WO2014083662A1 - Procédé de fabrication de gabarit pour moulage - Google Patents

Procédé de fabrication de gabarit pour moulage Download PDF

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Publication number
WO2014083662A1
WO2014083662A1 PCT/JP2012/080962 JP2012080962W WO2014083662A1 WO 2014083662 A1 WO2014083662 A1 WO 2014083662A1 JP 2012080962 W JP2012080962 W JP 2012080962W WO 2014083662 A1 WO2014083662 A1 WO 2014083662A1
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WO
WIPO (PCT)
Prior art keywords
film
composite material
release film
manufacturing
resin
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PCT/JP2012/080962
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English (en)
Japanese (ja)
Inventor
深川　仁
泰晴 吉川
卓志 三宅
Original Assignee
国立大学法人岐阜大学
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Application filed by 国立大学法人岐阜大学 filed Critical 国立大学法人岐阜大学
Priority to PCT/JP2012/080962 priority Critical patent/WO2014083662A1/fr
Priority to JP2014549711A priority patent/JP6110406B2/ja
Publication of WO2014083662A1 publication Critical patent/WO2014083662A1/fr

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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
    • B29C70/30—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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
    • B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
    • B29C35/08—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
    • B29C35/0866—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using particle radiation

Definitions

  • the present invention relates to a method for manufacturing a forming jig, and in particular, a forming die and a cowl plate used when forming a composite product using a carbon fiber composite material (CFRP: Carbon Fiber Reinforced Plastic).
  • CFRP Carbon Fiber Reinforced Plastic
  • the present invention relates to a manufacturing method for manufacturing a forming jig.
  • carbon fiber composite materials made of carbon fiber are used as main structural materials such as aircraft fuselage and main wing parts.
  • carbon fiber composite materials are superior in light weight and durability compared to metal materials such as duralumin alloys used in conventional aircraft, and do not rust even after long-term use. It has special properties.
  • the composite material product using this carbon fiber composite material is molded by heating and pressurizing a material called “prepreg” in an autoclave.
  • This prepreg is a semi-cured sheet-like material in which carbon fibers are impregnated with a thermosetting resin such as an uncured liquid epoxy resin.
  • This prepreg is an intermediate product for forming a carbon fiber composite material, and has flexibility that easily deforms according to force and adhesiveness that allows prepregs to adhere to each other when a plurality of prepregs are stacked. I have.
  • a molding method for producing a composite product by heating and pressurizing the above prepreg in an autoclave will be described.
  • a plurality of sheet-shaped prepregs are cut in a predetermined size in advance, and the cut prepregs are placed on a molding die. Laminate in multiple layers so that they stick together.
  • a molding jig as a backing plate called a cowl plate is placed on the laminated prepreg, and a bag film for sealing the molding space is placed thereon.
  • the multilayer prepreg is sandwiched between the molding die and the cowl plate by sucking out air from the molding die, the cowl plate, and the bag film and performing vacuum forming.
  • the prepreg is deformed according to the shape of the mold surface of the molding die and the plate surface of the cowl plate. Then, the bag film is removed, and the prepreg deformed while sandwiched between the molding die and the cowl plate is put into the autoclave and heated at a predetermined temperature while being pressurized, thereby curing the thermosetting resin in the prepreg. Let Thereafter, after a predetermined heating time has elapsed, the composite material product made of the carbon fiber composite material formed from the prepreg is completed by taking out from the autoclave and removing from the molding die. After demolding, trim processing is performed to remove unnecessary parts such as the part of the thermosetting resin that protrudes and hardens, or the manufactured composite material product meets the standards such as size and strength. It is also possible to perform an inspection process for confirming whether or not.
  • the cowl plate used in the above-described autoclave molding functions as a “pad” during vacuum molding and heating by the autoclave, and presses the multilayer prepreg against the molding die. Therefore, it is used for the purpose of increasing the surface roughness of the composite material product and equalizing the product thickness of the composite material product.
  • the cowl plate is often made of a metal material such as aluminum or stainless steel, or an elastic material such as CFRP or elastically deformable silicone rubber.
  • CFRP cross-stylene
