WO1998055674A1 - Monofilament en polyester(amide) aromatique thermotrope - Google Patents
Monofilament en polyester(amide) aromatique thermotrope Download PDFInfo
- Publication number
- WO1998055674A1 WO1998055674A1 PCT/EP1998/003386 EP9803386W WO9855674A1 WO 1998055674 A1 WO1998055674 A1 WO 1998055674A1 EP 9803386 W EP9803386 W EP 9803386W WO 9855674 A1 WO9855674 A1 WO 9855674A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- monofilament
- monofilaments
- tex
- polymer
- spinning
- Prior art date
Links
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
- D01F6/78—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products
- D01F6/84—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from copolyesters
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/08—Melt spinning methods
- D01D5/088—Cooling filaments, threads or the like, leaving the spinnerettes
-
- 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
- D01F6/82—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from polyester amides or polyether amides
Definitions
- the present invention relates to polyester (amide) aromatic thermotropic fibers. more specifically to the monofilaments of such polymers, as well as to the processes for obtaining such monofilaments.
- thermotropic aromatic polyester amide
- amide thermotropic aromatic polyester
- the raw spinning monofilament thus obtained is taken from a winding device at a speed of 590 m / min, to then be subjected to the post-polycondensation heat treatment on the receiving coil: this particularly long post-polycondensation phase on this type of polymer ( several hours) in fact implies that the treatment is carried out on a reel, generally in an oven, and not on a monofilament running continuously through this oven.
- the monofilaments have the following mechanical properties for a diameter of around 180 ⁇ m: initial modulus of 4300 cN / tex. 2.5% elongation at break and 130 cN / tex toughness.
- the monofilaments already have a very high initial modulus in the raw spinning state, greater than 4000 cN / tex.
- the postpolycondensation heat treatment being essentially intended to increase the toughness of the spun products.
- the primary purpose of the invention is to overcome the aforementioned drawbacks by proposing a new monofilament made of thermotropic aromatic polyester (amide) which, in the raw spinning state ("spun"), has the characteristic of not contracting hot.
- D being its diameter (in ⁇ m), or its thickness in the case of an oblong or flattened shape, Te its toughness (in cN / tex) and ⁇ L its variation in length (in%) after 2 minutes at 235 ⁇ 5 ° C under a pretension of 0.2 cN / tex.
- D is preferably included in a range from 80 to 230 ⁇ m, more preferably from 100 to 200 ⁇ m.
- the raw spinning monofilament of the invention has the advantage of having, for a given polymer and a given diameter D, a lower extension modulus combined with an elongation at break which is generally higher, which constitutes an advantageous compromise. It is known in fact that, in general, for fibers of liquid crystal origin with very high mechanical properties, such a combination is favorable to better properties in bending-compression, which are particularly stressed when articles made of it are to be reinforced. plastic and / or rubber, in particular tire casings; this better compromise observed on the raw spinning monofilaments is preserved on the heat-treated monofilaments which are derived therefrom.
- the raw spinning monofilament of the invention verifies the relationships:
- Mi being its initial modulus (in cN / tex) and Ar its elongation at break (in%).
- the monofilament of the invention is obtained by a new and specific spinning process which constitutes another object of the invention, this process being characterized in that it comprises the following stages:
- the raw spinning monofilament of the invention can be used as it is, or else heat-treated to obtain a post-polycondensed thermotropic aromatic polyester (amide) monofilament which constitutes another object of the invention.
- the invention further relates to the use of the monofilaments of the invention, whether in the assembled state or in a unitary thread, for the reinforcement of plastic and / or rubber articles, as well as its articles themselves, in particular the plies of rubber intended for the manufacture of tires and these tires themselves.
- optical anisotropy of the polymers is tested by observing in the molten phase (i.e. above the melting temperature of the polymer) a drop of polymer between crossed linear polarizer and analyzer of an optical polarization microscope (Olympus type BH2). at rest, that is to say in the absence of dynamic constraint.
- Olympus type BH2 optical polarization microscope
- the above preparation is optically anisotropic, that is to say that it depolarizes the light: thus placed between crossed linear polarizer and analyzer, it exhibits light transmission (more or less colored texture); an optically isotropic preparation, under the same observation conditions, does not have the above depolarization property, the field of the microscope remaining black.
- the term “monofilament” or “monofilament” is understood to mean a unitary filament whose diameter or thickness (that is to say the smallest transverse dimension of its cross section when this is not not circular), noted D. is at least equal to 40 ⁇ m (minimum titer of 1.7 tex).
- the above definition therefore covers both monofilaments of essentially cylindrical shape (ie with circular section) and oblong monofilaments. flattened monofilaments, or strips or films of thickness D.
- prior conditioning is meant the storage of the monofilaments (after drying) for at least 24 hours, before measurement, in a standard atmosphere. according to European standard DIN EN 20139 (temperature of 20 ⁇ 2 ° C; humidity of 65 ⁇ 2%).
