US3416302A - Differential shrinkage yarn - Google Patents
Differential shrinkage yarn Download PDFInfo
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- US3416302A US3416302A US667095A US66709567A US3416302A US 3416302 A US3416302 A US 3416302A US 667095 A US667095 A US 667095A US 66709567 A US66709567 A US 66709567A US 3416302 A US3416302 A US 3416302A
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- yarn
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- shrinkage
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Classifications
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- D—TEXTILES; PAPER
- D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
- D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
- D02G1/00—Producing crimped or curled fibres, filaments, yarns, or threads, giving them latent characteristics
- D02G1/18—Producing crimped or curled fibres, filaments, yarns, or threads, giving them latent characteristics by combining fibres, filaments, or yarns, having different shrinkage characteristics
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- 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
- D01D5/22—Formation of filaments, threads, or the like with a crimped or curled structure; with a special structure to simulate wool
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- 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
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- 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
Definitions
- a yarn comprising a plurality of differentially shrin-kable drawn continuous filaments including a high shrinkage group of filaments and a lower shrinkage group of filaments, the filaments of each said group being constituted by a polycarbonamide wherein at least 50 mol percent of the repeating units are of the formula:
- x represents 1 or 2
- y represents an integer in the range of 7-14
- R represents the same or different member of the class consisting of hydrogen and methyl
- said yarn being typified by exhibiting a DFL greater than 1.0% after being subjected to a load of 4 mg. per denier during boil-off and increasing at least 0.5% in DFL after being subjected to heat-setting at 177 C. for two minutes under the same total load.
- the yarn of the present invention comprises a plurality of continuous, oriented polycarbonamide filaments selected from at least two groups of different shrinkage.
- the filaments consist of polycarbonamides, wherein at least 50 mol percent of the repeating units are of the formula R R I wherein x is 1 or 2, y is an integer in the range of 7-14, R is the same or different member of the class consisting of hydrogen and methyl.
- the yarns of the invention when subjected to boiling water exhibit a DFL greater than 1.0% under a load of 4 mg.d., and increasingat least 0.5 in DFL when subjected to heat setting as described below.
- one of the aforesaid groups of filaments in the yarn comprise a high shrinkage group and the other, a low shrinkage group. Their selection will be described in more detail below.
- the diamino portion of Formula I due to its carbocyclic nature, is a mixture of isomers having trans-trans (tt), cis-trans (ct), and cis-cis (cc) configurations.
- Hydrogenation conditions employed in preparing the diamines used in the polymer synthesis results in a mixture of isomers, different conditions of hydrogenation producing a different isomer distribution as shown in US. 2,494,563 and US. 2,606,924.
- the different groups of filaments in the yarn are provided by combining a first group of filaments consisting essentially of a polycarbonamide having repeating units of Formula I and a second group of filaments consisting of a polyamide containing from 50 to mol percentage of the repeating units of Formula I and 5 to 50 mol percentage of another polyamide unit prepared from a member of a class consisting of (1) the same diamine as employed for production of the Formula I repeat unit with a different dicarboxylic acid and (2) the same dicarboxylic acid as employed for production of the Formula I repeat unit with the different diamine.
- both groups of filaments are constituted by polymers which consist essentially of the units of Formula I, there being substantially less, i.e., at least about 10% by weight less of the trans-trans, cistrans or cis-cis diamino units in the polymer units of the polycarbonamide constituting the second group of filamerits than in the polycarbonamide constituting the first group of filaments.
- both groups of filaments are prepared from polymers which consist essentially of the units of Formula I, the second group of filaments being constituted by polycarbonamide having a lower relative viscosity, i.e., at least about 9 units less than the polycarbonamide constituting the first group of filaments.
- the percent difference in filament length (DFL) between the high and low shrinkage filaments is determined as follows: A strand of yarn such as a representative 40- centimeter strand, containing both high and low shrinkage filaments, is separated from the boiled and dried skein, cut at each tie point, doubled and the free ends tied together to form a loop. The free ends above the knot are taped to a meter rule and the length of the in dividual filament loops measured by hanging a 0.6 g. paper clip in each loop. At least low shrinkage and 5 high shrinkage filaments are measured in this manner. The percent DFL is calculated from the following equation:
- L is the average length of the longer filaments and L is the average length of the shorter filaments.
- the DFL after exposure to heat setting temperature is measured by hanging a similarly boiled-off, air dried skein in an oven at 177 C. for 2 minutes under the same total load as was used in boil-off and then determining the DFL as described above for the boiled-oif skein.
- relative viscosity signifies the ratio of the flow time in a viscometer of a polymer solution relative to the flow time of the solvent by itself. Measurements of relative viscosities as referred to herein and as measured in the examples is determined from a solution of 3.7 grams of polyamide in 50 ml. of a 1:1 mixture of 98100% formic acid and phenol at 25 C., unless otherwise noted.
- Orientation index is measured on the high and low shrinkage filaments separately by means of flat-plate wide-angle X-ray diffraction patterns.
- the oriented fibers, spun and drawn as described herein, show a unique diffraction feature consisting of a well-defined meridional reflection which occurs at a Bragg spacing of about 11.4 A. for polymers prepared with dodecanedioic acid and at slightly different spacings for polymers of different unit lengths.
- the existence of this well defined meridional spot allows the development of the orientation parameter, herein called the orientationindex, in samples of widely varying degrees of crystallinity.
- This orientation index is obtained by measuring the peak or maximum intensities of this meridional diffraction spot and that of the equatorial diffraction, or amorphous halo, found at the Bragg spacing of about 4.7 A. This index is calculated as the ratio of the meridional spot of maximum intensity divided by the maximum intensity of the equatorial region. The intensities are measured on the X-ray negatives using conventional microphotometry techniques. The diffraction patterns are obtained in a conventional manner on a sample of the yarn taking care to assure that all of the filaments in the yarn are aligned in an exactly parallel fashion. A sample thickness of no more than 20 mils is used with a sample to film distance of 7.5 cm.
