WO2024043288A1 - Composition adhésive, couche adhésive, feuille adhésive, corps multicouche, corps assemblé, procédé de production de corps assemblé, et procédé de démontage de corps assemblé - Google Patents

Composition adhésive, couche adhésive, feuille adhésive, corps multicouche, corps assemblé, procédé de production de corps assemblé, et procédé de démontage de corps assemblé Download PDF

Info

Publication number
WO2024043288A1
WO2024043288A1 PCT/JP2023/030393 JP2023030393W WO2024043288A1 WO 2024043288 A1 WO2024043288 A1 WO 2024043288A1 JP 2023030393 W JP2023030393 W JP 2023030393W WO 2024043288 A1 WO2024043288 A1 WO 2024043288A1
Authority
WO
WIPO (PCT)
Prior art keywords
adhesive
adhesive layer
adhesive composition
resin
base material
Prior art date
Application number
PCT/JP2023/030393
Other languages
English (en)
Japanese (ja)
Inventor
悠斗 鈴木
悟司 上田
Original Assignee
日東電工株式会社
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 日東電工株式会社 filed Critical 日東電工株式会社
Publication of WO2024043288A1 publication Critical patent/WO2024043288A1/fr

Links

Images

Classifications

    • 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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • 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
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • 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
    • C09J7/38—Pressure-sensitive adhesives [PSA]

