US20020029842A1 - Apparatus and method for manufacturing resin-impreganated cured sheet, and apparatus and method for manufacturing carbonaceous material sheet - Google Patents
Apparatus and method for manufacturing resin-impreganated cured sheet, and apparatus and method for manufacturing carbonaceous material sheet Download PDFInfo
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- US20020029842A1 US20020029842A1 US09/903,680 US90368001A US2002029842A1 US 20020029842 A1 US20020029842 A1 US 20020029842A1 US 90368001 A US90368001 A US 90368001A US 2002029842 A1 US2002029842 A1 US 2002029842A1
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- resin
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- carbonaceous material
- uncured
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
- B29C43/32—Component parts, details or accessories; Auxiliary operations
- B29C43/44—Compression means for making articles of indefinite length
- B29C43/48—Endless belts
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
- B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
- B29C35/04—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould using liquids, gas or steam
- B29C35/06—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould using liquids, gas or steam for articles of indefinite length
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
- B29C70/28—Shaping operations therefor
- B29C70/40—Shaping or impregnating by compression not applied
- B29C70/42—Shaping or impregnating by compression not applied for producing articles of definite length, i.e. discrete articles
- B29C70/44—Shaping or impregnating by compression not applied for producing articles of definite length, i.e. discrete articles using isostatic pressure, e.g. pressure difference-moulding, vacuum bag-moulding, autoclave-moulding or expanding rubber-moulding
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
- B29C70/28—Shaping operations therefor
- B29C70/40—Shaping or impregnating by compression not applied
- B29C70/50—Shaping or impregnating by compression not applied for producing articles of indefinite length, e.g. prepregs, sheet moulding compounds [SMC] or cross moulding compounds [XMC]
- B29C70/502—Shaping or impregnating by compression not applied for producing articles of indefinite length, e.g. prepregs, sheet moulding compounds [SMC] or cross moulding compounds [XMC] by first forming a mat composed of short fibres
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
- B29C70/28—Shaping operations therefor
- B29C70/40—Shaping or impregnating by compression not applied
- B29C70/50—Shaping or impregnating by compression not applied for producing articles of indefinite length, e.g. prepregs, sheet moulding compounds [SMC] or cross moulding compounds [XMC]
- B29C70/504—Shaping or impregnating by compression not applied for producing articles of indefinite length, e.g. prepregs, sheet moulding compounds [SMC] or cross moulding compounds [XMC] using rollers or pressure bands
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
- B29C70/28—Shaping operations therefor
- B29C70/40—Shaping or impregnating by compression not applied
- B29C70/50—Shaping or impregnating by compression not applied for producing articles of indefinite length, e.g. prepregs, sheet moulding compounds [SMC] or cross moulding compounds [XMC]
- B29C70/504—Shaping or impregnating by compression not applied for producing articles of indefinite length, e.g. prepregs, sheet moulding compounds [SMC] or cross moulding compounds [XMC] using rollers or pressure bands
- B29C70/508—Shaping or impregnating by compression not applied for producing articles of indefinite length, e.g. prepregs, sheet moulding compounds [SMC] or cross moulding compounds [XMC] using rollers or pressure bands and first forming a mat composed of short fibres
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B30—PRESSES
- B30B—PRESSES IN GENERAL
- B30B5/00—Presses characterised by the use of pressing means other than those mentioned in the preceding groups
- B30B5/04—Presses characterised by the use of pressing means other than those mentioned in the preceding groups wherein the pressing means is in the form of an endless band
- B30B5/06—Presses characterised by the use of pressing means other than those mentioned in the preceding groups wherein the pressing means is in the form of an endless band co-operating with another endless band
- B30B5/062—Presses characterised by the use of pressing means other than those mentioned in the preceding groups wherein the pressing means is in the form of an endless band co-operating with another endless band urged by directly-acting fluid pressure
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
- B29C43/32—Component parts, details or accessories; Auxiliary operations
- B29C43/44—Compression means for making articles of indefinite length
- B29C43/48—Endless belts
- B29C2043/483—Endless belts cooperating with a second endless belt, i.e. double band presses
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
- B29C43/32—Component parts, details or accessories; Auxiliary operations
- B29C43/52—Heating or cooling
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
- B29K2105/08—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts of continuous length, e.g. cords, rovings, mats, fabrics, strands or yarns
- B29K2105/0854—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts of continuous length, e.g. cords, rovings, mats, fabrics, strands or yarns in the form of a non-woven mat
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- 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
- Y10T156/00—Adhesive bonding and miscellaneous chemical manufacture
- Y10T156/10—Methods of surface bonding and/or assembly therefor
- Y10T156/1052—Methods of surface bonding and/or assembly therefor with cutting, punching, tearing or severing
- Y10T156/108—Flash, trim or excess removal
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- 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
- Y10T156/00—Adhesive bonding and miscellaneous chemical manufacture
- Y10T156/17—Surface bonding means and/or assemblymeans with work feeding or handling means
- Y10T156/1702—For plural parts or plural areas of single part
- Y10T156/1712—Indefinite or running length work
Definitions
- a substrate of a printed circuit board which comprises fiber reinforced plastics, is produced by using an organic fiber reinforced pre-preg that is obtained by impregnating matrix resin into a sheet made of para-aramid fiber and meta-aramid pulp or fusion-liquid-crystal aromatic polyester fiber and pulp thereof, for example, as described in Japanese Patent Application Laid-Open No. 2000-77803 as a conventional technology.
- an organic fiber reinforced pre-preg that is obtained by impregnating matrix resin into a sheet made of para-aramid fiber and meta-aramid pulp or fusion-liquid-crystal aromatic polyester fiber and pulp thereof, for example, as described in Japanese Patent Application Laid-Open No. 2000-77803 as a conventional technology.
- there is a method of obtaining a flexible substrate by impregnating epoxy resin into a dry sheet which is obtained by integrating a mixed web comprising aramid fiber and thermoplastic fiber such as polyester or the like by means of a hot calendar.
