WO2018181768A1 - 粘着シート - Google Patents

粘着シート Download PDF

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Publication number
WO2018181768A1
WO2018181768A1 PCT/JP2018/013355 JP2018013355W WO2018181768A1 WO 2018181768 A1 WO2018181768 A1 WO 2018181768A1 JP 2018013355 W JP2018013355 W JP 2018013355W WO 2018181768 A1 WO2018181768 A1 WO 2018181768A1
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WO
WIPO (PCT)
Prior art keywords
pressure
sensitive adhesive
resin
coating film
adhesive layer
Prior art date
Application number
PCT/JP2018/013355
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
高志 阿久津
揮一郎 加藤
晃司 土渕
Original Assignee
リンテック株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by リンテック株式会社 filed Critical リンテック株式会社
Priority to KR1020197027701A priority Critical patent/KR102573604B1/ko
Priority to CN201880022513.9A priority patent/CN110506089B/zh
Priority to JP2019510155A priority patent/JP6764525B2/ja
Publication of WO2018181768A1 publication Critical patent/WO2018181768A1/ja

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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
    • 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
    • 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
    • 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

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) containing an adhesive resin, 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 laminated
  • 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 laminate is A coating film (x1 ′) comprising a composition (x1) containing an adhesive resin, 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) containing an adhesive resin, which is a material for forming the adhesive layer (X2);
  • the coated sheets (x1 ′), (y ′) and (x2 ′) are simultaneously dried to form the pressure-sensitive adhesive sheet according to [6] above.
  • the pressure-sensitive adhesive sheet according to any one of [1] to [7], wherein the thermally expandable particles have an average particle diameter before expansion at 23 ° C. of 3 to 100 ⁇ m.
  • 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 material for forming the pressure-sensitive adhesive layer (X1), and is a coating film (x1 ′) made of a composition (x1) containing a pressure-sensitive resin and a thermally expandable substrate (Y).
  • the coating film (y ′) made of the composition (y) containing the resin and the heat-expandable particles, in this order, the coating film (x1 ′) and the coating film (y ′) It was formed by drying at the same time.
  • 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 ), A coating film (x1 ′) made of a composition (x1) containing an adhesive resin, and a composition containing a resin and thermally expandable particles, which is a forming material of the thermally expandable substrate (Y).
  • the coating film (y ′) made of the product (y) is directly laminated in this order, and then the coating film (x1 ′) and the coating film (y ′) are dried at the same time.
  • the coating film (x1 ′) and the coating film (y ′) are dried “simultaneously” to form a laminate, the coating film (x1 ′) and the coating film (y ′) are “separated”. Compared with the method of drying and forming a laminated body, the interface adhesiveness of an adhesive layer (X1) and a thermally expansible base material (Y) can be improved.
  • 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 substrate ( It is considered that the interfacial adhesion with Y) is improved.
  • a composition (x1) containing an adhesive resin is applied onto a release-treated surface of a release material such as a release film to form a coating film (x1 ′), and the coating film (x1 ′) is dried to form an adhesive layer.
  • (X1) is formed.
  • 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. ') Is dried to form a thermally expandable substrate (Y). Then, the surface which is not in contact with the release material of the pressure-sensitive adhesive layer (X1) and the surface which is not in contact with the release material of the thermally expandable base material (Y) are bonded together to form a laminate.
  • 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 at the same time, 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 dried. Is formed.
  • the composition (x1) and the composition (y) it becomes difficult to form a dry film of the thin film on the surface of the coating film as compared with the case of sequentially applying each composition. Interfacial adhesion between 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
  • an adhesive layer (X2) is a layer formed from the composition (x2) containing adhesive resin.
  • Examples of a method for forming a laminate further including the above-mentioned pressure-sensitive adhesive layer (X2) include, for example, a method in which the composition (x2) is heated and melted and extrusion-laminated on the expandable substrate (Y), or a composition ( There is a method in which x2) is applied on the expandable substrate (Y) to form a coating film (x2 ′), and the coating film (x2 ′) is dried to form. Further, for example, the pressure-sensitive adhesive layer (X2) prepared in advance by a method such as extrusion molding or drying the coating film (x2 ′) may be directly pasted on the expandable substrate (Y).
  • the laminate further comprising the pressure-sensitive adhesive layer (X2) is preferably a coating film (x1 ′) made of a composition (x1) containing a pressure-sensitive resin, which is a material for forming the pressure-sensitive adhesive layer (X1).
  • a coating material (y ′) composed of a composition (y) containing a resin and thermally expandable particles, which is a forming material of the thermally expandable base material (Y), and an adhesive material which is a forming material of the adhesive layer (X2)
  • the coating film (x2 ′) composed of the composition (x2) containing the conductive resin is directly laminated in this order, and then the coating films (x1 ′), (y ′) and (x2 ′) are simultaneously dried. It is a thing.
  • 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 dried at the same time.
  • 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 “coating film” is a film formed from a composition as a forming material by a known coating method, and the residual ratio of volatile components such as a solvent contained in the film is This refers to those in a state of 10 to 100% by mass with respect to 100% by mass of the total amount of volatile components contained in the composition before coating. That is, in the present invention, the coating films (x1 ′), (y ′), and (x2 ′) contain a certain amount of a volatile component such as a solvent. By drying these coating films, the volatile components are removed, and the pressure-sensitive adhesive layer (X1), the thermally expandable substrate (Y), and the pressure-sensitive adhesive layer (X2) are formed.
  • the thickness of the laminate of the pressure-sensitive adhesive sheet of the present invention is preferably 10 to 150 ⁇ m, more preferably 15 to 125 ⁇ m, still more preferably 20 to 100 ⁇ m, and still more preferably 25 to 75 ⁇ 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 60 ⁇ m, more preferably 2 to 50 ⁇ m, still more preferably 3 to 40 ⁇ m, and still more preferably 5 to 30 ⁇ m.
  • the thickness of the heat-expandable base material (Y) of the pressure-sensitive adhesive sheet of the present invention is preferably 5 to 140 ⁇ m, more preferably 9 to 110 ⁇ m, still more preferably 13 to 80 ⁇ m, and still more preferably 17 to 50 ⁇ 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 60 ⁇ m, more preferably 2 to 50 ⁇ 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 3.0 or more, from the viewpoint of preventing positional displacement of the object.
  • it is preferably 20 or less, more preferably 15 or less, still more preferably 10 or less, and even more preferably 5 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. Preferably, it is 3.0 or more, preferably 20 or less, more preferably 15 or less, still more preferably 10 or less, and still more preferably 5 or less.
