WO2020189568A1 - 粘着シート及び半導体装置の製造方法 - Google Patents

粘着シート及び半導体装置の製造方法 Download PDF

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Publication number
WO2020189568A1
WO2020189568A1 PCT/JP2020/011177 JP2020011177W WO2020189568A1 WO 2020189568 A1 WO2020189568 A1 WO 2020189568A1 JP 2020011177 W JP2020011177 W JP 2020011177W WO 2020189568 A1 WO2020189568 A1 WO 2020189568A1
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WIPO (PCT)
Prior art keywords
pressure
sensitive adhesive
adhesive layer
adhesive sheet
layer
Prior art date
Application number
PCT/JP2020/011177
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
康彦 垣内
高志 阿久津
慎弥 高岡
Original Assignee
リンテック株式会社
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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 JP2021507314A priority Critical patent/JP7530347B2/ja
Priority to KR1020217026249A priority patent/KR20210141929A/ko
Priority to CN202080020753.2A priority patent/CN113613893B/zh
Publication of WO2020189568A1 publication Critical patent/WO2020189568A1/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
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • 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
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • 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
    • C09J7/29—Laminated material
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C09J2301/416—Additional features of adhesives in the form of films or foils characterized by the presence of essential components use of irradiation

Definitions

  • the present invention relates to an adhesive sheet and a method for manufacturing a semiconductor device using the adhesive sheet.
  • Adhesive sheets are not only used for semi-permanently fixing members, but also for processing and inspection of building materials, interior materials, electronic parts, etc. (hereinafter, “adhesion”). It may be used as a temporary fixing sheet for temporarily fixing (also called “body”). For example, in the manufacturing process of a semiconductor device, a temporary fixing sheet is used when processing a semiconductor wafer.
  • a semiconductor wafer is processed into a semiconductor chip through a grinding process of reducing the thickness by grinding, an individualizing process of cutting and separating and individualizing.
  • the semiconductor wafer is subjected to a predetermined process in a state of being temporarily fixed to the temporary fixing sheet.
  • the semiconductor chips obtained by performing the predetermined processing are separated from the temporary fixing sheet, and then, if necessary, an expanding step of widening the distance between the semiconductor chips and a re-arrangement of a plurality of semiconductor chips having the widened distances.
  • an inversion process for inverting the front and back of the semiconductor chip, and the like are appropriately performed, the semiconductor chip is mounted on the substrate.
  • a temporary fixing sheet suitable for each application can be used.
  • Patent Document 1 discloses a heat-release type pressure-sensitive adhesive sheet for temporary fixing at the time of cutting an electronic component, in which a heat-expandable pressure-sensitive adhesive layer containing heat-expandable microspheres is provided on at least one surface of a base material. .. According to the document, the heat-removable adhesive sheet can secure a contact area of a predetermined size with respect to the adherend when cutting an electronic component, and thus exhibits adhesiveness capable of preventing adhesive defects such as chip skipping. On the other hand, there is a description that it can be easily peeled off by reducing the contact area with the adherend by expanding the heat-expandable microspheres by heating after use.
  • the pressure-sensitive adhesive layer contains the heat-expandable particles as in the pressure-sensitive adhesive sheet disclosed in Patent Document 1
  • the residue derived from the heat-expandable particles adheres to the surface of the adherend and heat.
  • the surface of the adherend after being peeled off by heating due to the adhesion of some of the pressure-sensitive adhesive layers to the surface of the adherend due to the deformation and alteration of the pressure-sensitive adhesive layer due to the expansion of the expansive particles (so-called "glue residue"). Is concerned that it will be contaminated.
  • the present invention has been made in view of the above problems, and the temporarily fixed adherend can be easily peeled off by heating, and the contamination of the adherend surface after peeling can be suppressed. It is an object of the present invention to provide an adhesive sheet capable of being formed and a method for manufacturing a semiconductor device using the adhesive sheet.
  • the present inventors arranged the structure of the pressure-sensitive adhesive sheet in this order: (1) a pressure-sensitive adhesive layer, a heat-expandable base material layer containing heat-expandable particles, and a non-heat-expandable base material layer. Having a laminated structure, (2) adjusting the Young ratio of the pressure-sensitive adhesive layer to a specific range, and (3) the Young ratio of the pressure-sensitive adhesive layer and the Young ratio of the non-thermally expandable base material layer.
