EP0540608B1 - Verfahren zur herstellung von subdenier fasern, pulpeähnlichen kurzen fasern, fibriden, vorgarnen und matten aus isotropen polymeren lösungen - Google Patents

Verfahren zur herstellung von subdenier fasern, pulpeähnlichen kurzen fasern, fibriden, vorgarnen und matten aus isotropen polymeren lösungen Download PDF

Info

Publication number
EP0540608B1
EP0540608B1 EP91913576A EP91913576A EP0540608B1 EP 0540608 B1 EP0540608 B1 EP 0540608B1 EP 91913576 A EP91913576 A EP 91913576A EP 91913576 A EP91913576 A EP 91913576A EP 0540608 B1 EP0540608 B1 EP 0540608B1
Authority
EP
European Patent Office
Prior art keywords
fibrids
fibers
polymer
stream
poly
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
Application number
EP91913576A
Other languages
English (en)
French (fr)
Other versions
EP0540608A1 (de
Inventor
Steven R. Allen
David Mark Gale
Aziz Ahmed Mian
Sam L. Samuels
Hsiang Shih
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
EIDP Inc
Original Assignee
EI Du Pont de Nemours and Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=24216340&utm_source=***_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP0540608(B1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Publication of EP0540608A1 publication Critical patent/EP0540608A1/de
Application granted granted Critical
Publication of EP0540608B1 publication Critical patent/EP0540608B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

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
    • D04H13/00—Other non-woven fabrics
    • 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
    • D01D5/11—Flash-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
    • D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/18—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polymers of unsaturated nitriles, e.g. polyacrylonitrile, polyvinylidene cyanide
    • 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
    • D01F6/60—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyamides
    • D01F6/605—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyamides from aromatic polyamides
    • 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
    • D04H1/56—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 in association with fibre formation, e.g. immediately following extrusion of staple fibres
    • 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
    • D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
    • D21H13/10—Organic non-cellulose fibres
    • D21H13/20—Organic non-cellulose fibres from macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H13/26—Polyamides; Polyimides

