WO2022131110A1 - 接着シート、並びに物品及び物品の製造方法 - Google Patents

接着シート、並びに物品及び物品の製造方法 Download PDF

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Publication number
WO2022131110A1
WO2022131110A1 PCT/JP2021/045256 JP2021045256W WO2022131110A1 WO 2022131110 A1 WO2022131110 A1 WO 2022131110A1 JP 2021045256 W JP2021045256 W JP 2021045256W WO 2022131110 A1 WO2022131110 A1 WO 2022131110A1
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WO
WIPO (PCT)
Prior art keywords
adhesive
heat
main surface
adhesive sheet
adherend
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2021/045256
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English (en)
French (fr)
Japanese (ja)
Inventor
翔太 谷井
彰規 森野
澄生 下岡
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
DIC Corp
Original Assignee
DIC Corp
Dainippon Ink and Chemicals Co Ltd
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 DIC Corp, Dainippon Ink and Chemicals Co Ltd filed Critical DIC Corp
Priority to CN202180080577.6A priority Critical patent/CN116600988A/zh
Priority to JP2022566676A priority patent/JP7231128B2/ja
Publication of WO2022131110A1 publication Critical patent/WO2022131110A1/ja
Priority to JP2023020712A priority patent/JP2023065455A/ja
Priority to US18/327,244 priority patent/US12516227B2/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
    • C09J5/06—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving heating of the applied adhesive
    • 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]
    • C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/385—Acrylic polymers
    • 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
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/10—Adhesives in the form of films or foils without carriers
    • 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
    • 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
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/354—Applications of adhesives in processes or use of adhesives in the form of films or foils for automotive applications
    • 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
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
    • C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
    • C09J2301/124—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present on both sides of the carrier, e.g. double-sided adhesive tape
    • C09J2301/1242—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present on both sides of the carrier, e.g. double-sided adhesive tape the opposite adhesive layers being different
    • 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
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/20—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive itself
    • C09J2301/204—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive itself the adhesive coating being discontinuous
    • 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
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/20—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive itself
    • C09J2301/206—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive itself the adhesive layer comprising non-adhesive protrusions
    • 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
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/20—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive itself
    • C09J2301/208—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive itself the adhesive layer being constituted by at least two or more adjacent or superposed adhesive layers, e.g. multilayer adhesive
    • 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
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/304—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being heat-activatable, i.e. not tacky at temperatures inferior to 30°C
    • 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
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C09J2301/408—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the adhesive layer
    • 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
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C09J2301/412—Additional features of adhesives in the form of films or foils characterized by the presence of essential components presence of microspheres
    • 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
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/50—Additional features of adhesives in the form of films or foils characterized by process specific features
    • 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
    • C09J2463/00—Presence of epoxy 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
    • C09J2479/00—Presence of polyamine or polyimide
    • C09J2479/08—Presence of polyamine or polyimide polyimide
    • C09J2479/086—Presence of polyamine or polyimide polyimide in the substrate

Definitions

  • the present invention relates to an adhesive sheet having an adhesive layer that can be expanded by heating.
  • the fixing method of inserting and fixing one member into a gap formed in the other member or a gap formed between two or more other members is used in various product manufacturing situations such as automobiles and electric devices.
  • a magnet is inserted and fixed in a gap provided at a predetermined position in a core portion (rotor core).
  • a member to be inserted into the gap is referred to as an insertion member, and a member having a gap or a set of two or more members constituting the gap is referred to as a member to be inserted.
  • the insertion member in order to prevent the member inserted into the gap from falling, the insertion member is usually inserted into the gap of the inserted member, and then the gap is filled with a liquid adhesive to join the insertion member and the inserted member. ing.
  • the insertion member may be displaced in the gap or dropped from the gap until the adhesive is cured.
  • the adhesive since it is necessary to adjust the viscosity and filling amount of the liquid adhesive, the process is complicated and the process time may become long. Further, in the above method, the adhesive adheres to the outside of the voids of the member and causes contamination.
  • the adhesive sheet used for joining the adherend which is the insertion member and the adherend which is the insertion member needs to be inserted into the gap between the members before joining the members by heating and expansion.
  • the adhesive sheet at room temperature before insertion is required to have low or no initial adhesiveness so as not to impair the insertability.
  • the adhesive sheet is attached from a predetermined bonding position of the adherend before the adhesive sheet is expanded, adhered and fixed.
  • the adhesive sheet is required to have high initial adhesiveness at room temperature so as not to be displaced.
  • the above-mentioned adhesive sheet exhibits excellent adhesive strength not only in a normal temperature environment but also in a high-temperature environment, and is an insertion member. And the member to be inserted are required to be firmly joined.
  • the present invention has been made in view of the above circumstances, and is an adhesive sheet that can be expanded by heating. Before expansion, it is temporarily fixed at room temperature and it is easy to insert one member into the gap of the other member.
  • an adhesive sheet that can firmly bond members to each other while maintaining excellent adhesive strength even in a high temperature environment after expansion, and an article using the adhesive sheet and a method for producing the same.
  • the present invention is an adhesive sheet having a first main surface and a second main surface facing each other, and the first main surface of the adhesive sheet is a heat-expandable heat-curable adhesive layer and The first main surface of the heat-expandable heat-curable adhesive layer is composed of a plurality of adhesive portions provided in a pattern, and the second main surface of the adhesive sheet is the first main surface of the adhesive sheet.
  • an adhesive sheet composed of the heat-expandable heat-curable adhesive layer constituting the surface or another heat-expandable heat-curable adhesive layer.
  • the present invention has a first adherend and a second adherend, the second adherend has a gap formed therein, and the first adherend is the first.
  • the second adherend is arranged in the voids of the second adherend, and in the voids, the first adherend and the second adherend are adhered to each other via the swelling material of the adhesive sheet. Providing goods. I will provide a.
  • the present invention has a first adherend, a third adherend and a fourth adherend, and there is a gap between the third adherend and the fourth adherend.
  • the first adherend is arranged in the void, and in the void, the first adherend and the third adherend, and the first adherend and the above-mentioned first adherend.
  • a fourth adherend provides an article to which each is adhered via an inflatable material of the adhesive sheet described above.
  • the present invention relates to the step of adhering the first main surface of the above-mentioned adhesive sheet to the surface of the first adherend or the surface of the void formed in the second adherend [1A].
  • the adhesive sheet is heated to expand and cure the heat-expandable heat-curable adhesive layer, and the expanded product of the adhesive sheet is expanded and cured.
  • a method for producing an article which comprises a step [3A] of adhering the first adherend and the second adherend to the second adherend.
  • the first main surface of the above-mentioned adhesive sheet is bonded to the surface of the first adherend or the surface of the void composed of the third adherend and the fourth adherend.
  • the adhesive sheet of the present invention has heat-expandability, can achieve both temporary fixing at room temperature before expansion and ease of insertion when inserting a member into a gap, and can be inserted at a high temperature after expansion. Members can be firmly joined to each other while maintaining excellent adhesive strength even in an environment.
  • the adhesive sheet of the present invention is an adhesive sheet having a first main surface and a second main surface facing each other, and the first main surface of the adhesive sheet is a heat-expandable heat-curable adhesive layer.
  • the second main surface of the adhesive sheet is composed of a plurality of adhesive portions provided in a pattern on the first main surface of the heat-expandable heat-curable adhesive layer. It is composed of the above-mentioned heat-expandable heat-curable adhesive layer or another heat-expandable heat-curable adhesive layer constituting the main surface.
  • thermosetting expandable adhesive layer is easily temporarily fixed to the adherend at room temperature because the initial adhesiveness is low or absent. Is difficult. There is also a method of heat laminating and temporarily fixing to the adherend, but if it is difficult to sufficiently temporarily fix by heat laminating due to the material of the adherend, or equipment for heat laminating is required, the process is complicated. May become. On the other hand, since the thermoplastic pressure-sensitive adhesive layer is inferior in heat resistance, the pressure-sensitive adhesive layer is thermally deteriorated in a high temperature environment and the adhesive strength is reduced or disappears, so that the insertion member and the inserted member are firmly bonded. It is difficult to make it.
  • the insertion member may be caught during insertion into the void or may be bonded to a position other than the predetermined position. Misalignment may occur.
  • the conventional expandable adhesive sheet it is difficult to achieve both temporary fixing property and insertability at room temperature and heat resistance.
  • the adhesive sheet of the present invention it is possible to achieve both good temporary fixing and insertability at room temperature, and further, it has excellent heat resistance after expansion and maintains excellent adhesive strength even in a high temperature environment. Is possible. More specifically, in the adhesive sheet of the present invention, since the first main surface of the sheet surface has a plurality of adhesive portions provided in a pattern, the high initial adhesiveness of the adhesive portions is utilized. It can be temporarily fixed to the adherend at room temperature, while the second main surface is composed of a heat-expandable heat-curable adhesive layer, so that the second main surface is a heat-expandable heat-curable type.
  • the heat-expandable thermosetting adhesive layer expands by heating to fill the gap between the inserted member and the inserted member, and is cured by heating to exhibit high adhesive strength.
  • the adhesive portion is filled or the adhesive portion is buried due to the expansion of the heat-expandable thermosetting adhesive layer, so that the heat-expandable thermosetting type after expansion is performed.
  • the adhesive layer comes into contact with one of the members and can be firmly adhered.
  • the expanded heat-expandable thermosetting adhesive layer comes into contact with the other member and can be firmly adhered.
  • the expanded adhesive sheet of the present invention can exhibit high adhesive force even in a high temperature environment by adhering the expanded thermosetting adhesive layer and the member on both sides of the sheet. Therefore, the members can be firmly fixed to each other.
  • the first main surface of the adhesive sheet of the present invention is composed of a heat-expandable heat-curable adhesive layer and a plurality of adhesive portions arranged in a pattern on the surface of the heat-expandable heat-curable adhesive layer.
  • the first main surface of the adhesive sheet may be an uneven surface formed by providing a convex adhesive portion on the surface of the heat-expandable thermosetting adhesive layer, and may be a surface of the heat-expandable thermosetting adhesive layer. It may be a flat surface in which the surface of the adhesive portion is in the same plane.
  • the adhesive portion has a first surface and a second surface on the opposite side thereof, and before expansion, the adhesive portion is the first in the thickness direction of the adhesive sheet.
  • One surface is located outside the first main surface of the heat-expandable heat-curable adhesive layer provided with the adhesive portion, and the second surface of the adhesive portion is the heat provided with the adhesive portion. It is located in contact with the first main surface of the expandable heat-curable adhesive layer or between the first main surface of the heat-expandable heat-curable adhesive layer and the second main surface on the opposite side thereof.
  • the first surface of the adhesive portion in the thickness direction of the adhesive sheet after expansion, the first surface of the adhesive portion is the expanded thermosetting adhesive layer provided with the adhesive portion.
  • the second surface of the adhesive portion is after expansion in which the adhesive portion is provided. It is located between the first main surface of the heat-expandable thermosetting adhesive layer and the second main surface on the opposite side thereof.
  • the above-mentioned aspect may be referred to as a first aspect of the adhesive sheet.
  • FIGS. 1A and 1B are schematic cross-sectional views showing an example of the first aspect of the adhesive sheet of the present invention, FIG. 1 shows before expansion and FIG. 2 shows after expansion.
  • the Z-side surface in the thickness direction is the first main surface of the adhesive sheet
  • the Z'side surface is the second surface.
  • the adhesive portion 2 is provided on the first surface b1 of the adhesive portion 2 in the thickness direction ZZ'of the sheet.
  • the outside of the first main surface a1 of the heat-expandable thermosetting adhesive layer 1 (opposite to the first main surface a1 of the heat-expandable thermosetting adhesive layer 1 as opposed to the heat-expandable thermosetting adhesive layer.
  • the second surface b2 of the adhesive portion 2 is in contact with the first main surface a1 of the heat-expandable thermosetting adhesive layer 1 provided with the adhesive portion 2.
  • the heat-expandable thermosetting adhesive layer 1 provided with the adhesive portion 2 is located between the first main surface a1 and the second main surface a2.
  • the expanded adhesive sheet 10' there is a region between the adhesive portions 2, that is, a region (non-adhesive portion region) on the first main surface of the adhesive sheet where the adhesive portion 2 is not provided. , It is filled with the heat-expandable thermosetting adhesive layer 1'after expansion.
  • the first surface b1 of the adhesive portion 2 is a heat-expandable thermosetting type after expansion provided with the adhesive portion 2, as shown in FIG. 2A. It is located at the same position as the first main surface a1 of the adhesive layer 1', or between the first main surface a1 and the second main surface a2 on the opposite side as shown in FIG. 2 (b). Further, at this time, the second surface b2 of the adhesive portion 2 is the first main surface a1 of the heat-expandable thermosetting adhesive layer 1'after the expansion provided with the adhesive portion 2, and the second surface a1 on the opposite side thereof. It is located between the main surfaces a2.
  • the adhesive portion is arranged on the first main surface of the heat-expandable thermosetting adhesive layer, or the adhesive portion is formed.
  • a part is in the heat-expandable thermosetting adhesive layer, and the rest protrudes from the first main surface of the heat-expandable thermosetting adhesive layer. That is, the first surface of the adhesive sheet is an uneven surface in which the adhesive portion is convex and the surface region (non-adhesive portion region) of the heat-expandable thermosetting adhesive layer in which the adhesive portion is not provided is concave.
  • the adhesive sheet before expansion can exhibit temporary fixing property by having the adhesive portion in contact with one of the insertion member and the inserted member on the first main surface.
  • the second main surface of the adhesive sheet is a surface formed of a heat-expandable thermosetting adhesive layer and does not have an adhesive portion, the insertability of the insertion member can be exhibited.
  • the expansion of the heat-expandable thermosetting adhesive layer fills the space between the adhesive portions on the first surface of the sheet, and the adhesive portions are embedded in the heat-expandable thermosetting adhesive layer. Further, the heat-expandable thermosetting adhesive layer expands and cures by heating to exhibit high adhesive strength.
  • the expanded adhesive sheet can be firmly adhered to the inserted member and the inserted member by the expanded thermosetting adhesive layer on the first main surface and the second main surface. ..
  • the adhesive sheet of the present invention when the adhesive sheet of the present invention before expansion is temporarily fixed to the adherend which is an insertion member at room temperature, air bubbles caught in the interface of the adherend are quickly generated. It is preferable in that it can prevent bubbles from remaining on the interface and suppress poor adhesion of the adhesive sheet.
