WO2023080183A1 - Feuille de liaison moléculaire et procédé de liaison - Google Patents

Feuille de liaison moléculaire et procédé de liaison Download PDF

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Publication number
WO2023080183A1
WO2023080183A1 PCT/JP2022/041094 JP2022041094W WO2023080183A1 WO 2023080183 A1 WO2023080183 A1 WO 2023080183A1 JP 2022041094 W JP2022041094 W JP 2022041094W WO 2023080183 A1 WO2023080183 A1 WO 2023080183A1
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Prior art keywords
group
sheet
bonding
molecular bonding
base material
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PCT/JP2022/041094
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English (en)
Japanese (ja)
Inventor
達也 鈴木
香織 赤松
香 溝端
哲士 本田
繁樹 石黒
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日東電工株式会社
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Priority to JP2023558066A priority Critical patent/JPWO2023080183A1/ja
Publication of WO2023080183A1 publication Critical patent/WO2023080183A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • 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
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • 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
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • 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
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/35—Heat-activated

Definitions

  • the present invention relates to a molecular bonding sheet and a bonding method using a molecular bonding sheet.
  • CFRP Carbon Fiber Reinforced Plastics
  • adherends a laminate or a bonding method capable of obtaining a strong bond without using a general adhesive regardless of the materials of two members to be bonded.
  • Patent Document 1 discloses a laminate in which substrates having a large surface roughness are laminated, an entropy elastic layer is interposed between the two substrates, and the entropy elastic layer and the substrate contain a specific compound. Adhesive bonded laminates have been proposed.
  • Patent Document 2 discloses a bonding method for bonding a base A and a base B, in which an agent containing a specific compound is provided on the surface of the base A, and then the base B is placed and force is applied. Furthermore, a bonding method is disclosed in which the compound is irradiated with light.
  • Patent Document 3 two bonding laminates having a molecular adhesive layer on one side of a thermoplastic resin layer are prepared, and the molecular adhesive layer of one bonding laminate is adhered to one adherend.
  • a method of bonding two adherends by adhering the molecular adhesive layer of the other bonding laminate to the other adherend and heat-sealing the thermoplastic resin layers to each other is disclosed.
  • Patent Document 4 discloses an adhesive sheet in which a molecular adhesive layer containing a specific molecular adhesive is laminated on an adhesive layer containing an adhesive resin, wherein the adhesive resin acts as a reactive group of the molecular adhesive.
  • Adhesive sheets having reactive moieties capable of forming chemical bonds and having a limited storage modulus and thickness of the adhesive layer are disclosed.
  • the laminate described in Patent Document 1 has improved adhesiveness when laminating substrates with large surface roughness, and it is necessary to perform processing to roughen the bonding surface, and the process required for bonding is increased. To increase.
  • the bonding method described in Patent Document 2 since the adhesive layer is provided on the surface of one substrate and then the other substrate is adhered, it is necessary to appropriately control the range in which the adhesive layer is provided, which complicates the process. become.
  • Patent Document 4 since the adhesive sheet described in Patent Document 4 also requires an adhesive layer, the number of work processes increases as in Patent Document 2.
  • the adhesive layer requires a certain amount of time to harden, and the adhesive oozes out after adhesion, requiring a wiping step, resulting in reduced workability.
  • the present invention has been made in view of the above-described circumstances, and provides a molecularly bonded sheet that has excellent adhesive strength capable of firmly bonding difficult-to-bond materials and that can improve workability for bonding. With the goal.
  • Another object of the present invention is to provide a bonding method using the molecular bonding sheet.
  • the inventor of the present invention has made intensive studies to solve the above problems.
  • the molecularly bonded sheet in which the molecularly bonded layers are formed on both sides of the sheet base material whose elastic modulus is controlled within a specific range, provides an excellent adhesive strength capable of firmly bonding difficult-to-bond materials, and is effective for bonding.
  • the inventors have found that the workability can be improved, and have completed the present invention.
  • Means for solving the above problems are as follows. [1] a sheet base material; and a molecular bonding layer provided on both sides of the sheet base material,
  • the sheet base material is a molecular bonding sheet having a storage elastic modulus G1 of 3.5 ⁇ 10 6 Pa to 1.0 ⁇ 10 10 Pa at 23°C.
  • the sheet substrate has a storage elastic modulus G2 of 1.0 ⁇ 10 3 Pa to 1.0 at a temperature T1 that satisfies Tg+10° C. ⁇ T1 ⁇ Tg+60° C., where Tg is the glass transition temperature of the sheet substrate. ⁇ 10 9 Pa, and the storage elastic modulus G1 is greater than the storage elastic modulus G2.
  • the sheet base material has a storage elastic modulus G2′ of 1.0 ⁇ 10 3 Pa to 1 at a temperature T2 that satisfies Tm ⁇ 30° C. ⁇ T2 ⁇ Tm+50° C., where Tm is the melting point of the sheet base material. 0 ⁇ 10 9 Pa, and the storage elastic modulus G1 is greater than the storage elastic modulus G2′.
  • the molecular bonding agent forming the molecular bonding layer contains a compound having a reactive group A and a reactive group B, and the reactive group A is an amino group, an azide group, a mercapto group, an isocyanate group, or a ureido group.
  • the reactive group B is at least one selected from a silanol group and a group that generates a silanol group by hydrolysis reaction [1] to The molecularly bonded sheet according to any one of [3].
  • a bonding method for bonding a first member and a second member using a molecular bonding sheet has a sheet base material and molecular bonding layers provided on both sides of the sheet base material,
  • the sheet base material has a storage elastic modulus G1 at 23° C.
  • the storage elastic modulus G2′′ of the molecularly bonded sheet at the temperature during bonding is 1.0 ⁇ 10 3 Pa to 1.0 ⁇ 10 9 Pa, and the storage elastic modulus G1 is greater than the storage elastic modulus G2′′.
  • the present invention provides a molecular bonding sheet in which molecular bonding layers are formed on both sides of a sheet substrate whose elastic modulus is controlled within a specific range.
  • a sheet base material whose elastic modulus is controlled within a specific range to improve workability, and utilizes chemical bonds between the sheet base material and the molecular bonding layer, and between the molecular bonding layer and the adherend. By doing so, the adherends are joined to each other, so excellent adhesive strength can be obtained.
  • the molecular bonding layer is a sheet-like molecular bonding sheet that is integrated with the sheet base material, there is no protruding of the adhesive, etc., and even if the adherend is a different material or a difficult-to-bond material, the bonding can be performed in a short time. can be joined, and workability for joining can be improved.
  • FIG. 1 is a schematic cross-sectional view showing a molecule-bonded sheet according to an embodiment of the invention.
  • FIG. 2 is a schematic cross-sectional view for explaining a bonding method using a molecular bonding sheet according to an embodiment of the present invention.
  • FIG. 3 is a diagram for explaining the bonding method using the molecular bonding sheet according to the embodiment of the present invention, and is a schematic cross-sectional view showing the next step of FIG.