Definitions

  • the present invention relates to a process for preparing subdenier fibers from isotropic polymer solutions which may be collected in the form of pulp-like short fibers, fibrids, rovings, and mats.
  • the invention also contemplates and includes products having novel subdenier fiber structures which are produced according to the aforementioned process.
  • US-A-4 187 143 discloses for preparing poly(amide-imide) fibrids a process in which solutions of poly(amide-imide) resins are introduced into a liquid precipitation medium whilst exposed to shearing forces, whereby discrete fibrids exhibiting a high degree of fibrillation and a high tendency to form a web are obtained directly.
  • EP-A-0 381 206 (which has an elder priority than, but was published after the priority date of, the subject application) discloses a process for preparing subdenier fibers from a stream of optically anisotropic solution.
  • An object of the present invention is to prepare new pulp-like poly(meta-phenylene isophthalamide) fibrids. These pulp-like fibrids may be used to prepare sheet structures, such as papers which demonstrate improved porosity and electrical properties. These sheet structures may be used in preparing laminate and composite structures.
  • This invention provides a process for preparing subdenier fiber from isotropic polymer solutions.
  • the -process comprises 1) extruding a stream of an isotropic solution of a polymer through a spinneret orifice into a chamber, 2) introducing a pressurized gas into said chamber, 3) directing the gas in the flow direction of and in surrounding contact with said stream within the chamber, 4) passing both the gas and stream through an aperture into a zone of lower pressure at a velocity sufficient to attenuate the stream and fragment it into fibers, and 5) contacting the fragmented stream in said zone with a coagulating fluid.
  • a suitable gas for contacting the extruded stream in the chamber is air and the zone of lower pressure wherein both the gas and stream pass may be air at atmospheric pressure.
  • the coagulating fluids are water, dimethylsulfoxide or dimethylacetamide.
  • Preferred embodiments of the present invention include spinning isotropic polymer solutions of polyacrylonitrile, poly(m-phenylene isophthalamide), a copolymer of 3,4'-diaminodiphenyl ether and isophthaloyl-bis-(capro-lactam), and a mixture of poly(m-phenylene isophthalamide) and a copolymer of 3,4'-diaminodiphenyl ether and isophthaloyl-bis-(caprolactam).
  • the fragmented stream of subdenier fibers may be collected in the form of pulp-like short fibers, fibrids, rovings, or nonwoven mats, and such products are contemplated as part of the present invention.
  • poly(m-phenylene isophthalamide) pulp-like fibrids are produced by spinning a polymer solution comprising about 12 to 19% by weight poly(m-phenylene isophthalamide) polymer. Hot air having a pressure equal to or greater than about 6 kg/cm 2 is introduced into the chamber.
  • Suitable solvents for the poly(m-phenylene isophthalamide) polymer include dimethylacetamide, and a mixture of dimethylacetamide and dimethylsulfoxide.
  • the invention also includes pulp-like fibrids produced from such a process.
  • pulp-like fibrids have a diameter of about 0.1 to 50 micrometers, a length of about 0.2 to 2 millimeters, and a Schopper-Riegler freeness value according to ISO Standard 5267/1-1979 ( ⁇ ) of about 100 to 2000 milliliters, wherein the fibrids are capable of forming 100% by weight poly(m-phenylene isophthalamide) porous sheets.
  • These wet-laid porous sheets preferably have a porosity measured according to the Technical Association of the Pulp and Paper Industry (TAPPI) test method T 460 om-88 of about 0.1 to 200 seconds, and more preferably from about 0.1 to 2.0 seconds, per 100 cubic centimeters.
  • TAPPI Technical Association of the Pulp and Paper Industry
  • These sheets have a dielectric strength equal to or greater than about 10170 volts per g per m 2 (300 volts per ounce per square yard), and typically between about 10170 to 23730 volts per g per m 2 (300 to 700 volts).
  • wet-laid sheets comprising about 5 to 95% by weight of the above poly(m-phenylene isophthalamide) pulp-like fibrids are also contemplated. These wet-laid sheets may comprise a composition of the pulp-like fibrids, poly(m-phenylene isophthalamide) film-like fibrids, and poly(m-phenylene isophthalamide) staple floc.
  • Figs. 1 - 6 are cross-sectional schematic views of apparatus, primarily spin-cells, for practicing the invention.
  • nylon 66 in sulfuric or formic acid polyacrylonitrile, for example, co- and ter-polymers of acrylonitrile, methyl acrylate, and DEAM (diethylaminoethyl methacrylate) in dimethylsulfoxide, dimethylacetamide, or dimethylformamide solvents
  • polyether-ureaurethane polymers for example, a polymer made from the reactants, polytetramethylene glycol, methylene-bis-(p-phenylene isocyanate), ethylene diamine, and 1,3-cyclohexane diamine in dimethylacetamide solvent
  • polyimides for example, a terpolymer of oxydianiline, hexafluoropropylidene-bis-phthalic anhydride and sulfone dianiline in N-methylpyrrolidone solvent
  • melt-processable aramids for example, a terpolymer of oxydianiline, hexafluoropropy
  • isotropic polymer solutions which are well known in the art may also be used. If desired, more than one polymer may be incorporated in the same isotropic solution to form suitable polymer blends.
  • the isotropic polymer solutions used in this invention may be prepared by techniques known in the art.
  • the isotropic polymer solution is extruded through a spinneret orifice into a chamber in the vicinity of a generally convergent-walled aperture through which it will exit the chamber.
  • a pressurized gas which is inert to the isotropic polymer solution, is introduced into the chamber also in the vicinity of the aperture and in surrounding contact with the solution stream.
  • the gas preferably air, is at a pressure between 1.7 kg/cm 2 and 7.2 kg/cm 2 and is at a temperature from 20° to 300°C as it is fed into the chamber.
  • the velocity of the gas is such as to attenuate and fragment the stream as it exits the chamber through the aperture.
  • the gas and stream upon leaving the chamber enter a zone of lower pressure, preferably air, at atmospheric pressure. It is in this zone that the stream is contacted either before or after collection, with coagulating fluid.
  • suitable coagulating fluids include water, alcohol, and mixed solvents. A variety of products may be obtained depending upon the type of coagulating fluid used, and the method of contacting the stream with the coagulating fluid.
  • the fragmented stream is contacted with a jet of coagulating fluid, for example, water, at some distance such as, for example, 15 to 30 cm from the aperture.
  • a jet of coagulating fluid for example, water
  • the water jet will coagulate and disperse the stream which may then be collected as a mat on a screen belt moving transersely to the dispersed stream.
  • the stream comprises an acid solution of polymer
  • contact with water dilutes the acid and causes the polymer to come out of solution.
  • the collected material may be washed further or neutralized with dilute base, as is known in the art while on the screen belt.
  • the resulting mat is formed by the random laydown of jet-attenuated spun, oriented, subdenier, discontinuous fibers having widely varying morphology.
  • the mat may be tacked at fiber cross-over points to form a dimensionally stable sheet structure.
  • pulp-like product To make pulp-like product, coagulating fluid is caused to contact the exiting solution stream at the aperture and the product is collected over a pool of coagulating fluid.
  • the pulp-like product consists of short, oriented, subdenier fibers with varying morphology and lengths up to 15.0 mm.
  • a jet of coagulating fluid is directed against the fragmented stream at a distance from the aperture between about 1.0 to 10.0 cm and the coagulated product is collected on a relatively fast moving screen; however, in this case, the jet employed is one that lacks sufficient force to disperse the coagulated product before it is collected.
