EP1540070A2 - Fibres organiques et produits textiles - Google Patents

Fibres organiques et produits textiles

Info

Publication number
EP1540070A2
EP1540070A2 EP03793284A EP03793284A EP1540070A2 EP 1540070 A2 EP1540070 A2 EP 1540070A2 EP 03793284 A EP03793284 A EP 03793284A EP 03793284 A EP03793284 A EP 03793284A EP 1540070 A2 EP1540070 A2 EP 1540070A2
Authority
EP
European Patent Office
Prior art keywords
fiber
fibers
thin film
combinations
emulsion
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP03793284A
Other languages
German (de)
English (en)
Inventor
Satoko Iwato
Hideo Nakamura
Mureo Kaku
Kazuhiko Kosuge
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Du Pont Toray Co Ltd
EIDP Inc
Original Assignee
Du Pont Toray Co Ltd
EI Du Pont de Nemours and Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2002241122A external-priority patent/JP2004076231A/ja
Application filed by Du Pont Toray Co Ltd, EI Du Pont de Nemours and Co filed Critical Du Pont Toray Co Ltd
Publication of EP1540070A2 publication Critical patent/EP1540070A2/fr
Withdrawn legal-status Critical Current

Links

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
    • 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
    • D06M13/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms
    • D06M13/51—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond
    • D06M13/513—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond with at least one carbon-silicon bond
    • 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
    • D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
    • D06M15/657—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain containing fluorine
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D171/02—Polyalkylene oxides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C09D183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
    • 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
    • D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
    • 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
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/34—Polyamides
    • D06M2101/36—Aromatic polyamides
    • 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
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/01—Stain or soil resistance
    • 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
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/10—Repellency against liquids
    • D06M2200/11—Oleophobic properties
    • 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
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/10—Repellency against liquids
    • D06M2200/12—Hydrophobic properties
    • 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
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/30—Flame or heat resistance, fire retardancy properties

