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WO2018181769A1 - Feuille adhésive - Google Patents

Feuille adhésive Download PDF

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Publication number
WO2018181769A1
WO2018181769A1 PCT/JP2018/013356 JP2018013356W WO2018181769A1 WO 2018181769 A1 WO2018181769 A1 WO 2018181769A1 JP 2018013356 W JP2018013356 W JP 2018013356W WO 2018181769 A1 WO2018181769 A1 WO 2018181769A1
Authority
WO
WIPO (PCT)
Prior art keywords
pressure
sensitive adhesive
thermally expandable
adhesive layer
coating film
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2018/013356
Other languages
English (en)
Japanese (ja)
Inventor
高志 阿久津
揮一郎 加藤
晃司 土渕
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.)
Lintec Corp
Original Assignee
Lintec Corp
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 Lintec Corp filed Critical Lintec Corp
Priority to JP2019510156A priority Critical patent/JP6808817B2/ja
Priority to CN201880022422.5A priority patent/CN110461978B/zh
Priority to KR1020197027704A priority patent/KR102509251B1/ko
Publication of WO2018181769A1 publication Critical patent/WO2018181769A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/40—Adhesives in the form of films or foils characterised by release liners
    • 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
    • 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
    • C09J2301/312—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 parameters being the characterizing feature
    • 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
    • C09J2301/416—Additional features of adhesives in the form of films or foils characterized by the presence of essential components use of irradiation

Definitions

  • the present invention relates to an adhesive sheet.
  • the pressure-sensitive adhesive sheet may be used not only for semi-permanent fixing of members but also for temporary fixing for temporarily fixing building materials, interior materials, electronic parts and the like. Such a pressure-sensitive adhesive sheet for temporarily fixing is required to satisfy both adhesiveness at the time of use and peelability after use.
  • a heat-peelable pressure-sensitive adhesive sheet in which a pressure-sensitive adhesive layer containing thermally expandable particles is provided on a base material is known as a pressure-sensitive adhesive sheet for temporary fixing that satisfies the above-described requirements.
  • the heat-peelable pressure-sensitive adhesive sheet has a feature that the adhesive force is reduced by foaming or expanding the thermally expandable particles by heating, and can be easily peeled off from the adherend. For this reason, it is used as a temporary fixing means, a recycling label, etc. during the manufacturing process of the electronic component.
  • Patent Document 1 discloses a heat-peelable pressure-sensitive adhesive sheet in which a heat-expandable pressure-sensitive adhesive layer containing heat-expandable microspheres is provided on at least one side of a substrate, and the thickness of the heat-expandable pressure-sensitive adhesive layer The center line average roughness of the surface of the thermally expandable adhesive layer before heating is set to 0.4 ⁇ m or less by adjusting the maximum particle size of the thermally expandable microspheres added to the adhesive layer.
  • a heat-peelable pressure-sensitive adhesive sheet for temporary fixing at the time of cutting an electronic component is disclosed.
  • the heat-peelable pressure-sensitive adhesive sheet described in Patent Document 1 can secure an effective contact area with the pressure-sensitive adhesive sheet by suppressing the surface roughness of the heat-expandable pressure-sensitive adhesive layer, and prevents the occurrence of adhesive defects such as chip jumping. There is a statement that it can be done.
  • the conventional heat-peelable pressure-sensitive adhesive sheet expands the pressure-sensitive adhesive layer containing the thermally expandable particles by foaming or expanding the thermally expandable particles by heating. Due to the expansion of the pressure-sensitive adhesive layer, the surface of the pressure-sensitive adhesive layer in contact with the adherend is deformed into an uneven shape, and the adhesion area between the pressure-sensitive adhesive layer and the adherend is reduced. As a result, the adhesive force by the pressure-sensitive adhesive layer is reduced, and the pressure-sensitive adhesive sheet can be easily peeled off from the adherend.
  • the heat-expandable particles are foamed or expanded by heating, destruction inside the pressure-sensitive adhesive layer containing the heat-expandable particles, that is, cohesive failure of the pressure-sensitive adhesive layer is likely to occur.
  • the heat-peelable pressure-sensitive adhesive sheet described in Patent Document 1 suppresses the surface roughness of the heat-expandable pressure-sensitive adhesive layer from the viewpoint of improving adhesiveness at the time of temporary fixing. It is designed to reduce the particle size of the thermally expandable microspheres to be added. However, if the particle size of the heat-expandable microspheres is too small, the surface roughness becomes small, resulting in poor interfacial adhesion and concern about adhesive residue on the adherend surface after heat peeling.
  • the present invention has been made in view of the above problems, and has little adhesive residue on the adherend surface after heat peeling, and has good interface adhesion between the substrate and the pressure-sensitive adhesive layer. It aims at providing the adhesive sheet which is excellent in the adhesiveness at the time of temporary fixing, and heat peelability.
  • the present inventors have found that the above problem can be solved by including a thermally expandable particle in a base material and forming a laminate including the base material and the pressure-sensitive adhesive layer by a specific method.
  • the present invention has been completed.
  • a pressure-sensitive adhesive sheet having a laminate in which a pressure-sensitive adhesive layer (X1) and a non-adhesive thermally expandable substrate (Y) are directly laminated in this order,
  • the laminate is A coating film (x1 ′) comprising a composition (x1) which is a forming material of the pressure-sensitive adhesive layer (X1);
  • a coating film (y ′) comprising a composition (y) containing a resin and thermally expandable particles, which is a forming material of the thermally expandable substrate (Y), are directly laminated in this order, and then the pressure-sensitive adhesive sheet is formed by simultaneously irradiating the coating film (x1 ′) and the coating film (y ′) with energy rays.
  • the storage elastic modulus E ′ (23) of the thermally expandable substrate (Y) at 23 ° C. is 1.0 ⁇ 10 6 Pa or more.
  • the laminate further includes an adhesive layer (X2), and the adhesive layer (X1), the thermally expandable substrate (Y), and the adhesive layer (X2) are directly laminated in this order.
  • the pressure-sensitive adhesive sheet according to any one of [1] to [6] above.
  • the laminate is A coating film (x1 ′) comprising a composition (x1) which is a forming material of the pressure-sensitive adhesive layer (X1);
  • a coating film (y ′) comprising a composition (y) containing a resin and thermally expandable particles, which is a forming material of the thermally expandable substrate (Y),
  • a coating film (x2 ′) comprising a composition (x2) which is a forming material of the pressure-sensitive adhesive layer (X2);
  • the pressure-sensitive adhesive sheet of the present invention has little adhesive residue on the adherend surface after heat peeling, has good interface adhesion between the base material and the pressure-sensitive adhesive layer, and is excellent in adhesion and heat peelability during temporary fixing. .
  • the “active ingredient” refers to a component excluding a diluent solvent among components contained in a target composition.
  • the mass average molecular weight (Mw) is a value in terms of standard polystyrene measured by a gel permeation chromatography (GPC) method, specifically a value measured based on the method described in the examples.
  • (meth) acrylic acid indicates both “acrylic acid” and “methacrylic acid”, and the same applies to other similar terms.
  • the lower limit value and upper limit value which were described in steps can be combined independently, respectively. For example, from the description “preferably 10 to 90, more preferably 30 to 60”, “preferable lower limit (10)” and “more preferable upper limit (60)” are combined to obtain “10 to 60”. You can also.
  • the pressure-sensitive adhesive sheet of the present invention is a pressure-sensitive adhesive sheet having a laminate in which a pressure-sensitive adhesive layer (X1) and a non-adhesive thermally expandable substrate (Y) are directly laminated in this order.
  • the laminate is a coating material (x1 ′) made of the composition (x1) that is a forming material of the pressure-sensitive adhesive layer (X1), and a resin that is a forming material of the thermally expandable substrate (Y) and After directly laminating the coating film (y ′) composed of the composition (y) containing thermally expandable particles in this order, the coating film (x1 ′) and the coating film (y ′) are simultaneously irradiated with energy rays. It is formed.
  • the aforementioned “direct lamination” refers to a configuration in which a layer and a layer are in direct contact with each other without any other layer between the two layers. That is, in the present invention, the pressure-sensitive adhesive layer (X1) and the thermally expandable base material (Y) are in direct contact with no other layer interposed therebetween.
  • the heat-expandable particles in the heat-expandable substrate (Y) are expanded by heating, and irregularities are formed on the surface of the heat-expandable substrate (Y).
  • the pressure-sensitive adhesive layer (X1) laminated on the irregularities is also pushed up, and irregularities are also formed on the surface of the pressure-sensitive adhesive layer (X1).
  • the contact area between the adherend and the surface of the pressure-sensitive adhesive layer (X1) is reduced, and the adherend and pressure-sensitive adhesive layer (X1).
