EP0609159B1 - Filamente, Fasern und pigmentierte Fäden zum Aussengebrauch - Google Patents

Filamente, Fasern und pigmentierte Fäden zum Aussengebrauch Download PDF

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Publication number
EP0609159B1
EP0609159B1 EP94420019A EP94420019A EP0609159B1 EP 0609159 B1 EP0609159 B1 EP 0609159B1 EP 94420019 A EP94420019 A EP 94420019A EP 94420019 A EP94420019 A EP 94420019A EP 0609159 B1 EP0609159 B1 EP 0609159B1
Authority
EP
European Patent Office
Prior art keywords
ppm
copper
fibres
filaments
polyamide
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP94420019A
Other languages
English (en)
French (fr)
Other versions
EP0609159A1 (de
Inventor
Charles Cavalie
Olivier Chaubet
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Novalis Fibres
Original Assignee
Novalis Fibres
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Publication date
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Application filed by Novalis Fibres filed Critical Novalis Fibres
Publication of EP0609159A1 publication Critical patent/EP0609159A1/de
Application granted granted Critical
Publication of EP0609159B1 publication Critical patent/EP0609159B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • 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
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/04—Pigments
    • 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
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • 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

Definitions

  • the present invention relates to filaments, fibers, mono- or multifilament yarns, cables pigmented on the basis of polyamides, for interior or exterior uses designated as threads below from the description.
  • the colored threads must have an unalterable tint over time with respect to light rays.
  • compositions for pigmented nylon with improved stability against atmospheric agents and light containing 400 to 600 ppm Cu, based on the weight of nylon and 0.4 to 2.2% by weight of mineral halide, the Cu: halide ratio being between 325: 1 and 1150: 1, optionally in the presence of a phosphorus compound.
  • Patent DE 2 107 406 describes a stabilization system comprising a copper stearate, manganese acetate and potassium iodide. This system is suitable for stabilizing colorless polyamides, because the colors of the stabilizing system can alter or modify the colors of pigments.
  • the filaments, threads and fibers according to the invention simultaneously contain 15 to 100 ppm copper as a copper compound, 800 to 2000 ppm halogen as a metal halide and 50 to 100 ppm manganese as a manganese compound.
  • metal halide present in the wires is preferably potassium or sodium iodide, preferably potassium, at a rate of 800 to 2000 ppm of iodine relative to the weight of polyamide and preferably 1000 to 1600 ppm.
  • the manganese compound, preferably manganese acetate, is present at 50 to 100 ppm based on the weight of polyamide.
  • the present invention also relates to textile surfaces, such as nonwovens, carpet, flocked surfaces usable for indoor and outdoor jobs as described above.
  • the yarns according to the present invention can have very diverse strand titles according to desired use. In particular, they may have a title for the flocked surfaces. less than 1 dtex up to 40 or 50 dtex. For very stressed surfaces important, very large stranded yarns can be used, for example yarns spun from fibers or monofilaments which can have a unit titer of 40 dtex to 500 or 600 dtex or even more. The same textile surface may also have strands of different titles for obtain particular appearance or touch effects without departing from the scope of the invention.
  • the sons according to the invention can have round, flattened or multilobed shapes depending on the effect sought and intended use.
  • polyamide means polyhexamethylene adipamide (PA 6.6), the polycaproamide (PA 6) as well as copolyamides such as PA 6.6 containing percentages variables in caproamide units, or other units likely to be fixed in the PA chain 6.6 or PA 6 in order to improve certain properties, for example the dyeing properties.
  • the yarns according to the invention are preferably colored by pigmentation by any means known.
  • a large number of pigments can be used for coloring threads according to the invention.
  • Such dyes and / or pigments must also be very well dispersed in the yarns and fibers used for the preparation of textile surfaces according to the invention.
  • the dyes and pigments preferably used according to the present invention are in the form of masterbatches, for example with 25% pigment in polyamide 6, generally in the form of granules.
  • the granules are then mixed, for example in the form solid, by mixing the granules of masterbatch and granules of the polymer to be conformed, in the desired proportions.
  • Polymers preferably containing 0.5 to 2.5% of pigment are obtained.
  • the heat and light stabilizers are preferably introduced according to any process known, for example in the form of a masterbatch, or in polycondensation, with the monomers according to any process known to those skilled in the art.
  • Naturally other adjuvants can also be introduced during the polycondensation or in the melt of the polyamide to be conformed; for example oxide of titanium, preferably coated, or any other adjuvant capable of modifying certain properties of the sons obtained.
  • the yarns according to the present invention are obtained by molten spinning of the polyamide charged with pigments and various light and heat stabilizers, under known conditions of the skilled person.
  • the cooling conditions are adapted to the strand titer of the filaments: these are generally cooled in air or in a liquid medium when the strand titer is less than 40 - 50 dtex. For higher stranded titles, cooling in a liquid medium is preferable because more efficient.
