EP2627806B1 - Fibres, textiles et tapis résistants aux taches - Google Patents

Fibres, textiles et tapis résistants aux taches Download PDF

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Publication number
EP2627806B1
EP2627806B1 EP11770102.9A EP11770102A EP2627806B1 EP 2627806 B1 EP2627806 B1 EP 2627806B1 EP 11770102 A EP11770102 A EP 11770102A EP 2627806 B1 EP2627806 B1 EP 2627806B1
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EP
European Patent Office
Prior art keywords
polymer composition
fiber according
polyamide
nonanediamine
octanediamine
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.)
Not-in-force
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EP11770102.9A
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German (de)
English (en)
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EP2627806A1 (fr
Inventor
Glenn P. Desio
Amy Marie Cuevas
Maryam Momtaz
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Solvay Specialty Polymers USA LLC
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Solvay Specialty Polymers USA LLC
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Priority to EP11770102.9A priority Critical patent/EP2627806B1/fr
Publication of EP2627806A1 publication Critical patent/EP2627806A1/fr
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Publication of EP2627806B1 publication Critical patent/EP2627806B1/fr
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Classifications

    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/58Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/60Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyamides
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/78Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products
    • D01F6/80Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from copolyamides
    • D01F6/805Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from copolyamides from aromatic copolyamides
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00General methods for the manufacture of artificial filaments or the like
    • D01F1/02Addition of substances to the spinning solution or to the melt
    • D01F1/04Pigments
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/58Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/60Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyamides
    • D01F6/605Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyamides from aromatic polyamides
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/78Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products
    • D01F6/80Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from copolyamides
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/88Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/90Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyamides
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/249921Web or sheet containing structurally defined element or component
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/20Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
    • Y10T442/2861Coated or impregnated synthetic organic fiber fabric
    • Y10T442/2893Coated or impregnated polyamide fiber fabric

