WO2003044091A2 - Melange polymere - Google Patents

Melange polymere Download PDF

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Publication number
WO2003044091A2
WO2003044091A2 PCT/EP2002/012805 EP0212805W WO03044091A2 WO 2003044091 A2 WO2003044091 A2 WO 2003044091A2 EP 0212805 W EP0212805 W EP 0212805W WO 03044091 A2 WO03044091 A2 WO 03044091A2
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WO
WIPO (PCT)
Prior art keywords
polymer
polyamide
acid
fiber
polymer mixture
Prior art date
Application number
PCT/EP2002/012805
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German (de)
English (en)
Other versions
WO2003044091A3 (fr
Inventor
Volker Rauschenberger
Martin Laun
Jutta Kissel
Walter Heckmann
Bernd-Steffen Von Bernstorff
Hans Christoph Horn
Original Assignee
Basf Aktiengesellschaft
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Basf Aktiengesellschaft filed Critical Basf Aktiengesellschaft
Priority to AU2002366216A priority Critical patent/AU2002366216A1/en
Publication of WO2003044091A2 publication Critical patent/WO2003044091A2/fr
Publication of WO2003044091A3 publication Critical patent/WO2003044091A3/fr

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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
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/88—Monocomponent 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
    • D01F6/90—Monocomponent 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids

