WO2019188020A1 - Agent de démoulage interne pour matériau composite renforcé par des fibres, matériau composite renforcé par des fibres, procédé de moulage associé et procédé d'assemblage pour produit moulé en résine renforcé par des fibres - Google Patents

Agent de démoulage interne pour matériau composite renforcé par des fibres, matériau composite renforcé par des fibres, procédé de moulage associé et procédé d'assemblage pour produit moulé en résine renforcé par des fibres Download PDF

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Publication number
WO2019188020A1
WO2019188020A1 PCT/JP2019/008409 JP2019008409W WO2019188020A1 WO 2019188020 A1 WO2019188020 A1 WO 2019188020A1 JP 2019008409 W JP2019008409 W JP 2019008409W WO 2019188020 A1 WO2019188020 A1 WO 2019188020A1
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WIPO (PCT)
Prior art keywords
fiber
release agent
composite material
reinforced resin
resin molded
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PCT/JP2019/008409
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English (en)
Japanese (ja)
Inventor
佐藤智麻
松本賢
川嶋茂
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東レ株式会社
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Priority to JP2019518018A priority Critical patent/JPWO2019188020A1/ja
Publication of WO2019188020A1 publication Critical patent/WO2019188020A1/fr

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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
    • C08J5/243—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using carbon fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
    • B29C41/34—Component parts, details or accessories; Auxiliary operations
    • B29C41/42—Removing articles from moulds, cores or other substrates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/06—Fibrous reinforcements only
    • 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
    • C08J5/10—Reinforcing macromolecular compounds with loose or coherent fibrous material characterised by the additives used in the polymer mixture

Definitions

  • the present invention relates to a release agent for fiber reinforced composite material, a fiber reinforced composite material using the release agent, a molding method thereof, and a method of joining fiber reinforced resin molded products.
  • a combination structure of a resin material represented by a steel plate, an aluminum alloy material, or a fiber reinforced resin material has been studied (patent) Reference 1).
  • Typical joining methods for joining parts made of such different materials include mechanical fastening and adhesive joining.
  • adhesive bonding is considered to be an effective means for bonding different materials because there is no stress concentration around the hole, which is a concern in mechanical fastening, and because the bonding is high due to the bonding by lines or surfaces.
  • the release agent used to improve mold release during molding creates a release layer on the bonding surface, which may cause peeling. It is known.
  • post-processing such as sanding and plasma treatment is applied to the bonded surface after forming the fiber-reinforced composite material (Patent Documents 2 and 3).
  • the release agent used to improve the demolding property at the time of molding creates a release layer on the bonding surface and causes peeling. It becomes.
  • WBL WeakBoundary Layer
  • the present invention has been made in view of the above-mentioned various problems, and the precipitation of the internal mold release agent (bleed out) on the surface of the molded product after the matrix resin is cured, and the interface between the molded product and the mold release agent.
  • Another object of the present invention is to provide a bonding method that realizes high quality in a bonded body using a molded article of the fiber reinforced composite material.
  • the internal mold release agent for fiber-reinforced composite material of the present invention has the following configuration. That is, An internal mold release agent added to a fiber reinforced composite material including a reinforced fiber and an uncured matrix resin, wherein the internal mold release agent has a reactive functional group chemically bonded when the matrix resin is cured An internal mold release agent for the material.
  • the fiber-reinforced composite material of the present invention has the following configuration. That is, A fiber-reinforced composite material, wherein the internal mold release agent for the fiber-reinforced composite material is added in an amount of 0.01 to 10 wt% of the uncured matrix resin.
  • the method for molding a fiber-reinforced composite material of the present invention has the following configuration. That is, In a method for molding a fiber reinforced composite material including a reinforced fiber and a matrix resin, a step of adding an internal release agent having a reactive functional group in an uncured matrix resin, and the step of adding the internal release agent
  • a method for molding a fiber-reinforced composite material comprising: curing a cured matrix resin by heat, and chemically bonding at least a part of the internal mold release agent and the matrix resin via the reactive functional group.
