EP0446870B1 - Hochfestpapiere aus Flocken und Fasern - Google Patents

Hochfestpapiere aus Flocken und Fasern Download PDF

Info

Publication number
EP0446870B1
EP0446870B1 EP91103757A EP91103757A EP0446870B1 EP 0446870 B1 EP0446870 B1 EP 0446870B1 EP 91103757 A EP91103757 A EP 91103757A EP 91103757 A EP91103757 A EP 91103757A EP 0446870 B1 EP0446870 B1 EP 0446870B1
Authority
EP
European Patent Office
Prior art keywords
fibrids
floc
phenylene
radicals
handsheet
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
EP91103757A
Other languages
English (en)
French (fr)
Other versions
EP0446870A1 (de
Inventor
Gary Lee Hendren
Hamid Moayed Ghorashi
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
Priority claimed from US07/640,592 external-priority patent/US5126012A/en
Application filed by EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Publication of EP0446870A1 publication Critical patent/EP0446870A1/de
Application granted granted Critical
Publication of EP0446870B1 publication Critical patent/EP0446870B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • 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
    • 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
    • D21H13/36—Inorganic fibres or flakes
    • D21H13/38—Inorganic fibres or flakes siliceous
    • D21H13/40—Inorganic fibres or flakes siliceous vitreous, e.g. mineral wool, glass 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
    • D21H13/36—Inorganic fibres or flakes
    • D21H13/46—Non-siliceous fibres, e.g. from metal oxides
    • D21H13/50—Carbon 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
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/902—High modulus filament or fiber
    • 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
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/903—Microfiber, less than 100 micron diameter
    • 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
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y10T428/2933—Coated or with bond, impregnation or core
    • Y10T428/2964—Artificial fiber or filament
    • Y10T428/2967—Synthetic resin or polymer
    • Y10T428/2969—Polyamide, polyimide or polyester

