[go: up one dir, main page]

WO2025186861A1 - Composite gel-métal et procédé de production de composite gel-métal - Google Patents

Composite gel-métal et procédé de production de composite gel-métal

Info

Publication number
WO2025186861A1
WO2025186861A1 PCT/JP2024/008017 JP2024008017W WO2025186861A1 WO 2025186861 A1 WO2025186861 A1 WO 2025186861A1 JP 2024008017 W JP2024008017 W JP 2024008017W WO 2025186861 A1 WO2025186861 A1 WO 2025186861A1
Authority
WO
WIPO (PCT)
Prior art keywords
hydrogel
metal
gel
metal composite
thin film
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/JP2024/008017
Other languages
English (en)
Japanese (ja)
Other versions
WO2025186861A8 (fr
Inventor
匠吾 檜森
陸 高橋
あや 田中
真澄 山口
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
NTT Inc
NTT Inc USA
Original Assignee
Nippon Telegraph and Telephone Corp
NTT Inc USA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nippon Telegraph and Telephone Corp, NTT Inc USA filed Critical Nippon Telegraph and Telephone Corp
Priority to PCT/JP2024/008017 priority Critical patent/WO2025186861A1/fr
Publication of WO2025186861A1 publication Critical patent/WO2025186861A1/fr
Publication of WO2025186861A8 publication Critical patent/WO2025186861A8/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • C08J3/075—Macromolecular gels
    • 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
    • C08J5/12—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/05—Insulated conductive substrates, e.g. insulated metal substrate

