US20060035548A1 - Prepreg, intermediate material for forming frp, and method for production thereof and method for production of fiber-reinforced composite material - Google Patents

Prepreg, intermediate material for forming frp, and method for production thereof and method for production of fiber-reinforced composite material Download PDF

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Publication number
US20060035548A1
US20060035548A1 US10/521,433 US52143305A US2006035548A1 US 20060035548 A1 US20060035548 A1 US 20060035548A1 US 52143305 A US52143305 A US 52143305A US 2006035548 A1 US2006035548 A1 US 2006035548A1
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US
United States
Prior art keywords
prepreg
resin
reinforcing fiber
sheet
matrix resin
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
Application number
US10/521,433
Other languages
English (en)
Inventor
Kazuya Goto
Kazuki Koga
Tadayoshi Saitou
Akihiro Ito
Tsuneo Takano
Kouki Wakabayashi
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mitsubishi Rayon Co Ltd
Original Assignee
Mitsubishi Rayon Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2002210123A external-priority patent/JP4177041B2/ja
Priority claimed from JP2002234861A external-priority patent/JP4116361B2/ja
Priority claimed from JP2002271850A external-priority patent/JP2004106347A/ja
Priority claimed from JP2002353759A external-priority patent/JP2004182923A/ja
Priority claimed from JP2003063166A external-priority patent/JP2004268440A/ja
Application filed by Mitsubishi Rayon Co Ltd filed Critical Mitsubishi Rayon Co Ltd
Assigned to MITSUBISHI RAYON CO., LTD. reassignment MITSUBISHI RAYON CO., LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: GOTO, KAZUYA, ITO, AKIHIRO, KOGA, KAZUKI, SAITOU, TADAYOSHI, TAKANO, TSUNEO, WAKABAYASHI, KOUKI
Publication of US20060035548A1 publication Critical patent/US20060035548A1/en
Priority to US12/244,676 priority Critical patent/US20090123717A1/en
Priority to US13/037,696 priority patent/US20110151206A1/en
Priority to US13/446,722 priority patent/US8679991B2/en
Priority to US14/072,139 priority patent/US20140057514A1/en
Abandoned legal-status Critical Current

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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/55—Epoxy resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B15/00—Pretreatment of the material to be shaped, not covered by groups B29B7/00 - B29B13/00
    • B29B15/08—Pretreatment of the material to be shaped, not covered by groups B29B7/00 - B29B13/00 of reinforcements or fillers
    • B29B15/10—Coating or impregnating independently of the moulding or shaping step
    • B29B15/12—Coating or impregnating independently of the moulding or shaping step of reinforcements of indefinite length
    • B29B15/122—Coating or impregnating independently of the moulding or shaping step of reinforcements of indefinite length with a matrix in liquid form, e.g. as melt, solution or latex
    • 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
    • B29C70/06—Fibrous reinforcements only
    • B29C70/10—Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres
    • B29C70/16—Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres using fibres of substantial or continuous length
    • B29C70/22—Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres using fibres of substantial or continuous length oriented in at least two directions forming a two dimensional structure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B32B5/022—Non-woven fabric
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B32B5/26—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
    • C08J5/243—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using carbon fibres
    • 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
    • B29C70/06—Fibrous reinforcements only
    • B29C70/08—Fibrous reinforcements only comprising combinations of different forms of fibrous reinforcements incorporated in matrix material, forming one or more layers, and with or without non-reinforced layers
    • B29C70/081—Combinations of fibres of continuous or substantial length and short fibres
    • 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
    • B29C70/06—Fibrous reinforcements only
    • B29C70/08—Fibrous reinforcements only comprising combinations of different forms of fibrous reinforcements incorporated in matrix material, forming one or more layers, and with or without non-reinforced layers
    • B29C70/086—Fibrous reinforcements only comprising combinations of different forms of fibrous reinforcements incorporated in matrix material, forming one or more layers, and with or without non-reinforced layers and with one or more layers of pure plastics material, e.g. foam layers
    • 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
    • B29C70/30—Shaping by lay-up, i.e. applying fibres, tape or broadsheet on a mould, former or core; Shaping by spray-up, i.e. spraying of fibres on a mould, former or core
    • B29C70/34—Shaping by lay-up, i.e. applying fibres, tape or broadsheet on a mould, former or core; Shaping by spray-up, i.e. spraying of fibres on a mould, former or core and shaping or impregnating by compression, i.e. combined with compressing after the lay-up operation
    • B29C70/342—Shaping by lay-up, i.e. applying fibres, tape or broadsheet on a mould, former or core; Shaping by spray-up, i.e. spraying of fibres on a mould, former or core and shaping or impregnating by compression, i.e. combined with compressing after the lay-up operation using isostatic pressure
    • 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
    • B29C70/46—Shaping or impregnating by compression not applied for producing articles of definite length, i.e. discrete articles using matched moulds, e.g. for deforming sheet moulding compounds [SMC] or prepregs
    • B29C70/465—Shaping or impregnating by compression not applied for producing articles of definite length, i.e. discrete articles using matched moulds, e.g. for deforming sheet moulding compounds [SMC] or prepregs and impregnating by melting a solid material, e.g. sheets, powders of fibres
    • 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
    • B29C70/54—Component parts, details or accessories; Auxiliary operations, e.g. feeding or storage of prepregs or SMC after impregnation or during ageing
    • B29C70/546—Measures for feeding or distributing the matrix material in the reinforcing structure
    • 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
    • B29K2063/00—Use of EP, i.e. epoxy resins or derivatives thereof, as moulding material
    • 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
    • B29K2101/00—Use of unspecified macromolecular compounds as moulding material
    • B29K2101/10—Thermosetting resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/02—Composition of the impregnated, bonded or embedded layer
    • B32B2260/021—Fibrous or filamentary layer
    • B32B2260/023—Two or more layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
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    • B32B2262/106—Carbon fibres, e.g. graphite fibres
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    • B32B2305/00—Condition, form or state of the layers or laminate
    • B32B2305/07—Parts immersed or impregnated in a matrix
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    • Y10T156/10—Methods of surface bonding and/or assembly therefor
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    • Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
    • Y10T442/2926—Coated or impregnated inorganic fiber fabric
    • 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
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
    • Y10T442/2926—Coated or impregnated inorganic fiber fabric
    • Y10T442/2951—Coating or impregnation contains epoxy polymer or copolymer or polyether
    • 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
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
    • Y10T442/2926—Coated or impregnated inorganic fiber fabric
    • Y10T442/2984—Coated or impregnated carbon or carbonaceous fiber fabric
    • 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
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
    • Y10T442/2926—Coated or impregnated inorganic fiber fabric
    • Y10T442/2992—Coated or impregnated glass fiber fabric
    • 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
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/30—Woven fabric [i.e., woven strand or strip material]
    • Y10T442/3854—Woven fabric with a preformed polymeric film or sheet

Definitions

  • the present invention relates to a prepreg that functions as an intermediate material for FRP molding.
  • Fiber-reinforced composite materials are lightweight, while offering good strength and high rigidity, and are consequently widely used in a variety of applications from sports and leisure through to industrial applications such as vehicles and aircraft.
  • CFRP carbon fiber reinforced composite materials
  • CFRPs used for structural members within train bodies and aircraft frames are typically produced by autoclave molding, using an intermediate material known as a prepreg.
  • the reason for this preference is that by conducting the molding under high pressure using an autoclave, not only can the occurrence of voids within the molded product be reduced, enabling the strength of the molded product to meet expectations, but the occurrence of surface pinholes can also be suppressed, enabling the production of a molded product with a favorable external appearance.
  • autoclave facilities are extremely expensive, which not only acts as a large barrier to new entrants, but also means that once autoclave facilities are purchased, the size of the molded products is restricted by the size of the autoclave, meaning the production of larger products is effectively impossible.
  • Oven molding does not require the application of pressure, meaning the molding can be conducted without the need for a proper pressure-resistant vessel such as an autoclave, and molding can be conducted simply with a furnace for raising the temperature. Molding can also be conducted with a simple device comprising an adiabatic board and a hot air heater. However, because these processes do not involve the application of pressure, residual voids tend to remain within the molded product, the strength of the molded product is inferior to that of a molded product produced in an autoclave, and pinhole formation is also a problem.
  • WO 00/27632 discloses technology relating to materials comprising a resin layer and a reinforcing fiber layer, which display minimal void generation, and enable the production of molded products with extremely clean surfaces, even when used with oven molding.
  • this technology almost all of the resin is impregnated during molding, and depending on the molding conditions, portions of the resin that display unsatisfactory impregnation can occur, leading to the occurrence of internal voids and surface pinholes.
  • workability problems such as difficulty in bonding the product to the molding die can also be a concern.
  • An object of the present invention is to provide an intermediate material, which retains the level of workability associated with conventional prepregs, while enabling the production of a FRP with no internal voids or surface pinholes, but with excellent external appearance, using molding at only vacuum pressure, without the use of an autoclave.
  • a first aspect of the present invention is a prepreg comprising reinforcing fiber, a sheet-like reinforcing fiber substrate containing reinforcing fiber, and a matrix resin, wherein the matrix resin is impregnated into the sheet-like reinforcing fiber substrate and also covers one surface of the sheet-like reinforcing fiber substrate, and the matrix resin impregnation ratio is within a range of 35% to 95%.
  • a second aspect of the present invention is a prepreg comprising a matrix resin, and a sheet-like reinforcing fiber substrate, wherein the prepreg comprises reinforcing fiber, a sheet-like reinforcing fiber substrate containing reinforcing fiber, and a matrix resin, wherein the matrix resin exists on both surfaces of the sheet-like reinforcing fiber substrate, and the portion inside the sheet-like reinforcing fiber substrate into which the matrix resin has not been impregnated is continuous.
  • a third aspect of the present invention is a prepreg comprising a sheet-like reinforcing fiber substrate formed from a reinforcing fiber woven fabric, and a matrix resin, wherein at least one surface displays a sea-and-island-type pattern comprising resin-impregnated portions (island portions) where the matrix resin is present at the surface and fiber portions (sea portions) where the matrix resin is not present at the surface, the surface coverage ratio of the matrix resin on surfaces with the sea-and-island-type pattern is within a range of 3% to 80%, and the weave intersection coverage ratio for the island portions, as represented by a formula (1) below, is at least 40%.
  • Island portions weave intersection coverage ratio (%) ( T/Y ) ⁇ 100 (1) (wherein, T represents the number of island portions that cover weave intersections, and Y represents the total number of weave intersections of the reinforcing fiber fabric on the surface with the sea-and-island-type pattern).
  • a fourth aspect of the present invention is an intermediate material for FRP molding comprising a prepreg containing reinforcing fiber and a matrix resin, and a substrate containing essentially no impregnated thermosetting resin composition, which is provided on at least one side of the prepreg, wherein the ratio (B)/(A) between the thickness (A) of the prepreg, and the thickness (B) of the substrate is within a range of 0.1 to 2.5.
  • the level of workability associated with conventional prepregs can be retained, while FRP with no internal voids or surface pinholes, but with excellent external appearance can be produced using molding at only vacuum pressure, without the use of an autoclave.
  • FIG. 1 is a schematic illustration of a prepreg that uses a sheet with the fibers aligned unidirectionally as the sheet-like reinforcing fiber substrate, viewed in a cross section cut perpendicularly to the direction of the fibers.
  • FIG. 2 is a schematic illustration of a prepreg that uses a plain weave fabric as the sheet-like reinforcing fiber substrate, viewed in a cross section cut perpendicularly to the warp.
