WO2019188020A1 - Internal mold release agent for fiber-reinforced composite material, fiber-reinforced composite material, molding method therefor, and joining method for fiber-reinforced resin molded product - Google Patents

Internal mold release agent for fiber-reinforced composite material, fiber-reinforced composite material, molding method therefor, and joining method for fiber-reinforced resin molded product 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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Prior art keywords
fiber
release agent
composite material
reinforced resin
resin molded
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PCT/JP2019/008409
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French (fr)
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/en
Publication of WO2019188020A1 publication Critical patent/WO2019188020A1/en

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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

Provided is an internal mold release agent that is added to a fiber-reinforced composite material containing reinforcement fibers and uncured matrix resin, wherein the internal mold release agent for the fiber-reinforced composite material is characterized by having a reactive functional group that forms a chemical bond when curing the matrix resin. Also provided is a joining method for a fiber-reinforced resin molded product, the method causing a fiber-reinforced resin molded product containing the internal mold release agent to be joined with a counterpart member, wherein the joining method is characterized in that, before joining the fiber-reinforced resin molded product and the counterpart member, a pre-treatment step for reforming a surface of the fiber-reinforced resin molded product by externally imparting energy to the surface of the fiber-reinforced resin molded product is performed, and the free energy at the surface of the fiber-reinforced resin molded product after the pre-treatment step is 35 to 60 mN/m and/or the contact angle with respect to water is 40 to 80 degrees. The present invention provides, in order to suppress bleeding out after curing the matrix resin and peeling originating from an interface between a molded body and a mold release agent: an internal mold release agent having a functional group that is capable of forming a chemical bond with a resin composition of a fiber-reinforced resin composite material; a fiber-reinforced resin composite material containing this internal mold release agent; and a method for joining the fiber-reinforced resin composite material.

Description

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Internal mold release agent for fiber reinforced composite material, fiber reinforced composite material, molding method thereof, and joining method of fiber reinforced resin molded product
　本発明は、繊維強化複合材料用離型剤とその離型剤を用いた繊維強化複合材料、その成形方法および繊維強化樹脂成形品の接合方法に関する。 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.
　近年、排ガス規制や燃費向上を目的として、自動車ボディは軽量化が図られており、複数種の材料を用い、それぞれの材料の特性を活かしたマルチマテリアル構造の採用が拡大している。 In recent years, automobile bodies have been reduced in weight for the purpose of exhaust gas regulations and fuel efficiency improvement, and the use of multi-material structures that take advantage of the characteristics of each material is expanding.
　自動車のフードやドアのような板状のアウター部材とインナー部材の接合構造体においては、鋼板、アルミ合金材、または繊維強化樹脂材料に代表される樹脂材料の組み合わせ構造が検討されている（特許文献１）。このような異種材料からなる部品同士を接合する際の代表的な接合方法として、機械締結や接着接合などが挙げられる。このうち接着接合は機械締結において懸念される穴周りの応力集中が無く、また線ないし面による接合であるため接合効率も高いことから異種材料の接合方法として有効な手段として考えられている。 In a joint structure of a plate-like outer member and inner member such as a hood or door of an automobile, 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. Among them, 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.
　一方で、特に繊維強化複合材料を用いた接着接合を行う際には、成形時の脱型性向上のために用いた離型剤が接合表面に離型層を作り、剥離などの原因となることが知られている。この剥離を防ぐ方法として、繊維強化複合材料成形後には接着面に対してサンディング、プラズマ処理などの後加工が加えられる（特許文献２、３）。 On the other hand, especially when performing adhesive bonding using fiber reinforced composite materials, 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. As a method for preventing this peeling, 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).
　マトリックス樹脂としてエポキシ樹脂を使用した場合、金属との高い接着性から金型表面に外部離型剤として塗布する方法では十分ではなく、マトリックス樹脂内に内部離型剤として添加する方法が採られる。このように添加された内部離型剤はマトリックス樹脂の硬化時に成形品表面側に押し出される形で析出（ブリードアウト）するため、接着接合を行う場合、離型剤成分が逆に接着性を阻害することになる。そのため、接着を行う際には、通常繊維強化樹脂成形品の表面をサンディング処理やブラスト処理、または成形品最外層にピールプライ層を設けて成形後ピールプライ層を剥ぐといった方法により成形品表面の離型剤層を除去する前処理工程が必要になる（特許文献４）。
特開２０１５－１６４８４０号公報 特開２００４－５８６１３号公報 特開２００３－２２１４５８号公報 特開２０１２－４６８５０号公報 When an epoxy resin is used as the matrix resin, a method of applying it as an external mold release agent to the mold surface is not sufficient because of its high adhesion to metal, and a method of adding it as an internal mold release agent in the matrix resin is adopted. The internal mold release agent added in this way precipitates (bleeds out) in the form of being extruded to the surface of the molded product when the matrix resin is cured. Therefore, when performing adhesive bonding, the release agent component adversely inhibits adhesion. Will do. Therefore, when bonding, the surface of the molded product surface is usually released by sanding or blasting the surface of the molded product, or by peeling off the peel ply layer after forming the peel ply layer on the outermost layer of the molded product. A pretreatment process for removing the agent layer is required (Patent Document 4).
Japanese Patent Laying-Open No. 2015-164840 JP 2004-58613 A JP 2003-221458 A JP 2012-46850 A
　特許文献１のように繊維強化複合材料を用いた接着接合を行う際には、成形時の脱型性向上のために用いた離型剤が接合表面に離型層を作り、剥離などの原因となる。 When performing adhesive bonding using a fiber reinforced composite material as in Patent Document 1, 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.
　特許文献２、３のように接着面に対してサンディング、プラズマ処理などの後加工を行う場合には、処理後の成形面性状のバラツキの問題や、処理時間やコストがかかるという問題がある。 When performing post-processing such as sanding and plasma treatment on the bonded surface as in Patent Documents 2 and 3, there are problems of variations in the properties of the molded surface after treatment, and processing time and cost.
　特許文献４のように成形品最外層にピールプライ層を設けて成形後ピールプライ層を剥ぐといった方法により成形品表面の離型剤層を除去する前処理工程を行う場合にも、処理後の成形面性状のバラツキの問題や、処理時間やコストがかかるという問題がある。 Even in the case of performing the pretreatment step of removing the release agent layer on the surface of the molded product by a method in which a peel ply layer is provided on the outermost layer of the molded product and the peel ply layer is peeled off after molding as in Patent Document 4, the molded surface after the treatment There are problems of variation in properties, and processing time and cost.
　また、内部離型剤を用いた場合、添加した全ての離型剤が成形品表面に完全に析出（ブリードアウト）するわけではなく、その一部は成形品内部に凝集しているため、部品接着後に離型剤成分が成形品内部から接着剤／成形品界面側に拡散することで、接合界面に接合強度が相対的に低いＷｅａｋＢｏｕｎｄａｒｙ Ｌａｙｅｒ（以下、ＷＢＬ）が形成され接着強度が低下するおそれがある。 In addition, when an internal mold release agent is used, not all of the added mold release agent is completely deposited (bleeded out) on the surface of the molded product. When the release agent component diffuses from the inside of the molded product to the adhesive / molded product interface side after bonding, a weakly bound WeakBoundary Layer (hereinafter referred to as WBL) is formed at the bonded interface, which may reduce the adhesive strength. There is.