- Exposure times for the X-ray negatives should be such that the microphotometer registers optical densities not exceeding 1.0 and not less than 0.10. Analysis of both regions must be made on the same X-ray negative. Careful microphotometer technique must be employed to be certain of measuring the maximum densities in both the meridional and equatorial directions and also in order to compute the proper background correction pertinent to each trace, which is subtracted from the total density prior to calculating the orientation index.
- the yarn of the invention will consist of about an equal amount (by wgt.) of high and low shrinkage filaments. These proportions can of course be varied.
- Percent DFL As a rule, the higher the difference in shrinkage, the lower the weight percentage of high shrinkage filaments required to produce meaningful results in fabric. A minimum of about 10% by weight of high shrinkage filaments is believed necessary for the yarn to display the desired effect. Within the range of shrinkage differential of about 1.5% to about 10%, at least about 25% by weight of each (the high and low shrinkage) component is preferred. To improve yarn stability, i.e., to keep coring (migration and aggregation of the high shrinkage component) and/0r cracking (separation of components) to a minimum when yarn shrinkage occurs, the filaments of the yarn should be cospun or intimately interlaced.
- Example 1 A polymer is prepared in an autoclave containing 50 parts water and 50 parts of the salt of bis-(4-aminocyclohexyl)methane and dodecanedioic acid.
- the diamine consists of 70% of the tt isomer.
- a viscosity stabilizer 12 millimoles of acetic acid are added for each mole of the polyamide salt.
- the solution also contains 0.005% manganous hypophosphite, based on the weight of the salt.
- This solution is heated under 350 p.s.i. for 2 hours while the temperature is raised a sufficient amount of a 20% aqueous slurry of finely-divided kaolinite being added when the temperature reaches 210 C. to provide a concentration of 2% by weight of the kaolinite in the final polymer.
- the pressure is then reduced to atmospheric while the temperature is raised to 315 C. and the polymer held under 14.3" vacuum for 1 hour. It is then extruded and cut to flake.
- the relative viscosity of the flake is 45.9.
- a copolymer is prepared from a salt of bis-(4-aminocyclohexyl)methane and a mixture of dodecanedioic and isophthalic acids.
- the mixed acids contain 8.7% -by weight of isophthalic acid which is sufficient to provide 10% by weight or 12.3 mole percent of the isophthalic copolymer component in the final polymer.
- the diamine contains 70% of the tt isomer and 6.8 millimoles acetic acid per mole of salt is used.
- the relative viscosity of the flake is 52.5.
- the polymer and copolymer are melted separately at 325 C. in screw type melters. They are then extruded simultaneously through different holes in the same spinneret at 325 C. to form 34 trilobal filaments (17 from each polymer), as described in U.S. 3,225,534.
- the relative viscosity of the homopolymer filaments is 36.2 while that of the copolymer filaments is 34.7.
- the filaments from the two polymers are quenched and' then passed over a finish applicator roll where a conventional lubricating finish is applied.
- the filaments then pass to a pair of power-driven feed rolls rotating at a peripheral speed of 800 yds./min. After the feed rolls, the yarn passes around a draw pin heated at C.
- the yarn then passes to a pair of annealing rolls rotating at a peripheral speed of 1680 yds./ min., the yarn being heated at ISO- C. on these rolls.
- the yarn is then interlaced to provide a cohesive filament bundle as described by Bunting and Nelson in US. 2,985,995.
- the yarn is then passed to a pair of unheated rolls, rotating at a peripheral speed of 1689 yds./min., and is then wound into a package in the conventional manner at 1650 yds./min.
- the yarn is given six passes around the feed rolls, eight passes around the draw and annealing rolls, and six passes around the final unheated rolls.
- the denier of the final yarn is 63.
- the shrinkage of the yarn in boiling water with 4 mg.d. load is 9.4% and the DFL is 5.7%.
- the yarn shrinkage is 32% and the DFL is 34.5%.
- mild mechanical treatment may, for instance, consist of striking, rubbing, brushing, or vibrating. Such treatment during the electrical treatment will not only fold out but also spread the material out.
- the sheet material is in a spread-out condition wherein the individual fibrils, making up the material, are parallel to the longitudinally axis of the sheet material.
- this is a desirable configuration.
- the yarn used in the manufacture therein should not be lean and smooth but rather should have a high percentage of loose-fibrils along the surface of the web or sheet as the case may be.
- it is essential to use a bulky yarn which is not produced under the process described in the above-identified patent.
- My invention resides in forming a pile fabric from this polymeric sheet material as it emerges from the foldingout step.
- a plurality of rollers 54 are shaped to form a crown 56 at their centers.
- the fibrils in the central portion of film 10 passing over the crown 56 will break while those in the edge portion of the film passing over the edge of the roller will not.
- This action of crowned rollers 54 causes the fibrils in the center portion of sheet 10 to break.
- This web is particularly useful in making yarn and as such it is twisted by conventional yarn twisting means as it is wound onto a spool 58.
- rollers 13, 54 (only one roller is shown; however, it would be within the skill of the art to connect a plurality of crowned rollers into the mechanism) and 29 are connected to a suitable driving mechanism 30.
- This mechanism comprises an endless belt or chain 32 which passes over a pulley or sprocket 34 which is fixed to roller 54, then over a sprocket 36 which is fixed to roller 13, then over a sprocket 38 which is fixed to roller 29, then over an idler sprocket 40, then over a drive sprocket 42, which is driven by any suitable power source such as electric motor 44, and finally back over sprocket 34.
- the rollers 12, 13, 54, 28, and 29 are rotated in the directions shown by the arrows.
- roller 22 is provided with a plurality of grooves 24 and a plurality of needles 26- or other similar sharp, pointed implements, which project radially from the center of the grooves 24. These needles may be secured in the grooves 24 in any suitable manner.
- portions of it are channelled into the grooves 24 and become impaled upon the needles which penetrate through the sheet material and cause a portion of the individual fibrils to be severed.
