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
  • D06M15/667—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing phosphorus in the main chain
  • D06M15/673—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing phosphorus in the main chain containing phosphorus and nitrogen in the main chain
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L97/00—Compositions of lignin-containing materials
  • C08L97/02—Lignocellulosic material, e.g. wood, straw or bagasse
• • 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
  • D06M15/667—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing phosphorus in the main chain
• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
  • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
  • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
  • D21H21/34—Ignifugeants
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
  • B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
  • B27K2240/00—Purpose of the treatment
  • B27K2240/30—Fireproofing
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
  • B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
  • B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
  • B27K3/02—Processes; Apparatus
  • B27K3/15—Impregnating involving polymerisation including use of polymer-containing impregnating agents
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/49—Phosphorus-containing compounds
  • C08K5/51—Phosphorus bound to oxygen
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
  • C08L75/02—Polyureas
• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
  • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
  • D21H17/03—Non-macromolecular organic compounds
  • D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
  • D21H17/07—Nitrogen-containing compounds
• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
  • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
  • D21H17/03—Non-macromolecular organic compounds
  • D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
  • D21H17/10—Phosphorus-containing compounds
• • 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
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/4935—Impregnated naturally solid product [e.g., leather, stone, etc.]
  • Y10T428/662—Wood timber product [e.g., piling, post, veneer, etc.]
• • 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

