US3200033A - Method of making paper and non-woven fabric from synthetic fibers - Google Patents

Method of making paper and non-woven fabric from synthetic fibers Download PDF

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Publication number
US3200033A
US3200033A US234673A US23467362A US3200033A US 3200033 A US3200033 A US 3200033A US 234673 A US234673 A US 234673A US 23467362 A US23467362 A US 23467362A US 3200033 A US3200033 A US 3200033A
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fibers
lubricant
binder
adhesive composition
lubricant material
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US234673A
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English (en)
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Grossteinbeck Rolf
Schulze Walter
Willicks Winfried
Mindermann Herfried
Tepel Gert
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Battelle Institut eV
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Battelle Institut eV
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    • 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
    • D21H13/24—Polyesters
    • 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
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/03—Non-macromolecular organic compounds
    • D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
    • D21H17/07—Nitrogen-containing compounds
    • D21H17/08—Isocyanates
    • 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
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/53—Polyethers; Polyesters
    • 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
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/60—Waxes
    • 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
    • D21H5/00—Special paper or cardboard not otherwise provided for
    • D21H5/12—Special paper or cardboard not otherwise provided for characterised by the use of special fibrous materials
    • D21H5/1272—Special paper or cardboard not otherwise provided for characterised by the use of special fibrous materials of fibres which can be physically or chemically modified during or after web formation
    • D21H5/129—Special paper or cardboard not otherwise provided for characterised by the use of special fibrous materials of fibres which can be physically or chemically modified during or after web formation by thermal treatment
    • 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
    • D21H5/00—Special paper or cardboard not otherwise provided for
    • D21H5/12—Special paper or cardboard not otherwise provided for characterised by the use of special fibrous materials
    • D21H5/20—Special paper or cardboard not otherwise provided for characterised by the use of special fibrous materials of organic non-cellulosic fibres too short for spinning, with or without cellulose fibres

