WO2023190322A1 - Feuille adhésive - Google Patents

Feuille adhésive Download PDF

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Publication number
WO2023190322A1
WO2023190322A1 PCT/JP2023/012171 JP2023012171W WO2023190322A1 WO 2023190322 A1 WO2023190322 A1 WO 2023190322A1 JP 2023012171 W JP2023012171 W JP 2023012171W WO 2023190322 A1 WO2023190322 A1 WO 2023190322A1
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WO
WIPO (PCT)
Prior art keywords
adhesive sheet
adhesive
thickness
epoxy resin
measured
Prior art date
Application number
PCT/JP2023/012171
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English (en)
Japanese (ja)
Inventor
弘樹 東島
丹娜 銭
誠司 ▲高▼木
Original Assignee
三菱ケミカル株式会社
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.)
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Application filed by 三菱ケミカル株式会社 filed Critical 三菱ケミカル株式会社
Publication of WO2023190322A1 publication Critical patent/WO2023190322A1/fr

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Classifications

    • 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
    • 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
    • C09J7/35—Heat-activated

Definitions

  • the present invention relates to adhesive sheets, and more particularly to structural adhesive sheets, particularly structural adhesive sheets for joining dissimilar materials useful in the automotive industry.
  • Patent Document 1 proposes an adhesive using glass beads to control the thickness of the bonded body.
  • the present invention provides an adhesive sheet that can ensure adhesive reliability, improve work efficiency, and further achieve both adhesive strength and film thickness maintenance.
  • the present inventors impregnated the support with an adhesive to form a sheet with a specific thickness, and also made the adhesive sheet (more specifically, the inorganic filler in the adhesive sheet) with a specific composition (configuration). It has been found that by doing so, adhesive strength does not decrease while ensuring a constant thickness maintenance rate of the sheet before and after curing when the adhesive sheet is thermally cured and used.
  • thermosetting adhesive sheet formed by impregnating a support with an adhesive, which has a film thickness retention rate of 56% or more and 95% or less according to the following formula (1), and has a film thickness of 200 ⁇ m or more before thermosetting. sheet.
  • Film thickness maintenance rate (%) Tb/Ta ⁇ 100 (1)
  • Ta is the thickness of the adhesive sheet before heat curing measured using a digital thickness gauge
  • Tb is the thickness of the adhesive sheet before heat curing, which is measured using a digital thickness gauge
  • Tb is the thickness of the adhesive sheet that is This is the thickness of the cured adhesive sheet existing between SPCCs as measured using a digital microscope after heating to 150°C under a pressure of 1 MPa and curing by holding for 20 minutes.
  • Ta and Tb are the thicknesses of the adhesive sheet excluding the release film.
  • the adhesive sheet of the present invention is an adhesive sheet with a film thickness of 200 ⁇ m or more obtained by impregnating a support with an adhesive, and has a film thickness retention rate of 56% or more and 95% or less, ensuring adhesive reliability. At the same time, it is possible to improve work efficiency, and it is also possible to achieve both adhesive strength and film thickness maintenance.
  • epoxy resin is generally used as the name of a category of thermosetting resins or as the name of a category of chemical substances, which are compounds having one or more epoxy groups in the molecule. However, in this specification, it is used in the latter sense. Furthermore, in this specification, not only polymers having a specific degree of polymerization but also monomers are included in the definition of epoxy resin as long as they are compounds having one or more epoxy groups in the molecule. In this specification, “molecular weight” means number average molecular weight unless otherwise specified.
  • normal temperature means 25°C
  • solid at room temperature (25°C) means that the softening point is 25°C or higher, or the viscosity at 25°C is 1000 Pa ⁇ s or higher. do.
  • Liquid at room temperature (25°C) means that the softening point is less than 25°C and the viscosity at 25°C is less than 1000 Pa ⁇ s.
  • the adhesive sheet of the present invention is made of an adhesive and a support, and is further made by impregnating the support with a resin composition that is the adhesive.
  • Ta is the thickness of the adhesive sheet before curing as measured using a digital thickness gauge
  • Tb is the thickness of the adhesive sheet sandwiched between cold rolled steel plates (SPCC) at a surface pressure of 1 MPa. This is the thickness of the cured adhesive sheet existing between the SPCCs measured using a digital microscope after heating to 150° C. under pressure and curing by holding for 20 minutes.
  • SPCC cold rolled steel plates
  • Ta is the thickness of the adhesive sheet excluding the release film.
  • an adhesive sheet with a thickness of 200 ⁇ m or more with a film thickness maintenance rate of 56% or more and 95% or less for example, it is necessary to adjust the type, components, viscosity, etc. of the adhesive, or add a spacer such as an inorganic filler.
  • a spacer such as an inorganic filler. Examples include methods such as adding a support, and introducing a support.
  • the resin composition that is the adhesive used in the present invention is characterized by containing a curable resin that reacts and hardens during adhesion.
  • curable resins are not particularly limited as long as they have a film thickness retention rate of 56% or more and 95% or less as measured by the method specified in the present invention, but examples include epoxy resins, second generation acrylic resins, Examples include urethane resin and silicone resin.
  • epoxy resin is preferred from the viewpoint of adhesiveness with different materials, durability, and heat resistance. That is, the resin composition that is the adhesive used in the present invention is preferably an epoxy resin composition containing such an epoxy resin as a main component.
  • the "main component” means the component having the highest content (% by mass) among the components constituting the adhesive (resin composition).
  • the content of the main component in the adhesive (resin composition) is preferably 50% by mass or more, more preferably 70% by mass or more, particularly preferably 80% by mass or more, and most preferably 90% by mass or more.
  • the curable resin is an epoxy resin
  • the epoxy resin composition uses epoxy resin (A) as a curable resin.
  • the epoxy resin (A) preferably contains three components as constituents: bisphenol A epoxy resin (A1), bisphenol F epoxy resin (A2), and rubber-modified epoxy resin (A3).
  • the epoxy resin composition usually further contains a curing agent (B) and an inorganic filler (E), and more preferably contains polymer particles having a core-shell structure (C) and a curing accelerator (D). and may contain other components (G).
