EP0360708A1 - Polyamide imide yarns and their production - Google Patents

Polyamide imide yarns and their production Download PDF

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Publication number
EP0360708A1
EP0360708A1 EP89420348A EP89420348A EP0360708A1 EP 0360708 A1 EP0360708 A1 EP 0360708A1 EP 89420348 A EP89420348 A EP 89420348A EP 89420348 A EP89420348 A EP 89420348A EP 0360708 A1 EP0360708 A1 EP 0360708A1
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Prior art keywords
filaments
threads
fibers according
units
solvent
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EP89420348A
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German (de)
French (fr)
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EP0360708B1 (en
Inventor
Pascal Barthelemy
Bruno Testard
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Rhone Poulenc Fibres SA
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Rhone Poulenc Fibres SA
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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/74—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polycondensates of cyclic compounds, e.g. polyimides, polybenzimidazoles
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/78—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products

Definitions

  • the present invention relates to thermostable synthetic yarns based on polyamide-imide with improved properties.
  • the strands according to the invention are also characterized by a polydispersity index I ⁇ 2.2 and tenacity> 45 cN / tex, a Young's modulus ⁇ 3.8 GPa, an elongation ⁇ 25% and a color defined by the luminance y > 25%, the degree of white DB ⁇ 30, the yellow index IJ> 170.
  • the toughness is of the order of 50 to 55 cN / tex, the module ⁇ 4 GPa, the luminance y> 30%, of degree of white ⁇ 28, and the index of yellow> 190.
  • the light stability of the PAIs according to the invention is also much improved compared to that of the PAI wires known hitherto. It is evaluated by the retention of mechanical properties: tenacity at break ⁇ 50%, working at break at 18%, elongation ⁇ 35%. The light stability is measured according to the method described below.
  • the yarns according to the invention have a chemical structure as defined above in which R is a radical such that and preferably and R 1 preferably a radical R 2 preferably a radical and M is preferably Na or K.
  • the PAI wires are also characterized by a value of the polydispersity index 1 ⁇ 2.2.
  • This index corresponds to the ratio M w , the values of M not and M w being determined by gel exclusion chromatography (GPC) in the NMP Mn . at 80 ° C. and 0.1 mole / liter of lithium bromide, the masses being expressed relative to a polystyrene calibration.
  • the polydipersity index of the PAI yarns according to the invention remains low: it corresponds to a narrowing of the distribution of the molecular masses. Surprisingly, it remains weak at the level of the finished threads despite the various treatments undergone by the filaments during their preparation.
  • the threads according to the invention also have excellent mechanical and thermal characteristics, much superior to those of the polyamide-imide threads according to FR 2 079 785.
  • the toughness is greater than or equal to 45 cN / tex, of preferably 50 or 55 cN / tex.
  • the measurement is carried out on a manual or automatic dynamometer with constant gradient of elongation on a wire test piece subjected to longitudinal traction until it breaks.
  • the elongation at break is measured as indicated above. It is less than or equal to 25%.
  • the longitudinal Young E modulus of the PAI wires according to the invention is ⁇ 3.8 GPa, preferably ⁇ 4 GPa. This is the report obtained at the start of the force / elongation curve.
  • the specific force (tenacity) corresponds to the ratio: ⁇ 1 being the increase in the length of the test piece at time t to which the actual titer corresponds and Io the initial length of the test piece.
  • the degree of white defines a point of color in the chromaticity plane.
  • the Yellow index is an expression of the color purity in the yellow.
  • the light stability measurements are carried out in an enclosure which makes it possible to experimentally study the photoaging of polymers in a dry atmosphere.
  • the samples to be tested are placed on a cylindrical turret driven by a circular rotational movement located in the center of a parallelepipedic enclosure, the four corners of which are occupied by a "medium pressure" mercury vapor lamp type MAZDA MA 400 Watts.
  • the envelope allows only radiation above 300 nm (solar spectrum) to pass through.
  • the temperature in the enclosure is 60 ° C.
  • the 1.4 cm paper window on which the sample is fixed when determining the mechanical properties on INSTRON is itself placed on one of the 24 supports of the chamber turret. After the exposure, the paper window is recovered and the mechanical characteristics of the monofilament are determined according to the method of determining the mechanical properties indicated above.
  • the yarns according to the invention have a clear superiority compared to known PAI yarns.
  • the yarns according to the invention also have a much better thermal resistance than that of known PAI yarns: it is evaluated by the rate of degradation corresponding to a percentage of weight loss as a function of time at a temperature of 375 °, in air.
  • the isothermal degradation of PAI yarns according to the invention is generally ⁇ 3% per hour, and preferably ⁇ 2% per hour.
  • the filaments, threads, fibers according to the present invention can be used alone or mixed with natural or synthetic threads or fibers in order to modify or improve certain properties. They are particularly interesting for the production of work and protective clothing, thanks to their mechanical properties and their thermal and light resistance. In addition, the yarns obtained are easy to dye in all colors with basic dyes.
  • the PAI yarns according to the present invention are obtained by wet spinning from solutions of polymer in a solvent or solvent mixture.
  • concentration of the spinning solutions is between 4 and 35%, preferably between 5 and 35%.
  • the polymers are dissolved in a solvent or solvent mixture containing from 5 to 100% by weight of dimethylethylene urea of pH ⁇ 7 and 0 to 55% of an anhydrous aprotic polar solvent such as N-methylpyrrolidone, dimethylacetamide, dimethylformamide, tetramethylurea or y butyrolactone.
  • the solutions which can be used in the process according to the invention must have a viscosity of between 100 and 200 poises, preferably between 150 and 160 poises. They can also contain various adjuvants such as pigments, matifiers to improve certain properties.
  • the PAI solutions are spun in a binary or ternary aqueous coagulating bath containing a solvent or solvent mixture in proportion of 30 to 80% of solvent and 20 to 70% of water, preferably 40 to 70% of solvent (s).
  • the solvent used can be dimethylformamide, dimethylethylene urea or a mixture thereof.
  • the spinning bath is maintained between 15 and 40 ° C, preferably 20 to 30 ° C.
  • the length of the coagulating bath is adaptable generally depending on the solvent concentration and the temperature. Baths with a higher solvent content generally make it possible to obtain yarns with better stretchability, therefore better final properties. However, when the solvent concentration is higher, a longer bath length is necessary.
  • the filaments leaving the coagulating bath in the gel state are then drawn, for example in air at a rate defined by the ratio x 100, V2 being the speed of the drawing rollers, V1 those of the delivery rollers.
  • the rate of drawing of the strands in the gel state is at least 100%, preferably at least 110% or even more.
  • the washed filaments are then dried by known means, for example in a dryer or on rollers.
  • the temperature of this drying can vary within wide limits as well as the speed which is higher the higher the temperature. It is generally advantageous to carry out drying with a gradual rise in temperature, this temperature possibly reaching and even exceeding 200 ° C. for example.
  • the filaments are then subjected to hot over-stretching to improve their mechanical qualities and in particular their toughness, which may be advantageous for certain jobs.
  • This hot over-stretching can be carried out by any known means: oven, plate, roll, roll and plate, preferably in a closed enclosure. It must be carried out at a temperature of at least 150 ° C, which can reach and even exceed 200 to 300 ° C. Its rate is generally at least 150% but it can vary within wide limits depending on the qualities desired for the wire. finished.
  • the total draw ratio is at least 250%, preferably at least 260%.
  • the drawing and overdrawing assembly can be carried out in one or more stages, continuously or discontinuously with the preceding operations.
  • secondary stretching can be combined with drying. For this, it is sufficient to provide, at the end of the drying, a higher temperature zone allowing overstretching.
  • a PAI solution is prepared from: in dimethylethylene urea of pH ⁇ 7 so as to obtain a concentration of 21 0/0, the polydispersity index of the polymer is 1.78.
  • the solution of viscosity 598 poises, is extruded in an aqueous coagulating bath containing dimethylethylene urea.
  • the filaments leave the coagulating bath in the gel state and are drawn in air at ordinary temperature. They are washed with water in a bath to remove the solvent and dried on rollers.
  • the solution of this polymer in the DMEU has a concentration of 21% and a viscosity of 781 poises. It is spun under the following conditions:
  • the mechanical properties of the wires are as follows:
  • a PAI solution of the same chemical structure as that described in Example 1 is prepared in a mixture of DMEU / DMF in proportion 72/28.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Artificial Filaments (AREA)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Hydrogenated Pyridines (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)
  • Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
  • Materials For Medical Uses (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Organic Insulating Materials (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)