  • the pressure-sensitive adhesive sheet can be easily peeled off with a slight force from the adherend adhered to the surface of the pressure-sensitive adhesive layer (X1).
  • the heat-expandable particles are not included in the pressure-sensitive adhesive layer (X1) but in the heat-expandable base material (Y), thereby suppressing cohesive failure of the pressure-sensitive adhesive layer (X1) due to heating. can do. Thereby, the adhesive residue on the adherend surface after heat peeling can be reduced.
  • the interface adhesiveness of an adhesive layer (X1) and a thermally expansible base material (Y) is made high. Can do. Thereby, even if the thermally expansible particle
  • FIG.1 and FIG.2 is a cross-sectional schematic diagram which shows an example of a structure of the adhesive sheet of this invention.
  • a pressure-sensitive adhesive layer (X1) 12 and a thermally expandable substrate (Y) 11 are directly laminated in this order.
  • the adhesive sheet 1a which has the laminated body 10 currently used is mentioned.
  • FIG. 2A As a specific configuration of the pressure-sensitive adhesive sheet of another aspect of the present invention, as shown in FIG. 2A, a pressure-sensitive adhesive layer (X1) 121, a thermally expandable substrate (Y) 11, and a pressure-sensitive adhesive layer
  • the double-sided pressure-sensitive adhesive sheet 2a having the laminate 10 in which (X2) 122 is directly laminated in this order is exemplified.
  • a release material 131 is further provided on the surface of the pressure-sensitive adhesive layer (X1) 121, and further peeled on the pressure-sensitive adhesive surface of the pressure-sensitive adhesive layer (X2) 122. It is good also as a structure which has the material 132.
  • FIG. 2A a pressure-sensitive adhesive layer (X1) 121, a thermally expandable substrate (Y) 11, and a pressure-sensitive adhesive layer
  • the double-sided pressure-sensitive adhesive sheet 2a having the laminate 10 in which (X2) 122 is directly laminated in this order is exemplified.
  • a release material 131 is
  • the peeling force when peeling the release material 131 from the pressure-sensitive adhesive layer (X1) 121 and the peeling time when peeling the peeling material 132 from the pressure-sensitive adhesive layer (X2) 122 are removed.
  • the force is approximately the same, when the two release materials are pulled outward to be peeled off, a phenomenon may occur in which the pressure-sensitive adhesive layer is divided and peeled off along with the two release materials. From the viewpoint of suppressing such a phenomenon, it is preferable to use two types of release materials designed so that the two release materials 131 and 132 have different release forces from the adhesive layer attached to each other.
  • one surface of the pressure-sensitive adhesive layer (X1) 121 and the pressure-sensitive adhesive layer (X2) 122 is peeled off on both surfaces.
  • a double-sided pressure-sensitive adhesive sheet having a configuration in which materials are laminated in a roll shape may be used.
  • the laminate of the pressure-sensitive adhesive sheet of the present invention is a laminate in which the pressure-sensitive adhesive layer (X1) and the non-adhesive thermally expandable substrate (Y) are directly laminated in this order, and the pressure-sensitive adhesive layer (X1 ) And a coating composition (x1 ′) comprising the composition (x1) as a forming material, and a composition (y) comprising a resin and a thermally expandable particle as a forming material for the thermally expandable substrate (Y).
  • the coating film (y ′) and the coating film (x ′ ′) and the coating film (y ′) are simultaneously irradiated with energy rays after being directly laminated in this order.
  • the energy ray irradiation examples include ultraviolet ray irradiation and electron beam irradiation, but ultraviolet ray irradiation is preferable from the viewpoint of preventing unnecessary reactions.
  • the coating film (x1 ′) and the coating film (y ′) are “simultaneously” formed into an energy ray-irradiated laminate, so that the coating film (x1 ′) and the coating film (y ′) are “separated”.
  • the interfacial adhesion between the pressure-sensitive adhesive layer (X1) and the thermally expandable substrate (Y) can be enhanced.
  • a mixed layer of the coating film is formed in the vicinity of the interface, and the molecular chains of the resins contained in each composition are intertwined, so that the pressure-sensitive adhesive layer (X1) and the thermally expandable group It is considered that the interfacial adhesion with the material (Y) is improved.
  • a method of forming a laminate by irradiating the coating film (x1 ′) and the coating film (y ′) with energy rays “separately” the following method may be mentioned.
  • the composition (x1) is applied onto the release-treated surface of a release material such as a release film to form a coating film (x1 ′), and the coating film (x1 ′) is irradiated with energy rays to form an adhesive layer (X1).
  • a coating (y ′) is formed by applying a composition (y) containing a resin and thermally expandable particles on a release-treated surface of a release material such as a release film prepared separately.
  • the pressure-sensitive adhesive layer (X1) and the thermally expandable substrate (Y ) are formed separately, the interfacial adhesion between the pressure-sensitive adhesive layer (X1) and the thermally expandable substrate (Y) is low.
  • the laminate of the pressure-sensitive adhesive sheet of one embodiment of the present invention is preferably a composition (x1) that is a material for forming the pressure-sensitive adhesive layer (X1) and a material that is a material for forming the thermally expandable substrate (Y).
  • (Y) is applied simultaneously, and the coating film (x1 ′) and the coating film (y ′) are directly laminated in this order, and then the coating film (x1 ′) and the coating film (y ′) are simultaneously energized. It is formed by irradiation.
  • the composition (x1) and the composition (y) By simultaneously applying the composition (x1) and the composition (y), the entanglement of the molecular chains of the resins contained in each composition is promoted compared to the case where each composition is sequentially applied. Interfacial adhesion between the pressure-sensitive adhesive layer (X1) and the thermally expandable substrate (Y) can be further increased.
  • the laminate of the pressure-sensitive adhesive sheet of one embodiment of the present invention further includes a pressure-sensitive adhesive layer (X2), and the pressure-sensitive adhesive layer (X1), the thermally expandable substrate (Y), and the pressure-sensitive adhesive layer (X2) are in this order. It is good also as a structure laminated
  • the pressure-sensitive adhesive layer (X2) is a layer formed from the composition (x2).
  • the composition (x2) is applied on the expandable substrate (Y) to form a coating film (x2 ′)
  • a method of forming the coating film (x2 ′) by irradiating with energy rays can be mentioned.
  • the pressure-sensitive adhesive layer (X2) prepared in advance by irradiating the coating film (x2 ′) with energy rays may be directly attached on the expandable substrate (Y).
  • the laminate further including the above-mentioned pressure-sensitive adhesive layer (X2) is preferably a coating film (x1 ′) composed of the composition (x1) which is a forming material of the pressure-sensitive adhesive layer (X1), and a thermally expandable substrate ( A coating material (y ′) composed of a composition (y) containing a resin and thermally expandable particles, which is a forming material of Y), and a coating composition (x2), which is a forming material of an adhesive layer (X2).
  • the coating films (x1 ′), (y ′) and (x2 ′) are simultaneously irradiated with energy rays.
  • the laminate further including the pressure-sensitive adhesive layer (X2) is more preferably a composition (x1) which is a material for forming the pressure-sensitive adhesive layer (X1) and a material for forming the heat-expandable base material (Y).
  • the composition (y) and the composition (x2), which is a material for forming the pressure-sensitive adhesive layer (X2), are applied simultaneously, and the coating films (x1 ′), (y ′), and (x2 ′) are applied in this order. After the direct lamination, the coating films (x1 ′), (y ′) and (x2 ′) are simultaneously irradiated with energy rays.
  • the interfacial adhesion between the thermally expandable base material (Y) and the pressure-sensitive adhesive layer (X2) can be further improved for the reason described above. it can.
  • the laminated body which an adhesive sheet has is specified by the manufacturing method as mentioned above, the situation which must specify by such a manufacturing method exists.
  • the interface between the pressure-sensitive adhesive layer (X1) and the heat-expandable substrate (Y) as an evaluation based on objective physical property values, for example, the pressure-sensitive adhesive layer (X1) and heat in a cross section cut in the thickness direction of the laminate
  • a method for measuring the roughness of the interface by observing the interface with the expandable substrate (Y) using an electron microscope or the like can be considered.
  • the roughness of the interface is very small, it cannot be measured accurately, and the difference in the roughness state depending on the region to be observed is very large.
  • the adhesive layer (X1) and the thermally expandable material can be obtained using an electron microscope or the like. Even if it is attempted to observe the interface with the substrate (Y), the interface may become unclear, and the roughness measurement itself may be difficult in the first place. Furthermore, when the laminate is cut in the thickness direction in order to obtain a cross section of the laminate, the laminate is formed of a resin, and thus the pressure-sensitive adhesive layer (X1) and the thermally expandable substrate There is also a situation that the shape of the interface with (Y) collapses and the state of the interface cannot be accurately evaluated.
