WO2016178399A1 - Frp前駆体の製造方法及びその製造装置 - Google Patents
Frp前駆体の製造方法及びその製造装置 Download PDFInfo
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- WO2016178399A1 WO2016178399A1 PCT/JP2016/063263 JP2016063263W WO2016178399A1 WO 2016178399 A1 WO2016178399 A1 WO 2016178399A1 JP 2016063263 W JP2016063263 W JP 2016063263W WO 2016178399 A1 WO2016178399 A1 WO 2016178399A1
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- aggregate
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- heating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
- B29C70/28—Shaping operations therefor
- B29C70/40—Shaping or impregnating by compression not applied
- B29C70/50—Shaping or impregnating by compression not applied for producing articles of indefinite length, e.g. prepregs, sheet moulding compounds [SMC] or cross moulding compounds [XMC]
- B29C70/504—Shaping or impregnating by compression not applied for producing articles of indefinite length, e.g. prepregs, sheet moulding compounds [SMC] or cross moulding compounds [XMC] using rollers or pressure bands
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- 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
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
- C08J5/043—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with glass fibres
-
- 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
- B29B11/00—Making preforms
- B29B11/14—Making preforms characterised by structure or composition
- B29B11/16—Making preforms characterised by structure or composition comprising fillers or reinforcement
-
- 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
- B29B11/00—Making preforms
- B29B11/04—Making preforms by assembling preformed material
-
- 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
- B29B11/00—Making preforms
- B29B11/06—Making preforms by moulding the material
- B29B11/12—Compression moulding
-
- 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
- B29B13/00—Conditioning or physical treatment of the material to be shaped
- B29B13/02—Conditioning or physical treatment of the material to be shaped by heating
-
- 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
-
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/68—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts by incorporating or moulding on preformed parts, e.g. inserts or layers, e.g. foam blocks
- B29C70/681—Component parts, details or accessories; Auxiliary operations
- B29C70/683—Pretreatment of the preformed part, e.g. insert
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D7/00—Producing flat articles, e.g. films or sheets
- B29D7/01—Films or sheets
-
- 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
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- 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
- C08J5/244—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using glass fibres
-
- 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
- C08J5/246—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using polymer based synthetic fibres
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2101/00—Use of unspecified macromolecular compounds as moulding material
- B29K2101/10—Thermosetting resins
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2031/00—Other particular articles
- B29L2031/34—Electrical apparatus, e.g. sparking plugs or parts thereof
- B29L2031/3425—Printed circuits
-
- 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
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
-
- 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
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
- C08J2363/04—Epoxynovolacs
-
- 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
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
Definitions
- the present invention relates to an FRP precursor and a manufacturing apparatus thereof.
- FRP Fiber Reinforced Plastics
- a material with high elastic modulus such as fiber is used as an aggregate, and the aggregate is placed in a matrix (matrix) such as plastic to improve the strength.
- matrix matrix
- FRP is used in a wide range of fields. For example, since FRP has moldability and high strength, it is used as a structural material for housing equipment, ships, vehicles, aircraft, and the like. In addition, it is also used in the field of electronic components such as electric devices and printed wiring boards by taking advantage of insulation.
- FRP manufacturing methods include RTM (resin transfer molding) method in which resin is poured into a laminated mold in which aggregates are spread, a hand layup method in which aggregates are spread and multiple layers are laminated while degassing the resin, and Examples thereof include a spray-up method and a SMC (Sheet-Molding-Compound) press method in which a sheet-like material in which aggregate and resin are mixed in advance is compression-molded with a mold.
- RTM resin transfer molding
- SMC Sheet-Molding-Compound
- the thickness of the FRP for the printed wiring board is required to be thinner than the thickness of the FRP for other uses.
- the FRP for printed wiring boards is required to have high specifications such as a narrow tolerance range of thickness variation after molding the FRP and no voids. For this reason, many FRPs for printed wiring boards are manufactured by the hand lay-up (HLU) method.
- the hand lay-up method is a manufacturing method in which a resin-dissolved varnish is applied to an aggregate using a coating machine and dried to remove the solvent and perform thermosetting (Patent Document 1). In the hand lay-up method, when a thermosetting resin is applied to the aggregate in advance, the workability is improved and the load on the surrounding environment can be reduced.
- FRP for printed wiring boards
- a plurality of types of FRP precursors can be obtained with one type of aggregate, such as one having a resin amount different by several mass%, one in which the curing time of a thermosetting resin is changed, or a combination thereof. It must be manufactured and is cumbersome. Furthermore, since each of the coating conditions is changed for manufacturing, the loss of materials used for manufacturing is large.
- thermosetting resin instead of directly applying the thermosetting resin to the aggregate, prepare a resin film in the form of a thermosetting resin in advance, adhere the aggregate and the resin film by heating and pressurizing, There is a method of using an FRP precursor (Patent Document 2).
- the resin is filled into the aggregate gaps of the aggregate. Therefore, if the bonding is performed in a vacuum, the efficiency in terms of trouble handling and workability is not good. On the other hand, when pasting is performed in the air, the filling of the resin into the aggregate is poor and voids may occur. In order to increase the filling property, if the lamination temperature is increased to lower the viscosity of the resin, or the pressurizing pressure is increased to increase the filling property to the aggregate, the resin may blow out from the end, In this case, the thickness of the resin varies, and it is difficult to obtain a good product.
- the viscosity of the resin is reduced by heating.
- the heat source is a heat and pressure roll
- the surface of the resin impregnated in the aggregate is farthest from the heat source.
- the heat of the heat and pressure roll is taken away by the aggregate, so that the temperature of the resin is lowered and the fluidity (impregnation) is remarkably deteriorated due to the increase in viscosity.
- the object of the present invention is to provide a method for producing an FRP precursor with good productivity and the resin filling ability into the bulk void of the aggregate and prevention of resin ejection from the end, and the FRP precursor under normal pressure. It is to provide a manufacturing apparatus.
- the inventors have conducted heating from the side that adheres to the aggregate of the thermosetting resin film in the air with good workability (under normal pressure), or by heating the aggregate in advance. It has been found that it is possible to provide a method for producing an FRP precursor and an apparatus for producing an FRP precursor that are compatible with the resin filling ability into the bulk void of the aggregate and the prevention of the resin ejection from the end portion, and have high productivity. It was. That is, the present invention is as follows.
- a method for producing an FRP precursor in which a FRP precursor is produced by melting and pasting a thermosetting resin film on one surface of a sheet-like aggregate, An aggregate surface heating step of heating one surface of the aggregate; Under normal pressure, among the two surfaces of the film, the aggregate-side film surface, which is the aggregate-side surface, is pressed against the aggregate surface, which is one surface of the heated aggregate, to produce the FRP precursor.
- the film pressure welding step is a step of pressure welding the film and the aggregate while heating, and the heating temperature of one surface of the aggregate in the aggregate surface heating step is the film pressure welding step.
- the film pressure welding step is a step of pressure welding the film and the aggregate while heating, and the heating temperature of the aggregate side film surface in the film preheating step is the heating in the film pressure welding step.
- a method for producing an FRP precursor in which a pair of thermosetting resin films are fused and adhered to both surfaces of a sheet-like aggregate to produce an FRP precursor, An aggregate surface heating step of heating both aggregate surfaces which are both surfaces of the aggregate; Under normal pressure, of the two surfaces of one of the pair of films, one aggregate-side film surface that is the aggregate-side surface is pressed against one surface of the heated aggregate surfaces. The other aggregate-side film surface, which is the aggregate-side surface, of both surfaces of the other film of the pair of films is pressed against the other surface of the heated aggregate surfaces.
- a film pressure welding process for obtaining an FRP precursor and a method for producing an FRP precursor.
- the film pressing step is a step of pressing the pair of films and the aggregate while heating, and the heating temperature of both surfaces of the aggregate in the aggregate surface heating step is the film pressing step.
- the one aggregate side film surface is heated by radiation from the one aggregate side film surface side, and the other aggregate side film surface is heated to the other aggregate side film surface side.
- the manufacturing method of the FRP precursor as described in said [7] including the film preheating process heated by the radiation from.
- the film pressing step is a step of pressing the pair of films and the aggregate while heating, and the one aggregate-side film surface and the other aggregate side in the film preheating step
- An apparatus for producing an FRP precursor used in the method for producing an FRP precursor according to any one of [1] to [5]
- An aggregate surface heating means for heating one surface of the aggregate Under normal pressure, among the two surfaces of the film, the aggregate-side film surface, which is the aggregate-side surface, is pressed against the aggregate surface, which is one surface of the heated aggregate, to produce the FRP precursor.
- An apparatus for producing an FRP precursor is provided.
- the FRP precursor manufacturing method and the FRP precursor manufacturing method with good productivity can be achieved by satisfying both the resin filling property to the bulk void of the aggregate and the resin ejection prevention from the end portion under normal pressure.
- An apparatus can be provided.
- the FRP precursor manufacturing apparatus 1 will be described as an apparatus that melts and bonds a pair of resin films (thermosetting resin films) 54 to both surfaces of a sheet-like aggregate 40, respectively.
- 54 may be a device that melts and affixes only one surface of the sheet-like aggregate 40.
- the resin film heating device 11a (or 11b) is not necessary.
- the FRP precursor production apparatus 1 is placed under normal pressure.