- the titer of the monofilaments is determined on at least three samples, each corresponding to a length of 50 m, by weighing this length of monofilament.
- the title 45 is given in tex (weight in grams of 1000 m of monofilament - reminder: 0.1 1 1 tex equal to 1 denier).
- the mechanical properties in extension are measured in known manner using a ZWICK GmbH & Co (Germany) type 1435 or type 1445 traction machine.
- the monofilaments undergo a traction over an initial length of 400 mm at a nominal speed of 50 mm / min. All the results given are an average of 10 measurements.
- the toughness (breaking force divided by the title) and the initial modulus are indicated in cN / tex (centinewton per tex - reminder: 1 cN / tex equal to 0.11 g / den (gram per denier)).
- the initial modulus is defined as the slope of the linear part of the Force-Elongation curve, which occurs just after a standard pretension of 0.5 cN / tex.
- the elongation at break is indicated as a percentage.
- the diameter D of the monofilaments is determined by calculation from the titer of the monofilaments and their density, according to the formula:
- D being expressed in ⁇ m
- Ti being the titer in tex
- p being the density in g / cn (p is equal to approximately 1, 4 in the present case).
- the parameter D which then represents the smallest dimension of the monofilament in a plane normal to the axis of the latter, is determined no longer by calculation but experimentally, by optical microscopy on a cross section of this monofilament. the latter being for example previously coated in a resin to facilitate cutting.
- the thermal behavior of the monofilaments is analyzed, after prior conditioning, using a test known as a "length variation thermal test", the principle of which is well known to those skilled in the art in the field of textile fibers.
- the thermal variation in length denoted ⁇ L is measured by introduction of the monofilaments. under a pretension of 0.2 cN / tex, in a previously equilibrated oven at the temperature of 235 ° C ⁇ 5 ° C.
- the starting polymer is any polyester or thermotropic aromatic polyester amide which can be spun in the molten state.
- polyesters or polyester-amides called “fully aromatic” are known to those skilled in the art and have been described in a very large number of documents.
- thermotropic aromatic polyester this polymer consists essentially of repeating units (A) of 6-oxy-2-naphthoyl and (B) of 4-oxybenzoyl:
- the A: B molar ratio being in a range from 10:90 to 90:10. preferably from 20:80 to 30:70.
- Such a polymer sold in particular by the company Hoechst Celanese under the name of Vectra, has been described in US 4,161,470 and can be obtained by copolymerization of p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid . these two acids being optionally substituted. In known manner, it has an excellent compromise of properties in terms of thermal resistance, chemical resistance, ease of processing and spinning ability, due in particular to a relatively low melting point (hereinafter denoted Tm). low.
- Tm relatively low melting point
- a polymer of this type - Vectra type 900 or 950 with a molar ratio A: B equal to 27:73 - is widely known for conventional multifilament fibers (see for example J. Text. Inst. 1990. 81 No 4. pp. 561 -574) and was also used to obtain the monofilaments of the prior art described in the aforementioned application WO92 / 12018.
- the starting polymer for example in the form of granules or powder, is dried under vacuum and then introduced into an extruder having one or more different heating zones.
- the temperatures and the residence times imposed in these different zones are such that they allow the complete melting of the polymer, stable conditions of rotation and torque of extrusion screws and offering a regular supply of the spinning pump, and finally to avoid degradation of the polymer in the extruder.
- Tx extruder outlet temperature
- the die may comprise a single extrusion capillary or more depending on whether one wishes to spin a single monofilament or several monofilaments in parallel; we will consider below the case of a sector comprising a single capillary.
- the diameter of the capillary is not a critical parameter of the process: it can vary over a wide range, for example from 200 to 1500 ⁇ m, or even more, depending on the diameter D targeted.
- the invention also relates to cases where the monofilaments have a cross section other than circular, such a shape being obtainable for example by modifying the cross section of the extrusion capillary; for such monofilaments.
- parameter d then represents the smallest transverse dimension of the capillary, i.e. its smallest dimension measured in a plane normal to the direction of flow of the polymer.
- the die temperature denoted Tf is lower than the temperature T (polymer melting temperature).
- a liquid extrudate is thus obtained (flow of polymer) consisting of an elementary liquid vein having the form of a monofilament still liquid.
- This liquid polymer vein is then structured, oriented by drawing (see below drawing factor FEF spinning) in a layer of gaseous fluid, for a predetermined time ts, this before entering a liquid zone of thermal quenching.
- structuring duration means the total duration of passage of the flow of polymer in the layer of gaseous fluid, whatever the profile or gradient of stretching of the flow in this layer of gaseous fluid. .
- the layer of gaseous fluid is preferably air, the thickness of which, denoted Ag, can vary for example from a few centimeters to several meters, depending on the particular conditions of implementation of the invention, in particular according to the durations ts targeted.
- the thickness Ag of the layer of gaseous fluid is understood to mean the distance separating the outlet from the die and the inlet from the liquid thermal quenching zone.