  • the laminate that the pressure-sensitive adhesive sheet has is specified by the manufacturing method as described above.
  • a laminated body is the structure by which the adhesive layer (X1), the thermally expansible base material (Y), and the adhesive layer (X2) are directly laminated
  • the thickness of the laminate of the pressure-sensitive adhesive sheet of the present invention is preferably 10 to 1200 ⁇ m, more preferably 25 to 500 ⁇ m, still more preferably 40 to 300 ⁇ m, and still more preferably 55 to 200 ⁇ m.
  • the thickness of the pressure-sensitive adhesive layer (X1) of the pressure-sensitive adhesive sheet of the present invention is based on the viewpoint of developing an excellent pressure-sensitive adhesive force, and the expansion of the heat-expandable particles in the heat-expandable substrate (Y) by heat treatment. From the viewpoint of easily forming irregularities on the surface of the pressure-sensitive adhesive layer (X1), the thickness is preferably 1 to 100 ⁇ m, more preferably 2 to 70 ⁇ m, still more preferably 3 to 40 ⁇ m, and still more preferably 5 to 30 ⁇ m.
  • the thickness of the thermally expandable substrate (Y) of the pressure-sensitive adhesive sheet of the present invention is preferably 10 to 1000 ⁇ m, more preferably 20 to 500 ⁇ m, still more preferably 25 to 400 ⁇ m, and still more preferably 30 to 300 ⁇ m.
  • the laminated body which the adhesive sheet of 1 aspect of this invention further contains an adhesive layer (X2)
  • the viewpoint which expresses the outstanding adhesive force, and the thermal expansion in the thermally expansible base material (Y) by heat processing From the viewpoint of easily forming irregularities on the surface of the pressure-sensitive adhesive layer (X2) due to the expansion of the adhesive particles, it is preferably 1 to 100 ⁇ m, more preferably 2 to 70 ⁇ m, still more preferably 3 to 40 ⁇ m, still more preferably 5 to 30 ⁇ m.
  • the thickness of the laminate is a value measured using a constant pressure thickness measuring instrument based on JIS K6783, Z1702, and Z1709, and specifically measured based on the method described in the examples. Means the value.
  • the thickness of each layer constituting the laminate may be measured by the same method as the thickness of the laminate described above. For example, a cross section of the laminate cut in the thickness direction is observed with a scanning electron microscope. Then, the ratio of the thickness of each layer may be measured and calculated from the thickness of the laminate measured by the method described above.
  • the ratio of the thickness of the heat-expandable base material (Y) and the thickness of the pressure-sensitive adhesive layer (X1) at 23 ° C. is preferably 0.2 or more, more preferably 0.5 or more, still more preferably 1.0 or more, and still more preferably 5.0 or more, from the viewpoint of preventing positional displacement of the object.
  • it is preferably 1000 or less, more preferably 200 or less, still more preferably 60 or less, and even more preferably 30 or less. .
  • the ratio of the thickness of a thermally expansible base material (Y) and the thickness of an adhesive layer (X2) in 23 degreeC is preferably 0.2 or more, more preferably 0.5 or more, still more preferably 1.0 or more, and still more.
  • it is 5.0 or more, preferably 1000 or less, more preferably 200 or less, still more preferably 60 or less, and still more preferably 30 or less.
  • a mixed layer arises between two coating films in the energy ray irradiation process of a coating film, and an adhesive layer (X1) and a thermally expansible base material (Y ) And the interface between the thermally expandable base material (Y) and the pressure-sensitive adhesive layer (X2) may be unclear enough to disappear.
  • a mixed layer is formed between the two coating films and between the formed layers, for example, as described above, the cross section of the laminate cut in the thickness direction is observed with a scanning electron microscope to determine the thickness of each layer.
  • the intermediate point in the thickness direction of the mixed layer may be measured on the assumption that an interface exists on a plane parallel to the surface of the pressure-sensitive adhesive layer (X1) opposite to the thermally expandable substrate (Y). .
  • the heat-expandable substrate (Y) of the pressure-sensitive adhesive sheet of the present invention is a layer formed by irradiating a coating film (y ′) made of a composition (y) containing a resin and heat-expandable particles by energy rays.
  • a non-adhesive substrate is determined if the probe tack value measured in accordance with JIS Z0237: 1991 is less than 50 mN / 5 mm ⁇ with respect to the surface of the target substrate.
  • the said base material is judged as a "non-adhesive base material".
  • the probe tack value on the surface of the thermally expandable substrate (Y) is usually less than 50 mN / 5 mm ⁇ , preferably less than 30 mN / 5 mm ⁇ , more preferably less than 10 mN / 5 mm ⁇ , and even more preferably 5 mN / 5 mm ⁇ . Is less than.
  • the specific measuring method of the probe tack value in the surface of a thermally expansible base material (Y) is based on the method as described in an Example.
  • the heat-expandable substrate (Y) that the pressure-sensitive adhesive sheet of the present invention has is preferably a non-adhesive substrate that satisfies the following requirement (1).
  • the storage elastic modulus E ′ (t) of the thermally expandable substrate (Y) at the expansion start temperature (t) of the thermally expandable particles is 1.0 ⁇ 10 7 Pa or less.
  • the storage elastic modulus E ′ of the thermally expandable substrate (Y) at a predetermined temperature means a value measured by the method described in the examples.
  • the heat-expandable particles in the heat-expandable substrate (Y) are heated to a temperature equal to or higher than the expansion start temperature (t) of the heat-expandable particles. Expands and irregularities are formed on the surface of the heat-expandable substrate (Y), and the pressure-sensitive adhesive layer (X1) laminated on the irregularities is also pushed up to form irregularities on the adhesive surface. And by forming unevenness on the adhesive surface of the pressure-sensitive adhesive layer (X1), the contact area between the adherend and the adhesive surface is reduced, and a space is created between the adherend and the adhesive surface.
  • the pressure-sensitive adhesive sheet can be easily peeled off from the adherend with a slight force.
  • the storage elastic modulus E ′ (t) of the thermally expandable substrate at the expansion start temperature (t) of the thermally expandable particles is defined. It can also be said that the index indicates the rigidity of the thermally expandable substrate immediately before expansion. That is, according to the study by the present inventors, the storage elastic modulus E ′ (t) of the thermally expandable substrate (Y) at the expansion start temperature (t) of the thermally expandable particles is 1.0 ⁇ 10 7 Pa. With the following, when heating to a temperature equal to or higher than the expansion start temperature (t) and trying to expand the thermally expandable particles, the expansion is not suppressed and the surface of the thermally expandable substrate (Y) is not suppressed. The unevenness
  • stacked can fully be formed.
  • the storage elastic modulus E ′ (t) defined by the requirement (1) of the thermally expandable substrate (Y) used in one embodiment of the present invention is preferably 9.0 ⁇ 10 6 Pa or less, more preferably. Is 8.0 ⁇ 10 6 Pa or less, more preferably 6.0 ⁇ 10 6 Pa or less, and still more preferably 4.0 ⁇ 10 6 Pa or less. Further, from the viewpoint of suppressing the flow of the expanded thermally expandable particles, improving the shape maintaining property of the unevenness formed on the adhesive surface of the pressure-sensitive adhesive layer (X1), and further improving the peelability, the thermally expandable group.
  • the storage elastic modulus E ′ (t) defined by the requirement (1) of the material (Y) is preferably 1.0 ⁇ 10 3 Pa or more, more preferably 1.0 ⁇ 10 4 Pa or more, and still more preferably 1. 0 ⁇ 10 5 Pa or more.
  • the storage elastic modulus E ′ (23) of the thermally expandable substrate (Y) at 23 ° C. is 1.0 ⁇ 10 6 Pa or more.
  • the heat-expandable base material (Y) that satisfies the above requirement (2), it is possible to prevent positional deviation when attaching an object such as a semiconductor chip. Moreover, when a target object is stuck, excessive sinking into the pressure-sensitive adhesive layer can also be prevented.
  • the storage elastic modulus E ′ (23) of the thermally expandable substrate (Y) defined by the requirement (2) is preferably 5.0 ⁇ 10 6 to 5.0 ⁇ 10 12 Pa, more preferably Is 1.0 ⁇ 10 7 to 1.0 ⁇ 10 12 Pa, more preferably 5.0 ⁇ 10 7 to 1.0 ⁇ 10 11 Pa, and still more preferably 1.0 ⁇ 10 8 to 1.0 ⁇ 10 10. 10 Pa.
  • composition (y) which is a material for forming the thermally expandable substrate (Y), contains a resin and thermally expandable particles.