  • the laminate of the pressure-sensitive adhesive sheet of the present invention has a mixed layer between the two coating films in the drying process of the coating film, and the pressure-sensitive adhesive layer (X1) and the thermally expandable substrate (Y) And the interface between the thermally expandable base material (Y) and the pressure-sensitive adhesive layer (X2) may become so unclear that they 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 drying a coating film (y ′) made of a composition (y) containing a resin and heat-expandable particles, It is an adhesive substrate.
  • a coating film (y ′) made of a composition (y) containing a resin and heat-expandable particles, It is an adhesive substrate.
  • whether or not the 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.
  • the composition (y), which is a material for forming the thermally expandable substrate (Y), contains a resin and thermally expandable particles.
  • it contains the additive for the substrate contained in the substrate which the diluting solvent and / or the general adhesive sheet has as needed. Also good.
  • 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.
  • the mass average molecular weight (Mw) of the resin contained in the composition (y) is preferably 1,000 to 1,000,000, more preferably 1,000 to 700,000, and still more preferably 1,000 to 500,000. Further, when the resin is a copolymer having two or more kinds of structural units, the form of the copolymer is not particularly limited, and any of a block copolymer, a random copolymer, and a graft copolymer It may be.
  • the content of the resin is preferably 50 to 99% by mass, more preferably 60 to 95% by mass, and still more preferably 65 to 90% by mass with respect to the total amount (100% by mass) of the active ingredients of the composition (y). %, More preferably 70 to 85% by mass.
  • the resin contained in the resin composition (y) includes one or more selected from acrylic urethane resins and olefin resins. Is preferred.
  • the following resin (U1) is preferable.
  • An acrylic urethane resin (U1) obtained by polymerizing a urethane prepolymer (UP) and a vinyl compound containing a (meth) acrylic acid ester.
  • the acrylic urethane-based resin (U1) has a structural unit derived from a vinyl compound containing a (meth) acrylic acid ester at both ends of the linear urethane prepolymer while having the main chain of the linear urethane prepolymer as a skeleton. is there.
  • the acrylic urethane resin (U1) since the site derived from the linear urethane polymer is interposed between the acrylic sites in the main chain skeleton, the distance between the crosslinking points becomes long, and the molecular structure thereof is a two-dimensional structure (network structure). It is easy to become.
  • the urethane prepolymer of the main chain is linear, the stretching effect is high when an external force is applied.
  • the side chain of the structural unit derived from the vinyl compound containing (meth) acrylic acid ester is easily entangled with the adhesive resin contained in the adhesive layer (X1) and the adhesive resin contained in the adhesive layer (X2). It has a structure. Therefore, the acrylic urethane-based resin (U1) is thermally expandable when the adhesiveness between the adhesive layer (X1) and the thermally expandable substrate (Y) and the adhesive layer (X2) are present. It is thought that it can contribute to the improvement of the interfacial adhesion between the base material (Y) and the adhesive layer (X2).
  • urethane prepolymer (UP) serving as the main chain of the acrylic urethane resin (U1) include a reaction product of a polyol and a polyvalent isocyanate.
  • the urethane prepolymer (UP) is preferably obtained by further performing a chain extension reaction using a chain extender.
  • 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) serving as the main chain of the acrylic urethane resin (U1) is a reaction product of a diol and a diisocyanate, and is a straight chain having ethylenically unsaturated groups at both ends.
  • a urethane prepolymer is preferred.
  • an NCO group at the end of the linear urethane prepolymer obtained by reacting a diol and a diisocyanate compound, and a hydroxyalkyl (meth) acrylate And a method of reacting with.
  • 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 (meth) acrylic acid ester is preferably one or more selected from alkyl (meth) acrylates and hydroxyalkyl (meth) acrylates, and more preferably used in combination with alkyl (meth) acrylates and hydroxyalkyl (meth) acrylates.
  • the proportion of hydroxyalkyl (meth) acrylate to 100 parts by mass of alkyl (meth) acrylate is preferably 0.1 to 100 parts by mass, The amount is preferably 0.5 to 30 parts by mass, more preferably 1.0 to 20 parts by mass, and still more preferably 1.5 to 10 parts by mass.
  • the carbon number of the alkyl group of the alkyl (meth) acrylate is preferably 1 to 24, more preferably 1 to 12, still more preferably 1 to 8, and still more preferably 1 to 3.
  • hydroxyalkyl (meth) acrylate the same thing as the hydroxyalkyl (meth) acrylate used in order to introduce
  • vinyl compounds other than (meth) acrylic acid esters include aromatic hydrocarbon vinyl compounds such as styrene, ⁇ -methylstyrene, and vinyl toluene; vinyl ethers such as methyl vinyl ether and ethyl vinyl ether; vinyl acetate and vinyl propionate.
  • Polar group-containing monomers such as (meth) acrylonitrile, N-vinylpyrrolidone, (meth) acrylic acid, maleic acid, fumaric acid, itaconic acid, and meta (acrylamide). These may be used alone or in combination of two or more.
  • the content of the (meth) acrylic acid ester in the vinyl compound is preferably 40 to 100% by mass, more preferably 65 to 100% by mass, and still more preferably based on the total amount (100% by mass) of the vinyl compound. It is 80 to 100% by mass, more preferably 90 to 100% by mass.
  • the total content of alkyl (meth) acrylate and hydroxyalkyl (meth) acrylate in the vinyl compound is preferably 40 to 100% by mass, more preferably 65 to 100% by mass with respect to the total amount (100% by mass) of the vinyl compound.
  • the amount is 100% by mass, more preferably 80 to 100% by mass, and still more preferably 90 to 100% by mass.
  • the acrylic urethane-based resin (U1) used in one embodiment of the present invention is obtained by mixing a urethane prepolymer (UP) and a vinyl compound containing a (meth) acrylic acid ester and polymerizing both.
  • the polymerization is preferably performed by adding a radical initiator.
  • the content ratio of the structural unit (u11) derived from the urethane prepolymer (UP) and the structural unit (u12) derived from the vinyl compound [(u11 ) / (U12)] is preferably 10/90 to 80/20, more preferably 20/80 to 70/30, still more preferably 30/70 to 60/40, and still more preferably 35 by mass ratio. / 65 to 55/45.
  • the olefin resin suitable as the resin contained in the composition (y) is 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.
  • olefinic resins 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 less than 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), linear low density polyethylene, etc .; 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); ethylene-propylene Olefinic terpolymers such as-(5-ethylid)
  • the olefin resin may be a modified olefin resin further modified by one or more selected from acid modification, hydroxyl group modification, and acrylic modification.