  • the joining method of the fiber reinforced resin molded product of this invention has the following structure. That is, A method of joining a fiber reinforced resin molded product made of a thermosetting resin to a mating member, wherein the fiber reinforced resin molding is joined before joining the fiber reinforced resin molded product and the mating member. A pre-treatment process is performed in which energy is externally applied to the surface of the product to modify the surface of the fiber-reinforced resin molded product, and the surface free energy of the surface of the fiber-reinforced resin molded product after the pre-treatment step is 35 mN / m to 60 mN / m and / or a joining method of fiber reinforced resin molded products having a contact angle with water of 40 degrees or more and 80 degrees or less.
  • the reactive functional group is preferably composed of at least one of amine, epoxy, carboxylic acid, and thiol.
  • the internal mold release agent for fiber-reinforced composite material of the present invention, is preferably a silicone-based mold release agent.
  • the amount of the internal release agent added is preferably 0.01 to 10 wt% with respect to the uncured matrix resin.
  • the fiber-reinforced composite material of the present invention it is preferable that less than 40% of the total weight of the internal release agent is deposited on the surface layer.
  • the matrix resin is preferably a thermosetting resin.
  • the uncured matrix resin to which the internal release agent has been added it is preferable to heat the uncured matrix resin to which the internal release agent has been added at 30 to 250 ° C.
  • the energy is added at the time of molding or before molding of the fiber reinforced resin molded product, and the release agent layer deposited on the surface of the fiber reinforced resin molded product after molding. Is preferably given.
  • the energy application to the fiber reinforced resin molded product surface is performed by an atmospheric pressure plasma treatment method.
  • the counterpart member is preferably selected from at least one material selected from metal, non-reinforced resin, and fiber-reinforced resin.
  • the mating member is joined via an adhesive.
  • the adhesive is preferably a urethane adhesive.
  • the internal mold release agent of the present invention when the fiber reinforced composite material is molded using the internal mold release agent, the internal mold release agent is deposited on the surface of the molded body after curing (bleed out). ), And the effect of removing and modifying the mold release agent on the surface of the molded body for painting and bonding processes is maintained. Moreover, peeling at the interface between the release agent layer and the molded body can be prevented. Furthermore, according to the joining method concerning this invention, simplification of a joining process is also realizable.
  • FIG. 1 is a flow diagram.
  • FIG. 4 is a TOF-SIMS measurement diagram comparing the distribution state in the range of 20 ⁇ m in depth from the matrix resin surface layer of the internal mold release agent having a reactive functional group and the internal mold release agent having no reactive functional group. It is a graph which shows an example of the relationship between the contact angle with respect to the water after the plasma processing of the fiber reinforced resin molded product (2) which concerns on embodiment of this invention, and surface free energy. It is a graph which shows the relationship with the contact strength thru
  • the internal mold release agent (1) in the present invention is a silicone-based mold release agent having a reactivity in which a functional group R is introduced into the side chain and / or terminal of the polysiloxane represented by the general formula (I) (wherein the formula M and n in (I) are integers of 1 or more).
  • a functional group R include an amino group, an epoxy group, a carboxyl group, a thiol group, a carbinol group, a methacryl group, and a phenol group, and can be appropriately selected from these.
  • the amount of the internal mold release agent (1) added is preferably 0.01 to 10 wt%, more preferably 0.1% to 5% with respect to the uncured matrix resin.
  • the addition amount of the internal mold release agent (1) is within the above preferable range, the mold release property is exhibited at the time of mold release, and precipitation (bleed out) on the molded product surface after curing can be suppressed.
  • general formula (II) is a silicone type mold release agent which does not have a reactive functional group, and makes this a conventional product.
  • the target to which the internal mold release agent is added may be either the main agent or the curing agent when the two-component matrix resin is used, or may be added after mixing the main agent and the curing agent.
