US2948583A - Process for producing shaped oriented polyester articles having a metallic luster - Google Patents

Process for producing shaped oriented polyester articles having a metallic luster Download PDF

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Publication number
US2948583A
US2948583A US719124A US71912458A US2948583A US 2948583 A US2948583 A US 2948583A US 719124 A US719124 A US 719124A US 71912458 A US71912458 A US 71912458A US 2948583 A US2948583 A US 2948583A
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Prior art keywords
yarn
drawn
filament
temperature
metallic luster
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US719124A
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English (en)
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Dustin S Adams
Ernst Albert
Robert S Prengle
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EIDP Inc
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EI Du Pont de Nemours and Co
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Priority to NL236752D priority Critical patent/NL236752A/xx
Priority to BE576348D priority patent/BE576348A/xx
Application filed by EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Priority to US719124A priority patent/US2948583A/en
Priority to GB7024/59A priority patent/GB903914A/en
Priority to CH7033959A priority patent/CH373859A/de
Priority to FR788312A priority patent/FR1224340A/fr
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Publication of US2948583A publication Critical patent/US2948583A/en
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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
    • 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
    • D01F6/62—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyesters
    • 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
    • Y10S8/04—Polyester fibers

Definitions

  • This invention relatesto synthetic polyester films and filaments. More particularly, it relates to a process for producing polyethylene terephthalate films, ribbons and filaments which have a metallic luster.
  • process- 2 V producing the lustrous articles comprises drawing an article of the aforementioned polymeric ester, which has an initial birefringence of not more than'tltll, at its natural draw ratio at a temperature below 80 C. to at least 5.0 times its original length at a drawing speed of at least 0.75 yard per minute and less than 50 yards per minute.
  • a polyethylene terephthalate article is shaped so that the initial birefringence is below 0.01, the drawing temperature is between 25 C. and 75 C., and drawing from 5.0 to 7.0 times the original length is accomplished at a drawing speed of from 2.to 17 yards ing baths and the like must be selected so that they will not damage the material.
  • surface abrasion and adhesion problems that is, separation of the metal coating from the polymer base, have been experienced.
  • the elasticity of the polymer base can not be fully utilized because the elasticity of the metal coating is a limiting feature.
  • the manufacturing proc esses and the equipment required to perform these processes are complicated and expensive.
  • High molecular weight condensation polymers particularly the polyesters of the type described in Whinfield and Dickson, US. Patent No. 2,465,319 have been utilized in preparing films and filaments.
  • polyester filaments of uniform denier which have a metallic luster have heretofore been unknown.
  • Markwood, 'U .S. Patent No. 2,352,- 725 does describe a process for producing a pearlescent effect in polyamide filaments.
  • a highly oriented and uniformly drawn shaped article comprised of a cold-drawn highly polymeric ester of a dicarboxylic acid and a dihydric alcohol, said ester being. capable of being formed into filaments which when cold-drawnshow by'characteristic X-ray pattern molecular orientation along the fiber axis, elongated voids along the fiber axis, a metallic luster, and a densityof from 0.6 to 1.3 grams per cubic centimeter. The processfor per minute.
  • films, ribbons and filaments are meant to include and will be used interchangeably throughoutthe specification with the term yarn.
  • the phrase natural draw ratio is meant a draw ratio at which a certain degree of permanent, nonreversible extension, which is just sufiicient to change it from its undrawn state to'a uniformly drawn'and highly oriented state without straining the polymeric material so as to introduce surface cracks or failure, is given to the polymeric material.
  • a draw ratio at which a certain degree of permanent, nonreversible extension, which is just sufiicient to change it from its undrawn state to'a uniformly drawn'and highly oriented state without straining the polymeric material so as to introduce surface cracks or failure, is given to the polymeric material.
  • the plastic flow method of drawing is used to elongate a polymeric material 10, 2O oreven times its original length. However, in the plastic-flowprocess only slight orientation of the material occurs. Plastic flow drawing isnormally carried out eitherat high temperatures or in the presence of plasticizers, or both.
  • Drawing speed is another critical term in the process which must be defined.
  • the present process employs a necking-down step in which the yarn diameter is sharply reduced within a short axial length. Immediately preceding the neck the yarn is essentially unoriented and beyond the neck the yarn is highly oriented.
  • drawing speed it is meant the rate at which fullydrawn material'is caused to move'relative to -the drawing neck. For purposes of convenience the drawing speed is measured in yards per minute. r V
  • the temperature at which this drawingtakes place is also highly critical. In citing the drawing temperature, the temperature of the yarn just prior to the point where it starts to draw is referred to. At this point the temperature is controlled by the temperature of the surroundings. If the yarn is wrapped on a pin or caused to contact a flat surface for some distance, it will approach thermal equilibrium with the-surface it contacts. If the yarn is keptfor severalminutes in contact with air;heat to-a certain temperature, equilibrium will also be established.
  • the yarn At the drawing point or' neck, the yarn will, of course, be much hotter. It has not been possible to measure this temperature accurately, but it is estimated that the yarn temperature approaches the melting point of the polymer.
