EP1774095B1 - Pate a base de fibres acryliques et para-aramides et procedes de fabrication de cette derniere - Google Patents

Pate a base de fibres acryliques et para-aramides et procedes de fabrication de cette derniere Download PDF

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Publication number
EP1774095B1
EP1774095B1 EP05766040A EP05766040A EP1774095B1 EP 1774095 B1 EP1774095 B1 EP 1774095B1 EP 05766040 A EP05766040 A EP 05766040A EP 05766040 A EP05766040 A EP 05766040A EP 1774095 B1 EP1774095 B1 EP 1774095B1
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Prior art keywords
para
aramid
pulp
acrylic
fiber
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EP05766040A
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German (de)
English (en)
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EP1774095A1 (fr
Inventor
Jill A. Conley
Edmund A. Merriman
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EIDP Inc
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EI Du Pont de Nemours and Co
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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
    • 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
    • D21H5/205—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 acrylic 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
    • D21H13/12—Organic non-cellulose fibres from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H13/18—Polymers of unsaturated acids or derivatives thereof, e.g. polyacrylonitriles
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • Y10T428/249924—Noninterengaged fiber-containing paper-free web or sheet which is not of specified porosity

Definitions

  • This invention relates to acrylic and para-aramid pulp for use as reinforcement material in products, such as seals and friction materials.
  • the invention further relates to processes for making such pulp.
  • Fibrous and non fibrous reinforcement materials have been used for many years in friction products, sealing products and other plastic or rubber products. Such reinforcement materials typically must exhibit high wear and heat resistance.
  • Asbestos fibers have historically been used as reinforcement materials, but due to their health risks, replacements have been made or proposed. However, many of these replacements do not perform as well as asbestos in one way or another.
  • the publication also discloses the use of pulp from KEVLAR ® brand para-aramid fiber alone, or with KEVLAR ® brand para-aramid short staple, in friction materials to replace a fraction of the asbestos volume, with the remainder of the asbestos volume being replaced by fillers or other fibers.
  • U.S. Patent 5,811,042 discloses a composite friction or gasketing material made of a thermoset or thermoplastic matrix resin, fiber reinforcing material, and substantially fibril free aramid particles.
  • Poly (p-phenylene terephthalamide) and poly(m-phenylene isophthalamide) are preferred fiber reinforcing materials, and the fibers can be in the form of floc or pulp.
  • U.S. Patent Application 2003/0022961 discloses friction materials made from a friction modifier, a binder and a fibrous reinforcement made of a mixture of (a) a dry aramid pulp and (b) wet aramid pulp, wood pulp or acrylic pulp.
  • Dry aramid pulp is defined as an aramid pulp obtained by "the dry fibrillation method”.
  • the dry fibrillation method is dry milling the aramid fibers between a rotary cutter and a screen to prepare the pulp.
  • Wet aramid pulp is defined as an aramid pulp obtained by "the wet fibrillation method”.
  • the wet fibrillation method is milling short aramid fibers in water between two rotary discs to form fibrillated fibers and then dehydrating the fibrillated fibers, i.e., the pulp.
  • Kusaka et al further disclose a method of mix-fibrillating fibers by first mixing plural types of organic fibers that fibrillate at a definite ratio, and then fibrillating the mixture to produce a pulp.
  • JP 10 008036 A discloses the use of a composition of fiber base material, thermosetting resin binding material and a filler as a principle component, wherein the fiber base material contains an aramid pulp, acryl pulp, cellulose fiber, sepiolid fiber and glass fiber, for the preparation of a friction material with reduced generation of noise.
  • the invention relates to a first embodiment of a process for making an acrylic and para-aramid pulp for use as reinforcement material, comprising:
  • the invention is further related to a second embodiment of a process for making an acrylic and para-aramid pulp for use as reinforcement material, comprising:
  • the invention is further directed to an acrylic and para-aramid pulp for use as reinforcement material, comprising:
  • the invention is further directed to a friction material, comprising a friction modifier; optionally at least one filler; a binder; and a fibrous reinforcement material comprising the pulp of the present invention.
  • the invention is directed to a sealing material, comprising a binder; optionally at least one filler; and a fibrous reinforcement material comprising the pulp of the present invention.
  • Fiber means a relatively flexible, unit of matter having a high ratio of length to width across its cross-sectional area perpendicular to its length.
  • the term “fiber” is used interchangeably with the term “filament” or "end”.
  • the cross section of the filaments described herein can be any shape, but are typically circular or bean shaped. Fiber spun onto a bobbin in a package is referred to as continuous fiber. Fiber can be cut into short lengths called staple fiber. Fiber can be cut into even smaller lengths called floc.
  • Yarns, multifilament yarns or tows comprise a plurality of fibers. Yarn can be intertwined and/or twisted.
  • Fibril means a small fiber having a diameter as small as a fraction of a micrometer to a few micrometers and having a length of from about 10 to 100 micrometers. Fibrils generally extend from the main trunk of a larger fiber having a diameter of from 4 to 50 micrometers. Fibrils act as hooks or fasteners to ensnare and capture adjacent material. Some fibers fibrillate, but others do not or do not effectively fibrillate and for purposes of this definition such fibers do not fibrillate. Poly(para-phenylene terephthalamide) fiber fibrillates readily upon abrasion, creating fibrils. Acrylic fibers of this invention also fibrillate.
  • Fibrillated fibrous structures means particles of material having a stalk and fibrils extending therefrom wherein the stalk is generally columnar and about 10 to 50 micrometers in diameter and the fibrils are hair-like members only a fraction of a micron or a few microns in diameter attached to the stalk and about 10 to 100 micrometers long.
  • Floc means short lengths of fiber, shorter than staple fiber.
  • the length of floc is about 0.5 to about 15 mm and a diameter of 4 to 50 micrometers, preferably having a length of 1 to 12 mm and a diameter of 8 to 40 micrometers. Floc that is less than about 1 mm does not add significantly to the strength of the material in which it is used. Floc or fiber that is more than about 15 mm often does not function well because the individual fibers may become entangled and cannot be adequately and uniformly distributed throughout the material or scurry.