  • the present invention relates to the following [1] to [15].
  • [1] A laminated structure in which a pressure-sensitive adhesive layer (X1), a heat-expandable base material layer (Y1) containing heat-expandable particles, and a non-heat-expandable base material layer (Y2) are arranged in this order.
  • Have and The Young's modulus of the pressure-sensitive adhesive layer (X1) at 23 ° C. is 5.0 MPa or less.
  • a pressure-sensitive adhesive sheet in which the Young's modulus of the non-thermally expandable base material layer (Y2) at 23 ° C. is higher than the Young's modulus of the pressure-sensitive adhesive layer (X1) at 23 ° C.
  • Adhesive sheet described in Crab [5] The pressure-sensitive adhesive sheet according to the above [4], wherein the isocyanate-based cross-linking agent contains an isocyanurate-type modified product having an isocyanurate ring. [6] The pressure-sensitive adhesive sheet according to any one of [1] to [5] above, wherein the non-thermally expandable base material layer (Y2) has a Young's modulus of 700 MPa or more at 23 ° C. [7] The pressure-sensitive adhesive sheet according to any one of [1] to [6] above, wherein the non-thermally expandable base material layer (Y2) is a polyethylene terephthalate film.
  • the non-thermally expandable base material layer (Y2) further has an adhesive layer (X2) on a surface opposite to the laminated surface of the heat expandable base material layer (Y1). ] To [7]. [9] The pressure-sensitive adhesive sheet according to any one of [1] to [7] above, wherein the thermally expandable particles have an expansion start temperature (t) of 50 ° C. or higher and lower than 125 ° C. [10] The pressure-sensitive adhesive sheet according to the above [8], wherein the thermally expandable particles have an expansion start temperature (t) of 50 ° C. or higher and lower than 125 ° C.
  • the object to be processed and inspected is attached to the adhesive sheet according to any one of [1] to [11] above.
  • a method for manufacturing a semiconductor device including.
  • Step 1A A process of attaching the object to be processed to the pressure-sensitive adhesive layer (X2) of the pressure-sensitive adhesive sheet, and attaching a support to the pressure-sensitive adhesive layer (X1) of the pressure-sensitive adhesive sheet
  • Step 2A For the object to be processed
  • Step 3A A process of performing one or more treatments selected from a grinding process and an individualization process
  • Step 3A A thermocurable surface of the processed object to be processed, which is opposite to the pressure-sensitive adhesive layer (X2).
  • First separation step The pressure-sensitive adhesive sheet is heated to a temperature equal to or higher than the expansion start temperature (t) and lower than 125 ° C. to separate the pressure-sensitive adhesive layer (X1) from the support.
  • Second separation step Step of separating the pressure-sensitive adhesive layer (X2) from the object to be processed [14] Using the pressure-sensitive adhesive sheet according to the above [10] or [11], the following steps 1B to 3B, the following A method for manufacturing a semiconductor device including a first separation step and the following second separation step.
  • Step 1B A process of attaching the object to be processed to the pressure-sensitive adhesive layer (X1) of the pressure-sensitive adhesive sheet, and attaching a support to the pressure-sensitive adhesive layer (X2) of the pressure-sensitive adhesive sheet
  • Step 2B For the object to be processed
  • Step 3B A process of performing one or more treatments selected from a grinding treatment and an individualizing treatment. The surface of the processed object to which the treatment has been subjected to the treatment is heat-curable on the surface opposite to the adhesive layer (X1).
  • First separation step The pressure-sensitive adhesive sheet is heated to a temperature equal to or higher than the expansion start temperature (t) and lower than 125 ° C., and the pressure-sensitive adhesive layer (X1) and the object to be processed are separated from each other.
  • Second separation step Step of separating the pressure-sensitive adhesive layer (X2) and the support [15] Using the pressure-sensitive adhesive sheet according to the above [11], The method for manufacturing a semiconductor device according to the above [13] or [14], wherein the second separation step includes a step of curing the pressure-sensitive adhesive layer (X2) by irradiating the pressure-sensitive adhesive layer (X2) with energy rays. ..
  • the adhesive sheet of the present invention can easily peel off the temporarily fixed adherend by heating, and can suppress contamination of the surface of the adherend after peeling.
  • the "active ingredient” refers to an ingredient contained in the target composition excluding the diluting solvent.