- the method for producing an FRP precursor according to the present invention can be performed by the FRP precursor production apparatus 1.
- the FRP precursor manufacturing apparatus 1 includes an aggregate delivery device 2, a pair of resin film delivery devices 3 and 3, an aggregate heating device 10, a sheet heating and pressing device 6, and an FRP precursor winding device 8. .
- the FRP precursor manufacturing apparatus 1 further includes a sheet pressure cooling device 7, a pair of resin film heating devices 11a and 11b, a pair of protective film peeling mechanisms 4 and 4, a pair of protective film winding devices 5, 5 is preferably provided.
- the aggregate delivery device 2 is a device that rotates the roll around which the sheet-like aggregate 40 is wound in the direction opposite to the winding direction and sends out the aggregate 40 wound around the roll.
- the aggregate sending device 2 sends the aggregate 40 from the lower side of the roller toward the sheet heating and pressing device 6.
- the pair of resin film delivery devices 3 and 3 includes a roll around which the resin film 50 with a protective film is wound, and a support mechanism that rotatably supports the roll while applying a predetermined tension to the resin film 50 with the protective film to be delivered. , A roll around which the resin film with protective film 50 is wound is rotated in the direction opposite to the winding direction, and the resin film with protective film 50 wound around the roll is sent out. As will be described later, the resin film 50 with a protective film is laminated on the resin film 54 and one aggregate-side film surface (the surface on the aggregate 40 side of both surfaces of the resin film 54) 54a. The sheet-like film including the protective film 52.
- the pair of resin film delivery devices 3 and 3 are located on the front surface 40a side and the back surface 40b side of the delivered aggregate 40, respectively.
- One resin film delivery device 3 is positioned on the surface 40a side of the fed aggregate 40, and the one resin film 50 with the protective film is a roller so that the protective film 52 is on the delivered aggregate 40 side. It is an apparatus which sends out toward the one protective film peeling mechanism 4 from the lower side.
- the other resin film delivery device 3 is located on the back surface 40b side of the sent out aggregate 40, and the other resin film with a protective film is placed so that the protective film 52 is on the sent out aggregate 40 side.
- 50 is a device that feeds 50 toward the other protective film peeling mechanism 4 from the upper side of the roller.
- the pair of protective film peeling mechanisms 4 and 4 are turning rollers positioned on the front surface 40a side and the back surface 40b side of the fed aggregate 40, respectively.
- One protective film peeling mechanism 4 receives a resin film 50 with a protective film fed from one resin film delivery device 3 and proceeds toward one protective film peeling mechanism 4 on the surface of a rotating turning roller.
- One of the resin films 54 with the protective film 50 is advanced toward the sheet heating / pressurizing device 6, and one of the protective films 52 is advanced toward the one protective film take-up device 5. It is a mechanism which peels one protective film 52 from the resin film 50 with a protective film. Thereby, the aggregate side film surface 54a of one resin film 54 is exposed.
- the other protective film peeling mechanism 4 is fed from the other resin film delivery device 3 and moves toward the other protective film peeling mechanism 4 on the surface of the rotating turning roller.
- the other resin film 54 of the other resin film 50 with the protective film is advanced toward the sheet heating / pressurizing device 6 and the other protective film 52 is advanced toward the other protective film winding device 5.
- it is a mechanism which peels off the other protective film 52 from the other resin film 50 with a protective film. Thereby, the aggregate side film surface 54a of the other resin film 54 is exposed.
- the pair of protective film winding devices 5 and 5 are located on the front surface 40a side and the back surface 40b side of the fed aggregate 40, respectively, and are peeled off by the pair of protective film peeling mechanisms 4 and 4 and This is a winding device that winds up 52.
- the aggregate heating device 10 includes heating bodies 10a and 10b positioned on the front surface 40a side and the back surface 40b side of the delivered aggregate 40, respectively.
- the heating body 10a is a radiant heating body that heats the surface 40a of the aggregate 40 under normal pressure
- the heating body 10b is a radiant heating body that heats the back surface 40b of the aggregate 40 under normal pressure.
- the heating method of an aggregate can use various things, such as radiation, a contact, and a convection, it will become simple and preferable if the heating method of the resin film mentioned later is utilized.
- the heating position is preferably a position within 20 seconds, more preferably a position within 5 seconds, by calculating the line speed before the heating and compression roller.
- the heating temperature of the front surface 40a and the back surface 40b of the aggregate 40 is preferably 5 to 70 ° C. higher than the heating temperature of the subsequent film pressing step, and 7 to 60 ° C. higher. More preferably, the temperature is preferably 10 to 50 ° C.
- the resin film heating device 11a is capable of heating the aggregate-side film surface 54a of one of the resin films 54 to be sent out, and the surface 40a of the sent-out aggregate 40 and the aggregate side of the one resin film 54.
- the resin film heating device 11b can heat the aggregate-side film surface 54a of the other resin film 54 to be sent out, and the rear surface 40b of the sent-out aggregate 40 and the aggregate side of the other resin film 54.
- the pair of resin film heating devices 11a and 11b are heating bodies that heat the aggregate-side film surface 54a of one and the other resin films 54 and 54, respectively, under normal pressure.
- the heating body is, for example, a radiation type heating body.
- the heating position is preferably a position within 20 seconds, more preferably within 5 seconds, by calculating the line speed before the heating and pressing roll.
- the heating temperature is preferably in the range of minus 20 ° C. to plus 30 ° C. of the minimum melt viscosity temperature of the resin surface temperature measured with a rheometer of the thermosetting resin composition.
- the heating temperature of the aggregate-side film surfaces 54a and 54a of the pair of resin films 54 and 54 in the film preheating process is 5 to 70 ° C. higher than the heating temperature of the subsequent film pressing process, respectively.
- the temperature is preferably 7 to 60 ° C., more preferably 10 to 50 ° C.
- the sheet heating and pressing device 6 includes a pair of heating and compression rollers and a compression force application mechanism (not shown) that applies a compression force to the pair of heating and compression rollers.
- the pair of heating and compression rollers have a heating body therein so that heating can be performed at a predetermined temperature.
- the sheet heating / pressurizing device 6 presses the resin film 54, 54 with the pair of heating and compression rollers that rotate to the aggregate 40 that has entered to form a sheet-like FRP precursor 60 (film pressing process), and FRP precursor The body 60 is sent out toward the sheet pressure cooling device 7.
- the resin films 54 and 54 sent out from the pair of protective film peeling mechanisms 4 and 4 are laminated on the front surface 40a and the back surface 40b of the aggregate 40 sent out from the aggregate sending device 2, respectively.
- the aggregate 40 delivered from the aggregate delivery device 2 and the resin films 54 and 54 delivered from the pair of protective film peeling mechanisms 4 and 4 respectively enter between the pair of heating and compression rollers.
- one resin film 54 is laminated on the aggregate 40 so that the aggregate-side film surface 54 a side of one resin film 54 is bonded to the surface 40 a side of the aggregate 40, and the other resin film 54
- the other resin film 54 is laminated on the aggregate 40 so that the aggregate-side film surface 54 a side is bonded to the back surface 40 b side of the aggregate 40, thereby forming the FRP precursor 60.
- the FRP precursor 60 sent out from the sheet heating and pressing apparatus 6 is in a high temperature state.
- the sheet pressure cooling device 7 includes a pair of cooling and compression rollers and a compression force applying mechanism (not shown) that applies a compression force to the pair of cooling and compression rollers.
- the pair of cooling and compression rollers compress and cool the high-temperature FRP precursor 60 sent from the sheet heating and pressing device 6 with the rotating pair of cooling and compression rollers, and send it to the FRP precursor winding device 8.
- the FRP precursor winding device 8 has a roll for winding the sheet-like FRP precursor 60 fed from the sheet pressurizing and cooling device 7 and a drive mechanism (not shown) for rotating the roll.
- the heating temperature to the aggregate 40 and the resin film 54 is preferably higher in the center in the width direction and lower in the end portion.
- the pressure applied to the roller laminate applies pressure to the end of the roller, and applies linear pressure to the whole using the rigidity of the roller.
- the roller is slightly deformed into an arcuate shape. Therefore, the same viscosity promotes the deformation of the bow shape. Therefore, by reducing the viscosity of the central portion of the resin film 54 and increasing the viscosity of the end portion, a difference in fluidity between the central portion and the end portion is obtained. It is generated to suppress bow-shaped deformation.
- the heating body is the same so that the heating amount is the same but the temperature during roller lamination is different. It is preferable that the distance between the central portion and the end roller is controlled by arranging in a V shape. Moreover, after roller lamination, it is preferable to cool with a cooling compression roller to remove unnecessary heat and flatten the product.
- the above FRP precursor production apparatus 1 operates as follows.
- the sheet-like aggregate 40 is sent from the aggregate sending device 2 toward the sheet heating and pressing device 6. At this time, the front surface 40a and the back surface 40b of the aggregate 40 are exposed.
- the surface 40a and the back surface 40b of the aggregate 40 are heated by the heating bodies 10a and 10b of the aggregate heating device 10 under normal pressure, respectively (aggregate surface heating step).
- one protective film-equipped resin film 50 is directed from the lower side of the roller of one resin film delivery device 3 to one protective film peeling mechanism 4 so that the protective film 52 is on the fed aggregate 40 side. Are sending out. Further, the other protective film-equipped resin film 50 is directed from the upper side of the roller of the other resin film delivery device 3 toward the other protective film peeling mechanism 4 so that the protective film 52 is on the fed aggregate 40 side. Sending out.