Abstract

The present invention relates to heat-resistant filaments, yarns and fibres based on polyamide-imide. They have a polydispersity index I </= 2.2, a tenacity at break >/= 45 cN/tex, a Young's modulus >/= 3.8 GPa, an elongation </= 25%, a colour defined by the luminance gamma > 25%, the whiteness W < 30 and the yellowing index YI > 170. In addition, they have very good stability to light, quantified by the retention of the mechanical characteristics. They find wide application in work and protective clothing.

Description

La présente invention concerne des fils synthétiques thermostables à base de polyamide-imide de propriétés améliorées.The present invention relates to thermostable synthetic yarns based on polyamide-imide with improved properties.

Elle concerne également un procédé d'obtention de tels fils.It also relates to a process for obtaining such threads.

Il est déjà connu, selon le FR 2 079 785 de préparer des fils brillants à base de polyamide-imide contenant au moins 3 % d'enchainement issus de dicarboxy-3,5 benzène sulfonate alcalin ou alcalinoterreux, par filage humide d'une solution de polymère dans la N-méthylpyrrolidone, dans un bain coagulant aqueux contenant également de la N-méthylpyrrolidone puis étirage, lavage, séchage.It is already known, according to FR 2 079 785, to prepare shiny yarns based on polyamide-imide containing at least 3% of chains originating from dicarboxy-3,5 benzene sulfonate alkali or alkaline earth, by wet spinning of a solution of polymer in N-methylpyrrolidone, in an aqueous coagulating bath also containing N-methylpyrrolidone then drawing, washing, drying.

Mais de tels fils possèdent des caractéristiques mécaniques trop faibles pour certaines applications et un coloration jaune-marron trop importante et présentent une dégradation thermique et une mauvaise résistance à la photodégradation.However, such wires have mechanical characteristics that are too weak for certain applications and too yellow-brown coloring and exhibit thermal degradation and poor resistance to photodegradation.

Les fils de polyamide-imide selon la présente invention possèdent des caractéristiques nettement supérieures à celles des fils de polyamide-imide de l'art antérieur. Ils possèdent la structure chimique suivante :

  • - des unités amide-imide (A) de formule
    Figure imgb0001
  • - des unités amide (B) de formule
  • -NH-R-NH-CO-R2-CO-
  • - et éventuellement des unités amide (C) de formule
    Figure imgb0002
    dans lesquelles R représente un radical aromatique divalent, R1 représente un radical aromatique trivalent, R2 représente un radical aromatique divalent et M un métal alcalin ou alcalino terreux, les unités A représentant 80 à 100 % de l'ensemble des unités, les unités B représentant 1 à 5 % de l'ensemble des unités et les unités C représentant 0 à 20 % de l'ensemble des unités.
The polyamide-imide threads according to the present invention have characteristics clearly superior to those of the polyamide-imide threads of the prior art. They have the following chemical structure:
  • - amide-imide units (A) of formula
    Figure imgb0001
  • - amide units (B) of formula
  • -NH-R-NH-CO-R 2 -CO-
  • - and optionally amide units (C) of formula
    Figure imgb0002
     in which R represents a divalent aromatic radical, R 1 represents a trivalent aromatic radical, R 2 represents a divalent aromatic radical and M an alkali or alkaline earth metal, the units A representing 80 to 100% of all the units, the units B representing 1 to 5% of all the units and C units representing 0 to 20% of all the units.

