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
  • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
  • D06M13/244—Treating 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
  • D06M13/282—Treating 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
  • D06M13/288—Phosphonic or phosphonous acids or derivatives thereof
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
  • C07F9/02—Phosphorus compounds
  • C07F9/06—Phosphorus compounds without P—C bonds
  • C07F9/08—Esters of oxyacids of phosphorus
  • C07F9/09—Esters of phosphoric acids
• • 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
  • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
  • D06M13/244—Treating 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
  • D06M13/282—Treating 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
  • D06M13/292—Mono-, di- or triesters of phosphoric or phosphorous acids; Salts thereof
• • Y—GENERAL 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
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S428/00—Stock material or miscellaneous articles
  • Y10S428/92—Fire or heat protection feature
  • Y10S428/921—Fire or flameproofing
• • Y—GENERAL 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
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
  • Y10T442/20—Coated 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
  • Y10T442/2631—Coating or impregnation provides heat or fire protection
  • Y10T442/2672—Phosphorus containing
  • Y10T442/2697—Phosphorus and halogen containing compound
• • Y—GENERAL 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
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
  • Y10T442/20—Coated 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
  • Y10T442/2861—Coated or impregnated synthetic organic fiber fabric
  • Y10T442/2869—Coated or impregnated regenerated cellulose fiber fabric