  • the temperature at the time of addition is lower than the reaction temperature of the release agent and the matrix resin, and is a temperature at which the viscosity of the matrix resin and the release agent can be stirred and mixed.
  • the matrix resin (3) contained in the fiber reinforced composite material in the present invention is preferably a thermosetting resin, and among them, epoxy resin, epoxy resin, unsaturated polyester resin, vinyl ester resin, diallyl phthalate resin, phenol resin, maleimide More preferably selected from resins, cyanate ester resins, etc.
  • an epoxy resin is more preferable.
  • the epoxy resin a compound having a plurality of epoxy groups in the molecule is used.
  • bisphenol A type epoxy resin bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD type epoxy resin, naphthalene type epoxy resin, novolac type epoxy resin, biphenyl type epoxy resin, alicyclic epoxy resin, or these A combination of resins is used.
  • the epoxy resin which has a bisphenol A type epoxy resin as a main component can be preferably used from a viewpoint of the balance of economical efficiency and a dynamic characteristic.
  • curing agent you may use any of an amine type and an acid anhydride type.
  • the matrix resin (3) may contain other fillers and additives within a range that does not impair the object of the present invention, depending on required properties.
  • other fillers and additives include inorganic fillers, flame retardants, conductivity imparting agents, crystal nucleating agents, ultraviolet absorbers, antioxidants, vibration damping agents, antibacterial agents, insect repellents, deodorants, and coloring.
  • examples thereof include an inhibitor, a heat stabilizer, a lubricant, an antistatic agent, a plasticizer, a colorant, a pigment, a dye, a foaming agent, an antifoaming agent, and a coupling agent.
  • the reinforcing fiber in the present invention is not particularly limited, and carbon fiber, glass fiber, aramid fiber, and the like, and these reinforcing fibers mixed therein can be used. Of these, carbon fiber is preferably included from the standpoints of developing high mechanical properties and ease of designing the properties. Also, the form of the fiber can be selected as appropriate, such as a continuous fiber form and a short fiber form. [Precipitation during curing reaction (bleed out)] The internal mold release agent (1) in the present invention precipitates (bleeds out) on the surface of the matrix resin (3) during the curing reaction of the matrix resin (3) to form the release layer (4).
  • the internal mold release agent (1) and the matrix resin (3) form a chemical bond (6) when the matrix resin is cured.
  • chemical bonds may be formed in any combination of the internal mold release agent and the main agent, the internal mold release agent and the curing agent, or both.
  • the release layer (surface layer) (4) and the remaining internal release agent (5) deposited (bleed out) are fixed to the matrix resin (3) and peeled off from the interface with the matrix resin (3) after curing. Or new precipitation (bleed out) can be suppressed.
  • the distribution of the remaining internal mold release agent (5) differs between the sample using the reactive mold release agent (1) and the conventional product within a depth of 20 ⁇ m from the surface layer. Whereas a small number of locations are localized within a depth of 20 ⁇ m, a large number of localized residual internal mold release agents (5) can be confirmed in the conventional product.
  • the molding flow in the present invention is as shown in FIGS. ⁇ Preparation of materials> In order to obtain a fiber-reinforced composite material, a reinforcing fiber, a matrix resin, and an internal release agent are prepared.
  • the fiber type, shape, fiber volume content, orientation, and the like of the reinforcing fibers can be appropriately selected.
  • the matrix resin a two-component mixed type of a main agent and a curing agent is preferable, but not limited thereto.
  • the target to which the internal release agent (1) is added may be either the main agent or the curing agent when the two-component matrix resin (3) is used, or may be added after mixing the main agent and the curing agent. .
  • the temperature at the time of addition is lower than the reaction temperature of the internal mold release agent (1) and the matrix resin (3), and is a temperature at which the internal mold release agent (1) and the matrix resin (3) have a viscosity capable of being stirred and mixed. If there is, it is preferable.