　本発明は上記に挙げた各種問題点に鑑みてなされたものであり、マトリックス樹脂硬化後の成形品表面への内部離型剤の析出（ブリードアウト）と、成形体と離型剤の界面を起点とした剥離を抑制するために、繊維強化樹脂複合材料の樹脂組成物と化学結合を形成することが出来る官能基を持つ内部離型剤、この内部離型剤を含む繊維強化樹脂複合材料、および前記繊維強化複合材料の成形品を用いた接合体にて高品質を実現する接合方法を提供することを目的とする。 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. An internal mold release agent having a functional group capable of forming a chemical bond with the resin composition of the fiber reinforced resin composite material in order to suppress peeling as a starting point, a fiber reinforced resin composite material containing the internal 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.
　上記課題を解決するため本発明の繊維強化複合材用内部離型剤は、次の構成を有する。すなわち、
強化繊維と未硬化のマトリックス樹脂を含む繊維強化複合材に添加される内部離型剤であって、前記内部離型剤は前記マトリックス樹脂の硬化時に化学結合する反応性官能基を有する繊維強化複合材用内部離型剤、である。 In order to solve the above problems, 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.
　本発明の繊維強化複合材は、次の構成を有する。すなわち、
前記繊維強化複合材用内部離型剤の添加量が前記未硬化のマトリックス樹脂の０．０１～１０ｗｔ％である繊維強化複合材、である。 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.
　本発明の繊維強化複合材の成形方法は、次の構成を有する。すなわち、
強化繊維とマトリックス樹脂を含む繊維強化複合材の成形方法において、未硬化のマトリックス樹脂中に反応性官能基を有する内部離型剤を添加する工程と、前記内部離型剤が添加された前記未硬化のマトリックス樹脂を加熱硬化し、前記反応性官能基を介して、前記内部離型剤の少なくとも一部と前記マトリックス樹脂とを化学結合させる工程を含む繊維強化複合材の成形方法、である。 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.
　本発明の繊維強化樹脂成形品の接合方法は、次の構成を有する。すなわち、
熱硬化性樹脂からなる繊維強化樹脂成形品を相手部材と接合する繊維強化樹脂成形品の接合方法であって、前記繊維強化樹脂成形品と前記相手部材を接合する前に、前記繊維強化樹脂成形品の表面に外部からエネルギーを付与して、前記繊維強化樹脂成形品の表面を改質する前処理工程を行い、前記前処理工程後の前記繊維強化樹脂成形品表面の表面自由エネルギーが３５ｍＮ／ｍ以上６０ｍＮ／ｍ以下および／または水に対する接触角が４０度以上８０度以下である繊維強化樹脂成形品の接合方法、である。 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.
　本発明の繊維強化複合材用内部離型剤は、前記反応性官能基が、アミン、エポキシ、カルボン酸、チオールのうち少なくとも１つからなることが好ましい。 In the internal mold release agent for fiber-reinforced composite material of the present invention, the reactive functional group is preferably composed of at least one of amine, epoxy, carboxylic acid, and thiol.
　本発明の繊維強化複合材用内部離型剤は、前記内部離型剤がシリコーン系離型剤であることが好ましい。 In the internal mold release agent for fiber-reinforced composite material of the present invention, the internal mold release agent is preferably a silicone-based mold release agent.
　本発明に用いられる繊維、強化複合材としては、未硬化のマトリックス樹脂に対し、前記内部離型剤の添加量が０．０１～１０ｗｔ％であることが好ましい。 In the fiber and reinforced composite material used in the present invention, the amount of the internal release agent added is preferably 0.01 to 10 wt% with respect to the uncured matrix resin.
　本発明の繊維強化複合材は、前記内部離型剤の全重量の４０％未満が表層に析出していることが好ましい。 In 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.
　本発明の繊維強化複合材は、前記マトリックス樹脂が熱硬化性樹脂であることが好ましい。 In the fiber-reinforced composite material of the present invention, the matrix resin is preferably a thermosetting resin.
　本発明の繊維強化複合材の成形方法は、未硬化のマトリックス樹脂に対し、前記内部離型剤を０．０１～１０ｗｔ％添加することが好ましい。 In the method for molding a fiber reinforced composite material of the present invention, it is preferable to add 0.01 to 10 wt% of the internal mold release agent to the uncured matrix resin.
　本発明の繊維強化複合材の成形方法は、前記内部離型剤が添加された前記未硬化のマトリックス樹脂を３０～２５０℃で加熱することが好ましい。 In the method for molding a fiber-reinforced composite material of the present invention, it is preferable to heat the uncured matrix resin to which the internal release agent has been added at 30 to 250 ° C.
　本発明の繊維強化樹脂成形品の接合方法は、前記エネルギーが、繊維強化樹脂成形品の成形時または成形前に添加され、成形後の繊維強化樹脂成形品表面に析出した離型剤層に対して付与されることが好ましい。 According to the fiber reinforced resin molded product joining method of the present invention, 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.
　本発明の繊維強化樹脂成形品の接合方法は、前記繊維強化樹脂成形品表面への前記エネルギー付与が大気圧プラズマ処理方法によることが好ましい。 In the fiber reinforced resin molded product joining method of the present invention, it is preferable that the energy application to the fiber reinforced resin molded product surface is performed by an atmospheric pressure plasma treatment method.
　本発明の繊維強化樹脂成形品の接合方法は、前記相手部材が、金属、非強化の樹脂、繊維強化樹脂のうち少なくともひとつの材料から選ばれることが好ましい。 In the method for joining fiber-reinforced resin molded products of the present invention, the counterpart member is preferably selected from at least one material selected from metal, non-reinforced resin, and fiber-reinforced resin.
　本発明の繊維強化樹脂成形品の接合方法は、前記相手部材との接合が接着剤を介して接合されることが好ましい。 In the method for joining fiber reinforced resin molded products of the present invention, it is preferable that the mating member is joined via an adhesive.
　本発明の繊維強化樹脂成形品の接合方法は、前記接着剤がウレタン接着剤であることが好ましい。 In the method for joining fiber-reinforced resin molded products of the present invention, the adhesive is preferably a urethane adhesive.
　このように本発明の内部離型剤を利用することにより、内部離型剤を用いて繊維強化複合材料を成形した際に、硬化後の成形体表面への内部離型剤の析出（ブリードアウト）を抑制し、塗装や接着工程に向けた成形体表面の離型剤の除去、改質効果が持続する。また、離型剤層と成形体との界面での剥離を防ぐことが出来る。さらに本発明にかかる接合方法によれば、接合工程の簡略化も実現することができる。 Thus, by using 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.
本発明における内部離型剤の特性と、内部離型剤（１）を含む繊維強化複合材料と、その成形方法を図にて表したものである。The characteristic of the internal mold release agent in this invention, the fiber reinforced composite material containing an internal mold release agent (1), and its shaping | molding method are represented with a figure. 図１をフロー図として表したものである。FIG. 1 is a flow diagram. 反応性官能基を持つ内部離型剤と持たない内部離型剤のマトリックス樹脂表層から深さ２０μｍ範囲の分布状態を比較した、ＴＯＦ－ＳＩＭＳの測定図である。FIG. 4 is a TOF-SIMS measurement diagram comparing the distribution state in the range of 20 μm 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. 本発明の実施の形態に係る繊維強化樹脂成形品（２）のプラズマ処理後の水に対する接触角と表面自由エネルギーとの関係の一例を示すグラフである。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. 本発明の実施の携帯に係る繊維強化樹脂成形品（２）のプラズマ処理後の水に対する接触角ないし表面自由エネルギーとの接着強度との関係を示すグラフである。It is a graph which shows the relationship with the contact strength thru | or the surface free energy with respect to the water after the plasma processing of the fiber reinforced resin molding (2) which concerns on carrying of this invention, and the adhesive strength.