- the degree of breakage would be determined by the number of grooves in the roller and the number of pins in the grooves; however, no more than one-half of the fibers passing over the roller should be broken in order to retain sufiicient web strength.
- rollers 28 and 29 which are also rotatably mounted in the frame plates 14 and 16. These rollers feed the bulky sheet material to a suitable take-up mandrel (not shown).
- FIGURE 5 illustrates another embodiment of my invention.
- a roller 46 contains a plurality of grooves 48 around the perimeter thereof. These grooves are cut at an angle of 45 to the horizontal axis 50 of the roller 46.
- This roller 46 is attached to frames 14 and 16 in place of roller 22.
- a plurality of knife blades 52 are positioned around the circumference of roller 53 rotatably mounted between the vertical frames 14 and 16 a predetermined distance from roller 46.
- the sheet 10 is passed between the roller and the blade.
- the blade 52 is rotated in close enough proximity to the roller 46 so that portions of the film 10 pass over the crown of the grooves 48 and are cut by the rotating blades 52.
- a 60-inch wide fibrillated web of 0.8 mil polyethylene, having a density of 0.95 gram/cc. and a melt index of 0.3 (ASTM D 123 8-5DT, Condition E), is threaded through the machine described in FIGURE 2.
- a chopper roller 53 is provided with 12 tempered spring steel blades 52 around its circumference. The blades 52 coact with a 12-inch diameter grooved roller 46, made of mild steel and coated to a thickness of 60 mils with durometer rubber.
- Each groove 48 in roller 46 defines an ellipse in a plane making a 45 angle with the roller axis.
- These grooves are Aa-inch wide, Aa-inch deep, and spaced so that their centers are fli-inch apart, and having all their edges and corners chamfered and rounded on a -inch radius.
- Bulk film is fed to roller 12 at the rate of 20 feet per minute while the machine is being adjusted to insure clean, uniform cuts. After adjustment, the rate is increased to feet per minute and about 2000 feet of the material is fed through the machine.
- Air filters 2 /2 feet square are produced from some of this material by laminating 21 layers of this bulked film together, each layer being laid at right angles to the adjacent layers 21 and being stitched together in both directions across the film at 6-inch intervals with cotton string and subsequently edged with an aluminum channel having a As-inch flange.
- Example 11 The rollers 46 and 53 are replaced with a 12-inch diameter pin-studded roller 22 similar to that shown in FIGURE 4.
- the grooves 24 are /2-inch center-to-center with a sharp 60 included angle peak between the grooves.
- equally spaced cylindrical pins 26 are positioned wherein each pin is 7 -inch in diameter and has a flat, sharp edged top portion located -inch below the peaks.
- Web material similar to that used in Example I is threaded through the machine and the machine is started and run at an initial rate of about 15 feet per minute output while adjustments of the film tension over the pinstudded roller 22 are made. After adjustment, the rate is increased to 150 feet per minute to produce approximately raised to 375 p.s.i. The temperature is then raised to 300 C.
- Titanium dioxide is added as described for the A polymer.
- the pressure is then reduced to atmospheric over a 90-minute period while the temperature is raised to 320 C.
- the polymer is held with a nitrogen sweep at this temperature for 1 hour and then extruded and cut to flake in the conventional manner.
- Polymers A and B are melted separately in screw-type melters at temperatures of 290 and 320 C. respectively and extruded simultaneously as described in Example 1 at 306 C. to form 34 trilobal filaments.
- the relative viscosity (measured with 5.5 grams of polyamide in 50 ml. of 98% formic acid) of the filaments containing 55% tt isomer is 56.7 while that of the 70% tt filaments is 39.4.
- the filaments from the two polymers are quenched and passed over a finish applicator roll where a conventional lubricating finish is applied. The filaments are then wound into a package at 750 y.p.m.
- the yarn is drawn and given a hot annealing treatment as follows:
- the yarn passes from the supply package around the feed rolls and then is given 5 passes around a first heating element, which is heated to a temperature of 120 C.
- the yarn is given five passes around an unheated draw roll and associated separator roll, the draw roll having a peripheral speed of 454 y.p.m. sufiicient to draw the yarn to a ratio of 2.43.
- From the draw roll the yarn passes to another roll having the same peripheral speed as the draw roll Where it passes 5 times around this roll and an associated separator roll and heating element, the heating element being at a temperature of 175 C.
- the yarn passes to a third roll having the same peripheral speed as the draw roll where it passes 5 times around this roll and an associated separator roll and heating element, the heating element being at a temperature of 175 C. From this roll the yarn passes to a fourth roll having the same peripheral speed where it is given two turns around the roll and its associated separator roll to permit the yarn to cool before being wound into the package.
- the denier of the final yarn is 66.
- the yarn shrinkage under a load of 4 mg.d. in boiling Water is 9% while the DFL is 6.2%.
- Example 1 When the yarn is woven into a plain weave fabric and given a fabric finishing treatment involving relaxed scouring and heat-setting as in Example 1, the resulting fabric is found to be much superior to similar fabrics of mixed shrinkage 66 nylon yarn in regard to wash-wear characteristics, bulk, covering power and aesthetics.
- Example 5 A 26-denier, 10 filament yarn contain ng 5 trilobal high shrinkage and 5 trilobal low shrinkage filaments is prepared following substantially the same procedure as described in Example 3 except that the draw ratio is 2.7 and the spinning speed is 465 yds./min. The molecular weight of the 45 tt filaments is 17,500 while that of the 80 tt filaments is 10,900. The DFL is 3.0%. The yarn is processed into a long float tricot knit fabric of 64 wales and 50 courses. The fabric is scoured in boiling water and then dried. The fabric is then heat-set in a relaxed state at 190 C. for seconds. The fabric bulk is 6.18 cc./gram as compared to 3.76 cc./gram for a 30-denier, 10 filament commercial nylon tricot fabric of 60 wales and 58 courses which was finished in identical fashion.
- Example 6 Following the general procedure of Example 3, a 45 tt isomer polymer having a relative viscosity of 40.2 and an 80 tt isomer polymer having a relative viscosity of 23.9 are prepared.