  • a molecularly bonded sheet according to an embodiment of the present invention includes a sheet base material and molecularly bonded layers provided on both sides of the sheet base material, and the sheet base material has a storage elastic modulus G1 at 23°C of 3.5 ⁇ 10 6 Pa to 1.0 ⁇ 10 10 Pa.
  • FIG. 1 is a schematic cross-sectional view showing a molecularly bonded sheet according to an embodiment of the present invention.
  • the molecularly bonded sheet 10 according to the present embodiment has a sheet substrate 20 and molecularly bonded layers 30a and 30b provided on both surfaces of the sheet substrate 20 perpendicular to the thickness direction.
  • the first member and the second member can be joined together by thermocompression bonding in a direction to bring them into close contact with each other.
  • the first member and the second member are not bonded by the intermolecular force of the adhesive, but the first member and the second member and the molecular bonding layers 30a and 30b are bonded by chemical bonding. be.
  • the sheet substrate 20 is provided between the molecular bonding layer 30a and the molecular bonding layer 30b.
  • the sheet base material 20 has a storage elastic modulus G1 at 23° C. specified within a specific range. Therefore, when both heat and pressure are applied during bonding, the degree of adhesion at the interface between the first member and the molecular bonding layer 30a and the interface between the second member and the molecular bonding layer 30b increases, and the chemical bond required for chemical bonding increases. Since the frequency of contact between reactive groups can be increased, chemical bonds can be efficiently used to achieve stronger adhesion.
  • the sheet base material 20 and the molecular bonding layers 30a and 30b are integrated to form the molecular bonding sheet 10 into a single sheet.
  • the adhesive or the like does not protrude, so workability can be improved.
  • the sheet base material 20 and the molecular bonding layers 30a and 30b that constitute the molecular bonding sheet will be described in detail below.
  • a sheet base material according to an embodiment of the present invention is a sheet-like base material.
  • the sheet base material 20 constituting the molecular bonding sheet 10 according to the present embodiment uses its elastic force to connect the first member and the molecular bonding layer 30a, and the second member and the molecular bonding layer 30a. It has the effect of increasing the degree of adhesion with 30b. If the storage elastic modulus G1 at 23° C. (room temperature) is less than 3.5 ⁇ 10 6 Pa, the properties of the liquid will be high and workability will be poor.
  • the sheet base material in the molecularly bonded sheet according to the embodiment of the present invention has a storage elastic modulus G2 of 1.0 at a temperature T1 that satisfies Tg+10° C. ⁇ T1 ⁇ Tg+60° C., where Tg is the glass transition temperature of the sheet base material. It may be 0 ⁇ 10 3 Pa to 1.0 ⁇ 10 9 Pa, and the storage elastic modulus G1 may be greater than the storage elastic modulus G2.
  • the storage elastic modulus when the sheet substrate does not have Tg can be the storage elastic modulus at a temperature T2 that satisfies Tm ⁇ 30° C. ⁇ T2 ⁇ Tm+50° C., where Tm is the melting point of the sheet substrate. .
  • the sheet base material in the molecularly bonded sheet according to the embodiment of the present invention has a storage elastic modulus G2′ at a temperature T2 that satisfies Tm ⁇ 30° C. ⁇ T2 ⁇ Tm+50° C., where Tm is the melting point of the sheet base material. is 1.0 ⁇ 10 3 Pa to 1.0 ⁇ 10 9 Pa, and the storage elastic modulus G1 may be greater than the storage elastic modulus G2′.
  • the storage elastic moduli G2 and G2' are 1.0 ⁇ 10 9 Pa or less, the material followability is more excellent, and the shape of the adherend is less limited. Further, when the storage elastic moduli G2 and G2' are 1.0 ⁇ 10 3 Pa or more, the properties of the liquid are lowered, the paste is less likely to ooze out, and the yield is improved.
  • the glass transition temperature Tg and melting point Tm are obtained by DSC measurement.
  • the sheet base material according to the embodiment of the present invention when the storage elastic modulus G1 at 23° C. is larger than the storage elastic modulus G2 or G2′, the sheet can be sufficiently deformed by the pressure and temperature during bonding. is preferable because high-strength adhesion can be achieved by efficiently utilizing chemical bonding.
  • the storage elastic modulus G1 of the sheet base material at 23° C. should be 3.5 ⁇ 10 6 Pa to 1.0 ⁇ 10 10 Pa, and the lower limit of G1 should be more than 3.5 ⁇ 10 6 Pa. It is preferably 3.7 ⁇ 10 6 Pa or more, more preferably 3.7 ⁇ 10 6 Pa or more.
  • the upper limit of G1 is preferably 5.0 ⁇ 10 9 Pa or less, more preferably 1.0 ⁇ 10 9 Pa or less, and even more preferably 1.0 ⁇ 10 8 Pa or less.
  • the storage elastic moduli G2 and G2' in the sheet base material according to the embodiment of the present invention are preferably 1.0 ⁇ 10 3 Pa to 1.0 ⁇ 10 9 Pa, and the lower limits of G2 and G2' is more preferably greater than 1.0 ⁇ 10 3 Pa.
  • the lower limits of G2 and G2′ may be 1.0 ⁇ 10 4 Pa or higher, or 1.0 ⁇ 10 5 Pa or higher. Further, the upper limit of G2 and G2′ is preferably less than 1.0 ⁇ 10 9 Pa, more preferably 1.0 ⁇ 10 8 Pa or less, and 1.0 ⁇ 10 7 Pa or less. is more preferred.
  • the lower limit of Tm-30°C ⁇ T2 ⁇ Tm+50°C is preferably Tm-20°C or higher, more preferably Tm-10°C or higher, and the upper limit The value is preferably Tm+20° C. or less, more preferably Tm+10° C. or less.
  • the storage elastic modulus G2' is preferably the storage elastic modulus at the temperature at which the molecular bonding sheet according to the embodiment of the present invention is used for bonding members, and that temperature constitutes the sheet base material. It can be arbitrarily selected depending on the material. That is, T2 satisfying Tm ⁇ 30° C. ⁇ T2 ⁇ Tm+50° C.
  • T2 satisfying Tm ⁇ 30° C. ⁇ T2 ⁇ Tm+50° C. may be 90 to 170° C.
  • Tm ⁇ 30° C. ⁇ T2 satisfying T2 ⁇ Tm+50°C may be 70 to 150°C.
  • the storage elastic modulus G1 of the sheet base material according to the embodiment of the present invention is preferably larger than the storage elastic modulus G2 or G2'.
  • the storage elastic moduli G1, G2, and G2' of the sheet base material according to the embodiment of the present invention are obtained by measurement using a temperature-variable viscoelasticity measuring device.
  • G1 is the storage modulus at 23° C. (room temperature).
  • G2 is the storage elastic modulus at a temperature T1 that satisfies Tg+10° C. ⁇ T1 ⁇ Tg+60° C., where Tg is the glass transition temperature of the sheet substrate, and G2′ is Tm ⁇ , where Tm is the melting point of the sheet substrate. It is the storage modulus at a temperature T2 that satisfies 30°C ⁇ T2 ⁇ Tm + 50°C.