- the temperature denoted Te of the layer of gaseous fluid is notably lower than Tf, Te being generally close to ambient temperature (approximately 20 ° C.).
- the structuring time ts (in seconds) is linked to the diameter D (in ⁇ m) of the raw spinning monofilament by the following relation (1):
- a structuring time ts lower than the critical value to above is a necessary condition to guarantee, whatever the diameter D aimed, the obtaining of a raw monofilament of spinning not contracting hot (ie showing a variation ⁇ L> 0 in the thermal variation test of length).
- the following relation (2) is verified: 1.5.10 -6 D 2 ⁇ ts ⁇ 6.10 "6 D 2 .
- the spinning speed (see below Vf ) is within a range of 500 to 1000 m / min and the thickness of the layer of gaseous fluid (Ag) is chosen to be greater than 0.50 meters and less than 2.0 meters.
- the flow of polymer thus structured, oriented enters the liquid thermal quenching zone where, in contact with the liquid agent, it solidifies and thus forms a monofilament.
- the liquid thermal quenching agent is water and its temperature, denoted Tl, is preferably lower than ambient temperature, for example of the order of 10 to 15 ° C.
- liquid thermal quenching operation simple means can be used, for example consisting of a bath containing the quenching liquid and through which the monofilament in formation circulates.
- the liquid quenching time is not a critical parameter and can vary, for example, from a few milliseconds to a few tenths of a second, or even a few seconds, depending on the particular conditions of implementation of the invention.
- the drawing factor and the spinning speed can vary within a very wide range, for example from 2 to 50 for the FEF and from 100 to 1500 m / min for Vf.
- the raw spinning monofilament thus obtained is then wound at the speed Vf. on a receiving coil 5. It can optionally be dried before winding, for example by continuous scrolling on heating rollers, or else be wound in the wet state and then dried on a reel, for example in ambient air or at a higher temperature in an oven, before pre-conditioning for the measurement of its thermal and mechanical properties.
- the initial modulus Mi and the elongation at break Ar of the monofilament of the invention can be largely modulated by the choice of the starting polymer and the spinning conditions, the initial modulus in particular being all the higher that the rigidity of the polymer is greater (use for example of thermotropic polyester amides).
- the raw spinning monofilament of the invention verifies the following relationships:
- their tenacity in the raw spinning state is preferably greater than 55 cN / tex, more preferably greater than 65 cN / tex ; their initial modulus, in the raw spinning state, is preferably between 2500 and 4000 cN / tex. more preferably at least equal to 3000 cN / tex and less than 4000 cN / tex.
- the post-polycondensation heat treatment, after spinning, essentially makes it possible to increase the toughness available on the monofilaments, by increasing the degree of polymerization of the polymer; generally, the more the heat treatment is carried out, the higher the toughness obtained after treatment.
- monofilaments made of thermotropic aromatic polyester (amide) said to be post-polycondensed, which derive directly from the raw spinning monofilaments described above.
- the coils of raw spinning monofilaments are treated in ovens in a known manner, at high temperatures, under vacuum or under inert gas, for example under flux.
- the post-polycondensed thermotropic aromatic polyester (amide) monofilament derived from the raw spinning monofilaments of the invention of diameter D at least equal to 40 ⁇ m. checks the following relationships:
- Mi being its initial modulus (in cN / tex), Ar its elongation at break (in%), and Te its toughness (in cN / tex). More preferably, its Mi module is between 2500 and 4000 cN / tex. more preferably still at least equal to 3000 cN / tex and less than 4000 cN / tex; its elongation at break Ar is preferably at least equal to 2.5.
- the raw spinning monofilaments of the invention can be used in various applications, in particular for the manufacture or reinforcement of different articles, in particular articles made of plastic and / or rubber. , for example belts, hoses, tire casings.
- a diameter at least equal to 80 ⁇ m is preferred in view of the wiring costs (need to limit the number of wires in the cables, for a given breaking strength), while a diameter greater than 230 ⁇ m is generally avoid to limit damage in bending-compression (disadvantage of large diameters with small radius of curvature). In addition, a diameter greater than 230 ⁇ m is hardly compatible with obtaining sufficient toughness, in particular for reinforcing tires.
- thermotropic aromatic polyester monofilament of determined diameter D, at the structuring time ts.
- 6 examples of raw spinning monofilaments are produced, including 5 examples in accordance with the invention (examples A1 to El), and a comparative example F-1 not in accordance with the invention.
- thermotropic aromatic polyester used here is a known polymer of the Vectra A900 type. in the form of granules, sold by the company Hoechst Celanese, consisting of repeating units (A) and (B) as defined above, according to a molar ratio A: B equal to approximately 27:73 (Tm equal to 280 ° C according to DSC analysis).
- the following spinning pump also being maintained at the temperature Tx of 340 ° C.
- the temperature Tf and the diameter d of the single capillary of the die are respectively equal to 270 ° C and 800 ⁇ m.