Definitions

  • the invention relates to a method for the preparation of paper and non-woven fabric from synthetic fibers and more particularly to a method of bonding the fibers at their crossing points.
  • a binder is generally applied to the fibers or to an already formed sheet or mat, whereby the fibers are bonded at their crossing points. Subsequently, the binder is cured or hardened by a heat treatment of the mat.
  • the thus obtained web has the drawback that each fiber is coated with a thin cured film of the binder and that, therefore, not the original fiber but the binder film largely determines the properties of the Web.
  • a dry process has been developed where a conventional staple fiber is treated with a hydrophobic or water repellant agent and the dry felt of such fibers is sprayed with an aqueous solution or dispersion of a binder.
  • the droplets or globules of such solution or dispersion do not spread on the hydrophobic fiber surface but flow thereon to the crossing points of superposed fibers and remain there suspended.
  • the water is evaporated and the binder cured.
  • Another object of the invention is to provide a method where the binder is added only in the amount required for bonding the crossing points of the fibers.
  • a further object of the invention is to provide a method which allows of bonding the fibers at their crossing points in a very simple manner.
  • T ese and other objects of the invention are accomplished by admixing to the fibers, prior to the formation of a mat or web, a lubricant which is insoluble in water and in the binder, and a binder which at normal temperature, for instance at 20 C., is solid and as little adhesive as possible but is fluid and becomes adhesive at elevated temperature of about 80 to 129 C. In the liquid state, lubricant and binder must be incompatible under the operating conditions, that is they must be insoluble in each other.
  • the fiber mixture is then formed to a sheet which is subjected to a heat treatment in the drying part of the paper machine. Due to the admixture of lubricant and binding agent to the fibers prior to the sheet forma- ICC tion, the additives are distributed very evenly in the sheet as it is being formed.
  • the term synthetic fiber is employed herein to designate man-made fibers which have a smooth non-fibrillated surface. Also stretched, crimped or hollow fibers may be used.
  • the synthetic fibers include polyarnides such as nylon 66 (hexamethylene diamine-adipic acid condensation product), nylon 6 (polycaprolactam) and other nylon products (nylon 6/ 10; nylon 11); polyesters from dicarboxylic acids, such as terephthalic or isophalic acid and diols or polyols (Dacron, Diolen, Terylene); vinyl polymers and copolymers on Vinyl chloride or vinyl acetate basis (Vinyon); vinylidene chloride polymers and copolymers (Saran); polyacrylics (Dralon; Orlon; Acrylan; Creslan; Acrylast) and copolymers, e.g., of acrylonitrile with styrene; polyolefines such as polyethylene or polypropylene; poly
  • lubricants the compounds used to produce the coating film on the fiber which presents the gliding surface on which the molten latent adhesive composition glides along in forms of droplets to collect at the crosing points of the fibers.
  • the lubricant must be insoluble in water and is either liquid at room temperature or must have a melting point below 120 0, preferably not higher than about C. Suitable such lubricants" are rosin and rosin soaps; waxes such as paraffin wax; organic compounds conventionally used as plasticizers such as alkylenglycol esters of alphatic monocarboxylic acids. Also esters of aliphatic and aromatic dicarboxylic acids with monohydric and dihydric alcohols may be used.
  • the preferred latent adhesive is a polyurethane forming mixture of polyesters and polyisocyanates whose isocyanate groups are blocked by an alcohol or phenol and become reactive only at a temperature of about 100 C.
  • Suitable blocking agents are, for instance, phenol, butanol, aliphatic amines, etc. [see Angewandre Chemie, vol. 59A, pp. 265-266 (1947)].
  • polyesters and polyisocyanates useful for the polyurethane formation are well known and described in many publications, for instance, in the book Polyurethanes by Bernard A. Dombrow, publ. by Reinhold Publishing Corp, New York. and in the various publications on Desmodur (:polyisocyanates) and Desmophen (:polyester) by the German Bayer company; see also the article on Desmodur and Desmophen in Rompp, Chemie-Lexikon.
  • polyurethane forming polyisocyanates An illustrative list of polyurethane forming polyisocyanates is given in Brit. Patent No. 892,137, pages 11 and 12. Particularly suitable are, for instance, 2,4 tolylene diisocyanate, hexamethylene diisocyanate, triphenylmethane triisocyanate, naphthylen-l,5-diisocyanate, and others.
  • Suitable polyesters are those of aliphatic'polyols such as ethylene glycols, diethylene glycol, hexamethylene glycol, glycerol, and many others with one or more polycarboxylic acids such as adipic acid, sebacic acid, isosebacic acid, phthalic acids and others.
  • Another binder which, like the polyurethane forming mixtures, can be spun to filaments is a mixture of epichlo rohydrine resins and oil modified unsaturated polyesters.
  • resins and esters are a resin prepared from parts by weight of epichlorolydrine and 5 parts by weight of diphenylpropane, and a polyester of 184 parts by Weight of glycerol and 296 parts by weight of phthalic anhydride, modified with 35 percent of linseed oil.
  • a suitable lubricant for use with this binder is ethyleneglycol stearate.