Definitions

  • the present invention broadly relates to low color fibers, textiles and carpets comprising a semi-aromatic polyamide that feature surprisingly anti-staining properties.
  • the invention relates also in particular to the use of a semi-aromatic polyamide in the manufacture of fibers, textiles and carpets for its anti-staining properties.
  • Polyamides are polymers having excellent mechanical, physical and chemical properties which make them useful for a wide variety of different applications.
  • Polyamide fibers are relatively inexpensive and offer a desirable combination of qualities such as durability, comfort, and ease of manufacture into a broad range of colors, patterns, and textures.
  • polyamide fibers are widely used in the home and industry as carpets, drapery material, upholstery, and clothing. Carpets and rugs made from polyamide fibers are a popular floor covering for residential and commercial applications.
  • Polyamide fibers dye easily with dyes.
  • Typical staining agents include artificial or natural colorants (such as those found in soft drinks, coffee, red wine, food) and makeup (such as lipstick, lip gloss, lip liner, lip plumper, lip balm, foundation, powder, blush).
  • artificial or natural colorants such as those found in soft drinks, coffee, red wine, food
  • makeup such as lipstick, lip gloss, lip liner, lip plumper, lip balm, foundation, powder, blush
  • US 3,579,414 discloses melt-spun filaments and yarns with superior heat durability, Young's modulus and dyeability made from a specific copolyamide obrained through the polycondensation of 1,11-diaminoundecane, terephthalic acid and ⁇ -caprolactam.
  • the present invention relates to a fiber as claimed in claim 1.
  • a further aspect of the present invention is directed to textiles and carpets comprising the fiber according to the present invention featuring outstanding anti-staining properties.
  • the present invention relates to fibers, textiles and carpets having a stain-resistance with respect to dyes or pigments made of a polymer comprising more than 50 mol % of recurring units made of an aromatic diacid such as terephthalic acid and at least one aliphatic diamine selected from the group consisting of 1,8-octanediamine, 1,9-nonanediamine, 2-ethyl-1,8-octanediamine, 1,10-decanediamine, 1,12-dodecanediamine, 2,2,4-trimethyl-1,6-hexanediamine, 2,4,4-trimethyl-1,6-hexanediamine, 5-methyl-1,9-nonanediamine, methylcyclohexanediamine, isophoronediamine and mixtures thereof
  • the present invention relates to a method for conferring anti-staining properties to fibers, textiles or carpets comprising using a semi-aromatic polyamide comprising recurring units resulting from the condensation of terephthalic acid and at least one aliphatic diamine selected from the group consisting of 1,8-octanediamine, 1,9-nonanediamine, 2-methyl-1,8-octanediamine, 1,10-decanediamine, 1,12-dodecanediamine, 2,2,4-trimethyl-1,6-hexanediamine, 2,4,4-trimethyl-1,6-hexanediamine, 5-methyl-1,9-nonanediamine, methylcyclohexanediamine, isophoronediamine and mixtures thereof, for the manufacture of said fibers, textiles or carpets.
  • a semi-aromatic polyamide comprising recurring units resulting from the condensation of terephthalic acid and at least one aliphatic diamine selected from the group consisting of 1,8-octan
  • the fibers, carpets and textiles according to the present invention exhibit outstanding anti-staining properties. More precisely, the fibers, carpets and textiles according to the present invention have a stain-resistance rating of 1 on the Stain Rating Scale of the Stain Test Method described below.
  • the staining is herein intended to denote a coloration produced by a staining agent that penetrates a material. In many cases, stains can be affected by heat and moisture, and may become reactive enough to bond with the underlying material. Extreme heat can cause a chemical reaction on an otherwise removable stain, turning it into a chemical compound that is impossible to remove.
  • staining agent is intended to denote any agent that causes the material that comes in contact with it to stain.
  • staining agents comprise at least one dye or pigment. Both dyes and pigments appear to be colored because they absorb and reflect some wavelengths of light preferentially.
  • Typical staining agents include : makeup (such as lipstick, lip gloss, lip liner, lip plumper, lip balm, foundation, powder, blush), artificial or natural colorants (such as those found in soft drinks, coffee, red wine, mustard and ketchup), dyes and pigments (such as those found in dyed textiles and leather).
  • the fiber, textile and carpet according to the present invention have advantageously a lightness (L*) of at least 60 in the CIE 1976 ( L*, a*, b* ) color space when measured according to ASTM E308-08.
  • L* lightness
  • ASTM E308-08 The procedure used to measure the luminance is detailed here below:
  • the fiber, textile and carpet according to the present invention have preferably a lightness (L*) of at least 65, more preferably at least 70, still more preferably of at least 75 and most preferably of at least 80.
  • a fiber is intended to denote a class of materials that are continuous filaments or are in discrete elongated pieces, similar to lengths of thread.