- a long printed circuit board is cut at a desired dimension at a final stage of the production process and then laminated to be stored, as disclosed in Japanese Patent Application Laid-Open No. 5-24165.
- the term “flexible” as mentioned above means that flexibility is locally imparted to a substrate.
- the conventional mainstream has been a porous carbon electrode, which is produced by impregnating thermosetting resin into a short carbon fiber sheet made of carbon fiber, and after curing the resin, sintering it to be carbonized.
- the conventional substrate of a porous carbon electrode has a large thickness and fragility, many of such substrates are easy to be destructed when being bent. Further, since the conventional electrodes are bonded at intersection portions of carbon fibers at most, there are little numbers of bonded points. Therefore, electroconductivity in a thickness direction is not always high as compared with that in a direction of the fiber axis. Furthermore, in order that the efficiency of chemical-electrical energy conversion is raised by smoothing the flow of gas and water in a fuel cell, when the porocity of the substrate of the porous carbon electrode is raised, there raises a problem that the electroconductivity itself is lowered.
- a porous carbon electrode which is disclosed in Japanese Patent Application Laid-Open No. 1-160867, uses a combination of a self-curing type resol-based phenol resin, which is thermosettable, and a non self-curing type novolak-base phenol resin, as a resin that can be carbonized.
- a self-curing type resol-based phenol resin which is thermosettable
- a non self-curing type novolak-base phenol resin as a resin that can be carbonized.
- a carbonaceous milled fiber which has a fiber length of 0.1 mm or less, exists in a thickness direction of the electrode substrate at a matrix portion of the porous-structural electrode substrate comprising a - carbon. Therefore, the fibers, which are arranged in the thickness direction, are mutually bonded even at portions other than the intersection portions. Accordingly, the electrode substrate having such structure improves the whole electroconductivity, in particular, the electroconductivity in the thickness direction of the electrode substrate.
- Japanese Patent Application Laid-Open No. 8-2979 discloses a porous carbon material with grooves for a phosphoric acid type fuel cell.
- the carbon material can be obtained by using a sheet containing a fiber capable of being made into carbon fiber and/or a carbon fiber and a thermosetting resin which can be carbonized or graphitized to make paper, heating, pressuring and molding the sheet, then arranging it in a mold in which an uneven portion is formed with a clearance, after the arrangement, heating the sheet again to be expanded and perfectly cured, and then baking it.
- groove-shaped gas flow paths are formed with a high precision. Furthermore, it is possible to obtain a substrate, which has a light weight, with highly mechanical strength and excellent in uniformity, thermal conductivity and gas permeability.
- the diffusion property and permeability of gas, the strength and flexibility for enduring a handling, and further, the strength for enduring the compression at the production of the electrode or at the assembling of the electrode, and the like are required for the porous electrode for the solid polymer type fuel cell.
- Japanese Patent Application Laid-Open No. 9-157052 discloses a porous carbon plate for the solid polymer type fuel cell. Since the porous carbon plate disclosed in this Publication is applied to the solid polymer type fuel cell, the gas permeability in the thickness direction is enhanced in particular. According to this Publication, in order to enhance the gas permeability in the thickness direction, there is obtained a sheet made of carbon short fibers, in which the carbon short fibers are dispersed in a random direction in a substantially two dimensional plane, the sheet being impregnated with a desired amount of mixed resin in which the mix ratio of a resol-based phenol resin to a novolak-base phenol resin is 2:1 to 1:3, and heated to be carbonized.
- the current density of the porous electrode for the solid polymer type fuel cell is higher than that of the porous electrode for the phosphoric acid type fuel cell, a requirement for making the solid polymer type fuel cell into a small size has been stronger. In order to realize it, it is required to make the porous electrode thinner.
- the thickness of the electrode of the solid polymer type fuel cell is 0.2 mm for an automobile at present time, and about 0.3 mm for a stationary cell.
- a porous carbon plate, which has a thickness of about 0.2 mm, is disclosed in the above-mentioned Japanese Patent Application Laid-Open No. 9-157052, but it is anticipated to make the plate further thinner in the future.
- the substrate is cut into a short plate having a predetermined dimension at the final stage of the production process of the printed circuit board, and then, it is processed to a desired dimension in accordance with application in various instruments to be used. Further, even the porous electrode substrate has a short sheet form as described above, and the substrate is generally cut into a predetermined electrode dimension of about 15 cm ⁇ 15 cm for use.
- the present invention is to overcome the above-mentioned problems.
- One object of the invention is to provide an apparatus and a method for continuously manufacturing a flexible and windable resin-impregnated cured sheet that is obtained by impregnating resin into a long fiber sheet with and curing the sheet.
- Another object of the invention is to provide an apparatus and a method for continuously manufacturing a flexible and windable carbonaceous material sheet that is obtained by impregnating carbonizable resin into a long fiber sheet and carbonizing the sheet.
- an apparatus for manufacturing a resin-impregnated cured sheet characterized by comprising conveyance means for conveying a long uncured fiber sheet, which is obtained by using short fibers to make paper and which contains uncured resin; and resin curing means for curing uncured resin of the uncured fiber sheet to be formed into a resin-impregnated cured sheet, wherein the conveyance means is equipped with at least one rotation belt set comprising a driving roll, a follower roll, and an endless belt to be put on and around the drive roll and the follower roll.
- the apparatus for manufacturing the resin-impregnated cured sheet can perform a curing treatment while continuously conveying the long uncured fiber sheet, the curing can be carried out uniformly over the uncured fiber sheet in a length direction thereof. Accordingly, it is possible to produce a resin-impregnated cured sheet that has uniform quality in the length direction with a high productivity, without generating any local fragile portions or broken portions.