  • FIG. 3 is a schematic illustration showing one example of a prepreg according to a second embodiment of the present invention.
  • FIG. 4 is a schematic illustration of a prepreg of a comparative example, wherein the matrix resin has been supplied from one surface.
  • FIG. 5 is a schematic illustration of a prepreg of another comparative example, wherein although the matrix resin has been supplied from both sides, portions that have not been impregnated with the matrix resin do not exist in a continuous state.
  • FIG. 6 is a schematic illustration showing the surface of a prepreg according to a third embodiment of the present invention.
  • FIG. 7 is a schematic illustration of a comparative example, showing the surface of a prepreg wherein a island portions weave intersection coverage ratio is low.
  • FIG. 8 is an example of a graph showing the results of measuring the dynamic modulus of elasticity of a matrix resin, as well as a method of determining the value of Tg from such a graph.
  • a first embodiment of the present invention is a prepreg comprising a sheet-like reinforcing fiber substrate formed from reinforcing fiber that has been impregnated with a matrix resin, wherein only one surface of the sheet-like reinforcing fiber substrate is covered with the matrix resin, and the resin impregnation ratio is within a range of 35% to 95%.
  • suitable fibers include carbon fiber, glass fiber, aramid fiber, high-strength polyethylene fiber, boron fiber, and steel fiber. Carbon fiber is preferred as it results in more favorable properties for the generated FRP, particularly in terms of reduced weight and favorable mechanical properties such as high strength and high rigidity.
  • sheet-like reinforcing fiber substrate used in the prepreg of this first embodiment
  • suitable examples include plain weave fabric, twill fabric, satin weave fabric, stitched sheets such as non-crimped fabric (NCF) wherein fiber bundles are layered, either unidirectionally or at various angles, and then stitched to prevent the layers coming apart, as well as non-woven fabric, mats, and unidirectional materials in which a bundle of reinforcing fibers is aligned unidirectionally.
  • NCF non-crimped fabric
  • woven fabrics and stitched sheets which offer superior levels of handling, are preferred.
  • thermosetting resins include epoxy resins, phenol resins, vinyl ester resins, unsaturated polyester resins, bismaleimide resins, BT resins, cyanate ester resins, and benzoxazine resins, although in terms of handling properties and the properties of the resulting cured product, epoxy resins, bismaleimide resins, BT resins, and cyanate ester resins are preferred, and of these, epoxy resins are particularly desirable.
  • a prepreg of the first embodiment is completely covered with resin on one surface, and the resin impregnation ratio must fall within a range of 35% to 95%.
  • the deaeratingdeaerating circuit refers to the portions within the prepreg that have not been impregnated with resin, and these portions act as air pathways. However, if this deaeratingdeaerating circuit is too large, then the deaeratingdeaerating circuit can remain even after molding, and can cause internal voids and surface pinholes.
  • FIG. 1 is a schematic illustration of a prepreg 10 with a reinforcing fiber substrate in which the fibers are aligned unidirectionally, viewed in a cross section cut perpendicularly to the direction of the fibers.
  • the matrix resin is supplied from underneath in FIG. 1 , and the matrix resin 1 impregnates upwards into the sheet-like reinforcing fiber substrate.
  • the portion into which the matrix resin 1 has impregnated is shown by the diagonal shading.
  • the matrix resin is supplied from underneath, but in the present invention, the matrix resin can also be supplied from above, and then allowed to impregnate down into the substrate.
  • the cross section is inspected across at least 80% of the width of the sheet-like reinforcing fiber substrate, and the highest point to which the resin has penetrated is determined (or in those cases where the resin is supplied from above, the lowest point of penetration is determined).
  • the average thickness t 1 , of the sheet-like reinforcing fiber substrate can be determined in the manner described below.
  • the length of the line joining the bottom edge 10 a and the top edge 10 b in a cross section through the prepreg 10 (this line is deemed the thickness line) is taken as the thickness of the sheet-like substrate.
  • This thickness is measured at 10 random points, and the average of the thickness values is calculated and used as the average thickness t 1 of the sheet-like reinforcing fiber substrate.
  • the outer contours of the substrate essentially coincide with the thickness line.
  • the substrate is best viewed in a cross section perpendicular to the direction of the reinforcing fibers, and consequently in the case of a multiaxial stitched sheet, wherein unlike the sheet-like reinforcing fiber substrate of the FIG. 1 in which the fibers are aligned unidirectionally, the fibers are layered in all different directions, a cross sectional photograph can be taken through a cross section at any suitable angle.
  • the cut can be performed with a sharp blade such as a razor blade, and is made with a single cut.
  • the photograph is preferably taken at a magnification of 50 to 100 ⁇ .
  • FIG. 2 shows a method of determining the resin impregnation ratio in those cases where a plain weave fabric is used as the sheet-like reinforcing fiber substrate.
  • the matrix resin 1 moves along the open portions 21 in the weave, meaning the resin impregnation ratio is best observed at a cross-section through those open portions 21 .
  • the highest point B to which the matrix resin 1 has penetrated is determined from the cross section of FIG. 2 .
  • the resin impregnation ratio can be determined by a formula (4 ) shown below.
  • the average thickness t 2 is measured using a similar method to that described for the case of a reinforcing fiber substrate in which the fibers are aligned unidirectionally, although in the case of a woven fabric, the outer contours of the sheet-like reinforcing fiber substrate do not coincide with the thickness line (see FIG. 2 ).
  • Resin impregnation ratio b/t 2 ⁇ 100 (%) (4)
  • the resin impregnation ratio in a prepreg according to the first embodiment is preferably within a range of 35% to 95%. If the resin impregnation ratio is less than 35%, then the resin is unable to completely fill the non-impregnated portions during molding, meaning internal voids and surface pinholes remain following molding. If the resin impregnation ratio is at least 40%, then internal voids and surface pinholes tend not to remain following molding, and ratios of at least 50% are particularly preferred. In contrast, if the resin impregnation ratio exceeds 95%, then the formation of a deaerating circuit can no longer be ensured, which can also cause residual internal voids and surface pinholes. If the resin impregnation ratio is no more than 90%, then it is easier to ensure an adequate deaerating circuit, and resin impregnation ratios of no more than 80% are particularly preferred.
  • a prepreg of the present invention must have at least one surface completely covered with resin.
  • the prepreg is used either by sticking to a molding die, or by generating a multi-ply laminate of the prepreg, and consequently the prepreg requires a suitable level of tackiness.
  • a prepreg of the present invention has at least one surface completely covered with resin, and consequently has a suitable level of tackiness and superior handling properties.
  • the weight of the sheet-like reinforcing fiber substrate in a prepreg according to the first embodiment is preferably at least 400 g/m 2 .
  • a prepreg of the first embodiment contains a deaerating circuit, but during molding the resin penetrates to all corners of the sheet-like reinforcing fiber substrate, enabling the formation of a completely impregnated molded product with no internal voids or surface pinholes, and consequently the prepreg is suited to sheet-like reinforcing fiber substrate with a certain level of thickness.
  • sheet-like reinforcing fiber substrates with a weight of at least 400 g/m 2 are preferred. Weights of at least 600 g/m 2 are even more desirable, and weights of at least 700 g/m 2 are particularly preferred.
  • the thickness of the sheet-like reinforcing fiber substrate in a prepreg of the first embodiment is preferably at least 200 ⁇ m.
  • a prepreg of the first embodiment can yield a favorable molded product with no internal voids at atmospheric. pressure, even if the fluidity of the matrix resin is poor. Accordingly, a favorable molded product can be achieved even if the sheet-like reinforcing fiber substrate is considerably thick, and in actual fact, the effects of the present invention are manifested most markedly with thicker substrates.
  • the effects are particularly marked for thick materials where the thickness of the sheet-like reinforcing fiber substrate is at least 300 ⁇ m.
  • the thickness is determined by dividing the mass per unit of surface area of the sheet-like reinforcing fiber substrate by the density of the reinforcing fibers.
  • the thermosetting resin composition preferably comprises a thermoplastic resin that is not dissolved within the thermosetting resin composition.
  • This thermoplastic resin is preferably in the form of short fibers, and the length of those short fibers is preferably within a range of 1 to 50 mm. Furthermore, the size of the fibers is preferably no more than 300 tex.
  • the short fibers of thermoplastic resin within the thermosetting resin composition are filtered by the reinforcing fibers that make up the sheet-like reinforcing fiber substrate, and end up positioned at the surface of each of the laminated sheet-like reinforcing fiber substrates, namely, positioned between the layers of the laminate. This improves the interlayer peeling resistance markedly, providing a superior interlayer reinforcement effect.
  • the thermoplastic resin preferably exist as fibers. If other shapes such as fine particles are used instead of the aforementioned short fibers, then the thermoplastic resin is not efficiently filtered. by the sheet-like reinforcing fiber substrate during the molding process, and migrates into the interior of the sheet-like reinforcing fiber substrate together with the thermosetting resin during the impregnation process, meaning efficient interlayer reinforcement can not be achieved.
  • the thermoplastic resin is preferably in the form of short fibers.
  • the length of these fibers is preferably within a range of 1 to 50 mm. If the length of the short fibers is less than 1 mm, then the fibers penetrate into the interior of the sheet-like reinforcing fiber substrate, in a similar manner to fine particles, making it difficult to achieve an efficient improvement in the interlayer peeling resistance. Considering the fact that a certain size is necessary, fibers with a length of at least 3 mm are particularly preferred.
  • Fiber lengths of no more than 30 mm are particularly preferred.
  • the size of those fibers is preferably no more than 300 tex.
  • the short fibers of the thermoplastic resin may exist either as filaments formed from single strands of fiber, or as multifilaments comprising a plurality of individual fiber strands. If the size of the fibers exceed 300 tex, then the thickness of the layer formed by the accumulated short fibers between the substrate layers becomes overly thick, and there is a danger of the short fibers interfering with the reinforcing fibers of the sheet-like reinforcing fiber substrates, causing bending of the reinforcing fibers, and an undesirable deterioration in the mechanical strength of the molded composite material. Fiber sizes of no more than 100 tex are even more desirable, and sizes of no more than 50 tex are particularly preferred. There are no particular restrictions at the fine end of the size scale, and satisfactory effects can be achieved for sizes of at least 1 tex.
  • thermoplastic resins examples include polyaramid, polyester, polyacetal, polycarbonate, polyphenylene oxide, polyphenylene sulfide, polyallylate, polyimide, polyetherimide, polysulfone, polyamide, polyamide-imide, and polyetheretherketone.
  • elastomers can also be used favorably instead of the thermoplastic resin.
  • suitable elastomers include synthetic rubbers such as butyl rubber, isoprene rubber, nitrile rubber, and silicon rubber, as well as natural rubbers such as latex.
  • the quantity of the thermoplastic resin within the thermosetting resin composition is preferably within a range of 1 to 100 parts by mass per 100 parts by mass of the thermosetting resin composition. If the quantity of the thermoplastic resin is less than 1 part by mass, then the effect of the invention in improving the FRP interlayer peeling resistance weakens undesirably. Quantities of the thermoplastic resin of at least 5 parts by mass are even more desirable, and quantities of at least 10 parts by mass are particularly preferred.
  • the proportion of the thermoplastic resin becomes overly high, which can cause a deterioration in the impregnation of the matrix resin into the sheet-like reinforcing fiber substrate, and the quantity of the matrix resin relative to the sheet-like reinforcing fiber substrate can become too high, causing an undesirable deterioration in the FRP mechanical strength.