  • the length of the fiber according to the present invention may vary widely. It is usually from 2 to 50 mm, preferably from 10 to 40 mm, more preferably from 20 to 30 mm.
  • the diameter of the fiber can also vary greatly. It is generally from 1.10 -6 m to 1.10 -4 m, preferably from 5.10 -6 m to 5.10 -5 m, more preferably about 1.10 -5 m.
  • the fiber, textile and carpets according to the present invention may be manufactured by various methods known in the art.
  • a textile is intended to denote a flexible material consisting of a network of natural or artificial fibres often referred to as thread or yarn. Yarn is produced by spinning fibers on a spinning wheel to produce long strands. Textiles are formed by weaving, knitting, crocheting, knotting, or pressing fibres together.
  • a carpet is intended to denote a textile floor covering consisting of an upper layer of "pile" attached to a backing.
  • the pile usually consists of twisted tufts which are often heat-treated to maintain their structure.
  • the fiber, textile and carpet of the present invention may be dyed in various colors.
  • the semi-aromatic polyamide according to the present invention comprises recurring units (R) resulting from the condensation of terephthalic acid and at least one aliphatic diamine selected from the group consisting of 1,8-octanediamine, 1,9-nonanediamine, 2-methyl-1,8-octanediamine, 1,10-decanediamine, 1,12-dodecanediamine, 2,2,4-trimethyl-1,6-hexanediamine, 2,4,4-trimethyl-1,6-hexanediamine, 5-methyl-1,9-nonanediamine, methylcyclohexanediamine, isophoronediamine and mixtures thereof.
  • the at least one aliphatic diamine is selected from the group consisting of 1,8-octanediamine, 1,9-nonanediamine, 2-methyl-1,8-octanediamine, 1,10-decanediamine, 1,12-dodecanediamine, 2,2,4-trimethyl-1,6-hexanediamine, 2,4,4-trimethyl-1,6-hexanediamine, 5-methyl-1,9-nonanediamine and mixtures thereof. More preferably, the at least one aliphatic diamine is selected from the group consisting of 1,9-nonanediamine, 2-methyl-1,8-octanediamine, 1,10-decanediamine, 1,12-dodecanediamine and mixtures thereof.
  • the at least one aliphatic diamine is selected from the group consisting of 1,9-nonanediamine, 2-methyl-1,8-octanediamine, 1,10-decanediamine and mixtures thereof Most preferably, the at least one aliphatic diamine is selected from the group consisting of 1,9-nonanediamine, 1,10-decanediamine and mixtures thereof.
  • the aliphatic diamine having more than 8 carbon atoms is a C9 diamine.
  • the diamine may be 1,9-nonanediamine (NDA) and/or 2-methyl-1,8-octanediamine (MODA).
  • NDA 1,9-nonanediamine
  • MODA 2-methyl-1,8-octanediamine
  • the 2-methyl-1,8-octanediamine (MODA) may be present from 0 to 50 mole %, based on the total number of moles of the diamine.
  • the molar ratio [(NDA) : (MODA)] is advantageously of at least 1, preferably of at least 2, more preferably of at least 3 and still more preferably of at least 4; besides, it is advantageously of at most 9, preferably of at most 7, and more preferably of at most 6.”
  • Preferred polyamides are those often referred to as PA 9T, PA 10T, PA 12T and mixtures thereof.
  • PA 9T when made using 1,9-nonanediamine, is a polyamide the recurring units of which have the following structure :
  • PA 10T is a polyamide the recurring units of which have the following structure :
  • PA10T may be prepared by various ways. It is advantageously prepared at least partially from decanediamine derived from a renewable raw material such as castor bean.
  • the semi-aromatic polyamide according to the present invention may comprise other recurring units than recurring units (R).
  • the semi-aromatic polyamide according to the present invention may bei obtained by the condensation of one or more dicarboxylic acids and one or more diamines, and/or one or more aminocarboxylic acids, and/or ring-opening polymerization products of one or more cyclic lactams.
  • suitable dicarboxylic acids include, but are not limited to, succinic acid, glutaric acid, sebacic acid, adipic acid, azelaic acid, 1, 6-cyclohexanedicarboxylic acid, naphthalenedicarboxylic acid and isophthalic acid (abbreviated as "I” in polyamide designations).
  • adipic acid is present in an amount of at most 30 mol %, more preferably at most 20 mol %, even more preferably at most 10 mol %, based on the total number of moles of the diacid component. Most preferably the diacid component is free of adipic acid.
  • Suitable diamines include, but are not limited to, tetramethylenediamine, hexamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, dodecamethylenediamine, 2-methylpentamethylenediamine, 2-methyloctamethylenediamine, trimethylhexamethylenediamine, bis(p-aminocyclohexyl)methane, m-xylylenediamine, and p-xylylenediamine.
  • fibers are obtained from a polymer composition (C) where the at least one semi-aromatic polyamide comprises in addition to the above described recurring units (R) (resulting from the condensation of terephthalic acid and at least one aliphatic diamine selected from the group consisting of 1,8-octanediamine, 1,9-nonanediamine, 2-methyl-1,8-octanediamine, 1,10-decanediamine, 1,12-dodecanediamine, 2,2,4-trimethyl-1,6-hexanediamine, 2,4,4-trimethyl-1,6-hexanediamine, 5-methyl-1,9-nonanediamine, methylcyclohexanediamine, isophoronediamine and mixtures thereof), other recurring units (R') resulting from the condensation of dicarboxylic acids selected from succinic acid, glutaric acid, sebacic acid, adipic acid, azelaic acid, 1, 6-cyclohexanedicarboxylic acid, n