- the resin-impregnated cured sheet which is manufactured according to the above-mentioned apparatus, can be supplied to users in a rolled form as, for example, a printed circuit board, so that it is easy to be treated and is convenient for transport. Further, even when it is used after being cut into pieces of dimensions in accordance with various electric instruments, wasted material is little so that the production efficiency can be also improved.
- the apparatus further comprises a winding device in which a trimming cutter for trimming both side edges of the resin-impregnated cured sheet, a press roll for retaining a winding face pressure, and winding shafts are arranged along a conveyance path of the resin-impregnated cured sheet.
- the fiber sheet Before being winded after cured, the fiber sheet is reeled on the winding shaft after the both side edges thereof are trimmed by a trimming cutter. At the time of winding, since a peripheral face of the wounded body is pressed by a press roll with a preliminarily set pressuring force, the sheet can be continuously reeled in good order with a fixed winding density, in cooperation with the trimming.
- the conveyance means is equipped with at least two rotation belt sets, which are arranged in a paired manner so as to oppose to each other via the conveyance path of the uncured fiber sheet.
- the sheet can be sandwiched at a required length by the endless belts. Therefore, a thickness of the resin-impregnated cured sheet can be more precisely controlled and the uniformity of the thickness thereof in the length direction can be also enhanced.
- heating means is adopted as the resin curing means.
- the heating system may be conductive heating such as heating rolls, or convection heating, in which a heating area is provided, or radiant heating such as far infrared radiation or the like.
- the conductive heating such as heating rolls or the like is rather preferable.
- a pitch between each pair of the heating and pressuring rolls in the conveyance direction and a diameter of the heating and pressuring roll can be determined in consideration of a temperature change of the endless belt before and after the heating and pressuring rolls, a pressure fluctuation that is applied to the uncured fiber sheet itself, and the like.
- a heating temperature (temperature at the curing) and a pressure of the heating and pressing rolls can be suitably set.
- the temperature at the curing is 350° C. or less, and the pressure is within a range of 1.5 ⁇ 10 4 N/m to 1.0 ⁇ 10 5 N/m at linear lead.
- a continuously heating liquid-pressure apparatus that nips the uncured fiber sheet and the endless belts by a fluid pressure, in place of the heating and pressuring rolls.
- the pressuring fluid which is applied to the present continuously heating liquid-pressure apparatus, is not limited to a specific one as far as it satisfies a heat resistance that does not cause any deterioration, alteration and the like at a desired temperature. Therefore, it may be appropriately determined in accordance with the desired temperature.
- a silicon-based oil which is excellent in heat resistance, is preferably used.
- Gas can be used as the pressuring fluid, but a liquid is usually advantageous because of its high thermal conduction efficiency.
- the continuously heating liquid-pressure apparatus is different from the above-mentioned heating and pressuring rolls in that it can continuously impart face pressure while the sheet passes the continuously heating liquid-pressure apparatus. Therefore, it is preferably used when a long treatment time is required. Further, in accordance with the requirement, a plurality of apparatuses may be arranged in a face direction of the fiber sheet to be treated.
- heating and pressuring rolls may be provided in combination with it.
- the pressuring fluid with high temperature is introduced.
- the pressuring fluid with high temperature is recycled, but occasionally is utilized by being enclosed in the apparatus.
- the continuously heating liquid pressure apparatus which is a “continuously pressuring apparatus” that is manufactured and sold by Mitsubishi Rayon Engineering Co., Ltd.
- the detail is disclosed in, for example, Japanese Patent Publications No. 3-51205, No. 2-62371, and No. 2-62370.
- the thickness of the resin-impregnated cured sheet can be controlled well at the heating and pressuring section which follows the preheating section. At this time, it is preferable that the temperature at the preheating section is not less than the temperature at which the viscosity of the thermosetting resin becomes lowest. Further, it is preferable that the temperature at the heating and pressuring section is higher than the temperature at the preheating section by 50° C. or more. Thus, the thermosetting resin can be sufficiently cured.
- the present invention includes a method for manufacturing a resin-impregnated cured sheet by means of the above-mentioned apparatus for manufacturing the resin-impregnated cured sheet, wherein the uncured resin of the long uncured fiber sheet is cured, the long cured fiber sheet is continuously produced and then wound up.
- the fiber-made sheet which is obtained by using short fibers to make paper, may preferably contains a carbon short fiber and an organic polymer-based binder.
- the short fibers of the fiber sheet which is obtained by using short fibers to make paper, may be various synthetic fibers such as polyacrylonitrile-based fibers, polyester-based fibers, polyvinyl alcohol-based fibers or the like, or carbon fibers.
- synthetic fibers such as polyacrylonitrile-based fibers, polyester-based fibers, polyvinyl alcohol-based fibers or the like, or carbon fibers.
- glass fibers, aramid fibers or ceramic-based fibers may be used for reinforcement.
- the uncured fiber sheet is obtained by using these short fibers added with organic polymer-based binders to make paper, and then impregnating the obtained fiber sheet with the uncured resin and drying it.
- the uncured resin it is preferable to use the one that has agglomerating property or flowability at normal temperature.
- the carbonaceous material sheet is obtained by carbonizing the resin-impregnated cured sheet.
- a burning furnace for carbon fibers can be used.
- a vertical type burning furnace has such an advantageous point that guide rolls do not need to be provided.
- the guide roll it is preferable to employ a round bar or a round pipe made of graphite. Even if it is such a simple structure that both ends of each roll are supported by a roll supporting stand made of graphite, the roll can easily rotate because of the self-lubricating property of the graphite itself.
- the roll pitch can be suitably determined in accordance with the weight of a curing paper impregnated with resin and the tensile force at the carbonization treatment.
- the obtained long carbonaceous material sheet can be cut into a predetermined length as required as, for example, a porous carbon electrode substrate, but the curing and the carbonization are continuously carried out as described above, so that the obtained carbonaceous material sheet has uniform and adequate flexibility in the length direction. Therefore, it can be wound up in a roll form.