Definitions

  • the present invention relates to a gel-metal composite and a method for producing a gel-metal composite.
  • Hydrogels are polymeric materials containing a large amount of liquid, and have characteristics similar to biological tissues, such as high water content and flexibility. Metals have characteristics such as high electrical conductivity, high modulus of rigidity, and catalytic activity. Therefore, a gel-metal composite, which is a composite material of hydrogel and metal, possesses the characteristics of both hydrogel and metal. Gel-metal composites are expected to be applied to soft electronics and materials engineering, such as the creation of electronic devices by metal wiring on the hydrogel and the creation of anisotropic soft materials by increasing the local elastic modulus of the metal attachment area.
  • One known method for manufacturing a gel-metal composite is to introduce an adhesive into the composite interface between the hydrogel and the metal (see, for example, Non-Patent Document 1).
  • Non-Patent Document 2 In the field of soft electronics, a method is known in which a metal thin film formed on a solid substrate is transferred to an elastomer material to produce a composite material of elastomer material and metal without using adhesive (see, for example, Non-Patent Document 2).
  • the present invention aims to provide a technology that allows for the direct attachment of a thin metal film to any part of the surface of a hydrogel, regardless of the type of material.
  • One aspect of the present invention is a gel-metal composite comprising a hydrogel and a thin metal film formed on one surface of the hydrogel, with the hydrogel and the thin metal film directly bonded together.
  • One aspect of the present invention is a method for producing a gel-metal composite, comprising the steps of: providing a mask seal having an opening on one surface of a solid substrate; applying a metal coating to an exposed portion of the surface of the solid substrate that is exposed within the opening, thereby forming a thin metal film on the exposed portion; removing the mask seal from the one surface of the solid substrate; providing a hydrogel to cover the one surface of the solid substrate and the thin metal film; drying the hydrogel; and swelling the dried hydrogel in a liquid.
  • This invention makes it possible to directly attach a thin metal film to any part of the surface of a hydrogel, regardless of the type of material.
  • 1 is a cross-sectional view schematically showing a gel-metal composite according to one embodiment of the present invention.
  • 1 is a cross-sectional view schematically showing a method for producing a gel-metal composite according to one embodiment of the present invention.
  • 1 is a cross-sectional view schematically showing a method for producing a gel-metal composite according to one embodiment of the present invention.
  • 1 is a cross-sectional view schematically showing a method for producing a gel-metal composite according to one embodiment of the present invention.
  • 1 is a cross-sectional view schematically showing a method for producing a gel-metal composite according to one embodiment of the present invention.
  • FIG. 1 is a cross-sectional view schematically showing a method for producing a gel-metal composite according to one embodiment of the present invention.
  • 1 is a cross-sectional view schematically showing a method for producing a gel-metal composite according to one embodiment of the present invention.
  • 1 is a photograph of an acrylamide gel-gold complex obtained in an example.
  • 1 is a photograph of an acrylamide gel-gold complex obtained in a comparative example.
  • FIG. 1 shows the results of measuring the electrical resistance by the four-electrode method on the surface of a thin gold film and on the surface of an acrylamide gel for an acrylamide gel-gold complex obtained in an example.
  • FIG. 1 is a cross-sectional view schematically showing a gel-metal composite according to one embodiment of the present invention.
  • a gel-metal composite 1 of this embodiment includes a hydrogel 2 and a metal thin film 3 formed on one surface 2 a of the hydrogel 2 .
  • hydrogel 2 and the metal thin film 3 are directly bonded at their composite interface without the use of an adhesive.
  • Hydrogel 2 is not particularly limited, but examples include hydrogels composed of synthetic polymers such as polyacrylamide and polyvinyl alcohol, and biopolymers such as gelatin and alginic acid. Other examples of hydrogel 2 include copolymer gels such as a combination of acrylamide and aminophenylboronic acid, and gels with an interpenetrating network structure such as a combination of polyvinyl alcohol and polyaniline. Other examples of hydrogel 2 include functional gels in which gold nanoparticles or carbon nanotubes are supported on the above gels.
  • the metal that constitutes the thin metal film 3 is not particularly limited, but metals with high chemical stability are preferred. Examples of such metals include gold and platinum.
  • the thin metal film 3 may be divided into small pieces on one surface 2a of the hydrogel 2. This increases the surface area of the thin metal film 13.
  • another metal thin film 3 may be bonded via a metal that is directly bonded to one surface 2a of the hydrogel 2.
  • a metal such as gold or platinum may be directly bonded to one surface 2a of the hydrogel 2, and the metal thin film 3 may be bonded onto that metal.
  • the gel-metal composite 1 according to this embodiment, by providing a thin metal film 3 on a portion of one surface 2a of the hydrogel 2, it becomes possible to apply electrical stimulation or receive electrical signals using the hydrogel 2, making it possible to use it as a soft electronics substrate. Furthermore, because the gel-metal composite 1 according to this embodiment allows for localized electrical stimulation or reception of electrical signals to the hydrogel 2, it can be used as a cell culture substrate that allows electrical manipulation.
  • the gel-metal composite 1 of this embodiment is able to be treated as a highly reliable composite because the thin metal film 3 is less likely to peel off due to frictional forces on the surface or expansion and contraction of the hydrogel 2. Furthermore, because the thickness of the thin metal film 3 can be reduced to a few nanometers, the thin metal film 3 can be provided in a very small area on one surface 2a of the hydrogel 2. Furthermore, because the hydrogel 2 and the thin metal film 3 are directly bonded without the use of an adhesive, material design that takes advantage of the transparency of the hydrogel 2 and the thin metal film 3 becomes possible.
  • the gel-metal composite 1 of this embodiment has a thin metal film 13 (on the order of GPa) with a high elastic modulus provided on the surface of a hydrogel 14 (on the order of kPa) with a low elastic modulus, it can be used as a soft material that undergoes characteristic deformation due to the difference in the mechanical properties of the thin metal film 13 and the hydrogel 14.
