 1981-02-09 1983-07-19 Scapa Dryers, Inc. Flame retardant dryer fabrics
US4343854A (en) * 1981-03-12 1982-08-10 Witco Chemical Corporation Flame retardant composition
US4522872A (en) * 1982-04-12 1985-06-11 Milliken Research Corporation Industrial fabrics
US4524170A (en) * 1983-04-25 1985-06-18 Milliken Research Corporation Flame retardant finishing composition for synthetic textiles
US4719256A (en) * 1984-07-23 1988-01-12 Occidental Chemical Corporation Fire retardant thermoplastic polyester and polyesterether compositions
US4695507A (en) * 1985-05-06 1987-09-22 Burlington Industries, Inc. Low toxic ceiling board facing
US4842609A (en) * 1986-06-05 1989-06-27 Burlington Industries, Inc. Flame retardant treatments for polyester/cotton fabrics
USRE34951E (en) * 1986-08-29 1995-05-23 Interface, Inc. Flame retardant tufted carpet tile and method of preparing same
US4750911A (en) * 1986-09-26 1988-06-14 Burlington Industries, Inc. Flame-resistant nylon/cotton fabrics
US4732789A (en) * 1986-10-28 1988-03-22 Burlington Industries, Inc. Flame-resistant cotton blend fabrics
US4900377A (en) * 1988-04-29 1990-02-13 Weyerhaeuser Company Method of making a limited life pad
US4892769A (en) * 1988-04-29 1990-01-09 Weyerhaeuser Company Fire resistant thermoplastic material containing absorbent article
US4961930A (en) * 1988-04-29 1990-10-09 Weyerhaeuser Company Pet pad of thermoplastic containing materials with insecticide
US5290636A (en) * 1990-09-06 1994-03-01 Great Lakes Chemical Corp. Flame retardant brominated styrene-based coatings
US5438096A (en) * 1990-09-06 1995-08-01 Great Lakes Chemical Corporation Flame retardant brominated styrene-based latices
US5484839A (en) * 1992-11-18 1996-01-16 Great Lakes Chemical Corp. Flame retardant brominated styrene graft latex compositions
US5296306A (en) * 1992-11-18 1994-03-22 Great Lakes Chemical Corp. Flame retardant brominated styrene graft latex coatings
US5858159A (en) * 1995-04-25 1999-01-12 Hoover Universal, Inc. Method for manufacturing automotive seat assemblies using pre-bonded adhesives
US8209785B2 (en) 2010-02-09 2012-07-03 International Textile Group, Inc. Flame resistant fabric made from a fiber blend
US8528120B2 (en) 2010-02-09 2013-09-10 International Textile Group, Inc. Flame resistant fabric made from a fiber blend
US8793814B1 (en) 2010-02-09 2014-08-05 International Textile Group, Inc. Flame resistant fabric made from a fiber blend
US20140076587A1 (en) * 2012-09-18 2014-03-20 Osmose Holdings, Inc. Fire retardant device for protecting wooden structures from fire

Also Published As

Publication number Publication date Type
DE2352923A1 (en) 1974-05-02 application
CA987855A1 (en) grant
CA987855A (en) 1976-04-27 grant
LU68656A1 (en) 1975-06-24 application
NL172169B (en) 1983-02-16 application
FR2204675A1 (en) 1974-05-24 application
JPS49134772A (en) 1974-12-25 application
DE2352923C2 (en) 1987-08-20 grant
NL172169C (en) 1988-03-16 grant
BE806353A (en) 1974-04-22 grant
BE806353A1 (en) grant
NL7314508A (en) 1974-04-29 application
FR2204675B1 (en) 1979-06-22 grant

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