- the aggregate-side film surface 54a is exposed so that one of the protective films 50 is exposed.
- One protective film 52 is peeled off from the resin film 50 with a film, and one resin film 54 is advanced toward the sheet heating and pressing device 6. Thereby, the aggregate side film surface 54a of one resin film 54 is exposed.
- the other protective film-attached resin film 50 is placed on the turning roller which is the other protective film peeling mechanism 4 so that the aggregate-side film surface 54a is exposed when turning.
- the other protective film 52 is peeled off from the resin film with film 50 and the other resin film 54 is advanced toward the sheet heating and pressing device 6.
- the aggregate side film surface 54a of the other resin film 54 is exposed.
- the pair of peeled protective films 52 and 52 are wound up by the pair of protective film winding devices 5 and 5, respectively.
- the one and the other resin films 54 and 54 are respectively paired with a pair of resin film heating devices.
- the aggregate-side film surfaces 54a and 54a of one and the other resin films 54 and 54 are heated by radiation (film preheating step). Thereby, the aggregate side film surfaces 54a and 54a of the one and the other resin films 54 and 54 are melted.
- the FRP precursor 60 is obtained (film pressure welding process). At this time, by controlling the temperature of the heating bodies inside the pair of heating and compression rollers, the pair of heating and compression rollers are maintained at a predetermined temperature, and pressure is applied while heating in the film pressing process.
- the temperature of the heat compression roller ranges from minus 40 ° C. to plus 20 ° C. of the lowest melt viscosity temperature measured by a rheometer of the thermosetting resin composition used. Is preferred.
- the pressure may be any linear pressure, but IPC-TM-650 No.
- the heating and pressurization is carried out by roll laminating by the test method of 2.3.3.11, and the bleeding of 1.6 mm punch holes is preferably 50 ⁇ m or more and the bleeding of 6.4 mm punch holes is preferably 1200 ⁇ m or less. More preferably, the bleeding of a punch hole of 6 mm is 100 ⁇ m or more and the bleeding of a punch hole of 6.4 mm is 500 ⁇ m or less.
- the minimum melt viscosity temperature of the thermosetting resin composition is preferably 60 to 150 ° C., more preferably 80 to 140 ° C., and further preferably 100 to 130 ° C. from the viewpoint of productivity of the FRP precursor.
- the resin film 54 is bonded to the aggregate 40 in the air with good workability. At that time, the resin film 54 is not melted and flowed by heating the aggregate-side film surface 54a over the carrier film by the heating and compression roller of the sheet heating and pressing apparatus 6, but the resin film 54 is bonded to the aggregate 40.
- the aggregate 40 is heated from the side to be heated or in advance. As a result, the temperature of the resin melted on the front surface 40a and the back surface 40b of the aggregate 40 is not lowered, so that the resin can be heated to improve the impregnation property by reducing the viscosity, and the heating / heating of the sheet heating / pressurizing device 6 can be improved.
- the FRP precursor 60 sent out from the sheet heating and pressurizing device 6 is further pressurized and cooled by the sheet pressurizing and cooling device 7.
- the FRP precursor 60 sent out from the sheet pressure cooling device 7 is wound up by the FRP precursor winding device 8.
- the FRP precursor manufactured by the FRP precursor manufacturing apparatus 1 will be described.
- inorganic fiber base materials such as glass and carbon
- organic fiber base materials such as aramid and cellulose
- metal fiber base materials made of iron, copper, aluminum, alloys of these metals, etc. Examples thereof include woven fabrics and non-woven fabrics used alone or in combination.
- thermosetting resin composition a composition containing a thermosetting resin
- thermosetting resins examples include phenolic resins, urea resins, furan resins, and epoxy resins.
- an epoxy resin is preferable in terms of workability, handleability, and cost.
- the epoxy resin is preferably a bifunctional or higher epoxy resin.
- Bifunctional or higher epoxy resins include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AD type epoxy resins and the like; alicyclic epoxy resins; phenol novolac type epoxy resins and cresol novolac type epoxy resins. And bisphenol A novolac type epoxy resins, aralkyl novolac type epoxy resins and other novolak type epoxy resins; polyfunctional phenol diglycidyl etherified products; and hydrogenated products thereof. These epoxy resins may be used independently and may use 2 or more types together. When flame retardancy is required, a halogenated epoxy resin may be blended.
- flame retardant such as tetrabromobisphenol A, decabromodiphenyl ether, antimony oxide, tetraphenylphosphine, organophosphorus compound, zinc oxide You may add the compound called an adjuvant.
- an epoxy resin curing agent When using an epoxy resin as the thermosetting resin, an epoxy resin curing agent may be used.
- the epoxy resin curing agent include phenol resin, amine compound, acid anhydride, boron trifluoride monoethylamine, isocyanate, dicyandiamide, urea resin, and the like.
- a novolak type phenol resin such as a phenol novolak resin or a cresol novolak resin; a naphthalene type phenol resin, a high ortho type novolak phenol resin, a terpene modified phenol resin, a terpene phenol modified phenol resin, an aralkyl type phenol resin, a dicyclopentadiene type
- phenol resins salicylaldehyde type phenol resins, and benzaldehyde type phenol resins.
- a phenol novolak resin, a cresol novolak resin, and a partially modified aminotriazine novolak resin are preferable.
- Examples of the amine compound include aliphatic amines such as triethylenetetramine, tetraethylenepentamine, and diethylaminopropylamine; aromatic amines such as metaphenylenediamine and 4,4′-diaminodiphenylmethane.
- Examples of the acid anhydride include phthalic anhydride, methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride and the like. These epoxy resin curing agents may be used alone or in combination of two or more.
- the compounding amount of the epoxy resin curing agent is preferably such that the reactive group equivalent ratio of the curing agent is 0.3 to 1.5 equivalents with respect to the epoxy equivalent 1 of the epoxy resin.
- the blending amount of the epoxy resin curing agent is within the above range, it is easy to control the degree of curing and the productivity is improved.
- the thermosetting resin composition may further contain a curing accelerator.
- the curing accelerator include imidazole compounds, organic phosphorus compounds, tertiary amines, and quaternary ammonium salts.
- the imidazole compound may be an imidazole compound having a potential by masking the secondary amino group of imidazole with acrylonitrile, isocyanate, melamine, acrylate or the like.
- Examples of imidazole compounds used here include imidazole, 2-methylimidazole, 4-ethyl-2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 1-benzyl-2-methylimidazole, 2-heptadecylimidazole.
- the blending amount of the curing accelerator is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the epoxy resin. When it is 0.01 part by mass or more, a sufficient curing acceleration effect is obtained, and when it is 20 parts by mass or less, the preservability of the thermosetting resin composition and the physical properties of the cured product are excellent, and the economy is also excellent.
- the thermosetting resin composition may further contain a filler for improving the impermeability and wear resistance and increasing the amount.
- Fillers include oxides such as silica, aluminum oxide, zirconia, mullite and magnesia; hydroxides such as aluminum hydroxide, magnesium hydroxide and hydrotalcite; nitride ceramics such as aluminum nitride, silicon nitride and boron nitride Natural minerals such as talc, montmorillonite, saponite; metal particles, carbon particles, and the like.
- the filler Since the filler is wide from a small specific gravity to a large one compared with the resin, it is preferable to consider the addition amount of the filler not by mass but by volume ratio.
- the blending amount of the filler varies greatly depending on the purpose of addition, but is preferably in the range of 0.1 to 65 volume% in the solid content volume of the thermosetting resin composition. When it is 0.1% by volume or more, a sufficient effect is exhibited when it is added for the purpose of coloring and impermeability. Moreover, the increase in a viscosity can be suppressed as it is 65 volume% or less, and without increasing workability
- the solid content in the present specification refers to components in the composition other than water and a volatile substance such as an organic solvent described later. That is, the solid content includes liquid, water tank-like and wax-like substances at room temperature around 25 ° C., and does not necessarily mean solid.
- a flexible material may be added in order to impart tackiness of the resin to the cured resin and improve adhesion during adhesion.
- flexible materials polystyrene, polyolefin, polyurethane, acrylic resin, acrylonitrile rubber, polyvinyl alcohol, products modified with epoxy or carboxy group to incorporate them into the curing system, epoxy resin is reacted in advance to increase molecular weight Phenoxy and the like.
- the blending amount of the flexible material is preferably 3 to 200 parts by mass with respect to the solid content of the thermosetting resin composition.
- the upper limit value may be determined as appropriate according to the purpose without being limited to the above range.
- thermosetting resin composition is preferably in the form of a varnish dissolved and / or dispersed in an organic solvent in order to achieve uniformity.
- Organic solvents include acetone, methyl ethyl ketone, toluene, xylene, cyclohexanone, 4-methyl-2-pentanone, ethyl acetate, ethylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol monomethyl ether , N, N-dimethylformamide, N, N-dimethylacetamide and the like. These organic solvents may be used alone or in combination of two or more.
- powder mixing may be performed by mixing the above materials in powder form, or an aqueous solution may be formed by saponification or the like. Further, it may be made uniform by directly stirring and mixing at a temperature at which the curing of the thermosetting resin does not significantly progress and a temperature at which the thermosetting resin liquefies.
