EP0228224B1 - Aromatische Polyamidfasern und Verfahren zur Herstellung derselben - Google Patents

Aromatische Polyamidfasern und Verfahren zur Herstellung derselben Download PDF

Info

Publication number
EP0228224B1
EP0228224B1 EP86309756A EP86309756A EP0228224B1 EP 0228224 B1 EP0228224 B1 EP 0228224B1 EP 86309756 A EP86309756 A EP 86309756A EP 86309756 A EP86309756 A EP 86309756A EP 0228224 B1 EP0228224 B1 EP 0228224B1
Authority
EP
European Patent Office
Prior art keywords
fibers
water
steam
dye
tow
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.)
Expired - Lifetime
Application number
EP86309756A
Other languages
English (en)
French (fr)
Other versions
EP0228224A3 (en
EP0228224A2 (de
Inventor
Hamid Moayed Ghorashi
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.)
EIDP Inc
Original Assignee
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 US06/910,941 external-priority patent/US4755335A/en
Application filed by EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Publication of EP0228224A2 publication Critical patent/EP0228224A2/de
Publication of EP0228224A3 publication Critical patent/EP0228224A3/en
Application granted granted Critical
Publication of EP0228224B1 publication Critical patent/EP0228224B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/08—Melt spinning methods
    • D01D5/096—Humidity control, or oiling, of filaments, threads or the like, leaving the spinnerettes
    • 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
    • D06M13/322—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 nitrogen
    • D06M13/46—Compounds containing quaternary nitrogen atoms
    • D06M13/463—Compounds containing quaternary nitrogen atoms derived from monoamines
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D10/00—Physical treatment of artificial filaments or the like during manufacture, i.e. during a continuous production process before the filaments have been collected
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
    • D01F11/04—Chemical after-treatment of artificial filaments or the like during manufacture of synthetic polymers
    • D01F11/08—Chemical after-treatment of artificial filaments or the like during manufacture of synthetic polymers of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/60—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyamides
    • D01F6/605—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyamides from 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
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/01—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with hydrogen, water or heavy water; with hydrides of metals or complexes thereof; with boranes, diboranes, silanes, disilanes, phosphines, diphosphines, stibines, distibines, arsines, or diarsines or complexes thereof
    • D06M11/05—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with hydrogen, water or heavy water; with hydrides of metals or complexes thereof; with boranes, diboranes, silanes, disilanes, phosphines, diphosphines, stibines, distibines, arsines, or diarsines or complexes thereof with water, e.g. steam; with heavy water
    • 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
    • D06M2200/45—Shrinking resistance, anti-felting properties