Definitions

  • the present invention relates to a thermoplastic polymer mixture (I) containing
  • melt viscosity measured according to ISO 11443, of polymer (III) at 280 ° C. in the entire shear rate range from 100 to
  • 20000 s-1 is at most 75% of the melt viscosity, measured according to ISO 11443, of polyamide (II) at 280 ° C
  • the present invention further relates to a method for producing a fiber from a polymer which contains such a thermoplastic polymer mixture (I), a method for producing a fiber from such a thermoplastic polymer mixture (I), fibers obtainable according to such a method , the use of such fibers for the production of a carpet or a textile fabric, as well as a carpet containing such a fiber and a textile fabric containing such a fiber.
  • a fiber is understood to mean a staple fiber as well as an endless filament.
  • thermoplastic polymers such as polyamides
  • carpets and textile fabrics which contain such fibers, are generally known.
  • the carpets and textile fabrics are usually dyed to achieve the intended visual impression, for example by dipping in baths which contain the dyes or by printing. It is desirable that the carpets and textile fabrics bind the dyes quickly, evenly and permanently.
  • carpets and textile fabrics are subject to staining when they are used, often due to colored food or drinks, such as fruit juices, fruit juices, coffee, tea or colored lemonades.
  • colored food or drinks such as fruit juices, fruit juices, coffee, tea or colored lemonades.
  • the staining behavior can be influenced by the type of spinning of the polymer into the fiber.
  • the fiber In the case of the so-called "low elongation fiber", the fiber is stretched and relaxed in several stages. This leads to an improvement in the staining behavior; However, it is disadvantageous that this process is technically very complex and inefficient. In addition, a further improvement in the staining behavior is desirable.
  • the object of the present invention was to provide a fiber which combines good dyeability in the intended coloring and at the same time good stain repellency in later use and which can be produced in a technically simple and economical manner.
  • the polymer mixture (I) defined at the outset a method for producing a fiber from a polymer which contains such a thermoplastic polymer mixture (I), a method for producing a fiber from such a thermoplastic polymer mixture (I), was obtainable according to such a method Fibers, the use of such fibers for producing a carpet or a textile fabric, as well as a carpet containing such a fiber and a textile fabric containing such a fiber were found.
  • thermoplastic polymer mixture (I) contains a polyamide (II).
  • polyamide (II) is understood to mean homopolymers, copolymers, mixtures and grafts of synthetic long-chain polyamides which, as an essential constituent, repeatedly have amide groups in the polymer main chain.
  • polyamides are nylon 6 (polycaprolactam), nylon 6.6 (polyhexamethylene adipamide), nylon 4.6 (poly tetramethylene adipamide), nylon 6.10 (polyhexamethylene sebacamide), nylon 7 (polyenantholactam), nylon 11 (polyundecanolacta), Nylon 12 (polydodecanolactam). These polyamides are known to have the generic name of nylon.
  • Polyamides are also to be understood as the so-called aramids (aromatic polyamides), such as poly-metaphenylene-isophthalamide (NOMEX® fiber, US-A-3, 287, 324) or poly-paraphenylene-terephthalamide (KEVLAR® fiber, US-A-3,671,542 ).
  • aramids aromatic polyamides
  • poly-metaphenylene-isophthalamide NOMEX® fiber, US-A-3, 287, 324
  • KEVLAR® fiber US-A-3,671,542
  • the amino and carboxyl end groups of the starting monomers or starting oligomers react with one another to form an amide group and Water.
  • the water can then be removed from the polymer mass.
  • the amino and amide end groups of the starting monomers or starting oligomers react with one another to form an amide group and ammonia.
  • the ammonia can then be removed from the polymer mass. This polymerization reaction is usually referred to as polycondensation.
  • polyaddition The polymerization from lactams as starting monomers or starting oligomers is usually referred to as polyaddition.
  • Such polyamides can be prepared by methods known per se, as described, for example, in DE-A-14 95 198, DE-A-25 58 480, EP-A-129 196 or in: Polymerization Processes, Interscience, New York, 1977, p. 424-467, in particular pp.
  • 444-446 are obtained from monomers selected from the group consisting of lactams, o ega-aminocarboxylic acids, omega-aminocarboxylic acid nitriles, omega-aminocarboxylic acid amides, omega-aminocarboxylic acid salts, omega-aminocarboxylic acid esters, equimolar mixtures Diamines and dicarboxylic acids, dicarboxylic acid / diamine salts, dinitriles and diamines or mixtures of such monomers.