  • the addition amount of the internal release agent is preferably 0.01 to 10 wt%, more preferably 0.1 to 5 wt% with respect to the uncured matrix resin. By setting the addition amount within this range, precipitation (bleed out) of the internal mold release agent on the surface of the molded product after the bonding step can be suppressed, and problems such as poor adhesion can be prevented.
  • the reinforcing fiber may be impregnated in advance with an uncured matrix resin to which an internal mold release agent has been added, or may be impregnated in accordance with the curing step described later.
  • any method suitable for each molding method may be used as the method for introducing these materials. Among them, it is preferable to place the material in the cavity of the mold and close the mold when using press molding.
  • ⁇ A. Curing> the uncured matrix resin (3) to which the internal release agent (1) is added is impregnated into the reinforcing fibers and heated at a heating temperature of 30 to 250 ° C. to cure the uncured matrix resin.
  • the pressurizing condition for curing is not particularly limited as long as the shape of the material can be fixed.
  • the heating method is not particularly limited as long as the material can be appropriately heated and cooled, and for example, heating wire, electromagnetic induction, high-temperature fluid, microwave, or the like can be used. In particular, it is preferable to use a high-temperature fluid such as water vapor because reversible heat exchange can be performed during press molding.
  • a part of the internal mold release agent (1) and the uncured matrix resin (3) are chemically bonded via a reactive functional group containing at least one of amine, epoxy, carboxylic acid, and thiol.
  • a reactive functional group containing at least one of amine, epoxy, carboxylic acid, and thiol. By forming such a chemical bond, the bonding strength between the release layer (4) and the matrix resin interface is increased, and the space between the release layer (4) and the matrix resin interface becomes WBL when bonded to the mating member described later. Is suppressed.
  • the thickness of the release layer (4) may be about 100 nm to several hundred nm.
  • the internal release agent (1) deposited on the surface layer of the fiber reinforced composite material forms the release layer (4).
  • the mold release layer (4) present in the surface layer of the fiber reinforced composite material after curing exhibits a mold release action, so that the fiber reinforced composite material can be released from the mold.
  • the internal mold release agent (1) inside the fiber reinforced composite material forms a chemical bond with the matrix resin (3), and the internal mold release agent (1) inside the fiber reinforced composite material is It is difficult to precipitate (bleed out) on the surface layer. Therefore, if only the release layer (4) is subjected to surface treatment, it is possible to maintain the bonding with the adhesive or the paint without causing precipitation (bleed out) over time.
  • Surface treatment methods include atmospheric pressure plasma treatment, corona treatment, ultraviolet (UV) treatment, vacuum ultraviolet (VUV) treatment, flame treatment, etc.
  • high-speed processing environmental aspects such as no ozone generation
  • atmospheric pressure plasma treatment is particularly preferable from the viewpoint that a three-dimensional object can be treated.
  • the processing nozzle (7) is held by a transport mechanism such as a robot, and the processing nozzle (7) is scanned, so that high-speed processing is performed any number of times at an arbitrary place where processing is desired. be able to.
  • the process gas used in the atmospheric pressure plasma treatment nitrogen gas, oxygen gas, helium gas, argon gas, or a mixed gas of these gases can be used in addition to air.
  • the distance between the processing nozzle (7) and the fiber reinforced resin molded product (2) when performing the plasma processing is preferably 5 to 25 mm
  • the scanning speed of the processing nozzle (7) is preferably 2 to 20 m / min.
  • the surface free energy of the fiber reinforced resin molded article (2) after the treatment is 35 mN / m or more and 60 mN / m or less and / or the contact angle with water is 40. It is important to perform processing so that the angle is not less than 80 degrees and not more than 80 degrees.
  • the surface free energy is less than 35 mN / m and the contact angle of water exceeds 80 degrees, the surface is a hydrophobic surface, the elimination of methyl groups is not sufficient, and the surface does not lose its releasability.