  • the epoxy resin (A) contains three components as constituents: bisphenol A epoxy resin (A1), bisphenol F epoxy resin (A2), and rubber modified epoxy resin (A3). It is preferable.
  • Examples of bisphenol A epoxy resins (A1) include commercially available EPON825, jER826, jER827, jER828, jER834, jER1001 (manufactured by Mitsubishi Chemical Corporation), Epicron 850 (manufactured by DIC Corporation), Epototh YD-128 (new Nippon Steel & Sumikin Chemical Co., Ltd.), DER-331, DER-332 (manufactured by Dow Chemical Japan), Bakerite EPR154, Bakerite EPR162, Bakerite EPR172, Bakerite EPR173, Bakelite EPR174 (B akelite AG) etc. Can be mentioned. Among these, jER828 and jER1001 are preferred in terms of the elastic modulus and glass transition temperature of the cured product of the epoxy resin composition.
  • the bisphenol A type epoxy resin (A1) may be used alone or in combination of two or more types.
  • the number average molecular weight of the bisphenol A epoxy resin (A1) is preferably 200 to 100,000, more preferably 200 to 80,000, and even more preferably 200 to 60,000. If the number average molecular weight is too low, the viscosity decreases too much, which tends to reduce workability as an adhesive, while if it is too high, the solubility in other monomers decreases and the viscosity increases too much. Workability tends to decrease.
  • the "number average molecular weight” is a polystyrene equivalent value measured by gel permeation chromatography (GPC) method.
  • the epoxy equivalent of the bisphenol A epoxy resin (A1) is preferably 20,000 or less, more preferably 10,000 or less, still more preferably 6,000 or less. If the epoxy equivalent is too high, the solubility in other monomers tends to decrease, and workability during compounding tends to decrease.
  • the lower limit of the epoxy equivalent is not particularly limited, but is, for example, 50 or more. In this specification, "epoxy equivalent” is a value measured in accordance with JIS-K7236:2001.
  • the softening point of the bisphenol A epoxy resin (A1) is preferably 160°C or lower, more preferably 140°C or lower, still more preferably 120°C or lower. If the softening point is too high, the viscosity at room temperature after compounding increases, which tends to reduce workability as an adhesive.
  • the lower limit of the softening point is not particularly limited, but is, for example, ⁇ 50° C. or higher. In this specification, the "softening point" is a value measured in accordance with JIS-K7234:2008 (ring and ball method).
  • the bisphenol F type epoxy resin (A2) for example, commercially available products jER806, jER807, jER4005P, jER4007P, jER4010P, jER1750 (manufactured by Mitsubishi Chemical Corporation), Epiclon 830 (manufactured by DIC Corporation), Epotote YD-170, Epotote Examples include YD-175 (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), Bakerite EPR169 (manufactured by Bakerite AG), GY281, GY282, and GY285 (manufactured by Huntsman Advanced Materials).
  • jER806, jER807, and jER4005P are preferred because they have excellent adhesion after curing of the epoxy resin composition.
  • the bisphenol F type epoxy resin (A2) may be used alone, or two or more types may be used in combination.
  • the number average molecular weight of the bisphenol F type epoxy resin (A2) is preferably 200 to 100,000, more preferably 200 to 80,000, and still more preferably 200 to 60,000. If the number average molecular weight is too low, the viscosity decreases too much, which tends to reduce workability as an adhesive, while if it is too high, the solubility in other monomers decreases and the viscosity increases too much. Workability tends to decrease.
  • the epoxy equivalent of the bisphenol F type epoxy resin (A2) is preferably 20,000 or less, more preferably 10,000 or less, still more preferably 6,000 or less. If the epoxy equivalent is too high, the solubility in other monomers tends to decrease, and workability during compounding tends to decrease.
  • the lower limit of the epoxy equivalent is not particularly limited, but is, for example, 50 or more.
  • the softening point of the bisphenol F type epoxy resin (A2) is preferably 160°C or lower, more preferably 140°C or lower, still more preferably 120°C or lower. If the softening point is too high, the viscosity at room temperature after compounding increases, which tends to reduce workability as an adhesive.
  • the lower limit of the softening point is not particularly limited, but is, for example, ⁇ 50° C. or higher.
  • a commercially available product containing both bisphenol A type epoxy resin (A1) and bisphenol F type epoxy resin (A2) can also be used.
  • Examples include jER4250 and jER4275 (manufactured by Mitsubishi Chemical Corporation).
  • the rubber-modified epoxy resin (A3) is, for example, an epoxy-terminated adduct of an epoxy resin and at least one non-crosslinked liquid rubber having an epoxide-reactive group (for example, an amino group or a carboxy group).
  • the rubber-modified epoxy resin (A3) may be used alone or in combination of two or more.
  • Epoxy resins used as raw materials for the rubber-modified epoxy resin (A3) are not particularly limited, but include, for example, bisphenol-type epoxy resins, naphthalene-type epoxy resins, biphenyl-type epoxy resins, glycidylamine-type epoxy resins, cyclic epoxy resins, Examples include dicyclopentadiene type epoxy resin, phenol novolac type epoxy resin, ortho-cresol novolac type epoxy resin.
  • the non-crosslinked liquid rubber used as a raw material for the rubber-modified epoxy resin (A3) is preferably a conjugated diene homopolymer or a conjugated diene copolymer, particularly preferably a conjugated diene/nitrile copolymer.
  • the conjugated diene rubber is preferably butadiene or isoprene, particularly preferably butadiene.
  • a preferred nitrile monomer is acrylonitrile and a preferred copolymer is a butadiene-acrylonitrile copolymer.
  • the glass transition temperature (Tg) of such non-crosslinked liquid rubber is preferably 20°C or lower, more preferably 10°C or lower, and still more preferably 0°C or lower.
  • the lower limit of the glass transition temperature is not particularly limited, but is, for example, ⁇ 100° C. or higher.
  • the "glass transition temperature" is expressed by measuring the DSC curve of a sample using a differential scanning calorimeter, and the temperature at the inflection point of the obtained DSC curve.
  • the non-crosslinked liquid rubber preferably has an average of 1.5 to 2.5 epoxide-reactive end groups per molecule, more preferably an average of 1.8 to 2.2.
