US3322731A - Interpolymers of caprolactam, hexamethylene diamine, adipic acid and sebacic acid - Google Patents

Interpolymers of caprolactam, hexamethylene diamine, adipic acid and sebacic acid Download PDF

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US3322731A
US3322731A US275162A US27516263A US3322731A US 3322731 A US3322731 A US 3322731A US 275162 A US275162 A US 275162A US 27516263 A US27516263 A US 27516263A US 3322731 A US3322731 A US 3322731A
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shrinkage
yarn
tension
hose
filaments
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Cook Donald Bowker
Lange Ronald Frederick
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EIDP Inc
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EI Du Pont de Nemours and Co
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Priority to NL293085D priority Critical patent/NL293085A/xx
Application filed by EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Priority to US275162A priority patent/US3322731A/en
Priority to DEP31862A priority patent/DE1292308B/de
Priority to DK242963AA priority patent/DK114716B/da
Priority to FR935656A priority patent/FR1358008A/fr
Priority to LU43797D priority patent/LU43797A1/xx
Priority to CH640963A priority patent/CH456030A/de
Priority to GB20482/63A priority patent/GB1025098A/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/36—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino acids, polyamines and polycarboxylic acids
    • 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
    • D01F6/78—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products
    • D01F6/80—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from copolyamides
    • 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
    • Y10S264/56—Processes of molding lactams

