EP1534883A2 - Articles comprenant des fibres, et/ou fibrides, fibres et fibrides et leur procede d obtention - Google Patents
Articles comprenant des fibres, et/ou fibrides, fibres et fibrides et leur procede d obtentionInfo
- Publication number
- EP1534883A2 EP1534883A2 EP03753670A EP03753670A EP1534883A2 EP 1534883 A2 EP1534883 A2 EP 1534883A2 EP 03753670 A EP03753670 A EP 03753670A EP 03753670 A EP03753670 A EP 03753670A EP 1534883 A2 EP1534883 A2 EP 1534883A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- fibrids
- article according
- fibers
- polymer
- thermoplastic polymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000004519 manufacturing process Methods 0.000 title description 2
- 239000000835 fiber Substances 0.000 claims description 75
- 229920000642 polymer Polymers 0.000 claims description 57
- 239000000203 mixture Substances 0.000 claims description 31
- 229920001169 thermoplastic Polymers 0.000 claims description 31
- 239000002904 solvent Substances 0.000 claims description 30
- 238000009987 spinning Methods 0.000 claims description 26
- 229920006393 polyether sulfone Polymers 0.000 claims description 16
- 238000003825 pressing Methods 0.000 claims description 15
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 10
- 229920003235 aromatic polyamide Polymers 0.000 claims description 9
- 229920002492 poly(sulfone) Polymers 0.000 claims description 9
- 238000007596 consolidation process Methods 0.000 claims description 8
- 229920001021 polysulfide Polymers 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 239000005077 polysulfide Substances 0.000 claims description 7
- 150000008117 polysulfides Polymers 0.000 claims description 7
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- 238000002166 wet spinning Methods 0.000 claims description 6
- 239000004760 aramid Substances 0.000 claims description 5
- 238000000578 dry spinning Methods 0.000 claims description 5
- 238000010292 electrical insulation Methods 0.000 claims description 5
- 230000009477 glass transition Effects 0.000 claims description 5
- 239000004642 Polyimide Substances 0.000 claims description 4
- 229920001721 polyimide Polymers 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 3
- 239000004952 Polyamide Substances 0.000 claims description 2
- 239000004695 Polyether sulfone Substances 0.000 claims description 2
- -1 aromatic imide Chemical class 0.000 claims description 2
- 239000002798 polar solvent Substances 0.000 claims description 2
- 229920002647 polyamide Polymers 0.000 claims description 2
- 229920012287 polyphenylene sulfone Polymers 0.000 claims description 2
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 28
- 239000000243 solution Substances 0.000 description 25
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 15
- 239000004962 Polyamide-imide Substances 0.000 description 13
- 229920002312 polyamide-imide Polymers 0.000 description 13
- 239000004951 kermel Substances 0.000 description 11
- 239000011230 binding agent Substances 0.000 description 9
- 238000004090 dissolution Methods 0.000 description 8
- 230000001112 coagulating effect Effects 0.000 description 7
- 238000003490 calendering Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- 229920001059 synthetic polymer Polymers 0.000 description 5
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 230000015271 coagulation Effects 0.000 description 4
- 238000005345 coagulation Methods 0.000 description 4
- 239000002609 medium Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 239000004745 nonwoven fabric Substances 0.000 description 3
- 229920002959 polymer blend Polymers 0.000 description 3
- 239000013557 residual solvent Substances 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 239000002671 adjuvant Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 238000009960 carding Methods 0.000 description 2
- 230000001427 coherent effect Effects 0.000 description 2
- 230000003352 fibrogenic effect Effects 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 239000003880 polar aprotic solvent Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229920002994 synthetic fiber Polymers 0.000 description 2
- 239000012209 synthetic fiber Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 description 1
- 229920000784 Nomex Polymers 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- 229920000491 Polyphenylsulfone Polymers 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- FVICENFBEMJOCE-RTFNQGFNSA-N [(7r,8r,9s,10r,11s,13s,14s,17s)-7,11,13-trimethyl-3-oxo-2,6,7,8,9,10,11,12,14,15,16,17-dodecahydro-1h-cyclopenta[a]phenanthren-17-yl] undecanoate Chemical compound C([C@H]1C)C2=CC(=O)CC[C@@H]2[C@@H]2[C@@H]1[C@@H]1CC[C@H](OC(=O)CCCCCCCCCC)[C@@]1(C)C[C@@H]2C FVICENFBEMJOCE-RTFNQGFNSA-N 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000002788 crimping Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- GUVUOGQBMYCBQP-UHFFFAOYSA-N dmpu Chemical compound CN1CCCN(C)C1=O GUVUOGQBMYCBQP-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 238000009940 knitting Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000004763 nomex Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