  • the matrix resin (3) is in a state in which the matrix resin (3) is deteriorated by the treatment with the external energy up to the matrix resin (3). As a result, the surface roughness of the fiber reinforced resin molded product (2) is increased, and only the apparent wettability is improved. This deteriorated resin layer becomes WBL and causes a decrease in bonding strength.
  • the matrix resin (3) does not deteriorate and the release layer (4)
  • the methyl group constituting the silicone-based mold release agent is removed and substituted with a hydrophilic functional group, so that an adhesive surface (8) suitable for bonding can be formed.
  • the work load such as sanding and peeling off the ply ply previously prepared on the surface is large.
  • the release layer (4) is removed by performing surface treatment, and the exposed layer (9) from which the matrix resin is exposed becomes a new outermost layer.
  • the release agent precipitates (bleeds out) from the inside of the reinforcing fiber composite material, causing adhesion failure and peeling of the coating after adhesion and coating described below.
  • a liquid sample of about several ⁇ L is dropped on a measurement sample placed on a horizontal plane and analyzed from a droplet image captured from the side. It can be measured by a droplet method (Sessile Drop method).
  • a droplet method Sessile Drop method
  • the contact angle of water distilled water or purified water is used as the liquid sample, but various measurement theoretical formulas have been proposed for the surface free energy.
  • the surface energy is known 2 Using the seed solvent, the surface free energy can be calculated from the contact angle of each solvent dropped on the sample surface.
  • the solvent used examples include water (distilled water, purified water), diiodomethane (methylene iodide), ethylene glycol, formamide, hexadecane, and the like. In the present invention, water and diiodomethane are used.
  • Adhesion, painting> The fiber-reinforced composite material after the surface treatment is coated with an adhesive / paint (10). At this time, the adhesive layer (6) obtained by the previous treatment can be firmly bonded to the adhesive / paint (10).
  • the target member is not particularly limited, but can be appropriately selected from a metal material, a non-reinforced resin material, or the fiber reinforced resin material described above according to the application and specifications.
  • the adhesive is not particularly limited, and examples thereof include an epoxy adhesive, a urethane adhesive, an acrylic adhesive, a silicone adhesive, and the like, and preferably selected from at least one of these.
  • a urethane adhesive is more preferable.
  • thermoplastic resin material As an object member, it is also possible to join directly with a fiber reinforced resin molded product (2) by means, such as welding joining, without using an adhesive agent.
  • peeling (12) is caused by the residual internal mold release agent (11) deposited on the surface layer (bleed out).
  • the fiber reinforced resin molded product joining method of the present invention is, as described above, a fiber reinforced resin molded product joining method in which a fiber reinforced resin molded product made of a thermosetting resin is joined to a target member.
  • a pretreatment step is performed in which energy is applied from the outside to the surface of the fiber reinforced resin molded product to modify the surface of the fiber reinforced resin molded product.
  • the surface free energy of the surface of the fiber reinforced resin molded product after the step is 35 mN / m or more and 60 mN / m or less and / or the contact angle with respect to the water of the surface of the fiber reinforced resin molded product after the pretreatment step is 40 degrees or more and 80 degrees. It is characterized by the following.
  • the surface free energy of the surface of the fiber reinforced resin molded product after the pretreatment step is out of the range of 35 mN / m or more and 60 mN / m or less, and the surface of the fiber reinforced resin molded product after the pretreatment step is in contact with water.
  • the angle is out of the range of 40 degrees or more and 80 degrees or less, the surface state suitable for bonding cannot be improved, and high bonding strength cannot be realized.
  • the method for joining the fiber reinforced resin molded product of the present invention is applied to the release agent layer that is added to the fiber reinforced resin molded product or deposited before molding, and deposited on the surface of the fiber reinforced resin molded product after molding.
  • the release agent component deposited on the surface is deactivated and further modified to a surface suitable for adhesion. Therefore, it is possible to achieve both the releasability to the mold and the adhesiveness with the mating member.