  • Mw mass average molecular weight
  • GPC gel permeation chromatography
  • (meth) acrylic acid means both “acrylic acid” and “methacrylic acid”, and other similar terms are also used.
  • the lower limit value and the upper limit value described stepwise with respect to a preferable numerical range can be independently combined. For example, from the description of "preferably 10 to 90, more preferably 30 to 60", the “favorable lower limit value (10)” and the “more preferable upper limit value (60)” are combined to obtain “10 to 60". You can also do it.
  • the "energy beam” means an electromagnetic wave or a charged particle beam having an energy quantum, and examples thereof include ultraviolet rays, radiation, and electron beams.
  • Ultraviolet rays can be irradiated by using, for example, an electrodeless lamp, a high-pressure mercury lamp, a metal halide lamp, a UV-LED, or the like as an ultraviolet source.
  • the electron beam can be irradiated with an electron beam generated by an electron beam accelerator or the like.
  • the term "energy ray polymerizable” means the property of polymerizing by irradiating with energy rays.
  • whether the "layer” is a "non-thermally expanding layer” or a “thermally expanding layer” is determined as follows.
  • the layer to be judged contains the heat-expandable particles
  • the layer is heat-treated at the expansion start temperature (t) of the heat-expandable particles for 3 minutes. If the volume change rate calculated from the following formula is less than 5%, the layer is judged to be a "non-thermally expandable layer", and if it is 5% or more, the layer is a "thermally expandable layer”. Judge that there is.
  • volume change rate (%) ⁇ (volume of the layer after heat treatment-volume of the layer before heat treatment) / volume of the layer before heat treatment ⁇ ⁇ 100
  • the layer containing no thermally expandable particles is referred to as a "non-thermally expandable layer”.
  • the "front surface” of the semiconductor wafer and the semiconductor chip refers to the surface on which the circuit is formed (hereinafter, also referred to as the “circuit surface”), and the "back surface” of the semiconductor wafer and the semiconductor chip is the circuit formed. Refers to the surface that is not.
  • a pressure-sensitive adhesive layer (X1), a heat-expandable base material layer (Y1) containing heat-expandable particles, and a non-heat-expandable base material layer (Y2) are arranged in this order.
  • the pressure-sensitive adhesive layer (X1) has a young ratio of 5.0 MPa or less at 23 ° C.
  • the non-thermally expandable base material layer (Y2) has a young ratio at 23 ° C. It is an adhesive sheet having a higher Young's ratio of the agent layer (X1) at 23 ° C.
  • the heat-expandable particles contained in the heat-expandable base material layer (Y1) are heated to a temperature equal to or higher than the expansion start temperature (t) to expand, and the pressure-sensitive adhesive layer (X1) is adhered.
  • the contact area between the adherend attached to the adhesive surface of the adhesive layer (X1) and the adhesive surface is greatly reduced.
  • the adherend can be easily peeled off from the adhesive sheet.
  • the heat-expandable particles are contained in the heat-expandable base material layer (Y1), contamination of the adherend surface due to the heat-expandable particles is suppressed.
  • the Young's modulus of the pressure-sensitive adhesive layer (X1) at 23 ° C. is adjusted to 5.0 MPa or less. Therefore, the pressure-sensitive adhesive layer (X1) firmly follows the unevenness of the surface of the heat-expandable base material layer (Y1) on the pressure-sensitive adhesive layer (X1) side caused by the expansion of the heat-expandable particles, and the pressure-sensitive adhesive layer (X1) Unevenness is well formed on the adhesive surface of X1).
  • the pressure-sensitive adhesive layer (X1) cannot sufficiently follow the unevenness of the surface, and the surface unevenness on the pressure-sensitive adhesive layer (X1) side of the heat-expandable base material layer (Y1) is formed by the pressure-sensitive adhesive layer (X1). By at least one of being suppressed, unevenness is less likely to be formed on the adhesive surface of the adhesive layer (X1). Further, since the coefficient of thermal expansion of the non-thermally expandable base material layer (Y2) at 23 ° C.