  • the prepreg formed from carbon fiber includes an uncured liquid thermosetting resin. Therefore, a part of the thermosetting resin is formed on the mold surface of the molding die and the plate surface of the cowl plate that are in direct contact with the prepreg during processing by vacuum molding or heating using an autoclave. There is a possibility to adhere to. As a result, it firmly adheres to the mold surface of the composite product, etc., and when the composite product is removed from the mold, part of the composite product is lost or the product surface of the composite product is smooth. May decrease. In addition, demolding may take time.
  • a mold release agent such as a fluororesin or a silicone resin is applied in advance to the surface of the mold surface and the surface of the plate surface that is in direct contact with the prepreg before vacuum forming.
  • the mold release agent and the cowl plate were often manually applied by the operator.
  • the mold release agent mainly composed of fluororesin has poor adhesion to the mold surface of the mold and the plate surface of the cowl plate because of its mold releasability. Had to do. Therefore, a long time is required for the application work, and the work time of the vacuum forming process becomes long, or the application unevenness may occur on the mold surface due to manual work.
  • many release agents use organic solvents as solvents, and it is necessary to pay attention to the ventilation of the work space where the release agent is applied. In addition, it is necessary to newly install ventilation equipment. Sometimes it was.
  • the cowl plate is placed on top of the prepreg at the top of the multi-layer, and the composite product to be manufactured is of a large size such as an aircraft fuselage.
  • the cowl plate also becomes larger.
  • the work of placing the cowl plate on the prepreg becomes large and sometimes places a heavy burden on the operator.
  • many cowl plates are often made of a metal material such as stainless steel, and the lifting and lowering of the heavy weight cowl plate requires a lot of time, which reduces handling in the manufacture of composite products. It was also a factor.
  • the prepreg when the prepreg is heated by being sandwiched between a mold and a cowl plate in an autoclave and the thermosetting resin is cured, a metal product cowl plate and a composite material mainly composed of carbon fibers are used.
  • the difference in the thermal expansion coefficient between the two was significant, and the difference in the thermal expansion coefficient sometimes caused a large distortion in the composite material product during the molding process.
  • An object of the present invention is to provide a method for manufacturing a forming jig that can be formed.
  • the manufacturing method of the molding jig of the present invention is “a manufacturing method of a molding jig for molding a composite material product using a carbon fiber composite material, In order to laminate a release film in which a fluororesin is formed on the configured composite material layer, the layer surface of the composite material layer that serves as an interface between the composite material layer and the release film and the film of the release film A surface modification step for modifying one of the surfaces, wherein the surface modification step is one of a plasma modification step by plasma irradiation and an etching modification step by contact with a corrosive chemical solution. It is characterized by that.
  • the molding jig is used for molding a composite product (molded product) using a carbon fiber composite material, and examples thereof include a molding die and a cowl plate.
  • the composite material layer is formed using a carbon fiber composite material of the same type as the composite material product to be molded, while the release film is, for example, polytetrafluoroethylene resin (PTFE), modified Like polytetrafluoroethylene resin (modified PTFE), tetrafluoroethylene / hexafluoropropylene copolymer (FEP), perfluoroalkoxy fluororesin (PFA), and ethylene / tetrafluoroethylene copolymer (ETFE)
  • PTFE polytetrafluoroethylene resin
  • modified PTFE modified Like polytetrafluoroethylene resin
  • FEP tetrafluoroethylene / hexafluoropropylene copolymer
  • PFA perfluoroalkoxy fluororesin
  • ETFE ethylene
  • the surface modification step is performed on either the layer surface of the composite material layer or the film surface of the release film, and is intended to activate the surface. That is, by applying physical or chemical treatments to the layer surface, etc., fine scratches are generated on the layer surface, etc., and the surface roughness is increased to increase the surface area, and the functional groups on each surface. By substituting a part of this with another functional group, adhesion or adhesion is improved. For example, when the surface of a release film made of polytetrafluoroethylene resin is irradiated with plasma and subjected to surface modification treatment, physically fine scratches are caused on the film surface by the plasma hitting the film surface. At the same time, a part of functional groups (for example, fluorine atoms) existing on the film surface can be substituted with highly reactive functional groups such as a carboxyl group, an amino group, and a hydroxy group.