  • C - to CQ - preferably C 3 - to Cis - aminocarbonitriles, such as 6-aminocapronitrile, 11-aminoundecanenitrile, Monomers or oligomers of C 2 - to C 2 o - amino acid amides, such as 6-aminocaproic acid amide, 11-aminoundecanoic acid amide and their dimers, trimers, tetramers, pentamers or hexamers,
  • Esters preferably C ! -C 4 alkyl esters, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl esters, preferably from C - to C 20 - 1 C 3 - to C 3 . 8 - aminocarboxylic acids, such as 6-aminocaproic acid esters, for example methyl 6-aminocaproic acid ester, 11-aminoundecanoic acid esters, for example methyl 11-aminoundecanoic acid,
  • C - to C 2 o ⁇ preferably C 2 - to C ⁇ - aliphatic dicarboxylic acid or its mono- or dinitriles, such as sebacic acid, dodecanedioic acid, adipic acid, sebaconitrile, decanoic acid di-nitrile or adiponitrile,
  • Cs - to C 2 o - preferably Cs - to C ⁇ - aromatic dicarboxylic acid or its derivatives, for example chlorides, such as 2,6-naphthalenedicarboxylic acid, preferably isophthalic acid or terephthalic acid,
  • C 9 - to C 2 o - preferably C 9 - to ⁇ Q - arylaliphatic dicarboxylic acid or its derivatives, for example chlorides, such as o-, m- or p-phenylenediacetic acid,
  • Cs - to C 2 o - preferably Cs - to C ⁇ 2 - aromatic dicarboxylic acid or its derivatives, for example chlorides, such as 2,6-naphthalenedicarboxylic acid, preferably isophthalic acid or terephthalic acid,
  • Cg - to C 2 o ⁇ preferably C 9 - to C ⁇ 8 - arylaliphatic dicarboxylic acid or its derivatives, for example chlorides, such as o-, m- or p-phenylenediacetic acid,
  • C 2 - to C 2 o - preferably C 2 - to -C-aliphatic dicarboxylic acid or its mono- or dinitriles, such as sebacic acid, dodecanedioic acid, adipic acid, sebaconitrile, decanoic acid di-nitrile or adiponitrile,
  • aromatic dicarboxylic acid or its derivatives for example chlorides, such as 2,6-naphthalenedicarboxylic acid, preferably isophthalic acid or terephthalic acid,
  • C 9 - to C 2 o ⁇ > preferably C 9 - to C - see arylaliphatic dicarboxylic acid or derivatives thereof, for example chlorides, such as o-, m- or p-phenylenediacetic acid,
  • the lactam used is caprolactam
  • the diamine is tetramethylene diamine, hexamethylene diamine or mixtures thereof
  • the dicarboxylic acid is adipic acid, sebacic acid, dodecanedioic acid, terephthalic acid, isophthalic acid or mixtures thereof.
  • Caprolactam is particularly preferred as lactam, hexamethylene diamine as diamine and adipic acid or terephthalic acid or mixtures thereof as dicarboxylic acid.
  • starting monomers or starting oligomers which, when polymerized to give the polyamides nylon 6, nylon 6,6, nylon 4,6, nylon 6,10, nylon 6,12, nylon 7, nylon 11, nylon 12 or the aramids Poly-metaphenylene-isophthalamide or poly-paraphenylene-terephthalamide, in particular lead to nylon 6 or nylon 66.
  • one or more chain regulators can be used in the production of the polyamides.
  • Suitable chain regulators are advantageously compounds which contain one or more, such as two, three or four, in the case of systems in the form of fibers preferably two, amino groups which are reactive in the formation of polyamides or one or more, such as two, three or four, in the case of systems. in the form of fibers preferably have two carboxyl groups reactive in the formation of polyamide.
  • polyamides are obtained in which the monomers used to prepare the polyamide have a higher number of amine groups or their equivalents used to form the polymer chain than carboxylic acid groups or their equivalents used to form the polymer chain.
  • polyamides are obtained in which the monomers used to produce the polyamide have a higher number of carboxylic acid groups or used to form the polymer chain have their equivalents as amine groups used to form the polymer chain or their equivalents.
  • Chain regulators which can advantageously be monocarboxylic acids, such as alkane carboxylic acids, preferably having 1 to 20 carbon atoms, including carboxyl group, for example acetic acid, propionic acid, such as benzene or naphthalene monocarboxylic acid, for example benzoic acid, dicarboxylic acids, such as C 2 -C 8 -alkanedicarboxylic acid, for example adipic acid, Azelaic acid, sebacic acid, dodecanedioic acid, Cs-Cs-cycloalkanedicarboxylic acids, for example cyclohexane-1, 4-dicarboxylic acid, benzene or naphthalenedicarboxylic acid, for example terephthalic acid, isophthalic acid, naphthalene-2, 6-dicarboxylic acid, C 2 - to C 2 ⁇ C 2 - to C ⁇ 2 - alkylamines, such as cyclohex
  • Salts such as alkali or alkaline earth metal salts, cyano, or halogens, such as fluorine, chlorine, bromine.
  • substituted chain regulators are sulfoisophthalic acid, their alkali metal or alkaline earth metal salts, such as lithium, sodium or potassium salts, sulfoisophthalic acid esters, for example with C 1 -C 6 -alkanols, or sufoisophthalic acid mono- or diamides, in particular with at least one suitable for the formation of polyamides