  • the energy application to the surface of the fiber reinforced resin molded product is performed by the atmospheric pressure plasma treatment method in the method for joining the fiber reinforced resin molded product of the present invention.
  • Such a method enables high-speed and homogeneous processing.
  • the target member is selected from at least one material of metal, non-reinforced resin, and fiber-reinforced resin.
  • the target member is selected from at least one material of metal, non-reinforced resin, and fiber-reinforced resin.
  • the method for joining the fiber-reinforced resin molded products of the present invention is preferably joined to the target member via an adhesive.
  • the adhesive is preferably a urethane adhesive. It is possible to use the high bonding efficiency of adhesive bonding that joins wires and surfaces, and to mitigate the effects of thermal deformation due to the difference in linear expansion coefficient, which is a problem when bonding dissimilar materials, by the high extensibility of urethane adhesive Because it becomes possible.
  • Example 1 shows the results of confirming the distribution of the mold release agent with a resin casting plate that does not contain reinforcing fibers, as Example A and Comparative Example A.
  • the main agent and the curing agent were the same except that KF-868 was used as the release agent in Example A and KF-96-1000CS was used as the release agent in Comparative Example A.
  • the mixing ratio of the release agent was also the same.
  • the following results are considered to be the same also in the fiber reinforced composite material containing a reinforced fiber. The present invention is not limited to these.
  • a general-purpose film that is not coated with a release agent is placed inside a metal tool plate, and a resin composition in which the matrix resin and the internal release agent (1) are mixed is poured into the prepared jig, and is placed in an oven. After curing for 1 hour at 80 ° C., a fiber reinforced resin molded product (2) having a thickness of 2 mm was obtained.
  • a contact angle meter (DMo-501) manufactured by Kyowa Interface Science Co., Ltd. was used to measure the contact angle of water and the surface free energy of the fiber reinforced resin molded article (2) treated with atmospheric pressure plasma. The surface free energy was measured using the Owens-Wendt method with water and diiodomethane as liquid samples.
  • a fiber reinforced resin molded article (2) that has been subjected to atmospheric pressure plasma treatment and a target member that is not subjected to atmospheric pressure plasma treatment are added to JIS K 6850 (2017) using urethane adhesive (Priogrip 2400 / 2808B manufactured by Ashland).
  • the described single lap shear test piece (adhesion thickness: 0.5 mm) was prepared, a tensile shear test was performed with a universal testing machine, and visual observation of fracture strength and fracture state of the joint was performed.
  • the target member was sanded and degreased with # 320 sandpaper before bonding.
  • FIG. 4 shows the relationship between the contact angle with water and the surface free energy of the fiber-reinforced resin molded article (2)
  • FIG. 5 shows the relationship between the surface free energy and the contact angle with water and the adhesive strength (the curve is a polynomial approximation curve)
  • a list of test results (only for some levels) is shown.
  • FIG. 4 shows that there is a strong correlation between the contact angle of water and the surface free energy of the fiber reinforced resin molded product (2).
  • the above-mentioned fiber reinforced resin molded article (2) that is, the fiber reinforced resin molded article (2) was used as a base material A (bidirectional carbon fiber woven fabric).
  • a base material A bidirectional carbon fiber woven fabric.
  • main agent jER828 manufactured by Mitsubishi Chemical Co., Ltd.
  • curing agent TR-C38 curing agent manufactured by Toray Industries, Inc.
  • a reactive silicone release agent, Shin-Etsu Silicone KF-868, molded using a mixing ratio of the matrix resin main agent and the internal release agent at 100: 1 was used in common.
