WO2023153332A1 - Matériau en résine pour assemblage, procédé pour la fabrication de celui-ci et procédé d'assemblage utilisant un matériau en résine pour assemblage - Google Patents

Matériau en résine pour assemblage, procédé pour la fabrication de celui-ci et procédé d'assemblage utilisant un matériau en résine pour assemblage Download PDF

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WO2023153332A1
WO2023153332A1 PCT/JP2023/003621 JP2023003621W WO2023153332A1 WO 2023153332 A1 WO2023153332 A1 WO 2023153332A1 JP 2023003621 W JP2023003621 W JP 2023003621W WO 2023153332 A1 WO2023153332 A1 WO 2023153332A1
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Prior art keywords
bonding
resin material
joining
region
interface
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PCT/JP2023/003621
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English (en)
Japanese (ja)
Inventor
凪朝 濱田
公則 和鹿
直元 石川
伸樹 宮本
誠 山口
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株式会社ヒロテック
株式会社キグチテクニクス
国立大学法人秋田大学
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Publication of WO2023153332A1 publication Critical patent/WO2023153332A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/48—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding
    • 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
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
    • C09J5/02—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving pretreatment of the surfaces to be joined

Definitions

  • the present invention relates to a bonding resin material that can be used for bonding between resin materials and between a resin material and a metal material, a manufacturing method thereof, and a bonding method using the bonding resin material.
  • adhesives are used to join resin materials together
  • adhesives and riveting are generally used to join metal materials and resin materials.
  • bonding is achieved by physical or chemical adsorption force
  • riveting is used, bonding is achieved by mechanical fastening with rivets.
  • the parts that can be applied are limited due to the size and weight of the fastening part, which increases the size and weight of the parts and also reduces the degree of freedom in design.
  • general-purpose plastics such as polyethylene (PE), polypropylene (PP), polystyrene (PS), polyvinyl chloride (PVC) and ABS resin (ABS), polyethylene terephthalate (PET), polycarbonate (PC), etc.
  • engineering plastics and super engineering plastics such as polyetheretherketone (PEEK) and polyamide-imide (PAI) are used in large quantities in various fields. There is a strong demand for direct bonding between resin materials and metal materials.
  • thermoplastic resins have a stable molecular structure and are inert, direct bonding between thermoplastic resin materials and metal materials is extremely difficult. It is essential. In the case of surface treatment using metallic sodium, which is currently widely used in industrial applications, high adhesive strength can be expected by combining it with epoxy adhesives, but a clean alternative method is desired due to environmental concerns. In addition, since the adhesive has low heat resistance, it is difficult to use it continuously in a high-temperature atmosphere by making use of the characteristics of the thermoplastic resin, and it is limited to use at a relatively low temperature. Furthermore, the use of adhesives should be avoided as much as possible, especially in the medical and food fields, and direct bonding without using adhesives is desired from this point of view as well.
  • thermosetting resins have a more stable molecular structure than thermoplastic resins, and are more inert than thermoplastic resins. becomes even more difficult.
  • adhesives are mainly used to join thermosetting resin materials, but for carbon fiber reinforced plastics (CFRP), for which demand has been increasing in recent years, problems caused by the above adhesives are serious. is becoming
  • Patent Document 1 Japanese Patent Application Laid-Open No. 2005-104132
  • a method for joining thermoplastic resin members has been proposed, which includes a step of melting opposing surfaces of flat thermoplastic resin members and a step of fusing the melted thermoplastic resin members together.
  • thermoplastic resin material In the method for joining thermoplastic resin materials described in Patent Document 1, wettability is improved by forming a rough surface on at least one surface of each thermoplastic resin material in advance, and the liquid laser absorber heats. It is stated that the thermoplastic resin material can be stably joined by irradiating the laser beam because it spreads evenly on the surface of the plastic resin material and no welding unevenness occurs.
  • Patent Document 2 Japanese Patent Application Laid-Open No. 2016-56363
  • the surface temperature of a molded body containing an organic polymer compound is set to (the melting point of the organic polymer compound -120) ° C. or higher, and the surface of the molded body is
  • atmospheric pressure plasma treatment is performed on the surface of the molded body to introduce peroxide radicals into the molded body.
  • Patent Document 3 Japanese Patent Application Laid-Open No. 2019-123153
  • a method for directly joining one member to be joined and the other member to be joined wherein one member to be joined is thermoplastic.