Definitions

  • This invention relates generally to the melt-spinning of synthetic polymeric filaments and, more particularly, to the production of nylon filaments especially adapted for use in hosiery.
  • nylon has almost completely replaced silk and other fibers in the womens hosiery field.
  • nylon hosiery yarn is entirely suitable in most respects, there is a need for improvement, especially in connection with such factors as fit and comfort.
  • the hose which provides a good fit for one part of the leg does not provide an adequate fit in other places, e.g., if the hose fits properly at the ankle, the knee will be too tight.
  • stretch hose which provide improvements in fit and comfort due to their capability of adapting to the larger parts of the leg.
  • the greater portion of todays market is still held by nylon hose of standard construction and there is a continuing need for improvements in such factors as hose fit, comfort, aesthetics and durability, as well as in yarn processability.
  • the general objective of the present invention is to provide improved polyamide filaments for the production of hosiery.
  • a more specific objective is to provide uncrimped polyamide filaments which when processed into non-stretch hosiery provide better fit and comfort than can be obtained with commercially available synthetic filaments.
  • Another object is to provide hose having superior aesthetic qualities or, alternatively to provide hose of improved durability at equivalent aesthetic levels.
  • a filament prepared from the copolymer reaction product of hexamethylene diammonium adipate and caprolactam or from the terpolyrner reaction product of hexamethylene diammonium adipate, hexarnethylene diammonium sebacate, and caprolactam. Weight percentages of the above reactants may be varied within limits, as long as they fall in the area ABCDE shown in the appended drawing.
  • the filaments are further characterized by a Nuclear Magnetic Resonance (NMR) loosening factor of greater than 1.0 and an initial modulus no greater than 12 grams/ denier, as determined on filaments after boiling in water at 90l00 C. for 15 minutes.
  • NMR Nuclear Magnetic Resonance
  • the shrinkage tension of the yarn must be lower for a given shrinkage level than that found in prior art yarns, i.e., the ratio of shrinkage-tension/shrinkage must be low.
  • the yarn must have a low initial modulus and the shrinkage potential must be relatively high for use in hosiery leg yarn.
  • Filaments are prepared by melt extrusion of a copolymer or terpolymer fiake of the above-described composition, followed by quenching and cold-drawing to produce highly-oriented structures.
  • the drawn filaments are heat- 3322,73 l Patented May 30, 1967 ed under conditions of controlled relaxation, at a temperature and for a time sufficient to achieve an NMR loosening factor greater than 1.0 and a shrinkage-tension/ shrinkage ratio of less than 0.70.
  • a drawn filament of the prescribed composition has an NMR loosening factor of greater than 1.0, preferably at least 1.2, the desired shrinkage-tension/shrinkage ratio is achieved.
  • Nuclear magnetic resonance measurements indicate motional constraint of molecular segments in the filaments, the degree being shown by the width of a broad absorption band. This motional constraint has been labeled matrix rigidity. Since the shrinkage tension and shrinkage measurements are obtained in a hot 100 C.) water treatment, the matrix rigidity is measured in water at room temperature and at the boil. It is the difference in these measurements which is referred to herein as the loosening factor.
  • Matrix rigidity is measured using the nuclear magnetic resonance equipment of Varian Associates, model V-4302 dual purpose spectrometer, and using their high temperature probe insert Model No. V-433l-TWL and using 56.4 mc./s. radio frequency energy. Yarns are wrapped taut around very thin glass rods and the ends tied to prevent shrinkage during the heating experiment. This wrapping provides a random placement of the fiber axis with respect to the magnetic field direction so that an average NMR spectrum is obtained at any temperature. As described in J. G. Powles, Polymer, 1, 219-265 (1960), polymers give a broad absorption spectrum which can be characterized by halfwidth (peak-to-peak distance of the derivative output curve, expressed in gauss) herein called matrix rigidity.
  • Values are obtained, using 17 db attenuation of the RF field and with a sweep modulation of 1 gauss.
  • the vacuum dried yarns are soaked overnight in D 0 while wrapped taut and then are heated while immersed in excess D 0.
  • D 0 is used to prevent an NMR signal from the protons in H O.
  • Data points are obtained about every 5 C. while heating the yarn in the NMR instrument during an approximate two-hour period.
  • the matrix rigidity value at 100 C. is obtained as an extrapolation of the straight line through the data points between room temperature and about -98 C. This value at C. is subtracted from the matrix rigidity value of the soaked yarn at room temperature to obtain the loosening factor.
  • filament shrinkage is determined by measuring a length of the filament when held under sufiicient tension to keep it straight without stretching, subjecting the measured length to boiling water in a relaxed state for fifteen minutes, drying and measuring the boiled-off length. The percent shrinkage is then calculated from the two measurements.