  • a production process in which a resin is supplied, using a hot melt method, to one surface of a sheet-like reinforcing fiber substrate comprising reinforcing fibers, and the structure is then heating and pressed, causing the resin to migrate through to a position close to the opposite surface of the substrate is preferred.
  • the heating temperature and the pressure applied during the pressing step are adjusted to control the degree of migration of the resin and the manner of the migration, thus adjusting the resin impregnation ratio to a value within a range of 35% to 95%.
  • the hot melt method is a prepreg production process in which no solvent is used, and the viscosity of the resin is lowered by raising the temperature of the resin, thereby causing the resin to impregnate the substrate, and amongst the possible forms of the hot melt method that can be used for producing a prepreg, a double film process, in which the resin is supplied from both the upper and lower surfaces of the sheet-like reinforcing fiber substrate is usually preferred in terms of the impregnation results.
  • the double film process is not suitable as the process for producing a prepreg according to the first embodiment.
  • a single film process in which the resin is supplied from one surface of the sheet-like reinforcing fiber substrate is preferred.
  • the matrix resin in a prepreg of the first embodiment is a thermosetting resin composition, and in those cases where the composition also comprises a thermoplastic resin that has not been dissolved in the thermosetting resin composition, the thermoplastic resin is preferably blended into the composition during the mixing and preparation of the thermosetting resin composition, and the resulting composition is then converted to a film form, and impregnated into the sheet-like reinforcing fiber substrate.
  • a second embodiment of the present invention is a prepreg comprising a sheet-like reinforcing fiber substrate and a matrix resin, wherein the matrix resin exists on both surfaces of the sheet-like reinforcing fiber substrate, and the portion inside the sheet-like reinforcing fiber substrate into which the matrix resin has not been impregnated is continuous.
  • reinforcing fibers used in the sheet-like reinforcing fiber substrate used in a prepreg of this second embodiment include carbon fiber, graphite fiber, aramid fiber, silicon carbide fiber, alumina fiber, boron fiber, high-strength polyethylene fiber, PBO fiber, and glass fiber, and these fibers can be used either singularly, or in mixtures of two or more different types of fiber.
  • carbon fiber which offers superior specific strength and inelasticity, or glass fiber which offers more favorable cost performance is preferred.
  • the sheet-like reinforcing fiber substrate used in the prepreg of this second embodiment there are also no particular restrictions on the form of the sheet-like reinforcing fiber substrate used in the prepreg of this second embodiment, and suitable examples include unidirectional materials in which the reinforcing fibers are aligned unidirectionally, woven fabrics, knit fabrics, braided fabrics, stitched sheets wherein multiple fabrics are laminated, either unidirectionally or in various directions, and then stitched, as well as mats and non-woven fabrics comprising short fibers.
  • woven fabrics, stitched sheets, mats and non-woven fabrics offer superior levels of stability for the sheet-like reinforcing fiber substrate, and because an intermediate material for FRP molding of the present invention offers superior handling properties, it is preferred as the sheet-like reinforcing fiber substrate.
  • the portion inside the sheet-like reinforcing fiber substrate into which the matrix resin has not been impregnated must be a continuous portion.
  • this non-impregnated portion functions as the deaerating circuit, and the existence of this deaerating circuit means that the molded FRP can be formed without internal voids and surface pinholes.
  • this deaerating circuit is segmented by the matrix resin, then the air that is enclosed by the matrix resin becomes extremely difficult to remove, and can give rise to internal voids and surface pinholes.
  • the following method can be used for determining whether or not the portion inside the sheet-like reinforcing fiber substrate into which the matrix resin has not been impregnated is continuous.
  • the prepreg is cut at a right angle to the lengthwise direction of the prepreg.
  • the cut is performed in a single action, using an NT cutter or the like. If a number of cutting strokes are used, then the surface of the cut becomes undesirably messy.
  • the two edges of the cut surface in the width direction are trimmed off, with 10% of the width dimension removed from each edge.
  • the entirety of the remaining 80% portion across the width direction is then inspected to confirm that the portion into which the matrix resin has not been impregnated is continuous. The inspection is preferably conducted using a magnifying glass or the like.
  • FIG. 3 shows a prepreg 30 formed from a sheet-like reinforcing fiber substrate comprising matrix resin-impregnated layers 31 that have been impregnated with a matrix resin 1 , and a matrix resin non-impregnated layer 32 .
  • This figure represents an example where, when the matrix resin 1 is impregnated, the matrix resin non-impregnated layer 32 is formed as a continuous layer.
  • FIG. 5 shows a prepreg 50 formed from a sheet-like reinforcing fiber substrate comprising matrix resin-impregnated layers 51 that have been impregnated with a matrix resin 1 , and a matrix resin non-impregnated layer 52 .
  • This figure represents an example where, when the matrix resin 1 is impregnated, the matrix resin non-impregnated layer 52 is formed in a non-continuous manner.
  • thermosetting resins include epoxy resins, phenol resins, vinyl ester resins, unsaturated polyester resins, bismaleimide resins, BT resins, cyanate ester resins, and benzoxazine resins.
  • epoxy resins, bismaleimide resins, BT resins, and cyanate ester resins are preferred, and of these, epoxy resins are particularly desirable.
  • the weight of the sheet-like reinforcing fiber substrate in a prepreg according to the second embodiment is preferably at least 400 g/m 2 .
  • a prepreg of the second embodiment contains a deaerating circuit, but during molding the resin penetrates to all corners of the sheet-like reinforcing fiber substrate, enabling the formation of a completely impregnated molded product with no internal voids or surface pinholes. Consequently the prepreg is suited to sheet-like reinforcing fiber substrate with a certain level of thickness.
  • sheet-like reinforcing fiber substrates with a weight of at least 200 g/m 2 are preferred. Weights of at least 600 g/m 2 are even more desirable, and weights of at least 700 g/m 2 are particularly preferred.
  • the thickness of the sheet-like reinforcing fiber substrate in a prepreg of the second embodiment is preferably at least 200 ⁇ m.
  • a prepreg of the second embodiment can yield a favorable molded product with no internal voids at atmospheric pressure, even if the fluidity of the matrix resin is poor. Accordingly, a favorable molded product can be achieved even if the sheet-like reinforcing fiber substrate is considerably thick, and in actual fact, the effects of the present invention are manifested most markedly with thicker substrates.
  • the effects are particularly marked for thick materials where the thickness of the sheet-like reinforcing fiber substrate is at least 300 ⁇ m.
  • the thickness is determined by dividing the mass per unit of surface area of the sheet-like reinforcing fiber substrate by the density of the reinforcing fibers.
  • the thermosetting resin composition preferably comprises a thermoplastic resin that is not dissolved within the thermosetting resin composition.
  • This thermoplastic resin is preferably in the form of short fibers, and the length of those short fibers is preferably within a range of 1 to 50 mm. Furthermore, the size of the fibers is preferably no more than 300 tex.
  • the short fibers of thermoplastic resin within the thermosetting resin composition are filtered by the reinforcing fibers that make up the sheet-like reinforcing fiber substrate, and end up positioned at the surface of each of the laminated sheet-like reinforcing fiber substrates, namely, positioned between the layers of the laminate. This improves the interlayer peeling resistance markedly, providing a superior interlayer reinforcement effect.
  • the thermoplastic resin preferably exist as fibers. If other shapes such as fine particles are used instead of these thermoplastic resin short fibers, then the thermoplastic resin is not efficiently filtered by the sheet-like reinforcing fiber substrate during the molding process, and migrates into the interior of the sheet-like reinforcing fiber substrate together with the thermosetting resin during the impregnation process, meaning efficient interlayer reinforcement can not be achieved.
  • the thermoplastic resin is preferably in the form of short fibers.
  • the length of these fibers is preferably within a range of 1 to 50 mm. If the length of the short fibers is less than 1 mm, then the fibers penetrate into the interior of the sheet-like reinforcing fiber substrate, in a similar manner to fine particles, making it difficult to achieve an efficient improvement in the interlayer peeling resistance. Considering the fact that a certain size is necessary, fibers with a length of at least 3 mm are particularly preferred.
  • Fiber lengths of no more than 30 mm are particularly preferred.
  • the size of those fibers is preferably no more than 300 tex.
  • the short fibers of the thermoplastic resin may exist either as filaments formed from single strands of fiber, or as multifilaments comprising a plurality of individual fiber strands. If the size of the fibers exceed 300 tex, then the thickness of the layer formed by the accumulated short fibers between the substrate layers becomes overly thick, and there is a danger of the short fibers interfering with the reinforcing fibers of the sheet-like reinforcing fiber substrates, causing bending of the reinforcing fibers, and an undesirable deterioration in the mechanical strength of the molded composite material.
  • Single fiber sizes of no more than 100 tex are even more desirable, and sizes of no more than 50 tex are particularly preferred. There are no particular restrictions at the fine end of the single fiber size scale, and satisfactory effects can be achieved for sizes of at least 1 tex.
  • thermoplastic resins examples include polyaramid, polyester, polyacetal, polycarbonate, polyphenylene oxide, polyphneylene sulfide, polyallylate, polyimide, polyetherimide, polysulfone, polyamide, polyamide-imide, and polyetheretherketone.
  • elastomers can also be used favorably instead of the thermoplastic resin.
  • suitable elastomers include synthetic rubbers such as butyl rubber, isoprene rubber, nitrile rubber, and silicon rubber, as well as natural rubbers such as latex.
  • the quantity of the thermoplastic resin within the thermosetting resin composition is preferably within a range of 1 to 100 parts by mass per 100 parts by mass of the thermosetting resin composition. If the quantity of the thermoplastic resin is less than 1 part by mass, then the effect of the invention in improving the FRP interlayer peel resistance weakens undesirably. Quantities of at least 5 parts by mass are even more desirable, and quantities of at least 10 parts by mass are particularly preferred.
  • the proportion of the thermoplastic resin becomes overly high, which can cause a deterioration in the impregnation of the matrix resin into the sheet-like reinforcing fiber substrate, and the quantity of the matrix resin relative to the sheet-like reinforcing fiber substrate can become too high, causing an undesirable deterioration in the FRP mechanical strength.
  • thermosetting resin composition is preferably able to be cured at 90° C. for 2 hours, and even more preferably at 80° C. for 2 hours.
  • a prepreg of the second embodiment can yield a favorable molded product with no internal voids at atmospheric pressure, even if the fluidity of the thermosetting resin composition that functions as the matrix resin is poor, and consequently, the invention is suited to comparatively low temperature curing of the thermosetting resin composition.
  • prepregs must typically display favorable handling characteristics at room temperature.
  • Two major factors in determining the handling characteristics are the tack (the degree of stickiness) and the drape characteristics (the flexibility), and in order to optimize the tack and drape characteristics, the thermosetting resin composition that finctions as the matrix resin must have a viscosity that falls within a certain range. If the viscosity of the thermosetting resin composition is too low, then the tackiness is too powerful, making handling extremely difficult, whereas if the viscosity is too high, then the tackiness is overly weak, and the drape characteristics can effectively disappear, which also makes handling very difficult.
  • thermosetting resin composition in order to ensure favorable handling characteristics for the prepreg, the thermosetting resin composition must have a viscosity that falls within an appropriate range. Accordingly, if a thermosetting resin composition cures at lower temperatures, then this means that the composition is capable of curing while still at a relatively higher viscosity, and is consequently suitable as a thermosetting resin composition for a prepreg of the second embodiment, which is capable of yielding a favorable molded product even with comparatively poor fluidity.