  • the pressure-sensitive adhesive sheet of the present invention is heated to a temperature equal to or higher than the expansion start temperature (t) of the heat-expandable particles contained in the heat-expandable base material layer (Y1) so that the pressure-sensitive adhesive sheet and the adherend can be brought together. Adhesion can be significantly reduced. Therefore, when the pressure-sensitive adhesive sheet according to one aspect of the present invention is peeled off by heating, the pressure-sensitive adhesive sheet can be peeled off from the adherend without applying a force for peeling off the pressure-sensitive adhesive sheet. Specifically, in a laminated body in which an adhesive sheet is attached to an adherend, when the adhesive sheet is peeled off by heating, the adhesive sheet side is directed downward and the adhesive sheet is dropped from the adherend by gravity to peel off.
  • self-peeling property the state in which the adhesive sheet is peeled off from the adherend or peeled off without applying the force for peeling off the adhesive sheet. Moreover, such a property is called “self-peeling property”.
  • the Young's modulus of the pressure-sensitive adhesive layer (X1) at 23 ° C. enhances the followability of the pressure-sensitive adhesive layer (X1) to the deformation of the heat-expandable base material layer (Y1) and thermally expands. From the viewpoint of facilitating the formation of irregularities on the adhesive surface of the pressure-sensitive adhesive layer (X1) when the sex particles are expanded, it is preferably 4.5 MPa or less, more preferably 4.0 MPa or less, still more preferably 3.5 MPa or less.
  • the Young's modulus of the pressure-sensitive adhesive layer (X1) at 23 ° C. is measured by the method described in Examples described later.
  • a pressure-sensitive adhesive layer (X1), a heat-expandable base material layer (Y1) containing heat-expandable particles, and a non-heat-expandable base material layer (Y2) are arranged in this order.
  • the pressure-sensitive adhesive sheet according to one aspect of the present invention may have a laminated structure, but the pressure-sensitive adhesive sheet (X1), the heat-expandable base material layer (Y1), and the non-heat-expandable base material layer (Y2) It may have only, or it may have other layers, if desired.
  • a non-expandable base material layer is used from the viewpoint of improving the processability and inspectability of the adherend.
  • the pressure-sensitive adhesive layer (X2) is further provided on the surface of (Y2) opposite to the laminated surface of the heat-expandable base material layer (Y1).
  • the "double-sided pressure-sensitive adhesive sheet” refers to a pressure-sensitive adhesive layer (X1), a heat-expandable base material layer (Y1) containing heat-expandable particles, and a non-heat-expandable group. It is assumed that the material layer (Y2) and the pressure-sensitive adhesive layer (X2) mean a pressure-sensitive adhesive sheet having a laminated structure arranged in this order.
  • the pressure-sensitive adhesive sheet according to one aspect of the present invention may have a release material on the pressure-sensitive adhesive surface of the pressure-sensitive adhesive layer (X1). Further, when the pressure-sensitive adhesive sheet according to one aspect of the present invention has the structure of a double-sided pressure-sensitive adhesive sheet, it has a release material on the pressure-sensitive adhesive surface of at least one of the pressure-sensitive adhesive layer (X1) and the pressure-sensitive adhesive layer (X2). May be good.
  • the pressure-sensitive adhesive sheet according to one aspect of the present invention includes a pressure-sensitive adhesive layer (X1) as shown in FIG.
  • An adhesive sheet 1a having a laminated structure in which the base material layer (Y2) is arranged in this order can be mentioned.
  • the pressure-sensitive adhesive sheet according to one aspect of the present invention may have a structure in which the release material 10 is further provided on the pressure-sensitive adhesive surface of the pressure-sensitive adhesive layer (X1), as in the pressure-sensitive adhesive sheet 1b shown in FIG. 1 (b).
  • the pressure-sensitive adhesive sheet of the present invention those having the structure of the double-sided pressure-sensitive adhesive sheet can be mentioned.
  • the pressure-sensitive adhesive sheet having such a structure include a pressure-sensitive adhesive layer (X1), a heat-expandable base material layer (Y1) containing heat-expandable particles, and non-heat as shown in FIG.
  • Examples thereof include a pressure-sensitive adhesive sheet 2a having a laminated structure in which an expandable base material layer (Y2) and a pressure-sensitive adhesive layer (X2) are arranged in this order.
  • the release material 10a is further provided on the adhesive surface of the adhesive layer (X1), and the release material is further provided on the adhesive surface of the adhesive layer (X2). It may be configured to have 10b.
  • both release materials are pulled outward and attempted 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 release forces from the pressure-sensitive adhesive layers attached to the two release materials 10a and 10b are different from each other.