  • Thermally expandable particles As the heat-expandable particles used in the present invention, known heat-expandable particles can be used, and are appropriately selected according to the use of the pressure-sensitive adhesive sheet.
  • the thermally expandable particle is a microencapsulated foaming agent composed of an outer shell made of a thermoplastic resin and an encapsulated component encapsulated in the outer shell and vaporized when heated to a predetermined temperature. It is preferable.
  • thermoplastic resin constituting the outer shell of the microencapsulated foaming agent examples include vinylidene chloride-acrylonitrile copolymer, polyvinyl alcohol, polyvinyl butyral, polymethyl methacrylate, polyacrylonitrile, polyvinylidene chloride, and polysulfone.
  • Examples of the inclusion component contained in the outer shell include propane, butane, pentane, hexane, heptane, octane, nonane, decane, isobutane, isopentane, isohexane, isoheptane, isooctane, isononane, isodecane, cyclopropane, cyclobutane, cyclopentane.
  • the average particle diameter of the thermally expandable particles before expansion at 23 ° C. used in one embodiment of the present invention is preferably 3 to 100 ⁇ m, more preferably 4 to 70 ⁇ m, still more preferably 6 to 60 ⁇ m, still more preferably 10 to 50 ⁇ m.
  • the average particle diameter before expansion of the thermally expandable particles is the volume-median particle diameter (D 50 ), and is a laser diffraction particle size distribution measuring device (for example, product name “Mastersizer 3000” manufactured by Malvern).
  • the cumulative volume frequency calculated from the smaller particle diameter of the heat-expandable particles before expansion means a particle diameter corresponding to 50%.
  • the 90% particle diameter (D 90 ) before expansion at 23 ° C. of the thermally expandable particles used in one embodiment of the present invention is preferably 10 to 150 ⁇ m, more preferably 20 to 100 ⁇ m, still more preferably 25 to 90 ⁇ m, More preferably, it is 30 to 80 ⁇ m.
  • the 90% particle diameter (D 90 ) before expansion of the thermally expandable particles is the expansion measured by using a laser diffraction particle size distribution measuring apparatus (for example, product name “Mastersizer 3000” manufactured by Malvern). In the particle distribution of the previous thermally expandable particles, it means a particle diameter corresponding to 90% of the cumulative volume frequency calculated from the smaller particle diameter of the thermally expandable particles before expansion.
  • the thermally expandable particles used in the present invention are preferably particles having an expansion start temperature (t) adjusted to 120 to 250 ° C.
  • the expansion start temperature (t) of the thermally expandable particles can be adjusted by appropriately selecting the type of inclusion component.
  • the expansion start temperature (t) of the thermally expandable particles means a value measured based on the following method. [Measurement method of expansion start temperature (t) of thermally expandable particles] To an aluminum cup having a diameter of 6.0 mm (inner diameter 5.65 mm) and a depth of 4.8 mm, 0.5 mg of thermally expandable particles to be measured is added, and an aluminum lid (diameter 5.6 mm, thickness 0. 1 mm) is prepared.
  • the height of the sample is measured from the upper part of the aluminum lid while a force of 0.01 N is applied to the sample by a pressurizer. Then, in a state where a force of 0.01 N is applied by the pressurizer, heating is performed from 20 ° C. to 300 ° C. at a rate of temperature increase of 10 ° C./min, and the amount of displacement of the pressurizer in the vertical direction is measured.
  • the displacement start temperature be the expansion start temperature (t).
  • the volume expansion coefficient of the thermally expandable particles used in one embodiment of the present invention by heating at an expansion start temperature (t) or higher is preferably 1.5 to 100 times, more preferably 2 to 80 times, and still more preferably 2. It is 5 to 60 times, more preferably 3 to 40 times.
  • the content of the heat-expandable particles is preferably 1 to 40% by mass, more preferably 5 to 35% by mass, still more preferably 10 to 10% by mass with respect to the total amount (100% by mass) of the active ingredients in the composition (y). 30% by mass, and still more preferably 15 to 25% by mass.
  • the resin contained in the composition (y) may be a polymer that can form a non-adhesive thermally expandable substrate (Y).
  • non-adhesive resin may be sufficient and adhesive resin may be sufficient. That is, even if the resin contained in the composition (y) is an adhesive resin, the adhesive resin is polymerized with the polymerizable compound in the process of forming the thermally expandable substrate (Y) from the composition (y). It is sufficient that the resin obtained by the reaction becomes a non-adhesive resin and the thermally expandable substrate (Y) containing the resin becomes non-adhesive.
  • solvent-free resin composition (y1) As the composition (y) used in one embodiment of the present invention, an oligomer having an ethylenically unsaturated group having a mass average molecular weight (Mw) of 50000 or less, an energy ray polymerizable monomer, and the above-described thermally expandable particles are blended. And a solventless resin composition (y1) containing no solvent. In the solventless resin composition (y1), no solvent is blended, but the energy beam polymerizable monomer contributes to the improvement of the plasticity of the oligomer.
  • Mw mass average molecular weight
  • the mass average molecular weight (Mw) of the oligomer contained in the solventless resin composition (y1) is 50000 or less, preferably 1000 to 50000, more preferably 2000 to 40000, and still more preferably 3000 to 35000. More preferably, it is 4000-30000.
  • the oligomer may be any oligomer having an ethylenically unsaturated group having a mass average molecular weight of 50000 or less, but a urethane prepolymer (UP) described later is preferable.
  • a modified olefin resin having an ethylenically unsaturated group can also be used.
  • Urethane prepolymer includes a reaction product of a polyol and a polyvalent isocyanate.
  • Examples of the polyol used as a raw material for the urethane prepolymer (UP) include alkylene type polyols, ether type polyols, ester type polyols, ester amide type polyols, ester / ether type polyols, and carbonate type polyols. These polyols may be used independently and may use 2 or more types together.
  • the polyol used in one embodiment of the present invention is preferably a diol, more preferably an ester diol, an alkylene diol, and a carbonate diol, and even more preferably an ester diol and a carbonate diol.
  • ester type diols include alkane diols such as 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol; ethylene glycol, propylene glycol, One or more selected from diols such as alkylene glycols such as diethylene glycol and dipropylene glycol; phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, 4,4-diphenyldicarboxylic acid, diphenylmethane-4 , 4'-dicarboxylic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, het acid, maleic acid, fumaric acid, itaconic acid, cyclohexane-1,3-dicarboxylic acid, cyclohexane-1,4-dicarbox
  • alkylene type diol examples include alkane diols such as 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol; ethylene glycol, propylene glycol, And alkylene glycols such as diethylene glycol and dipropylene glycol; polyalkylene glycols such as polyethylene glycol, polypropylene glycol, and polybutylene glycol; polyoxyalkylene glycols such as polytetramethylene glycol; and the like.
  • alkane diols such as 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol
  • ethylene glycol, propylene glycol And alkylene glycols such as diethylene glycol and dipropylene glycol
  • Examples of the carbonate type diol include 1,4-tetramethylene carbonate diol, 1,5-pentamethylene carbonate diol, 1,6-hexamethylene carbonate diol, 1,2-propylene carbonate diol, and 1,3-propylene carbonate diol. 2,2-dimethylpropylene carbonate diol, 1,7-heptamethylene carbonate diol, 1,8-octamethylene carbonate diol, 1,4-cyclohexane carbonate diol, and the like.
  • polyvalent isocyanate used as a raw material for the urethane prepolymer (UP) examples include aromatic polyisocyanates, aliphatic polyisocyanates, and alicyclic polyisocyanates. These polyvalent isocyanates may be used alone or in combination of two or more. These polyisocyanates may be a trimethylolpropane adduct type modified product, a burette type modified product reacted with water, or an isocyanurate type modified product containing an isocyanurate ring.
  • the polyisocyanate used in one embodiment of the present invention is preferably diisocyanate, and 4,4′-diphenylmethane diisocyanate (MDI), 2,4-tolylene diisocyanate (2,4-TDI), 2,6 More preferred is at least one selected from tolylene diisocyanate (2,6-TDI), hexamethylene diisocyanate (HMDI), and alicyclic diisocyanate.
  • MDI 4,4′-diphenylmethane diisocyanate
  • 2,4-TDI 2,4-tolylene diisocyanate
  • 2,6 More preferred is at least one selected from tolylene diisocyanate (2,6-TDI), hexamethylene diisocyanate (HMDI), and alicyclic diisocyanate.
  • alicyclic diisocyanate examples include 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate, IPDI), 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane.
  • IPDI isophorone diisocyanate
  • Examples include diisocyanate, methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, and isophorone diisocyanate (IPDI) is preferred.