  • an acid-modified olefin resin obtained by subjecting an olefin resin to acid modification a modified polymer obtained by graft polymerization of the above-mentioned unmodified olefin resin with an unsaturated carboxylic acid or its anhydride.
  • unsaturated carboxylic acid or anhydride thereof include maleic acid, fumaric acid, itaconic acid, citraconic acid, glutaconic acid, tetrahydrophthalic acid, aconitic acid, (meth) acrylic acid, maleic anhydride, itaconic anhydride.
  • Glutaconic anhydride citraconic anhydride, aconitic anhydride, norbornene dicarboxylic anhydride, tetrahydrophthalic anhydride, and the like.
  • unsaturated carboxylic acid or its anhydride may be used independently and may use 2 or more types together.
  • an acrylic modified olefin resin obtained by subjecting an olefin resin to acrylic modification a modification obtained by graft polymerization of an alkyl (meth) acrylate as a side chain to the above-mentioned unmodified olefin resin as a main chain.
  • a polymer is mentioned.
  • 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.
  • said alkyl (meth) acrylate the same thing as the compound which can be selected as a below-mentioned monomer (a1 ') is mentioned, for example.
  • Examples of the hydroxyl group-modified olefin resin obtained by subjecting an olefin resin to hydroxyl group modification include a modified polymer obtained by graft polymerization of a hydroxyl group-containing compound to the above-mentioned unmodified olefin resin, which is the main chain.
  • Examples of the hydroxyl group-containing compound include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 3-hydroxybutyl.
  • Examples thereof include hydroxyalkyl (meth) acrylates such as (meth) acrylate and 4-hydroxybutyl (meth) acrylate; unsaturated alcohols such as vinyl alcohol and allyl alcohol.
  • the composition (y) may contain a resin other than the acrylic urethane-based resin and the olefin-based resin as long as the effects of the present invention are not impaired.
  • Such resins include vinyl resins such as polyvinyl chloride, polyvinylidene chloride, and polyvinyl alcohol; polyester resins such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate; polystyrene; acrylonitrile-butadiene-styrene copolymer Polycarbonate; Polyurethane not applicable to acrylic urethane resin; Polysulfone; Polyetheretherketone; Polyethersulfone; Polyphenylene sulfide; Polyimide resin such as polyetherimide and polyimide; Polyamide resin; Acrylic resin; Fluorine resin etc. are mentioned.
  • vinyl resins such as polyvinyl chloride, polyvinylidene chloride, and polyvinyl alcohol
  • polyester resins such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate
  • polystyrene acrylonitrile-butadiene-styren
  • the content ratio of the resin other than the acrylic urethane-based resin and the olefin-based resin in the composition (y) is preferably small.
  • the content of the resin other than the acrylic urethane-based resin and the olefin-based resin is preferably less than 30 parts by weight, more preferably less than 20 parts by weight with respect to 100 parts by weight of the total amount of the resin contained in the composition (y). More preferably, it is less than 10 mass parts, More preferably, it is less than 5 mass parts, More preferably, it is less than 1 mass part.
  • the composition (y) contains an acrylic urethane resin
  • a crosslinking agent the isocyanate type compound as a crosslinking agent is preferable, for example.
  • various isocyanate compounds can be used as long as they react with the functional group of the acrylic urethane resin to form a crosslinked structure.
  • the isocyanate compound is preferably a polyisocyanate compound having two or more isocyanate groups per molecule.
  • polyisocyanate compound examples include diisocyanate compounds, triisocyanate compounds, tetraisocyanate compounds, pentaisocyanate compounds, hexaisocyanate compounds, and the like. More specifically, aromatic polyisocyanate compounds such as tolylene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate; dicyclohexylmethane-4,4-diisocyanate, bicycloheptane triisocyanate, cyclopentylene diisocyanate, cyclohexylene diisocyanate, methylcyclohexylene Examples thereof include alicyclic isocyanate compounds such as diisocyanate and hydrogenated xylylene diisocyanate; aliphatic isocyanate compounds such as pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, trimethylhexamethylene diisocyan
  • biuret bodies isocyanurate bodies of these isocyanate compounds, adduct bodies that are reaction products of these isocyanate compounds with non-aromatic low-molecular active hydrogen-containing compounds such as ethylene glycol, trimethylolpropane, castor oil, etc. Modified products can also be used.
  • isocyanate compounds aliphatic isocyanate compounds are preferable, aliphatic diisocyanate compounds are more preferable, and pentamethylene diisocyanate, hexamethylene diisocyanate, and heptamethylene diisocyanate are still more preferable.
  • the isocyanate compound may be used alone or in combination of two or more.
  • the content ratio of the acrylic urethane resin and the isocyanate compound as a crosslinking agent is an isocyanate system as a crosslinking agent with respect to a total of 100 parts by mass of the acrylic urethane resin as a solid content ratio.
  • the compound is preferably 1 to 30 parts by mass, more preferably 2 to 20 parts by mass, and still more preferably 3 to 15 parts by mass.
  • the composition (y) when the composition (y) contains an acrylic urethane resin and the crosslinking agent, the composition (y) further preferably contains a catalyst together with the crosslinking agent.
  • a metal catalyst is preferable, and a metal catalyst excluding a tin compound having a butyl group is more preferable.
  • the metal catalyst include a tin catalyst, a bismuth catalyst, a titanium catalyst, a vanadium catalyst, a zirconium catalyst, an aluminum catalyst, and a nickel catalyst.
  • a tin-based catalyst or a bismuth-based catalyst is preferable, and a tin-based catalyst or a bismuth-based catalyst excluding a tin-based compound having a butyl group is more preferable.
  • the tin-based catalyst is an organometallic compound of tin, and includes compounds having a structure such as alkoxide, carboxylate, chelate, etc., preferably acetylacetone complex, acetylacetonate, octylic acid compound or naphthenic acid of these metals Compounds and the like.
  • the bismuth catalyst, titanium catalyst, vanadium catalyst, zirconium catalyst, aluminum catalyst, or nickel catalyst is an organometallic compound of bismuth, titanium, vanadium, zirconium, aluminum, or nickel, respectively.
  • compounds having a structure such as alkoxide, carboxylate, chelate and the like can be mentioned, and preferred examples thereof include acetylacetone complexes, acetylacetonates, octylic acid compounds and naphthenic acid compounds of these metals.
  • metal acetylacetone complex examples include acetylacetone tin, acetylacetone titanium, acetylacetone vanadium, acetylacetone zirconium, acetylacetone aluminum, and acetylacetone nickel.
  • acetylacetonate examples include tin acetylacetonate, bismuth acetylacetonate, titanium acetylacetonate, vanadium acetylacetonate, zirconium acetylacetonate, aluminum acetylacetonate, nickel acetylacetonate and the like.