  • the number average molecular weight of such crosslinked liquid rubber is preferably 500 to 100,000, more preferably 1,000 to 58,000.
  • a carboxy group-terminated butadiene nitrile rubber (CTBN) modified epoxy resin As the rubber-modified epoxy resin (A3), a carboxy group-terminated butadiene nitrile rubber (CTBN) modified epoxy resin, a nitrile butadiene rubber (NBR) modified epoxy resin is preferable, and a carboxyl group-terminated butadiene nitrile rubber (CTBN) modified epoxy resin is more preferable.
  • Commercially available products include, for example, ADEKA resin EPR series (EPR-1415-1, EPR-2000, EPR-2007, EPR-1630) manufactured by ADEKA, EPON Resin 58005 and EPON Resin 58006 manufactured by Momentive, and Hypox series manufactured by CVC ( Hypox RA 840, Hypox RA 1340, Hypox RF 1341) and the like.
  • the Adeka Resin EPR series manufactured by ADEKA Co., Ltd. is preferred, and EPR-1630 is more preferred since it has excellent adhesion and
  • the number average molecular weight of the rubber-modified epoxy resin (A3) is preferably 200 to 200,000, more preferably 200 to 100,000, even more preferably 200 to 80,000. If the number average molecular weight is too low, the viscosity decreases too much, which tends to reduce workability as an adhesive, while if it is too high, the solubility in other monomers decreases and the viscosity increases too much. Workability tends to decrease.
  • the epoxy equivalent of the rubber-modified epoxy resin (A3) is preferably 10,000 or less, more preferably 7,000 or less, still more preferably 5,000 or less. If the epoxy equivalent is too high, the flexible component will not be dispersed in the cured product, so that when stress occurs, stress will be concentrated in that area, and adhesive strength will tend to decrease.
  • the lower limit of the epoxy equivalent is not particularly limited, but is, for example, 50 or more.
  • the softening point of the rubber-modified epoxy resin (A3) is preferably 200°C or lower, more preferably 180°C or lower, still more preferably 160°C or lower. If the softening point is too high, the viscosity at room temperature after compounding increases, which tends to reduce workability as an adhesive.
  • the lower limit of the softening point is not particularly limited, but is, for example, ⁇ 50° C. or higher.
  • the above epoxy resin composition further includes an aromatic ring-containing epoxy resin (A4) that is solid at room temperature (however, bisphenol A epoxy resin (A1), bisphenol F epoxy resin (A2), and rubber-modified epoxy resin (A3). ) is preferable from the viewpoint of low water absorption, elastic modulus of cured product, and glass transition temperature.
  • aromatic ring-containing epoxy resin A4 that is solid at room temperature (however, bisphenol A epoxy resin (A1), bisphenol F epoxy resin (A2), and rubber-modified epoxy resin (A3). ) is preferable from the viewpoint of low water absorption, elastic modulus of cured product, and glass transition temperature.
  • Type epoxy resin a commercially available product is "YX4000" manufactured by Mitsubishi Chemical Corporation) and the like.
  • the aromatic ring-containing epoxy resin (A4) that is solid at room temperature may be used alone or in combination of two or more.
  • the number average molecular weight of the aromatic ring-containing epoxy resin (A4) that is solid at room temperature is preferably 200 to 100,000, more preferably 200 to 80,000, even more preferably 200 to 60,000. If the number average molecular weight is too low, the viscosity decreases too much, which tends to reduce workability as an adhesive, while if it is too high, the solubility in other monomers decreases and the viscosity increases too much. Workability tends to decrease.
  • the epoxy equivalent of the aromatic ring-containing epoxy resin (A4) that is solid at room temperature is preferably 10,000 or less, more preferably 7,000 or less, still more preferably 5,000 or less. If the epoxy equivalent is too high, the solubility in other monomers tends to decrease, and workability during compounding tends to decrease.
  • the lower limit of the epoxy equivalent is not particularly limited, but is, for example, 50 or more.
  • the softening point of the aromatic ring-containing epoxy resin (A4) that is solid at room temperature is preferably 160°C or lower, more preferably 140°C or lower, still more preferably 120°C or lower. If the softening point is too high, the viscosity at room temperature after blending tends to increase and the workability as an adhesive tends to decrease.
  • the lower limit of the softening point is not particularly limited, but is, for example, ⁇ 50° C. or higher.
  • the content of the epoxy resin (A) is preferably 30 to 100% by mass, more preferably 40 to 100% by mass, and even more preferably 50 to 100% by mass based on the entire epoxy resin composition.
  • the content of the bisphenol A epoxy resin (A1) is preferably 0.01 to 70% by mass, more preferably 0.1 to 60% by mass, even more preferably 1% by mass, based on the entire epoxy resin (A). ⁇ 50% by mass.
  • the content of the bisphenol F type epoxy resin (A2) is preferably 1 to 70% by mass, more preferably 5 to 60% by mass, and even more preferably 10 to 50% by mass based on the entire epoxy resin (A). It is.
  • the content is calculated by dividing the composition into composition mass ratios. For example, when the content of a composition in which bisphenol A type epoxy resin (A1) and bisphenol F type epoxy resin (A2) is 1:1 is 10% by mass, (A1) is 5% by mass and (A2) is 5% by mass. Calculate as a percentage.
  • the content ratio [(A1)/(A2)] of bisphenol A type epoxy resin (A1) to bisphenol F type epoxy resin (A2) is preferably less than 2.7, more preferably less than 2.5, and further It is preferably less than 1.5, particularly preferably less than 1.0, particularly preferably less than 0.9, particularly preferably less than 0.8. If this content ratio [(A1)/(A2)] is too high, the fracture form will be interfacial peeling and the effects of the present invention will tend not to be fully exhibited, which is not preferable. Note that the lower limit of this content ratio is not particularly limited, but is, for example, 0.01 or more.
  • the content of the rubber-modified epoxy resin (A3) is preferably 0.01 to 60% by mass, more preferably 1 to 50% by mass, and even more preferably 5 to 40% by mass based on the entire epoxy resin (A). %.
  • the content of the aromatic ring-containing epoxy resin (A4) that is solid at room temperature is preferably 0 to 80% by mass, more preferably 1 to 70% by mass, even more preferably It is 5 to 60% by mass.