Definitions

  • the present invention relates to an adhesive composition, an adhesive layer, an adhesive sheet, a laminate, a bonded body, a method for manufacturing a bonded body, and a method for dismantling a bonded body.
  • Adhesives are used to join members made of various materials such as resin, rubber, metal, glass, ceramics, and paper.
  • easy-to-disassemble adhesives that have both sufficient adhesive strength depending on the purpose of use and the property of being able to be easily peeled off (dismantled) by lowering the adhesive strength at any timing have been studied.
  • Demand for such easy-to-disassemble adhesives is increasing for purposes such as separate collection of bonding materials used to bond parts of dissimilar materials, repair/replacement of parts, and improved productivity through temporary adhesion during manufacturing processes. ing.
  • stimulation methods such as heating, voltage application, light irradiation, and chemical immersion are being considered. This involves decomposition, expansion of additives, etc., and inorganic expansion agents such as resin microcapsules containing liquid low-boiling hydrocarbons and expanded graphite are used as expansion agents.
  • Patent Document 1 discloses that the glass transition temperature after curing is 80° C. for the purpose of obtaining an epoxy resin adhesive and a bonded body that can be easily dismantled after use of the adhesive/joining member.
  • the above describes an epoxy resin adhesive in which the dynamic elastic modulus E'r of the rubber-like flat part in dynamic viscoelasticity is 20 MPa or less.
  • the present invention was made in view of the above-mentioned situation, and an object of the present invention is to provide an adhesive layer and an adhesive sheet that have both adhesion and disassembly properties.
  • the present invention also provides an adhesive composition for forming the adhesive layer and the adhesive sheet, a laminate using the adhesive sheet, a bonded body with excellent disassembly properties, a method for manufacturing the bonded body, and a method for dismantling the bonded body.
  • the purpose is to provide
  • an adhesive sheet using an adhesive composition containing a polyfunctional epoxy resin, a specific amount of a monofunctional epoxy compound, and a specific amount of a thermoplastic resin has excellent adhesive strength that firmly bonds adherends.
  • the present inventors have discovered that it is possible to obtain a bonded body that can be easily disassembled by a small stimulus when desired, and has excellent disassembly properties, and has completed the present invention.
  • Means for solving the above problem are as follows.
  • An adhesive composition containing a polyfunctional epoxy resin, a monofunctional epoxy compound, and a thermoplastic resin, wherein the content ratio of the monofunctional epoxy compound in the total amount of the polyfunctional epoxy resin and the monofunctional epoxy compound is 20 to 50% by mass, and the content of the thermoplastic resin in the adhesive composition is 20 to 60% by mass based on the total resin components.
  • An adhesive composition forming an adhesive layer, wherein the adhesive layer formed by the adhesive composition has a tensile storage modulus of 5 MPa or less at 200°C and a shear adhesive strength to a steel plate of 15 MPa or more.
  • An adhesive composition [3] The adhesive composition according to [1] or [2], further comprising thermally expandable particles.
  • thermoplastic resin has a number average molecular weight (Mn) of 10,000 or more.
  • An adhesive sheet comprising the adhesive layer according to [5].
  • a method for producing a bonded body comprising a bonding step of curing the adhesive layer in the laminate according to [8] and bonding the two or more adherends.
  • the present invention provides excellent adhesive strength for firmly adhering adherends to each other, and the bonded body bonded using the adhesive composition, adhesive layer, or adhesive sheet of the present invention can be easily bonded by a small stimulus when desired. It is possible to obtain an adhesive composition, an adhesive layer, and an adhesive sheet that can be disassembled into pieces and have excellent disassembly properties. Furthermore, the present invention provides a method for manufacturing a bonded body and a method for dismantling a bonded body, both of which have excellent adhesive strength and ease of dismantling.
  • FIG. 1 is a schematic cross-sectional view showing an adhesive sheet according to an embodiment of the present invention.
  • FIG. 2 is a schematic cross-sectional view showing an adhesive sheet according to another embodiment of the present invention.
  • FIG. 3 is a schematic cross-sectional view showing a joined body joined by an adhesive sheet according to an embodiment of the present invention.
  • FIG. 4 is an explanatory diagram schematically showing a method for measuring shear adhesive strength.
  • adheresiveness is a property that has both tackiness and adhesiveness. More specifically, “adhesiveness” refers to a property that can initially develop adhesive properties over time, and can develop adhesive properties after curing (reaction).
  • Adhesion refers to the ability of two surfaces to be temporarily joined by external pressure sensitivity (microscopic pressure) based on the cohesive force based on the chemical structure of the composition, and to be able to be peeled off if necessary.
  • Adhesion refers to the chemical reaction (curing) of the composition to produce a cured product, which allows two surfaces to be firmly joined.
  • main component refers to a component contained in an amount exceeding 50% by mass, unless otherwise specified.
  • percentages based on mass and the like are synonymous with percentages and the like based on weight.
  • An adhesive composition according to an embodiment of the present invention is an adhesive composition containing a polyfunctional epoxy resin, a monofunctional epoxy compound, and a thermoplastic resin, wherein the polyfunctional epoxy resin and the monofunctional epoxy compound
  • the content of the monofunctional epoxy compound in the total amount of is 20 to 50% by mass
  • the content of the thermoplastic resin in the adhesive composition is 20 to 60% by mass of the total resin components.
  • the adhesive composition according to the embodiment of the present invention contains a polyfunctional epoxy resin and a monofunctional epoxy compound, and by setting the content of the monofunctional epoxy compound within a specific range, By adjusting the crosslink density, it is possible to easily disassemble it by stimulation such as heating.
  • an adhesive composition according to another embodiment of the present invention is an adhesive composition forming an adhesive layer, and wherein the adhesive layer formed by the adhesive composition is subjected to tensile storage at 200°C.
  • the elastic modulus is 5 MPa or less, and the shear adhesive strength to the steel plate is 15 MPa or more.
  • the adhesive composition according to another embodiment of the present invention can be heated or It is easily disassembled by stimulation, and has the effect of suppressing the decline in adhesive strength.
  • the adhesive composition according to the embodiment of the present invention contains a polyfunctional epoxy resin and a monofunctional epoxy compound, and the content ratio of the monofunctional epoxy compound in the total amount of the polyfunctional epoxy resin and the monofunctional epoxy compound is 20%. ⁇ 50% by mass.
  • an epoxy resin is formed from a polyfunctional epoxy resin and a monofunctional epoxy compound.
  • a mixture of a polyfunctional epoxy resin and a monofunctional epoxy compound may be simply referred to as an epoxy resin.