- the polymers are cos-pun as described in Example 4 to form a 10 filament yarn which is then wound into a package in the conventional manner.
- the yarn is then cold drawn over a pin on a draw winder at a draw ratio of 2.35. From the draw roll, the yarn is passed to another power-driven roll and an associated separator roll, there being a C. heated shoe located between the power-driven roll and separator roll to contact the yarn as it passes around the two rolls.
- the yarn is given 5 wraps around these rolls, then passed to another powerdriven roll, and then wound into a package at a speed of 450' yds./min.
- the average DFL for the yarn is 4.1%.
- the yarn is processed into a tricot knit fabric, scoured and dried. Samples of the fabric are then heat-set in a relaxed state at various temperatures for 20 seconds. At C., the bulk is 5.8 cc./ gram, while at 192 C. the bulk has increased to 6.65 cc./gram.
- Example 7 A homopolymer is prepared in an autoclave containing 40 parts water and 60 parts of the salt of bis-(4-aminocyclohexyl)methane and dodecanedioic acid.
- the diamine contains 70% of the tt isomer.
- a viscosity stabilizer 12 millimoles of acetic acid are added for each mole of the polyamide salt.
- the solution also contains 0.005% manganous hypophosphite, based on the weight of the salt.
- This solution is heated under 350 p.s.i. for 2 hrs. while the temperature is raised. Heating is continued and a sufficient amount of finelydivided kaolinite is added when the temperature reaches 200 C. to provide a concentration of 5% by weight of the kaolinite in the final polymer.
- the pressure is then reduced to atmospheric while the temperature is raised to 315 C. and the polymer held under nitrogen for 3 hrs. During this period, nitrogen ispassed through the autoclave at a low rate to remove additional water. It is then extruded and cut to flake. The relative viscosity of the flake is 29.9.
- a copolymer (A) is prepared from a salt of dodecanedioic acid and a mixture of 70% tt bis- (4-aminocyclohexyl)methane and meta-xylylenediamine.
- the mixed diamines contain 8.1% by weight of metaxylylenediamine, which is sufiicient to provide 10% by weight of 11.90 mol percent of the corresponding polymer units in the final copolymer.
- Sutficient finely-divided kaolinite is added during polymerization to provide a concentration of 2% by weight of the polymer.
- the relative viscosity of the flake is 43.1.
- another copolymer (B) is prepared from the salt of dodecanedioic acidand a mixture of 70% tt bis- 4-aminocyclohexyl)methane and hexamethylenediamine.
- the mixed diamines contain 11.3% by weight of hexamethylenediamine, which is sufficient to provide 15% by Weight or 18.8 mol percent of the corresponding polymer units in the final copolymer.
- Sulficient finely-divided kaolinite is added during polymerization to provide 2% by weight of the polymer.
- the relative viscosity of the flake is 46.2.
- the homopolymer and the copolymer from dodecanedioic acid and the mixture of bis-(4-aminocyclohexyl) methane and meta-xylylenediamine are melted separately and extruded as in Example 1 to form a mixture of 17 round cross-section homopolymer filaments and 17 round cross-section copolymer filaments.
- the spinnert face is blanketed with steam at 250 C.
- the filaments are processed as in Example 1 except that the interlacing step is omitted and the feed roll speed is 1349 y.p.m., the draw roll speed 3000 y.p.m., the annealling roll speed 2804 y.p.m.
- the yarn is wound into a package at 2805 y.p.m. and the denier of the final yarn is 60.
- the relative viscosity of the homopolymer after extrusion is 31 and that of the copolymer is 44.8.
- a 60 denier yarn containing a mixture of 17 homopolymer filaments and 17 copolymer filaments is prepared from the homopolymer and the copolymer prepared from the mixture of bis-(4-aminocyclohexyl)methane and 'hexamethylenediamine and dodecanedioic acid following the procedure outlined above except that the speed of the final unheated rolls is 2848 y.p.m. and the winding speed Portions of this salt are placed in heavy walled glass polymer tubes.
- the tubes are flushed with nitrogen, evacuated, sealed, and heated for 2 hrs. at 250 C.
- the tubes are then opened and the solid from each tube transferred to a large test tube fitted with a stopper containing an inlet tube.
- the tube is then heated in a steam atmosphere at 305 C. for 2 or 3 hrs.
- the polymers from the various tubes are then combined.
- the relative viscosity of the combined polymer is 60.1.
- the salt of bis-(4-aminocyclohexyl)methane and isophthalic acid is added 21 g. of the salt of bis-(4-aminocyclohexyl)methane and isophthalic acid.
- the latter salt is prepared by adding a solution of 42.8 g. of 70% tt bis-(4-aminocyclohexy1)methane in about 200 ml. of isopropanol to 33.2 g. of isophthalic acid in about 1500 ml. of isopropanol, filtering off the salt and drying at 70 C. under vacuum.
- the salts are thoroughly blended together and the mixture placed in glass polymer tubes. The tubes are heated at 280300 C. for about 2 hrs.
- the tubes are then opened and the solid from each tube transferred to a larger test tube fitted with a stopper containing an inlet tube.
- the polymerization is then completed by heating this material in a steam atmosphere for 2 hrs. at 325 C.
- the combined polymer from these tubes has a relative viscosity of 50.7.
- the copolymer prepared in this manner should contain 10% by weight of the isophthalic polymer units.
- the filaments are processed in accordance with Example 11, except that the temperature of the hot shoe between the draw roll andseparator roll is 140 C. and the draw pin temperature is 65 C.
- the denier of the final yarn is 130.
- the relative viscosity of the polymer after extrusion, as measured on the extruded filaments, is 95.8 for the homopolymer and 83.9 for the copolymer.
- the shrinkage and DFL of the yarn after ;bo iling in water under a load of 4 mg.d. are 9.7% and 3.7%, respectively. After boiling and under a load of 4 mg.d. and heat-setting under the same total load, the shrinkage is 18.7% and the DFL is 6.3%.