  • a method for joining thermoplastic resins comprising: a second step of forming a joint interface by bringing a member to be joined into contact; and a third step of raising the temperature of the joint interface by laser irradiation. is suggesting.
  • thermoplastic resins described in Patent Document 3 the CF bond of the thermoplastic resin is separated by laser irradiation, and sodium and fluorine, which have a high bonding property with fluorine, are combined to form a molecular structure. can improve the bondability of stable and inert thermoplastic resins.
  • Patent Document 1 the joining method described in Patent Document 1 is intended only for joining thermoplastic resin materials together, and cannot join thermoplastic resin materials and metal materials.
  • the materials to be joined are limited to thermoplastic resin materials having laser transparency, a laser absorber that does not directly contribute to improving the strength of the joint interface remains at the joint interface.
  • thermoplastic resin material in the method for manufacturing a surface-modified molded body described in Patent Document 2, it is necessary to place a thermoplastic resin material in a chamber having an evacuation system and perform atmospheric pressure plasma treatment. It is necessary to raise the surface temperature of the plastic resin material to a specified temperature range. That is, the applicable size and shape of the thermoplastic resin material are restricted, and the process becomes complicated. Furthermore, only adherends having reactive functional groups can be adhered to thermoplastic resin materials.
  • thermoplastic resin joining method described in Patent Document 3 a metal thermoplastic resin joint having higher strength than other joining methods can be obtained. It has a wet process of coating, and there is room for improvement from the viewpoint of mass production of homogeneous and high-strength joints with high efficiency.
  • Patent Documents 1 to 3 are intended only for thermoplastic resins, and there are suitable techniques for firmly bonding thermosetting resin materials to each other and thermosetting resin materials to metal materials. do not.
  • the present invention provides a method that can be suitably used for joining resin materials together and resin materials and metal materials without using mechanical joining such as riveting. It is an object of the present invention to provide a bonding resin material capable of bonding, a simple and efficient manufacturing method thereof, and a bonding method using the bonding resin material. In addition, the present invention targets both thermoplastic resins and thermosetting resins, and is capable of improving the bonding strength and the reliability of joints in both direct bonding and bonding using an adhesive between materials to be bonded. It is also an object of the present invention to provide a bonding resin material capable of bonding, a simple and efficient manufacturing method thereof, and a bonding method using the bonding resin material.
  • the unsaturated graphitized regions having C ⁇ C bonds and/or C—C bonds in the bonding resin material of the present invention have a higher energy state and are more active than the other surfaces, A favorable direct bonding interface can be formed by contacting the bonding interface and applying heat and pressure.
  • the graphitized region is amorphous carbon.
  • the resin material is a thermoplastic resin. Since the thermoplastic resin softens as the temperature rises during bonding, it can ensure sufficient adhesion to the other bonding material, suppressing defect formation and promoting bonding between the graphitized region and the other bonded interface. Therefore, a good bonding interface can be stably formed.
  • the resin material is a thermosetting resin.
  • Graphitized regions formed on the surface of thermosetting resins which have extremely poor reactivity, form a strong bonding interface for both direct bonding and adhesives, improving the strength and reliability of the bonding interface. can be made
  • a method of manufacturing a resin material is also provided.
  • the graphitized region is amorphous carbon.
  • the surface state of the region irradiated with the pulse laser can be confirmed, for example, by microscopic FT-IR or Raman spectroscopic analysis. etc. can achieve this.
  • this can be achieved by lowering the output of the pulse laser, shortening the irradiation time, or the like.
  • the pulse laser is a nanosecond short pulse laser.
  • a nanosecond short pulse laser it is possible to easily and efficiently form an unsaturated graphitized region having C ⁇ C bonds and/or C—C bonds on the surface of a bonding resin material.
  • a continuous wave laser it is difficult to adjust the energy applied to the surface of the resin material for bonding. It is difficult to make the graphitized region unsaturated with C ⁇ C bonds and/or C—C bonds.