  • Aramid floc is made by cutting aramid fibers into short lengths without significant or any fibrillation, such as those prepared by processes described in U.S. Patent Nos. 3,063,966 , 3,133,138 , 3,767,756 , and 3,869,430 .
  • Lenght - weighted average ⁇ Each Individual pulp length 2 ⁇ Each Individual pulp length
  • Maximum dimension of an object means the straight distance between the two most distal points from one another in the object
  • “Staple fiber” can be made by cutting filaments into lengths of no more than 15 cm, preferably 3 to 15 cm; and most preferably 3 to 8 cm.
  • the staple fiber can be straight (i.e., non crimped) or crimped to have a saw tooth shaped crimp along its length, with any crimp (or repeating bend) frequency.
  • the fibers can be present in uncoated, or coated, or otherwise pretreated (for example, pre-stretched or heat-treated) form.
  • the invention is directed to processes for making an acrylic and para-aramid pulp for use as reinforcement material.
  • the invention is also directed to acrylic and para-aramid pulp, that can be made by the processes of the invention, for use as reinforcement material.
  • the invention is further directed to products, such as sealing materials and friction materials, incorporating the pulp of this invention, and processes for making them.
  • the process for making an acrylic and para-aramid pulp comprises the following steps. First, pulp ingredients are combined, added or contacted together. Second, the combined pulp ingredients are mixed to a substantially uniform slurry. Third, the slurry is simultaneously refined or co-refined. Fourth, water is removed from the refined slurry.
  • the pulp ingredients are preferably added together in a container.
  • the pulp ingredients include (1) acrylic fiber, (2) para-aramid fiber, (3) optionally substantially or completely fibril-free, granular, para-aramid particles, (4) optionally other minor additives, and (5) water.
  • the acrylic fiber is added to a concentration of 10 to 90 wt % of the total solids in the ingredients, preferably 25 to 60 wt % of the total solids in the ingredients, and most preferably 25 to 55 wt % of the total solids in the ingredients.
  • the acrylic fiber preferably has an average length of no more than 10 cm, more preferably 0.5 to 5 cm, and most preferably 0.6 to 2 cm. Prior to combining the pulp ingredients together, any acrylic fibers in the form of continuous filaments can be cut into shorter fibers, such as staple fibers or floc.
  • the acrylic fiber useful in this invention includes acrylonitrile units which are at least 85 wt % of the total acrylic fiber.
  • An acrylonitrile unit is - (CH2-CHCN)-.
  • the acrylic fiber can be made from acrylic polymers made up of 85 % by weight or more of acrylonitrile with 15 % by weight or less of an ethylenic monomer copolymerizable with acrylonitrile and mixtures of two or more of these acrylic polymers.
  • Examples of the ethylenic monomer copolymerizable with acylonitrile include acylic acid, methacrylic acid and esters thereof (methyl acrylate, ethyl acrylate, methyl methacylate, ethyl methacrylate, etc.), vinyl acetate, vinyl chloride, vinylidene chloride, acrylamide, methacylamide, methacrylonitrile, allylsulfonic acid, methanesulfonic acid and styrenesulfonic acid.
  • the para-aramid fiber is added to a concentration of 10 to 90 wt % of the total solids in the ingredients, preferably 40 to 75 wt % of the total solids in the ingredients, and most preferably 40 to 55 wt % of the total solids in the ingredients.
  • the para-aramid fiber preferably has a linear density of no more than 10 dtex, more preferably 0.5 to 10 dtex, and most preferably, 0.8 to 2.5 dtex.
  • the para-aramid fiber also preferably has an average length along its longitudinal axis of no more than 10 cm, more preferably an average length of 0.65 to 2.5 cm, and most preferably an average length of 0.65 to 1.25 cm.
  • the pulp ingredients further include substantially or completely fibril-free, granular, para-aramid particles. If these particles are added, they are added to a concentration of no more than 50 wt % of the total solids in the ingredients, preferably 20 to 50 wt % of the total solids in the ingredients, and most preferably 25 to 35 wt % of the total solids in the ingredients. Being made of para-aramid, they contribute superior wear resistance and dispersability to the pulp being produced. Because the particles are substantially fibril-free, they also serve as a compounding agent to assist in dispersing the other ingredients in the mixture and slurry. Particles that perform this function are often known as processing agents or aids.
  • the substantially or completely fibril-free, granular, para-aramid ,particles have an average maximum dimension of 50 to 2000 micrometers (0.05 to 2 mm), preferably 50 to 1500 micrometers, and most preferably 75 to 1000 micrometers. Particles below about 50 micrometers, however, lose effectiveness in friction and sealing applications. Particles above about 2000 micrometers do not adequately stay dispersed in the water with the other ingredients when mixed.
  • Figure 5 is an image of a photomicrograph of para-aramid particles capable of being used as an ingredient to the process of the present invention.
  • Polymers suitable for use in making the aramid fiber and aramid particles of this invention are synthetic aromatic polyamides.
  • the polymers must be of fiber-forming molecular weight in order to be shaped into fibers.
  • the polymers can include polyamide homopolymers, copolymers, and mixtures thereof which are predominantly aromatic, wherein at least 85% of the amide (-CONH-) linkages are attached directly to two aromatic rings.
  • the rings can be unsubstituted or substituted.
  • the polymers are para-aramid when the two rings are para oriented with respect to each other along the molecular chain.
  • copolymers have no more than 10 percent of other diamines substituted for a primary diamine used in forming the polymer or no more than 10 percent of other diacid chlorides substituted for a primary diacid chloride used in forming the polymer.
  • Additives can be used with the aramid; and it has been found that up to as much as 13 percent by weight of other polymeric material can be blended or bonded with the aramid.
  • the preferred para-aramids are poly(para-phenylene terephthalamide)(PPD-T) and its copolymers.