  • the lubricant and binder may be added to the fibers tail by the following specific examples.
  • the fibers are contacted with the liquid or liquefied lubricant so as to receive a thin coating of the lubricant; subsequently, a liquid or liquefied binder is' applied in a similar manner so as to produce a thin binder film on the lubricant coating.
  • the lubricant and binder are mixed to a homogeneous mixture which is added in form of a powder or fibers to the slurry of the synthetic fibers.
  • the binder is converted to a filament and coated with the lubricant, whereupon the. coated binder filament is comminuted to staple fiber and added to the aqueous slurry of the fibers forming the mat.
  • the use of the binder in a filamentary form has the advantage to prevent or reduce the risk that binder is carried awayby the white water during formation of the sheet. Therefore, 'itis not no essary to use an excess of the binder.
  • the lubricant is molten in the drying part of the machine and covers the fibers with a thin film.
  • the binder added in powdery or filamentary form melts also and flows on the coated fiber surfaces to the crossing point of the fibers.
  • the droplets or globules formed at said crossing points are then hardened or cured by further heating and form a kind of knot.
  • the even distribution of the binder in the mat ensures a bonding of the crossing points not only at the surface of the sheet but also in the insidelayers thereof.
  • FIG. 1 shows two interc'rossing fibers coated with a lubricant film
  • FIG. 2 shows the fibers of FIG. 1 after application of the binder
  • FIG. 3 shows the fibers after the binder has contracted at the crossing point and there displaced the lubricant film
  • FIG. 4 shows the fibers as they are in a finished web after removal of the lubricant.
  • the numeral 1 represents the synthetic fiber
  • 2 is the lubricant film and 3 the hinder or adhesive.
  • a batt of fibers, whichhad been pretreatedwith the lubricant and binder is heated, the binder and lubricant melt on the fiber surface, and the binder film contracts on the lubricant film, which is also fiuid, to drops collecting at the crossing points and displaces there the lubricant.
  • FIG. 2 shows the start, and FIG. 3 the end of this melting period.
  • the lubricant solidifies.
  • the lubricant can then be'washed out in a subsequent operation or removed in some other suitable manner.
  • tained end product as shown in FIG. 4 is a web in which the fibers are joined at their crossing points while the remaining portions are free of any coating.
  • Our novel method can be carried out in conventional paper-making equipment whereby the temperature of the heated rolls in the dryer part of the machine is adjusted to cure the bonding agent.
  • the lubricant was prepared by reacting rosin of a melting point of about 100 C(with ammonia in water.
  • the Dacronfibers were beaten in saidrosin soap solution in essentially parallel arrangement, thencentrifuged and dried, whereby the fibers were coated with a film of the soap and partly joined together.
  • the fiber lumps were beaten placed in the solution of a latent adhesive
  • Example 2 In this example, nylon 66 fibers were suspended in dimethylglycolphthalate as lubricant and centrifuged, thereby obtaining fibers coated with about 4 to 6 percent by Weight of lubricant. From these fibers, a stock was prepared containing'about 0.01 to 0.1 percent by weight of solids, and powdered bonding agent was added to the stock in an amount of about 50 percent by weight, calculated on the dry fiber weight.
  • a polyurethane forming mixture of blocked toluylene diisocyanate and Desmorphen 210i) (polyester of adipic acid and diols) was'homogenized in a roll mill at elevated temperature without a solvent, cooled to 0 C., and pulverized.
  • Example 3 As lubricant, we used a paraffin wax having a melting point of 7080 C.
  • the latent binder was the mixture The obof Example 1, which had a melting'point above 1G0" C. Lubricant and binder were homogenized together in a roller mill to a mixture which had not adhesive properties at room temperature. The mixture was pulverized and added to a slurry of Perlon staple fibers in the box. The stock was then processed in the same way as set forth in the preceding examples.
  • Thelubricant-binder mixture may also be prepared by spraying the liquefied wax on the powdery binder in a spray-drying procedure.
  • t a i The lubricant-binder mixture may contain about up to 5 percent by Weight of the 1ubricaut,.the balance being binder. About 30 to 50 percent, calculated on dry fiber weight, are added to the fiber slurry.
  • Example 4 In this example, the lubricant-binder mixture was applied in the form of fibers.
  • the polyurethane formingjmixture of Example 2 was molten at about C. and extruded through a spinneret to a filament. Prior to winding up, the solidified filament was coated with a film of parafiin wax having a melting point of 75 C. After cooling, the coated filament was wound up; for use, the filament was cut to staple fibers of the desired length.
  • Said lubricant-binder fiber was added in the box to Diolen polyester staple fibers which had been beaten in a Hollander, and the stock was flowed on the wire of a Fourdrinier.
  • the sheet passed over the heated rolls of the dry end of the machine, first the lubricant on the binder fiber melted and coated the polyester fibers with a thin film.
  • the binder fiber melted and separated into droplets which flowed along the lubricant-coated fibers of the sheet to the crossing points of the fibers and hardened there.