Les fils selon l'invention sont également caractérisés par un indice de polydispersité I ≦ 2,2 und ténacité > 45 cN/tex, un module de Young ≧ 3,8 GPa, un allongement ≦ 25 % et une couleur définie par la luminance y > 25 %, le degré de blanc DB < 30, l'indice de jaune IJ > 170.The strands according to the invention are also characterized by a polydispersity index I ≦ 2.2 and tenacity> 45 cN / tex, a Young's modulus ≧ 3.8 GPa, an elongation ≦ 25% and a color defined by the luminance y > 25%, the degree of white DB <30, the yellow index IJ> 170.

De préférence, la ténacité est de l'ordre de 50 à 55 cN/tex, le module ≧ 4 GPa, la luminance y > 30 %, de degré de blanc < 28, et l'indice de jaune > 190.Preferably, the toughness is of the order of 50 to 55 cN / tex, the module ≧ 4 GPa, the luminance y> 30%, of degree of white <28, and the index of yellow> 190.

La stabilité à la lumière des PAI selon l'invention est également très améliorée par rapport à celle des fils PAI connus jusque là. Elle est évaluée par la rétention des propriétés mécaniques : de ténacité à la rupture ≧ 50 %, de travail à la rupture a 18 %, d'allongement ≧ 35 %. La stabilité à la lumière est mesurée selon la méthode décrite ci-dessous.The light stability of the PAIs according to the invention is also much improved compared to that of the PAI wires known hitherto. It is evaluated by the retention of mechanical properties: tenacity at break ≧ 50%, working at break at 18%, elongation ≧ 35%. The light stability is measured according to the method described below.

Selon la présente invention on entend par polyamide-imide (PAI) des polymères obtenus par polycondensation dans tout solvant approprié :

  • - d'au moins un diisocyanate de formule : OCN-R-NCO dans laquelle R est un groupe aromatique divalent tel que le diphénylméthane-4,4 diisocyanate et de préférence le diphényléther 4,4' diisocyanate ou leurs mélanges, avec :
  • - un anhydrique acide aromatique tel que l'anhydride trimellique,
  • - un diacide aromatique tel que l'acide téréphtalique,
  • - et éventuellement un dicarboxybenzène sulfonate de métal alcalin ou alcalino terreux de préférence le dicarboxybenzène sulfonate de sodium ou de potassium.
According to the present invention, the term polyamide-imide (PAI) is understood to mean polymers obtained by polycondensation in any suitable solvent:
  • - at least one diisocyanate of formula: OCN-R-NCO in which R is a divalent aromatic group such as 4,4-diphenylmethane diisocyanate and preferably 4,4 'diphenyl ether diisocyanate or their mixtures, with:
  • - an anhydrous aromatic acid such as trimellic anhydride,
  • - an aromatic diacid such as terephthalic acid,
  • - And optionally an alkali or alkaline earth metal dicarboxybenzene sulfonate, preferably sodium or potassium dicarboxybenzene sulfonate.

Les fils selon l'invention possèdent une structure chimique telle que définie ci-dessus dans laquelle R est un radical tel que

Figure imgb0003
et de préférence
Figure imgb0004
et R1 de préférence un radical
Figure imgb0005
R2 de préférence un radical
Figure imgb0006
et M est de .préférence Na ou K.The yarns according to the invention have a chemical structure as defined above in which R is a radical such that
Figure imgb0003
 and preferably
Figure imgb0004
 and R 1 preferably a radical
Figure imgb0005
 R 2 preferably a radical
Figure imgb0006
 and M is preferably Na or K.

Selon la présente demande les fils de PAI sont aussi caractérisés par une valeur de l'indice de polydispersité 1 ≦ 2,2. Cet indice correspond au rapport
Mw, les valeurs de Mn et Mw étant déterminées par chromatographie d'exclusion sur gel (GPC) dans la NMP Mn.
à 80°C et 0,1 mole/litre de bromure de lithium, les masses étant exprimées par rapport à un étalonnage de polystyrène.According to the present application, the PAI wires are also characterized by a value of the polydispersity index 1 ≦ 2.2. This index corresponds to the ratio
M w , the values of M not and M w being determined by gel exclusion chromatography (GPC) in the NMP Mn .
at 80 ° C. and 0.1 mole / liter of lithium bromide, the masses being expressed relative to a polystyrene calibration.

L'indice de polydipersité des fils de PAI selon l'invention reste faible : il correspond à un resserrement de la distribution des masses moléculaires. De manière surprenante il reste faible au niveau des fils terminés malgré les différents traitements subis par les filaments au cours de leur élaboration.The polydipersity index of the PAI yarns according to the invention remains low: it corresponds to a narrowing of the distribution of the molecular masses. Surprisingly, it remains weak at the level of the finished threads despite the various treatments undergone by the filaments during their preparation.

De manière surprenante les fils selon l'invention possèdent également des caractéristiques mécaniques et thermiques excellentes, bien supérieures à celles des fils de polyamide-imide selon le FR 2 079 785. En particulier la ténacité est supérieure ou égale à 45 cN/tex, de préférence à 50 ou 55 cN/tex. La mesure est effectuée sur un dynamomètre manuel ou automatique à gradient d'allongement constant sur une éprouvette de fil soumise à une traction longitudinale jusqu'à sa rupture. Le dynamomètre est relié à un calculateur qui fournit les valeurs numériques du titre (dtex) de la force à la rupture (cN) de la ténacité à la rupture =

Figure imgb0007
et de l'allongement à la rupture %. Les valeurs correspondent à une moyenne de 20 mesures.Surprisingly, the threads according to the invention also have excellent mechanical and thermal characteristics, much superior to those of the polyamide-imide threads according to FR 2 079 785. In particular, the toughness is greater than or equal to 45 cN / tex, of preferably 50 or 55 cN / tex. The measurement is carried out on a manual or automatic dynamometer with constant gradient of elongation on a wire test piece subjected to longitudinal traction until it breaks. The dynamometer is connected to a calculator which provides the numerical values of the strength (dtex) of the breaking strength (cN) of the breaking toughness =
Figure imgb0007
 and elongation at break%. The values correspond to an average of 20 measurements.

