WO2023153061A1 - Structure adhésive - Google Patents

Structure adhésive Download PDF

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Publication number
WO2023153061A1
WO2023153061A1 PCT/JP2022/044390 JP2022044390W WO2023153061A1 WO 2023153061 A1 WO2023153061 A1 WO 2023153061A1 JP 2022044390 W JP2022044390 W JP 2022044390W WO 2023153061 A1 WO2023153061 A1 WO 2023153061A1
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WO
WIPO (PCT)
Prior art keywords
triangular wave
protrusions
triangular
probe
projections
Prior art date
Application number
PCT/JP2022/044390
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English (en)
Japanese (ja)
Inventor
洋平 前野
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三菱マテリアル株式会社
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Filing date
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Application filed by 三菱マテリアル株式会社 filed Critical 三菱マテリアル株式会社
Publication of WO2023153061A1 publication Critical patent/WO2023153061A1/fr

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    • 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
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16B—DEVICES FOR FASTENING OR SECURING CONSTRUCTIONAL ELEMENTS OR MACHINE PARTS TOGETHER, e.g. NAILS, BOLTS, CIRCLIPS, CLAMPS, CLIPS OR WEDGES; JOINTS OR JOINTING
    • F16B11/00—Connecting constructional elements or machine parts by sticking or pressing them together, e.g. cold pressure welding