- Example 13 A polymer prepared from the salt of 70% tt bis-(4- aminocyclohexyl)methane and dodecanedioio acid is extruded to form 34 trilobal cross-section filaments, and the filaments quenched following substantially the procedure of Example 7.
- the relative viscosity of the polymer flake prior to extrusion is 86.5 and the spinneret face is blanketed with steam at 160 C.
- the filaments are passed for 6 wraps around a pair of feed rolls rotating at a peripheral speed of 1150 y.p.m. On leaving the feed rolls, the filaments are separated into two bundles of 17 filaments.
- One filament bundle is passed to and around a 1% inch tube heated to 120 C., then to a pair of 150 C. draw rolls rotating at a peripheral speed of 1435 y.p.m., then to a pair of unheated rolls rotating at a peripheral speed of 1425 y.p.m.
- the other filament bundle is passed from the feed rolls to and around a 6-inch drum heated to 120 C., then to a pair of 180 C. draw rolls rotating at 1410 y.p.m. From the draw rolls the filaments are passed to the unheated rolls, referred to above, where they are combined with the first group of filaments and given 8 wraps around these rolls.
- the combined filament bundle is then passed successively through two interlacing jets of the type described by Dahlstrom and Wert in their US.
- Patent No. 3,069,836 the air flow of the two jets being in opposite directions.
- the yarn is then wound into a package in the conventional manner at 1390 y.p.m.
- the crystalline orientation index of the filaments measured as previously described, is 1.60 for the high shrinkage filaments, i.e., those heated at 150 C., and 2.86 for the low shrinkage filaments.
- the shrinkage is 10.3% and the DFL 4.6%.
- the yarns of this invention may be prepared by mixing the high and low shrinkage filaments as described in the examples or, if desired, the high and low shrinkage filaments may be extruded from diflerent spinnerets and combined as they pass over a finish roll or by other suitable means. Alternately, the filaments may be intermingled by passing them through an air jet or other device where they are subjected to the action of a turbulent fluid which interlaces and intermingles the filaments.
- the filaments may be of round or non-round shape as desired, but generally it is preferable to use non-round filaments such as the multilobal and shield shapes of US. 2,939,201 and US. 2,939,202.
- the yarns of this invention contain a durable antistatic agent.
- the antistatic agent should generally be present in a concentration of at least 2% by weight of the filament and may be added to either or both of the polymeric compositions used in producing these yarns.
- Suitable antistatic agents include the high molecular weight poly(alkylene ethers), i.e., those in the molecular weight of 1300 to 200,000. Agents of this type which may be used are described in England Patent No. 963,320.
- the yarns of this invention may also contain suitable heat stabilizers, antioxidants, light stabilizers, ultraviolet light absorbers, delustrants, pigments, dyes, and the like. Other polymer additives may be present to improve dyeability, soil repellence, crease resistance, hand, water repellence, wickability, strength, elongation, modulus, static propensity, or melting point of the fiber.
- the draw ratios employed with the yarns of this invention tend to be somewhat lower than those employed with yarns prepared from polymers such as 6 or 66. Draw ratios in the range of about 1.4 to 3.0 may be employed to produce satisfactory yarns, the exact ratio selected depending on the polymer viscosity and the spinning speed, the ratio being low when the viscosity and spinning speed are relatively high.
- the yarns may be cold drawn or may be hot drawn at temperatures up to -180 C. with satisfactory results. Application of heat in the drawing zone is not essential but is frequently desirable to reduce the drawing tension.
- the yarn may be run over a series of heated rolls, hot plates, or other suitable heating elements. Where heated rolls of the type described in the examples are employed, temperatures in the range of l10160 C. are usually adequate to achieve the desired reduction in yarn shrinkage. The exact temperature must, of course, be chosen depending on such variables as polymer viscosity, isomer content, copolymer compositions, etc.
- differential shrinkage yarns may be prepared from a single polymer by processing two groups of filaments in such a manner as to produce a lower orientation in mild mechanical treatment may, for instance, consist of striking, rubbing, brushing, or vibrating. Such treatment during the electrical treatment will not only fold out but also spread the material out.
- the sheet material is in a spread-out condition wherein the individual fibrils, making up the material, are parallel to the longitudinally axis of the sheet material.
- this is a desirable configuration.
- the yarn used in the manufacture therein should not be lean and smooth but rather should have a high percentage of loose-fibrils along the surface of the web or sheet as the case may be.
- it is essential to use a bulky yarn which is not produced under the process described in the above-identified patent.
- My invention resides in forming a pile fabric from this polymeric sheet material as it emerges from the foldingout step.
- a plurality of rollers 54 are shaped to form a crown 56 at their centers.
- the fibrils in the central portion of film 10 passing over the crown 56 will break while those in the edge portion of the film passing over the edge of the roller will not.
- This action of crowned rollers 54 causes the fibrils in the center portion of sheet 10 to break.
- This web is particularly useful in making yarn and as such it is twisted by conventional yarn twisting means as it is wound onto a spool 58.
- rollers 13, 54 (only one roller is shown; however, it would be within the skill of the art to connect a plurality of crowned rollers into the mechanism) and 29 are connected to a suitable driving mechanism 30.
- This mechanism comprises an endless belt or chain 32 which passes over a pulley or sprocket 34 which is fixed to roller 54, then over a sprocket 36 which is fixed to roller 13, then over a sprocket 38 which is fixed to roller 29, then over an idler sprocket 40, then over a drive sprocket 42, which is driven by any suitable power source such as electric motor 44, and finally back over sprocket 34.
- the rollers 12, 13, 54, 28, and 29 are rotated in the directions shown by the arrows.
- roller 22 is provided with a plurality of grooves 24 and a plurality of needles 26- or other similar sharp, pointed implements, which project radially from the center of the grooves 24. These needles may be secured in the grooves 24 in any suitable manner.
- portions of it are channelled into the grooves 24 and become impaled upon the needles which penetrate through the sheet material and cause a portion of the individual fibrils to be severed.