  • Shrinkage tension is determined by removing a length of yarn from the package, permitting it to relax for 24 hours, placing a sample of the yarn between the jaws of a commercial Instron tester, the jaws being spaced 10 inches part, immersing the yarn sample in 90 C. Water for five minutes, withdrawing the then tensioned sample and permitting it to cool and dry at room temperature for five minutes. The tension in grams is then read from the Instron chart and converted to grams/ denier, the denier of the yarn before the test being determined by weighing a known length on a suitable balance.
  • the relaxed sample used in the shrinkage tension determination is conditioned at 74 F. and 72% r.h. before placement between the spaced Instron jaws and the test is carried out under these conditions.
  • the water bath used for immersion of the yarn is contained in a cylindrical vessel of about 6" diameter and 16" length. The vessel is situated just below the lower clamp of the tester and is moved vertically upward to immerse the sample. Hot water is circulated through the container, which is insulated, to maintain a temperature of 90:1 C. After the 5-minute immersion period the Water bath is moved downwardly to its original position. The top of the Water container is sealed with a rubber gasket to prevent water vapor from the hot Water escaping into the atmosphere around the sample While the sample is being intially positioned or While it is drying after immersion.
  • the shrinkage-tension/ shrinkage ratio mentioned above is calculated by dividing the shrinkage tension, measured in grams per denier, by the percent shrinkage in boiling water and multiplying the resulting quotient by 100.
  • Initial modulus is indicative of the rate at which yarn. elongates With increasing load in the early stages of elongation. Practically, it is determined from the stress-strain curve (obtained when the boiled off yarn is elongated 2% in an Instron tester) by multiplying the load at 1% elongation by 100 and dividing by the denier of the yarn.
  • Example I After charging 60.3 lbs. of a 48.8% aqueous solution of hexa-methylene diammonium adipate (66 nylon salt solution), 1.9 lbs. of 35.1% aqueous solution of hexamethylene diammonium sebacate (6-10 nylon salt solution) and 3.9 lbs. of caprolactam (i.e., 4.5 lbs. of e-EiIIllIlO caproic acid to which it hydrolyzes) to an evaporator, 9.3 lbs. of water are removed by evaporative heating at atmospheric pressure. The charge is then transferred to an autoclave, heated to a temperature of about 210 C. and brought to a pressure of 250 p.s.i.
  • the various batche of polymer are melted on a grid, extruded, air quenched and wound into packages at 361 yards/minute in the conventional manner.
  • the filaments are then cold drawn over a pin at a ratio of 4.74 and wound into a filling wound drawtwister package (15- denier monofilaments having a 0.5 Z-twist).
  • the cold drawn filaments prepared from most of the tabulated compositions, after standing for 24 hours, are given a hot annealing and relaxation treatment to lower the shrinkage level. This is accomplished by several passes of the filaments over a 3-inch steam-heated hot plate placed between two stepped rollers, the rollers having sufficient variation in diameter to permit .a retraction in length of 2.5%.
  • the hot plate temperature is varied from 150 to 200 C. depending upon the severity of heat treatment required to reduce boil-off shrinkage into the desired range of 12-15%.
  • the filaments contact the hot plate at a speed of 205 y.p.m.
  • Shrinkage tensions initial moduli and tenacities are measured on relaxed filaments from the above compositions, the modulus and tenacity measurements being made after boiling in water in a relaxed state and drying. For comparison, similar tests are made on filaments from 6 and 6-6 nylon. Results of these tests are reported in Table 1. Values for shrinkage, shrinkage-tension/shrinkage factor (m) and NMR loosening factor are also given.
  • the compositions listed in Table 1 are based upon starting materials, i.e., hexamethylene diammonium adipate, hexamethylene diammonium sebacate and e-amino caproic acid (to which caprolactam hydrolyzes).
  • the IS-denier filaments are knitted into hose in the conventional manner on a single-feed Scott and Williams seamless knitting machine (400 needles) to yield preboarded course counts of about c.p.i. (courses/inch) in the knee when measured on the table top.
  • Forty denier, 13-filament yarn of the same polymer composition is used for the welt, heel and toe regions of these hose which are preboarded using a board having a width of 6 inches at the knee, 4% inches at the calf and 2% inches at the ankle.
  • the hose, pulled down loosely on the board, are exposed to 6 p.s.i. steam for three minutes.
  • a number of hose prepared as described above are dyed according to standard conditions except for a lower dye bath temperature (150 F.) and then post-boarded at 180 F. for one minute.
  • the hose were subjected to wear tests in which they were worn by women having small, average and large legs. Each wearer rated the hose on fit, wrinkling and bagging in the ankle, calf, and knee.