  • the content ratio [(A1)/(A3)] of bisphenol A type epoxy resin (A1) to rubber-modified epoxy resin (A3) is preferably less than 3.0, more preferably less than 2.5, and more preferably less than 2.5. It is preferably less than 2.0, particularly preferably less than 1.5. If this content ratio [(A1)/(A3)] is too high, the fracture form tends to be interfacial peeling, which is not preferable. Note that the lower limit of this content ratio is not particularly limited, but is, for example, 0.01 or more.
  • the content of bisphenol A type epoxy resin (A1) is lower than the content of bisphenol F type epoxy resin (A2), and the content of bisphenol A type epoxy resin (A1) is lower than that of rubber modified epoxy resin. It is also preferable that the content is less than 1.5 times the content of (A3).
  • the epoxy resin (A) may further contain epoxy resins other than (A1) to (A4). Specific examples thereof include alcohol type epoxy resin, naphthalene type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, phenol aralkyl type epoxy resin, biphenyl type epoxy resin, triphenylmethane type epoxy resin, dicyclo Various epoxy resins include pentadiene type epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, polyfunctional phenol type epoxy resin, and aliphatic epoxy resin. These may be used alone or in combination of two or more.
  • the epoxy resin (A) preferably contains 50% by mass or more of an epoxy resin that is solid at room temperature based on the entire epoxy resin (A), more preferably 55% by mass or more, still more preferably 60% by mass or more. .
  • the upper limit of the content of the epoxy resin that is solid at room temperature is not particularly limited, but is, for example, 100% by mass or less.
  • the epoxy resin composition usually contains a curing agent (B).
  • the curing agent (B) include amines, acid anhydrides (carboxylic acid anhydrides), phenols (such as novolak resins), mercaptans, Lewis acid amine complexes, onium salts, and imidazole. Specific examples include Chapter 3 of ⁇ Review of Epoxy Resins Volume 1 (Edited by Epoxy Resin Technology Association, first edition, published November 2003)'' and Chapter 3 of ⁇ Review of Epoxy Resins Volume 1 (Edited by Epoxy Resin Technology Association, published in November 2003)'' and ⁇ Review of Epoxy Resins Recent Progress I (Edited by Epoxy Resin Technology Association)''. , first edition, March 2009)” can be used. Among these, it is preferable to use amines from the viewpoint of adhesive properties.
  • the curing agent (B) may be used alone or in combination of two or more.
  • amines examples include aromatic amines such as diaminodiphenylmethane and diaminodiphenylsulfone, aliphatic amines, imidazole derivatives, dicyandiamide, tetramethylguanidine, thiourea-added amines, and isomers and modified products thereof.
  • aromatic amines such as diaminodiphenylmethane and diaminodiphenylsulfone
  • aliphatic amines such as diaminodiphenylmethane and diaminodiphenylsulfone
  • imidazole derivatives imidazole derivatives
  • dicyandiamide tetramethylguanidine
  • thiourea-added amines thiourea-added amines
  • isomers and modified products thereof examples include isomers and modified products thereof.
  • dicyandiamide is particularly preferred since it has an excellent pot life for the epoxy resin composition that serves as
  • the content of the curing agent (B) is preferably 0.01 to 30% by mass, more preferably 0.1 to 25% by mass, and even more preferably 1 to 20% by mass based on the entire epoxy resin (A). %.
  • the epoxy resin composition may contain polymer fine particles (C) having a core-shell structure. It refers to polymer fine particles whose molecular structure is different in the outer periphery (shell part).
  • Examples of the components constituting the core part of the polymer fine particles (C) having a core-shell structure include butadiene rubber (BR), acrylic rubber (ACM), silicone rubber (Si), butyl rubber (IIR), nitrile rubber (NBR), Examples include styrene butadiene rubber (SBR), isoprene rubber (IR), and ethylene propylene rubber (EPR). Among them, butadiene rubber is preferred.
  • the component constituting the shell part of the polymer fine particles (C) having a core-shell structure is graft-polymerized to the above-mentioned core part and covalently bonded to the polymer constituting the core component.
  • components constituting the shell portion include acrylic ester monomers, methacrylic ester monomers, and aromatic vinyl monomers.
  • the polymer fine particles (C) having a core-shell structure are, for example, commercially available KANE-ACE series (B-11A, B-22, B-561, FM-21, M-701, M-711, M- 300, FM-40, M-210, Pa-20, PA101, MR-01, MX-153, MX257, MX154, MX-960, MX-136, MX-965, MX-217, MX227M75, MX-334M75, MX-416, MX-451, etc.), Metablanes manufactured by Mitsubishi Chemical Corporation (Metablanes C, Metablanes E, Metablanes W, Metablanes S, etc.), and the like.
  • the polymer fine particles (C) may be used as they are in particle form or dispersed in other solutions or resins, but from the viewpoint of uniformly dispersing them in other resins, they are dispersed in epoxy resin. It is more preferable to use MX-153, MX-154, MX-136, and MX-267.
  • the polymer particles (C) having a core-shell structure may be used alone, or two or more types may be used in combination.
  • the primary particle diameter of the polymer fine particles (C) having a core-shell structure is preferably 10 to 100,000 nm, more preferably 15 to 50,000 nm, from the viewpoint of the elastic modulus, elongation properties, and shear strength of the cured product obtained from the epoxy resin. More preferably, it is 20 to 10,000 nm.
  • the primary particle size refers to the volume average particle size of primary particles, and can be measured using, for example, a Nanotrac particle size distribution analyzer (manufactured by Nikkiso Co., Ltd.).
  • the content ratio shall be calculated by adding the content of (A1) and (A2) used in the dispersion product.
  • the content of the polymer fine particles (C) having a core-shell structure is preferably 0 to 50% by mass, more preferably 1 to 40% by mass, and even more preferably It is 2 to 30% by mass.
  • the epoxy resin composition may contain a curing accelerator (D) from the viewpoint of increasing the curing activity of the curing agent (B).
  • a curing accelerator (D) can be used to increase the curing activity of dicyandiamide and the like.