  • the material constituting the sheet base material according to the embodiment of the present invention preferably has a partial structure that strongly chemically bonds with the compound contained in the molecular bonding layer described below.
  • Examples of such partial structures include hydroxy groups, carboxyl groups, aldehyde groups, amino groups, carbon-carbon single bonds, carbon-carbon double bonds, and carbon-hydrogen single bonds.
  • BR 1,4-cis-butadiene rubber
  • NBR acrylonitrile/butadiene copolymer Rubber
  • EPDM ethylene oxide-epichlorohydrin copolymer
  • chloroprene rubber chlorinated Acrylic rubber, brominated acrylic rubber, fluorine rubber (FKM), epichlorohydrin rubber (CHR), epichlorohydrin and its copolymer rubber, chlorinated ethylene propylene rubber, chlorinated butyl rubber, brominated butyl rubber Tetrafluoroethylene, Teflon (registered trademark)
  • resins examples include olefin-based resins, acrylic resins, olefin-based ionomer resins, polyester-based resins, and polyamide-based resins, with olefin-based resins, acrylic-based resins, polyester-based resins, and polyamide-based resins being preferred.
  • olefinic resins include resins having repeating units derived from olefinic monomers and cycloolefinic monomers.
  • Olefinic monomers include ethylene, propylene, cycloolefins (cyclopentene, cyclooctene, norbornene monomers, etc.), ⁇ -olefins (copolymers with ethylene, propylene, etc.), norbornene, cyclopentene, cyclooctene, norbornene. etc.
  • acrylic resins homopolymers of (meth)acrylic monomers, copolymers of (meth)acrylic monomers, (meth)acrylic monomers, and monomers copolymerizable therewith and copolymers with (Meth) acrylic monomers include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2- (Meth)acrylic acid esters such as ethylhexyl (meth)acrylate; (meth)acrylic acid; (Meth) acrylic monomers and copolymerizable monomers include ethylene; aromatic vinyl monomers such as styrene, ⁇ -methylstyrene and chlorostyrene; cyano group-containing ethylene such as acrylonitrile and methacrylonitrile; (meth)acrylamide-based monomers such as (meth)
  • the olefinic ionomer resin examples include a copolymer having a repeating unit derived from an olefinic monomer and a repeating unit derived from a carboxyl group-containing monomer, and a resin having ionic crosslinks connecting the copolymer chains. be done.
  • olefinic monomers include ethylene and propylene.
  • Carboxy group-containing monomers include acrylic acid, methacrylic acid, maleic acid, maleic anhydride, maleic acid monomethyl ester, maleic acid monoethyl ester, and the like.
  • the ionic cross-linking of the olefinic ionomer resin is composed of carboxylate ions produced by deprotonation of the carboxy group of the carboxy group-containing monomer and metal ions.
  • metal ions include sodium (I) ion, potassium (I) ion, lithium (I) ion, calcium (II) ion, magnesium (II) ion, zinc (II) ion, copper (I) ion, copper (II) ion, ) ion, cobalt (II) ion, cobalt (III) ion, nickel (II) ion, manganese (II) ion, aluminum (III) ion, and the like.
  • polyester-based resins include those obtained by a polycondensation reaction of polyhydric carboxylic acid and polyhydric alcohol.
  • Polyvalent carboxylic acids include terephthalic acid, isophthalic acid, phthalic acid, succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, decanoic acid, 1,4-cyclohexanedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, trimellitic acid and the like.
  • Polyhydric alcohols include ethylene glycol, propylene glycol, 1,4-butanediol, 2-methyl-1,3-propanediol, 1,5-pentanediol, neopentyl glycol, 3-methyl-1,5-pentane.
  • Diol, 1,2-hexanediol, 1,6-hexanediol, 1,9-nonanediol, 1,4-cyclohexanedimethanol, diethylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, trimethylolpropane, glycerin, etc. is mentioned.
  • any appropriate polyamide-based resin can be selected as the polyamide-based resin as long as it does not impair the effects of the present invention.
  • examples of such polyamide-based resins include aliphatic polyamide-based resins, alicyclic polyamide-based resins, aromatic polyamide-based resins, and fatty acid-modified polyamide-based resins. More specifically, nylon 6, nylon 66, nylon 12 and the like are preferred.
  • the materials constituting the sheet base material it is particularly preferable to use polyethylene, polyester, polyamide, polypropylene, polycycloolefin, and the like.
  • the thickness of the sheet substrate is preferably 1 ⁇ m or more, more preferably 20 ⁇ m or more, and even more preferably 50 ⁇ m or more, from the viewpoint of obtaining a desired amount of deformation.
  • the thickness is preferably 5000 ⁇ m or less, more preferably 3000 ⁇ m or less, even more preferably 1000 ⁇ m or less, even more preferably 400 ⁇ m or less, and 300 ⁇ m or less. is particularly preferred. That is, the thickness of the sheet substrate is preferably 1 ⁇ m to 5000 ⁇ m.
  • the melting point (Tm) of the sheet base material is preferably 40°C or higher, more preferably 50°C or higher, from the viewpoint of handling during adhesion.
  • the temperature is preferably 200° C. or lower, more preferably 180° C. or lower, and even more preferably 150° C. or lower.
  • the molecular bonding layers in the molecular bonding sheet according to the embodiment of the present invention are layers provided on both sides of the sheet substrate.
  • the molecular bonding layers provided on both sides of the sheet substrate are not adhered to the sheet substrate by intermolecular force like an adhesive, but the sheet substrate and the molecular bonding layer are chemically bonded through chemical bonding. do. Therefore, when the molecular bonding sheet according to the embodiment of the present invention is used for bonding the first member and the second member substrate, which are adherends, the first member and the second member are bonded together. It is possible to form a joined body with excellent adhesion strength and high adhesion even with different kinds of materials or difficult-to-adhere materials.
  • the molecular bonding sheet according to the embodiment of the present invention can be used for bonding adherends.
  • a first member and a second member which are adherends
  • Both can be joined.
  • the first member and the second member are not bonded by the intermolecular force of the adhesive, but the first member and the second member and the molecular bonding layers 30a and 30b are bonded by chemical bonding. be. For this reason, it is possible to obtain excellent adhesive strength compared to adhesion by intermolecular force using an adhesive.
  • the molecular bonding sheet according to the embodiment of the present invention even if the first member and the second member are made of different materials or are made of difficult-to-adhere materials, excellent adhesion strength and adhesion can be obtained. High conjugates can be formed.
  • the molecular bonding layer can be formed using a molecular bonding agent.
  • the molecular bonding agent that forms the molecular bonding layer according to the embodiment of the present invention can be selected according to the material that constitutes the sheet base material. It is preferable to contain a compound (molecular bonding compound) having a reactive group that chemically bonds with .
  • a reactive group that chemically bonds with the adherend or a reactive group that chemically bonds with the adherend is added. It is preferred to include a compound having a generating group.
  • the sheet base material when the material constituting the sheet base material according to the embodiment of the present invention is at least one selected from olefin-based resins, acrylic resins, olefin-based ionomer resins, polyester-based resins, and polyamide-based resins, the sheet base material
  • reactive groups possessed by the material include hydrocarbon groups such as alkyl groups, alkenyl groups and alkynyl groups, carbonyl groups, carboxyl groups and hydroxy groups.