  • the structure of the coagulated product is an essentially unidirectional laydown of oriented, subdenier, discontinuous fibers having widely varying morphology with essentially no tacking or bonding between fibers.
  • Fig. 1 shows, in schematic cross-section, a spin-cell having a tubular 1-hole spinneret (4) with an outlet (3) extending into chamber (9) of cylindrical manifold (6).
  • the manifold has an inlet (8) and a nozzle (10) with a convergent-walled aperture (11) serving as an exit from the cell.
  • an isotropic solution of polymer is metered through spinneret (4) and into chamber (9) where it is contacted by a pressurized gas introduced from inlet (8).
  • the gas attenuates and fractures the polymer solution into elongated fragments as it passes out of the chamber through aperture (11), whose walls converge into a narrower opening.
  • a variety of products may be obtained depending upon how the contact is made, and type of coagulating fluid used.
  • Fig. 2 shows a process wherein the elongated fragments or fibers exiting spin-cell (6) are contacted at a distance below aperture (11) with a fluid (26) from spray jet nozzles (20) which acts to coagulate and spread the fragments of stream (30) which are then deposited as a nonwoven sheet onto moving screen (32).
  • a sequence of such jets may be employed.
  • These fragments are subdenier fibers with widely different cross sections and have lengths up to 10 cm, diameters up to 10 microns, and length to diameter ratios of at least 1000.
  • the fibers on the screen can be washed, dried and wound onto a bobbin (not shown) in a continuous process.
  • Fig. 3 shows an alternate method for contacting the stream leaving aperture (11) with coagulating fluid to produce roving or sliver.
  • an atomized jet of coagulating fluid (28) from spray jet nozzle(s) (24) impinges on the stream exiting aperture (11) at a distance up to 10 cm below the aperture.
  • the fibers in the stream have a momentum greater than the atomized jet of coagulating fluid and consequently deflection of the stream and dispersal of the fibers is low.
  • the subsequent fiber deposition of the moving screen (32) is essentially unidirectional and the product is suitable for sliver or roving.
  • the stream exiting aperture (11) may be prevented from spreading by surrounding the stream with a curtain of coagulating fluid flowing in the same direction. The curtain of the coagulating fluid initiates fiber coagulation and prevents spreading.
  • the stream containing coagulated fibers is intercepted by a moving screen conveyor belt causing the fibers to lay down essentially unidirectionally over the screen.
  • the sliver or roving which forms can be wrapped on a bobbin (not shown).
  • the fibers are similar to those of the previously described nonwoven mat.
  • Fig. 4 shows a method for producing pulp-like short fibers.
  • Fig. 4 shows spin-cell (40) which is similar to that of Fig. 1, except for having a conical nozzle (30) and a jet (35) which is built into the spin cell housing. Coagulating fluid from jet (35) is impinged on the outer surface of nozzle (30) and trickles down the slope of nozzle (30) to aperture (12) and contacts the exiting stream. This method results in formation of pulp-like short length coagulated fragments which can be spread over a moving screen or recovered in a receptacle (not shown) located below the spin-cell.
  • Fig. 5 shows a spin-cell (50) with inlet (51) for admitting hot air to heat the spinneret to prevent plugging while inlet (52) admits cold processing air to be introduced at the second stage. Seal (54) prevents the hot air from mixing with the cold air in the spin cell. Spent hot air may be removed from the chamber through exit (53). Polymer solution and cold air leave through exit aperture (55).
  • Fig. 6 shows a spin-cell (150) with inlet (151) for admitting hot air which heats the spinneret (104) to facilitate the flow characteristics of solutions.
  • the hot air then passes through a narrow ringlet gap (154) before exerting drag force on the extruded solution at the outlet of the spinneret (103).
  • the air attenuates and fractures the filaments as it passes out of the chamber through the aperture (130).
  • the aperture (130) is a constant diameter opening of finite length.
  • the polymer solution, exiting air and coagulant are collected in a pool of water.
  • the important process variables include solution viscosity, solution extrusion rate, pressure of hot air entering the cell, opening of the air aperture (130), and length of the air gap (measured as the distance between the outlet of the spinneret (103) and the outlet of the aperture (130)).
  • Solution viscosity is controlled by the solution temperature and polymer concentration in the solution. For work described herein, solution viscosity was controlled through the adjustment of polymer concentration. Solution extrusion rate was controlled by nitrogen back pressure applied to generate the forward movement of the solution. Air pressure can be readily adjusted through a regulator.
  • Polymer concentration in poly(m-phenylene isophthalamide) solutions was varied between about 12 weight % and 19 weight % to study the effect of solution viscosity on the quality of the pulp-like fibrids.
  • the fibrid diameter decreases with decreasing solution viscosity, whereas the concentration of large particle defects increases dramatically at the lower polymer concentrations.
  • 16 wt% solids solution was determined to give the best results.
  • Optimum polymer concentration will vary with the specific polymer/solvent combination being used.
  • Other possible solvents for poly(m-phenylene isophthalamide) polymer are known in the art and include dimethylacetamide by itself.
  • Solution extrusion rate was controlled by nitrogen back pressure.
  • High nitrogen pressure results in high extrusion rate which is preferred from productivity considerations, however, it is often accompanied by a high concentration of large particle defects.
  • MPD-I poly(m-phenylene isophthalamide) spun using a 0.004 inch (0:102 mm) spinneret
  • a nitrogen back pressure of no greater than 35.2 Kg/cm 2 gauge (500 psig) was required, and preferably no greater than 28.1 Kg/cm 2 gauge (400 psig), in order to achieve high quality pulp-like fibrids.
  • Air pressure determines the air velocity and velocity changes near the capillary and the aperture. It was found from this work that the best fibrid quality was obtained when air pressure was set at its highest possible setting which is about 80 psig (6.65 kg/cm 2 ) for the apparatus shown in Fig. 6 having the dimensions described in Examples 6-16.
  • the pulp-like MPD-I fibrids of the current invention have different characteristics and properties than fibrids known in the art.
  • fibrids of MPD-I that are described in the art are flat, filmy materials, with typical dimensions of 0.1 micrometers thick, 100 micrometers wide, and refined to various lengths. The filmy nature of these fibrids results in sealing of papers containing them, which results in low porosity.
  • the improved pulp-like fibrids of the current invention have a basically round cross-section, with an irregular, fibrillar morphology.
  • the pulp-like MPD-I fibrids of the current invention have a refined fibrid look, openness, and paper-making capability, without having to refine them.
  • the pulp-like fibrids of the current invention do not result in sealing of papers containing them. Therefore, when the pulp-like fibrids comprising aromatic polyamides such as MPD-I, are used to make electrical papers, an improved combination of electrical properties and porosity is achieved versus similar papers in the art which incorporate filmy fibrids.
  • the pulp-like fibrids are 0.1 - 50 micrometers in diameter and 0.2 - 2.0 mm in length. More preferably, the pulp-like fibrids have diameters of 0.2 - 5.0 micrometers and lengths of 0.2 - 1.3 mm.
  • the pulp-like fibrids of the current invention also have high freeness values. It is preferred that the freeness values, measured of a Schopper-Riegler apparatus, are 100 - 2000 ml. More preferably, the pulp-like fibrids have freeness values of 500 - 1000 ml.
  • the MPD-I pulp-like fibrids of the current invention may be used alone or as blends with filmy fibrids and staple floc to produce papers having good electrical properties.