  • the content of the monofunctional epoxy compound in the total amount of the polyfunctional epoxy resin and the monofunctional epoxy compound is less than 20% by mass. It becomes difficult to demonstrate disassembly properties, and if it exceeds 50% by mass, the adhesive strength will decrease.
  • the adhesive composition according to the embodiment of the present invention by containing a specific amount of a monofunctional epoxy compound, the epoxy resin obtained by the crosslinking reaction with the polyfunctional epoxy resin when the adhesive composition is cured is improved. The crosslinking density is reduced, resulting in improved disassembly.
  • the polyfunctional epoxy resin may be any compound having two or more epoxy groups in one molecule, such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, hydrogenated bisphenol A type.
  • Bisphenol-based epoxy resins such as epoxy resins, such as naphthalene-type epoxy resins, e.g., biphenyl-type epoxy resins, e.g., dicyclo-type epoxy resins, e.g., alicyclic-based epoxy resins, e.g., triglycidyl isocyanurate epoxy resins, e.g.
  • hydantoin epoxy resins include glycidyl ether epoxy resins, such as glycidylamino epoxy resins.
  • the polyfunctional epoxy resin is preferably a bisphenol epoxy resin, more preferably a bisphenol A epoxy resin.
  • Polyfunctional epoxy resins can be used alone or in combination of two or more.
  • the content of the polyfunctional epoxy resin in the solid content of the adhesive composition is preferably 15 to 80% by mass, more preferably 25 to 72% by mass.
  • the monofunctional epoxy compound may be any compound having one epoxy group in one molecule, such as 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, 2-phenylphenol glycidyl ether, N-glycidyl phthalimide, p-isopropyl Examples include phenyl glycidyl ether, p-sec-butylphenyl glycidyl ether, phenol (EO) 5 glycidyl ether, p-tert-butylphenyl glycidyl ether, and lauryl alcohol (EO) 15 glycidyl ether.
  • the monofunctional epoxy compound preferably has a cyclic skeleton such as an aromatic type from the viewpoint of suppressing a decrease in heat resistance, such as phenylglycidyl ether, 2-phenylphenol glycidyl ether, N-glycidyl phthalimide, p-isopropylphenylglycidyl.
  • a cyclic skeleton such as an aromatic type from the viewpoint of suppressing a decrease in heat resistance, such as phenylglycidyl ether, 2-phenylphenol glycidyl ether, N-glycidyl phthalimide, p-isopropylphenylglycidyl.
  • Examples include ether, p-sec-butylphenyl glycidyl ether, p-tert-butylphenyl glycidyl ether, and the like.
  • Monofunctional epoxy compounds can be used alone or in combination of two or more.
  • the content of the monofunctional epoxy compound in the solid content of the adhesive composition is preferably 6 to 50% by mass, more preferably 10 to 45% by mass.
  • the content of the monofunctional epoxy compound in the total amount of the polyfunctional epoxy resin and the monofunctional epoxy compound must be 20 to 50% by mass, preferably 25 to 45% by mass, and more preferably 30 to 40% by mass. preferable.
  • the blending ratio of the polyfunctional epoxy resin and the monofunctional epoxy compound is within the above range, it is possible to obtain an adhesive layer that has both adhesive strength and disassembly properties.
  • the content of epoxy resin in the solid content of the adhesive composition is preferably 30 99% by mass, more preferably 50 to 90% by mass.
  • the adhesive composition according to the embodiment of the present invention contains a thermoplastic resin, and the content of the thermoplastic resin is 20 to 60% by mass of the total resin components in the adhesive composition. If the content of the thermoplastic resin is less than 20% by mass of the total resin components, the effect of suppressing a decrease in adhesive strength cannot be obtained. Further, if the content of the thermoplastic resin exceeds 60% by mass of the total resin components, sufficient adhesive strength cannot be obtained.
  • the content of the thermoplastic resin is preferably 25 to 55% by mass, more preferably 30 to 50% by mass.
  • thermoplastic resins include natural rubber, butyl rubber, isoprene rubber, chloroprene rubber, acrylic resin, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-acrylic acid ester copolymer, polybutadiene resin,
  • examples include polycarbonate resins, thermoplastic polyimide resins, polyamide resins such as polyamide 6 and polyamide 6,6, phenoxy resins, vinyl butyral resins, saturated polyester resins such as PET and PBT, polyamideimide resins, and fluororesins.
  • the thermoplastic resin is preferably selected from the group consisting of phenoxy resin, acrylic resin, and polyvinyl butyral resin from the viewpoint of compatibility with epoxy resin.
  • the above thermoplastic resins may be used alone or in combination of two or more.
  • the thermoplastic resin preferably has a number average molecular weight (Mn) of 10,000 or more, more preferably 10,000 to 200,000, 12, More preferably 000 to 150,000.
  • thermoplastic resins may be used.
  • commercially available phenoxy resins include “jER1256”, “jER1256B40", “jER4250” (manufactured by Mitsubishi Chemical Corporation), “YP-50S”, and “YP-50”.
  • YP-70 "FX-316” (manufactured by Nippon Steel Chemical & Materials), “PKHH” (manufactured by Huntsman Co., Ltd.), etc.
  • acrylic resins include “Nanostrength M-22" and “Nanostrength M-22N”. ", “Nanostrength M-65N” (manufactured by Arkema), etc.
  • a curing agent may be added to the adhesive composition according to the embodiment of the present invention.
  • the curing agent is a component that reacts with the epoxy resin contained in the adhesive composition to harden the adhesive.
  • a curing agent may be added to the adhesive composition. This improves the cohesive force of the adhesive layer and the adhesive force between the adhesive layer and the adherend, making it easier to form an adhesive layer with excellent adhesive force.
  • the curing agent may be a thermosetting or photocuring curing agent, preferably a thermosetting curing agent. Further, it may be a nitrogen-containing curing agent that contains a nitrogen atom and reacts with an epoxy group. Examples include amine compounds such as tetramethylguanidine, imidazole compounds or derivatives thereof, carboxylic acid hydrazides, aromatic amines, aliphatic amines, dicyandiamide, and derivatives thereof.
  • imidazole compounds include methylimidazole, 2-ethyl-4-methylimidazole, 1-isobutyl-2-methylimidazole (IBMI12), 1-benzyl-2-methylimidazole (1B2MZ), and 1,2-dimethylimidazole ( 1,2DMZ), 1-butylimidazole (1BZ), 1-decyl-2-methylimidazole (1D2MZ), 1-octylimidazole (1OZ), 2-ethyl-4-methylimidazole, ethylimidazole, isopropylimidazole, 2, 4-dimethylimidazole (2E4MZ), 1-phenylimidazole (1PZ), undecylimidazole, heptadecylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4 -Methyl-5-hydroxymethylimidazole and the
  • amine compound examples include ethylene diamine, propylene diamine, diethylene triamine, triethylene tetramine, amine adducts thereof, metaphenylene diamine, diaminodiphenylmethane, and diaminodiphenyl sulfone.
  • epoxy resin curing agents include dicyandiamide, 3-methyl-1,2,3,6-tetrahydrophthalic anhydride, 4-methyl-1,2,3,6-tetrahydrophthalic anhydride, diethylenetriamine, triethylene Examples include tetramine.
  • the curing agent can be used alone or in combination of two or more.
  • the blending ratio of the curing agent is preferably blended in consideration of chemical equivalence with respect to the epoxy groups of the epoxy resin, and may be adjusted as appropriate within a range that can cure the epoxy resin.
  • the blending ratio of the curing agent is, for example, 3 to 15 parts by weight with respect to 100 parts by weight of an epoxy resin having an epoxy equivalent of 190.