Definitions

• the flame-proofing agent is I preferably a tris(polybro moaliphatic)phosphate and mostl preferably a tris(dibromopropyl)phosphate.
• the finish- ⁇ .30 ing composition may also contain a flame-proofing agent.
• This invention relates to the production of finished flame-resistant textile filaments, fibers, yarns, threads and fabrics.
• Fabrics such as those made from polyvinylidene chloride compositions, for example those sold under the tradename Saran are flame-resist ant since they will not take fire nor support combustion when held in the flame, but they are not heat-resistant in that they decompose readily when heated at about 180 C.
• Silicone polymers such as silicone rubber and silicone resin are heat-resistant in so far as they will withstand temperatures up to about 300 C. Such silicone polyers, however, may be flammable at their decomposition temperatures and are not therefore flame-resistant.
• Fabrics made from cellulose acetate fibres which have been produced from filaments, fibers or yarns made by spinning from a solution containing such a flame-resistant additive as tris(dibromopropyl) phosphate are flameresistant but they are not heat-resistant, and indeed thedecomposition temperature of such fabrics is lower than that of those prepared from ordinary cellulose acetate.
• finishing composition When a cellulose acetate material is to be treated with a finishing composition the nature of such a finishing composition may vary widely according to the particular handle or drape required. Such finishing compositions include starch derivatives, gelatine, ureaformaldehyde resins, melamine-formaldehyde resins, acrylic polymers and in fact almost any synthetic polymeric material. A common finishing material used on cellulose acetate fabrics is based on gelatine.
• the process for finishing filaments, fibres, yarns, threads and fabrics of flame resistant cellulose acetate which flame-resistant cellulose acetate has been produced by spinning from a solution containing cellulose acetate and a flame-proofing agent dispersed therein, comprises applying to the filaments, fibres, yarns, threads and fabrics a coating of an organic polymer composition which composition has a temperature of thermal decomposition not substantially greater than that of the flame-resistant cellulose acetate and which decomposes at its decomposition temperature to form soft and fusible products.
• finishing composition It is not generally necessary to apply very large amounts of finishing composition and a suitable amount is from about 0.1 percent to about 5.0 percent by weight of the weight of the filaments, fibres, yarns or fabrics. A preferred amount is from about 0.5 to about 3.0 percent. In view of the small amount of finishing composition used it is not essential that the finishing composition should itself be flame-resistant, since the flame-resistant properties of the cellulose acetate are quite sufficient to inhibit flaming of the finishing composition. However, it is preferred that the finish should itself be flame-resistant.
• the criteria for the selection of the finishing composition are such as to ensure that the composition does not prevent the heat from the applied flame from reaching the flame-resistant cellulose acetate material freely. In this way the abnormal decomposition may take place at the lower temperature as described above.
• the finish should decompose at a temperature not substantially greater than that at which the flame-resistant cellulose acetate decomposes, and that the decomposition product shall be soft and fusible so that the coating may melt away from the surface of the material and allow the heat and air to reach that surface so that the above described abnormal decomposition can take place.
• the synthetic organic polymers which are used in the finishing of cellulose acetate in accordance with the invention include synthetic materials from at least four different groups.
• the first group includes organic derivatives of cellulose which are film-forming but non-tacky at room tempera tures, eg. the non-tacky film-forming cellulose ethers such as ethyl cellulose.
• the second group includes those polymers of vinyl and vinylidene monomers which form long carbon chains, at least a proportion of which carbon atoms are linked to acyloxy, carboxylic acid, carboxylic acid anhydride, carboxamide, N-substituted carboxamide, carbalkoxy and carbalkoxyalkyl groups.
• other groups of different character which do not interfere with the aforesaid groups may also be present such as aromatic. and halo-aromatic groups.
• examples of compounds are the non-tacky film-forming homopolymers and copolymers of vinyl acetate and methyl methacrylate,
• copolymers of partial alkyl esters of maleic acid with vinylidene monocyclic aromatic hydrocarbons such as styrene, copolymers of acrylic acid and methacrylie acid, polymers of alkyloxyalkyl methacrylates and co polymers of alkylated N-methylolacrylamide with vinyl-- .idene monocycli aromatic hydrocarbons.
• the third group includes the alkylated aminoplastforming condensation products such as the alkylated dimethylolureas and the alkylated methylol urea-melamine co-condensation products.
• the fourth. group includes halogenated polymeric hydrocarbons such as chlorinated synthetic rubber.
• the temperature of decomposition of the flame-resistant cellulose acetate and of the dressing composition can be determined by heating 0.05 to 0.1 g. of the fabric or the solids of the dressing composition in an open test-tube, 3 inches long and 0.375 inch wide, at a rate of temperature rise of 5 C. per minute and noting the temperature at which a substantial carbonisation of the sample takes place, which temperature is referred to as the temperature of decomposition.
• the nature of the decomposition products of the dress ing composition can be determined by heating a sample of the film-forming solids obtained from the dressing composition in an open test-tube 3 inches long and 0.375 inch wide by immersing the test-tube for 5 minutes in an oil bath maintained at the temperature of decomposition. The tube is then removed from the oil bath and the decomposed residue therein is probed with a wire. If the decomposition products are soft and fusible when hot, when so tested, it will be found that the dressing com-- position will have a satisfactory performance for use as a non-flammable finish for the flame-resistant cellulose acetate fabric.
• a mixture of equal parts by weight of the flame-resistant cellulose acetate and the solids of the dressing composition may be subjected to the above-mentioned test at the temperature of decomposition to ascertain that the decomposition products of the mixure are soft and fusible.