  • octylic acid compound examples include bismuth 2-ethylhexylate, nickel 2-ethylhexylate, zirconium 2-ethylhexylate, tin 2-ethylhexylate and the like.
  • naphthenic acid compound examples include bismuth naphthenate, nickel naphthenate, zirconium naphthenate, tin naphthenate, and the like.
  • RxSn (L) (4-X) (wherein R is an alkyl group having 1 to 25 carbon atoms, preferably an alkyl group having 1 to 3 or 5 to 25 carbon atoms, or It is an aryl group, L is an organic group other than an alkyl group and an aryl group, or an inorganic group, and x is 1, 2 or 4).
  • the alkyl group of R is more preferably an alkyl group having 5 to 25 carbon atoms, further preferably an alkyl group having 5 to 20 carbon atoms, and the aryl group of R is The number of carbon atoms is not particularly limited, but an aryl group having 6 to 20 carbon atoms is preferable. When two or more R are present in one molecule, each R may be the same or different.
  • L is preferably an aliphatic carboxylic acid, aromatic carboxylic acid or aromatic sulfonic acid having 2 to 20 carbon atoms, more preferably an aliphatic carboxylic acid having 2 to 20 carbon atoms.
  • Examples of the aliphatic carboxylic acid having 2 to 20 carbon atoms include an aliphatic monocarboxylic acid having 2 to 20 carbon atoms and an aliphatic dicarboxylic acid having 2 to 20 carbon atoms.
  • each L may be the same or different.
  • the catalyst may be used alone or in combination of two or more.
  • the content ratio of the acrylic urethane resin and the catalyst is preferably 0.001 to 5 parts by mass in terms of solid content of the catalyst with respect to 100 parts by mass in total of the acrylic urethane resin.
  • the amount is preferably 0.01 to 3 parts by mass, more preferably 0.1 to 2 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 additive for base materials is the total amount of resin selected from the group consisting of acrylurethane resins and olefin resins contained in the composition (y). The amount is preferably 0.0001 to 20 parts by mass, more preferably 0.001 to 10 parts by mass with respect to 100 parts by mass.
  • the composition (y) may contain water or an organic solvent as a diluent solvent together with the various active ingredients described above, and may be in the form of a solution.
  • organic solvent include toluene, xylene, ethyl acetate, butyl acetate, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, methanol, ethanol, isopropyl alcohol, tert-butanol, s-butanol, acetylacetone, cyclohexanone, n-hexane, and cyclohexane.
  • these dilution solvents may be used independently and may be used in combination of 2 or more type.
  • the active ingredient concentration of the composition (y) is preferably independently 0.1 to 60% by mass, more preferably 0. It is 5 to 50% by mass, more preferably 1.0 to 40% by mass.
  • the pressure-sensitive adhesive layer (X1) of the pressure-sensitive adhesive sheet of the present invention is a layer formed by drying a coating film (x1 ′) made of a composition (x1) containing a pressure-sensitive adhesive resin, and has pressure-sensitive 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 said adhesive force is 0.1 N / 25mm or more, to-be-adhered bodies, such as a semiconductor chip, can fully be fixed.
  • 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.
  • the composition (x1) that is a material for forming the pressure-sensitive adhesive layer (X1) contains a pressure-sensitive adhesive resin.
  • components other than adhesive resin contained in a composition (x1) can be suitably adjusted according to the use application of the adhesive sheet of this invention.
  • the composition (x1) may further contain a tackifier and / or a cross-linking agent from the viewpoint of obtaining a pressure-sensitive adhesive sheet with improved adhesive strength.
  • And / or an adhesive additive used in a diluting solvent and / or a general adhesive used in a diluting solvent and / or a general adhesive.
  • 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 mass average molecular weight (Mw) of the adhesive resin is preferably 10,000 to 2,000,000, more preferably 20,000 to 1,500,000, and even more preferably 30,000 to 1,000,000 from the viewpoint of improving the adhesive strength.
  • the adhesive resin contained in the composition (x1) include rubber resins such as acrylic resins, urethane resins, polyisobutylene resins, polyester resins, and olefins that satisfy the adhesive force as the above-mentioned adhesive resins. Resin, silicone resin, polyvinyl ether resin and the like. These adhesive resins may be used alone or in combination of two or more.
  • these adhesive resins are copolymers having two or more kinds of structural units, 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.
  • these pressure-sensitive adhesive resins are UV non-curable pressure-sensitive adhesives having no polymerizable functional group. A resin is preferred.
  • the content of the adhesive resin in the composition (x1) is preferably 30 to 99.99% by mass, more preferably 40 to 99%, based on the total amount (100% by mass) of the active ingredients of the composition (x1). .95% by mass, more preferably 50 to 99.90% by mass, still more preferably 55 to 99.80% by mass, and still more preferably 60 to 99.50% by mass.
  • the pressure-sensitive resin contained in the composition (x1) is an acrylic resin. It is preferable to contain.
  • the content ratio of the acrylic resin in the adhesive resin is preferably from 30 to the total amount (100% by mass) of the adhesive resin contained in the composition (x1) from the viewpoint of further improving the interfacial adhesion.
  • the amount is 100% by mass, more preferably 50 to 100% by mass, still more preferably 70 to 100% by mass, and still more preferably 85 to 100% by mass.
  • the mass average molecular weight (Mw) of the acrylic resin is preferably 100,000 to 1,500,000, more preferably 200,000 to 1,300,000, still more preferably 350,000 to 1,200,000, still more preferably 500,000 to 1,100,000. .
  • an acrylic polymer having a structural unit (a1) derived from alkyl (meth) acrylate (a1 ′) (hereinafter also referred to as “monomer (a1 ′)”).
  • (A0) is preferred, and the acrylic copolymer having the structural unit (a2) derived from the functional group-containing monomer (a2 ′) (hereinafter also referred to as “monomer (a2 ′)”) together with the structural unit (a1).
  • A1 is more preferable.
  • the number of carbon atoms of the alkyl group contained in the monomer (a1 ′) is preferably 1 to 24, more preferably 1 to 12, still more preferably 1 to 8, and still more preferably 4 to 6 from the viewpoint of improving adhesive properties. It is.
  • the alkyl group contained in the monomer (a1 ′) may be a linear alkyl group or a branched alkyl group.
  • Examples of the monomer (a1 ′) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, tridecyl ( Examples include meth) acrylate and stearyl (meth) acrylate. These monomers (a1 ′) may be used alone or in combination of two or more.
  • methyl (meth) acrylate, butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate are preferable, and methyl (meth) acrylate and butyl (meth) acrylate are more preferable.