Definitions

  • the present invention relates to an organic fiber having water repellence and oil repellence, to a textile product comprising the fiber, and to a method for producing the fiber and textile product.
  • the fiber or textile product is immersed in an emulsion or solution of a silicone polymer, fluorocarbon polymer, polyurethane polymer, vinyl polymer or a copolymer of any of the above, or a spray containing ingredients such as the above polymers is applied to the fiber or the textile product, following which drying is carried out so as to form a film on the surface of the fibers.
  • a silicone polymer fluorocarbon polymer, polyurethane polymer, vinyl polymer or a copolymer of any of the above
  • a spray containing ingredients such as the above polymers is applied to the fiber or the textile product, following which drying is carried out so as to form a film on the surface of the fibers.
  • Another method in current use involves polymerizing monomers or oligomers as precursors to these polymers on the fiber surface so as to form a film.
  • Such textile products can be woven products, knit products or nonwoven fabric.
  • Preferred applications include firefighting apparel, gloves and woven fabric for protective clothing.
  • a composition which comprises an organic fiber comprising a thin film which comprises a fluorocarbon silane.
  • a textile product comprising an organic fiber comprising a thin film which comprises a fluorocarbon silane.
  • a process that can be used for manufacturing a high- strength, heat-resistant fiber or textile product which comprises contacting a fiber or textile product with an aqueous emulsion comprising, or produced by combining, (1) a fluorocarbon silane or its hydrolyzate and (2) optionally a surfactant, an alkoxysilane compound, catalyst, or combinations or two or more thereof to produce a fiber or textile-containing mixture and optionally heating the mixture.
  • any organic fibers of high-strength, heat-resistance can be used.
  • the fiber can be coated with a thin film comprising a fluorocarbon silane or a thin film comprising a copolycondensate of a fluorocarbon silane with an alkoxysilane.
  • a suitable fiber has a strength of about 10 g/D to about 50 g/D, preferably 15 g/D to 50g/D, and a pyrolysis temperature of at least about 300°C, and preferably at least 350°C.
  • preferred high-strength, heat-resistant organic fibers include wholly aromatic polyamide fibers, wholly aromatic polyester fibers and heterocyclic aromatic fibers, and mixture of two or more fibers.
  • Suitable wholly aromatic polyamide fibers may be any known aromatic polyamide fibers.
  • Wholly aromatic polyamide fibers are also known as aramid fibers, which are broadly categorized as para-aramid fibers or meta-aramid fibers. Such aramid fibers may be produced and used by any methods known to one skilled in the art.
  • Para-aramid fibers may be any known para-aramid fiber.
  • Illustrative examples of such para-aramid fibers include, but are not limited to, commercial products such as poly(p-phenylene terephthalamide) fibers (produced by E. I. du Pont de Nemours and Company and Du Pont-Toray Co., Ltd.
  • Meta-aramid fibers may be any known meta-aramid fibers. Illustrative examples of such meta-aramid fibers include, but are not limited to, commercial products such as poly(m-phenylene terephthalamide) fibers (produced by E. I. du Pont de Nemours and Company under the trademark NOMEX ® ).
  • Suitable wholly aromatic polyester fibers may be any known aromatic polyester fibers.
  • Illustrative examples of such wholly aromatic polyester fibers include, but are not limited to, self-condensed polymers of p-hydroxybenzoic acid, polyesters comprising repeat units derived from terephthalic acid and a glycol, polyesters comprising repeat units derived from terephthalic acid and hydroquinone, polyester fibers comprising repeat units derived from p- hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid, or combinations of two or more thereof.
  • Such wholly aromatic polyester fibers may be produced and used by any methods known to one skilled in the art.
  • suitable wholly aromatic polyester fibers include such commercial products made by Kuraray Co., Ltd. under the trade name designation NECTRAN.
  • Heterocyclic aromatic fibers used in the invention may be any fibers known to one skilled in the art.
  • Illustrative examples of such heterocyclic aromatic fibers include, but are not limited to, poly p-phenylene benzobisthiazole) fibers, poly(p-phenylene benzobisoxazole) fibers (PBO), polybenzimidazole fibers, or combinations of two or more thereof.
  • Such heterocyclic aromatic fibers may be produced and used by any methods known to one skilled in the art.
  • heterocyclic aromatic fibers include commercial PBO fibers such as those made by Toyobo Co., Ltd. under the trade name designation ZYLON.
  • the preferred high-strength, heat-resistant organic fibers are aramid fibers made of a para-type homopolymer which are known to one skilled in the art as KENLAR ® or TWARO ⁇ (made by Teijin Ltd.) for their stability to dimensional change at elevated temperatures such as, for example, peeling of the thin film, for their heat resistance, and for their relatively low cost and good versatility.
  • the thin film has a thickness of about 1,000 nm or lower and a strength of 10 to 50 g/D.
  • the textile products comprise fibers comprising, or coated thereon with a thin film, which comprises or is produced from a fluorocarbon silane or its hydrolyzate, or a copolycondensate of a fluorocarbon silane with an alkoxysilane.
  • suitable textile products include, but are not limited to, products obtained by the processing of fibers, such as yarn, batting, woven goods, knit goods, a broad range of nonwoven fabrics, including felt and paper, as well as roving and cord, and combinations of two or more thereof.
  • the textile products can also include finished goods which are products obtained by these products alone, in combinations thereof, or in combination with other materials, such as resins or metals.
  • the textile products are preferably woven goods, knit goods or nonwoven fabrics. Fire-fighting apparel, gloves and woven fabric for protective clothing are especially preferred.
  • the high-strength, heat-resistant organic fibers or textile products comprising, or coated thereon with (that is, having a thin film formed on the surface), a thin film of a copolycondensate of a fluorocarbon silane with an alkoxysilane can be produced by treating the organic fibers or the textile products with an aqueous emulsion comprising (1) a fluorocarbon silane hydrolyzate or hydrolyzate thereof, (2) water and optionally (3) a surfactant, an alkoxysilane compound, and a catalyst to produce a fiber- or textile-containing mixture followed by optionally heating the mixture.