Definitions

  • the field of art to which this invention pertains is aromatic polyamide fibers and, more particularly, it is directed to processes for making such fibers.
  • such invention is a process for dyeing a fiber structure of poly(meta-phenylene isophthalamide) fibers with a water-soluble dye by heating the amorphous, water-swollen fibers, as spun and prior to drying, with steam at a temperature from 110°C to 140°C, and preferably at 120°C, for a time sufficient to diffuse substantially all of the dye into the minute pores in the fibers, throughout the fiber structure.
  • An organic water-insoluble material such as an ultraviolet light screener, may also be mixed with the water-soluble dye and padded onto the water-swollen fibers prior to heating. While the dye is effectively diffused into the fiber structure at temperatures between 110°C and 140°C, such structure must also be heated with steam at a sublimation temperature below the glass transition temperature of the fibers in order to sublime the screener into the pores of the fibers. The fibers are then, preferably, further heated with steam at 165°C for a time sufficient to collapse the pores in the fibers and lock the dye therein. At this temperature the fibers also will crystallize and the fiber structure is thereby stabilized against progressive laundry shrinkage.
  • an ultraviolet light screener may also be mixed with the water-soluble dye and padded onto the water-swollen fibers prior to heating. While the dye is effectively diffused into the fiber structure at temperatures between 110°C and 140°C, such structure must also be heated with steam at a sublimation temperature below the glass transition temperature of the fibers in order to sublime the screener into the
  • Various water-insoluble materials including disperse dyes, may be driven into the fibers in this manner (e.g., by contacting the water-swollen, never-dried fibers with a dispersion containing the dye and heating with steam to 165°C).
  • this sublimation step follows the diffusion step previously described.
  • Aromatic polyamide fibers are well known to the art. They have high tensile strength, are flame and heat resistant, possess good flex life, and have very high melting points, etc. which make them particularly suited to be formed into fabrics usable as protective clothing, and for many other uses.
  • aromatic polyamide fibers possess many desired properties as manufactured they also require, for given uses, that various steps be taken to improve a property or properties of the fibers to meet a specific end use.
  • various additives such as dyes, ultraviolet light screeners, flame retardants, antistatic agents or water repellents, may be incorporated into the fibers during basic manufacture or in subsequent processing steps to improve their performance levels.
  • This invention is specifically directed to aromatic polyamide fibers 'of a poly(meta-phenylene isophthalamide) polymer, hereinafter referred to as "MPD-I fibers".
  • MPD-I fibers Such fibers, which are described in greater detail in U.S. Patent 3,287,324 to Sweeny, for example, possess many useful properties. It is well known to the art, however, that these fibers are very difficult to dye.
  • This invention solves these and other problems found in the prior art by surprisingly finding that by heating as-spun, never-dried, water-swollen MPD-I fibers with steam, heated within certain temperature ranges, it is possible effectively to dye the fibers. Specifically, it has been found that such fibers may be dyed, using a water-soluble dye, by heating the fibers with steam heated at a temperature from 110°C to 140°C for a time sufficient to diffuse the dye into the pores of the fibers.
  • various organic water-insoluble materials such as ultraviolet light screeners, may be mixed with the water-soluble dye and driven, by a sublimation heating step, into the fiber pores. Again, heating is accomplished with steam, while the pores remain open and sublimation temperatures from 110°C to 150°C are required to sublime the water-insoluble materials into the open pores.
  • this invention provides improved processes for making aromatic polyamide fibers, using steam in all cases as a key step, to dye a water-swollen fiber structure of poly(meta-phenylene isophthalamide) fibers with a water-soluble dye, before they are dried, or to add an organic water-insoluble material to the fibers, either mixed with the dye or alone, and to lock the dye and/or other impregnant into the pores of the fibers.
  • This is accomplished by using critical steam temperatures (e.g., 110°C to 140°C) to diffuse the dye into the fiber pores and up to 165°C to sublime the water-insoluble material into such pores. At this latter temperature the dye is also locked into the fibers, while stabilizing such fibers against progressive laundry shrinkage.
  • this invention is a process for making synthetic fibers including the steps of:
  • the water-swollen fibers are heated with steam at a temperature of 120°C for a time sufficient to diffuse substantially all of the water-soluble material into the pores of the fibers throughout such fiber structure.
  • the water-soluble material diffused into the fibers preferably is a dye. It may also be a surfactant, for example, in which case the fiber structure is dried after diffusion. Other water-soluble organic or inorganic salts may be used. Water-soluble nonionic organic compounds or water-soluble resins may also be diffused into the fibers.
  • the water-swollen, dye-containing fibers are then further heated with steam at a temperature above the glass transition temperature of the fibers for a time sufficient to collapse the pores and irreversibly lock the dye within the fibers and to crystallize such fibers and stabilize them against progressive laundry shrinkage.