  • a method for producing a gel-metal composite according to one embodiment of the present invention includes the steps of providing a mask seal having an opening on one surface of a solid substrate (hereinafter referred to as the "first step”), applying a metal coating to an exposed portion of one surface of the solid substrate that is exposed in the opening, and forming a metal thin film on the exposed portion (hereinafter referred to as the "second step"), removing the mask seal from one surface of the solid substrate, and providing a hydrogel so as to cover one surface of the solid substrate and the metal thin film (hereinafter referred to as the "third step"), drying the hydrogel (hereinafter referred to as the "fourth step”), and swelling the dried hydrogel in a liquid (hereinafter referred to as the "fifth step”).
  • Figures 2 to 7 are cross-sectional views that schematically show a method for manufacturing a gel-metal composite according to one embodiment of the present invention.
  • a solid substrate 11 is prepared for determining the surface shape and metal portion of the gel-metal composite.
  • the solid substrate 11 is not particularly limited, but may be, for example, glass or a polymer film.
  • a mask seal 12 having an opening 12a is attached to the portion of one surface 11a of the solid substrate 11 where no metal thin film is to be formed.
  • a metal coating is applied to an exposed portion 11b exposed in the opening 12a on one surface 11a of the solid substrate 11, and a metal thin film 13 is formed on the exposed portion 11b.
  • the metal thin film 13 can be formed on the exposed portion 11b by sputtering or vapor deposition.
  • the mask seal 12 is removed from the one surface 11 a of the solid substrate 11 , and a hydrogel 14 is provided so as to cover the one surface 11 a of the solid substrate 11 and the metal thin film 13 .
  • the method for providing the hydrogel 14 is not particularly limited, but can be, for example, a method in which a gel precursor solution is dropped onto the metal thin film 13 and the gel precursor solution is gelled on-site by light irradiation, or a method in which a gel prepared elsewhere is swelled to a desired swelling ratio and then placed on the metal thin film 13.
  • “Fourth step” 5 the hydrogel 14 covering the surface 11a of the solid substrate 11 and the thin metal film 13 is dried.
  • the drying process increases the density of the polymer bond chains that make up the hydrogel 14, and the adhesive strength between the thin metal film 13 and the hydrogel 14 is strengthened by hydrophobic interactions. Drying of the hydrogel 14 can be accelerated by heating or reducing pressure.
  • the fifth step As shown in Figure 6, the dried hydrogel 14 is swollen in liquid. By swelling the hydrogel 14 in liquid, the hydrogel 14 changes to a shape suitable for practical use. The swollen state of the hydrogel 14 is its practical shape. The hydrophobic interaction is further enhanced when the hydrogel 14 is swollen in liquid.
  • Liquids used to swell the hydrogel 14 include water, urea solution, polymer solution, ionic liquid, etc.
  • the hydrogel 14 When the hydrogel 14 is dried in the fourth step and when the hydrogel 14 is swelled in the fifth step, it is desirable that the surface of the hydrogel 14 in contact with the metal thin film 13 (the interface between the metal thin film 13 and the hydrogel 14) does not deform. In order to carry out the fourth and fifth steps without deforming the interface between the metal thin film 13 and the hydrogel 14, it is desirable to carry out the following treatment.
  • the glass substrate used as the solid substrate 11 can be removed by treating it with hydrofluoric acid or by severing the bonds within the adhesion molecules that make up the adhesion molecule layer.
  • the swelling rate of the hydrogel 14 can be controlled, and deformation due to drying can be suppressed.
  • the thickness of the metal thin film 3 can be increased by connecting the surface of the metal thin film 3 of the gel-metal composite 1 obtained by the gel-metal composite manufacturing method of this embodiment to an electrode and performing electrolytic plating. Furthermore, the thickness of the metal thin film 3 can be increased by performing electroless plating on the surface of the metal thin film 3 of the gel-metal composite 1 obtained by the gel-metal composite manufacturing method of this embodiment.
  • the interaction between the solid substrate 11 and the hydrogel 14 can be reduced, thereby facilitating the peeling of the metal thin film 13 from the solid substrate 11.
  • the manufacturing method for a gel-metal composite according to this embodiment directly bonds the thin metal film 13 and the hydrogel 14, making production easy, and the strong adhesion makes it possible to obtain a gel-metal composite 1 that is highly stable against external insults.
  • the swelling of the hydrogel 14 causes the thin metal film 13 to break up into small pieces, increasing the surface area of the thin metal film 13. This improves the metal catalytic activity of the thin metal film 13 and maintains the permeability of the hydrogel 14, resulting in a gel-metal composite 1 that functions as a substrate surface possessing the material properties of both the thin metal film 13 and the hydrogel 14.
  • electricity can be passed through the gel-metal composite 1 in liquid via the metal.
  • the manufacturing method for a gel-metal composite of this embodiment provides a thin metal film 13 with a high elastic modulus (on the order of GPa) only at selected locations on the surface of a hydrogel 14 with a low elastic modulus (on the order of kPa), thereby obtaining a gel-metal composite 1 that can be used as a soft material that exhibits characteristic deformation due to the difference in the mechanical properties of the thin metal film 13 and the hydrogel 14.
  • the manufacturing method for the gel-metal composite of this embodiment consists of only steps that allow multiple processes to be performed simultaneously, such as forming the metal thin film 13 and drying the hydrogel 14, making it easy to scale up the production of the gel-metal composite 1.
  • Example 10 As an example of a gel-metal composite, an acrylamide gel-gold composite having an acrylamide gel as the hydrogel and a gold thin film as the metal thin film will be described.
  • the acrylamide gel was prepared by irradiating a gel precursor solution containing acrylamide as a monomer, bisacrylamide as a cross-linking agent, and lithium phenyl(2,4,6-trimethylbenzoyl)phosphinate as a polymerization initiator with ultraviolet light in a low-oxygen environment.
  • the acrylamide gel covering one surface of the glass substrate and the gold thin film was dried.
  • the dried acrylamide gel was swelled in water to transfer a gold thin film from the glass substrate to one side of the acrylamide gel (the side in contact with one side of the glass substrate), thereby obtaining an acrylamide gel-gold complex.
  • a photograph of the resulting acrylamide gel-gold complex is shown in Figure 8. As shown in Figure 8, the gold thin film formed on the exposed glass surface was transferred to the acrylamide gel.
  • the gel-metal composite of the present invention is useful as a soft material that takes advantage of the metal's high conductivity, catalytic properties, and high rigidity, and is widely applicable to fields such as soft electronics and materials engineering.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Laminated Bodies (AREA)