  • the double-sided pressure-sensitive adhesive sheet 2a shown in FIG. 2A is peeled off on both sides of the pressure-sensitive adhesive layer (X1) and the pressure-sensitive adhesive layer (X2).
  • a double-sided adhesive sheet having a structure in which the treated release material is laminated in a roll shape may be used.
  • the pressure-sensitive adhesive sheet according to one aspect of the present invention is between the pressure-sensitive adhesive layer (X1) and the heat-expandable base material layer (Y1), and between the heat-expandable base material layer (Y1) and the non-heat-expandable base material layer (Y2). It may or may not have another layer between at least one of the layers between and.
  • a heat-expandable base material layer is provided between the pressure-sensitive adhesive layer (X1) and the heat-expandable base material layer (Y1).
  • the pressure-sensitive adhesive sheet according to one aspect of the present invention has the viewpoint of transmitting the deformation of the heat-expandable base material layer (Y1) due to the expansion of the heat-expandable particles to the pressure-sensitive adhesive layer (X1) satisfactorily.
  • the heat-expandable base material layer (Y1) are preferably directly laminated.
  • the pressure-sensitive adhesive sheet of the present invention after explaining the heat-expandable particles required for forming irregularities on the pressure-sensitive adhesive surface of the pressure-sensitive adhesive layer (X1) by heating, the pressure-sensitive adhesive layer (X1) and the heat-expanding
  • the sex substrate layer (Y1), the non-thermally expandable substrate layer (Y2), and the pressure-sensitive adhesive layer (X2) will be described.
  • the thermally expandable particles used in the pressure-sensitive adhesive sheet of the present invention may be particles that expand by heating, and the expansion start temperature (t) is appropriately selected according to the use of the pressure-sensitive adhesive sheet.
  • thermosetting film-like adhesive called a die attach film (hereinafter, also referred to as "DAF").
  • DAF die attach film
  • the process is adopted.
  • the DAF is attached to one surface of the semiconductor wafer or a plurality of fragmented semiconductor chips, and is divided into the same shape as the semiconductor chip at the same time as the semiconductor wafer is fragmented or after being attached to the semiconductor chip.
  • the semiconductor chip with DAF obtained by individualizing is attached (diatached) to the substrate from the DAF side, and then the semiconductor chip and the substrate are fixed by thermosetting the DAF.
  • the DAF needs to retain the property of adhering by pressure sensitivity or heating until it is attached to the substrate.
  • the DAF is cured before the die attachment due to the heating when the thermally expandable particles are expanded, and the DAF with respect to the substrate is cured.
  • Adhesive strength may decrease. It is desirable to suppress the decrease in the adhesive strength of the DAF because it causes a decrease in the bonding reliability between the semiconductor chip and the substrate. That is, it is desirable that the thermal change of the adherend is suppressed at the time of heat peeling.
  • the expansion start temperature (t) of the heat-expandable particles is preferably less than 125 ° C., more preferably 120 ° C. or lower, still more preferably 115 ° C. or lower, still more preferable. Is 110 ° C. or lower, more preferably 105 ° C. or lower.
  • the expansion start temperature (t) of the heat-expandable particles is preferably 50 ° C. or higher, more preferably 55 ° C. or higher, still more preferably 60 ° C. or higher, still more preferably. Is 70 ° C. or higher.
  • the expansion start temperature (t) of a heat-expandable particle means a value measured based on the following method.
  • the thermally expandable particles are microencapsulated foaming agents composed of an outer shell made of a thermoplastic resin and an contained component contained in the outer shell and vaporized when heated to a predetermined temperature. It is preferable to have.
  • the thermoplastic resin constituting the outer shell of the microencapsulating foaming agent include vinylidene chloride-acrylonitrile copolymer, polyvinyl alcohol, polyvinyl butyral, polymethylmethacrylate, polyacrylonitrile, polyvinylidene chloride, polysulfone and the like.
  • Examples of the contained component which is a component contained in the outer shell of the microencapsulating foaming agent include propane, propylene, butene, n-butane, isopentane, isopentane, neopentane, n-pentane, n-hexane, isohexane, and n-.
  • Examples thereof include low boiling point liquids such as heptane, n-octane, cyclopropane, cyclobutane and petroleum ether.
  • the inclusion components are preferably propane, isobutane, n-pentane, and cyclopropane.