Definitions

  • the present invention relates to adhesive structures. This application claims priority based on Japanese Patent Application No. 2022-018074 filed in Japan on February 8, 2022, the content of which is incorporated herein.
  • Patent Literature 1 discloses an adhesive structure having protrusions whose tips are spherical with a radius of 300 nm or less and whose cross-sectional radius perpendicular to the longitudinal direction is 500 nm or less. It is said that this adhesive structure having nano-level protrusions can exhibit strong adhesive strength as the protrusions enter into the unevenness of the surface of the adherend at the nano-level.
  • the adhesive structure is preferably one that can stably adhere and hold the adherend in various environments and that does not easily contaminate the adherend.
  • the adhesive structure described in Patent Document 1 is made of a resin material.
  • a resin material may be decomposed or deteriorated by heat, resulting in a decrease in adhesive strength.
  • the resin material may contaminate the adherend with decomposition products.
  • the present invention has been made in view of the circumstances described above, and an object thereof is to provide a bonded structure that is resistant to thermal decomposition and deterioration and has high bonding strength.
  • the adhesive structure of the present invention has a substrate and triangular wave-like projections provided on at least a part of the surface of the substrate, is made of an inorganic material, and has the triangular wave-like projections.
  • the pitch is in the range of 100 nm or more and 1000 nm or less
  • the height of the triangular wave-shaped protrusions is in the range of 100 nm or more and 1000 nm or less.
  • the adhesive structure of the present invention has a substrate and triangular wave-like protrusions provided on at least a part of the surface of the substrate, and is made of an inorganic material, so that decomposition and deterioration due to heat are unlikely to occur, and the adherend is less likely to be polluted.
  • the average pitch of the triangular wave-shaped protrusions is in the range of 100 nm or more and 1000 nm or less and the average height of the triangular wave-shaped protrusions is in the range of 100 nm or more and 1000 nm or less
  • the surface elastic modulus is high and the adherend is
  • the amount of deformation of the triangular wave-shaped projection is large when pressurized with . Therefore, the adhesive structure of the present embodiment has high adhesive strength, and can stably adhere and hold the adherend under various environments.
  • the ratio of the height to the pitch of the triangular wave-like projections may be in the range of 0.8 or more and 2.0 or less.
  • the adhesive force of the triangular wave-like protrusions to the adherend is increased, and the adhesive force of the triangular wave-like protrusions is easily restored when the adherend is separated from the triangular wave-like protrusions.
  • the pitch of the triangular wave-like projections may be 500 nm or less.
  • the pitch of the triangular wave-shaped projections is narrowed, the triangular wave-shaped projections are easily deformed along the surface shape of the adherend, so that the adhesive force is further improved.
  • the inorganic substance may be a metal.
  • the surface elastic modulus of the triangular wave-like protrusions is higher, the restoring force after deformation is improved, and the repeatability is improved.
  • the metal may include any one of copper, a copper alloy, aluminum, an aluminum alloy, and a NiP alloy.
  • the adhesive force is further increased.
  • a nanoindenter is used to press a spherical indenter with a diameter of 40 ⁇ m into the triangular wave-like protrusions under conditions where the depth of indentation is at least one of 10 nm and 20 nm. It may be configured such that the force is 35 N/cm 2 or more. In this case, since the adhesive strength is high, decomposition and deterioration due to heat are unlikely to occur, and it can be suitably used as an adhesive structure with high adhesive strength.
  • FIG. 1 is a perspective view of an adhesive structure according to one embodiment of the present invention
  • FIG. FIG. 2 is a cross-sectional view taken along the line II-II of FIG. 1
  • 2 is a plan view of the adhesive structure shown in FIG. 1
  • FIG. 4 is a focus curve of triangular wave-like projections of an adhesive structure according to one embodiment of the present invention.
  • FIG. 4 is a conceptual diagram showing a state (A in FIG. 4) before the probe of the nanoindenter is pushed into the triangular wave-like protrusion of the adhesive structure according to one embodiment of the present invention.
  • FIG. 4B is a conceptual diagram showing a state (B in FIG.
  • FIG. 4C is a conceptual diagram showing a state (C in FIG. 4 ) in which the tip of the nanoindenter pushed into the triangular wave-like protrusion of the adhesive structure according to one embodiment of the present invention is pulled up.
  • FIG. 4D is a conceptual diagram showing a state (D in FIG. 4 ) in which the probe tip of the nanoindenter pushed into the triangular wave-like protrusion of the bonding structure according to one embodiment of the present invention is separated from the bonding structure.
  • FIG. 1 is a perspective view of an adhesive structure according to one embodiment of the present invention.
  • 2 is a cross-sectional view taken along line II-II of FIG. 1