  • the urethane prepolymer (UP) is preferably a linear urethane prepolymer that is a reaction product of a diol and a diisocyanate and has ethylenically unsaturated groups at both ends.
  • a method for introducing an ethylenically unsaturated group into both ends of a linear urethane prepolymer an NCO group at the end of a linear urethane prepolymer obtained by reacting a diol and a diisocyanate compound, a hydroxyalkyl (meth) acrylate, The method of making this react is mentioned.
  • hydroxyalkyl (meth) acrylate examples include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 3-hydroxy Examples thereof include butyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate.
  • the modified olefin resin having an ethylenically unsaturated group is obtained by introducing an ethylenically unsaturated group into a polymer having at least a structural unit derived from an olefin monomer.
  • the olefin monomer is preferably an ⁇ -olefin having 2 to 8 carbon atoms, and specifically includes ethylene, propylene, butylene, isobutylene, 1-hexene and the like. Among these, ethylene and propylene are preferable.
  • modified olefin resin having an ethylenically unsaturated group examples include an acrylic modified olefin resin obtained by subjecting an olefin resin to acrylic modification.
  • An acrylic modified olefin resin obtained by subjecting an olefin resin to acrylic modification is a modified polymer obtained by graft-polymerizing an alkyl (meth) acrylate as a side chain to an unmodified olefin resin as a main chain. Is mentioned.
  • olefin resin for example, ultra low density polyethylene (VLDPE, density: 880 kg / m 3 or more 910 kg / m less than 3), low density polyethylene (LDPE, density: 910 kg / m 3 or more 915 kg / m 3 ), medium density polyethylene (MDPE, density: 915 kg / m 3 or more and less than 942 kg / m 3 ), high density polyethylene (HDPE, density: 942 kg / m 3 or more), polyethylene resin such as linear low density polyethylene Polypropylene resin (PP); Polybutene resin (PB); Ethylene-propylene copolymer; Olefin elastomer (TPO); Poly (4-methyl-1-pentene) (PMP); Ethylene-vinyl acetate copolymer (EVA) ); Ethylene-vinyl alcohol copolymer (EVOH); And olefinic terpolymers such as lopyrene- (5-
  • the number of carbon atoms in the alkyl group of the alkyl (meth) acrylate is preferably 1-20, more preferably 1-16, and still more preferably 1-12.
  • the alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, Examples include tridecyl (meth) acrylate and stearyl (meth) acrylate.
  • the total content of the oligomer and the energy beam polymerizable monomer in the solventless resin composition (y1) is preferably 50 to 100% with respect to the total amount (100% by mass) of the solventless resin composition (y1). It is 99% by mass, more preferably 60 to 95% by mass, still more preferably 65 to 90% by mass, and still more preferably 70 to 85% by mass.
  • Examples of the energy ray polymerizable monomer include isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyloxy (meth) acrylate, cyclohexyl (meth) acrylate, adamantane ( Cycloaliphatic polymerizable compounds such as (meth) acrylate and tricyclodecane acrylate; Aromatic polymerizable compounds such as phenylhydroxypropyl acrylate, benzyl acrylate and phenol ethylene oxide modified acrylate; Tetrahydrofurfuryl (meth) acrylate, morpholine acrylate, N- And heterocyclic polymerizable compounds such as vinylpyrrolidone and N-vinylcaprolactam. These energy beam polymerizable monomers may be used independently and may use 2 or more types together.
  • the content ratio of the oligomer to the energy beam polymerizable monomer [oligomer / energy beam polymerizable monomer) is preferably 20/80 to 90 / in mass ratio. 10, more preferably 30/70 to 85/15, still more preferably 35/65 to 80/20.
  • the solventless resin composition (y1) preferably further contains a photopolymerization initiator.
  • the curing reaction can be sufficiently advanced even by irradiation with a relatively low energy beam.
  • photopolymerization initiator examples include 1-hydroxy-cyclohexyl-phenyl-ketone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzyl phenyl sulfide, tetramethylthiuram monosulfide, azobisisobutyrol. Nitrile, dibenzyl, diacetyl, 8-chloroanthraquinone and the like can be mentioned. These photoinitiators may be used independently and may use 2 or more types together.
  • the blending amount of the photopolymerization initiator is preferably 0.01 to 5 parts by mass, more preferably 0.01 to 4 parts by mass with respect to the total amount (100 parts by mass) of the oligomer and the energy ray polymerizable monomer.
  • the amount is preferably 0.02 to 3 parts by mass.
  • the composition (y) used in one embodiment of the present invention may contain a base material additive contained in a base material included in a general pressure-sensitive adhesive sheet as long as the effects of the present invention are not impaired.
  • base material additives include ultraviolet absorbers, light stabilizers, antioxidants, antistatic agents, slip agents, antiblocking agents, and colorants. These base material additives may be used alone or in combination of two or more.
  • the content of each base material additive is preferably 0.0001 to 20 with respect to 100 parts by mass of the total amount of the resin contained in the composition (y). Part by mass, more preferably 0.001 to 10 parts by mass.
  • the composition (y) may contain a diluting solvent such as water or an organic solvent together with the above-mentioned various active ingredients as long as it is in a trace amount, but it is preferably not contained.
  • the pressure-sensitive adhesive layer (X1) of the pressure-sensitive adhesive sheet of the present invention is a layer formed by irradiating a coating film (x1 ′) comprising the composition (x1) with energy rays, and has adhesiveness.
  • the adhesive force on the adhesive surface of the adhesive layer (X1) at 23 ° C. before expansion of the thermally expandable particles is preferably 0.1 to 10.0 N / 25 mm, more preferably 0.
  • the range is from 0.2 to 8.0 N / 25 mm, more preferably from 0.4 to 6.0 N / 25 mm, still more preferably from 0.5 to 4.0 N / 25 mm.
  • the adherend of the semiconductor chip or the like can be sufficiently fixed to the extent that positional displacement can be prevented in the next step such as the sealing step.
  • the said adhesive force is 10.0 N / 25mm or less, it can peel easily by slight force by heating to the expansion start temperature (t) at the time of peeling.
  • said adhesive force means the value measured by the method as described in an Example.
  • composition (x1) should just be a composition which can form an adhesive layer (X1) by energy ray irradiation. That is, the resin obtained by irradiating the composition (x1) with energy rays may be an adhesive resin. That is, the component itself contained in the composition (x1) may be non-adhesive or adhesive. Even if the component contained in the composition (x1) is non-adhesive, the resin obtained in the process of forming the adhesive layer (X1) from the composition (x1) may be an adhesive resin.
  • the adhesive resin obtained from the composition (x1) a resin having adhesiveness is preferable.
  • the adhesive resin include rubber resins such as acrylic resins, urethane resins, acrylic urethane resins, and polyisobutylene resins, polyester resins, olefin resins, silicone resins, and polyvinyl ether resins. Etc. These adhesive resins may be used independently and may use 2 or more types together.
  • the form of the copolymer is not particularly limited, and a block copolymer, a random copolymer, and a graft copolymer are not limited. Any of polymers may be used.
  • the surface of the pressure-sensitive adhesive layer (X1) is uneven due to the viewpoint of developing excellent adhesive force and the expansion of the thermally expandable particles in the thermally expandable substrate (Y) by heat treatment.
  • the adhesive resin preferably contains an acrylic urethane-based resin.
  • the content of the acrylic urethane-based resin in the adhesive resin is preferably 30 to 100% by mass, more preferably 50%, based on the total amount (100% by mass) of the adhesive resin contained in the adhesive layer (X1). To 100% by mass, more preferably 70 to 100% by mass, and still more preferably 85 to 100% by mass.
  • the composition (x1) for obtaining the acrylic urethane resin will be described.
  • the acrylic urethane-based resin can be produced by irradiating the composition (x1) containing the following (1) polymerization component with energy rays.
  • the composition (x1) may contain (2) a polymerization initiator and (3) various additives as necessary.
  • the composition (x1) is at least one polymerization component selected from the group consisting of a polymerizable vinyl monomer, a polymerizable vinyl prepolymer, a polyfunctional (meth) acrylate monomer, and a polyfunctional (meth) acrylate oligomer. Containing.
  • the composition (x1) preferably contains at least a polymerizable vinyl monomer and a polyfunctional (meth) acrylate oligomer among the above-described four kinds of polymerization components.
  • the polymerization component contains these compounds, the cohesive force of the obtained pressure-sensitive adhesive is improved, and adhesive residue on the adherend can be suppressed.
  • polymerizable vinyl monomer is not particularly limited as long as it has a vinyl group-containing group, and conventionally known monomers can be appropriately used.
  • the polymerizable vinyl monomer in this embodiment means the polymerizable vinyl monomer which has one vinyl group containing group, and does not overlap with the polyfunctional (meth) acrylate monomer mentioned later.