• Patent ()7 ABSTRACT OF THE DISCLOSURE A method for rendering cellulosic textiles durably flame retardant, even after repeated laundering, comprising treating the textiles with an aqueous solution containing a miXture of thiourea and tris(l-aziridinyl) phosphine oxide (APO).
• APO tris(l-aziridinyl) phosphine oxide
• This invention relates to an improved composition and method for the treatment of cellulose and/or cellulosic-containing materials. More particularly, the present invention relates to the treatment of cellulose-based or cellulose-containing woven and non-woven textiles (such as cotton and rayon), paper, wood, cardboard, rope and jute with a mixture containing tris(1-aziridinyl)phosphine oxide and at least one thiourea compound.
• cellulose-based or cellulose-containing woven and non-woven textiles such as cotton and rayon
• paper, wood, cardboard, rope and jute with a mixture containing tris(1-aziridinyl)phosphine oxide and at least one thiourea compound.
• APO tris(1-aziridinyl)phosphine oxide
• the finished cellulosiccontaining fabric has better fiber strength and retains its finish much longer than can be achieved with other APO- containing compositions.
• Another advantage of the invention is that dye shade changes in fabrics either do not occur with APO-thiourea treating compositions, or else occur uniformly over the fabric during treatment.
• a mixture of a thiourea compound and APO is incorporated into a treating bath and a cellulosic-containing material is impregnated with the bath composition. The impregnated material is then cured to form a flame-resistant product.
• mixture containing a thiourea compound and APO in a mole ratio of from about .3:1 to 3:1 (preferably from about .5 :1 to 2:1, thioureazAPO) is dissolved or dispersed in a solvent such as Water to form a treating bath in which the concentration of the combined thiourea- APO composition is from 15 percent to percent by weight based upon the total weight of the treating bath.
• a catalyst is not necessary to accomplish polymerization of the treating materials on and within the fibers which are to be treated
• a conventional catalyst for example, Zn(BF an organic acid such as acetic acid, perfluoroacetic acid, citric acid, oxalic acid or other known APO polymerization agent
• Zn(BF an organic acid such as acetic acid, perfluoroacetic acid, citric acid, oxalic acid or other known APO polymerization agent
• the cellulosic material to be treated is then contacted with this bath composition to form a product of any desired degree of impregnation, and the impregnated product is then cured by any suitable method.
• Heat curing is the preferred method, but curing can be carried out at ambient room temperatures over extended time periods (several Weeks).
• Curing is probably accomplished by the reaction of the thiourea compounds and aziridinyl phosphine oxide to give polymers containing phosphorus, nitrogen and sulfur which are bound to the cellulosic materials by reaction of the'aziridinyl rings'with the cellulosic hydroxyl groups, or other reactive substituents.
• the cellulosic material which is to be treated is a textile
• other known conventional fabric treating agents such as fabric softeners, wetting agents and emulsifiers may be incorporated into the treating bath. Amounts of up to a total of about 10l5 percent by (dry) weight (based on the total weight of the bath) of such treating agents may be employed.
• Typical fabric softening agents which may be-incorporated into such a treating bath include quaternary ammonium salts such as the dimethyl benzylamine quaternary formed by combination with the reaction product of a polyethoxylated nonylphenol and epichlorohydrin, emulsified polyethylene and emulsified stearamide.
• Typical non-ionic wetting agents include polyoxyalkylene polyethers and hydroxy-containing polyethers such as are obtained by the reaction of alkylated phenols with 8-15 moles of ethylene oxide.
• other flame-proofing ingredients for example, lower alkyl ammonium phosphates such as methyl ammonium phosphate, ethyl ammonium phosphate, etc.
• Amounts of'urea of up to about 5 percent by weight may be incorporated into the treating bath without the production of undesirable fumes.
• Water is the preferred carrier for the treating mixtures, although other solvents may be used if desired.
• the compositions maybe heated to form a prepolyrnerprior to deposition on the cellulosic material.
• Typical treating bath concentrations using water as the carrier and/or solvent are summarized in Table v1 (all percentages are based upon the total weight of the bath).
• a fabric softener and wetting agent was used in each bath composition.
• the fabric softener used was Moropol-700 softener (containing 30 percent by Weight of emulsified polyethylene).
• the concentration used ' was from 3.0 to 5.0 percent by weight based on the total Weight of the bath.
• the wetting agent was Dowfax 9N9 non-ionic surfactant, The concentration used was from 0.1 to 0.5 percent by weight based upon the total weight of the bath.
• the treating bath is generally held at a temperature of from about 32 to 100 F. during the impregnation of the material to be treated.
• N-lower alkyl 1-4 carbon atoms, methyl, ethyl, n-propyl, i-propyl, n-butyl, sec.-butyl, tertbutyl, i-butyl
• Any cellulose-containing material may be treated with the bath compositions of the invention by merely impregnating the material with a treating bath (solution, mixture or dispersion) at ambient temperature containing APO and a thiourea compound, followed by curing the impregnated material at temperatures of from about 200 to 350 F. for from about 1 to 2 minutes to /2 hour (higher temperatures requiring less time).
• the material may be dried prior to the curing step.
• the textile material to be treated is dipped in the bath once or twice followed by a squeezing or wringing operation to remove excess bath solution.
• the impregnated fabric is then dried and cured.
• the treated fabric contains from 5 to percent of APO based upon the dry weight of the fabric and from 5 to 15 percent of the thiourea compound.
• Typical fabrics which may be efiiciently rendered flame retardant according to the present invention include cotton, viscose rayon, rayon acetate, cotton blend fabrics, as well as other cellulosebased natural and synthetic textiles.
• Wood specimens which are treated with compositions containing APO and thiourea char when placed in a Bunsen burner flame but do not burn when the flame is removed. When wood is treated according to the invention, it is not necessary to impregnate the fibers deeply. Only an amount of APO- thiourea mixture sufficient to inhibit the burning of the surface of the wood is used.