  • At least one member to be joined is the joining resin material of the present invention, a joining interface forming step of forming a joining interface by bringing the joining resin material and the other joining material into contact with each other through the graphitized region on the surface of the joining resin material; a bonding step of increasing the temperature of the interface to be bonded by external heating means to achieve bonding; directly bonding the bonding resin material and the other material to be bonded through the graphitized region;
  • a method for joining resin materials characterized by
  • the method for joining the resin materials of the present invention includes (1) joining of the joining resin materials of the present invention, (2) joining of the joining resin material of the present invention with an arbitrary resin material, and (3) joining of the joining resin materials of the present invention. Bonding between a bonding resin material and any metal material is included. In any of these modes, by raising the temperature of the interface to be joined by the external heating means, it is possible to obtain a good joint in which the materials to be joined are directly joined via the graphitized region.
  • the external heating means can raise the temperature of the interface to be joined, various conventionally known external heating means can be used as long as they do not impair the effects of the present invention.
  • the interfaces to be bonded need only be in close contact with each other, but it is preferable to apply a bonding pressure.
  • the other material to be joined is a metal material
  • the surface of the metal material is irradiated with a pulsed laser in an oxidizing atmosphere to form metal oxide particle clusters in which metal oxide particles having a particle size of 5 to 500 nm are continuously bonded.
  • a surface modification region Contacting the graphitized region and the surface modified region at the interface to be bonded; is preferred.
  • the surface-modified region having metal oxide particle clusters in which metal oxide particles having a particle size of 5 to 500 nm are continuously bonded to C C bonds and/or C- It promotes the dissociation of C-bonds, and efficiently obtains strong joints.
  • the maximum height (Sz) of the surface of the metal oxide particle cluster, which is the interface to be bonded on the metal material side, to 50 nm to 3 ⁇ m the adhesion between the metal oxide particle cluster and the bonding resin material is improved. can be secured.
  • the temperature of the interface to be joined it is preferable to raise the temperature of the interface to be joined by laser irradiation.
  • laser irradiation as the external heating means, the temperature of the interface to be bonded can be easily and efficiently raised regardless of the shape and size of the region to be bonded.
  • the present invention provides At least one member to be joined is the joining resin material of the present invention, a bonding interface forming step of forming a bonding interface by bringing the bonding resin material and the other bonding material into contact via the graphitized region and an adhesive; and a bonding step of curing the adhesive;
  • a method for joining resin materials characterized by
  • a bonding resin material that can be suitably used for bonding resin materials together or resin materials and metal materials without using mechanical bonding such as riveting, and a simple and efficient bonding resin material thereof. It is possible to provide a manufacturing method and a bonding method using the bonding resin material. In addition, according to the present invention, both thermoplastic resins and thermosetting resins are targeted, and the bonding strength and the reliability of the joint are improved in both direct bonding between the materials to be bonded and bonding using an adhesive. It is also possible to provide a bonding resin material capable of bonding, a simple and efficient manufacturing method thereof, and a bonding method using the bonding resin material.
  • FIG. 4 is a schematic diagram of the microstructure in the cross section of the graphitized region 4.
  • FIG. It is process drawing in the case of performing direct joining in this invention. It is process drawing in the case of adhering in this invention.
  • It is an optical micrograph of the surface of a PEEK plate irradiated with a laser. It is an optical microscope photograph of a cross section of a PEEK plate irradiated with a laser. IR spectra from a laser-irradiated portion and an untreated portion, and their difference spectra. It is an IR mapping image obtained in an example.
  • FIG. 1 is a schematic cross-sectional view showing one embodiment of the bonding resin material of the present invention.
  • An unsaturated graphitized region 4 having C ⁇ C bonds and/or C—C bonds is formed on at least part of the surface of the bonding resin material 2 of the present invention.
  • the graphitized region 4 is preferably formed with a thickness of 50 to 200 ⁇ m from the outermost surface of the bonding resin material 2 .
  • the thickness of the graphitized region 4 is more preferably 100 to 150 ⁇ m.
  • a schematic diagram of the microstructure in the cross section of the graphitized region 4 is shown in FIG.
  • fine black dots 6 are preferably dispersed.
  • the diameter of the black dots 6 is preferably 1 to 100 ⁇ m. By setting the diameter of the black dots 6 to 1 ⁇ m or more, unsaturated bonds including C ⁇ C bonds and/or C—C bonds are reliably formed. can do. In addition, by setting the diameter of the black dots 6 to 100 ⁇ m or less, it is possible not only to suppress excessive destruction of the resin structure, but also to homogenize the distribution of unsaturated bonds including C ⁇ C bonds and/or C—C bonds. can be done.