L'allongement à la rupture est mesuré comme indiqué ci-dessus. Il est inférieur ou égal à 25 %.The elongation at break is measured as indicated above. It is less than or equal to 25%.

Le module de Young E longitudinal des fils PAI selon l'invention est ≧ 3,8 GPa, de préférence ≧ 4 GPa. C'est le rapport

Figure imgb0008
obtenu au départ de la courbe force/allongement. La force spécifique (ténacité) correspond au rapport:
Figure imgb0009
Δ1 étant l'accroissement de la longueur de l'éprouvette à l'instant t auquel correspond le titre réel et Io la longueur initiale de l'éprouvette.The longitudinal Young E modulus of the PAI wires according to the invention is ≧ 3.8 GPa, preferably ≧ 4 GPa. This is the report
Figure imgb0008
 obtained at the start of the force / elongation curve. The specific force (tenacity) corresponds to the ratio:
Figure imgb0009
 Δ1 being the increase in the length of the test piece at time t to which the actual titer corresponds and Io the initial length of the test piece.

Le fil PAI est selon l'invention également caractérisé par une faible coloration de surface qui est évaluée par trois valeurs essentielles :

  • - la luminance Y % > 25 %, de préférence > 30 %
  • - le degré de blanc DB < 30, de préférence < 28
  • - l'indice de jaune IJ > 170, de préférence > 190, mesurées de la manière suivante :
  • - l'échantillon est broyé dans un moulin à café de façon à obtenir une bourre de quelques millimètres d'épaisseur et 4 cm2. La bourre est placée entre 2 plaques de verre, le tout placé dans un appareil de marque "Elrepho" (Zeiss). Les résultats suivants sont obtenus :
  • - γ % : la luminance qui donne un classement de l'échantillon dans l'échelle des gris et qui traduit l'impression de clair et de foncé :
  • - γ % = 100 correspond à un blanc parfait
  • - γ % = 0 correspond à un noir parfait
According to the invention, the PAI yarn is also characterized by a low surface coloration which is evaluated by three essential values:
  • - luminance Y%> 25%, preferably> 30%
  • - the degree of white DB <30, preferably <28
  • - the yellow index IJ> 170, preferably> 190, measured as follows:
  • - the sample is ground in a coffee grinder so as to obtain a flock a few millimeters thick and 4 cm 2 . The wad is placed between 2 glass plates, the whole placed in an apparatus of mark "Elrepho" (Zeiss). The following results are obtained:
  • - γ%: the luminance which gives a classification of the sample in the gray scale and which translates the impression of light and dark:
  • - γ% = 100 corresponds to a perfect white
  • - γ% = 0 corresponds to a perfect black

Le degré de blanc définit un point de couleur dans le plan de chromaticité.The degree of white defines a point of color in the chromaticity plane.

L'indice de Jaune est une expression de la pureté colorimétrique dans le jaune.The Yellow index is an expression of the color purity in the yellow.

Les fils PAI selon l'invention possèdent également une bonne stabilité à la lumière mesurée après exposition dans des conditions sévères de vieillissement et quantifiée par :

  • - une rétention de ténacité à la rupture ≧ 50 o/o, de préférence ≧ 52 %.
  • - une rétention de travail à la rupture ≧ 18 %, de préférence > 20 %.
  • -une rétention de l'allongement a 35 %, de préférence 380/o.
PAI yarns according to the invention also have good light stability measured after exposure under severe aging conditions and quantified by:
  • - a retention of fracture toughness ≧ 50 o / o, preferably ≧ 52%.
  • - a work retention at break ≧ 18%, preferably> 20%.
  • -a retention of the elongation at 35%, preferably 380 / o.

Les mesures de stabilité à la lumière sont effectuées dans une enceinte qui permet d'étudier expérimentalement le photovieillissement des polymères en atmosphère sèche. Les échantillons à éprouver sont disposés sur une tourelle cylindrique animée d'un mouvement de rotation circulaire située au centre d'une enceinte parallélépipédique dont les quatre coins sont occupés par une lampe à vapeur de mercure "moyenne pression" type MAZDA MA 400 Watts. L'envloppe ne laisse passer que les radiations supérieures à 300 nm (spectre solaire). La température dans l'enceinte est de 60°C.The light stability measurements are carried out in an enclosure which makes it possible to experimentally study the photoaging of polymers in a dry atmosphere. The samples to be tested are placed on a cylindrical turret driven by a circular rotational movement located in the center of a parallelepipedic enclosure, the four corners of which are occupied by a "medium pressure" mercury vapor lamp type MAZDA MA 400 Watts. The envelope allows only radiation above 300 nm (solar spectrum) to pass through. The temperature in the enclosure is 60 ° C.

Mode opératoire :Procedure:

La fenêtre en papier de 1,4 cm sur laquelle est fixé l'échantillon lors de la détermination des propriétés mécaniques sur INSTRON est elle même placée sur un des 24 supports de la tourelle de la chambre. Après l'exposition on récupère la fenêtre en papier et l'on détermine les caractéristiques mécaniques du monofilament selon la méthode de détermination des propriétés mécaniques indiquée ci-dessus.The 1.4 cm paper window on which the sample is fixed when determining the mechanical properties on INSTRON is itself placed on one of the 24 supports of the chamber turret. After the exposure, the paper window is recovered and the mechanical characteristics of the monofilament are determined according to the method of determining the mechanical properties indicated above.

Les résultats sont présentés sous forme de courbes donnant le pourcentage des caractéristiques mécaniques restant à une fibre exposée par rapport à une non exposée en fonction de la durée d'exposition. Les valeurs obtenues dépendent des monomères de départ, les meilleurs résultats étant obtenus avec le diisocyanate 4,4' diphényléther.The results are presented in the form of curves giving the percentage of mechanical characteristics remaining in an exposed fiber compared to an unexposed fiber as a function of the duration of exposure. The values obtained depend on the starting monomers, the best results being obtained with the 4,4 'diphenyl ether diisocyanate.