  • thermosetting resin composition can be cured in 2 hours at 90° C.
  • the thermosetting resin composition by itself, or a sheet-like reinforcing fiber substrate that has been impregnated with the thermosetting resin composition is molded for 2 hours at 90° C. in an oven. If the external appearance suggests that the resulting cured product has definitely cured, then the composition is deemed to be curable in 2 hours at 90° C.
  • a determination as to whether or not a thermosetting resin composition can be cured in 2 hours at 80° C. can be conducted in a similar manner. In those cases where determining whether or not the composition has cured is difficult, the Tg value of the molded product is measured, and the composition is deemed to have cured if the Tg value is at least 30° C.
  • the process for impregnating the matrix resin into the sheet-like reinforcing fiber substrate involves applying a thin coating of a thermosetting resin composition on the surface of a release sheet or a polyolefin film or the like, and then supplying the thermosetting resin composition on the surface of a reinforcing fiber substrate to achieve impregnation.
  • impregnation processes can be broadly classified into single film processes in which the resin composition is supplied and impregnated from only one surface of the reinforcing fiber substrate, and double film processes in which the resin composition is supplied and impregnated from both surfaces of the reinforcing fiber substrate.
  • FIG. 3 and FIG. 4 are schematic illustrations showing the prepregs obtained when the same quantity of resin is supplied to sheet-like reinforcing fiber substrates of identical thickness, using a double film process and a single film process respectively.
  • FIG. 3 shows a prepreg 30 comprising matrix resin-impregnated layers 31 and a matrix resin non-impregnated layer 32 , formed by impregnating a matrix resin 1 from both surfaces of a sheet-like reinforcing fiber substrate.
  • FIG. 4 shows a prepreg 40 comprising a matrix resin-impregnated layer 41 and a matrix resin non-impregnated layer 42 , formed by impregnating a matrix resin 1 from one surface of a sheet-like reinforcing fiber substrate.
  • prepregs of the second embodiment are produced by either a single film process or a double film process
  • the prepreg produced by the double film process tends to have a wider non-impregnated layer 42 than the prepreg produced by the single film process.
  • using a double film process is preferred, as it enables a reduction in the quantity of thermosetting resin composition that must migrate in order to fill the deaerating circuit during the molding step, thus ensuring that the deaerating circuit is completely filled prior to the completion of curing.
  • the matrix resin When the matrix resin is supplied to the sheet-like reinforcing fiber substrate, it is preferably stuck to the substrate at room temperature, without heating. However, in those cases where the viscosity of the matrix resin at room temperature is very high, the resin may be heated slightly to improve the level of fluidity. However even in such cases, in order to ensure that a continuous resin non-impregnated portion such as that described below is left inside the substrate, any heating is preferably conducted at no more than 40° C., and even more preferably at no more than 30° C.
  • the matrix resin for a prepreg according to the second embodiment is a thermosetting resin composition
  • that composition comprises a thermoplastic resin that is not dissolved within the thermosetting resin composition
  • the thermoplastic resin is preferably blended into the composition during the mixing and preparation of the thermosetting resin composition, and the resulting composition is then converted to a film form, and impregnated into the sheet-like reinforcing fiber substrate.
  • a prepreg according to a third embodiment of the present invention comprises a matrix resin impregnated into a reinforcing fiber woven fabric, wherein at least one surface displays a sea-and-island-type pattern comprising resin-impregnated portions (island portions) where the matrix resin is present at the surface and fiber portions (sea portions) where the matrix resin is not present at the surface, the surface coverage ratio of the matrix resin on surfaces with the sea-and-island-type pattern is within a range of 3% to 80%, and the weave intersection coverage ratio for the island portions, as represented by a formula (5) shown below, is at least 40%.
  • Island portions weave intersection coverage ratio (%) ( T/Y ) ⁇ 100 (5) (wherein, T represents the number of island portions that cover weave intersections, and Y represents the total number of weave intersections of the reinforcing fiber fabric on the surface with the sea-and-island-type pattern).
  • a prepreg of the third embodiment is formed by impregnating a reinforcing fiber woven fabric with a matrix resin.
  • Suitable examples of the reinforcing fibers used in forming the woven fabric include carbon fiber, glass fiber, aramid fiber, boron fiber, metal fiber, PBO fiber, and high-strength polyethylene fiber, although of these, carbon fiber is particularly preferred as it results in more favorable mechanical properties following molding, and is also very lightweight.
  • suitable examples of the form of the woven fabric include plain weave fabric, twill fabric, satin weave fabric, stitched sheets in which long fibers that have been aligned unidirectionally are stitched together, and blind weave. Woven fabrics in which the warp and the woof use different fibers can also be used.
  • a reinforcing fiber woven fabric used in the third embodiment preferably displays a fiber weight of no more than 1500 g/m 2 . If the fiber weight exceeds 1500 g/m 2 , then the density of the reinforcing fibers becomes overly high, and achieving a fabric with superior mechanical properties becomes difficult. Fiber weights of no more than 1000 g/m 2 are even more desirable. There are no particular restrictions on the lower limit for the fiber weight. However, the weight is preferably at least 50 g/m 2 , and even more preferably 75 g/m 2 or greater. If the fiber weight is less than 50 g/m 2 , then in those cases where a large FRP is required, the number of layers of prepreg must be increased significantly, which can lead to cost increases.
  • suitable resins include thermosetting resins such as epoxy resins, polyester resins, vinyl ester resins, phenol resins, maleimide resins, polyimide resins, and BT resins comprising a combination of a cyanate and a bismaleimide resin, as well as thermoplastic resins such as acrylic resins and polyetheretherketones.
  • thermosetting resins such as epoxy resins, polyester resins, vinyl ester resins, phenol resins, maleimide resins, polyimide resins, and BT resins comprising a combination of a cyanate and a bismaleimide resin
  • thermoplastic resins such as acrylic resins and polyetheretherketones.
  • Matrix resins that improve the strength of the product FRP are preferred, and of the above resins, epoxy resins are particularly preferred, as their superior adhesion to reinforcing fibers improves the mechanical properties of the product FRP.
  • suitable epoxy resins include bifinctional resins such as bisphenol A epoxy resins, bisphenol F epoxy resins, bisphenol S epoxy resins, biphenyl epoxy resins, naphthalene epoxy resins, dicyclopentadiene epoxy resins, fluorene epoxy resins, and modified resins thereof; and trifunctional or greater polyfunctional epoxy resins such as phenol novolac epoxy resins, cresol epoxy resins, glycidylamine epoxy resins such as tetraglycidyldiaminodiphenylmethane, triglycidylaminophenol and tetraglycidylamine, glycidyl ether epoxy resins such as tetrakis(glycidyloxyphenyl)ethane and tris(glycidyloxymethane), as well as modified resins thereof; and combinations of one or more of the above resins can also be used as the matrix resin.
  • bifinctional resins such as bisphenol A epoxy resins,
  • the above epoxy resin compositions may also contain curing agents such as diphenylmethane, diaminodiphenylsulfone, aliphatic amines, imidazole derivatives, dicyandiamide, tetramethylguanidine, thiourea adducts of amines, carboxylic acid hydrazides, carboxylic acid amides, polyphenol compounds, polymercaptans, and boron trifluoride ethyl amine complex, or materials obtained by preliminary reaction between an epoxy resin and a portion of one of the above curing agents.
  • curing agents such as diphenylmethane, diaminodiphenylsulfone, aliphatic amines, imidazole derivatives, dicyandiamide, tetramethylguanidine, thiourea adducts of amines, carboxylic acid hydrazides, carboxylic acid amides, polyphenol compounds, polymercaptans, and boro
  • the curing time can be shortened, thereby shortening the molding time.
  • the minimum viscosity for the thermosetting resin composition is preferably no more than 1000 poise. If a high-viscosity thermosetting resin composition with a minimum viscosity exceeding 1000 poise is used, then the fluidity of the thermosetting resin composition deteriorates.
  • the thermosetting resin composition fills the deaerating circuit, which has been complete the role, during molding, but if the fluidity of the thermosetting resin composition is poor, then the molding process may finish before this filling step is complete, meaning there is a danger that any portions of residual deaerating circuit will form internal voids. In order to prevent this occurring, the weight of the resin must be increased, resulting in an undesirable increase in cost. Accordingly, lower minimum viscosity values are preferred, and values of no more than 500 poise are particularly desirable.
  • the minimum viscosity refers to the lowest viscosity value observed when the temperature of the thermosetting resin is raised from room temperature at a rate of 5° C./minute.
  • the minimum viscosity of the thermosetting resin composition can be determined by measuring the dynamic viscoelasticity of the composition, while the temperature is raised from room temperature at a rate of 5° C./minute.
  • At least one surface displays a sea-and-island-type pattern comprising resin-impregnated portions (island portions) where the resin composition is present at the surface and fiber portions (sea portions) where the resin composition is not present at the surface, and the surface coverage ratio of the resin on surfaces with the sea-and-island-type pattern is within a range of 3% to 80%.
  • FIG. 6 is a schematic illustration showing the surface of a prepreg according to a third embodiment of the present invention, wherein a resin composition has been impregnated into one surface of a plain weave reinforcing fiber woven fabric to form a sea-and-island-type pattern.
  • the surface of the woven fabric 60 produced from woven reinforcing fibers comprises island portions 61 and sea portions 62 .
  • island portions 61 those that exist in isolation at a single weave intersection 64 are labeled as island portions 61 a , and those that are linked with adjacent island portions are labeled as island portions 61 b .
  • the sea portions 62 act as the deaerating circuit during molding of the prepreg.
  • the spacing between adjacent weave intersections 64 is labeled as the distance 63 .
  • the surface coverage ratio of the resin on those surfaces with the sea-and-island-type pattern must fall within a range of 3% to 80%.
  • the surface coverage ratio refers to the ratio of the area of the island portions 61 relative to the surface area of the entire surface with the sea-and-island-type pattern.
  • this surface coverage ratio is less than 3%, then the tackiness of the sea-and-island-type patterned surface of the prepreg is overly poor, causing a deterioration in the prepreg handling properties. In contrast, if the surface coverage ratio exceeds 80%, then the deaerating circuit for the prepreg is almost completely blocked off, which can cause internal voids and surface pinholes. In terms of achieving a favorable balance between tackiness and the size of the deaerating circuit, surface coverage ratios of 5% or more is preferred, and 60% or less is particularly preferred.
  • the weave intersection coverage ratio for the island portions 61 on the sea-and-island-type patterned surface is at least 40%.
  • Island portions weave intersection coverage ratio (%) ( T/Y ) ⁇ 100 (6)
  • T represents the number of island portions that cover weave intersections
  • Y represents the total number of weave intersections of the reinforcing fiber woven fabric on the surface with the sea-and-island-type pattern.
  • a weave intersection 64 refers to an intersection between the warp and the woof.
  • FIG. 7 represents a case where the surface of the woven fabric 60 contains a larger proportion of linked island portions 61 b .
  • the resin surface coverage ratio is within the range from 3% to 80%, if the weave intersection coverage ratio for the island portions 61 is less than 40%, then as shown in FIG. 7 , the probability of the existence of a sea portion 62 that is totally enclosed by an island portion 61 on the sea-and-island-type patterned surface increases. In such a case, the air that reaches the fabric surface through the deaerating circuit during molding has no where to escape, increasing the likelihood of undesirable pinhole formnation.