  • highly reactive functional groups such as a carboxyl group, an amino group, and a hydroxy group.
  • each layer of the molding jig having a two-layer structure of the composite material layer and the release film does not peel off during use.
  • a fluororesin and a fluororesin film formed by depositing the fluororesin have an excellent releasability and therefore have inferior adhesive properties. Therefore, by performing a surface modification treatment such as plasma irradiation, the adhesion of the film surface on one side of the release film can be improved.
  • etching modification process for example, a corrosive chemical solution containing an active sodium component is brought into contact with the film surface of the fluororesin film, so that a part of the film surface is corroded by a chemical action to cause scratches and unevenness.
  • a part of the functional group in the course of corrosion, the same effect as the above-mentioned plasma irradiation is obtained chemically.
  • the etching modification process can be performed more easily than the plasma modification process because it does not require a relatively large plasma processing apparatus.
  • either the plasma treatment or the etching treatment is selected for the layer surface or film surface at the interface between the composite material layer and the release film, Surface modification treatment is performed.
  • the adhesiveness between a composite material layer and a release film improves, and it becomes possible to manufacture the shaping
  • the manufacturing method of the molding jig of the present invention includes, in addition to the above configuration, “applying a powder or liquid fluororesin to the substrate surface of the film-forming substrate and heating the mold release film to A sheet made of carbon fiber after a melt film formation process for forming a melt film on the substrate surface, and a surface modification process by the surface modification process on the film surface of the release film to form a modified film surface And a prepreg laminating step of laminating a prepreg in a shape on the surface of the modified film, and a firing step of firing in a state where the release film and the prepreg are laminated.
  • the surface of the release film formed from the fluororesin is subjected to surface modification treatment by plasma treatment or etching treatment, and the modified release film is modified.
  • a two-layer forming jig having a release layer and a composite material layer made of a carbon fiber composite material is manufactured by laminating prepregs in multiple layers on the film surface and firing.
  • the manufacturing method of the molding jig of the present invention includes, in addition to the above-described configuration, “a porous carbon fiber cloth material formed from carbon fibers, which is one of a polyimide resin, a polybenzimidazole resin, and a bismaleimide resin.
  • a powdery or liquid fluororesin is applied to the modified layer surface and heated to release the release film from the modified layer.
  • a melt film forming step of forming a melt film on the surface is one of a polyimide resin, a polybenzimidazole resin, and a bismaleimide resin.
  • the carbon fiber cloth material is a fabric formed from carbon fibers, and is a porous member having a large number of voids between the carbon fibers.
  • a polyimide resin is a polymer having an imide bond having a strong intermolecular force, and has high heat resistance.
  • the polybenzimidazole resin also has high heat resistance having a thermal decomposition temperature of 600 ° C. or higher.
  • the bismaleimide resin has a property that it is excellent in flexibility and fast in curability as compared with a polyimide resin or the like.
  • polyimide resin or the like is generally a thermosetting resin, and is not completely cured when the carbon fiber cloth material is impregnated in the resin impregnation step. However, since it is exposed to a high temperature in the melt film forming process described later, the polyimide resin or the like is completely cured at this stage.
  • a composite layer made of a carbon fiber composite material having heat resistance is formed by impregnating a carbon fiber cloth material with a liquid polyimide resin or the like. .
  • a composite material layer that can withstand the film formation temperature when performing the fluororesin melt film formation described later is formed.
  • the above-described plasma treatment or surface modification treatment with a chemical is performed on the surface of the composite material layer. The details are the same as those already described, and a description thereof is omitted here.
  • a method for manufacturing a forming jig can be provided.
  • cowl plate manufacturing method 1 (hereinafter, simply referred to as “manufacturing method 1”) according to the first embodiment of the present invention will be described with reference to FIGS. 1 and 2.
  • the cowl plate 2 manufactured by the manufacturing method 1 corresponds to the forming jig of the present invention.