  • the filaments are then drawn and sized in the usual way, possibly textured according to the desired application.
  • the yarns pigmented in the bulk of the polymer and protected by various protectors light and heat in the proportions recommended according to the invention must undergo favorably the test carried out using the apparatus known in the trade under the name of Q.U.V-B. (Accelerated Weathering Tester).
  • This device can reproduce in a few days or a few weeks the harmful effects that could occur after months or years of exposure to severe weather.
  • the deteriorations particularly observed are the loss of mechanical qualities, in particular the resistance, and the color alteration.
  • the coloristic result is considered good when the grading on the gray scale determined visually is approximately 3 - 4 after the number of hours of exposure indicated above.
  • the value of 5 corresponds to the best result, the value of 1 to the most degraded.
  • the pigments used are in the form of masterbatches known under the brand name: Renol GG-AN (green), Renol AN CNW FO2 (yellow), Renol B2G AN (blue). They are manufactured and sold by the Hoechst-Novacrome Company. Masterbatches contain 25% of pigment in PA 6 and are in the form of granules which are then mixed in solid form with the granules of the polymer to be conformed, in the desired proportions, to obtain polyamides containing approximately from 0.5 to 2.5% by weight of pigment.
  • a polyhexamethylene adipamide of relative viscosity 44 (measured on an 8.4% solution by weight by volume of polyamide in 90% formic acid) containing 0.3% by weight of oxide of coated titanium, 100 ppm of Mn (relative to the weight of PA) in the form of Mn acetate, 20 ppm copper as Cu acetate and 1147 ppm iodine as copper iodide, is dried and then melted at 285 ° C. After drying 5.32% of the masterbatch is added to this polymer yellow Renol AN CNW FO2 and 0.62% blue masterbatch Renol AN B2G.
  • the molten and additive polymer is filtered and then spun through a die comprising 60 orifices, with a diameter of 0.60 mm each.
  • the filaments are cooled by means of an air blower with a flow rate of 346 m 3 / hour, then sized in the usual way, drawn at a rate of 3.4 X in an aqueous bath maintained at 60 ° C, by passage between two sets of rollers and re-sized.
  • the cables collected in pots are intended for cutting.
  • the results of the wires (A) according to the invention are recorded in Table 1 below, compared with wires (B) obtained in the manner indicated above and containing as stabilizers, only 20 ppm of copper in the form of acetate and 1147 ppm iodine as potassium iodide.
  • the wire (C) is obtained according to the process indicated above but does not contain any stabilizer or pigment.
  • the wire (D) obtained according to the above process contains only the pigments.
  • the exposures according to the Q UV-B test were carried out over a period of 500 hours and the mechanical characteristics measured before and after exposure.
  • Color fastness gray scale rating after exposure of 950 hours according to the QUV-B test: Ex 1 (A) 4/5 (B) 4/5 (VS) --- (D) 4/5
  • LOCR-SM oxide coated titanium
  • the polymer thus added and melted is filtered and spun through a die comprising 48 holes of diameter 0.6 mm each.
  • the filaments are cooled by means of an air blower with a flow rate of 240 m 3 / hour. They are then taken up by successive roller trains and stretched between the first and the second train at a rate of 3.7 X and are simultaneously subjected to heat treatment by water vapor; between the second train and the third train of rollers, the filaments spread out in the form of a sheet undergo a slight relaxation and are then sized by passing through a bath.
  • the cable of filaments obtained having a moisture content of approximately 30%, is bambooed in the usual way.
  • the cable obtained is made up of strand title filaments 46.2 dtex, of tenacity 28.3 CN / tex, 45.6 CN / tex breaking stress and 62.8% elongation.
  • the green cable thus obtained, allows the production of flocked surfaces in the usual manner.
  • the loss of toughness is 50% after 890 hours of exposure to the Q UV-B test.
  • Color stability is good: 4/5 on the gray scale after exposure of 1000 hours.
  • the flocked surfaces thus produced are perfectly suited for outdoor uses described above, with regard to both mechanical characteristics and color.
  • compositions are prepared based on hexamethylene adipamide containing light and heat stabilizers as well as pigments and 0.3% of coated titanium oxide as indicated in Table 2 below:
  • VR Stabilizers Masterbatch containing the pigments 3 54 - Mn: 50 ppm (acetate) 6.2% Renol AN CNW FO2 (yellow) 2.8% Renol GG AN (green) (masterbatch) - Iodine: 1147 ppm (K iodide) - Cu: 20 ppm (Cu acetate) 4 54 - Mn: 50 ppm (acetate) 4.8% Renol HN CNW FO2 (yellow) 0.8% Renol B 2G AN (blue) - Iodine: 1147 ppm (K iodide) - Cu: 20 ppm (Cu acetate) 5 54 - Mn: 50 ppm (acetate) 4.8% Renol HN CNW FO2 (yellow)
  • the additive polymer is melted at 295 ° C. then filtered and spun through a die comprising 42 0.4 mm diameter holes each.
  • Monofilaments leaving the sector after a short passage in the air are cooled in an aqueous cooling tank. They are then taken up on rollers, and generally arranged in a sheet. They are stretched for the first time between two trains of rolls keeping them in the form of a sheet at a rate of 3.2 X while passing in a first oven then stretched a second time while passing through a second oven maintained at high temperature, then heat treated in a third oven in which they undergo a relaxation. After passing over a last set of rollers, the monofilaments are sized then rewound by any known means, in the form of reels.

