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 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 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 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.
• polyester is used in its usual sense to mean highly polymeric, essentially linear polyester resins made by the reaction of a dicarboxylic acid or ester 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 US-A-2,465,319 and US-A-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 fibrous materials which can be provided with a flame-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 undyed, or as textiles which have already been further processed.
• THP tetrakis(hydroxymethyl) phosphonium salt
• TPO Pyroset (Registered Trade Mark) TPO is a THPS/urea precondensate of tetrakis-(hydroxymethyl) phosphonium sulphate and urea available from American Cyanamid Co.
• Retardol AC (Registered Trade Mark) 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 THPS/urea is known as the PROBAN porches as licenced by Albright & Wilson.
• the THP salt/urea precondensate process itself is described in the following US patents: 4,078,101; 4,145,463; 4,311,855 and 4,494,951, all to Albright & Wilson. This process is considered effective and is widely promoted by at least two US companies for imparting flame resistance to 100% cotton fabrics.
• the THP salt/urea precondensate process by itself is ineffective to adequately protect polyester/cotton blends containing more than about 35 to 40% polyester as discussed previously.
• 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 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.
• Another flame retardant material used in accordance with the present invention specific for the polyester 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: where a is 0 or 1; b is 0, 1 or 2, c is 1, 2 or 3 and a+b+c is 3; R and R' are the same or different and are alkyl (C1-C8), phenyl, halophenyl, hydroxyphenyl, tolyl, xylyl, benzyl, phenethyl, hydroxyethyl, phenoxyethyl, or dibromophenoxymethyl; R2 is alkyl (C1-C4); and R3 is lower alkyl (C1-C4) or hydroxyalkyl (C1-C4) or where d is 0, 1 or 2;
• the preferred compounds are represented by the formula: in which X is 0 or 1, and usually a 50:50 mixture of the mono- and di-esters.
• X is 0 or 1
• a 50:50 mixture of the mono- and di-esters usually a 50:50 mixture of the mono- and di-esters.
• the preparation of these cyclic phosphonate esters and their use as flame retardants are described in US-A-3,789,091 and US-A-3,849,368, the disclosures of which are hereby incorporated by reference.
• Antiblaze 19T 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 C12H18Br6, 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 ( THPC/urea ) 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. Bath formula: Water 30.6% Aerosol C 61 wetting agent 0.2% Sodium acetate (60%) 0.5% Pyroset TPO 68.7%
• 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 and after 25 launderings.
• TP0/ammonia-treated style 9886 fabric of comparative 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.

Landscapes

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

Priority Applications (1)

Applications Claiming Priority (5)

Publications (3)

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Family Applications (1)

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• 1987
  • 1987-09-25 WO PCT/US1987/002432 patent/WO1988002283A1/en active IP Right Grant
  • 1987-09-25 EP EP87906715A patent/EP0325610B1/en not_active Expired - Lifetime
  • 1987-09-25 DE DE87906715T patent/DE3789553D1/de not_active Expired - Lifetime
  • 1987-09-25 AU AU80716/87A patent/AU603391B2/en not_active Ceased
  • 1987-09-25 JP JP62506118A patent/JPH02500454A/ja active Pending
• 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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