  • the curing agent is of a catalytic polymerization type such as an imidazole compound
  • the blending ratio may be adjusted as appropriate, regardless of the chemical equivalence, within a range that can cure the epoxy resin.
  • the amount is, for example, 0.05 parts by mass or more, preferably 0.15 parts by mass or more, and is, for example, 10 parts by mass or less, preferably 5 parts by mass or less, per 100 parts by mass of the epoxy resin.
  • a curing accelerator may be added to the adhesive composition according to the embodiment of the present invention.
  • imidazole compounds for example, imidazole compounds, tertiary amine compounds, phosphine compounds, urea compounds, etc. can be used.
  • imidazole-based compounds various grades are on the market, for example, in the "Curezol” series from Shikoku Kasei Kogyo Co., Ltd.
  • Curezol 2MZA-PW manufactured by Shikoku Kasei Kogyo Co., Ltd.
  • Curesol 2PHZ-PW manufactured by Shikoku Kasei Kogyo Co., Ltd.
  • Curezol 2MA-OK manufactured by Shikoku Kasei Kogyo Co., Ltd.
  • urea-based compounds examples include Omicure U-52 (manufactured by CVC Thermoset Specialties) and 3-(3,4-dichlorophenyl)-1,1-dimethylurea (DCMU) (manufactured by Hodogaya Chemical Industry Co., Ltd.). It will be done.
  • the curing accelerator can be used alone or in combination of two or more.
  • the blending ratio of the curing accelerator can be appropriately selected depending on the type of curing agent and curing accelerator.
  • the adhesive layer (adhesive composition) according to the embodiment of the present invention may contain thermally expandable particles.
  • thermally expandable particles include inorganic expansion agents.
  • an inorganic expanding agent When an inorganic expanding agent is contained, by stimulating the adhesive layer, the inorganic expanding agent in the adhesive layer is expanded at a desired timing, destroying the adhesive layer and reducing the adhesive strength, thereby creating a bonded product. can be dismantled.
  • the type of stimulation is not particularly limited, and examples include stimulations such as heat, electricity, light, and chemical reactions, with heat being preferred. When disassembling the conjugate by thermal stimulation, heating is preferred.
  • the means for heating is not particularly limited, and examples include heating using a heating oven and electromagnetic induction heating.
  • the heating temperature is preferably 130°C or higher, more preferably 150°C or higher, and even more preferably 180°C or higher. Further, from the viewpoint of disassembling the adherend without deforming or altering its quality, the temperature is preferably 400°C or lower, more preferably 370°C or lower, and even more preferably 350°C or lower.
  • inorganic expanding agent examples include expanded graphite, vermiculite, silicates, vermelundite, aluminum phosphate, tanmagite, and hydrosultite, with expanded graphite being preferred.
  • the inorganic swelling agent may be used alone or in combination of two or more.
  • Expanded graphite is produced by treating natural graphite, pyrolytic graphite, quiche graphite, etc. with sulfuric acid, sodium nitrate, potassium permanganate, oxalic acid, halides, etc. to form intercalation compounds between the layers of graphite. .
  • sulfuric acid sodium nitrate, potassium permanganate, oxalic acid, halides, etc.
  • gas is generated from the intercalation compound, thereby expanding the graphite interlayers in a direction perpendicular to the carbon plane.
  • the adhesive layer according to the embodiment of the present invention contains an inorganic expansion agent, when heat is applied to the bonded body formed using the adhesive sheet, the inorganic expansion agent expands and easily destroys the adhesive layer. However, the bonded body can be dismantled without damaging the adherend.
  • the average particle size of the expanded graphite particles before expansion is preferably 0.1 to 400 ⁇ m, more preferably 10 to 200 ⁇ m. If the particle size is 0.1 ⁇ m or more, the degree of expansion is excellent, and if the particle size is 400 ⁇ m or less, the influence of decrease in adhesive strength is small.
  • the expansion start temperature is preferably 130 to 400°C, more preferably 180 to 350°C, in view of the temperature at which the adhesive layer is formed by the adhesive composition, and the relationship between heat resistance and durability during use of the joined body and disassembly. It is.
  • the adhesive layer may contain an expansion aid if necessary.
  • the amount of inorganic swelling agent used varies depending on its type, but it is 1% by mass or more based on the resin component contained in the adhesive composition from the viewpoint of facilitating cohesive failure and interfacial failure of the adhesive layer. It is preferably at least 2% by mass, more preferably at least 5% by mass. Further, from the viewpoint of workability of the adhesive, the content is preferably 40% by mass or less, more preferably 35% by mass or less, and even more preferably 30% by mass or less.
  • the thermally expandable particles include substances that easily gasify and expand when heated, such as isobutane, propane, and pentane, in a shell (inside the outer shell) made of an elastic outer shell material. Encapsulated microcapsules can also be used.
  • Examples of the outer shell material (material forming the outer shell) of the microcapsules used in the present invention include vinylidene chloride-acrylonitrile copolymer, polyvinyl alcohol, polyvinyl butyral, polymethyl methacrylate, polyacrylonitrile, polyvinylidene chloride, and polysulfone. Can be mentioned. Microcapsules can be produced by conventional methods such as coacervation and interfacial polymerization.
  • the glass transition temperature (Tg) of the outer shell material of the microcapsules is preferably 92°C or higher, more preferably 92 to 200°C, and even more preferably 93 to 180°C.
  • microcapsules Commercially available products can also be used as the above microcapsules.
  • Commercial products of such microcapsules are not particularly limited, and for example, the product names are "Matsumoto Microsphere F-80S” (expansion start temperature: 140 to 150°C), “Matsumoto Microsphere F-190D” (expansion start temperature: : 160-170°C), “Matsumoto Microsphere F-230D” (expansion start temperature: 180-190°C), “Matsumoto Microsphere F-260D” (expansion start temperature: 190-200°C) (all of the above, Matsumoto Yushi Pharmaceutical Co., Ltd.
  • the average particle size of the microcapsules is generally about 1 to 80 ⁇ m, preferably about 3 to 50 ⁇ m, from the viewpoint of dispersibility and thin layer formation.
  • the descriptions regarding the above-mentioned inorganic expansion agent can be used as is.
  • the adhesive composition may contain appropriate additives depending on the use of the adhesive sheet.
  • additives include, for example, tackifiers (for example, rosin derivative resins, polyterpene resins, petroleum resins, oil-soluble phenolic resins, etc. that are solid, semi-solid, or liquid at room temperature), leveling agents, and crosslinking agents. , crosslinking aids, plasticizers, softeners, antistatic agents, ultraviolet absorbers, fillers, antiaging agents, antioxidants, light stabilizers, colorants (pigments, dyes, etc.), foaming agents, adhesive compositions Examples include compositions other than the above. Regarding such various additives, conventionally known ones can be used in a conventional manner, and since they do not particularly characterize the present invention, detailed explanations will be omitted.