  • the aqueous emulsion can be produced using a fluorocarbon silane and, optionally, a surfactant, a catalyst and an alkoxysilane. It is preferably carried out by dispersing a fluorocarbon silane and an amount of surfactant corresponding to 0.01 to 10, preferably 0.1 to 1 part by weight per part by weight of the overall fluorocarbon silane in water such as to make the fluorocarbon silane content, based on the total weight of the emulsion, from about 0.1 to about 20 wt %, and preferably from 1 to 10 wt %.
  • An acid or alkali catalyst can be added in a catalytic amount (i.e., about 1 to about 1000 ppm final concentration of the emulsion) to the resulting aqueous dispersion, following which an alkoxysilane can be added in an amount corresponding to a mole fraction of 0.1 to 10, and preferably 0.4 to 0.6, based on the fluorocarbon silane to produce a mixture.
  • a catalytic amount i.e., about 1 to about 1000 ppm final concentration of the emulsion
  • an alkoxysilane can be added in an amount corresponding to a mole fraction of 0.1 to 10, and preferably 0.4 to 0.6, based on the fluorocarbon silane to produce a mixture.
  • the mixture of the ingredients can be gently mixed.
  • the fluorocarbon silane is preferably at least one type of hydrolyzable fluorocarbon silane having the formula R f -(CH 2 ) p -Si ⁇ -(O-CH 2 CH 2 ) deliberately-OR 1 ⁇ 3 .
  • R f is a C 3 . 18 perfluoroalkyl group or a mixture of such groups; the plurality of R 1 groups can be the same or different and are independently one or more C ⁇ alkyl groups; p is 2 to 4; and n is 2 to 10.
  • R f is preferably a mixture of perfluoroalkyl groups having an average of 8 to 12 carbon atoms; R 1 represents methyl groups; p is 2; and n is from 2 to 4, preferably 2 to 3. More specifically, when n is 2, a perfluoroalkylethyltris(2-(2-methoxyethoxy)ethoxy)silane is especially preferred.
  • n 3
  • a (2-(2-(2- methoxyethoxy)ethoxy)ethoxy)silane is especially preferred.
  • This type of fluorocarbon silane can be produced by any methods known to one skilled in the art. Two or more fluorocarbon silanes can also be used.
  • Exemplary alkoxysilanes include organosilicon compounds having at least two alkoxy groups on the molecule, and partial condensation products thereof.
  • Illustrative examples include (1) silicate of the formula Si(R) wherein R is one or more group selected from among OCH 3 , OCH 2 CH 3 and (OCH 2 CH 2 ) m OCH 3 (m being from 1 to 10); and (2) organoalkoxysilanes of the formula R n Si(OR ) .
  • R is one or more Cno alkyls; the plurality of R groups are the same or different and independently one or more C ⁇ alkyls; and q is from 1 to 3).
  • the alkyl group R 2 may be substituted with suitable substituents, such as amino groups, epoxy groups, vinyl groups, methacryloxy groups, thiol groups, urea groups or mercapto groups.
  • suitable alkoxysilanes include, but are not limited to, dimethyldimethoxysilane, methyltrimethoxysilane, 3- aminopropyltriethoxy silane, N-(2-aminoethyl)-3- aminopropylmethyldiethoxysilane and 3-glycidoxypropyltrimethoxysilane, and well as mixtures and partial condensation products of any of the above.
  • Any acid or an alkalilinic substance may be used as the catalyst.
  • suitable acids include, but are not limited to, phosphoric acid, boric acid, hydrochloric acid, sulfuric acid, nitric acid, acetic acid, formic acid, and mixtures of two or more thereof.
  • suitable alkalis include, but are not limited to, ammonia, pyridine, sodium hydroxide, potassium hydroxide, and mixtures of two more thereof.
  • the use of hydrochloric acid or phosphoric acid as the catalyst in carrying out the invention is especially preferred.
  • the surfactant generally is a surfactant having an HLB value sufficiently high to inhibit self-condensation of the fluorocarbon silane hydrolysis product.
  • HLB refers to the HLB system published by ICI America's, Inc., Wilmington, Delaware; Adamson, A.W., "Physical Chemistry of Surfaces", 4 th edition, John Wily & Sons, New York, 1982).
  • the surfactant can be anionic, cationic, nonionic, amphoteric, or combinations thereof.
  • the preferred surfactants are those with HLB values greater than 5, preferably greater than 12, and more preferably greater than 16.
  • nonionic surfactants include, but are not limited to, R f 1 -CH 2 CH2-O-(CH 2 CH2 ⁇ ) ⁇ -H, C 9 H 19 -C 6 H 4 -O-(CH 2 CH 2 O) 50 -H, other nonionic surfactants, and combinations thereof.
  • cationic surfactants include, but are not limited to R f 1 - CH 2 CH 2 SCH 2 CH(OH)CH 2 N(CH 3 ) 3 + Cl " , other cationic surfactants, and combinations thereof.
  • anionic surfactants include, but are not limited to, C 12 H 25 (OCH 2 CH 2 ) 4 OSO 3 " NH 4 + , C 12 H 27 -C 6 H 4 -SO 3 " Na + , other anionic surfactants, and combinations or two or more thereof.
  • R f is aperfluoroalkyl group generally having about 3-18 carbon atoms.
  • the preferred surfactants are nonionic surfactants having polyethylene glycol in the molecular chain.
  • the use of a nonionic surfactant, such as R f 1 -CH 2 CH 2 -O- (CH 2 CH 2 O) ⁇ -H wherein R f 1 is a C 3 . 18 perfluoroalkyl group is preferred.
  • additives including inorganic and organic fillers, antioxidants, heat stabilizers, ultraviolet absorbers, lubricants, waxes, colorants and crystallization promoters, either independently or combinations of a plurality thereof may be used.
  • the emulsion can be used as is or, if necessary, after dilution or other modification to the desired concentration, by application to the fibers or textile products according to the invention using any means known to one skilled in the art and most suitable to the processing operation carried out in each case such as, for example, impregnation, dipping, coating, or spraying.
  • the emulsion-treated fibers or textile products can be heat-treated at about 150 to about 500, preferably 200 to 450°C, and more preferably at least 250 to 400°C for about 1 minute to about 10 hours, thereby bringing to completion not only hydrolysis of the fluorocarbon silane or hydrolysis of the fluorocarbon silane and hydrolysis of the alkoxysilane, but also copolycondensation of the hydrolyzate.
  • a thin film containing a copolycondensate of a fluorocarbon silane, or its hydrolyzate, and an alkoxysilane can be formed.