  • the blackened region 4 since the blackened region 4 is formed by irradiation with a pulse laser, the blackened region 4 has fine foam traces 8 scattered about.
  • the diameter of the foam traces 8 is preferably 500 ⁇ m or less, more preferably 250 ⁇ m or less, and most preferably 100 ⁇ m or less.
  • the bonding state of carbon atoms in the graphitized region 4 can be confirmed using Raman spectroscopic analysis. Specifically, the laser spot diameter is set to about 1 ⁇ m, and the graphitized region 4 and the untreated region (region not affected by pulse laser irradiation) are measured in microscopic mode, and the obtained Raman spectrum is Just compare.
  • Raman spectrum from the black point 6 broad Raman bands near 1600 cm ⁇ 1 and 1350 cm ⁇ 1 may be confirmed.
  • the Raman band is attributed to low-crystalline carbon, and indicates a state in which the formation of an unsaturated structure has progressed particularly.
  • the state of the graphitized region 4 can also be confirmed using microscopic FT-IR. Specifically, FT-IR-ATR measurement may be performed on the graphitized region 4 and the untreated region, and the obtained spectra and mapping images may be compared. For example, by evaluating the baseline drift due to the presence of carbon in the spectrum from the graphitized region 4, the progress of the formation of the unsaturated structure in the graphitized region 4 can be confirmed.
  • the graphitized region 4 may be formed in a region that will be the interface to be joined of the joining resin material 2 .
  • the graphitized regions 4 are preferably formed over the entire area of the interface to be joined, but may be formed in a linear or dotted pattern, for example.
  • the resin material is preferably a thermoplastic resin. Since the thermoplastic resin is softened by the temperature rise at the time of bonding, it is possible to ensure sufficient adhesion with the other bonding material, suppress the formation of defects, and improve the bonding between the graphitized region 4 and the other bonded interface. Acceleration can stably form a good bonding interface.
  • thermoplastic resin is not particularly limited as long as it does not impair the effects of the present invention, and may be various conventionally known thermoplastic resins, such as polyetheretherketone resin (PEEK).
  • PEEK polyetheretherketone resin
  • thermosetting resin in the bonding resin material 2, a thermosetting resin can be suitably used as the resin material. Even with a thermosetting resin that has extremely poor reactivity, the graphitized region 4 formed on the surface forms a strong bonding interface in both direct bonding and adhesive, increasing the strength and reliability of the bonding interface. can be improved.
  • thermosetting resin is not particularly limited as long as it does not impair the effects of the present invention, and can be various conventionally known thermoplastic resins, such as epoxy resins and thermosetting polyimide resins.
  • the surface of a resin material is irradiated with a pulse laser, and unsaturated graphite having a C ⁇ C bond and/or a C—C bond is formed on the surface. forming a softening region.
  • the chemical structure of the surface of the resin material changes, forming an unsaturated graphitized region 4 having C ⁇ C bonds and/or C—C bonds in the region. can be done.
  • it is necessary to apply appropriate energy to the region which can be achieved by using a pulse laser.
  • the graphitized region 4 is preferably amorphous carbon.
  • the surface state of the region irradiated with the pulse laser can be confirmed, for example, by microscopic FT-IR or Raman spectroscopic analysis. etc. can achieve this.
  • this can be achieved by lowering the output of the pulse laser, shortening the irradiation time, or the like.
  • a continuous wave laser it is difficult to adjust the energy applied to the surface of the resin material for bonding. It is difficult to make the graphitized region 4 in an unsaturated state with C ⁇ C bonds and/or C—C bonds.
  • the irradiation of the pulse laser should be applied to the range that will be the area to be bonded. Although at least a part of the region to be bonded may be irradiated, it is preferable to irradiate the entire surface of the region.
  • the scanning pattern of the pulse laser is not particularly limited, and the linear irradiation area may be wrapped, or any pattern shape may be used. Alternatively, a large number of dot-like irradiation regions may be formed.
  • the type of resin material is not particularly limited as long as it does not impair the effects of the present invention, and various conventionally known resin materials can be used.
  • the resin material may be a thermoplastic resin or a thermosetting resin.
  • the size and shape of the resin material are not particularly limited, and may be the size and shape desired as the material to be joined.
