Cotton Flammability Issues: An Update COTTON INCORPORATED MARY ANKENY Topics Is flammability a concern for cotton? What s the issue? Review of past and present chemistries, applications and markets Durable and Semi Durable Non Durable New flame retardant treatments on the horizon Integration of performance finishes with flame retardant chemistry Need more info? 1
Clothing Recalls CPSC Clothing Recalls (1980 to Present) 9/12/2016 Children's Clothing GWA Adult Clothing (Flammablility Concerns) Since '94 (Flammability Concerns) Since '94 Number of Recalls 5 Number of Recalls 43 Total Garments Recalled 59,230 Total Garments Recalled 1,691,159 100% Cotton 0.0% 100% Cotton 21.8% Cotton Blends 3.1% Cotton Blends 48.2% All Cotton Containing 3.1% All Cotton Containing 70.0% Other Fibers** 96.9% Other Fibers 30.0% Of the cotton containing recalls: ** Other fibers contains recalls where fiber content is not reported Raised Surface 91.7% Children's Sleepwear Total Adult & Children's (Flammability Concerns) Since '94 GWA Flammability Recalls Since '94 Number of Recalls 52 Number of Recalls 48 Total Garments Recalled 1,876,423 Total Garments Recalled 1,750,389 100% Cotton 56.4% 100% Cotton 21.0% Cotton Blends 1.3% Cotton Blends 46.7% All Cotton Containing 57.7% All Cotton Containing 67.7% Other Fibers** 42.3% Other Fibers 32.3% Recalls Since 1994 Adult s Garment Recalls Since 1994 Total Adult and Children's Clothing GWA Flammability Recall Cotton Cotton Blends Other Fibers Children s Garment Recalls Since 1994 Children's Garment Recalls Adult's Garment Recalls Cotton Cotton Blends Other Fibers 2
Children s Sleepwear Recalls Since 1994 Children's Sleepwear Recalls Cotton Cotton Blends Other Fibers Home Products Fire Data 3000 2500 2000 1500 1000 500 0 Deaths Injuries Property Damage ($M) Other home textile 60 390 177 Apparel 130 400 185.9 Mattress/Bedding 340 1150 273.1 Upholstered Furniture 390 660 237.8 (source: CPSC/NFIRS) * 3
Durable and Semi Durable Finishes N methylol dimethyl phosphonopropionamide (MDPPA) (Reactive phosphorous process) Advantages No special equipment required Typical pad dry cure process Disadvantages Acid catalysts degrade fibers causing strength loss and alter dye shade Hydrolyzes in storage at high humidity and temperature Need resin to improve fixation and efficiency and afterwash Formaldehyde release RO RO P O CH 2 n C O NH CH 2 OH 4
Tetrakis(hydroxymethyl)phosphonium chloride (THPX or pre condensate process) Advantages Durable to 100+ HL (life of the garment) Disadvantages Curing is complicated and requires peroxide oxidation & afterwash Gaseous ammoniation step requires process safety rules Formaldehyde release Only vat dyes are fast HO Expensive CH 2 Limited # of licensees 4 P + Cl- Oligomeric phosphonate phosphate ester (OPPE) Advantages Standard pad dry cure process No more effect on strength or shade than typical resin process Disadvantages Formaldehyde release Co applied with DMDHEU resin for durability HO R O O P O where R = alkyl, alkoxy, or hydroxyalkoxy O P O R R n 5
Antimony/Halogen + Binder Sb 2 O 3 Binder needed to coat fabric and obtain durability Synergistic effect Toxicity issues with both active components Decabromodiphenyl ether (DecaBDE or decabrom) has been listed for regulation by EPA, REACh, etc. Production of polybromodiphenyl ethers (PBDEs) in general has been phased out in Europe and U.S. Antimony is a known/suspected carcinogen and also on REACh list Additional Flame Retardant Options Archroma Pekoflam ECO/SYN Non halogenated Formaldehyde and amine emissions below detectable limits Application compatible with existing equipment Alexium International Alexiflam NF Non halogenated, phosphorus based Claimed durable to 50+ HLTD Application compatible with existing equipment 6
Non durable Finishes Boric acid ATH or Aluminum hydroxide Ammonium (Poly)phosphate 7
Novel Finishes DNA and Chitosan Applied in a layer by layer technique Intumescent The DNA promotes the charring of the chitosan By releasing phosphoric and polyphosphoric acid 8
Novel Application Routes Polymer nanocomposites Sol gel coatings using inorganic organic polymers Other Desired Performance Characteristics Cotton Protective Workwear that lasts longer before developing holes and wrinkles less Breathable, more comfortable cotton protective apparel with moisture management features 9
Improving Wrinkle Resistance and Shrinkage Combining a durable press finish with a flame retardant Depending on the FR treatment system a one or two bath application is needed The MDPPA can be combined in one bath with an uncapped DMDHEU/DMUG blend. A two bath system is needed to effectively combine wrinkle resistance with the THPOH/Ammonia Durable press finish will impart smoothness to wovens and improve shrinkage to knits. Improving Physical Durability TOUGH COTTON finish improves resistance to abrasion and wrinkling combined with flame resistance In this case a glycolated resin plus a DMUG are combined with polyethlene and MDPPA One bath: pad, dry, cure, afterwash Can be applied to knits and wovens Does not impact the durability of the FR treatment 10
Adding Protection from Weather Cotton Incorporated has developed STORM COTTON technology, a durable water repellant treatment for cotton. This finish was combined with denim and knits treated with FR The STORM COTTON finish did not interfere with the FR treatment The FR treatment reduced the durability of the STORM COTTON treatment. Improve Comfort of Protective Apparel Cotton Incorporated has developed TransDRY technology, a durable water repellant yarn treatment for cotton. Engineer fabric constructions to take advantage of both treated and untreated yarns to effectively move moisture Channels sweat away from body for evaporation Does not affect breathability Can reduce cling Does not interfere with FR application or performance Durable to 30+ HLTD 11
Summary Durable Flame Retardancy Currently Phosphorus based Level of durability depends on market/regulations Several options on the market Compatible with existing equipment lines Beyond just flame resistant fabric Wrinkle resistance Abrasion resistance Moisture management Combining with other performance features to increase appeal COTTON INCORPORATED FR Technical Bulletins TRI 4002: Precondensate /Ammonia Process TRI 4003: FR Cotton Fabrics: Frequently Asked Questions TRI 4004: Flammability Testing TRI 4006: Color Systems for FR Fabrics 12