  • Another suitable lubricant-binder fiber is, for instance, a filament of an unsaturated linseed-oil modified polyested coated with ethyleneglycol stearate or other ethyleneglycol ester which in the liquid state is immiscible with the polyester.
  • Example 5 Viscose rayon staple fibers of a length of 6 mm. were stirred in dimethylglycol phthalate. After about 1 hour, the slurry was centrifuged. The thus obtained fibers retained on their surface about 4 to 6 percent by weight of dimethylglycol phthalate.
  • Said fibers were beaten in the Hollander with staple fibers of a latent adhesive prepared from a homogeneous mixture of blocked toluylene diisocyanate and unsaturated polyester (Desmophen 950), which had also a length of 6 mm.
  • the ratio of the two types of fibers was 1:1.
  • the fiber slurry was pumped into the tub and diluted with water to a solids concentration of about 0.1 percent. Said stock was used to prepare on the screen portion of a paper machine a sheet containing the two kinds of fibers in ideal random distribution. After removal of the major portion of the water in the wet end of the machine, the sheet was passed over heated rolls. There, the remaining water was removed, the adhesive fibers melted and the formed droplets of the adhesive flowed along the rayon fibers to their crossing points where they were activated and cured and formed a hard and firm fiber bond.
  • Example 6 Polyamide staple fibers of commerce (perlon) are dipped at room temperature into a bath of dimethylglycol phthalate. The excess of the dimethylglycol phthalate is centrifuged ofi? so as to leave about 4 to 6 percent on the fibers. The thus coated staple fibers are beaten in the Hollander so long as to be completely individualized. Said stock is passed into the box of a paper machine to gether with the same amount of adhesive fibers cut to staple fiber length of about 6 mm. As adhesive fibers, the same or a similar mixture may be used as described in Example 5. Water is then added in an amount to reduce the solids concentration to about 0.01 percent. The stock is then passed from the box into the wet portion of the paper machine where the sheet is formed and the major part of the water is removed. Thereby, the adhesive fibers are distributed throughout the sheet.
  • the sheet passes over a large number of heated rolls, the first of which has a surface temperature of about 120 C.
  • the sheet passes through a heating zone of about 150 m. length in a period of about 15 minutes and is then wound up.
  • the adhesive fibers melt and form individual droplets or globules which run on the thin layer of the liquid dimethylglycol phthalate to the crossing points of the crossing points and start there hardening.
  • polyisocyanate-polyester mixtures used as adhesive, other addition polymers or compounds or mixtures capable of condensation or esterification can be used.
  • a method of preparing an unwoven web material consisting to at least 50 percent of synthetic fibers, the balance being natural fibers comprising treating the fibers with a water insoluble lubricant material forming in the liquid state a removable film on said fibers, and with a latent adhesive composition comprising essentially a polyurethane forming mixture of a polyester having at least one free hydroxyl group and a polyisocyanate whose isocyanate groups are blocked by a member of the group consisting of alcohols and phenols but are reactive at a temperature of about 0., both said material and adhesive composition having a melting point not higher than C.
  • said latent adhesive composition having a melting point higher than said lubricant material, being solid at room temperatures and being immiscible With said lubricant material in the liquid state, passing an aqueous slurry of the fibers with said lubricant material and latent adhesive composition through a paper machine to form a sheet, said lubricant material and latent adhesive composition being added in a total amount of 30 to 50 percent by weight, based on the weight of the dry fibers, subjecting the fibers in said machine to a temperature sufiicient to melt and activate said latent adhesive composition, said molten composition collecting as droplets on the film of the lubricant material formed on the fibers at the crossing points of the fibers, and finally curing said composition to a solid binder bonding the fibers at said crossing points.
  • An unwoven web consisting at least of 50 percent of synthetic fibers, the balance being natural fibers, the fibers being joined at their crossing points only by a cured polyurethane and being otherwise substantially disconnected and free of coating.
US234673A 1961-11-02 1962-11-01 Method of making paper and non-woven fabric from synthetic fibers Expired - Lifetime US3200033A (en)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
DEG33481A DE1159257B (de) 1961-11-02 1961-11-02 Verfahren zur Herstellung von Papier bzw. flaechenartigen Gebilden aus Synthesefasern
DEG34052A DE1164818B (de) 1961-11-02 1962-01-18 Verfahren zur Herstellung von Papier bzw. flaechenartigen Gebilden aus Synthesefasern
DEG34836A DE1176993B (de) 1961-11-02 1962-04-27 Verfahren zur Herstellung von nichtgewebten Stoffen aus synthetischen Fasern
DEG35413A DE1176994B (de) 1961-11-02 1962-07-07 Verfahren zur Herstellung von nichtgewebten Stoffen aus synthetischen Fasern
DEB73276A DE1229376B (de) 1961-11-02 1963-08-27 Verfahren zur Herstellung von synthetischen Papieren und nichtgewebten Stoffen aus synthetischen Fasern