  • the bonding method of the present invention is most characterized in that the bonding resin material 2 is used as at least one of the materials to be bonded. It includes bonding between the material 2 and any resin material and bonding between the bonding resin material 2 and any metal material.
  • the method is roughly divided into a method of directly joining materials to be joined and a method of joining using an adhesive. In the following, the case of directly joining and the case of using an adhesive (adhesion) will be described in detail, taking the case of joining the joining resin material 2 and the metal material as a representative example.
  • FIG. 3 is a process diagram for performing direct bonding in the present invention.
  • the resin material bonding method of the present invention includes a bonding interface forming step (S01) for forming a bonding interface, and a bonding step (S02) for achieving bonding by raising the temperature of the bonding interface. .
  • the metal material and the bonding resin material 2 may be brought into contact with each other so that their planes are in contact with each other in a general overlapping state. , a so-called T-shaped joint.
  • a heat-resistant glass plate or the like is brought into contact with the surface of one or both of the materials to be bonded to constrain the entire surface.
  • the materials can be brought into closer contact with each other, and misalignment or the like of the interface to be joined in the joining step (S02) can be suppressed. It is preferable to use a heat-resistant glass having excellent laser transmittance.
  • the jig to be used is not particularly limited, and conventionally known various jigs can be used.
  • the thermoplastic resin is not particularly limited as long as it does not impair the effects of the present invention, and conventionally known general-purpose plastics, engineering plastics and super engineering plastics can be suitably used. can. More specifically, for example, polyethylene (PE), polypropylene (PP), polystyrene (PS), polyacetal (POM), polyvinyl chloride (PVC), polyethylene terephthalate (PET), ABS resin (ABS), polyamide (PA ), polycarbonate (PC), PET (polyethylene terephthalate), and various carbon fiber reinforced plastics (CFRP) and glass fiber reinforced plastics (GFRP).
  • PE polyethylene
  • PP polypropylene
  • PS polystyrene
  • POM polyacetal
  • PVC polyvinyl chloride
  • PET polyethylene terephthalate
  • ABS resin ABS resin
  • PA polyamide
  • PC polycarbonate
  • PET polyethylene terephthalate
  • GFRP glass fiber reinforced plastics
  • thermosetting resin is not particularly limited as long as it does not impair the effects of the present invention, and conventionally known various thermosetting resins can be used.
  • thermosetting resins include epoxy resins, phenol resins, unsaturated polyester resins, urethane resins, and silicone resins.
  • the metal material used as the material to be joined is not particularly limited as long as it does not impair the effects of the present invention, and various conventionally known metal materials can be used.
  • steel materials, aluminum materials, aluminum alloy materials, titanium materials, Any one of titanium alloy material, nickel-titanium alloy material, copper material, and copper alloy material can be used. From such viewpoints, it is preferable to use stainless steel, titanium and titanium alloys, and from the viewpoint of material cost, it is preferable to use various carbon steels including galvanized steel sheets.
  • the surface of the metal material used as the material to be bonded is irradiated with a pulse laser in an oxidizing atmosphere, and metal oxide particles having a particle size of 5 to 500 nm are formed continuously. It is preferable to form a surface modified region having metal oxide particle clusters that are physically bonded together, and bring the graphitized region 4 into contact with the surface modified region at the interface to be bonded.
  • the maximum height (Sz) of the surface of the metal oxide particle cluster, which is the interface to be bonded on the metal material side is set to 50 nm to 3 ⁇ m, the adhesion between the metal oxide particle cluster and the bonding resin material is improved. can be secured.
  • the bonding step (S02) is a step for achieving bonding by raising the temperature of the interface to be bonded using an external heating means.
  • an external heating means can raise the temperature of the interface to be joined
  • various conventionally known external heating means can be used as long as they do not impair the effects of the present invention, but laser irradiation is preferably used.
  • the temperature of the interface to be joined can be easily and efficiently raised regardless of the shape and size of the area to be joined.
  • the laser can also be used to form a graphitized region on the surface of a resin material and to form a surface-modified region on the surface of a metal material, thereby streamlining the bonding line. can be planned.
  • the bonding resin material 2 When the bonding resin material 2 is transparent, it is preferable to irradiate the laser from the bonding resin material 2 side, and when the bonding resin material 2 is opaque, it is preferable to irradiate the laser from the metal material side.
