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
• • 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

Definitions

• This invention relates to a process for imparting flame-retardant properties to cotton/synthetic fiber blends, specifically polyester/cotton and nylon/cotton blended fabrics, using two flame-retardant chemicals or flame-retardant systems, one specific to the synthetic component and the other specific to the cotton component.
• THPS When THPS is applied to a polyester/cotton or nylon/cotton blend, a degree of flame resistance results, but it remains stiff and generally unacceptable. Since the THPS is specific to cotton, it does not react with the polyester or nylon content of the fabric but simply physically coats the synthetic component. As a result, after multiple launderings, that portion of the flame retardant surrounding the polyester or nylon fiber is partially lost. In consequence, it was not unusual to use as much as 5.5% phosphorus add-on for a polyester/cotton blend, at least initially, in order to result in the target 3% of fixed phosphorus after 50 launderings in hot water.
• polyester/cotton blends were flame retarded using tris-2,3-dibromopropyl phosphate ("Tris") in combination with THPS.
• Tris tris-2,3-dibromopropyl phosphate
• An object of the present invention is to produce acceptable flame-resistant polyester/cotton and nylon/cotton blends using multiple flame-retardant chemicals or chemical systems, and to employ processing conditions or adjuvants that produce a commercially acceptable, attractive product having good color and acceptable hand.
• the process of the present invention employs two flame-retardant (FR) systems, one specific to the synthetic component and the other specific to the cotton component of the synthetic/cotton blends being flame-retarded.
• FR flame-retardant
• the amount of flame retardant, such as THPS, required to satisfy flame-resistance standards can be reduced significantly and the resulting fabrics have not only better flame resistance, but also better aesthetics.
• different flame-retardant chemicals are applied together in a single step, or in separate processing steps. Processing conditions, especially temperatures and humidities, are carefully controlled in order to optimize the use of the flame-retardant chemicals and to ensure good fixation to the synthetic/cotton blends, even after several launderings.
• polyester/cotton blends treated in accordance with the present invention contain between 35% and 80% of polyester, the balance being cotton.
• the nylon/cotton blends contain between 10% and 65% nylon or, when a single treatment step is used, from 3% to 55% nylon, preferably from 35 to 55% nylon.
• polyester is used in its usual sense to mean highly polymeric, essentially linear polyester resins made by the reaction of a dicarboxylic acid orester with a diol in the presence of an esterification or ester interchange catalyst.
• dicarboxylic acids are malonic, succinic, adipic, azelaic, maleic, fumaric, hydromuconic, isophthalic, terephthalic, and cyclohexane-dicarboxylic acids.
• Representative diols are ethylene glycol, propylene glycol, butylene glycol and 1,6-hexanediol. See U.S. 2,465,319 and U.S. 2,901,446.
• the common commercial polyester resins are polyethylene terephthalate and polyethylene terephthalate modified by inclusion of minor proportions of a different glycol or dicarboxylic acid during the polyesterification process.
• the polyester used in the working examples that follow was polyethylene terephthalate.
• nylon is used to describe a manufactured fiber in which the fiber-forming substances are long-chain synthetic polyamides having recurring polyamide groups (-CONH-) as an integral part of the polymer chain. These polyamides are formed from various combinations of diacids, diamines and amino acids. See generally Kirk-Othmer Encyclopedia of Chemical Technology, Vol. 16 (Interscience, New York, 2nd. ed., 1968) pp. 1-105.
• polyester/cotton and nylon/cotton fibrous materials which can be provided with a fleme-retardant finish according to the invention can be in any desired stage of processing, i.e., they can be treated as woven or knitted fabrics, dyed or imdyed, or as textiles which have already been further processed.
• Flame-resistant properties are imparted to the fabric in two distinct steps, one for the cotton component and the other for the synthetic (polyester or nylon) component.
• the order in which these steps are conducted is not critical; good results can be obtained when the cotton component of the blend is treated either first or second.
• THP salt/urea preoondensate is applied to the fabric and dried to a specific moisture level.
• ammonia usually ammonia gas
• ammonia gas oxidized, usually with hydrogen peroxide, to form a three-dimensional flame retardant polymer network within the cotton fiber structure.
• This process results in a fabric having a softer hand than other treatments, such as THPS/urea, which tends to stay on the outside of the fibers and stiffen the fibers and is more susceptible to removal by repeated laundering.