  • "Staple floc", or "floc”, as used herein, refers to fibers in the form of short fibers.
  • the floc comprises fibers less than 2.54 cm in length with the optimum length being about 0.6 cm.
  • Appropriate yarns or tows of the polyamide are cut to the desired floc length by any suitable manner, e.g., by the use of a helical saw cutter.
  • Suitable fibers are those having a denier of from about 0.5 and up to 10 or more. Deniers less than about 5 are preferred. Most preferred are fibers having a denier of between about 1 and about 3.
  • the preferred compositions of the blends are: 5 - 100 weight % pulp-like fibrids, 0 - 60 weight% filmy fibrids, and 0 - 90 weight % staple floc. More preferably, 10 - 60 weight % pulp-like fibrids, 0 - 33 weight % filmy fibrids, and 10 - 50 weight % staple floc blends are used.
  • the sample fibers' denier must be calculated before determining tensile properties.
  • Techniques for measuring the denier of such non-round and varying diameter fibers are known and include Specific Surface Area Measurement, Scanning Electron Microscope Measurement and direct measurement of a sample group of fibers under the optical microscope.
  • An Instron 1122 was employed for determining tenacity and modulus following ASTM D2101 Section 10.6 (strain ⁇ 10%).
  • the clamps (grips with 0.95 cm (6/16 inch) x 0.95 cm (6/16 inch) neoprene faces) were set between 3.2 cm (1-1/4) and 3.81 cm (1-1/2 inches) apart and operated at a crosshead speed of 0.254 cm/min (0.1 inch/min.), while for 0.64 cm (0.25 inch) sample lengths, the clamps were set at 1.91 cm (0.75 inch) between faces and translated at a crosshead speed of 0.064 cm (0.025 inch/min).
  • Each end of a filament sample was taped to opposite ends of a rectangular tab with a rectangular cut-out (opening) of the specified length (2.54 cm or 0.64 cm (1 inch or 0.25 inch)). Taping was at a distance away from the opening and some slack in the fiber was allowed. A drop of adhesive was placed close to the edges of the tab opening to bond the designated length of the filament to correspond to the length of the tab opening.
  • the tab was mounted in the top clamp of the Instron and one side of the tab was cut. The opposite end of the tab was then mounted in the lower clamp and the other side of the tab was cut leaving the filament extended across the gap between the clamps.
  • the Instron was turned on and the stress-strain relationship of the filament was directly fed into the computer which calculated the tensile properties.
  • Porosity was measured using TAPPI test method T 460 om-88 "Air Resistance of Paper". The results of the test are reported in seconds which refers to the number of seconds required for a mass of 567 grams to force 100 cc of air through 6.4 square centimeters (1 square inch) of the paper being tested. The greater the test result number in seconds, the lower the porosity of the paper.
  • Average fiber length for pulp materials was determined on a Kajaani Model FS 100 instrument per manufacturer's test procedure in "Kajaani FS100 Standard Procedure for Analysis," Document T3501.0-e, Copyright 2 September 1985, Kajaani Electronic Ltd., Kajaani, Finland.
  • a 25% solution of a terpolymer of acrylonitrile, having a composition of 91% acrylonitrile, 6% methyl acrylate, and 3% DEAM (diethylaminoethyl methacrylate) with an inherent viscosity of 1.4, in dimethylsulfoxide was prepared.
  • the solution was prepared by placing the polymer powder and solvent in a resin kettle, and then dissolving the polymer in the solvent by agitation. The solution was then pushed hydraulically into a spin cell similar to the one shown in Fig. 4 and spun through a single hole spinneret, according to conditions shown in Table I.
  • the spinneret had a diameter of 0.004 inches (0.1016 mm) and a length to diameter (L/D) ratio of 3.0.
  • the spin cell had an air gap of 0.176 inches, (4.47 mm) as measured from the outlet (3) of the spinneret to the narrowest diameter (or throat) of the aperture (12) of the nozzle (30) of the spin cell.
  • the narrowest diameter of the aperture (12) was 0.062 inches (1.57 mm).
  • the convergent wall of the aperture (12) was at an angle of 40 degrees to the spinneret's axis making a conical angle of 80 degrees.
  • the discontinuous fibers leaving the spin cell were contacted with a stream of tap water over a moving screen conveyor belt at a distance of 17.375 inches (44.1 cm) from the tip of the aperture (12) to produce fibers having a length up to 8 cm.
  • the fibers were laid over a moving screen conveyor belt forming a random web which moved along with the conveyor belt from the spinning chamber to a washing chamber. In this chamber, the web was washed to remove the last traces of solvent and then moved to a drying chamber where the washed web was dewatered, partially dried and then wound up over a bobbin (or roll).
  • the fibers on the bobbin looked like a carded sliver and could possibly be directly used to produce spun yarns.
  • the fibers were tested for physical properties and the results are given in Table I.
  • the discontinuous fibers leaving the spin cell were contacted with a stream of tap water at the tip of the aperture (12) to produce fibers having a length less than 15 mm. These medium length fibers were collected over a pool of water which was later separated from the fibers by a standard filtration method. Finally, the fibers were washed to remove any residual solvent. These fibers may be wet laid to form a paper by using conventional techniques known to the art.
  • a 20% solution of poly(m-phenylene isophthalamide) in dimethylacetamide solvent was pushed hydraulically into a spin cell similar to the one shown in Fig. 4 and spun through a single hole spinneret according to the conditions in Table II.
  • the single hole spinneret had a diameter of 0.004 inches (0.1016 mm) and a L/D ratio of 3.0.
  • the single hole spinneret had a diameter of 0.010 inches (0.254 mm) and a L/D ratio of 3.0.
  • the solution was spun from both types of spinnerets.
  • the spin cell had an air gap of 0.176 inches (4.47 mm) as measured from the outlet (3) of the spinneret to the narrowest diameter (or throat) of the aperture (12) of the nozzle (30) of the spin cell.
  • the narrowest diameter of the aperture (12) was 0.062 inches (1.57 mm).
  • the convergent wall of the aperture was at an angle of 40 degrees to the spinneret's axis making a conical angle of 80 degrees.
  • the discontinuous fibers leaving the spin cell were contacted with a spray of tap water at approximately 11 inches (28 cm) from the tip of the aperture (12) and collected over a moving stainless steel screen.
  • the web, washed and dried, can be used as an inner layer to prepare laminates with similar layers of poly(p-phenylene terephthalamide) and can be used for high temperature insulation.
  • the discontinuous fibers leaving the spin cell were contacted with a spray of tap water at the tip of the aperture (12) and collected over a pool of water (not shown). Fibers were filtered, washed and slurried in water using a "Waring" Blender to further reduce the fiber-length.
  • the product was a sub-denier pulp having fiber length up to 5 mm. These subdenier pulps are useful in making high quality paper, as bonding agents for poly(p-phenylene terephthalamide) papers and as thickening agents.
  • a 30% solution of a copolymer of (3,4'-diamino diphenyl ether and isophthaloyl-bis-(caprolactam) was prepared by dissolving the copolymer in dimethylacetamide. The solution was then pushed hydraulically into a spin cell similar to the one shown in Fig. 4 and spun through a single hole spinneret.
  • the spinneret had a diameter of 0.004 inches (0.1016 mm) and a L/D ratio of 3.0.
  • the air gap was 0.176 inches (4.47 mm) as measured from the outlet (3) of the spinneret to the narrowest diameter (or throat) of the aperture (12) of the nozzle (30) of the spin cell.
  • the narrowest diameter of the aperture (12) was 0.062 inches (1.57 mm).
  • the convergent wall of the aperture was at an angle of 40 degrees to the spinneret's axis making a conical angle of 80 degrees.
  • Air heated to 80°C and pressurized to 83 psig (6.9 kg/cm 2 ) was introduced into the spin cell as attenuating fluid.