  • propane, isobutane, n-pentane, and cyclopropane One of these inclusion components may be used alone, or two or more thereof may be used in combination.
  • the expansion start temperature (t) of the thermally expandable particles can be adjusted by appropriately selecting the type of the inclusion component.
  • the average particle diameter of the heat-expandable particles used in one embodiment of the present invention before expansion at 23 ° C. is preferably 3 to 100 ⁇ m, more preferably 4 to 70 ⁇ m, still more preferably 6 to 60 ⁇ m, still more preferably 10 to 10. It is 50 ⁇ m.
  • the average particle size of the heat-expandable particles before expansion is the volume medium particle size (D 50 ), and is a laser diffraction type particle size distribution measuring device (for example, manufactured by Malvern, product name “Mastersizer 3000”).
  • the cumulative volume frequency calculated from the smaller particle size of the heat-expandable particles before expansion means the particle size corresponding to 50%.
  • the 90% particle diameter (D 90 ) of the thermally expandable particles used in one embodiment of the present invention before expansion at 23 ° C. is preferably 10 to 150 ⁇ m, more preferably 15 to 100 ⁇ m, still more preferably 20 to 90 ⁇ m. Even more preferably, it is 25 to 80 ⁇ m.
  • the 90% particle size (D 90 ) of the thermally expandable particles before expansion is the expansion measured using a laser diffraction type particle size distribution measuring device (for example, manufactured by Malvern, product name "Mastersizer 3000"). In the particle distribution of the previous heat-expandable particles, it means the particle size in which the cumulative volume frequency calculated from the smaller particle size of the heat-expandable particles before expansion corresponds to 90%.
  • the maximum volume expansion rate when the thermally expandable particles used in one embodiment of the present invention are heated to a temperature equal to or higher than the expansion start temperature (t) is preferably 1.5 to 200 times, more preferably 2 to 150 times, and further. It is preferably 2.5 to 120 times, and even more preferably 3 to 100 times.
  • the pressure-sensitive adhesive layer (X1) contained in the pressure-sensitive adhesive sheet of the present invention has a Young's modulus of 5.0 MPa or less at 23 ° C. Further, the adhesive layer (X1) of the pressure-sensitive adhesive sheet of the present invention has a Young's modulus at 23 ° C. lower than that of the non-thermally expandable base material layer (Y2) at 23 ° C.
  • the pressure-sensitive adhesive layer (X1) may be a heat-expandable layer or a non-heat-expandable layer, but is preferably a non-heat-expandable layer.
  • the volume change rate (%) of the pressure-sensitive adhesive layer (X1) calculated from the above formula is less than 5%, preferably less than 2%. It is preferably less than 1%, more preferably less than 0.1%, and even more preferably less than 0.01%.
  • the pressure-sensitive adhesive layer (X1) preferably does not contain thermal-expandable particles, but may contain thermal-expandable particles within a range not contrary to the object of the present invention.
  • the pressure-sensitive adhesive layer (X1) contains thermally expandable particles
  • the pressure-sensitive adhesive layer (X1) contained in the pressure-sensitive adhesive sheet of the present invention can be formed from the pressure-sensitive adhesive composition (x-1) containing a pressure-sensitive adhesive resin.
  • x-1 a pressure-sensitive adhesive resin
  • Adhesive resin examples include polymers having adhesiveness by themselves and having a mass average molecular weight (Mw) of 10,000 or more.
  • the mass average molecular weight (Mw) of the adhesive resin is preferably 10,000 to 2 million, more preferably 20,000 to 1.5 million, still more preferably 30,000 to 100, from the viewpoint of improving the adhesive strength of the pressure-sensitive adhesive layer (X1). It is ten thousand.
  • the adhesive resin include rubber-based resins such as acrylic resins, urethane-based resins, and polyisobutylene-based resins, polyester-based resins, olefin-based resins, silicone-based resins, and polyvinyl ether-based resins.
  • Rubber-based resins such as acrylic resins, urethane-based resins, and polyisobutylene-based resins
  • polyester-based resins such as acrylic resins, urethane-based resins, and polyisobutylene-based resins
  • olefin-based resins such as polypropylene-based resins
  • silicone-based resins such as polyvinyl ether-based resins
  • polyvinyl ether-based resins such as polyvinyl ether-based resins.