  • FIG. 3 is a plan view of the bonding structure shown in FIG.
  • the adhesive structure 1 according to this embodiment has a base 2 and triangular wave-like projections 3 provided on one surface of the base 2 .
  • the base body 2 and the triangular wave-like protrusions 3 are integrated.
  • the triangular wavy projections 3 have the property of being deformed under pressure and restoring their original shape when released from the pressure.
  • the adhesive structure 1 is made of an inorganic substance.
  • the inorganic material metals, ceramics, and glass can be used, although not limited thereto.
  • the inorganic substance preferably has a melting point of 100° C. or higher and a decomposition temperature of 100° C. or higher, preferably a melting point of 300° C. or higher and a decomposition temperature of 300° C. or higher, and a melting point of 500° C. or higher and a decomposition temperature of 300° C. or higher. It is preferably 500° C. or higher.
  • the metal may be a metal simple substance or an alloy. Alloys include those composed of multiple metallic elements and those composed of metallic elements and non-metallic elements. Examples of simple metals include aluminum, nickel, iron, and copper.
  • alloys include aluminum alloys, NiP, stainless steel and copper alloys.
  • ceramics oxides, nitrides, and carbides can be used.
  • Alumina can be mentioned as an example of a ceramic.
  • the inorganic substance forming the bonding structure 1 is preferably a metal, and more preferably contains any one of copper, copper alloy, aluminum, aluminum alloy, and NiP alloy.
  • the base 2 is plate-shaped.
  • the size of the substrate 2 is not particularly limited.
  • the thickness of the substrate 2 is, for example, within the range of 10 ⁇ m or more and 10 cm or less.
  • the triangular wavy protrusion 3 is configured by arranging a plurality of (for example, 5 or more) elongated protrusions 4 along the longitudinal direction.
  • the cross-sectional shape of the projection 4 is triangular.
  • the cross-sectional shape of the protrusion 4 is preferably an isosceles triangle.
  • the base angle ( ⁇ in FIG. 2) of the protrusion 4 is preferably 60 degrees or more, preferably within the range of 60 degrees or more and 80 degrees or less.
  • the average pitch of the triangular wavy projections 3 is in the range of 100 nm or more and 1000 nm or less, preferably 500 nm or less.
  • the average pitch of the triangular wave-shaped protrusions 3 is the average value of the distance (P in FIGS. 2 and 3) between the tops 4a of the adjacent protrusions 4 of the triangular wave-shaped protrusions 3.
  • FIG. The average pitch of the triangular wavy protrusions 3 can be measured from a cross-sectional SEM photograph of the adhesive structure 1 taken with a SEM (scanning electron microscope).
  • the average height of the triangular wavy protrusions 3 is in the range of 100 nm or more and 1000 nm or less, preferably 500 nm or less.
  • the average height of the triangular wave-like protrusions 3 is the average of the heights of the protrusions 4 (H in FIG. 2) with the base between the troughs 4b of the protrusions 4 of the triangular wave-like protrusions 3.
  • FIG. The average height of the triangular wave-like projections 3 can be measured from a cross-sectional SEM photograph of the adhesive structure 1 taken with an SEM.
  • the ratio of the average height to the average pitch of the triangular wavy protrusions 3 is preferably in the range of 0.8 or more and 2.0 or less, more preferably 1.0 or more and 1.5. Within the following range.
  • the average height/average pitch is 0.8 or more, the projections 4 are easily deformed along the adherend, and the conformability of the shape to the adherend is enhanced. Since the triangular wave-like projections 3 are periodically arranged with the protrusions 4 having a high conformability to the shape of the adherend, when the triangular wave-like protrusions 3 are pressed by the adherend, the triangular wave-like protrusions 3 are not deformed.
  • the amount of deformation is large, and the contact area between the adherend and the triangular wave-like projections 3 is large. For this reason, the adhesive strength of the triangular wave-like protrusions 3 to the adherend is increased.
  • the average height/average pitch is 2.0 or less, when the adherend is separated from the triangular wave-like protrusions 3, the protrusions 4 are easily restored to their original shape, and the triangular wave-like protrusions 3 are adhered. It is easier to recover strength. Therefore, the triangular wave-like projections 3 can be used repeatedly over a long period of time.
  • the width of the protrusion 4 in the longitudinal direction is, for example, within the range of 0.0005 mm or more and 1000 mm or less.
  • the adhesive force of the triangular wavy protrusions 3 of the adhesive structure 1 can be obtained by creating a focus curve using a nanoindenter.
  • FIG. 4 is a focus curve of the triangular wave-like projections 3 of the adhesive structure 1 measured using a nanoindenter.
  • FIG. 5 is a conceptual diagram showing a state (A in FIG. 4) before the probe 10 of the nanoindenter is pushed into the triangular wave-like protrusion 3 of the bonding structure 1.
  • FIG. 6 is a conceptual diagram showing a state (B in FIG. 4) in which the probe 10 of the nanoindenter is pushed into the triangular wave-like protrusion 3 of the bonding structure 1, and FIG. FIG.