　以下、本発明に係る実施の形態について図面を参照しながら説明する。
［内部離型剤］
　本発明における内部離型剤（１）は、一般式（Ｉ）に示すポリシロキサンの側鎖および／または末端に官能基Ｒを導入した反応性を有するシリコーン系離型剤である（なお、式（Ｉ）中のｍならびにｎは１以上の整数）。このような官能基Ｒの例としては、アミノ基、エポキシ基、カルボキシル基、チオール基、カルビノール基、メタクリル基、フェノール基などが挙げられ、これらの中から適宜選択可能である。また、これらの内部離型剤（１）の添加量は、未硬化のマトリックス樹脂に対して０．０１～１０ｗｔ％であることが好ましく、０．１％～５％であることがより好ましい。内部離型剤（１）の添加量を上記好ましい範囲にすると、離型時に離型性を発揮し、硬化後の成形品表面への析出（ブリードアウト）を抑制することが出来る。なお、一般式（ＩＩ）に示すのは反応性官能基を持たないシリコーン系離型剤であり、これを従来品とする。 Embodiments according to the present invention will be described below with reference to the drawings.
[Internal release agent]
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). Examples of such 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. When 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. In addition, what is shown to general formula (II) is a silicone type mold release agent which does not have a reactive functional group, and makes this a conventional product.
Figure JPOXMLDOC01-appb-C000001
Figure JPOXMLDOC01-appb-C000001
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000002
　このとき、内部離型剤を添加する対象は二液系のマトリックス樹脂を用いる際には主剤、硬化剤のいずれでも良く、また主剤と硬化剤を混合した後に添加しても良い。さらに、添加する際の温度は離型剤とマトリックス樹脂の反応可能温度を下回り、マトリックス樹脂、離型剤が攪拌混合可能な粘度となる温度であることが好ましい。
［マトリックス樹脂］
　本発明における繊維強化複合材に含まれるマトリックス樹脂（３）は熱硬化性樹脂であることが好ましく、中でもエポキシ樹脂、エポキシ樹脂、不飽和ポリエステル樹脂、ビニルエステル樹脂、ジアリルフタレート樹脂、フェノール樹脂、マレイミド樹脂、シアン酸エステル樹脂などから選ばれることがより好ましく、特に、力学特性の優れた繊維強化樹脂部材を得るためには、熱硬化性樹脂と強化繊維の配合が容易であること、成形が容易であることから、エポキシ樹脂がさらに好ましい。エポキシ樹脂としては、分子内に複数のエポキシ基を有する化合物が用いられる。例えば、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ビスフェノールＳ型エポキシ樹脂、ビスフェノールＡＤ型エポキシ樹脂、ナフタレン型エポキシ樹脂、ノボラック型エポキシ樹脂、ビフェニル型エポキシ樹脂、脂環式エポキシ樹脂、あるいはこれらの樹脂の組み合わせが用いられる。なかでも、ビスフェノールＡ型エポキシ樹脂を主成分としたエポキシ樹脂が経済性、力学特性のバランスの観点から好ましく用いることができる。また硬化剤としてはアミン系、酸無水物系いずれを用いても良い。 At this time, 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. Furthermore, it is preferable that 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.
[Matrix resin]
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. In particular, in order to obtain a fiber reinforced resin member having excellent mechanical properties, it is easy to mix a thermosetting resin and a reinforced fiber, and molding is easy. Therefore, an epoxy resin is more preferable. As the epoxy resin, a compound having a plurality of epoxy groups in the molecule is used. For example, 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. Especially, 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. Moreover, as a hardening | curing agent, you may use any of an amine type and an acid anhydride type.
　さらに、マトリックス樹脂（３）には、要求される特性に応じて、本発明の目的を損なわない範囲で他の充填材や添加剤を含有しても良い。他の充填材や添加剤としては、例えば、無機充填材、難燃剤、導電性付与剤、結晶核剤、紫外線吸収剤、酸化防止剤、制振剤、抗菌剤、防虫剤、防臭剤、着色防止剤、熱安定剤、滑材、帯電防止剤、可塑剤、着色剤、顔料、染料、発泡剤、制泡剤、カップリング剤などが挙げられる。
［強化繊維］
　本発明における強化繊維は特に限定されず、炭素繊維やガラス繊維、アラミド繊維など、さらにこれらの混在した強化繊維の使用が可能である。なかでも、高い機械特性の発現やその特性の設計のし易さ等の面からは、炭素繊維を含むことが好ましい。また、繊維の形態についても、連続繊維形態、短繊維形態など適宜選択可能である。
［硬化反応時の析出（ブリードアウト）］
　本発明における内部離型剤（１）はマトリックス樹脂（３）の硬化反応時にマトリックス樹脂（３）の表面に析出（ブリードアウト）して離型層（４）を形成する。この時、内部離型剤（１）のうち一部は表層に析出（ブリードアウト）せず、残存内部離型剤（５）となる。
［化学結合］
　本発明において内部離型剤（１）とマトリックス樹脂（３）はマトリックス樹脂の硬化時に化学結合（６）を形成する。この時、内部離型剤と主剤との間、内部離型剤と硬化剤との間、またはその両方のいずれの組み合わせにおいて化学結合が形成されても良い。このため、析出（ブリードアウト）した離型層（表層）（４）および残存内部離型剤（５）はマトリックス樹脂（３）に固定され、硬化後にマトリックス樹脂（３）との界面から剥離したり、新たに析出（ブリードアウト）したりすることを抑制出来る。
［離型剤とマトリックス樹脂の反応確認方法］
　本発明における内部離型剤（１）とマトリックス樹脂（３）の反応はＤＳＣ（パーキンエルマー　ＤＩＡＭＯＮＤ　ＤＳＣ）にて確認することができる。この時、室温から成形温度まで１０℃／ｍｉｎにて加熱した際に主剤と離型剤、硬化剤と離型剤、もしくはその両方の少なくとも１つの系で主剤と硬化剤の反応ピーク以外の熱量ピークを確認できれば反応が起きているとする。
［離型剤のマトリックス樹脂中の分布確認方法］
　本発明における内部離型剤（１）のマトリックス樹脂（３）中の分布状態はＴＯＦ－ＳＩＭＳ（飛行時間型二次イオン質量分析法）を用いて確認した。図３に示すように、反応性離型剤（１）を用いたサンプルと従来品では表層から深さ２０μｍの範囲で残存内部離型剤（５）の分布が異なり、反応性離型剤は深さ２０μｍの範囲で局在化している箇所が少数なのに対し、従来品では多数の局在化した残存内部離型剤（５）が確認できる。
［成形フロー］
　本発明における成形フローは図１、図２に示すとおりである。
＜材料の準備＞
　繊維強化複合材を得るため、強化繊維、マトリックス樹脂、内部離型剤を準備する。得ようとする繊維強化複合材の物性等に応じて、強化繊維の繊維種類、形状、繊維体積含有量、配向等を適宜選択することができる。マトリックス樹脂としては主剤と硬化剤の二液混合型が好ましいがこの限りではない。内部離型剤（１）を添加する対象は、二液系のマトリックス樹脂（３）を用いる際には主剤、硬化剤のいずれでも良く、また主剤と硬化剤を混合した後に添加しても良い。さらに、添加する際の温度は内部離型剤（１）とマトリックス樹脂（３）の反応温度を下回り、内部離型剤（１）、マトリックス樹脂（３）が攪拌混合可能な粘度となる温度であれば好ましい。 Furthermore, 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. Examples of 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.