  • One type of these adhesive resins may be used alone, or two or more types may be used in combination.
  • the form of the copolymer is not particularly limited, and block copolymers, random copolymers,
  • the adhesive resin may be an energy ray-curable adhesive resin in which a polymerizable functional group is introduced into the side chain.
  • the polymerizable functional group include those having a carbon-carbon double bond such as a (meth) acryloyl group, a vinyl group and an allyl group.
  • the energy ray among the above-mentioned ones, ultraviolet rays that are easy to handle are preferable.
  • the adhesive resin is acrylic from the viewpoint of exhibiting excellent adhesive strength in the pressure-sensitive adhesive layer (X1) and adjusting the Young's modulus of the pressure-sensitive adhesive layer (X1) within the above range. It is preferable to contain a based resin.
  • the content of the acrylic resin in the adhesive resin is preferably 30 with respect to the total amount (100% by mass) of the adhesive resin contained in the adhesive composition (x-1) or the adhesive layer (X1). It is -100% by mass, more preferably 50 to 100% by mass, still more preferably 70 to 100% by mass, still more preferably 85 to 100% by mass.
  • the acrylic resin that can be used as the adhesive resin includes, for example, a polymer containing a structural unit derived from an alkyl (meth) acrylate having a linear or branched alkyl group, and a cyclic structure. Examples thereof include polymers containing a structural unit derived from (meth) acrylate having.
  • the mass average molecular weight (Mw) of the acrylic resin is preferably 100,000 to 1.5 million, more preferably 200,000 to 1.3 million, still more preferably 350,000 to 1.2 million, and even more preferably 500,000 to 1.1 million. ..
  • the acrylic resin used in one embodiment of the present invention includes a structural unit (a1) derived from an alkyl (meth) acrylate (a1') (hereinafter, also referred to as “monomer (a1')”) and a functional group-containing monomer (a2).
  • An acrylic copolymer (A1) having a structural unit (a2) derived from') hereinafter, also referred to as “monomer (a2')
  • A1 having a structural unit (a2) derived from')
  • the number of carbon atoms of the alkyl group of the monomer (a1') is preferably from the viewpoint of exhibiting excellent adhesive strength in the pressure-sensitive adhesive layer (X1) and adjusting the Young's modulus of the pressure-sensitive adhesive layer (X1) within the above range. Is 1 to 24, more preferably 1 to 12, still more preferably 2 to 10, and even more preferably 4 to 8.
  • the alkyl group contained in the monomer (a1') may be a straight chain alkyl group or a branched chain 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, and tridecyl (). Examples thereof include meta) acrylate and stearyl (meth) acrylate. One of these monomers (a1') may be used alone, or two or more thereof may be used in combination. As the monomer (a1'), butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate are preferable.
  • the content of the structural unit (a1) is preferably 50 to 99.9% by mass, more preferably 60 to 99.0% by mass, based on the total structural unit (100% by mass) of the acrylic copolymer (A1). %, More preferably 70 to 97.0% by mass, and even more preferably 80 to 95.0% by mass.
  • Examples of the functional group contained in the monomer (a2') include a hydroxyl group, a carboxy group, an amino group, an epoxy group and the like. That is, 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. One of these monomers (a2') may be used alone, or two or more thereof may be used in combination. Among these, as the monomer (a2'), a hydroxyl group-containing monomer and a carboxy group-containing monomer are preferable, and a hydroxyl group-containing monomer is more 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 acrylates and 4-hydroxybutyl (meth) acrylates
  • hydroxyl group-containing compounds such as unsaturated alcohols such as vinyl alcohols and allyl alcohols.
  • 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 their anhydrides. , 2- (Acryloyloxy) ethyl succinate, 2-carboxyethyl (meth) acrylate and the like.
  • the content of the structural unit (a2) is preferably 0.1 to 30% by mass, more preferably 0.5 to 20% by mass, based on the total structural unit (100% by mass) of the acrylic copolymer (A1). %, More preferably 1.0 to 15% by mass, and even more preferably 3.0 to 10% by mass.
  • the acrylic copolymer (A1) may further have a structural unit (a3) derived from a monomer (a3') other than the monomers (a1') and (a2').
  • the total content of the structural units (a1) and (a2) is preferably relative to the total structural units (100% by mass) of the acrylic copolymer (A1). It is 70 to 100% by mass, more preferably 80 to 100% by mass, still more preferably 90 to 100% by mass, and even more preferably 95 to 100% by mass.