  • the reactive groups that chemically bond with the sheet substrate include, for example, amino group, azide group, mercapto group, isocyanate group, ureido group, epoxy group, and silanol group. , and a group that generates a silanol group by a hydrolysis reaction can be selected.
  • the molecular bonding sheet according to the embodiment of the present invention when used for bonding the first member and the second member, which are adherends, it depends on the materials constituting the first member and the second member. can be used to select reactive groups.
  • the first member is a metal material containing Al or Ti
  • reactive groups that chemically bond include, for example, an amino group, an azide group, a mercapto group, an isocyanate group, a ureido group, an epoxy group, a silanol A group, a group that generates a silanol group by a hydrolysis reaction, and the like can be selected.
  • the second member contains CFRP, thermosetting polyimide resin, thermosetting polyimide fluoride resin, fluororesin, epoxy resin, polyamide resin, etc., in the compound (molecular bonding compound) contained in the molecular bonding agent.
  • the reactive group that chemically bonds to the adherend (second member) for example, an amino group, a silanol group, a group that generates a silanol group by hydrolysis reaction, and the like are preferable.
  • the molecular bonding layers 30a and 30b and the sheet base material 20 are strongly bonded to each other through chemical bonding. spliced. Further, when the molecular bonding sheet 10 according to the embodiment of the present invention is used for bonding the first member and the second member, which are adherends, the When the compound has a partial structure that strongly chemically bonds with the reactive group, the molecular bonding layers 30a and 30b and the adherend are firmly molecularly bonded by chemical bonding. Then, the first member and the second member in the joined body are strongly joined by chemical bonding through the molecular joining sheet 10 .
  • the molecular bonding agent forming the molecular bonding layer contains a compound having a reactive group A and a reactive group B, and the reactive group A is an amino group, an azide group, or a mercapto group. , an isocyanate group, a ureido group and an epoxy group, and the reactive group B is at least one selected from a silanol group and a group that generates a silanol group by hydrolysis reaction. is preferred.
  • Examples of compounds having the reactive group A and the reactive group B include compounds represented by the following formula (1).
  • RA represents a reactive group A or a monovalent substituent having one or more reactive groups A
  • RB represents a reactive group B
  • Z represents a divalent organic group.
  • the divalent organic group represented by Z in formula (1) includes an optionally substituted alkylene group having 1 to 20 carbon atoms, and an optionally substituted alkylene group having 2 to 20 carbon atoms. an alkenylene group, an alkynylene group having 2 to 20 carbon atoms which may have a substituent, an arylene group having 6 to 20 carbon atoms which may have a substituent; and the like.
  • Examples of the alkylene group having 1 to 20 carbon atoms represented by Z include methylene group, ethylene group, propylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group and the like. A propylene group is preferred, and a propylene group is more preferred.
  • the alkenylene group having 2 to 20 carbon atoms represented by Z includes vinylene group, propenylene group, butenylene group, pentenylene group and the like.
  • Examples of the alkynylene group having 2 to 20 carbon atoms represented by Z include an ethynylene group and a propynylene group.
  • the arylene group having 6 to 20 carbon atoms represented by Z includes o-phenylene group, m-phenylene group, p-phenylene group, 2,6-naphthylene group, 1,5-naphthylene group and the like.
  • substituents that the alkylene group, alkenylene group, and alkynylene group may have include halogen atoms such as a fluorine atom and a chlorine atom; alkoxy groups such as a methoxy group and an ethoxy group; alkylthio groups such as a methylthio group and an ethylthio group; groups; alkoxycarbonyl groups such as a methoxycarbonyl group and an ethoxycarbonyl group; and the like.
  • substituents that the arylene group may have include a cyano group; a nitro group; a halogen atom such as a fluorine atom, a chlorine atom and a bromine atom; an alkyl group such as a methyl group and an ethyl group; a methoxy group, an ethoxy group and the like. alkoxy group; alkylthio group such as methylthio group and ethylthio group; and the like. These substituents may be bonded to any position in a group such as an alkylene group, an alkenylene group, an alkynylene group, and an arylene group. good too.
  • the reactive group A represented by RA in formula (1) includes an amino group, an azide group, a mercapto group, an isocyanate group, a ureido group, an epoxy group, a thiol group, and R 3 and R 4 in the following formula (2) are hydrogen.
  • R 3 and R 4 in the following formula (2) are hydrogen atoms; It is more preferably at least one selected from the group consisting of a certain group, and more preferably at least one selected from the group consisting of an amino group, an azide group, a mercapto group, an isocyanate group, a ureido group and an epoxy group. Preferably, it is an amino group or an azide group.
  • the molecular bonding layer and the sheet base material are more strongly bonded when the reactive group A represented by RA in formula (1) is an azide group. It is preferable for adhesion.
  • Examples of the “monovalent group having at least one reactive group A” represented by R 1 A in formula (1) include groups represented by the following formulas (2) to (4).
  • R 2 represents a divalent hydrocarbon group having 1 to 10 carbon atoms.
  • R 3 , R 4 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R 5 and R 6 each independently represent a reactive group A or a group represented by the above formula (2) (this , in formula (2), * represents a bond with a carbon atom constituting the triazine ring in formula (4), and R 7 is a single bond or -N(R 8 )- represents a divalent group.
  • R 8 represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms
  • the divalent hydrocarbon group having 1 to 10 carbon atoms represented by R 2 is preferably a divalent hydrocarbon group having 2 to 6 carbon atoms.
  • R 2 include an alkylene group having 1 to 10 carbon atoms or an arylene group, and specific examples include an alkylene group such as an ethylene group, a trimethylene group and a propylene group; an o-phenylene group and an m-phenylene group. , an arylene group such as a p-phenylene group;
  • R 3 and R 4 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, preferably a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms.
  • Examples of the hydrocarbon group having 1 to 20 carbon atoms represented by R 3 and R 4 include an alkyl group, an alkenyl group, an alkynyl group, or an aryl group having 1 to 20 carbon atoms, and specifically, a methyl group.
  • R 5 and R 6 are each independently a reactive group A or a group represented by the above formula (2) (in this case, in formula (2), * represents a carbon atom constituting an aromatic ring represents a bond with an atom.). R 5 and R 6 are preferably the same reactive group A.
  • R 7 represents a single bond or a divalent group represented by -N(R 8 )-.
  • R 8 represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. Examples of the hydrocarbon group for R 8 include the same hydrocarbon groups as those described above for R 3 and R 4 .
  • R 7 preferably represents -NH-.
  • R A in formula (1) is preferably a group represented by formula (4) among the groups represented by formulas (2) to (4) above, and a group represented by formula (4) and R 5 or R 6 preferably represents an azide group or a group represented by the above formula (2).
  • RA is a group represented by formula (4) and R 5 or R 6 represents a group represented by formula (2)
  • RA is, for example, represented by the following formula (5) group.