  • Figure 1 is a schematic drawing-showing a preferred embodiment of apparatus for the continuous drawing process of this invention
  • Figure 2 is a schematic drawing in section showin suitable apparatus for drawing small lengths of yarn.
  • Figure 3 is a graph showing the relationship between the drawing temperature of a polyethylene terephthalate yarn and the natural draw ratio at certain drawing'speeds.
  • reference numeral 1 represents an essentially unoriented yarn which is withdrawn from a source not shown and passed around feed rollers 2 and '3.
  • the axes of the feed rollers are positioned at a slight angle to each other to cause a separation of the yarn helices and an advancement of the 'yarn'along the rollers-
  • the yarn is arranged with a 'sufficient number of turns about the feed rollers to prevent "slippage.
  • Yam 1 must have a birefringence of not more than 0.01 and is preferably at room temperature.
  • the yarn is passed from the feed rollers over or adjacent to a heated tube 4 whereby it is heated to a temperature of not'more than 80 C., preferably from 25 C. to 75 C.
  • the yarn is then passed to drawing rollers 5 and 6 which are operated at a speed sufiiciently greater than the feeding rollers to draw the yarn from 5.0 to 7.0 times its original length.
  • the speed of the drawing rollers is regulated so that the drawing takes place at the natural draw ratio.
  • the axes of the drawing rollers are positioned at a slight angle in the same manner as described for the feed rollers.
  • the yarn is arranged with a sufficient number of turns about the set of rollers to prevent slippage.
  • the yarn is passed through traversing device 7 and then wound up on bobbin 8 which "may be rotated'by means of the surface of drive roller 9.
  • the yarn draws at its natural draw ratio with a sharp necklocated within a stable narrow zone near heated tube 4.
  • reference numeral 10 represents an insulated box in which electrical heating means 12 and temperature control "means 13 are positioned, A sample of yarn 14 is placed in'the box, heated, and withdrawn through opening 11. "This apparatus and its use will :be further described in "discussing the graph of Figure 3.
  • the natural draw ratio of polyester filaments is primarily controlled by the drawing temperature and the "'drawing speed.
  • a particular drawing temperature there will be a corresponding natural draw ratio at which the undrawn polyester material will preferentially elongate to the highly oriented, uniformly drawn, lustrous state. Therefore, when the drawing temperature is selected according -to'the process of this invention, the draw ratio is determined-to conform to this condition.
  • concrete board box 10 was made with a small opening 11, one inch by one-half inch, on one side. Electrical heating means 12 and temperature control means 13 were placed inside the box. Forced air circulation was used to maintain a constant, uniform temperature throughout the box.
  • a sample of undrawnpolyethylene terephthalate yarn 14 having a birefringence of 0.0003 was attached to a fixture 15 on the insideof the box opposite the small opening and creased at the fixture. The box was maintained at the desired temperature for ten minutes, during which time the yarn reached thermal equilibrium with this temperature. The loose end of the yarn was then attached to a windup roller 16 and the yarn pulled from the box at a constant speed. As soon as the slack was removed from the yarn, thematerialstarted to neck-draw at the crease.
  • the neck of the drawn yarn moved toward the windup roll at'a speed governed by the windup speed and the natural draw ratio.
  • the yarn selected its own natural drawratio as determined by the temperature and the windup speed. .
  • the drawing operation was stopped when the draw point emerged from the box.
  • the temperature gradient in the yarn can be provided by various means other than the heated tube 4 shown in Figure 1.
  • a hot surface which the yarn is caused to contact, having heating units distributed below the Surface so that the yarn temperature increases along the path, may be used.
  • the yarn may be passed between two heated elements.
  • other thermal barriers such as a liquid or gas interface can be employed. as can other radiant heating-apparatus.
  • the filament will draw at its natural draw ratio in a very short distance.
  • the polymeric material becomes interspersed with a'large number of tiny, elongated voids.
  • These voids are gener-' ated within the boundaries of the ribbon or filament and are in no way to be confused with a milky appearance due to surface cracks or internal, brittle failure which is
  • the drawn ribbon has a very thin, clear skin.
  • filaments produced by this process have a metallic luster.
  • the products of the present invention are superior to and entirely different from laminated or coated structures containing, for example, metal foil or deposited metal film.
  • the lustrous product of this invention reflects and refracts light which strikes the filament at any angle.
  • the physical properties of the materials of this invention are not limited by the elasticity of a metal or by'a bond between the'filamentnn'd laminate,*orby'thephemical stability of a metal or Comparison of laminated and deposited metal, (alumiestates coarser materials can be used to prepare products as have beenconventionally prepared with the prior art metallized structures.
  • the finer forms have many new applications in the area of decorative fabrics, for example, lam fabrics which heretofore were produced only with relatively heavy yarn to give the metallic appearance.
  • These new materials may be used in'fabrics now employing conventional polyester fibers for making articles such as blouses, shirts, sheer knitted goods, tricot fabrics, and the like.
  • the density of the material is extremely low due tothe presence of theincluded voids.
  • Commercial polyethylene terephthalate fibers have a density of about 1.4.
  • the present materials are produced with a density range of from 0.6 to 1.3 with a density of from 0.6 to 1.0 being preferred. Of course, if the density is below 1.0, the yarn will float on water. Because of the low density, a greater length of yarn of a given cross-sectional area may be obtained from When the products of the present invention are ob tained in physical dimensions equivalent to prior art laminated structures, the new products exhibit outstanding advantages in strength and elasticity. Table 1 shows the superior tenacity and elongation of the products of the present invention.