  • the discontinuous fibers leaving the spin cell were contacted with a spray of tap water at a distance of approximately 11 inches (28 cm) from the tip of the aperture (12) and collected over a moving screen. A web of subdenier fibers formed on the screen.
  • the discontinuous fibers leaving the spin cell were contacted with water at the tip of the aperture (12) and collected over a pool of water as explained in EXAMPLE 3.
  • the product in this case was subdenier pulp which can be used, for example, in paper making, in asbestos replacement, or as a bonding agent between layers of poly(p-phenylene terephthalamide) for high temperature applications..
  • a 20% solution of a polymer blend of 70% poly(m-phenylene isophthalamide) and 30% of a copolymer of 3,4'-diaminodiphenyl ether and isophthaloyl- bis-(caprolactam) was prepared in dimethylacetamide.
  • the solution was then spun using a spin cell similar to the one shown in Fig. 4, having a single-hole spinneret with a diameter of 0.004 inches (0.1016 mm).
  • the same solution was also spun using the same spin cell, but with a spinneret having a diameter of 0.010 inches (0.254 mm). Both spinnerets had a L/D ratio of 3.0.
  • the spin cell had an air gap of 0.125 inches 3.175 mm) as measured from the outlet (3) of the spinneret to the narrowest diameter (or throat) of the aperture (12) of the nozzle (30) of the spin cell.
  • the narrowest diameter of the aperture (12) was 0.062 inches (1.57 mm).
  • the convergent wall of the aperture was at an angle of 40 degrees to the spinneret's axis making a conical angle of 80 degrees. Heated air at 90°C and 60 psig (5.3 kg/cm 2 ) was introduced into the spin cell as attenuating fluid.
  • the discontinuous fibers leaving the spin cell were contacted with a spray of tap water at the tip of the aperture (12) and collected over a pool of water as explained in EXAMPLE 3.
  • the fibers were then filtered, washed and dried.
  • the product was pulp-like short fibers which can be used as a replacement for asbestos or as bonding agents. Thin filter cakes of the pulp-like short fibers were hot pressed at about 260°C to form non porous membranes.
  • the pulp-like fibrids used in these examples were prepared as follows. A 19% solution of poly(m-phenylene isophthalamide) in dimethylacetamide was diluted to 16% solids with dimethylsulfoxide. The solution was spun at 25 °C through a 0.004 inch (0.102 mm) single hole spinneret having a L/D ratio of 3. The spin cell was similar to that depicted in Fig. 6 and had an air-gap of 0.155 inch (3.94 mm), as measured from the outlet (103) of the spinneret to the outlet of the aperture (130), which had a diameter of 0.062 inches (1.575 mm), and a length of 0.062 inches (1.575 mm). The spinning solution pressure was 28.1 kg/cm 2 (400 psig) and the attenuating air pressure was 5.2 kg/cm 2 (74 psig).
  • the discontinuous fibers leaving the spin cell were contacted with a spray of tap water at the tip of the aperture (130) and collected over a pool of water.
  • the fibers were then washed with water in a home blender several times to remove solvent (final dimethylacetamide content was 0.16% with no detectable dimethylsulfoxide present).
  • the fibers obtained were in the form of pulp-like fibrids.
  • Fibrid quality was evaluated by blending at 0.04 weight % solids in distilled water for about one minute at high speed in a home kitchen blender. The high quality fibrids were easily separated in the blender and stayed uniformly dispersed in water without clumping. The aqueous dispersions were cast into tissue-thin handsheets (3-4 g/m 2 ), dewatered, and dried. The sheets were examined for clumps of pulp. The sheets were found to be fine and uniform with few or no clumps, which is indicative of high quality pulp-like fibrids. Clumps can be knotted filaments or solid polymer that has escaped fibrillation during spinning.
  • Fibrid diameters measured using scanning electron microscopy were 1-20 micrometers with very few particulate defects.
  • An average length for the pulp-like fibrids of 0.47 mm was determined by the kajaani method.
  • the pulp-like fibrids had a freeness of 773 ml measured on a Schopper-Riegler apparatus.
  • the pulp-like fibrids Prior to preparation of sheets, the pulp-like fibrids were opened by putting the total weight required of wet-lap pad into an ordinary 0.95 l (1 quart) household blender that was approximately 3/4 filled with water and blending at medium speed for 1-2 minutes so that no lumps or strings were present. A total of 2.8 g of ingredients were used to make nominal 2.0 oz/yd 2 basis weight, 20.3 cm by 20.3 cm (8 by 8 inch) sheets.
  • Handsheets comprised of the pulp were cast in a standard Deckle box. The pulp-like fibrids (supplied in dilute slurry form) were gently mixed in the Deckle box with 10 liters of water. A vacuum was applied, allowing the sheet to be formed on a removable wire screen.
  • the pulp-like fibrids (P) were used alone or in combination with poly(m-phenylene isophthalamide) filmy fibrids (F) and/or poly(m-phenylene isophthalamide) staple floc (S).
  • the filmy fibrids were prepared according to the procedure disclosed in Gross, US-A-3,756,908, the disclosure of which is hereby incorporated by reference, and had a Kajaani average length of 0.25 mm and Schopper-Riegler freeness of 330 ml.
  • the staple floc was prepared according to the procedure disclosed in Alexander, US-A-3,133,138, the disclosure of which is hereby incorporated by reference, and had a cut length of 6 mm and was 2.22 dtex (2 denier) per filament.
  • the pulp-like fibrids, filmy fibrids, and/or staple floc were mixed together in the Deckle box prior to application of the vacuum.
  • Samples of the sheets were hot-pressed for 1 min at 70.4 Kg/cm 2 (1000 psi) on a Farrel Watson-Stillman press, Model No. 9175-MR.
  • the sheets were tested for basis weight, dielectric strength, porosity, elongation-to-break (Elong-b), modulus, and density. Sheet properties are reported in Table III below.
  • Example 13 with 50 wt % filmy fibrids and 50 wt % staple floc, is representative of compositions of commercially available papers.
  • Example 13 Comparing Examples 6 and 7 with Example 13, note the dramatic increase in porosity for Examples 6 and 7 which is accompanied by good dielectric properties. Furthermore, it should be noted that the papers of Examples 6 and 7 have high elongation and low modulus when compared to those of Example 13. The high elongation and low modulus, i.e., high flexibility, is an advantage for certain applications which require winding the paper. However, because these papers are also highly porous, they can be saturated with resins or varnishes to make them more rigid. Therefore, these papers have better versatility. Saturation with resins or varnishes is also well known in the art as a method of improving mechanical and electrical properties.
  • Example 9 illustrates a ter-blend of pulp-like fibrids, filmy fibrids, and floc with improved porosity and dielectric strength. These benefits can be obtained with 33% pulp-like fibrids, 33% filmy fibrids, and 33% floc concentration. However, the filmy fibrids tend to act against the porosity advantage introduced by the pulp-like fibrids ( See , Examples 10, 14 and 16).
  • Porosity in unpressed sheets is a useful indicator of porosity in pressed sheets, especially when porosity in the pressed sheets is very low (high porosity values, i.e., greater than 1800 seconds). It would be inconvenient or impractical to run a porosity experiment for such a length of time. In addition, for sheets having high porosity/low porosity values, i.e., less than 0.1 seconds), the porosity readings may be controlled by the practical ability to make time measurements at these points.
  • Example 11 Comparing Example 11 with Example 12 illustrates that porosity benefits can be obtained by replacing the filmy fibrids in a 25% filmy fibrid/75% floc sheet with 25% pulp-like fibrids.
  • Dielectric strengths above about 200 are commercially significant and for papers with high porosity, these values can be raised by saturation with resins and varnishes.
  • Example 15 also shows the porosity benefits obtained when pulp-like fibrids are added.