  • the surface coverage ratio must be within a range of 3% to 80% on both surfaces, and the weave intersection coverage ratio for the island portions 61 is preferably at least 40% on both surfaces.
  • the most preferred process for producing a prepreg according to the third embodiment is a process in which a resin composition is applied to a resin support sheet, this matrix resin supported on the resin support sheet is bonded to one surface of a reinforcing fiber woven fabric, a protective film is affixed to the other surface of the reinforcing fiber woven fabric to prevent the adhesion of any foreign matter, and heating and/or pressure is then used to impregnate the matrix resin into the reinforcing fiber woven fabric, thus forming a prepreg wherein the surface of the reinforcing fiber woven fabric on the side of the protective film displays a sea-and-island-type pattern comprising resin-impregnated portions (island portions) where the matrix resin is present at the surface, and fiber portions (sea portions) where the resin composition is not present at the surface.
  • the heating conditions used within this process preferably employ a temperature that ensures that the viscosity of the matrix resin reaches no more than 5000 poise, whereas the pressure conditions preferably use a linear pressure of 49 to 780 kPa, thus ensuring a prepreg with a satisfactory deaerating circuit.
  • the temperature required to ensure a viscosity of no more than 5000 poise is typically within a range of 40 to 80° C.
  • the protective film used in the process for producing a prepreg according to the third embodiment preferably displays favorable releasability relative to the matrix resin, and suitable examples include release sheets or polyethylene film that have been surface-treated with silicone.
  • the resin support sheet can also use a resin film formed from a polyolefin and a release sheet or the like.
  • a process can be used which employs a resin support sheet with an irregular surface, so that when the matrix resin is applied to this resin support sheet, and the matrix resin-coated surface of the resin support sheet and the reinforcing fiber woven fabric are stuck together, only the matrix resin applied to the convex portions of the resin support sheet is transferred to, and impregnated into the reinforcing fiber woven fabric, thus generating a sea-and-island-type pattern.
  • the matrix resin is impregnated into the reinforcing fiber woven fabric mainly at the weave intersections points, and is exuded out at the weave intersections on the opposite surface (the protective film side) of the fabric, impregnating the reinforcing fibers in the vicinity of the surface.
  • this process results in almost no island portions that do not cover weave intersections.
  • the matrix resin can be applied directly to the surface of the reinforcing fiber woven fabric that is to become the sea-and-island-type patterned surface, either uniformly or in a non-uniform manner, or by sticking a resin support sheet to the surface, and in a similar manner to that described above, this process also causes the matrix resin to impregnate into the fabric along the weave intersections, so that following impregnation, almost all of the matrix resin is connected to an island portion that covers a weave intersection.
  • the matrix resin penetrates into the interior of the woven fabric along the weave intersections from the surface, and exudes from the weave intersections on the opposite surface, meaning the number of island portions that do not cover weave intersections is essentially nil.
  • a fourth embodiment of the present invention is an intermediate material for FRP molding in which a substrate containing essentially no impregnated thermosetting resin composition is bonded to at least one side of a prepreg comprising a matrix resin and reinforcing fibers, wherein the ratio (B)/(A) between the thickness (A) of the prepreg, and the thickness (B) of the substrate is within a range of 0.1 to 2.5.
  • thermosetting resin compositions are preferred.
  • the thermosetting resin that forms the main component of the thermosetting resin composition include epoxy resins, phenol resins, bismaleimide resins, BT resins, cyanate ester resins, and benzoxazine resins, although epoxy resins are preferred, as their superior adhesion to reinforcing fibers improves the mechanical properties of the product FRP.
  • phenol resins are also preferred, as not only do they display excellent flame retardancy, but they are also ideally suited to lacquer-type prepreg production processes.
  • reinforcing fibers used in the prepreg of this fourth embodiment there are no particular restrictions on the reinforcing fibers used in the prepreg of this fourth embodiment, and any reinforcing fibers that offer high strength and high elasticity can be used, including glass fiber, carbon fiber, aramid fiber, boron fiber, and PBO fiber. Of these, reinforcing fibers that use either glass fiber or carbon fiber are preferred, as they offer excellent balance between elasticity and strength, and yield FRPs with excellent mechanical properties.
  • the process for producing a prepreg used in the fourth embodiment may utilize the hot melt process described above, although even when a prepreg that has been produced by a lacquer process is used, oven molding is still capable of producing a molded product with no internal voids or surface pinholes, meaning the effects of the present invention are particularly significant for prepregs produced by a lacquer process.
  • a lacquer process is a prepreg production process in which the reinforcing fibers are impregnated with a thermosetting resin composition that has been diluted with a solvent, and the solvent is subsequently removed.
  • Suitable methods for impregnating the reinforcing fibers with the solvent solution include immersing the reinforcing fibers in the thermosetting resin composition solution, or applying the solution to a roller and then transferring the solution to the reinforcing fibers using the roller.
  • suitable methods for removing the solvent include warm or hot air dryers, or drying under reduced pressure, although warm air drying is the most preferred in terms of productivity.
  • An intermediate material for FRP molding according to the presen t invention comprises an aforementioned prepreg with a substrate containing essentially no impregnated thermosetting resin composition bonded to at least one side of the prepreg.
  • this substrate By allowing this substrate to function as a deaerating circuit, any internal air pockets can be removed easily during molding, meaning the substrate performs an important role in preventing the occurrence of internal voids and surface pinholes within the molded product. If a substrate is bonded to both surfaces of a prepreg, then the deaerating circuit is larger than that generated when a substrate is bonded to only one surface, which can offer advantages in some cases.
  • a substrate is preferably only bonded to one surface, and the other surface is left with the prepreg exposed, thus retaining favorable tackiness.
  • the substrate acts as a deaerating circuit during molding, acting as a pathway for guiding air out of the structure during the molding process.
  • the substrate must also become impregnated with the matrix resin that is impregnated within the reinforcing fibers, so that following molding, a single integrated body molded product is obtained that contains no internal voids or surface pinholes.
  • the substrate must comprise sufficient air gaps to fimction satisfactorily as the deaerating circuit, but must also have a quantity of air gaps that can be completely filled by the matrix resin during the molding process. Accordingly, the quantity of air gaps within the substrate must be matched with the prepreg used in the fourth embodiment of the present invention.
  • the ratio (B)/(A) between the thickness (A) of the prepreg, and the thickness (B) of the substrate must be within a range of 0.1 to 2.5.
  • the substrate must comprise sufficient air gaps to function satisfactorily as the deaerating circuit, but those air gaps must be completely filled by the matrix resin during the molding process.
  • the lower limit of the above range is even more preferably 0.15 or greater, and most preferably 0.2 or greater.
  • the ratio is less than 0.1, then ensuring sufficient air gaps for the substrate to function satisfactorily as the deaerating circuit becomes difficult, and air can remain trapped following molding.
  • the upper limit of the above range is even more preferably no more than 1.5, and is most preferably 1.1 or less. If the ratio exceeds 2.5, then the air gaps may not be completely filled during the molding process, meaning residual air may be left following molding.
  • the thickness (A) of the prepreg and the thickness (B) of the substrate refer to values measured using vernier calipers. During measurement, care must be taken to ensure that the vernier calipers are pressed against the prepreg or the substrate so that the thickness does not vary. Particularly in the case of the substrate, if there is a concern that, even with the vernier calipers pressed against the substrate, the measurement error during measurement is overly large, then a photograph is preferably taken of the substrate cross section and enlarged, so that measurements can be conducted with minimal error. In addition, in those cases where a substrate is bonded to both surfaces of the prepreg, the sum of the individual thickness values for the two substrates is used as the thickness value (B).
  • Suitable examples of the material used for forming the substrate include fibrous thermoplastic resins and reinforcing fibers.
  • fibrous thermoplastic resins is preferred as it enables an improved interlayer reinforcement effect to be achieved when layers of the intermediate material for FRP molding are laminated.
  • Suitable examples of such materials include nylon, polyester, polyethylene, and polypropylene, and provided a deaerating circuit can be ensured, the material may be a net-like material, a material in which rods or fibers of the thermoplastic resin are aligned unidirectionally, or a laminated material in which these materials are overlaid at different angles.
  • thermoplastic resin is most preferably in the form of a fibrous material, and suitable materials include woven fabrics formed from fibers, as well as materials in which the fibers are aligned unidirectionally and non-woven fabrics. Of these, non-woven fabrics are particularly desirable as they offer ready formation of the deaerating circuit.
  • the material for the substrate can also use non-thermoplastic resin fibers, and reinforcing fibers are particularly favorable.
  • reinforcing fibers are used as the material for the substrate, the same reinforcing fibers that were used to form the prepreg can be used, although different fibers may also be used.
  • the substrate can be bonded to the prepreg so that the angle of alignment of the reinforcing fibers in the substrate matches the angle of alignment of the reinforcing fibers in the prepreg.
  • bonding the two together so that the respective angles of alignment are different enables the lamination step during quasi-isotropic lamination or the like to be conducted with greater ease, and is consequently preferred.
  • Quasi-isotropic lamination involves laminating layers with the angles of alignment set to [ ⁇ 45°/0°/45°/90°], so that overall, the FRP is isotropic and displays no anisotropy in terms of the FRP properties.
  • a hybrid FRP can be produced with considerable ease, which is ideal.
  • an FRP produced using an intermediate material in which glass fiber is used as the reinforcing fibers for forming the prepreg, and carbon fiber is used as the reinforcing fibers for forming the substrate becomes a glass/carbon fiber hybrid FRP, enabling optimal design of the cost performance balance.
  • the respective angles of alignment of the reinforcing fibers of the substrate and the reinforcing fibers of the prepreg may be either the same or different.
  • vacuum bag molding is the most preferred process, although molding using an autoclave or press molding can also be used.
  • primary curing is preferably conducted for at least 10 minutes at a primary curing temperature of no more than 150° C., and then the curing is preferably completed at a temperature equal to, or greater than, the primary curing temperature.
  • Processes in which the primary curing is conducted at a temperature of no more than 100° C. are particularly preferred as a resin mold can be used instead of a metal mold, and heating can be conducted using solely steam, which provide significant cost reductions.
  • the product is preferably subjected to further curing at a temperature either equal to, or higher than, the primary curing temperature, thus enabling a further reduction in the high-temperature molding time.
  • a prepreg or intermediate material for FRP molding according to the present invention provides a deaerating circuit during molding, meaning air from the voids can be guided out through the deaerating circuit and expelled outside the FRP, thus making these materials ideally suited to vacuum bag molding and oven molding.
  • the prepreg or FRP molding intermediate material is preferably laminated, and then placed under a vacuum, so that the air contained within the prepreg or FRP molding intermediate material can be completely removed before the temperature is raised.
  • a degree of vacuum of no more than 600 mmHg is preferred, and a degree of vacuum of no more than 700 mmHg is even more desirable. If the temperature is raised before satisfactory deaerating has been completed, then the viscosity of the matrix resin may fall too far, causing the deaerating circuit to become undesirably blocked before the air within the prepreg or FRP molding intermediate material has been completely removed.
  • the vacuum is preferably maintained throughout the molding process.
  • the structure is preferably held for at least 1 hour, prior to curing, and while the viscosity of the matrix resin is no more than 10,000 poise, before the curing step is conducted. During this holding period, the matrix resin can migrate, making it easier to force the air out of the molded product. Holding the structure while the viscosity of the matrix resin is no more than 5000 poise before the curing step is even more desirable. Furthermore, holding the structure in this state for at least 2 hours before curing is also particularly preferred.