  • FIG. 8 is a conceptual diagram showing a state in which the tip 10 of the nanoindenter pushed into the projection 3 is pulled up (C in FIG. 4), and FIG. 5 is a conceptual diagram showing a state in which the probe 10 is detached from the bonding structure 1 (D in FIG. 5).
  • the probe 10 is a spherical indenter with a diameter of 40 ⁇ m.
  • the probe 10 is pushed into the triangular wave-like protrusion 3 of the adhesive structure 1 with a predetermined load.
  • the conditions for pushing the probe 10 differ depending on the shape of the probe 10 .
  • the load is in the range of 20 ⁇ N to 100 ⁇ N and the indentation speed is in the range of 10 nm/sec to 20 nm/sec.
  • the triangular wave-like projections 3 of the adhesive structure 1 are deformed along the shape of the probe 10 .
  • the pushing of the probe 10 is stopped (B in FIG. 4).
  • the pushing depth of the probe 10 is set to 10 nm or 20 nm.
  • the probe 10 is pulled up from the triangular wave-like protrusion 3 .
  • the conditions for pulling up the probe 10 differ depending on the shape of the probe 10 .
  • the pull-up speed is in the range of 10 nm/sec to 20 nm/sec.
  • the probe 10 and the triangular wave-like protrusion 3 do not separate even if the load is removed, and the adhesive force is observed as a negative load. Further, when the probe 10 is pulled up, the probe 10 separates from the triangular wave-like protrusion 3 and the load applied to the triangular wave-like protrusion 3 becomes zero. Then, as shown in FIG. 7, the probe 10 and the triangular wave-like protrusion 3 are completely separated (D in FIG. 4). The negative maximum value (C in FIG.
  • the adhesive force of the triangular wave-like protrusion 3 varies depending on the shape of the probe 10 and the depth of pushing of the probe 10 .
  • the adhesive structure 1 of the present embodiment preferably has an adhesive strength of 35 N/cm 2 or more at least one of the indentation depth of 10 nm and 20 nm.
  • the adhesive structure 1 of this embodiment can also be manufactured by a method including, for example, a polishing process, a cutting process, and an etching process.
  • the polishing step the surface of the raw inorganic material substrate is polished.
  • the polishing of the inorganic material substrate for example, grinder polishing, water-resistant paper polishing, and buffing can be used.
  • the surface of the inorganic material substrate after polishing preferably has a surface roughness Ra of, for example, 0.02 ⁇ m or less.
  • the surface of the inorganic material substrate that has been polished in the polishing step is cut to form triangular wave-like protrusions.
  • the cutting method is not particularly limited, and various methods can be selected.
  • a cutting method for example, a method of forming a groove by moving the cutting tool in a direction orthogonal to the blade surface while periodically moving the cutting tool vertically (NP method: nanopecking method), A method using a method (conventional method) in which grooves are formed by moving linearly without moving can be used.
  • a processing device having a cutting tool and an ultrasonic vibration device that ultrasonically vibrates the cutting tool can be used as the processing device.
  • the shape of the blade surface of the cutting tool is not particularly limited, and may be triangular or quadrangular, for example.
  • the cutting tool is obliquely pushed into the surface of the inorganic material substrate while being ultrasonically vibrated, and then the cutting tool is moved in a direction perpendicular to the blade surface while periodically moving up and down. .
  • triangular wave-shaped protrusions having a plurality of inverted triangular grooves extending in a direction orthogonal to the moving direction of the cutting tool are formed on the surface of the inorganic material base material.
  • a processing apparatus having a cutting tool and an ultrasonic vibration device for ultrasonically vibrating the cutting tool can be used as the processing apparatus.
  • the shape of the blade surface of the cutting tool shall be triangular.
  • the cutting tool is vertically vibrated into the surface of the inorganic material base material, and then, while the cutting tool is fixed so as not to move up and down, the cutting tool is moved in a direction orthogonal to the blade surface. move.
  • inverted triangular grooves extending parallel to the moving direction of the cutting tool are formed on the surface of the inorganic material substrate.
  • the base 2 and the triangular wave-like projections 3 provided on at least a part of the surface of the base 2 are provided, and the triangular wave-like projections Since 3 is made of an inorganic material, it is less likely to be decomposed or degraded by heat, and less likely to contaminate the adherend.
  • the adhesive structure 1 of the present embodiment has high adhesive strength, and can stably adhere and hold the adherend under various environments.
  • the pitch of the triangular wave-like protrusions when the pitch of the triangular wave-like protrusions is 500 nm or less, the pitch of the triangular wave-like protrusions 3 becomes narrower, so that the triangular wave-like protrusions conform to the surface shape of the adherend. Since 3 becomes easy to deform, the adhesive strength is further improved. Further, when the inorganic substance forming the triangular wave-like protrusions 3 is metal, the surface elastic modulus of the triangular wave-like protrusions 3 is higher, so that the restoring force after deformation is improved and the repeatability is improved.