- the degree of breakage would be determined by the number of grooves in the roller and the number of pins in the grooves; however, no more than one-half of the fibers passing over the roller should be broken in order to retain sufiicient web strength.
- rollers 28 and 29 which are also rotatably mounted in the frame plates 14 and 16. These rollers feed the bulky sheet material to a suitable take-up mandrel (not shown).
- FIGURE 5 illustrates another embodiment of my invention.
- a roller 46 contains a plurality of grooves 48 around the perimeter thereof. These grooves are cut at an angle of 45 to the horizontal axis 50 of the roller 46.
- This roller 46 is attached to frames 14 and 16 in place of roller 22.
- a plurality of knife blades 52 are positioned around the circumference of roller 53 rotatably mounted between the vertical frames 14 and 16 a predetermined distance from roller 46.
- the sheet 10 is passed between the roller and the blade.
- the blade 52 is rotated in close enough proximity to the roller 46 so that portions of the film 10 pass over the crown of the grooves 48 and are cut by the rotating blades 52.
- a 60-inch wide fibrillated web of 0.8 mil polyethylene, having a density of 0.95 gram/cc. and a melt index of 0.3 (ASTM D 123 8-5DT, Condition E), is threaded through the machine described in FIGURE 2.
- a chopper roller 53 is provided with 12 tempered spring steel blades 52 around its circumference. The blades 52 coact with a 12-inch diameter grooved roller 46, made of mild steel and coated to a thickness of 60 mils with durometer rubber.
- Each groove 48 in roller 46 defines an ellipse in a plane making a 45 angle with the roller axis.
- These grooves are Aa-inch wide, Aa-inch deep, and spaced so that their centers are fli-inch apart, and having all their edges and corners chamfered and rounded on a -inch radius.
- Bulk film is fed to roller 12 at the rate of 20 feet per minute while the machine is being adjusted to insure clean, uniform cuts. After adjustment, the rate is increased to feet per minute and about 2000 feet of the material is fed through the machine.
- Air filters 2 /2 feet square are produced from some of this material by laminating 21 layers of this bulked film together, each layer being laid at right angles to the adjacent layers 21 and being stitched together in both directions across the film at 6-inch intervals with cotton string and subsequently edged with an aluminum channel having a As-inch flange.
- Example 11 The rollers 46 and 53 are replaced with a 12-inch diameter pin-studded roller 22 similar to that shown in FIGURE 4.
- the grooves 24 are /2-inch center-to-center with a sharp 60 included angle peak between the grooves.
- equally spaced cylindrical pins 26 are positioned wherein each pin is 7 -inch in diameter and has a flat, sharp edged top portion located -inch below the peaks.
- Web material similar to that used in Example I is threaded through the machine and the machine is started and run at an initial rate of about 15 feet per minute output while adjustments of the film tension over the pinstudded roller 22 are made. After adjustment, the rate is increased to 150 feet per minute to produce approximately 17 ments in the steric configuration of the diamino constituent by at least 10% by weight in a steric form.
- a yarn consisting essentially of two groups of continuous oriented polycarbonamide filaments of different shrinkage, the first group of said filaments being constituted by a polycarbonamide wherein at least 50 mol percent of the repeating units are of the formula:
- x is 1 or 2
- y is an integer in the range of 7-14
- R is the same or difierent member of the class consisting of hydrogen and methyl
- the second group of said filaments being constituted by a polycarbonamide consisting essentially of the units of Formula I and having a relative viscosity that is at least about 9 units less than that of the polycarbonamide constituting the said first group of filaments.
- a yarn consisting essentially of two groups of continuous oriented polycarbonamide filaments of different shrinkage, the first group of said filaments being constituted by a polycarbonamide wherein at least 50 mol percent of the repeating units are of the formula:
- R is the same or different member of the class consisting of hydrogen and methyl, and the second group of said filaments being constituted by a polycarbonamide consisting essentially of the units of Formula I wherein the chain length of the diacid constituent of the polymer units constituting the said second group of filaments is less than the chain length of the diacid constituent of the polymer units constituting the said first group of filaments.
- a yarn consisting essentially of two groups of continuous oriented polycarbonamide filaments of diiferent shrinkage, the first group of said filaments being constituted by a polycarbonamide where at least 50 mol percent of the repeating units are of the formula:
- H r r r t R X R R wherein x is 1 or 2, y is an integer in the range of 7-14, R is the same or different member of the class consisting of hydrogen and methyl, and the second group of said filaments being constituted by a polycarbonamide consisting essentially of the units of Formula I, the said second group of filaments having an Orientation Index that is at least about 1.0 greater than that of said first group of filaments.
- a yarn consisting essentially of two groups of continuous oriented polycarbonamide filaments of different composition and diflFerent shrinkage, the first group of said filaments being constituted by a polycarbonamide wherein at least 50 mol percent of the repeating units are of the formula:
- x is 1 or 2
- y is an integer in the range of 7-14
- R is the same or different member of the class consisting of hydrogen and methyl
- the second group of said filaments being constituted by a copolyamide containing from 50 to mol percent of the repeating units of Formula I and 5 to 50 mol percent of another polyamide unit prepared from a member of the class consisting of (1) the same diamine as employed for production of Formula I repeat unit with a different dicarboxylic acid and (2) the same dicarboxylic acid as employed for production of the Formula I repeat unit with a ditferent diamine, said yarn exhibiting a DFL greater than 1.0% after being subjected to a load of 4 mg.d. during boil-01f and increasing at least 0.5% in DFL after being subjected to heat-setting at 177 C. for two minutes under the same total load.
- each of said first and second groups of filaments is present to the extent of at least 25% by weight of the yarn.
- the yarn of claim 13 consisting essentially of said first and second groups of filaments, wherein about 5% by weight of the diamino constituent of the repeating units of Formula I in both of said groups of filaments is in the cis-cis configuration and at least 50% by Weight of the repeating units of one of said groups is in the trans-trans configuration.
