US3102323A - Textile - Google Patents

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US3102323A
US3102323A US757370A US75737058A US3102323A US 3102323 A US3102323 A US 3102323A US 757370 A US757370 A US 757370A US 75737058 A US75737058 A US 75737058A US 3102323 A US3102323 A US 3102323A
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Prior art keywords
dye
filament
filaments
polymer
drawn
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US757370A
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Inventor
Dustin S Adams
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EIDP Inc
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EI Du Pont de Nemours and Co
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Priority to NL242714D priority Critical patent/NL242714A/xx
Application filed by EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Priority to US757370A priority patent/US3102323A/en
Priority to GB28426/59A priority patent/GB905833A/en
Priority to FR803349A priority patent/FR1236688A/fr
Priority to CH7741059A priority patent/CH395418A/de
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    • D—TEXTILES; PAPER
    • D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02J—FINISHING OR DRESSING OF FILAMENTS, YARNS, THREADS, CORDS, ROPES OR THE LIKE
    • D02J1/00—Modifying the structure or properties resulting from a particular structure; Modifying, retaining, or restoring the physical form or cross-sectional shape, e.g. by use of dies or squeeze rollers
    • D02J1/22—Stretching or tensioning, shrinking or relaxing, e.g. by use of overfeed and underfeed apparatus, or preventing stretch
    • D02J1/228—Stretching in two or more steps, with or without intermediate steps
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • 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
    • D01D5/12—Stretch-spinning methods
    • D01D5/16—Stretch-spinning methods using rollers, or like mechanical devices, e.g. snubbing pins
    • 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
    • D01D5/20—Formation of filaments, threads, or the like with varying denier along their length
    • D—TEXTILES; PAPER
    • D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02J—FINISHING OR DRESSING OF FILAMENTS, YARNS, THREADS, CORDS, ROPES OR THE LIKE
    • D02J1/00—Modifying the structure or properties resulting from a particular structure; Modifying, retaining, or restoring the physical form or cross-sectional shape, e.g. by use of dies or squeeze rollers
    • D02J1/22—Stretching or tensioning, shrinking or relaxing, e.g. by use of overfeed and underfeed apparatus, or preventing stretch
    • D02J1/223—Stretching in a liquid bath
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S264/00—Plastic and nonmetallic article shaping or treating: processes
    • Y10S264/08—Fibrillating cellular materials
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S264/00—Plastic and nonmetallic article shaping or treating: processes
    • Y10S264/47—Processes of splitting film, webs or sheets
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
    • Y10S8/18—Grafting textile fibers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
    • Y10S8/21—Nylon

Definitions

  • This invention has to do with syntheticorganic polymers. More specifically, it has-to do with fibers,- filam'ents,
  • Synthetic fibers are well known articlesdofcomrnerce andtheir use has become increasingly widespread during the pastseveral years. Suchfibers are in general based on synthetic organic polymers, and they show-anumber ofjadvantages which have ledto their wideacceptance.
  • both natural;andsyntheticfibers are dyed by a number of different processes, all of which cause dye like composed of V molecules. orparticles either to adhere to the 'surface' of the fiber or to penetrate into the interior structure thereof.
  • ject of this invention is to provide a process by which additives and modifiers can be infused into the interior of synthetic organic fibers, filaments,'filrns, and the like so that the permanence of the additive is greater than is the case when such additives aremerelysurface coated onto thefilarnent.
  • a further object is to provide a process by which synthetic fibers and filaments and films can be more deeply and effectively dyed by a wide variety of dyestuffs, including those which are not substantive or possessing of any affinity for the polymeric structure itself or which lack :dififwsibility.
  • a still furtherobject is to provide a process by which synthetic'organic fibers and known to apply other additives, such as antistatic agents, 7
  • crosslinking agents and polymer-forming reactants, and the like have been added to a polymer structure orcoated I onto the surface of a synthetic polymer filament to permit 7, modification of the properties thereof 'by' cross-linking filaments and films can be simultaneously oriented and have applied a modifier or additive in deep penetration .into theint-erior structure of the polymeric material.
  • products of the type useful in the present invention can be prepared by a process for infusing a modifier with an orientable synthetic organic polymeric structure, comprising the. stepsof tensioning the. structure prior to complete orientation'while in contact with a surface-crack-pr'omot- 'olution.
  • the modifier is .taken up by the polymeric structure during the process of orientation.
  • the orientation step should proceed by a sharp-neck process rather than a long-taper process which is frequently employed in drawing or elongating synthetic fibers.
  • the sharp necks suit-able for producing the desired products of this invention are initiated by the cracks caused by the combined action of tension and surface-cnack-promoting agent.
  • modifiers introduced by the present process are distributed within the interior structure of the final oriented material in a unique and novel manner.
  • the penetration in the radial sense is deep-much deeper and more uniform than conventional surface-dyeing, for example.
  • the distribution of modifier in the axial sense is non-uniform, and occurs in short length fluctuations randomly distributed in high-frequency recurrence along the length of the filament.
  • the modifier penetrates into the interior of the structure through the cracks which appear randomly and at closely-spaced intervals in the surface of the polymer when it is tensioned in the presence of the crack-promoting agent, and that the extent, depth and permanence of the penetration is augmented by the freshness and lability of surface of the polymer in the area of the crack.