[Reinforcing fiber]
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). At this time, a part of the internal mold release agent (1) does not precipitate (bleed out) on the surface layer but becomes the remaining internal mold release agent (5).
[Chemical bond]
In the present invention, the internal release agent (1) and the matrix resin (3) form a chemical bond (6) when the matrix resin is cured. At this time, 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. For this reason, 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.
[Method for confirming reaction between release agent and matrix resin]
The reaction between the internal mold release agent (1) and the matrix resin (3) in the present invention can be confirmed by DSC (Perkin Elmer DIAMOND DSC). At this time, when heated from room temperature to molding temperature at 10 ° C./min, the amount of heat other than the reaction peak of the main agent and the curing agent in at least one system of the main agent and the release agent, the curing agent and the release agent, or both. If the peak can be confirmed, it is assumed that the reaction has occurred.
[Method for confirming distribution of release agent in matrix resin]
The distribution state of the internal release agent (1) in the present invention in the matrix resin (3) was confirmed using TOF-SIMS (time-of-flight secondary ion mass spectrometry). As shown in FIG. 3, 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 μm from the surface layer. Whereas a small number of locations are localized within a depth of 20 μm, a large number of localized residual internal mold release agents (5) can be confirmed in the conventional product.
[Molding flow]
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. Depending on the physical properties of the fiber-reinforced composite material to be obtained, the fiber type, shape, fiber volume content, orientation, and the like of the reinforcing fibers can be appropriately selected. As 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. . Furthermore, 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.
　ここで、未硬化のマトリックス樹脂に対し、内部離型剤の添加量は０．０１～１０ｗｔ％であることが好ましく、より好ましくは０．１％～５ｗｔ％である。この範囲の添加量とすることで、接着工程後の成形品表面への内部離型剤の析出（ブリードアウト）を抑制し、接着不良等の不具合を防ぐことが出来る。 Here, 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.
　内部離型剤を添加した未硬化のマトリックス樹脂を強化繊維にあらかじめ含浸させておいてもよく、後述する硬化工程時にあわせて含浸させるようにしてもよい。 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.
　これらの材料の投入法については各成形法に適した方法であればよく、中でもプレス成形を用いるときには成形型のキャビティ内に配置し、成形型を閉じるのが好ましい。
＜ａ．硬化＞
　次に、内部離型剤（１）が添加された未硬化のマトリックス樹脂（３）を強化繊維に含浸し、３０～２５０℃の加熱温度で加熱し、未硬化のマトリックス樹脂を硬化させる。硬化させるときの加圧条件としては材料の形状を固定することができれば特に機構および形態を限定するものではない。また、加熱方法についても材料を適切に加熱、冷却できるものであれば、特に機構及び形態を限定するものではなく、例えば電熱線や電磁誘導、高温流体、マイクロ波等を利用することができる。特にプレス成形を行うときには可逆的な熱交換を行えることから水蒸気等の高温流体を用いることが好ましい。 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>
Next, 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. Also, 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.
　硬化工程において、アミン、エポキシ、カルボン酸、チオールのうち少なくとも１つを含む反応性官能基を介して、内部離型剤（１）の一部と未硬化のマトリックス樹脂（３）とが化学結合を形成する。このような化学結合の形成により、離型層（４）とマトリックス樹脂界面の接合強度が高められ、後述の相手部材との接合時に離型層（４）とマトリックス樹脂界面間がＷＢＬとなることが抑制される。このような離型層（４）が金型と十分な離型性を発現させるためには、離型層（４）の厚みとして１００ｎｍから数百ｎｍ程度あればよい。 In the curing step, 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. Form. 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. In order for such a release layer (4) to exhibit sufficient release properties from the mold, the thickness of the release layer (4) may be about 100 nm to several hundred nm.
　一方で、添加した内部離型剤（１）の全重量の４０％未満は、内部のマトリックス樹脂と化学結合する前に、繊維強化複合材の表層に析出（ブリードアウト）する。繊維強化複合材の表層に析出した内部離型剤（１）は離型層（４）を形成する。
＜ｂ．脱型＞
　硬化後に繊維強化複合材の表層に存在する離型層（４）が離型作用を発揮することで、繊維強化複合材の成形型からの脱型が可能となる。
＜ｃ．表面処理＞
　脱型後、接着処理、塗装工程に進む前に離型層（４）を表面処理する工程が必要になる。これは、離型層（４）の最表面にあるシリコーン側鎖のメチル基が、接着剤や塗料と、繊維強化複合材との接合性を阻害することを防ぐためである。 On the other hand, less than 40% of the total weight of the added internal release agent (1) precipitates (bleeds out) on the surface layer of the fiber-reinforced composite material before chemically bonding with the internal matrix resin. The internal release agent (1) deposited on the surface layer of the fiber reinforced composite material forms the release layer (4).
<B. Demolding>
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.
<C. Surface treatment>
After demolding, a process of surface-treating the release layer (4) is required before proceeding to the adhesion process and the painting process. This is to prevent the methyl group of the silicone side chain on the outermost surface of the release layer (4) from inhibiting the bonding property between the adhesive or paint and the fiber-reinforced composite material.
　硬化工程において、繊維強化複合材の内部にある内部離型剤（１）はマトリックス樹脂（３）と化学結合を形成しており、繊維強化複合材の内部にある内部離型剤（１）が表層に析出（ブリードアウト）することが困難となっている。したがって、離型層（４）のみ表面処理すれば、経時的に析出（ブリードアウト）することなく、接着剤や塗料との接合を持続することが可能となる。 In the curing step, 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.
　表面処理の方法としては大気圧プラズマ処理やコロナ処理、紫外線（ＵＶ）処理、真空紫外線（ＶＵＶ）処理、フレーム処理などが挙げられるが、このうち処理の高速性、オゾン非発生などの環境面、また三次元対象物の処理が可能な点から、特に大気圧プラズマ処理が好ましい。大気圧プラズマ処理においては、処理ノズル（７）をロボットなどの搬送機構に把持し、処理ノズル（７）を走査することによって、処理を行いたい任意の場所に任意の回数だけ高速な処理を行うことができる。また、大気圧プラズマ処理において用いられるプロセスガスについては、空気以外に窒素ガス、酸素ガス、ヘリウムガス、アルゴンガスなどやこれらのガスの混合ガスを採用することができる。また、プラズマ処理を行う際の処理ノズル（７）と繊維強化樹脂成形品（２）との距離は５～２５ｍｍ、処理ノズル（７）の走査速度は２～２０ｍ／ｍｉｎが好ましい。 Surface treatment methods include atmospheric pressure plasma treatment, corona treatment, ultraviolet (UV) treatment, vacuum ultraviolet (VUV) treatment, flame treatment, etc. Among these, high-speed processing, environmental aspects such as no ozone generation, In addition, atmospheric pressure plasma treatment is particularly preferable from the viewpoint that a three-dimensional object can be treated. In the atmospheric pressure plasma processing, 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. As 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. In addition, 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, and the scanning speed of the processing nozzle (7) is preferably 2 to 20 m / min.