  • the adhesive portion has a first surface and a second surface on the opposite side thereof, and the adhesive portion is formed in the thickness direction of the adhesive sheet before expansion.
  • the first surface of the adhesive portion is located at the same position as the first main surface of the heat-expandable heat-curable adhesive layer provided with the adhesive portion, and the second surface of the adhesive portion is provided with the adhesive portion. It is located between the first main surface of the heat-expandable heat-curable adhesive layer and the second main surface on the opposite side thereof.
  • the first surface of the adhesive portion in the thickness direction of the adhesive sheet after expansion, is the expanded thermosetting adhesive layer provided with the adhesive portion.
  • the second surface of the adhesive portion is after expansion in which the adhesive portion is provided. It is located between the first main surface of the heat-expandable thermosetting adhesive layer and the second main surface on the opposite side thereof.
  • the above-mentioned aspect may be referred to as a second aspect of the adhesive sheet.
  • FIG. 3 and 4 are schematic cross-sectional views showing an example of a second aspect of the adhesive sheet of the present invention, FIG. 3 shows before expansion and FIG. 4 shows after expansion.
  • the Z-side surface in the thickness direction is the first main surface of the adhesive sheet
  • the Z'side surface is the second surface.
  • the adhesive sheet 10 of the present invention has a thermal expansion property in which the first surface b1 of the adhesive portion 2 is provided with the adhesive portion 2 in the thickness direction ZZ'of the sheet before expansion.
  • the second surface b2 of the adhesive portion 2 is located at the same position as the first main surface a1 of the thermosetting adhesive layer 1, and the first main surface b2 of the adhesive portion 2 is the first main surface of the thermosetting adhesive layer 1 provided with the adhesive portion 2. It is located between the surface a1 and the second main surface a2 on the opposite side thereof.
  • the first surface b1 of the adhesive portion 2 is provided with the adhesive portion 2 in the thickness direction ZZ' of the sheet after expansion. It is located at the same position as the first main surface a1 of the heat-expandable thermosetting adhesive layer 1'(FIG.
  • the second surface b2 of the adhesive portion 2 is the first main surface a1 of the heat-expandable thermosetting adhesive layer 1'after expansion provided with the adhesive portion 2 and the opposite side thereof. It is located between the second main surfaces a2.
  • the adhesive portion is embedded in the thermosetting adhesive layer, and the first main surface of the adhesive sheet is formed.
  • the region of the first main surface of the heat-expandable thermosetting adhesive layer and the region of the first surface of the adhesive portion are provided in the same plane.
  • the adhesive portion comes into contact with the member and can exhibit temporary fixing property.
  • the second main surface of the adhesive sheet is a surface formed of a heat-expandable thermosetting adhesive layer and does not have an adhesive portion, the insertability of the insertion member can be exhibited.
  • the heat-expandable thermosetting adhesive layer expands and hardens by heating to exhibit high adhesive force. Therefore, the expanded adhesive sheet has a first main surface and a first surface of the adhesive sheet. On the main surface of No. 2, the expanded thermosetting adhesive layer comes into contact with the other member and can be firmly adhered.
  • the second aspect of the adhesive sheet of the present invention it is possible to ensure that the first main surface of the heat-expandable thermosetting adhesive layer is uniformly filled between the adhesive portions before expansion. It is preferable that the heat-expandable thermosetting adhesive layer between the adhesive portions after heating is less likely to be poorly filled and can be more uniformly adhered to the adherend as an insertion member.
  • the adhesive portion When the first surface of the adhesive portion is in the same position as the first main surface of the thermosetting adhesive layer provided with the adhesive portion in the thickness direction of the adhesive sheet, the adhesive portion is heated. It means that the first surface of the adhesive portion and the first main surface of the heat-expandable thermosetting adhesive layer are in the same surface because they are buried in the expandable thermosetting adhesive layer.
  • the first main surface of the adhesive sheet is formed of a plurality of adhesive portions provided in a pattern. It has a region (adhesive portion region) and a region where the surface of the heat-expandable thermosetting adhesive layer is exposed (non-adhesive portion region).
  • the second surface of the adhesive portion is between the first main surface of the heat-expandable thermosetting adhesive layer provided with the adhesive portion and the second main surface on the opposite side thereof.
  • the position does not include the case where the second surface of the adhesive portion and the first main surface or the second main surface of the heat-expandable thermosetting adhesive layer are at the same position (in the same surface) in the thickness direction. It shall be.
  • the first surface of the adhesive portion is located between the first main surface and the second main surface of the expanded thermosetting adhesive layer in the thickness direction of the expanded adhesive sheet.
  • the first surface b1 of the adhesive portion 2 may be entirely covered with the expanded thermosetting adhesive layer 1', and as shown in FIG. 5, A part of the first surface b1 of the adhesive portion 2 may be exposed from the first main surface a1 of the heat-expandable thermosetting adhesive layer 1'after expansion.
  • the adhesive sheet of the present invention when at least the second surface of the adhesive portion is located between the first main surface and the second main surface of the heat-expandable thermosetting adhesive layer, that is, one of the adhesive portions.
  • some or all of the adhesive parts are in the heat-expandable thermosetting adhesive layer, some or all of the adhesive parts in the heat-expandable thermosetting adhesive layer permeate the heat-expandable thermosetting adhesive layer. It may or may not have penetrated.
  • the fact that the adhesive portion has penetrated into the heat-expandable thermosetting adhesive layer means that the adhesive composition constituting the heat-expandable thermosetting adhesive layer is mixed in the adhesive portion before expansion. That is, after expansion, it means that at least a cured product of the thermosetting resin contained in the adhesive composition constituting the heat-expandable thermosetting adhesive layer is mixed in the adhesive portion.
  • the surface of the heat-expandable heat-curable adhesive layer after expansion and the adherend bonded via the adhesive sheet are formed on both the first main surface and the second main surface. It suffices if a state of close contact can be ensured, and the form of the adhesive portion in the adhesive sheet after expansion is not particularly limited.
  • the shape of the adhesive portion in the adhesive sheet after expansion may be the same as or different from the shape of the adhesive portion in the adhesive sheet before expansion. If the first surface and / or the second surface of the adhesive portion cannot be specified in the expanded adhesive sheet, the adhesive portion is buried in the expanded heat-expandable thermosetting adhesive layer. , The first surface and the second surface of the adhesive portion in the expanded adhesive sheet described in the first aspect and the second aspect described above, and the first main surface and the second surface of the heat-expandable thermosetting adhesive layer. Satisfy the relationship with the main surface.
  • the shear adhesive strength of the first main surface is usually the second so that the temporary fixing property can be exhibited on the first main surface and the insertability can be exhibited on the second main surface. Greater than the shear bond strength of the main surface of.
  • the difference between the shear adhesive strength of the first main surface of the adhesive sheet and the shear adhesive strength of the second main surface is preferably 0.01 MPa or more, and more preferably 0.1 MPa or more. Is more preferable, 0.4 MPa or more is more preferable, and 0.5 MPa or more is more preferable.
  • the difference in the shear adhesive strength between the first main surface and the second main surface of the adhesive sheet is within the above range, so that the first main surface and the second main surface can sufficiently perform the above-mentioned functions, respectively. This is because it is possible to exert the function, and it is possible to prevent the function exerted on one side from being impaired by the function exerted on the other side.
  • the first main surface of the adhesive sheet of the present invention may have a shear adhesive strength capable of exhibiting temporary fixing property, and usually has a higher shear adhesive strength than the second main surface.
  • the shear adhesive strength of the first main surface of the adhesive sheet can be set to such a size that the difference from the shear adhesive strength of the second main surface can be within the above range, specifically 0.2 MPa.
  • the above is preferable, and among them, 0.3 MPa or more is preferable, 0.5 MPa or more is further preferable, and 1.0 MPa or more is from the viewpoint that higher temporary fixing property can be exhibited on the first main surface of the adhesive sheet. More preferred.
  • the shear adhesive strength of the first surface of the adhesive sheet is mainly due to the shear adhesive strength of the adhesive portion constituting the first main surface and the heat-expandable thermosetting adhesive layer, but it depends on the layer structure of the adhesive sheet and the like. It can be adjusted as appropriate.
  • the second main surface of the adhesive sheet may have a shear adhesive strength capable of exhibiting insertability, and usually has a lower shear adhesive strength than the first main surface.
  • the shear adhesive strength of the second main surface of the adhesive sheet can be set to such a size that the difference from the shear adhesive strength of the first main surface can be within the above range, specifically, 0.5 MPa.
  • the second main surface of the adhesive sheet of the present invention is preferably less than, more preferably 0.3 MPa or less, further preferably 0.2 MPa or less, and 0.1 MPa or less. It is more preferable from the viewpoint that it is possible to prevent the occurrence of problems such as sticking to a position different from a predetermined position and to improve the insertability when the insertion member is inserted into the gap.
  • the lower limit value is preferably 0 MPa. It may be 0.01 MPa or more.
  • the shear adhesive strength of the second main surface of the adhesive sheet is mainly due to the shear adhesive strength of the heat-expandable thermosetting adhesive layer constituting the second main surface, but is adjusted according to the layer structure of the adhesive sheet and the like. Is possible.
  • the shear bond strength of each surface of the adhesive sheet can be measured by the following method according to the tensile shear test described in JIS Z 1541.
  • first surface and the second surface of the cut adhesive sheet one surface (non-measurement target surface) is fixed with a strong adhesive, and the other surface (measurement target surface) of the adhesive sheet is the other aluminum plate.
  • the adhesive sheet is sandwiched between two aluminum plates A and B, and the test piece is crimped with a load of 23 ° C. and 0.5 MPa for 10 seconds.
  • the ends of the two aluminum plates A and B are chucked, respectively, and using a Tensilon tensile tester, 10 mm / min in the 180 degree direction. Do a tensile test at. The value obtained at this time can be used as the shear adhesive strength of the surface (measurement target surface) of the adhesive sheet on the aluminum B side.
  • the non-measurement target surface of the adhesive sheet is strongly fixed to the aluminum plate A using a strong adhesive, peeling does not occur on the non-measurement target surface side of the adhesive sheet in the tensile test, and the measurement target surface is shear-bonded. It can be measured as strength.
  • the first surface and the second surface of the adhesive sheet refer to one outermost surface and the other outermost surface of the adhesive sheet excluding the release liner.
  • adheresive sheet or "heat-expandable heat-curable adhesive layer”
  • it means “adhesive sheet” or “heat-expandable heat-curable adhesive layer” before expansion.
  • the "expandable material of the adhesive sheet” and “expandable material of the heat-expandable heat-curable adhesive layer” are “adhesive sheet after expansion” and "heat-expandable heat-curable adhesive layer after expansion", respectively.
  • Means. "After expansion” means after expansion and curing of the heat-expandable thermosetting adhesive layer, and means “after heating at 150 ° C. for 60 minutes” unless otherwise specified.
  • Thermally expandable thermosetting adhesive layer The thermally expandable thermosetting adhesive layer in the present invention is a layer that expands and cures by heating.
  • the adhesive sheet of the present invention may have one or more thermosetting adhesive layers.
  • the two or more heat-expandable thermosetting adhesive layers may be directly laminated or may be laminated via an intermediate layer described later.
  • the second main surface of the adhesive sheet constitutes the first main surface of the adhesive sheet. It is composed of a curable adhesive layer. That is, a plurality of adhesive portions are provided in a pattern on the first main surface of the heat-expandable thermosetting adhesive layer which is a single layer, and the second main surface becomes the second main surface of the adhesive sheet.
  • the second main surface of the adhesive sheet constitutes the first main surface of the adhesive sheet. It is composed of a heat-expandable thermosetting adhesive layer different from the heat-expandable thermosetting adhesive layer. That is, among the two or more heat-expandable thermosetting adhesive layers, the heat-expandable thermosetting adhesive layer located on the outermost side of one in the thickness direction of the adhesive sheet is provided with a plurality of the adhesive portions.
  • the first main surface of the adhesive sheet is formed by, and the second main surface of the adhesive sheet is formed by the heat-expandable thermosetting adhesive layer located on the outermost side of the other.
  • each heat-expandable thermosetting adhesive layer may have the same composition and thickness or may be different. ..
  • the heat-expandable heat-curable adhesive layer constituting the second main surface of the adhesive sheet of the present invention causes problems such as the second main surface of the adhesive sheet sticking to a position different from a predetermined position. It is usually more preferable that the shear adhesive strength is lower than that of the adhesive portion, and the initial adhesiveness (adhesiveness) is low or absent, in order to prevent and enhance the insertability.
  • the shear adhesive strength of the heat-expandable thermosetting adhesive layer constituting the second main surface of the adhesive sheet of the present invention is preferably less than 0.5 MPa, particularly preferably 0.3 MPa or less, and is 0. It is more preferably 2 MPa or less, and more preferably 0.1 MPa or less.
  • the thermosetting adhesive layer constituting the second main surface of the adhesive sheet has the above-mentioned shear adhesive strength.
  • the other heat-expandable thermosetting adhesive layer may have a shear adhesive strength within the above range, or may be larger than the above range.
  • the shear adhesive strength of the heat-expandable thermosetting adhesive layer provided with the adhesive portion is higher than the shear adhesive strength of the thermosetting thermosetting adhesive layer constituting the second main surface, the first adhesive sheet is formed. It is possible to enhance the temporary fixing property on the main surface of the.
  • the preferable range of the shear adhesive strength of the heat-expandable thermosetting adhesive layer provided with the adhesive portion can be the same as the preferable range of the shear adhesive strength of the adhesive portion described later.
  • the shear adhesive strength of the heat-expandable thermosetting adhesive layer can be adjusted in a timely manner by, for example, blending a resin component contained in a thermosetting adhesive composition described later, an additive such as an inorganic filler or a slip agent, and the like. be.
  • the shear bond strength of the heat-expandable heat-curable adhesive layer can be measured by the following method according to the tensile shear test described in JIS Z 1541.
  • a sheet is molded using an adhesive having the same composition so as to have the same thickness as the heat-expandable thermosetting adhesive layer in the adhesive sheet, and the molded product is cut into a size of 10 mm ⁇ 10 mm and degreased.
  • the test piece is sandwiched between two treated aluminum plates having a smooth surface (width 15 mm ⁇ length 70 mm ⁇ thickness 0.5 mm) and crimped with a load of 23 ° C. and 0.5 MPa for 10 seconds. After the test piece was left in an environment of 23 ° C.