  • the semi-aromatic polyamide according to the present invention comprises at least 20 wt. %, preferably at least 40 wt. %, more preferably at least 50 wt. %, even more preferably at least 60 wt. % and most preferably at least 80 wt. % of recurring units (R) based on the total weight of the semi-aromatic polyamide. Excellent results were obtained when the semi-aromatic polyamide was essentially free or even completely free of recurring units other than recurring units (R).
  • More than one semi-aromatic polyamide may be present in the polymer composition (C).
  • the semi-aromatic polyamide comprising recurring units resulting from the condensation of terephthalic acid and at least one aliphatic diamine comprising more than 8 carbon atoms detailed above is preferably present in at least 20 wt. %, more preferably at least 40 wt. %, even more preferably at least 50 wt. %, still more preferably at least 60 wt. % and most preferably at least 70 wt. %, based on the total weight of the semi-aromatic polyamides.
  • the semi-aromatic polyamide according to the present invention has advantageously a high melting point. Its melting point is preferably above 200°C, more preferably above 240°C, even more preferably above 280°C and most preferably above 300°C. Excellent results were obtained with a semi-aromatic polyamide featuring a melting point of 316°C.
  • the semi-aromatic polyamide according to the present invention has advantageously a high heat deflection temperature. Its heat deflection temperature is preferably above 200°C, more preferably above 250°C, even more preferably above 270°C and most preferably above 290°C. Excellent results were obtained with a semi-aromatic polyamide featuring a heat deflection temperature of 295°C.
  • the semi-aromatic polyamide according to the present invention having advantageously a high heat deflection temperature and a high melting point, it features therefore excellent high temperature resistance.
  • the semi-aromatic polyamide according to the present invention is present in the polymer composition (C) in an amount of at least 20 wt. %, preferably of at least 30 wt. % and most preferably of at least 40 wt. %, based on the total weight of the polymer composition (C).
  • the semi-aromatic polyamide according to the present invention is preferably present in the polymer composition (C) in an amount of at most 99 wt. %, more preferably of at most 95 wt. %, still more preferably of at most 90 wt. % and most preferably of at most 85 wt. %, based on the total weight of the polymer composition (C).
  • Excellent results were for example obtained when the semi-aromatic polyamide according to the present invention was present in the polymer composition (C) in about 50 wt. %, based on the total weight of the polymer composition (C).
  • the polymer composition (C) may further comprise at least one filler selected from the group consisting of fibrous fillers, particulate fillers and mixture thereof
  • filler include, but are not limited to, glass fiber, carbon fiber, glass fibers having a non-circular cross section, glass flakes, carbon fibers, wollastonite, calcined clay, kaolin, and the like.
  • the filler is preferably a particulate filler.
  • particulate filler include carbon black, talc, glass balls, calcium silicate, calcium metasilicate, kaolin, chalk, powdered quartz, mica, barium sulfate, aluminium silicate, calcium carbonate, clay and the like.
  • the filler is preferably a fibrous filler.
  • the fibrous filler may have a circular or a non-circular cross section having a major axis lying perpendicular to a longitudinal direction of the reinforcing agent and corresponding to the longest linear distance in the cross section.
  • the non-circular cross section has a minor axis corresponding to the longest linear distance in the cross section in a direction perpendicular to the major axis.
  • the ratio of the length of the major axis to that of the minor access is preferably between about 1.5:1 and about 6:1.
  • the ratio is more preferably between about 2:1 and 5:1 and yet more preferably between about 3:1 to about 4:1.
  • the fibrous reinforcing agent may be glass, carbon fibers, or other materials. Glass fibers are preferred.
  • the fibrous reinforcing agent may be in the form of long glass fibers, chopped strands, milled short glass fibers, or other suitable forms known to those skilled in the art. Particularly preferred according to the invention are glass fibers having a fiber diameter between 7 and 18 ⁇ m, preferably between 9 and 15 ⁇ m.
  • the filler is preferably a mixture of particulate and fibrous filler.
  • the polymer composition (C) comprises at least 20 wt. %, more preferably at least 30 wt. %, still more preferably at least 40 wt. % and most preferably at least 45 wt. % of the filler, based on the total weight of the polymer composition (C).