Des comparaisons ont aussi été faites par rapport aux fils de PAI selon le FR 2 079 785.Comparisons have also been made with the sons of PAI according to FR 2 079 785.

Les fils selon l'invention ont une nette supériorité par rapport aux fils PAI connus.The yarns according to the invention have a clear superiority compared to known PAI yarns.

Les fils selon l'invention possèdent aussi une bien meilleure tenue thermique que celle des fils PAI connus : elle est évaluée par la vitesse de dégradation correspondant à un pourcentage de perte de poids en fonction du temps à une température de 375°, sous air.The yarns according to the invention also have a much better thermal resistance than that of known PAI yarns: it is evaluated by the rate of degradation corresponding to a percentage of weight loss as a function of time at a temperature of 375 °, in air.

La dégradation isothermique des fils de PAI selon l'invention est généralement ≦ 3 % par heure, et de préférence ≦ 2 % par heure.The isothermal degradation of PAI yarns according to the invention is generally ≦ 3% per hour, and preferably ≦ 2% per hour.

Le niveau de cette dégradation dépend également des monomères de départ, les meilleurs résultats étant obtenus avec le diisocyanate 4,4' diphényléther.The level of this degradation also depends on the starting monomers, the best results being obtained with 4,4 'diphenyl ether diisocyanate.

Les filaments, fils, fibres selon la présente invention peuvent être utilisés seuls ou mélangés avec des fils ou fibres naturels ou synthétiques dans le but de modifier ou d'améliorer certaines propriétés. Ils sont particulièrement intéressants pour le réalisation de vêtements de travail, de protection, gràce à leurs propriétés mécaniques et à leur résistance thermique et à la lumière. De plus les fils obtenus sont faciles à teindre dans tous les coloris avec des colorants basiques.The filaments, threads, fibers according to the present invention can be used alone or mixed with natural or synthetic threads or fibers in order to modify or improve certain properties. They are particularly interesting for the production of work and protective clothing, thanks to their mechanical properties and their thermal and light resistance. In addition, the yarns obtained are easy to dye in all colors with basic dyes.

Les fils de PAI selon la présente invention sont obtenus par filage à l'humide à partir de solutions de polymère dans un solvant ou mélange solvant. La concentration des solutions de filage est comprise entre 4 et 35 %, de préférence entre 5 et 35 %. Les polymères sont dissous dans un solvant ou mélange solvant contenant de 5 à 100 % en poids de diméthyléthylène urée de pH < 7 et 0 à 55 % d'un solvant polaire aprotique anhydre tel que la N-méthylpyrrolidone, le diméthylacétamide, le diméthyformamide, la tétraméthylurée ou la y butyrolactone.The PAI yarns according to the present invention are obtained by wet spinning from solutions of polymer in a solvent or solvent mixture. The concentration of the spinning solutions is between 4 and 35%, preferably between 5 and 35%. The polymers are dissolved in a solvent or solvent mixture containing from 5 to 100% by weight of dimethylethylene urea of pH <7 and 0 to 55% of an anhydrous aprotic polar solvent such as N-methylpyrrolidone, dimethylacetamide, dimethylformamide, tetramethylurea or y butyrolactone.

Les solutions utilisables dans le procédé selon l'invention doivent posséder une viscosité comprise entre 100 et 200 poises, de préférence entre 150 et 160 poises. Elles peuvent également contenir divers adjuvants tels que pigments, matifiants pour améliorer certaines propriétés.The solutions which can be used in the process according to the invention must have a viscosity of between 100 and 200 poises, preferably between 150 and 160 poises. They can also contain various adjuvants such as pigments, matifiers to improve certain properties.

Les solutions de PAI sont filées dans un bain coagulant aqueux binaire ou ternaire contenant un solvant ou mélange solvant en proportion de 30 à 80 % de solvant et 20 à 70 % d'eau, de préférence 40 à 70 % de solvant(s).The PAI solutions are spun in a binary or ternary aqueous coagulating bath containing a solvent or solvent mixture in proportion of 30 to 80% of solvent and 20 to 70% of water, preferably 40 to 70% of solvent (s).

Le solvant utilisé peut être le diméthylformamide, la diméthylèthylène urée ou leur mélange. La bain de filage est maintenu entre 15 et 40°C de préférence 20 à 30°C. La longueur du bain coagulant est adaptable en fonction généralement de la concentration en solvant et de la température. Des bains ayant une plus forte teneur en solvant permettent généralement d'obtenir des fils de meilleure étirabilité, donc de meilleures propriétés finales. Toutefois, lorsque la concentration en solvant est plus élevée une plus grande longueur de bain est nécessaire. Les filaments sortant du bain coagulant à l'état de gel sont ensuite étirés, par example dans l'air à un taux défini par le rapport

Figure imgb0010
x 100, V2 étant la vitesse des rouleaux d'étirage, V1 celles des rouleaux délivreurs. Le taux d'étirage des fils à l'état de gel est d'au moins 100 o/o, de préférence au moins 110 % ou même plus.The solvent used can be dimethylformamide, dimethylethylene urea or a mixture thereof. The spinning bath is maintained between 15 and 40 ° C, preferably 20 to 30 ° C. The length of the coagulating bath is adaptable generally depending on the solvent concentration and the temperature. Baths with a higher solvent content generally make it possible to obtain yarns with better stretchability, therefore better final properties. However, when the solvent concentration is higher, a longer bath length is necessary. The filaments leaving the coagulating bath in the gel state are then drawn, for example in air at a rate defined by the ratio
Figure imgb0010
 x 100, V2 being the speed of the drawing rollers, V1 those of the delivery rollers. The rate of drawing of the strands in the gel state is at least 100%, preferably at least 110% or even more.

Après étirage les filaments sont lavés par des moyens connus pour les débarrasser du ou des solvants. Ce lavage peut être effectué par exemple dans des bacs successifs dans lesquels de l'eau circule à contre-courant ou sur des rouleaux laveurs ou par tout autre moyen, de préférence à température ambiante.After drawing the filaments are washed by known means to rid them of the solvent (s). This washing can be carried out for example in successive tanks in which water circulates against the current or on washing rollers or by any other means, preferably at room temperature.

