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
  • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
  • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
  • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • D06M15/39—Aldehyde resins; Ketone resins; Polyacetals
  • D06M15/423—Amino-aldehyde resins
  • D06M15/43—Amino-aldehyde resins modified by phosphorus compounds
  • D06M15/431—Amino-aldehyde resins modified by phosphorus compounds by phosphines or phosphine oxides; by oxides or salts of the phosphonium radical
• • 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
  • C07F9/28—Phosphorus compounds with one or more P—C bonds
  • C07F9/54—Quaternary phosphonium compounds
  • C07F9/5407—Acyclic saturated phosphonium compounds
• • 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
  • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
  • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
  • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • D06M15/244—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of halogenated hydrocarbons
• • 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
  • Y10T442/268—Phosphorus and nitrogen containing compound

Definitions

• This invention relates to a process for the preparation of flame-retardant cellulosic materials and to the compositions produced thereby. More particularly, this invention relates to the treatment of cellulosic textiles with a solution containing a hydroxymethyl phosphonium chloride compound and a high softening point polyvinyl chloride resin to yield flame-retardant cellulosic textiles having markedly improved hand.
• the fibers of the textile tend to swell, and remain in a swollen state after treatment, thereby significantly increasing the thickness of the cloth. This increase in thickness appears to adversely afiect the hand of the treated cloth.
• a further object of the invention is to provide novel flame-retardant cellulosic materials.
• Another object of the invention is to provide a method of improving the flame retardance and hand of cellulosic textiles.
• Still another object of the invention is to provide novel cellulosic textiles which retain their flame-retarding properties after frequent washings.
• Another object of the invention is to provide flameretardant cellulosic textiles having an improved hand, even after being subjected to fiequent ironing.
• flame-retardant cellulosic materials having improved physical properties may be prepared by impregnating the cellulosic material with an aqueous resin dispersion containing a hydroxymethyl phosphonium chloride compound having the formula (CH OED RPCI, where R is as defined below, a water soluble cyclic nitrogen-containing compound, a water soluble tertiary alkyl amine, urea, and a polyvinyl chloride resin having a high softening point, and then drying and curing the resulting resin impregnated cellulosic material.
• a hydroxymethyl phosphonium chloride compound having the formula (CH OED RPCI, where R is as defined below a water soluble cyclic nitrogen-containing compound, a water soluble tertiary alkyl amine, urea, and a polyvinyl chloride resin having a high softening point
• the resin impregnated textile has markedly improved hand, tear strength, tensile strength and flame retarding properties, when compared With textiles treated with resin compounds by techniques of the prior art.
• Hydroxymethyl phosphonium chloride compounds suitable for use in the instant invention are those water soluble compounds having the formula (CH OH) RPCl, where R is hydroxymethyl, lower alkyls having between about one and about eight carbon atoms, and chlorinated lower alkyls having between about one and about eight carbon atoms.
• Suitable water soluble hydroxymethyl phosphonium compounds are tetrakis(hydroxymethyl) phosphonium chloride, tris(hydroxymethyl) methyl phosphonium chloride, tris(hydroxymethyl) ethyl phosphonium chloride, tris(hydroxymethyl) butyl phosphonium chloride, tris(hydroxymethyl) octyl phosphonium chloride, tris(hydroxymethyl) chlorooctyl phosphonium chloride, and mixtures thereof.
• the phosphonium chloride may be used in monomer form or in a partially polymerized form, so long as it is still water soluble.
• tetrakis(hydroxymethyl) phosphonium chloride may be heated to effect partial polymerization before dissolving in the aqueous solution.
• Water soluble cyclic nitrogen-containing compounds suitable for use in the instant invention include triazines and dimethylol cyclic alkylene ureas.
• suitable triazines include methylol melamine, modified methylol melamine, such as the trimethyl ether of methylol melamine, triazones, and mixtures thereof.
• suitable cyclic alkylene ureas include dimethylol ethylene urea and dimethylol propylene urea.
• Water soluble tertiary alkyl amines which are suitable for use in the instant invention include triethylamine, triethanolamine, triisopropanolamine, and the like.
• Polyvinyl chloride resin suitable for use a a component of the novel flame-proofing composition are polyvinyl chloride resins having a softening point between about one hundred and seventy and about two hundred degrees centigrade.
• the polyvinyl chloride resin is preferably unplasticized and substantially pure, but may contain minor proportions of other monomers such as polyvinyl acetate, acrylics and plasticizers, but the proportions of these ingredients in the polyvinyl chloride resin should be less than those proportions that will reduce the softening point of the resulting mixture to below about one hundred and sixty degrees centigrade.
• the polyvinyl chloride resin is preferably employed as an aqueous dispersion or emulsion containing between about forty-five and about fifty-five percent by weight of polyvinyl chloride resin in the dispersion.