  • Monomers bearing amine groups such as hexamethylenediamine or 6-aminoaproic acid.
  • a chain regulator can advantageously be used in amounts of at least 0.01 mol%, preferably at least 0.05 mol%, in particular at least 0.2 mol%, based on 1 mol of acid amide groups of the polyamide.
  • a chain regulator can advantageously be used in amounts of at most 1.0 mol%, preferably at most 0.6 mol%, in particular at most 0.5 mol%, based on 1 mol of acid amide groups of the polyamide.
  • the polyamide (II) can contain as a chain regulator a sterically hindered piperidine derivative chemically bound to the polymer chain.
  • the polyamide can also contain mixtures of such sterically hindered piperidine derivatives as sterically hindered piperidine derivative.
  • Preferred sterically hindered piperidine derivatives are those of the formula
  • R 1 represents a functional group which is capable of forming amides with respect to the polymer chain of the polyamide
  • a group - (NH) R 5 where R 5 is hydrogen or Ci-Cs-alkyl, or a carboxyl group or a carboxyl derivative or a group - (CH 2 ) X (NH) R 5 , where X is 1 to 6 and R5 is hydrogen or Ci-Cs-alkyl, or a group - (CH 2 ) y COOH, where Y is 1 to 6, or a - (CH 2 ) y C00H acid derivative, where Y is 1 to 6 , in particular represents a group -NH 2 ,
  • R 2 represents an alkyl group, preferably a C 1 -C 4 alkyl group, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, s-butyl, in particular a methyl group .
  • R 3 represents hydrogen, C 1 -C 4 -alkyl or OR 4 , where R 4 represents hydrogen or C 1 -C 7 alkyl, in particular R 3 represents hydrogen,
  • the tertiary, in particular secondary, amino groups of the piperidine ring systems usually do not react because of steric hindrance.
  • 4-Amino-2, 2,6, 6-tetramethylpiperidine is particularly preferred as the sterically hindered piperidine derivative.
  • the sterically hindered piperidine derivative can advantageously be used in amounts of at least 0.01 mol%, preferably at least 0.05 mol%, in particular at least 0.1 mol%, based on 1 mol of acid amide groups of the polyamide.
  • Compound (II) can advantageously be used in amounts of at most 0.8 mol%, preferably at most 0.6 mol%, in particular at most 0.4 mol%, based on 1 mol of amide groups of the polyamide.
  • the polymerization or polycondensation is carried out by the process according to the invention in the presence of at least one pigment.
  • Preferred pigments are titanium dioxide, titanium dioxide preferably being in the anatase modification, or coloring compounds of an inorganic or organic nature.
  • the pigments are preferably added in an amount of 0 to 5 parts by weight, in particular 0.02 to 2 parts by weight, based in each case on 100 parts by weight of polyamide.
  • the pigments can be fed to the reactor with the starting materials or separately therefrom.
  • polyamide (II) can contain stabilizers of an organic or inorganic nature.
  • Polyamides which can advantageously be used as component (II) and contain a sterically hindered piperidine derivative chemically bonded to the polymer chain, and processes for producing such polyamides are described, for example, in WO 95/28443, WO 97/05189, WO 98/50610, WO 99 / 46323, WO 99/48949, EP-A-822 275, EP-A-843 696 and German applications 10030515.6, 10030512.1 and 10058291.5.
  • polyamide (II) should have a molecular weight M w determined in accordance with DIN 55672-2 in hexafluoroisopropanol as eluent, in the range from 30,000 to 300,000, preferably 50,000 to 150,000 g / mol.
  • M w molecular weight determined in accordance with DIN 55672-2 in hexafluoroisopropanol as eluent
  • thermoplastic polymer mixture (I) contains polyamide (II) in amounts of 50 to 99.9, preferably 70 to 98, in particular 80 to 95% by weight, based on the total weight of polymers in polymer mixture (I). According to the invention, the thermoplastic polymer mixture (I) further contains 0.1 to 50, preferably 2 to 30, in particular 5 to 20% by weight, based on the total weight of polymers in polymer mixture (I), of a polymer (III).
  • melt viscosity of polymer (III) is at most 75%, preferably at most 50%, of the melt viscosity of polyamide (II).
  • the melt viscosity is to be measured at a melt temperature of 280 ° C. in a stamp or nitrogen capillary viscometer with a suitable capillary, in accordance with ISO 11443.
  • the interfacial tension between a melt of polyamide (II) and a melt of polymer (III) at 280 ° C. is in the range from 0 mN / m to 10 mN / m.
  • Suitable polymers (III) are polymers which have functional groups in the main polymer chain or those which have no functional groups in the main polymer chain, such as polyolefins, for example polyethylene, polypropylene, polyisobutylene.
  • polyolefins for example polyethylene, polypropylene, polyisobutylene.