- the spinning conditions are adjusted in a known manner, by varying the speed of the spinning pump and the speed of extrusion through the die, so as to obtain a monofilament with a diameter D of approximately 180 ⁇ m (titer equal to 34.5 tex approximately).
- the flow of the polymer ie the liquid stream leaving the capillary
- a layer of air ambient temperature 20 ° C.
- ts variable time ts
- the polymer flow thus structured is thermally quenched by forced passage of the monofilament under a pulley immersed in a water bath at 15 ° C; the length of the submerged monofilament is approximately 10 cm, which corresponds to a very short but sufficient thermal quenching time of approximately 10 milliseconds.
- the monofilament is taken up and wound up in several turns on a drive device consisting of a call-out wafer, at the speed Vf indicated above of 590 m / min.
- the monofilament is then taken from a reel, in the wet state, and allowed to air dry for 24 hours, before being conditioned for the measurement of its thermal and mechanical properties.
- the structuring time ts was thus varied according to the indications in Table 1 - ie from 0.02 to 0.40 s - by gradually increasing the thickness Ag of the air-gap by 0.2 m (eg Al ) to 3.9 m (ex. Fl), passing successively through Ag values of 0.55 m (ex. Bl), 0.75 m (ex. Cl), 1.10 m (ex. Dl) and 1, 60 m (ex. El). All the spinning conditions are in accordance with the invention, with the exception of the duration ts for example F-1 which does not verify the above-mentioned relation (1) (ts ⁇ to).
- Table 1 also indicates the properties of the monofilaments obtained.
- Examples A-1 to D-1 further verify the following preferential relationships: Mi ⁇ 4000; Ar> 2.
- examples A-1 to B-1. obtained for the shortest structuring times ts verify the following preferential relationships: ⁇ L> 0.20; Ar> 2.5.
- the initial modulus can thus be lowered to values between 2500 and 4000 cN / tex without affecting the toughness which remains in all cases greater than 65 cN / tex.
- Example F1 prepared according to a spinning process not in accordance with the invention (ts> to), it exhibits a "hot" contraction ( ⁇ L negative) and is therefore not in accordance with the invention: it also has a particularly high initial modulus, greater than 4000 cN / tex, and an Ar value less than 2%.
- the monofilaments in accordance with the invention exhibit a significant thermal expansion ( ⁇ L> 0.2 for all the examples: ⁇ L> 0.4 in the majority of cases): advantageously, from such properties can in particular allow their winding under a high voltage, during spinning, before the subsequent post-polycondensation treatment.
- Table 2 also indicates the properties of the raw spinning monofilaments thus obtained.
- the spinning speed is constant (Vf ⁇ 590 m / min); the diameter D is adjusted from 95 ⁇ m (eg 40 A-3) to 320 ⁇ m (eg G-3) by modifying in a known manner the speed of the spinning pump (FEF varying from approximately 3.5 to approximately 40 ).
- These monofilaments in accordance with the invention also verify the following preferential relationships: Mi ⁇ 4000 and Ar> 2; the Te is greater than 55 cN / tex for the E-3 and F-3 monofilaments.
- examples A-3 to D-3 prepared according to a process not in accordance with the invention (ts> to). if they certainly have, as for examples C-2 and D-2 above, an initial module Mi of less than 4000 cN / tex (polymer less rigid than for test 1), they are all characterized by a negative variation ⁇ L, ie by a hot thermal contraction in the thermal variation test of length; they are therefore not in accordance with the invention.
- test 2 the monowires of Examples A-2 to D-2 above (test 2) are subjected to a post-polycondensation heat treatment.
- rewinding is carried out at low speed (cross-trenching of approximately 30 °) on flexible coils capable of more or less shrinking under the effect of the thermal contraction of the monofilaments which they support.
- This heat treatment is carried out by placing the coils in ovens, under vacuum, and by applying three thermal stages thereto: 50 min at 88 ° C. (for drying under vacuum); 40 min at 178 ° C; then 10 hours at 280 ° C.
- Table 4 shows the properties of monofilaments in the post-polycondensed state A-4, B-4, C- 4. D-4 thus obtained, respectively from the raw spinning monofilaments A-2, B-2, C-2 , D-2.
- the raw spinning monofilaments in accordance with the invention are those which, after heat treatment, lead to the products (A-4 and B-4) having the strongest toughness (Te > 100 cN / tex) and the highest elongations at break (Ar> 2.5%).
- the monofilaments C-4 and D-4 prepared according to the prior art have a markedly lower tenacity, a lower elongation at break, and a general appearance which is degraded: they contain especially a large number of "kink-bands" at the crossover points of the turns, on the processing coil.
- Tf die temperature
- the height of the air layer, at the outlet of the die is 150 mm. which corresponds to a structuring time ts of 0.05 seconds.
- This monofilament is then subjected to a post-polycondensation heat treatment.