  • the bonding resin material 2 When the bonding resin material 2 is transparent, the pulse laser is irradiated from the bonding resin material 2 side. can be raised effectively.
  • the laser from the metal material side it can be used as a material to be bonded regardless of the type of the bonding resin material 2 .
  • a space can be provided on the bonding resin material 2 side, and pressure can be applied from the surface of the bonding resin material 2 as necessary.
  • the bonding step (S02) it is preferable to apply a bonding pressure to the interface to be bonded.
  • a bonding pressure By applying pressure to the interface to be bonded, the adhesion between the metal material and the bonding resin material 2 can be improved, the formation of defects can be suppressed, and the bonding strength of the bonding interface can be improved.
  • the joints obtained by the resin material joining method of the present invention have sufficiently high strength, but by adding a pressure process, it is possible to reduce quality variations.
  • the softened thermoplastic resin material spreads beyond the range of the heat-affected zone of the metal material by the pressurization, so that the joint interface between the metal material and the thermoplastic resin material can be expanded.
  • FIG. 4 is a process diagram for bonding in the present invention.
  • the resin material bonding method of the present invention includes a bonding interface forming step (S01) of forming a bonding interface and a bonding step (S02) of curing an adhesive on the bonding interface to achieve bonding. ing.
  • the adhesive applied to the interface to be joined is not particularly limited as long as it does not impair the effects of the present invention, and various conventionally known adhesives can be used. It may be appropriately selected according to the joint characteristics and the like. Examples of adhesives include epoxies, acrylics, cyanoacrylates, urethanes, and silicones.
  • the bonding step (S02) is a step for achieving bonding by curing the adhesive on the interface to be bonded. If the adhesive needs to be heated to cure, the interface to be bonded may be heated using a suitable external heating means. Also, the effect of the adhesive may be advanced by adding suitable ingredients. By curing the adhesive, it is possible to obtain a good bonded portion in which the materials to be bonded are bonded via the graphitized region 4 and the adhesive layer.
  • a YLP pulse laser manufactured by IPG was used as the laser, and the laser irradiation conditions were an average output of 50 W (one pulse energy: 1 mj), a focus diameter of 59 ⁇ m, and a laser of 30 ⁇ m in the plate width direction and 70 ⁇ m in the longitudinal direction. Irradiated at intervals of .
  • the laser pulse width is 100 ns.
  • FIGS. 5 and 6 Optical micrographs of the surface and cross section of the laser-irradiated PEEK plate are shown in FIGS. 5 and 6, respectively.
  • the laser-irradiated region is blackened, and this region is the graphitized region.
  • the cross-sectional photograph is a cross section cut along the dotted line of the surface photograph, and discoloration is observed up to a depth of 150 to 200 ⁇ m from the surface, and it can be seen that a large number of fine black dots are dispersed in the discolored area.
  • the diameter of the black dots is several ⁇ m to several tens of ⁇ m, and many foam marks are also confirmed along with the black dots.
  • brown areas are present around the black spots, and black spots, brown areas, and foam marks are dispersed in the graphitized areas. These are formed by pulsed laser irradiation.
  • FT-IR-ATR imaging measurements were performed on the cross section shown in FIG.
  • the apparatus used for the measurement is a microscopic infrared apparatus (Hyperion 3000) manufactured by Bruker, and the measurement conditions are light source: special ceramics, purge: nitrogen gas, detector: two-dimensional detector, detection pixel size: 4 ⁇ m/pixel, Resolution: 4 cm ⁇ 1 , measurement wavelength range: 3900 to 750 cm ⁇ 1 , number of times of accumulation: 256 times.
  • the peak intensity differs depending on the state of adhesion to the ATR prism, so it is necessary to perform normalization with a reference peak . was standardized as the reference peak.
  • FIG. 7 shows the spectra from the laser-irradiated portion and the untreated portion and their difference spectra. From the difference spectrum, the laser-irradiated surface shows a clear decrease in ketones (1650 cm ⁇ 1 ) and ethers (1280 cm ⁇ 1 ), hydroxyl groups (3300 cm ⁇ 1 ) and carbonyls (1760 to 1700 cm ⁇ 1 ) derived from oxidation, compared to the untreated surface. -1 ) did not increase, it is considered that no oxidized/denatured product occurred.