Definitions

  • wet-laid nonwoven sheets of synthetic polymeric fibrids and short length staple fibers are known from US-A-2,999,788. Increased bonding of these sheets can be obtained by application of heat and/or pressure.
  • the fibrids are prepared by shear precipitation of solutions of the polymer, preferably in an aqueous medium.
  • the fibrids are directly converted into nonwoven sheet structures or paper by paper-forming techniques similar to those employed with wood pulp.
  • the aqueous mix used to prepare the nonwoven sheets by paper-making methods will include short fiber or floc in addition to the fibrids. Other materials may be added as desired.
  • the invention provides a high strength nonwoven sheet structure consisting of floc and fused fibrids, characterised in that it consists of from 10 to 90 wt. % of floc of carbon, aramid or glass fiber held in place with from 90 to 10 wt.
  • % of fused fibrids consisting essentially of the following units and where n is 4 or 5; X is from 0.01 to 0.50, preferably from 0.03 to 0.30, and Ar is a radical selected from 3,4'-oxydiphenylene, 4,4'-oxydiphenylene, 4,4'-sulfonyldiphenylene, 1,3-phenylene, 1-methyl-2,4-phenylene, and mixtures of such radicals with each other or mixtures of such radicals with up to 50 mol percent of 1,4-phenylene radicals based on the mixture of such radicals.
  • the novel fibrids are also part of this invention.
  • Sheet products of the present invention are wet-laid, hot-pressed sheets of floc of carbon, aramid or glass and certain novel fibrids.
  • floc is used to describe short length fibers as customarily used in the preparation of wet-laid sheets. Floc suitable for use in this invention will normally have lengths less than 2.5 cm. In the examples, the floc fibers had a linear density of 2.2 dtex and a cut length of about 0.68 cm. Such floc provides maximum strength and resistance to shrinkage of resultant sheet.
  • Fibrids are very small, nongranular, flexible, fibrous or film-like particles. At least one of their three dimensions is of minor magnitude relative to the largest dimension. They are prepared by precipitation of a solution of polymeric material using a non-solvent under very high shear. Suitable fibrids and methods for their preparation are described in US-A-2,999,788 issued September 12, 1961, to P. W. Morgan. Fibrids are always prepared as dispersions in liquid. They can be converted to aqueous slurries by suitable washing techniques. Fibrids characteristically have a high absorptive capacity for water and when deposited on a screen have sufficient strength even when wet to permit processing on a paper machine.
  • Suitable sheets can be made by uniformly depositing an aqueous slurry of the paper-making fibrous material onto a foraminous surface (e.g., a fine-mesh screen or fabric) through which much of the water quickly drains to form an initial sheet.
  • a foraminous surface e.g., a fine-mesh screen or fabric
  • Handsheets Sheets prepared one at a time on laboratory-scale paper-forming equipment are designated "handsheets".
  • the fibrids employed in the present invention are prepared from a polymer having the following repeat units in the indicated proportions: and where n is 4 or 5; x is from 0.01 to 0.50; and Ar is a radical selected from 3,4'-oxydiphenylene, 1,3-phenylene, 1-methyl-2,4-phenylene, and mixtures of such radicals with each other or with up to equimolar amounts of 1,4-phenylene radicals.
  • This example shows preparation of fibrids of this invention.
  • a polymer having the following repeat units was prepared in accordance with the procedures of coassigned EP-A-0366316. and About 36 g of the polymer (inherent viscosity 0.5) was combined with 264 g of dimethylacetamide (DMAc) containing 4% LiCl to yield a 12% polymer solution. This solution was heated to 85°C to dissolve the polymer until a clear, light brown/gold solution is obtained.
  • DMAc dimethylacetamide
  • a Waring 7011 blender (model 31BL02) was filled with 50 ml of DMAc (4% Licl) and 200 ml distilled water. With the blender run on high speed, 75 ml of polymer solution was poured slowly into top of the blender (stream ⁇ 0.3 cm wide at top of blender). The resulting fibrids were vacuum filtered onto Whatman International Ltd. #41 filter paper and washed 5 times with with ⁇ 500 ml of water to remove excess DMAc. The fibrid care obtained was not allowed to dry out.
  • This example shows the preparation of a nonwoven sheet structure of the present invention using the fibrids of Example 1 and an aramid floc.
  • This floc was prepared from paraphenylene terephthalamide fiber (PPD-T) Kevlar 29 fiber from E. I. du Pont de Nemours and Company, Inc.
  • PPD-T paraphenylene terephthalamide fiber
  • a handsheet containing 70 wt. % of the fibrids and 30 wt. % of the floc described above was prepared from 683 ml of a 0.3% solids fibrid slurry and 1.1052 g of 0.32 cm (0.125 inch) floc.
  • the handsheet was produced by putting the fibrids and floc and 2400 ml of water into British Pulp Evaluation Apparatus (Mavis Engineering, Ltd. No. 8233) and dispersing them for 5 minutes. This stock was added to a Noble and Woods handsheet mold and additional water added. The stock solution was agitated 10 times with an agitator plate, then vacuum drained through a screen having screen openings of 0.15 mm diameter (100 mesh screen).
  • the sample was couched between 2 plies (each side) of blotter paper to remove excess moisture.
  • the handsheet was then transferred to blotter paper by slapping the sample and screen onto a table top.
  • the sample was dried on handsheet hot plate drier (Noble & Wood Model No. F10). Sample strength was judged to be sufficient to produce on a fourdrinier paper machine.