Claims (6)

  1. Pigmentierte Filamente, Fasern und mono- oder multifilamentäre Fäden auf der Basis von Polyamid, die eine verbesserte Stabilität gegenüber Abbaureaktionen durch ultraviolette Strahlungen und atmosphärische Mittel aufweisen, dadurch gekennzeichnet, daß sie enthalten:
    15 ppm bis 100 ppm Kupfer in Form einer Kupferverbindung, bezogen auf das Gewicht des Polyamids,
    800 ppm bis 2000 ppm Halogen in Form eines Metallhalogenides, bezogen auf das Gewicht des Polyamids,
    50 ppm bis 100 ppm Mangan in Form einer Manganverbindung, bezogen auf das Gewicht des Polyamids.
  2. Pigmentierte Filamente, Fasern und mono- oder multifilamentäre Fäden nach Anspruch 1, dadurch gekennzeichnet, daß die Kupferverbindung Kupferacetat oder Kupferiodid ist.
  3. Pigmentierte Filamente, Fasern und mono- oder multifilamentäre Fäden nach Anspruch 1 und 2, dadurch gekennzeichnet, daß das Kupfer in einem Verhältnis von 15 ppm bis 50 ppm vorliegt.
  4. Pigmentierte Filamente, Fasern und mono- oder multifilamentäre Fäden nach Anspruch 1, dadurch gekennzeichnet, daß das Metallhalogenid Kaliumiodid oder Kaliumbromid ist.
  5. Pigmentierte Filamente, Fasern und mono- oder multifilamentäre Fäden nach Anspruch 1 und 4, dadurch gekennzeichnet, daß das Kaliumiodid in einem Verhältnis von 1000 ppm bis 1600 ppm von Iod vorliegt.
  6. Textile, nicht gewebte Flächengebilde, Tücher, beflockte Flächengebilde, die Filamente, Fasern und Fäden nach Anspruch 1 bis 5 enthalten.
EP94420019A 1993-01-28 1994-01-21 Filamente, Fasern und pigmentierte Fäden zum Aussengebrauch Expired - Lifetime EP0609159B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR9301328A FR2700780B1 (fr) 1993-01-28 1993-01-28 Filaments, fibres, fils pigmentés pour emploi extérieur.
FR9301328 1993-01-28

Publications (2)

Publication Number Publication Date
EP0609159A1 EP0609159A1 (de) 1994-08-03
EP0609159B1 true EP0609159B1 (de) 1998-10-28

Family

ID=9443808

Family Applications (1)

Application Number Title Priority Date Filing Date
EP94420019A Expired - Lifetime EP0609159B1 (de) 1993-01-28 1994-01-21 Filamente, Fasern und pigmentierte Fäden zum Aussengebrauch

Country Status (6)

Country Link
EP (1) EP0609159B1 (de)
AT (1) ATE172759T1 (de)
DE (1) DE69414143T2 (de)
DK (1) DK0609159T3 (de)
ES (1) ES2122200T3 (de)
FR (1) FR2700780B1 (de)