  • curing accelerators for dicyandiamide include 3-phenyl-1,1-dimethylurea, 3-(3,4-dichlorophenyl)-1,1-dimethylurea (DCMU), and 2,4-diamino-6-( 2-Methylimidazolyl-(1))-ethyl-s-triazine, 3-(3-chloro-4-methylphenyl)-1,1-dimethylurea, 4,4'-methylenebis(1,1-dimethyl-3 -phenylurea), urea derivatives such as 2,4-bis(3,3-dimethylureido)toluene, and imidazole derivatives.
  • urea derivatives are preferred, and 4,4'-methylenebis(1,1-dimethyl-3-phenylurea) is more preferred.
  • the content of the curing accelerator (D) is preferably 0.01 to 30% by mass, more preferably 0.05 to 25% by mass, and even more preferably 0.1 to 20% by mass, based on the entire epoxy resin composition. %.
  • the epoxy resin composition preferably contains an inorganic filler (E).
  • the inorganic filler (E) include metal oxides such as aluminum oxide and magnesium oxide; metal carbonates such as calcium carbonate and magnesium carbonate; diatomaceous earth powder, basic magnesium silicate, calcined clay, and finely powdered silica.
  • silicon compounds such as fused silica; metal hydroxides such as aluminum hydroxide; kaolin, mica, quartz powder, glass, ceramic, silicon carbide, graphite, carbon black, carbon nanotubes, molybdenum disulfide, boron, boron nitride, nitride Examples include silicon and aluminum nitride.
  • the inorganic filler (E) may be used alone or in combination of two or more.
  • the shape of the inorganic filler (E) is not particularly limited, but for example, powder, spherical, etc. are preferable, and spherical particles (beads) are more preferable. Among these, an ellipsoid having a ratio of short side to long side (short side/long side) of 1/2 or less is preferable. Further, the inorganic filler (E) is preferably insulating from the viewpoint of preventing metal corrosion (electrolytic corrosion), and glass beads are particularly preferred.
  • the average particle diameter of the inorganic filler (E) is preferably from 50 to 300 ⁇ m, more preferably from 80 to 260 ⁇ m, still more preferably from 100 to 250 ⁇ m, particularly preferably from 100 to 150 ⁇ m.
  • the average particle diameter can be measured, for example, using an optical microscope, etc., and more specifically, it can be measured by observing the particle diameters of 50 inorganic fillers using a digital microscope and calculating their average value. can.
  • the content of the inorganic filler (E) is preferably 5 to 80 parts by mass, more preferably 5 to 50 parts by mass, and even more preferably 10 to 30 parts by mass based on 100 parts by mass of the epoxy resin (A). Department. If the content is too low, it tends to be difficult to maintain the film thickness, and if the content is too high, the area weight of the adhesive sheet increases, making it difficult to use it in fields where weight reduction is required.
  • the content of the inorganic filler (E) is preferably 5 to 70 parts by mass, more preferably 5 to 50 parts by mass, even more preferably 10 to 100 parts by mass, based on 100 parts by mass of all resin components constituting the adhesive. It is 30 parts by mass. If the content is too small, it tends to be difficult to maintain the film thickness, and if the content is too large, the adhesive sheet tends to have an increased basis weight, making it difficult to use it in fields where weight reduction is required.
  • all resin components constituting the adhesive refers to "epoxy resin (A) + polymer fine particles having a core-shell structure (C) + resin used as other components (G)" in the epoxy resin composition. ” means.
  • the particle size of the inorganic filler (E) is preferably 1 or more and 50 or less, more preferably 5 to 40, and still more preferably 10 to 30, satisfying the following formula (2) relative to the thickness of the adhesive sheet. be. It is more preferably 5 or more, and even more preferably 10 or more, from the viewpoint of preventing resin flow during adhesion and ensuring sufficient thickness when producing an adhesive sheet.
  • the average molecular weight is preferably 40 or less, and even more preferably 30 or less.
  • Ta is the thickness of the adhesive sheet before thermosetting measured using a digital thickness gauge
  • Tc is the average particle diameter of the inorganic filler measured using an optical microscope.
  • the total thickness of the average particle diameter of the inorganic filler and the support is preferably 10 or more and 200 or less, which satisfies the following formula (3) with respect to the thickness of the adhesive sheet. It is more preferably 80 or more, and even more preferably 100 or more, since resin flow occurs during adhesion and it is difficult to ensure a sufficient thickness. On the other hand, it is more preferably 160 or less, and even more preferably 180 or less, since fillers and the like are exposed on the surface of the adhesive sheet and it is difficult to adhere to the adherend.
  • Ta is the thickness of the adhesive sheet before thermosetting measured using a digital thickness gauge
  • Tc is the average particle diameter of the inorganic filler measured using an optical microscope
  • Td is the thickness of the support.
  • the adhesive may contain resins other than those mentioned above, dispersants, surfactants, plasticizers, antioxidants, pigments, coupling agents, diluents, flexibility-imparting agents, It may contain various additives such as dispersants, wetting agents, colorants, ultraviolet absorbers, light stabilizers such as hindered amine light stabilizers, defoamers, mold release agents, flow regulators, and solvents.
  • the amount of the other components mentioned above is preferably 5% by mass or less based on the entire adhesive (epoxy resin composition).
  • the lower limit is not particularly limited, but is usually 0% by mass, and may be 0.1% by mass or more.
  • the adhesive may contain a dispersant.
  • the dispersant refers to a compound that has the effect of uniformly dispersing the inorganic filler (E) in the adhesive and in the manufactured laminate.
  • examples of the dispersant include polysiloxane compounds and their salts such as methylhydrogenpolysiloxane, polymethoxysilane, dimethylpolysiloxane, and dimethicone PEG-7 succinate; silane compounds, etc.
  • the carboxylic acid amine compound refers to a compound having both a carboxy group and an amino group
  • the phosphoric acid amine compound refers to a compound having both a phosphoric acid group and an amino group.
  • the adhesive epoxy resin composition
  • one type of the dispersants exemplified above may be used alone, or two or more types may be used in combination in any combination and ratio.
  • Surfactants described below may also function as dispersants. Note that the dispersant may be completely decomposed, partially decomposed, or not decomposed after the laminate is manufactured.