  • hose knitted from commercial 6 and 6-6 nylon yarns were tested and rated in a similar fashion.
  • Many wearers having average size legs noticed an improvement in fit and comfort over hose from commercial yarns.
  • Those wearers with small legs found a very substantial improvement in fit and comfort when wearing the hose of this invention as compared to the commercial hose.
  • those wearers with large legs found the hose of this invention to be more comfortable and improved in fitting properties compared to hose from commercial yarn.
  • Copolymer fiage containing 85% 6 6 and 15% 6 poly mer units is prepared as described in Example I.
  • the polymer flake is coated with dry calcium terephthalate by the overlying filaments.
  • Such microcrimp reduces the yarn coefiicient of friction relative to that in the inner and outer layers.
  • the elfect is .a variation in length of successive hose knitted from the same yarn package.
  • Example III yarns F and G (Table 2) is 4.88, while that for yarns A copolymer Containing 85% 66 and 6 polymfir and J 18 15 units is prepared, extruded and cold drawn at a ratio
  • the yams are stlblected to 21,1101 anneahngfind relaxa' of 4.75 as described in Example H, except that the caltreengent' g 1S aeeempclllshed by g fi eg cium terephthalate is omitted. From the drawing step the m a er 0 Passes areun a Steppe.
  • the temperature of the heating element is shown the rollers and two passes around the smaller portions, in Table 3
  • Yams K and L are given 5 passes around the the percentage relaxanen. aehleved m gemg. from the larger portions of the rollers for constant length anneal- $552; 2. 3: g g g 323?; g i e g Table ing and 5 passes around the smaller portions to provide 0 5 hour ective] pbetween g i a 5 t 13% retraction in length.
  • Yarn M is given 10 passes treatment Whige H I and J a ng ea around the larger portions of the rollers and the relaxatinuousl with: n z r e eg i tion step is omitted.
  • the yarn is passed in contact with dully h k a i k i g i g 1a the heating element at a speed of 788 y.p.m.
  • Table Also shown 15 the factor and NMR loosening factor are shown in Table 3.
  • the coefficient of friction of the filaments containing calcium terephthalate is found to be about 0.51, as compared to a value of about 0.85 for similar filaments containing no calcium terephthalate.
  • the lower value indicates a modification of the surface to produce a filament which develops less friction and consequently less tension in passing through yarn guides in textile machinery.' This is confirmed when it is found that tension on the filaments during knitting is much more constant than is usually the case. Normally the tension varies appreciable due to the fact that the yarn in the middle of a package has a microcrimp as a result of having been compressed Hose prepared from the filaments of tihs invention are observed to have a softer and more pleasing hand than 6-6 nylon hose prepared from the same denier yarn.
  • the exemplified 20 denier filaments produce hose which are equivalent in hand and superior in durability to 15 denier 6-6 nylon hose.
  • the NMR loosening factor must be greater than 1.0 and preferably at least 1.2. It is also necessary that the filaments have a low initial modulus.
  • the desired structure is obtained by selection of a polymer compositron from those copolymers and terpolymers defined by the area ABCDE in the drawing and by processing of filaments from this composition under carefully selected conditions. While it will be noted that cold-drawn fila ments from the polymer composition of this invention sometimes yield a low shrinkage-tension/ shrinkage factor, such filaments have a much lower tenacity than the heattreated filaments and the shrinkage is undesirably high. Such filaments do not exhibit the desired NMR loosening factor.
  • the colddrawn filaments must be allowed to stand for at least about 30 minutes and then subjected to a hot annealing and relaxation treatment, the relaxation being of the order of 2-3%.
  • the cold drawing and heat treatment may be carried out continuously, in which case a relaxation of about 12-15% is required to achieve the desired structure.
  • polymer systems outside the area ABCDE do not give the desired shrinkage-tension/ shrinkage factor and, in some instances, the filament tenacity is too low. Tenacities below about 4.0 g.p.d. after boil-off are undesirable for producing hosiery of satisfactory durability.
  • the preferred polymers are the copolymers of 6-6 and 6 nylon which fall within the prescribed area.
  • the shrinkage of the filament in boiling water should fall in the range of about 845%, in order that hose of the desired fit and comfort be attained. With lower shrinkages, hose cannot be shrunk down to fit a board having the necessary dimensions to achieve satisfactory fit for wearers having legs of smaller than average size. Welt yams will, of course, have a lower shrinkage.