  • the cowl plate 2 manufactured by the manufacturing method 1 of the first embodiment is formed by processing a composite material product (not shown) manufactured using, for example, a carbon fiber composite material (CFRP) constituting a fuselage portion of an aircraft. Used to do.
  • CFRP carbon fiber composite material
  • the cowl plate 2 is formed as a thin film, and a release film 3 having a thickness of 1 mm or less and a plurality of prepregs 4 laminated on one modified film surface 3b of the release film 3 are laminated in multiple layers. It is comprised from the composite material layer 5 formed. That is, the cowl plate 2 has a two-layer structure including a CFRP composite material layer 5 of the same quality as a composite product manufactured using the cowl plate 2. In addition, in order to simplify description in FIG. 1, the example which manufactures the flat-shaped cowl plate 2 is shown.
  • the manufacturing method 1 of the cowl plate 2 will be described in detail.
  • a powdery film is formed on a flat film-forming substrate 6 placed with a smooth substrate surface 6a facing upward.
  • Polytetrafluoroethylene resin 7 (hereinafter referred to as “PTFE resin 7”) is uniformly applied, and the applied PTFE resin 7 is heated at a melt film formation temperature (baking temperature) of 330 ° C. to be defined from the substrate surface 6a.
  • Prepreg lamination step S3 and release film 3 And a multi-layer prepreg 4 stacked in an autoclave (not shown) and fired at a firing temperature of about 180 ° C., and a thermosetting epoxy resin contained in the prepreg 4 by the firing step S4
  • the plasma modification step S2 corresponds to the surface modification step of the present invention.
  • the plasma reforming step S2 is performed using a plasma processing apparatus P that generates high-frequency plasma.
  • the processing conditions of the plasma processing apparatus are performed by setting the plasma output value of the high frequency plasma to 100 W and the plasma processing time to 30 minutes in the manufacturing method 1 of the first embodiment.
  • the gas introduced into the plasma processing apparatus is made of nitrogen, hydrogen, and argon. It aims at substituting a part of functional group with an amino group by the composition of the gas component.
  • the cowl plate 2 having the CFRP composite material layer 5 and the release film 3 made of fluororesin is manufactured by the above-described method.
  • the release film 3 is provided on the inner surface side of the cowl plate 2, in other words, on the side in contact with the prepreg used for manufacturing the composite material product.
  • the prepreg and the cowl plate 2 are not fused during the vacuum forming process and the heating of the autoclave due to the release property of the release film 3.
  • work of the mold release agent currently implemented conventionally can be abbreviate
  • the release film 3 is formed on the flat film-formation substrate 6, the prepreg 4 is laminated thereon, and heated together with the film-formation substrate 6 by an autoclave.
  • the present invention is not limited to this. For example, even if the release film 3 is formed on a film formation substrate having a curved surface that matches the shape of a cowl plate, or the release film 3 is formed on a flat film formation substrate 6. After the formation, the release film 3 may be moved to the surface of a mold (not shown) for forming the cowl plate, and the prepreg 4 may be laminated thereon according to the shape of the mold.
  • the plasma modification step S2 is performed.
  • an etching step S6 may be performed as the surface modification step. Specifically, in the etching step S6, after the dirt on the film surface 3a of the release film 3 is removed with alcohol or the like and dried, the corrosion applied to the flat bat with the release film 3 side facing downward. The release film 3 is immersed in the chemical solution 16. Alternatively, the corrosive chemical 16 may be applied to the film surface 3a using a brush or the like.
  • etching process S6 is completed.
  • the immersion time of the corrosive chemical 16 is set to 5 to 10 seconds in the manufacturing method 1 of the first embodiment. If the immersion time is short, the surface modification effect cannot be sufficiently obtained. On the other hand, if the immersion time is long, the adhesion with the composite material layer 5 made of the prepreg 4 may be affected. It adjusts according to the property of the fluororesin which comprises the mold film 3.
  • the above-mentioned prepreg lamination process S3 and subsequent steps are performed again with the release film 3 side facing upward. Thereby, the cowl plate 2 is manufactured similarly.
  • cowl plate manufacturing method 10 (hereinafter simply referred to as “manufacturing method 10”) according to a second embodiment of the present invention will be described with reference to FIG.
  • the cowl plate 11 manufactured by the manufacturing method 10 corresponds to the molding jig of the present invention.
  • manufacturing method 1 of 1st embodiment detailed description shall be abbreviate