• the decomposition products are otherwise than soft and fusible, i.e. if they form a hard black film on the test-tube or a hard sintered mass, then the dressing composition when applied to a flame-resistant cellulose acetate fabric will seriously impair its flame-resistant properties.
• the flammability of the above-mentioned synthetic polymers is in no case substantially greater than that of the ordinary cellulose acetates and in those instances in. which the decomposition temperature of the polymer and/or the nature of the decomposition products produced therefrom is such that it does not accord with the requirements set forth above, the decomposition temperature may be lowered and the nature of the decomposition products produced rendered soft, generally soft and sticky, by the incorporation in the dressing composition of a tris(polybromoaliphatic)phosphate as referred to above in connection with the cellulose acetate spinning dope. It is believed that the soft products produced on decomposition of the cellulose acetate and those produced on decomposition of the dressing become fused together. Since the proportion of flame-proofing agent exceeds the minimum required to secure the desired flame-resistant properties in the cellulose acetate, it suflfices to impart flame-resistance to the small per" centage of additional material becoming fused therewith.
• Ethyl cellulose is an example of a dressing material which is not readily fusible on heating but, when admixed with increasing quantities of tris(dibromopropyl) phosphate or with tricresyl phosphate, it becomes more and more fusible and, when the former is admixed therewith, less and less flammable.
• ethyl cellulose may form the basis of a satisfactory dressing composition from which will be deposited a coating layer which will fulfill the requirements of the invention.
• a satisfactory dressing composition may similarly be obtained from a butyl ether of a methylolurea by admixture with the tris(dibromopropyl)phosphate. In all cases it is preferable that the compound which is added to the essential coating component of the dressing composition should be compatible therewith.
• a preferred cellulose acetate fabric is formed from yarns, threads, filaments or fibres produced from a cellulose acetate spinning dope containing a tris(polybromoaliphatic)phosphate having a bromine content a bromine content of at least 50 percent by weight in an amount of 2.5 to percent by weight of the cellulose acetate, preferably in an amount of from 5 to 7 percent; the organic polymer or polymer composition is preferably applied in the form of a solution of emulsion, or dispersions thereof may be employed in each case dis solved or suspended in a volatile liquid carrier.
• the dressing compositions may be applied to the cellulose acetates in solution in water, as an aqueous solution of an ammonia or volatile amine salt thereof when a polymer containing free carboxyl groups or carboxylic acid anhydride groups is used, in solution in an organic solvent in which the cellulose acetate employed is substantially insoluble or in the form of an aqueous emulsion or suspension.
• the tris(polybromoaliphatic)phosphates are readily soluble in certain organic solvents such as toluene and xylene in which the cellulose acetates are substantially insoluble, and such solvents may remove some of these compounds from the fabric it they are used.
• the dressing compositions may be applied to the filaments, fibres, yarns, threads or fabrics of cellulose acetate by passing through a bath containing a solution, suspension or emulsion containing the dressing composition in the form in which it is to be applied to the material to be treated.
• a bath containing a solution, suspension or emulsion containing the dressing composition in the form in which it is to be applied to the material to be treated.
• the impregnated material is passed between rollers to remove excess of the composition and ensure uniform impregnation.
• the concentration of the bath employed should be correlated with the pressure applied on passage between the rollers to secure the desired take-up of the film-forming ingredients.
• the material is then dried.
• the invention also includes within its scope flame-resistant, filaments, fibres, yarns, threads and fabrics of a cellulose acetate having uniformly distributed therethrough a flame-proofing agent formed by spinning from a cellulose acetate, for example up to 10 percent, preferably 5 to 7 percent, by weight of the cellulose acetate of a flame-proofing agent which is preferably tris(polybromoaliphatic)phosphate, the said filaments, fibres, yarns, threads and fabrics having a coating of a synthetic organic polymer or polymer-containing composition, the flammability of which polymer is not substantially greater than the flammability of the cellulose acetate Whilst the temperature of thermal decompositon of said polymer or polymer-containing composition does not substantially exceed that of the flam-proof cellulose acetate and th decomposition products of the polymer or polymer-containing composition, at the temperature of decomposition, are soft and may be sticky.
• a flame-proofing agent formed by spinning from a cellulose acetate
• flame-proofing agents which may be used are tris(chloroethyl)phosphate, aluminium pyrophosphate and the materials sold under the tradename Phosgard which are complex organic halogencontaining polyphosphonate esters (those containing at least some bromine and having a total halogen content of at least 50 percent by weight are preferred).
• the finishing treatment Whilst it is often convenient to apply the finishing treatment to a fabric woven from one or more fiame-proofed cellulose acetates, it should be appreciated that the com positions comprising a film-forming synthetic organic polymer may readily be applied to fiame-proofed yarns as a size prior to weaving; such yarns may have been dyed.
• the woven cloth is not then desized after weaving. Examples of such materials are a bridal satin and a poult taffeta which, when Woven, do not require the application of a further finish, are not spotted by water and do not become raggy after dry cleaning.
• Such sizes may be applied on a conventional sizing or slashing machine.
• the amount of solids taken up by the yarns is normally higher than that applied as a finishing composition and may be from 2.5 to 6 percent, preferably 3 to 4 percent, of the weight of the yarns.
• the sizing composition may be more con centrated than the finishing composition, e.g. from 5 to 7 percent, in order to permit the larger tape-up envisaged from the sizing bath, and the bath itself may be held at a temperature above room temperature, e.g. from 40 to 50 C. Additional ingfedients may be present in such a sizing bath in order to modify the hand of the woven fabric.