  • the handsheet was pressed on a hot press (Farrel Watson-Stillman, Model No. 9175-MR) at 690 kPa (100 psi), 279°C (535°F) for 1 minute. Sample was measured per ASTM D-828 and determined to have break strength of 0.52 N/m width (29.44 lbs/inch width) and modulus of 4227 MPa (613 kpsi).
  • This example employs the fibrids of Example 1 in making sheet structures with several different types of floc. In some instances, proportions were varied.
  • Item G is a control using fibrids of metaphenylene isophthalamide (MPD-I). Items A and B use floc similar to that of Example 2 while Items E and F employ an aramid floc from MPD-I fiber.
  • the break strength and modulus are "normalized" to the same density and basis weight as the Item G control.
  • the carbon papers will not densify as much as less stiff fibers under the same pressing conditions. As one can see, Items A-F are superior to Item G.
  • Example 2 About 22.7 kg (50 lbs) of the polymer described in Example 1 (0.5-0.6 inherent) was dissolved in enough DMAc (4% LiCl) to produce a 30% solids solution.
  • the 30% solids solution above was passed to a fibridator of the type disclosed in US-A-3,018,091. The resulting fibrids are washed with water to reduce DMAc and chloride content to about 1.0% and 0.3%, based on polymer, respectively.
  • This stock was diluted to 0.35% solids and then pumped, through a double-disc refiner (Sprout-Waldron 12 ⁇ 254 cm (12'') Twin-Flo, Model no. 12-MA, Serial No. 67-1432, to a standard fourdrinier paper machine at a rate of 4.26 l/min/cm width (2.86 gallons per min./inch width) to form a sheet of 27.2 kg/914 m ream (60 lbs/3000 ft. ream) at 15.2 m (50 ft.) per min. wire speed. This sheet was dried to a moisture level of 1.15%.
  • Break Strength and Modulus values of this paper and a comparably made paper using MPD-I fibrids is given below for the machine direction MD and the cross direction CD.
  • the sheet samples were pressed on a hot press (Farrel Watson-Stillman, Model No. 9175-MR) at 6.895 MPa (1000 psi), 279°C (535°F) for 1 minute.
  • Break strength was measured and is shown below. Included is data for the same comparably made paper using MPD-I fibrids and PPD-T floc as a control.
  • the fibrids were prepared from a polymer consisting essentially of the following repeat units in the indicated mol ar proportions. and wherein Ar is a 70/30 mixture of 1,3-phenylene and 1,4-phenylene radicals, and a PPD-T floc was employed
  • the copolymer was prepared in a 2 liter resin kettle fitted with a stirrer, heating mantle, and continuous nitrogen flow. A mixture of IBC (862.5 g, 2.4 mol), MPD (183.2 g, 1.7 mol), and PPD (78.5 g, 0.73 mol) was maintained at a temperature between 250° and 260°C for 4 hours. The clear amber plasticized copolymer produced, in solution with residual caprolactam was allowed to cool to room temperature. The inherent viscosity of the copolymer was determined to be 0.8 and its Tg was 217°C. Its proton - NMR spectrum showed X to be 0.27.
  • a Waring 7011 blender was filled with 50 ml of DMAc (4% Licl) and 200 ml distilled water. With the blender run on high speed, 75 ml of polymer solution were poured slowly into top of blender (stream ⁇ 0.3 cm wide at top of blender). The fibrids (Fibrid A) were vacuum filtered and washed 5 times with ⁇ 500 ml of water to remove excess DMAc. The fibrid cake obtained was not allowed to dry out.
  • a handsheet comprising 70% of Fibrid A/30% PPD-T floc was made using 683 ml of the 0.3% solids fibrid slurry and 1.1052 g 0.32 cm (0.125 in.) PPD-T floc.
  • the handsheet was produced by putting the fibrids and floc and an additional 2000 ml of water into British Pulp Evaluation Apparatus (Mavis Engineering, Ltd. No. 8233) and dispersing them for 5 minutes. This stock was added to a handsheet mold and additional water added. The stock solution was agitated 10 times with an agitator plate, then vacuum drained through a screen having openings of 0.15 mm diameter (100 mesh screen).
  • the sample was couched between 2 plies (each side) of blotter paper to remove excess moisture.
  • the handsheet was then transferred to blotter paper by slapping the sample and screen onto a table top.
  • the sample dried on a handsheet hot plate drier.
  • a similar sample was produced using the MPD-I fibrid slurry mentioned above as a control.
  • the handsheet was then pressed on a hot press at 6.895 MPa (1000 psi), 279°C (535°F) for 1 minute.
  • This example is a control showing the use of thermoplastic polymer fibrids.
  • polyetherimide (PEI, ULTEM 1000 produced by G.E.) polymer were combined with 270 g of DMAc to yield 10% polymer solution. This solution was heated to 85°C to dissolve the polymer until a clear, light brown/gold solution is obtained.
  • a Waring blender was filled with 50 ml of DMAc (4% LiCl) and 200 ml distilled water. With the blender run on high speed, 75 ml of polymer solution were poured slowly into the top of the blender (stream ⁇ 0.3 cm wide at top of blender). The fibrids were vacuum filtered onto Whatman International Ltd. #41 filter paper and washed 5 times with ⁇ 500 ml of water to remove excess DMAc. The fibrid cake obtained was not allowed to dry out.
  • DMAc 4% LiCl
  • a handsheet 60% PEI fibrids/40% PPD-T floc was prepared using 308 ml of a 0.3% solids fibrid slurry and 0.616 dry g 0.64 cm (0.25 in) floc.
  • the handsheet was produced by putting the fibrids and floc and 2400 ml of water into the British Pulp Evaluation Apparatus and dispersing them for 5 minutes. This stock was added to a handsheet mold and additional water added. The stock solution was agitated 10 times with an agitator plate, then vacuum drained through a screen having screen openings of 0.15 mm diameter (100 mesh screen). The sample was couched between 2 plies (each side) of blotter paper to remove excess moisture.