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Mechanical Engineering (AREA)
  • Artificial Filaments (AREA)
  • Paper (AREA)
  • Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)

Claims (18)

  1. Ein Verfahren zur Herstellung von Subdenier-Faser aus isotropen Polymerlösungen, umfassend 1) Extrudieren eines Strahls einer isotropen Lösung eines Polymers durch eine Spinndüsenöffnung in eine Kammer, 2) Einbringen eines Druckgases in die Kammer, 3) Führen des Gases in der Flußrichtung von und in umgebendem Kontakt mit dem Strahl innerhalb der Kammer, 4) Leiten sowohl des Gases als auch des Strahls durch eine Öffnung in einen Bereich niedrigeren Drucks mit einer Geschwindigkeit, die ausreicht, um den Strahl zu schwächen und ihn zu Fasern zu fragmentieren, und 5) Inkontaktbringen des fragmentierten Strahls mit einem koagulierendem Fluid in dem genannten Bereich.
  2. Ein Verfahren gemäß Anspruch 1, worin das Polymer in Lösung Polyacrylnitril ist.
  3. Ein Verfahren gemäß Anspruch 1, worin das Polymer in Lösung Poly(m-phenylenisophthalamid) ist.
  4. Ein Verfahren gemäß Anspruch 1, worin das Polymer in Lösung ein Copolymer aus 3,4'-Diaminodiphenylether und Isophthaloylbis(caprolactam) ist.
  5. Ein Verfahren gemäß Anspruch 1, worin das Polymer in Lösung eine Mischung aus Poly(m-phenylenisophthalamid) und einem Copolymer aus 3,4'-Diaminodiphenylether und Isophthaloylbis(caprolactam) ist.
  6. Ein Verfahren gemäß Anspruch 1, worin der Bereich niedrigeren Drucks Luft bei Atmosphärendruck ist.
  7. Ein Verfahren gemäß Anspruch 1, worin das Gas, das mit dem Extrudat in der Kammer in Kontakt ist, Luft ist.
  8. Ein Verfahren gemäß Anspruch 1, worin die Subdenier-Faser in Form von Fasern, Vorgarnen oder Vliesstoffbahnen gesammelt wird.
  9. Ein Verfahren gemäß Anspruch 1, worin das koagulierende Fluid ausgewählt ist aus der Gruppe, bestehend aus Wasser, Dimethylsulfoxid und Dimethylacetamid.
  10. Das Verfahren nach Anspruch 1, worin die Polymerlösung etwa 12 bis 19 Gew.-% Poly(m-phenylenisophthalamid) enthält und das Gas Luft mit einem Druck von etwa 6 kg/cm2 oder größer ist.
  11. Das Verfahren nach Anspruch 10, worin die Polymerlösung etwa 12 bis 19 Gew.-% Poly(m-phenylenisophthalamid) in Dimethylacetamid-Lösungsmittel enthält.
  12. Das Verfahren nach Anspruch 10, worin die Polymerlösung etwa 12 bis 19 Gew.-% Poly(m-phenylenisophthalamid) in einem gemischten Lösungsmittel aus Dimethylacetamid und Dimethylsulfoxid enthält.
  13. Ein pulpeähnliches Poly(m-phenylenisophthalamid)-Fibrid mit einem Durchmesser von etwa 0,1 bis 50 Mikrometer, einer Länge von etwa 0,2 bis 2 Millimeter und einem Schopper-Riegler-Freeness-Wert gemäß ISO-Standard 5267/1-1979(E) von etwa 100 bis 2000 Milliliter, wobei das Fibrid zur Bildung von 100gew.-%igen porösen Poly(m-phenylenisophthalamid)-Flächengebilden in der Lage ist, und worin die Flächengebilde eine Porosität, gemessen gemäß dem TAPPI-Testverfahren T 460 om-88, von etwa 0,1 bis 200 Sekunden pro 100 Kubikzentimeter besitzen.
  14. Ein naßabgelegtes Flächengebilde, das aus den Fibriden nach Anspruch 13 besteht und durch eine dielektrische Festigkeit von etwa 10 170 Volt pro g pro m2 (300 Volt pro Unze pro Quadratyard) oder größer gekennzeichnet ist.
  15. Das naßabgelegte Flächengebilde nach Anspruch 14, worin die gemäß dem TAPPI-Testverfahren T 460 om-88 gemessene Porosität etwa 0,1 bis 2,0 Sekunden pro 100 Kubikzentimeter beträgt.
  16. Ein naßabgelegtes Flächengebilde, das etwa 5 bis 95 Gew.-% der Fibride nach Anspruch 13 enthält und durch eine dielektrische Festigkeit von etwa 10 170 Volt pro g pro m2 (300 Volt pro Unze pro Quadratyard) oder größer gekennzeichnet ist.
  17. Das naßabgelegte Flächengebilde nach Anspruch 16, worin die gemäß dem TAPPI-Testverfahren T 460 om-88 gemessene Porosität etwa 0,1 bis 2,0 Sekunden pro 100 Kubikzentimeter beträgt.
  18. Ein naßabgelegtes Flächengebilde, das eine zusammensetzung aus den Fibriden nach Anspruch 13, folienartigen Poly(m-phenylenisophthalamid)-Fibriden und Poly(m-phenylenisophthalamid)-Stapel enthält und durch eine dielektrische Festigkeit von etwa 10 170 Volt pro g pro m2 (300 Volt pro Unze pro Quadratyard) oder größer gekennzeichnet ist.
EP91913576A 1990-07-20 1991-07-19 Verfahren zur herstellung von subdenier fasern, pulpeähnlichen kurzen fasern, fibriden, vorgarnen und matten aus isotropen polymeren lösungen Expired - Lifetime EP0540608B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US55519490A 1990-07-20 1990-07-20
US555194 1990-07-20
PCT/US1991/005000 WO1992001829A1 (en) 1990-07-20 1991-07-19 A process for preparing subdenier fibers, pulp-like short fibers, fibrids, rovings and mats from isotropic polymer solutions