- the yarn of claim 6 consisting essentially of said first and second groups of filaments, wherein about 5% by weight of the diamino constituent of the repeating units of Formula I in both of said groups of filaments is in the cis-cis configuration and at least 50% by Weight of the repeating units of one of said groups is in the transtrans configuration.
- each of said first and second groups of filaments is present to the extent of at least 25 by weight of the yarn.
- the yarn of claim 7 consisting essentially of said first and second groups of filaments, wherein about 5% by weight of the diamino constituent of the repeating units of Formula I in both of said groups of filaments is in the cis-cis configuration and at least 50% by weight of the repeating units of one of said groups is in the trans-trans configuration.
- each of said first and second groups of filaments is present to the extent of at least 25 by weight of the yarn.
- the yarn of claim 8 consisting essentially of said first and second groups of filaments, wherein about 5% by weight of the diamino constituent of the repeating units of Formula I in both of said groups of filaments is in the cis-cis configuration and at least 50% by weight of the repeating units of one of said groups is in the trans-trans configuration.
- each of said first and second groups of filaments is present to the extent of at least 25 by weight of the yarn.
- the yarn of claim 9 consisting essentially of said first and second groups of filaments, wherein about 5% by weight of the diamino constituent of the repeating units of Formula I in both of said groups of filaments is in the cis-cis configuration and at least 50% by weight of the repeating units of one of said groups is in the trans-trans configuration.
- each of said first and second groups of filaments is present to the extent of at least 25% by weight of the yarn.
- the yarn of claim 25 consisting essentially of said high and low shrinkage groups of filaments.
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Artificial Filaments (AREA)
- Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
- Polyamides (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Priority Applications (14)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US667095A US3416302A (en) | 1967-01-10 | 1967-09-12 | Differential shrinkage yarn |
IL29206A IL29206A (en) | 1967-01-10 | 1967-12-25 | Polycarbonamide yarn |
DK657967A DK132340C (da) | 1967-01-10 | 1967-12-29 | Blandet polyamidfilamentgarn |
SE18123/67A SE325100B (pt) | 1967-01-10 | 1967-12-29 | |
PL1968124509A PL88874B1 (pt) | 1967-01-10 | 1968-01-03 | |
ES348990A ES348990A1 (es) | 1967-01-10 | 1968-01-05 | Un procedimiento de preparacion de un hilo de encogido mix-to de filamentos continuos orientados de poliamida. |
AT16768A AT303951B (de) | 1967-01-10 | 1968-01-08 | Endloses Garn aus Polycarbonamid |
NL686800315A NL144673B (nl) | 1967-01-10 | 1968-01-09 | Werkwijze voor de vervaardiging van een gemengde kunstmatige draad of garen bestaande uit een aantal georienteerde polyamide-elementairdraden met verschillend krimpvermogen. |
FR1583192D FR1583192A (pt) | 1967-01-10 | 1968-01-09 | |
GB0489/68A GB1216883A (en) | 1967-01-10 | 1968-01-10 | New polyamide yarns |
CH31868A CH529239A (de) | 1967-01-10 | 1968-01-10 | Multifilamentgarn aus orientierten Polycarbonamid-Einzelfilamenten |
BE709143D BE709143A (pt) | 1967-01-10 | 1968-01-10 | |
DE19681794328 DE1794328C3 (de) | 1967-01-10 | 1968-01-10 | Polyamid-Mischgarn |
SU1210424A SU381233A3 (pt) | 1967-01-10 | 1968-01-10 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US60828167A | 1967-01-10 | 1967-01-10 | |
US667095A US3416302A (en) | 1967-01-10 | 1967-09-12 | Differential shrinkage yarn |
Publications (1)
Publication Number | Publication Date |
---|---|
US3416302A true US3416302A (en) | 1968-12-17 |
Family
ID=27085717
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US667095A Expired - Lifetime US3416302A (en) | 1967-01-10 | 1967-09-12 | Differential shrinkage yarn |
Country Status (13)
Country | Link |
---|---|
US (1) | US3416302A (pt) |
AT (1) | AT303951B (pt) |
BE (1) | BE709143A (pt) |
CH (1) | CH529239A (pt) |
DK (1) | DK132340C (pt) |
ES (1) | ES348990A1 (pt) |
FR (1) | FR1583192A (pt) |
GB (1) | GB1216883A (pt) |
IL (1) | IL29206A (pt) |
NL (1) | NL144673B (pt) |
PL (1) | PL88874B1 (pt) |
SE (1) | SE325100B (pt) |
SU (1) | SU381233A3 (pt) |
Cited By (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3495392A (en) * | 1968-06-26 | 1970-02-17 | Du Pont | Bulky dyed yarns |
US3526084A (en) * | 1967-12-11 | 1970-09-01 | Burlington Industries Inc | Production of unique yarns |
US3583147A (en) * | 1969-06-30 | 1971-06-08 | Du Pont | Heat-set mechanically crimped filaments having different polyamide compositions |
US3725358A (en) * | 1971-04-12 | 1973-04-03 | Phillips Petroleum Co | Polyamide fibers from mixture of 1,3-bis-(4-piperidyl) propane and bis(p-aminocyclohexyl) methane |
US3732684A (en) * | 1971-02-23 | 1973-05-15 | Du Pont | Product and process |