  • the non-uniform axial distribution of modifier in the products of this invention is an unexpected and valuable property, useful in a variety of applications, and variable to a considerable degree.
  • the effect of-the modifier in the final product can be controlled by altering the periodicity of the fluctuations in concentration of modifier. This may be done by selection of a cracking agent to give more or fewer cracks per unit length of polymer structure, or by changing the rate of drawing, or, to a lesser extent, by changing the temperature of drawing.
  • the final concentration of modifier may be varied by changing the concentration of modifier in the cracking bath. Other methods of control, involving interaction of temperature, rate of treatment and the like, are also possible.
  • the present products have fluctuations which range from just barely detectible to the naked eye, up to those which require an electron microscope for res- Such a range of fluctuations offers great advantage in control of properties of the final products.
  • modifiers can now be employed which have not heretofore been satisfactory because the modifier could not be permanently combined with the polymer.
  • fluctuations in modifier content can now be achieved in combination with a polymeric structure which is uniform in diameter or thickness and is uniformly oriented as well.
  • the product of the invention may be in the form of fibers, filaments, films, and the like prepared from synthetic organic polymers which are orientable by a sharpneck drawing process.
  • These structures contain a modifying additive which may be one or a mixture of those hereinafter described distributed non-uniformly and nonhomogeneously along the length of the filament or film, and when magnified show a short-range variation in concentration along the length of the polymeric structure.
  • These non-uniformities are of very short length and occur in general from about 10 to 20,000 per inch and preferably from 500 to 20,000 per inch.
  • Each section of modi fier concentration results from a crack or fissure. It will be apparent therefore that there will be as many dye or other modifier concentrations as there were cracks or fissures produced by drawing.
  • the effect of the modifier can be controlled by concentration such as by, for example, dye depth, electrical conductivity, formation of voids and the like.
  • concentration such as by, for example, dye depth, electrical conductivity, formation of voids and the like.
  • Two or more modifiers may be imbibed successively or they may be imbibed simultaneously.
  • two or more modifiers When two or more modifiers are introduced into the fiber successively they may be of such a nature as to react within the fiber where they meet for special purposes such as precipitation, formation of a large molecule, formation of gas, reduction of metal salts to the metal, etc.
  • FIGURE 1 is a diagrammatic view of a yarn undergoing a short drawing of the type suitable for the present invention.
  • FIGURE 2 is a similar view of conventional drawing in which the drawing section is represented by a long taper.
  • FIGURE 3 is a diagrammatic section of apparatus suitable for carrying out the invention.
  • FIGURE 4 is an enlarged view of a filament in which cracks have been introduced by drawing about 1.1X in a crack-enhancing liquid.
  • FIG- URE 5 is a diagrammatic view of the filament of FIGURE 4 which has been contacted with the crack-enhancing liquid, but has not been drawn appreciably.
  • FIGURE 6 is a diagrammatic cross-section along the line 66 of FIG- URE 4 of a yarn having a brittle outer shell suitable for treatment by the present invention.
  • 1 represents the undrawn yarn and 2 is the drawn yarn.
  • a container 3 is supplied with a crack-enhancing liquid 4 and immersed in the liquid are guide roll 5, and a pair of driven draw rolls 5A and 5B which draw the yarn 1 as it passes through the liquid 4.
  • the filament 1 is drawn 1.1X to produce cracks 8. Between the cracks are raised portions 9.
  • the incipient cracks or fissures are indicated as 8.
  • FIGURE 6 6 represents the brittle outside shell of the filament and 7 is the inside core as will be more completely described hereinafter.
  • the angle A should be of the order of 30 to and the length of the draw neck should be short; i.e., distance B should be less than 3 times the diameter D of the undrawn filament or thickness of the undrawn film. In other words should be less than 3.
  • the process of the present invention is based on new, additional features which are not comprehended present invention it is possible "to' obtain many results which have hitherto not been obtainable.
  • the present invention has the feature that during the drawing process the fiber is exposed tofa modifying'additive which surprisingly and" unexpectedly is infusedra'pidly and th-or- I oughly into the polymer structure. This infusion of the additive does not appear to be particularlydependent upon substantiveness between the polymer and is not excluded.
  • the surprising nature of the present invention may in part be illustrated by the fact that basic dyes, which have hitherto been considered: as quite.
  • the liquid chosen should not in general be a solvent or strong swelling agent for the polymer. Solvent action by a liquid necessarily eliminates the formation of surface cracks.
  • Desirable cracking agents in'general have a low surface tension.
  • Prefe'rred compositions are those with a surface tension measured relative to air of not greater than 60 dynes per centimeter measured at the temperature at which it is proposed to employ the agent.
  • the desirability of a low surface tension is not completely understood, but it is possible that the cracking agent aids in the progress of the modifying additive from the bulk liquid phase down into the cracks and;thence into the interior structure of the polymer.
  • nonaqueous cracking agents are preferred. Water by itself was found not to be a satisfactory cracking agent, except possibly for especially treated polymers.
  • the cracking solution should contain at least 10%..