  • the cowl plate 11 is a thin film with a film thickness of 1 mm or less formed on a composite material layer 13 composed of a block-like carbon fiber cloth material 12 and one modified layer surface 13b of the composite material layer 13.
  • the porous carbon fiber cloth material 12 made of carbon fiber and having a large number of voids therein has a heat-resistant liquid state.
  • a high-frequency plasma is irradiated under vacuum conditions to perform a plasma modification step T2 for modifying the surface of the layer surface 13a, and a powdery PTFE resin 17 is applied on the modified layer surface 13b by the plasma modification step T2.
  • the plasma modification step T2 corresponds to the surface modification step in the present invention. Note that surface modification may be performed by chemical treatment as an alternative to the plasma modification step T2.
  • the cowl plate 11 having the CFRP composite material layer 13 and the release film 14 made of fluororesin is manufactured by the method described above. Thereby, similarly to the cowl plate 2 manufactured by the manufacturing method 1 of the first embodiment, the epoxy resin contained in the prepreg is fused during the vacuum forming process and the heating of the autoclave due to the releasability of the release film 14. There is no problem. Accordingly, it is possible to omit the conventional application of the release agent. Since the release film 14 is integrally formed as a part of the cowl plate 11, it is not lost when the composite material product is removed. Therefore, since the mold release property of the release film 14 is not impaired by a single molding process, the mold release property can be maintained even by a plurality of molding processes.
  • the cowl plate 11 according to the second embodiment can improve the overall heat resistance of the cowl plate 11 because the composite material layer 13 is impregnated with the heat-resistant polyimide resin 15. Therefore, when a composite material product is molded by an autoclave, it can be repeatedly used due to the heat resistance.
  • the manufacturing method 10 of 2nd embodiment showed what manufactured the flat cowl plate 11 similarly to the manufacturing method 1 of 1st embodiment, it is not limited to this, Curved shape A cowl plate having the above may be manufactured.
  • the carbon fiber cloth material 12 is formed into a cowl plate shape before impregnating the polyimide resin 15 or the like, or is formed into a cowl plate shape after impregnating the polyimide resin 15, and then the plasma modification step T ⁇ b> 2.
  • a cowl plate having a desired shape and having a release film 14 formed on the surface can be manufactured.
  • the cowl plates 2 and 11 manufactured by the manufacturing methods 1 and 10 of the first embodiment and the second embodiment of the present invention are both formed mainly of CFRP. Therefore, the weight can be reduced compared to a conventional cowl plate formed of a metal material such as stainless steel. As a result, the work of raising and lowering the cowl plates 2 and 11 is facilitated, and the handling property in the production of the composite product can be improved. Further, it has a coefficient of thermal expansion that approximates that of a composite product molded using the cowl plates 2 and 11. Therefore, when it is heated in the autoclave, it exhibits a behavior of thermal deformation close to that of the composite product (or prepreg before curing), so that no distortion or biased pressure is applied to the composite product during molding.
  • the method of manufacturing the cowl plates 2 and 11 as the forming jig is shown, but the present invention is not limited to this.
  • a CFRP mold having a release film formed thereon may be manufactured.
  • the plasma modification process is selected as the surface modification process.
  • the present invention is not limited to this, and the degree of surface modification at the layer interface and the film interface is not limited thereto. It can be arbitrarily selected depending on the case.
  • the film obtained by melting the release film 3 made of a fluororesin on the film formation substrate 6 is very thin, so that the release film 3 is very thin.
  • immersing the release film 3 in the corrosive chemical solution 16 may cause surface modification to the back surface. There is a risk of losing moldability. Therefore, in the manufacturing method 1 of the first embodiment, as shown in the drawing, a surface modification process by irradiating high-frequency plasma or a method of brushing the corrosive chemical solution 16 on the film surface 3a of the release film 3 is adopted. It seems to be preferable.
  • the one impregnated with the polyimide resin 15 is used for the purpose of improving the heat resistance of the composite material layer 13 made of the carbon fiber cloth material 12, but is not limited thereto.
  • polybenzimidazole resin or bismaleimide resin may be used.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Composite Materials (AREA)
  • Mechanical Engineering (AREA)
  • Moulding By Coating Moulds (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Reinforced Plastic Materials (AREA)
  • Laminated Bodies (AREA)
  • Casting Or Compression Moulding Of Plastics Or The Like (AREA)