  • R 7 represents a single bond or a divalent group represented by —N(R 8 )—.
  • R 8 represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, each R 2 independently represents a divalent hydrocarbon group having 1 to 10 carbon atoms, and R 3 and R 4 are Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R 2 , R 3 and R 4 may be the same or different.
  • R 7 examples include those similar to those shown in formula (4).
  • R 2 , R 3 and R 4 include the same as R 2 , R 3 and R 4 in formula (2).
  • the reactive group B represented by RB is a silanol group or a group that generates a silanol group by hydrolysis reaction, and may be, for example, a group represented by the following formula (6).
  • X represents a hydroxy group or an alkoxy group having 1 to 10 carbon atoms
  • Y represents a hydrocarbon group having 1 to 20 carbon atoms
  • a represents an integer of 1 to 3.
  • the alkoxy group having 1 to 10 carbon atoms represented by X includes methoxy group, ethoxy group, n-propoxy group, isopropoxy group and the like, and ethoxy group is preferred.
  • the hydrocarbon group having 1 to 20 carbon atoms represented by Y includes the same hydrocarbon groups as R 3 and R 4 in formula (2).
  • X represents a hydroxy group or an alkoxy group having 1 to 10 carbon atoms, preferably a represents 3, X represents a hydroxy group or an ethoxy group, and a represents 3 more preferred.
  • the following compounds can be exemplified as the molecular bonding compound having the reactive group A and the reactive group B.
  • Molecular bonding compounds in which RA is an amino group include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldimethoxymethylsilane, 3-aminopropyldiethoxymethylsilane, [3-( N,N-dimethylamino)propyl]trimethoxysilane, [3-(phenylamino)propyl]trimethoxysilane, trimethyl[3-(triethoxysilyl)propyl]ammonium chloride, trimethyl[3-(trimethoxysilyl)propyl ] and ammonium chloride.
  • Molecular bonding compounds in which RA is an azide group include (11-azidoundecyl)trimethoxysilane, (11-azidoundecyl)triethoxysilane, and the like.
  • Molecular bonding compounds in which RA is a mercapto group include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropyldimethoxymethylsilane, and the like.
  • Molecular bonding compounds in which RA is an isocyanate group include 3-(trimethoxysilyl)propylisocyanate, 3-(triethoxysilyl)propylisocyanate, and the like.
  • Molecular bonding compounds in which RA is a ureido group include 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, and the like.
  • Molecular bonding compounds in which RA is an epoxy group include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyl diethoxysilane and the like.
  • Molecular bonding compounds in which R A is a monovalent group having one or more reactive groups A include, for example, 3-(2-aminoethylamino)propyltrimethoxysilane, 3-(2-aminoethylamino)propyltri Examples include ethoxysilane, 3-(2-aminoethylamino)propyldimethoxymethylsilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and compounds (11) to (19) below.
  • the compounds (11) to (19) are preferable, and among them, (11) N,N'-bis(2-aminoethyl)-6 -(3-trihydroxysilylpropyl)amino-1,3,5-triazine-2,4-diamine or (19) 6-(3-triethoxysilylpropyl)amino-1,3,5-triazine-2, Compounds of 4-diazide are preferred.
  • the thickness of the molecular bonding layer is the same as when using a general adhesive. It can be made very thin compared to the adhesive layer. Therefore, the molecular bonding sheet according to the embodiment of the present invention can exhibit excellent adhesive strength due to the extremely thin molecular bonding layer laminated on the sheet base material, and when used for bonding of adherends, It is possible to suppress peeling at the joint of and exhibit excellent joint strength.
  • the thickness of the molecular bonding layer is preferably 5 nm or more, more preferably 10 nm or more, and even more preferably 30 nm or more. From the viewpoint of bonding strength, the thickness is preferably 300 nm or less, more preferably 200 nm or less, and even more preferably 100 nm or less.
  • the manufacturing method of the molecule-bonded sheet according to the embodiment of the present invention is not particularly limited, it is manufactured, for example, as follows. First, the sheet base material 20 having a predetermined storage elastic modulus G1, G2 or G2' is prepared as described above, and a molecular bonding agent is applied to both surfaces thereof. Next, by drying the applied solution, the molecular bonding layers 30a and 30b can be formed.
  • the molecular bonding agent contains a molecular bonding compound and can be prepared by dissolving the molecular bonding compound (preferably a compound having a reactive group A and a reactive group B) in a solvent. Next, by drying the applied molecular bonding agent, the molecular bonding layers 30a and 30b can be formed.
  • the applied solution contains a compound having an azide group, it is preferable to irradiate ultraviolet rays (UV: ultraviolet).
  • UV ultraviolet
  • the solution contains a compound having an amino group
  • the heating temperature is preferably 60° C. or higher, more preferably 70° C. or higher, from the viewpoint of hydrogen bond formation in silane coupling.
  • the temperature is preferably 150° C. or lower, more preferably 100° C. or lower, and even more preferably 90° C. or lower.
  • the process of applying and drying a molecular bonding agent containing a compound having an azide group or a compound having an amino group may be repeated multiple times. Thereby, the concentrations of the reactive group A and the reactive group B in the molecular bonding layers 30a and 30b can be increased.
  • Different types of molecular bonding agents molecular bonding compounds
  • a molecular bonding agent containing a compound having an amino group may be applied and dried one or more times.
  • a joining method according to an embodiment of the present invention is a joining method for joining a first member and a second member using a molecularly joined sheet according to an embodiment of the present invention, disposing the molecular bonding sheet between the bonding surface of the first member and the bonding surface of the second member; and heating the first member and the second member while pressing the first member and the second member in a direction in which they are brought into close contact with each other.
  • the bonding method according to the embodiment of the present invention is a bonding method for bonding a first member and a second member using a molecular bonding sheet
  • the molecular bonding sheet has a sheet base material and molecular bonding layers provided on both sides of the sheet base material,
  • the sheet base material has a storage elastic modulus G1 at 23° C. of 3.5 ⁇ 10 6 Pa to 1.0 ⁇ 10 10 Pa, disposing the molecular bonding sheet between the bonding surface of the first member and the bonding surface of the second member; and heating the first member and the second member while pressing the first member and the second member in a direction in which they are brought into close contact with each other.
  • a joining method is a joining method for bonding a first member and a second member, disposing the molecular bonding sheet between the bonding surface of the first member and the bonding surface of the second member; a heating step of heating the first member and the second member while pressing them in a direction to bring them into close contact with each other,
  • the storage elastic modulus G2′′ of the molecularly bonded sheet at the temperature during bonding is 1.0 ⁇ 10 3 Pa to 1.0 ⁇ 10 9 Pa, and the storage elastic modulus G1 is greater than the storage elastic modulus G2′′.
  • a joining method may be used.
  • the temperature during bonding refers to the heating temperature in the heating step of the bonding method according to the embodiment of the present invention.
  • the molecular bonding sheet according to the embodiment of the invention may be used in the bonding method according to the embodiment of the invention.
  • the lower limit of the storage elastic modulus G2′′ in the molecular bonding sheet according to the embodiment of the present invention is more preferably more than 1.0 ⁇ 10 3 Pa.