• the fabrics used were broadcloth, sateen and twill with an untreated weight per square yard of 3 /2 ounces, 8 ounces and 9 ounces, respectively.
• the fabrics were padded through the treating bath once and pressed once with rollers to remove excess bath fluid.
• the wet fabric was dried at about 240 F. for about 2 minutes and then cured for two minutes at 325 F.
• the treated fabric was then given a standard after wash in an automatic home laundry washer (ten gallons of water at F., /2 cup of a commercial alkylbenzene sulfonate detergent, ten minute wash cycle, followed by one spray rinse and one deep rinse).
• the fabrics were rated according to the hand and to the flame retardance (AATCC Standard Test 34-1952, Vertical Char test). No conditioning was given to the fabrics before testing for the vertical char, except the conditioning existing in the laboratory at the time of the test. These conditions were (1) temperature: approximately 70-75 F. and (2) relative humidity: approximately 30-40 percent.
• a durability wash consists of the following treatment: The fabric is washed for 45 minutes at 200- 212 F. in an agitator-type washing machine with 100 grams of soda ash (Na CO 100 grams of Ivory Flakes neutral soap and 10 grams of Tide detergent in 88 pounds of water for every 4 pounds of fabric. The washed 1 fabric is then given a 15 minute rinse in water at F.
• the vertical char test . (AATCC Test No. 34-1952) is carried out using strips of cloth 10 inches long by 2% inches wide held vertically in a standard apparatus while a preadjusted flame is applied to the bottom inch of the fabric for a fixed standard time. Average values of three samples are taken.
• the tear strengths and breaking strengths (both warp and fill) of the treated fabrics were excellent even after 4 durability washes.
• Example XVII The following 'ingredientslwere combined to form an aqueous bath solution (all percentages by weight based on the total weight vof the bath solution).
• Example XIX Ina mill comparison of APO-thiourea and APO-urea mixtures with identical fabric softener, catalyst and nonionic wetting agent, smoke-like fumes were formed with the APO-urea mixture during the curing step. The venting system would not remove the fumes as they were No fumes were obtained with the APO-thiourea mixture.
• Example XX A bath composition consisting of the following ingredients was prepared by simply mixing the components.
• Example XXI A bath containing 31 percent by weight of an APO- thiourea mixture (mole. ratio of thiourea to APO of 1.5 :1) was prepared as follows.
• the running speed was 75 yards per minute. Drying was accomplished with infrared preheaters and a tenter frame heated to 240 F. (A tenter frame is a conveyor equipped with parallel clips which keep the wet fabric taut while the fabric is moved through a drying oven.) The f-abricrwas cured at 330335 F. in a 150 yard curing oven. The fabric was then washed in a small amount of wetting agent, rinsed and dried. The treated fabric had excellent flame retardant characteristics as measured by AATCC Test No. 34-1952.
• Example XXII A bath composed of the following ingredients was prepared at room temperature.
• Unfinished broadcloth was treated in accordance with the procedure of Examples I-XVI.
• the wet pick-up was about 65 percent.
• the percent dry add-on per 100 grams of dry fabric was 13.6 grams for the APO and 9.0 grams for the thiourea.
• the breaking strength (as measured according to ASTM D-39-49, Section 10) and tear strength (as measured according to ASTM D-1424-56T) I were as follows Finished Control Fabric Breaking strength (lbs):
• cellulosic is meant to include materials which contain cellulose as well as materials which are basedupon cellulose derivatives.
• viscose rayon based upon the reaction of the hydroxyl groups of cellulose with carbon disulfide in the presence of NaOH to give xanthates
• oxidized cellulose and rayon acetate are typical examples of cellulosic materials.
• Method of treating cellulosic material which comprises contacting said material with a treating bath containing from 10 to 50% by weight of a mixture of (1) tris(l-aziridinyl)phosphine oxide, and (2) a thiourea compound of the formula N s H R1I IH l I-R: wherein each of R and R is selected from the group consisting of (a) (CHfi H and f TH wherein x is an integer of from 0 to 4 and y is an integer of from 1 to 2, to form an impregnated materialand curing said impregnated material, wherein the mole ratio of (2)1(1) is from 0.3:1 to 3.011.
• a method of treating a cellulose-containing fabric which comprises:
• a method of treating a cellulose-based textile which comprises contacting said textile with a treating bath containing from 10 to 50 percent by Weight of a mixture of N,N'-dimethy1ol thiourea and tris(1-aziridinyl)phosphine oxide in a mole ratio of from 0.5 :1 to 20:1, respectively, to form an impregnated textile and curing said impregnated textile at a temperature of from 200 to 350 F. to produce a flame retardant product.
• a method of flame-proofing wood which comprises contacting the Wood with a treating bath containing from 10 to 50 percent by weight of a mixture of thiourea and tris(1-aziridiny1)phosphine oxide in a mole ratio of from 0.5 :1 to 2.0:1, respectively, to form an impregnated wood product and curing said impregnated wood product at a temperature of from 200 to 350 F.
• a treating bath for flame-proofing cellulose-containing material which comprises an aqueous solution of from 10 to 50 percent by weight of a mixture of (1) tris(1-aziridinyl)phosphine oxide, and
• each of R and R is selected from the group consisting of (a) ⁇ CH hH and (b) 4CH OH wherein x is an integer of from 0 to 4 and y is an integer of from 1 to 2 and wherein the mole ratio of (2):(1) is from 0.3:1 to 30:1.

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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Textile Engineering (AREA)
• Wood Science & Technology (AREA)
• Materials Engineering (AREA)
• Health & Medical Sciences (AREA)
• Life Sciences & Earth Sciences (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
• Fireproofing Substances (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Paper (AREA)

Priority Applications (7)

Applications Claiming Priority (1)

Publications (1)

Family

ID=23495302

Family Applications (1)

Country Status (6)

Cited By (2)

Citations (9)

• 1964
  • 1964-06-29 US US378973A patent/US3376160A/en not_active Expired - Lifetime
• 1965
  • 1965-06-02 GB GB23473/65A patent/GB1063273A/en not_active Expired
  • 1965-06-28 BE BE666043D patent/BE666043A/xx unknown
  • 1965-06-28 SE SE8516/65A patent/SE307929B/xx unknown
  • 1965-06-28 DE DE19651469328 patent/DE1469328A1/de active Pending
  • 1965-06-29 NL NL6508322A patent/NL6508322A/xx unknown

Patent Citations (9)

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