　ここで、繊維強化樹脂成形品（２）の前処理は、処理後の繊維強化樹脂成形品（２）の表面自由エネルギーが３５ｍＮ／ｍ以上６０ｍＮ／ｍ以下、および／または水に対する接触角が４０度以上８０度以下となるように処理することが重要である。表面自由エネルギーが３５ｍＮ／ｍ未満、かつ水の接触角が８０度を超えた場合、表面は疎水表面であり、メチル基の脱離が十分ではなく、表面は離型性を失っていない。また、表面自由エネルギーが６０ｍＮ／ｍを超えかつ水の接触角が４０度未満の場合、濡れ性が向上し接合に好適な表面が形成されているように見えるが、実際には離型層直下のマトリックス樹脂（３）にまで外部エネルギーによる処理が行われることでマトリックス樹脂（３）の劣化が起きた状態となっている。その結果、繊維強化樹脂成形品（２）の表面粗さが増加することで、見かけ上濡れ性が向上しているだけであり、この劣化した樹脂層がＷＢＬとなり、接合強度の低下を引き起こす。一方、表面自由エネルギーが３５ｍＮ／ｍ以上６０ｍＮ／ｍ以下、および／または水に対する接触角が４０度以上８０度以下の場合、マトリックス樹脂（３）の劣化を起こさずかつ離型層（４）内のシリコーン系離型剤を構成するメチル基が除去、親水性官能基への置換が十分に行われ、接合に好適な接着性表面（８）を形成することができる。 Here, in the pretreatment of the fiber reinforced resin molded article (2), 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. When 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. In addition, when the surface free energy exceeds 60 mN / m and the contact angle of water is less than 40 degrees, it seems that the wettability is improved and a surface suitable for bonding is formed. 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. On the other hand, when the surface free energy is not less than 35 mN / m and not more than 60 mN / m and / or the contact angle with water is not less than 40 degrees and not more than 80 degrees, 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.
　これに対し、反応性官能基を持たない従来の内部離型剤（１）を用いて成形した繊維強化複合材に対しては、サンディング、あらかじめ表面に仕込んだピールプライを剥がす等といった作業負担が大きな表面処理を行って離型層（４）が取り除かれ、マトリックス樹脂が露出した露出層（９）が新たな最表層となる。しかしながら、処理後の時間の経過とともに強化繊維複合材の内部から離型剤が表層に析出（ブリードアウト）し、後述する接着や塗装後、接着不良や塗装の剥離を引き起こす。 On the other hand, for the fiber reinforced composite material molded using the conventional internal mold release agent (1) having no reactive functional group, 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. However, with the passage of time after the treatment, 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.
　なお、接触角ならびに表面自由エネルギーの測定については、例えば公知の接触角計を用いて、水平面に置いた測定サンプルに数μＬ程度の液体試料を滴下し、横から撮像した液滴画像から解析する液滴法（Ｓｅｓｓｉｌｅ　Ｄｒｏｐ法）によって測定することができる。水の接触角の場合、液体試料として蒸留水や精製水を使用するが、表面自由エネルギーについては種々の測定理論式が提唱されており、例えば、Ｏｗｅｎｓ－Ｗｅｎｄｔ法では、表面エネルギーが既知の２種の溶媒を使用し、サンプル表面に滴下した各溶媒の接触角から表面自由エネルギーを算出することができる。用いる溶媒の一例としては、水（蒸留水、精製水）、ジヨードメタン（ヨウ化メチレン）、エチレングリコール、ホルムアミド、ヘキサデカンなどが挙げられるが、本発明では水とジヨードメタンを使用する。
＜ｄ．接着、塗装＞
　表面処理後の繊維強化複合材料は接着剤・塗装（１０）が塗布される。この時、先の処理によって得られた接着層（６）は接着剤・塗装（１０）と強固に結合出来る。接着接合を行う場合、対象部材としては特に限定されないが、金属材料、非強化の樹脂材料ないし前述に記載の繊維強化樹脂材料から用途・仕様に応じて適宜選択できる。また、接着剤についても、特に限定されず、例えばエポキシ系接着剤、ウレタン系接着剤、アクリル系接着剤、シリコーン系接着剤等が挙げられ、このうちの少なくとも一種類から選択されることが好ましく、繊維強化樹脂成形品（２）と線膨張係数の異なる材料と接合する場合にはウレタン接着剤がさらに好ましい。 For the measurement of the contact angle and the surface free energy, for example, using a known contact angle meter, a liquid sample of about several μL 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). In the case of 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. For example, in the Owens-Wendt method, 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. Examples of the solvent used 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.
<D. 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). In the case of performing adhesive bonding, 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. Also, 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. When bonding to a material having a different linear expansion coefficient from that of the fiber reinforced resin molded product (2), a urethane adhesive is more preferable.
　なお、対象部材として熱可塑性樹脂材料を用いる場合には、接着剤を用いずに、溶着接合などの手段によって繊維強化樹脂成形品（２）と直接接合することも可能である。
＜ｅ．保管（経時）＞
　接着、塗装工程を終えた本発明における繊維強化複合材料は長期の保存時にも残存内部離型剤（５）が表層に析出（ブリードアウト）することが無く、接着強度、塗装が保たれる。従来品のように反応性官能基を持たない内部離型剤（１）を用いると表層に析出（ブリードアウト）してきた残存内部離型剤（１１）により剥離（１２）が引き起こされる。 In addition, when using a 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.
<E. Storage (Aging)>
The fiber-reinforced composite material according to the present invention that has been subjected to the bonding and painting process does not precipitate (bleed out) the remaining internal mold release agent (5) on the surface layer even during long-term storage, and the adhesion strength and painting are maintained. When the internal mold release agent (1) having no reactive functional group as in the conventional product is used, peeling (12) is caused by the residual internal mold release agent (11) deposited on the surface layer (bleed out).
　本発明の繊維強化樹脂成形品の接合方法は、前記のとおり、熱硬化性樹脂からなる繊維強化樹脂成形品を対象部材と接合する繊維強化樹脂成形品の接合方法であって、前記繊維強化樹脂成形品と前記対象部材を接合する前に、前記繊維強化樹脂成形品の表面に外部からエネルギーを付与して、前記繊維強化樹脂成形品の表面を改質する前処理工程を行い、前記前処理工程後の前記繊維強化樹脂成形品表面の表面自由エネルギーが３５ｍＮ／ｍ以上６０ｍＮ／ｍ以下および／または前記前処理工程後の前記繊維強化樹脂成形品表面の水に対する接触角が４０度以上８０度以下であることを特徴とする。前記前処理工程後の前記繊維強化樹脂成形品表面の表面自由エネルギーが３５ｍＮ／ｍ以上６０ｍＮ／ｍ以下の範囲を外れ、かつ、前記前処理工程後の前記繊維強化樹脂成形品表面の水に対する接触角が４０度以上８０度以下の範囲を外れる場合には、接合に好適な表面状態に改質することができず、高い接合強度を実現することができない。 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. Before joining the molded product and the 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. When 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.
　本発明の繊維強化樹脂成形品の接合方法は、前記のとおり、繊維強化樹脂成形品の成形時または成形前に添加され、成形後の繊維強化樹脂成形品表面に析出した離型剤層に対して、前記エネルギーを付与することが好ましい。繊維強化樹脂成形品表面の離型剤層に対して前記エネルギーを付与することにより、表面に析出（ブリードアウト）した離型剤成分を失活させた上、更に接着に好適な表面に改質することができ、金型への離型性と相手部材との接着性の両方を両立することが可能になる。 As described above, 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. Thus, it is preferable to apply the energy. By applying the energy to the release agent layer on the surface of the fiber reinforced resin molded product, the release agent component deposited on the surface (bleed out) 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.