  • additives can optionally be added as long as they stay suspended in solution in the mixing step and do not significantly change the effect of the refining step on the mandatory solid ingredients listed above.
  • Suitable additives include pigments, dyes, anti-oxidants, flame-retardant compounds, and other processing and dispersing aids.
  • the pulp ingredients do not include asbestos. In other words, the resulting pulp is asbestos free or without asbestos.
  • Water is added to a concentration of 95 to 99 wt % of the total ingredients, and preferably 97 to 99 wt % of the total ingredients. Further, the water can be added first. Then other ingredients can be added at a rate to optimize dispersion in the water while simultaneously mixing the combined ingredients.
  • the ingredients are mixed to a substantially uniform slurry.
  • substantially uniform is meant that random samples of the slurry contain the same wt % of the concentration of each of the starting ingredients as in the total ingredients in the combination step plus or minus 10 wt %, preferably 5 wt % and most preferably 2 wt %.
  • a substantially uniform mixture in the mixing step means each random sample of the slurry has (1) a concentration of the acrylic fiber of 50 wt % plus or minus 10 wt %, preferably 5 wt % and most preferably 2 wt % and (2) a concentration of para-aramid fiber of 50 wt % plus or minus 10 wt %, preferably 5 wt % and most preferably 2 wt %.
  • the mixing can be accomplished in any vessel containing rotating blades or some other agitator. The mixing can occur after the ingredients are added or while the ingredients are being added or combined.
  • the pulp ingredients are simultaneously co-refined, converted or modified as follows.
  • the acrylic fiber and the para-aramid fiber are fibrillated, cut and masticated to irregularly shaped fibrous structures having stalks and fibrils. If para-aramid particles are added with the other ingredients, at least some of the para-aramid particles are masticated into smaller, rounder, substantially fibril-free, particles. All solids are dispersed such that the refined slurry is substantially uniform. "substantially uniform" is as defined above.
  • the refining step preferably comprises passing the mixed slurry through one or more disc refiner, or recycling the slurry back through a single refiner.
  • disc refiner is meant a refiner containing one or more pair of discs that rotate with respect to each other thereby refining ingredients by the shear action between the discs.
  • the slurry being refined is pumped between closely spaced circular rotor and stator discs rotatable with respect to one another. Each disc has a surface, facing the other disc, with at least partially radially extending surface grooves.
  • a preferred disc refiner that can be used is disclosed in U.S. Patent 4,472,241 . If necessary for uniform dispersion and adequate refining, the mixed slurry can be passed through the disc refiner more than once or through a series of at least two disc refiners.
  • any one type of non-pulp ingredient for example, para-aramid fiber
  • non-pulp ingredients for example, aramid material pieces and optionally para-aramid particles
  • This co-refining of non-pulp ingredients forms a pulp that is superior to a pulp blend generated by merely mixing two pulps together. Adding two pulps and then merely mixing them together does not form the substantially uniform, intimately connected, fibrous components of the pulp generated by co-refining of non-pulp ingredients into pulp in accordance with the present invention.
  • water is removed from the refined slurry to no more than 60 total wt % water, preferably 4 to 60 total wt % water, most preferably, 5 to 58 total wt % water.
  • the water can be removed by collecting the pulp on a dewatering device such as a horizontal filter, and if desired, additional water can be removed by applying pressure or squeezing the pulp filter cake.
  • the dewatered pulp can optionally then be dried to a desired moisture content, and/or can be packaged or wound up on rolls.
  • FIG. 1 there is a block diagram of an embodiment of a wet process for making "wet” pulp in accordance with the present invention.
  • Pulp ingredients 1 are added to container 2.
  • Container 2 is provided with an internal mixer, similar to a mixer in a washing machine.
  • the mixer disperses the ingredients into the water creating the substantially uniform slurry.
  • the mixed slurry is transferred to a first refiner 3 which refines the slurry.
  • the refined slurry can be transferred to a second refiner 4, and optionally then to a third refiner 5.
  • Three refiners are illustrated but any number of refiners can be used depending on the degree of uniformity and refining desired.
  • the refined slurry is optionally transferred to a filter or sorter 6 that allows slurry with dispersed solids below a chosen mesh or screen size to pass and recirculates dispersed solids larger than a chosen mesh or screen size back to one or more of the refiners such as through line 7 or to a refiner 8 dedicated to refine this recirculated slurry from which refined slurry is again passed to the filter or sorter 6.
  • a filter or sorter 6 that allows slurry with dispersed solids below a chosen mesh or screen size to pass and recirculates dispersed solids larger than a chosen mesh or screen size back to one or more of the refiners such as through line 7 or to a refiner 8 dedicated to refine this recirculated slurry from which refined slurry is again passed to the filter or sorter 6.
  • Suitably refined slurry passes from the filter or sorter 6 to a horizontal water vacuum filter 9 which removes water such that the pulp has a concentration of water of no more than 75 w
  • Slurry can be transferred from point to point by any conventional method and apparatus such as with the assistance of one or more pump 10. Then the pulp is conveyed to a dryer 11 that removes more water until the pulp has a concentration of water of no more than 60 wt % of the total ingredients. Then the refined pulp is packaged in a baler 12.
  • FIG. 2 there is a block diagram of an embodiment of a dry process for making "dry” pulp in accordance with the present invention.
  • This dry process is the same as the wet process except after the horizontal water vacuum filter 9.
  • the pulp goes through a press 13 which removes more water until the pulp has a concentration of water of no more than 20 wt % of the total ingredients.
  • the pulp goes through a fluffer 14 to fluff the pulp and then a rotor 15 to remove more water.
  • the pulp is passed through a dryer 11 and packaged in a baler 12.
  • the process for making the acrylic fiber and para-aramid pulp is the same as the first embodiment of the process described above with the following differences.