Abstract

L'invention concerne un composite gel-métal (1) comprenant un hydrogel (2) et une couche mince métallique (3) formée sur une surface (2a) de l'hydrogel (2), l'hydrogel (2) et la couche mince métallique (3) étant directement liés.
PCT/JP2024/008017 2024-03-04 2024-03-04 Composite gel-métal et procédé de production de composite gel-métal Pending WO2025186861A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/JP2024/008017 WO2025186861A1 (fr) 2024-03-04 2024-03-04 Composite gel-métal et procédé de production de composite gel-métal

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/JP2024/008017 WO2025186861A1 (fr) 2024-03-04 2024-03-04 Composite gel-métal et procédé de production de composite gel-métal

Publications (2)

Publication Number Publication Date
WO2025186861A1 true WO2025186861A1 (fr) 2025-09-12
WO2025186861A8 WO2025186861A8 (fr) 2025-10-02

Family

ID=96990110

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2024/008017 Pending WO2025186861A1 (fr) 2024-03-04 2024-03-04 Composite gel-métal et procédé de production de composite gel-métal

Country Status (1)

Country Link
WO (1) WO2025186861A1 (fr)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1190213A (ja) * 1997-09-18 1999-04-06 Tokuyama Corp 無機微粒子超薄膜の製造方法
JP2013060505A (ja) * 2011-09-12 2013-04-04 Institute Of Physical & Chemical Research 異種材料が接合した重合体、及びその製造方法
KR101498186B1 (ko) * 2013-09-29 2015-03-04 전자부품연구원 하이드로겔을 이용한 전도성 기판 및 그의 패턴 형성 방법
WO2023238375A1 (fr) * 2022-06-10 2023-12-14 日本電信電話株式会社 Procédé et système d'évaluation de cellules