  • the adhesive may contain a surfactant.
  • a surfactant By containing a surfactant, it is possible to prevent the formation of dents or uneven drying in the laminate due to minute bubbles or adhesion of foreign matter during the production of the laminate. Furthermore, the surfactant can improve the wettability of the adhesive.
  • the surfactant is not particularly limited, and known surfactants (cationic surfactants, anionic surfactants, nonionic surfactants) can be used. Among these, silicon-based surfactants, fluorine-based surfactants, and acetylene glycol-based surfactants are preferred.
  • surfactants include Triton X100 (manufactured by Dow Chemical) as a nonionic surfactant, Zonyl FS300 (manufactured by DuPont) as a fluorine-based surfactant, BYK-310 as a silicon-based surfactant, BYK-320, BYK-345 (manufactured by BYK Chemie Co., Ltd.); as the acetylene glycol surfactant, Surfynol 104, Surfynol 465 (manufactured by Air Products Co., Ltd.), Olfine EXP4036, Olfine EXP4200 (manufactured by Nissin Chemical Industry Co., Ltd.) are used. Can be mentioned.
  • one type of the surfactants exemplified above may be used alone, or two or more types may be used in combination in any combination and ratio. Note that the surfactant may be completely decomposed, partially decomposed, or not decomposed after the laminate is manufactured.
  • An epoxy resin composition (and eventually an adhesive composition) is obtained by blending each of the above components, and an adhesive is obtained by mixing this adhesive composition.
  • the viscosity of the adhesive used in the present adhesive sheet at 100° C. and 1 atm is preferably 0.1 to 500 Pa ⁇ s, more preferably 1 to 100 Pa ⁇ s. If the viscosity is too high or too low, the impregnating properties into a support and the coating properties onto a substrate when used as an adhesive tend to deteriorate. In addition, this viscosity is when measured using a rheometer ("MARS II" manufactured by ThermoFisher Scientific) at a temperature of -20 to 180 ° C., a heating rate of 3 ° C./min, a frequency of 1 Hz, and a strain of 0.5%. The viscosity at 100°C.
  • MARS II manufactured by ThermoFisher Scientific
  • the support used in the present adhesive sheet for example, nonwoven fabrics, porous materials, etc. can be used, and nonwoven fabrics are particularly preferred.
  • the density of the support is 0.05 g/cm 3 or more from the viewpoints of suppressing resin flow during pressurization during laminate production, resin retention in the adhesive sheet, and improving adhesiveness due to rigidity of the adhesive sheet. is preferable, more preferably 0.08 g/cm 3 or more, still more preferably 0.1 g/cm 3 or more.
  • the density of the support is preferably 1.0 g/cm 3 or less, more preferably 0.0 g/cm 3 or less. It is 9 g/cm 3 or less, more preferably 0.8 g/cm 3 or less. Note that the density here refers to an apparent density rather than a true density, and can be measured by a general method.
  • ⁇ Adhesive sheet>> This adhesive sheet is obtained by impregnating a support with the adhesive described above. Further, the present adhesive sheet may have a release film on at least one outermost surface, such as one in which the adhesive is provided on the release film. When laminating an adhesive sheet between layers of different materials, the adhesive sheet is used after peeling off the release film.
  • the release film for example, a PET film, a polyethylene film, a polypropylene film, a fluorine film, a polyimide film, etc. that has been subjected to a release treatment such as silicone or melamine can be used.
  • the thickness of the adhesive sheet before thermosetting is 200 ⁇ m or more, preferably 200 to 5000 ⁇ m, more preferably 300 to 4000 ⁇ m, and still more preferably 400 to 3000 ⁇ m.
  • the thickness of the adhesive layer can be made uniform, so it is less likely to cause uneven application of adhesive, so it is highly reliable after bonding, and parts can be joined at the factory. It is particularly useful in production lines that include processes.
  • film thickness maintenance rate refers to the adhesive sheet after curing when the adhesive sheet is sandwiched between cold rolled steel plates (SPCC) and heated and cured under a surface pressure of 1 MPa. This shows how much the thickness has decreased compared to before curing.
  • the film thickness maintenance rate can be determined in more detail using the following equation (1).
  • Film thickness maintenance rate (%) Tb/Ta ⁇ 100 (1)
  • Ta is the thickness of the adhesive sheet (before hardening) measured using a digital thickness gauge
  • Tb is the thickness of the adhesive sheet (before hardening) measured using a digital thickness gauge
  • Tb is the thickness of the adhesive sheet measured using a digital thickness gauge.
  • the film thickness maintenance rate calculated from the above formula (1) is 56% or more, preferably 60% or more, and more preferably 65% or more. Maintaining the thickness of the adhesive sheet is effective in suppressing warpage of dissimilar materials of the adherend and ensuring adhesion reliability. Further, the film thickness maintenance rate is preferably 90% or less, with an upper limit of 95%. On the other hand, if it exceeds 95%, the followability to the adhesive is poor and the adhesion reliability is poor.
  • the content of the inorganic filler (E) in the present adhesive sheet consisting of an adhesive and a support is preferably 3 to 45% by mass, more preferably 5 to 40% by mass, even more preferably 5 to 30% by mass. , particularly preferably 7 to 20% by weight. If the content of the inorganic filler (E) is too low, it tends to be difficult to maintain the film thickness, and if it is too high, the area weight of the adhesive sheet increases, making it difficult to use it in fields where weight reduction is required. be.
  • the adhesive sheet preferably has a tensile shear adhesive strength of 10 MPa or more, more preferably 15 MPa or more, still more preferably 20 MPa or more.
  • the tensile shear adhesive strength of the adhesive sheet is preferably 50 MPa or less, more preferably 45 MPa or less, still more preferably 40 MPa or less.
  • the tensile shear adhesive strength can be determined, for example, by the method described in JIS K6850. More details are as follows.
  • the adhesive sheet was cut to a width of 25 mm and a length of 12.5 mm. After degreasing and cleaning a cold rolled steel plate (SPCC) with width 25 mm x length 100 mm x thickness 1.6 mm with ethanol, a cut adhesive sheet was inserted between the two pieces of SPCC and a surface pressure of 1 MPa was applied.