　本発明の繊維強化樹脂成形品の接合方法は、前記のとおり、前記繊維強化樹脂成形品表面への前記エネルギー付与が大気圧プラズマ処理方法によることが好ましい。このような方法により、高速かつ均質な処理が可能になる。 As described above, it is preferable that 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.
　本発明の繊維強化樹脂成形品の接合方法は、前記のとおり、前記対象部材が、金属、非強化の樹脂、繊維強化樹脂のうち少なくともひとつの材料から選ばれることが好ましい。このような材料により構成されていることにより、表面意匠性や軽量性、強度・剛性を活かすことができ、接合体全体の機能をより高めることが可能になる。 In the method for joining fiber-reinforced resin molded products of the present invention, as described above, it is preferable that the target member is selected from at least one material of metal, non-reinforced resin, and fiber-reinforced resin. By being comprised with such a material, surface design property, lightness, strength, and rigidity can be utilized, and the function of the entire joined body can be further enhanced.
　本発明の繊維強化樹脂成形品の接合方法は、前記のとおり、前記対象部材との接合が接着剤を介して接合されることが好ましい。また、前記接着剤がウレタン接着剤であることが好ましい。線・面で接合する接着接合の高い接合効率を利用するとともに、異種材料同士の接合の際に問題となる線膨張係数差による熱変形の影響をウレタン接着剤の高い伸び性により緩和することが可能になるからである。 As described above, 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.
　以下、実施例により本発明をさらに具体的に説明する。
（実施例Ａ、１～３および比較例Ａ、１～３）
　成形品内部の分布状態については分析の都合上、強化繊維を含まない樹脂注型板にて離型剤の分布を確認した結果を実施例Ａおよび比較例Ａとして表１に示す。ここで、実施例Ａにおいては離型剤としてＫＦ－８６８を、比較例Ａにおいては離型剤としてＫＦ－９６－１０００ＣＳを用いた以外は、主剤、硬化剤とも同じで、主剤、硬化剤および離型剤の混合比も同じとした。なお、以下の結果は強化繊維を含む繊維強化複合材料においても同様の結果になると考えられる。また、本発明はこれらに限定されるものではない。 Hereinafter, the present invention will be described more specifically with reference to examples.
(Examples A, 1-3 and Comparative Examples A, 1-3)
Table 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. Here, 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. In addition, 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.
　内部離型剤の析出（ブリードアウト）状態を以下の通りに確認した。
［マトリックス樹脂（３）］
・主剤　三菱化学（株）製ｊＥＲ８２８
・硬化剤　東レ（株）製ＴＲ－Ｃ３８硬化剤
・混合比　主剤：硬化剤：離型剤＝１００：９９：１
　［内部離型剤（１）］
・反応性シリコーン離型剤　信越シリコーン（株）製ＫＦ－８６８
・混合比　マトリックス樹脂主剤：内部離型剤＝１００：１
　＜注型板作成＞
　金属製ツール板の内側に離型剤の塗布されていない汎用フィルムを配置し、作成した治具に対して上記マトリックス樹脂と内部離型剤（１）を混合した樹脂組成物を流し込み、オーブンにて８０℃で１時間硬化の後、厚み２ｍｍの繊維強化樹脂成形品（２）を得た。 The state of precipitation (bleed out) of the internal release agent was confirmed as follows.
[Matrix resin (3)]
・ Main agent jER828 manufactured by Mitsubishi Chemical Corporation
Curing agent TR-C38 curing agent manufactured by Toray Industries, Inc. Mixing ratio Main agent: Curing agent: Mold release agent = 100: 99: 1
[Internal release agent (1)]
・ Reactive silicone release agent KF-868 manufactured by Shin-Etsu Silicone Co., Ltd.
-Mixing ratio Matrix resin main component: Internal mold release agent = 100: 1
<Creating cast plate>
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.
　＜内部分布確認＞
　作成した注型板を１０ｍｍ角に切り出し、ＴＯＦ－ＳＩＭＳにて表層と、表層から深さ２０μｍの範囲における離型剤の分布を確認した。その結果、マトリックス樹脂の表層に２００ｎｍ程度の離型剤層が検出され、表層から深さ２０μｍの範囲には図３の左図３－１に示す通り、内部離型剤の局在化は見られなかった。 <Internal distribution confirmation>
The prepared casting plate was cut into a 10 mm square, and the distribution of the release agent in the range of 20 μm in depth from the surface layer and the surface layer was confirmed by TOF-SIMS. As a result, a release agent layer having a thickness of about 200 nm was detected on the surface layer of the matrix resin, and the localization of the internal release agent was observed in the range of 20 μm from the surface layer as shown in FIG. I couldn't.
　一方で、前記一般式（ＩＩ）に示す、反応性官能基を持たない従来の内部離型剤である信越シリコーン（株）製ＫＦ－９６－１０００ＣＳを用いて同様に成形を行い、離型性の確認を行ったところ、離型性は良好であった。しかし、注型板を作成した後に１０ｍｍ角に加工し、表層と表層から深さ２０μｍにおける内部離型剤（１）の分布を確認したところ、実施例と同様にマトリックス樹脂の表層に２００ｎｍの離型剤層が検出され、表層から２０μｍの範囲には多くの局在化した残存内部離型剤（５）が確認された。この局在化した残存内部離型剤（５）はマトリックス樹脂（３）と従来の内部離型剤の相溶性が低い事を示しており、硬化後に表層に析出（ブリードアウト）する可能性が高いため、接着、塗装不良を引き起こすことが予想できる。
また、接合方法について以下の通りの検討を実施した。
［繊維強化樹脂成形品（２）］
　［基材Ａ］
・二方向性炭素繊維織物：東レ（株）製ＢＴ７０－３０（糸種：Ｔ７００Ｓ、平織）
　［マトリックス樹脂（３）］
・主剤　三菱化学（株）製ｊＥＲ８２８
・硬化剤　東レ（株）製ＴＲ－Ｃ３８硬化剤
・混合比　主剤：硬化剤＝１００：９９
　　［内部離型剤（１）］
・反応性シリコーン離型剤　信越シリコーン（株）ＫＦ－８６８
・混合比　マトリックス樹脂主剤：内部離型剤＝１００：１
［対象部材］
　［基材Ｂ］
・一方向性炭素繊維プリプレグ　東レ（株）製Ｐ３８３２－Ｗ１９（糸種：Ｔ７００Ｓ）
（繊維強化樹脂成形品の成形）
　金属製ツール板の上に基材を７枚積層し、ＶａＲＴＭ成形により、内部離型剤を添加したマトリックス樹脂を基材Ａに含浸させ、オーブンにて８０℃で１時間硬化の後、厚み２ｍｍの繊維強化樹脂成形品（２）を得た。また、繊維強化樹脂成形品（２）とは別に、繊維強化樹脂成形品（２）と同曲げ剛性となるように、繊維方向を全て揃えた基材Ｂを１０枚積層し、プレス成形法により厚み１．８ｍｍの対象部材を得た。その後、各成形品を１００ｍｍ×２５ｍｍの短冊片に切削加工を行った。
＜離型性確認＞
　内部離型剤を添加したマトリックス樹脂をアルミカップに注ぎ、オーブンにて８０度で１時間硬化させた後、アルミカップからの離型性の確認を行った。その結果、硬化させたマトリックス樹脂とアルミカップとの離型性は良好であった。
＜大気圧プラズマ処理＞
　続いて、短冊片に加工した繊維強化樹脂成形品（２）に対して、プロセスガスとして空気を用いた大気圧プラズマ処理を１回行った。なお、成形品とプラズマ処理ノズルの処理距離、処理ノズルの走査速度は以下の条件とした。
・処理距離　５ｍｍ、１０ｍｍ、１５ｍｍ、２０ｍｍ
・処理速度　２ｍ／ｍｉｎ、５ｍ／ｍｉｎ、１０ｍ／ｍｉｎ
＜接触角・表面自由エネルギー測定＞
　大気圧プラズマ処理した繊維強化樹脂成形品（２）を協和界面科学（株）製接触角計（ＤＭｏ－５０１）により、水の接触角測定ならびに表面自由エネルギーの測定を行った。なお、表面自由エネルギー測定は水ならびにジヨードメタンを液体試料として、Ｏｗｅｎｓ－Ｗｅｎｄｔ法を用いて算出した。
（接着作業・強度試験）
　大気圧プラズマ処理を行った繊維強化樹脂成形品（２）と、大気圧プラズマ処理を行わない対象部材とをウレタン接着剤（Ａｓｈｌａｎｄ社製Ｐｌｉｏｇｒｉｐ２４００／２８０８Ｂ）を用いて、ＪＩＳ　Ｋ　６８５０（２０１７）に記載のシングルラップシェア試験片（接着厚み：０．５ｍｍ）を作成し、万能試験機により引張せん断試験を実施し、破壊強度ならびに接合部の破壊状態の目視観察を行った。なお、対象部材は、接着前に＃３２０番のサンドペーパーでサンディングならびにアセトン脱脂を行った。 On the other hand, molding was carried out in the same manner using KF-96-1000CS manufactured by Shin-Etsu Silicone Co., Ltd., which is a conventional internal mold release agent having no reactive functional group, as shown in the general formula (II). As a result, it was confirmed that the releasability was good. However, after forming the casting plate, it was processed into a 10 mm square and the distribution of the internal mold release agent (1) at a depth of 20 μm from the surface layer and the surface layer was confirmed. As in the example, the surface of the matrix resin was separated by 200 nm. The mold layer was detected, and many localized residual internal mold release agents (5) were confirmed in the range of 20 μm from the surface layer. This localized residual internal mold release agent (5) shows that the compatibility between the matrix resin (3) and the conventional internal mold release agent is low, and there is a possibility that it will precipitate (bleed out) on the surface layer after curing. Because it is high, it can be expected to cause poor adhesion and painting.