- the apparatus of the present invention comprises a winding device in which a trimming cutter for trimming the both side edges of the carbonaceous material sheet, a press roll for retaining the winding face pressure, and a winding shaft are arranged in order along the running path of the carbonaceous material sheet.
- a winding device a biaxial turret winding device, by which winding bobbins can be easily switched, is preferable for improving productivity.
- a method for manufacturing a carbonaceous material sheet characterized by including: continuously producing a long cured fiber sheet by curing uncured resin of the long uncured fiber sheet by using an apparatus for manufacturing a resin-impregnated cured sheet, comprising conveyance means for conveying a long uncured fiber sheet which is obtained by using short fibers to make paper and which contains uncured resin and resin curing means for curing the resin of the uncured fiber sheet, wherein the conveyance means is equipped with at least one rotation belt set comprising a drive roll, a follower, and an endless belt which is put on and around the drive roll and the follower roll; and continuously producing a carbonaceous material sheet by carbonizing the long resin-impregnated cured sheet by means of the above-mentioned carbonization apparatus; and then winding up the carbonaceous material sheet.
- the sheet has a thickness of 0.05 to 0.5 mm, a bulk density of 0.35 to 0.8 g/cm 2 , and a bending strength of 45 MPa or more. It is further preferable that as a short fiber, extremely fine short fibers, each of which has an average diameter of less than 5 ⁇ m and a fiber length of 3 to 10 mm, are contained at 50% or more of the total weight of fibers.
- the short fibers of the fiber sheet which is obtained by using short fibers to make paper may be, besides carbon fibers, organic polymer fibers such as polyarylonitrile-based, polyvinylalcohol, or polyester-based.
- organic polymer fibers such as polyarylonitrile-based, polyvinylalcohol, or polyester-based.
- glass fibers, aramid fibers, or ceramic-based fibers can be further used for reinforcement.
- the uncured resin a resin which has adherence property or flowability at normal temperature is preferable.
- a resin which has adherence property or flowability at normal temperature is preferable.
- a phenol resin, a furan resin or the like that remains as an electroconductive substance after the carbonization is preferably used as the uncured resin.
- the concentration of the resin is preferably from 5% by weight or more to 70% by weight or less.
- the fiber-made sheet which is obtained by using short fibers to make paper, contains carbon short fibers and organic polymer-based binders.
- carbon short fibers when the carbon short fibers are being made, a strength of the fiber-made sheet can be secured.
- the average diameter of the carbon short fiber is preferably less than 5 ⁇ m.
- the length of the fiber is preferably 3 mm or more and 10 mm or less from a viewpoint of a dispersion property of the papering.
- the carbonization yield of the organic polymer-based binder is 40% by weight or less.
- the gas permeability of the carbonaceous material sheet can be secured.
- the organic polymer-based binder for example, a pulp article or a short fiber of polyvinylalcohol is preferable.
- the content rate of the organic polymer-based binders with respect to the fiber-made sheet is preferably 5% by weight or more and 40% by weight or less.
- the resin-impregnated cured sheet by preliminarily heating a fiber sheet which is impregnated with the uncured resin and then heating and pressuring it.
- the thickness of the resin-impregnated cured sheet can be well controlled by softening thermosetting resin due to the preheating and by the successive heating and pressuring.
- the temperature at the heating and pressuring is higher than the preheating temperature by 50° C. or more. Thereby, the thermosetting resin can be sufficiently cured.
- the preheating temperature is not less than a temperature at which the viscosity of the thermosetting resin becomes the lowest.
- FIG. 1 is a schematic view of an apparatus for manufacturing a preferred resin-impregnated cured sheet according to the present invention.
- FIG. 2 is a schematic view of an apparatus for manufacturing another preferred resin-impregnated cured sheet according to the present invention.
- FIG. 3 is a schematic sectional view of a heating and pressuring apparatus in an apparatus for manufacturing another preferable resin-impregnated cured sheet according to the present invention.
- FIG. 4 is a schematic view of an apparatus for manufacturing a preferred carbonaceous material sheet according to the present invention.
- FIG. 5 is a schematic view of a winding device of the carbonaceous material sheet according to the present invention.
- FIG. 1 schematically shows an apparatus 10 for manufacturing a resin-impregnated cured sheet, which is a preferable first embodiment of the present invention.
- an apparatus 10 for manufacturing a resin-impregnated cured sheet which is a preferable first embodiment of the present invention.
- a resin-impregnated cured sheet which is impregnated with carbonizable thermosetting resin and cured is produced, the resin-impregnated cured sheet being an intermediate product in producing a carbonaceous material sheet.
- the apparatus for manufacturing the resin-impregnated cured sheet of the present invention should not be limited to the one for manufacturing the resin-impregnated cured sheet which is an intermediate product in producing a carbonaceous material sheet, but it can be also used for producing a printed circuit board or the like.
- the apparatus 10 for manufacturing the resin-impregnated cured sheet serves to continuously heat an uncured fiber sheet la in which uncured thermosetting resin is imparted to a long fiber-made sheet which is obtained by using short fibers to make paper so that the thermosetting resin is cured and continuously produce a long resin-impregnated cured sheet 1 b.
- the apparatus 10 for manufacturing the resin-impregnated cured sheet is equipped with conveyance means for continuously conveying a long sheet article 1 (the uncured fiber sheet 1 a , the resin-impregnated cured sheet 1 b ).
- conveyance means for continuously conveying a long sheet article 1 (the uncured fiber sheet 1 a , the resin-impregnated cured sheet 1 b ).
- the conveyance means there are arranged a drive roll 2 a at an upstream side in a conveying direction, an follower roll 2 b at a downstream side in the same conveying direction, and at least one rotation belt set 2 which is constituted by an endless belt 2 c being put on and around the drive roll 2 a and the follower roll 2 b .
- An upper face of the endless belt 2 c is a conveying face of the sheet articles 1 a and 1 b .