- D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/90—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyamides
- D01F6/905—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyamides of aromatic polyamides
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/94—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of other polycondensation products
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/54—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by welding together the fibres, e.g. by partially melting or dissolving
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H15/00—Pulp or paper, comprising fibres or web-forming material characterised by features other than their chemical constitution
- D21H15/02—Pulp or paper, comprising fibres or web-forming material characterised by features other than their chemical constitution characterised by configuration
- D21H15/10—Composite fibres
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T292/00—Closure fasteners
- Y10T292/03—Miscellaneous
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249924—Noninterengaged fiber-containing paper-free web or sheet which is not of specified porosity
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/60—Nonwoven fabric [i.e., nonwoven strand or fiber material]
- Y10T442/637—Including strand or fiber material which is a monofilament composed of two or more polymeric materials in physically distinct relationship [e.g., sheath-core, side-by-side, islands-in-sea, fibrils-in-matrix, etc.] or composed of physical blend of chemically different polymeric materials or a physical blend of a polymeric material and a filler material
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/60—Nonwoven fabric [i.e., nonwoven strand or fiber material]
- Y10T442/69—Autogenously bonded nonwoven fabric
Definitions
- Articles comprising fibers and / or fibrids. fibers and fibrids and process for obtaining them
- the present invention relates in particular to new articles, in particular non-woven articles comprising fibers and / or fibrids. It also relates to new fibers and fibrids as well as a process for obtaining these fibers and fibrids.
- thermostable fibers In the field of electrical insulation in particular, it is sought to obtain products having good temperature resistance and good mechanical properties and / or good dielectric properties.
- These products can for example be nonwoven articles produced from thermostable fibers.
- good cohesion of the thermostable fibers is necessary for obtaining a good level of mechanical properties, even also a homogeneous and dense structure of the article for obtaining the dielectric properties.
- These articles depending on their structure (in particular their density) and / or their formulation, can have a mechanical and / or dielectric reinforcement function.
- Document FR 2,163,383 proposes to prepare non-woven fabrics consisting of a web of fibers made of a material infusible or having a melting point above 180 C C, the fibers being bonded together by means of a binder polyamide-imide, used in proportion from 5 to 150% of the weight of dry fibers used.
- a binder polyamide-imide used in proportion from 5 to 150% of the weight of dry fibers used.
- the impregnation of the resin is carried out in solution in a solvent, which has harmful effects on the characteristics of the nonwovens.
- the document FR 2 156 452 proposes to prepare wet nonwoven webs of fibers made of " infusible material or having a melting point higher than 180 ° C, linked together by powdered thermoplastic polymer. If these plies can, in theory, be produced by papermaking, in practice, their industrial production is difficult: in fact the mixture of synthetic fibers and binder based on resin has too weak cohesion to be able to be handled and in particular, such a mixture does not have sufficient cohesion to be able to be prepared dynamically, for example on a commercial paper machine; such plies can be produced mainly on laboratory apparatus of the "Formette Franck" type, that is to say statically and discontinuously as is apparent from the examples.
- Document FR 2 685 363 proposes to prepare a wet paper consisting of fibers having a thermal resistance greater than or equal to 180 ° C., bonded together by means of a fibrous binder and a chemical binder.
- binders to ensure the cohesion of the fibers in articles, for example nonwovens, in particular causes difficulties and costs in the implementation of these binders.
- the present invention provides new articles, in particular non-woven articles, which do not have the above drawbacks, comprising fibers and / or fibrids.
- the invention also provides new fibers and fibrids, and a process for obtaining these fibers and fibrids, as well as articles obtained from these fibers and fibrids, such as nonwoven articles.
- the thermoplastic part of the fiber or fibrid of the invention plays in particular the role of the chemical binder described above. In particular, it has the property of "creeping" under pressure and temperature constraints. Thus the cohesion of the thermostable fibers in these articles is ensured, their level of thermal and mechanical properties is very satisfactory.