  • the lower limit of the storage elastic modulus G2′′ is 1.0 ⁇ It may be 10 4 Pa or more, or 1.0 ⁇ 10 5 Pa or more.
  • the upper limit of G2′′ is preferably 1.0 ⁇ 10 8 Pa or less, more preferably 1.0 ⁇ 10 7 Pa or less.
  • FIG. 2 is a schematic cross-sectional view for explaining the bonding method using the molecular bonding sheet according to the embodiment of the present invention
  • FIG. 3 shows the bonding method using the molecular bonding sheet according to the embodiment of the present invention.
  • FIG. 3 is a diagram for explaining, and is a schematic cross-sectional view showing the next step of FIG. 2 ;
  • FIG. A joining method according to an embodiment of the present invention will be described below with reference to FIGS.
  • the molecular bonding sheet 10 according to this embodiment, the first member 40 (for example, CFRP material) and the second member 50 (for example, Al material or Ti material) that require strong bonding are prepared.
  • the molecule-bonded sheet 10 has the sheet substrate 20 and the molecule-bonded layers 30a and 30b provided on both surfaces of the sheet substrate 20 perpendicular to the thickness direction.
  • the joint surface 40a of the first member 40 and the joint surface 50a of the second member 50 are arranged to face each other, and the joint surface 40a with the first member and the joint surface 50a of the second member are arranged. and a molecule-bonded sheet 10 is arranged between them.
  • the first member 40 and the second member 50 are heated by, for example, a hot press or the like while being pressed in a direction to bring them into close contact with each other.
  • the direction of heating may be from the side of the first member or the side of the second member, and it is preferable to heat from both sides.
  • the pressing force, heating temperature, and the like are not particularly limited. good.
  • a pressure of 0.1 MPa to 5 MPa is applied in a direction to bring them into close contact with each other, and the first member 40 and the second member are heated to a temperature of 60° C. to 250° C. and held for 1 minute to 15 minutes. member 50 can be joined.
  • the materials of the first member 40 and the second member 50 are not limited as long as they chemically bond with the molecular bonding layers 30a and 30b. can be strongly bonded.
  • the reaction for chemical bonding between the molecular bonding layers 30a and 30b and the first member 40 and the second member 50 takes a very short time to form the first member 40 as compared with general adhesives. and the second member 50 can be joined.
  • the molecule bonding sheet 10 is placed on the second member 50, and the first member 40 is placed thereon to form the first member 40.
  • the second member 50 is pressurized and heated, the bonding process can be completed at once. Therefore, the joining process can be significantly simplified, and the manufacturing cost of the structural member obtained by joining can be reduced.
  • the first member 40 and the second member 50 may be made of the same material or different materials.
  • the effects of the molecule-bonded sheet 10 according to the embodiment can be further exhibited. Therefore, it is preferable that the first member and the second member are made of different materials.
  • the material that constitutes the first member 40 and the second member 50 includes resin, rubber, metal, glass, and ceramics.
  • metal materials include materials containing metals selected from gold, silver, copper, aluminum, iron, titanium, alloys containing one or more of these, and the like. Among these, materials containing copper, aluminum, or titanium are preferable, and materials containing aluminum or titanium are preferable.
  • the resin contained in the resin material may be a thermoplastic resin or a thermosetting resin, and the resin material is preferably CFRP.
  • thermoplastic resins include PP (polypropylene), PA (polyamide), PPE (polyphenylene ether), PPS (polyphenylene sulfide), PET (polyethylene terephthalate), PBT (polybutylene terephthalate), POM (polyacetal), PEEK ( polyether ether ketone), PC (polycarbonate), PES (polyether sulfide), EP (epoxy), and the like.
  • thermoplastic resins that can advantageously exhibit the effects of the present invention.
  • a fiber reinforced thermoplastic may be employed as the thermoplastic.
  • Fiber reinforced thermoplastic resins include, for example, carbon fiber reinforced thermoplastic resins (CFRTP) and glass fiber reinforced thermoplastic resins (GFRTP).
  • Carbon fiber reinforced thermoplastic resins include, for example, PPS carbon fiber reinforced thermoplastic resins, PA carbon fiber reinforced thermoplastic resins, PES carbon fiber reinforced thermoplastic resins, EP carbon fiber reinforced thermoplastic resins, A PP-based carbon fiber reinforced thermoplastic resin and the like are included.
  • Glass fiber reinforced thermoplastic resins include, for example, PPS glass fiber reinforced thermoplastic resins, PA glass fiber reinforced thermoplastic resins, PP glass fiber reinforced thermoplastic resins, and the like.
  • thermosetting resins examples include unsaturated polyester resins, vinyl ester resins, epoxy resins, melamine resins, phenol resins, urethane resins, polyisocyanate resins, polyisocyanurate resins, and polyimide resins.
  • the joining method according to the present invention is particularly useful for structural members using a resin material such as a CFRP material for weight reduction and strength enhancement.
  • a resin material such as a CFRP material for weight reduction and strength enhancement.
  • it can be suitably used when joining a metal material containing titanium and a resin material such as a CFRP material. That is, it is preferable that the first member is a metal material containing aluminum or titanium, and the second member is a carbon fiber reinforced plastic material (CFRP).
  • CFRP carbon fiber reinforced plastic material
  • the pretreatment step first, the first member 40 and the second member 50 are prepared, and the bonding surface 40a of the first member 4 and the second member 50 are prepared before the step of arranging the molecular bonding sheet. is activated by cleaning or surface treatment.
  • Examples of the cleaning treatment include alkali degreasing treatment and the like.
  • Alkaline degreasing treatment is a treatment in which the surface is washed with distilled water after washing with an alkaline washing liquid and then dried.
  • Examples of surface treatment include corona treatment, sputter etching treatment, and plasma treatment.
  • the pretreatment process allows the first member 40 and the second member 50 to be joined more firmly.
  • corona treatment for example, there is a method of discharging in normal pressure air using a corona treatment machine.
  • the corona treatment is carried out by irradiating the surface of the substrate with electric discharge using a corona surface treatment apparatus with a high frequency power supply.
  • the discharge output intensity is preferably 0.5 kW or more, more preferably 0.8 kW or more, and still more preferably 0.10 kW or more.
  • a sputter etching process for example, bombards the surface of a substrate with energetic particles from a gas. At the part of the substrate that the particles collide with, atoms or molecules present on the surface of the substrate are released to form reactive groups, thereby improving adhesion.
  • the sputter etching process can be performed, for example, by placing the base material in a chamber, depressurizing the chamber, and applying a high-frequency voltage while introducing an atmospheric gas.
  • Atmospheric gas is, for example, at least one selected from the group consisting of rare gases such as helium, neon, argon and krypton, nitrogen gas and oxygen gas.
  • the frequency of the high frequency voltage to be applied is, for example, 1 to 100 MHz, preferably 5 to 50 MHz.
  • the pressure in the chamber when applying the high-frequency voltage is, for example, 0.05 to 200 Pa, preferably 1 to 100 Pa.