  • these drawn structures have an extremely low dyeability.
  • the fabric can be dyed by conventional processes, and under such conditions the portion of the fabric prepared from the metallic-lusteryarn will not accept the dye, Thus, striking dyed efiects can be obtained in different colors in the same fabric with a pattern of metallic-luster yarn which'retains its original color.
  • the drawn structures of this invention also have a higher fiber stillness than conventionally drawn fibers.
  • they are particularly well suited for embroidery work, gold braid, rugs, and fiberfill. They may also be used as a reinforcing agent in resin sheets or slabs. Their greater stillness provides excellent reinforcingproperties in addition to the highly decorative effect. Because of the presence of the tiny voids or air spaces, these materials have a high covering power: and high opacity as well as low heat transfer. For these reasonsthey are suitable for use as batting for quilts, con1 forters, sleeping bags, and other insulating structures.
  • the metallic luster imparted to the products prepared the metallic luster The metallic luster imparted to the products prepared the metallic luster.
  • the yarn drew within the box from the fixed end at a draw ratio of 6.8x.
  • the resulting yarn monofilament had a final diameter of 0.08 mm.
  • the drawn monofilament had a bright metallic luster and had a density of slightly below 0.62 g./cm. was wound up on the roller corresponds to a drawing speed of 14.7 yards per minute.
  • EXAMPLE III was drawn to 5.7 times its original length.
  • the resulting drawn material was a ribbon 0.80 mm. wide and 0.04 mm.
  • the ribbon having a large number of elongated internal voids.
  • the ribbon had afinal density of about 0.7 g./om.
  • Example HI was repeated except that the undrawn ribbon was heated to 70 C. and was drawn at a speed of 1.2 yards per minute to give a ribbon with a continuous metallic luster.
  • the density of the ribbon was less than 0.80 g./cm.
  • the draw ratio in this test was 5.05 X
  • EXAMPLE V Another sample of the undrawn ribbon described in Example I11 was conditioned in a room at a temperature of 25 C. The yarn was then slowly drawn on an lnstron tensile tester at a draw speed of 0.75 yard .per minute, at a draw ratio of 5 .2 The resulting ribbonwas'0.80 mm. wide and 0.035 thick, and had a continuousluster. It was not possible to draw the ribbon at lower speeds and get a continuous luster. At lower speeds, for example 0.36 yard per minute, the resulting drawn material drew at a lower draw ratio, 5.0 times its original length, and did not have a continuous luster. At even lower speeds, the draw ratio decreased and the luster entirely absent. (This example illustrates the lowest drawing speed for practicing the process of this invention.)
  • EXAMPLE v1 A sample of the undrawn ribbon described in Example III was conditioned in the box .at 68 C. and was then drawn at a draw speed of 45 yards per minute. Under these conditions, the natural draw ratio was 6.8.x. The resulting product was a ribbon 0.90 wide and 0.05 mm. thick, having a continuous luster. This material had a density of 0.62 to 0.65 g. cm. It was possible although difiicult to draw ribbon under these conditions at this speed to produce a continuous filament. Breakageo-f the filament, however, occurred occasionally. When the same experimentwas repeated at the same temperature but at a speed of 49 yards per minute, .it was not-possible (The speed at which this-monofilament' to maintain a steady drawing. The yarn broke at every trial.
  • Example VII Thisexample shows that an upper limit for the temperature of the process'of this invention exists.
  • Example III it was shown that it was possibleto drawapolyethylene terephthalate ribbon at a temperature of 75 C. and at a draw ratio of 5.7x.
  • a sample of the same undrawn ribbon was conditioned in the box shown in Figure 2at a temperature of C. An attempt was made to draw theribbon at the same speed, that is, 16.9 yards per minute.
  • EXAMPLE VIII Two flat n'bbons of polyethylene terephthalate were melt-spun. One-of. the ribbons had a denier of 205 and was 0.40 mm. .wide and 0.03 mm. thick. The birefringence of this ribbonwas- 0.01. This higher birefringence 2. The box was held at ajternperature of 25 C. After reaching thermal equilibrium, the ribbon was drawn at a speed of 14.85 yards per minute, under which conditions the yarn had a natural draw ratio of 5.2x. The resulting ribbon was-0.-25 mm. wide and 0.005 mm. thick and had a density of 1.293 g. /cm. The ribbon was faintly lustrous but drawing was difficult under the conditions stated.
  • the process of this invention is operable only at temperatures below 80f C., temperatures in the range of 25 C. to 75 (3. being preferred. At very low temperatures thetension necessary to draw the polyethylene terephthalate increases greatly and breakage of the material *in' either'the drawn or undrawn state may occur.
  • Suitable dyes for application to the melt-spun undrawn ribbon or filamerit include 1-amino-2-bromo-4-hydroxyanthraquinone and l-(p-ethylolamino)-4,5-dihydroxy 8 nitroanthraquinone.
  • a dyestuif such as those described in US. Patent No. 2,571,319 in the melt prior to spinning.
  • Small amounts, up to 0.5% by weight of the polymer of opaque white pigment such as titanium dioxide and barium sulfate can be added.
  • other opaque colored pigments such as cadmium sulfide, lamp black, and the like, may be used.
  • the opaque solid pigments give a more subdued metallic luster. The small amount of foreign material, pigment. or dye, does not interfere with the drawing process.
  • the neck produced in the present invention is extremely sharp, i.e., the shoulder of the neck forms an abrupt angle greater than 44 with the fiber axis, which indicates that the present process employs anew type of drawing with a very high rate of shear being produced in a very short distance. In .the clear drawing process, the neck angle is only about 35. While it is not intended that theoretical considerations or hypotheses should limit the scope of this invention, it
  • polyesters prepared as described in the aforementioned Whinfield and Dickson Patent U.S. 2,465,319 are preferably used.
  • the polymers may contain small'amounts of impurities and reaction byproducts which generally appear in continuous polymerization processes without adversely affecting the proc-, ess' of the present invention.