  • the cracking agent should also preferably have a high tendency to wet the surface of the filament being cracked.
  • the wetting angle between a liquid and a polymer is determined by measuring the contact angle between a film of the polymer and a droplet of theliquid. Such a wetting angle is normally measured so as to include rather than exclude the liquid phase; that is, the wetting angle of a poor wettingagent will be more than 90".
  • the wetting angle be less "than 90, and under many circumstances it is found that wetting angles as low as are obtained with the best cracking agents.
  • the'liquids (not considering the-modifying additive) form a single liquid phase.
  • the additive be soluble in the cracking agent. It may be observed that certain liquids which have some solvent or swelling, tendency on the polymer can be employed if they are otherwise suitable, provided that the contact time between the liquid and the polymer is kept short; that is, the cracking must occur before the swelling or plasticizing action has a chance to occur, since such action would prevent the formation of fissures or cracks, therefore, the entire process must be completed before any observable degree of plasticization occurs.
  • the crackor fissure-promoting agent can also be the modifying agent which is 'infused' into [the polymer Surfaoe-cracking agents suitable for the practice of .rner. One I extremely simple criterion is available, and
  • the present invention is applicable to a widenumber of different synthetic organic polymers.
  • these are polyamides, polyesters, polyurethanes, vinyl polymers and polyhydrocarbons. So far as is known, any synthetic organic polymer capable of being formed into filaments which can be cold-draw oriented by a process involving a sharp neck are suitable for the present invention.
  • EXAMPLE I A sample of polyethylene terephthalate as spun and prior to drawing was placed in a purified hydrocarbon in kerosene range and hand drawn. It was observed that the fiber cracked during the drawing process. This experiment was conducted with equal results at three different temperatures, -l C., 0, and +13 C. In a similar experiment the same fibers were placed in water at 0 and 13 C. At 13 C. drawing proceeded by conventional process, and there was no cracking observed. At 0 C. some cracks developed, but they would not propagate around the surface of the filament and drawing was unsuccessful.
  • EXAMPLE II A monofilament of undrawn polyethylene terephthalate of 1800 denie-r was immersed at room temperature in ethanol containing approximately 2% of a basic blue dye C.I. 42,595. The monofilament was drawn 6x by hand, and an intense blue color developed in the monofilament. A portion of the monofilament was crosssectioned, and it was observed that the penetration of the dye was very deep, the color being uniform except at the very core. This deep penetration into a very heavy filament was unusual and unexpected. The dye was found to be fast to washing in spite of the fact that basic dyes in general are not satisfactory for dyeing drawn polyethylene terephthalate. The blue color was very much darker than a control filament which was drawn by conventional process and then immersed in an equivalent solution of the basic dye in ethanol. This latter filament was practically colorless after washing.
  • a cracking and drawing dye bath was prepared by mixing 80 parts of ethanol and 20 parts of water by weight with 1% of a basic green dye, C.I. 42,000.
  • a sample of undrawn polyethylene terephthalate yarn containing 34 filaments was machine drawn (FIG. 3) through this dye bath to 5X its original length, to give a drawn yarn of 70 denier.
  • the dye bath temperature was approximately 15 C.
  • the feed rolls operated at 9 yards per minute peripheral speed and the draw rolls at 45 yards per minute.
  • This particular dye was chosen because it has little or no dyeability on conventionally drawn polyethylene terephathalate yarns or on undrawn polyethylene terephthalate.
  • a deep rich green color was obtained. Under the microscope, it was seen that the coloration was present in discontinuous sections along the filaments.
  • the dyed sections alternated with undyed sections with an average frequency of about 500 per inch.
  • EXAMPLE IV A film of undrawn polyethylene terephthalate was placed on top of a piece of taffeta fabric woven from Dacron polyester yarn. The sandwich of film and cloth was soaked heavily with an alcoholic solution of a basic green dye, CI. 42,000 of a composition identical with that prepared for the previous example. This wet layered combination was fed through the pinch of a rubber mill, and Where the cloth threads contacted the film under the pressure from the mill there was suificient pressure to cause cracking, drawing and orientation, and deep dyeing occurred at those points. Little or no dyeing occurred at other points. The result was that the film took on a patterned effect comparable to the weave of the fabric, with great dye depth differences between the points of pressure and the points of no pressure.
  • a basic green dye CI. 42,000
  • EXAMPLE V A room temperature solution of 5% acrylic acid in ethanol was employed as a cracking bath and modifying additive.
  • a sample of undrawn polyethylene terephthalate ribbon was hand drawn through the bath. The solution caused cracking, and the ribbon drew to a uniform denier and was highly oriented. Following the drawing process, the ribbon was after-dyed by normal procedures using a basic green dye, C.I. 42,000, and a deep color resulted.
  • the acrylic acid acted :as a dye fixer for the fiber.
  • the same dyeing treatment was tried on another sample of ribbon after washing it thoroughly and carefully in water to remove all surface traces of acrylic acid. No difference in dye depth was seen between the two samples, indicating that the acrylic acid had penetrated thoroughly into the interior structure of the ribbon.