• Urea is also employed as a component of the flameproofing composition in the proportions defined below.
• any cellulosic material such as cotton, rayon, ramie, ute, wool, paper, cardboard and the like may be treated m accordance with the instant invention, but the inven- 3 tion is particularly effective when applied to the treatment of cellulosic textiles, since the treated textiles have a markedly improved hand as well as flame retarding properties.
• aqueous dispersion or emulsion/the aforesaid components are admixed with sufiicient water to yield an aqueous resin dispersion or emulsion containing between about forty-five and about eighty percent,
• total solids as used throughout the description'and claims, is intended to include both the solids that are dissolved in the aqueous component, as well as those solids which are colloidally dispersed or otherwise dispersed in the aqueous dispersion or emulsion.
• dispersion as used throughout the description and claims, is intended to include the dispersion and/or emulsion that results from admixing the above defined hydroxymethyl phosphonium chloride compound, the cyclic nitrogen-containing compound, the water soluble tertiary alkyl amine, urea, polyvinyl chloride resin and water in the proportions defined above. Greater or lesser proportions of the aforesaid components may be employed so long as the concentration of total solids in the aqueous dispersion is sufiicient .to provide an adequate resin add-on for the cellulosic material being treated.
• the cellulosic material is impregnated with the aque ous resin dispersion by padding, by spraying, by rolling, or by other impregnating techniques well known to the art. It is preferred to immerse the cellulosic material in the aqueous dispersion until the cellulosic material is completely saturated, and then pass the cellulosic material through squeeze rolls to remove resin dispersion in excess of that amount necessary to saturate the cellulosic material.
• the saturated cellulosic material is then subjected to conditions of temperature and time, sufficient to effect drying of the saturated cellulosic material and curing of the resin. Drying and curing can be effected by any commercially feasible technique. For example, drying of the cellulosio material can be effected in a conventional forced hot air oven wherein the saturated cellulosic material is heated at a temperature between about eighty and about one hundred andtwenty degrees centigrade for between about two and about four minutes. Curing of the dried cellulosic material can be effected in the same apparatus by heating the dried 'cellulosic material to a temperature of between about one hundred and forty and about one hundred and sixty degrees centigrade, for between about two and about four minutes. If desired, curing of the dry, treated cellulosic material can be effected in an infrared oven at a temperature between about five hundred and about seven hundred degrees Fahrenheit, for a period between about five and about twelve seconds.
• the resin impregnated cellulosic material is preferably subjected to a scouring step in order to remove unpolymerized resin.
• scouring can be effected by immersing the cured cellulosic material in an aqueous solution containing about 0.2 percent by weight of soap and about 0.2 percent by weight of sodium carbonate. After immersing the. resin impregnated eellulosic material in the solution, it is then dried as described above.
• the proportion of resin added to the cellulosic material by the aforesaid novel technique is generally between about fifteeen and about thirty-five percent by weight of the cellulosic material. This proportion of resin is referred to throughout the description and claims as resin add-on.
• the resin formed on the cellulosic material by the instant novel process is the reaction product of the non-aqueous components of the aqueous resin dispersion, i.e., the hydroxymethyl phosphonium chloride compound, the cyclic nitrogen-containing compound, the water-soluble tertiary alkyl amine, urea, and the high softening point polyvinyl chloride fresin.
• the resulting resin which impregnates the cellulosic material is the reaction product of hydroxyrnethyl phosphonium chloride compound in a proportion equivalent to between about ten and about sixty percent, the cyclic nitrogen-containing compound in a proportion equivalent to between about five and about forty percent by weight, the water-soluble tertiary alkyl amine in a proportion equivalent to between about one and about twenty percent by weight, urea in a proportion equivalent to between about five and about forty percent by weight, and the high softening point polyvinyl chloride resin in a proportion equivalent to between about ten and about seventy percent by weight of the resin forming in gredients.
• Cellnlosic materials treated in accordance with the instant invention have improved flame retarding properties, which are retained even after the treated cellulosic material is contacted with water and other solvents.
• the textile is not only flame-retardant, but also has a markedly improved hand, that is, the textile is soft and flexible, and these properties are retained after repeated washings and ironings.
• EXAMPLE 1 An aqueous dispersion was prepared from the following components in the following proportions.
• the resulting aqueous dispersion contained forty-six percent solids.
• a nine-ounce battle-ax fabric of the type conventionally used for Work garments was immersed in the above-described aqueous dispersion, then passed through squeeze rolls to remove excess liquid, and then dried at a temperature of two hundred and fifty degrees Fahrenheit.
• the 'dried, treated fabric was then placed in an infrared oven for about ten seconds at a temperature of about seven hundred degrees Fahrenheit to effect curing of the resin.