  • either the acrylic fiber or the para-aramid fiber, or both the acrylic fiber and the para-aramid fiber may need to be shortened. This is done by combining water with the fiber ingredient. Then the water and fiber are mixed to form a first suspension and processed through a first disc refiner to shorten the fiber. The disc refiner cuts the fiber to an average length of no more than 10 cm. The disc refiner will also partially fibrillate and partially masticate the fiber. The other fiber, that was not previously added, can be shortened this way too forming a second processed suspension. Then the other fiber (or the second suspension, if processed in water) is combined with the first suspension.
  • More water is added before or after, or when, other ingredients are added, if necessary, to increase the water concentration to 95 - 99 wt % of the total ingredients. After all ingredients are combined, they can be mixed, if necessary, to achieve a substantially uniform slurry.
  • This refining step includes fibrillating, cutting and masticating solids in the suspension such that all or substantially all of the acrylic and para-aramid fiber is converted to irregularly shaped fibrillated fibrous structures.
  • This refining step also disperses all solids such that the refined slurry is substantially uniform.
  • water is removed as in the first embodiment of the process. Both processes produce the same or substantially the same acrylic and para-aramid pulp.
  • the resulting product produced by the process of this invention is an acrylic and para-aramid pulp for use as reinforcement material in products.
  • the pulp comprises (a) irregularly shaped, acrylic fibrous structures, (b) irregularly shaped, para-aramid fibrous structures, (c) optionally substantially fibril-free, granular, para-aramid particles, (d) optionally other minor additives, and (e) water.
  • the concentration of the separate ingredient components in the pulp correspond, of course, to the concentrations described beforehand of the corresponding ingredients used in making the pulp.
  • the irregularly shaped, acrylic and para-aramid fibrillated fibrous structures have stalks and fibrils.
  • the acrylic fibrils and/or stalks are substantially entangled with the para-aramid fibrils and/or stalks.
  • the fibrils are important and act as hooks or fasteners or tentacles which adhere to and hold adjacent particles in the pulp and final product thereby providing integrity to the final product.
  • the acrylic and para-aramid fibrillated fibrous structures preferably have an average maximum dimension of no more than 5 mm, more preferably 0.1 to 4 mm, and most preferably 0.1 to 3 mm.
  • the acrylic and para-aramid fibrillated fibrous structures preferably have a length-weighted average of no more than 1.3 mm, more preferably 0.7 to 1.2 mm, and most preferably 0.75 to 1.1 mm.
  • the acrylic and para-aramid fibrous structures also additionally contact and are wrapped partially around at least some of these rounder, substantially fibril-free, para-aramid particles.
  • These para-aramid particle also preferably have a dimension of at least 50 micrometers, more preferably, 50 to 100 micrometers, and most preferably 50 to 75 micrometers. Fibrils on and along the acrylic and para-aramid fibrous structures can contact and form a partial cocoon around the rounder, substantially fibril-free, para-aramid particles
  • the acrylic and para-aramid pulp is without substantial aggregates or conglomerates of the same material. Further, the pulp has a Canadian Standard Freeness (CSF) as measured per TAPPI test T 227 om-92, which is a measure of its drainage characteristics, of 100 to 700 ml, and preferably 250 to 450 ml.
  • CSF Canadian Standard Freeness
  • Surface area of pulp is a measure of the degree of fibrillation and influences the porosity of the product made from the pulp.
  • the surface area of pulp of this invention is 7 to 11 square meters per gram.
  • Figure 4 is an image of a photomicrograph of acrylic and para-aramid pulp made according to the process of the present invention.
  • aramid particles and fibrous structures dispersed substantially homogeneously throughout the reinforcement material, and the friction and sealing materials, provide, by virtue of the high temperature characteristics of the para-aramid polymers and the fibrillation propensity of the para-aramid fibers, many sites of reinforcement and increased wear resistance.
  • the blending of the acrylic and para-aramid materials is so intimate that in a friction or sealing material there is always some para-aramid fibrous structures close to the acrylic structures, so the stresses and abrasion of service are always shared.
  • the invention is further directed to sealing material and processes for making the sealing materials.
  • Sealing materials are used in or as a barrier to prevent the discharge of fluids and/or gases and used to prevent the entrance of contaminants where two items are joined together.
  • An illustrative use for sealing material is in gaskets.
  • the sealing material comprises a binder; optionally at least one filler; and a fibrous reinforcement material comprising the acrylic and para-aramid pulp of this invention.
  • Suitable binders include nitrile rubber, butadiene rubber, neoprene, styrene-butadiene rubber, nitrile-butadiene rubber, and mixtures thereof.
  • the binder can be added with all other starting materials.
  • the binder is typically added in the first step of the gasket production process, in which the dry ingredients are mixed together.
  • Other ingredients optionally include uncured rubber particles and a rubber solvent, or a solution of rubber in solvent, to cause the binder to coat surfaces of the fillers and pulp.
  • Suitable fillers include barium sulfate, clays, talc, and mixtures thereof.
  • Suitable processes for making sealing materials are, for example, a beater-add process or wet process where the gasket is made from a slurry of materials, or by what is called a calendering or dry process where the ingredients are combined in an elastomeric or rubber solution.
  • the pulp of the present invention can be used as a reinforcement material in friction materials.
  • friction materials is meant materials used for their frictional characteristics such as coefficient of friction to stop or transfer energy of motion, stability at high temperatures, wear resistance, noise and vibration damping properties, etc.
  • Illustrative uses for friction materials include brake pads, brake blocks, dry clutch facings, clutch face segments, brake pad backing/insulating layers, automatic transmission papers, and friction papers.
  • the invention is further directed to friction material and processes for making the friction material.
  • the friction material comprises a friction modifier; optionally at least one filler; a binder; and a fibrous reinforcement material comprising the acrylic and para-aramid pulp of this invention.
  • Suitable friction modifiers are metal powders such as iron, copper and zinc; abrasives such as oxides of magnesium and aluminum; lubricants, such as synthetic and natural graphites, and sulfides of molybdenum and zirconium; and organic friction modifiers such as synthetic rubbers and cashew nut shell resin particles.