  • a preferred process for molding a FRP using either a prepreg or a FRP molding intermediate material according to the present invention involves raising the temperature from a temperature at least 20° C. below the molding temperature to the molding temperature at a rate of no more than 1° C./minute.
  • the raising of the temperature is initiated once the vacuum has been established, and is conducted with the vacuum state maintained, although during the temperature raising step, if the resin starts to move very suddenly, then small quantities of residual air can become trapped in the cured product under vacuum conditions, namely, under reduced pressure conditions of no more than 50 Torr, and this trapped air can cause residual interlayer voids and surface pinholes.
  • the rate of temperature increase can be kept low, although at very low temperatures, the viscosity of the matrix resin is high, and the movement of the air is too slow, meaning an extremely long time would be required for the matrix resin to impregnate right into the corners of the sheet-like reinforcing fiber substrate, causing a problematic deterioration in productivity.
  • a matrix resin was prepared by uniformly mixing the resin constituents described below.
  • the mixing conditions were as follows. All of the components except for DICY7 and DCMU99 were mixed uniformly in a kneader set to 100° C., and the temperature of the kneader was then lowered to 50° C., the DICY7 and DCMU99 were added, and mixing was continued to generate a uniform mixture.
  • Epikote 828 (a bisphenol A epoxy resin, manufactured by Japan Epoxy Resins Co., Ltd.) 40 parts by mass
  • Epikote 1001 (a bisphenol A epoxy resin (solid at room temperature), manufactured by Japan Epoxy Resins Co., Ltd.) 40 parts by mass
  • Epiclon N740 (a phenol novolac epoxy resin, manufactured by Dainippon Ink and Chemicals, Incorporated) 20 parts by mass
  • DCMU99 (3,4-dichlorophenyl-N,N-dimethylurea, manufactured by Hodogaya Chemical Co., Ltd.) 5 parts by mass
  • Nylon 12 was subjected to melt spinning to generate a short fiber with a size of 200 tex, and these fibers were then cut to a length of 5 mm to complete, preparation of the short fibers.
  • short fibers are referred to simply as short fibers.
  • the temperature was raised from approximately 0° C. at a rate of 2° C./minute, and the dynamic modulus of elasticity (G′) of the sample was measured.
  • the results of the measurements were graphed with temperature along the horizontal axis and logarithm of G′ along the vertical axis as shown in FIG. 8 , a tangent L1 was drawn from the glass region and another tangent L2 was drawn from the transition region, and the temperature corresponding with the point of intersection C of the two tangents was used as Tg (see FIG. 8 ).
  • a smooth and transparent polyethylene film of thickness 20 ⁇ m was bonded to a sea-and-island-type patterned surface of a prepreg by application of a metal heated roll press under conditions including a temperature of 40° C., a pressure of 1 atom, and a roll speed of 5 m/minute.
  • the surface was then photographed using a CCD camera of at least 2 megapixels, and an image analysis system (detailed fine image analysis “IP1000”) manufactured by Asahi Engineering Co., Ltd.
  • thermosetting resin was used to determine the surface area covered by the thermosetting resin, by measuring the surface area of those regions where the thermosetting resin had stuck to the polyethylene film causing a change in coloring, and the ratio of this surface area relative to the total surface area of the prepreg was then used to determine the surface coverage ratio.
  • a smooth and transparent polyethylene film of thickness 20 ⁇ m was bonded to a prepreg by application of a metal heated roll press under conditions including a temperature of 40° C., a pressure of 1 atom, and a roll speed of 5 m/minute.
  • the coated prepreg was then cut into a 10 cm ⁇ 10 cm square, the surface of the prepreg to which the polyethylene film had been bonded was photographed using a CCD camera, and the aforementioned image analysis system was used to determine the number of individual regions (T: the number of islands) where the thermosetting resin had stuck to the polyethylene film causing a change in coloring.
  • the flat sheet of FRP was cut through the center in a direction perpendicular to the thickness direction, and the cross section was photographed at 20 ⁇ magnification. An evaluation of whether or not any voids exist was then made by inspecting the cross section photograph.
  • the matrix resin was applied uniformly to a release sheet at a resin weight of 430 g/m 2 , thus forming a resin film.
  • This resin film was supplied to a piece of carbon fiber cloth TRK510, manufactured by Mitsubishi Rayon Co., Ltd. (fiber weight 646 g/m 2 , 2/2 twill) from the bottom surface of the cloth, thus impregnating the carbon fiber cloth with the resin.
  • the temperature during impregnation was 60° C., and the pressure was adjusted to complete the preparation of a prepreg. When the resin impregnation ratio of the thus produced prepreg was measured, the result was 90%, thus confirming the prepreg as conforming to the present invention.
  • the molding conditions used for the prepreg laminate were as follows. Namely, the temperature was raised from room temperature to 50° C. at a rate of 3° C./minute, the laminate was then held at 50° C. for 30 minutes under reduced pressure at 20 Torr to allow deaerating, and subsequently, with the reduced pressure state maintained at 20 Torr, the temperature was raised to 120° C. at a rate of 1° C./minute. The temperature was then held at 120° C. for 1 hour, thus yielding a 30 cm square panel.
  • the thus obtained panel had no surface voids, and when the panel was cut through the center and the resulting cross section was inspected, no internal voids were visible.
  • a prepreg was prepared in the same manner as the example 1.
  • the resin had migrated right through to the opposite surface from the release sheet, producing a resin impregnation ratio of 100%.
  • This prepreg was then laminated, and a panel was molded in the same manner as the example 1.
  • the operation of laminating the prepregs presented absolutely no problems, but the surface of the molded panel contained pinholes. Furthermore, when a central cross section of the panel was inspected in the same manner as the example 1, a plurality of internal voids was observed.
  • a resin film was prepared in the same manner as the example 1, and a prepreg was then formed.
  • the impregnation of the carbon fiber cloth with the resin was conducted at room temperature, with only pressure being applied. Almost no impregnation occurred, and absolutely no resin was visible at the opposite surface to where the resin was supplied.
  • the resin impregnation ratio of the thus produced prepreg was measured, the result was 30%.
  • This prepreg was then laminated, and a panel was molded in the same manner as the example 1. The lamination was conducted with the release sheet side of the prepregs facing the tool surface.
  • a piece of carbon fiber cloth TR3110 (number of filaments 3000, plain weave, weight 200 g/m 2 , manufactured by Mitsubishi Rayon Co., Ltd.) was impregnated with the same resin composition as that used in the example 1, thus forming a prepreg of the present invention.
  • the resin impregnation ratio was measured, the result was 70%.
  • a 16-ply laminate of this prepreg was formed using an alignment pattern of [0°/45°/ 90°/ ⁇ 45°/0°/45°/90°/ ⁇ 45°/ ⁇ 45°/90°/45°/0°/ ⁇ 45°/90°/45°/0°], and a 1 m square panel was molded.
  • the lamination was conducted with the release sheet side of the prepregs facing the tool surface.
  • the operation of laminating the prepregs presented absolutely no problems.
  • the temperature was raised from room temperature to 45° C. at a rate of 5° C./minute, the laminate was then held at 45° C. for 60 minutes under reduced pressure at 7 Torr to allow deaerating, and subsequently, the temperature was raised to 80° C. at a rate of 2° C./minute, and from 80° C. to 120° C. at a rate of 0.7° C./minute. The temperature was then held at 120° C. for 1 hour, thus yielding a 1 m square panel.
  • the thus obtained panel had no surface pinholes, and when the interior was inspected in the same manner as the example 1, no internal voids were visible.
  • An epoxy resin composition #830 manufactured by Mitsubishi Rayon Co., Ltd. was used as the matrix resin.
  • a resin film was prepared in the same manner as the example 1, and this was then impregnated into a TRK510.
  • the impregnation temperature was set to 50° C.
  • the resin impregnation ratio of the thus obtained prepreg was measured, the result was 60%, thus confirming the prepreg as conforming to the present invention.
  • a molded product of the shape shown in FIG. 3 was molded.
  • a wooden female mold was used as the molding die.
  • An 8-ply laminate was formed using an alignment pattern of [0°/45°/90°/ ⁇ 45°/ ⁇ 45°/90°/45°/0°], with the release sheet side of the prepreg facing the tool surface, and subsequently prepregs arranged so that the release sheet side faced the opposite side of the previous layer.
  • the operation of laminating the prepregs presented absolutely no problems.
  • the temperature was raised from room temperature to 45° C. at a rate of 2° C./minute, the laminate was then held at 45° C. under reduced pressure at 2 Torr for 4 hours to allow deaerating, and subsequently, the temperature was raised to 80° C. at a rate of 0.5° C./minute. The temperature was then held at 80° C. for 2 hours, thus yielding a molded product.
  • the thus obtained molded product had no surface pinholes, and when the product was cut open and the exposed cross section was inspected, no internal voids were visible.
  • thermosetting resin composition 8.1 parts by mass of the short fibers were added to 100 parts by mass of the thermosetting resin, and then mixed uniformly in a kneader at 50° C., thus yielding a thermosetting resin composition.
  • this resin composition was applied to a release sheet with a resin weight of 133 g/m 2 .
  • This resin film was supplied at room temperature to one surface of a piece of carbon fiber cloth TR3110, a sheet-like reinforcing fiber substrate manufactured by Mitsubishi Rayon Co., Ltd. (fiber weight 200 g/m 2 , plain weave), and a prepreg of the present invention was prepared by heating to 40° C., applying pressure from a roller, and ensuring that the resin did not migrate from the supply surface right through to the opposite surface.
  • the resin impregnation ratio of the thus produced prepreg was measured, the result was 60%.
  • a 24-ply laminate of this prepreg was formed with the fiber alignment direction (of the warp) set to [45°/0°/ ⁇ 45°/90°/45°/0°/ ⁇ 45°/90°/45°/0°/ ⁇ 45°/90°/90°/ ⁇ 45°/0°/45°/90°/ ⁇ 45°/0°/45°/90°/ ⁇ 45°/0°/45°/90°/ ⁇ 45°/0°/45°/90°/ ⁇ 45°/0°/45°/90°/ ⁇ 45°/0°/45°], and oven molding was used to mold a 500 mm ⁇ 500 mm panel.
  • the laminate Under the molding conditions used, following lamination of the prepregs, the laminate was first placed under vacuum, and was then heated for 2 hours at 50° C., and then a further 2 hours at 80° C., before being returned to normal pressure and held for 1 hour at 130° C., thus yielding a CFRP panel.
  • the rate of temperature increase used was 0.5° C./minute, and the rate of cooling following the 1 hour at 130° C. was 2° C./minute.
  • CFRP panel had no pinholes and displayed an extremely favorable external appearance. Furthermore, when the panel was cut though the center, no internal voids were visible. When a test specimen was cut from the panel and the compressive strength after impact was measured, the result was an extremely high 262 MPa.
  • a prepreg was prepared in the same manner as the example 6. However, during the step for integrating the resin film with the sheet-like reinforcing fiber substrate, the level of impregnation was increased, so that almost no non-impregnated portions remained on the opposite surface to the surface from which the resin was supplied. The resin impregnation ratio was 100%.
  • the thus obtained prepreg was laminated and molded in the same manner as the example 6, yielding a CFRP panel.
  • This CFRP panel displayed pinholes, and the external appearance was poor. Furthermore, when the panel was cut through the center, a plurality of internal voids was visible. When the compressive strength after impact was measured for this panel, the result was low, and 222 MPa.