- the drive roll 2 a is arranged at the upstream side in the conveying direction and the follower roll 2 b is arranged at the downstream side in the conveying direction, but the drive roll 2 a and the follower roll 2 b may be inversely arranged.
- the apparatus 10 for manufacturing the resin-impregnated cured sheet is further equipped with resin curing means 3 for curing the thermosetting resin of the uncured fiber sheet 1 a and molding it into the resin-impregnated cured sheet 1 b .
- resin curing means 3 As shown in FIG. 1, as the resin curing means 3 , three pairs of upper and lower heating and pressuring rolls 3 a , which are respectively disposed on the sheet article 1 and under the endless belt 2 c , are arranged in the conveying direction of the sheet article 1 so as to nip the sheet article 1 with the endless belt 2 c .
- the heating and pressuring rolls 3 a are supported at both ends or multi-points thereof. For a heat source of the heating and pressuring rolls 3 a , electricity, heating medium or the like can be appropriately adopted.
- a diameter of each of the heating and pressuring rolls 3 a and a pitch of the three pairs of the heating and pressuring rolls 3 a are appropriately determined considering a temperature change of the endless belt before and after the heating and pressuring rolls 3 a , a pressure fluctuation which the sheet article 1 itself receives or the like. Further, the temperature and the pressure of a press of the heating and pressuring rolls are suitably set in accordance with the thermosetting resin materials. For example, when the resin-impregnated cured sheet 1 b , which is an intermediate product in producing the carbonaceous material sheet, is produced, it is preferable that the temperature range at curing the carbonizable resin is 350° C. or less, and the pressure is 1.5 ⁇ 10 4 N/m or more and 1.0 ⁇ 10 5 N/m or less at linear load.
- FIG. 2 schematically shows an apparatus 11 for manufacturing a resin-impregnated cured sheet according to a modified example of the above-mentioned preferable first embodiment according to the present invention.
- the same reference numerals are imparted to the same structures as the above-mentioned embodiment, so the detailed description is omitted.
- a pair of upper and lower rotation belt sets 2 each of which is constituted of a drive roll 2 a , a follower roll 2 b and an endless belt 2 c which are put on and around the drive roll 2 a and the follower roll 2 b , are arranged so as to sandwich the sheet article 1 a , 1 b which are being conveyed. That is, the sheet article 1 a , 1 b are conveyed while being sandwiched by the respective endless belts 2 c of the upper and lower rotation belt sets 2 .
- two heating and pressuring rolls 3 a are arranged so as to nip the sheet article 1 which is sandwiched by the upper and lower endless belts 2 c , from the outside of the endless belt 2 c.
- the sheet article 1 is sandwiched by the endless belts 2 c at not only the installation positions of the heating and pressuring rolls 3 a but also at a required length. Therefore, a thickness of the obtained resin-impregnated cured sheet 1 b can be accurately controlled so that the uniformity of the thickness in the longitudinal direction can be enhanced.
- FIG. 3 shows another preferable embodiment of the resin curing means for continuously heating and pressuring a thermosetting resin which is impregnated in an uncured fiber sheet.
- a “continuously pressuring apparatus” which is disclosed in Japanese Patent Publication No. 2-62371 and which is also manufactured and sold by Mitsubishi Rayon Engineering Co., Ltd., can be applied, as already described.
- the continuously heating and pressuring device 30 as the resin curing means nips the uncured fiber sheet 1 a and the endless belt 2 c by a fluid having high temperature and high pressure to heat and pressurize it.
- the continuously heating and pressuring device 30 as illustrated is equipped with metal box bodies 31 , each of which has front, back and lateral side wall portions 31 a and an opening face facing a rear face of each of the pair of upper and lower endless belts 2 c .
- metal box bodies 31 each of which has front, back and lateral side wall portions 31 a and an opening face facing a rear face of each of the pair of upper and lower endless belts 2 c .
- an introduction port 31 c which introduces a heating fluid having high temperature and high pressure from outside into a pressuring space between the metal box body 31 and the rear face of the endless belt 2 c
- a discharge port 31 d for discharging the heating fluid to outside.
- the metal box body 31 has a seal portion 32 at a continuous end face of an opening side of all the side wall portions 31 a .
- the seal part 32 is equipped with a sliding-member-fitting groove 32 a which is continuously formed along the end face of the opening side of the side wall portions 31 a , and a sliding member 33 which is slidably fit into the sliding-member-fitting groove 32 a .
- a suction path 32 a - 1 for fluid for damper which lowers the pressure of a space portion between the bottom face of the sliding-member-fitting groove 32 a and an fitting end face of the sliding member 33 , is formed at the side wall portions 31 a of the metal box body. Springs may be provided at the space portion in place of the suction of the fluid for damper.
- the suction path 32 a - 1 a suction source which is not shown here, supply pipes for the purpose and the like can be excluded.
- a fluid-for-seal path 33 a which communicates between the end face opposing to the endless belt 2 c and the fit face with the sliding-member-fitting groove 32 a and which opens in a slit form at the end face opposing to the endless belt 2 c .
- a fluid-for-seal introducing path 32 a - 2 for introducing the fluid for seal from outside is formed at the corresponding part of the sliding-member-fitting groove 32 a which opposes to the introducing side end portion of the fluid-for-seal path 33 a .
- the metal box body 31 is fixedly supported by a frame body of the apparatus, which is not shown here.
- the pressuring fluid having high temperature which is applied to the present apparatus, should not be limited to a specific one as far as it has such heat resistance that does not generate deterioration, change of quality or the like at a desired temperature. Therefore, it can be appropriately selected in accordance with the curing temperature of resin.
- silicon-based oil which is good in heat resistance, is used.
- Gas can be used as the pressuring fluid, but a liquid is usually advantageous because of its high heat conductance efficiency.
- the fluid having high temperature is introduced into the inner space of the metal box body 31 from the introduction port 31 c of the metal box body 31 , and discharged to outside from the discharge port 31 d .