  • Suitable binders are thermosetting resins such as phenolic resins (i.e., straight (100%) phenolic resin and various phenolic resins modified with rubber or epoxy), melamine resins, epoxy resins and polyimide resins, and mixtures thereof.
  • Suitable fillers include barite, calcium carbonate, wollastonite, talc, various clays, and mixtures thereof.
  • the actual steps for making the friction material can vary, depending on the type of friction material desired.
  • methods for making molded friction parts generally involve combining the desired ingredients in a mold, curing the part, and shaping, heat treating and grinding the part if desired.
  • Automotive transmission and friction papers generally can be made by combining the desired ingredients in a slurry and making a paper on a paper machine using conventional paper making processes.
  • Canadian Standard Freeness is a well-known measure of the facility for water to drain from a slurry or dispersion of particles. Freeness is determined by TAPPI test T227. Data obtained from conduct of that test are expressed as Canadian Freeness Numbers, which represent the milliliters of water which drain from an aqueous slurry under specified conditions. A large number indicates a high freeness and a high tendency for water to drain. A low number indicates a tendency for the dispersion to drain slowly. The freeness is inversely related to the degree of fibrillation of the pulp, since greater numbers of fibrils reduce the rate at which water drains through a forming paper mat.
  • Length-weighted average is measured using a "FiberExpert” tabletop analyzer (also now known as “PulpExpertFS", available from Metso Automation of Helsinki, Finland).
  • This analyzer takes photographic images of the pulp with a digital CCD camera as the pulp slurry flows through the analyzer and then an integrated computer analyzes the fibers in these images and calculates their length-weighted average.
  • Denier is measured according to ASTM D 1577 and is the linear density of a fiber as expressed as weight in grams of 9000 meters of fiber. The denier is measured on a Vibroscope from Textechno of Kunststoff, Germany. Denier times (10/9) is equal to decitex (dtex).
  • the pulp of this invention was produced from a feedstock of para-aramid fiber and acrylic staple.
  • Acrylic staple having a cut length of 5 cm (2 inches) and having a filament linear density of 3 dpf (3.3 dtex per filament) was obtained from Solutia, Inc., with offices in St. Louis, MO.
  • Acrylic staple and water together were fed directly into a Sprout-Waldron 12" Single Disc Refiner using a 10 mil plate gap setting and pre-pulped to reach an acceptable processing length in the range of 13mm.
  • the pre-pulped acrylic fiber and the cut para-aramid fiber plus water were then combined into a highly agitated mixing tank at a solids concentration of 50 wt % para-aramid fiber and 50 wt% acrylic staple and mixed to form a uniform, pumpable slurry of about 2-3 wt % of the total ingredients concentration
  • the slurry was then recirculated and co-refined through a Sprout-Waldron 12" Single Disc Refiner.
  • the fibrous structures had an average maximum dimension of no more than 5 mm and a length-weighted average of no more than 1.3 mm, as measured by FiberExpert ® .
  • This example illustrates another method by which a co-refined pulp can be made from a feedstock of para-aramid fiber and acrylic fiber.
  • Acrylic staple having a cut length of 5 cm (2 inches) and having a filament linear density of 3 dpf (3.3 dtex per filament) available from Solutia, Inc., is cut with a guillotine cutter two to three times at right angles in order to produce a random-length fiber with most fibers shorter than 3 ⁇ 4 inch (1.91 cm) and averaging about'/z inch (1.27 cm) long.
  • KEVLAR ® brand para-aramid fiber which initially is not on bobbins and is of multiple long lengths, is cut by a guillotine cutter two to three times at right angles in order to produce a random-length fiber with most fibers shorter than 3 ⁇ 4 inch (1.91 cm) and averaging about 1 ⁇ 2 inch (1.27 cm) long.
  • the two ingredients prepared as described above plus water are then combined into a highly agitated mixing tank called a hydrapulper at a solids concentration of 50 wt % para-aramid fiber and 50 wt % acrylic fiber and mixed to form a substantially uniform, pumpable slurry having a total solids concentration of about 2-3 wt % of the total ingredients.
  • the slurry is pumped through a series of three refiners, as described in U.S. Patent 4,472,241 . The refiners simultaneously:
  • This refined slurry is then dewatered using a horizontal filter and dried in an oven to a desired moisture content of 50 total wt % for wet pulp.
  • the wet pulp is then packaged into bales by a baler.
  • all of the ingredients in the pulp have a length-weighted average of no more than 1.3 mm.
  • Example 2 illustrates further process steps and another embodiment of the pulp of this invention.
  • the procedure of Example 2 is followed. However, after the pulp is dewatered on the horizontal filter, the pulp is pressed in a mechanical press to further remove water; and the pulp is then fluffed using a Fluffer (available from Bepex Corporation with offices at Santa Rosa, California) to better separate the pressed wet pulp.
  • the fluffed wet pulp is then dried in an oven to approximately 8 total wt % moisture and is then further processed in an ultra rotor (model IIIA available from Altenburger Machinen Jackering GmbH with offices in Voisterhauser, Germany) such as is disclosed in U.S. Patent 5,084,136 to further fluff and disperse the dried pulp.
  • the dried pulp is then packaged into bales.
  • FiberExpert ® all of the ingredients in the pulp have a length-weighted average of no more than 1.3 mm.
  • Example 2 illustrates another embodiment of the pulp of this invention.
  • the process of Example 2 is followed with the exception that one third by weight of the para-aramid fiber is replaced by para-aramid particles.
  • the para-aramid resin particles are prepared by reacting para-phenylenediamine and teraphthaloyl chloride continuously in a screw extruder as is generally disclosed in U.S. Patent 3,884,881 , but using N, methyl pyrollidone/calcium chloride as the solvent, producing a crumb-like polymer that precipitates from the solvent. The solvent is extracted, and the polymer crumb washed and dried to a particulate powder of mixed particle size.