  • polymerizable vinyl monomer examples include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, and cyclohexyl (meth).
  • butyl acrylate, 2-ethylhexyl acrylate, isobornyl acrylate, phenoxyethyl acrylate, benzyl acrylate, and cyclohexyl acrylate are preferably used, and 2-ethylhexyl acrylate or isobornyl acrylate is particularly preferably used.
  • the polymerizable vinyl monomer may further have a functional group other than a vinyl group-containing group in the molecule.
  • the functional group include an amide group in addition to the active hydrogen group described above, that is, a hydroxy group, a carboxy group, a thiol group, and a primary or secondary amino group.
  • the amino group a tertiary amino group is particularly mentioned.
  • polymerizable vinyl monomer having such a functional group examples include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) ) Hydroxyalkyl (meth) acrylates such as acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate; acrylamide, methacrylamide, N-methylacrylamide, N-methylmethacrylamide, N-methylolacrylamide, Hydroxy group-containing acrylamides such as N-methylol methacrylamide; NN-dimethyl (meth) acrylamide, NN-diethyl (meth) acrylamide, N- (meth) acryloylmorpholine, Data) acrylic acid N-N-diethylaminoethyl, acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid and e
  • polymerizable vinyl monomers include vinyl esters such as vinyl acetate and vinyl propionate; olefins such as ethylene, propylene and isobutylene; halogenated olefins such as vinyl chloride and vinylidene chloride; styrene and ⁇ -methylstyrene.
  • Styrene monomers such as butadiene, isoprene, chloroprene, etc .; nitrile monomers such as acrylonitrile, methacrylonitrile, etc .; acrylamide, methacrylamide, N-methylacrylamide, N-methylmethacrylamide Amide monomers such as NN-dimethyl (meth) acrylamide, NN-diethyl (meth) acrylamide, N- (meth) acryloylmorpholine, N-vinylpyrrolidone; (meth) acrylic acid NN -Diethylaminoethyl, - (meth) acryloyl morpholine tertiary amino group-containing monomers such as are exemplified.
  • the polymerizable vinyl prepolymer is not particularly limited, and any conventionally known one can be used as appropriate, and is obtained by polymerizing the polymerizable vinyl monomer described above. It is preferred to use a polymerizable vinyl prepolymer.
  • one kind of the monomer may be polymerized alone, or a plurality of kinds may be copolymerized.
  • the polymerizable vinyl prepolymer may be obtained by free radical polymerization or may be obtained by living polymerization.
  • the RAFT (Reversible Addition-Fragmentation Chain Transfer Polymerization) terminal is left. It may be a polymer.
  • the mass average molecular weight of the polymerizable vinyl prepolymer is preferably 6,000 or more, particularly preferably 7,500 or more, and more preferably 10,000 or more.
  • the mass average molecular weight is preferably 1,500,000 or less, particularly preferably 1,000,000 or less, and more preferably 100,000 or less. It becomes easy to make the viscosity of a composition (x1) into a desired range because the said mass mean molecular weight is in the said range.
  • polyfunctional (meth) acrylate monomer is not particularly limited, and conventionally known ones can be appropriately used.
  • the polyfunctional (meth) acrylate monomer a monomer having two or more (meth) acryloyl groups in one molecule can be preferably exemplified.
  • monomers include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, Neopentyl glycol adipate di (meth) acrylate, hydroxypivalate neopentyl glycol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, caprolactone modified dicyclopentenyl di (meth) acrylate, ethylene oxide modified di (meth) phosphate ) Acrylate, di (acryloxyethyl) isocyanurate, allylated cyclohexyl di (meth) acrylate
  • polyfunctional (meth) acrylate oligomer is not particularly limited, and conventionally known ones can be used as appropriate, but two or more in one molecule It is preferable to use a polyfunctional (meth) acrylate oligomer having a (meth) acryloyl group.
  • examples of such oligomers include urethane acrylates, polyester acrylates, epoxy acrylates, polyether acrylates, polybutadiene acrylates, silicone acrylates and the like.
  • the urethane acrylate oligomer is, for example, a polyurethane oligomer obtained by a reaction of a polyisocyanate with a compound such as polyalkylene polyol, polyether polyol, polyester polyol, hydrogenated isoprene having a hydroxyl group terminal, or hydrogenated butadiene having a hydroxyl group terminal.
  • a compound such as polyalkylene polyol, polyether polyol, polyester polyol, hydrogenated isoprene having a hydroxyl group terminal, or hydrogenated butadiene having a hydroxyl group terminal.
  • examples of the polyalkylene polyol used for the production of the urethane acrylate oligomer include polypropylene glycol, polyethylene glycol, polybutylene glycol, polyhexylene glycol and the like, and it is particularly preferable to use polypropylene glycol.
  • examples of the polyalkylene polyol used for the production of the urethane acrylate oligomer include polypropylene glycol, polyethylene glycol, polybutylene glycol, polyhexylene glycol and the like, and it is particularly preferable to use polypropylene glycol.
  • glycerol a trimethylol propane, a triethanolamine, a pentaerythritol, an ethylenediamine, a diethylenetriamine, sorbitol, sucrose etc. suitably, when making the number of functional groups of the urethane acrylate oligomer obtained into 3 or more.
  • polyisocyanates examples include aliphatic diisocyanates such as hexamethylene diisocyanate and trimethylene diisocyanate; aromatic diisocyanates such as tolylene diisocyanate, xylylene diisocyanate and diphenyl diisocyanate; alicyclic diisocyanates such as dicyclohexylmethane diisocyanate and isophorone diisocyanate.
  • aromatic diisocyanates such as tolylene diisocyanate, xylylene diisocyanate and diphenyl diisocyanate
  • alicyclic diisocyanates such as dicyclohexylmethane diisocyanate and isophorone diisocyanate.
  • polyisocyanate can use not only bifunctional but trifunctional or more.
  • (meth) acrylic acid derivatives include hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl acrylate and 4-hydroxybutyl acrylate, 2-isocyanate ethyl acrylate, 2-isocyanate ethyl methacrylate, and 1,1-bis (acrylic acid). Roxymethyl) ethyl isocyanate and the like, and 2-isocyanatoethyl acrylate is particularly preferable.
  • a urethane acrylate oligomer As another method for producing a urethane acrylate oligomer, a polyalkylene polyol, a polyether polyol, a polyester polyol, a hydroxy group-containing hydrogenated isoprene, a hydroxy group-terminated hydrogenated butadiene compound, an isocyanate alkyl (
  • a urethane acrylate oligomer can also be obtained by a reaction between the —N ⁇ C ⁇ O moiety of the (meth) acrylate.
  • the isocyanate alkyl (meth) acrylate as the isocyanate alkyl (meth) acrylate, the above-mentioned 2-isocyanate ethyl acrylate, 2-isocyanate ethyl methacrylate, 1,1-bis (acryloxymethyl) ethyl isocyanate and the like can be used.
  • Polyester acrylate oligomers can be produced, for example, by esterifying the hydroxy groups of polyester oligomers having hydroxy groups at both ends obtained by condensation of polycarboxylic acid and polyhydric alcohol with (meth) acrylic acid, It can be obtained by esterifying the terminal hydroxy group of an oligomer obtained by adding an alkylene oxide to a carboxylic acid with (meth) acrylic acid.
  • the epoxy acrylate oligomer can be obtained, for example, by reacting (meth) acrylic acid with an oxirane ring of a relatively low molecular weight bisphenol type epoxy resin or novolak type epoxy resin and esterifying it. Further, a carboxyl-modified epoxy acrylate oligomer obtained by partially modifying an epoxy acrylate oligomer with a dibasic carboxylic acid anhydride can also be used.
  • the polyether acrylate oligomer can be obtained, for example, by esterifying the hydroxy group of the polyether polyol with (meth) acrylic acid.
  • the mass average molecular weight of the polyfunctional (meth) acrylate oligomer is preferably 10,000 or more, and particularly preferably 20,000 or more.
  • the mass average molecular weight is preferably 350,000 or less, particularly preferably 200,000 or less.
  • (2) Polymerization initiator It is preferable that the composition (x1) which concerns on this embodiment further contains a polymerization initiator. By containing the polymerization initiator, the composition (x1) can be efficiently cured.
  • the polymerization initiator is not particularly limited, and conventionally known polymerization initiators can be used, but it is preferable to select them according to the curing mode of the composition (x1). That is, when the composition (x1) is cured by irradiation with ultraviolet rays as active energy rays, it is preferable to use a photopolymerization initiator as a polymerization initiator. In addition, when the composition (x1) is cured by heating, it is preferable to use a thermal polymerization initiator. A photopolymerization initiator and a thermal polymerization initiator may be used in combination.