  • a prepreg of the present invention was formed in exactly the same manner as the example 6.
  • the resin impregnation ratio of the thus obtained prepreg was 45%.
  • the thus obtained prepreg was laminated and molded in the same manner as the example 6, yielding a CFRP panel. When the panel was cut through the center, no internal voids were visible. When the compressive strength after impact was measured for this panel in the same manner as the example 6, the result was a very high 325 MPa.
  • a prepreg was prepared in the same manner as the example 7. However, during the step for integrating the resin film with the sheet-like reinforcing fiber substrate, the level of impregnation was increased, so that resin exuded from the opposite surface to the surface from which the resin was supplied. The resin impregnation ratio was 100%.
  • a carbon fiber cloth TRK510 (fiber weight 646 g/m 2 , 2/2 twill, thickness 355 ⁇ m), manufactured by Mitsubishi Rayon Co., Ltd., was used as the sheet-like reinforcing fiber substrate, and
  • the curable resin composition (B) was applied to a release sheet with a resin weight of 175 g/m 2 .
  • One of these release sheets was then bonded to both the top and bottom surfaces of the sheet-like reinforcing fiber substrate (A), with both of the curable resin composition surfaces facing inwards.
  • the bonding was conducted at room temperature, with the tackiness of the curable resin composition (B) used to effect the bonding.
  • a 10-ply laminate of the thus produced prepreg of the present invention was prepared, with the prepregs aligned in the same direction, and a 800 mm ⁇ 800 mm CFRP panel was molded. Under the molding conditions used, atmospheric pressure was first confirmed as having fallen to no more than 700 mmHg, and the temperature was then raised from room temperature at a rate of 1° C./minute, and held at 50° C. for 3 hours, before the temperature increase was resumed and heating was continued at 80° C. for 2 hours, thus curing the laminate.
  • the viscosity of the #830 resin at 50° C. measured using a DSR200 device manufactured by Rheometrics, Inc., with a rate of temperature increase of 2° C./minute, was 3500 poise.
  • the surface of the produced CFRP panel displayed absolutely no pinholes. Furthermore, when the FRP panel was cut though the center and the cut cross section was inspected, no internal voids were visible.
  • a prepreg was prepared using the same material as the example 8. However, the resin was applied at a weight of 350 g/m 2 , and was bonded to only one surface of the sheet-like reinforcing fiber substrate (A). The thus obtained FRP molding intermediate material was molded in the same manner as the example 1, thus yielding a FRP panel.
  • a prepreg was prepared using the same material as the example 8.
  • the resin was applied at a weight of 175 g/m 2 in the same manner as the example 8, but rather than simply bonding the resin to both surfaces of the sheet-like reinforcing fiber substrate (B), the structure was passed twice through a fusing press under conditions of 60° C., 0.1 MPa, and a speed of 25 cm/minute, thus ensuring good impregnation.
  • the curable resin composition had impregnated right into the center of the substrate, and although a few portions with no curable resin composition were visible, each of these non-impregnated portions was partitioned off by the curable resin composition.
  • the produced prepreg was molded in the same manner as the example 8, yielding a FRP panel, but the surface of the thus obtained FRP panel contained a plurality of pinholes. Furthermore, when the panel was cut though the center and the cut cross section was inspected, a large number of variously sized internal voids were visible.
  • a prepreg was prepared in the same manner as the example 8. However, an epoxy resin composition that was capable of being cured by heating at 80° C. for 2 hours, formed by uniformly mixing the resin components listed below at a temperature of 55° C., was used as the curable resin composition (B), and when this curable resin composition (B) was applied to the release sheet, a resin weight of 215 g/m 2 was used.
  • Epikote 1001 (a bisphenol A epoxy resin (solid at room temperature), manufactured by Japan Epoxy Resins Co., Ltd.) 70 parts by mass
  • Epiclon N740 (a phenol novolac epoxy resin, manufactured by Dainippon Ink and Chemicals, Incorporated) 20 parts by mass
  • Novacure HX3722 (a microcapsule based latent curing agent, manufactured by Asahi Kasei Corporation) 10 parts by mass
  • Omicure 94 (an amine based curing agent, manufactured by PTI Japan Co., Ltd.) 5 parts by mass
  • a CFRP panel was produced in the same manner as the example 8.
  • the surface of the produced CFRP panel displayed absolutely no pinholes. Furthermore, when the CFRP panel was cut though the center and the cut cross section was inspected, no internal voids were visible.
  • the flexural strength of the product CFRP panel was measured in accordance with ASTM D790, a high strength value of 680 MPa was obtained.
  • a prepreg was prepared in the same manner as the example 9. However, following bonding of the resin film, the structure was passed twice through a fusing press under conditions of 60° C., 0.1 MPa, and a speed of 25 cm/minute, thus ensuring good impregnation.
  • the matrix resin had impregnated right into the center of the substrate, and although a few portions with no matrix resin were visible, each of these non-impregnated portions was partitioned off by the matrix resin, and no continuous non-impregnated portion existed.
  • a CFRP panel was produced in the same manner as the example 9.
  • the surface of the thus obtained CFRP panel contained a plurality of pinholes. Furthermore, when the panel was cut though the center and the cut cross section was inspected, a large number of variously sized internal voids were visible. Furthermore, when the CFRP panel was cut though the center and the cut cross section was inspected, no internal voids were visible.
  • the flexural strength of the product CFRP panel was measured in accordance with ASTM D790, a value of 420 MPa, which was lower than that observed for the example 9, was obtained.
  • An epoxy resin composition (#340, manufactured by Mitsubishi Rayon Co., Ltd., minimum viscosity 20 poise) was applied uniformly to a release sheet wherein one surface thereof is release-treated, using a roll coater, at a weight of 133 g/m 2 .
  • a carbon fiber woven fabric manufactured by Mitsubishi Rayon Co., Ltd. (TRK510 (fiber weight: 646 g/m 2 )) was then bonded to the resin composition side of this resin support sheet.
  • Another release sheet that had undergone release-treatment in the same manner as described above was then overlaid on the carbon fiber fabric side such that a release-treated surface is provided on the fabric.
  • the resulting structure was then pressed and heated by passage through a pair of heated rollers at 40° C., thus forming a prepreg.
  • the thus obtained prepreg had a resin composition surface coverage ratio of 3%, and the weave intersection coverage ratio for the island portions of the resin composition that existed at the surface was 60%. Furthermore, evaluation of the workability revealed that the prepreg displayed favorable tackiness, and stuck favorably to a steel plate.
  • a FRP was produced in the manner described below. 10 prepreg sheets that had been cut to dimensions of 20 cm long ⁇ 20 cm wide were laminated. This laminate was provided on a steel base plate (thickness 2 mm), the surface of which had been treated with a releasing agent. Subsequently, a polytetrafluoroethylene film containing holes of 2 mm diameter at 10 cm intervals, a nylon cloth of weight 20 g/m 2 , and a glass fiber non-woven fabric of weight 40 g/m 2 were placed in sequence on top of the laminate. The resulting structure was then covered and sealed using a nylon film.
  • the space sealed within the outer nylon film was then placed under reduced pressure, and while the pressure was maintained at no more than 600 mmHg, the temperature was raised from room temperature to 130° C. at a rate of 2° C./minute, and was then held at 130° C. for 2 hours, thus yielding a FRP.
  • a series of fiber-reinforced fabric prepregs with the respective surface coverage ratios shown in Table 1 were prepared by conducting a plurality of repetitions of pressing and heating with a roller heated to 40°. Each of the prepregs had an island portions weave intersection coverage ratio of 60%.
  • Prepregs were prepared in the same manner as the example 11, but with the conditions altered to produce a resin composition surface coverage ratio of 40%. The number of repetitions of the impregnation step using the heated roll press was adjusted to produce island portions weave intersection coverage ratios of 100% and 50% respectively. Evaluation of these prepregs in the same manner as the example 10 revealed that both of the prepregs had favorable handling properties, and the produced FRPs both had favorable external appearances, and also displayed no interlayer or intralayer voids.
  • prepregs were prepared in the same manner as the example 10. All of the prepregs displayed favorable tackiness, and the produced FRPs all had favorable external appearances, and displayed no voids.
  • prepregs were prepared in the same manner as the example 10. The tackiness of these prepregs was good. On the other hand, the FRPs produced from these prepregs did contain internal voids, although FRPs with no pinholes were obtained.
  • This prepreg also stuck favorably to a steel sheet, and was adjudged to have a good level of tackiness. Furthermore, when this prepreg was used to conduct the molding evaluations described above, the molded FRP had a favorable external appearance with no surface pinholes, and no internal voids were observed.
  • the island portions weave intersection coverage ratios, and the fiber weights to the values shown in Table 3 prepregs were prepared in the same manner as the example 9 and then evaluated.
  • the evaluation results showed that the comparative example 8, which had a lower surface coverage ratio than the example 10, displayed only weak tackiness, and had poor handling properties.
  • the comparative example 9, which had an overly high surface coverage ratio when compared with the example 10, and the comparative example 10, which had a lower island portions weave intersection coverage ratio than the example 10, produced molded products with pinholes and interlayer voids, meaning products with satisfactory external appearances and mechanical characteristics could not be obtained.
  • thermosetting resin composition acetone solution used in the examples 25 to 30 and the comparative examples 11 to 14 employed an acetone solution containing 60% by mass of the epoxy resin composition, and was prepared by dissolving an epoxy resin composition (solid at room temperature), comprising the constituents listed below, in acetone to generate a homogenous solution (hereafter referred to simply as the epoxy solution).
  • Epikote 828 (a bisphenol A epoxy resin (liquid at room temperature), manufactured by Japan Epoxy Resins Co., Ltd.) 50 parts by mass
  • Epikote 1004 (a bisphenol A epoxy resin (solid at room temperature), manufactured by Japan Epoxy Resins Co., Ltd.) 30 parts by mass
  • Epiclon N740 (a phenol novolac epoxy resin, manufactured by Dainippon Ink and Chemicals, Incorporated) 20 parts by mass
  • DCMU99 (3,4-dichlorophenyl-N,N-dimethylurea, manufactured by Hodogaya Chemical Co., Ltd.) 5 parts by mass
  • a carbon fiber woven fabric Pyrofil TRK510 that used carbon fiber for both the warp and the woof (manufactured by Mitsubishi Rayon Co., Ltd., 2/2 twill fabric, fiber weight 646 g/m 2 , thickness 0.57 mm) was impregnated by immersion in the epoxy solution, and was then dried by warm air drying at 40° C. to remove the solvent, thus yielding a prepreg with a resin content of 46.7% by mass (a resin weight of 564 g/m 2 ).
  • the thickness of the prepreg was measured with vernier calipers, the measured thickness (A) was 0.85 mm.
  • the prepreg side surface of the thus obtained FRP molding intermediate material was stuck to a molding die, and a 3-ply laminate was then formed by overlaying the intermediate materials with the same angle of alignment and the same surfaces facing the same direction, and the thus formed 500 mm ⁇ 500 mm flat sheet was then subjected to oven molding.
  • the molding conditions were as follows. Namely, under a vacuum of no more than 5 Torr, the temperature was raised from room temperature to 50° C. at a rate of 3° C./minute, held at 50° C. for 3 hours, and then raised to 120° C. at a rate of 0.5° C./minute, and subsequently held at 120° C. for 2 hours, thus yielding a FRP panel.
