EP0360708B1 - Fils à base de polyamide imide et leur procédé d'obtention - Google Patents
Fils à base de polyamide imide et leur procédé d'obtention Download PDFInfo
- Publication number
- EP0360708B1 EP0360708B1 EP89420348A EP89420348A EP0360708B1 EP 0360708 B1 EP0360708 B1 EP 0360708B1 EP 89420348 A EP89420348 A EP 89420348A EP 89420348 A EP89420348 A EP 89420348A EP 0360708 B1 EP0360708 B1 EP 0360708B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- units
- solvent
- yarns
- filaments
- polyamide
- 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.)
- Expired - Lifetime
Links
- 229920002312 polyamide-imide Polymers 0.000 title claims abstract description 28
- 239000004962 Polyamide-imide Substances 0.000 title claims abstract description 26
- 238000004519 manufacturing process Methods 0.000 title description 2
- 239000002904 solvent Substances 0.000 claims description 15
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 14
- 230000001112 coagulating effect Effects 0.000 claims description 9
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 6
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 150000001408 amides Chemical group 0.000 claims description 5
- 239000011877 solvent mixture Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 238000002166 wet spinning Methods 0.000 claims description 3
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 2
- 239000002798 polar solvent Substances 0.000 claims description 2
- 230000014759 maintenance of location Effects 0.000 abstract description 8
- 230000001681 protective effect Effects 0.000 abstract description 2
- 238000004383 yellowing Methods 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 description 13
- 230000015556 catabolic process Effects 0.000 description 9
- 238000006731 degradation reaction Methods 0.000 description 9
- 239000000835 fiber Substances 0.000 description 6
- 125000005442 diisocyanate group Chemical group 0.000 description 5
- 238000004040 coloring Methods 0.000 description 4
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 4
- SDGNNLQZAPXALR-UHFFFAOYSA-N 3-sulfophthalic acid Chemical compound OC(=O)C1=CC=CC(S(O)(=O)=O)=C1C(O)=O SDGNNLQZAPXALR-UHFFFAOYSA-N 0.000 description 3
- 150000008064 anhydrides Chemical class 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- QQVIHTHCMHWDBS-UHFFFAOYSA-N perisophthalic acid Natural products OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 229920000784 Nomex Polymers 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000004763 nomex Substances 0.000 description 2
- 238000001782 photodegradation Methods 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- -1 trimellic anhydride Chemical compound 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- 0 C*c1cc(*)cc([*+]*NC)c1 Chemical compound C*c1cc(*)cc([*+]*NC)c1 0.000 description 1
- WMTLVUCMBWBYSO-UHFFFAOYSA-N N=C=O.N=C=O.C=1C=CC=CC=1OC1=CC=CC=C1 Chemical compound N=C=O.N=C=O.C=1C=CC=CC=1OC1=CC=CC=C1 WMTLVUCMBWBYSO-UHFFFAOYSA-N 0.000 description 1
- 206010051246 Photodermatosis Diseases 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 241001639412 Verres Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000000981 basic dye Substances 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-M benzenesulfonate Chemical compound [O-]S(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-M 0.000 description 1
- 229940077388 benzenesulfonate Drugs 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000002270 exclusion chromatography Methods 0.000 description 1
- 244000144992 flock Species 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000008845 photoaging Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- FGGFFWDXACTIPJ-UHFFFAOYSA-M potassium;2,3-dicarboxybenzenesulfonate Chemical compound [K+].OC(=O)C1=CC=CC(S([O-])(=O)=O)=C1C(O)=O FGGFFWDXACTIPJ-UHFFFAOYSA-M 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
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
- D01F6/58—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 yarns according to the invention are also characterized by a polydispersity index I ⁇ 2, 2 a toughness ⁇ 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%, the degree of white ⁇ 28, the index of yellow> 190.
- the light stability of PAIs according to the invention can also be greatly improved compared to that of PAI yarns known hitherto. It is evaluated by the retention of mechanical properties: tenacity at break ⁇ 50%, working at break ⁇ 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 R1 preferably a radical R2 preferably a radical and M is preferably Na or K.
- the PAI wires are also characterized by a value of the polydispersity index I ⁇ 2.2.
- This index corresponds to the ratio Mw / Mn , the values of Mn and Mw being determined by gel exclusion chromatography (GPC) in the NMP 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 low 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: ⁇ l being the increase in the length of the test piece at time t to which the actual titer corresponds and lo 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 color purity in 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 animated 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 only lets through radiation above 300 nm (solar spectrum).
- the temperature in the enclosure is 60 ° C.