  • the content of the structural unit (a1) is preferably 50 to 100% by weight, more preferably based on the total structural unit (100% by weight) of the acrylic polymer (A0) or the acrylic copolymer (A1). It is 60 to 99.9% by mass, more preferably 70 to 99.5% by mass, and still more preferably 80 to 99.0% by mass.
  • the functional group possessed by the monomer (a2 ′) refers to a functional group capable of reacting with a crosslinking agent that may be contained in the composition (x1) described later to serve as a crosslinking starting point or a functional group having a crosslinking accelerating effect.
  • a crosslinking agent that may be contained in the composition (x1) described later to serve as a crosslinking starting point or a functional group having a crosslinking accelerating effect.
  • Carboxy group, amino group, epoxy group and the like examples of the monomer (a2 ′) include a hydroxyl group-containing monomer, a carboxy group-containing monomer, an amino group-containing monomer, and an epoxy group-containing monomer. These monomers (a2 ′) may be used alone or in combination of two or more.
  • a hydroxyl group-containing monomer and a carboxy group-containing monomer are preferable.
  • hydroxyl group-containing monomer examples include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 3-hydroxybutyl (meth) )
  • hydroxyalkyl (meth) acrylates such as 4-hydroxybutyl (meth) acrylate; and unsaturated alcohols such as vinyl alcohol and allyl alcohol.
  • carboxy group-containing monomer examples include ethylenically unsaturated monocarboxylic acids such as (meth) acrylic acid and crotonic acid; ethylenically unsaturated dicarboxylic acids such as fumaric acid, itaconic acid, maleic acid and citraconic acid, and anhydrides thereof.
  • the monomer (a2 ′) 2-hydroxyethyl (meth) acrylate is preferable.
  • the content of the structural unit (a2) is preferably 0.1 to 40% by weight, more preferably 0.3 to 30%, based on the entire structural unit (100% by weight) of the acrylic copolymer (A1). % By mass, more preferably 0.5 to 20% by mass, still more preferably 0.7 to 10% by mass.
  • the acrylic copolymer (A1) may further have a structural unit (a3) derived from another monomer (a3 ′) other than the monomers (a1 ′) and (a2 ′).
  • the content of the structural units (a1) and (a2) is preferably 70 with respect to the total structural units (100% by mass) of the acrylic copolymer (A1).
  • To 100% by mass more preferably 80 to 100% by mass, still more preferably 90 to 100% by mass, and still more preferably 95 to 100% by mass.
  • olefins such as ethylene, propylene and isobutylene; halogenated olefins such as vinyl chloride and vinylidene chloride; diene monomers such as butadiene, isoprene and chloroprene; cyclohexyl (meth) acrylate, It has a cyclic structure such as benzyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, imide (meth) acrylate, etc.
  • (Meth) acrylate styrene, ⁇ -methylstyrene, vinyl toluene, vinyl formate, vinyl acetate, acrylonitrile, (meth) acrylamide, (meth) acrylonitrile, (meth) acryloyl mole Phosphorus, N- vinylpyrrolidone and the like.
  • vinyl acetate is preferable.
  • the urethane resin that can be used as the adhesive resin is not particularly limited as long as it is a polymer having at least one of a urethane bond and a urea bond in at least one of the main chain and the side chain.
  • Specific examples of the urethane resin include a urethane prepolymer (UX) obtained by reacting a polyol and a polyvalent isocyanate compound.
  • the urethane prepolymer (UX) may be obtained by further subjecting to a chain extension reaction using a chain extender.
  • the mass average molecular weight (Mw) of the urethane resin is preferably 10,000 to 200,000, more preferably 12,000 to 150,000, still more preferably 15,000 to 100,000, and still more preferably 20,000 to 70,000.
  • polyol used as a raw material for the urethane-based prepolymer (UX) examples include polyol compounds such as alkylene type polyols, polyether type polyols, polyester type polyols, polyester amide type polyols, polyester / polyether type polyols, and polycarbonate type polyols. Although it is mentioned, if it is a polyol, it will not specifically limit, Bifunctional diol and a trifunctional triol may be sufficient. These polyols may be used alone or in combination of two or more. Among these polyols, diols are preferable and alkylene type diols are more preferable from the viewpoints of availability, reactivity, and the like.
  • 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.
  • glycols having a mass average molecular weight (Mw) of 1,000 to 3,000 are preferred from the viewpoint of suppressing gelation when the reaction with a chain extender is performed.
  • Examples of the polyvalent isocyanate compound that is a raw material for the urethane prepolymer (UX) include aromatic polyisocyanates, aliphatic polyisocyanates, and alicyclic polyisocyanates.
  • aromatic polyisocyanate include 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate (MDI), 2,4-tolylene diisocyanate (2,4-TDI), 2 , 6-Tolylene diisocyanate (2,6-TDI), 4,4′-toluidine diisocyanate, 2,4,6-triisocyanate toluene, 1,3,5-triisocyanate benzene, dianisidine diisocyanate, 4,4 ′ -Diphenyl ether diisocyanate, 4,4 ', 4 "-triphenylmethane triisocyanate, 1,4-tetramethylxylylene di
  • aliphatic polyisocyanate examples include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HMDI), pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, and dodeca.
  • HMDI hexamethylene diisocyanate
  • pentamethylene diisocyanate 1,2-propylene diisocyanate
  • 2,3-butylene diisocyanate 1,3-butylene diisocyanate
  • dodeca examples include methylene diisocyanate and 2,4,4-trimethylhexamethylene diisocyanate.
  • Examples of the alicyclic polyisocyanate include 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (IPDI: isophorone diisocyanate), 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4- Cyclohexane diisocyanate, methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), 1,4-bis (isocyanatemethyl) cyclohexane, 1,4-bis (isocyanate) Methyl) cyclohexane and the like.
  • IPDI isophorone diisocyanate
  • 1,3-cyclopentane diisocyanate 1,3-cyclohexane diisocyanate
  • these polyisocyanate compounds may be a trimethylolpropane adduct modified product of the polyisocyanate, a burette modified product reacted with water, or an isocyanurate modified product containing an isocyanurate ring.
  • polyvalent isocyanate compounds 4,4′-diphenylmethane diisocyanate (MDI), 2,4-tolylene diisocyanate (2,4-TDI), 2, from the viewpoint of obtaining a urethane polymer having excellent adhesive properties.
  • MDI 4,4′-diphenylmethane diisocyanate
  • 2,4-TDI 2,4-tolylene diisocyanate
  • One or more selected from 6-tolylene diisocyanate (2,6-TDI), hexamethylene diisocyanate (HMDI), 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (IPDI) and modified products thereof are preferable. From the viewpoint of weather resistance, at least one selected from HMDI, IPDI, and modified products thereof is more preferable.