  • the production of such polyolefins is known per se, for example from: Kirk-Othmer, Encyclopedia of Chemical Technology, 4th Ed., Vol. 17, John Wiley & Sons, New York, 1996, pages 705-839, or Ulimann's Encyclopedia of Industrial Chemistry, 5th Ed., Vol. A21, VCH Verlagsgesellschaft mbH, Weinheim, 1992, pages 487-577.
  • the polymer (III) used can be a polymer which has at least one functional group of the structure recurring in the polymer main chain
  • R 1 , R 2 oxygen or nitrogen incorporated independently into the main polymer chain, two nitrogen bonds being advantageously linked to the polymer chain and the third bond being a substituent selected from the group consisting of hydrogen, alkyl, preferably C 1 -C 10 -alkyl, in particular Ci - C alkyl, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, aryl, heteroaryl or -C (0) -, where the group -C (0) - is another polymer chain Alkyl, preferably Ci-Cio-alkyl, especially Ci-C-alkyl, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, aryl, heteroaryl,
  • polymer (III) is a polyamide.
  • polymer (III) is a polyamide
  • monomers, chain regulators, additives and processes for polyamide production described for polymer (III) come into consideration for the production of polymer (III).
  • Fibers which achieve the object on which the present invention is based can be produced from the polymer mixture (I) according to the invention by spinning a polymer which contains a polymer mixture (I) into fibers by processes such as those used for producing fibers from thermoplastic polymers are known per se.
  • Processes with low take-off speeds such as 200 to 2000 m / s, can be used.
  • Processes with high take-off speeds such as over 2000 to 8000 m / s, can also be used.
  • Fibers which achieve the object on which the present invention is based can be produced from the polymer mixture (I) according to the invention by spinning a polymer mixture (I) into fibers by processes which are known per se for producing fibers from thermoplastic polymers ,
  • Polymer mixture (I) should advantageously have a melt viscosity at 280 ° C. of at least 10 Pas, measured in accordance with ISO 11443.
  • Polymer mixture (I) should advantageously have a melt viscosity at 280 ° C. of at most 5000 Pas, measured according to ISO 11443.
  • Processes with low take-off speeds such as 200 to 2000 m / s, can be used.
  • Processes with high take-off speeds such as over 2000 to 8000 m / s, can also be used.
  • yarns, carpets or textile fabrics can be produced by methods known per se, which according to the task have good dyeability with low stainability.
  • Such yarns, carpets or textile fabrics contain a fiber according to the invention or mixtures of such fibers.
  • Ultramid BS3300 (polyamide 6 from BASF Aktiengesellschaft) was spun into continuous filaments in accordance with Table 1.
  • the continuous filaments obtained according to Table 1 were cold drawn to 40% residual elongation on a J5 / 10a drawn twisting machine (Rieter AG) at a winding speed of 145 m / min and each using a Lawson-Hemphill circular knitting machine Knitted tube processed.
  • the knitted pieces were then competitively dyed in a dye bath with MSOL acidol black, that is to say the knitted pieces were simultaneously immersed in the same dyebath.
  • the color depth was evaluated with a Colorflash color analyzer, the color depth of the pure polymer according to Example 1 being set to 100%.
  • the relative color depth achieved is a measure of the tendency to staining.
  • the relative color depths are summarized in Table 2.
  • Example 1 in which only a single polyamide of the type described for polyamide (II) was used, serves as a reference point.
  • Example 2 the ratio of the melt viscosities and the interfacial tension are according to the invention.
  • the relative color depth is only 17% of the relative color depth of the pure polyamide according to Example 1.
  • the tendency to stain is significantly reduced.
  • Example 3 the ratio of the melt viscosities is according to the invention, the interfacial tension is not according to the invention.
  • the relative color depth is 80% of the relative color depth of the pure polyamide according to Example 1. Since the polypropylene used in Example 3 - in contrast to the 80% by weight Ultramid BS3300 in the mixture - cannot be colored by the dye used, acidol black MSRL, the relative color depth and thus the tendency to stain corresponds to the value to be expected from the chemical composition of the mixture.
  • Example 4 the interfacial tension is according to the invention; the ratio of the melt viscosities is not according to the invention over the entire shear rate range from 100 to 20,000 s- 1 .
  • the relative color depth and thus the tendency to stain is practically unchanged at 98% compared to the pure polyamide according to Example 1.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Artificial Filaments (AREA)
  • Polyamides (AREA)