  • the method for preparing the adhesive composition is not particularly limited, and for example, it can be obtained by preparing a liquid composition containing each component and a solvent and using a rotation-revolution stirrer. Another method for preparing the adhesive composition is to heat and knead each component using a kneader such as a twin-screw kneader or a kneader.
  • a kneader such as a twin-screw kneader or a kneader.
  • the adhesive composition can form an adhesive layer, and the adhesive layer may be formed into a sheet shape.
  • the adhesive layer according to the embodiment of the present invention is formed from the adhesive composition according to the embodiment of the present invention.
  • the adhesive layer according to the embodiment of the present invention may be made of the adhesive composition according to the embodiment of the present invention.
  • the adhesive layer may be a sheet-like layer.
  • the adhesive sheet according to the embodiment of the present invention includes an adhesive layer.
  • the adhesive sheet according to the embodiment of the present invention further includes a supporting base material, and the adhesive layer is provided on at least one surface of the supporting base material, and the supporting base material may be a film-like base material. good.
  • the adhesive layer may be formed by applying an adhesive composition onto the base material, drying it, and removing the solvent.
  • the resin contained in the adhesive layer corresponds to the resin contained in the adhesive composition forming the adhesive layer
  • the resin contained in the adhesive composition forming the adhesive layer corresponds to the functional group such as a crosslinkable group contained in the resin contained in the adhesive composition forming the adhesive layer. At least a portion of the group may be crosslinked.
  • a conventional coater such as a gravure roll coater, reverse roll coater, kiss roll coater, dip roll coater, bar coater, knife coater, or spray coater is used. It can be implemented by In the adhesive sheet having a support base material described below, the adhesive layer is provided on the support base material using a direct method in which an adhesive composition is directly applied to the support base material to form an adhesive layer. Alternatively, a transfer method may be used in which the adhesive layer formed on the release surface is transferred to the base material.
  • the adhesive layer may be obtained by forming the adhesive composition into a sheet shape by compressing and stretching the adhesive composition by calender molding, extrusion molding, press molding, or the like.
  • the adhesive layer according to the embodiment of the present invention can be strongly bonded to an adherend by curing it after being applied to the adherend, and can connect two or more adherends with the adhesive layer (not an adhesive sheet). ) may be used to form a bonded body.
  • the thickness of the adhesive layer is not particularly limited, and is, for example, 1 ⁇ m or more, preferably 5 ⁇ m or more, more preferably 10 ⁇ m or more, and, for example, 3000 ⁇ m or less, preferably 1000 ⁇ m or less, more preferably 500 ⁇ m. It is as follows.
  • FIG. 1 is a schematic cross-sectional view showing an adhesive sheet according to an embodiment of the present invention.
  • the adhesive sheet 100 according to this embodiment may consist of only the adhesive layer 11.
  • FIG. 1 shows an adhesive layer having a single layer structure, the adhesive layer may have a multilayer structure of two or more layers.
  • the adhesive sheet of this embodiment may include a support base material as shown in FIG. 2. Further, the adhesive sheet of this embodiment may include an adhesive layer other than the adhesive layer 11 or an adhesive layer. There are no particular restrictions on the adhesive layer or the adhesive layer other than the adhesive layer 11, and known ones can be used depending on the purpose of the adhesive sheet, the material of the adherend, etc.
  • FIG. 3 is a schematic cross-sectional view showing a joined body joined by an adhesive sheet according to an embodiment of the present invention.
  • the bonded body bonded by the adhesive sheet according to the embodiment of the present invention has a first member 14 and a second member 15 bonded together as adherends through an adhesive layer 11.
  • the conjugated body 200 may also be the same.
  • An adhesive sheet according to an embodiment of the present invention includes the adhesive layer described above.
  • the adhesive sheet of this embodiment may be a sheet with a supporting base material having an adhesive layer on one side (FIG. 2) or both sides of a sheet-like base material (supporting base material), and the adhesive layer is a release sheet. It may also be an adhesive sheet without a base material, such as in a form in which it is held in place.
  • the concept of adhesive sheet here may include what is called an adhesive tape, an adhesive label, an adhesive film, and the like.
  • the adhesive layer is typically formed continuously, it is not limited to this form; for example, the adhesive layer may be formed in a regular or random pattern such as dots or stripes. It may be. Further, the adhesive sheet of this embodiment may be in the form of a roll or a sheet. Alternatively, the adhesive sheet may be further processed into various shapes.
  • the adhesive layer formed from the adhesive composition has a tensile storage modulus at 200° C. of 5 MPa or less.
  • the tensile storage modulus is preferably 0.01 to 5 MPa, more preferably 0.05 to 3 MPa, and even more preferably 0.1 to 1 MPa.
  • the tensile storage modulus can be adjusted by the crosslinking density of the epoxy resin.
  • the above tensile storage modulus is calculated by applying a liquid composition containing an adhesive composition and a solvent to a release-treated film, removing the solvent, and forming the film into a sheet with a thickness of 50 ⁇ m.
  • a cured resin is obtained by storing in a heating oven at 130°C for 60 minutes, or by injecting the adhesive composition into a silicone mold to a thickness of 50 ⁇ m and storing in a heating oven at 130°C for 60 minutes. .
  • the thus obtained cured resin was cut out into a piece 5 mm wide x 50 mm long, and measured using a dynamic viscoelasticity measurement device (device name "RSA-G2", manufactured by TA Instruments) with a gap distance of 20 mm.
  • RSA-G2 dynamic viscoelasticity measurement device
  • shear adhesive strength of the adhesive layer formed by the adhesive composition to the steel plate is 15 MPa or more.
  • the shear adhesive strength is more preferably 17 MPa or more, and even more preferably 20 MPa or more.
  • the shear adhesive strength can be adjusted by adjusting the crosslinking density of the epoxy resin, the amount of the thermoplastic resin, etc.
  • the shear adhesive strength is measured at a temperature below the glass transition temperature of the adhesive composition in accordance with JIS K 6850. Specifically, it is a value measured by the method described in Examples.
  • the adhesive sheet of this embodiment may include a support base material as shown in FIG. 2. That is, the adhesive sheet of this embodiment may further include a supporting base material, and the above-mentioned adhesive layer may be provided on at least one surface of the supporting base material. Thereby, the adhesive sheet can be processed with high precision by punching or the like. Such an adhesive sheet is also preferable for applications in which it is processed into a specific shape or made narrower.
  • the thickness of the support base material in this embodiment is preferably 100 ⁇ m or less, more preferably 80 ⁇ m or less, even more preferably 70 ⁇ m or less, even more preferably 50 ⁇ m or less, particularly preferably 30 ⁇ m or less.