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US234673A Expired - Lifetime US3200033A (en) 1961-11-02 1962-11-01 Method of making paper and non-woven fabric from synthetic fibers
US391281A Expired - Lifetime US3227608A (en) 1961-11-02 1964-08-21 Manufacture of synthetic paper sheet

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US391281A Expired - Lifetime US3227608A (en) 1961-11-02 1964-08-21 Manufacture of synthetic paper sheet

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US (2) US3200033A (zh)
BE (2) BE652341A (zh)
CH (1) CH435965A (zh)
DE (5) DE1159257B (zh)
DK (1) DK115449B (zh)
GB (2) GB1009120A (zh)
LU (2) LU42620A1 (zh)
NL (3) NL146235B (zh)

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3401078A (en) * 1962-10-19 1968-09-10 Battelle Institut E V Paper and process for making same of synthetic fibers bonded at their intercrossing points by a thermoplastic polyamide resin
FR2430652A1 (fr) * 1978-07-04 1980-02-01 Comp Generale Electricite Papier synthetique pour l'isolement electrique a bain liquide, et son procede de fabrication
US4210515A (en) * 1975-02-10 1980-07-01 Basf Wyandotte Corporation Thermoplastic fibers as separator or diaphragm in electrochemical cells
US4392861A (en) * 1980-10-14 1983-07-12 Johnson & Johnson Baby Products Company Two-ply fibrous facing material
US4410411A (en) * 1973-01-17 1983-10-18 Diamond Shamrock Corporation Dimensionally stable asbestos diaphragms
US4425126A (en) 1979-12-28 1984-01-10 Johnson & Johnson Baby Products Company Fibrous material and method of making the same using thermoplastic synthetic wood pulp fibers
US4489025A (en) * 1973-01-17 1984-12-18 Diamond Shamrock Chemicals Company Preparation of dimensionally stable asbestos diaphragms
US4701250A (en) * 1973-01-17 1987-10-20 Eltech Systems Corporation Dimensionally stable asbestos diaphragm coated foraminous cathode
US20090020247A1 (en) * 2002-09-13 2009-01-22 Agne Swerin Paper with improved stiffness and bulk and method for making same
US20100051220A1 (en) * 2008-08-28 2010-03-04 International Paper Company Expandable microspheres and methods of making and using the same
US8317976B2 (en) 2000-01-26 2012-11-27 International Paper Company Cut resistant paper and paper articles and method for making same
US8377526B2 (en) 2005-03-11 2013-02-19 International Paper Company Compositions containing expandable microspheres and an ionic compound, as well as methods of making and using the same

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3501431A (en) * 1966-11-25 1970-03-17 Us Air Force Sizing system for high modulus fibers and method and apparatus for applying same
GB8526158D0 (en) * 1985-10-23 1985-11-27 Albright & Wilson Paper sizing compositions

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB572962A (en) * 1942-05-25 1945-10-31 Sylvania Ind Corp Paper products and methods of making the same
US2680995A (en) * 1950-12-01 1954-06-15 Stimson Lumber Company Method of making hardboard
US2962762A (en) * 1957-02-13 1960-12-06 Hoechst Ag Manufacture of non-woven two dimensional structures from fibers
US3049466A (en) * 1957-04-23 1962-08-14 Reeves Bros Inc Method of bonding fibrous structures made from fibers or filaments of polyolefine polymers
US3053609A (en) * 1958-11-17 1962-09-11 Du Pont Textile
US3096231A (en) * 1960-04-18 1963-07-02 Eastman Kodak Co Method of manufacturing paper from partially esterified cellulose fibers