  • EXAMPLE VI A sample of the same multifilament yarn employed in Example III was machine drawn through a bath of 100% ethanol containing 1% of a basic green dye, C.I. 42,000. This process was run at a higher speed than before, the draw rolls operating at a peripheral speed of 327 yards per minute. The dye depth obtained was equivalent to that obtained in Example III. The frequency of fluctuations was too great to be resolved with an optical microscope. A further experiment was performed employing a dye bath containing 25% ethanol and 75% water with the same concentration of dye as before. In the second bath, cracking proceeded as before, and the fibers drew to the same deep green color. Microscopic examinations showed longer fluctuations, about 60 per inch.
  • EXAMPLE VII The sample of undrawn polyethylene terephthalate yarn employed in this experiment had been specially treated to provide a surface which was readily cracked. The procedure consisted of quenching of the threadline from the melt spinning process with vapors of S0 gas. The surface of this filament was much more brittle than conventional undrawn polyethylene terephthalate. It was found possible to perform the cracking and the infusion process of the present invention on this specially treated yarn using a water bath containing a basic green dye, C.I. 42,000. Similarly, this yarn could be cracked and drawn in air without any water present, although, of course, it was not possible to infuse a solution of a modifying additive'into the polymer structure in this manner. However, gases or vapors could be infused in this way.
  • EXAMPLE VIII A sample of undrawn polyethylene terephthalate tow was ozonized with 2% ozone in oxygen for 60 minutes at room temperature. This specially embrittled yarn was hand drawn through a mixture containing methyl acrylate, ethanol, and aqueous ferrous sulfate. During the drawing, which proceeded with the formation of cracks, the methyl acrylatew-as infused into the interior structure of the yarn. The tow was dried and then dyed with a violet disperse dye, 1,4-diamino-2,3-dichloroanthraquinone, for 30 minutes. The shade obtained was very deep, whereas, the control without the crack drawing process dyed to only pale violet color.
  • a violet disperse dye 1,4-diamino-2,3-dichloroanthraquinone
  • EXAMPLE 1X "contained also 2% of a basic green'dye, C.I. 42,000.
  • Undrawn polyethylene terepht-halate was infused with potassium dichromate in accordance with the present invention, employing a bath of ethanol and 75% water by Weight, containing about 2% by weight of the salt.
  • the potassium dichromate infuscdinto the interior structure of the yarn during drawing and gave a highly drawn polyethylene terephthalate fiber of a rich orange color.
  • the presence of this highly reactive inorganic chemical provided good fixative'powers for other modifiers for the fiber which could be introduced following the drawing process.
  • Example x1 This example is similar in principle to Example X above, in that nickel chloride was again imbibed into an undrawn yarn of polyethylene terephthalate. However, in this experiment, successive imbibitionwas practiced in the following manner; Two diiierent baths were made up, the first contained nickel chloride in ethanol and the second contained sodium borohydride in a 50-50 mixture of ethanol and water. The undnawn yarn was immersed in the'nlckel chloride bath and partiallylcrack-drawn dur- 1 ing which process it imbibed nickel chloride into the interior of the yarn.
  • the dark color was in weight duet'o calcium chloride take-up as determined gnavimetrically.
  • the saltacontaining filament was dried under vacuum to remove all water, weighed, and then a exposed to air at 85% relative humidity. The water takef up was measured, and it was found that .the drawn filaments gained 12% in weight based on the polymer. This may be compared with the moisture regain of conventional polyethylene terephthalate drawn yarns of less than I.
  • each bath contained 50% by weight of ethanol and 50% by weight of water.
  • the-first bath contained 1% by weight of a yellow basic dye C.I.. 41,000; the second bath contained 1% by weight of CI.
  • denier, 34 filaments which contained in random distribution segments dyed yellow, red, blue, or not dyed at all. Since only approximate control was exerted to give uniform imbibition of the three dyes, the resulting yarn had a dark brown appearance to the naked eye. However, when viewed under a microscope at 50X it was quite easy to distinguish the separate portions of the filament which had been dyed with the individual colors. The distribution was random within each filament as well as within the total filament bundle.
  • modifying agents has also been added to undrawn polyethylene terephthalate and other fibers from many cracking baths particularly those comprising ethanol alone or mixtures of water and ethanol.
  • antistatic agents N-vinylpyrolidone and a surface active organic phosphate ester are satisfactory when applied to both fibers and films.
  • Sodium styrene sulfonate has been added to fibers to provide dye sites and anti-static properties.
  • Acidic dyes such as orange, C.I. 18,875, have been applied from ethanol-water mixtures containing 50% by weight of each liquid to give extremely deep colors.
  • EXAMPLE XV A sample of undrawn 66 nylon yarn was placed in a cracking bath consisting of 100% ethanol, containing 2% of a basic green dye, C.I. 42,000. The yarn was drawn to give a highly oriented, 70 denier, 34 filament yarn which contained a high concentration of the green dye, giving EXAMPLE XVI A sample of undrawn nylon was drawn by the process of the present invention employing a cracking bath containing ethanol and water, 50% each by weight, and 1% of a blue basic dye, C.I. 42,595. The filament cracked readily and was drawn in the bath. The dyestufii infused into the interior structure of the yarn and gave an intense blue color much deeper than that obtained by contacting either the drawn or the undrawn nylon filament with the dyestulf bath.