Cited By (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5855655A (en) 1996-03-29 1999-01-05 Kimberly-Clark Worldwide, Inc. Colorant stabilizers
US5858586A (en) 1993-08-05 1999-01-12 Kimberly-Clark Corporation Digital information recording media and method of using same
US5891229A (en) 1996-03-29 1999-04-06 Kimberly-Clark Worldwide, Inc. Colorant stabilizers
US5908495A (en) 1993-08-05 1999-06-01 Nohr; Ronald Sinclair Ink for ink jet printers
US6017471A (en) 1993-08-05 2000-01-25 Kimberly-Clark Worldwide, Inc. Colorants and colorant modifiers
US6017661A (en) 1994-11-09 2000-01-25 Kimberly-Clark Corporation Temporary marking using photoerasable colorants
US6033465A (en) 1995-06-28 2000-03-07 Kimberly-Clark Worldwide, Inc. Colorants and colorant modifiers
US6060200A (en) 1993-08-05 2000-05-09 Kimberly-Clark Worldwide, Inc. Photo-erasable data processing forms and methods
US6063551A (en) 1995-06-05 2000-05-16 Kimberly-Clark Worldwide, Inc. Mutable dye composition and method of developing a color
US6099628A (en) 1996-03-29 2000-08-08 Kimberly-Clark Worldwide, Inc. Colorant stabilizers
US6211383B1 (en) 1993-08-05 2001-04-03 Kimberly-Clark Worldwide, Inc. Nohr-McDonald elimination reaction
US6228157B1 (en) 1998-07-20 2001-05-08 Ronald S. Nohr Ink jet ink compositions
US6242057B1 (en) 1994-06-30 2001-06-05 Kimberly-Clark Worldwide, Inc. Photoreactor composition and applications therefor
US6265458B1 (en) 1998-09-28 2001-07-24 Kimberly-Clark Worldwide, Inc. Photoinitiators and applications therefor
US6277897B1 (en) 1998-06-03 2001-08-21 Kimberly-Clark Worldwide, Inc. Photoinitiators and applications therefor
US6294698B1 (en) 1999-04-16 2001-09-25 Kimberly-Clark Worldwide, Inc. Photoinitiators and applications therefor
US6331056B1 (en) 1999-02-25 2001-12-18 Kimberly-Clark Worldwide, Inc. Printing apparatus and applications therefor
US6368395B1 (en) 1999-05-24 2002-04-09 Kimberly-Clark Worldwide, Inc. Subphthalocyanine colorants, ink compositions, and method of making the same
US6368396B1 (en) 1999-01-19 2002-04-09 Kimberly-Clark Worldwide, Inc. Colorants, colorant stabilizers, ink compositions, and improved methods of making the same
US6503559B1 (en) 1998-06-03 2003-01-07 Kimberly-Clark Worldwide, Inc. Neonanoplasts and microemulsion technology for inks and ink jet printing
US6524379B2 (en) 1997-08-15 2003-02-25 Kimberly-Clark Worldwide, Inc. Colorants, colorant stabilizers, ink compositions, and improved methods of making the same

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5236652A (en) * 1992-02-11 1993-08-17 E. I. Du Pont De Nemours And Company Process for making polyamide fiber useful as staple for papermaking machine felt
US5782963A (en) 1996-03-29 1998-07-21 Kimberly-Clark Worldwide, Inc. Colorant stabilizers
MX9705708A (es) * 1995-11-28 1997-10-31 Kimberly Clark Co Estabilizadores de colorante mejorados.

Family Cites Families (7)

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FR878983A (fr) * 1941-02-03 1943-02-10 Ig Farbenindustrie Ag Procédé permettant d'améliorer la résistance à la lumière des polyamides linéaires formant des fibres
BE443687A (de) * 1941-03-21
FR906893A (fr) * 1943-01-09 1946-02-22 Ig Farbenindustrie Ag Procédé pour empêcher des polymères linéaires contenant des groupes amides dans leur chaîne de devenir cassants
NL94412C (de) * 1951-04-11
US2705227A (en) * 1954-03-15 1955-03-29 Du Pont Heat stabilization of polyamides
ZA71465B (en) * 1970-02-17 1971-10-27 Du Pont Colorless polyamide compositions and shaped articles stabilized for weatherability
DE2516565B2 (de) * 1975-04-16 1979-06-28 Basf Ag, 6700 Ludwigshafen Verfahren zum Stabilisieren von Polyamiden