  • the para-aramid resin particles are then treated substantially the same as the para-aramid fiber is treated in Example 2.
  • the refiner not only refines the fibers but also cuts and/or masticates the para-aramid particles into rounder, substantially fibril-free particles. After dewatering, some of the resulting pulp having a moisture content of 50 total wt percent is then packaged into bales. The remainder of the resulting pulp is further pressed to a moisture content of approximately 8 total wt percent and then fluffed, dispersed, and packaged as in Example 3. When measured by FiberExpert ® , all of the ingredients in the pulp have a length-weighted average of no more than 1.3 mm.
  • Disc brake pads incorporating the pulp of this invention were made in the following manner. Approximately 20 kilograms of a non-asbestos-containing base compound powder comprising a mixture of 7 wt % cashew nut shell resin, 17 wt % inorganic fillers, 21 wt % graphite, coke and lubricants, 18 wt % inorganic abrasives, and 16 wt % soft metals was mixed together for 10 to 20 minutes in a 50-liter Littleford mixer. The mixer had two high-speed choppers with blades of the "stars and bars" configuration and a slower rotating plough.
  • the brake pad composition was then poured into a single-cavity steel mold for a front disc brake pad and cold pressed to a standard thickness of about 5/8 inch (16 mm) then removed from the mold to form a pre-formed brake pad having an approximate weight of 200 grams.
  • the pre-form had no excessive spring-back or swelling, and was robust enough to endure normal handling without damage. Twelve replicate pre-forms were made.
  • the pre-forms were then placed in two multi-cavity molds, placed in a commercial press, and press-cured (the binder phenolic cross-linking and reacting) at 300°F (149°C) for about 15 minutes, with periodic pressure release to allow phenolic reaction gases to escape, followed by lightly constrained oven curing at 340°F (171°C) for 4 hours to complete the phenolic binder crosslinking.
  • the cured, molded pad was then ground to the desired thickness of about half an inch (13 mm). When compared visually with a commercial brake pad containing an equivalent amount of all para-aramid pulp or acrylic pulp, the test pad was indistinguishable and had good compound flow into the backing plate holes and no edge chipping.
  • a sample of the brake pad incorporating the pulp of this invention was then tested to determine its frictional performance. Coupons, typically one inch by one inch and about 3/16 inch (5 mm) thick, from test pads were assessed on the Chase Machine available from Link Engineering, Detroit, MI, using test protocol Society of Automotive Engineers (SAE) J661 to determine the hot and cold friction coefficient during constant pressure and controlled temperature drag tests against a heated steel drum. The sample was periodically measured for wear (thickness loss). This was repeated with two more test samples cut from other replicate pads. The samples of the brake pad incorporating the pulp of this invention exhibited hot and cold friction performance substantially equivalent to commercially available pads containing a substantially equivalent amount of all para-aramid pulp. The test further indicated the pad-to-pad uniformity and an average friction rating was also substantially equivalent.
  • the pad was then tested for friction and wear under various braking conditions using a dynamometer (single piston dynamometer with a rolling radius of 289.0 mm at Link Testing Laboratories, Inc., in Detroit, MI) using test protocol J2681 (ISO-SWG4).
  • This test was comprised of seventeen scenarios of from 5 to 200 brake applications each, and measured coefficient of friction as a function of applied brake pressure, temperature, braking speed and deceleration rate.
  • This test also had two high-temperature fade sections, during which the brake pad was subjected to increasingly high initial temperatures during constant deceleration, and reached temperatures exceeding 600°C.
  • This example illustrates how the pulp of this invention can be incorporated into a beater-add gasket for sealing applications.
  • Water, rubber, latex, fillers, chemicals, and the pulp of this invention are combined in desired amounts to form a slurry.
  • a circulating wire sieve such as a paper machine screen or wire
  • the slurry is largely drained of its water content, is dried in a heating tunnel, and is vulcanized on heated calender rolls to form a material having a maximum thickness of around 2.0 mm. This material is compressed in a hydraulic press or two-roll calender, which increases the density and improves sealability.
  • beater-add gasket materials generally do not have as good sealability as equivalent compressed-fiber materials and are best suited for moderate-pressure high-temperature applications.
  • Beater-add gaskets find applicability in the making of auxiliary engine gaskets or, after further processing, cylinder head gaskets.
  • the semi-finished product is laminated onto both sides of a spiked metal sheet and is physically fixed in place by the spikes.
  • This example illustrates how the pulp of this invention can be incorporated into a gasket made by a calendering process.
  • the same ingredients as in Example 6, minus the water, are thoroughly dry mixed together and are then blended with a rubber solution prepared using an appropriate solvent.
  • the compound is then generally conveyed batchwise to a roll calender.
  • the calender consists of a small roll that is cooled and a large roll that is heated.
  • the compound is fed and drawn into the calender nip by the rotary movement of the two rolls.
  • the compound will adhere and wrap itself around the hot lower roll in layers generally about 0.02 mm thick, depending on the pressure, to form a gasketing material made from the built-up compound layers.
  • the solvent evaporates and vulcanization of the elastomer commences.