  • the plasma treatment conditions were changed as shown in Table 2. That is, in Examples 1 to 3, the distance between the molded product and the plasma processing nozzle was set to 20 mm, 20 mm, and 15 mm, respectively, and the processing speed was set to 2 m / min, 10 m / min, and 10 m / min, respectively. As a result, the surface free energy was 35 mN / m or more and 60 mN / m or less, and / or the contact angle with water was 40 degrees or more and 80 degrees or less. In addition, the adhesive strength was 12.1 MPa, 12.2 MPa, 10.5 MPa, respectively, and it was observed that the fracture mode was cohesive failure indicating that the adhesive was broken inside the adhesive, and had good and stable adhesiveness. I found out.
  • the joining structure according to the present invention can be applied to all joining structures, but is particularly suitable for joining structures in which an outer member and an inner member of different materials are joined in a panel structure such as a hood or a door of an automobile body.

Abstract

L'invention concerne un agent de démoulage interne qui est ajouté à un matériau composite renforcé par des fibres contenant des fibres de renforcement et une résine de matrice non durcie, l'agent de démoulage interne pour le matériau composite renforcé par des fibres étant caractérisé en ce qu'il possède un groupe fonctionnel réactif qui forme une liaison chimique lors du durcissement de la résine de matrice. L'invention concerne également un procédé d'assemblage pour un produit moulé en résine renforcée par des fibres, le procédé amenant un produit moulé en résine renforcée par des fibres contenant l'agent de démoulage interne à être assemblé à un élément de contrepartie, le procédé d'assemblage étant caractérisé en ce que, avant d'assembler le produit moulé en résine renforcée par des fibres et l'élément de contrepartie, une étape de prétraitement pour reformer une surface du produit moulé en résine renforcée par des fibres par application externe d'énergie à la surface du produit moulé en résine renforcée par des fibres est effectuée et l'énergie libre à la surface du produit moulé en résine renforcée par des fibres après l'étape de prétraitement est de 35 mN/m à 60 mN/m et/ou l'angle de contact par rapport à l'eau est de 40 degrés à 80 degrés. La présente invention concerne, afin de supprimer l'écoulement après durcissement de la résine de matrice et le pelage provenant d'une interface entre un corps moulé et un agent de démoulage : un agent de démoulage interne ayant un groupe fonctionnel qui est susceptible de former une liaison chimique avec une composition de résine d'un matériau composite de résine renforcée par des fibres ; un matériau composite de résine renforcée par des fibres contenant cet agent de démoulage interne ; et un procédé d'assemblage du matériau composite de résine renforcée par des fibres.
PCT/JP2019/008409 2018-03-27 2019-03-04 Agent de démoulage interne pour matériau composite renforcé par des fibres, matériau composite renforcé par des fibres, procédé de moulage associé et procédé d'assemblage pour produit moulé en résine renforcé par des fibres WO2019188020A1 (fr)

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JP2019518018A JPWO2019188020A1 (ja) 2018-03-27 2019-03-04 繊維強化複合材料用内部離型剤、繊維強化複合材、その成形方法および繊維強化樹脂成形品の接合方法

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Application Number Priority Date Filing Date Title
JP2018-059717 2018-03-27
JP2018-059716 2018-03-27
JP2018059716 2018-03-27
JP2018059717 2018-03-27

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WO2019188020A1 true WO2019188020A1 (fr) 2019-10-03

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WO2021166698A1 (fr) * 2020-02-21 2021-08-26 東レ株式会社 Article moulé composite renforcé par des fibres contenant un agent de démoulage interne
WO2021166241A1 (fr) * 2020-02-21 2021-08-26 東レ株式会社 Article moulé composite renforcé par des fibres et procédé de moulage associé
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WO2023109152A1 (fr) * 2021-12-15 2023-06-22 振石集团华智研究院(浙江)有限公司 Pièce moulée et procédé sans tissu de démoulage pour sa fabrication
CN114347513A (zh) * 2021-12-29 2022-04-15 振石集团华智研究院(浙江)有限公司 一种模具成型件及其无脱模布生产方法
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CN114700240A (zh) * 2022-01-25 2022-07-05 上海克络蒂材料科技发展有限公司 一种纤维增强树脂型材喷漆处理工艺

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