- a coupling agent may be added to improve the dispersibility of the filler and improve the adhesion to the aggregate or the object.
- silane coupling agents having a vinyl group such as vinyltrichlorosilane and vinyltriethoxysilane; 3-glycidoxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and the like
- Silane coupling agent having amino group such as 3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane
- Titanate coupling agent Etc is a vinyl group such as vinyltrichlorosilane and vinyltriethoxysilane; 3-glycidoxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and the like
- the addition amount of the coupling agent is preferably 0.01 to 5 parts by mass with respect to the solid content of the thermosetting resin composition.
- the amount is 0.01 parts by mass or more, the surface of the aggregate and the surface of the filler can be sufficiently covered, and when the amount is 5 parts by mass or less, generation of an excess coupling agent can be suppressed.
- thermosetting resin film can be obtained by applying the thermosetting resin composition obtained by the above blending to a carrier film, removing an unnecessary organic solvent, and thermosetting the composition.
- the thermosetting here is intended to bring the thermosetting resin composition into a so-called semi-cured (B-staged) state, and the thermosetting is performed so that the workability of the laminate has a good viscosity. It is preferable to semi-cure the conductive resin composition.
- carrier films include organic films such as polyethylene terephthalate (PET), biaxially oriented polypropylene (OPP), polyethylene, polyvinyl fluorate, and polyimide; films of copper, aluminum, and alloys of these metals; The film etc.
- thermosetting resin composition which performed the mold release process by the mold release agent on the surface are mentioned. Moreover, workability
- the thickness of the thermosetting resin film used is arbitrary, and when using a thermosetting resin film thinner than the aggregate thickness, the thermosetting resin is used.
- a film of thermosetting resin may be laminated again on the laminate of the above film on the aggregate.
- thermosetting resin films those having different thermosetting degrees, blending compositions, and the like may be used in combination.
- an FRP precursor obtained by laminating a thermosetting resin film on an aggregate is obtained, it may be cut into an arbitrary size, adhered to a predetermined object, and thermally cured. Moreover, you may use by a roll to roll.
- thermosetting resin varnish A having a nonvolatile content of 70% by mass.
- thermosetting resin varnish A was applied to a 580 mm wide PET film (G-2; manufactured by Teijin DuPont Films Ltd.) so that the coating width was 525 mm and the thickness after drying was 20 ⁇ m. A was produced.
- the minimum melt viscosity temperature of the produced thermosetting resin film A was measured using a rheometer (AR-200ex; manufactured by TA Instruments Japan Co., Ltd., ⁇ 20 mm jig) at a temperature rising rate of 3 ° C./min.
- the minimum melt viscosity temperature was 128 ° C.
- thermosetting resin film A is applied from both sides to a glass woven fabric (basis weight 48 g / m 2 , IPC # 1080, base material width 530 mm: manufactured by Nitto Boseki Co., Ltd.) which is a pre-warmed aggregate. Then, sandwiched between heat and pressure rolls, the aggregate was pressure impregnated with a thermosetting resin, then cooled with a cooling roll, wound up, and FRP precursor A was produced.
- the pressure roll conditions for the laminate were a roll temperature of 100 ° C., a linear pressure of 0.2 MPa, and a speed of 2.0 m / min.
- Heating of the thermosetting resin film A to the aggregate-side film surface was performed using a halogen heater (UH-USF-CL-700; manufactured by Ushio Inc.). The heating position was adjusted so that the center of the heating surface of the halogen heater was 30 mm before the pressure roll, and the heating temperature was adjusted so that the surface temperature was 135 ° C. at the center of the heating surface.
- Aggregate surface heating was also performed using the same halogen heater as described above, and the aggregate surface temperature was adjusted to 140 ° C.
- thermosetting resin varnish A of Example 1 was applied to a 580 mm wide PET film so that the coating width was 525 mm and the thickness after drying was 50 ⁇ m to prepare a thermosetting resin film B.
- the minimum melt viscosity temperature of the thermosetting resin film B measured under the same conditions as in Example 1 was 122 ° C.
- FRP precursor B was produced in the same manner as in Example 1 except that instead of thermosetting resin film A in Example 1, thermosetting resin film B was used.
- thermosetting resin varnish A of Example 1 was applied to a PET film having a width of 580 mm so that the coating width was 525 mm and the thickness after drying was 80 ⁇ m, thereby preparing a thermosetting resin film C.
- the minimum melt viscosity temperature of the thermosetting resin film C measured under the same conditions as in Example 1 was 117 ° C.
- a glass woven fabric (basis weight 209 g / m 2 , IPC # 7628, substrate width 530 mm: manufactured by Nitto Boseki Co., Ltd.) is used as an aggregate, and the thermosetting resin film A is used instead of the thermosetting resin film A.
- FRP precursor C was produced in the same manner as in Example 1 except that C was used.
- thermosetting resin varnish A of Example 1 was applied to a PET film having a width of 580 mm so that the coating width was 525 mm and the thickness after drying was 40 ⁇ m to prepare a thermosetting resin film D.
- the minimum melt viscosity temperature of the thermosetting resin film D measured under the same conditions as in Example 1 was 108 ° C.
- thermosetting resin film D both sides of the pre-warmed thermosetting resin film D are placed on a pre-warmed aggregate aramid paper (Nomex 411, nominal thickness 0.18 mm, basis weight 175 g / m 2 , manufactured by DuPont Teijin Advanced Paper Co., Ltd.). Then, it was sandwiched between heat and pressure rolls, and the aggregate was pressure impregnated with thermosetting resin, and then cooled and wound with a cooling roll to prepare FRP precursor D.
- the pressure roll conditions for the laminate were a roll temperature of 80 ° C., a linear pressure of 0.2 MPa, and a speed of 2.0 m / min.
- Heating of the thermosetting resin film D to the aggregate-side film surface is performed with the same halogen heater as in Example 1, and the heating position is 50 mm before the center of the heating surface of the heater from the pressure roll.
- the heating temperature was adjusted so that the surface temperature was 120 ° C. at the center of the heating surface.
- Aggregate surface heating was also performed using the same halogen heater as described above, and the aggregate surface temperature was adjusted to 140 ° C.
- thermosetting resin film A was prepared in the same manner as in Example 1, and both surfaces of an aggregate glass woven fabric (basis weight 48 g / m 2 , IPC # 1080, substrate width 530 mm: manufactured by Nitto Boseki Co., Ltd.) Laminated. Heating of the thermosetting resin film A and the aggregate before lamination was not performed.
- the pressure roll conditions for the laminate were a roll temperature of 100 ° C., a linear pressure of 0.2 MPa, and a speed of 2.0 m / min.
- thermosetting resin film A was prepared in the same manner as in Example 1, and both surfaces of an aggregate glass woven fabric (basis weight 48 g / m 2 , IPC # 1080, substrate width 530 mm: manufactured by Nitto Boseki Co., Ltd.) Laminated. Heating of the thermosetting resin film A and the aggregate before lamination was not performed.
- the pressure roll conditions for the laminate were a roll temperature of 150 ° C., a linear pressure of 0.3 MPa, and a speed of 1.5 m / min.
- thermosetting resin varnish A of Example 1 was prepared, and the thermosetting resin varnish A was applied to a glass woven fabric (basis weight 48 g / m 2 , IPC # 1080: manufactured by Nittobo Co., Ltd.) as an aggregate. After coating using a machine, the coating was dried to remove the solvent and thermally cure. The coating weight was adjusted by a squeeze roll method, and the amount of the adhered resin was applied with a target equivalent to that in Example 2.
- thermosetting resin film C in the same manner as in Example 3, a glass woven fabric is a bone material (basis weight 209g / m 2, IPC # 7628 : manufactured by Nitto Boseki Co., Ltd.) was laminated on both sides of. Heating of the thermosetting resin film C and the aggregate before lamination was not performed.
- the pressure roll conditions for the laminate were a roll temperature of 150 ° C., a linear pressure of 0.3 MPa, and a speed of 1.2 m / min.
- Impregnation to aggregate After cooling the FRP precursor with liquid nitrogen, cutting and returning to room temperature (25 ° C.), the fracture surface was observed with an optical microscope and evaluated according to the following criteria. A: Presence of unfilled portion was not confirmed. B: Presence of an unfilled portion was confirmed.
- the FRP precursor obtained by the production method of the present invention is excellent in resin filling properties into the bulk voids of the aggregate, and is able to achieve prevention of resin ejection from the end. I understand.