- Procedure The 1.4 cm paper window to 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, we recover the paper window and determine the mechanical characteristics monofilament according to the method for 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 ⁇ 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 V2 V1 x 100, V2 being the speed of the stretching 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 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-drawing 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 finished yarn. The total draw rate 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: - trimellic anhydride (ANTM) 40 mole% - isophthalic acid (AI) 8 mole% - sodium salt of 5 isophthalic acid (AiSNa) 2 mole% - 4,4 ′ diphenyl ether diisocyanate (DIDE) 50 mole% in dimethylethylene urea of pH ⁇ 7 so as to obtain a concentration of 21%, 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 come out of the coagulating bath in the gel state and are drawn into air at ordinary temperature. They are washed with water in a bath to remove the solvent and dried on rollers.
- M w goes from 116,400 to 99,720, ie a loss of 16,680.
- 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.
- 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: Ex. Elongation% Tenacity cN / tex GPa module Temperature TG ° C Polydipersity index. I 4 23 51 6.3 265 2.2
- a solution of PAI with the same chemical structure as that described in Example 1 is prepared in a mixture of DMEU / DMF in proportion 72/28.
Landscapes
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Artificial Filaments (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Hydrogenated Pyridines (AREA)
- Materials For Medical Uses (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Organic Insulating Materials (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Treatments Of Macromolecular Shaped Articles (AREA)
- Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8812560 | 1988-09-21 | ||
| FR8812560A FR2643089B1 (fr) | 1988-09-21 | 1988-09-21 | Fils a base de polyamide-imide et leur procede d'obtention |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0360708A1 EP0360708A1 (fr) | 1990-03-28 |
| EP0360708B1 true EP0360708B1 (fr) | 1995-11-29 |
Family
ID=9370402
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP89420348A Expired - Lifetime EP0360708B1 (fr) | 1988-09-21 | 1989-09-14 | Fils à base de polyamide imide et leur procédé d'obtention |
Country Status (15)
| Country | Link |
|---|---|
| US (1) | US5159052A (pt) |
| EP (1) | EP0360708B1 (pt) |
| JP (1) | JP2744084B2 (pt) |
| CN (1) | CN1031290C (pt) |
| AT (1) | ATE130879T1 (pt) |
| BR (1) | BR8904858A (pt) |
| CA (1) | CA1334612C (pt) |
| DE (1) | DE68924946T2 (pt) |
| DK (1) | DK464489A (pt) |
| ES (1) | ES2079384T3 (pt) |
| FI (1) | FI894450A (pt) |
| FR (1) | FR2643089B1 (pt) |
| IE (1) | IE69380B1 (pt) |
| NO (2) | NO893257D0 (pt) |
| RU (1) | RU1838468C (pt) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7820151B2 (en) | 2004-02-13 | 2010-10-26 | L'oreal S.A. | Composition for coating keratin fibers, comprising at least one tacky wax and fibers |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2685354B1 (fr) * | 1991-12-24 | 1996-03-29 | Rhone Poulenc Fibres | Procede de filage de solutions de polyamides-imides (pai) a base de toluylene ou de metaphenylene diisocyanates et fibres ainsi obtenues. |
| US5756635A (en) * | 1991-12-24 | 1998-05-26 | Rhone-Poulenc Fibres | Process for spinning from solution of polyamide-imides (PAI) based on tolylene or met-phenylene diisocyanates and fibres thus obtained |
| 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 |
| JPH07310232A (ja) * | 1994-05-13 | 1995-11-28 | Toyobo Co Ltd | バグフィルター用ポリアミドイミド繊維 |
| US7923002B2 (en) | 2002-09-06 | 2011-04-12 | L'oreal S.A. | Composition for coating keratin fibres comprising a tacky wax |
| ATE328643T1 (de) | 2002-09-06 | 2006-06-15 | Oreal | Kosmetische zusammensetzung die ein klebriges wachs enthält |