  • the fibers may be heated with steam at a temperature from 150°C to 165°C and preferably are heated with steam at a temperature of 165°C.
  • this invention is a process for making synthetic fibers including the following steps:
  • the water-swollen fibers are heated with steam at a sublimation temperature from 110°C to 150°C.
  • the water-insoluble material may be an ultraviolet light screener or a disperse dye, for example.
  • the screener or disperse dye After the screener or disperse dye has been sublimed into the open pores of the water-swollen fibers, such fibers preferably are heated with steam at a temperature of 165°C to close the pores and lock the dye therein.
  • This invention offers improvements over the prior art by providing processes for diffusing and subliming water-soluble and water-insoluble materials, such as dyes, into never-dried, water-swollen aromatic polyamide fibers, using steam heated within critical temperature ranges. These fibers are typically dyed after drying.
  • This invention gives to the art a novel process for dyeing, or incorporating both water-soluble or water-insoluble materials into these fibers, prior to drying, using only pressurized steam as the transfer means. In so doing, it provides the art an easy-to-use, effective method of accomplishing this objective.
  • This invention is an improved process for making aromatic polyamide fibers.
  • a water-soluble material and, if desired, a water-insoluble material are diffused or sublimed into a fiber structure of MPD-I amorphous synthetic fibers to improve their properties.
  • the fibers are water-swollen, with open pores. Steam, at critical temperatures, is used to perfect the process.
  • the fibers of this invention are prepared from aromatic polyamide polymers such as are disclosed in U.S. patent 3,063,966 to Kwolek, Morgan and Sorenson; 3,094,511 to Hill, Kwolek and Sweeny; and 3,287,324 to Sweeny, for example. These patents, and their teachings, are incorporated by reference into this application.
  • aromatic polyamide means a synthetic polymeric material of sufficiently high molecular weight to be fiber-forming, and characterized predominantly by the recurring structural unit wherein each R 1 independently is hydrogen or lower alkyl and wherein Ar 1 and Ar 2 may be the same or different and may be an unsubstituted divalent aromatic radical or a substituted divalent aromatic radical, the chain-extending bonds of these divalent aromatic radicals being oriented predominantly meta to one another and the substituents attached to any aromatic nucleus being one or more or a mixture of lower alkyl, lower alkoxy, halogen, nitro, lower carbalkoxy, or other group which do not form a polyamide during polymerization.
  • These polymers may be prepared by following the teachings of U.S. Patents 3,094,511; 3,287,324 or 3,063,966 mentioned above.
  • a preferred aromatic polyamide is poly(metaphenylene isophthalamide).
  • aromatic polyamides which have been prepared by procedures shown in the above-mentioned patents are combined with various solvents such as dimethylacetamide to form a spinning solution as shown, for example, in U.S. Patent 3,063,966 and the fibers or filaments are formed by extruding the spinning solution through orifices in a spinneret.
  • Such fibers may be dry-spun or wet-spun to form a-water-swollen fiber structure. In either case, the fibers as spun are substantially amorphous.
  • “Dry-spinning” refers to a process in which the spinning solution is extruded in the form of thin streams into a heated cell wherein sufficient solvent is caused to evaporate so that the streams are converted into individual filaments which are "dry” enough even though .still containing appreciable quantities of residual solvent that they are self.-supporting.
  • “Wet-spinning” involves a process wherein the polymer spinning solution exits in the form of thin streams which are generated within, or are conducted into, a liquid coagulating bath which causes the polymer to precipitate in the form of self-supporting filaments which may be conducted out of the coagulating bath, and commonly also through subsequent processing steps. Depending on the composition of the coagulating bath, the temperature and time of contact of the filaments with the bath, the filaments may still retain an appreciable quantity of the original polymer solvent at the time they exit the bath.
  • the fibers whether dry-spun or wet-spun contain a substantial amount of solvent after having been solidified in a dry-spinning evaporation cell or coagulated in a wet-spinning precipitation bath.
  • solvent such fibers are brought into contact with an aqueous extraction bath, as is known in the art.
  • the fibers become "water-swollen" with a water content of 35% or more.
  • these water swollen fibers which have not been dried, are contacted with an aqueous solution containing a water-soluble material and heated with steam at a temperature from 110°C to 140°C for a time sufficient to diffuse substantially all of the water-soluble material into the pores of the fibers throughout such fiber structure.
  • the material diffused into the fibers preferably is a dye. It may also be a surfactant.
  • the water-swollen, dye-containing fibers are then further heated with steam at a temperature above the glass transition temperature of the fibers for a time sufficient to collapse the pores and irreversibly lock the dye within the fibers and to crystallize such fibers and stabilize them against progressive laundry shrinkage.
  • Temperatures in the range from 150°C to 165°C will accomplish these objectives.