  • photopolymerization initiators include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, acetophenone, dimethylaminoacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl]- 2-morpholino-propan-1-one, 4- (2-hydroxyethoxy) phenyl-2- (hydroxy-2-propyl) ketone, benzophenone, p-phenylbenzophenone, 4,4'-diethylamino Nzophenone, dichlorobenzophenone, 2-methylanthraquinone, 2-ethylanth
  • thermal polymerization initiator examples include persulfates such as potassium persulfate and ammonium persulfate, peroxides such as benzoyl peroxide and laurium peroxide, and azo compounds such as azobisisobutyronitrile. These may be used alone or in combination of two or more.
  • the content of the polymerization initiator in the composition (x1) is preferably 0.1 parts by mass or more, particularly preferably 0.3 parts by mass or more, with respect to 100 parts by mass of the polymerization component. Is preferably 0.5 parts by mass or more. Moreover, it is preferable that the said content is 10 mass parts or less with respect to 100 mass parts of polymerization components, It is especially preferable that it is 5 mass parts or less, Furthermore, it is preferable that it is 3 mass parts or less.
  • the content is 0.1 part by mass or more, curing of the composition (x1) can be efficiently advanced.
  • the content is 10 parts by mass or less, it is possible to eliminate or reduce the polymerization initiator remaining unreacted in curing, and it is easy to set the obtained pressure-sensitive adhesive to desired physical properties.
  • composition (x1) various additives, for example, silane coupling agents, ultraviolet absorbers, antistatic agents, tackifiers, antioxidants, light stabilizers, softeners, A filler, a refractive index adjusting agent, etc. can be added.
  • the content of each additive is independently preferably 0.0001 to 20 parts by mass, more preferably 0.001 to 10 parts by mass with respect to 100 parts by mass of the polymerization component. It is.
  • the composition (x1) may contain a small amount of a diluting solvent such as water or an organic solvent together with the above-mentioned various active ingredients, but it is preferable not to contain it.
  • the heat-expandable base material (Y) contains heat-expandable particles
  • the pressure-sensitive adhesive sheet of the present invention exhibits heat peelability, so that the composition (x1) that is the pressure-sensitive adhesive layer (X1) forming material is used. It is not necessary to include thermally expandable particles.
  • the composition (x1) may contain a small amount of thermally expandable particles within a range not impairing the effects of the present invention, and the content of thermally expandable particles is determined by the composition (x1). ) Is preferably 0 to 50% by weight, more preferably 0 to 20% by weight, still more preferably 0 to 10% by weight, based on the total amount of active ingredients (100% by weight).
  • the pressure-sensitive adhesive layer (X2) included in the pressure-sensitive adhesive sheet of one embodiment of the present invention is a layer formed from the composition (x2) and has adhesiveness. Suitable physical properties of the pressure-sensitive adhesive layer (X2) are the same as those of the pressure-sensitive adhesive layer (X1). Moreover, about the composition (x2) which is a forming material of an adhesive layer (X2), the thing similar to the composition (x1) which is a forming material of an adhesive layer (X1) can be used.
  • release material As the release materials 13, 131, and 132 included in the pressure-sensitive adhesive sheet of one embodiment of the present invention, a release sheet that has been subjected to a double-sided release process, a release sheet that has been subjected to a single-sided release process, and the like are used. The thing etc. which apply
  • the two release materials 131 and the release material 132 that sandwich the laminate are preferably adjusted so that the difference in the release force is different.
  • Examples of the base material for the release material include papers such as high-quality paper, glassine paper, and kraft paper; polyester resin films such as polyethylene terephthalate resin, polybutylene terephthalate resin, and polyethylene naphthalate resin; and olefins such as polypropylene resin and polyethylene resin.
  • a plastic film such as a resin film;
  • release agent examples include silicone-based resins, olefin-based resins, isoprene-based resins, rubber-based elastomers such as butadiene-based resins, long-chain alkyl-based resins, alkyd-based resins, and fluorine-based resins.
  • the thickness of the release material is not particularly limited, but is preferably 10 to 200 ⁇ m, more preferably 25 to 170 ⁇ m, and still more preferably 35 to 80 ⁇ m.
  • the manufacturing method of the adhesive sheet of this invention is a method including the following process (1A) and (2A). Since the manufacturing method of the adhesive sheet of this invention can reduce the number of processes at the time of manufacturing an adhesive sheet compared with the conventional manufacturing method, it can improve productivity.
  • steps (1A) and (2A) will be described.
  • the coating film (x1 ′) and the coating film (y ′) for example, after the coating film (x1 ′) is formed, the coating film (x1 ′) is coated on the coating film (x1 ′).
  • ') May be sequentially formed, but from the viewpoint of productivity and interfacial adhesion, the composition (x1) and the composition (y) are simultaneously applied to form the coating film (x1') and the coating film ( A method of simultaneously forming y ′) is preferred.
  • the coater used for coating the composition (x1) and the composition (y) when sequentially forming the coating film (x1 ′) and the coating film (y ′) for example, a spin coater, a spray coater, a bar coater, Examples include knife coaters, roll coaters, knife roll coaters, blade coaters, gravure coaters, curtain coaters, and die coaters.
  • Examples of the coater used when the composition (x1) and the composition (y) are simultaneously applied include a multilayer coater, and specifically, a multilayer curtain coater, a multilayer die coater, and the like. Among these, a multilayer die coater is preferable from the viewpoint of operability.
  • the coating (x1 ′) and the coating (y ′) are simultaneously irradiated with energy rays to form the laminate.
  • a mixed layer is formed at the interface between the coating film (x1 ′) and the coating film (y ′), and the adhesive resin in the coating film (x1 ′) and the resin in the coating film (y ′). It is considered that the interfacial adhesion between the pressure-sensitive adhesive layer (X1) and the heat-expandable base material (Y) is improved by irradiating with energy rays in a state where they are intertwined with each other.
  • Examples of the energy ray irradiation of the coating film in the step (2A) include ultraviolet ray irradiation and electron beam irradiation, but ultraviolet ray irradiation is preferable from the viewpoint of preventing unnecessary reactions.
  • UV irradiation, high-pressure mercury lamp, a metal halide lamp, an electrodeless UV lamp, UV-LED can be effected by a xenon lamp or the like, the dose of ultraviolet ray is illuminance 50 mW / cm 2 or more, is 1000 mW / cm 2 or less It is preferable.
  • Amount is preferably at 50 mJ / cm 2 or more, more preferably 80 mJ / cm 2 or more, and particularly preferably 200 mJ / cm 2 or more.
  • the light amount is preferably at 10000 mJ / cm 2 or less, more preferably 5000 mJ / cm 2 or less, particularly preferably 2000 mJ / cm 2 or less.
  • the electron beam irradiation can be performed by an electron beam accelerator or the like, and the irradiation amount of the electron beam is preferably 10 krad or more and 1000 krad or less.
  • the manufacturing method of this invention is the adhesive of a thermally expansible base material (Y). If it is a method further including the process of forming an adhesive layer (X2) on the surface on the opposite side to a layer (X1), it will not specifically limit.
  • the manufacturing method of the following embodiment (A) and the manufacturing method of embodiment (B) are mentioned, and the viewpoint of the interfacial adhesion between the productivity and the thermally expandable substrate (Y) and the pressure-sensitive adhesive layer (X2). To the embodiment (B) is more preferable.
  • the manufacturing method of the embodiment (A) includes the following steps (3A-1) or (3A-2) in addition to the steps (1A) and (2A) described above.
  • Step (3A-1) A coating film (x2 ′) comprising the composition (x2) is formed on the surface of the thermally expandable substrate (Y) obtained in the step (2A), and the coating film A step of irradiating (x2 ′) with energy rays.
  • Step (3A-2) The composition (x2) is applied on the release treatment surface of the release material to form a coating film (x2 ′), and the coating film (x2 ′) is irradiated with energy rays to adhere The step of forming the adhesive layer (X2) in advance and directly sticking the pressure-sensitive adhesive layer (X2) formed on the release material onto the surface of the thermally expandable substrate (Y) obtained in the step (2A) .
  • the method of forming the coating film (x2 ′) in the steps (3A-1) and (3A-2) is, for example, a spin coater, spray coater, bar coater, knife coater, roll coater, knife roll coater, blade coater, gravure coater. , Curtain coater, die coater and the like.
  • the energy beam irradiation conditions for the coating film (x2 ′) in the steps (3A-1) and (3A-2) are the same as those for the energy beam irradiation of the coating film in the step (2A).
  • Step (3A-1) is preferable from the viewpoint of productivity and interfacial adhesion between the thermally expandable substrate (Y) and the pressure-sensitive adhesive layer (X2).