- These articles can have a homogeneous and dense structure, and therefore a good level of dielectric properties.
- the first object of the invention relates to an article comprising at least fibers and / or fibrids, characterized in that the fibers and fibrids are formed from a mixture of polymers comprising at least: • a thermostable polymer and • a thermoplastic polymer chosen from the group of polysulfides and polysulfones.
- the second subject of the invention relates to a fiber and a fibride as described above and their process for obtaining.
- the invention proposes the use of articles as described above in the field of electrical insulation.
- thermostable polymer of the invention is preferably infusible or has a glass transition temperature greater than 180 ° C, preferably greater than or equal to 230 ° C, or greater.
- the thermostable polymer of the invention exhibits thermal resistance (that is to say a conservation of its physical properties in particular) long-term at a temperature above 180 ° C.
- This thermostable polymer is preferably chosen from polyaramides and polyimides. Examples of polyaramides that may be mentioned are aromatic polyamides such as the polymer known under the trade name Nomex®, or imide polyamides such as the polymer known under the trade name Kermel®. As an example of polyimides, mention may be made of the polyimides obtained according to document EP 0119185, known under the trade name P84®.
- the aromatic polyamides can be as described in patent EP 0360707. They can be obtained according to the process described in patent EP 0360707.
- thermoplastic polymer is chosen from the group of polysulfides and polysulfones.
- polysulfide mention may be made of the polyphenylene sulphide noted
- PPS polysulfones denoted PSU
- PSU polysulfones
- PESU polyether sulfone
- PPSU polyphenylene sulfone
- thermoplastic polymers have a glass transition temperature less than or equal to 250 ° C., which allows them in particular to play the role of chemical binder in the articles of the invention, and to "creep" under pressure and temperature constraints. These polymers also exhibit good thermostability, since they belong to a thermal class (thermal index) greater than 130 ° C. This has an advantage in obtaining articles having good thermostability.
- the thermoplastic polymer and the thermostable polymer are soluble in the same solvent.
- the solvent is aprotic polar. It is more preferably chosen from DMEU, DMAC, NMP, DMF.
- the fiber or fibrid according to the invention comprises at least 10% by weight of thermoplastic polymer.
- Fibrids are small, non-granular, fibrous or film-like particles that are not rigid. Two of their three dimensions are of the order of a few microns. Their small size and their flexibility allow them to be deposited in physically intertwined configurations such as those commonly found in papers formed from pulp.
- the fiber according to the invention preferably has a titer between 0.5 dtex and 13.2 dtex.
- the fiber of the invention preferably has a length of between 1 and 100 mm.
- the fiber according to the invention can have various cross-sectional shapes such as a round, three-lobed, “flat” shape.
- the term “fiber with a flat section shape” means a fiber whose length / width ratio is greater than or equal to 2.
- the fiber or fibrid according to the invention can be treated by sizing.
- the fibers are obtained by mixing the thermostable polymer and the thermoplastic polymer, then spinning the mixture.
- the mixture of polymers is obtained by dissolving the polymers in at least one common solvent.
- the thermoplastic polymer and the thermostable polymer can be dissolved together, simultaneously or successively in a solvent or a mixture of solvents miscible with each other, in a single reactor for example.
- the polymers can also be dissolved separately in the same solvent or in different solvents miscible with each other, for example in two different containers, then the polymer solutions mixed together.
- dissolution conditions such as the temperature, are determined by a person skilled in the art according to the nature of the polymers and of the solvent (s) used. Dissolution can for example be carried out hot, with stirring, to facilitate dissolution.
- Dissolution can be carried out at room temperature.
- the dissolution temperature is between 50 and 150 ° C.
- the dissolution solvent (s) is (are) advantageously an aprotic polar solvent.
- Dimethylalkylene urea can be used, for example dimethylethylene urea (DMEU) or dimethylpropylene urea. Preferably it is chosen from DMEU, dimethylacetamide (DMAC), N-methyl pyrrolidone (NMP), dimethylformamide (DMF).