- the high pressured fluid which is discharged from a flow pump not shown here, and is provided at the outside, is heated to a desired temperature by a heating apparatus not shown here.
- the pressured fluid having high temperature is introduced into the inside of the metal box body 31 , discharged to outside through the discharge port 31 d , and returned back to the fluid pump.
- the heating and pressuring fluid can be also sealed in the metal box body 31 instead of being circulated. In this case, it is required to provide the metal box body 31 with a heating apparatus having a control mechanism for heating temperature.
- the fluid for seal is simultaneously introduced from the above-mentioned fluid-for-seal introducing path 32 a - 2 through the fluid-for-seal path 33 a of the sliding member 33 and gushed at high pressure from the end face of the sliding member 33 opposing to the endless belt 2 c .
- the pressured fluid having high temperature introduced into the inner space of the metal box body 31 is prevented from being leaked out to the outside of the metal box body 31 , owing to the gushing of the fluid for seal.
- the heating and pressuring fluid is introduced into the inner space of the metal box body 31 , the uncured fiber sheet 1 a which is being conveyed via the endless belt 2 c is continuously and uniformly heated and pressurized simultaneously by the heating and pressuring fluid through the endless belt 2 c .
- the thermosetting resin is cured, and the resin-impregnated cured sheet 1 b having uniform thickness is continuously produced.
- the above-mentioned sliding member 33 which is slidingly fit into the sliding-member-fitting groove 32 a formed in the metal box body 31 always makes a slight gap with respect to the endless belt 2 c by combination of the damper function between the sliding-member-fitting groove 32 a and the sliding member 33 and the gushing of the fluid for seal. Therefore, since the sliding member 33 does not slide in contact with the rear face of the endless belt 2 c , the endless belt 2 c is prevented from being damaged.
- the continuously heating and pressuring device 30 is different from the heating and pressuring rolls 3 a in the embodiment shown in FIG. 1 in that the sheet article 1 is only pressurized by the fluid pressure while passing through the device 30 so that the device can continuously impart a face pressure. Therefore, any mechanical sliding action does not act on the surface of the endless belt 2 c , and moreover, it is preferable when the treatment time is long. Furthermore, if required, a plurality of pairs of devices can be arranged in the conveying direction of the sheet article or the width direction thereof. Further, the above-mentioned heating and pressuring rolls 3 a can be used in combination with the present embodiment.
- the apparatus 10 for manufacturing the resin-impregnated cured sheet according to the present invention can simultaneously heat and pressurize the long sheet article 1 while continuously conveying it, the long sheet article 1 can be uniformly heated and pressurized in the length direction thereof.
- the resin-impregnated cured sheet 1 b having uniform quality in the length direction can be produced with a high productivity, without generating any fragment, any local fragile portion or the like.
- FIG. 4 schematically shows an apparatus 20 for manufacturing a carbonaceous material sheet, which is a second embodiment of the present invention.
- the apparatus 20 for manufacturing the carbonaceous material sheet is the one that carbonizes the resin of the long resin-impregnated cured sheet 1 b and continuously produces a carbonaceous material sheet 1 c.
- the apparatus 20 for manufacturing the carbonaceous material sheet employs a horizontal baking furnace which conveys a sheet article (the long resin-impregnated cured sheet 1 b , the carbonaceous material sheet 1 c ) in a horizontal direction and carbonizes it.
- a plurality of guide-roll-supporting stands 5 a are disposed with a constant interval on a bottom wall 4 a of a carbonization treatment chamber 4 in the horizontal baking furnace, and guide rolls 5 b are supported on the guide-roll-supporting stands 5 a at both ends or a plurality of points.
- the sheet article 1 b , 1 c is conveyed in a horizontal direction on an upper face of a plurality of the guide rolls 5 b .
- the reference numeral 4 b in the Figure shows a ceiling plate of the carbonization treatment chamber.
- the guide roll 5 b has a simple structure in which both ends of a round bar made of graphite or a round pipe are only supported by the supporting stands 5 a made of graphite.
- the guide roll 5 b can be easily rotated because of the self lubricity of the graphite itself.
- a pitch of the plurality of the guide rolls 5 b can be suitably determined in accordance with a weight and a tensile force of the sheet article 1 b , 1 c at the time of the carbonization treatment such that the sheet article 1 b , 1 c do not contact with the bottom wall 4 a of the carbonization treatment chamber 4 and do not rub it.
- the temperature in the carbonization treatment chamber 4 is set to be at 100° C. or more when the carbonaceous material sheet 1 c is produced.
- the resin-impregnated cured sheet 1 b and the carbonaceous material sheet 1 c can run steadily at a predetermined height over the full length of the treatment chamber 4 .
- the resin-impregnated cured sheet 1 b and the carbonaceous material sheet 1 c are prevented from contacting with the bottom wall 4 a of the carbonization treatment chamber 4 by its own weight to cause any inductive factors for a crack or a fragment. Therefore, the carbonaceous material sheet 1 c with good quality can be produced.
- FIG. 5 schematically shows one example of a preferable winding device 13 according to the present invention.
- a double-axis-turret winder 6 which is equipped with a winding bobbin 6 a under winding up and stand-bye bobbins 6 b.
- the winding device 13 is further equipped with a trimming cutter 7 for trimming both ends in the width direction of the long carbonaceous material sheet 1 c on the upstream side of the turret winder 6 . Further, the device is equipped with a press roll 8 in the vicinity of the winding bobbin 6 a for constantly keeping a winding face pressure of the carbonaceous material sheet 1 c with respect to the winding bobbin 6 a .
- the press roll 8 may be disposed so as to contact with the winding face, or alternatively it may be disposed without contacting with the winding face.
- the carbonaceous material sheet 1 c obtained after being finished with the carbonization treatment is cut at the both ends in the width direction thereof by the trimming cutter 7 so that the end faces are made even, and then is wound up on the winding bobbin 6 a in a state that the winding face pressure is kept constant by the press roll 8 .