  • the thickness of the heat-expandable thermosetting adhesive layer is preferably 1 ⁇ m or more, more preferably 10 ⁇ m to 400 ⁇ m, and more preferably 15 ⁇ m to 250 ⁇ m in order to obtain even more excellent adhesive strength. It is more preferably present, and particularly preferably in the range of 20 ⁇ m to 200 ⁇ m. When there are two or more heat-expandable thermosetting adhesive layers, the thickness is set to one layer.
  • the thickness of the heat-expandable thermosetting adhesive layer is preferably 10% or more, more preferably 30% or more with respect to the total thickness of the adhesive sheet.
  • the thickness of the heat-expandable thermosetting adhesive layer is preferably 10% or more, more preferably 30% or more with respect to the total thickness of the adhesive sheet.
  • the heat-expandable heat-curable adhesive layer is a layer that expands by heating, and the expansion coefficient in the thickness direction of the heat-expandable heat-curable adhesive layer after heating at 150 ° C. for 60 minutes is 150% or more. Above all, it is more preferably 175% or more, and even more preferably 200% or more.
  • the expansion coefficient is preferably 1000% or less, more preferably 800% or less, and even more preferably 500% or less. If the adhesive sheet exhibits an expansion coefficient to which the heat-expandable heat-curable adhesive layer is applied, even if the height (thickness) of the voids of the inserted member is large, the adhesive sheet is expanded to enter the voids.
  • the other adherend can be suitably fixed, or the voids can be filled with the adhesive sheet. Further, even if the surface of the adherend is a rough surface or an uneven surface, the adherend can be sufficiently adhered, and the other adherend can be suitably fixed. Further, if the expansion coefficient is too high, the density of the layer decreases and deterioration is likely to occur due to high temperature exposure. However, when the expansion coefficient is within the above range, thermal deterioration is unlikely to occur and high adhesive strength is maintained even in a high temperature environment. It becomes possible to do. When two or more heat-expandable thermosetting adhesive layers are provided, the expansion rate per layer is used.
  • the expansion coefficient (%) in the thickness direction of the heat-expandable thermosetting adhesive layer after heating at 150 ° C. for 60 minutes shall be a value calculated based on the following method and formula.
  • the adhesive sheet is allowed to stand in an environment of 150 ° C. for 60 minutes and heated, then the adhesive sheet is taken out in an environment of 23 ° C. and immediately heated (after expansion), the heat-expandable thermosetting type adhesive is applied to the adhesive sheet. Measure the thickness of the layer.
  • the coefficient of expansion is calculated based on the above measurement results and the following formula.
  • Expansion rate (%) in the thickness direction of the heat-expandable heat-curable adhesive layer after heating [Thickness of the heat-expandable heat-curable adhesive layer after heating / Of the heat-expandable heat-curable adhesive layer before heating Thickness] x 100 (%)
  • a test sample in which a heat-expandable thermosetting adhesive layer having the same composition and thickness as the heat-expandable thermosetting adhesive layer in the adhesive sheet is formed on a release liner is used as a test sample.
  • the expansion coefficient may be calculated based on the thickness before and after heating the sample at 150 ° C. for 60 minutes and the above formula.
  • the thickness of the thermally expandable thermosetting adhesive layer after expansion in other words, the expansion adhesive layer formed by expanding and curing the thermally expandable thermosetting adhesive layer by heating, provides even better adhesive strength. In obtaining it, it is preferably in the range of 20 ⁇ m to 2500 ⁇ m, and more preferably in the range of 40 ⁇ m to 1500 ⁇ m. Further, the heat-expandable thermosetting adhesive layer after expansion preferably has a porous structure.
  • the glass transition temperature of the heat-expandable thermosetting adhesive layer after expansion is preferably 80 ° C. or higher. This is because the expanded adhesive layer can exert excellent adhesive force even when exposed to a high temperature environment, and can firmly hold the joint between the insertion member and the inserted member used for applications that are particularly susceptible to high temperatures. be. More specifically, the glass transition temperature of the heat-expandable thermosetting adhesive layer after expansion is preferably 80 ° C. or higher, more preferably 100 ° C. or higher, further preferably 120 ° C. or higher, and more preferably 150 ° C. or higher. More preferred.
  • the upper limit of the glass transition temperature of the heat-expandable thermosetting adhesive layer after expansion is not particularly limited, but the insertion member and the inserted member can be joined without being damaged by, for example, 300 ° C. or lower.
  • the adhesive sheet of the present invention has two or more heat-expandable heat-curable adhesive layers, at least the heat-expandable heat-curable adhesive constituting the first main surface and the second main surface of the adhesive sheet. It is preferable that the layer has the glass transition temperature in the above range after expansion (after curing), and it is preferable that all the heat-expandable heat-curable adhesive layers have the glass transition temperature after expansion (after curing). ..
  • the glass transition temperature of the heat-expandable thermosetting adhesive layer after expansion is measured by using a dynamic viscoelastic modulus measuring device (manufactured by Leometrics, trade name: RSA-II) with a gripper, which is the measuring part of the same testing machine.
  • the test piece was chucked, the storage elastic modulus (E') and the loss elastic modulus (E ") at a frequency of 1 Hz were measured, and the loss elastic modulus (E") was divided by the storage elastic modulus (E'). It refers to the peak temperature confirmed by the spectrum of loss tangent (tan ⁇ ) calculated from the value (E "/ E').
  • the test piece used for the above measurement is a heat-expandable thermosetting adhesive layer at 150 ° C. It can be measured by heating for 60 minutes and punching the heat-expandable heat-curable adhesive layer after expansion into the shape of the test piece type 5 of JIS K7127 using a dumbbell cutter.
  • the heat-expandable thermosetting adhesive layer after expansion has a curing rate of 80% or more.
  • excellent adhesive strength can be exhibited even when exposed to a high temperature environment, and it is possible to firmly hold the joint between the insertion member and the inserted member used for applications that are particularly liable to reach high temperatures. Will be.
  • the heat-expandable thermosetting adhesive layer after expansion it is more preferable to set the curing rate to 90% or more, and further preferably to set the curing rate to 99% or more.
  • the curing rate of the heat-expandable thermosetting adhesive layer after expansion is expressed as a gel fraction, and the heat-expandable thermosetting adhesive layer is heated at 150 ° C. for 60 minutes to have thermal expandability after expansion.
  • the thermosetting adhesive layer was immersed in a toluene solution adjusted to 23 ° C. for 24 hours, and the mass of the thermosetting adhesive layer remaining in the solvent after drying and the value calculated based on the following formula. Point to.
  • the heat-expandable thermosetting adhesive layer is a layer containing at least a thermosetting resin and a swelling agent.
  • the thermosetting thermosetting adhesive layer is a layer formed by a thermosetting thermosetting adhesive composition containing at least a thermosetting resin and a leavening agent.
  • the heat-expandable thermosetting adhesive layer can be formed by applying, for example, an adhesive composition containing a thermosetting resin, a leavening agent, or the like to a release liner or the like and drying it.
  • the heat-expandable heat-curable adhesive layer after expansion is an expansion-adhesive layer whose volume is increased by the expansion of the expander contained in the heat-expandable heat-curable adhesive composition by heating, and is heat-expandable. It is formed by a cured product of a heat-curable adhesive composition.
  • thermosetting adhesive layer (all resin components)
  • the heat-expandable thermosetting adhesive composition (all resin components) forming the heat-expandable thermosetting adhesive layer. It can be "medium”.
  • the resin component is a resin component constituting the adhesive composition excluding the leavening agent.
  • thermosetting resin The heat-expandable thermosetting adhesive layer contains at least a thermosetting resin as a resin component.
  • a thermosetting resin for example, one or more thermosetting tree species selected from urethane resin, phenol resin, unsaturated polyester resin, epoxy resin, acrylic resin and the like can be used. Among them, it is preferable to use an epoxy resin and / or a phenol resin as the thermosetting resin in order to impart good adhesion to the adherend during heat curing, and it is preferable to use an epoxy resin. Is more preferable in order to secure good heat curability and to have high heat resistance.
  • epoxy resin a compound having one or more epoxy groups in one molecule can be used.
  • bisphenol type epoxy resin such as bisphenol A type epoxy resin and bisphenol F type epoxy resin and its modified resin
  • dicyclopentadiene type epoxy resin such as dicyclopentadiene-phenol addition reaction type epoxy resin
  • biphenyl type epoxy resin a compound having one or more epoxy groups in one molecule.
  • Tetramethylbiphenyl type epoxy resin polyhydroxynaphthalene type epoxy resin, isocyanate modified epoxy resin, 10- (2,5-dihydroxyphenyl) -9,10-dihydro 9-oxa-10-phosphaphenanthrene-10-oxide modification Epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, triphenylmethane type epoxy resin, tetraphenylethane type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, phenol aralkyl type epoxy resin, naphthol novolac type epoxy Resin, hexanediol type epoxy resin, naphthol aralkyl type epoxy resin, naphthol-phenol co-shrink novolak type epoxy resin, naphthol-cresol co-shrink novolak type epoxy resin, aromatic hydrocarbon formaldehyde resin modified phenol resin type epoxy resin, biphenyl-modified novolak Use type epoxy resin, trimettan
  • the epoxy resin may be used alone or in combination of two or more. Further, the epoxy resin may be solid, semi-solid, or liquid. Among them, as the epoxy resin, it is preferable to use a polyfunctional epoxy resin having two or more epoxy groups in one molecule and / or a mixture thereof. When the epoxy resin is used, the glass transition temperature of the heat-expandable thermosetting adhesive layer after expansion can be increased, and the decrease in adhesive strength at high temperatures can be suppressed. Further, as the epoxy resin, an epoxy resin other than the polyfunctional epoxy resin may be used in combination. By using the above epoxy resin in combination, the flexibility, softening point, melt viscosity, glass transition temperature, etc. of the heat-expandable thermosetting adhesive layer can be easily adjusted.
  • the thermosetting resin contained in the heat-expandable thermosetting adhesive layer has a total epoxy equivalent of 2,000 g / eq. It is preferable to use the one in the following range. It is preferable because the glass transition temperature of the heat-expandable thermosetting adhesive layer after expansion can be increased and the decrease in adhesive strength at high temperatures can be suppressed.
  • the total epoxy equivalent is preferably 50 g / eq. 1500 g / eq. The following is 100 g / eq. More than 1000 g / eq. The following is 150 g / eq. More than 500 g / eq. It is as follows.
  • the epoxy equivalent is 500 g / eq.
  • the epoxy equivalent is preferably 50 g / eq. 450 g / eq.
  • the following is 100 g / eq. 400 g / eq.
  • the following is 150 g / eq. More than 300 g / eq. It is as follows.
  • the content of the epoxy resin having an epoxy equivalent in the above range is preferably in the range of 35% by mass or more and 65% by mass or less in the total resin components of the heat-expandable heat-curable adhesive layer, and is 40% by mass. It is within the range of 60% by mass or less, and is within the range of 45% by mass and 55% by mass or less.
  • the content of the epoxy resin having an epoxy equivalent in the above range is the total amount when two or more kinds of epoxy resins having an epoxy equivalent are contained in the above range.
  • epoxy equivalent is defined by the molecular weight of the epoxy resin per epoxy group, and is described in JIS K7236, How to determine the epoxy equivalent of an epoxy resin (2001) (perchloric acid-odorization). It can be determined by the tetraethylammonium method) or the like.
  • the thermosetting adhesive layer preferably contains one or more types of solid thermosetting resin (hereinafter referred to as solid resin) as the thermosetting resin.
  • the "solid resin” refers to a resin having a high softening point or a semi-solid or solid resin at 25 ° C.
  • the softening point of the solid resin is preferably 5 ° C. or higher.
  • the thermosetting resin preferably contains a solid resin having a softening point of 30 ° C. or higher and 150 ° C. or lower, and more preferably 50 ° C. or higher and 100 ° C. or lower.
  • the content of the solid resin in the heat-expandable heat-curable adhesive layer can be appropriately set according to the shear bond strength required for the heat-expandable heat-curable adhesive layer and the like.
  • the content of the solid resin is 30% by mass or more in the total resin components of the heat-expandable heat-curable adhesive layer. It is preferably 50% by mass or more, 60% by mass or more, 70% by mass or more, 80% by mass or more, 85% by mass or more, and 90% by mass or more.
  • the content is preferably 99% by mass or less, more preferably 97% by mass or 95% by mass, in the total resin component of the heat-expandable heat-curable adhesive layer constituting the second main surface of the adhesive sheet. .. More specifically, the content of the solid resin is preferably 30% by mass or more, more preferably 50% by mass or more and 99% by mass or less, and further preferably 70% by mass or more and 95% by mass or less.
  • the initial adhesiveness (adhesiveness) of the heat-expandable thermosetting adhesive layer can be reduced, and when the inserting member is inserted into the gap of the inserted member, the adhesive sheet is used.
  • the content of the solid resin is the total amount of the two or more types of solid resin.
  • the solid resin examples include phenol novolac type epoxy resin, cresol novolac type epoxy resin, triphenylmethane type epoxy resin, tetraphenylethane type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, and phenol aralkyl type epoxy.
  • examples thereof include a resin, a naphthol novolak type epoxy resin, a naphthol aralkyl type epoxy resin, a naphthol-phenol co-shrink novolak type epoxy resin, and a naphthol-cresol co-shrink novolak type epoxy resin. These resins may be used alone or in combination of two or more.
  • thermosetting adhesive layer may be used in combination with a thermosetting resin that is liquid at room temperature (hereinafter, may be referred to as a liquid resin), if necessary.
  • a thermosetting resin that is liquid at room temperature
  • the liquid resin preferably has a viscosity at 25 ° C. of 3 million mPa ⁇ sec or less, and more preferably 10,000 mPa ⁇ sec or more and 2 million mPa ⁇ sec or less. It is more preferably 1.5 million mPa ⁇ sec or less.
  • the content of the liquid resin in the heat-expandable heat-curable adhesive layer can be appropriately set according to the shear bond strength required for the heat-expandable heat-curable adhesive layer and the like. At least in the heat-expandable heat-curable adhesive layer constituting the second main surface of the adhesive sheet of the present invention, the content of the liquid resin is 40% by mass or less in the total resin component of the heat-expandable heat-curable adhesive layer. Of these, 30% by mass or less is preferable, 20% by mass or less is more preferable, and 10% by mass or less is more preferable.
  • the content of the liquid resin may be 0% by mass, more than 0% by mass, 1% by mass or more, 3% by mass or more, or 5% by mass or more.
  • the content can be 40% by mass or less, 1% by mass or more and 30% by mass or less, 3% by mass or more and 20% by mass or less, and 5% by mass or more and 10% by mass or less.