- the dissolution solvent can be a mixture of polar aprotic solvents, for example a mixture of dimethylethylene urea and an anhydrous polar aprotic solvent such as NMP, DMAC, DMF, tetramethylurea or ⁇ -butyrolactone.
- the polymer solution obtained after dissolution is called collodion.
- the solution obtained is preferably clear.
- the total concentration by weight of the polymers relative to the solution is preferably between 5 and 40%.
- the solution can also include additives such as pigments, reinforcing agents, stabilizers, matifiers.
- the solution must also have a viscosity allowing its spinning, generally between 100 and 1000 poises.
- the viscosity is preferably between 400 and 800 poises measured using a viscometer known in the trade under the brand EPPRECHT RHEOMAT 15.
- the viscosity is preferably between 1500 and 3000 poise.
- the mixing of the polymers can also be carried out online during the spinning step, for example by online injection of each polymer - dissolved or not in a solvent - during the spinning process.
- the filaments at the outlet of the evaporative enclosure are freed of their residual solvent.
- they can be washed with water, possibly boiling and under pressure; dried in the usual way, preferably at a temperature above 80 ° C. They can also be heat treated at a temperature greater than or equal to 160 ° C. under reduced pressure, and / or under an inert atmosphere. After being freed from their residual solvent, they can be drawn, for example, at a temperature above 250 ° C., preferably above 300 ° C., preferably in the absence of oxygen.
- the spinning method is a wet spinning, according to which the solution of polymers (solution of fibrogenic substance) is extruded in a coagulating bath.
- the temperature of the spinning solution can vary within wide limits depending on the viscosity of the spinning solution.
- a solution with a low viscosity can easily be extruded at ordinary temperature, while it is preferable to hot extrude, for example at 120 ° C. or even more, a solution of high viscosity to avoid using too much great pressures on the sector.
- the spinning solution is advantageously maintained between 15 and 40 ° C, preferably between 15 and 25 ° C.
- the coagulating bath used in the process according to the invention is preferably an aqueous solution containing from 30 to 80% by weight, preferably from 40 to 70% by weight of a solvent or solvent mixture, preferably a dimethylalkylene urea (DMAU ) where the
- the polymers of the solution to be spun have close coagulation rates.
- the spinning speed in the coagulating bath can vary within wide limits, depending on its solvent concentration and the distance the filaments travel in this bath. This spinning speed in the coagulating bath can be easily chosen between 10 and 60 / min, for example, although higher speeds can be reached. It is generally not advantageous to spin at lower speeds for reasons of cost-effectiveness of the process. Furthermore, excessively high spinning speeds in the coagulating bath reduce the stretchability of the filaments in the air. The spinning speed in the coagulating bath will therefore be chosen to take into account both the profitability and the qualities desired on the finished filament.
- the filaments leaving the coagulating bath in the gel state are then drawn, for example in air, at a rate defined by the ratio (V2 / V1) * 100, V2 being the speed of the drawing rollers, V1 that delivery rollers.
- the rate of drawing of the son in the gel state is greater than 100%, preferably greater than or equal to 110% or even greater, for example greater than or equal to 200%.
- the residual solvent is removed from the filaments by known means, generally by means of washing with water circulating against the current or on washing rollers, preferably at room temperature.
- the spinning method is a dry spinning.
- 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 gradual rise in temperature, this temperature possibly reaching and even exceeding 200 ° C. for example.
- the filaments can then undergo a hot over-stretching to improve their mechanical qualities and in particular their toughness, which can 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 is 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 total drawing rate is then at least 250%, preferably at least 260%.
- the whole drawing and possibly over-drawing can be carried out in one or more stages, continuously or discontinued with the previous operations.
- over-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.
- the filaments obtained are then cut in the form of fibers according to a method known to a person skilled in the art.
- the fibrids are obtained by mixing the thermostable polymer and the thermoplastic polymer, then precipitation of the mixture under shear stress.
- thermostable polymer and the thermoplastic polymer can be carried out in a manner analogous to that described above for the fibers.
- the fibrids of the invention can in particular be obtained by precipitating a solution of polymers in a fibridation apparatus of the type described in US Pat. No. 3,018,091, in which the polymers are sheared while they precipitate.
- the articles are non-woven articles.
- the nonwoven articles are in the form of sheets, films, felts and generally they designate any coherent fibrous structure not involving any textile operation such as spinning, knitting, weaving.