Publications (2)

Publication Number Publication Date
EP0540608A1 EP0540608A1 (de) 1993-05-12
EP0540608B1 true EP0540608B1 (de) 1998-01-28

Family

ID=24216340

Family Applications (1)

Application Number Title Priority Date Filing Date
EP91913576A Expired - Lifetime EP0540608B1 (de) 1990-07-20 1991-07-19 Verfahren zur herstellung von subdenier fasern, pulpeähnlichen kurzen fasern, fibriden, vorgarnen und matten aus isotropen polymeren lösungen

Country Status (9)

Country Link
EP (1) EP0540608B1 (de)
JP (1) JP3022597B2 (de)
KR (1) KR0178360B1 (de)
AT (1) ATE162857T1 (de)
AU (1) AU658827B2 (de)
CA (1) CA2087727A1 (de)
DE (1) DE69128834T2 (de)
PL (1) PL297657A1 (de)
WO (1) WO1992001829A1 (de)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6001303A (en) * 1997-12-19 1999-12-14 Kimberly-Clark Worldwide, Inc. Process of making fibers
CN105705689B (zh) * 2013-10-30 2017-11-07 纳幕尔杜邦公司 包含聚(间苯二甲酰间苯二胺)和由5(6)‑氨基‑2‑(对氨基苯基)苯并咪唑制成的共聚物的混合物的片材和沉析纤维
JP2018123434A (ja) * 2015-06-07 2018-08-09 株式会社大木工藝 繊維集合体製造方法
WO2018099855A1 (en) * 2016-11-30 2018-06-07 Teijin Aramid B.V. Aramid paper suitable for use in electronic applications
KR102353324B1 (ko) * 2020-12-24 2022-01-19 에너진(주) 여과성을 향상시킨 정전필터의 제조장치