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Abstract
Description
これらの性能を生かして、FRPは幅広い分野で使用されている。例えば、FRPは、造型性及び高い強度を有することから、住宅機器、船舶、車両、航空機などの構造材として使用されている。また、絶縁性を生かして、電気装置、プリント配線板などの電子部品分野でも使用されている。
そのため、プリント配線板用のFRPの多くが、ハンドレイアップ(Hand Lay-up;HLU)法で製造されている。ハンドレイアップ法は、塗工機を用いて、骨材に、樹脂を溶解したワニスを塗布し、乾燥させて溶剤除去及び熱硬化を行う製造方法である(特許文献1)。ハンドレイアップ法は、予め、骨材に熱硬化性樹脂を塗布しておくと、作業性が向上し、また、周辺の環境にかかる負荷を低減させることができる。
すなわち、本発明は、以下のとおりである。
前記骨材の一方の表面を加熱する骨材表面加熱工程と、
常圧下において、前記フィルムの両表面のうち、前記骨材側の表面である骨材側フィルム表面を、加熱された前記骨材の一方の表面である骨材表面に圧接させてFRP前駆体を得るフィルム圧接工程と、を含む、FRP前駆体の製造方法。
[2]前記フィルム圧接工程が、前記フィルムと前記骨材とを加熱しながら圧接する工程であり、前記骨材表面加熱工程における、前記骨材の一方の表面の加熱温度が、前記フィルム圧接工程の加熱温度より、5~70℃高温である、上記[1]に記載のFRP前駆体の製造方法。
[3]さらに、前記骨材側フィルム表面を、前記骨材側フィルム表面側からの輻射により加熱するフィルム予備加熱工程を含む、上記[1]又は[2]に記載のFRP前駆体の製造方法。
[4]前記フィルム圧接工程が、前記フィルムと前記骨材とを加熱しながら圧接する工程であり、前記フィルム予備加熱工程における、前記骨材側フィルム表面の加熱温度が、前記フィルム圧接工程の加熱温度より、5~70℃高温である、上記[3]に記載のFRP前駆体の製造方法。
[5]前記フィルム圧接工程を、前記熱硬化性樹脂のフィルムの最低溶融粘度温度のマイナス40℃からプラス20℃の範囲で行う、上記[1]~[4]のいずれかに記載のFRP前駆体の製造方法。
[6]シート状の骨材の両方の表面にそれぞれ熱硬化性樹脂の一対のフィルムを溶融貼付してFRP前駆体を製造するFRP前駆体の製造方法であって、
前記骨材の両方の表面である骨材両表面を加熱する骨材表面加熱工程と、
常圧下において、前記一対のフィルムのうち一方のフィルムの両表面のうち、前記骨材側の表面である一方の骨材側フィルム表面を、加熱された前記骨材両表面の一方の表面に圧接させ、前記一対のフィルムのうち他方のフィルムの両表面のうち、前記骨材側の表面である他方の骨材側フィルム表面を、加熱された前記骨材両表面の他方の表面に圧接させてFRP前駆体を得るフィルム圧接工程と、を含む、FRP前駆体の製造方法。
[7]前記フィルム圧接工程が、前記一対のフィルムと前記骨材とを加熱しながら圧接する工程であり、前記骨材表面加熱工程における、前記骨材両表面の加熱温度が、前記フィルム圧接工程の加熱温度より、5~70℃高温である、上記[6]に記載のFRP前駆体の製造方法。
[8]さらに、前記一方の骨材側フィルム表面を、前記一方の骨材側フィルム表面側からの輻射により加熱し、前記他方の骨材側フィルム表面を、前記他方の骨材側フィルム表面側からの輻射により加熱するフィルム予備加熱工程を含む、上記[7]に記載のFRP前駆体の製造方法。
[9]前記フィルム圧接工程が、前記一対のフィルムと前記骨材とを加熱しながら圧接する工程であり、前記フィルム予備加熱工程における、前記一方の骨材側フィルム表面及び前記他方の骨材側フィルム表面の加熱温度は、それぞれ、前記フィルム圧接工程の加熱温度より、5~70℃高温である、上記[8]に記載のFRP前駆体の製造方法。
[10]前記フィルム圧接工程を、前記熱硬化性樹脂のフィルムの最低溶融粘度温度のマイナス40℃からプラス20℃の範囲で行う、上記[6]~[9]のいずれかに記載のFRP前駆体の製造方法。
[11]上記[1]~[5]のいずれかに記載のFRP前駆体の製造方法に用いられるFRP前駆体の製造装置であって、
前記骨材の一方の表面を加熱する骨材表面加熱手段と、
常圧下において、前記フィルムの両表面のうち、前記骨材側の表面である骨材側フィルム表面を、加熱された前記骨材の一方の表面である骨材表面に圧接させてFRP前駆体を得るフィルム圧接手段と、を含む、FRP前駆体の製造装置。
[12]上記[6]~[10]のいずれかに記載のFRP前駆体の製造方法に用いられるFRP前駆体の製造装置であって、
前記骨材の両方の表面である骨材両表面を加熱する骨材表面加熱手段と、
常圧下において、前記一対のフィルムのうち一方のフィルムの両表面のうち、前記骨材側の表面である一方の骨材側フィルム表面を、加熱された前記骨材両表面の一方に圧接させ、前記一対のフィルムのうち他方のフィルムの両表面のうち、前記骨材側の表面である他方の骨材側フィルム表面を、加熱された前記骨材両表面の他方に圧接させてFRP前駆体を得るフィルム圧接手段と、を含む、FRP前駆体の製造装置。
FRP前駆体の製造装置1は、常圧下におかれる。本発明に係るFRP前駆体の製造方法は、FRP前駆体の製造装置1で行うことができる。
一方の樹脂フィルム送出装置3は、送り出された骨材40の表面40a側に位置し、保護フィルム52が、送り出された骨材40側になるように、一方の保護フィルム付き樹脂フィルム50をローラの下側から一方の保護フィルム剥がし機構4に向けて送り出す装置である。
同様に、他方の樹脂フィルム送出装置3は、送り出された骨材40の裏面40b側に位置し、保護フィルム52が、送り出された骨材40側になるように、他方の保護フィルム付き樹脂フィルム50をローラの上側から他方の保護フィルム剥がし機構4に向けて送り出す装置である。
一方の保護フィルム剥がし機構4は、一方の樹脂フィルム送出装置3から送り出され、一方の保護フィルム剥がし機構4に向けて進む保護フィルム付き樹脂フィルム50を、回転する転向ローラの表面で受け、一方の保護フィルム付き樹脂フィルム50のうち一方の樹脂フィルム54をシート加熱加圧装置6に向けて進ませると共に、一方の保護フィルム52を一方の保護フィルム巻取装置5に向けて進ませることにより、一方の保護フィルム付き樹脂フィルム50から一方の保護フィルム52を剥がす機構である。これにより、一方の樹脂フィルム54の骨材側フィルム表面54aが露出する。
同様に他方の保護フィルム剥がし機構4は、他方の樹脂フィルム送出装置3から送り出され、他方の保護フィルム剥がし機構4に向けて進む他方の保護フィルム付き樹脂フィルム50を、回転する転向ローラの表面で受け、他方の保護フィルム付き樹脂フィルム50のうち他方の樹脂フィルム54をシート加熱加圧装置6に向けて進ませると共に、他方の保護フィルム52を他方の保護フィルム巻取装置5に向けて進ませることにより、他方の保護フィルム付き樹脂フィルム50から他方の保護フィルム52を剥がす機構である。これにより、他方の樹脂フィルム54の骨材側フィルム表面54aが露出する。
なお、骨材の加熱方法は、輻射、接触、対流など種々使用できるが、後述する樹脂フィルムの加熱方法を利用すると簡便になり好ましい。加熱位置は、放冷を抑制する観点から、加熱圧縮ローラの手前でライン速度を計算して20秒以内の位置が好ましく、5秒以内の位置がより好ましい。
骨材表面加熱工程における、骨材40の表面40a及び裏面40bの加熱温度は、それぞれ、後のフィルム圧接工程の加熱温度より、5~70℃高温であることが好ましく、7~60℃高温であることがより好ましく、10~50℃高温であることが好ましい。
樹脂フィルム加熱装置11bは、送り出される他方の樹脂フィルム54の骨材側フィルム表面54aを加熱することができるように、送り出された骨材40の裏面40bと、他方の樹脂フィルム54の骨材側フィルム表面54aとの間に位置する。
一対の樹脂フィルム加熱装置11a及び11bは、それぞれ、常圧下において、一方及び他方の樹脂フィルム54及び54の骨材側フィルム表面54aを加熱する加熱体である。加熱体は、例えば、輻射型加熱体である。
また、フィルム予備加熱工程における、一対の樹脂フィルム54及び54の骨材側フィルム表面54a及び54aの加熱温度は、それぞれ、後のフィルム圧接工程の加熱温度より、5~70℃高温であることが好ましく、7~60℃高温であることがより好ましく、10~50℃高温であることが好ましい。
シート加熱加圧装置6は、入り込んだ骨材40に樹脂フィルム54、54を回転する一対の加熱圧縮ローラで圧接させてシート状のFRP前駆体60を形成する(フィルム圧接工程)と共に、FRP前駆体60をシート加圧冷却装置7に向けて送り出す。具体的には、骨材送出装置2から送り出された骨材40の表面40a及び裏面40bに、それぞれ、一対の保護フィルム剥がし機構4及び4から送り出された樹脂フィルム54及び54が積層するように、骨材送出装置2から送り出された骨材40と、一対の保護フィルム剥がし機構4、4からそれぞれ送り出された樹脂フィルム54、54とが、一対の加熱圧縮ローラの間に入り込む。
このとき、一方の樹脂フィルム54の骨材側フィルム表面54a側が骨材40の表面40a側に接着するように、一方の樹脂フィルム54が骨材40に積層し、また、他方の樹脂フィルム54の骨材側フィルム表面54a側が骨材40の裏面40b側に接着するように、他方の樹脂フィルム54が骨材40に積層してFRP前駆体60が形成される。シート加熱加圧装置6から送り出されたFRP前駆体60は高温状態である。