  • the crystallinity was lower than that in the inner layer to a depth of about 100 to 150 ⁇ m from the surface. It is considered that the melting effect due to the heat of the laser irradiation occurs to a depth of about 100 to 150 ⁇ m from the surface.
  • Raman spectroscopic analysis was performed on the cross section shown in FIG.
  • a near-infrared Raman spectrometer manufactured by Photon Design and an inVia manufactured by RENISHAW were used for Raman spectroscopic analysis, and both were analyzed in a microscopic Raman measurement mode.
  • the excitation wavelengths used for the measurements were 1064 nm and 532 nm, and the laser spot diameter was about 1 ⁇ m.
  • the measurement points were an untreated portion, a discolored portion (brown portion), and a black portion (black spot), and three points were measured at different locations for each portion.
  • the Raman spectrum of the untreated portion obtained by near-infrared light excitation (1064 nm) is shown in FIG. 9, the Raman spectrum of the discolored portion is shown in FIG. 10, and the Raman spectra of the untreated portion and the discolored portion are shown in FIG.
  • a PEEK-derived Raman band and fluorescence (increased background) were obtained from all of them.
  • the spectral shape of PEEK is similar, and it is considered that the composition of PEEK is not significantly modified in the discolored portion. As a slight change, a broadening of the band width was recognized, and it is considered that the crystallinity is lowered in the discolored portion (Fig. 12).
  • the black part was damaged by near-infrared light excitation, and the Raman spectrum could not be obtained.
  • the damage is caused by the absorption of the excitation light and the heat generated thereby, meaning that the absorption in the near-infrared region is large in the black portion. It is presumed that the formation of an unsaturated structure proceeds in the black part and a large ⁇ -electron conjugated structure is formed.
  • FIG. 13 shows an untreated portion
  • FIG. 14 shows a discolored portion
  • FIG. 15 shows a black portion
  • FIG. 16 shows comparison of each Raman spectrum
  • FIG. 17 shows a Raman spectrum detected in a very small portion of the black portion.
  • the intensity of fluorescence is determined by the magnitude of absorption and the probability of emission at the excitation wavelength, which depend on the molecular structure and accompanying electronic states. It is considered that the formation of unsaturated bonds progressed in the discolored portion and the absorbance increased. Since no significant change was observed in the primary structure of PEEK by measurement using near-infrared excitation, it is presumed that slight terminal modification has occurred. In the black part, as was inferred from the measurement of near-infrared excitation, a large ⁇ -electron conjugated structure is thought to be formed, which is thought to reduce the luminescence probability.
  • the PEEK bonds are cut and recombined to form unsaturated bonds and form a large ⁇ -electron conjugated structure. Modification has progressed to a level corresponding to carbon in a very small portion, but carbonization has not occurred in most of the portions, and a structure similar to its precursor is considered to be formed. In the discolored portion around the black portion, the crystallinity is lowered and the formation of unsaturated bonds (increase in fluorescence) progresses slightly, but the structure of PEEK is maintained as a whole.
  • the A2024 aluminum alloy plate has a size of 1.5 mm ⁇ 10 mm ⁇ 45 mm. spliced.
  • a 4 kW semiconductor laser manufactured by Laserline was used for laser irradiation, and a line laser of 5 mm x 12 mm was used using a zoom homogenizer for the optical system.
  • temperature feedback control was used to vary the laser output so as to keep the bonding temperature constant.
  • the laser scanning speed was set to 0.3 mm/s, and the temperature of the interface to be joined was controlled to 380°C.
  • the average maximum load and shear strength are 2309.6 N and 45.8 MPa, respectively, indicating that a strong and highly reliable joint is formed. In addition, when the graphitized region was not formed, a joint capable of strength measurement could not be obtained.
  • the average maximum load and shear strength are 3063.8 N and 26.4 MPa, respectively, and it can be seen that a strong and highly reliable joint is formed.
  • the maximum load and shear strength obtained are significantly higher than those without graphitized regions.
  • a region (20 mm ⁇ 25 mm) on the surface of a 0.5 mm ⁇ 20 mm ⁇ 45 mm filler (carbon) containing polytetrafluoroethylene (PTFE) plate that will be the interface to be joined is subjected to laser irradiation in the atmosphere and graphitized.
  • a region was formed.