  • the flexibility of the heat-expandable heat-curable adhesive layer before expansion and the fluidity at the time of heating are made suitable, and the handleability of the adhesive sheet of the present invention and the expansion coefficient of the adhesive sheet at the time of heating are made suitable. Can be done.
  • the content of the liquid resin is the total amount of the two or more types of liquid resin.
  • the heat-expandable heat-curable adhesive layer constituting the second main surface of the adhesive sheet of the present invention contains a liquid resin
  • the liquid resin should be used in an appropriate combination of the above-mentioned viscosity range and content range. Can be done.
  • the liquid resin can be used in an appropriate combination of the above-mentioned viscosity range and content range.
  • a liquid resin having a viscosity of 3 million mPa ⁇ sec or less is contained in an amount of 20% by mass or less.
  • the liquid resin having a viscosity in the range of 1000 mPa ⁇ sec to 2 million mPa ⁇ sec is contained in the range of 1% by mass to 15% by mass, and the viscosity is 10,000 mPa ⁇ sec to 1.5 million mPa ⁇ . It is preferable that the liquid resin in the range of sec is contained in the range of 3% by mass to 10% by mass. This is because the shear adhesive strength of the second main surface of the adhesive sheet can be made sufficiently smaller than that of the first main surface, and the insertability is improved.
  • the content of the liquid resin is not particularly limited for the heat-expandable thermosetting adhesive layer other than the heat-expandable thermosetting adhesive layer constituting the second main surface of the adhesive sheet, and the required shear adhesion is required. It can be adjusted as appropriate according to the strength.
  • liquid resin examples include bisphenol type epoxy resins such as bisphenol A type epoxy resin and bisphenol F type epoxy resin, modified resins thereof, trimethylolpropane type epoxy resin, and alicyclic epoxy resin.
  • the liquid resin may be used alone or in combination of two or more.
  • the heat-expandable heat-curable adhesive layer constituting the second main surface of the adhesive sheet of the present invention contains the above-mentioned solid resin and liquid resin
  • the blending ratio of the solid resin and the liquid resin (solid resin: liquid resin). It may be any ratio as long as it is possible to set the shear adhesive strength of the heat-expandable heat-curable adhesive layer in a desired range, and for example, the mass ratio is preferably in the range of 99.9: 0.1 to 60:40. , 99: 1 to 70:30 is preferable, and the range of 95: 5 to 80:20 is preferable. This is because the shearing adhesive strength of the second main surface of the adhesive sheet can be sufficiently made lower than that of the first main surface by setting the blending ratio of the solid resin and the liquid resin in the above range.
  • thermosetting resin is preferably contained in the total resin component of the heat-expandable thermosetting adhesive layer in an amount of 10% by mass or more and 99% by mass or less, and more preferably 20% by mass or more and 90% by mass or less. It is more preferably contained in an amount of 30% by mass or more and 80% by mass or more, and further preferably contained in an amount of 40% by mass or more and 70% by mass or less.
  • the heat-expandable thermosetting adhesive layer and the heat-expandable thermosetting adhesive composition constituting the same preferably contain a curing agent capable of reacting with the thermosetting resin. This is because when the heat-expandable thermosetting adhesive layer is heated, the thermosetting resin is sufficiently cured and high adhesive strength can be exhibited.
  • the curing agent is preferably contained before the thermosetting adhesive layer is thermally cured or before it is formed into a sheet-shaped thermosetting adhesive layer.
  • a compound corresponding to the type of the thermosetting resin, particularly the type of the functional group of the thermosetting resin can be appropriately selected and used.
  • a curing agent having a functional group capable of reacting with the epoxy group examples include amine-based compounds, amide-based compounds, acid anhydride-based compounds, and phenol-based compounds.
  • the curing agent it is preferable to use a powdery one.
  • amine-based compound diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, imidazole derivative, BF3-amine complex, guanidine derivative and the like can be used.
  • amide compound examples include a polyamide resin synthesized from a dimer of dicyandiamide and linolenic acid and ethylenediamine.
  • Examples of the acid anhydride-based compound include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, and methyl. Hexahydrophthalic anhydride and the like can be mentioned.
  • phenolic compound examples include phenol novolac resin, cresol novolak resin, aromatic hydrocarbon formaldehyde resin-modified phenol resin, dicyclopentadienephenol-added resin, phenol aralkyl resin (Zyroc resin), naphthol aralkyl resin, and trimethylolmethane resin.
  • polyhydric phenol compounds such as (a polyhydric phenol compound in which a phenol nucleus and an alkoxy group-containing aromatic ring are linked with formaldehyde).
  • the ratio of the functional group equivalent that can react with the epoxy group contained in the curing agent to the total epoxy equivalent of the thermosetting resin is The range is preferably 0.3 or more and 2.0 or less, more preferably 0.5 or more and 1.5 or less, and further preferably 0.7 or more and 1.0 or less. By using it in the above range, the thermosetting resin can be sufficiently cured and the heat resistance of the adhesive sheet can be improved.
  • the curing temperature of the thermosetting material is preferably equal to or higher than the expansion temperature of the leavening agent described later, and the curing time is preferably equal to or longer than the expansion time.
  • the leavening agent can be sufficiently expanded in the thermosetting material softened by heating, and the sheet thickness after expansion can be made uniform.
  • the heat-expandable thermosetting adhesive layer and the heat-expandable thermosetting adhesive composition constituting the same may contain a curing accelerator.
  • the curing accelerator is preferably contained before the thermosetting adhesive layer A is thermally cured or before it is formed into a sheet-shaped thermosetting adhesive layer A.
  • the curing accelerator a phosphorus compound, an amine compound, an imidazole derivative, or the like can be used.
  • the amount used is preferably 0.1 part by mass to 10 parts by mass with respect to 100 parts by mass of all the resin components contained in the heat-expandable heat-curable adhesive layer. It is more preferably in the range of 5 parts by mass to 5 parts by mass.
  • the curing accelerator it is preferable to use a powdery one. Since the powdery curing accelerator suppresses the thermosetting reaction at a low temperature as compared with the liquid curing accelerator, the storage stability of the thermosetting material before the thermosetting at room temperature is further improved. Can be improved.
  • thermosetting adhesive layer and the heat-expandable thermosetting adhesive composition constituting the same can be used even when used in an environment where the temperature changes significantly after expansion and curing.
  • a material containing a thermoplastic resin can be used as long as the fixing property is not impaired.
  • thermoplastic resin examples include thermoplastic polyurethane (TPU); phenoxy resins such as polyhydroxypolyether synthesized from bisphenols and epichlorohydrin; polycarbonate (PC); polyvinyl chloride (PVC), vinyl chloride-vinyl acetate.
  • TPU thermoplastic polyurethane
  • PC polycarbonate
  • PVC polyvinyl chloride
  • Vinyl chloride resin such as copolymer resin; acrylic resin such as polyacrylic acid, polymethacrylic acid, methylpolyacrylate, polymethylmethacrylate (PMMA), ethylpolymethacrylate; polyethylene terephthalate (PET), Polyester resins such as polybutylene terephthalate, polytrimethylene terephthalate, polyethylene naphthalate, and polybutylene naphthalate; polyamide resins such as nylon (registered trademark); polystyrene (PS), imide Polyplastic resins such as modified polystyrene, acrylonitrile-butadiene-styrene (ABS) resin, imide-modified ABS resin, styrene-acrylonitrile copolymerized (SAN) resin, acrylonitrile-ethylene-propylene-diene-styrene (AES) resin, polyethylene (PE) ) Resins, polypropylene (PP) resins, cycloolef
  • the thermosetting thermosetting adhesive layer contains one or more types of thermoplastic resin having a reactive group that reacts with the thermosetting resin (hereinafter, may be referred to as a reactive thermoplastic resin). Is preferable. This is because the reactive group of the reactive thermoplastic resin reacts with the thermosetting resin, so that the heat-expandable thermosetting adhesive layer after curing can develop stronger adhesive force. ..
  • the reactive group that reacts with the thermosetting resin include an epoxy group, a hydroxyl group, a carboxyl group, an amino group, and an isocyanate group.
  • the thermoplastic resin having such a reactive group include thermoplastic polyurethane (TPU), polyhydroxypolyether (phenoxy resin), acrylic resin and the like.
  • the thermoplastic resin can be used in the range of 1 part by mass to 200 parts by mass with respect to 100 parts by mass of the thermosetting resin. Above all, it is preferable to use it in the range of 10 parts by mass to 150 parts by mass with respect to 100 parts by mass of the thermosetting resin, and when it is used in the range of 30 parts by mass to 100 parts by mass, strong adhesive strength is exhibited. It is more preferable from the viewpoint that it is possible to do so.
  • the heat-expandable thermosetting adhesive layer after expansion forms a porous structure in the layer. It is preferable to use what can be used.
  • a swelling agent include inorganic compounds such as ammonium carbonate, ammonium hydrogencarbonate, ammonium nitrite, ammonium hydride and azide, alkane fluorides such as trichloromonofluoromethane, and azo compounds such as azobisisobutyronitrile.
  • Hydrazine compounds such as paratoluenesulfonyl hydrazide, semicarbazide compounds such as p-toluenesulfonyl semicarbazide, triazole compounds such as 5-morpholyl-1,2,3,4-thiatriazole, N, N'-dinitrosoterephthalamide and the like. N-nitroso compounds can be used.
  • the above-mentioned leavening agent for example, an expandable capsule in which a hydrocarbon solvent is microencapsulated can be used.
  • the above-mentioned leavening agent can be used alone or in combination of two or more.
  • the leavening agent among the above, using an expandable capsule in which a hydrocarbon solvent is microencapsulated is used, for example, in order to prevent deterioration of the thermally expandable thermosetting adhesive layer due to the influence of heat or the like. More preferred.
  • a leavening agent that can expand at a temperature around the softening point of the heat-expandable heat-curable adhesive layer because the adhesive sheet can be sufficiently expanded.
  • expandable capsules examples include Expandel (manufactured by Nippon Phillight Co., Ltd.), Matsumoto Microsphere (manufactured by Matsumoto Yushi Pharmaceutical Co., Ltd.), Microsphere (manufactured by Kureha Corporation), and the like.
  • the inflatable capsule it is preferable to use a capsule having a volume (volume expansion rate) of 8 to 60 times after expansion with respect to the volume of the capsule before expansion.
  • the amount of the swelling agent used preferably the amount of the heat-expandable capsule, is in the range of 0.3 parts by mass to 30 parts by mass with respect to 100 parts by mass of all the resin components of the heat-expandable heat-curable adhesive layer. It is preferably in the range of 0.5 parts by mass to 25 parts by mass, more preferably in the range of 1 part by mass to 20 parts by mass.
  • the heat-expandable thermosetting adhesive layer and the heat-expandable thermosetting adhesive composition constituting the same include, for example, a filler, a softening agent, and the like, in addition to the above-mentioned ones, as long as the effects of the present invention are not impaired.
  • Adhesive portion A plurality of adhesive portions in the present invention are provided in a pattern on the first main surface of the heat-expandable thermosetting adhesive layer constituting the first main surface of the adhesive sheet, and the first of the adhesive sheets. Consists of the main surface of.
  • the first main surface of the adhesive sheet has a plurality of adhesive portions, it is possible to exhibit a desired shear adhesive strength by at least the initial adhesive force of the adhesive portions, and the inserted member is placed in the gap of the inserted member. After insertion, the adhesive sheet can be temporarily fixed so as not to be displaced from a predetermined position until the adhesive sheet is expanded to bond and fix the inserted member and the inserted member.
  • the shear adhesive strength of the plurality of adhesive portions is increased. It is preferably 0.2 MPa or more, more preferably 0.3 MPa or more, further preferably 0.5 MPa or more, and even more preferably 1.0 MPa or more. Within the above range, an adhesive sheet having higher temporary fixing property can be obtained.
  • the higher the shear adhesive strength of the plurality of adhesive portions is, the more preferable it is, and the upper limit thereof is not particularly limited, but may be, for example, 2 MPa or less, and may be 1 MPa.
  • the shear adhesive strength of a plurality of adhesive parts is determined by adjusting the adhesive component described later, the pattern and shape of the adhesive parts, the size per piece, and the area of the plurality of adhesive parts occupying the first main surface of the adhesive sheet. It can be adjusted by the ratio of the total.
  • the shear adhesive strength of the plurality of adhesive portions means, in other words, the shear adhesive strength of the pressure-sensitive adhesive layer composed of the plurality of adhesive portions and the non-adhesive portion region in which the adhesive portions are not provided.
  • the shear adhesive strength of the plurality of adhesive parts can be measured according to the tensile shear test described in JIS Z 1541, and the plurality of adhesive parts are formed in a pattern on the release liner as in the case of the plurality of adhesive parts in the adhesive sheet.
  • the adhesive portion is transferred to one of the two smooth adherends (aluminum plates), and then the other adherend and the adhesive portion are overlapped so as to be in contact with each other, and the pressure is 0.5 MPa.
  • the test piece was crimped at 23 ° C for 10 seconds and left at 23 ° C for 30 minutes, and the ends of the two aluminum plates of the above test piece were chucked and 180 using a tensile tester. A value subjected to a tensile test at 10 mm / min in the degree direction can be used.
  • the peak temperature of the loss tangent (tan ⁇ ) based on the dynamic viscoelastic spectrum measured at a frequency of 1 Hz of the adhesive portion is not particularly limited, but is preferably -30 ° C to 20 ° C, preferably -20 ° C to 10 ° C. It is more preferable that the temperature is -10 ° C to 5 ° C, because good adhesive strength can be maintained.
  • a viscoelastic tester manufactured by Leometrics, trade name: Ares 2KSTD
  • the peak temperature refers to the peak temperature confirmed by the spectrum of tan ⁇ with respect to the measurement temperature region (-50 ° C to 150 ° C).
  • a pressure-sensitive adhesive layer having a thickness of 0.5 mm to 2.5 mm, which is formed by using the pressure-sensitive adhesive used for forming the pressure-sensitive adhesive portion, can be used.
  • a plurality of adhesive portions in the present invention are provided in a pattern on the first main surface of the heat-expandable thermosetting adhesive layer, and there is no component constituting the adhesive portion between adjacent adhesive portions. It has an adhesive area.
  • the plurality of adhesive parts are basically independent of each other, but there may be a place where two or more adhesive parts are partially connected.
  • Examples of the pattern of the adhesive portion include a dot shape (so-called island shape), a strip shape (strip shape), and a grid shape.