  • gasketing material thickness is reached, the rolls are stopped and the gasketing material is cut from the hot roll and cut and/or punched to the desired size. No additional pressing or heating is required, and the material is ready to perform as a gasket. In this manner gaskets up to about 7 mm thick can be manufactured. However, most gaskets made in this manner are much thinner, normally being about 3 mm or less in thickness.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Paper (AREA)
  • Sealing Material Composition (AREA)
  • Nonwoven Fabrics (AREA)

Claims (22)

  1. Procédé de fabrication d'une pâte d'acrylique et para-aramide pour l'utilisation comme matériau de renforcement, comprenant:
    (a) la combinaison des ingrédients pour la pâte incluant:
    (1) de la fibre acrylique comprenant des motifs d'acrylonitrile qui sont au moins de 85 % en pds de la fibre acrylique totale, la fibre étant de 10 à 90 % en pds des matières solides totales dans les ingrédients, et ayant une longueur moyenne de pas plus de 10 cm;
    (2) de la fibre de para-aramide étant de 10 à 90 % en pds des matières solides totales dans les ingrédients, et ayant une longueur moyenne de pas plus de 10 cm; et
    (3) de l'eau étant de 95 à 99 % en pds des ingrédients totaux;
    (b) le mélange des ingrédients jusqu'à l'obtention d'une suspension substantiellement uniforme;
    (c) le co-raffinage de la suspension en simultanément:
    (1) fibrillant, découpant et mastiquant la fibre acrylique et la fibre de para-aramide en structures fibreuses fibrillées de forme irrégulière avec des tiges et des fibrilles; et
    (2) dispersant toutes les matières solides de sorte que la suspension raffinée soit substantiellement uniforme; et
    (d) l'élimination de l'eau de la suspension raffinée jusqu'à pas plus de 60 % en pds totaux d'eau,
    produisant de là une pâte d'acrylique et para-aramide avec les structures fibreuses d'acrylique et de para-aramide ayant une dimension maximale moyenne de pas plus de 5 mm, une moyenne pondérée dans la longueur de pas plus de 1,3 mm, et les fibrilles et/ou les tiges d'acryliques sont substantiellement entremêlées avec les fibrilles et/ou les tiges de para-aramide.
  2. Procédé selon la revendication 1, dans lequel
    la fibre acrylique a une densité linéaire de pas plus de 10 dtex; et
    la fibre de para-aramide a une densité linéaire de pas plus de 2,5 dtex.
  3. Procédé selon la revendication 1, dans lequel la pâte se trouve sans agrégats substantiels du même matériau.
  4. Procédé selon la revendication 1, dans lequel
    les ingrédients comprennent en outre des particules de para-aramide, granuleuses, substantiellement ou complètement exemptes de fibrilles étant de pas plus de 50 % en pds des matières solides totales dans les ingrédients, et ayant une dimension maximale moyenne de 50 à 2000 microns, et
    dans l'étape de raffinage, la mastication d'au moins une partie des particules de para-aramide en particules plus petites, plus rondes, substantiellement exemptes de fibrilles,
    moyennant quoi dans la pâte d'acrylique et para-aramide produite, les structures fibreuses d'acrylique et de para-aramide entrent en contact et sont enveloppées partiellement autour d'au moins une partie des particules de para-aramide plus rondes, substantiellement exemptes de fibrilles.
  5. Procédé selon la revendication 1, dans lequel dans l'étape de combinaison, la fibre d'acrylique comprend 25 à 60 % en pds de matières solides totales.
  6. Procédé selon la revendication 1, dans lequel dans l'étape de combinaison, la fibre de para-aramide comprend 40 à 75 % en pds de matières solides totales.
  7. Procédé selon la revendication 1, dans lequel après l'étape d'élimination, l'eau étant de 4 à 60 % en pds de la pâte entière, et la pâte ayant un indice canadien d'égouttage (CSF) de 100 à 700 ml.
  8. Procédé selon la revendication 1, dans lequel l'étape de raffinage comprend le fait de faire passer la suspension mixte à travers une série de raffineurs à disque.
  9. Procédé de fabrication d'une pâte d'acrylique et para-aramide pour l'utilisation comme matériau de renforcement, comprenant:
    (a) la combinaison des ingrédients incluant l'eau et une première fibre à partir du groupe constitué de:
    (1) fibre acrylique comprenant des motifs d'acrylonitrile qui sont d'au moins 85 % en pds de la fibre acrylique totale, la fibre étant de 10 à 90 % en pds des matières solides totales dans la pâte; et
    (2) fibre de para-aramide étant de 10 à 90 % en pds des matières solides totales dans la pâte;
    (b) le mélange des ingrédients combinés jusqu'à l'obtention d'une suspension substantiellement uniforme;
    (c) le raffinage de la suspension dans un raffineur à disque découpant de là la fibre pour avoir une longueur moyenne de pas plus de 10 cm, et la fribrillation et la mastication d'au moins une partie de la fibre jusqu'à des structures fibreuses fibrillées de forme irrégulière;
    (d) la combinaison des ingrédients incluant la suspension raffinée, la seconde fibre du groupe de (a) (1 et 2) ayant une longueur moyenne de pas plus de 10 cm, et de l'eau, si nécessaire, pour augmenter la concentration de l'eau jusqu'à 95 à 99 % en pds des ingrédients totaux;
    (e) le mélange des ingrédients, si nécessaire, pour former une suspension substantiellement uniforme;
    (f) le co-raffinage de la suspension mixte en simultanément:
    (1) fibrillant, découpant et mastiquant les matières solides dans la suspension de sorte que toute ou substantiellement toute la fibre d'acrylique et para-aramide soit convertie en structures fibreuses d'acrylique et de para-aramide fibrillées de forme irrégulière avec des tiges et des fibrilles; et
    (2) dispersant toutes les matières solides de sorte que la suspension raffinée soit substantiellement uniforme; et
    (g) l'élimination de l'eau de la suspension raffinée jusqu'à pas plus de 60 % en pds d'eau au total,
    produisant de là une pâte d'acrylique et para-aramide avec les structures fibreuses d'acrylique et de para-aramide ayant une dimension maximale moyenne de pas plus de 5 mm, une moyenne pondérée dans la longueur de pas plus de 1,3 mm, et les fibrilles et/ou les tiges d'acrylique sont substantiellement entremêlées avec les fibrilles et/ou les tiges de para-aramide.