  • EXAMPLE XVII A sample of undrawn poly(meta-phenylene isophthalamide) was drawn by the process of the present invention in a bath containing 50% by weight of ethanol and 50% by weight of water with an additional 5% of formic acid.
  • the bath contained 2% by weight of a basic green dye, C.I. 42,000. Undrawn filaments were run through the dye bath and cracked and drawn. During the drawing the filaments imbibed the dye to give a good depth of green color.
  • the yarn was then heat-set by running it over a hot pin at 120 C., giving a filament with a boil-oif shrinkage of only 3%.
  • EXAMPLE XVIII Filaments of quenched polypropylene were spun with a residual draw of 2X. These were drawn according to the present invention through a bath of the same composition as that described in the preceding example. Normally, it has not been found possible to obtain coloration at all with this dyestuif on polypropylene, but in the present operation a deep green color was obtained. This infusion dyeing process is particularly advantageous with this and similar hydrocarbon polymers, since there are very few ways in which such filaments can be dyed.
  • EXAMPLE XVIV A copolymer of polyacrylonitrile polymerized from a mixture of 94% acrylonitrile and the residue methyl acrylate plus sodium styrene sulfonate was spun into filaments. When the filaments were tensioned in ethanol, a few surface'cracks developed. A 10% solution of dimethylformamide at 10 C. in ethanol was found to be a better cracking agent, and when the filaments Were stretched 1.1X in this bath the surface became heavily cracked, developing a white appearance. When 1% by weight of a basic red dye, C.I. Basic Red 14, was added to the bath and the fibers cold-drawn therein, a deep intense red color was obtained in the drawn filaments.
  • a basic red dye C.I. Basic Red 14
  • the bath contained 5% of a basic red dye, C.I. Basic Red 14. Good penetration of the dyestuif was observed.
  • Other equivalent cracking baths included lauryl alcohol, decyl alcohol and kerosene.
  • EXAMPLE XXI A series of experiments were performed in which the effect of surface tension of the cracking bath was investigated. In all of these experiments, undrawn polyethylene terephthalate yarn was crack-drawn to 4X its original length to give a yarn of 70 denier, 34 filaments after the complete processing. The dye used in all cases was C.I. Basic Blue 9. The first set of experiments illustrates the effect of changing surface tension by employing mixtures of acetic acid and water at different concentrations. The results are shown in Table I, and it will be seen that I 13 the best processing and best infusion of dyeing was achieved when the surface tension of the bath was below 60 dynes/cm. I i i I i s Table I i The second series of experiments employed four different cracking baths, all of the same surface tension; namely,
  • a polyamidea polyhydrocar-bon, a polyacrylonitrile, or other polymeric material is employed.
  • the imbibing process can be caused to occup step wise to imbibition of two, three or more different modifiers, one or more at each step, as already shown.
  • additives are in themselves non-reactive.
  • a large number of reactive materials can be added to the polymer by the process of the present invention and subsequently or simultaneously reacted with another m aterial. Examples above illustrate this principle, but further modifications arealso operative.
  • a dye mordant or dye assistant can be added during the crackdrawing process to facilitate later dyeing of the fiber.
  • mixtures of polymers can be spun to form an undrawn filament, and then by the process of the present 40 invention one can imbibe a reactant which responds differentially to twoadiflerent types of polymer simultaneously during the process of the present invention. That 7 is, for example, an addition polymer and a compatible monomer or low molecular weight polymer can be combined in the spinning process, and during the drawing process of the present invention the low molecular weight material can be activated for further addition polymerization by imbibing .a'catalyst into the polymeric filament or film.
  • the present invention offers an improved method of obtaining grafted copolymer structures, for a graftable additive can be infused with a polymer structure during drawing, and then caused to graft onto the cific embodiment could prove extre-melyvaluable in laboratory techniques or chemical processing industries.
  • Photographic chemicals such as silver nitrate or potasslum dichromate, can be employed to give a filamentary material which is photographically active.
  • such invention can be highly valuable for chromatographic penetrate the filamentary structure and modify volume surface properties.
  • Lubricants such as silicone oils, Syl
  • Organic and inorganic additives can be employed which can be'caused v to change form following the infusion process.
  • Metallic salts can be added and subsequently reduced as already shown to give a filament which is an unusually good conductor of heat or electricity.
  • Chemical modification can also be employed following the irnbibition of a cross-linking agent as, for example, with diisocyanates, or phosgene, the introduction of methylborate followed by hydrolysis and heat linking, the introduction of pentaerythritol, glycerol and the like followed by ester interchange and similar cross linking cations.
  • non-reactive modifiers which can be employed include long rigid molecules such as quinquephenyl, and cheap organic or inorganic fillers.
  • Additional reactions which can be caused to take place within the fiber include the introduction of an organic salt such as hex-amethy-lene diarnmonium adipate followed by thermal polymerization within the fiber, deposition of low molecular weight, macrointermediates for long-chain polymers or monomers such as isobutylene butadiene, cross-linking polymers such as divinylbenzene, glycol dimethacrylate or other vinyl monomers.