Moreover, the following examination was implemented about the joining method.
[Fiber-reinforced resin molded product (2)]
[Substrate A]
-Bidirectional carbon fiber fabric: BT70-30 manufactured by Toray Industries, Inc. (Thread type: T700S, plain weave)
[Matrix resin (3)]
・ Main agent jER828 manufactured by Mitsubishi Chemical Corporation
-Curing agent TR-C38 curing agent manufactured by Toray Industries, Inc.-Mixing ratio Main agent: Curing agent = 100: 99
[Internal release agent (1)]
・ Reactive silicone release agent Shin-Etsu Silicone KF-868
-Mixing ratio Matrix resin main component: Internal mold release agent = 100: 1
[Target material]
[Base material B]
・ Unidirectional carbon fiber prepreg P3832-W19 (thread type: T700S) manufactured by Toray Industries, Inc.
(Molding of fiber reinforced resin molded products)
Seven base materials are laminated on a metal tool plate, the base resin A is impregnated with a matrix resin to which an internal release agent is added by VaRTM molding, cured at 80 ° C. for 1 hour in an oven, and then a thickness of 2 mm. A fiber reinforced resin molded product (2) was obtained. Separately from the fiber reinforced resin molded product (2), 10 base materials B with all the fiber directions aligned are laminated so as to have the same bending rigidity as that of the fiber reinforced resin molded product (2). A target member having a thickness of 1.8 mm was obtained. Thereafter, each molded product was cut into strips of 100 mm × 25 mm.
<Verification of releasability>
The matrix resin to which the internal release agent was added was poured into an aluminum cup and cured in an oven at 80 degrees for 1 hour, and then the release property from the aluminum cup was confirmed. As a result, the mold release property between the cured matrix resin and the aluminum cup was good.
<Atmospheric pressure plasma treatment>
Subsequently, an atmospheric pressure plasma treatment using air as a process gas was performed once on the fiber reinforced resin molded product (2) processed into strips. The processing distance between the molded product and the plasma processing nozzle and the scanning speed of the processing nozzle were set as follows.
・ Processing distance 5mm, 10mm, 15mm, 20mm
・ Processing speed 2m / min, 5m / min, 10m / min
<Contact angle / surface free energy measurement>
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.
(Adhesion work / strength test)
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.
　図４に繊維強化樹脂成形品（２）の水に対する接触角と表面自由エネルギーの関係、図５に表面自由エネルギーならびに水に対する接触角と接着強度の関係（曲線は多項式近似曲線）、表２に試験結果の一覧（一部水準のみ）を示す。図４より、繊維強化樹脂成形品（２）の水に対する接触角と表面自由エネルギーには強い相関関係があることが分かる。 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).
　実施例１～３および比較例１～３においては、前記の繊維強化樹脂成形品（２）、すなわち、繊維強化樹脂成形品（２）は、基材として基材Ａ（二方向性炭素繊維織物）、マトリックス樹脂として、主剤：三菱化学（株）製ｊＥＲ８２８、硬化剤：東レ（株）製ＴＲ－Ｃ３８硬化剤、主剤と硬化剤の混合比を１００：９９として用い、内部離型剤として、反応性シリコーン離型剤である信越シリコーン（株）ＫＦ－８６８を、マトリックス樹脂主剤と内部離型剤の混合比を１００：１として用いて成形したものを共通して用いた。 In Examples 1 to 3 and Comparative Examples 1 to 3, 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). ), As matrix resin, main agent: jER828 manufactured by Mitsubishi Chemical Co., Ltd., curing agent: TR-C38 curing agent manufactured by Toray Industries, Inc., and a mixing ratio of the main agent and the curing agent as 100: 99, 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.
　そして、プラズマ処理条件を表２に示すとおりに変更した。すなわち、実施例１から３においては、成形品とプラズマ処理ノズルとの距離をそれぞれ２０ｍｍ、２０ｍｍ、１５ｍｍに設定し、処理速度をそれぞれ２ｍ／ｍｉｎ、１０ｍ／ｍｉｎ、１０ｍ／ｍｉｎとしてプラズマ処理を行ったところ、表面自由エネルギーが３５ｍＮ／ｍ以上６０ｍＮ／ｍ以下、および／または水に対する接触角が４０度以上８０度以下となった。また、接着強度はそれぞれ１２．１ＭＰａ、１２．２ＭＰａ、１０．５ＭＰａとなり、破壊形態が接着剤内部で破壊したことを示す凝集破壊であることが観察され、良行且つ安定した接着性を有していることが分かった。一方で、比較例１においてはプラズマ処理未実施とし、比較例２、３においては成形品とプラズマ処理ノズルとの距離を５ｍｍに設定し、処理速度をそれぞれ２ｍ／ｍｉｎ、１０ｍ／ｍｉｎとしてプラズマ処理を行ったところ、表面自由エネルギーが３５ｍＮ／ｍ未満または６０ｍＮ／ｍを超えた値となり、かつ、水に対する接触角が４０度未満または８０度を超えた値となった。その結果、接着強度が１０ＭＰａ未満となり、繊維強化樹脂成形品（２）と接着剤との界面で破壊する界面破壊が観察され、接着性は不十分であった。 And 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. On the other hand, plasma processing is not performed in Comparative Example 1, and in Comparative Examples 2 and 3, the distance between the molded product and the plasma processing nozzle is set to 5 mm, and the processing speed is set to 2 m / min and 10 m / min, respectively. As a result, the surface free energy was less than 35 mN / m or more than 60 mN / m, and the contact angle with water was less than 40 degrees or more than 80 degrees. As a result, the adhesive strength was less than 10 MPa, interface fracture that was broken at the interface between the fiber-reinforced resin molded article (2) and the adhesive was observed, and the adhesiveness was insufficient.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
　本発明に係る接合構造は、あらゆる接合構造に適用できるが、特に自動車ボディのフードやドアなどのパネル構造などにおいて、異種材料のアウター部材とインナー部材を接合する接合構造に好適である。 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.