  10. Procédé selon la revendication 9, dans lequel
    les ingrédients comprennent en outre:
    des particules de para-aramide, granuleuses, substantiellement ou complètement exemptes de fibrilles étant de pas plus de 50 % en pds des matières solides totales dans les ingrédients, et ayant une longueur maximale moyenne de 50 à 2000 microns; et
    dans soit la première soit la seconde étape de raffinage, la mastication d'au moins une partie des particules de para-aramide en particules plus petites, plus rondes, substantiellement exemptes de fibrilles,
    moyennant quoi dans la pâte d'acrylique et para-aramide produite, les structures fibreuses d'acrylique et de para-aramide entrent en contact et sont enveloppées partiellement autour d'au moins une partie des particules de para-aramide plus rondes, substantiellement exemptes de fibrilles.
  11. Procédé selon la revendication 9, dans lequel après l'étape d'élimination, les structures fibreuses d'acrylique de forme irrégulière étant de 25 à 60 % en pds des matières solides totales.
  12. Procédé selon la revendication 9, dans lequel après l'étape d'élimination, les structures fibreuses et de para-aramide de forme irrégulière étant de 40 à 75 % en pds des matières solides totales.
  13. Procédé selon la revendication 9, dans lequel après l'étape d'élimination, l'eau étant de 4 à 60 % en pds de la pâte entière, et la pâte ayant un indice canadien d'égouttage (CSF) de 100 à 700 ml.
  14. Pâte d'acrylique et para-aramide pour l'utilisation comme matériau de renforcement, comprenant:
    (a) des structures fibreuses d'acrylique de forme irrégulière comprenant des motifs d'acrylonitrile qui sont d'au moins 85 % en pds des structures fibreuses acryliques totales, les structures étant de 10 à 90 % en pds des matières solides totales;
    (b) des structures fibreuses de para-aramide, de forme irrégulière étant de 10 à 90 % en pds des matières solides totales; et
    (c) de l'eau étant de 4 à 60 % en pds de la pâte entière,
    moyennant quoi les structures fibreuses d'acrylique et de para-aramide ayant une dimension maximale moyenne de pas plus de 5 mm, une moyenne pondérée dans la longueur de pas plus de 1,3 mm, et des tiges et des fibrilles où les fibrilles et/ou les tiges d'acrylique sont substantiellement entremêlées avec les fibrilles et/ou les tiges de para-aramide.
  15. Pâte d'aramide selon la revendication 14, comprenant en outre
    des particules de para-aramide, granuleuses, substantiellement ou complètement exemptes de fibrilles étant de pas plus de 50 % en pds des matières solides totales.
  16. Pâte selon la revendication 14, dans laquelle
    les structures fibreuses d'acrylique de forme irrégulière étant de 25 à 60 % en pds des matières solides totales.
  17. Pâte selon la revendication 14, dans laquelle
    les structures fibreuses de para-aramide, de forme irrégulière étant de 40 à 75 % en pds des matières solides totales.
  18. Pâte selon la revendication 14, dans laquelle l'eau étant de 4 à 60 % en pds de la pâte entière, et la pâte ayant un indice canadien d'égouttage (CSF) de 100 à 700 ml.
  19. Matériau de friction, comprenant:
    un agent de modification de la friction;
    un liant; et
    un matériau de renforcement fibreux comprenant la pâte selon la revendication 14.
  20. Matériau de friction selon la revendication 19, dans lequel
    l'agent de modification de la friction est choisi parmi le groupe constitué des poudres métalliques, des abrasifs, des lubrifiants, des agents organiques de modification de la friction, et des mélanges de ceux-ci; et
    le liant est choisi parmi le groupe constitué des résines thermodurcissables, des résines de type mélamine, des résines époxy et des résines de type polyimide, et des mélanges de celles-ci.
  21. Matériau d'étanchéité, comprenant:
    un liant; et
    un matériau de renforcement fibreux comprenant la pâte selon la revendication 14.
  22. Matériau d'étanchéité selon la revendication 21, dans lequel
    le liant est choisi parmi le groupe constitué du caoutchouc de nitrile, du caoutchouc de butadiène, du néoprène, du caoutchouc de styrène-butadiène, du caoutchouc de nitrile-butadiène, et des mélanges de ceux-ci.
EP05766040A 2004-06-25 2005-06-16 Pate a base de fibres acryliques et para-aramides et procedes de fabrication de cette derniere Active EP1774095B1 (fr)

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US10/877,843 US20050287344A1 (en) 2004-06-25 2004-06-25 Acrylic and para-aramid pulp and processes of making same
PCT/US2005/021342 WO2006012040A1 (fr) 2004-06-25 2005-06-16 Pate a base de fibres acryliques et para-aramides et procedes de fabrication de cette derniere

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US8398906B2 (en) * 2007-04-05 2013-03-19 Teijin Aramid B.V. Particles comprising composite of para-aramid and additive material
US10227730B2 (en) 2013-05-03 2019-03-12 Teijin Aramid Gmbh Process to manufacture a mixture of p-aramid pulp with chopped fibers, mixture and its use
WO2017109893A1 (fr) * 2015-12-24 2017-06-29 日立化成株式会社 Composition de matériau de friction et matériau de friction et élément de friction utilisant la composition de matériau de friction
WO2018037015A1 (fr) 2016-08-24 2018-03-01 Teijin Aramid B.V. Matériau de friction comprenant de l'aramide
CN117425756A (zh) 2021-06-08 2024-01-19 帝人芳纶有限公司 改性芳族聚酰胺纸浆和包含改性芳族聚酰胺纸浆的摩擦材料

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BRPI0512484A (pt) 2008-03-04
KR20080092979A (ko) 2008-10-16
KR100917963B1 (ko) 2009-09-21
JP2008503660A (ja) 2008-02-07
EP1774095A1 (fr) 2007-04-18
MXPA06014287A (es) 2007-02-19
US20050287344A1 (en) 2005-12-29
JP5209303B2 (ja) 2013-06-12
CN1973085B (zh) 2010-05-12
KR20070030227A (ko) 2007-03-15
KR100864357B1 (ko) 2008-10-17
DE602005013966D1 (de) 2009-05-28
CA2568016C (fr) 2013-03-19
CA2568016A1 (fr) 2006-02-02
WO2006012040A1 (fr) 2006-02-02

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