• the resin treated fabric was then scoured by immersing it in an aqueous solution containing 0.2 percent non-ionic detergent and 0.2 percent sodium carbonate. After scouring, the fabric was dried.
• the resin add-on-of the resin treated fabric after scouring and drying was 33.6 percent.
• the tensile strength of the treated fabric was one hundred and thirty-five pounds, as compared to a tensile strength of one hundred and thirty for the untreated fabric.
• the resin treated fabric was subjected to the standard char test.
• the char test was carried out in accordance with the American Association of Textile Chemists and colorists, Test AATC 34-4952.
• a strip of cloth to be tested is secured on each of its long sides in a vertical position, leaving an exposed area of approximately ten inches by two and one-quarter inches.
• a Bunsen burner is positioned ,below the bottom of the cloth so that the top of the burner is about three-quarters of an inch from the cloth.
• the burner produces a flame which is about one and one-half inches high.
• the flame is produced by burning natural gas in the absence of air.
• the cloth is exposed to the flame for a period of twelve seconds, and the flame is then turned off.
• a weight is 6 between about forty-five and about eighty percent by weight of water, between about six and about twenty percent by weight of a hydroxymethyl phosphonium chloride compound having the formula (CH OH) RPC1,
• the Weight being q where R is selected from hydroxymethyl, lower alkyls 316m PF 0f the teal" Strength f the 010thhaving between one and about eight carbon atoms, and The pp slde of the cloth is then pulled to produce chlorinated lower alkyls having between one and about a tea!
• the length of the tear is then eight carbon atoms, between about three and about twelve measured F determine h char in inchespercent by weight of a member of the group consisting of
• the E5111 trehted tabl'lc had a y good hand, and had triazines and dimethylol cyclic alkylene ureas, between a char of lhches y h Standard char test-
• the treatftd cloth 'f a soluble tertiary alkyl :amine between about three and char of 3.3 1nches; after thirty commercial launderings, about twelve percent by Weight f urea and between f a char of lnches-
• the tr?ated th after h about seven and about twenty-five percent by weight of sub ected to these extreme laundering cond1t1ons,st1llrea polyvinyl chloride resin having a
• Example 1 The procedure of Example 1 was repeated, employing The P of claim 2 wherein Said hYdIOXYIIIEthYI polyvinylchloride resins of various softening points, as PhOSPhOBiUm fihlol'ide is Y Y Y P indicated in the table below.
• Examples 6 and 7 show the improved results that are 4.
• the process of claim 2 wherein said cellulosic maobtained by the technique of the instant novel invention, terial is a cellulosic textile. while Examples 2, 3, 4 and 5 show the results obtained 5.
• the process of claim 2 wherein the resin add-0n of by procedures of the prior art.
• the cloths produced in the treated cellulosic material after curing is between Examples 6 and 7 had a superior hand as compared to the about fifteen and about thirty-five percent by weight of treated cloths produced in Examples 2 to 5, and the cloths the cellulosic material. of Examples 6 and 7 also were significantly less bulky 6.
• Example 2 A process for preparing a flexible, flame retardant of Example 2.
• cellulosic textile which comprises impregnating the cellu- It will be recognized by those skilled in the art that losic textile to be treated with an aqueous dispersion convarious modifications within the invention are possible, taining between about forty-five and about eighty persome of which have been referred to above. Therefore, cent by weight of water, between about six and about I do not wish to be limited except as defined by the aptwenty percent by weight of tetrakis(hydroxymethyl) pended claims.
• phosphonium chloride between about one and about four I claim: percent by weight of triethanolamine, between about 1.
• a process for preparing a flame-retardant, cellulosic three and about tWelVe Percent y Weight of trimethylmaterial which comprises impregnating the cellulosic maolmelamine, bE W about three and about tWfilVe P terial to be treated with an aqueous dispersion of a hycent by weight of urea, and between about seven and droxymethyl phosphonium chloride compound having the about twenty-five percent by weight of a polyvinyl chloformula (CH OH) RPCl, where R is selected from hyride resin having a softening point between about one droxymethyl, lower alkyls having between one and about 5 hundred and seventy and about two hundred degrees eight carbon atoms, and chlorinated lower alkyls having centigrade, and drying and curing the treated cellulosic between one and about eight carbon atoms, a member of material.
• CH OH polyvinyl
• the resin add-on of alkylene ureas, a water-soluble tertiary alkyl amine, urea, the treated cellulosic material after curing is between and a polyvinyl chloride resin having a softening point about fifteen and about thirty-five percent by weight of between about one hundred and seventy and about two the cellulosic textile. hundred degrees centigrade, and drying and curing the 9.
• the cellulosic textile treated cellulosic material. impregnated with said aqueous dispersion is dried at a 2.
• a process for preparing a flame-retardant, cellulosic temperature between about eighty and about one hundred material which comprises impregnating the cellulosic maand tweny degrees centigrade, for a period between about terial to be treated with an aqueous dispersion containing two and about four minutes, and curing of the resulting 10.