  • amorphous MPD-I fibers of the type described are contacted with an aqueous mixture containing both a water-soluble material, such as a dye, and an organic water-insoluble material which sublimes in steam at a temperature below the glass transition temperature of the fibers.
  • the water-swollen fibers are then heated with steam at a temperature from 110°C to 140°C for a time sufficient to diffuse substantially all of the water-soluble dye into the pores of such fibers and at a sublimation temperature below the glass transition temperature of the fibers to sublime the water-insoluble material into the open pores of such fibers.
  • organic water-insoluble material which sublimes in steam refers to a member of the class of water-insoluble organic materials which are activated by steam to migrate from the surface of the fibers into the pores of the fibers, and the term “sublimation temperature” refers to the temperature at which the material is so activated to migrate.
  • the fibers may be further heated with steam at a temperature above the glass transition temperature of the fibers for a time sufficient to collapse the pores and irreversibly lock the material within the fibers and to stabilize the fibers against progressive laundry shrinkage.
  • the glass transition temperature (Tg) of a polymeric fiber is a characteristic of the amorphous phase of the polymer of which the fiber is made.
  • the glass transition temperature which is a relatively narrow temperature range rather than a sharply defined temperature, the fiber tends to remain in the same structural configuration in which it was originally formed. Above the glass transition temperature, the fiber readily undergoes such changes in structure as relaxation of stresses, collapse of pores within the fiber, and crystallization of the polymer of which the fiber is made.
  • the glass transition temperature is 150°C.
  • fiber includes both staple fibers and continuous filaments.
  • the continuous filaments may be in the form of a tow containing a large number of filaments or in the form of a yarn.
  • a fiber structure of never-dried, water-swollen fibers, as spun, in large bundles called tow, as indicated by the reference numeral 1 is supplied from a supply source 2 and passed over guide rolls 3 to nip rolls 4 and 4'.
  • An aqueous bath 5 of constant level is maintained at the entrance to the nip rolls.
  • the tow 1 of water-swollen fibers is brought into contact with the bath 5 which contains the material (e.g., a water-soluble dye, or surfactant, or ultraviolet light screener, for example) to be diffused or sublimed into the fibrous tow.
  • the pick-up of material on the never-dried tow may be adjusted by suitably controlling the speed of the tow and the pressure applied between the nip rolls.
  • the tow 1 coated with the desired amount of material is deposited on a belt 6, moving at a speed slower than the speed of the tow passing between the nip rolls 4 and 4'.
  • the tow is then withdrawn from the moving belt 6, moved over a guide roll 7, and passed into a steam chamber 8, which is suitably an elongated cylindrical tube having two or more heating zones 9 and 10 within which steam heated at different temperatures and under appropriate pressure can be supplied.
  • the entrance and exit of the steam chamber 8 are suitably sealed to prevent escape of steam, e.g., by supplying the tow to the steam chamber in folds which effectively prevents escape of the steam from the chamber; likewise, passage of the steam at different temperatures and pressures between zones 9 and 10 is prevented by suitable means, e.g., by passing the tow through the chamber in folds.
  • the tow is heated in these zones 9 and 10 at the required critical temperatures to diffuse the water-soluble material and to sublime the insoluble material into the fibers, after which such fibers may be further heated to stabilize the fiber structure against progressive laundry shrinkage.
  • the processed tow is then withdrawn from the chamber 8 by rolls 11 and 11 or other suitable means and deposited in a container 12.
  • the selective steam treatment of the tow provides an MPD-I fiber having the properties sought in the treatment.
  • the wet filaments were gathered together to form a tow, a conventional antistatic finish was applied to the tow, and the tow was crimped in a stuffer box crimper at a temperature of 80°C in the presence of steam. The tow was then collected, still moist (containing an amount of water about equal to the weight of the dry tow), in a plastic-lined cardboard box.
  • the individual filaments had a linear density of about 1.55 decitex (dtex) (1.7 dpf).
  • the linear density of the never-dried filaments here and elsewhere herein is based on the weight of dry filaments.
  • Acid Black 58 dye (a water-soluble dye), 100 g/I of C. I. No. Acid Black 218 dye (a water-soluble dye), 8 g/I of cellulosic thickener, and 5 g/I of anionic surfactant, adjusted to a pH of 7 (adding acetic acid or caustic soda as needed until the desired pH was obtained).
  • the pick-up of the dye solution on the tow was 30 wt.%.
  • the tows were then packed into the rectangular shaped steam chamber and carried through the chamber by a chain moving at about 1 m/min, one tow on each side of the chain.
  • the filaments coated with the solution were exposed to steam at 120°C in a first zone in the steam chamber for two minutes and then to steam in a second zone at 165°C for 5 minutes.
  • the tows were washed with water. It was observed that very good exhaustion of the dye into the filaments was obtained, so that there was very little dye remaining on the surface of the filaments to be removed in the washing step.
  • the tows were washed, they were fed into a forced air dryer, wherein their moisture level was reduced to 7% moisture. Finish was applied to the tows at the exit of the dryer. The tows were dyed a deep shade of gray.