  • the thickness of the support substrate may be 20 ⁇ m or less, 12 ⁇ m or less, 7 ⁇ m or less, or 3 ⁇ m or less.
  • the lower limit of the thickness of the supporting base material is not particularly limited. From the viewpoint of handleability and processability of the adhesive sheet, the thickness of the supporting base material is usually 0.5 ⁇ m or more (for example, 1 ⁇ m or more). In one embodiment, the thickness of the supporting base material may be 3 ⁇ m or more. In another embodiment, the thickness of the supporting base material can be 8 ⁇ m or more, 13 ⁇ m or more, or 16 ⁇ m or more.
  • the structure and material of the supporting base material are not particularly limited, and are typically film-like base materials (also referred to as "base film").
  • base film a base film containing a resin film can be preferably used.
  • the base film is typically an independently shape-maintainable (independent) member.
  • the base film in this embodiment may be substantially composed of such a base film.
  • the base film may include an auxiliary layer in addition to the base film. Examples of the auxiliary layer include a colored layer, a reflective layer, an undercoat layer, an antistatic layer, etc. provided on the surface of the base film.
  • the base film may be a porous film.
  • the porous film is not particularly limited as long as it has a plurality of holes in the film (as long as the holes are formed), and examples thereof include foamed films, nonwoven fabrics, and the like.
  • the adhesive sheet according to the embodiment of the present invention preferably has a space in the adhesive sheet in which thermally expandable particles such as an inorganic expansion agent expand. Therefore, if the base film is a porous film, when thermally expandable particles such as an inorganic expanding agent expand, the pores (spaces) of the porous film facilitate the expansion of the expanding agent, making it easier to use. The zygote can be disassembled.
  • the resin film is a film whose main component is a resin material (for example, a component contained in the resin film in an amount exceeding 50% by mass).
  • resin films include polyolefin resin films such as polyethylene (PE), polypropylene (PP), and ethylene-propylene copolymers; polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), etc.
  • the resin film may be a rubber film such as a natural rubber film or a butyl rubber film. Among these, polyester films are preferred from the viewpoint of handling and processability, and among these, PET films are particularly preferred.
  • the adhesive composition, adhesive layer, and adhesive sheet according to the embodiments of the present invention are suitable for fixing and joining metal parts, resin parts, and metal/resin composite parts used in boats, aircraft, automobiles, etc. .
  • automobile batteries, bodies, motors, etc. must be collected separately due to environmental issues, and may require dismantling.
  • the adhesive composition, adhesive layer, and adhesive sheet according to the embodiments of the present invention have excellent processing accuracy, they can be used in applications where they can be processed into a specific shape or narrowed in width, such as mobile phones.
  • Suitable for fixing and joining members in electronic devices Electronic devices such as such portable electronic devices may need to be dismantled for purposes such as separate collection, repair/replacement of components, and productivity improvement through temporary adhesion during the manufacturing process.
  • the adhesive sheet according to the embodiment of the present invention can be used for joining various adherends.
  • the adhesive sheet according to the embodiment of the present invention can easily destroy the adhesive layer by stimulation such as heating, and the bonded body can be disassembled without damaging the adherend. It can be suitably used for bonding adherends together or temporarily fixing members.
  • the adhesive composition, adhesive layer, and adhesive sheet according to the embodiments of the present invention can be used in a laminate, a bonded body, and a method for manufacturing a bonded body.
  • the laminate according to the embodiment of the present invention is a laminate in which two or more adherends are attached using the adhesive composition, adhesive layer, or adhesive sheet according to the embodiment of the present invention.
  • the bonded body according to the embodiment of the present invention is a bonded body in which two or more adherends are bonded using the adhesive composition, adhesive layer, or adhesive sheet according to the embodiment of the present invention, It is preferable that the above-mentioned adherend is a joined body joined using the adhesive sheet according to the embodiment of the present invention.
  • the adhesive sheet may be a sheet consisting only of an adhesive layer without a base material, or a sheet consisting of only an adhesive layer without a base material, or a sheet consisting of only an adhesive layer without a base material, or a sheet consisting of only an adhesive layer without a base material.
  • the sheet is a sheet provided with the adhesive layer, or a sheet provided with the adhesive layer on one side of a supporting base material and another pressure-sensitive adhesive layer or an adhesive layer on the other side. That is, in the laminates and bonded bodies according to the embodiments of the present invention, a supporting base material, an adhesive layer other than the adhesive layer, an adhesive layer, etc. are provided between the adherend and the adhesive layer. May exist.
  • the bonded body according to the embodiment of the present invention preferably has a space in the adhesive layer or adhesive sheet in which thermally expandable particles such as an inorganic expansion agent expand.
  • the space in the adhesive layer or adhesive sheet in which the inorganic expansion agent expands is not particularly limited, but may include, for example, voids in the supporting base material.
  • the adhesive sheet has a supporting base material, and the supporting base material is, for example, a porous film, when the inorganic expanding agent expands, the pores (spaces) of the porous film facilitate the expansion of the expanding agent, The joined body can be disassembled more easily.
  • the method for manufacturing a bonded body according to an embodiment of the present invention includes a joining step of curing the adhesive layer in the laminate according to an embodiment of the present invention and joining the two or more adherends.
  • a method for disassembling a bonded body according to an embodiment of the present invention is a method for disassembling a bonded body according to an embodiment of the present invention, wherein the bonded body is dismantled by applying stimulation to the adhesive layer in the bonded body. This includes the dismantling process.
  • the adhesive composition the adhesive layer, the adhesive sheet, and the adherend in the laminate, bonded body, method of manufacturing the bonded body, and method of disassembling the bonded body according to the embodiments of the present invention, the above explanations will be followed. It can be used as is.
  • an adhesive layer, and an adhesive sheet configured in this way, for example, an adhesive sheet is placed between a first member and a second member, which are adherends.
  • both can be attached to obtain a laminate.
  • the first member and the second member are joined via the adhesive sheet (which may be an adhesive layer) by curing the adhesive layer of the laminate attached using the adhesive sheet.
  • a zygote is obtained.
  • the inorganic expansion agent in the adhesive layer expands, destroying the adhesive layer in the bonded object, and disassembling the bonded object without damaging the adherend. , the first member and the second member can be separated.