- the article can be obtained from a single type of fiber or, on the contrary, from mixtures of fibers.
- the nonwoven article of the invention at least partially comprises fibers and / or fibrids according to the invention.
- the article of the invention can comprise fibers of different natures and / or fibrids of different natures.
- the nonwoven article may for example comprise fibers and / or thermostable or reinforcing fibrids of the para-aramid, meta-aramid, polyamide imide etc. type.
- the nonwoven article may for example comprise fibers according to the invention and thermostable fibers.
- the article may for example comprise fibers according to the invention and fibrids of thermostable polymer according to a first embodiment; or the article may for example comprise thermostable fibers and fibrids according to the invention according to another embodiment.
- the nonwoven article of the invention can be obtained by a method and apparatus for preparing a nonwoven article known to those of skill in the art.
- the article of the invention is generally obtained by implementing a "coating" step, that is to say a step of distributing the fibers and / or fibrids on a surface, then a step of "Consolidation" of the structure obtained.
- the “topping” step is carried out by “dry route” (for example “drylaid”), for example from fibers of the invention whose length is between 40 and 80 mm.
- the fibers can for example be treated using an ordinary carding machine.
- the "coating” step is carried out by “wet process” or “paper process” ("wetlaid”).
- the fibers used in this embodiment generally have a length of between 2 and 12 mm, preferably between 3 and 7 mm, and their titer, expressed in decitex, is generally between 0.5 and 20. It is theoretically possible to use fibers longer than 12 mm, but in practice longer fibers become entangled, requiring a greater amount of water, which makes the process heavier and more complicated.
- the nonwoven article is obtained by introducing into the water, the various constituents of the article: the fibers and a fibrous binder composed of a pulp based on a synthetic polymer having thermal resistance greater than or equal to 180 ° C (such as a para-aramid pulp) and / or fibrids based on a synthetic polymer having a thermal resistance greater than or equal to 180 ° C and / or fibrids according to the invention, and possibly other desired adjuvants, additives or fillers.
- a fibrous binder composed of a pulp based on a synthetic polymer having thermal resistance greater than or equal to 180 ° C (such as a para-aramid pulp) and / or fibrids based on a synthetic polymer having a thermal resistance greater than or equal to 180 ° C and / or fibrids according to the invention, and possibly other desired adjuvants, additives or fillers.
- the pulp based on a synthetic polymer having a thermal resistance greater than or equal to 180 ° C. has generally been obtained from fibers of usual length, in particular fibrils, in known manner, to give it a large number of points of attachment and thus increase its specific surface.
- synthetic fibers only highly crystallized fibers can be fibrillated. This is the case of fully aromatic polyamides and polyesters, but other highly crystallized polymers are cleavable along the axis of the fibers or fibrillable.
- adjuvants, additives or fillers can also be used in various proportions depending on the desired properties; for example mica can be introduced to further increase the dielectric properties of the article.
- the “papermaking route” for preparing nonwoven articles is known to a person skilled in the art.
- the “consolidation” step of the structure obtained by coating as described above can be carried out according to any method known to those skilled in the art.
- the “consolidation” is carried out thermally, for example by thermal pressing of the article.
- the thermal pressing temperature is generally higher than the glass transition temperature of the thermoplastic polymer of the fibers and / or fibrids according to the invention contained in the article.
- the temperature of thermal pressing is between the glass transition temperature and the softening temperature of the thermoplastic polymer.
- the thermal pressing temperature is between 200 and 350 ° C.
- the pressure is greater than or equal to 5 bars.
- This pressing ensures the densification and consolidation of the article of the invention. It is generally accompanied by a creep of the thermoplastic polymer of the fibers and / or fibrids according to the invention contained in the article through the structure of the article.
- Thermal pressing is not limited in terms of its implementation. Any means of thermal pressing of a nonwoven article can be used.
- Pressing can for example be carried out using a press or a calender with heated rollers. It is possible to make several passes on the pressing device so as to obtain the desired density.
- the preferred thermal pressing method of the invention is calendering. According to a particular embodiment of the invention, the thermal pressing is carried out using a continuous press.