１　内部離型剤
２　繊維強化樹脂成形品
３　マトリックス樹脂
４　離型層（表層）
５　残存内部離型剤
６　化学結合
７　処理ノズル
８　接着性改質層
９　露出面
１０　接着剤、塗装
１１　硬化後、表層に析出した残存内部離型剤
１２　剥離部
１３　残存内部離型剤の析出前の存在位置 DESCRIPTION OF SYMBOLS 1 Internal mold release agent 2 Fiber reinforced resin molding 3 Matrix resin 4 Release layer (surface layer)
5 Remaining internal mold release agent 6 Chemical bond 7 Processing nozzle 8 Adhesive modified layer 9 Exposed surface 10 Adhesive, coating 11 Remaining internal mold release agent deposited on surface layer after curing 12 Peeling portion 13 Precipitation of residual internal mold release agent Previous location

Claims (15)

  1. 　強化繊維と未硬化のマトリックス樹脂を含む繊維強化複合材に添加される内部離型剤であって、前記内部離型剤は前記マトリックス樹脂の硬化時に化学結合する反応性官能基を有する繊維強化複合材用内部離型剤。 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 Internal mold release agent for materials.
  2. 　前記反応性官能基が、アミン、エポキシ、カルボン酸、チオールのうち少なくとも１つからなる請求項１に記載の繊維強化複合材用内部離型剤。 The internal mold release agent for a fiber-reinforced composite material according to claim 1, wherein the reactive functional group comprises at least one of amine, epoxy, carboxylic acid, and thiol.
  3. 　前記離型剤がシリコーン系離型剤である請求項２に記載の繊維強化複合材用内部離型剤。 The internal release agent for fiber-reinforced composite materials according to claim 2, wherein the release agent is a silicone-based release agent.
  4. 　請求項１～３のいずれかに記載の繊維強化複合材用内部離型剤の添加量が前記未硬化のマトリックス樹脂の０．０１～１０ｗｔ％である繊維強化複合材。 A fiber-reinforced composite material, wherein the amount of the internal mold release agent for fiber-reinforced composite material according to any one of claims 1 to 3 is 0.01 to 10 wt% of the uncured matrix resin.
  5. 　前記内部離型剤の全重量の４０％未満が表層に析出している繊維強化複合材。 A fiber-reinforced composite material in which less than 40% of the total weight of the internal release agent is deposited on the surface layer.
  6. 　前記マトリックス樹脂が熱硬化性樹脂である請求項１～５のいずれかに記載の繊維強化複合材。 The fiber reinforced composite material according to any one of claims 1 to 5, wherein the matrix resin is a thermosetting resin.
  7. 　強化繊維とマトリックス樹脂を含む繊維強化複合材の成形方法において、未硬化のマトリックス樹脂中に反応性官能基を有する内部離型剤を添加する工程と、前記内部離型剤が添加された前記未硬化のマトリックス樹脂を加熱硬化し、前記反応性官能基を介して、前記内部離型剤の少なくとも一部と前記マトリックス樹脂とを化学結合させる工程を含む繊維強化複合材の成形方法。 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.
  8. 　前記成形方法において、未硬化のマトリックス樹脂に対し、前記内部離型剤を０．０１～１０ｗｔ％添加する請求項７に記載の繊維強化複合材の成形方法。 The method for molding a fiber-reinforced composite material according to claim 7, wherein 0.01 to 10 wt% of the internal mold release agent is added to the uncured matrix resin in the molding method.
  9. 　前記内部離型剤が添加された前記未硬化のマトリックス樹脂を３０～２５０℃で加熱する請求項７または８のいずれかに記載の繊維強化複合材の成形方法。 The method for molding a fiber-reinforced composite material according to any one of claims 7 and 8, wherein the uncured matrix resin to which the internal release agent has been added is heated at 30 to 250 ° C.
  10. 　熱硬化性樹脂からなる繊維強化樹脂成形品を相手部材と接合する繊維強化樹脂成形品の接合方法であって、前記繊維強化樹脂成形品と前記相手部材を接合する前に、前記繊維強化樹脂成形品の表面に外部からエネルギーを付与して、前記繊維強化樹脂成形品の表面を改質する前処理工程を行い、前記前処理工程後の前記繊維強化樹脂成形品表面の表面自由エネルギーが３５ｍＮ／ｍ以上６０ｍＮ／ｍ以下および／または前記前処理工程後の前記繊維強化樹脂成形品表面の水に対する接触角が４０度以上８０度以下である繊維強化樹脂成形品の接合方法。 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 and 60 mN / m or less, and / or the fiber-reinforced resin molded product joining method wherein the contact angle with water on the surface of the fiber reinforced resin molded product after the pretreatment step is 40 degrees or greater and 80 degrees or less.
  11. 　前記エネルギーが、前記繊維強化樹脂成形品の成形時または成形前に添加され、成形後の前記繊維強化樹脂成形品表面に析出した離型剤層に対して付与される請求項１０に記載の繊維強化樹脂成形品の接合方法。 The fiber according to claim 10, wherein the energy is added to a release agent layer that is added to the fiber-reinforced resin molded article or before molding and deposited on the surface of the fiber-reinforced resin molded article after molding. A method for joining reinforced resin molded products.
  12. 　前記繊維強化樹脂成形品表面への前記エネルギー付与が大気圧プラズマ処理方法による請求項１０ないし１１のいずれかに記載の繊維強化樹脂成形品の接合方法。 The method for joining fiber reinforced resin molded products according to any one of claims 10 to 11, wherein the application of energy to the surface of the fiber reinforced resin molded product is performed by an atmospheric pressure plasma treatment method.
  13. 　前記相手部材が、金属、非強化の樹脂、繊維強化樹脂のうち少なくともひとつの材料から選ばれる請求項１０ないし１２のいずれかに記載の繊維強化樹脂成形品の接合方法。 The method for joining fiber reinforced resin molded products according to any one of claims 10 to 12, wherein the counterpart member is selected from at least one material selected from metal, non-reinforced resin, and fiber reinforced resin.
  14. 　前記相手部材との接合が接着剤を介して接合される請求項１０ないし１３のいずれかに記載の繊維強化樹脂成形品の接合方法。 The method for joining fiber reinforced resin molded products according to any one of claims 10 to 13, wherein the joining with the mating member is joined via an adhesive.
  15. 　前記接着剤がウレタン接着剤である請求項１４に記載の繊維強化樹脂成形品の接合方法。 The method for joining fiber reinforced resin molded products according to claim 14, wherein the adhesive is a urethane adhesive.
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