- Sheet article made of carbon short fibers [0096] Sheet article made of carbon short fibers:
- Binder PVA short fiber, carbon fiber ratio containing 15% by weight
- the apparatus for manufacturing a resin-impregnated cured sheet as shown in FIG. 2 was employed, in which two upper and lower rotation belt sets 2 were set so as to sandwich the conveyance path of a sheet article and in which 6 pairs of heating and pressuring rolls 3 a were arranged in the conveyance direction with a constant interval. All of the heating and pressuring rolls 3 a were set to have a diameter of 160 mm, and the pitch of the pair of the heating and pressuring rolls 3 a was set to be 220 mm in the conveyance direction of the sheet article.
- the temperature of the heating and pressuring rolls 3 a was set at 300° C.
- the nip pressure condition was 5 ⁇ 10 4 N/m
- the residential time from the first pair of the heating and pressuring rolls to the sixth pair of the heating and pressuring rolls was set to be 2 minutes
- the curing treatment was continuously carried out at a treatment speed of 0.66 m/min.
- the apparatus for manufacturing a carbonaceous material sheet as shown in FIG. 4 was used, in which a horizontal baking furnace having the guide rolls 5 b for the resin-impregnated cured sheet inside the carbonization treatment chamber 4 is adopted, so that carbonization treatment was carried out.
- the guide rolls 5 b were set to have a diameter of 12 mm, and the pitch of the guide rolls was set to be 30 mm in the conveyance direction of the sheet article.
- the maximum temperature of the inside of the treatment chamber 4 was set to at 2000° C., and the residential time of the treatment chamber 4 was set to be 10 minutes.
- the obtained carbonaceous material sheet was wound up in a roll form by the winding device shown in FIG. 5.
- the obtained carbonaceous material sheet had no problem of a crack, a fragment or the like, and was a high quality sheet excellent in its handling property with a high bending strength. Further, a long carbonaceous material sheet can be continuously produced, so that productivity is also high.
- An apparatus for manufacturing a resin-impregnated cured sheet which was equipped with a preheating section, heating and pressuring rolls, and two sets of endless belts, was used. Hot wind of 200° C. was flown into the preheating section, such that the belt temperature was set at 135° C. Further, the press was carried out by the successive first heating and pressuring roll at 300° C. and under a line pressure of 6.6 ⁇ 10 4 N/m, so that the curing treatment was continuously carried out.
- the obtained carbonaceous material sheet had no problem of a crack, a fragment or the like, and was excellent in its handling property with a bending strength of 82 Mpa, so that it had a good quality. Further, it was verified that productivity is also high since a long carbonaceous material sheet can be continuously produced,.
- the curing treatment was continuously carried out in the same condition as in Example 1 in the apparatus for manufacturing the resin-impregnated cured sheet of Example 1, except that the heating and pressuring device shown in FIG. 3 was used as the resin curing means in place of the heating and pressuring rolls, the nip pressure was set to be 5 ⁇ 10 4 N/m 2 , and the residential time in the device was set to be 2 minutes.
- the obtained carbonaceous material sheet had smooth surface and uniform thickness, had no crack, fragment or the like, and was excellent in its handling property with a bending strength of 85 Mpa. Thus, it has a good quality. Further, since a long carbonaceous material sheet can be continuously produced, productivity is also extremely high.
- a long carbonaceous material sheet was produced in a condition similar to Example 1, except that a hot press was adopted as the apparatus for manufacturing the resin-impregnated cured sheet, and the curing treatment was carried out on the long uncured fiber sheet by semi-batch-type.
- the production was carried out by changing various conditions concerning the treatment temperature, pressure, and treatment time by the hot press.
- the carbonaceous material sheet as a final product produced by the carbonization treatment was very fragile at a press boundary line, its quality was lowered, the flexibility was deficient, and the handling property was poor.
- a long carbonaceous material sheet was produced in a condition similar to Example 1, except that the carbonization was carried out using a horizontal baking furnace in which no guide rolls 5 b were provided.
- the obtained carbonaceous material sheet obtained had naps, which appeared to be generated by being rubbed with the bottom wall of the baking furnace, on the surface thereof. Further, fragments occur at the end portions of the carbonaceous material sheet in the width direction thereof orthogonal to the conveyance direction, so that its quality and product yield were low.
- the apparatus for manufacturing a resin-impregnated cured sheet of the present invention since the apparatus for manufacturing a resin-impregnated cured sheet of the present invention is applied, the heating and pressuring can be continuously and simultaneously carried out with respect to a long uncured fiber sheet which is continuously conveyed. Therefore, the productivity and the handling property of the carbonaceous material sheet can be remarkably improved as compared with a conventional batch-type curing process. Further, it is possible to produce a carbonaceous material sheet having a good quality, without generating any crack or fragment in the carbonaceous material sheet, by using the apparatus for manufacturing a carbonaceous material sheet of the present invention. Since such a long carbonaceous material sheet can be continuously produced, the productivity can be improved, and the long carbonaceous material sheet with a high quality can be supplied in a rolled form.