Les filaments lavés sont alors séchés par des moyens connus, par exemple dans un séchoir ou sur des rouleaux. La température de ce séchage peut varier dans de grandes limites ainsi que la vitesse qui est d'autant plus grande que la température est plus élevée. On a généralement avantage a effectuer un séchage avec élévation progressive de la température, cette température pouvant atteindre et même dépasser 200° C par exemple.The washed filaments are then dried by known means, for example in a dryer or on rollers. The temperature of this drying can vary within wide limits as well as the speed which is higher the higher the temperature. It is generally advantageous to carry out drying with a gradual rise in temperature, this temperature possibly reaching and even exceeding 200 ° C. for example.

Les filaments subissent ensuite un surétirage à chaud pour améliorer leurs qualités mécaniques et en particulier leur ténacité, ce qui peut être intéressant pour certains emplois.The filaments are then subjected to hot over-stretching to improve their mechanical qualities and in particular their toughness, which may be advantageous for certain jobs.

Ce surétirage à chaud peut être effectué par tout moyen connu : four, plaque, rouleau, rouleau et plaque, de préférence dans une enceinte fermée. Il doit être effectué à température d'au moins 150°C, pouvant atteindre et même dépasser 200 à 300° C. Son taux est généralement d'au moins 150 % mais il peut varier dans de grandes limites selon les qualités désirées pour le fil fini. Le taux d'étirage total est d'au moins 250 %, de préférence au moins 260 %.This hot over-stretching can be carried out by any known means: oven, plate, roll, roll and plate, preferably in a closed enclosure. It must be carried out at a temperature of at least 150 ° C, which can reach and even exceed 200 to 300 ° C. Its rate is generally at least 150% but it can vary within wide limits depending on the qualities desired for the wire. finished. The total draw ratio is at least 250%, preferably at least 260%.

L'ensemble étirage et surétirage peut être effectué en un ou plusieurs stades, en continu ou en discontinu avec les opérations précédentes. De plus l'étirage secondaire peut être combiné avec le séchage. Il suffit pour cela de prévoir, à la fin du séchage, une zone de température plus élevée permettant le surétirage.The drawing and overdrawing assembly can be carried out in one or more stages, continuously or discontinuously with the preceding operations. In addition, secondary stretching can be combined with drying. For this, it is sufficient to provide, at the end of the drying, a higher temperature zone allowing overstretching.

EXEMPLES 1 à 3 -EXAMPLES 1 to 3 -

On prépare une solution de PAI à partir :

Figure imgb0011
dans la diméthyléthylène urée de pH < 7 de manière à obtenir une concentration de 21 0/0, l'indice de polydispersité du polymère est de 1,78. La solution, de viscosité 598 poises, est extrudée dans un bain coagulant aqueux contenant de la diméthyléthylène urée. Les filaments sortent du bain coagulant à l'état de gel et sont étirés dans l'air à température ordinaire. Ils sont lavés à l'eau dans un bain pour éliminer le solvant et séchés sur des rouleaux.A PAI solution is prepared from:
Figure imgb0011
 in dimethylethylene urea of pH <7 so as to obtain a concentration of 21 0/0, the polydispersity index of the polymer is 1.78. The solution, of viscosity 598 poises, is extruded in an aqueous coagulating bath containing dimethylethylene urea. The filaments leave the coagulating bath in the gel state and are drawn in air at ordinary temperature. They are washed with water in a bath to remove the solvent and dried on rollers.

Les filaments lavés et séchés subissent un surétirage dans un four maintenu à une température élevée puis renvidés. Les conditions précises du procédé sont réunies dans le tableau 1 ci-dessous :

Figure imgb0012
The washed and dried filaments are over drawn in an oven maintained at a high temperature and then rewound. The precise conditions of the process are gathered in table 1 below:
Figure imgb0012

Les propriétés mécaniques des fils obtenus à partir des essais de traction sont réunies dans le tableau 2 suivant, comparativement à des fils obtenus à partir d'une solution de PAI dans la N-méthypyrrolidone et filés dans les conditions du brevet français FR 2079 785 déposé le 12/02/1970 (Exemple 3C).

Figure imgb0013
Figure imgb0014
Figure imgb0015
- Après exposition dans l'enceinte pendant 20 heures seulement, selon la méthode décrite ci-dessus, on remarque également de fàçon spectaculaire la chute importante en masse de polymère PAI selon l'exemple 3C : Mw passe de 147120 à 62950 soit une perte de 84170. Par contre un polymère selon l'invention perd nettement moins : Mw passe de 116400 à 99720 soit une perte de 16680. De même l'indice de polydispersité du polymère selon l'invention après exposition passe de 2,05 à 2,13 alors que selon l'exemple 3C, l'indice de polydispersité passe de 3 à 4,12.The mechanical properties of the wires obtained from the tensile tests are brought together in the following table 2, compared to wires obtained from a solution of PAI in N-methypyrrolidone and spun. under the conditions of French patent FR 2079 785 filed on 02/12/1970 (Example 3C).
Figure imgb0013
Figure imgb0014
Figure imgb0015
 - After exposure in the enclosure for only 20 hours, according to the method described above, we also notice spectacularly the significant drop in mass of PAI polymer according to Example 3C: Mw goes from 147,120 to 62,950, ie a loss of 84170. On the other hand, a polymer according to the invention loses significantly less: Mw goes from 116,400 to 99,720, ie a loss of 16,680. Similarly, the polydispersity index of the polymer according to the invention after exposure goes from 2.05 to 2.13 whereas according to Example 3C, the polydispersity index goes from 3 to 4.12.

On constate donc que la chute des propriétés mécaniques traduit une dégradation des chaines de polymère plus importante pour les fils de l'exemple 3C que pour les fils selon l'invention.

Figure imgb0016
It is therefore found that the drop in mechanical properties reflects a more significant degradation of the polymer chains for the wires of Example 3C than for the wires according to the invention.
Figure imgb0016

- EXEMPLE 4 -- EXAMPLE 4 -

On prépare un polymère identique à celui décrit dans les exemples 1,2,3 mais possédant un indice de polydipersité I = 1,85.A polymer identical to that described in Examples 1,2,3 is prepared, but having a polydipersity index I = 1.85.