  • the plan view shape of the adhesive portion (the shape observed from the plane of the adhesive sheet) is preferably a substantially circular shape, a substantially square shape, or a substantially hexagonal shape.
  • the substantially circular shape is not particularly limited, but the ratio [maximum diameter / minimum diameter] of the maximum diameter to the minimum diameter of any one adhesive portion is preferably 1 to 4.
  • the above [maximum diameter / minimum diameter] is more preferably 1 to 2, and most preferably 1 to 1.5.
  • examples of the substantially square shape include a substantially square shape, a substantially rectangular shape, a substantially trapezoidal shape, a substantially rhombus shape, and the like.
  • the "abbreviation" in each shape includes, for example, a shape in which the square and hexagonal corners are rounded due to pressing of the adhesive portion, and a shape in which the straight portion is a curved portion.
  • the substantially square corner portion is preferably a substantially rhombus shape in which the angle of the corner portion facing the flow direction of the adhesive sheet is less than 90 °, and is temporarily fixed in the range of 45 ° to 70 °. It is more preferable because it can maintain a good adhesive force for exhibiting sex.
  • the size of each of the adhesive portions is preferably in the range of 0.02 mm 2 to 0.50 mm 2 . It is more preferably in the range of 0.03 mm 2 to 0.30 mm 2 , and particularly preferably in the range of 0.05 mm 2 to 0.20 mm 2 .
  • the plan view shape of the adhesive portion may be, for example, a linear shape, and the linear shape may be a linear shape or a wavy line shape (meandering). Shape, zigzag shape) may be used.
  • the width of the adhesive portion is not particularly limited as long as the above effect is obtained, and the area of the adhesive portion occupying the first main surface of the adhesive sheet described later. It can be set as appropriate according to the ratio of the total.
  • each of the plurality of adhesive portions may be different or the same, but it is preferable that the shape and the size of each adhesive portion are substantially the same.
  • the shortest distance between any first adhesive portion selected from the plurality of adhesive portions and the second adhesive portion close to (closest to) the first adhesive portion is preferably 0.05 mm or more. It is in the range of 0.60 mm, more preferably in the range of 0.10 mm to 0.40 mm, and more preferably in the range of 0.15 mm to 0.30 mm.
  • the distance between the first adhesive portion and the second adhesive portion close to the first adhesive portion is the distance between the first adhesive portion and the second adhesive portion close to the first adhesive portion.
  • the pattern of the adhesive portion is a grid pattern or a strip shape
  • the shortest distance between an arbitrary first adhesive portion and a second adhesive portion close to (closest to) the first adhesive portion is used. Refers to the distance between the first adhesive portion and the second adhesive portion that extends in the same direction as the extending direction of the first adhesive portion and is close to the first adhesive portion.
  • the ratio of the total area of the plurality of adhesive portions to the first main surface of the adhesive sheet of the present invention before expansion is preferably 20% or more and 80% or less, preferably 30% or more and 70% or more. % Or less, more preferably 40% or more and 60% or less.
  • the ratio of the area of the adhesive portion to the first main surface of the adhesive sheet within the above range, the first main surface of the adhesive sheet retains good temporary fixing property before expansion and expands.
  • the expanded heat-expandable heat-curable adhesive layer is formed on the first main surface of the sheet without hindering the filling between the adhesive parts due to the expansion of the heat-expandable heat-curable adhesive layer or the burial of the adhesive parts. It can be more firmly adhered to the adherend.
  • the ratio of the total area of the plurality of adhesive portions is also referred to as the area occupancy ratio of the adhesive portion in the area of the first main surface of the adhesive sheet.
  • the shape and size of the adhesive portion, the shortest distance between an arbitrary first adhesive portion selected from a plurality of adhesive portions and a second adhesive portion close to (closest to) the first adhesive portion, etc. can be obtained, for example, by observing a plane with an electron microscope.
  • the thickness of the adhesive portion is preferably 1 ⁇ m or more and 50 ⁇ m or less, preferably 2 ⁇ m or more and 30 ⁇ m or less, and more preferably 3 ⁇ m or more and 10 ⁇ m or less.
  • the adhesive portion may have thermal expansion property or may not have thermal expansion property, and may be appropriately set according to the composition of the pressure-sensitive adhesive constituting the adhesive portion. Above all, the fact that the adhesive portion does not have thermal expansion property does not hinder the filling between the adhesive portions due to the expansion of the thermally expandable heat-curable adhesive layer or the burial of the adhesive portion after the expansion of the adhesive sheet. It is preferable from the viewpoint that the heat-expandable heat-curable adhesive layer after expansion can be more firmly adhered to the adherend on the first main surface of the adhesive sheet.
  • the expansion rate in the thickness direction of the adhesive portion after heating at 150 ° C. for 60 minutes is preferably 120% or less, preferably 115% or less, and the expansion ratio is 100% (substantially the adhesive portion is substantially). (Does not swell) is most preferable.
  • the expansion coefficient (%) in the thickness direction of the adhesive portion is the thickness of the adhesive portion after heating with respect to the thickness of the adhesive portion before heating when the adhesive sheet of the present invention is heated in an environment of 150 ° C. for 60 minutes.
  • the adhesive portion preferably has a gel fraction of 60% by mass or less, more preferably 10% by mass to 55% by mass, and even more preferably 20% by mass to 50% by mass.
  • a gel fraction of 60% by mass or less more preferably 10% by mass to 55% by mass, and even more preferably 20% by mass to 50% by mass.
  • the pressure-sensitive adhesive composition constituting the pressure-sensitive adhesive portion has an excellent initial adhesive strength (adhesive strength) at room temperature (23 ° C.), and has excellent adhesion even after the adhesive sheet of the present invention is heated and expanded. It is preferable to use one that can express force.
  • a pressure-sensitive adhesive composition include compositions containing at least an adhesive resin.
  • the adhesive resin contained in the pressure-sensitive adhesive composition for example, acrylic resin, rubber resin, polyurethane resin, polyester resin, silicone resin and the like can be used. Above all, it is preferable that the pressure-sensitive adhesive composition contains an acrylic resin as a main component.
  • the main component refers to the component most contained in the pressure-sensitive adhesive composition.
  • the acrylic resin for example, one obtained by polymerizing a monomer containing an alkyl (meth) acrylate can be used, and for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl ( Meta) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-eth-1 ruhexyl ( Meta)
  • One type of acrylate or the like or two or more types can be used in combination.
  • alkyl (meth) acrylate using an alkyl (meth) acrylate having an alkyl group having 4 to 12 carbon atoms is excellent in followability and adhesion to an adherend having surface irregularities, and is attached. It is more preferable to obtain an adhesive sheet having excellent workability.
  • acrylic nitrile, (meth) acrylic acid, maleic anhydride, acrylamide, itaconic acid, styrene, vinyl acetate and the like can be used as the above-mentioned monomers.
  • the rubber-based resin examples include styrene-based AB type diblock copolymers such as styrene-ethylene-butylene copolymer (SEB); styrene-butadiene-styrene copolymer (SBS), and hydrogenated additives of SBS (SBS).
  • SEB styrene-ethylene-butylene copolymer
  • SBS styrene-butadiene-styrene copolymer
  • SBS hydrogenated additives of SBS
  • Styrene-ethylene-butylene-styrene copolymer SEBS
  • SEBS Styrene-ethylene-butylene-styrene copolymer
  • SIS styrene-isoprene-styrene copolymer
  • SEPS SIS hydrogenated additive
  • SIBS isobutylene-styrene copolymer
  • SIBS Styrene-based ABAB-type tetrablock copolymer such as styrene-butadiene-styrene-butadiene (SBSB); styrene-butadiene-styrene-butadiene -Styrene-based ABAB
  • A-type pentablock copolymer such as styrene (SBSBS); Styrene-based multi-block copolymer having these or more AB repeating
  • the pressure-sensitive adhesive composition may contain, if necessary, a pressure-sensitive adhesive resin, a cross-linking agent, other additives, and the like, in addition to the above-mentioned resin.
  • the pressure-sensitive adhesive resin includes, for example, a rosin-based pressure-sensitive adhesive resin, a polymerized rosin-based pressure-sensitive adhesive resin, a polymerized rosin ester-based pressure-sensitive adhesive resin, and a rosin-phenol-based pressure-sensitive adhesive resin for the purpose of adjusting the strong adhesiveness of the adhesive portion.
  • Stabilized rosin ester-based tackifier resin, disproportionate rosin ester-based tackifier resin, terpene-based tackifier resin, terpenephenol-based tackifier resin, petroleum resin-based tackifier resin, and the like can be used.
  • cross-linking agent examples include known isocyanate-based cross-linking agents, epoxy-based cross-linking agents, aziridine-based cross-linking agents, polyvalent metal salt-based cross-linking agents, and metal chelate-based cross-linking agents for the purpose of improving the cohesive force of the adhesive portion.
  • a keto-hydrazide-based cross-linking agent, an oxazoline-based cross-linking agent, a carbodiimide-based cross-linking agent, a silane-based cross-linking agent, a glycidyl (alkoxy) epoxysilane-based cross-linking agent and the like can be used.
  • the above-mentioned additives include bases (such as aqueous ammonia), acids, foaming agents, plasticizers, softeners, antioxidants, etc. for adjusting the pH, as long as they do not impair the desired effect of the present invention.
  • bases such as aqueous ammonia
  • Acids such as aqueous ammonia
  • foaming agents plasticizers, softeners, antioxidants, etc.
  • Fiber-like, balloon-like, bead-like, metal powder-like fillers made of glass or plastic, colorants such as pigments and dyes, pH adjusters, film forming aids, leveling agents, thickeners, water repellents, erasing agents.
  • Known materials such as foaming agents and swelling agents can be used.
  • Examples of the form of the pressure-sensitive adhesive composition include solvent-based, emulsion-type pressure-sensitive adhesive, water-based such as water-soluble pressure-sensitive adhesive, hot-melt type pressure-sensitive adhesive, UV-curable pressure-sensitive adhesive, solvent-free type such as EB-curable pressure-sensitive adhesive, and the like. Be done.
  • the pressure-sensitive adhesive composition one containing a solvent can be used in order to maintain good coating workability and the like.
  • a solvent for example, toluene, xylene, ethyl acetate, butyl acetate, acetone, methyl ethyl ketone, hexane and the like can be used.
  • water or an aqueous solvent mainly composed of water can be used as the solvent.
  • the amount of the solvent is not included in the "total amount of the pressure-sensitive adhesive composition" when defining the content of each component.
  • the adhesive sheet of the present invention has at least an adhesive portion and a heat-expandable thermosetting adhesive layer, but may have an arbitrary configuration if necessary.
  • the adhesive sheet of the present invention has, for example, as illustrated in FIG. 6, a first heat-expandable heat-curable adhesive layer 1A having a first main surface a11 and a second main surface a21, and a first main surface.
  • a second heat-expandable heat-curable adhesive layer 1B having a21 and a second main surface a22, and a first heat-expandable heat-curable adhesive layer 1A and a second heat-expandable heat-curable adhesive layer 1B.
  • An intermediate layer 3 arranged between them and adhered to the second main surface a21 of the first heat-expandable heat-curable adhesive layer 1A and the first main surface a12 of the second heat-expandable heat-curable adhesive layer 1B. And may have a plurality of adhesive portions 2 provided in a pattern on the first main surface a11 of the first heat-expandable heat-curable adhesive layer 1A.
  • the first main surface is composed of the adhesive portion 2 and the first heat-expandable thermosetting adhesive layer 1A
  • the second main surface is the second heat-expandable thermosetting type.
  • the adhesive sheet of the present invention composed of the adhesive layer 1B can have good rigidity by having the intermediate layer 3, and is excellent in sticking workability.
  • the intermediate layer is preferably a base material having heat resistance.
  • the level of heat resistance of the base material varies depending on the application, but the melting point of the base material is preferably 150 ° C. or higher, more preferably 200 ° C. or higher, still more preferably 250 ° C. or higher.
  • the melting point is confirmed when the temperature of the intermediate layer (base material) is raised from 30 ° C. to a temperature rise rate of 10 ° C./min using a differential scanning calorimetry device (DSC). , Refers to the temperature indicating the maximum endothermic peak.
  • DSC differential scanning calorimetry device
  • the heat-resistant substrate include polybutylene terephthalate, polyethylene naphthalate (PEN), polyamide, polyimide, polyetherimide, polysulfone, polyetherketone (PEEK), polyphenylene sulfide (PPS), and modified polyphenylene. Examples include oxides.
  • the intermediate layer preferably has a thickness of 1 ⁇ m or more and 200 ⁇ m or less, more preferably 5 ⁇ m or more and 150 ⁇ m or less, and further preferably 10 ⁇ m or more and 100 ⁇ m or less.
  • the intermediate layer may be composed of a single layer of the above-mentioned heat-resistant base material, or may be formed by laminating two or more layers of the same or different above-mentioned heat-resistant base materials.
  • the adhesive sheet of the present invention may be provided with a release liner on the first main surface having the adhesive portion and the second main surface on the side opposite to the side having the adhesive portion.
  • a release liner a known one such as a resin film can be used.
  • the total thickness of the adhesive sheet of the present invention before expansion (before heating) is preferably 10 ⁇ m or more and 600 ⁇ m or less, more preferably 50 ⁇ m or more and 500 ⁇ m or less, and further preferably 100 ⁇ m or more and 400 ⁇ m or less.
  • the total thickness after expansion (after heating) is preferably 20 ⁇ m or more and 2500 ⁇ m or less, more preferably 40 ⁇ m or more and 2000 ⁇ m or less, and further preferably 100 ⁇ m or more and 1000 ⁇ m or less.
  • the total thickness of the adhesive sheet does not include the thickness of the release liner.
  • the adhesive sheet of the present invention preferably has a shear adhesive strength after expansion of 3 MPa or more in a room temperature (23 ° C.) environment, particularly preferably 5 MPa or more, further preferably 6 MPa or more, and further preferably 9 MPa.
  • the above is more preferable. This is because the adhesive holding performance for the inserted member and the inserted member is excellent.
  • the shear adhesive strength after expansion is preferably 1 MPa or more, more preferably 4 MPa or more, and even more preferably 7 MPa or more in an environment of 150 ° C. Since the adhesive sheet of the present invention exhibits desired shear adhesive strength under the above temperature environment, the adhesive sheet of the present invention after expansion has excellent adhesive holding performance for the inserted member and the inserted member even in normal temperature and high temperature environments. This is because higher holding performance can be exhibited.