また、幅方向の加熱温度に差を付けると、幅方向における溶融した樹脂の硬化性の差が生じてしまうので、加熱量は同じであるがローララミネート時の温度が異なるように、加熱体をVの字型に配置して中央部と端部のローラまでの距離を制御することが好ましい。また、ローララミネート後は冷却圧縮ローラで冷却し、不要な熱の除去と製品の平坦化を行うことが好ましい。
剥がされた一対の保護フィルム52及び52は、それぞれ、一対の保護フィルム巻取装置5及び5で巻き取られる。
骨材側フィルム表面54aが露出した一方及び他方の樹脂フィルム54及び54がシート加熱加圧装置6に到達する前に、一方及び他方の樹脂フィルム54及び54を、それぞれ、一対の樹脂フィルム加熱装置11a及び11bで、一方及び他方の樹脂フィルム54及び54の骨材側フィルム表面54a及び54a側から輻射により加熱する(フィルム予備加熱工程)。これにより、一方及び他方の樹脂フィルム54及び54の骨材側フィルム表面54a及び54aが溶融する。
シート加圧冷却装置7から送り出されたFRP前駆体60を、FRP前駆体巻取装置8により、巻き取る。
難燃性が必要とされる場合は、ハロゲン化エポキシ樹脂を配合してもよい。また、ハロゲン化エポキシ樹脂を添加せずに難燃性を満足させるためにテトラブロモビスフェノールA、デカブロモジフェニルエーテル、酸化アンチモン、テトラフェニルフォスフィン、有機リン化合物、酸化亜鉛などの一般に難燃剤、難燃助剤と称される化合物を添加してもよい。
エポキシ樹脂硬化剤としては、フェノール樹脂、アミン化合物、酸無水物、3フッ化ホウ素モノエチルアミン、イソシアネート、ジシアンジアミド、ユリア樹脂などが挙げられる。
フェノール樹脂としては、フェノールノボラック樹脂、クレゾールノボラック樹脂等のノボラック型フェノール樹脂;ナフタレン型フェノール樹脂、ハイオルソ型ノボラックフェノール樹脂、テルペン変性フェノール樹脂、テルペンフェノール変性フェノール樹脂、アラルキル型フェノール樹脂、ジシクロペンタジエン型フェノール樹脂、サリチルアルデヒド型フェノール樹脂、ベンズアルデヒド型フェノール樹脂などが挙げられる。これらの中でも、フェノールノボラック樹脂、クレゾールノボラック樹脂、一部修飾されたアミノトリアジンノボラック樹脂が好ましい。
アミン化合物としては、トリエチレンテトラミン、テトラエチレンペンタミン、ジエチルアミノプロピルアミン等の脂肪族アミン;メタフェニレンジアミン、4,4’-ジアミノジフェニルメタン等の芳香族アミンなどが挙げられる。
酸無水物としては、無水フタル酸、メチルテトラヒドロ無水フタル酸、テトラヒドロ無水フタル酸、ヘキサヒドロ無水フタル酸などが挙げられる。これらのエポキシ樹脂硬化剤は単独で用いてもよく、2種以上を併用してもよい。
エポキシ樹脂硬化剤の配合量は、エポキシ樹脂のエポキシ当量1に対して、硬化剤の反応基当量比が0.3~1.5当量となる量が好ましい。エポキシ樹脂硬化剤の配合量が前記範囲内であると、硬化度の制御が容易であり、生産性が良好になる。
硬化促進剤としては、イミダゾール化合物、有機リン化合物、第3級アミン、第4級アンモニウム塩などが挙げられる。イミダゾール化合物は、イミダゾールの2級アミノ基をアクリロニトリル、イソシアネート、メラミン、アクリレートなどでマスク化して潜在性を持たしたイミダゾール化合物であってもよい。ここで用いられるイミダゾール化合物としては、イミダゾール、2-メチルイミダゾール、4-エチル-2-メチルイミダゾール、2-フェニルイミダゾール、2-ウンデシルイミダゾール、1-ベンジル-2-メチルイミダゾール、2-ヘプタデシルイミダゾール、4,5-ジフェニルイミダゾール、2-メチルイミダゾリン、2-エチル-4-メチルイミダゾリン、2-ウンデシルイミダゾリン、2-フェニル-4-メチルイミダゾリンなどが挙げられる。
また、光分解によりラジカル、アニオン又はカチオンを生成し硬化開始する光開始剤を使用してもよい。
これらの硬化促進剤は単独で用いてもよく、2種以上を併用してもよい。
充填材としては、シリカ、酸化アルミニウム、ジルコニア、ムライト、マグネシア等の酸化物;水酸化アルミニウム、水酸化マグネシウム、ハイドロタルサイト等の水酸化物;窒化アルミニウム、窒化珪素、窒化ホウ素等の窒化系セラミックス;タルク、モンモリロナイト、サポナイト等の天然鉱物;金属粒子、カーボン粒子などが挙げられる。
充填材の配合量は添加目的により大きく異なるが、熱硬化性樹脂組成物の固形分体積中、0.1~65体積%範囲が好ましい。0.1体積%以上であると、着色及び不透化目的で添加する場合に十分効果を発揮する。また、65体積%以下であると、粘度の増加を抑制し、作業性及び接着性を悪化させることなく増量することができる。
ここで、本明細書における固形分とは、水分、後述する有機溶剤等の揮発する物質以外の組成物中の成分のことをいう。すなわち、固形分は、25℃付近の室温で液状、水飴状及びワックス状のものも含み、必ずしも固体であることを意味するものではない。
可とう性材料としては、ポリスチレン、ポリオレフィン、ポリウレタン、アクリル樹脂、アクリルニトリルゴム、ポリビニルアルコール、それらを硬化系内に取り込むためエポキシ又はカルボキシ基などで変性した物、エポキシ樹脂を予め反応させ大分子化したフェノキシなどが挙げられる。これらの可とう性材料は単独で用いてもよく、2種以上を併用してもよい。
可とう性材料の配合量は、熱硬化樹脂組成物の固形分に対して、3~200質量部が好ましい。3質量部以上であると、可とう性を十分に付与することができ、200質量部以下であると、硬化物の弾性率を良好に保つことができる。ただし、弾性率の低下が目的の仕様に影響を与えない場合は、前記範囲に限らず、目的に応じて適宜上限値を決定すればよい。
有機溶剤としては、アセトン、メチルエチルケトン、トルエン、キシレン、シクロヘキサノン、4-メチル-2-ペンタノン、酢酸エチル、エチレングリコールモノエチルエーテル、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコールモノエチルエーテル、トリプロピレングリコールモノメチルエーテル、N,N-ジメチルホルムアミド、N,N-ジメチルアセトアミドなどが挙げられる。これらの有機溶剤は単独で用いてもよく、2種以上を併用してもよい。また特性上問題がなければ、上記材料を粉末状にして混合する粉体混合を行ってもよく、鹸濁化などにより水溶液化してもよい。また、熱硬化性樹脂の硬化が著しく進行しない温度且つ熱硬化性樹脂が液状化する温度下において直接攪拌し混合して均一化を図ってもよい。
カップリング剤の添加量は、熱硬化性樹脂組成物の固形分に対して、0.01~5質量部が好ましい。0.01質量部以上であると、骨材の表面及び充填材の表面を十分に被覆することができ、5質量部以下であると、余剰のカップリング剤の発生を抑制できる。
キャリアファルムとしては、ポリエチレンテレフタレート(PET)、二軸延伸ポリプロピレン(OPP)、ポリエチレン、ポリビニルフルオレート、ポリイミド等の有機フィルム;銅、アルミニウム、これら金属の合金のフィルム;これらの有機フィルム又は金属フィルムの表面に離型剤で離型処理を行ったフィルムなどが挙げられる。
また、熱硬化性樹脂組成物を塗布し半硬化させた面にキャリアフィルムを積層し熱硬化性樹脂組成物を挟んで巻き取ると作業性がよい。
また熱硬化性樹脂のフィルムを複数枚使用する場合、熱硬化性樹脂のフィルムの熱硬化度、配合組成等が異なるものを組み合わせて使用してもよい。
骨材に熱硬化性樹脂のフィルムをラミネートしたFRP前駆体を得る際、これを任意のサイズに切断し所定の物と接着、熱硬化を行ってもよい。また、ロールtoロールで使用してもよい。
(実施例1)
フェノールノボラック型エポキシ樹脂(N-660;DIC株式会社製)100質量部、クレゾールノボラック樹脂(KA-1165;DIC株式会社製)60質量部に、シクロヘキサン15質量部、メチルエチルケトン130質量部を加え、良く撹拌して溶解した。そこに、充填材として水酸化アルミニウム(CL-303;住友化学株式会社製)180質量部、カップリング剤(A-187;モメンティブ パフォーマンス マテリアルズ社製)1質量部、硬化促進剤としてイソシアネートマスクイミダゾール(G8009L;第一工業製薬株式会社製)2.5質量部を加え、撹拌して溶解及び分散を行い、不揮発分70質量%の熱硬化性樹脂ワニスAを得た。
作製した熱硬化性樹脂フィルムAの最低溶融粘度温度を、レオメータ(AR-200ex;ティー エイ インスツルメント ジャパン株式会社製、φ20mm冶具)を用いて昇温速度3℃/分の条件で測定したところ、最低溶融粘度温度は128℃であった。
ラミネートの加圧ロール条件は、ロール温度100℃、線圧0.2MPa、速度2.0m/分とした。
熱硬化性樹脂フィルムAの骨材側フィルム表面への加熱(フィルム予備加熱工程)はハロゲンヒータ(UH-USF-CL-700;ウシオ電機株式会社製)を用いて行った。加熱位置はハロゲンヒータの加熱面中心部が加圧ロールから30mm手前となる位置とし、加熱温度は加熱面中心で表面温度が135℃になるように調整した。
骨材の表面の加熱(骨材表面加熱工程)も上記と同様のハロゲンヒータを用いて行い、骨材の表面温度が140℃になるように調整した。
実施例1の熱硬化性樹脂ワニスAを、580mm幅のPETフィルムに、塗布幅525mm、乾燥後の厚みが50μmになるように塗布して熱硬化性樹脂フィルムBを作製した。実施例1と同様の条件で測定した熱硬化性樹脂フィルムBの最低溶融粘度温度は122℃であった。
次に、実施例1において、熱硬化性樹脂フィルムAに変えて、熱硬化性樹脂フィルムBを用いた以外は、実施例1と同様の方法により、FRP前駆体Bを作製した。
実施例1の熱硬化性樹脂ワニスAを、580mm幅のPETフィルムに、塗布幅525mm、乾燥後の厚みが80μmになるように塗布して熱硬化性樹脂フィルムCを作製した。実施例1と同様の条件で測定した熱硬化性樹脂フィルムCの最低溶融粘度温度は117℃であった。