- the articles obtained by this pressing are diverse and varied according to the conditions of the thermal pressing implemented -in particular the temperature, the pressure and the pressing time- and according to the formulation of the article -in particular the quantity of fibers and / or fibrids according to the invention contained in the article and the amount of thermoplastic polymer present in these fibers and / or fibrids.
- the articles of the invention can be implemented in particular in the field of electrical insulation.
- the role of the articles varies according to their density and therefore according to their stiffness / dielectric properties. They can for example be used in an insulation system in which the main insulator is an oil or a resin, as a mechanical "spacer” or “reinforcement” to be inserted between two parts to be electrically insulated.
- the articles can also be used directly as insulation in “dry” type insulation systems.
- thermostable polymer • a thermoplastic polymer chosen from the group of polysulfides and polysulfones and in that it has a titer less than or equal to 13.2 dtex
- thermoplastic polymer chosen from the group of polysulfides and polysulfones and in that it has a titer less than or equal to 13.2 dtex
- the invention also relates to a fibrid, characterized in that it is formed from a mixture of polymers comprising at least:
- thermostable polymer • a thermostable polymer
- thermoplastic polymer chosen from the group of polysulfides and polysulfones All that has been described previously concerning the thermostable polymer, the thermoplastic polymer, the fibers and fibrids of the articles of the invention, the process for obtaining the fibers and the process for obtaining fibrids, applies here identically to the fibers and fibrids of the invention above.
- the invention also relates, in a third object, to the use of the articles of the invention as described above in the field of electrical insulation.
- DMEU solvent 180 kg are introduced into a heated and stirred reactor. This solvent is first heated to a temperature between 60 ° C and 120 ° C.
- the PESU polymer (MW 80,000 to 90,000 g / mol) in the form of lenticular granules is introduced into the hot solvent, in 10 equal fractions. The time required between each fraction is a function of the intensity of the stirring, and of the temperature. The polymer is introduced until it represents 20 to 40% by weight of the mixture.
- the polymer content in the medium influences its viscosity. For example, at 21% the viscosity at 25 ° C is 350 poises; at 28% the viscosity is 460 poises.
- thermoplastic polymer PESU with the polyamide imide Kermel® is produced by hot mixing, between 60 and 120 ° C., of the medium described above containing PESU and a 21% by weight solution of Kermel® polyamide imide in DMEU solvent (MW 150,000 g / mol in polystyrene equivalents, viscosity: 600 poises at 25 ° C).
- the proportion of the two solutions in the mixture is expressed as the proportion of PESU polymer in the dry matter and is between 40 and 60%.
- a Kermel® / PESU polyamide-imide mixture is obtained directly by dissolving the PESU polymer in a 13% by weight solution of Kermel® polyamide imide in DMEU solvent, using a high shear gradient mixing device. , and high recycling rate.
- a medium containing the PESU is prepared according to the procedure of Example 1.
- the mixture with the polyamide imide Kermel® (in the form of a solution at 21% by weight of polyamide imide Kermel® in the solvent DMEU) is carried out during the spinning, by joint injection of the two solutions in a common pipe, upstream static mixers installed in this pipe which supplies the spinning loom. Respect for the proportions of the two solutions in the mixture is ensured by adjusting the rotational speeds of positive displacement pumps.
- the Kermel® PESU / polyamide imide mixtures of Examples 1 to 3 are spun according to a wet spinning process.
- the proportion of PESU polymer is 40% by weight.
- the conditions below show by way of example the spinning parameters used:
- the Kermel® PESU / polyamide imide mixtures of Examples 1 to 3 are spun according to a wet spinning process.
- the share of PESU polymer is 50%.
- the conditions below show, as an example, the spinning parameters used: 10.000 dies of 40 ⁇ m holes Coagulation bath at 60% solvent, 19 ° C
- the fiber is dried under conventional conditions. Crimping and cutting are done under conventional conditions
- Nonwoven articles of different grammages are prepared from the fibers of Example 4 by "dry process” and “consolidation” (carding, coating, calendering) according to a method known to those skilled in the art.
- Table 1 describes the operating conditions used and the characteristics of the articles obtained.
- the mechanical properties of force and elongation at break are measured according to standard NF-EN 29073-3 of December 1992.
- the thickness of the articles is measured using a Palmer® type micrometer.