  • the polymer composition (C) comprises preferably at most 80 wt. %, more preferably at most 70 wt. %, still more preferably at most 60 wt. % and most preferably at most 55 wt. % of the filler, based on the total weight of the polymer composition (C).
  • the polymer composition (C) may further comprise at least one pigment.
  • Such pigment may be chosen from inorganic and organic pigments.
  • pigments are well known from the skilled person and are notably chosen from : titanium dioxide, zinc sulfide pigments, iron oxide pigments, chromium oxide green, lead chromate molybdate pigments, cadmium pigments, mixed metal oxide pigments, ultramarine blue, etc
  • the pigments according to the present invention are preferably present in the composition (C) in an amount of at least 1 wt. %, more preferably of at least about 2 wt. %, yet more preferably of at least about 3 wt. %, or still more preferably of at least about 4 wt. %, based on the total weight of the polymer composition (C).
  • the pigments according to the present invention are preferably present in the polymer composition (C) in an amount of at most 15 wt. %, more preferably of at most 10 wt. %, yet more preferably of at most 8 wt. %, or still more preferably of at most 6 wt. %, based on the total weight of the composition. Excellent results were obtained when the pigments were present in the polymer composition (C) in about 5 wt. %, based on the total weight of the polymer composition (C).
  • the polymer composition (C) comprises preferably at least one white pigment.
  • the white pigment according to the present invention is preferably selected from titanium dioxide, barium sulfate and zinc sulfide. More preferably, the white pigment is titanium dioxide or zinc sulfide.
  • the polymer composition (C) may further comprise other polymer(s).
  • the polymer composition (C) may further comprise other polyamides including aliphatic polyamides such as polyamide 6 ; polyamide 6,6 ; polyamide 4,6 ; polyamide 6,10 ; polyamide 6,12 ; polyamide 11 ; polyamide 12 ; polyamide 9,10 ; polyamide 9,12 ; polyamide 9,13 ; polyamide 9,14 ; polyamide 9,15 ; polyamide 6,16 ; polyamide 9,36 ; polyamide 10,10 ; polyamide 10,12 ; polyamide 10,13 ; polyamide 10,14 ; polyamide 12,10 ; polyamide 12,12 ; polyamide 12,13 ; polyamide 12,14 ; polyamide 6,14 ; polyamide 6,13 ; polyamide 6,15 ; polyamide 6,16 ; polyamide 6,13 ; and semi-aromatic polyamides such as poly(m-xylylene adipamide) (polyamide MXD,6), poly(dodecamethylene terephthalamide) (polyamide 12,T
  • the polymer composition (C) may further optionally comprise additional additives such as ultraviolet light stabilizers, heat stabilizers, antioxidants, processing aids, lubricants, flame retardants, and/or conductivity additive such as carbon black and carbon nanofibrils.
  • additional additives such as ultraviolet light stabilizers, heat stabilizers, antioxidants, processing aids, lubricants, flame retardants, and/or conductivity additive such as carbon black and carbon nanofibrils.
  • the polymer composition (C) comprises preferably:
  • the polymer composition (C) comprises preferably:
  • the polymer composition (C) molded into a plaque has preferably a lightness (L*) of at least 60, more preferably at least 65, still more preferably at least 70, even more preferably of at least 75 and most preferably of at least 85 in the CIE 1976 (L*, a*, b*) color space when measured according to ASTM E308-08.
  • the color of the plaques were measured, and in particular the lightness (L*) of the samples were determined using a CE7000 Gretag MacBeth spectrophotometer using Cool White Fluorescent (F2) illuminant and the 10° observer, as detailed above.
  • L* Lightness
  • a mixture of staining agent is prepared by heating sebum until it is liquid, then mixing 3 parts of the heated sebum to one part of the makeup and finally heating the mixture to maintain liquidity.
  • the prepared staining agent mixture is applied to the surface of the molded plaques with a cotton swab.
  • the plaques are placed in an environmental chamber at 65°C and 90 % humidity for 24 hours.
  • the molded plaques are then placed at room temperature before wiping their surface with isopropyl alcohol. Once cleaned, the plaques are finally inspected for staining.
  • the color of the fiber made of the polymer composition (C) according to the present invention is always lighter than the color of the same composition (C) as measured on a plaque.
  • the anti-staining effect can however be detected more easily and more accurately on a plaque than on a fiber.
  • the inspection step comprises the measurement of the lightness (L*), as detailed above.
  • the difference between the original L* measured and the L* measured after the staining treatment is calculated.
  • Stain Rating Scale the stains can be categorized according to the following standards:
  • a stain-rating of 1 is excellent, showing good stain resistance, whereas 3 is a poor rating, showing persistence of heavy staining.
  • a substrate to be considered to have adequate stain resistance it should have a rating of 1 on the above-described Stain Rating Scale.
  • Table 2 Staining test results CE1 CE2 CE3 CE4 CE5 E1 E2 Initial L* value 61.6 91.0 93.9 90.9 90.8 89,7 89.4 L* value after staining treatment 58.4 90.0 92.7 84.3 84 89.7 89.0 Staining rating 2 2 2 3 3 1 1