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1190213A (ja) * 1997-09-18 1999-04-06 Tokuyama Corp 無機微粒子超薄膜の製造方法
JP2013060505A (ja) * 2011-09-12 2013-04-04 Institute Of Physical & Chemical Research 異種材料が接合した重合体、及びその製造方法
KR101498186B1 (ko) * 2013-09-29 2015-03-04 전자부품연구원 하이드로겔을 이용한 전도성 기판 및 그의 패턴 형성 방법
WO2023238375A1 (fr) * 2022-06-10 2023-12-14 日本電信電話株式会社 Procédé et système d'évaluation de cellules

Also Published As

Publication number Publication date
WO2025186861A8 (fr) 2025-10-02

Similar Documents

Publication Publication Date Title
Park et al. Rewritable, printable conducting liquid metal hydrogel
Pan et al. Mechanically interlocked hydrogel–elastomer hybrids for on‐skin electronics
Min et al. Tough Carbon Nanotube‐Implanted Bioinspired Three‐Dimensional Electrical Adhesive for Isotropically Stretchable Water‐Repellent Bioelectronics
CN110970232B (zh) 以水凝胶为基底的可拉伸微型电子器件及制备方法
CN114088254B (zh) 灵敏度可调的高线性度柔性压力传感器及其制备方法
Chen et al. Transparent, highly-stretchable, adhesive, and ionic conductive composite hydrogel for biomimetic skin
Jeong et al. A highly conductive and electromechanically self-healable gold nanosheet electrode for stretchable electronics
JP4408177B2 (ja) パターン形成体の製造方法
Luo et al. Stretchable and flexible non‐enzymatic glucose sensor based on poly (ether sulfone)‐derived laser‐induced graphene for wearable skin diagnostics
CN108318161A (zh) 可穿戴压力传感器及其制造方法
Li et al. All‐Paper‐Based, Flexible, and Bio‐Degradable Pressure Sensor with High Moisture Tolerance and Breathability Through Conformally Surface Coating
Verma et al. Biodegradable photolithography compatible substrate for transparent transient electronics and flexible energy storage devices
KR20110073296A (ko) 금속-탄소 하이브리드형 나노복합체 필름 및 그 제조 방법
JP2020062843A (ja) 積層体、積層体の製造方法および形状制御デバイス
WO2014157550A1 (fr) Corps d'électrode à substrat poreux et son procédé de fabrication
CN115337011B (zh) 一种金属包覆的水凝胶电极及其制备方法
CN110526198A (zh) 一种基于半球形微结构的柔性压力传感器及其制造方法
Ge et al. Intrinsically conductive bifunctional nanocellulose-reinforced robust and self-healable electronic skin: deep insights into multiple bonding network, property reinforcement, and sensing mechanism
Zhang et al. Rapid, Tough, and Trigger‐Detachable Hydrogel Adhesion Enabled by Formation of Nanoparticles In Situ
KR102187349B1 (ko) 체액포집 및 청정점착이 가능한 하이브리드 미세 흡착구조의 건식 점착 패치 및 이의 제작 방법
KR101269650B1 (ko) 유연성, 접착성 및 전도성을 갖는 금속-탄소 하이브리드형 접착제 및 상기를 이용한 전도성 패턴
WO2025186861A1 (fr) Composite gel-métal et procédé de production de composite gel-métal
WO2025224858A1 (fr) Procédé de fabrication de composite gel-métal
CN104192789B (zh) 一种纳米/微米金膜及其制备方法
WO2006133440A2 (fr) Metal electroconducteur impregne de matieres elastomeres et procede de realisation correspondant

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 24928523

Country of ref document: EP

Kind code of ref document: A1