Abstract

L'invention concerne un mélange polymère (I) contenant a) 50 99,9 % en poids d'un polyamide (II) par rapport au poids total des polymères dans le mélange polymère (I), et b) 0,1 à 50 % en poids d'un polymère (III) par rapport au poids total des polymères dans le mélange polymère (I). Selon l'invention, la viscosité de fusion mesurée selon ISO 11443 du polymère (III) à 280 °C vaut au plus 75 % de la viscosité de fusion mesurée selon ISO 11443 du polyamide (II) à 280 °C sur l'ensemble de la gamme du taux cisaillement de 100 à 20000 s-1. Par ailleurs, la tension interfaciale entre une fusion du polyamide (II) et une fusion du polymère (III) à 280 °C mesurée selon US Patent Nr. 5,150,607 avec la méthode de la goutte tournante, vaut de 0 mN/m à 10 mN/m.
PCT/EP2002/012805 2001-11-19 2002-11-15 Melange polymere WO2003044091A2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2002366216A AU2002366216A1 (en) 2001-11-19 2002-11-15 Polymer mixture

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10156293.4 2001-11-19
DE2001156293 DE10156293A1 (de) 2001-11-19 2001-11-19 Polymermischung

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Publication Number Publication Date
WO2003044091A2 true WO2003044091A2 (fr) 2003-05-30
WO2003044091A3 WO2003044091A3 (fr) 2003-12-18

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AR (1) AR037198A1 (fr)
AU (1) AU2002366216A1 (fr)
DE (1) DE10156293A1 (fr)
TW (1) TW200301286A (fr)
WO (1) WO2003044091A2 (fr)

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2344334A1 (de) * 1973-09-03 1975-03-06 Hoechst Ag Mischungen thermoplastischer polyamide
EP0279342A1 (fr) * 1987-02-19 1988-08-24 Bayer Ag Mélanges de polyamides et objets moulés à partir de ceux-ci
EP0355547A1 (fr) * 1988-08-09 1990-02-28 BASF Aktiengesellschaft Masses à mouler à partir de polyamides
EP0378088A2 (fr) * 1989-01-09 1990-07-18 BASF Aktiengesellschaft Masses à mouler thermoplastiques à base de mélanges de polyamides contenant des charges
EP0475720A2 (fr) * 1990-09-11 1992-03-18 Mitsubishi Gas Chemical Company, Inc. Composition de résine polyamide et feuille fabriquée à partir de celle-ci
US5242992A (en) * 1991-06-12 1993-09-07 Huls Aktiengesellschaft Polyamide molding compound
WO2000077097A1 (fr) * 1999-06-11 2000-12-21 Alliedsignal Inc. Compositions polyamides transparentes
EP1088852A1 (fr) * 1999-09-29 2001-04-04 Toyo Boseki Kabushiki Kaisha Compositions de polyamide renforcées inorganiquement

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2344334A1 (de) * 1973-09-03 1975-03-06 Hoechst Ag Mischungen thermoplastischer polyamide
EP0279342A1 (fr) * 1987-02-19 1988-08-24 Bayer Ag Mélanges de polyamides et objets moulés à partir de ceux-ci
EP0355547A1 (fr) * 1988-08-09 1990-02-28 BASF Aktiengesellschaft Masses à mouler à partir de polyamides
EP0378088A2 (fr) * 1989-01-09 1990-07-18 BASF Aktiengesellschaft Masses à mouler thermoplastiques à base de mélanges de polyamides contenant des charges
EP0475720A2 (fr) * 1990-09-11 1992-03-18 Mitsubishi Gas Chemical Company, Inc. Composition de résine polyamide et feuille fabriquée à partir de celle-ci
US5242992A (en) * 1991-06-12 1993-09-07 Huls Aktiengesellschaft Polyamide molding compound
WO2000077097A1 (fr) * 1999-06-11 2000-12-21 Alliedsignal Inc. Compositions polyamides transparentes
EP1088852A1 (fr) * 1999-09-29 2001-04-04 Toyo Boseki Kabushiki Kaisha Compositions de polyamide renforcées inorganiquement

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AU2002366216A1 (en) 2003-06-10
AR037198A1 (es) 2004-10-27
TW200301286A (en) 2003-07-01
AU2002366216A8 (en) 2003-06-10
WO2003044091A3 (fr) 2003-12-18
DE10156293A1 (de) 2003-05-28

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