次に、骨材としてガラス織布(坪量209g/m2、IPC#7628、基材幅530mm:日東紡績株式会社製)を用い、熱硬化性樹脂フィルムAに変えて、熱硬化性樹脂フィルムCを用いた以外は、実施例1と同様の方法により、FRP前駆体Cを作製した。
実施例1の熱硬化性樹脂ワニスAを、580mm幅のPETフィルムに、塗布幅525mm、乾燥後の厚みが40μmになるように塗布して熱硬化性樹脂フィルムDを作製した。実施例1と同様の条件で測定した熱硬化性樹脂フィルムDの最低溶融粘度温度は108℃であった。
ラミネートの加圧ロール条件は、ロール温度80℃、線圧0.2MPa、速度2.0m/分とした。
熱硬化性樹脂フィルムDの骨材側フィルム表面への加熱(フィルム予備加熱工程)は実施例1と同様のハロゲンヒータで行い、加熱位置はヒータの加熱面中心部が加圧ロールから50mm手前となる位置とし、加熱温度は加熱面中心で表面温度が120℃になるように調整した。
骨材の表面の加熱(骨材表面加熱工程)も上記と同様のハロゲンヒータを用いて行い、骨材の表面温度が140℃になるように調整した。
実施例1と同様の手法で熱硬化性樹脂フィルムAを作製し、骨材であるガラス織布(坪量48g/m2、IPC#1080、基材幅530mm:日東紡績株式会社製)の両面にラミネートした。ラミネート前における熱硬化性樹脂フィルムA及び骨材の加熱は行わなかった。ラミネートの加圧ロール条件は、ロール温度100℃、線圧0.2MPa、速度2.0m/分とした。
実施例1と同様の手法で熱硬化性樹脂フィルムAを作製し、骨材であるガラス織布(坪量48g/m2、IPC#1080、基材幅530mm:日東紡績株式会社製)の両面にラミネートした。ラミネート前における熱硬化性樹脂フィルムA及び骨材の加熱は行わなかった。ラミネートの加圧ロール条件は、ロール温度150℃、線圧0.3MPa、速度1.5m/分とした。
実施例1の熱硬化性樹脂ワニスAを作製し、該熱硬化性樹脂ワニスAを、骨材であるガラス織布(坪量48g/m2、IPC#1080:日東紡績株式会社製)に塗工機を用いて塗布した後、乾燥させて溶剤除去及び熱硬化させた。塗布重量の調整はスクイズロール法で行い、付着樹脂量は実施例2相当量を目標に塗工した。
実施例3と同様の手法で熱硬化性樹脂フィルムCを作製し、骨材であるガラス織布(坪量209g/m2、IPC#7628:日東紡績株式会社製)の両面にラミネートした。ラミネート前における熱硬化性樹脂フィルムC及び骨材の加熱は行わなかった。ラミネートの加圧ロール条件は、ロール温度150℃、線圧0.3MPa、速度1.2m/分とした。
実施例及び比較例で得られたFRP前駆体について、以下の評価を行った。結果を表1に示す。
各例で得られたFRP前駆体の幅方向の中心から50mm単位で幅方向に計11点、前記11点を各々起点として長さ方向に50mm単位で10点(すなわち、11点×10点=110点)の厚みを、アップライトゲージを用いて0.001mm単位で測定し、その最大値と最小値との間の差を求め、厚みのばらつきとした。
端部からの樹脂染み出しは、IPC-TM-650 No.2.3.17.1の試験方法により測定した。
FRP前駆体を液体窒素で冷却後、切断し、室温(25℃)に戻した後、光学顕微鏡により破断面を観察し、下記基準に従って評価した。
A:未充填部分の存在が確認されなかった。
B:未充填部分の存在が確認された。
2 骨材送出装置
3 樹脂フィルム送出装置
4 保護フィルム剥がし機構
5 保護フィルム巻取装置
6 シート加熱加圧装置(フィルム圧接手段)
7 シート加圧冷却装置
8 FRP前駆体巻取装置
10 骨材加熱装置(骨材表面加熱手段)
11a、11b 樹脂フィルム加熱装置
40 骨材
40a 骨材の表面(骨材の一方の表面、骨材両表面の一方)
40b 骨材の裏面(骨材の他方の表面、骨材両表面の他方)
50 保護フィルム付き樹脂フィルム
52 保護フィルム
54 樹脂フィルム(フィルム)
54a 樹脂フィルムの骨材側の表面(骨材側フィルム表面)
60 FRP前駆体
Claims (12)
- シート状の骨材の一方の表面に熱硬化性樹脂のフィルムを溶融貼付してFRP前駆体を製造するFRP前駆体の製造方法であって、
前記骨材の一方の表面を加熱する骨材表面加熱工程と、
常圧下において、前記フィルムの両表面のうち、前記骨材側の表面である骨材側フィルム表面を、加熱された前記骨材の一方の表面である骨材表面に圧接させてFRP前駆体を得るフィルム圧接工程と、を含む、FRP前駆体の製造方法。 - 前記フィルム圧接工程が、前記フィルムと前記骨材とを加熱しながら圧接する工程であり、前記骨材表面加熱工程における、前記骨材の一方の表面の加熱温度が、前記フィルム圧接工程の加熱温度より、5~70℃高温である、請求項1に記載のFRP前駆体の製造方法。
- さらに、前記骨材側フィルム表面を、前記骨材側フィルム表面側からの輻射により加熱するフィルム予備加熱工程を含む、請求項1又は2に記載のFRP前駆体の製造方法。
- 前記フィルム圧接工程が、前記フィルムと前記骨材とを加熱しながら圧接する工程であり、前記フィルム予備加熱工程における、前記骨材側フィルム表面の加熱温度が、前記フィルム圧接工程の加熱温度より、5~70℃高温である、請求項3に記載のFRP前駆体の製造方法。
- 前記フィルム圧接工程を、前記熱硬化性樹脂のフィルムの最低溶融粘度温度のマイナス40℃からプラス20℃の範囲で行う、請求項1~4のいずれか1項に記載のFRP前駆体の製造方法。
- シート状の骨材の両方の表面にそれぞれ熱硬化性樹脂の一対のフィルムを溶融貼付してFRP前駆体を製造するFRP前駆体の製造方法であって、
前記骨材の両方の表面である骨材両表面を加熱する骨材表面加熱工程と、
常圧下において、前記一対のフィルムのうち一方のフィルムの両表面のうち、前記骨材側の表面である一方の骨材側フィルム表面を、加熱された前記骨材両表面の一方の表面に圧接させ、前記一対のフィルムのうち他方のフィルムの両表面のうち、前記骨材側の表面である他方の骨材側フィルム表面を、加熱された前記骨材両表面の他方の表面に圧接させてFRP前駆体を得るフィルム圧接工程と、を含む、FRP前駆体の製造方法。 - 前記フィルム圧接工程が、前記一対のフィルムと前記骨材とを加熱しながら圧接する工程であり、前記骨材表面加熱工程における、前記骨材両表面の加熱温度が、前記フィルム圧接工程の加熱温度より、5~70℃高温である、請求項6に記載のFRP前駆体の製造方法。
- さらに、前記一方の骨材側フィルム表面を、前記一方の骨材側フィルム表面側からの輻射により加熱し、前記他方の骨材側フィルム表面を、前記他方の骨材側フィルム表面側からの輻射により加熱するフィルム予備加熱工程を含む、請求項7に記載のFRP前駆体の製造方法。
- 前記フィルム圧接工程が、前記一対のフィルムと前記骨材とを加熱しながら圧接する工程であり、前記フィルム予備加熱工程における、前記一方の骨材側フィルム表面及び前記他方の骨材側フィルム表面の加熱温度は、それぞれ、前記フィルム圧接工程の加熱温度より、5~70℃高温である、請求項8に記載のFRP前駆体の製造方法。
- 前記フィルム圧接工程を、前記熱硬化性樹脂のフィルムの最低溶融粘度温度のマイナス40℃からプラス20℃の範囲で行う、請求項6~9のいずれか1項に記載のFRP前駆体の製造方法。
- 請求項1~5のいずれか1項に記載のFRP前駆体の製造方法に用いられるFRP前駆体の製造装置であって、
前記骨材の一方の表面を加熱する骨材表面加熱手段と、
常圧下において、前記フィルムの両表面のうち、前記骨材側の表面である骨材側フィルム表面を、加熱された前記骨材の一方の表面である骨材表面に圧接させてFRP前駆体を得るフィルム圧接手段と、を含む、FRP前駆体の製造装置。 - 請求項6~10のいずれか1項に記載のFRP前駆体の製造方法に用いられるFRP前駆体の製造装置であって、
前記骨材の両方の表面である骨材両表面を加熱する骨材表面加熱手段と、
常圧下において、前記一対のフィルムのうち一方のフィルムの両表面のうち、前記骨材側の表面である一方の骨材側フィルム表面を、加熱された前記骨材両表面の一方に圧接させ、前記一対のフィルムのうち他方のフィルムの両表面のうち、前記骨材側の表面である他方の骨材側フィルム表面を、加熱された前記骨材両表面の他方に圧接させてFRP前駆体を得るフィルム圧接手段と、を含む、FRP前駆体の製造装置。
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018181513A1 (ja) * | 2017-03-28 | 2018-10-04 | 日立化成株式会社 | Frp前駆体の製造方法及びfrpの製造方法 |
| JP2018165339A (ja) * | 2017-03-28 | 2018-10-25 | 日立化成株式会社 | コアレス基板用プリプレグ、コアレス基板用プリプレグの製造方法及び製造装置、並びにコアレス基板及びその製造方法 |
| JP2019102503A (ja) * | 2017-11-28 | 2019-06-24 | 藤森工業株式会社 | カバーレイフィルムおよびそれを用いた電子機器 |
| JP2020015259A (ja) * | 2018-07-26 | 2020-01-30 | 日立化成株式会社 | Frp前駆体の製造方法及びその製造装置 |
| WO2022054928A1 (ja) * | 2020-09-11 | 2022-03-17 | 昭和電工マテリアルズ株式会社 | Frp前駆体の製造方法 |
| JP2023036041A (ja) * | 2021-09-01 | 2023-03-13 | 臺灣塑膠工業股▲ふん▼有限公司 | 繊維プリプレグの含浸装置及びその方法 |