  • the inorganic substance constituting the triangular wave-shaped protrusions 3 is any one of copper, copper alloy, aluminum, aluminum alloy, and NiP alloy
  • the surface elastic modulus of the triangular wave-shaped protrusions 3 becomes higher, so that the adhesive strength is increased. get higher
  • a nanoindenter using a spherical indenter with a diameter of 40 ⁇ m is used as the probe 10, and the probe 10 is pushed into the triangular wave-like protrusion 3 to a depth of at least 10 nm or 20 nm.
  • the adhesive force is 35 N/cm 2 or more when pressed under one condition, the adhesive strength is high, so decomposition and deterioration due to heat are unlikely to occur, and it is suitable for use as an adhesive structure with high adhesive strength. can.
  • the adhesive structure 1 of the present embodiment when the ratio of the average height to the average pitch of the triangular wave-shaped protrusions 3 (average height/average pitch) is in the range of 0.8 or more and 2.0 or less, The adhesive force of the triangular wave-like protrusions 3 to the adherend is increased, and the adhesive force of the triangular wave-like protrusions 3 is easily restored when the adherend is separated from the triangular wave-like protrusions 3 . Furthermore, the adhesive structure 1 of the present embodiment has triangular wave-shaped projections, and therefore has an effect that it is difficult to have planar anisotropy of the adhesive force.
  • the present invention is not limited to this, and can be modified as appropriate without departing from the technical idea of the invention.
  • the triangular wave-like protrusions 3 are provided on the entire surface of one surface (upper surface) of the substrate 2, but the position of the triangular wave-like protrusions 3 is limited to this. not a thing
  • the triangular wave-like protrusions 3 may be provided on both sides of the base 2 .
  • the triangular wave-like projections 3 may be provided on a part of the surface of the base 2 .
  • a metal aluminum substrate (length: 30 mm, width: 30 mm, plate thickness: 30 mm) was prepared as a substrate.
  • the surface of the prepared metal aluminum substrate was polished to a surface roughness Ra of 0.02 ⁇ m or less to obtain a smooth surface.
  • a processing apparatus having a cutting tool and an ultrasonic vibration device for ultrasonically elliptical vibration of the cutting tool was used.
  • the cutting tool is obliquely inserted while being ultrasonically vibrated, and then, while the cutting tool is being subjected to ultrasonic elliptical vibration, it is moved by 1000 nm in the direction perpendicular to the blade surface, and the cutting edge is moved in the vertical direction by 1000 nm.
  • the triangular wavy protrusions of the substrate with triangular wavy protrusions had an average pitch of 1000 nm, an average height of 1000 nm, and an average height/average pitch of 1.0.
  • the adhesive force was measured by the method described above.
  • a spherical indenter (made of titanium) with a diameter of 40 ⁇ m was used as the probe.
  • the indentation depth of the spherical indenter was set to the depth shown in Table 1 in the same manner as in the method for measuring the surface elastic modulus.
  • the indentation speed of the probe was set to 10 nm/sec when the indentation depth was 10 nm, and to 20 nm/sec when the indentation depth was 20 nm.
  • the speed of pulling up the probe was set to 10 nm/sec when the indentation depth was 10 nm, and to 20 nm/sec when the indentation depth was 20 nm. Measurements were performed at room temperature (25°C).
  • the substrates with triangular wavy protrusions obtained in Examples 1 to 3 of the present invention were obtained in Comparative Examples 1 and 2. It was confirmed that the adhesive strength is higher than that of the substrate with triangular wave-like protrusions, and that it is useful as an adhesive structure.
  • the reason why the substrates with triangular wave-like projections obtained in Examples 1 to 3 of the present invention have high adhesive strength is that the surface elastic modulus is low and the amount of deformation of the projections is large when pressed by an adherend.
  • the substrate with triangular wavy protrusions obtained in Comparative Example 1 in which the average pitch and average height of the triangular wavy protrusions are larger than the range of the present invention, has the same average height/average pitch as Inventive Examples 1 to 3. Yes, but the adhesive strength is low. This is because the average pitch was large and the size of the protrusions was too large, resulting in a high surface elastic modulus.
  • the substrate with protrusions obtained in Comparative Example 2 in which the average pitch and average height of the triangular wave-shaped protrusions are smaller than the range of the present invention has the same average height/average pitch as Examples 1 to 3 of the present invention. , the probe did not adhere. This is because the surface elastic modulus increased due to the average height becoming too small.
  • the adhesive structure of this embodiment has high heat resistance and high adhesive strength, so it can be used as a structure for adhesion and temporary fixing.
  • the adhesive structure of the present embodiment can be suitably used particularly in fields such as aerospace, semiconductors, and medical fields where environmental changes are large and low contamination by impurities is required.