  • the thus obtained FRP panel displayed no surface pinholes, and when the FRP panel was cut through the center and the interior was inspected, no internal voids were visible.
  • a prepreg was prepared in the same manner as the example 25.
  • the substrate was bonded to one surface of the prepreg, with the direction of alignment of the reinforcing fibers inclined 45° relative to that of the prepreg, thus forming an intermediate material for FRP molding.
  • This intermediate material displayed a (B)/(A) ratio of 0.52, the overall fiber weight of the entire intermediate material was 1292 g/m 2 , and the resin content was 40% by mass.
  • the thus obtained FRP molding intermediate material was laminated with the angle of alignment of the warp fibers set to [ ⁇ 45°/0°/45°/90°/90°/45°/0°/ ⁇ 45°], and was then oven molded in the same manner as the example 24, yielding a FRP panel.
  • the intermediate material was a 0°/45° double layered structure, a 4-ply laminate of intermediate material units was formed.
  • the thus obtained FRP panel displayed no surface pinholes, and when the FRP panel was cut through the center and the interior was inspected, no internal voids were visible.
  • a prepreg was prepared in the same manner as the example 25.
  • a 4-ply laminate was then formed by overlaying the thus obtained intermediate material with the same angle of alignment and the same surfaces facing the same direction, and the laminate was then subjected to oven molding in the same manner as the example 25, yielding a glass fiber/carbon fiber hybrid FRP.
  • a hybrid FRP was able to be molded with considerable ease.
  • the thus obtained FRP panel displayed no surface pinholes, and when the FRP panel was cut through the center and the interior was inspected, no internal voids were visible.
  • a prepreg was prepared in the same manner as the example 25.
  • substrates were bonded to both the upper and lower surfaces of the prepreg so that the warp and woof were aligned in the same direction as in the prepreg, thus yielding an intermediate material for FRP molding.
  • This intermediate material displayed a (B)/(A) ratio of 0.24, the overall carbon fiber weight of the entire intermediate material was 1064 g/m 2 , and the resin content was 40% by mass.
  • a 10-ply laminate was then formed by overlaying the thus obtained intermediate material of the present invention, with the same angle of alignment and the same surfaces facing the same direction, and the laminate was then subjected to oven molding in the same manner as the example 25, yielding a FRP panel.
  • the thus obtained FRP panel displayed no surface pinholes, and when the FRP panel was cut through the center and the interior was inspected, no internal voids were visible.
  • a prepreg was prepared in the same manner as the example 25.
  • a sheet of Pyrofil TR3110 was then bonded to one surface of the prepreg so that the carbon fibers were aligned in the same direction as in the prepreg, thus yielding an intermediate material for FRP molding.
  • This intermediate material displayed a (B)/(A) ratio of 0.21, the overall carbon fiber weight of the entire intermediate material was 1292 g/m 2 , and the resin content was 40% by mass.
  • a 3-ply laminate was then formed by overlaying the thus obtained intermediate material with the same alignment, and the resulting 1000 mm ⁇ 1000 mm FRP panel was then subjected to oven molding.
  • the molding was conducted under a vacuum of no more than 5 Torr, and the temperature was raised from room temperature to 90° C. at a rate of 0.5° C./minute, and then held at 90° C. for 20 hours.
  • the thus obtained FRP panel displayed no surface pinholes, and when the FRP panel was cut through the center and the interior was inspected, no internal voids were visible.
  • This comparative example presents an example in which a substrate is not bonded to the prepreg.
  • a prepreg was prepared in the same manner as the example 25.
  • an 8-ply laminate was formed using only the prepreg, with the prepreg alignments set to [ ⁇ 45°/0°/45°/90°/90°/45°/0°/ ⁇ 45°], and the resulting laminate was then subjected to oven molding in the same manner as the example 24, thus yielding a FRP panel.
  • the thus obtained FRP panel contained a plurality of surface pinholes, and when the FRP panel was cut through the center and the interior was inspected, a plurality of internal voids was also visible.
  • a prepreg was prepared in the same manner as the example 25.
  • This intermediate material displayed a (B)/(A) ratio of 0.05.
  • This FRP molding intermediate material was subjected to oven molding in the same manner as the example 25, yielding a FRP panel.
  • the thus obtained FRP panel contained surface pinholes, and when the FRP panel was cut through the center and the interior was inspected, internal voids were also visible.
  • a prepreg was prepared in the same manner as the example 25.
  • This FRP molding intermediate material was subjected to oven molding in the same manner as the example 25, yielding a FRP panel.
  • the surface of thus obtained FRP panel contained a plurality of resin non-impregnated portions, and when the FRP panel was cut through the center and the interior was inspected, a plurality of internal voids was also visible.
  • a 24-ply laminate was then formed by overlaying the thus obtained FRP molding intermediate material with the alignment of the carbon fibers set to [ ⁇ 45°/0°/45°/90°] 3s (wherein, 3s means a laminate produced by repeating the lamination repeating unit 3 times is then bonded to another laminate which is a mirror image.
  • 3s means a laminate produced by repeating the lamination repeating unit 3 times is then bonded to another laminate which is a mirror image.
  • the initial 12-ply laminate is arranged with the carbon fiber side facing the die, and the subsequent 12-ply laminate is then arranged with the carbon fiber side facing the opposite direction to the die.
  • the resulting laminate was subjected to oven molding in the same manner as the example 24, yielding a FRP panel.
  • the thus obtained FRP panel contained no pinholes in either the surfaces or between the layers, and when the FRP panel was cut through the center and the interior was inspected, no internal voids were visible.
  • a CAI (residual compressive strength after impact) measurement was performed for the panel. The CAI measurement was conducted in accordance with the SRM2-88 method of SACMA. The applied impact was 1500 inch-pounds/inch. The result of the CAI measurement on the panel was 350 MPa, a high value for a FRP.
  • a prepreg was prepared in the same manner as the example 25.
  • a 24-ply laminate was produced using only the thus obtained prepreg, with the alignment set to [ ⁇ 45°/0°/45°/90°] 3s, and the resulting laminate was subjected to oven molding in the same manner as the example 25, thus forming a FRP panel.
  • the thus obtained FRP panel had a few surface pinholes and interlayer voids, and when the FRP panel was cut through the center and the interior was inspected, internal voids were also visible. Furthermore, when a CAI measurement was conducted on the panel, the result was a comparatively low 210 MPa.
  • Comparative Comparative Comparative example 8 example 9 example 10 Surface coverage ratio (%) 2 81 70 Island portions weave 60 60 35 intersection coverage ratio (%) Minimum viscosity (poise) 20 20 20 20 Fiber weight of reinforcing 650 650 650 fiber fabric (g/m 2 ) External appearance No No Yes (existence of pinholes) Existence of voids Yes Yes Yes Tackiness Poor Good Good
  • TR3110 carbon fiber woven fabric Pyrofil TR3110, manufactured by Mitsubishi Rayon Co., Ltd.
  • WR800 roving glass cloth WR800, manufactured by Nitto Boseki Co., Ltd.
  • TR50S-12L Unidirectional material comprising carbon fibers Pyrofil TR50S-12L, manufactured by Mitsubishi Rayon Co., Ltd.
  • H20 glass cloth H20 F5 104, manufactured by Unitika Glass Fiber Co., Ltd.

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US10/521,433 2002-07-18 2003-07-18 Prepreg, intermediate material for forming frp, and method for production thereof and method for production of fiber-reinforced composite material Abandoned US20060035548A1 (en)

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US12/244,676 US20090123717A1 (en) 2002-07-18 2008-10-02 Prepreg, intermediate material for forming frp, and method for production thereof and method for production of fiber-reinforced composite material
US13/037,696 US20110151206A1 (en) 2002-07-18 2011-03-01 Prepreg, intermediate material for forming frp, and method for production thereof and method for production of fiber-reinforced composite material
US13/446,722 US8679991B2 (en) 2002-07-18 2012-04-13 Prepreg, intermediate material for forming FRP, and method for production thereof and method for production of fiber-reinforced composite material
US14/072,139 US20140057514A1 (en) 2002-07-18 2013-11-05 Prepreg, intermediate material for forming frp, and method for production thereof and method for production of fiber-reinforced composite material

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JP2002210123A JP4177041B2 (ja) 2002-07-18 2002-07-18 繊維強化複合材料の製造方法
JP2002-210123 2002-07-18
JP2002-234861 2002-08-12
JP2002234861A JP4116361B2 (ja) 2002-08-12 2002-08-12 Ｆｒｐ成形用中間材料及びその製造方法
JP2002271850A JP2004106347A (ja) 2002-09-18 2002-09-18 Ｆｒｐ成形用中間材料及びその製造方法
JP2002-271850 2002-09-18
JP2002353759A JP2004182923A (ja) 2002-12-05 2002-12-05 プリプレグ及びそれを用いた繊維強化複合材料の製造方法
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JP2003063166A JP2004268440A (ja) 2003-03-10 2003-03-10 プリプレグ並びにその製造方法および繊維強化複合材料の製造方法。
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PCT/JP2003/009176 WO2004009314A1 (fr) 2002-07-18 2003-07-18 Pre-impregne, matiere intermediaire pour former du plastique renforce par fibres, procede pour le produire et procede pour produire une matiere composite renforcee par fibres

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US13/037,696 Abandoned US20110151206A1 (en) 2002-07-18 2011-03-01 Prepreg, intermediate material for forming frp, and method for production thereof and method for production of fiber-reinforced composite material
US13/446,722 Expired - Lifetime US8679991B2 (en) 2002-07-18 2012-04-13 Prepreg, intermediate material for forming FRP, and method for production thereof and method for production of fiber-reinforced composite material
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US20060135452A1 (en) * 2002-12-02 2006-06-22 Anges Mg, Inc. Methods for treating or preventing angiogenesis-dependent symptoms
US20070129509A1 (en) * 2005-12-02 2007-06-07 Henkel Corporation Curable compositions
US20080131645A1 (en) * 2006-11-30 2008-06-05 Jamco Corporation Sandwich panel
WO2008076244A1 (fr) * 2006-12-13 2008-06-26 Henkel Corporation Stratifiés de préimprégnés
US20080185757A1 (en) * 2002-11-28 2008-08-07 Mitsubishi Rayon Co., Ltd. Epoxy resin for prepreg, prepreg, fiber-reinforced composite material, and processes for producing these
US20080274657A1 (en) * 2004-03-31 2008-11-06 Hirohumi Yashiro Woven Fabric and Articles Made by Using the Same
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EP2311618A3 (fr) 2013-08-14
US8679991B2 (en) 2014-03-25
EP2298522A2 (fr) 2011-03-23
CN100431815C (zh) 2008-11-12
US20120276795A1 (en) 2012-11-01
WO2004009314A1 (fr) 2004-01-29
ES2387333T3 (es) 2012-09-20
EP1541312B1 (fr) 2012-05-30
US20110151206A1 (en) 2011-06-23
EP2314434A3 (fr) 2013-08-21
US20140057514A1 (en) 2014-02-27
EP2311618A2 (fr) 2011-04-20
EP2314434A2 (fr) 2011-04-27
EP2298522A3 (fr) 2013-02-06
EP2298522B1 (fr) 2014-10-08
US20090123717A1 (en) 2009-05-14
EP1541312A1 (fr) 2005-06-15
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EP1541312A4 (fr) 2010-08-11
EP2578388A3 (fr) 2013-08-14
ES2527168T3 (es) 2015-01-21

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