  • the isocyanate group content (NCO%) in the urethane prepolymer (UX) is preferably 0.5 to 12% by mass, more preferably 1 to 4 in a value measured according to JIS K1603-1: 2007. % By mass.
  • chain extender a compound having at least one of hydroxyl group and amino group, or a compound having at least three of hydroxyl group and amino group is preferable.
  • the compound having at least one of a hydroxyl group and an amino group is preferably at least one compound selected from the group consisting of aliphatic diols, aliphatic diamines, alkanolamines, bisphenols, and aromatic diamines.
  • aliphatic diol examples include alkanediols such as 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, and 1,7-heptanediol.
  • Alkylene glycols such as ethylene glycol, propylene glycol, diethylene glycol and dipropylene glycol;
  • the aliphatic diamine include ethylenediamine, 1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, and the like.
  • the alkanolamine include monoethanolamine, monopropanolamine, isopropanolamine and the like.
  • Examples of bisphenol include bisphenol A and the like.
  • aromatic diamine include diphenylmethanediamine, tolylenediamine, xylylenediamine, and the like.
  • Examples of the compound having at least three hydroxyl groups and amino groups include polyols such as trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol; 1-amino-2,3-propanediol, 1-methyl And amino alcohols such as amino-2,3-propanediol and N- (2-hydroxypropylethanolamine); ethylene oxide or propylene oxide adducts of tetramethylxylylenediamine;
  • the polyisobutylene resin (hereinafter also referred to as “PIB resin”) that can be used as an adhesive resin is not particularly limited as long as it has a polyisobutylene skeleton in at least one of a main chain and a side chain.
  • the mass average molecular weight (Mw) of the PIB resin is preferably 20,000 or more, more preferably 30,000 to 1,000,000, still more preferably 50,000 to 800,000, and still more preferably 70,000 to 600,000.
  • PIB resin examples include polyisobutylene which is a homopolymer of isobutylene, a copolymer of isobutylene and isoprene, a copolymer of isobutylene and n-butene, a copolymer of isobutylene and butadiene, and these copolymers.
  • examples thereof include halogenated butyl rubber that has been brominated or chlorinated.
  • the structural unit composed of isobutylene is contained in the largest amount among all the structural units.
  • the content of the structural unit composed of isobutylene is preferably 80 to 100% by mass, more preferably 90 to 100% by mass, and still more preferably 95 to 100% by mass with respect to all the structural units (100% by mass) of the PIB resin. %.
  • These PIB-based resins may be used alone or in combination of two or more.
  • PIB-type resin when using PIB-type resin, it is preferable to use together PIB-type resin with a high mass average molecular weight (Mw) and PIB-type resin with a low mass average molecular weight (Mw). More specifically, a PIB resin (p1) having a mass average molecular weight (Mw) of 270,000 to 600,000 (hereinafter also referred to as “PIB resin (p1)”), and a mass average molecular weight (Mw) of 5 It is preferable to use 10,000 to 250,000 PIB resin (p2) (hereinafter also referred to as “PIB resin (p2)”) in combination.
  • the durability and weather resistance of the pressure-sensitive adhesive layer to be formed can be improved, and the adhesive strength can also be improved.
  • a PIB resin (p2) having a low mass average molecular weight (Mw) it can be well compatible with the PIB resin (p1), and the PIB resin (p1) can be appropriately plasticized.
  • the wettability of the pressure-sensitive adhesive layer to the adherend can be improved, and the physical properties of adhesive, flexibility and the like can be improved.
  • the mass average molecular weight (Mw) of the PIB resin (p1) is preferably 270,000 to 600,000, more preferably 290,000 to 480,000, still more preferably 310,000 to 450,000, and even more preferably 320,000 to 400,000. It is.
  • the mass average molecular weight (Mw) of the PIB resin (p2) is preferably 50,000 to 250,000, more preferably 80,000 to 230,000, still more preferably 140,000 to 220,000, and still more preferably 180,000 to 210,000. It is.
  • the content ratio of the PIB resin (p2) to 100 parts by mass of the PIB resin (p1) is preferably 5 to 55 parts by mass, more preferably 6 to 40 parts by mass, still more preferably 7 to 30 parts by mass, and even more.
  • the amount is preferably 8 to 20 parts by mass.
  • the olefin resin that can be used as the adhesive resin is not particularly limited as long as it is a polymer having a structural unit derived from an olefin compound such as ethylene or propylene.
  • the said olefin resin may be used independently and may be used in combination of 2 or more type.
  • the olefin-based resin examples include polyethylenes such as low density polyethylene, medium density polyethylene, high density polyethylene, and linear low density polyethylene, polypropylene, copolymers of ethylene and propylene, ethylene and other ⁇ - Copolymers of olefins, copolymers of propylene and other ⁇ -olefins, copolymers of ethylene, propylene and other ⁇ -olefins, copolymers of ethylene and other ethylenically unsaturated monomers Examples thereof include ethylene (vinyl-vinyl acetate copolymer, ethylene-alkyl (meth) acrylate copolymer, etc.) and the like.
  • Examples of the ⁇ -olefin include 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 4-methyl-1-pentene, 4-methyl-1-hexene and the like.
  • Examples of the ethylenically unsaturated monomer include vinyl acetate, alkyl (meth) acrylate, vinyl alcohol, and the like.
  • the composition (x1) further contains a tackifier from the viewpoint of obtaining a pressure-sensitive adhesive sheet with improved adhesive strength.
  • the “tackifier” is a component that assists in improving the adhesive strength of the adhesive resin, and refers to an oligomer having a mass average molecular weight (Mw) of less than 10,000. It is a distinction.
  • the weight average molecular weight (Mw) of the tackifier is preferably 400 to 10,000, more preferably 500 to 8,000, and still more preferably 800 to 5,000.
  • tackifiers include rosin resins such as rosin resins, rosin ester resins, and rosin-modified phenol resins; hydrogenated rosin resins obtained by hydrogenating these rosin resins; terpene resins, aromatic modified terpene resins, and terpene phenols.
  • Terpene resins such as epoxy resins; hydrogenated terpene resins obtained by hydrogenating these terpene resins; styrene obtained by copolymerizing a styrene monomer such as ⁇ -methylstyrene or ⁇ -methylstyrene with an aliphatic monomer Hydrogenated styrene resins obtained by hydrogenating these styrene resins; C5 systems obtained by copolymerizing C5 fractions such as pentene, isoprene, piperine, 1,3-pentadiene generated by thermal decomposition of petroleum naphtha Petroleum resin and hydrogenated petroleum resin of this C5 petroleum resin; indene and vinyli produced by thermal decomposition of petroleum naphtha And C9 petroleum resins obtained by copolymerizing C9 fractions such as toluene and hydrogenated petroleum resins.