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  • Engineering & Computer Science (AREA)
  • General Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Standing Axle, Rod, Or Tube Structures Coupled By Welding, Adhesion, Or Deposition (AREA)

Abstract

Une structure adhésive (1) qui est pourvue d'un substrat (2) et de saillies en forme d'onde triangulaire (3) disposées sur la surface d'au moins une partie du substrat (2), et qui comprend un matériau inorganique, le pas moyen des saillies en forme d'onde triangulaire (3) se situant dans la plage de 100 nm à 1000 nm, et la hauteur moyenne des saillies en forme d'onde triangulaire (3) se situant dans la plage de 100 nm à 1000 nm.
PCT/JP2022/044390 2022-02-08 2022-12-01 Structure adhésive WO2023153061A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2022-018074 2022-02-08
JP2022018074A JP2023115708A (ja) 2022-02-08 2022-02-08 接着構造体

Publications (1)

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WO2023153061A1 true WO2023153061A1 (fr) 2023-08-17

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PCT/JP2022/044390 WO2023153061A1 (fr) 2022-02-08 2022-12-01 Structure adhésive

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JP (1) JP2023115708A (fr)
TW (1) TW202340079A (fr)
WO (1) WO2023153061A1 (fr)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000511583A (ja) * 1996-06-03 2000-09-05 ミネソタ・マイニング・アンド・マニュファクチャリング・カンパニー 熱変形感圧接着剤
JP2007083317A (ja) * 2005-09-20 2007-04-05 Nissan Motor Co Ltd 接合構造体及びその製造方法
JP2013082056A (ja) * 2011-10-06 2013-05-09 Qinghua Univ 三次元ナノ構造体アレイ
JP2013118378A (ja) * 2011-12-03 2013-06-13 Qinghua Univ 発光ダイオード
JP2020503483A (ja) * 2016-12-20 2020-01-30 スリーエム イノベイティブ プロパティズ カンパニー 構成要素の高摩擦接続のための接続要素、接続要素の製造方法、及び接続要素の使用

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000511583A (ja) * 1996-06-03 2000-09-05 ミネソタ・マイニング・アンド・マニュファクチャリング・カンパニー 熱変形感圧接着剤
JP2007083317A (ja) * 2005-09-20 2007-04-05 Nissan Motor Co Ltd 接合構造体及びその製造方法
JP2013082056A (ja) * 2011-10-06 2013-05-09 Qinghua Univ 三次元ナノ構造体アレイ
JP2013118378A (ja) * 2011-12-03 2013-06-13 Qinghua Univ 発光ダイオード
JP2020503483A (ja) * 2016-12-20 2020-01-30 スリーエム イノベイティブ プロパティズ カンパニー 構成要素の高摩擦接続のための接続要素、接続要素の製造方法、及び接続要素の使用

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TW202340079A (zh) 2023-10-16

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