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Artificial Filaments (AREA)
  • Carpets (AREA)
  • Polyamides (AREA)

Claims (13)

  1. Fibre constituée d'une composition polymère (C) comprenant au moins 20 % en poids d'au moins un polyamide semi-aromatique comprenant au moins 20 % en poids de motifs récurrents (R) résultant de la condensation d'acide téréphtalique et d'au moins une diamine aliphatique choisie dans le groupe constitué parla 1,8-octanediamine, la 1,9-nonanediamine, la 2-méthyl-1,8-octanediamine, la 1,10-décanediamine, la 1,12-dodécanediamine, la 2,2,4-triméthyl-1,6-hexanediamine, la 2,4,4-triméthyl-1,6-hexanediamine, la 5-méthyl-1,9-nonanediamine, la méthylcyclohexanediamine, l'isophoronediamine et les mélanges de celles-ci, la couleur de ladite composition polymère (C) lorsqu'elle est moulée en une plaque ayant une clarté (L*) d'au moins 60 dans l'espace colorimétrique CIE 1976 (L*, a*, b*) lorsqu'elle est mesurée selon l'ASTM E308-08.
  2. Fibre selon la revendication 1, la couleur de ladite composition polymère (C) lorsqu'elle est moulée en une plaque ayant une clarté (L*) d'au moins 70 dans l'espace colorimétrique CIE 1976 (L*, a*, b*) lorsqu'elle est mesurée selon l'ASTM E308-08.
  3. Fibre selon la revendication 1 ou 2, dans laquelle l'au moins une diamine aliphatique est choisie dans le groupe constitué par la 1,9-nonanediamine, la 2-méthyl-1,8-octanediamine, la 1,10-décanediamine, la 1,12-dodécanediamine et les mélanges de celles-ci.
  4. Fibre selon la revendication 3, dans laquelle l'au moins une diamine aliphatique est choisie dans le groupe constitué par la 1,9-nonanediamine, la 1,10-décanediamine et les mélanges de celles-ci.
  5. Fibre selon l'une quelconque des revendications précédentes, dans laquelle le polyamide semi-aromatique est choisi dans le groupe constitué par le PA9T, le PA10T, le PA12T et les mélanges de ceux-ci.
  6. Fibre selon l'une quelconque des revendications précédentes, la composition polymère (C) comprenant plus de 30 % en poids du polyamide semi-aromatique, rapporté au poids total de la composition polymère (C).
  7. Fibre selon l'une quelconque des revendications précédentes, la composition polymère (C) comprenant en outre au moins 1 % en poids d'un ou plusieurs pigments, rapporté au poids total de la composition polymère (C).
  8. Fibre selon la revendication 7, dans laquelle les pigments comprennent un pigment blanc.
  9. Fibre selon la revendication 8, dans laquelle le pigment blanc est choisi parmi le dioxyde de titane, le sulfate de baryum et le sulfure de zinc.
  10. Textile comprenant la fibre selon l'une quelconque des revendications précédentes.
  11. Tapis comprenant la fibre selon l'une quelconque des revendications précédentes.
  12. Fibre selon l'une quelconque des revendications précédentes ayant une note de résistance aux taches de 1 sur l'échelle de résistance aux taches de la méthode d'essai de tache.
  13. Procédé pour conférer des propriétés antitaches à des fibres, des textiles ou des tapis comprenant l'utilisation d'une composition polymère (C) comprenant au moins 20 % en poids d'un polyamide semi-aromatique comprenant au moins 20 % en poids de motifs récurrents (R) résultant de la condensation d'acide téréphtalique et d'une diamine aliphatique choisie dans le groupe constitué par la 1,8-octanediamine, la 1,9-nonanediamine, la 2-méthyl-1,8-octanediamine, la 1,10-décanediamine, la 1,12-dodécanediamine, la 2,2,4-triméthyl-1,6-hexanediamine, la 2,4,4-triméthyl-1,6-hexanediamine, la 5-méthyl-1,9-nonanediamine, la méthylcyclohexanediamine, l'isophoronediamine et les mélanges de celles-ci pour la fabrication desdites fibres, textiles ou tapis.
EP11770102.9A 2010-10-13 2011-10-13 Fibres, textiles et tapis résistants aux taches Not-in-force EP2627806B1 (fr)