  • the low initial modulus of the filaments of this invention contributes a great deal to improvements in fit and comfort and is also important inproducing a hose with a softer hand. It is thus possible to produce a more durable hose by increasing the filament denier Without suffering any disadvantage in aesthetics. For instance, 20 denier monofilaments of the present invention may be substituted for 15 denier monofilaments of 6-6 nylon with no loss in aesthetic properties. In order to achieve the desired level of aesthetics, the initial modulus after heating in 90100C. water should be no higher than 12 g.p-.d.
  • Filament properties are further enhanced by the incorporation therein of a finely divided salt of terephthalic acid as a surface modifying agent.
  • the salt should be dispersed in amounts ranging from 0.l%, preferably 0.253%, by weight of the interpolymer.
  • the preferred salt is calcium terephthalate.
  • An oriented filament consisting essentially of an interpolymer composition selected from the group consisting of:
  • the terpolymer of from 5% to 20% of e-amino caproic acid, up to 20% of hexamethylene diammonium sebacate and from 75% to 90% of hexamethylene diammonium adipate, all percentages expressed being by weight, the said filament being characterized by a shrinkage tension to shrinkage ratio of less than 0.7 and a boil-off shrinkage of 815%, wherein the shrinkage tension is determined by immersing a given length of yarn into water at a temperature of 90 C.il C. for about five minutes, restraining the yarn to prevent shrinkage, withdrawdrawing the sample and allowing it to dry at room temperature for about five minutes, and measuring the yarn tension in grams/ denier.
  • the filament of claim 1 further characterized by an initial modulus no greater than 12 grams/denier and a tenacity of at least 4 grams/ denier, said initial modulus and said tenacity being determined after relaxed state boil-01f of said filament.
  • the filament of claim 1 further characterized by an nuclear magnetic resonance loosening factor greater than 1 and an initial modulus no greater than 12 grams/ denier, said initial modulus being determined after relaxed state boil-off of said filament.
  • interpolymer composition is a substantially 85:15 co olymer of hexamethylene diammonium adipate and e-amino caproic acid, respectively, all percentages expressed being by weight.
  • interpolymer composition is a substantially 85:2: 13 terpolymer of hexamethylene diammonium adipate, hexamethylene diammonium sebacate and eamino caproic acid, respectively, all percentages expressed being by weight.
  • An oriented nylon filament consisting essentially of an interpolymer composition selected from the group consisting of (l) the copolymer of from 10% to 20% of e-amino caproic acid and from 80% to 90% of hexamethylene diammonium adipate, and
  • the terpolymer of from 5% to 20% of e-amino caproic acid, up to 20% of hexamethylene diammonium sebacate and from to 90% of hexamethylene diammonium adipate, all percentages expressed being by weight, the said filament being characterized by an nuclear magnetic resonance loosening factor greater than 1 and an initial modulus no greater than 12 grams/denier, said initial modulus being determined after relaxed state boil-off of said filament.
  • An oriented nylon filament useful in the knitting of hosiery consisting essentially of the copolymer of from 10% to 20% of e-amino caproic acid and from to hexamethylene diammonium adipate, all percentages expressed being by weight, the said filament characterized by a shrinkage tension to shrinking ratio of less than 0.7, a boil-off shrinkage of 8-15%, an initial modulus no greater than 12 grams/denier and a tenacity of at least 4 grams/denier, wherein the shrinkage tension is deter mined by immersing a given length of yarn into water at a temperature of 90 Oil C.
  • the filament of claim 7 further characterized by an nuclear magnetic resonance loosening factor of at least 1.2.
  • An oriented nylon filament useful in the knitting of hosiery consisting essentially of the terpolymer of from 2% to 20% or hexamethylene diammonium sebacate, from 5% to 20% of eamino caproic acid, and from 75% to 90% of hexamethylene diammonium adipate, all percentages expressed being by weight, the said filament characterized by a shrinkage tension to shrinkage ratio of less than 0.7, a boil-off shrinkage of 8-15%, an initial modulus no greater than 12 grams/denier and a tenacity of at least 4 grams/denier, wherein the shrinkage tension is determined by immersing a given length of yarn into water at a temperature of 90 C.i1 C.
  • the filament of claim 9 further characterized by an nuclear magnetic resonance loosening factor of at least 1.2.
  • composition of matter consisting essentially of the terpolymer of from 2% to 20% hexamethylene diammonium sebacate, from 5% to 13% of e-amino caproic acid and from 75% to 90% of hexamethylene di-arnmonium adipate, all percentages expressed being by Weight,
  • an oriented filament consisting essentially of said 1 composition is characterized by an nuclear magnetic resonance loosening factor greater than 1 and a boil-01f shrinkage of from 8%-15%.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Proteomics, Peptides & Aminoacids (AREA)
  • Medicinal Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Artificial Filaments (AREA)
  • Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
US275162A 1962-05-22 1963-04-23 Interpolymers of caprolactam, hexamethylene diamine, adipic acid and sebacic acid Expired - Lifetime US3322731A (en)