• a flame retardant cellulosic material comprised of p a cellulosic material impregnated with a resinous material comprised of the reaction product of a hydroxymethyl phosphonium chloride compound having the formula (CH OH) RPCl, where R is selected from bydroxymethyh'lower alkyls having between one and about eight carbon atoms, and chlorinated lower alkyls having between one and abou-t eight carbon atoms, a member of the group consisting of triazines and dimethylol cyclic alkylene ureas, a water-soluble tertiary allcyl amine, urea, and a polyvinyl chloride resin having a softening point between about one hundred and seventy and about two hundred degrees centigrade.
• R is selected from bydroxymethyh'lower alkyls having between one and about eight carbon atoms, and chlorinated lower alkyls having between one and abou-t eight
• a flame retardant cellulosic material comprised of a cellulosic material impregnated with a resinous material, said resinous material being thetreaction product formed from resin forming ingredients comprised of a hydroxymethyl phosphonium chloride compound having the formula (CH OH) RPCl, where R is selected from by droxymethyl, lower alkyls having between one and about eight carbon atoms, and chlorinated lower alkyls-having between one and about eight carbon atoms, in atpropon tion equivalent to between about ten and about sixty percent by weight, a member of the group consisting of triazines and dimethylol cyclic alkylene ureas in a proportion equivalent to between about five and about forty percent by weight, a water-soluble tertiary alkyl amine in a proportion equivalent to between about one and about twenty percent by weight, urea in a proportion equivalent to between about five and about forty percent by weight, and a polyvinyl chloride resin having a softening point
• the flame retardant cellulosic material of claim 11 wherein the resin add-on is between about fifteen and about thirty-five percent by weight of the cellulosic ma terial.
• a flame retardant cellulosic material comprised of a cellulosic material impregnated with a resinous material, said resinous material being the reaction product formed from resin forming ingredients comprised of tetrakis(hydroxymethyl) phosphonium chloride in a proportion equivalent to between about ten and about sixty percent by weight, trimethylol melamine in a proportion equivalent to between about five and about forty percent by weight, triethanol amine in a proportion equivalent to between about one and about twenty percent by weight, urea in a proportion equivalent to between about five and about forty percent by weight, and a polyvinyl chloride resin having a softening point between about one hundred and seventy and about two hundred degrees centigrade in a proportion equivalent to between about ten and about seventy percent by weight of the resin forming ingredients.
• resin forming ingredients comprised of tetrakis(hydroxymethyl) phosphonium chloride in a proportion equivalent to between about ten and about sixty percent by weight, trimethylol melamine in a
• a cellulosic material treating composition comprised of a hydroxymethyl phosphonium chloride compound having the formula (CH OH) RPCl, where R is selected from hydroxymethyh lower alkyls having between one and about eight carbon atoms, and chlorinated lower alkyls having between one and about eight carbon atoms, a member of the group consisting of triazines and dimethylol cyclic alkylene ureas, a water-soluble tertiary alkyl amine, urea, a polyvinyl chloride resin having a softening point between about one hundred and seventy and about two hundred degrees centigrade, and water.
• R is selected from hydroxymethyh lower alkyls having between one and about eight carbon atoms, and chlorinated lower alkyls having between one and about eight carbon atoms, a member of the group consisting of triazines and dimethylol cyclic alkylene ureas, a water-soluble terti
• a cellulosic material treating composition comprised of an aqueous dispersion containing between about six and about twenty percent by weight of a hydroxymethyl phosphonium chloride compound having the formula (CH- OH) RPCI, where R is selected from hydroxymethyl, lower alkyls having betweentone and about eight carbon atoms, and chlorinated lower alkyls having between one and about eight carbon atoms, between about three and about twelve percent by weight of a member of the group consisting of triazines and dimethylol cyclic alkylene areas, between about one and about four percent by weight of a water-soluble tertiary alkyl amine, between about three and abouttwelve percent by weight of urea, between about seven and about twenty-five percent by weight of a polyvinyl chloride resin having a softening point between about one hundred and seventy one hundred and seventy and about two hundred degrees centigrade, and between about forty-five and about eighty .percent by weight of water.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Engineering & Computer Science (AREA)
• Textile Engineering (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)

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Cited By (15)

Citations (2)

• 0
  • NL NL271608D patent/NL271608A/xx unknown
  • NL NL126452D patent/NL126452C/xx active
• 1960
  • 1960-11-21 US US7038760 patent/US3054698A/en not_active Expired - Lifetime
• 1961
  • 1961-11-20 DE DE19611419474 patent/DE1419474A1/de not_active Withdrawn
  • 1961-11-20 GB GB4146961A patent/GB975095A/en not_active Expired

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