  • the shear adhesive strength of the adhesive sheet of the present invention after expansion is measured by the method described in Examples described later.
  • the adhesive sheet of the present invention is a step of forming a heat-expandable thermosetting adhesive layer by applying, for example, a heat-expandable thermosetting adhesive composition to a release film and drying it, and an adhesive is applied to another release liner.
  • a step of forming a plurality of patterned adhesive portions by printing the composition in a desired pattern with a gravure coater or the like and drying the composition, a plurality of patterns on the first main surface of the heat-expandable thermosetting adhesive layer. It can be manufactured by going through a process of transferring and crimping the adhesive portion of.
  • the load amount and temperature of the pressure-bonding can be determined.
  • the adhesive portion is formed on the first main surface of the heat-expandable heat-curable adhesive layer (aspect shown in FIG. 1A), and a part of the adhesive portion is thermally expandable. Either a mode in which the heat-curable adhesive layer protrudes from the surface (a mode shown in FIG. 1 (b)) or a mode in which the adhesive portion is embedded in the heat-expandable heat-curable adhesive layer (a mode shown in FIG. 3).
  • the adhesive sheet of the above aspect can also be manufactured.
  • the adhesive sheet of the present invention has an intermediate layer as illustrated in FIG. 6, as a method for producing the adhesive sheet, for example, a heat-expandable heat-curable adhesive composition is applied to a release film and dried.
  • the pressure-sensitive adhesive composition is printed on another release liner in a desired pattern by a gravure coater or the like and dried to form a plurality of patterned pressure-sensitive adhesive portions. It can be manufactured by a step and a step of transferring a plurality of patterned adhesive portions to the first main surface of the first heat-expandable heat-curable adhesive layer and crimping them.
  • the adhesive sheet of the present invention preferably expands in the thickness direction by heating, and preferably does not substantially expand in the surface direction (flow direction or width direction).
  • the adhesive sheet of the present invention is not limited to the use of adhering the insertion member and the inserted member, and may be used only for joining two members or for filling the voids of the adherend. can.
  • it is also used when the adhesive sheet of the present invention is placed in the voids of the adherend and then expanded to form a structure in which two or more portions in the voids are bonded by the adhesive sheet. be able to.
  • Article One aspect of the article of the present invention has a first adherend and a second adherend, the second adherend having voids formed therein, and the first adherend.
  • the body is arranged in the void of the second adherend, and in the void, the first adherend and the second adherend are in the section of "I. Adhesive Sheet”. It is adhered via the inflatable material of the adhesive sheet described in the above.
  • the swelling material of the sheet is filled, and the first adherend and the second adherend are adhered to each other via the swelling material of the adhesive sheet.
  • the heat-expandable heat-curable adhesive layer is cured by heating to develop an adhesive force, and further expanded, so that only the second main surface of the adhesive sheet is formed.
  • the heat-expandable heat-curable adhesive layer after expansion can be adhered to the adherend, and high adhesive strength can be maintained even in a high temperature environment.
  • the first adherend is fixed in the gap of the second adherend with high position accuracy, and the first adherend and the second adherend are firmly connected even in a high temperature environment. It can be an article that can hold the joint.
  • one of the first adherend and the second adherend adheres to the first main surface of the expanded adhesive sheet, and the other is the expanded adhesive sheet. It is adhered to the second main surface.
  • the article can be easily manufactured regardless of the width and size of the gap by inserting the adhesive sheet into the gap in a state where the adhesive sheet is attached to the first adherend. It is preferable that the adherend of 1 is adhered to the first main surface of the expanded adhesive sheet, and the second adherend is adhered to the second main surface of the expanded adhesive sheet.
  • another aspect of the article of the present invention has a first adherend, a third adherend and a fourth adherend, and the third adherend and the fourth adherend.
  • the first adherend is arranged in the void, and in the void, the first adherend, the third adherend, and the first adherend are arranged.
  • the adherend and the fourth adherend are adhered to each other via the swelling material of the adhesive sheet described in the above-mentioned "I. Adhesive sheet" section.
  • the article of this aspect in the gap provided between the third adherend and the fourth adherend, between the first adherend and the third adherend, and in the third adherend.
  • the expanded material of the adhesive sheet described in the above-mentioned "I. Adhesive sheet" section is filled between the first adherend and the fourth adherend, respectively, and the first adherend and the fourth adherend are filled.
  • the adherend of No. 3 and the first adherend and the fourth adherend are respectively adhered to each other via the swelling material of the adhesive sheet.
  • the heat-expandable heat-curable adhesive layer is cured by heating to develop an adhesive force, and further expanded, so that only the second main surface of the adhesive sheet is formed.
  • the heat-expandable heat-curable adhesive layer after expansion can be adhered to the adherend, and high adhesive strength can be maintained even in a high temperature environment.
  • the first adherend is fixed with high positional accuracy in the gap provided between the third adherend and the fourth adherend, and the first adherence is made even in a high temperature environment. It can be an article capable of retaining a strong bond between the body and the third adherend and the fourth adherend.
  • the first adherend and the third and fourth adherends are adhered to the first main surface of the expanded adhesive sheet, and the third and fourth adherends are adhered to each other. It is preferable that each of the fourth adherends is adhered to the second main surface of the expanded adhesive sheet. From the viewpoint of ease of manufacturing an article, the article can be easily manufactured regardless of the width and size of the gap by inserting the adhesive sheet into the gap with the adhesive sheet attached to the first adherend. It is preferable that the adherend is adhered to the first main surface of the expanded adhesive sheet, and the third and fourth adherends are respectively adhered to the second main surface of the expanded adhesive sheet.
  • the "expanded material of the adhesive sheet" in the article of the present invention is the product after the heat expansion of the adhesive sheet described in the above-mentioned "I. Adhesive sheet” section, and the details have been described in detail in the above items. The explanation in is omitted.
  • the first to fourth adherends are not particularly limited and may be appropriately selected depending on the type of the article.
  • the article of the present invention is not particularly limited because the type of each adherend can be appropriately selected, and examples thereof include motors used in automobiles, consumer devices, robots, and the like. Can be. If the article of the present invention is a motor, for example, a combination in which a magnet is used as a first adherend and a rotor in which a slot is formed is used as a second adherend, or a stator in which a slot is formed and the same. Examples thereof include a combination in which an insulating paper for insulating a wire arranged in a slot is used as a first adherend, and a stator in which the slot is formed is used as a second adherend.
  • the article of the present invention can be manufactured, for example, by the method for manufacturing an article described later.
  • the method for producing an article of the present invention is a manufacturing method for adhering two members via an expanded material of the adhesive sheet described in the above-mentioned section "I. Adhesive sheet", and particularly has a gap. It is a manufacturing method in which an inserted member and an insertion member arranged in the void are bonded to each other via an expanded material of the adhesive sheet described in the above-mentioned section "I. Adhesive sheet”.
  • One aspect of the method for producing an article of the present invention is the adhesion described in the above section "I. Adhesive Sheet" to the surface of the first adherend or the surface of the void formed in the second adherend.
  • the present invention comprises a step [3A] of expanding and curing the mold adhesive layer and adhering the first adherend to the second adherend via the expanded material of the adhesive sheet.
  • FIG. 7 is a process diagram showing an example of a method for manufacturing an article of the present invention.
  • the first main surface (the surface having the adhesive portion 2) of the adhesive sheet 10 described in the above section "I. Adhesive sheet” is attached to both sides of the first adherend 51 (FIG. 7 (a). ), Step [1A]).
  • the first adherend 51 to which the adhesive sheet 10 is attached is inserted into the gap S formed in the second adherend 52 (FIG. 7 (b), step [2A]).
  • the adhesive sheet 10 is heated to expand and cure the heat-expandable thermosetting adhesive layer (reference numeral 1 in FIG. 7C), and the expanded second main surface of the adhesive sheet 10'.
  • Adhesive sheet is formed on the surface of a first adherend or the surface of a void composed of a third adherend and a fourth adherend.
  • the heat-expandable heat-curable adhesive layer is expanded and cured, and the first adherend, the third adherend, and the fourth adherend are formed through the expanded material of the adhesive sheet. It has a step [3B] of adhering the above.
  • FIG. 8 is a process diagram showing another example of the method for manufacturing the article of the present invention.
  • the first main surface (the surface having the adhesive portion 2) of the adhesive sheet 10 described in the above section "I. Adhesive sheet” is attached to both sides of the first adherend 51 (FIG. 8 (a), step [1B]).
  • the first adherend 51 to which the adhesive sheet 10 is attached is inserted into the gap S between the third adherend 53 and the fourth adherend 54 (FIG. 8 (b)). , Step [2B]).
  • the adhesive sheet 10 is heated to expand and cure the heat-expandable thermosetting adhesive layer (reference numeral 1 in FIG. 8C), and the expanded second main surface of the adhesive sheet 10'.
  • the surface opposite to the surface having the adhesive portion 2 is bonded to the third adherend 53 and the fourth adherend 54 (FIG. 8 (c), step [3B]).
  • the void S is filled with the expanded heat-expandable heat-curable adhesive layer (reference numeral 1'in FIG. 8C), and the expanded heat-expandable heat-curable adhesive layer (FIG. 8).
  • the surface of reference numeral 1') in (c) is adhered to the third adherend 53 and the fourth adherend 54.
  • one surface of the first adherend 51 and the third adherend 53, and the other surface of the first adherend 51 and the fourth adherend 54 are each expanded.
  • the article 50 bonded via the adhesive sheet 10' is obtained.
  • the first adherend corresponds to the insertion member.
  • the second adherend in which the void is formed, and the set of the third adherend and the fourth adherend constituting the void correspond to the inserted member.
  • the void in the second adherend include holes, grooves, openings and the like formed in the adherend.
  • the gap between the third adherend and the fourth adherend is, for example, a separation space in a state where the third adherend and the fourth adherend are arranged apart from each other. Examples thereof include holes, grooves, openings and the like formed by the third adherend and the fourth adherend.
  • the first main surface of the adhesive sheet is bonded to the surface of one of the adherends to be the insert member or the insert member.
  • the first main surface of the adhesive sheet is bonded to both sides (two facing surfaces) of the first adherend, but the first cover is attached.
  • the first main surface of the adhesive sheet may be attached to at least one surface of the body, or the first main surface of the adhesive sheet may be attached to three or more surfaces.
  • the first main surface of the adhesive sheet may be attached to the first adherend, and in the case of the step [1A], the first adhesive sheet may be attached.
  • the main surface of the above may be bonded to the surface of the void formed in the second adherend, while in the case of step [1B], the third adherend and the fourth adherend may be used. It may be bonded to the surface of the formed void.
  • the first main surface of the adhesive sheet may be bonded to one surface of the surface of the void, or the first main surface of the adhesive sheet may be bonded to two or more surfaces.
  • Adhesive sheets may be individually attached to each surface of the adherend.
  • the adhesive sheet is attached to the first adherend, the first main surfaces of the separate adhesive sheets are attached to the two opposing surfaces of the first adherend, and the first surface is attached.
  • the adherend may be sandwiched between two adhesive sheets, or one adhesive sheet may be bonded so as to cover a plurality of surfaces of the first adherend.
  • the adhesive sheet is attached to the surface of the void formed in the second adherend or the void formed by the third adherend and the fourth adherend (the surface of the adherend). May adhere the first main surfaces of separate adhesive sheets to two facing surfaces of the voids, or may adhere the adhesive sheets so as to cover the plurality of surfaces of the voids. good.
  • the conditions for bonding the first main surface of the adhesive sheet to the surface of the adherend are not particularly limited, but for example, the bonding is preferably in the range of normal temperature (23 ° C) to 40 ° C, and normal temperature (23 ° C). ) Is more preferable. Adhesion at room temperature (23 ° C) can be easily bonded using the initial adhesiveness of the first main surface of the adhesive sheet, and the initial adhesive force of the second main surface of the adhesive sheet is enhanced. It is preferable in that it can suppress the above-mentioned and maintain the insertability.
  • the first adherend is inserted into the gap formed in the second adherend. Further, in the step [2B], the first adherend is inserted into the gap between the third adherend and the fourth adherend.
  • the adhesive sheet is attached to the first adherend. If this is the case, the adhesive sheet does not easily adhere to the surface of the void and can be easily inserted. Similarly, when the adhesive sheet is attached to the surface of the void, the adhesive sheet does not easily adhere to the first adherend and can be easily inserted, and even if it adheres, the adhesive sheet does not easily come off due to the force received during insertion. Therefore, the temporary fixing property can be maintained, and the insertability is improved.
  • the adhesive sheet is heated to expand and cure the heat-expandable thermosetting adhesive layer with the first adherend inserted in the gap.
  • the heating may be performed directly on the heat-expandable thermosetting adhesive layer of the adhesive sheet, or may be performed on the entire body including the adherend.
  • a non-contact type or a contact type may be used, and heating methods such as hot air heating, heating by contact with an electric heater, heating by light irradiation such as an infrared heater or a halogen heater, dielectric heating, and induction heating shall be used. Can be done.
  • the heating temperature in the steps [3A] and [3B] can be set at a temperature at which the heat-expandable thermosetting adhesive layer can expand and cure.
  • the temperature is preferably a temperature corresponding to the curing temperature of the heat-expandable heat-curable adhesive layer and the expansion temperature (expansion start temperature) of the expansion agent, and is preferably equal to or higher than the expansion temperature of the expansion agent. Specifically, it is preferably 80 ° C. to 350 ° C., more preferably 100 ° C. to 250 ° C., and even more preferably 150 ° C. to 200 ° C.
  • the heating time in the steps [3A] and [3B] can be set to a time during which the heat-expandable thermosetting adhesive layer can expand and cure, and is preferably equal to or longer than the expansion time. Specifically, it is preferably 5 minutes to 300 minutes, more preferably 10 ° C. to 200 minutes, and even more preferably 20 minutes to 100 minutes.
  • the heating time is preferably suppress thermal damage to the adherend and firmly join the members.
  • the gap is filled by expanding the adhesive sheet by heating in the gap, and in the case of the step [3A], the first cover is formed through the expanded material of the adhesive sheet.
  • the adherend and the second adherend are adhered, while in the case of the step [3B], the first adherend, the third adherend and the fourth adherend are adhered to each other. Will be done.
  • the adhesive sheet expands due to heating in the voids, the second main surface of the adhesive sheet can come into contact with the adherend to which the adhesive sheet is not provided.
  • the expanded material of the heat-expandable heat-curable adhesive layer constituting the first main surface and the second main surface of the adhesive sheet is an insertion member because the adhesive force is developed by heat curing.