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB572962A (en) * 1942-05-25 1945-10-31 Sylvania Ind Corp Paper products and methods of making the same
US2680995A (en) * 1950-12-01 1954-06-15 Stimson Lumber Company Method of making hardboard
US2962762A (en) * 1957-02-13 1960-12-06 Hoechst Ag Manufacture of non-woven two dimensional structures from fibers
US3049466A (en) * 1957-04-23 1962-08-14 Reeves Bros Inc Method of bonding fibrous structures made from fibers or filaments of polyolefine polymers
US3053609A (en) * 1958-11-17 1962-09-11 Du Pont Textile
US3096231A (en) * 1960-04-18 1963-07-02 Eastman Kodak Co Method of manufacturing paper from partially esterified cellulose fibers

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3401078A (en) * 1962-10-19 1968-09-10 Battelle Institut E V Paper and process for making same of synthetic fibers bonded at their intercrossing points by a thermoplastic polyamide resin
US4410411A (en) * 1973-01-17 1983-10-18 Diamond Shamrock Corporation Dimensionally stable asbestos diaphragms
US4489025A (en) * 1973-01-17 1984-12-18 Diamond Shamrock Chemicals Company Preparation of dimensionally stable asbestos diaphragms
US4701250A (en) * 1973-01-17 1987-10-20 Eltech Systems Corporation Dimensionally stable asbestos diaphragm coated foraminous cathode
US4210515A (en) * 1975-02-10 1980-07-01 Basf Wyandotte Corporation Thermoplastic fibers as separator or diaphragm in electrochemical cells
FR2430652A1 (fr) * 1978-07-04 1980-02-01 Comp Generale Electricite Papier synthetique pour l'isolement electrique a bain liquide, et son procede de fabrication
US4425126A (en) 1979-12-28 1984-01-10 Johnson & Johnson Baby Products Company Fibrous material and method of making the same using thermoplastic synthetic wood pulp fibers
US4392861A (en) * 1980-10-14 1983-07-12 Johnson & Johnson Baby Products Company Two-ply fibrous facing material
US8317976B2 (en) 2000-01-26 2012-11-27 International Paper Company Cut resistant paper and paper articles and method for making same
US20090020247A1 (en) * 2002-09-13 2009-01-22 Agne Swerin Paper with improved stiffness and bulk and method for making same
US8460512B2 (en) 2002-09-13 2013-06-11 International Paper Company Paper with improved stiffness and bulk and method for making same
US8790494B2 (en) 2002-09-13 2014-07-29 International Paper Company Paper with improved stiffness and bulk and method for making same
US8377526B2 (en) 2005-03-11 2013-02-19 International Paper Company Compositions containing expandable microspheres and an ionic compound, as well as methods of making and using the same
US20100051220A1 (en) * 2008-08-28 2010-03-04 International Paper Company Expandable microspheres and methods of making and using the same
US8382945B2 (en) 2008-08-28 2013-02-26 International Paper Company Expandable microspheres and methods of making and using the same
US8679294B2 (en) 2008-08-28 2014-03-25 International Paper Company Expandable microspheres and methods of making and using the same

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Publication number Publication date
DE1159257B (de) 1963-12-12
CH435965A (de) 1967-05-15
DE1176993B (de) 1964-08-27
US3227608A (en) 1966-01-04
GB1009120A (en) 1965-11-03
DK115449B (da) 1969-10-06
NL146235B (nl) 1975-06-16
BE624231A (zh)
DE1176994B (de) 1964-08-27
DE1229376B (de) 1966-11-24
GB1044925A (en) 1966-10-05
NL285026A (zh)
DE1164818B (de) 1964-03-05
NL135829C (zh)
LU42620A1 (zh) 1962-12-31
LU46832A1 (zh) 1964-10-26
BE652341A (zh) 1964-12-16
NL6408415A (zh) 1965-03-01

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