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Application Number Priority Date Filing Date Title
NL293085D NL293085A (xx) 1962-05-22
US275162A US3322731A (en) 1962-05-22 1963-04-23 Interpolymers of caprolactam, hexamethylene diamine, adipic acid and sebacic acid
DK242963AA DK114716B (da) 1962-05-22 1963-05-21 Fremgangsmåde til fremstilling af et strakt polyamidfilament til anvendelse i trikotagegarn.
DEP31862A DE1292308B (de) 1962-05-22 1963-05-21 Faeden aus Mischpolyamiden
FR935656A FR1358008A (fr) 1962-05-22 1963-05-22 Perfectionnements aux filaments formés d'amides polymérisés plus spécialement destinés à la bonneterie
LU43797D LU43797A1 (xx) 1962-05-22 1963-05-22
CH640963A CH456030A (de) 1962-05-22 1963-05-22 Verstreckter Polyamidfaden
GB20482/63A GB1025098A (en) 1962-05-22 1963-08-22 Improvements relating to nylon filaments

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US19674462A 1962-05-22 1962-05-22
US275162A US3322731A (en) 1962-05-22 1963-04-23 Interpolymers of caprolactam, hexamethylene diamine, adipic acid and sebacic acid

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CH (1) CH456030A (xx)
DE (1) DE1292308B (xx)
DK (1) DK114716B (xx)
GB (1) GB1025098A (xx)
LU (1) LU43797A1 (xx)
NL (1) NL293085A (xx)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3417174A (en) * 1964-10-26 1968-12-17 Du Pont Process of preparing yarn and knitting hose
US3520949A (en) * 1966-07-26 1970-07-21 Nat Patent Dev Corp Hydrophilic polymers,articles and methods of making same
US3542745A (en) * 1968-10-29 1970-11-24 Monsanto Co Terpolyamides useful in preparing textile fibers consisting essentially of nylon 66,nylon 6,and nylon 2-6ia
US3607610A (en) * 1967-01-31 1971-09-21 Asahi Chemical Ind Crimped composite filaments of polycaprolactam or polyhexamethylene adipamide, and a terpolyamide of e-caprolactam, hexamethylenediammonium adipate, hexamethylene diammonium sebacate
US3621089A (en) * 1965-09-16 1971-11-16 Ici Ltd Process for spinning dye-resistant copolyamide filaments
US3632416A (en) * 1967-10-27 1972-01-04 Nat Patent Dev Corp Fibrous textile materials impregnated with hydroxyalkyl methacrylate casting syrups
US3667207A (en) * 1970-05-01 1972-06-06 Du Pont Crimpable composite polyamide yarn
US3675408A (en) * 1969-12-31 1972-07-11 Ici Ltd Polyamide filaments
US3989678A (en) * 1972-09-13 1976-11-02 Toyo Boseki Kabushiki Kaisha Hot melt adhesives comprising copolymeric polyamides
US4559196A (en) * 1984-04-12 1985-12-17 E. I. Du Pont De Nemours And Company Process for improving the dyeability of nylon carpet fiber