| WO2023218969A1 (ja) * | 2022-05-10 | 2023-11-16 | 株式会社レゾナック | Frp前駆体の製造方法及びfrpの製造方法 |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5878724A (ja) * | 1981-11-04 | 1983-05-12 | Toshiba Corp | 半硬化材料の製造方法 |
| JPH04219213A (ja) * | 1990-03-30 | 1992-08-10 | Kuraray Co Ltd | 繊維強化樹脂シート、その製造方法および製造装置 |
| JPH05200748A (ja) * | 1991-09-03 | 1993-08-10 | Kurt Held | 樹脂含浸された材料ウェブを連続的に製造する方法および装置 |
| JP2011132389A (ja) * | 2009-12-25 | 2011-07-07 | Toray Ind Inc | シート状プリプレグおよびその製造方法 |
| WO2013014893A1 (ja) * | 2011-07-22 | 2013-01-31 | 住友ベークライト株式会社 | 積層シート製造装置および積層シートの製造方法 |
| JP2013108058A (ja) * | 2011-10-28 | 2013-06-06 | Toray Ind Inc | プリプレグの製造方法 |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01272416A (ja) | 1988-04-25 | 1989-10-31 | Hitachi Chem Co Ltd | プリプレグの製造方法 |
| JP4086942B2 (ja) | 1997-10-20 | 2008-05-14 | 東邦テナックス株式会社 | プリプレグの製造装置 |
| CN101973146B (zh) | 2005-09-30 | 2012-09-26 | 住友电木株式会社 | 带有载体的预浸料及其制造工艺、薄双面板及其制造工艺和多层印刷电路板的制造工艺 |
| KR20120078465A (ko) * | 2010-12-31 | 2012-07-10 | 주식회사 효성 | 섬유 함량이 균일한 일방향 프리프레그의 제조 방법 및 장치 |
| TWI458766B (zh) * | 2011-03-03 | 2014-11-01 | Mitsubishi Rayon Co | 基質樹脂組成物、預浸體及其製造方法以及纖維強化複合材料 |
| JP6353184B2 (ja) * | 2012-07-26 | 2018-07-04 | 味の素株式会社 | 保護フィルム付き接着シート、積層体の製造方法、及びプリント配線板の製造方法 |
| CN103660308B (zh) * | 2012-08-30 | 2018-02-27 | 上海杰事杰新材料(集团)股份有限公司 | 连续纤维织物增强热塑性树脂复合材料及其制作方法 |
| CN204282016U (zh) * | 2014-11-03 | 2015-04-22 | 中国石油化工股份有限公司 | 一种用于树脂涂覆的织机附加机构 |
-
2016
- 2016-04-27 CN CN202310797668.2A patent/CN116834174A/zh active Pending
- 2016-04-27 JP JP2017516601A patent/JP6720967B2/ja active Active
- 2016-04-27 CN CN201680022798.7A patent/CN107530907A/zh active Pending
- 2016-04-27 WO PCT/JP2016/063263 patent/WO2016178399A1/ja not_active Ceased
- 2016-04-27 US US15/570,998 patent/US10933562B2/en active Active
- 2016-04-27 KR KR1020177030254A patent/KR102385212B1/ko active Active
- 2016-04-28 TW TW105113300A patent/TWI701126B/zh active
- 2016-04-28 TW TW109122348A patent/TWI771704B/zh active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5878724A (ja) * | 1981-11-04 | 1983-05-12 | Toshiba Corp | 半硬化材料の製造方法 |
| JPH04219213A (ja) * | 1990-03-30 | 1992-08-10 | Kuraray Co Ltd | 繊維強化樹脂シート、その製造方法および製造装置 |
| JPH05200748A (ja) * | 1991-09-03 | 1993-08-10 | Kurt Held | 樹脂含浸された材料ウェブを連続的に製造する方法および装置 |
| JP2011132389A (ja) * | 2009-12-25 | 2011-07-07 | Toray Ind Inc | シート状プリプレグおよびその製造方法 |
| WO2013014893A1 (ja) * | 2011-07-22 | 2013-01-31 | 住友ベークライト株式会社 | 積層シート製造装置および積層シートの製造方法 |
| JP2013108058A (ja) * | 2011-10-28 | 2013-06-06 | Toray Ind Inc | プリプレグの製造方法 |
Cited By (25)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP7063327B2 (ja) | 2017-03-28 | 2022-05-09 | 昭和電工マテリアルズ株式会社 | Frp前駆体の製造方法及びfrpの製造方法 |
| JP7371710B2 (ja) | 2017-03-28 | 2023-10-31 | 株式会社レゾナック | コアレス基板用プリプレグ、コアレス基板用プリプレグの製造方法及び製造装置、並びにコアレス基板及びその製造方法 |
| KR102401431B1 (ko) * | 2017-03-28 | 2022-05-23 | 쇼와덴코머티리얼즈가부시끼가이샤 | Frp 전구체의 제조 방법 및 frp의 제조 방법 |
| KR20190126821A (ko) * | 2017-03-28 | 2019-11-12 | 히타치가세이가부시끼가이샤 | Frp 전구체의 제조 방법 및 frp의 제조 방법 |
| CN110461559A (zh) * | 2017-03-28 | 2019-11-15 | 日立化成株式会社 | Frp前体的制造方法和frp的制造方法 |
| JP7095224B2 (ja) | 2017-03-28 | 2022-07-05 | 昭和電工マテリアルズ株式会社 | コアレス基板用プリプレグ、コアレス基板用プリプレグの製造方法及び製造装置、並びにコアレス基板及びその製造方法 |
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| EP3603918A4 (en) * | 2017-03-28 | 2021-01-13 | Hitachi Chemical Company, Ltd. | PROCESS FOR MANUFACTURING A FRP PRECURSOR AND PROCESS FOR MANUFACTURING FRP |
| CN116252407A (zh) * | 2017-03-28 | 2023-06-13 | 日立化成株式会社 | Frp前体的制造方法和frp的制造方法 |
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| US11446845B2 (en) | 2017-03-28 | 2022-09-20 | Showa Denko Materials Co., Ltd. | Method for manufacturing FRP precursor and method for manufacturing FRP |
| JP2022060296A (ja) * | 2017-03-28 | 2022-04-14 | 昭和電工マテリアルズ株式会社 | コアレス基板用プリプレグ、コアレス基板用プリプレグの製造方法及び製造装置、並びにコアレス基板及びその製造方法 |
| JP2018165339A (ja) * | 2017-03-28 | 2018-10-25 | 日立化成株式会社 | コアレス基板用プリプレグ、コアレス基板用プリプレグの製造方法及び製造装置、並びにコアレス基板及びその製造方法 |
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| US10933562B2 (en) | 2021-03-02 |
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| KR20170141203A (ko) | 2017-12-22 |
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| JP6720967B2 (ja) | 2020-07-08 |
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