US3839299A (en) * | 1972-11-27 | 1974-10-01 | Phillips Petroleum Co | Amorphous polyamide from bis(4-aminocyclohexyl)methane, bis(carboxyphenyl)methane and alkylene dicarboxylic acid |
US3846379A (en) * | 1970-07-04 | 1974-11-05 | Dynamit Nobel Ag | Polyamide shock absorber piston from terephthalic acid and branched diamine |
US3851457A (en) * | 1969-03-10 | 1974-12-03 | Ici Ltd | Core yarns and methods for their manufacture |
US3936426A (en) * | 1971-12-21 | 1976-02-03 | Phillips Petroleum Company | Amorphous, optically clear polyamide from a bis(4-aminocyclohexyl)methane and a phenylindan dicarboxylic acid |
US3939636A (en) * | 1973-08-24 | 1976-02-24 | Toray Industries, Inc. | Mixed yarn |
US3998042A (en) * | 1972-09-26 | 1976-12-21 | E. I. Du Pont De Nemours And Company | Mixed shrinkage yarn |
DE2715860A1 (de) * | 1976-04-15 | 1977-10-20 | Phillips Petroleum Co | Verfahren zur herstellung von polyamiden |
FR2374447A1 (fr) * | 1976-12-15 | 1978-07-13 | Du Pont | Fil multifilament a titre variable et son procede de fabrication |
US4100725A (en) * | 1975-07-25 | 1978-07-18 | E. I. Du Pont De Nemours And Company | Yarn having alternating entangled and unentangled lengths |
US4792624A (en) * | 1987-02-26 | 1988-12-20 | The Dow Chemical Company | Process for polymeric MDA, recycle of finished polymeric MDA |
US5058371A (en) * | 1989-11-30 | 1991-10-22 | Monsanto Company | Continuous filament yarn for trackless carpet |
CN102877182A (zh) * | 2011-07-15 | 2013-01-16 | 东丽纤维研究所(中国)有限公司 | 一种聚酰胺纤维缝纫线及其生产方法 |
-
1967
- 1967-09-12 US US667095A patent/US3416302A/en not_active Expired - Lifetime
- 1967-12-25 IL IL29206A patent/IL29206A/xx unknown
- 1967-12-29 DK DK657967A patent/DK132340C/da active
- 1967-12-29 SE SE18123/67A patent/SE325100B/xx unknown
-
1968
- 1968-01-03 PL PL1968124509A patent/PL88874B1/pl unknown
- 1968-01-05 ES ES348990A patent/ES348990A1/es not_active Expired
- 1968-01-08 AT AT16768A patent/AT303951B/de not_active IP Right Cessation
- 1968-01-09 NL NL686800315A patent/NL144673B/xx not_active IP Right Cessation
- 1968-01-09 FR FR1583192D patent/FR1583192A/fr not_active Expired
- 1968-01-10 CH CH31868A patent/CH529239A/de not_active IP Right Cessation
- 1968-01-10 SU SU1210424A patent/SU381233A3/ru active
- 1968-01-10 GB GB0489/68A patent/GB1216883A/en not_active Expired
- 1968-01-10 BE BE709143D patent/BE709143A/xx unknown
Non-Patent Citations (1)
Title |
---|
None * |
Cited By (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3526084A (en) * | 1967-12-11 | 1970-09-01 | Burlington Industries Inc | Production of unique yarns |
US3495392A (en) * | 1968-06-26 | 1970-02-17 | Du Pont | Bulky dyed yarns |
US3851457A (en) * | 1969-03-10 | 1974-12-03 | Ici Ltd | Core yarns and methods for their manufacture |
US3583147A (en) * | 1969-06-30 | 1971-06-08 | Du Pont | Heat-set mechanically crimped filaments having different polyamide compositions |
US3846379A (en) * | 1970-07-04 | 1974-11-05 | Dynamit Nobel Ag | Polyamide shock absorber piston from terephthalic acid and branched diamine |
US3732684A (en) * | 1971-02-23 | 1973-05-15 | Du Pont | Product and process |
US3725358A (en) * | 1971-04-12 | 1973-04-03 | Phillips Petroleum Co | Polyamide fibers from mixture of 1,3-bis-(4-piperidyl) propane and bis(p-aminocyclohexyl) methane |
US3936426A (en) * | 1971-12-21 | 1976-02-03 | Phillips Petroleum Company | Amorphous, optically clear polyamide from a bis(4-aminocyclohexyl)methane and a phenylindan dicarboxylic acid |
US3998042A (en) * | 1972-09-26 | 1976-12-21 | E. I. Du Pont De Nemours And Company | Mixed shrinkage yarn |
US3839299A (en) * | 1972-11-27 | 1974-10-01 | Phillips Petroleum Co | Amorphous polyamide from bis(4-aminocyclohexyl)methane, bis(carboxyphenyl)methane and alkylene dicarboxylic acid |
US3939636A (en) * | 1973-08-24 | 1976-02-24 | Toray Industries, Inc. | Mixed yarn |
US4100725A (en) * | 1975-07-25 | 1978-07-18 | E. I. Du Pont De Nemours And Company | Yarn having alternating entangled and unentangled lengths |
DE2715860A1 (de) * | 1976-04-15 | 1977-10-20 | Phillips Petroleum Co | Verfahren zur herstellung von polyamiden |
FR2374447A1 (fr) * | 1976-12-15 | 1978-07-13 | Du Pont | Fil multifilament a titre variable et son procede de fabrication |
US4792624A (en) * | 1987-02-26 | 1988-12-20 | The Dow Chemical Company | Process for polymeric MDA, recycle of finished polymeric MDA |
US5058371A (en) * | 1989-11-30 | 1991-10-22 | Monsanto Company | Continuous filament yarn for trackless carpet |
CN102877182A (zh) * | 2011-07-15 | 2013-01-16 | 东丽纤维研究所(中国)有限公司 | 一种聚酰胺纤维缝纫线及其生产方法 |
Also Published As
Publication number | Publication date |
---|---|
CH529239A (de) | 1972-10-15 |
DE1794328A1 (de) | 1971-08-12 |
BE709143A (pt) | 1968-07-10 |
PL88874B1 (pt) | 1976-10-30 |
DK132340C (da) | 1976-04-26 |
ES348990A1 (es) | 1969-08-16 |
SU381233A3 (pt) | 1973-05-15 |
NL6800315A (pt) | 1968-07-11 |
DK132340B (da) | 1975-11-24 |
DE1794328B2 (de) | 1976-09-09 |
AT303951B (de) | 1972-12-27 |
IL29206A (en) | 1971-04-28 |
GB1216883A (en) | 1970-12-23 |
NL144673B (nl) | 1975-01-15 |
SE325100B (pt) | 1970-06-22 |
FR1583192A (pt) | 1969-10-24 |
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