  • the shrinkage of the tow was measured and determined to be 2.4%.
  • the solution contained 394.4 g (6.26 wt.%), of C. I. No. Acid Black 58 dye (a water-soluble dye) and 5902 g (93.74 wt.%) water.
  • a sample of the tow with the dye padded on it was collected and immediately washed with water, without any steam treatment of the tow. It was observed that the tow was somewhat stained by the dye, but that the tow remained substantially undyed.
  • a tow of never-dried filaments was padded with a 6.26% aqueous solution of Acid Black 58 dye as in part (A) of this example, after which the tow was passed into the steam chamber and exposed to steam at 100°C for 2 minutes. The tow was then passed out of the steam chamber and was immediately washed with water. It was observed that the tow was tinted by the dye, but the shade of color was so light that the tow remained substantially undyed.
  • Part (B) of this example was repeated, except that the tow was exposed to steam at 110°C for 2 minutes.
  • the tow was passed out of the steam chamber and washed with water, it was observed that the tow was dyed to a light shade of gray.
  • 110°C steam in part (C) was compared with the effect of 100°C steam in path (B), it was concluded that the shade was beginning to build as the temperature of the steam was increased to 110°C.
  • Part (B) of this example was repeated, except that the tow was exposed to steam at 120°C for 2 minutes.
  • the tow was passed out of the steam chamber and washed with water, it was observed that the tow was dyed to a medium shade of gray. Also, there was very good exhaustion of the dye into the filaments of the tow, so that there was very little dye remaining on the surface of the filaments to be removed in the washing step.
  • Part (B) of this example was repeated, except that the tow was exposed to steam at 140°C for 2 minutes.
  • the tow was passed out of the steam chamber and washed with water, it was observed that the tow was dyed to a medium shade of gray, about the same as the shade observed in the tow prepared in part (D) above.
  • Part (B) of this example was repeated, except that the tow was exposed to steam at 165°C for 2 minutes.
  • the tow was passed out of the steam chamber and washed with water, it was observed that the tow was dyed only to a very light shade of gray.
  • the exhaustion of the dye into the filaments of the tow was poor, so that much of the dye remained on the surface of the filaments of the tow and was removed in the washing step.
  • Part (B) of this example was repeated, except that the tow was first exposed to steam at 120°C for 2 minutes and then passed directly from the 120°C steam zone into another zone in which it was exposed to steam at 165°C for 5 minutes.
  • the tow was passed out of the steam chamber and washed with water, it was observed that the tow was dyed to a medium shade of gray. Also, there was very good exhaustion of the dye into the filaments of the tow, so that there was very little dye remaining on the surface of the filaments to be removed in the washing step.
  • the shrinkage of filaments removed from the steam-treated tows of the preceding parts of this example was determined.
  • the shrinkage values were as follows:
  • determining the shrinkage of the filaments in a dry filamentary tow at least five filaments are removed from the tow and 50-cm (20-in) lengths are cut from each of the filaments removed. The exact length of each of the cut filaments is measured white it is held under very low tension, about 0.1 dtex. The cut filaments are then heated in an oven at 285°C in a condition free to relax, after which they are allowed to cool and their lengths are measured again while they are held under the same low tension under which their lengths were originally measured, The difference between their original lengths and their final lengths, divided by their original lengths, is multiplied by 100% to give the % shrinkage for each filament. The result is reported as the average of the % shrinkages of the filaments removed from the tow.
  • Part (D) of Example 2 was repeated, except that after the tow was exposed to 120°C steam for 2 minutes and washed, the.gray-colored tow was kept wet and was passed again through the nip rolls of the tow dyeing apparatus, wherein another aqueous dye solution was padded onto the tow.
  • the solution padded onto the tow contained 420 g (6.20 wt.%) of C. I. No. Basic Red 29 dye (a water-soluble dye) and 635 g (93.8 wt.%) of water.
  • the tow with the dye padded on was passed into the steam chamber and exposed to steam at 120°C for 2 minutes. The tow was then passed out of the tow dyeing apparatus and was immediately washed with water.
  • Part (G) of Example 2 was repeated, except that after the tow was exposed to 120°C steam and then to 165°C steam and washed, the gray-colored tow was kept wet and was passed again through the nip rolls of the tow dyeing apparatus, wherein another aqueous dye solution was padded onto the tow.
  • the solution was a 6.20 wt.% aqueous solution of C. I. Basic Red 29 dye, the same aqueous dye solution used in the paragraph just above.
  • the tow with the aqueous dye solution padded on was passed into the tow dyeing apparatus and exposed to steam at 120°C for 2 minutes. The tow was then passed out of the steam chamber and was immediately washed with water.
  • the tow with the anionic surfactant solution padded on was then passed to the steam chamber of the tow dyeing apparatus, wherein it was exposed to steam at 100°C for 2 minutes.
  • the steam-treated tow was then dried in an air oven at 90-110°C.
  • the dried tow contained about 16-17 wt.% of the surfactant. Inspection of the tow, both as to its tactility and as to its visual appearance, indicated that much of the surfactant remained on the surface of the filaments.