• Pyroset TPO is a THPS/urea precondensate of tetrakis-(hydroxymethyl)phosphonium sulfate and urea available from American Cyanamid Co.
• Retardol AC is a THPC/urea prepolymer condensate of tetrakis-(hydroxymethyl)phosphonium chloride and urea available from Albright & Wilson,
• the process of imparting flame resistance to 100% cotton fabrics using THPC/urea is known as the PROBAN process as licensed by Albright & Wilson.
• the THP salt/urea precondensate process itself is described in the following U.S. patents: 4,078,101; 4,145,463; 4,311,855 and 4,494,951, all to Albright & Wilson. This process is considered effective and iswidely peomoted by at least two U.S. companies for imparting flame resistance to 100% cotton fabrics; it is not promoted nor advertised for polyester/cotton blends or nylon/cotton blends.
• the THP salt/urea precondensate process by itself is ineffective to adequately protect polyester/cotton blends containing more than about 35 to 40% polyester.
• Hexabromocyclododecane is available as CD-75 from Great Lakes Chemical and as Saytex HBCD from the Ethyl Corporation. It is sold primarily for use as a flame retardant for plastics, in part because of its poor solubility in solvents commonly used for textile processing.
• Hexabromocyclododecane melts at about 182°C (360° F), and, when applied as a dispersion to a polyester/cotton or nylon/cotton fabric at elevated temperatures above its melting point, then cooled, hexabromocyclododecane fuses to the fiber, imparting the requisite flame-resistant properties to the fibers of the polyester or nylon.
• Another flame retardant material used in accordance with the present invention specific for the polyester or nylon component of the fabric is a thermally stable cyclic phosphonate ester prepared by reacting alkyl-halogen-free esters with a bicyclic phosphite.
• these cyclic phosphonate esters are represented by one of the formulas:
• R and R' are the same or different and are alkyl (C 1 -C 8 ), phenyl, halophenyl, hydroxyphenyl, tolyl, xylyl, benzyl, phenethyl, hydroxyethyl, phenoxyethyl, or dibromophenoxymethyl;
• R 2 is alkyl (C 1 -C 4 ); and
• R 3 is lower alkyl (C 1 -C 4 ) or hydroxyalkyl
• R 4 is alkyl (C 1 -C 4 ) phenyl, halophenyl, hydroxyphenyl, hydroxyethyl, phenoxyethyl, dibromophenoxymethyl, tolyl, xylyl, benzyl or phenethyl; and R 5 is monovalent alkyl (C 1 -C 6 ), chlorophenyl, bromophenyl, dibromophenyl, tribromophenyl, hydroxyphenyl, naphthyl, tolyl, xylyl, benzyl, or phenethyl; divalent alkylene (C 1 -C 6 ),vinylene, o-phenylene, m-phenylene, p-phenylene, tetrachlorophenylene (o, m, p), or tetrabromophenylene (o, m, or p); or trivalent phenyl
• a mixture of flame retardants is applied, one member of the mixture specific for cotton and the other for nylon, after the fabric is dyed.
• the same bath is used to apply a mixture of two (or more) flame-retardant chemicals, such as by padding onto the fabric with a fixed add-on typically in the range of 20-25% by weight.
• This combination pad bath is most effective for nylon/cotton blends containing from about 35% to about 55% nylon and is not recommended for fabrics dyed with direct dyes or reactive dyes as they tend to change color.
• naphthols, acid dyes and cationic dyes are fully acceptable.
• the hand of fabrics so treated is substantially superior to the hand of any flame-resistant nylon/cotton fabrics heretofore known to the art.
• the hand can be further improved by the use of a softener such as Aerotex H Softener, a cationic product with nonionic and anionic moieties, manufactured by American Cyanamid Co.
• the hand of the treated fabrics can be still further improved by conducting the curing operation in a moist, high-humidity environment.
• Antiblaze 19T as described by the supplier Albright & Wilson Inc., of Richmond, Virginia, U.S.A., is a cyclic phosphonate ester, available as an odorless viscous liquid (viscosity 250 Pa.s) with a flashpoint of 171°C (340°F) (ASTM D-93).
• Hexabromocyclododecane as described by its supplier Great Lakes Chemical Corporation of West Lafayette, Indiana, U.S.A., is a cyclic alkyl bromide, empirical formula C 12 H 18 Br 6 , CAS registry number 25637-99-4, composed of hexabromocyclododecane and related bromocycloalkanes. It is an odorless, water-insoluble, off-white powder having a melting point range of 142-182°C (288-360°F) and is preferably used in the process of this invention as a dispersion in water or an aqueous pad bath system.
• Tetrakis-(hydroxymethyl)phosphonium chloride/urea prepolymer condensate is available from Albright & Wilson, Inc., under the name Retardol AC.
• a related chemical, THPS/urea prepolymer condensate is available from American Cyanamid Co., under the name of Pyroset TPO.
• Aerotex H is described by its supplier, American Cyanamid. Co., as a cationic product with nonionic and anionic moieties, and is included in the pad bath formulation as a softener.
• TMN-10 is ethoxylated 2,6,8-trimethylnonanol, commercially available from Union Carbide Corporation.