  • an organic salt such as hex-amethy-lene diarnmonium adipate
  • thermal polymerization within the fiber deposition of low molecular weight, macrointermediates for long-chain polymers or monomers such as isobutylene butadiene, cross-linking polymers such as divinylbenzene, glycol dimethacrylate or other vinyl monomers.
  • soluble organic or inorganic fillers which can subsequently be leached away to provide voids within the filamentary structure or to imbibe successively two coreactive chemicals which when in contact
  • Volatile liquids can also be imbibed and can be explosively expelled from the filamentary structure by passing the filament over a hot pin or other heated surface to produce :a filament with eroded or cratered surface.
  • modifying agent is intended to include one or more of the additives and modifying agents discussed above.
  • the fibers without activation of the cross-linking material, can be cut into staple lengths and formed into non-woven batts or pellicles.
  • the cross-linking agent can be activated by known procedures to give a highly stable structure which is bonded in a much more intimate manner than is normally achievable.
  • the present invention can also be employed to give a filamentary threadline of varying appearance.
  • an undrawn filament containing a pigment or other agent introduced by either melt-dyeing or solutiondyeing can be drawn by the process of the present invention to introduce a second overdyeing material, coloring agent or other additive.
  • This process can be applied by intermittently exposing the threadline to the cracking liquid.
  • the threadline When the threadline is in the bath, it will draw according to the process of the present invention.
  • the threadline is not wet by the cracking agent, it will, of course, draw according to standard drawing processes known and described in the art. Equally well, the starting material can be an undrawn uncolored polymeric filament.
  • This can be drawn and simultaneously infused with a dye, dye-site-former, wetting agent or the like according to the present invention in an intermittent fashion as described above. Then, subsequently, the drawn filament or film can be overdyed, or, if appropriate, a reactant can be applied to combine with the intermittently imbibed additive.
  • two or more threadlines can be combined in parallel relationship, one having been treated according to the present invention, and another being of conventional nature.
  • Another possible modification comprises two threadlines of similar or different basic polymeric structure, each having been infused with a different modifying additive according to the present invention. The modifications in physical properties of the combined threadline can thus be due to each of the two components separately, or as a synergistic and cumulative effect.
  • the present invention is not only applicable to those polymers already specifically indicated, but also to any polymer which, in filamentary or film form, can be caused to undergo a process of substantial irreversible elongation accompanied by molecular orientation, provided that the elongation-orientation step, generally referred to as drawing,v can be made to proceed by a sharp-neck step involving an abrupt change from the undrawn to the drawn condition.
  • Drawn structures such as filaments, films, and the like consisting essentially of oriented synthetic organic linear fiber-forming polymeric material having a modifier other than a crack-inducing agent distributed within the said structure, the said modifier being present in short length variations of concentration along the length of the said structure.
  • a smooth drawn highly and continuously oriented structure such as filaments, films, and the like composed of synthetic organic linear fiber-forming polymeric material of essentially uniform density having a permanent modifier entrapped within the said structure, the said modifier being present in short length variations of at least 10 per inch along the length.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Artificial Filaments (AREA)
  • Coloring (AREA)
US757370A 1958-08-26 1958-08-26 Textile Expired - Lifetime US3102323A (en)

Priority Applications (5)

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NL242714D NL242714A (enrdf_load_stackoverflow) 1958-08-26
US757370A US3102323A (en) 1958-08-26 1958-08-26 Textile
GB28426/59A GB905833A (en) 1958-08-26 1959-08-19 Improvements in the treatment of filaments, films and other shaped articles of synthetic polymers
FR803349A FR1236688A (fr) 1958-08-26 1959-08-22 Nouvelles structures à base de polymères organiques synthétiques orientés
CH7741059A CH395418A (de) 1958-08-26 1959-10-01 Verfahren zur Einführung eines Veredlungsmittels in die Innenstruktur von Fasern oder Fäden aus orientierbaren synthetischen Polymeren

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CH (1) CH395418A (enrdf_load_stackoverflow)