  • Part (A) of this example was repeated, except that the tow was exposed to steam at 120°C for 2 minutes. Inspection of the tow, both as to its tactility and as to its visual appearance, indicated that substantially all of the surfactant had been diffused into the filaments.
  • the aqueous bath contained in a pool above the nip rolls was maintained at 80-95°C and was prepared by adding 128.4 kg (283 lbs) of a 93 wt.% aqueous solution of isopropylammonium dodecylbenzenesulfonate salt (mixture of isomers), a water-soluble anionic surfactant, to 350 I of hot (90 ⁇ 95°C) water with only very mild agitation to minimize aeration of the solution.
  • the calculated concentration of the anionic surfactant was 25.4 wt.%.
  • the tows were passed through the nip rolls at a speed of 17 m/min and the nip roll pressure was maintained at 152 kPa (1.5 atmospheres), padding the anionic surfactant solution onto the tow so that the individual filaments in the tow were coated with the solution.
  • the tows were then packed into the rectangular shaped steam chamber and carried through the chamber by a chain moving at 1.3 m/min, one tow on each side of the chain.
  • the filaments coated with the anionic surfactant solution were exposed to steam at a temperature of 120°C (gauge pressure about one atmosphere) for an exposure time of approximately 6 minutes, the steam chamber being operated as a single zone.
  • the tows were exposed to cold water injected into the chamber to wash off any excess surfactant. After exiting the steam chamber the tows were continuously transported through a forced air dryer wherein the tows were dried at 100 ⁇ 130°C. Fiber samples taken from the tows were analyzed for surfactant content by high pressure liquid chromatography. It was determined that the MPD-I fibers contained approximately 11.5-12.8 wt.% of the anionic surfactant, based on the total weight of the surfactant-containing fiber.
  • a staple fiber blend was then prepared by cutting the dried MPD-I tow, together with a dry tow of poly(p-phenylene terephthalamide) (PPD-T) filaments to form staple fibers having a cut length of 5 cm (2 in), the proportion of MPD-I staple fibers to PPD-T staple fibers being 95 to 5 by weight.
  • the PPD-T filaments were commercially available filaments having a modulus of about 600,000 kg/cm 2 (about 9,000,000 psi) and a linear density of 1.65 dtex (1.5dpf), prepared as described in U.S. Patent 3,767,756 to Blades (available as Type 29 "Kevlar” aramid fiberfrom E : I. du Pont de Nemours and Company).
  • a two-ply, 591-dtex (20/2 cotton count) spun yarn was then prepared from the staple fiber blend on the cotton system in the conventional manner.
  • a 255 g/m 2 (7.5 ozlyd 2 ) plain weave fabric having a construction of 18 ends/cm (45 ends/cm) in the warp and 17 ends/cm (42 ends/in) in the filling was then woven in conventional manner from the spun yarn.
  • the plain weave fabric was wetted out by passing it through a 21°C (70°F) water bath in an open width washer. A rope of the wet fabric was then placed in a pressure back, which was charged with 38°C (100°F) water, a nonionic polyether surfactant, and formic acid to achieve a pH of 3.5. The temperature was raised to 99°C (210°F) at about 1.7°C/min (3°F/min), held at 99°C (200°F) for 20 minutes, and cooled to 80°C (180°F).
  • the temperature was raised to 70°C (160°F) at 1.7°C/min, and held at 70°C for 20 minutes.
  • the bath was drained and the fabric was rinsed with cold water.
  • the fabric was dried on a tenter frame at 121°C (250°F). The fabric was a deep black shade.
  • the tows were first fed between nip rolls at the entrance of a steam chamber at a rate of 12.5 m/min under a pressure of 203 kPa (two atmospheres), wherein an aqueous dye mixture was padded onto the tow so that the individual filaments in the tow were coated with the mixture.
  • the mixture contained dyes, cellulosic thickener, and an anionic surfactant in solution together with a dispersed water-insoluble ultraviolet (UV) light screener and had the following composition: 86.4 g/I of C. I. (Colour Index) No. Acid Green 60 dye (a water-soluble dye), 14.7 g/I of C. I. No. Acid Red 404 dye (a water-soluble dye), 7.4 g/I of C. I. No.
  • UV water-insoluble ultraviolet
  • Acid Orange 127 dye (a water-soluble dye), 6 g/I of a cellulosic thickener, 132 g/I of 40% active 2-(2'-hydroxy-5'-methylphenyl)benzotriazole paste (Ciba-Geigy's "Tinuvin" P paste, a water-insoluble UV light screener having a melting point of about 129-134°C), and 62.7 g/I of a water-soluble anionic surfactant, adjusted to pH of 5 (adding acetic acid as needed until the desired pH was obtained).
  • the pick-up of the dye solution on the tow was 30 wt.%.
  • the tows were then packed into the rectangular shaped steam chamber and carried through the chamber by a chain moving at about 1 m/min, one tow on each side of the chain.
  • the filaments coated with the aqueous dye mixture were exposed to steam at 120°C in a first zone in the steam chamber for two minutes and then to steam in a second zone at 165°C for 5 minutes.
  • the tows were washed with water. It was observed that very good exhaustion of the dye into the filaments was obtained, so that there was very little dye remaining on the surface of the filaments to be removed in the washing step.
  • the tow was dyed to a deep shade of a color designated as stone gray. This dyed fiber was designated as "Test Fiber".
  • the above procedure was repeated, except that the water-insoluble UV light screener was omitted from the aqueous dye mixture padded onto the tow.
  • the tow made by the revised procedure was also dyed to the same deep shade of stone gray color.
  • the dyed tow made by the revised procedure was designated as "Control Fiber”.