  • the materials of the first member and second member constituting the adherend and laminate are not particularly limited, but examples include copper, silver, gold, iron, tin, palladium, aluminum, and nickel. , titanium, chromium, zinc, etc., or alloys containing two or more of these; for example, polyimide resins, acrylic resins, polyether nitrile resins, polyether sulfone resins, polyester resins (polyethylene terephthalate, etc.); resins, polyethylene naphthalate resins, etc.), polyvinyl chloride resins, polyphenylene sulfide resins, polyether ether ketone resins, polyamide resins (so-called aramid resins, etc.), polyarylate resins, polycarbonate resins, liquid crystal polymers Examples include various resin materials such as (typically plastic materials), and inorganic materials such as alumina, zirconia, soda glass, quartz glass, and carbon.
  • the adherend may have a single-layer structure or a multi
  • An adhesive composition containing a polyfunctional epoxy resin, a monofunctional epoxy compound, and a thermoplastic resin, wherein the content ratio of the monofunctional epoxy compound in the total amount of the polyfunctional epoxy resin and the monofunctional epoxy compound is 20 to 50% by mass, and the content of the thermoplastic resin in the adhesive composition is 20 to 60% by mass based on the total resin components.
  • An adhesive composition forming an adhesive layer, wherein the adhesive layer formed by the adhesive composition has a tensile storage modulus of 5 MPa or less at 200°C and a shear adhesive strength to a steel plate of 15 MPa or more.
  • An adhesive composition [3] The adhesive composition according to [1] or [2], further comprising thermally expandable particles.
  • thermoplastic resin has a number average molecular weight (Mn) of 10,000 or more.
  • An adhesive layer formed from the adhesive composition according to any one of [1] to [4].
  • An adhesive sheet comprising the adhesive layer according to [5].
  • the adhesive sheet according to [6] further comprising a supporting base material, the adhesive layer being provided on at least one surface of the supporting base material, and the supporting base material being a film-like base material.
  • the two or more adherends are the adhesive composition according to any one of [1] to [4], the adhesive layer according to [5], or the adhesive sheet according to [6] or [7]. A laminate attached using.
  • a method for manufacturing a bonded body comprising a bonding step of curing the adhesive layer in the laminate according to [8] and bonding the two or more adherends.
  • the method for disassembling a bonded body according to [9] which includes a disassembling step of disassembling the bonded body by applying stimulation to the adhesive layer in the bonded body.
  • Examples 1, 2, 4-10, Comparative Examples 4-6 An adhesive composition was prepared by blending each component in the amounts shown in Table 1, dissolving it with methyl ethyl ketone (MEK) as a solvent, and mixing at 23 ° C. for 15 minutes using a rotation-revolution stirrer.
  • MEK methyl ethyl ketone
  • the adhesive composition was applied to a release-treated polyethylene terephthalate film (Diafoil MRF #38 manufactured by Mitsubishi Chemical Corporation) using a bar coater, and then heated (dried) at 80° C. for 5 minutes in a heating oven. After removing the solvent, it was molded into a sheet having a thickness of 50 ⁇ m to form an adhesive layer. Thereafter, the adhesive layer was brought into contact with another polyethylene terephthalate film (Diafoil MRE #38 manufactured by Mitsubishi Chemical Corporation) such that the adhesive layer was sandwiched between the two polyethylene terephthalate films to obtain an adhesive sheet.
  • a release-treated polyethylene terephthalate film (Diafoil MRF #38 manufactured by Mitsubishi Chemical Corporation) using a bar coater, and then heated (dried) at 80° C. for 5 minutes in a heating oven. After removing the solvent, it was molded into a sheet having a thickness of 50 ⁇ m to form an adhesive layer. Thereafter, the adhesive layer was brought into contact with another polyethylene
  • Shear adhesive strength (adhesion evaluation) The shear adhesive strength was measured at 23°C in accordance with JIS K 6850. First, the adhesive sheet is cut into a size of 25 mm width x 10 mm length, and then, as shown in Figure 4, one polyethylene terephthalate film (Diafoil MRE #38 manufactured by Mitsubishi Chemical Corporation) is peeled off to expose the adhesive layer. The tip of an SPCC-SD steel plate 61 having a width of 25 mm, a length of 100 mm, and a thickness of 2 mm was placed on one side 50A of the steel plate 50. Then, the other polyethylene terephthalate film was peeled off.
  • SPCC-SD steel plate 61 having a width of 25 mm, a length of 100 mm, and a thickness of 2 mm was placed on one side 50A of the steel plate 50. Then, the other polyethylene terephthalate film was peeled off.
  • the adhesive sheet was cured by storing it in a heating oven at 130° C. for 60 minutes.
  • the cured resin thus obtained was cut into a piece measuring 5 mm in width and 50 mm in length. This was measured using a dynamic viscoelasticity measuring device (equipment name "RSA-G2", manufactured by TA Instruments) at a frequency of 1Hz and strain from 25°C to 300°C with a gap distance of 20mm and a heating rate of 5°C/min. Dynamic viscoelasticity measurements in tension were carried out at an amount of 0.1%.
  • the tensile storage modulus at 200°C is shown in the table as a disassembly index.
  • Shear adhesive strength (MPa) test force (N) / 250mm 2 If the value of the shear adhesive force obtained at this time has decreased to 1/3 or less compared to the value of the shear adhesive force in the adhesive evaluation, it is considered to be disassembly ⁇ (good), and if there is no decrease was rated as ⁇ (defective).
  • Example 3 Comparative Examples 1-3
  • the adhesive composition is prepared by mixing a curing agent and a curing accelerator at 80°C. I prepared something.
  • a cured resin was obtained by injecting the adhesive composition into a silicone mold to a thickness of 50 ⁇ m and storing it in a heating oven at 130° C. for 60 minutes.
  • the cured resin thus obtained was cut into a piece measuring 5 mm in width and 50 mm in length. This was measured using a dynamic viscoelasticity measuring device (equipment name "RSA-G2", manufactured by TA Instruments) at a frequency of 1Hz and strain from 25°C to 300°C with a gap distance of 20mm and a heating rate of 5°C/min. Dynamic viscoelasticity measurements were carried out at an amount of 0.1%.
  • the tensile storage modulus at 200°C is shown in the table as a disassembly index.
  • Table 1 Examples and comparative examples are shown in Table 1 below.
  • the unit of the blending amounts listed in Table 1 is parts by mass.
  • Phenoxy resin Phenoxy resin: PKHH manufactured by Huntsman Co., Ltd. (Mn13,000 Mw52,000) Acrylic block polymer: M65N Arkema Corporation (Mn108,000 Mw280,000) Acrylic block polymer: M22N Arkema Corporation (Mn77,000 Mw200,000)
  • an adhesive composition forming an adhesive layer and an adhesive sheet having excellent adhesive force and disassembly property, an adhesive layer and an adhesive sheet, and the adhesive composition, adhesive layer or adhesive sheet are used.
  • the present invention can provide a laminate using the adhesive sheet, a bonded body using the adhesive sheet, a method for manufacturing the bonded body, and a method for disassembling the bonded body.
  • Adhesive sheet 11 Adhesive layer 12 Support base material 200 Joined body 14 First member 15 Second member 50 Adhesive layer 50A, 50B Surfaces 61, 62 Steel plate