La solution de ce polymère dans la DMEU possède une concentration de 21 % et une viscosité de 781 poises. Elle est filée dans les conditions suivantes :

Figure imgb0017
Les propriétés mécaniques des fils sont les suivantes:
Figure imgb0018
Figure imgb0019
Figure imgb0020
 The solution of this polymer in the DMEU has a concentration of 21% and a viscosity of 781 poises. It is spun under the following conditions:
Figure imgb0017
 The mechanical properties of the wires are as follows:
Figure imgb0018
Figure imgb0019
Figure imgb0020

- Indice de polydispersité :- Polydispersity index:

après 20 heures d'exposition 2,2after 20 hours of exposure 2.2

- Tenue thermique :- Thermal resistance:

Cinétique de dégradation (%.h-1) : 2Degradation kinetics (% .h -1 ): 2

- EXEMPLES 5 à 7 :- EXAMPLES 5 to 7:

On prépare une solution de PAI de même structure chimique que celle décrite dans l'exemple 1 dans un mélange de DMEU/DMF en proportion 72/28. Le polymère obtenu a un indice de polydispersité 1=1,73 et la solution de concentration 21 % a une viscosité de 405 poises.A PAI solution of the same chemical structure as that described in Example 1 is prepared in a mixture of DMEU / DMF in proportion 72/28. The polymer obtained has a polydispersity index 1 = 1.73 and the concentration solution 21% has a viscosity of 405 poises.

Elle est extrudée dans un bain coagulant aqueux puis les filaments sont étirés et traités dans les conditions réunies dans le tableau 3 suivant :

Figure imgb0021
Les propriétés mécaniques des fils obtenus sont réunis dans le tableau 4 suivant :
Figure imgb0022
Figure imgb0023
Figure imgb0024
A titre de comparaison une fibre polymétaphénylèneisophtalamide connue dans le commerce sous la marque Nomex T 450 a été soumise au même test de photodégradation que les fibres de l'invention. La rétention de certaines propriétés est indiquée dans le tableau ci-dessus.
Figure imgb0025
 It is extruded in an aqueous coagulating bath, then the filaments are drawn and treated under the conditions set out in Table 3 below:
Figure imgb0021
 The mechanical properties of the wires obtained are collated in the following table 4:
Figure imgb0022
Figure imgb0023
Figure imgb0024
 By way of comparison, a polymetaphenyleneisophthalamide fiber known commercially under the brand Nomex T 450 was subjected to the same photodegradation test as the fibers of the invention. The retention of certain properties is indicated in the table above.
Figure imgb0025

Claims (15)