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2988782A (en) * 1958-12-09 1961-06-20 Du Pont Process for producing fibrids by precipitation and violent agitation
US3342921A (en) * 1966-03-16 1967-09-19 West Virginia Pulp & Paper Co Process for producing fibrous filler having high wet end retention
US4187143A (en) * 1975-10-01 1980-02-05 Basf Aktiengesellschaft Manufacture of fibrids from poly(amide-imide) resins
US4963298A (en) * 1989-02-01 1990-10-16 E. I. Du Pont De Nemours And Company Process for preparing fiber, rovings and mats from lyotropic liquid crystalline polymers
US5026456A (en) * 1990-06-14 1991-06-25 E. I. Du Pont De Nemours And Company Aramid papers containing aramid paper pulp

Also Published As

Publication number Publication date
DE69128834T2 (de) 1998-09-10
WO1992001829A1 (en) 1992-02-06
ATE162857T1 (de) 1998-02-15
AU8232191A (en) 1992-02-18
JP3022597B2 (ja) 2000-03-21
JPH05508451A (ja) 1993-11-25
DE69128834D1 (de) 1998-03-05
AU658827B2 (en) 1995-05-04
PL297657A1 (de) 1992-07-13
EP0540608A1 (de) 1993-05-12
KR0178360B1 (ko) 1999-02-01
CA2087727A1 (en) 1992-01-21

Similar Documents

Publication Publication Date Title
US5296286A (en) Process for preparing subdenier fibers, pulp-like short fibers, fibrids, rovings and mats from isotropic polymer solutions
US4963298A (en) Process for preparing fiber, rovings and mats from lyotropic liquid crystalline polymers
CA2070589C (en) Method of preparing a nonwoven web of poly (vinyl alcohol) fibers
EP1457591B1 (de) Polyvinylalkoholfasern und diese enthaltende Vliesstoffe
US4836507A (en) Aramid staple and pulp prepared by spinning
JPH07111039B2 (ja) 熱結合繊維質湿式集積ウェブ及びその製造方法
US5094913A (en) Oriented, shaped articles of pulpable para-aramid/meta-aramid blends
EP0540608B1 (de) Verfahren zur herstellung von subdenier fasern, pulpeähnlichen kurzen fasern, fibriden, vorgarnen und matten aus isotropen polymeren lösungen
EP0477019A2 (de) Hochwertiges Polyäthylenpapier
AU2012099A (en) Nonwoven web of superabsorbent fiber and method
JP2797482B2 (ja) 均繊度の良好な不織布
FI80078B (fi) Ny syntetisk i vatten dispergerande fiber.
EP0598536B1 (de) Feste, unterbrochene Polyethylenfasern
JP3026379B2 (ja) 耐熱シートおよびその製造法
EP0900288B1 (de) Flah-spinnvorrichtung und verfahren
JPS6012479B2 (ja) シ−ト状構造物の製造方法
JPH0748718A (ja) 溶融異方性ポリアリレ−トパルプ、その製造方法及びポリアリレ−ト紙
JPH0881868A (ja) 耐水性ポリビニルアルコール系不織布及びその製法

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19930120

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT CH DE FR GB IT LI

17Q First examination report despatched

Effective date: 19940125

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT CH DE FR GB IT LI

REF Corresponds to:

Ref document number: 162857

Country of ref document: AT

Date of ref document: 19980215

Kind code of ref document: T

REG Reference to a national code

Ref country code: CH

Ref legal event code: NV

Representative=s name: RITSCHER & SEIFERT PATENTANWAELTE VSP

Ref country code: CH

Ref legal event code: EP

REF Corresponds to:

Ref document number: 69128834

Country of ref document: DE

Date of ref document: 19980305

ET Fr: translation filed
ITF It: translation for a ep patent filed

Owner name: ING. C. GREGORJ S.P.A.

PLBQ Unpublished change to opponent data

Free format text: ORIGINAL CODE: EPIDOS OPPO

PLBI Opposition filed

Free format text: ORIGINAL CODE: 0009260

PLBF Reply of patent proprietor to notice(s) of opposition

Free format text: ORIGINAL CODE: EPIDOS OBSO

26 Opposition filed

Opponent name: AKZO NOBEL N.V.

Effective date: 19981028

PLBF Reply of patent proprietor to notice(s) of opposition

Free format text: ORIGINAL CODE: EPIDOS OBSO

PLBF Reply of patent proprietor to notice(s) of opposition

Free format text: ORIGINAL CODE: EPIDOS OBSO

PLBQ Unpublished change to opponent data

Free format text: ORIGINAL CODE: EPIDOS OPPO

PLAB Opposition data, opponent's data or that of the opponent's representative modified

Free format text: ORIGINAL CODE: 0009299OPPO

R26 Opposition filed (corrected)

Opponent name: AKZO NOBEL N.V.

Effective date: 19981028

PLBF Reply of patent proprietor to notice(s) of opposition

Free format text: ORIGINAL CODE: EPIDOS OBSO

PLBO Opposition rejected

Free format text: ORIGINAL CODE: EPIDOS REJO

PLBN Opposition rejected

Free format text: ORIGINAL CODE: 0009273

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: OPPOSITION REJECTED

27O Opposition rejected

Effective date: 20001201

REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

PLAB Opposition data, opponent's data or that of the opponent's representative modified

Free format text: ORIGINAL CODE: 0009299OPPO

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CH

Payment date: 20080815

Year of fee payment: 18

Ref country code: DE

Payment date: 20080724

Year of fee payment: 18

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20080731

Year of fee payment: 18

Ref country code: FR

Payment date: 20080718

Year of fee payment: 18

Ref country code: AT

Payment date: 20080711

Year of fee payment: 18

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20080723

Year of fee payment: 18

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20090719

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20100331

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20090731

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20090731

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20090731

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20090719

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20100202

Ref country code: AT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20090719

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20090719