  • the heat treatment temperature and time period are preferably set to the optimal values after taking into consideration such factors as the heat resistance of the target fibers or textile product and the cost effectiveness of treatment.
  • the preferred heat treatment temperature or time differs according to the fibers and the textile product.
  • the ratio of the weight of the copolycondensate coated onto the surface of the high- strength fibers, relative to the weight of the high-strength, heat-resistant organic fibers, is expressed in the dry state following heat treatment and is referred to herein as the "thin film-forming agent picku". This value is generally about 0.1 to 10%. Water generally makes up the rest of the emulsion.
  • extraneous substances such as finish may be removed from the surface of the fibers by a scouring or solvent scouring operation.
  • an operation such as a washing operation to remove residual catalyst and surfactant may be carried out by any means known to one skilled in the art such as water or solvent extraction.
  • the various above-described additives may be suitably added.
  • the invention can also be treated with the above-described copolycondensate textile products such as woven fabric composed of the above high-strength heat-resistant organic fibers, protective clothing made of such woven fabric, or protective gloves manufactured directly from the fibers, thereby forming a thin film on the surface of the fibers making up these textile products.
  • the fluorocarbon silane used was a mixture of perfluoroalkyl compounds having the formula R f -(CH 2 ) 2 -Si ⁇ -(O-CH 2 CH 2 ) 2 -OCH 3 ⁇ 3 wherein R f is F(CF 2 ) k .
  • the compound in which the letter k was 6 accounted for 1 to 2 wt % of the mixture, the compound in which k was 8 accounted for 62 to 64 wt %, the compound in which k was 10 accounted for 23 to 30 wt %, and compounds in which k was 12 to 18 accounted for 2 to 6 wt % of the mixture.
  • the surfactant was a nonionic surfactant of the formula R f '-CH 2 CH 2 -O- (CH 2 CH O) ⁇ -H wherein R f was a perfluoroalkyl group of 3 to 18 carbons.
  • the organoalkoxysilane was methyltrimethoxysilane (CH 3 )Si(OCH 3 ) 3 .
  • Example 1 Preparation of a Fluorocarbon Silane/ Alkoxysilane Emulsion.
  • One hundred parts by weight of a fluorocarbon silane and 30 parts by weight of surfactant were dissolved in water.
  • To the resulting aqueous emulsion was slowly added, under stirring by a conventional stirring technique, 2.5 wt % of the fluorocarbon silane, based on the overall weight of the emulsion, thereby suppressing self-condensation of the fluorocarbon silane and maintaining it in a hydrolyzed state.
  • phosphoric acid was added and addition was brought to completion when the pH became 3.
  • methyltrimethoxysilane (CH 3 )Si(OCH 3 ) 3 was added such as to make the molar fraction of the organoalkoxysilane with respect to the fluorocarbon silane 0.45 and stirring was carried out for 4 hours, yielding a fluorocarbon silane/alkoxysilane emulsion.
  • the gloves were immersed in the prepared fluorocarbon silane/alkoxysilane emulsion, then lightly wrung by hand so as to adjust the pickup of emulsion non-volatiles to 1%, based on the weight of the glove. Assuming that the fiber cross-section was circular, the film thickness, as computed from the thin film-forming agent pickup, was 22 nm.
  • the gloves were held in a 250°C oven for 30 minutes to effect heat treatment and curing. The gloves were then taken out of the oven and cooled to room temperature, after which they were washed in tepid water and dried.
  • the treated gloves showed no change in hand or appearance compared with prior to treatment. However, when the treated gloves were sprayed with water, the drops of water scattered. The treated gloves demonstrated a striking difference in water repellency compared with untreated gloves.
  • Example 2 Preparation of Woven Product.
  • KENLAR 29 ® yarn (made by Du Pont-Toray Co., Ltd., Tokyo) having a density per filament of 1.67 decitex and composed of 2,000 filaments was used to manufacture plain- weave fabric having a warp density of 17.5 ends/25 mm, a weft density of 16.8 picks/25 mm, and a basis weight of 444 g/m .
  • a 5x5 cm square of the resulting woven fabric was immersed for 5 minutes in the prepared fluorocarbon silane/alkoxysilane emulsion, following which it was drawn out and wrung free of excess fluid so as to adjust the pickup of emulsion non-volatiles, based on the weight of the fabric square, to 1%.
  • This woven fabric was held in a 250°C oven for 30 minutes to effect heat treatment and curing.
  • the film thus obtained had a thickness of about 22 nm.
  • Example 2 A comparison of the results obtained for woven fabric in Example 2 with the results obtained for the woven fabric in the comparative example showed that water and hexadecane penetrated the untreated fabric, making it impossible to measure the contact angle.
  • Example 2 in which the test was carried out on a fabric treated with fluorocarbon silane/alkoxysilane emulsion the fabric exhibited high water and oil repellencies.
  • the treated woven fabric was placed in a 250°C oven and the contact angle was measured after the period of time shown in Table 2 had elapsed. The test results are shown in Table 2.
  • Example 2 a high water repellency was maintained even after 24 hours at 250°C.
  • the present invention provides high-strength, heat-resistant organic fibers endowed with excellent heat resistance and durability and also an excellent stainproofing performance with no loss of hand.
  • textile products such as firefighting apparel or gloves which, in addition to having excellent cut resistance, flame resistance and dimensional stability at high temperatures, are coated on the fiber surfaces with a water and oil-repelling thin film.
  • Such textile products are resistant to staining and easy to clean.
  • the thin film has a very small thickness, textile products can be obtained in which the characteristics inherent to the constituent fibers, such as their hand, are essentially retained with little or no loss.
  • the invention provides a method capable of manufacturing the above-described fibers and textile products, which method readily imparts a high stainproofing performance due to such water and oil repellency without any loss in the characteristics inherent to high-strength, heat-resistant organic fibers, such as the hand.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Textile Engineering (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Inorganic Chemistry (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Silicon Polymers (AREA)