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Coloring (AREA)
  • Artificial Filaments (AREA)
  • Chemical Treatment Of Fibers During Manufacturing Processes (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)

Claims (13)

1. Verfahren zur Herstellung synthetischer Fasern, welches die folgenden Schritte einschließt:
Extrudieren einer Lösung von Poly(meta-phenylen-isophthalamid) und eines Lösungsmittels durch Öffnungen in einer Spinndüse unter Bildung von amorphen Fasern, die zusammen eine Faserstruktur definieren, wobei diese Fasern winzige Poren in sich aufweisen,
Bewegen dieser amorphen Fasern in Kontakt mit einem wässrigen Extraktionsbad zur Entfernung des Lösungsmittels, wobei diese Fasern wasser-gequollen werden, Inberührungsbringen dieser wasser-gequollenen Fasern mit einer wässrigen Lösung, die ein wasserlösliches Material enthält, und
Erhitzen der wasser-gequollenen Fasern mit Dampf auf eine Temperatur von 110°C bis 140°C für eine Zeit, die ausreicht, im wesentlichen das ganze wasserlösliche Material in die Poren der Fasern dieser Faserstruktur zu diffundieren.
2. Verfahren nach Anspruch 1, worin die wasser-gequollenen Fasern mit Dampf auf eine Temperatur von 120°C für eine Zeit erhitzt werden, die ausreicht, im wesentlichen das ganze wasserlösliche Material in die Poren der Fasern in dieser Faserstruktur zu diffundieren.
3. Verfahren nach Anspruch 1 oder Anspruch 2, worin das wasserlösliche Material ein oberflächenaktives Mittel ist.
4. Verfahren nach Anspruch 1 oder 2, worin das wasserlösliche Material ein Farbstoff ist.
5. Verfahren nach Anspruch 3, worin die Faserstruktur getrocknet wird, nachdem des oberflächenaktive Mittel in die Fasern diffundiert worden ist.
6. Verfahren nach Anspruch 4, worin die wasser-gequollenen farbstoffhaltigen Fasern danach weiter mit Dampf auf eine Temperatur über der Glasübergangstemperatur der Fasern für eine Zeit erhitzt werden, die ausreicht, die Poren zum Zusammenbruch zu bringen und den Farbstoff irreversibel innerhalb der Fasern einzuschließen und diese Fasern zu kristallisieren und sie gegen zunehmenden Waschschrumpf zu stabilisieren.
7. Verfahren nach Anspruch 6, worin die Fasern mit Dampf auf eine Temperatur von 150°C bis 165°C erhitzt werden.
8. Verfahren nach Anspruch 6, worin die Fasern auf eine Temperatur von 165°C erhitzt werden.
9. Verfahren zur Herstellung synthetischer Fasern, welches die folgenden Schritte einschliesst:
Extrudieren einer Lösung von Poly(metaphenylenisophthalamid) und eines Lösungsmittels durch Öffnungen in einer Spinndüse unter Bildung amorpher Fasern, die zusammen eine Faserstruktur definieren, wobei die Fasern winzige Poren in sich aufweisen,
Bewegen dieser amorphen Fasern in Kontakt mit einem wäßrigen Extraktionsbad zur Entfernung des Lösungsmittels, wobei diese Fasern wasser-gequollen werden,
Inberührungbringen dieser wasser-gequollenen Fasern mit einer einen wasserlöslichen Farbstoff und ein organisches, wasserunlösliches Material, das im Dampf bei einer Temperatur unterhalb der Glasübergangstemperatur der Fasern sublimiert, enthaltenden wässrigen Mischung,
Erhitzen der wasser-gequollenen Fasern mit Dampf auf eine Temperatur von 110°C bis 140°C für eine Zeit, die ausreicht, im wesentlichen den ganzen wasserlöslichen Farbstoff in die Poren dieser Fasern in der Faserstruktur zu diffundieren,
Erhitzen der wasser-gequollenen Fasern mit Dampf auf eine Sublimationstemperatur unterhalb der Glasübergangstemperatur der Fasern für eine Zeit, die ausreicht, das wasserunlösliche Material in die
Poren der Fasern in der Faserstruktur zu sublimieren, und denach
Erhitzen der wasser-gequollenen Fasern mit Dampf auf eine Temperatur über der Glasübergangstemperatur der Fasern für eine Zeit, die ausreicht, die Poren zum Zusammenbruch zu bringen und den Farbstoff innerhalb der Fasern irreversibel einzuschließen und die Fasern gegen zunehmenden Waschschrumpf zu stabilisieren.
10. Verfahren nach Anspruch 9, worin die wasser-gequollenen Fasern mit Dampf auf eine Sublimationstemperatur von 110 bis 150°C erhitzt werden.
11. Verfahren nach Anspruch 9 oder 10, worin das wasserunlösliche Material ein UV-Abschirmer ist.
12. Verfahren nach Anspruch 9 oder 10, worin das wasserunlösliche MAterial ein Dispersionsfarbstoff ist.
13. Verfahren nach Anspruch 9, 10, 11 oder 12, worin die wasser-gequollenen Fasern mit Dampf auf eine Temperatur von 165°C erhitzt werden.
EP86309756A 1985-12-16 1986-12-15 Aromatische Polyamidfasern und Verfahren zur Herstellung derselben Expired - Lifetime EP0228224B1 (de)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
US80894685A 1985-12-16 1985-12-16
US808946 1985-12-16
US90555686A 1986-09-12 1986-09-12
US905556 1986-09-12
US06/910,941 US4755335A (en) 1986-09-12 1986-09-26 Method of improving impregnation of poly (meta-phenylene isophthalamide) fibers
US910941 1986-09-26

Publications (3)

Publication Number Publication Date
EP0228224A2 EP0228224A2 (de) 1987-07-08
EP0228224A3 EP0228224A3 (en) 1988-02-03
EP0228224B1 true EP0228224B1 (de) 1990-05-09

Family

ID=27420045

Family Applications (1)

Application Number Title Priority Date Filing Date
EP86309756A Expired - Lifetime EP0228224B1 (de) 1985-12-16 1986-12-15 Aromatische Polyamidfasern und Verfahren zur Herstellung derselben

Country Status (7)

Country Link
EP (1) EP0228224B1 (de)
JP (1) JP2626974B2 (de)
KR (1) KR940002692B1 (de)
CA (1) CA1282213C (de)
DE (1) DE3671047D1 (de)
ES (1) ES2015883B3 (de)
MX (1) MX160847A (de)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1340008C (en) * 1988-08-18 1998-08-25 Tony Dominic Zatkulak Process of treating shrinkable fibers
DE69305913T2 (de) * 1992-05-07 1997-05-07 Teijin Ltd Aromatische Polyamidfäden mit verbesserter Wetterwiderstandsfähigkeit
JP2971338B2 (ja) * 1994-09-09 1999-11-02 帝人株式会社 易染性メタ型芳香族ポリアミド繊維
US5852087A (en) * 1996-02-13 1998-12-22 Teijin Limited Easily dyeable meta-linkage-containing aromatic polyamide fibers
JP2003074341A (ja) * 2001-08-31 2003-03-12 Futaba Industrial Co Ltd 排気管製造方法
JP4647680B2 (ja) 2008-09-29 2011-03-09 帝人テクノプロダクツ株式会社 易染色性メタ型全芳香族ポリアミド繊維
JP6632111B2 (ja) * 2014-12-19 2020-01-15 東レ・デュポン株式会社 湿潤剤が付与されたアラミド繊維およびそれを染色したアラミド繊維
JP7017039B2 (ja) * 2017-02-20 2022-02-08 東洋紡株式会社 着色ポリエチレン繊維およびその製造方法