FR (1) FR1236688A (enrdf_load_stackoverflow)
GB (1) GB905833A (enrdf_load_stackoverflow)
NL (1) NL242714A (enrdf_load_stackoverflow)

Cited By (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3214234A (en) * 1963-05-21 1965-10-26 Phillips Petroleum Co Oriented foamed polyolefin extrudates and the production and dyeing of the same
US3215486A (en) * 1962-04-17 1965-11-02 Toyo Spinning Co Ltd Fixation of polypropylene fibers impregnated with dyestuffs and other treating agents
US3247300A (en) * 1962-10-25 1966-04-19 Du Pont Process for producing highly crimped fibers having modified surfaces
US3313591A (en) * 1958-03-06 1967-04-11 Du Pont Process of graft polymerizing ethylenically unsaturated monomers to solid, shaped polycarbonamides employing heat as the sole graft initiator
US3329557A (en) * 1955-04-06 1967-07-04 Du Pont Static resistant filament and process therefor
US3439999A (en) * 1964-09-28 1969-04-22 Uniroyal Inc Cross-dyed carpets
US3446886A (en) * 1963-12-04 1969-05-27 Du Pont Process for treating linear polyesters to modify the surface appearance and characteristics thereof
US3472608A (en) * 1962-11-23 1969-10-14 Ici Ltd Polyester filaments and like structures
US3494994A (en) * 1966-10-11 1970-02-10 Kuraray Co Method of producing polyurethane elastomer staple fibre
US3772747A (en) * 1968-03-18 1973-11-20 Rhodiaceta Process for producing textured yarn
DE2354756A1 (de) * 1972-11-02 1974-05-09 Du Pont Aromatische polyamidfaser und verfahren zur herstellung derselben
US3899563A (en) * 1971-12-06 1975-08-12 Allied Chem Synthetic fibers having improved soil and stain repellency
US3903221A (en) * 1974-05-08 1975-09-02 Du Pont Process and product
US3920785A (en) * 1969-11-13 1975-11-18 Celanese Corp Process for increasing the porosity of opencelled microporous film
US3957936A (en) * 1971-07-22 1976-05-18 Raduner & Co., Ag High temperature process for modifying thermoplastic filamentous material
US3960686A (en) * 1974-01-04 1976-06-01 Chemische Werke Huls Aktiengesellschaft Method for preparing low pilling effect polyester fiber products
FR2290528A2 (fr) * 1972-11-27 1976-06-04 M & T Chemicals Inc Nouveau procede de traitement de fibres et fibres obtenues
US4001367A (en) * 1974-03-29 1977-01-04 M & T Chemicals Inc. Method for permanently and uniformly incorporating an additive into an undrawn fiber
US4013753A (en) * 1973-10-09 1977-03-22 Bayer Aktiengesellschaft Process for the production of spontaneously crimping polyacrylonitrile composite fibres with improved crimp properties
US4050892A (en) * 1973-09-13 1977-09-27 Martin Processing Co., Inc. Coloring polyester materials with acid dyes
US4147749A (en) * 1975-08-14 1979-04-03 Allied Chemical Corporation Varied orientation of fibers
US4495126A (en) * 1982-12-02 1985-01-22 The Goodyear Tire & Rubber Company Adhesive activated emulsion to a polyester yarn
US5443898A (en) * 1993-06-29 1995-08-22 Fiberweb North America, Inc. Nonwoven webs and method of making same
US5516473A (en) * 1993-09-30 1996-05-14 E. I. Du Pont De Nemours And Company Imbibition process
US5688596A (en) * 1992-05-07 1997-11-18 Teijin Limited Aromatic polyamide filament having an enhanced weathering resistance
EP3135464A1 (en) * 2015-08-27 2017-03-01 Okia Optical Company Limited Method of making eyewear by 3d printing
CN106476263A (zh) * 2015-08-27 2017-03-08 澳加光学有限公司 运用3d打印制备眼镜的方法
CN114585778A (zh) * 2019-10-23 2022-06-03 兰精股份公司 辊表面

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU6198373A (en) * 1972-11-27 1975-05-01 M & T Chemicals Inc Improving fibre properties

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US2071251A (en) * 1931-07-03 1937-02-16 Du Pont Fiber and method of producing it
US2137235A (en) * 1937-02-15 1938-11-22 Du Pont Shaped articles from polymeric materials
US2278888A (en) * 1938-11-02 1942-04-07 Du Pont Artificial structure and process for producing same
US2289232A (en) * 1939-07-14 1942-07-07 Du Pont Method and apparatus for producing filamentary structures
US2302077A (en) * 1939-02-25 1942-11-17 Fibres Associates Inc Artificial wool filament and yarn
US2321635A (en) * 1940-11-26 1943-06-15 Du Pont Treatment of polyamide films
US2353023A (en) * 1940-08-06 1944-07-04 Freund Ernest Process for the treatment of cellulose acetate films
US2352725A (en) * 1941-11-04 1944-07-04 Du Pont Shaped product
US2423182A (en) * 1943-04-29 1947-07-01 Du Pont Method of cold-drawing tapered filaments
US2514088A (en) * 1948-07-23 1950-07-04 Plax Corp Heat-treatment for plastic articles
US2612679A (en) * 1950-10-23 1952-10-07 Ladisch Rolf Karl Filaments containing fillers
US2674025A (en) * 1949-08-15 1954-04-06 Texiclon Corp Polymeric filaments
US2736946A (en) * 1952-07-03 1956-03-06 Dow Chemical Co Polyacrylonitrile fibers having a scaly integument
US2767435A (en) * 1952-06-05 1956-10-23 Du Pont Process for longitudinally stretching polymeric film

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2071251A (en) * 1931-07-03 1937-02-16 Du Pont Fiber and method of producing it