  • the sputter etching energy (product of processing time and applied power) is, for example, 1 to 1000 J/cm 2 , preferably 2 to 200 J/cm 2 .
  • Plasma treatment includes, for example, a method of discharging in normal pressure air using a plasma discharger. It can be carried out by setting the substrate in a plasma apparatus and irradiating it with a predetermined gas.
  • the plasma processing conditions can be set to any appropriate conditions as long as the effects of the present invention can be obtained.
  • the plasma treatment may be a plasma treatment performed under atmospheric pressure or a plasma treatment performed under reduced pressure.
  • the pressure (degree of vacuum) during plasma processing is, for example, 0.05 Pa to 200 Pa, preferably 0.5 Pa to 100 Pa.
  • the frequency of the high frequency power source used for plasma processing is, for example, 1 MHz to 100 MHz, preferably 5 MHz to 50 MHz.
  • the amount of energy during plasma treatment is preferably 0.1 J/cm 2 to 100 J/cm 2 , more preferably 1 J/cm 2 to 20 J/cm 2 .
  • the plasma treatment time is preferably 1 second to 5 minutes, more preferably 5 seconds to 3 minutes.
  • the amount of gas supplied during plasma processing is preferably 1 sccm to 150 sccm, more preferably 10 sccm to 100 sccm.
  • reactive gases used in the plasma treatment include gases such as water vapor, air, oxygen, nitrogen, hydrogen, ammonia, and alcohols (eg, ethanol, methanol, isopropyl alcohol). By using such a reaction gas, it is possible to obtain an adhesive sheet with excellent adhesiveness.
  • inert gases such as helium, neon, and argon may be used in combination with the reaction gas.
  • the type of surface treatment can be appropriately selected according to the material that constitutes the adherend.
  • the second member 50 which is an adherend
  • hydroxyl groups are present on the surface without performing a pretreatment process such as a cleaning treatment or a surface treatment. Therefore, it can react with the reactive groups of the molecular bonding layer 30b.
  • a pretreatment process such as a cleaning treatment or a surface treatment. Therefore, it can react with the reactive groups of the molecular bonding layer 30b.
  • by cleaning the bonding surface 50a of the second member 50 by washing and performing an alkaline degreasing treatment it is possible to increase the number of hydroxyl groups appearing on the bonding surface 50a. It becomes easy to react and can further improve adhesive strength.
  • CFRP containing an epoxy resin is used as the first member 40, since hydroxyl groups are present on the surface of the CFRP, the reactivity of the molecular bonding layer can be improved without washing or surface treatment. can be reacted with groups. However, if a pretreatment process such as surface treatment is performed, the number of hydroxy groups appearing on the surface can be increased, making it easier to react with the reactive groups of the molecular bonding layer 30a, and the adhesive strength can be further improved. .
  • a surface-treated commercially available film substrate or the like can also be used as the substrate.
  • the material constituting the adherend is a material that does not have hydroxyl groups on the surface
  • the hydroxyl groups are generated in the pretreatment step to chemically bond with the molecular bonding layers 30a and 30b, Adhesion can be further improved.
  • the sheet base material is a molecular bonding sheet having a storage elastic modulus G1 of 3.5 ⁇ 10 6 Pa to 1.0 ⁇ 10 10 Pa at 23°C.
  • the sheet substrate has a storage elastic modulus G2 of 1.0 ⁇ 10 3 Pa to 1.0 at a temperature T1 that satisfies Tg+10° C. ⁇ T1 ⁇ Tg+60° C., where Tg is the glass transition temperature of the sheet substrate. ⁇ 10 9 Pa, and the storage elastic modulus G1 is greater than the storage elastic modulus G2.
  • the sheet base material has a storage elastic modulus G2′ of 1.0 ⁇ 10 3 Pa to 1 at a temperature T2 that satisfies Tm ⁇ 30° C. ⁇ T2 ⁇ Tm+50° C., where Tm is the melting point of the sheet base material. 0 ⁇ 10 9 Pa, and the storage elastic modulus G1 is greater than the storage elastic modulus G2′.
  • the molecular bonding agent forming the molecular bonding layer contains a compound having a reactive group A and a reactive group B, and the reactive group A is an amino group, an azide group, a mercapto group, an isocyanate group, or a ureido group.
  • the reactive group B is at least one selected from a silanol group and a group that generates a silanol group by hydrolysis reaction [1] to The molecularly bonded sheet according to any one of [3].
  • a bonding method for bonding a first member and a second member using a molecular bonding sheet has a sheet base material and molecular bonding layers provided on both sides of the sheet base material,
  • the sheet base material has a storage elastic modulus G1 at 23° C.
  • the storage elastic modulus G2′′ of the molecularly bonded sheet at the temperature during bonding is 1.0 ⁇ 10 3 Pa to 1.0 ⁇ 10 9 Pa, and the storage elastic modulus G1 is greater than the storage elastic modulus G2′′.
  • ARES-G2 TA Instruments was used for the measurement.
  • a sheet base material cut into strips with a width of 1 cm and a length of 5 cm was used as a sample, and measured under the conditions of a temperature increase rate of 10 ° C./min, a distance between chucks of 20 mm, and a frequency of 1.0 Hz, and stored at 23 ° C.
  • the elastic modulus was taken as G1.
  • the elastic modulus exceeding Tm was measured using ARES-G2 TA Instruments, the samples were overlapped to a thickness of 1 mm, and a parallel plate of 8 mm ⁇ was used.
  • the measurement frequency was 1 Hz, the temperature was raised at 5 ° C./min, and the stress was measured when a strain of 0.1% was applied.
  • ) is the melting point of Tm
  • the ratio was taken as G2'.
  • the storage elastic modulus of the molecule-bonded sheets obtained in Examples and Comparative Examples at the temperature during bonding was measured by the same method as that for the sheet base material, and was designated as G2′′.
  • Tm measurement> Using Q2000 TA Instruments for measurement, 7 mg of sample (sheet base material) was added to an aluminum pan, measured from 0 ° C. to 200 ° C. at a temperature increase rate of 2 ° C./min, and the resulting inflection point was Tg , the endothermic peak was taken as Tm.
  • a polyethylene sheet (manufactured by Kolgo Co., Ltd.) with a thickness of 300 ⁇ m and a polyester hot-melt sheet FB-ML-80 (manufactured by Nitto Shinko Co., Ltd.) with a thickness of 50 ⁇ m were prepared as sheet base materials. Then, an aqueous solution containing a compound (molecular bonding reagent) constituting the molecular bonding layer was applied to both surfaces of these sheets to form the molecular bonding layer, thereby manufacturing the molecular bonding sheet of the example.
  • a compound (molecular bonding reagent) constituting the molecular bonding layer was applied to both surfaces of these sheets to form the molecular bonding layer, thereby manufacturing the molecular bonding sheet of the example.
  • the polyethylene sheet has a G1 (storage modulus at 23°C) of 3.0 ⁇ 10 9 Pa and a G2′ (storage modulus at 90°C to 170°C) of 1.5 ⁇ 10 8 to 5.3 ⁇ 10 5 Pa. be.