  • the handsheet was then transferred to blotter paper to remove excess moisture.
  • the handsheet was then transferred to blotter paper by slapping the sample and screen onto a table top.
  • the sample dried on a handsheet hot plate drier. Sample strength was judged to be sufficient to produce on a fourdrinier paper machine.
  • the handsheet was then pressed on a hot press at 6.895 MPa (1000 psi), 279°C (535°F) for 1 minute. Sample was determined to have break strength of 0.02 N/m (0.86 lbs/inch width) and modulus of 168 MPa (24.43 kpsi).
  • the break strength and modulus of all samples are "normalized" to a basis weight of 33.9 g/m2 (1.00 ounces per square yard). As one can see the B fibrid paper are superior to both the A and the C fibrid papers.
  • a series of copolymers was prepared from IBC and an aromatic diamine, Ar(CH2) 2, or a mixture of aromatic diamines. Each copolymer was prepared in a test tube fitted with a cap lined with polytetrafluoroethylene. In each of the copolymer preparations, IBC (10.0 g, 28 mmol) and the appropriate diamine or diamines (28 mmol total, see table below) were held at 250°C in the test tube under nitrogen for four hours. The molten mixture was swirled during the initial part of the reaction.
  • the aromatic diamines used to make the copolymers were the following diamines:
  • the bis(lactam) monomer used to make the copolymers were N,N'-isophthaloyl bis(caprolactam) (IBC).
  • a 12% polymer solution was produced by dissolving each of the above copolymers in the appropriate amount of solvent, which was 100% DMAc for items A, B, E, F, I, or DMAc containing 4% LiCl for items C, D, G, H.
  • a light brown/gold solution was obtained, and it was filtered through glass wool. This solution was heated to 85°C.
  • a Waring 7011 blender was filled with 50 ml of DMAc (4% LiCl) and 200 ml distilled water. With the blender run on high speed, 75 ml of polymer solution was poured slowly into the top of the blender, the stream being about 0.32 cm (1/8 in.) wide at the top of the blender. Each sample of fibrids (Fibrids A-I) was vacuum filtered and washed 5 times with about 500 ml of water to remove excess DMAc. The fibrid cake obtained was not permitted to dry out.
  • DMAc 4% LiCl
  • Each fibrid cake was mixed with the proper amount of water to produce a 1.2% solids slurry. This slurry was dispersed for 5 minutes as described in Example 2. 750ml of this fibrid slurry was added to 2250 ml of water to produce a 0.3% solids slurry. The o.3% fibrid slurry was "refined” in a Waring Commercial Blender (CB-6, Model 33BL12) for 30 seconds on high speed.
  • CB-6 Waring Commercial Blender
  • a handsheet comprising 70% of fibrids A-I/30%PPD-T floc was made using 683 ml of the 0.3% solids fibrid slurry and 1.1052 g of 0.32 cm (0.125 in.) PPD-T floc.
  • the handsheet was produced by putting the fibrids and floc and an additional 2000 ml of water into British Pulp Evaluation Apparatus (Mavis Engineering, Ltd. No. 8233) and dispersing them for 5 minutes. This stock was added to a handsheet mold and additional water added. The stock solution was agitated 10 times with an agitator plate, then vacuum drained through a fine screen with 0.15-mm openings.
  • the sample was couched between 2 plies (each side) of blotter paper to remove excess moisture.
  • the handsheet was then transferred to blotter paper by slapping the sample and 0.15 mm (100 mesh) screen onto a table top.
  • the sample was produced using the MPD-I fibrid slurry mentioned above as a control (Item J). All handsheets were judged to have sufficient strength to be produced on a fourdrinier paper machine.
  • Each handsheet was then pressed on a hot press at 6895 kPa (1000 psi), 280°C (535°F) for 1 minute.
  • the breaking strength and modulus are "normalized" to the same density and basis weight as the Item J control. As will be seen from these data, Items A-I are superior to Item J.
  • the fibrid cake was mixed with the proper amount of water to produce a 1.2% solids slurry. This slurry was dispersed for 5 minutes as described in Example 2 above. 750 ml of this fibrid slurry was added. The 0.3% fibrid slurry was refined in a Waring Commercial Blender (CB-6, Model 33BL12) for 30 seconds at high speed.
  • CB-6 Waring Commercial Blender
  • a handsheet comprising 70% of Fibrids A-I/30% PPD-T floc was made using 683 ml of the 0.3% solids fibrid slurry and 1.1052 g 0.32 cm (0.125 in.) PPD-T floc.
  • the handsheet was produced by putting the fibrids and floc and an additional 2000 ml of water into British Pulp Evaluation Apparatus (Mavis Engineering, Ltd. No. 8223) and dispersing them for 5 minutes. This stock was added to a handsheet mold, and additional water was added. The stock solution was agitated 10 times with an agitator plate, then vacuum drained through a 0.15 mm (100 mesh) screen.
  • the sample was couched between 2 plies (each side) of blotter paper to remove excess moisture.
  • the handsheet was then transferred to blotter paper by slapping the sample and 0.15 mm (100 mesh) screen onto a table top.
  • the sample dried on a handsheet hot plate drier.
  • a similar sample was produced using the MPD-I fibrid slurry mentioned above as a control (Example 7, Item J). All handsheets were judged to have sufficient strength to be produced on a fourdrinier paper machine.
  • Each handsheet was then pressed on a hot press at 6895 kPa (1000 psi), 280°C (535°F) for 1 minute.
  • the breaking strength and modulus are "normalized" to the same density and basis weight as the Item J control. As will be seen from these data, Item A is superior to Item J.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Paper (AREA)