1) - Filaments, fils et fibres synthétiques à base de polyamides-imides résistants à la chaleur, caractérisés par le fait qu'ils comportent :- des unités amide-imide (A) de formule :
Figure imgb0026
 - des unités amide (B) de formule : -NH-R-NH-CO-R2-CO - éventuellement des unités amide (C) de formule :
Figure imgb0027
dans lesquelles R et R2 représentent chacun un radical aromatique divalent, Ri un radical aromatique trivalent et M un métal alcalin ou alcalino terreux, les unités (A) représentant 80 à 100 % de l'ensemble des unités, les unités (B) 1 à 5 % de l'ensemble des unités, les unités (C) 0 à 20 % de l'ensemble des unités, et qu'ils possèdent : - un indice de polydispersité 1 < 2,2 - une ténacité de rupture ≧ 45 cN/tex - un module de Young ≧ 3,8 GPa - un allongement ≦ 25 % - une couleur définie par la luminance γ > 25 %, le degré de blanc DB < 30, l'indice de jaune IJ > 170. 1) - Filaments, yarns and synthetic fibers based on heat-resistant polyamide-imides, characterized in that they comprise: - amide-imide units (A) of formula:
Figure imgb0026
 - amide units (B) of formula: -NH-R-NH-CO-R 2 -CO - optionally amide units (C) of formula:
Figure imgb0027
 in which R and R 2 each represent a divalent aromatic radical, Ri a trivalent aromatic radical and M an alkali or alkaline earth metal, the units (A) representing 80 to 100% of all the units, the units (B) 1 at 5% of all units, units (C) 0 to 20% of all units, and that they have: - a polydispersity index 1 <2.2 - a fracture toughness ≧ 45 cN / tex - a Young's module ≧ 3.8 GPa - an elongation ≦ 25% - a color defined by the luminance γ> 25%, the degree of white DB <30, the yellow index IJ> 170. 2) - Filaments, fils et fibres selon la revendication 1 caractérisés par le fait qu'ils possèdent une stabilité à la lumière quantifiée par une rétention de ténacité de rupture > 50 %, de travail à la rupture ≧ 18 %, d'allongement ≧ 35 %.2) - Filaments, threads and fibers according to claim 1, characterized by the fact that they have a light stability quantified by a retention of breaking toughness> 50%, of working at break ≧ 18%, of elongation ≧ 35%. 3) - Filaments, fils et fibres selon la revendication 2 caractérisés par le fait qu'ils possèdent une rétention de ténacité > 52 %, de travail à la rupture > 20 %, d'allongement ≧ 38 %.3) - Filaments, threads and fibers according to claim 2 characterized in that they have a tenacity retention> 52%, work at break> 20%, elongation ≧ 38%. 4) - Filaments, fils et fibres selon la revendication 1 caractérisés par le fait qu'ils possèdent une stabilité thermique définie par la cinétique de dégradation correspondant à une perte de poids en fonction de la température ≦ 3 % par heure.4) - Filaments, threads and fibers according to claim 1 characterized in that they have a thermal stability defined by the kinetics of degradation corresponding to a weight loss as a function of the temperature ≦ 3% per hour. 5) - Filaments, fils et fibres selon la revendication 4 caractérisés par le fait qu'ils possèdent une cinétique de dégradation ≦ 2 % par heure.5) - Filaments, threads and fibers according to claim 4, characterized in that they have a kinetics of degradation ≦ 2% per hour. 6) - Filaments, fils et fibres selon la revendication 1 caractérisés par le fait que la ténacité de rupture est ≧ 55 cN/tex6) - Filaments, threads and fibers according to claim 1, characterized in that the fracture toughness is ≧ 55 cN / tex 7) - Filaments, fils et fibres selon la revendication 1 caractérisés par le fait que le module de Young est ≧ 5 GPa.7) - Filaments, threads and fibers according to claim 1 characterized in that the Young's modulus is ≧ 5 GPa. 8) - Filaments, fils et fibres selon la revendication 1 caractérisés par le fait que la luminance est a 300/0.8) - Filaments, threads and fibers according to claim 1 characterized in that the luminance is at 300/0. 9) - Filaments, fils et fibres selon la revendication 1 caractérisés par le fait que le degré de blanc est < 28.9) - Filaments, threads and fibers according to claim 1, characterized in that the degree of white is <28. 10) - Filaments, fils et fibres selon la revendication 1 caractérisés par le fait que l'indice de jaune est > 190.10) - Filaments, threads and fibers according to claim 1, characterized in that the yellowness index is> 190. 11) - Filaments, fils et fibres selon la revendication 1 caractérisés par le fait que R est un radical de formule
Figure imgb0028
 11) - Filaments, threads and fibers according to claim 1, characterized in that R is a radical of formula
Figure imgb0028
 12) - Filaments, fils et fibres selon la revendication 1 caractérisés par le fait que Ri est un radical de formule
Figure imgb0029
 12) - Filaments, threads and fibers according to claim 1, characterized in that R i is a radical of formula
Figure imgb0029
 13) - Filaments, fils et fibres selon la revendication 1 caractérisés par le fait que R2 est un radical de formule
Figure imgb0030
 13) - Filaments, threads and fibers according to claim 1, characterized in that R 2 is a radical of formula
Figure imgb0030
 14) - Procédé pour l'obtention de filaments, fils et fibres synthétiques à base de polyamides-imides selon la revendication 1) caractérisé par le fait qu'ils sont obtenus dans un solvant ou mélange solvant contenant 5-100 % en poids de diméthyléthylène urée et 0-55 % d'un solvant polaire anhydre tel que la N-méthylpyrrolidone, le diméthylacétamide, le diméthylformamide, la tétraméthylurée ou la y butyrolactone, dans un bain coagulant aqueux binaire ou ternaire contenant un mélange solvant en proportion de 30-80 % en poids de solvant et 20-70 % d'eau, maintenu à température comprise entre 15 et 40°C, étirage des filaments à l'état de gel d'au moins 100 %, lavage à l'eau à contre-courant, séchage par des moyens connus, surétirage à température d'au moins 150° C, de 150% au moins, le taux total d'étirage étant d'au moins 250 %.14) - Process for obtaining filaments, threads and synthetic fibers based on polyamide-imides according to claim 1) characterized in that they are obtained in a solvent or solvent mixture containing 5-100% by weight of dimethylethylene urea and 0-55% of an anhydrous polar solvent such as N-methylpyrrolidone, dimethylacetamide, dimethylformamide, tetramethylurea or y butyrolactone, in a binary or ternary aqueous coagulant bath containing a solvent mixture in proportion of 30-80 % by weight of solvent and 20-70% of water, maintained at temperature between 15 and 40 ° C, drawing of the filaments in the gel state of at least 100%, washing with water against the current , drying by known means, over-drawing at temperature of at least 150 ° C., of at least 150%, the total rate of drawing being at least 250%. 15) - Procédé pour l'obtention de filaments, fils et fibres synthétiques à base de polyamides-imides résistants à la chaleur caractérisé par le fait que le bain coagulant contient comme solvant du diméthylformamide, de la diméthyléthylène urée ou leur mélange.15) - Process for obtaining filaments, threads and synthetic fibers based on heat-resistant polyamide-imides, characterized in that the coagulating bath contains as solvent dimethylformamide, dimethylethylene urea or their mixture.
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EP0549494A1 (en) * 1991-12-24 1993-06-30 Rhone-Poulenc Fibres Process for spinning solutions of polyamide-imides based on totuylene or metaphenylene diisocyanates and fibres made thereof
US6258916B1 (en) 1991-12-24 2001-07-10 Rhone-Poulenc Fibres Process for spinning from solution of polyamide-imides (PAI) based on tolylene or meta-phenylene diisocyanates and fibers thus obtained
EP0770714A1 (en) * 1994-05-13 1997-05-02 Toyo Boseki Kabushiki Kaisha Polyamide-imide fibers for a bug filter
US7887788B2 (en) 2002-09-06 2011-02-15 L'oreal S.A. Cosmetic composition comprising a tacky wax
US7923002B2 (en) 2002-09-06 2011-04-12 L'oreal S.A. Composition for coating keratin fibres comprising a tacky wax

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JPH02104721A (en) 1990-04-17
DE68924946T2 (en) 1996-07-04
CN1031290C (en) 1996-03-13
CA1334612C (en) 1995-03-07
IE69380B1 (en) 1996-09-04
CN1041406A (en) 1990-04-18
US5159052A (en) 1992-10-27
FI894450A0 (en) 1989-09-20
ATE130879T1 (en) 1995-12-15
FR2643089B1 (en) 1991-05-10
FI894450A (en) 1990-03-22
DK464489A (en) 1990-03-22
BR8904858A (en) 1990-05-08
ES2079384T3 (en) 1996-01-16
IE893013L (en) 1990-03-21
FR2643089A1 (en) 1990-08-17
DE68924946D1 (en) 1996-01-11
NO893499L (en) 1990-03-22
EP0360708B1 (en) 1995-11-29
JP2744084B2 (en) 1998-04-28
NO893257D0 (en) 1989-08-14
DK464489D0 (en) 1989-09-20
RU1838468C (en) 1993-08-30
NO893499D0 (en) 1989-08-31

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