  • the G1 (storage modulus at 23°C) of the polyester hot-melt sheet is 4.0 ⁇ 10 6 Pa
  • the G2' (storage modulus at 70°C to 150°C) is 3.3 ⁇ 10 5 to 1.5 ⁇ 10. 4 Pa.
  • Table 2 shows the storage elastic modulus at the temperature during bonding of the molecule-bonded sheets of each example and comparative example.
  • a wire bar #14 was used to coat both sides of the sheet substrate with a molecular bonding compound (19) 6-(3-triethoxysilylpropyl)amino-1,3 represented by the following formula (19).
  • ,5-triazine-2,4-diazide manufactured by Io Kagaku Kenkyusho Co., Ltd.
  • 0.5% by mass ethanol solution molecular bonding agent
  • UV irradiation to form a molecular bonding layer.
  • a Quark Technology UV-LED irradiation device was used with a wavelength of 265 nm and an irradiation dose of 100 mJ/cm 2 .
  • a molecular bonding agent was applied on the molecular bonding layer formed above by the same operation, dried, and then UV-irradiated to form a molecular bonding layer.
  • a molecular bonding compound (11) N,N'-bis(2-aminoethyl)-6-(3-trihydroxysilylpropyl)amino- represented by the following formula (11)
  • the temperature is adjusted to 80 ° C.
  • a molecular bonding layer was formed by heating in a heated oven for 10 minutes to obtain a molecular bonding sheet of Example.
  • a CFRP material, a Ti material, and an Al material were prepared as adherends (first member and second member).
  • CFRP material matte CFRP (manufactured by Standard Test Piece Co., Ltd.) (CFRP for JIS K6850 adhesion test) was used.
  • Ti material one made of 64 titanium alloy (JIS 60 type) and having a plate thickness of 1.5 mm was used.
  • Al material 5052P (manufactured by Standard Test Piece Co., Ltd.) having a plate thickness of 1.5 mm was used.
  • As the alkaline cleaning liquid a 5 mass % aqueous solution of treatment chemical SK-144 (manufactured by JCU Corporation) was used.
  • Example 1 to 11 the Ti material and the Al material were used after being washed with an alkaline cleaning liquid, then the surface was washed with distilled water and dried. CFRP materials were used as they were without washing or surface treatment. In Examples 1 to 11, the first member and the second member were not subjected to any pretreatment other than cleaning treatment, and only the molecular bonding sheet was used.
  • Examples 1 to 5 a molecularly bonded sheet whose sheet base material (base material sheet) is a polyester hot melt sheet FB-ML-80 (hot melt sheet) was used. Further, in Examples 6 to 11, a molecular bonding sheet whose sheet base material is a polyethylene sheet was used.
  • Example 1 in which a hot-melt sheet was used as the sheet base material, the heating temperature was set to 150° C., the pressure was set to 1 MPa, and the pressure was maintained for 10 minutes. Also in Examples 6 to 10 using a polyethylene sheet as the sheet base material, the heating temperature was set to 150° C., the pressure was set to 1 MPa, and the pressure was maintained for 10 minutes. In Example 11, the heating temperature was set to 120° C., the pressure was set to 1 MPa, and the pressure was maintained for 10 minutes.
  • Comparative Examples 1 to 5 after applying a two-liquid mixing type epoxy adhesive to the bonding surface of the first member and the bonding surface of the second member, the bonding surface of the first member and the second member were applied.
  • a joined body sample was obtained by stacking both members so that the joined surfaces of the members of (1) were in contact with each other, sandwiched with a clip, and allowed to stand in a fixed state for one day.
  • Araldite Rapid manufactured by Huntsman Japan Co., Ltd. was used as the two-liquid mixing type epoxy adhesive.
  • an epoxy adhesive sheet was placed between the joint surface of the first member and the joint surface of the second member, and these were sandwiched and fixed with clips, and the temperature was adjusted to 130 ° C.
  • a sample of the joined body was obtained by heating to 200 rpm and holding for 1 hour.
  • As the epoxy adhesive sheet a thermosetting adhesive sheet P-EF11 (manufactured by Nitto Shinko Co., Ltd.) having a thickness of 300 ⁇ m was used.
  • the hot-melt sheet or polyethylene sheet used as the sheet base material in the examples was placed between the joint surface of the first member and the joint surface of the second member.
  • a joined body sample was obtained by heating while pressing the first member and the second member in a direction to bring them into close contact with each other under the conditions of .
  • the heating temperature was set to 150° C.
  • the pressure was set to 1 MPa, and held for 10 minutes.
  • Comparative Examples 16 to 20 using polyethylene sheets the heating temperature was set to 150° C., the pressure was set to 1 MPa, and the pressure was maintained for 10 minutes.
  • the bonding evaluation was performed by measuring the shear strength of the bonded body samples obtained as described above.
  • the shear strength was measured by fixing both ends of each joined body sample to a precision universal testing machine AGX-V (manufactured by Shimadzu Corporation) and pulling at a tensile speed of 1.0 mm/min.
  • Bonding conditions materials of the first member and the second member, storage elastic modulus G2 ′′ of the molecular bonding sheet, type of sheet base material, presence or absence of molecular bonding treatment process, bonding time
  • evaluation results shear strength, glue Presence or absence of protrusion
  • Examples 1 to 11 using the molecularly bonded sheet according to the embodiment of the present invention exhibit excellent shear strength, and excellent adhesive strength capable of firmly adhering difficult-to-adhere materials is obtained. was taken. Further, as shown in Table 2 above, in Examples 1 to 11, since the bonding was performed after the pretreatment process was performed, excellent shear strength could be obtained. On the other hand, in Comparative Examples 11 to 20, the bonding surfaces of the first member and the second member were bonded without performing the pretreatment step and the molecular bonding treatment, and compared with Examples 1 to 11. As a result, the shear strength decreased.

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Abstract

La présente invention concerne une feuille de liaison moléculaire comprenant une feuille de base et des couches de liaison moléculaire disposées sur les deux surfaces de la feuille de base, la feuille de base ayant un module de conservation de 23 °C G1 de 3,5×106-1,0×1010 Pa.
PCT/JP2022/041094 2021-11-05 2022-11-02 Feuille de liaison moléculaire et procédé de liaison WO2023080183A1 (fr)

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WO2020026575A1 (fr) * 2018-08-02 2020-02-06 株式会社クレハ Corps assemblé et procédé de production d'un corps assemblé

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WO2018181517A1 (fr) * 2017-03-30 2018-10-04 リンテック株式会社 Feuille adhésive et procédé de production d'un corps stratifié
WO2018181518A1 (fr) * 2017-03-30 2018-10-04 リンテック株式会社 Feuille adhésive et procédé de production d'un corps stratifié
WO2019189667A1 (fr) * 2018-03-29 2019-10-03 リンテック株式会社 Produit en couches pour collage, procédé de collage de deux parties adhérées, et procédé de production d'une structure liée
WO2020026575A1 (fr) * 2018-08-02 2020-02-06 株式会社クレハ Corps assemblé et procédé de production d'un corps assemblé

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