  • These tackifiers may be used alone or in combination of two or more different softening points and structures.
  • the softening point of the tackifier is preferably 60 to 170 ° C, more preferably 65 to 160 ° C, and still more preferably 70 to 150 ° C.
  • the “softening point” of the tackifier means a value measured according to JIS K2531.
  • the weighted average of the softening point of these several tackifier belongs to the said range.
  • the content of the tackifier in the composition (x1) is preferably 0.01 to 65% by mass, more preferably 0.00%, based on the total amount (100% by mass) of the active ingredients in the composition (x1). It is 05 to 55% by mass, more preferably 0.1 to 50% by mass, still more preferably 0.5 to 45% by mass, and still more preferably 1.0 to 40% by mass.
  • the total content of the adhesive resin and the tackifier in the composition (x1) is preferably 70% by mass or more, more preferably based on the total amount (100% by mass) of the active ingredients in the composition (x1). Is 80% by mass or more, more preferably 85% by mass or more, still more preferably 90% by mass or more, and still more preferably 95% by mass or more.
  • the composition (x1) further contains a crosslinking agent together with the above-mentioned pressure-sensitive adhesive resin having a functional group such as an acrylic copolymer having the structural units (a1) and (a2). It is preferable to do.
  • the said crosslinking agent reacts with the functional group which the said adhesive resin has, and bridge
  • cross-linking agent examples include tolylene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, and the like, and adducts thereof; epoxy cross-linking agents such as ethylene glycol glycidyl ether; hexa [1- (2- Methyl) -aziridinyl] triphosphatriazine and other aziridine crosslinkers; aluminum chelates and other chelate crosslinkers; and the like.
  • These cross-linking agents may be used alone or in combination of two or more.
  • an isocyanate-based crosslinking agent is preferable from the viewpoints of increasing cohesive force and improving adhesive force, and availability.
  • the content of the cross-linking agent is appropriately adjusted depending on the number of functional groups of the adhesive resin.
  • the amount is preferably 0.01 to 10 parts by mass, more preferably 0.03 to 7 parts by mass, and still more preferably 0.05 to 5 parts by mass.
  • the composition (x1) contains an additive for pressure-sensitive adhesives used for general pressure-sensitive adhesives other than the above-described tackifier and cross-linking agent as long as the effects of the present invention are not impaired. You may do it.
  • the adhesive additive include an antioxidant, a softening agent (plasticizer), a rust inhibitor, a pigment, a dye, a retarder, a catalyst, and an ultraviolet absorber. These pressure-sensitive adhesive additives may be used alone or in combination of two or more. When these pressure-sensitive adhesive additives are contained, the content of each pressure-sensitive adhesive additive is preferably independently 0.0001 to 20 parts by mass, more preferably 100 parts by mass of the adhesive resin. 0.001 to 10 parts by mass.
  • the composition (x1) may contain water or an organic solvent as a diluent solvent together with the various active ingredients described above, and may be in the form of a solution.
  • an organic solvent the same thing as the organic solvent used when preparing the above-mentioned composition (y) in the form of a solution is mentioned.
  • the dilution solvent contained in a composition (x1) may be used independently, and may be used in combination of 2 or more type.
  • the active ingredient concentration of the composition (x1) is preferably 0.1 to 60% by mass, more preferably 0.5 to 50% by mass. %, More preferably 1.0 to 45% by mass.
  • 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 a composition (x2) containing a pressure-sensitive adhesive resin, and has pressure-sensitive 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.
  • Step (1A) A step of directly laminating a coating film (x1 ′) made of the composition (x1) and a coating film (y ′) made of the composition (y) in this order.
  • 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.
  • a composition (x1) and a composition (y) contain a dilution solvent each independently further from a viewpoint of making each coating film easy to form and improving productivity.
  • a dilution solvent the above-mentioned dilution solvent demonstrated in the column of the adhesive sheet can be used.
  • blending a dilution solvent with each composition is as having mentioned above in the column of the adhesive sheet.
  • this process (1A) after forming the coating film of 1 layer or more of a coating film (x1 ') and a coating film (y'), before the process (2A) mentioned later, the hardening reaction of the said coating film is carried out.
  • the drying temperature at the time of performing the pre-drying treatment is usually appropriately set within a temperature range in which the formed coating film does not cure, but preferably in step (2A). Below the drying temperature.
  • the specific drying temperature indicated by the phrase “below the drying temperature in step (2A)” is preferably 10 to 45 ° C., more preferably 10 to 34 ° C., and further preferably 15 to 30 ° C.
  • the coating film (x1 ′) and the coating film (y ′) are simultaneously dried 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 ′) are separated. It is thought that the interfacial adhesion between the pressure-sensitive adhesive layer (X1) and the thermally expandable substrate (Y) is improved by drying and curing in an intertwined state.
  • the drying temperature of the coating film in the step (2A) is preferably 60 to 150 ° C, more preferably 70 to 145 ° C, still more preferably 80 to 140 ° C, and still more preferably 90 to 135 ° C.
  • 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 any of the following steps (3A-1) to (3A-4) in addition to the steps (1A) and (2A) described above.
  • Step (3A-1) A step of heat-melting the composition (x2) containing an adhesive resin and extrusion laminating it on the surface of the thermally expandable substrate (Y) obtained in the step (2A).
  • Step (3A-2) Forming a coating film (x2 ′) composed of a composition (x2) containing an adhesive resin on the surface of the thermally expandable substrate (Y) obtained in step (2A) And drying the coating film (x2 ′).
  • Step (3A-3) The composition (x2) containing the adhesive resin is heated and melted, and the pressure-sensitive adhesive layer (X2) is prepared in advance on the release-treated surface of the release material by extrusion molding. The step of directly sticking the pressure-sensitive adhesive layer (X2) formed on the release material onto the surface of the thermally expandable substrate (Y) obtained in (1).
  • Step (3A-4) A composition (x2) containing an adhesive resin is applied to the release treatment surface of the release material to form a coating film (x2 ′), and the coating film (x2 ′) is dried. The pressure-sensitive adhesive layer (X2) is formed in advance, and the pressure-sensitive adhesive layer (X2) formed on the release material is directly formed on the surface of the thermally expandable substrate (Y) obtained in the step (2A). The process of sticking.
  • Examples of the method for forming the coating film (x2 ′) in the steps (3A-2) and (3A-4) include spin coater, spray coater, bar coater, knife coater, roll coater, knife roll coater, blade coater, and gravure coater. , Curtain coater, die coater and the like.