Claims (10)

  1. Folienstruktur mit hoher Festigkeit, bestehend aus flockigen und geschmolzenen Fibriden, dadurch gekennzeichnet, daß sie aus 10 bis 90 Gew.-% Flockenmasse aus Kohlenstoff-, Aramid- oder Glasfaser besteht, die mit 90 bis 10 Gew.-% geschmolzenen Fibriden an Ort und Stelle festgehalten wird, die im wesentlichen aus den folgenden Einheiten bestehen:
    Figure imgb0026
     und
    Figure imgb0027
     worin n 4 oder 5 bedeutet; X 0,01 bis 0,50 bedeutet und Ar für ein Radikal steht, ausgewählt aus 3,4'-Oxidiphenylen, 4,4'-Oxidiphenylen, 4,4'-Sulfonyldiphenylen, 1,3-Phenylen, 1-Methyl-2,4-phenylen und aus Gemischen solcher Radikale miteinander oder aus Gemischen solcher Radikale mit, bezogen auf das Gemisch der Radikale, bis zu 50 Mol-% 1,4-Phenylenradikalen, besteht.
  2. Folienstruktur nach Anspruch 1, worin die Kohlenstoffflockenmasse eingesetzt wird.
  3. Folienstruktur nach Anspruch 1, worin die Aramidflockenmasse eingesetzt wird.
  4. Folienstruktur nach Anspruch 1, worin die Glasfaserflockenmasse eingesetzt wird.
  5. Folienstruktur nach Anspruch 1, worin X 0,03 bis 0,30 bedeutet.
  6. Folienstruktur nach Anspruch 1, worin die Fibride im wesentlichen aus den folgenden Einheiten bestehen:
    Figure imgb0028
    Figure imgb0029
     worin X 0,01 bis 0,50 bedeutet.
  7. Folienstruktur nach Anspruch 1, worin die Fibride im wesentlichen aus den folgenden Einheiten bestehen:
    Figure imgb0030
     worin X 0,01 bis 0,50 bedeutet.
  8. Folienstruktur nach Anspruch 1, worin die Fibride im wesentlichen aus den folgenden Einheiten bestehen:
    Figure imgb0031
     worin Ar ein 70/30-Gemisch aus 1,3-Phenylen- und 1,4-Phenylenradikalen ist und X 0,01 bis 0,50 bedeutet.
  9. Fibride, bestehend aus den folgenden Einheiten:
    Figure imgb0032
     worin n 4 oder 5 bedeutet; X 0,01 bis 0,50 bedeutet und Ar fur ein Radikal steht, ausgewahlt aus 3,4'-Oxidiphenylen, 4,4'-Oxidiphenylen, 4,4'-Sulfonyldiphenylen, 1,3-Phenylen und Gemischen solcher Radikale miteinander oder aus Gemischen solcher Radikale mit, bezogen auf das Gemisch der Radikale, bis zu 50 Mol-% 1,4-Phenylenradikalen.
  10. Fibride nach Anspruch 9, worin x 0,03 bis 0,30 bedeutet.
EP91103757A 1990-03-12 1991-03-12 Hochfestpapiere aus Flocken und Fasern Expired - Lifetime EP0446870B1 (de)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US49158190A 1990-03-12 1990-03-12
US07/640,592 US5126012A (en) 1990-03-12 1991-01-18 High strength papers from floc and fibrids
US491581 1991-01-18
US640592 1991-01-18