Priority Applications (1)

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US39286410P 2010-10-13 2010-10-13
EP11157969 2011-03-11
PCT/EP2011/067902 WO2012049254A1 (fr) 2010-10-13 2011-10-13 Fibres, textiles et tapis résistants aux taches
EP11770102.9A EP2627806B1 (fr) 2010-10-13 2011-10-13 Fibres, textiles et tapis résistants aux taches

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EP2627806B1 true EP2627806B1 (fr) 2015-09-16

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EP (1) EP2627806B1 (fr)
JP (1) JP5933566B2 (fr)
KR (1) KR20130117790A (fr)
CN (1) CN103403237A (fr)
BR (1) BR112013008851A2 (fr)
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Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6211419B2 (ja) 2010-10-13 2017-10-11 ソルベイ スペシャルティ ポリマーズ ユーエスエー, エルエルシー 耐汚染性物品
US10053799B2 (en) 2014-01-31 2018-08-21 Shakespeare Company, Llc Nylon based filaments, yarns, and fabrics
EP3099745A4 (fr) 2014-01-31 2017-09-27 Shakespeare Company, LLC Nouveau mélange de nylons pour obtenir des monofilaments et des fibres multifilaments ayant des propriétés mécaniques améliorées
KR20170119703A (ko) * 2015-02-23 2017-10-27 디에스엠 아이피 어셋츠 비.브이. 고강도 폴리아마이드 얀