  • the composition (x2) further contains the aforementioned dilution solvent.
  • blending a dilution solvent with a composition (x2) is also as above-mentioned.
  • the drying temperature of the coating film (x2 ′) in the steps (3A-2) and (3A-4) is preferably 60 to 150 ° C., more preferably 70 to 145 ° C., still more preferably 80 to 140 ° C., and still more The temperature is preferably 90 to 135 ° C.
  • the step (3A-2) 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 composition (x2), the composition (y), and the composition (x1) each independently further contain a dilution solvent.
  • a dilution solvent the above-mentioned dilution solvent demonstrated in the column of the adhesive sheet can be used.
  • blending a dilution solvent with each composition is as having mentioned above in the column of the adhesive sheet.
  • this process (1B) after forming the coating film of 1 layer or more of a coating film (x1 '), a coating film (y'), and a coating film (x2 '), before the process (2B), You may perform the predrying process of the grade which does not advance the hardening reaction of a coating film. For example, a pre-drying treatment may be performed each time a coating film (x1 ′), a coating film (y ′), and a coating film (x2 ′) are formed. After the two-layer coating film of the coating film (y ′) is formed, the two layers may be pre-dried simultaneously, and then the coating film (x2 ′) may be formed.
  • the drying temperature at the time of performing the pre-drying treatment is usually appropriately set within a temperature range in which the formed coating film does not proceed, but preferably in the step (2B). Below the drying temperature.
  • the specific drying temperature indicated by the phrase “below the drying temperature in step (2B)” is preferably 10 to 45 ° C., more preferably 10 to 34 ° C., and further preferably 15 to 30 ° C.
  • the coating film (x1 ′), the coating film (y ′), and the coating film (x2 ′) are simultaneously dried 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 ′) are separated.
  • a mixed layer is formed at the interface with the resin, and the resin in the coating film (y ′) and the adhesive resin in the coating film (x2 ′) are dried and cured in a state where they are entangled with each other. ) And the pressure-sensitive adhesive layer (X2) are considered to be improved.
  • the drying temperature of the coating film in the step (2B) is preferably 60 to 150 ° C, more preferably 70 to 145 ° C, still more preferably 80 to 140 ° C, and still more preferably 90 to 135 ° C.
  • 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).
  • Acrylic copolymer (i): having a structural unit derived from a raw material monomer consisting of 2-ethylhexyl acrylate (2EHA) / 2-hydroxyethyl acrylate (HEA) 80.0 / 20.0 (mass ratio), A solution containing an acrylic copolymer having a Mw of 600,000. Diluting solvent: ethyl acetate, solid content concentration: 40% by mass.
  • Acrylic copolymer (ii): n-butyl acrylate (BA) / methyl methacrylate (MMA) / 2-hydroxyethyl acrylate (HEA) / acrylic acid 86.0 / 8.0 / 5.0 / 1.
  • Heavy release film manufactured by Lintec Corporation, product name “SP-PET382150”, a polyethylene terephthalate (PET) film provided with a release agent layer formed from a silicone release agent on one side, thickness: 38 ⁇ m.
  • Light release film manufactured by Lintec Co., Ltd., product name “SP-PET381031”, a PET film provided with a release agent layer formed from a silicone release agent on one side, thickness: 38 ⁇ m.
  • composition (x1) The isocyanate-based crosslinking agent (i) 5.0 parts by mass (solid content ratio) is blended with 100 parts by mass of the solid content of the acrylic copolymer (i), which is an adhesive resin, and diluted with toluene. It stirred uniformly and the composition (x1) of solid content concentration (active ingredient density
  • composition (x2) The isocyanate-based crosslinking agent (i) 0.8 parts by mass (solid content ratio) is blended with 100 parts by mass of the acrylic copolymer (ii), which is an adhesive resin, and diluted with toluene, It stirred uniformly and the composition (x2) of 25 mass% of solid content concentration (active ingredient density
  • composition (y) With respect to 100 parts by mass of the solid content of the solution of the acrylic urethane resin obtained in (2) above, 6.3 parts by mass of the isocyanate-based crosslinking agent (i) (solid content ratio) ), 1.4 parts by weight (solid content ratio) of dioctyltin bis (2-ethylhexanoate) as a catalyst, and the thermally expandable particles (i) are diluted with toluene, stirred uniformly, A composition (y) having a solid content concentration (active ingredient concentration) of 30% by mass was prepared. In addition, content of the thermally expansible particle (i) with respect to the whole quantity (100 mass%) of the active ingredient in the obtained composition (y) was 20 mass%.
  • 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 3, and Production Example 2 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.
  • (2) Drying treatment The formed coating film (x1 ′), coating film (y ′) and coating film (x2 ′) are simultaneously dried at a drying temperature of 125 ° C. for 60 seconds, and sequentially from the release agent layer of the heavy release film.
  • a layered body in which the layer (X1), the layer (Y), and the layer (X2) were directly stacked was formed. And 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 ′) composed of the composition (x1) prepared in Production Example 1 is formed and dried at a drying temperature of 110 ° C. for 120 seconds, and the layer (X1 ) Was formed.
  • the coating film (y ') which consists of a composition (y) prepared by manufacture example 3 is formed on the release agent layer of the light release film prepared separately from the release film on layer (X1), and drying temperature It was dried at 110 ° C. for 120 seconds to form a layer (Y).
  • a coating film (x2 ′) is formed and dried at a drying temperature of 110 ° C. for 120 seconds, Layer (X2) was formed. Then, 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.
  • the pressure-sensitive adhesive sheets of Examples 1 and 2 have good interfacial adhesion, and further have good adhesive strength before heating, but to the extent that they cannot be measured after heating at or above the expansion start temperature. Since the adhesive force was lowered, it was proved that the film could be easily peeled with a slight force during peeling.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Adhesive Tapes (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Laminated Bodies (AREA)
PCT/JP2018/013355 2017-03-31 2018-03-29 粘着シート WO2018181768A1 (ja)

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JP2006291137A (ja) * 2005-04-14 2006-10-26 Nitto Denko Cs System Kk 粘着テープ類およびその使用方法
JP2015120809A (ja) * 2013-12-20 2015-07-02 王子ホールディングス株式会社 両面粘着シート、剥離シート付き両面粘着シート、その製造方法および透明積層体
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CN113613890B (zh) * 2019-03-29 2023-10-24 东丽薄膜先端加工股份有限公司 层叠膜

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JPWO2018181768A1 (ja) 2020-02-06
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TWI825012B (zh) 2023-12-11
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