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3760054A (en) * 1969-09-08 1973-09-18 Du Pont Process for preparing porous aromatic polyamide fibers
JPS4962722A (de) * 1972-10-24 1974-06-18
IT1024071B (it) * 1973-04-09 1978-06-20 Du Pont Processo per l'impregnazione di fibre tessili di polimero lineare sintetico difficilmente fusibile e fibre prparate con detto processo
DE2550518A1 (de) * 1975-11-11 1977-05-12 Bayer Ag Verfahren zur herstellung stabilisierter faeden aus aromatischen polyamiden
JPS542295A (en) * 1977-06-09 1979-01-09 Mitsui Eng & Shipbuild Co Ltd Slag cooling apparatus
US4525168A (en) * 1984-01-27 1985-06-25 Professional Chemical & Color, Inc. Method of treating polyaramid fiber

Also Published As

Publication number Publication date
KR940002692B1 (ko) 1994-03-30
JP2626974B2 (ja) 1997-07-02
EP0228224A3 (en) 1988-02-03
JPS62184127A (ja) 1987-08-12
MX160847A (es) 1990-06-05
DE3671047D1 (de) 1990-06-13
EP0228224A2 (de) 1987-07-08
ES2015883B3 (es) 1990-09-16
KR870006247A (ko) 1987-07-10
CA1282213C (en) 1991-04-02

Similar Documents

Publication Publication Date Title
US4755335A (en) Method of improving impregnation of poly (meta-phenylene isophthalamide) fibers
EP0212948B1 (de) Aromatische Polyamidfasern und Verfahren zur Stabilisierung derselben
US4883496A (en) Process for dyeing crystalline aromatic polyamide fibers with water-insoluble dyes
US5096459A (en) Method of dyeing aromatic polyamide fibers with water-soluble dyes
CA1083768A (en) Impregnated fibers of difficultly meltable nitrogen containing polymers
AU675555B2 (en) Nylon fibers with improved dye washfastness and heat stability
EP0330163B1 (de) Flammfeste Stapelfasermischung
JP2913204B2 (ja) カチオン性染料で染色可能なポリ（ｐ―フエニレンテレフタラミド）繊維の製造方法
CA1229209A (en) Method of producing non-flammable, high- temperature resistant polyimide fibers
EP0488294A2 (de) Insektenbeständige Fasern und Verfahren zur Herstellung derselben
EP0228224B1 (de) Aromatische Polyamidfasern und Verfahren zur Herstellung derselben
US5074889A (en) Aromatic polyamide fibers and method of printing such fibers with acid dyes in the presence of hexamethylene diamine dihydrochloride impregnated in fiber
EP0668942B2 (de) Fasern und folien mit verbesserter flammfestigkeit
US4919869A (en) Apparatus for and process of treating shrinkable fibers
US5344708A (en) Bulked random copolyamide yarns of nylon 6 and nylon 6,6 having enhanced dyeability
EP0018523A1 (de) Kern-Mantel-Fasern aus aromatischen Polyamiden und Verfahren zu deren Herstellung
JP2003530479A (ja) ポリアミドの特性を改善する方法
RU2136791C1 (ru) Текстильные волокна из сульфированного поли(п-фенилентерефталамида)
US3558763A (en) Process for treating wet spun filaments with shrinking agents
JPH07238436A (ja) 耐熱、耐炎布帛
CA1340008C (en) Process of treating shrinkable fibers
US5660779A (en) Process of making textile fibers of sulfonated poly(p-phenylene terephthalamide)
JP2979058B2 (ja) 結晶性芳香族ポリアミド繊維を水不溶性染料で染色する方法
JPH08260363A (ja) 染色均一性に優れたポリアミド繊維製染色布帛及びその製造方法
JPH08269880A (ja) 染色均一性に優れたポリアミド繊維製染色布帛及びその製造法

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): DE ES FR GB IT

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Kind code of ref document: A3

Designated state(s): DE ES FR GB IT

17P Request for examination filed

Effective date: 19880713

17Q First examination report despatched

Effective date: 19890510

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): DE ES FR GB IT

ITF It: translation for a ep patent filed
REF Corresponds to:

Ref document number: 3671047

Country of ref document: DE

Date of ref document: 19900613

ET Fr: translation filed
PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
ITTA It: last paid annual fee
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 19921127

Year of fee payment: 7

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19941216

REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 19950112

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20050825

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20051209

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20051214

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20051228

Year of fee payment: 20

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

Effective date: 20061214

REG Reference to a national code

Ref country code: GB

Ref legal event code: PE20