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB8915736D0 (en) * 1989-07-10 1989-08-31 Du Pont Improvements to multifilament apparel yarns of nylon
US5185428A (en) * 1991-06-21 1993-02-09 E. I. Du Pont De Nemours And Company Copolyadipamide containing pentamethyleneadipamide units and products prepared therefrom

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US2252555A (en) * 1939-04-04 1941-08-12 Wilmington Trust Co Polymeric material
US2285009A (en) * 1941-02-24 1942-06-02 Du Pont Interpolyamide
US2298868A (en) * 1940-04-03 1942-10-13 Du Pont Synthetic polyamide filaments of high impact strength and process of making same
GB574956A (en) * 1943-12-31 1946-01-28 Ici Ltd Improvements in or relating to the manufacture of synthetic linear polyamide yarn
US2880057A (en) * 1958-01-22 1959-03-31 Du Pont Treatment of filaments to improve strength in tension
US3003222A (en) * 1958-11-17 1961-10-10 Du Pont Controlled relaxation of freshly drawn nylon

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Publication number Priority date Publication date Assignee Title
FR895906A (fr) * 1942-06-20 1945-02-07 Zellwolle Kunstseide Ring Gmbh Procédé de fabrication de corps conformés en produits de polycondensation du type superpolyamide

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2252555A (en) * 1939-04-04 1941-08-12 Wilmington Trust Co Polymeric material
US2298868A (en) * 1940-04-03 1942-10-13 Du Pont Synthetic polyamide filaments of high impact strength and process of making same
US2285009A (en) * 1941-02-24 1942-06-02 Du Pont Interpolyamide
GB574956A (en) * 1943-12-31 1946-01-28 Ici Ltd Improvements in or relating to the manufacture of synthetic linear polyamide yarn
US2880057A (en) * 1958-01-22 1959-03-31 Du Pont Treatment of filaments to improve strength in tension
US3003222A (en) * 1958-11-17 1961-10-10 Du Pont Controlled relaxation of freshly drawn nylon

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3417174A (en) * 1964-10-26 1968-12-17 Du Pont Process of preparing yarn and knitting hose
US3621089A (en) * 1965-09-16 1971-11-16 Ici Ltd Process for spinning dye-resistant copolyamide filaments
US3520949A (en) * 1966-07-26 1970-07-21 Nat Patent Dev Corp Hydrophilic polymers,articles and methods of making same
US3607610A (en) * 1967-01-31 1971-09-21 Asahi Chemical Ind Crimped composite filaments of polycaprolactam or polyhexamethylene adipamide, and a terpolyamide of e-caprolactam, hexamethylenediammonium adipate, hexamethylene diammonium sebacate
US3632416A (en) * 1967-10-27 1972-01-04 Nat Patent Dev Corp Fibrous textile materials impregnated with hydroxyalkyl methacrylate casting syrups
US3542745A (en) * 1968-10-29 1970-11-24 Monsanto Co Terpolyamides useful in preparing textile fibers consisting essentially of nylon 66,nylon 6,and nylon 2-6ia
US3675408A (en) * 1969-12-31 1972-07-11 Ici Ltd Polyamide filaments
US3667207A (en) * 1970-05-01 1972-06-06 Du Pont Crimpable composite polyamide yarn
US3989678A (en) * 1972-09-13 1976-11-02 Toyo Boseki Kabushiki Kaisha Hot melt adhesives comprising copolymeric polyamides
US4559196A (en) * 1984-04-12 1985-12-17 E. I. Du Pont De Nemours And Company Process for improving the dyeability of nylon carpet fiber

Also Published As

Publication number Publication date
LU43797A1 (xx) 1964-11-22
NL293085A (xx)
DK114716B (da) 1969-07-28
DE1292308B (de) 1969-04-10
GB1025098A (en) 1966-04-06
CH456030A (de) 1968-05-15

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