• FR Federal Test Method 5903 is intended for use in determining the resistance of cloth to flame and glow propagation and tendency to char.
• a rectangular cloth test specimen (70mm x 120mm) with the long dimension parallel to the warp or fill direction is placed in a holder and suspended, vertically in a cabinet with the lower end 1.9 cm above the top of a Fisher gas burner.
• a synthetic gas mixture consisting primarily of hydrogen and methane is supplied to the burner. After the specimen is mounted in the cabinet and the door closed, the burner flame is applied vertically at the middle of the lower edge of the specimen for 12 seconds. The specimen continues to flame after the burner is extinguished.
• the time in seconds the specimen continues to glow after the specimen has ceased to flame is reported as afterglow time; if the specimen glows for more than 30 seconds, it is removed from the test cabinet, taking care not to fan the glow, and suspended in a draft-free area in the same vertical position as in the test cabinet.
• Char length the distance (in centimeters) from the end of the specimen, which was exposed to the flame, to the end of a lengthwise tear through the center of the charred area to the highest peak in the charred area, is also measured. Five specimens from each sample are usually measured and the results averaged.
• Fabric style 9886 (50/50 nylon/cotton) was padded to a wet pickup of 61% with Pyroset TPO (THPS-urea precondensate from American Cyanamid; see bath formula), and heated at 54°C for 48 seconds. The moisture content was found to be 15.5-16% as measured with a Mahlo meter .
• the fabric was equilibrated in a plastic bag for 1-2 hours. The fabric was then exposed to ammonia gas at 6:1 ammonia: phosphorus mole ratio. Oxidation of the fabric by a hydrogen peroxide/sodium silicate solution followed. The amount of peroxide used was 5% on the weight of fabric. The sodium silicate was used to maintain a pH of 9-9.5. The fabric was rinsed and tumble dried.
• the TPO/ammonia-treated style 9886 fabric was subsequently padded with a 15% Antiblaze 19 (Albright & Wilson) solution, heated in an oven at 193°C for 45 seconds and tested for flame resistance as prepared andafter 25 launderings.
• a 15% Antiblaze 19 Albright & Wilson
• TPO/ammoni a- treated style 9886 fabric of Example 1A was also subsequently padded with a 15% dispersion of hexabromocyclododecane (HBCD), heated at 182°C (360°F) for 45 seconds, and tested for flame resistance as prepared and after 25 launderings.
• HBCD hexabromocyclododecane
• Example 1A or 1B None of the treated fabrics of Example 1A or 1B exhibited either afterflame or afterglow. The results show a high level of flame resistance, and the treated fabrics had satisfactory aesthetic properties.
• Aerosol C 61 wetting agent 0 .2%
• Aerotex H softener 2 .0%
• Example 3 A bath containing 50% of a tetrakis- (hydroxymethyl) phosphonium sulfate preparation (Retardol S from Albright & Wilson), 15.7% urea, 9.3% cyclic phosphonateate ester (Antiblaze 19 from Albright & Wilson), 2% disodium phosphate, 2% fabric softener (Aerotex H from American Cyanamid) and 0.1% nonionic surfactant was prepared. This bath was padded onto a dyed and printed nylon/cotton twill (ca. 55% nylon, 264 g/m 2 . Wet pickup was 61.5%. The fabric was dried and cured for 90 seconds in an oven at 182°C. The treated fabric was oxidized in a solution contaiing hydrogen peroxide and sodium hydroxide, rinsed well and dried.
• a tetrakis- (hydroxymethyl) phosphonium sulfate preparation (Retardol S from Albright & Wilson), 15.7% urea, 9.3%
• Antiblaze 19 9.3 9.3 Aerotex H 2.0 2.0 Surfactant 0.1 0.1
• Fabric A was a ripstop weave, 210 g/m 2 , 2.8% nylon.
• Fabric B was a twill, 179 g/m 2 , 53.1% nylon. The fabric samples were dried and cured for 60 seconds in an oven at 182oC.
• Antiblaze 19 9.3 9.3 9.3 9.3 disodium phosphate 2.0 2.0 2.0 2.0 2.0
• the treated fabric containing at least 1.6% of phosphorus had excellent flame resistance and good aesthetic properties.

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• Engineering & Computer Science (AREA)
• Textile Engineering (AREA)
• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
• Nonwoven Fabrics (AREA)
• Polyesters Or Polycarbonates (AREA)
• Compositions Of Macromolecular Compounds (AREA)

Priority Applications (5)

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Cited By (4)

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Citations (5)

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• 1987
  • 1987-09-25 JP JP62506118A patent/JPH02500454A/ja active Pending
  • 1987-09-25 DE DE87906715T patent/DE3789553D1/de not_active Expired - Lifetime
  • 1987-09-25 EP EP87906715A patent/EP0325610B1/en not_active Expired - Lifetime
  • 1987-09-25 AU AU80716/87A patent/AU603391B2/en not_active Ceased
  • 1987-09-25 WO PCT/US1987/002432 patent/WO1988002283A1/en active IP Right Grant
• 1988
  • 1988-05-25 NO NO882310A patent/NO173790C/no unknown
  • 1988-05-26 DK DK289288A patent/DK289288A/da not_active Application Discontinuation

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