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

La présente invention concerne une composition adhésive contenant une résine époxy multifonctionnelle, un composé époxy monofonctionnel et une résine thermoplastique, dans laquelle : le rapport de la teneur en composé époxy monofonctionnel par rapport à la quantité totale de résine époxy multifonctionnelle et de composé époxy monofonctionnel est de 20 % en masse à 50 % en masse ; et la teneur en résine thermoplastique dans la composition adhésive est de 20 % en masse à 60 % en masse par rapport à l'ensemble des composants de la résine.
PCT/JP2023/030393 2022-08-24 2023-08-23 Composition adhésive, couche adhésive, feuille adhésive, corps multicouche, corps assemblé, procédé de production de corps assemblé, et procédé de démontage de corps assemblé WO2024043288A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2022133305 2022-08-24
JP2022-133305 2022-08-24

Publications (1)

Publication Number Publication Date
WO2024043288A1 true WO2024043288A1 (fr) 2024-02-29

Family

ID=90013451

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2023/030393 WO2024043288A1 (fr) 2022-08-24 2023-08-23 Composition adhésive, couche adhésive, feuille adhésive, corps multicouche, corps assemblé, procédé de production de corps assemblé, et procédé de démontage de corps assemblé

Country Status (1)

Country Link
WO (1) WO2024043288A1 (fr)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002030266A (ja) * 2000-07-13 2002-01-31 Nitto Denko Corp エポキシ樹脂系液状接着剤組成物およびそれを用いたリペアー方法
JP2006225544A (ja) * 2005-02-18 2006-08-31 Nagase Chemtex Corp エポキシ樹脂接着剤
JP2011114037A (ja) * 2009-11-24 2011-06-09 Hitachi Chem Co Ltd 回路接続材料及び接続体

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002030266A (ja) * 2000-07-13 2002-01-31 Nitto Denko Corp エポキシ樹脂系液状接着剤組成物およびそれを用いたリペアー方法
JP2006225544A (ja) * 2005-02-18 2006-08-31 Nagase Chemtex Corp エポキシ樹脂接着剤
JP2011114037A (ja) * 2009-11-24 2011-06-09 Hitachi Chem Co Ltd 回路接続材料及び接続体

Similar Documents

Publication Publication Date Title
JP5716339B2 (ja) 粘接着シートおよびそれを用いた接着方法
JP5969217B2 (ja) 両面接着テープ
WO2011016315A1 (fr) Feuille de renforcement pour aube d’éolienne, structure de renforcement pour aube d’éolienne, éolienne, et procédé de renforcement d’aube d’éolienne
TW201831321A (zh) 金屬-纖維強化樹脂材料複合體、其製造方法以及接著片
JP5660443B2 (ja) 粘接着シートおよびそれを用いた接着方法
WO2014103040A1 (fr) Composition adhésive et feuille d'assemblage l'utilisant
KR20070112180A (ko) 표면 마무리 및/또는 접합 방법
US20080194163A1 (en) Adhesive Article Comprising Fibrous Webs
JP2013006974A (ja) 接着剤組成物およびそれを用いた接着シート
TWI283637B (en) Resin composition and adhesive agent, laminates using it
JP5540814B2 (ja) 粘接着シート
JP5743211B2 (ja) 接着剤組成物およびそれを用いた接着シート
JP5560746B2 (ja) 粘接着シート
JP5295509B2 (ja) 画像表示装置用補強シート、画像表示装置およびその補強方法
WO2024043288A1 (fr) Composition adhésive, couche adhésive, feuille adhésive, corps multicouche, corps assemblé, procédé de production de corps assemblé, et procédé de démontage de corps assemblé
JP2011054743A (ja) 太陽電池パネル端部用粘着シール材、太陽電池パネルの端部の封止構造、封止方法、太陽電池モジュールおよびその製造方法
KR100609804B1 (ko) 접착제 조성물 및 그의 전구체
JP2007515496A (ja) Ｆｐｃｂの接着法
JP2014070221A (ja) 接着剤組成物およびそれを用いた接着シート
KR101994149B1 (ko) 열융착 접착제 조성물, 열융착 양면 접착 테이프 및 열융착 양면 접착 테이프의 제조 방법 및 열융착 양면 접착 테이프의 사용 방법
JP2006517604A (ja) フレキシブルプリント基板接合のための熱活性化しうる接着剤
JP5560747B2 (ja) 粘接着シート
JP7405832B2 (ja) 硬化型粘接着シート、及び硬化型粘接着シートの製造方法
WO2023176800A1 (fr) Feuille adhésive facilement démontée, stratifié, corps assemblé, procédé de production de corps assemblé, et procédé de démontage de corps assemblé
JP6332764B2 (ja) 接着剤組成物およびそれを用いた接着シート

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: 23857396

Country of ref document: EP

Kind code of ref document: A1