• the amount of synthetic polymeric material or composition containing such material which is present on the surface of the filaments, fibres, yarns, threads or woven material will depend upon the stage at which it is applied and the purpose or purposes which it is intended to serve. From 0.1 to 10 percent of the weight of the material being treated may be used. In those cases in which the higher proportions of finish are used it is desirable that the dressing or sizing used should include a flameproofing agent.
• EXAMPLE 1 For application to a secondary cellulose acetate yarn or fabric, which cellulose acetate had substantially uniformly dispersed therethrough 7 percent of tris(dibromopropyl)phosphate and had a decomposition temperature in the range of 220 C., a finishing composition containing polyvinyl acetate is used. This composition contains 2 parts by weight of polyvinyl acetate, 1 part of tris(dibromopropyl)phosphate and 1 part of zinc resinate. A 3 percent solution of this finishing composition in toluene is made. The cellulose acetate material is passed therethrough and then between rollers by means of which the take-up is adjusted to 60 percent of the weight of the cellulose acetate. The treated material is then dried.
• EXAMPLE 2 A fiame-proofed primary cellulose acetate fabric was used, the yarns of which had uniformly dispersed there-- EXAMPLE 3 The procedures of Examples 1 and 2 are repeated using a finishing composition containing 3 parts of ethyl cellulose and 1 part of the tris(dibromopropyl)phosphate.
• EXAMPLE 4 A coating composition is prepared from 10 parts by Weight of a butylated urea-formaldehyde condensation product (supplied as a viscous solution of 66 percent total solids content), 10 parts of Zinc resinate and 1.75 parts of tris(dibromopropyl)phosphate. A 3 percent solution in toluene was prepared and applied to the same kind of flame-resistance cellulose acetate as that used in Example 1: the subsequent procedure was the same as that described in that example.
• Example 5 The procedure of Example 4 is repeated using a coating composition prepared from 1 part by weight of chlo rinated rubber and 3 parts of tris(dibromopropyl)phosphate. A 2 percent solution of this composition was similarly prepared and used.
• EXAMPLE 6 Nine parts by weight of a textile finishing emulsion which is reputed to contain a copolymer of a butylated methacrylamide of the kind described in French Patent No. 1,162,967, Example 15, and which contains 33 percent by weight of solids is admixed with 1 part of tris- (dibromopropyl)phosphate dispersed in water. Additional water is added until the solids content is reduced to 3 percent and a flame-proofed cellulose acetate of the kind used in Example 1 is then passed through the resulting bath. The further treatment is as described in Example 1.
• Example 7 The procedure of Example 6 is repeated using four parts by weight of a vinyl acetate-vinyl chloride copolymer emulsion of 55 percent solids content admixed with 1 part of tris(dibromopropyl)phosphate and dispersed in water to 3 percent total solids content.
• emulsion (a), (b) and (e) have a substantially 3 percent total solids content whilst emulsions (c) and (d) have a substantially 2 percent total solids content.
• EXAMPLE 9 Two parts of a. solid polymer of styrene and maleic anhydride and/or a partial allcyl ester of maleic acid sold under the registered trademark Stymer LP is dissolved, with heating, in water containing 0.24 part of aqueous ammonia. sp. gr. 0.880. Sufficient water to make a total of 100 parts is then added.
• This solution is applied to a primary cellulose acetate fabric by passage through a bath thereof and then between a. pair of rollers adjusted to limit the take-up to 60 percent of the dry weight of the fabric.
• the treated material is then dried. On heating and drying ammonia. is evolved and the polymer becomes insoluble in water.
• EXAMPLE 10 Three parts of an alkali soluble copolymer of vinyl acetate sold under the trade name Bevaloid is dissolved, with heating, in water containing 0.12 part of aqueous ammonia sp. gr. 0.880. Sufficient water to make a total of 100 parts is then added. The subsequent procedure is the same as in Example 9. On heating and drying ammonia is evolved and the polymer becomes insoluble in water.
• decomposition temperatures of the polymers or of the polymer-containing compositions remaining upon the cellulose acetate after drying in all the above examples are within the range to 220 C, and all yield decomposition products which. are soft and, in most cases, sticky at their decomposition temperatures. Films cast therefrom are either non-flammable or they have a low degree of flammability not substantially exceeding that of the cellulose acetates employed.
• Yarns and fabrics when subjected to the several treat ments described in the examples were found to have a satisfactory degree of non-flammability. They do not propagate a flame when out of contact with an externally applied flame and do not exhibit afterglow when tested in accordance with the method described in British stand ard specification No. 2,963/58.
• organic polymer composition used for coating is selectcd from the group consisting of film-forming cellu lose ethers, homopolymers and copolymers of vinyl and vinylidene monomers, amino-aldehyde condensation prod ucts and halogenated polymeric hydrocarbons.
• the coating composition also contains a modifier of tris- (polybromoaliphatic)phosphates.
• Flame-resistant cellulose acetate coated with an organic polymer composition the flame-resistant cellulose acetate being the product of spinning a solution containing cellulose acetate and a flame-proofing agent and the organic polymer coating having a temperature of thermal decomposition within the range of 180 to 220 C. and not, substantially greater than that of. the flame-resistant cellulose acetate, and decomposing at its decomposition temperature to form soft and fusible products,

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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Textile Engineering (AREA)
• Organic Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Life Sciences & Earth Sciences (AREA)
• Biochemistry (AREA)
• General Health & Medical Sciences (AREA)
• Molecular Biology (AREA)
• Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
• Artificial Filaments (AREA)
• Chemical Or Physical Treatment Of Fibers (AREA)

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Citations (9)

• 0
  • BE BE610903D patent/BE610903A/xx unknown
  • NL NL271928D patent/NL271928A/xx unknown
• 1960
  • 1960-11-28 GB GB4081060A patent/GB973355A/en not_active Expired
• 1961
  • 1961-11-25 FI FI207161A patent/FI41736B/fi active
  • 1961-11-27 CH CH1376661A patent/CH380076A/fr unknown
  • 1961-11-28 DE DE19611419599 patent/DE1419599A1/de active Pending
• 1966
  • 1966-08-31 US US3471318D patent/US3471318A/en not_active Expired - Lifetime

Patent Citations (9)

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