- FIG. 1 is a photograph of the surface of the article according to Example 8 after calendering.
- Figure 2 is a photograph of the section of the article according to Example 8 after calendering.
- Table 2 describes the conditions for preparing the fibrids.
- the characteristics of the fibrids were measured on a MORFI device (conventional device for measuring paper cellulosic fibers). Table 3 describes these characteristics.
- the fibrids of Examples 9 to 12 were mixed with an equal weight of Kermel® polyamide imide fibers 6 mm in length. These four preparations were used to make papers on a FRANK type device by the wet method and according to a conventional papermaking process.
- the target density of the samples is 80g / m 2 .
- the characteristics of the papers are listed in Table 4.
- the retention rate is defined as follows:
- Retention rate (%) (1- [(mass introduced (g) -mass after passage (g)) / mass introduced (g)] * 100
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Paper (AREA)
- Artificial Filaments (AREA)
- Nonwoven Fabrics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR0210913A FR2843975B1 (fr) | 2002-09-04 | 2002-09-04 | Fibres et fibrides, leur procede d'obtention, articles obtenus a partir de ces fibres et/ou fibrides. |
FR0210913 | 2002-09-04 | ||
PCT/FR2003/002495 WO2004022823A2 (fr) | 2002-09-04 | 2003-08-08 | Articles comprenant des fibres, et/ou fibrides, fibres et fibrides et leur procede d'obtention |
Publications (2)
Publication Number | Publication Date |
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EP1534883A2 true EP1534883A2 (fr) | 2005-06-01 |
EP1534883B1 EP1534883B1 (fr) | 2009-02-25 |
Family
ID=31503090
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP20030753670 Expired - Lifetime EP1534883B1 (fr) | 2002-09-04 | 2003-08-08 | Articles comprenant des fibres, et/ou fibrides, fibres et fibrides et leur procede d obtention |
Country Status (12)
Country | Link |
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US (3) | US7459407B2 (fr) |
EP (1) | EP1534883B1 (fr) |
JP (1) | JP4596914B2 (fr) |
CN (1) | CN100335692C (fr) |
AT (1) | ATE423862T1 (fr) |
AU (1) | AU2003271832A1 (fr) |
DE (1) | DE60326358D1 (fr) |
ES (1) | ES2323687T3 (fr) |
FR (1) | FR2843975B1 (fr) |
RU (1) | RU2315827C2 (fr) |
TW (1) | TWI268968B (fr) |
WO (1) | WO2004022823A2 (fr) |
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US7771638B2 (en) * | 2007-12-19 | 2010-08-10 | E. I. Du Pont De Nemours And Company | Rapid plasticization of quenched yarns |
US7998575B2 (en) * | 2007-12-19 | 2011-08-16 | E.I. Du Pont De Nemours And Company | Low shrinkage, dyeable MPD-I yarn |
DK2384375T3 (en) * | 2009-01-16 | 2017-10-16 | Zeus Ind Products Inc | ELECTROSPINING PTFE WITH HIGH-VISUAL MATERIALS |
US20130337246A1 (en) * | 2012-06-15 | 2013-12-19 | 3M Innovative Properties Company | Electrical insulation material |
US9314993B2 (en) | 2013-03-15 | 2016-04-19 | National Nonwovens Inc. | Composites and articles made from nonwoven structures |