Cited By (29)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6127073A (en) 1993-08-05 2000-10-03 Kimberly-Clark Worldwide, Inc. Method for concealing information and document for securely communicating concealed information
US6017471A (en) 1993-08-05 2000-01-25 Kimberly-Clark Worldwide, Inc. Colorants and colorant modifiers
US6066439A (en) 1993-08-05 2000-05-23 Kimberly-Clark Worldwide, Inc. Instrument for photoerasable marking
US5908495A (en) 1993-08-05 1999-06-01 Nohr; Ronald Sinclair Ink for ink jet printers
US5858586A (en) 1993-08-05 1999-01-12 Kimberly-Clark Corporation Digital information recording media and method of using same
US6120949A (en) 1993-08-05 2000-09-19 Kimberly-Clark Worldwide, Inc. Photoerasable paint and method for using photoerasable paint
US6211383B1 (en) 1993-08-05 2001-04-03 Kimberly-Clark Worldwide, Inc. Nohr-McDonald elimination reaction
US6054256A (en) 1993-08-05 2000-04-25 Kimberly-Clark Worldwide, Inc. Method and apparatus for indicating ultraviolet light exposure
US6060223A (en) 1993-08-05 2000-05-09 Kimberly-Clark Worldwide, Inc. Plastic article for colored printing and method for printing on a colored plastic article
US6060200A (en) 1993-08-05 2000-05-09 Kimberly-Clark Worldwide, Inc. Photo-erasable data processing forms and methods
US6342305B1 (en) 1993-09-10 2002-01-29 Kimberly-Clark Corporation Colorants and colorant modifiers
US6242057B1 (en) 1994-06-30 2001-06-05 Kimberly-Clark Worldwide, Inc. Photoreactor composition and applications therefor
US6017661A (en) 1994-11-09 2000-01-25 Kimberly-Clark Corporation Temporary marking using photoerasable colorants
US6235095B1 (en) 1994-12-20 2001-05-22 Ronald Sinclair Nohr Ink for inkjet printers
US6063551A (en) 1995-06-05 2000-05-16 Kimberly-Clark Worldwide, Inc. Mutable dye composition and method of developing a color
US6033465A (en) 1995-06-28 2000-03-07 Kimberly-Clark Worldwide, Inc. Colorants and colorant modifiers
US5891229A (en) 1996-03-29 1999-04-06 Kimberly-Clark Worldwide, Inc. Colorant stabilizers
US6168654B1 (en) 1996-03-29 2001-01-02 Kimberly-Clark Worldwide, Inc. Colorant stabilizers
US6099628A (en) 1996-03-29 2000-08-08 Kimberly-Clark Worldwide, Inc. Colorant stabilizers
US5855655A (en) 1996-03-29 1999-01-05 Kimberly-Clark Worldwide, Inc. Colorant stabilizers
US6524379B2 (en) 1997-08-15 2003-02-25 Kimberly-Clark Worldwide, Inc. Colorants, colorant stabilizers, ink compositions, and improved methods of making the same
US6277897B1 (en) 1998-06-03 2001-08-21 Kimberly-Clark Worldwide, Inc. Photoinitiators and applications therefor
US6503559B1 (en) 1998-06-03 2003-01-07 Kimberly-Clark Worldwide, Inc. Neonanoplasts and microemulsion technology for inks and ink jet printing
US6228157B1 (en) 1998-07-20 2001-05-08 Ronald S. Nohr Ink jet ink compositions
US6265458B1 (en) 1998-09-28 2001-07-24 Kimberly-Clark Worldwide, Inc. Photoinitiators and applications therefor
US6368396B1 (en) 1999-01-19 2002-04-09 Kimberly-Clark Worldwide, Inc. Colorants, colorant stabilizers, ink compositions, and improved methods of making the same
US6331056B1 (en) 1999-02-25 2001-12-18 Kimberly-Clark Worldwide, Inc. Printing apparatus and applications therefor
US6294698B1 (en) 1999-04-16 2001-09-25 Kimberly-Clark Worldwide, Inc. Photoinitiators and applications therefor
US6368395B1 (en) 1999-05-24 2002-04-09 Kimberly-Clark Worldwide, Inc. Subphthalocyanine colorants, ink compositions, and method of making the same

Also Published As

Publication number Publication date
DE69414143T2 (de) 1999-04-08
DK0609159T3 (da) 1999-07-05
ATE172759T1 (de) 1998-11-15
EP0609159A1 (de) 1994-08-03
FR2700780B1 (fr) 1995-03-10
FR2700780A1 (fr) 1994-07-29
DE69414143D1 (de) 1998-12-03
ES2122200T3 (es) 1998-12-16

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