  • SPCC cold rolled steel plate
  • the adhesive sheet is placed in a constant temperature bath and heated at 150° C. for 20 minutes to harden the adhesive sheet, thereby producing a peel test piece.
  • the tensile shear adhesive strength of the prepared peel test piece is measured using a tensile testing machine ("Autograph AG-X" manufactured by Shimadzu Corporation) at a speed of 5 mm/min.
  • the adhesive used in this adhesive sheet can be manufactured by mixing each component.
  • the mixing temperature is preferably 30°C or higher, more preferably 40°C or higher, still more preferably 50°C or higher.
  • the mixing temperature is preferably 150°C or lower, more preferably 140°C or lower, and even more preferably 120°C or lower.
  • the mixing time is usually 1 minute or more, preferably 10 minutes or more, more preferably 20 minutes or more, and usually 24 hours or less, preferably 18 hours or less, more preferably 12 hours or less.
  • the mixing time is less than the lower limit, uniform mixing tends to be impossible, and when it exceeds the upper limit, the mixture tends to polymerize and gel during mixing.
  • various methods of applying shearing force that are generally used for mixing epoxy adhesives such as stirring, shaking, and kneading, can be used.
  • This mixing method is selected depending on the physical properties of the adhesive, production amount, etc.
  • the state of the obtained epoxy adhesive may be a uniform state or a non-uniform state in which particles are dispersed. This state is variously selected depending on the use as an adhesive.
  • the epoxy adhesive used in this adhesive sheet is preferably a one-component adhesive from the viewpoint of ease of handling.
  • a one-component adhesive it is usually heated to a temperature of 80°C or higher, preferably 130°C or higher, more preferably 150°C or higher, and preferably By curing within 60 minutes, more preferably within 30 minutes, a laminate in which different types of members are joined can be obtained.
  • the adhesive is formed into a sheet shape to obtain an adhesive sheet.
  • the method for forming into a sheet include a method of laminating or applying an adhesive onto a base film to obtain a laminate of base film/adhesive/base film.
  • extrusion lamination such as T-die
  • sheet forming equipment such as calendar roll, double belt press, comma coating method, gravure coating method, reverse coating method, knife coating method, dip coating method, spray coating method.
  • the sheet forming step includes an impregnating step of impregnating the support with the adhesive.
  • a known method can be used for the adhesive impregnation method in the impregnation step.
  • the adhesive is provided on the base film in the sheet forming process and the support is combined into base film/adhesive/support/adhesive/base film, or base film.
  • /Adhesive/Support/Base material A lamination method in which the adhesive is laminated to form a film and impregnated using a vacuum laminator, calendar roll, double belt press, etc., a comma coating method in which the adhesive is directly impregnated into the support, and a gravure method.
  • Examples include a coating method, a reverse coating method, a dip/nip method, a kiss coating method, a spray method, and a curtain coating method.
  • a vacuum laminator, gravure coating method, or reverse coating method is desirable. Note that the step of impregnating the support with an adhesive and the step of forming it into a sheet may be performed simultaneously or separately.
  • the thickness of the support and the amount of adhesive impregnated into the support are preferably adjusted so that the thickness of the sheet-like adhesive layer is 100 to 2000 ⁇ m, more preferably 200 to 1000 ⁇ m.
  • the support In the impregnation step, it is desirable to impregnate the support while controlling the basis weight, which is the weight per unit area of the support. It is preferable to impregnate the support with a resin so that the basis weight is 100 to 2000 g/m 2 , more preferably 300 to 1000 g/m 2 . If it is too large, the resin tends to leak during curing, and if it is too small, the resin tends to wither.
  • the adhesive In the impregnation step, it is desirable to impregnate the adhesive while controlling its viscosity. It is preferable to impregnate the support with the resin so that the viscosity is 1 to 500 Pa ⁇ s, more preferably 10 to 100 Pa ⁇ s. If the viscosity is too high, the resin tends to flow during impregnation, and if the viscosity is too low, the resin tends to dry up during impregnation.
  • the above viscosity is the viscosity when measured using a rheometer (“MARS II” manufactured by ThermoFisher Scientific) at a temperature of -20 to 180°C, a heating rate of 3°C/min, a frequency of 1Hz, and a strain of 0.5%. shall be.
  • the adhesive viscosity can be adjusted without a solvent or with a solvent, but when adjusting the adhesive viscosity with a solvent, the amount of solvent used is preferably 1 part by mass or less per 1 part by mass of the adhesive, The amount is more preferably 0.1 parts by mass or less, even more preferably 0.01 parts by mass or less, and most preferably the support is impregnated with the adhesive without a solvent.
  • This adhesive sheet has a high film thickness retention rate after curing, so it can be used, for example, in vehicles, aircraft, ships, etc. that require improved strength and weight reduction, and that require the use of relatively large materials. It can be suitably used as an adhesive for structural members of transportation equipment (panel parts, frame parts, undercarriage parts, etc.), that is, a structural adhesive (a reliable adhesive that can withstand large loads for a long period of time). However, it is particularly preferred for use as a structural adhesive for structural panels of vehicles.
  • each component of the epoxy resin composition for adhesive used in Examples and Comparative Examples was prepared.
  • Example 1 24 parts of bisphenol A type epoxy resin (A1), 32 parts of bisphenol F type epoxy resin (A2), 17 parts of rubber modified (CTBN modified) epoxy resin (A3), 20 parts of aromatic ring-containing epoxy resin (A4). After mixing 7 parts of polymer fine particles (C) having a core-shell structure, the mixture was stirred at 90°C until uniform.
  • a glass fiber nonwoven fabric (thickness: 380 ⁇ m, “SB-050” manufactured by Olivest Co., Ltd.) as a support, density: 0.13 g/cm 3 ) was sandwiched from both sides and laminated to produce an adhesive sheet in which glass fiber nonwoven fabric was impregnated with resin to have a basis weight of 660 g/m 2 .
  • the content of glass beads (E-1) in the adhesive sheet was 9%.
  • Example 2 The content of glass beads (E-1) was 25 parts (27 parts per 100 parts of epoxy resin (A), 25 parts per 100 parts in total of epoxy resin (A) and polymer fine particles having a core-shell structure (C)).