  • the first adherend and the second adherend or the third adherend and the fourth adherend, which are the members to be inserted, can be firmly adhered to each other. Further, since the expanded product of the thermosetting heat-curable adhesive layer is a thermosetting product and has high heat resistance, it is possible to maintain high adhesive strength in a high temperature environment.
  • the article obtained by the method for manufacturing the article of the present invention is not particularly limited, and examples thereof include a motor mounted on a hybrid vehicle or the like.
  • the motor is a component in which a first main surface of an adhesive sheet and a part of a component such as a magnet are previously bonded, and the adhesive sheet is bonded to a gap of a core member constituting the motor. It can be manufactured by heating the adhesive sheet to expand and cure the heat-expandable thermosetting adhesive layer after inserting and placing the adhesive. Therefore, the method for manufacturing an article of the present invention is useful as a method for manufacturing a motor.
  • the present disclosure is not limited to the above embodiment.
  • the above embodiment is an example, and any one having substantially the same structure as the technical idea described in the claims of the present disclosure and having the same effect and effect is the present invention. Included in the technical scope of the disclosure.
  • thermosetting adhesive composition (a-1) Epoxy resin 1 (BPA type, epoxy equivalent 8,000 g / eq., Solid (25 ° C.), softening point 200 ° C. or higher) was added to 35 parts by mass, and epoxy resin 2 (modified BPA type, epoxy equivalent 400 g / eq., 140).
  • thermosetting adhesive composition (a-2) ⁇ Preparation of thermally expandable thermosetting adhesive composition (a-2)> Epoxy resin 4 (BPA type, epoxy equivalent 188 g / eq., 11,000 mPa ⁇ s (25 ° C.)) was used in place of epoxy resin 2 in 7 parts by mass, and epoxy resin 5 (modified novolak) was used in place of epoxy resin 3.
  • Preparation Example 1 except that the mold, epoxy equivalent 160 g / eq., Semi-solid (25 ° C.)) is 58 parts by mass, and the amount of the curing agent 1 used is changed from 3.8 parts by mass to 6.7 parts by mass.
  • the heat-expandable thermosetting adhesive composition (a-2) was prepared in the same manner as in the above.
  • thermosetting adhesive composition (a-3) ⁇ Preparation of thermally expandable thermosetting adhesive composition (a-3)> The amount of epoxy resin 1 used was changed from 35 parts by mass to 25 parts by mass, the amount of epoxy resin 2 used was changed from 7 parts by mass to 17 parts by mass, and the amount of curing agent 1 used was changed from 3.8 parts by mass to 4 parts.
  • the heat-expandable thermosetting adhesive composition (a-3) was prepared in the same manner as in Preparation Example 1 except that the composition was changed to 1 part by mass.
  • the pressure-sensitive adhesive (b-1) was obtained by mixing and stirring the above-mentioned pressure-sensitive adhesive solution and 1.2 parts by mass of "NC40" (isocyanate-based cross-linking agent manufactured by DIC Corporation).
  • the peak temperature of tan ⁇ of the pressure-sensitive adhesive layer obtained by using the above-mentioned pressure-sensitive adhesive (b-1) was 0 ° C., and the gel fraction was 20% by mass.
  • Example 1 The heat-expandable thermosetting adhesive composition (a-1) obtained in Adjustment Example 1 was applied to the surface of a release liner (one side of a polyethylene terephthalate film having a thickness of 50 ⁇ m was peeled off with a silicone compound). Using a rod-shaped metal applicator, coat the coated product so that the thickness after drying is 62 ⁇ m, and put the coated product in a dryer at 85 ° C. for 5 minutes to dry it into a sheet with a thickness of 62 ⁇ m. A sheet in which the heat-expandable thermosetting adhesive layer (A-1) was formed on one side of the release liner was obtained. Two sheets were prepared.
  • thermosetting adhesive layer (A-1) of one of the sheets was laminated on the surface of the thermosetting adhesive layer (A-1) of one of the sheets, and the linear pressure was applied with a laminator preheated to 50 ° C. It was applied at 3 N / mm, and a polyimide film was laminated on one side of the thermosetting expandable adhesive layer (A-1).
  • the heat-expandable thermosetting adhesive layer (A-1) of the other sheet is laminated on the polyimide film side of the laminated body, and attached at a linear pressure of 3 N / mm with a laminator preheated to 50 ° C.
  • the above pressure-sensitive adhesive (b-1) was dot-printed on the surface of a release liner (one side of a polyethylene terephthalate film having a thickness of 25 ⁇ m peeled off with a silicone compound) using a gravure coater, and 85 By drying at ° C. for 2 minutes, a plurality of substantially circular island-shaped adhesive portions (B-1) having a thickness of 3 ⁇ m and an area of 0.5 mm per piece were formed.
  • the shortest distance between an arbitrary adhesive portion (b1) selected from two or more adhesive portions (B-1) and an adhesive portion (b2) close to the adhesive portion (b1) was 0.2 mm.
  • the release liner on one surface of the adhesive sheet (x-1) is peeled off, and the heat-expandable thermosetting adhesive layer (A-1) on one side of the adhesive sheet (x-1) is attached to the adhesive.
  • An adhesive sheet (X-1) was obtained by superimposing the portions (B-1) and attaching them with a laminator at 23 ° C. at a linear pressure of 3 N / mm.
  • the total thickness of the adhesive sheet (X-1) is 152 ⁇ m, and the adhesive portion (B-1) is laminated on one surface of the heat-expandable thermosetting adhesive layer (A-1). Met. That is, as illustrated in FIG. 1 (a), in the thickness direction of the adhesive sheet (X-1), the first surface of the adhesive portion (B-1) is one of the heat-expandable thermosetting adhesive layers ( Located outside the first main surface of A-1), the second surface of the adhesive portion (B-1) is the first main surface of one of the heat-expandable thermosetting adhesive layers (A-1). Was in contact with. The ratio of the total area of the adhesive portion (B-1) to the area of the first main surface of the adhesive sheet (X-1) was 60%.
  • the first surface of the adhesive portion (B-1) has one heat in the thickness direction. It is located at the same position as the first main surface of the expandable thermosetting adhesive layer (A-1), and the second surface of the adhesive portion (B-1) is one of the heat-expandable thermosetting adhesive layers (A-). It was located between the first main surface and the second main surface of 1).
  • the heat-expandable thermosetting adhesive layer (A-1) after curing (after expansion) in the adhesive sheet (X-1) heated at 150 ° C. for 60 minutes has an expansion coefficient of 390% and a glass transition temperature of 157 ° C., respectively. Met.
  • the expansion coefficient and the glass transition temperature were measured by the method described in the above-mentioned "I. Adhesive sheet" section. The same shall apply to the following examples and comparative examples.
  • Example 2 The laminating temperature at the time of superimposing and pasting the heat-expandable thermosetting adhesive layer (A-1) of the adhesive sheet (x-1) and the adhesive portion (B-1) is changed from 23 ° C. to 50 ° C.
  • An adhesive sheet (X-2) was obtained in the same manner as in Example 1 except for the above.
  • the shortest distance between an arbitrary adhesive portion (b1) selected from two or more adhesive portions (B-1) and an adhesive portion (b2) close to the adhesive portion (b1) was 0.2 mm.
  • the total thickness of the adhesive sheet (X-2) is 149 ⁇ m, and the adhesive portion (B-1) is embedded in one surface of the heat-expandable thermosetting adhesive layer (A-1). there were. That is, as illustrated in FIG. 3, in the thickness direction of the adhesive sheet (X-2), the first surface of the adhesive portion (B-1) is one of the heat-expandable thermosetting adhesive layers (A-1). ) Is at the same position as the first main surface, and the second surface of the adhesive portion (B-1) is the first main surface and the second surface of one of the heat-expandable thermosetting adhesive layers (A-1). It was located between the main surface of the. The ratio of the total area of the adhesive portion (B-1) to the area of the first main surface of the adhesive sheet (X-2) was 60%.
  • the first surface of the adhesive portion (B-1) has one heat in the thickness direction. It is located at the same position as the first main surface of the expandable thermosetting adhesive layer (A-1), and the second surface of the adhesive portion (B-1) is one of the heat-expandable thermosetting adhesive layers (A-). It was located between the first main surface and the second main surface of 1).
  • the heat-expandable thermosetting adhesive layer (A-1) after curing (after expansion) in the adhesive sheet (X-2) heated at 150 ° C. for 60 minutes has an expansion coefficient of 390% and a glass transition temperature of 157 ° C., respectively. Met.
  • Example 3 Instead of the adhesive portion (B-1), a plurality of substantially circular adhesive portions (B- 2 ) having a thickness of 3 ⁇ m and an area of 0.3 mm per piece are formed on the release liner, and the adhesive sheet is formed.
  • An adhesive sheet in the same manner as in Example 1) except that one of the heat-expandable thermosetting adhesive layers (A-1) of (x-1) and the adhesive portion (B-2) are overlapped. X-3) was obtained.
  • the shortest distance between an arbitrary adhesive portion (b1) selected from two or more adhesive portions (B-2) and an adhesive portion (b2) close to the adhesive portion (b1) was 0.2 mm.
  • the total thickness of the adhesive sheet (X-3) is 152 ⁇ m, and the adhesive portion (B-2) is laminated on one surface of the heat-expandable thermosetting adhesive layer (A-1). Met. That is, as illustrated in FIG. 1A, in the thickness direction of the adhesive sheet (X-3), the first surface of the adhesive portion (B-2) is one of the heat-expandable thermosetting adhesive layers (A). -1) is located outside the first main surface, and the second main surface of the adhesive portion (B-2) is the first main surface of one of the heat-expandable thermosetting adhesive layers (A-1). Was in contact with.
  • the ratio of the total area of the adhesive portion (B-2) to the area of the first main surface of the adhesive sheet (X-3) was 37%.
  • the first surface of the adhesive portion (B-2) has one heat in the thickness direction. It is located at the same position as the first main surface of the expandable thermosetting adhesive layer (A-1), and the second surface of the adhesive portion (B-2) is one of the heat-expandable thermosetting adhesive layers (A-). It was located between the first main surface and the second main surface of 1).
  • the heat-expandable thermosetting adhesive layer (A-1) after curing (after expansion) in the adhesive sheet (X-3) heated at 150 ° C. for 60 minutes has an expansion coefficient of 390% and a glass transition temperature of 157 ° C., respectively. Met.
  • Example 4 Instead of the sheet-shaped heat-expandable heat-curable adhesive layer (A-1), a sheet-shaped heat-expandable heat-curable adhesive layer (A-2) having a thickness changed from 62 ⁇ m to 75 ⁇ m is used as a release liner. Two sheets formed on one side of the above are prepared, and the other heat-expandable heat-curable adhesive layer (A-2) is laminated on the surface of one heat-expandable heat-curable adhesive layer (A-2) in advance.
  • an adhesive sheet (x-4) having a thickness of 150 ⁇ m was obtained by laminating the heat-expandable heat-curable adhesive layer (A-2). ..
  • An adhesive sheet (X-4) was obtained in the same manner as in Example 1 except that the adhesive sheet (x-4) was used instead of the adhesive sheet (x-1).
  • the total thickness of the adhesive sheet (X-4) is 153 ⁇ m, and the adhesive portion (B-1) is laminated on one surface of the heat-expandable thermosetting adhesive layer (A-2). rice field. That is, as illustrated in FIG. 1 (a), in the thickness direction of the adhesive sheet (X-4), the first surface of the adhesive portion (B-1) is one of the heat-expandable thermosetting adhesive layers (A). -2) Located outside the first main surface, the second surface of the adhesive portion (B-1) is with the first main surface of one of the heat-expandable thermosetting adhesive layers (A-2). I was in contact. The ratio of the total area of the adhesive portion (B-1) to the area of the first main surface of the adhesive sheet (X-4) was 60%.
  • the first surface of the adhesive portion (B-1) has one heat in the thickness direction. It is located at the same position as the first main surface of the expandable thermosetting adhesive layer (A-2), and the second surface of the adhesive portion (B-1) is one of the thermally expandable thermosetting adhesive layers (A-). It was located between the first main surface and the second main surface of 2).
  • the heat-expandable thermosetting adhesive layer (A-2) after curing (after expansion) in the adhesive sheet (X-4) heated at 150 ° C. for 60 minutes has an expansion coefficient of 390% and a glass transition temperature of 157 ° C., respectively. Met.
  • thermosetting adhesive layer (A-3) using a thermosetting adhesive composition (a-2) instead of the thermosetting adhesive composition (a-1). ) was formed on one side of the release liner, and the heat-expandable thermosetting adhesive layer (A-3) was replaced with the heat-expandable thermosetting adhesive layer (A-1) on both sides of the polyimide film. ) was used to obtain an adhesive sheet (X-5) in the same manner as in Example 1 except that the polyimide film was laminated on both sides.
  • the total thickness of the adhesive sheet (X-5) is 152 ⁇ m, and the adhesive portion (B-1) is laminated on one surface of the heat-expandable thermosetting adhesive layer (A-3). rice field. That is, as illustrated in FIG. 1A, in the thickness direction of the adhesive sheet (X-5), the first surface of the adhesive portion (B-1) is one of the heat-expandable thermosetting adhesive layers (A). -3) is located outside the first main surface, and the second surface of the adhesive portion (B-1) is with the first main surface of one of the heat-expandable thermosetting adhesive layers (A-3). I was in contact. The ratio of the total area of the adhesive portion (B-1) to the area of the first main surface of the adhesive sheet (X-5) was 60%.
  • the first surface of the adhesive portion (B-1) has one heat in the thickness direction. It is located at the same position as the first main surface of the expandable thermosetting adhesive layer (A-3), and the second surface of the adhesive portion (B-1) is one of the heat-expandable thermosetting adhesive layers (A-). It was located between the first main surface and the second main surface of 3).
  • the heat-expandable thermosetting adhesive layer (A-3) after curing (after expansion) on the adhesive sheet (X-5) heated at 150 ° C. for 60 minutes has an expansion coefficient of 415% and a glass transition temperature of 172 ° C. there were.
  • thermosetting adhesive layer (A-4) using a thermosetting adhesive composition (a-3) instead of the thermosetting adhesive composition (a-1). ) was formed on one side of the release liner, and a thermosetting adhesive layer (A-4) was used instead of the thermosetting adhesive layer (A-1).
  • An adhesive sheet (X-6) was obtained in the same manner as in Example 1 except that it was laminated on both sides of the polyimide film.