US2137235A (en) * 1937-02-15 1938-11-22 Du Pont Shaped articles from polymeric materials
US2278888A (en) * 1938-11-02 1942-04-07 Du Pont Artificial structure and process for producing same
US2302077A (en) * 1939-02-25 1942-11-17 Fibres Associates Inc Artificial wool filament and yarn
US2289232A (en) * 1939-07-14 1942-07-07 Du Pont Method and apparatus for producing filamentary structures
US2353023A (en) * 1940-08-06 1944-07-04 Freund Ernest Process for the treatment of cellulose acetate films
US2321635A (en) * 1940-11-26 1943-06-15 Du Pont Treatment of polyamide films
US2352725A (en) * 1941-11-04 1944-07-04 Du Pont Shaped product
US2423182A (en) * 1943-04-29 1947-07-01 Du Pont Method of cold-drawing tapered filaments
US2514088A (en) * 1948-07-23 1950-07-04 Plax Corp Heat-treatment for plastic articles
US2674025A (en) * 1949-08-15 1954-04-06 Texiclon Corp Polymeric filaments
US2612679A (en) * 1950-10-23 1952-10-07 Ladisch Rolf Karl Filaments containing fillers
US2767435A (en) * 1952-06-05 1956-10-23 Du Pont Process for longitudinally stretching polymeric film
US2736946A (en) * 1952-07-03 1956-03-06 Dow Chemical Co Polyacrylonitrile fibers having a scaly integument

Cited By (30)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3329557A (en) * 1955-04-06 1967-07-04 Du Pont Static resistant filament and process therefor
US3313591A (en) * 1958-03-06 1967-04-11 Du Pont Process of graft polymerizing ethylenically unsaturated monomers to solid, shaped polycarbonamides employing heat as the sole graft initiator
US3215486A (en) * 1962-04-17 1965-11-02 Toyo Spinning Co Ltd Fixation of polypropylene fibers impregnated with dyestuffs and other treating agents
US3247300A (en) * 1962-10-25 1966-04-19 Du Pont Process for producing highly crimped fibers having modified surfaces
US3472608A (en) * 1962-11-23 1969-10-14 Ici Ltd Polyester filaments and like structures
US3214234A (en) * 1963-05-21 1965-10-26 Phillips Petroleum Co Oriented foamed polyolefin extrudates and the production and dyeing of the same
US3446886A (en) * 1963-12-04 1969-05-27 Du Pont Process for treating linear polyesters to modify the surface appearance and characteristics thereof
US3439999A (en) * 1964-09-28 1969-04-22 Uniroyal Inc Cross-dyed carpets
US3494994A (en) * 1966-10-11 1970-02-10 Kuraray Co Method of producing polyurethane elastomer staple fibre
US3772747A (en) * 1968-03-18 1973-11-20 Rhodiaceta Process for producing textured yarn
USRE28406E (en) * 1968-03-18 1975-05-06 Rhodiaceta Process for producing textured yarn
US3920785A (en) * 1969-11-13 1975-11-18 Celanese Corp Process for increasing the porosity of opencelled microporous film
US3957936A (en) * 1971-07-22 1976-05-18 Raduner & Co., Ag High temperature process for modifying thermoplastic filamentous material
US3899563A (en) * 1971-12-06 1975-08-12 Allied Chem Synthetic fibers having improved soil and stain repellency
DE2354756A1 (de) * 1972-11-02 1974-05-09 Du Pont Aromatische polyamidfaser und verfahren zur herstellung derselben
US3888821A (en) * 1972-11-02 1975-06-10 Du Pont Aromatic polyamide fibers containing ultraviolet light screeners
FR2290528A2 (fr) * 1972-11-27 1976-06-04 M & T Chemicals Inc Nouveau procede de traitement de fibres et fibres obtenues
US4050892A (en) * 1973-09-13 1977-09-27 Martin Processing Co., Inc. Coloring polyester materials with acid dyes
US4013753A (en) * 1973-10-09 1977-03-22 Bayer Aktiengesellschaft Process for the production of spontaneously crimping polyacrylonitrile composite fibres with improved crimp properties
US3960686A (en) * 1974-01-04 1976-06-01 Chemische Werke Huls Aktiengesellschaft Method for preparing low pilling effect polyester fiber products
US4001367A (en) * 1974-03-29 1977-01-04 M & T Chemicals Inc. Method for permanently and uniformly incorporating an additive into an undrawn fiber
US3903221A (en) * 1974-05-08 1975-09-02 Du Pont Process and product
US4147749A (en) * 1975-08-14 1979-04-03 Allied Chemical Corporation Varied orientation of fibers
US4495126A (en) * 1982-12-02 1985-01-22 The Goodyear Tire & Rubber Company Adhesive activated emulsion to a polyester yarn
US5688596A (en) * 1992-05-07 1997-11-18 Teijin Limited Aromatic polyamide filament having an enhanced weathering resistance
US5443898A (en) * 1993-06-29 1995-08-22 Fiberweb North America, Inc. Nonwoven webs and method of making same
US5516473A (en) * 1993-09-30 1996-05-14 E. I. Du Pont De Nemours And Company Imbibition process
EP3135464A1 (en) * 2015-08-27 2017-03-01 Okia Optical Company Limited Method of making eyewear by 3d printing
CN106476263A (zh) * 2015-08-27 2017-03-08 澳加光学有限公司 运用3d打印制备眼镜的方法
CN114585778A (zh) * 2019-10-23 2022-06-03 兰精股份公司 辊表面

Also Published As

Publication number Publication date
CH395418A (de) 1965-12-31
CH7741059A4 (enrdf_load_stackoverflow) 1965-12-31
FR1236688A (fr) 1960-07-22
NL242714A (enrdf_load_stackoverflow)
GB905833A (en) 1962-09-12

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