- the oblong monofilament thus obtained in the post-polycondensed state has, for a titer of 227 tex, a tenacity greater than 100 cN / tex (precisely 101 cN / tex, which corresponds to a breaking force of approximately 23 daN), a initial modulus Mi between 3000 and 4000 cN / tex (precisely 3600 cN / tex) and an elongation at break Ar greater than 3% (precisely 3.4%>).
- the monofilaments in accordance with the invention are preferably used for reinforcing rubber articles, in particular rubber plies intended for the manufacture of tires.
- twisting or wiring methods and devices known to those skilled in the art are used, which are not described here for the simplicity of the description.
- These cables or unit wires must be previously glued with one or more adhesive compositions capable of ensuring their adhesion to the rubber matrix which they are intended to reinforce.
- a two-step gluing process is used, as indicated below:
- the assemblies or the unitary monofilaments pass through a first bath of epoxy resin then they undergo a heat treatment between 210 and 260 ° C for a time between 20 and 120 seconds, for example at 250 ° C for 30 seconds;
- RRL a second adhesive bath
- latex for example butadiene-styrene-vinylpyridine terpolymer
- resorcinol and formaldehyde then they undergo a heat treatment between 210 and 260 ° C for a time between 20 and 120 seconds, for example at 250 ° C for 30 seconds.
- the assemblies or monofilaments can undergo a preliminary activation treatment such as a plasma treatment, for example, as described in the aforementioned application WO92 / 12018 or in the application WO92 / 12285, for aramid monofilaments.
- a plasma treatment for example, as described in the aforementioned application WO92 / 12018 or in the application WO92 / 12285, for aramid monofilaments.
- the monofilaments according to the invention can be used in an oblong form. therefore not requiring wiring operations, to reinforce the carcass or the crown of these radial tires, in place of conventional cables formed from several monofilaments twisted together.
- the very small thickness D of the oblong monofilaments, relative to the cables makes it possible to significantly reduce the thickness of the rubber plies which they reinforce, and therefore the manufacturing costs; a small thickness D is also favorable to the endurance in bending-compression of the monofilaments, and consequently to the endurance of the rubber plies themselves in the tires.
- the raw spinning monofilaments of the invention have a new and essential characteristic which is that of not shrinking when hot.
- the raw spinning monofilaments of the invention like those in the post-polycondensed state which are derived therefrom, have, compared to those of the prior art, the advantage of having, for a given polymer (given rigidity and anisotropy), a module in lower extension which is most often combined with a higher elongation at break: it has been found that such a combination gives the monofilaments, for a determined diameter D, a resistance in bending-compression which is improved.
- an advantageous characteristic of the spinning process of the invention is that it makes it possible to practically adjust the rate of thermal expansion of the raw spinning monofilaments, even their initial modulus and their elongation at break. , depending on the intended industrial application; such an adjustment is obtained by controlling the structuring time ts of the polymer flow before the liquid quenching, this structuring time ts being a direct function of the diameter D of the targeted monofilament.
- the raw spinning monofilaments of the invention can be used in the form of continuous monofilaments or of short fibers: they can optionally be combined with other fibers, threads or monofilaments . for example steel wires, to constitute for example hybrid reinforcing elements.
Abstract
Description
Claims
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU82139/98A AU8213998A (en) | 1997-06-06 | 1998-06-05 | Thermotropic aromatic polyester(amide) monofilament |
BR9809548-0A BR9809548A (pt) | 1997-06-06 | 1998-06-05 | Monofilamento bruto de fiação de poliéster (amida) aromática termotrópica, processo de fiação de uma poliéster (amida) aromática termotrópica, utilização de um monofilamento, artigo de material plástico e/ou de borracha, e, pneumático |
JP50154299A JP4010572B2 (ja) | 1997-06-06 | 1998-06-05 | サーモトロピック芳香族ポリエステル(アミド)モノフィラメント |