Family Cites Families (35)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1070327A (en) * 1963-05-25 1967-06-01 Kanegafuchi Spinning Co Ltd Improvements in the preparation of polyamide resins
JP3481729B2 (ja) * 1995-06-23 2003-12-22 株式会社クラレ ポリアミド繊維
US6488893B1 (en) 1999-10-01 2002-12-03 Trichromatic Carpet Inc. Polyamide substrate having stain resistance, composition and method
JP2004075994A (ja) * 2002-06-21 2004-03-11 Kuraray Co Ltd ポリアミド組成物
CA2432522C (fr) * 2002-06-21 2010-09-21 Hideaki Oka Compose de polyamide
JP2004107818A (ja) * 2002-09-18 2004-04-08 Univ Shinshu ポリアミド繊維及びその製造法
US20050183216A1 (en) * 2003-12-23 2005-08-25 Invista North America S.A R.I. Polamide composition comprising optical brightener yarns made therefrom, and process for heat setting such yarns
US20050159552A1 (en) * 2004-01-21 2005-07-21 Reed Jon S. Flame retarded fibers and filaments and process of production therefor
US7666944B2 (en) * 2004-01-21 2010-02-23 Albemarle Corporation Flame retarded fibers and filaments and process of production therefor
JP2005220447A (ja) * 2004-02-03 2005-08-18 Kuraray Co Ltd 耐熱性ポリアミドメルトブロー不織布
WO2006035614A1 (fr) * 2004-09-27 2006-04-06 Kuraray Co., Ltd. Fibre liante et separateur de cellule alcaline utilisant celle-ci
JP4525917B2 (ja) * 2005-03-18 2010-08-18 株式会社クラレ Ledリフレクタ成形用ポリアミド樹脂組成物およびledリフレクタ
CN101511944B (zh) * 2006-06-30 2011-08-24 东丽株式会社 热塑性树脂组合物和它的模制品
CN101484621B (zh) * 2006-07-03 2012-01-11 可乐丽股份有限公司 导电性皮芯型复合纤维及其制造方法
US7648928B2 (en) * 2006-09-11 2010-01-19 Trichromatic Carpet Inc. Composition and method for enhancing stain resistance and product of enhanced stain resistance therefrom
US20100130084A1 (en) * 2007-03-26 2010-05-27 Mitsui Chemicals, Inc. Mixed continuous fiber non-woven fabric and method for producing the same
JP2008297681A (ja) * 2007-06-01 2008-12-11 Kb Seiren Ltd 熱可塑性合成繊維
JPWO2009050864A1 (ja) * 2007-10-18 2011-02-24 株式会社クラレ 積層体、キャパシタ用セパレータおよびキャパシタ
KR101755044B1 (ko) * 2009-03-16 2017-07-06 보르벡크 머터리얼스 코포레이션 중합체 섬유 및 이로부터 제조된 물품
EP2264093A1 (fr) * 2009-06-16 2010-12-22 THOR GmbH Masses à mouler en polyamide ignifugées
CN102575099B (zh) * 2009-09-14 2014-05-07 三菱瓦斯化学株式会社 聚酰胺树脂组合物
WO2011118441A1 (fr) * 2010-03-26 2011-09-29 ユニチカ株式会社 Polyamide semi-aromatique et procédé de production associé
US20110319552A1 (en) * 2010-06-29 2011-12-29 Jos Bastiaens Polyamide-poly(arylene ether) fiber and method for its preparation
AU2012224318B2 (en) * 2011-02-28 2015-12-03 Toray Industries, Inc. Thermoplastic resin composition and molded product thereof
FR2976946B1 (fr) * 2011-06-24 2014-01-24 Arkema France Composition comprenant un polyamide semi-aromatique et ses utilisations, notamment pour un reflecteur a diode electroluminescente
JP5451940B2 (ja) * 2011-09-22 2014-03-26 ユニチカ株式会社 半芳香族ポリアミドおよびそれからなる成形体
JP5876693B2 (ja) * 2011-09-26 2016-03-02 ユニチカ株式会社 半芳香族ポリアミド繊維、半芳香族ポリアミド不織布及びその製造方法
JP5950921B2 (ja) * 2011-09-28 2016-07-13 株式会社クラレ 極細繊維シート
WO2013141033A1 (fr) * 2012-03-23 2013-09-26 東レ株式会社 Fibre conjuguée à base de polyméthylpentène ou fibre poreuse de polyméthylpentène et structure fibreuse les comprenant
US10465071B2 (en) * 2012-09-14 2019-11-05 Kuraray Co., Ltd. Polyamide resin
KR102066765B1 (ko) * 2012-09-28 2020-01-15 주식회사 쿠라레 폴리아미드 수지 조성물
EP2949704B1 (fr) * 2012-12-21 2019-04-24 Ems-Patent Ag Article résistant à la coloration et son utilisation
EP2746341B2 (fr) * 2012-12-21 2018-11-14 Ems-Patent Ag Articles résistant aux taches et leur utilisation
JP6282802B2 (ja) * 2013-03-12 2018-02-21 ユニチカ株式会社 半芳香族ポリアミド粉粒体およびその製造方法
JP6312364B2 (ja) * 2013-03-18 2018-04-18 ユニチカ株式会社 半芳香族ポリアミドおよびその成形体

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JP2013540909A (ja) 2013-11-07
US20130309928A1 (en) 2013-11-21
BR112013008851A2 (pt) 2016-06-21
KR20130117790A (ko) 2013-10-28
CN103403237A (zh) 2013-11-20
EP2627806A1 (fr) 2013-08-21
WO2012049254A1 (fr) 2012-04-19
JP5933566B2 (ja) 2016-06-15

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