  • the total thickness of the adhesive sheet (X-6) is 152 ⁇ m, and the adhesive portion (B-1) is laminated on one surface of the heat-expandable thermosetting adhesive layer (A-4). Met. That is, as illustrated in FIG. 1A, in the thickness direction of the adhesive sheet (X-6), the first surface of the adhesive portion (B-1) is one of the heat-expandable thermosetting adhesive layers (A). -4) is located outside the first main surface, and the second surface of the adhesive portion (B-1) is with the first main surface of one of the heat-expandable thermosetting adhesive layers (A-4). I was in contact. The ratio of the total area of the adhesive portion (B-1) to the area of the first main surface of the adhesive sheet (X-6) was 60%.
  • the first surface of the adhesive portion (B-1) has one heat in the thickness direction. It is located at the same position as the first main surface of the expandable thermosetting adhesive layer (A-4), and the second surface of the adhesive portion (B-1) is one of the thermally expandable thermosetting adhesive layers (A-). It was located between the first main surface and the second main surface of 4).
  • the heat-expandable thermosetting adhesive layer (A-4) after curing (after expansion) in the adhesive sheet (X-6) after heating at 150 ° C. for 60 minutes has an expansion coefficient of 424% and a glass transition temperature of 145 ° C., respectively. Met.
  • the total thickness of the adhesive sheet (X'-1) is 152 ⁇ m, and the adhesive layer (B'-1) is laminated on one surface of the heat-expandable thermosetting adhesive layer (A-1). It was in a state. Of the surfaces of the adhesive sheet (X'-1), the adhesive layer (B'-1) side is the first main surface, and the heat-expandable thermosetting adhesive layer (A-1) side is the second main surface. And said.
  • the first adhesive sheet (X'-1) is provided.
  • the ratio of the total area of the adhesive layer (B'-1) to the area of the main surface was 100%.
  • the expansion coefficient and the glass transition temperature of the heat-expandable heat-curable adhesive layer (A-1) after curing (after expansion) in the adhesive sheet (X'-1) after heating at 150 ° C. for 60 minutes are determined in Example 1. It was the same as the expansion coefficient and the glass transition temperature of the heat-expandable heat-curable adhesive layer (A-1) in.
  • the total thickness of the adhesive sheet (X'-2) was 149 ⁇ m.
  • the ratio of the total area of the adhesive portion to the area of one side of the adhesive sheet (X'-2) was 0%.
  • One of the surfaces of the adhesive sheet (X'-2) on the heat-expandable thermosetting layer (A-1) side is used as the first main surface, and the other surface is the heat-expandable thermosetting layer (A). -1)
  • the surface on the side was used as the second main surface.
  • the expansion coefficient and the glass transition temperature of the heat-expandable heat-curable adhesive layer (A-1) after curing (after expansion) in the adhesive sheet (X'-2) after heating at 150 ° C. for 60 minutes are the heat in Example 1. It was the same as the expansion coefficient and the glass transition temperature of the expandable heat-curable adhesive layer (A-1).
  • the release liner of the test sample crimped to the aluminum plate was peeled off, another aluminum plate having a smooth surface treated with degreasing was placed on the upper surface of the test sample, and the load was 0.5 MPa at 23 ° C. for 10 seconds. It was crimped. Leave it in an environment of 23 ° C for 30 minutes, chuck the ends of the above two aluminum plates, and use a Tensilon tensile tester [manufactured by A & D Co., Ltd., model: RTM-100] to 10 mm / min in the 180 degree direction. The adhesive force in the shear direction was measured in the tensile test at.
  • the release liner of the test sample crimped to the aluminum plate was peeled off, another aluminum plate having a smooth surface treated with degreasing was placed on the upper surface of the test sample, and the load was 0.5 MPa at 23 ° C. for 10 seconds. It was crimped. Leave it in an environment of 23 ° C for 30 minutes, chuck the ends of the above two aluminum plates, and use a Tensilon tensile tester [manufactured by A & D Co., Ltd., model: RTM-100] to 10 mm / min in the 180 degree direction. The adhesive force in the shear direction was measured in the tensile test at.
  • the adhesive sheets of the above Examples and Comparative Examples were cut into a size of 10 mm ⁇ 10 mm and used as a test sample.
  • Two aluminum plates with a smooth surface of width 15 mm x length 70 mm x thickness 0.5 mm are degreased, and a two-component mixed room temperature curing type is used as a strong adhesive for fixing the test sample on the upper surface of one of the aluminum plates.
  • Acrylic adhesive Metal Lock manufactured by Cemedine Co., Ltd.
  • the release liner on the second main surface side of the test sample is peeled off, and the second main surface of the test sample is passed through the above strong adhesive to one of the above.
  • the sample was placed on an aluminum plate and crimped at 23 ° C. using a 2 kg hand roller.
  • the release liner on the first main surface side of the test sample crimped to the aluminum plate was peeled off, and the other aluminum plate having a degreased smooth surface was placed on the upper surface of the test sample, and a load of 0.5 MPa was applied. It was crimped at 23 ° C. for 10 seconds. Leave it in an environment of 23 ° C for 5 minutes, chuck the ends of the above two aluminum plates, and use a Tensilon tensile tester [manufactured by A & D Co., Ltd., model: RTM-100] to 10 mm / min in the 180 degree direction. The adhesive force in the shear direction was measured in the tensile test at. The adhesive force at this time was defined as the shear adhesive force of the first main surface of the adhesive sheet.
  • the first main surface of the test sample from which the release liner was peeled off and one aluminum plate were crimped via the above strong adhesive, and the other aluminum plate and the second main surface of the test sample were crimped. Except for this, the adhesive force in the shear direction was measured in the same manner as the above-mentioned measuring method. At this time, the adhesive force was defined as the shear adhesive force of the second main surface of the adhesive sheet.
  • the SUS plate was erected at 90 ° to the floor at 23 ° C., and the SUS plate was lifted and dropped vertically so that the test sample attached to the SUS plate had a height of 15 cm from the floor. This was repeated 10 times. Then, the amount of deviation of the fixed test sample due to dropping was measured, and the temporary fixing property to the member was evaluated according to the following criteria.
  • ⁇ The amount of deviation of the test sample was 0 mm.
  • ⁇ The amount of deviation of the test sample was less than 1 mm.
  • ⁇ The amount of deviation of the test sample was 1 mm or more.
  • X The test sample was peeled off from the SUS plate.
  • the release liner on one main surface side was peeled off and crimped to a SUS plate to fix it. Then, the one from which the other release liner of the adhesive sheet was removed was used as a test sample.
  • two smooth glass plates having a width of 70 mm, a length of 50 mm, and a thickness of 1.5 mm were prepared, and two spacers having a width of 5 mm and a length of 50 mm were placed on one glass plate (C1) of 60 mm. They were lined up in parallel at intervals and glued together. Then, the other glass plate (C2) was placed on the spacer and adhered to the spacer to create a gap composed of two pieces of glass and two spacers.
  • test sample is allowed to stand at 90 ° to the floor, inserted vertically into a gap consisting of two pieces of glass and two spacers, and passed through, so that the test sample passes through without adhering to the glass.
  • the thickness of the formed spacer was measured, and the insertability of the test sample into the member was evaluated according to the following judgment.
  • ⁇ The test sample was able to pass even when the thickness of the spacer was increased by 50 ⁇ m with respect to the total thickness of the adhesive sheet and the SUS plate.
  • ⁇ The test sample could not pass when the thickness of the spacer was increased by 50 ⁇ m with respect to the total thickness of the adhesive sheet and the SUS plate, and could pass when the thickness was increased by 75 ⁇ m.
  • the test sample could not pass when the thickness of the spacer was increased by 75 ⁇ m with respect to the total thickness of the adhesive sheet and the SUS plate, and could pass when the thickness was increased by 100 ⁇ m.
  • X The test sample could not pass even when the thickness of the spacer was increased by 100 ⁇ m with respect to the total thickness of the adhesive sheet and the SUS plate, or the adhesive sheet was peeled off from the SUS plate when it was passed.
  • the adhesive sheets (X-1) to (X) of Examples and Comparative Examples which were previously cut to a size of 10 mm ⁇ 10 mm on the upper surface side of the aluminum plate 51 and between the two spacers 53. -6) and (X'-1) to (X'-2) (reference numeral 10 in FIG. 9) are each on the first main surface (adhesive portion or surface having the adhesive layer) side of the adhesive sheet.
  • the release liner was peeled off and attached, and crimped using a 2 kg hand roller.
  • the adhesive sheet (X'-2) prepared in Comparative Example 2 above the release liner on one main surface side was peeled off and attached, and crimped using a 2 kg hand roller.
  • the release liner on the second main surface (heat-expandable heat-curable adhesive layer) side of the adhesive sheet 10 is peeled off, and the second main surface (heat-expandable heat-curable adhesive layer) of the adhesive sheet 10 is peeled off.
  • Another aluminum plate 52 width 15 mm ⁇ length 70 mm ⁇ thickness 0.5 mm
  • the release liner on the other main surface side was peeled off and placed on another aluminum plate 52.
  • the fixed product was heated at 150 ° C. for 60 minutes and then left to cool in an environment of 23 ° C. for 30 minutes.
  • the adhesive sheets of Examples 1 to 6 had good temporary fixing property and insertability before expansion, and had high normal temperature and high temperature adhesive force after expansion.
  • Comparative Example 1 in which the adhesive portion is not provided in a pattern on the first main surface of the adhesive sheet (the adhesive layer is provided on the entire surface of one side of the heat-expandable heat-curable adhesive layer), it is before expansion.
  • the temporary fixing property and the insertability were good, the normal temperature and high temperature adhesive force after expansion was lower than that of the adhesive sheet of the example, suggesting that the high temperature adhesiveness was particularly inferior.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Adhesive Tapes (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Laminated Bodies (AREA)
PCT/JP2021/045256 2020-12-15 2021-12-09 接着シート、並びに物品及び物品の製造方法 Ceased WO2022131110A1 (ja)

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JP2023020712A JP2023065455A (ja) 2020-12-15 2023-02-14 接着シート、並びに物品及び物品の製造方法
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20240126793A (ko) * 2023-02-14 2024-08-21 주식회사 노바텍 차폐 자석의 제조방법

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114694915B (zh) * 2020-12-29 2022-12-30 天津三环乐喜新材料有限公司 带粘结层的磁体、制备方法及磁体组件的制备方法
EP4044221A1 (en) * 2021-02-10 2022-08-17 AT & S Austria Technologie & Systemtechnik Aktiengesellschaft Heat removal architecture for stack-type component carrier with embedded component

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07158171A (ja) * 1993-12-08 1995-06-20 Kurihara Sangyo Kk 建築用材のシーリング材及びシーリング工法
JPH07238276A (ja) * 1992-09-25 1995-09-12 Toyota Motor Corp 熱硬化性高発泡型シール材
JP2008007704A (ja) * 2006-06-30 2008-01-17 Nitto Denko Corp 発泡充填用組成物、発泡充填部材および充填用発泡体
JP2011054743A (ja) * 2009-09-01 2011-03-17 Nitto Denko Corp 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
JP2014005423A (ja) * 2012-06-27 2014-01-16 Sika Technology Ag 粘着性組成物及び粘着性発泡シート
WO2016163514A1 (ja) * 2015-04-10 2016-10-13 株式会社寺岡製作所 接着シート
WO2018123615A1 (ja) * 2016-12-26 2018-07-05 Dic株式会社 接着テープ、物品及び物品の製造方法
WO2019155896A1 (ja) * 2018-02-09 2019-08-15 Dic株式会社 接着テープ、物品及び物品の製造方法

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6565969B1 (en) * 1999-10-21 2003-05-20 3M Innovative Properties Company Adhesive article
JP2001207137A (ja) * 2000-01-31 2001-07-31 Toyo Ink Mfg Co Ltd 粘着シート及び該シートの製造方法
JP2012122027A (ja) * 2010-12-10 2012-06-28 Nitto Denko Corp 粘着テープ又はシート
JP2013181054A (ja) * 2012-02-29 2013-09-12 Nitto Denko Corp 粘着製品
WO2015190235A1 (ja) 2014-06-11 2015-12-17 Dic株式会社 接着テープ、物品、モーター及び物品の製造方法
JP6679239B2 (ja) * 2014-11-28 2020-04-15 日東電工株式会社 粘着シート
DE102016202479A1 (de) * 2016-02-18 2017-08-24 Tesa Se Haftklebestreifen
KR102520278B1 (ko) * 2017-08-10 2023-04-11 가부시키가이샤 데라오카 세이사쿠쇼 접착 시트
KR102422212B1 (ko) * 2017-08-10 2022-07-18 가부시키가이샤 데라오카 세이사쿠쇼 접착 시트 및 그 제조 방법
JP7141820B2 (ja) 2017-08-23 2022-09-26 旭化成建材株式会社 樹脂発泡体複合板及びこれを含む構造体
JP7077735B2 (ja) * 2018-04-09 2022-05-31 Dic株式会社 接着テープ、物品、モーター及び物品の製造方法
TWI679123B (zh) * 2018-05-29 2019-12-11 奇鋐科技股份有限公司 散熱貼合結構

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07238276A (ja) * 1992-09-25 1995-09-12 Toyota Motor Corp 熱硬化性高発泡型シール材
JPH07158171A (ja) * 1993-12-08 1995-06-20 Kurihara Sangyo Kk 建築用材のシーリング材及びシーリング工法
JP2008007704A (ja) * 2006-06-30 2008-01-17 Nitto Denko Corp 発泡充填用組成物、発泡充填部材および充填用発泡体
JP2011054743A (ja) * 2009-09-01 2011-03-17 Nitto Denko Corp 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
JP2014005423A (ja) * 2012-06-27 2014-01-16 Sika Technology Ag 粘着性組成物及び粘着性発泡シート
WO2016163514A1 (ja) * 2015-04-10 2016-10-13 株式会社寺岡製作所 接着シート
WO2018123615A1 (ja) * 2016-12-26 2018-07-05 Dic株式会社 接着テープ、物品及び物品の製造方法
WO2019155896A1 (ja) * 2018-02-09 2019-08-15 Dic株式会社 接着テープ、物品及び物品の製造方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20240126793A (ko) * 2023-02-14 2024-08-21 주식회사 노바텍 차폐 자석의 제조방법
KR102776920B1 (ko) * 2023-02-14 2025-03-10 주식회사 노바텍 차폐 자석의 제조방법

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US20230312995A1 (en) 2023-10-05
JP2023065455A (ja) 2023-05-12

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