EP98932129A EP0986658B1 (fr) | 1997-06-06 | 1998-06-05 | Monofilament en polyester(amide) aromatique thermotrope |
CA002292753A CA2292753A1 (fr) | 1997-06-06 | 1998-06-05 | Monofilament en polyester(amide) aromatique thermotrope |
DE69807871T DE69807871T2 (de) | 1997-06-06 | 1998-06-05 | Monofilament aus aromatischen thermotropen polyester(amide) |
US09/454,639 US6550507B1 (en) | 1997-06-06 | 1999-12-06 | Thermotropic aromatic polyester(amide) monofilament |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR9707142 | 1997-06-06 | ||
FR97/07142 | 1997-06-06 |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US09/454,639 Continuation US6550507B1 (en) | 1997-06-06 | 1999-12-06 | Thermotropic aromatic polyester(amide) monofilament |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1998055674A1 true WO1998055674A1 (fr) | 1998-12-10 |
Family
ID=9507786
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP1998/003386 WO1998055674A1 (fr) | 1997-06-06 | 1998-06-05 | Monofilament en polyester(amide) aromatique thermotrope |
Country Status (11)
Country | Link |
---|---|
US (1) | US6550507B1 (fr) |
EP (1) | EP0986658B1 (fr) |
JP (1) | JP4010572B2 (fr) |
CN (1) | CN1123657C (fr) |
AU (1) | AU8213998A (fr) |
BR (1) | BR9809548A (fr) |
CA (1) | CA2292753A1 (fr) |
DE (1) | DE69807871T2 (fr) |
RU (1) | RU2202012C2 (fr) |
TR (1) | TR199902977T2 (fr) |
WO (1) | WO1998055674A1 (fr) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0985750A2 (fr) * | 1998-09-10 | 2000-03-15 | Celanese Acetate, LLC. | Procédé de production de filaments à denier élevé en polymères cristallins liquides thermotropes |
EP0985748A2 (fr) * | 1998-09-10 | 2000-03-15 | Celanese Acetate, LLC. | Procédé de production de filaments multilobés à denier élevé en polymères cristallins liquides thermotropes |
EP0985749A2 (fr) * | 1998-09-10 | 2000-03-15 | Celanese Acetate, LLC. | Procédé pour le traitement thermique de filaments en polymères cristallins liquides thermotropes directement dans le corps de bobine |
WO2003048447A1 (fr) * | 2001-12-07 | 2003-06-12 | Societe De Technologie Michelin | Cable metallique utilisable dans une armature de carcasse d'un pneumatique |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
SK50132005A3 (sk) * | 2005-02-18 | 2006-09-07 | Matador, A. S. | Zariadenie na prípravu pogumovaného textilného kordu vhodného na použitie ako vinutého prekrývacieho nárazníka |
JP6038917B2 (ja) * | 2011-08-03 | 2016-12-07 | ミリケン・アンド・カンパニーMilliken & Company | テープ要素を伴う補強ゴム製品 |
ITFI20130162A1 (it) * | 2013-07-04 | 2015-01-05 | Golden Lady Co Spa | "metodo per la produzione di un filo sintetico ad alta ripresa di umidita' e filo ottenuto" |
US11124895B2 (en) * | 2013-10-29 | 2021-09-21 | Braskem America, Inc. | System and method for measuring out a polymer and first solvent mixture, device, system and method for extracting a solvent from at least one polymer strand, system and method for mechanically pre-recovering at least one liquid from at least one polymer strand, and a continuous system and method for the production of at least one polymer strand |
CN103952790B (zh) * | 2014-04-10 | 2017-01-11 | 中国石化仪征化纤有限责任公司 | 一种抗起毛起球聚酰胺酯短纤维 |
CN103952789B (zh) * | 2014-04-10 | 2016-06-22 | 中国石化仪征化纤有限责任公司 | 一种仿羊绒聚酰胺酯纤维 |
CN103952787B (zh) * | 2014-04-10 | 2016-05-25 | 中国石化仪征化纤有限责任公司 | 一种柔软聚酰胺酯纤维及其制备方法 |
CN103952788B (zh) * | 2014-04-10 | 2016-09-14 | 中国石化仪征化纤有限责任公司 | 一种改性聚酰胺酯短纤维及其制备方法 |
CN104250881B (zh) * | 2014-09-09 | 2017-01-25 | 江苏蓝品纤维科技发展有限公司 | 一种芳香聚酯絮片的制备方法 |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB828986A (en) * | 1957-01-15 | 1960-02-24 | Du Pont | Improvements in the manufacture of oriented melt-spun artificial fibres |
FR1517378A (fr) * | 1966-03-31 | 1968-03-15 | Bayer Ag | Préparation de monofilaments en polyester-amides |
US4161470A (en) * | 1977-10-20 | 1979-07-17 | Celanese Corporation | Polyester of 6-hydroxy-2-naphthoic acid and para-hydroxy benzoic acid capable of readily undergoing melt processing |
EP0091253A1 (fr) * | 1982-04-02 | 1983-10-12 | Celanese Corporation | Objet de forme allongée extrudé en phase fondue d'un polymère thermotrope formant des cristaux liquides pour utilisation en tant que support renforçant dans un câble de fibre optique, et câbles de fibres optiques contenant un tel objet de forme allongée |
US4734240A (en) * | 1986-01-24 | 1988-03-29 | Hoechst Celanese Corporation | Melt-extrusion of polymer which is capable of forming an anisotropic melt phase to form large shaped articles exhibiting improved polymeric orientation |