US9314995B2 (en) | 2013-03-15 | 2016-04-19 | National Nonwovens Inc. | Composites comprising nonwoven structures and foam |
KR102351348B1 (ko) * | 2013-10-30 | 2022-01-17 | 이 아이 듀폰 디 네모아 앤드 캄파니 | 폴리(m-페닐렌 아이소프탈아미드) 및 (6)-아미노-2-(p-아미노페닐)벤즈이미다졸로부터 제조된 공중합체의 혼합물을 포함하는 시트 및 피브리드 |
CN103774268B (zh) * | 2014-01-20 | 2016-05-11 | 江苏巨贤合成材料有限公司 | 一种聚酰胺酰亚胺沉析纤维的制备方法 |
CN104846473B (zh) * | 2014-02-14 | 2016-05-25 | 上海特安纶纤维有限公司 | 一种基于芳香族聚酰胺和聚芳砜的共混纤维、纱线、织物、制品及其制备方法 |
US9773583B2 (en) * | 2014-04-24 | 2017-09-26 | Essex Group, Inc. | Continously transposed conductor |
CN104674405B (zh) * | 2015-01-14 | 2018-01-05 | 上海特安纶纤维有限公司 | 含砜基的共混型芳族聚酰胺纤维混合物及其制品 |
CN104667630B (zh) * | 2015-01-14 | 2017-04-19 | 上海特安纶纤维有限公司 | 一种含砜基的共混型芳族聚酰胺纤维耐高温滤料及其制造方法 |
CN104611840B (zh) * | 2015-02-13 | 2018-05-01 | 上海特安纶纤维有限公司 | 包含芳香族聚酰胺和聚芳砜的混合聚合物纤维的絮片及其制备方法 |
CN104611839B (zh) * | 2015-02-13 | 2018-05-01 | 上海特安纶纤维有限公司 | 包含一种基于芳香族聚酰胺和聚芳砜的共混纤维和耐高温阻燃纤维的无纺织品及制备方法 |
CN104630959B (zh) * | 2015-02-13 | 2018-03-02 | 上海特安纶纤维有限公司 | 包含一种基于芳香族聚酰胺和聚芳砜的共混纤维和纤维素纤维的纱线、织物及制备方法 |
CN104651997B (zh) * | 2015-02-13 | 2018-05-01 | 上海特安纶纤维有限公司 | 包含一种含砜基的共混型芳族聚酰胺纤维的纤维混合物、及由其纱线、织物和制备方法 |
CN104630957B (zh) * | 2015-02-13 | 2017-11-17 | 上海特安纶纤维有限公司 | 由一种基于芳香族聚酰胺和聚芳砜的共混纤维和聚苯硫醚纤维制成的纱线和织物及制备方法 |
CN107287988B (zh) * | 2017-07-20 | 2019-04-02 | 清华大学 | 一种微/纳米复合纤维电气绝缘纸的制备方法 |
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- 2003-08-08 WO PCT/FR2003/002495 patent/WO2004022823A2/fr active Application Filing
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- 2003-08-08 EP EP20030753670 patent/EP1534883B1/fr not_active Expired - Lifetime
- 2003-08-08 AU AU2003271832A patent/AU2003271832A1/en not_active Abandoned
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- 2003-08-08 JP JP2004533552A patent/JP4596914B2/ja not_active Expired - Fee Related
- 2003-08-08 DE DE60326358T patent/DE60326358D1/de not_active Expired - Lifetime
- 2003-08-08 RU RU2005109419A patent/RU2315827C2/ru not_active IP Right Cessation
- 2003-08-08 US US10/526,676 patent/US7459407B2/en not_active Expired - Fee Related
- 2003-09-02 TW TW92124220A patent/TWI268968B/zh not_active IP Right Cessation
-
2008
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See references of WO2004022823A3 * |
Also Published As
Publication number | Publication date |
---|---|
ES2323687T3 (es) | 2009-07-23 |
WO2004022823A2 (fr) | 2004-03-18 |
DE60326358D1 (de) | 2009-04-09 |
TW200419024A (en) | 2004-10-01 |
TWI268968B (en) | 2006-12-21 |
RU2315827C2 (ru) | 2008-01-27 |
CN1678776A (zh) | 2005-10-05 |
ATE423862T1 (de) | 2009-03-15 |
US20120001359A1 (en) | 2012-01-05 |
AU2003271832A8 (en) | 2004-03-29 |
CN100335692C (zh) | 2007-09-05 |
US20060105157A1 (en) | 2006-05-18 |
RU2005109419A (ru) | 2006-01-20 |
FR2843975A1 (fr) | 2004-03-05 |
AU2003271832A1 (en) | 2004-03-29 |
EP1534883B1 (fr) | 2009-02-25 |
FR2843975B1 (fr) | 2008-11-14 |
US8293042B2 (en) | 2012-10-23 |
US20080302495A1 (en) | 2008-12-11 |
JP2005538261A (ja) | 2005-12-15 |
US7459407B2 (en) | 2008-12-02 |
JP4596914B2 (ja) | 2010-12-15 |
WO2004022823A3 (fr) | 2004-05-06 |
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