Publications (2)

Publication Number Publication Date
EP0446870A1 EP0446870A1 (de) 1991-09-18
EP0446870B1 true EP0446870B1 (de) 1994-05-18

Family

ID=27050489

Family Applications (1)

Application Number Title Priority Date Filing Date
EP91103757A Expired - Lifetime EP0446870B1 (de) 1990-03-12 1991-03-12 Hochfestpapiere aus Flocken und Fasern

Country Status (5)

Country Link
EP (1) EP0446870B1 (de)
JP (1) JP2841905B2 (de)
AU (1) AU645529B2 (de)
CA (1) CA2037232C (de)
DE (1) DE69101997T2 (de)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5232737A (en) * 1990-04-12 1993-08-03 E. I. Du Pont De Nemours And Company Method of coating a metal wire with a temperature and stress resistant polymeric coating
US5482773A (en) * 1991-07-01 1996-01-09 E. I. Du Pont De Nemours And Company Activated carbon-containing fibrids
IL102338A (en) * 1991-07-01 1996-11-14 Du Pont Polymeric fibers containing activated carbon
US5320892A (en) * 1993-02-22 1994-06-14 E. I. Du Pont De Nemours And Company Tough layered papers with improved surface adhesion
WO1998056987A1 (fr) * 1997-06-10 1998-12-17 Teijin Limited Appareil electronique pliable
US8118975B2 (en) * 2007-12-21 2012-02-21 E. I. Du Pont De Nemours And Company Papers containing fibrids derived from diamino diphenyl sulfone
US7803247B2 (en) * 2007-12-21 2010-09-28 E.I. Du Pont De Nemours And Company Papers containing floc derived from diamino diphenyl sulfone
US8114251B2 (en) * 2007-12-21 2012-02-14 E.I. Du Pont De Nemours And Company Papers containing fibrids derived from diamino diphenyl sulfone
WO2020201475A1 (en) * 2019-04-05 2020-10-08 Ahlstrom-Munksjö Oyj Flue gas filtration media