| JP2014031420A (ja) * | 2012-08-02 | 2014-02-20 | Hitachi Chemical Co Ltd | ポリアミドイミド樹脂の合成方法、ポリアミドイミド樹脂およびポリアミドイミド樹脂組成物 |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3843587A (en) * | 1969-05-16 | 1974-10-22 | Schenectady Chemical | Polyamide-imide resins prepared from the reaction of aromatic diisocyanates with mixtures of polycarboxylic acids and anhydrides |
| FR2079785A5 (en) * | 1970-02-12 | 1971-11-12 | Rhodiaceta | Lustrous polyamide-imide based fibres by new process |
| BE787500A (fr) * | 1971-08-12 | 1973-02-12 | Rhone Poulenc Textile | Procede pour l'obtention de fils brillants |
| FR2165236A5 (en) * | 1971-12-21 | 1973-08-03 | Rhone Poulenc Textile | Non-inflammable fibres - from copolymers with amide-imide and acrylonitrile recurring units |
| US4001186A (en) * | 1974-11-07 | 1977-01-04 | The Upjohn Company | Preparation of polyimide from organic diisocyanate with alkali metal salt of alcohol as catalyst |
| JPS51143724A (en) * | 1975-06-02 | 1976-12-10 | Asahi Chem Ind Co Ltd | A multifilament yarn of an aromatic polymer and the manufacturing proc ess thereof |
| JPS52151393A (en) * | 1976-06-11 | 1977-12-15 | Toyobo Co Ltd | Poly-(n-ethylenetrimellitateimide) fiber or film its preparation |
| FR2478116B1 (fr) * | 1980-03-14 | 1985-06-14 | Rhone Poulenc Textile | Solutions conformables a partir de melanges de cellulose et polyamide-imide et articles en forme obtenus |
| US4640972A (en) * | 1985-11-15 | 1987-02-03 | E. I. Du Pont De Nemours And Company | Filament of polyimide from pyromellitic acid dianhydride and 3,4'-oxydianiline |
| US4758649A (en) * | 1986-05-21 | 1988-07-19 | Kuraray Co., Ltd. | Heat resistant organic synthetic fibers and process for producing the same |
| FR2627497B1 (fr) * | 1988-02-22 | 1990-06-15 | Rhone Poulenc Fibres | Solutions de polyamides-imides et leur procede d'obtention |
-
1988
- 1988-09-21 FR FR8812560A patent/FR2643089B1/fr not_active Expired - Fee Related
-
1989
- 1989-08-14 NO NO893257A patent/NO893257D0/no unknown
- 1989-08-31 NO NO89893499A patent/NO893499L/no unknown
- 1989-09-14 DE DE68924946T patent/DE68924946T2/de not_active Expired - Lifetime
- 1989-09-14 EP EP89420348A patent/EP0360708B1/fr not_active Expired - Lifetime
- 1989-09-14 ES ES89420348T patent/ES2079384T3/es not_active Expired - Lifetime
- 1989-09-14 AT AT89420348T patent/ATE130879T1/de active
- 1989-09-19 CA CA000611856A patent/CA1334612C/fr not_active Expired - Fee Related
- 1989-09-19 RU SU894614932A patent/RU1838468C/ru active
- 1989-09-20 DK DK464489A patent/DK464489A/da not_active Application Discontinuation
- 1989-09-20 JP JP1244901A patent/JP2744084B2/ja not_active Expired - Lifetime
- 1989-09-20 FI FI894450A patent/FI894450A/fi not_active IP Right Cessation
- 1989-09-20 IE IE301389A patent/IE69380B1/en not_active IP Right Cessation
- 1989-09-20 CN CN89107401A patent/CN1031290C/zh not_active Expired - Fee Related
- 1989-09-21 BR BR898904858A patent/BR8904858A/pt not_active IP Right Cessation
-
1991
- 1991-11-12 US US07/790,163 patent/US5159052A/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7820151B2 (en) | 2004-02-13 | 2010-10-26 | L'oreal S.A. | Composition for coating keratin fibers, comprising at least one tacky wax and fibers |
Also Published As
| Publication number | Publication date |
|---|---|
| IE69380B1 (en) | 1996-09-04 |
| DE68924946D1 (de) | 1996-01-11 |
| ATE130879T1 (de) | 1995-12-15 |
| NO893499D0 (no) | 1989-08-31 |
| FI894450A0 (fi) | 1989-09-20 |
| IE893013L (en) | 1990-03-21 |
| ES2079384T3 (es) | 1996-01-16 |
| CN1031290C (zh) | 1996-03-13 |
| DE68924946T2 (de) | 1996-07-04 |
| EP0360708A1 (fr) | 1990-03-28 |
| RU1838468C (ru) | 1993-08-30 |
| CA1334612C (fr) | 1995-03-07 |
| US5159052A (en) | 1992-10-27 |
| BR8904858A (pt) | 1990-05-08 |
| CN1041406A (zh) | 1990-04-18 |
| NO893257D0 (no) | 1989-08-14 |
| DK464489A (da) | 1990-03-22 |
| FR2643089A1 (fr) | 1990-08-17 |
| FR2643089B1 (fr) | 1991-05-10 |
| FI894450A (fi) | 1990-03-22 |
| DK464489D0 (da) | 1989-09-20 |
| JPH02104721A (ja) | 1990-04-17 |
| NO893499L (no) | 1990-03-22 |
| JP2744084B2 (ja) | 1998-04-28 |
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