  • a YLP pulse laser manufactured by IPG was used as the laser, and the laser irradiation conditions were an average output of 50 W (one pulse energy: 1 mj), a focus diameter of 59 ⁇ m, and a laser of 30 ⁇ m in the plate width direction and 70 ⁇ m in the longitudinal direction. Irradiated at intervals of .
  • the laser pulse width is 100 ns.
  • the PTFE plates were placed on top of each other and the interface to be bonded was held at room temperature for about 60 minutes to cure the adhesive and bond. did A two-liquid mixed epoxy system was used as the adhesive and was applied uniformly over the entire surface of the interface to be joined.
  • the strength of the obtained joint was evaluated by a shear tensile test in the same manner as in the case of direct joint. Test temperature, test humidity, test chamber temperature and test chamber humidity are the same as for direct bonding. The obtained test force (N)-displacement (mm) curve is shown in FIG. After the joint exhibited a large elongation, the base material of the PTFE plate was broken at a maximum load of about 190N. The results indicate that the PTFE plate/PTFE plate bonding interface strength is extremely high.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Lining Or Joining Of Plastics Or The Like (AREA)

Abstract

L'invention concerne : un matériau en résine pour assemblage qui peut être utilisé de manière appropriée pour assembler des matériaux en résine les uns avec les autres ou un matériau en résine et un matériau métallique sans utiliser de fixation par rivet ou un autre assemblage mécanique ; un procédé pour la fabrication du matériau en résine pour assemblage de manière simple et efficace ; et un procédé d'assemblage utilisant le matériau en résine pour assemblage. L'invention concerne en outre : un matériau en résine pour assemblage qui peut être appliqué à la fois à des résines thermoplastiques et à des résines thermodurcissables et qui permet d'améliorer la résistance d'assemblage et la fiabilité de l'assemblage à la fois d'un assemblage direct de matériaux à assembler et d'un assemblage à l'aide d'un adhésif ; un procédé pour la fabrication du matériau en résine pour assemblage de manière simple et efficace ; et un procédé d'assemblage utilisant le matériau en résine pour assemblage. Ce matériau en résine pour assemblage est caractérisé en ce qu'au moins une partie d'une surface du matériau en résine comprend une région graphitisée insaturée qui comprend des liaisons C=C et/ou des liaisons C-C. Il est préférable que la région graphitisée soit du carbone amorphe.
PCT/JP2023/003621 2022-02-08 2023-02-03 Matériau en résine pour assemblage, procédé pour la fabrication de celui-ci et procédé d'assemblage utilisant un matériau en résine pour assemblage WO2023153332A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62501427A (ja) * 1985-06-18 1987-06-11 ザ　ダウ　ケミカル　カンパニ− 製品の少なくとも２つの表面間の接着剤結合からなる製品を製造する方法
JP2001345469A (ja) * 2000-06-01 2001-12-14 Canon Inc 光起電力素子および光起電力素子の製造方法
JP2018080360A (ja) * 2016-11-15 2018-05-24 株式会社デンソー 金属部材および金属部材と樹脂部材との複合体並びにそれらの製造方法
JP2019123153A (ja) * 2018-01-17 2019-07-25 株式会社ヒロテック フッ素樹脂の接合方法及び金属樹脂接合体
JP2021120196A (ja) * 2020-01-30 2021-08-19 オムロン株式会社 接合構造体
WO2021230025A1 (fr) * 2020-05-13 2021-11-18 株式会社ヒロテック Procédé de liaison de résine thermoplastique et de métal

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62501427A (ja) * 1985-06-18 1987-06-11 ザ　ダウ　ケミカル　カンパニ− 製品の少なくとも２つの表面間の接着剤結合からなる製品を製造する方法
JP2001345469A (ja) * 2000-06-01 2001-12-14 Canon Inc 光起電力素子および光起電力素子の製造方法
JP2018080360A (ja) * 2016-11-15 2018-05-24 株式会社デンソー 金属部材および金属部材と樹脂部材との複合体並びにそれらの製造方法
JP2019123153A (ja) * 2018-01-17 2019-07-25 株式会社ヒロテック フッ素樹脂の接合方法及び金属樹脂接合体
JP2021120196A (ja) * 2020-01-30 2021-08-19 オムロン株式会社 接合構造体
WO2021230025A1 (fr) * 2020-05-13 2021-11-18 株式会社ヒロテック Procédé de liaison de résine thermoplastique et de métal

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