  • An adhesive sheet was produced in the same manner as in Example 1, except that Example 1 was used.
  • the content of glass beads (E-1) in the adhesive sheet was 18%.
  • the thickness (Ta') of the adhesive sheet obtained above was measured using a digital thickness gauge ("SMD-565J-L" manufactured by Techlock Co., Ltd.) with release film attached to both sides. The release films on both sides were peeled off, and the thicknesses of the two release films were measured. The thickness of the two release films was removed from this thickness (Ta'), and the thickness Ta of the adhesive sheet was measured.
  • the adhesive sheet with the release film removed was sandwiched between cold-rolled steel plates (SPCC) with a width of 25 mm, a length of 100 mm, and a thickness of 1.6 mm, and heated to 150°C under a surface pressure of 1 MPa.
  • SPCC cold-rolled steel plates
  • Film thickness maintenance rate (%) Tb/Ta ⁇ 100 (1) (Evaluation criteria) ⁇ (Very good)...65% or more, within 95% ⁇ (Good)...56% or more, less than 65% ⁇ (Poor)...Less than 56%
  • the tensile shear adhesive strength was evaluated in accordance with JIS K6850.
  • the adhesive sheet obtained above was cut into 25 mm width x 12.5 mm length. After degreasing and cleaning a cold rolled steel plate (SPCC) with width 25 mm x length 100 mm x thickness 1.6 mm with ethanol, a cut adhesive sheet was inserted between the two pieces of SPCC and a surface pressure of 1 MPa was applied. The adhesive sheet was placed in a constant temperature bath and heated at 150° C. for 20 minutes to cure the adhesive sheet, thereby producing a peel test piece.
  • SPCC cold rolled steel plate
  • the prepared peel test piece was subjected to a tensile shear test at a speed of 5 mm/min using a tensile tester ("Autograph AG-X" manufactured by Shimadzu Corporation) to measure the tensile shear adhesive strength, and the tensile shear adhesive strength was measured according to the following criteria. It was evaluated. (Evaluation criteria) ⁇ (Excellent)...20MPa or more ⁇ (Very good)...15MPa or more, less than 20MPa ⁇ (Good)...10MPa or more, less than 15MPa ⁇ (Poor)...Less than 10MPa
  • the adhesive sheets of Examples 1 and 2 all make it possible to achieve both adhesive strength and maintain a thick film, which makes it possible to suppress thickness unevenness and reduce local stress concentration in the adhesive layer. Adhesive strength was easily developed and reliability could be improved. Furthermore, since it is an adhesive sheet, it does not take much time to coat a thick film, resulting in excellent work efficiency and improved productivity.
  • the adhesive sheets of Examples 1 and 2 are thick films, have a high film thickness retention rate, and have high adhesive strength, so they can be suitably used as structural adhesive sheets for automobiles.
  • this adhesive sheet has a high film thickness retention rate
  • the film thickness retention rate of the laminate obtained when multiple different materials are bonded using this adhesive sheet is also high, and it can be suitably used for various laminates. Among these, it is useful for exterior material applications such as automobiles, aircraft, and vehicles.

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

Abstract

La présente invention concerne une feuille adhésive qui peut garantir la fiabilité de l'adhérence, améliorer l'efficacité de travail, et obtenir également à la fois une force d'adhérence et une rétention de film épais.　Cette feuille adhésive thermodurcissable est obtenue par imprégnation d'un non-tissé avec un adhésif, le taux de rétention de film épais dans la formule (1) ci-dessous allant de 56 à 95 %, et l'épaisseur de film avant le thermodurcissement étant d'au moins 200 µm.　(1) : taux de rétention de l'épaisseur du film (%) = Tb/Ta×100 (dans la formule (1), Ta est l'épaisseur de la feuille adhésive mesurée en utilisant une jauge de rigidité numérique, et Tb est l'épaisseur de la feuille adhésive durcie présente entre les tôles d'acier laminé à froid de qualité commerciale (SPCC), mesurée en utilisant un microscope numérique après avoir serré la feuille adhésive entre les SPCC, chauffé à 150°C dans un état de pressurisation avec une pression de surface de 1 MPa, et maintenu pendant 20 minutes pour durcir la feuille adhésive. Lorsque la surface de la feuille adhésive comporte un film anti-adhésif, Ta est l'épaisseur de la feuille adhésive sans le film anti-adhésif.
PCT/JP2023/012171 2022-03-28 2023-03-27 Feuille adhésive WO2023190322A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011162577A (ja) * 2010-02-04 2011-08-25 Dainippon Printing Co Ltd 粘接着シート
JP2019503406A (ja) * 2015-11-19 2019-02-07 スリーエム イノベイティブ プロパティズ カンパニー 改善された破壊モードを備えた構造用接着剤
WO2020201982A1 (fr) * 2019-04-02 2020-10-08 3M Innovative Properties Company Ruban adhésif structural en une seule pièce élastique
WO2022124336A1 (fr) * 2020-12-09 2022-06-16 三菱ケミカル株式会社 Adhésif, adhésif pour lier des matériaux dissemblables, feuille adhésive, et feuille adhésive pour lier des matériaux dissemblables
JP2022147236A (ja) * 2021-03-23 2022-10-06 三菱ケミカル株式会社 接着シート及びこれを用いた硬化物、積層体並びに自動車用外装材

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011162577A (ja) * 2010-02-04 2011-08-25 Dainippon Printing Co Ltd 粘接着シート
JP2019503406A (ja) * 2015-11-19 2019-02-07 スリーエム イノベイティブ プロパティズ カンパニー 改善された破壊モードを備えた構造用接着剤
WO2020201982A1 (fr) * 2019-04-02 2020-10-08 3M Innovative Properties Company Ruban adhésif structural en une seule pièce élastique
WO2022124336A1 (fr) * 2020-12-09 2022-06-16 三菱ケミカル株式会社 Adhésif, adhésif pour lier des matériaux dissemblables, feuille adhésive, et feuille adhésive pour lier des matériaux dissemblables
JP2022147236A (ja) * 2021-03-23 2022-10-06 三菱ケミカル株式会社 接着シート及びこれを用いた硬化物、積層体並びに自動車用外装材

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