  • Polyester filaments comprised of modified polyethylene terephthalate, i.e., polyethylene terephthalate copolymcrs containing residues of other dicarboxylic acids such as isophthalic acid, phthalic acid, naphthalic acid, and bibenzoic acid, or other glycols may be drawn to a metallic luster.
  • the filaments will be spun, wound up ,on'bobbins andstored for a period of time before being drawn to a metallic luster. It has been found that the process is most readily controllable when the filamentary material to be drawn has been allowed to age at room temperature for periods iron 24 to 48 hours; however, material aged from 1 to 2 hours at from 60 C. to C. performs quite satisfactorily. While it is not intended that the scope of this invention be limited in any way by speculative theories, it is hypothesized that, during the aging period, a certain degree of amorphous association develops in the polymer which permits the generation of greater shear during the drawing process. When a multiplicity of filaments are being drawn simultaneously, the addition of an anti-static agent is frequently used. It has not been noted that ambient conditions of relative humidtiy have any significant effect on the drawing process or on the qualities of the polyester product.
  • a simple process is provided which is easily controllable whereby attractive decorative materials, yarns, films, and the like having a metallic luster are obtained.
  • This process not only gives a superior product with respect to physical properties but also eliminates the elaborate and expensive steps which have heretofore been required in preparing metallic-appearing yarns.
  • the present process gives an added advantage in that it can be adapted to produce both round and irregular yarns as well as flat ribbons.
  • single films or ribbons, yarn bundles or warp sheets may be drawn by this process.
  • a further advantage lies in the fact that the low denier multifilament and monofilament fibers while having a high metallic luster can be handled in the same manner as conventional polyester yarns and fibers.
  • a still further advantage lies in the fact that the yarns of this invention have increased strength, improved extensibility, are substantially chemically inert to conventional dyeing, bleaching, scouring, and other textile processing treatments to which many laminated metallic yarns cannot be subjected. Still another advantage lies in the unique and desirable properties of these yarns due to their low density, void-containing structure, and high covering power.
  • the shaped articles of this invention have a wide variety of end uses.
  • the articles, in film form may be used as base materials for the preparation of magnetic recording tapes and for fabricating a variety of other types of tapes such as pressure-sensitive adhesive tapes, adhesive tapes, binding tapes, surgical tapes, and tear tapes for opening cartons and packages. Due to their unique void-containing structure, the shaped articles are particularly desirable for use in electrical applications in the form of pressure-sensitive tapes, slot insulations for motors, as a dielectric in condensers, and as an insulating wrapping for wires and piping.
  • the lustrous filaments and ribbons of this invention may be woven or knitted into fabrics of all types. They may be used in preparing attractive drapery materials, clothing, upholstering, rugs, and the like,
  • window shades Included among the many other products which may be preparedfrom the shaped articles of this invention are window shades, tracing cloth, ticker tape, heat-shrinkable films and filaments, typewriter ribbons, and reflective thermal insulators.
  • films so treated may be used as a negative in preparing a number of copies of any desired subject matter on photosensitive paper.
  • Other end uses for the products prepared as described herein Will be apparent to those skilled in the art.
  • a shaped oriented article comprised of a highly polymeric ester of a dicarboxylic acid and a dihydric alcohol, said ester being capable of being formed into filaments which when cold drawn show by characteristic X-ray pattern molecular orientation along the fiber axis, which comprises drawing a shaped article of said ester which has a birefringence of not more than 0.01 at its natural draw ratio at a temperature below 80 C. to at least 5.0 times its original length at a drawing speed of at least 0.75 yard per minute and less than 50 yards per minute ,whereby a continuous metallic luster is imparted to said article.
  • the process of producing a textile yarn which comprises spinning a filament of a molten, highly polymeric ester of a dicarboxylic acid and a dihydric alcohol, said ester being capable of being formed into filaments which when cold drawn show by characteristic X-ray pattern molecular orientation along the fiber axis under conditions whereby the filament has an as-spun birefringence of not more than 0.01, aging the filament for a period of at least one hour, and drawing the filament at its natural draw ratio to more than 5.0 times its original length at a drawing speed of at least 0.75 yard per minute and less than 50 yards per minute at a temperature of less than C. whereby a metallic luster is imparted to said yarn and said yarn is highly oriented and uniformly drawn.
  • the method of producing a textile yarn which comprises heating a polyethylene terephthalate filament which has a birefringence not greater than 0.01 to a temperature between 25 C. and 75 C. and drawing said heated filament at its natural draw ratio at a drawing speed between 2 and 17 yards per minute to from 5.0 to 7.0 times its original length whereby said filament is fully drawn and a metallic luster is imparted tosaid filament.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Artificial Filaments (AREA)
  • Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
US719124A 1958-03-04 1958-03-04 Process for producing shaped oriented polyester articles having a metallic luster Expired - Lifetime US2948583A (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
NL236752D NL236752A (zh) 1958-03-04
BE576348D BE576348A (zh) 1958-03-04
US719124A US2948583A (en) 1958-03-04 1958-03-04 Process for producing shaped oriented polyester articles having a metallic luster
GB7024/59A GB903914A (en) 1958-03-04 1959-02-27 Drawing shaped articles of synthetic polyesters
CH7033959A CH373859A (de) 1958-03-04 1959-03-04 Verfahren zur Herstellung metallisch glänzender Formgebilde
FR788312A FR1224340A (fr) 1958-03-04 1959-03-04 Préparation des articles façonnés lustrés