  • the manufacturing method of embodiment (B) includes the following steps (1B) and (2B).
  • steps (1B) and (2B) will be described.
  • the coating film (x1 ′), the coating film (y ′), and the coating film (x2 ′) for example, after forming the coating film (x1 ′), the coating film (x1 A sequential formation method may be used in which a coating film (y ') is formed on') and a coating film (x2 ') is further formed on the coating film (y').
  • the composition It is preferable to apply x1), the composition (y), and the composition (x2) at the same time to form the coating film (x1 ′), the coating film (y ′), and the coating film (x2 ′) at the same time.
  • each coater mentioned above etc. are mentioned, for example.
  • coat at least 3 layers simultaneously is mentioned.
  • a multilayer curtain coater, a multilayer die coater, etc. are mentioned.
  • a multilayer die coater capable of simultaneously applying three or more layers is preferable.
  • the coating film (x1 ′), the coating film (y ′), and the coating film (x2 ′) are simultaneously irradiated with energy rays to form the laminate.
  • a mixed layer is formed at the interface between the coating film (x1 ′) and the coating film (y ′), and the adhesive resin in the coating film (x1 ′) and the resin in the coating film (y ′).
  • the energy ray irradiation of the coating film in the step (2B) is the same as the energy ray irradiation of the coating film in the step (2A).
  • the pressure-sensitive adhesive sheet of the present invention is useful as a temporary fixing means for an object during the manufacturing process of building materials, interior materials, electronic components, and the like, and is preferably used as a temporary fixing means for a semiconductor chip during the manufacturing process of a semiconductor device.
  • a semiconductor package (FOWLP (Fan out Wafer) in which a rewiring layer is provided on the surface of a semiconductor chip sealed with a sealing resin, and solder balls and the semiconductor chip are electrically connected via the rewiring layer. It can be suitably used as a temporary fixing means at the time of manufacturing (called Level Package).
  • ⁇ Thickness of laminate> It was measured using a constant pressure thickness measuring instrument (model number: “PG-02J”, standard: conforming to JIS K6783, Z1702, Z1709) manufactured by Teclock Co., Ltd. Specifically, after measuring the total thickness of the pressure-sensitive adhesive sheet to be measured, a value obtained by subtracting the thickness of the release material measured in advance was defined as “the thickness of the laminate”.
  • the particle distribution of the thermally expandable particles before expansion at 23 ° C. was measured using a laser diffraction particle size distribution measuring apparatus (for example, product name “Mastersizer 3000” manufactured by Malvern).
  • the particle diameters corresponding to 50% and 90% of the cumulative volume frequency calculated from the smaller particle diameter of the particle distribution are expressed as “average particle diameter (D 50 ) of thermally expandable particles” and “thermally expandable particles”, respectively.
  • Laminate sample (heavy release film / thermally expandable substrate / light release film) so that the thickness of the heat expandable substrate to be measured is 20 ⁇ m in a state of being sandwiched between the later described heavy release film and light release film It was created.
  • the prepared sample was cut into a square with a side of 10 mm and then allowed to stand for 24 hours in an environment of 23 ° C. and 50% RH (relative humidity) to remove the light release film and the heavy release film as a test sample. Then, in an environment of 23 ° C.
  • the probe tack value on the surface of the test sample is calculated.
  • a tacking tester manufactured by Nippon Special Instrument Co., Ltd., product name “NTS-4800”
  • NTS-4800 50% RH (relative humidity)
  • the probe tack value on the surface of the test sample is calculated.
  • ⁇ Storage elastic modulus E 'of thermally expandable substrate> The thermal expansible substrate to be measured was 5 mm long ⁇ 30 mm wide ⁇ 200 ⁇ m thick, and the sample from which the release material was removed was used as a test sample. Using a dynamic viscoelasticity measuring apparatus (TA Instruments, product name “DMAQ800”), a test start temperature of 0 ° C., a test end temperature of 300 ° C., a temperature increase rate of 3 ° C./min, a frequency of 1 Hz, and an amplitude of 20 ⁇ m Under the conditions, the storage elastic modulus E ′ of the test sample at a predetermined temperature was measured.
  • DMAQ800 dynamic viscoelasticity measuring apparatus
  • the adhesive strength after heating at a temperature equal to or higher than the expansion start temperature was also measured at a pulling rate of 300 mm / min by a 180 ° peeling method based on JIS Z0237: 2000.
  • the adhesive force was set to 0 (N / 25mm).
  • thermally expandable particles and the release material used in the formation of each layer in the following production examples are as follows.
  • Example 1 Formation of coating film On the release agent layer of the heavy release film as a release material, the composition (x1) prepared in Production Example 1, the composition (y) prepared in Production Example 2, and Production Example 1 The composition (x2) prepared in (1) was simultaneously applied in this order using a multilayer die coater (width: 250 mm), and the coating film (x1 ′), coating film (y ′) and coating film (x2 ′) were formed. They were formed simultaneously in this order.
  • the formed coating film (x1 ′), coating film (y ′) and coating film (x2 ′) were irradiated with an illuminance of 160 mW / cm 2 and a light amount of 1000 mJ / cm 2 using an ultraviolet irradiation device.
  • the coating film was cured by irradiating with ultraviolet rays under conditions to form a laminate in which the layer (X1), the layer (Y), and the layer (X2) were directly laminated in this order from the release agent layer of the heavy release film.
  • the above illuminance and light intensity during ultraviolet irradiation are values measured using an illuminance / light meter (product name “UV Power Pack II” manufactured by EIT).
  • the release agent layer of the light release film was laminated
  • Example 2 The composition (x1), the composition (y), and the composition (x2) were formed so that the thicknesses of the layer (X1), the layer (Y), and the layer (X2) were as shown in Table 1, respectively.
  • a pressure-sensitive adhesive sheet of Example 2 was obtained using the same method as Example 1 except that the coating amount was changed.
  • a coating film (x1 ′) made of the composition (x1) prepared in Production Example 1 is formed, and an illuminance of 160 mW / cm 2 using an ultraviolet irradiation device,
  • the layer (X1) was formed by irradiating with ultraviolet rays under the condition of a light amount of 1000 mJ / cm 2 to cure the coating film.
  • the coating film (y ') which consists of a composition (y) prepared by manufacture example 2 is formed on the release agent layer of the light release film prepared separately from the release film on layer (X1), and ultraviolet irradiation Using the apparatus, the layer (Y) was formed by ultraviolet irradiation under the same conditions as those described above. Furthermore, a coating film (x2 ′) is formed on the release agent layer of a light release film prepared separately using the composition (x2) prepared in Production Example 1, and the above-described irradiation is performed using an ultraviolet irradiation device. The layer (X2) was formed by irradiation with ultraviolet rays under the same conditions.
  • the layer (Y) is laminated on the surface of the exposed layer (X1), the light release film on the layer (Y) is removed, and the layer (Y) is exposed on the surface.
  • (X2) was laminated
  • the thickness of the laminated body which the adhesive sheet produced in the Example and the comparative example has, and the thickness of the layer (X1), layer (Y), and layer (X2) which comprise the said laminated body are used for the above-mentioned method. Measured in conformity. The measurement results are shown in Table 1.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)
  • Laminated Bodies (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

L'invention concerne une feuille adhésive comprenant un corps stratifié constitué d'une couche adhésive (X1) et d'un substrat non adhésif thermiquement expansible (Y) directement stratifiés dans cet ordre. Le corps stratifié est formé par stratification directe, dans cet ordre, d'un matériau pour former la couche adhésive (X1), à savoir, un film de revêtement (x1') comprenant une composition (x1), et d'un matériau pour former le substrat thermiquement expansible (Y), à savoir, un film de revêtement (y') comprenant une composition contenant une résine et des particules thermiquement expansibles, puis exposition simultanée du film de revêtement (x1') et du film de revêtement (y') à un faisceau d'énergie. La feuille adhésive laisse peu de résidus adhésifs sur la surface d'une pièce à coller après avoir été chauffée et pelée, présente une bonne adhérence interfaciale entre le substrat et la couche adhésive, une excellente adhérence pendant la fixation temporaire et une excellente aptitude au pelage quand elle est chauffée.
PCT/JP2018/013356 2017-03-31 2018-03-29 Feuille adhésive Ceased WO2018181769A1 (fr)

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KR20190131033A (ko) 2019-11-25
TW201842105A (zh) 2018-12-01
CN110461978A (zh) 2019-11-15
TWI817942B (zh) 2023-10-11
CN110461978B (zh) 2022-04-19
KR102509251B1 (ko) 2023-03-13
JP6808817B2 (ja) 2021-01-06

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