JPH04333616A (ja) * | 1991-05-10 | 1992-11-20 | Kuraray Co Ltd | 高強力モノフィラメントの製造方法 |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2671030A1 (fr) * | 1990-12-27 | 1992-07-03 | Michelin Rech Tech | Assemblages de renfort avec monofilaments en polymeres organiques. |
US5851668A (en) * | 1992-11-24 | 1998-12-22 | Hoechst Celanese Corp | Cut-resistant fiber containing a hard filler |
DE69527956D1 (de) * | 1994-05-16 | 2002-10-02 | Honeywell Int Inc | Gefüllte schnittfeste faser |
US6187437B1 (en) * | 1998-09-10 | 2001-02-13 | Celanese Acetate Llc | Process for making high denier multilobal filaments of thermotropic liquid crystalline polymers and compositions thereof |
US5945216A (en) * | 1998-09-10 | 1999-08-31 | Celanese Acetate Llc | Process for making high denier filaments of thermotropic liquid crystalline polymers and compositions thereof |
US6129878A (en) * | 1998-09-10 | 2000-10-10 | Celanese Acetate Llc | Process for direct on-bobbin heat treating of high denier filaments of thermotropic liquid crystalline polymers |
-
1998
- 1998-06-05 RU RU2000100372/04A patent/RU2202012C2/ru not_active IP Right Cessation
- 1998-06-05 CN CN98806623A patent/CN1123657C/zh not_active Expired - Fee Related
- 1998-06-05 TR TR1999/02977T patent/TR199902977T2/xx unknown
- 1998-06-05 CA CA002292753A patent/CA2292753A1/fr not_active Abandoned
- 1998-06-05 EP EP98932129A patent/EP0986658B1/fr not_active Expired - Lifetime
- 1998-06-05 WO PCT/EP1998/003386 patent/WO1998055674A1/fr active IP Right Grant
- 1998-06-05 DE DE69807871T patent/DE69807871T2/de not_active Expired - Fee Related
- 1998-06-05 JP JP50154299A patent/JP4010572B2/ja not_active Expired - Fee Related
- 1998-06-05 AU AU82139/98A patent/AU8213998A/en not_active Abandoned
- 1998-06-05 BR BR9809548-0A patent/BR9809548A/pt active Search and Examination
-
1999
- 1999-12-06 US US09/454,639 patent/US6550507B1/en not_active Expired - Fee Related
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB828986A (en) * | 1957-01-15 | 1960-02-24 | Du Pont | Improvements in the manufacture of oriented melt-spun artificial fibres |
FR1517378A (fr) * | 1966-03-31 | 1968-03-15 | Bayer Ag | Préparation de monofilaments en polyester-amides |
US4161470A (en) * | 1977-10-20 | 1979-07-17 | Celanese Corporation | Polyester of 6-hydroxy-2-naphthoic acid and para-hydroxy benzoic acid capable of readily undergoing melt processing |
EP0091253A1 (fr) * | 1982-04-02 | 1983-10-12 | Celanese Corporation | Objet de forme allongée extrudé en phase fondue d'un polymère thermotrope formant des cristaux liquides pour utilisation en tant que support renforçant dans un câble de fibre optique, et câbles de fibres optiques contenant un tel objet de forme allongée |
US4734240A (en) * | 1986-01-24 | 1988-03-29 | Hoechst Celanese Corporation | Melt-extrusion of polymer which is capable of forming an anisotropic melt phase to form large shaped articles exhibiting improved polymeric orientation |
JPH04333616A (ja) * | 1991-05-10 | 1992-11-20 | Kuraray Co Ltd | 高強力モノフィラメントの製造方法 |
Non-Patent Citations (1)
Title |
---|
PATENT ABSTRACTS OF JAPAN vol. 017, no. 176 (C - 1045) 6 April 1993 (1993-04-06) * |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0985750A2 (fr) * | 1998-09-10 | 2000-03-15 | Celanese Acetate, LLC. | Procédé de production de filaments à denier élevé en polymères cristallins liquides thermotropes |
EP0985748A2 (fr) * | 1998-09-10 | 2000-03-15 | Celanese Acetate, LLC. | Procédé de production de filaments multilobés à denier élevé en polymères cristallins liquides thermotropes |
EP0985749A2 (fr) * | 1998-09-10 | 2000-03-15 | Celanese Acetate, LLC. | Procédé pour le traitement thermique de filaments en polymères cristallins liquides thermotropes directement dans le corps de bobine |
EP0985749A3 (fr) * | 1998-09-10 | 2000-08-09 | Celanese Acetate, LLC. | Procédé pour le traitement thermique de filaments en polymères cristallins liquides thermotropes directement dans le corps de bobine |
EP0985748A3 (fr) * | 1998-09-10 | 2000-08-09 | Celanese Acetate, LLC. | Procédé de production de filaments multilobés à denier élevé en polymères cristallins liquides thermotropes |
EP0985750A3 (fr) * | 1998-09-10 | 2000-08-09 | Celanese Acetate, LLC. | Procédé de production de filaments à denier élevé en polymères cristallins liquides thermotropes |
WO2003048447A1 (fr) * | 2001-12-07 | 2003-06-12 | Societe De Technologie Michelin | Cable metallique utilisable dans une armature de carcasse d'un pneumatique |