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BE (1) BE576348A (zh)
CH (1) CH373859A (zh)
FR (1) FR1224340A (zh)
GB (1) GB903914A (zh)
NL (1) NL236752A (zh)

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3057825A (en) * 1959-07-29 1962-10-09 Du Pont Polymeric film having integral metallic luster and process for producing same
US3069726A (en) * 1958-03-04 1962-12-25 Du Pont Process for preparing articles having sections with metallic luster alternating with sections which are clear
US3088173A (en) * 1961-06-02 1963-05-07 Du Pont Process for preparing oriented polymeric linear terephthalate film with a deglossed writeable surface
US3107140A (en) * 1960-08-13 1963-10-15 Hoechst Ag Process for the manufacture of fibers and filaments of linear polyesters having improved properties
US3154461A (en) * 1960-03-07 1964-10-27 Minnesota Mining & Mfg Matte-finish polymeric film and method of forming the same
US3231557A (en) * 1960-05-19 1966-01-25 Minnesota Mining & Mfg Translucent film and method of making
US3242248A (en) * 1961-06-13 1966-03-22 Rhodiaceta Process for the thermal treatment of thermoplastic fibres
US3515626A (en) * 1965-02-22 1970-06-02 Ici Ltd Thermoplastic laminates having improved surface properties
US3539676A (en) * 1966-08-29 1970-11-10 Celanese Corp Process for producing filaments and films of polymers of alkylene sulfides
US3544671A (en) * 1965-07-14 1970-12-01 Ici Ltd Process for neck drawing block copolymer films and filaments
US3549743A (en) * 1967-05-15 1970-12-22 Chemcell Ltd Multistage drawing technique
DE2430772A1 (de) * 1973-06-28 1975-01-23 Nat Research Dev Corp London Verfahren zur herstellung orientierter polymerisatmaterialien
US3920785A (en) * 1969-11-13 1975-11-18 Celanese Corp Process for increasing the porosity of opencelled microporous film