Abstract

L'invention concerne une fibre organique et un produit textile thermorésistants haute ténacité qui comprennent ou sont enrobés tous deux d'une émulsion aqueuse. La couche d'enrobage comprend un silane fluorocarburé ou une émulsion, ou est préparé à partir de ces derniers. L'émulsion comprend un (1) silane de fluorocarbone ou un hydrolysat de celui- ci, (2) de l'eau, et (3) éventuellement un tensioactif, un composé alcoxysilane, un catalyseur ou des combinaison d'au moins deux de ceux-ci, ou est préparée à partir de ces composants. Ledit silane fluorocarboné présente la formule Rf-(CH2)p-Si{-(O-CH2CH2)n-OR1}3, dans laquelle Rf représente un groupe perfluoroalkyle C3-18 ou des combinaisons d'au moins deux de ceux-ci, et chaque R1 représente séparément un ou plusieurs groupes alkyle C1-3, p représente un nombre de 2 à 4; et n un nombre de 2 à 10. L'invention concerne également un procédé permettant de produire cette émulsion, cette fibre et ce produit textile.
EP03793284A 2002-08-21 2003-08-21 Fibres organiques et produits textiles Withdrawn EP1540070A2 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
JP2002241122 2002-08-21
JP2002241122A JP2004076231A (ja) 2002-08-21 2002-08-21 撥水撥油防汚性に優れた高強力耐熱有機繊維と繊維製品及びそれらの製造方法
US644237 2003-08-20
US10/644,237 US20040034941A1 (en) 2002-08-21 2003-08-20 Organic fibers and textile products
PCT/US2003/026329 WO2004018758A2 (fr) 2002-08-21 2003-08-21 Fibres organiques et produits textiles

Publications (1)

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AU2003265594A1 (en) 2004-03-11
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AU2003265594A8 (en) 2004-03-11
KR20060031792A (ko) 2006-04-13
CA2496263A1 (fr) 2004-03-04

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