FR2833277A1 (fr) * | 2001-12-07 | 2003-06-13 | Michelin Soc Tech | Cable metallique utilisable pour renforcer une armature de carcasse d'un pneumatique et un tel pneumatique |
Also Published As
Publication number | Publication date |
---|---|
US6550507B1 (en) | 2003-04-22 |
CN1123657C (zh) | 2003-10-08 |
JP4010572B2 (ja) | 2007-11-21 |
JP2002503295A (ja) | 2002-01-29 |
CN1261412A (zh) | 2000-07-26 |
BR9809548A (pt) | 2000-06-20 |
CA2292753A1 (fr) | 1998-12-10 |
DE69807871D1 (en) | 2002-10-17 |
RU2202012C2 (ru) | 2003-04-10 |
DE69807871T2 (de) | 2003-05-08 |
EP0986658A1 (fr) | 2000-03-22 |
EP0986658B1 (fr) | 2002-09-11 |
AU8213998A (en) | 1998-12-21 |
TR199902977T2 (xx) | 2000-10-23 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0986658B1 (fr) | Monofilament en polyester(amide) aromatique thermotrope | |
CA2074249C (fr) | Assemblages de renfort avec monofilaments en polymeres organiques cristaux liquides | |
JP4389142B2 (ja) | 高強度ポリエチレン繊維の製造方法 | |
FR2826379A1 (fr) | Fibre de polyethylene naphtalate de haute resistance | |
EP0564571B1 (fr) | Traitement par plasma d'un monofilament aramide | |
EP0657396A1 (fr) | Procédé de fabrication de fils de verre ensimés et fils de verre en résultant | |
EP0909348A1 (fr) | Filaments en polyester et procede de fabrication d'un tel filament | |
US5045257A (en) | Process for producing aromatic polyester fiber | |
WO1998017847A1 (fr) | Agent coagulant aqueux pour solutions cristal-liquide a base de matieres cellulosiques | |
EP0517880B1 (fr) | Monofilament aramide ayant une peau faiblement structuree - procede pour obtenir ce monofilament | |
FR2553794A1 (fr) | Fibre de polyhexamethylene adipamide ayant une haute stabilite dimensionnelle et une forte resistance a la fatigue, et procede pour sa preparation | |
JP2003055833A (ja) | 高強度ポリオレフィン繊維およびその製造方法 | |
WO1998035078A1 (fr) | Fibres cellulosiques d'origine cristal-liquide ayant un allongement a la rupture important et procedes pour les obtenir | |
FR2922223A1 (fr) | Fils, fibres ou filaments et leur utilisation notamment dans des cordes. | |
KR0160463B1 (ko) | 고무제품 보강재용 폴리아미드사 및 그의 제조방법 | |
KR101204390B1 (ko) | 폴리비닐클로라이드와의 접착력이 우수한 폴리에스테르섬유 및 이의 제조방법 | |
EP0530119B1 (fr) | Fibres à base de mélanges pvc/pvc chloré possèdant des propriétés mécaniques améliorées et files de fibres de ténacité améliorée obtenus à partir de ces fibres | |
BE466651A (fr) | ||
LU100712B1 (fr) | Fil multifilamentaire en polyamide 46 a retrait eleve | |
JP2744303B2 (ja) | 耐疲労性に優れた高強力高弾性率繊維 | |
FR2545107A1 (fr) | Procede pour ameliorer la regularite de structure des filaments a base de polymeres thermoplastiques | |
FR3123077A1 (fr) | Monofilament élémentaire textile constitué d’un polyester | |
FR2660941A1 (fr) | Monofilament aramide et procede pour l'obtenir. | |
BE549504A (fr) | ||
JP2004019049A (ja) | 高強度ポリオレフィン繊維およびその製造方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 98806623.8 Country of ref document: CN |
|
AK | Designated states |
Kind code of ref document: A1 Designated state(s): AL AM AT AU AZ BA BB BG BR BY CA CH CN CU CZ DE DK EE ES FI GB GE GH GM GW HU ID IL IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MD MG MK MN MW MX NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT UA UG US UZ VN YU ZW |
|
AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): GH GM KE LS MW SD SZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN ML MR NE SN TD TG |
|
DFPE | Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101) | ||
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
WWE | Wipo information: entry into national phase |
Ref document number: 1998932129 Country of ref document: EP |
|
ENP | Entry into the national phase |
Ref document number: 2292753 Country of ref document: CA Ref document number: 2292753 Country of ref document: CA Kind code of ref document: A |
|
ENP | Entry into the national phase |
Ref document number: 1999 501542 Country of ref document: JP Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 09454639 Country of ref document: US Ref document number: 1999/02977 Country of ref document: TR |
|
WWP | Wipo information: published in national office |
Ref document number: 1998932129 Country of ref document: EP |
|
REG | Reference to national code |
Ref country code: DE Ref legal event code: 8642 |
|
WWG | Wipo information: grant in national office |
Ref document number: 1998932129 Country of ref document: EP |