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2465319A (en) * 1941-07-29 1949-03-22 Du Pont Polymeric linear terephthalic esters
US2497376A (en) * 1946-03-30 1950-02-14 Ici Ltd Process of producing films
US2734794A (en) * 1951-07-12 1956-02-14 G cm-ton

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2465319A (en) * 1941-07-29 1949-03-22 Du Pont Polymeric linear terephthalic esters
US2497376A (en) * 1946-03-30 1950-02-14 Ici Ltd Process of producing films
US2734794A (en) * 1951-07-12 1956-02-14 G cm-ton

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3069726A (en) * 1958-03-04 1962-12-25 Du Pont Process for preparing articles having sections with metallic luster alternating with sections which are clear
US3057825A (en) * 1959-07-29 1962-10-09 Du Pont Polymeric film having integral metallic luster and process for producing same
US3154461A (en) * 1960-03-07 1964-10-27 Minnesota Mining & Mfg Matte-finish polymeric film and method of forming the same
US3231557A (en) * 1960-05-19 1966-01-25 Minnesota Mining & Mfg Translucent film and method of making
US3107140A (en) * 1960-08-13 1963-10-15 Hoechst Ag Process for the manufacture of fibers and filaments of linear polyesters having improved properties
US3088173A (en) * 1961-06-02 1963-05-07 Du Pont Process for preparing oriented polymeric linear terephthalate film with a deglossed writeable surface
US3242248A (en) * 1961-06-13 1966-03-22 Rhodiaceta Process for the thermal treatment of thermoplastic fibres
US3515626A (en) * 1965-02-22 1970-06-02 Ici Ltd Thermoplastic laminates having improved surface properties
US3544671A (en) * 1965-07-14 1970-12-01 Ici Ltd Process for neck drawing block copolymer films and filaments
US3539676A (en) * 1966-08-29 1970-11-10 Celanese Corp Process for producing filaments and films of polymers of alkylene sulfides
US3549743A (en) * 1967-05-15 1970-12-22 Chemcell Ltd Multistage drawing technique
US3920785A (en) * 1969-11-13 1975-11-18 Celanese Corp Process for increasing the porosity of opencelled microporous film
DE2430772A1 (de) * 1973-06-28 1975-01-23 Nat Research Dev Corp London Verfahren zur herstellung orientierter polymerisatmaterialien

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CH373859A (de) 1963-12-15
GB903914A (en) 1962-08-22
NL236752A (zh)
FR1224340A (fr) 1960-06-23
BE576348A (zh)

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