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL246230A (de) * 1958-12-09
US4183782A (en) * 1978-07-11 1980-01-15 Gaf Corporation Method of producing glass mats using novel glass fiber dispersion composition
US4515656A (en) * 1981-08-28 1985-05-07 E. I. Du Pont De Nemours And Company Low density nonwoven sheets
US4840838A (en) * 1988-09-08 1989-06-20 E. I. Du Pont De Nemours And Company High temperature filter felt
BR8905208A (pt) * 1988-10-14 1990-05-15 Du Pont Poliamida processavel a fusao;polimero;composicao processavel a fusao;fibra ou pelicula;e processo para a preparacao de poliamidas

Also Published As

Publication number Publication date
JPH0533289A (ja) 1993-02-09
DE69101997D1 (de) 1994-06-23
DE69101997T2 (de) 1994-12-01
EP0446870A1 (de) 1991-09-18
AU7274791A (en) 1991-09-12
AU645529B2 (en) 1994-01-20
JP2841905B2 (ja) 1998-12-24
CA2037232A1 (en) 1991-09-13
CA2037232C (en) 2002-01-29

Similar Documents

Publication Publication Date Title
US5126012A (en) High strength papers from floc and fibrids
US3756908A (en) Synthetic paper structures of aromatic polyamides
US20050230072A1 (en) Aramid paper blend
US5393601A (en) Non-woven solidified by means of a melt binder
JPS61160500A (ja) 高密度パラアラミド紙
CA2282256C (en) Dispersions of aramid fibres and aramid sheets
EP0446870B1 (de) Hochfestpapiere aus Flocken und Fasern
EP1354095B1 (de) Vlies aus aramidflocken
KR101538190B1 (ko) 다이아미노 다이페닐 설폰으로부터 유도되는 플록을 포함하는 종이
CA2286372C (en) Wholly aromatic polyamide fiber synthetic paper sheet
US5008306A (en) Reinforced thermoplastics sheet and its manufacturing process
US6120643A (en) Aramid and glass fiber absorbent papers
JP3340549B2 (ja) 多孔性アラミド成形物の製造方法
US5393872A (en) Sheetlike wholly aromatic polyamide shaped article and a method for producing the same
WO2007076364A2 (en) Pipd paper and components made therefrom
JP2543346B2 (ja) 合成紙
US3271237A (en) Process for the production of a fibrous polyamide laminar structure
JP2891071B2 (ja) パラ系芳香族ポリアミド紙の製造方法
JPH10292289A (ja) 薄葉多孔紙
EP0078617B1 (de) Steinwolleverbundmaterial
EP0123230A2 (de) Dämpfungsmaterial für die Schichtenbildung unter Heisspressung und für das Druckformen
JPH06313291A (ja) シート状全芳香族ポリアミド成形物及びその製造方法
JPH03133194A (ja) プリント配線板用シート
JPH0339539B2 (de)
JPH0617309A (ja) 合成高分子からなるパルプ状粒子の処理方法

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

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): BE CH DE FR GB IT LI NL SE

17P Request for examination filed

Effective date: 19920318

17Q First examination report despatched

Effective date: 19930830

RBV Designated contracting states (corrected)

Designated state(s): DE FR GB IT NL

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): DE FR GB IT NL

REF Corresponds to:

Ref document number: 69101997

Country of ref document: DE

Date of ref document: 19940623

ITF It: translation for a ep patent filed
ET Fr: translation filed
PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

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

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

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

Ref country code: NL

Payment date: 20050303

Year of fee payment: 15

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

Ref country code: FR

Payment date: 20050308

Year of fee payment: 15

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

Ref country code: DE

Payment date: 20050310

Year of fee payment: 15

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

Ref country code: IT

Payment date: 20060331

Year of fee payment: 16

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

Ref country code: GB

Payment date: 20060510

Year of fee payment: 16

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

Ref country code: NL

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

Effective date: 20061001

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: 20061003

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

Effective date: 20061001

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20061130

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

Effective date: 20070312

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

Ref country code: FR

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

Effective date: 20060331

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: 20070312

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: 20070312