Abstract

Le procédé de fabrication (1) de gabarit pour moulage de l'invention comporte : une étape de formation de film par fusion (S1) au cours de laquelle une résine PTFE (7) en poudre est appliquée sur une face de substrat (6a) d'un substrat pour moulage (6), et un film de démoulage (3) est formé par fusion sur la face de substrat (6a) par chauffage ; une étape de modification par plasma (S2) en tant qu'étape de modification de surface au cours de laquelle une irradiation au plasma est effectuée sur une surface de film (3a) du film de démoulage (3) ; une étape de stratification de pré-imprégné (S3) au cours de laquelle un pré-imprégné (4) sous forme de feuille configuré par des fibres de carbone, est stratifié sur une surface de film modifiée (3b) du film de démoulage (3) ; et une étape de cuisson (S4) au cours de laquelle le film de démoulage (3) et le pré-imprégné (4) sont cuits dans un état de stratification
PCT/JP2012/080962 2012-11-29 2012-11-29 Procédé de fabrication de gabarit pour moulage WO2014083662A1 (fr)

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PCT/JP2012/080962 WO2014083662A1 (fr) 2012-11-29 2012-11-29 Procédé de fabrication de gabarit pour moulage
JP2014549711A JP6110406B2 (ja) 2012-11-29 2012-11-29 成形用治具の製造方法

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Application Number Priority Date Filing Date Title
PCT/JP2012/080962 WO2014083662A1 (fr) 2012-11-29 2012-11-29 Procédé de fabrication de gabarit pour moulage

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WO2014083662A1 true WO2014083662A1 (fr) 2014-06-05

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Cited By (2)

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Publication number Priority date Publication date Assignee Title
CN113001834A (zh) * 2021-02-08 2021-06-22 北京航空航天大学 一种用于成型复杂结构复合材料零件的可循环利用芯模
EP3950249A4 (fr) * 2019-03-28 2022-12-14 Toray Industries, Inc. Article moulé en matériau composite renforcé par des fibres de carbone et procédé de production d'un article moulé en matériau composite renforcé par des fibres de carbone

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EP3950249A4 (fr) * 2019-03-28 2022-12-14 Toray Industries, Inc. Article moulé en matériau composite renforcé par des fibres de carbone et procédé de production d'un article moulé en matériau composite renforcé par des fibres de carbone
US11993688B2 (en) 2019-03-28 2024-05-28 Toray Industries, Inc. Molded article of carbon fiber composite material and production method for molded article of carbon fiber composite material
CN113001834A (zh) * 2021-02-08 2021-06-22 北京航空航天大学 一种用于成型复杂结构复合材料零件的可循环利用芯模

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