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Priority Applications (3)
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US10/872,519 US20040227265A1 (en) | 2000-07-14 | 2004-06-22 | Apparatus and method for manufacturing resin-impregnated cured sheet, and apparatus and method for manufacturing carbonaceous material sheet |
US11/701,405 US7959750B2 (en) | 2000-07-14 | 2007-02-02 | Apparatus and method for manufacturing resin-impregnated cured sheet, and apparatus and method for manufacturing carbonaceous material sheet |
US12/987,777 US20110226431A1 (en) | 2000-07-14 | 2011-01-10 | Apparatus and Method for Manufacturing Resin-Impregnated Cured Sheet, and Apparatus and Method for Manufacturing Carbonaceous Material Sheet |
Applications Claiming Priority (2)
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JPP2000-214441 | 2000-07-14 | ||
JP2000214441 | 2000-07-14 |
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US10/872,519 Division US20040227265A1 (en) | 2000-07-14 | 2004-06-22 | Apparatus and method for manufacturing resin-impregnated cured sheet, and apparatus and method for manufacturing carbonaceous material sheet |
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US20020029842A1 true US20020029842A1 (en) | 2002-03-14 |
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US09/903,680 Abandoned US20020029842A1 (en) | 2000-07-14 | 2001-07-13 | Apparatus and method for manufacturing resin-impreganated cured sheet, and apparatus and method for manufacturing carbonaceous material sheet |
US10/872,519 Abandoned US20040227265A1 (en) | 2000-07-14 | 2004-06-22 | Apparatus and method for manufacturing resin-impregnated cured sheet, and apparatus and method for manufacturing carbonaceous material sheet |
US11/701,405 Expired - Fee Related US7959750B2 (en) | 2000-07-14 | 2007-02-02 | Apparatus and method for manufacturing resin-impregnated cured sheet, and apparatus and method for manufacturing carbonaceous material sheet |
US12/987,777 Abandoned US20110226431A1 (en) | 2000-07-14 | 2011-01-10 | Apparatus and Method for Manufacturing Resin-Impregnated Cured Sheet, and Apparatus and Method for Manufacturing Carbonaceous Material Sheet |
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US10/872,519 Abandoned US20040227265A1 (en) | 2000-07-14 | 2004-06-22 | Apparatus and method for manufacturing resin-impregnated cured sheet, and apparatus and method for manufacturing carbonaceous material sheet |
US11/701,405 Expired - Fee Related US7959750B2 (en) | 2000-07-14 | 2007-02-02 | Apparatus and method for manufacturing resin-impregnated cured sheet, and apparatus and method for manufacturing carbonaceous material sheet |
US12/987,777 Abandoned US20110226431A1 (en) | 2000-07-14 | 2011-01-10 | Apparatus and Method for Manufacturing Resin-Impregnated Cured Sheet, and Apparatus and Method for Manufacturing Carbonaceous Material Sheet |
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US (4) | US20020029842A1 (ja) |
EP (1) | EP1302293B1 (ja) |
JP (1) | JP3699447B2 (ja) |
KR (1) | KR100544921B1 (ja) |
CA (1) | CA2415757C (ja) |
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- 2001-07-12 DE DE60131408T patent/DE60131408T2/de not_active Expired - Lifetime
- 2001-07-12 EP EP01947985A patent/EP1302293B1/en not_active Expired - Lifetime
- 2001-07-12 JP JP2002511953A patent/JP3699447B2/ja not_active Expired - Fee Related
- 2001-07-12 TW TW090117069A patent/TW540177B/zh not_active IP Right Cessation
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US20030194557A1 (en) * | 2002-04-12 | 2003-10-16 | Peter Wilde | Carbon fiber electrode substrate for electrochemical cells |
US7144476B2 (en) * | 2002-04-12 | 2006-12-05 | Sgl Carbon Ag | Carbon fiber electrode substrate for electrochemical cells |
US8574758B2 (en) | 2009-07-08 | 2013-11-05 | Mitsubishi Rayon Co., Ltd. | Porous electrode substrate and method for producing the same |
US9343751B2 (en) | 2009-11-24 | 2016-05-17 | Mitsubishi Rayon Co., Ltd. | Porous electrode substrate, method for producing the same, precursor sheet, membrane electrode assembly, and polymer electrolyte fuel cell |
US9825304B2 (en) | 2011-01-27 | 2017-11-21 | Mitsubishi Chemical Corporation | Porous electrode substrate, method for manufacturing same, precursor sheet, membrane electrode assembly, and polymer electrolyte fuel cell |
US9705137B2 (en) | 2011-01-27 | 2017-07-11 | Mitsubishi Rayon Co., Ltd. | Porous electrode substrate, method for manufacturing same, precursor sheet, membrane electrode assembly, and polymer electrolyte fuel cell |
US9716278B2 (en) | 2012-03-30 | 2017-07-25 | Mitsubishi Chemical Corporation | Porous electrode base material, method for manufacturing same, and precursor sheet |
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CN109137266A (zh) * | 2017-06-27 | 2019-01-04 | 赖芬豪泽机械工厂有限及两合有限公司 | 具有至少一个颗粒和/或纤维产生装置和至少一个连续带的设备 |
US11447894B2 (en) * | 2017-06-27 | 2022-09-20 | Reifenhaeuser Gmbh & Co. Kg Maschinenfabrik | Apparatus with particle- or fiber-making device and an endless belt |
US20210023799A1 (en) * | 2018-03-29 | 2021-01-28 | Mclaren Automotive Limited | Diaphragm forming |
US11826969B2 (en) * | 2018-03-29 | 2023-11-28 | Mclaren Automotive Limited | Diaphragm forming |
US11465374B2 (en) * | 2018-09-03 | 2022-10-11 | Subaru Corporation | Resin impregnation measurement system |
Also Published As
Publication number | Publication date |
---|---|
EP1302293A4 (en) | 2005-03-02 |
EP1302293B1 (en) | 2007-11-14 |
US20070163721A1 (en) | 2007-07-19 |
JP3699447B2 (ja) | 2005-09-28 |
DE60131408T2 (de) | 2008-09-18 |
KR20030019476A (ko) | 2003-03-06 |
US7959750B2 (en) | 2011-06-14 |
KR100544921B1 (ko) | 2006-01-24 |
CA2415757A1 (en) | 2003-01-13 |
DE60131408D1 (de) | 2007-12-27 |
TW540177B (en) | 2003-07-01 |
EP1302293A1 (en) | 2003-04-16 |
CA2415757C (en) | 2008-03-18 |
US20110226431A1 (en) | 2011-09-22 |
WO2002006032A1 (fr) | 2002-01-24 |
US20040227265A1 (en) | 2004-11-18 |
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