  • Examples of the monomer (a3') include 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) acrylates, It has a cyclic structure such as benzyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, and imide (meth) acrylate.
  • olefins such as ethylene, propylene and isobutylene
  • halogenated olefins such as vinyl chloride and vinylidene chloride
  • diene monomers such as butadiene, isoprene and chlor
  • (Meta) Acrylate examples thereof include styrene, ⁇ -methylstyrene, vinyltoluene, vinyl formate, vinyl acetate, acrylonitrile, (meth) acrylamide, (meth) acrylonitrile, (meth) acryloylmorpholine, and N-vinylpyrrolidone.
  • the acrylic copolymer (A1) may be an energy ray-curable acrylic copolymer in which a polymerizable functional group is introduced into at least one of a main chain and a side chain.
  • the polymerizable functional group and the energy ray are as described above.
  • the polymerizable functional group is a substituent capable of binding to the acrylic copolymer having the above-mentioned structural units (a1) and (a2) and the functional group of the structural unit (a2) of the acrylic copolymer. It can be introduced by reacting with a polymerizable compound (Xa) having a polymerizable functional group.
  • Examples of the polymerizable compound (Xa) include (meth) acryloyloxyethyl isocyanate, meta-isopropenyl- ⁇ , ⁇ -dimethylbenzyl isocyanate, (meth) acryloyl isocyanate, allyl isocyanate, glycidyl (meth) acrylate, and (meth). Acrylic acid and the like can be mentioned.
  • the pressure-sensitive adhesive composition (x-1) contains a pressure-sensitive adhesive resin having a functional group like the above-mentioned acrylic copolymer (A1), it further contains a cross-linking agent. Is preferable.
  • the cross-linking agent reacts with a tacky resin having a functional group to cross-link the tacky resins with the functional group as a cross-linking starting point.
  • cross-linking agent examples include isocyanate-based cross-linking agents, epoxy-based cross-linking agents, aziridine-based cross-linking agents, and metal chelate-based cross-linking agents.
  • One of these cross-linking agents may be used alone, or two or more thereof may be used in combination.
  • isocyanate-based cross-linking agents are preferable from the viewpoint of increasing the cohesive force to improve the adhesive force and the availability.
  • isocyanate-based cross-linking agent examples include aromatic polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, and xylylene diisocyanate; dicyclohexylmethane-4,4'-diisocyanate, bicycloheptane triisocyanate, cyclopentylene diisocyanate, and cyclohexylene diisocyanate.
  • Methylcyclohexylene diisocyanate Methylcyclohexylene diisocyanate, methylenebis (cyclohexylisocyanate), 3-isocyanatemethyl-3,5,5-trimethylcyclohexylisocyanate, and alicyclic polyisocyanates such as hydrogenated xylylene diisocyanate; hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, And polyisocyanate compounds such as acyclic aliphatic polyisocyanates such as lysine diisocyanate; and the like.
  • the isocyanate-based cross-linking agent examples include a trimethylolpropane adduct-type modified product of the polyhydric isocyanate compound, a burette-type modified product reacted with water, and an isocyanurate-type modified product containing an isocyanurate ring.
  • the isocyanurate ring is used from the viewpoint of suppressing the decrease in elastic modulus of the pressure-sensitive adhesive layer (X1) during heating and suppressing the adhesion of the residue derived from the pressure-sensitive adhesive layer (X1) to the adherend.
  • an isocyanurate-type modified product containing isocyanurate more preferably an isocyanurate-type modified product of an acyclic aliphatic polyisocyanate, and further preferably use an isocyanurate-type modified product of hexamethylene diisocyanate.
  • the content of the cross-linking agent is appropriately adjusted according to the number of functional groups of the adhesive resin, and is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the adhesive resin having functional groups. It is more preferably 0.03 to 7 parts by mass, and further preferably 0.05 to 5 parts by mass.
  • the Young's modulus of the pressure-sensitive adhesive layer (X1) can be easily adjusted to the above range.
  • the pressure-sensitive adhesive composition (x-1) may further contain a tackifier from the viewpoint of further improving the adhesive strength.
  • the "tacking agent” refers to a component that supplementarily improves the adhesive strength of the adhesive resin and has a mass average molecular weight (Mw) of less than 10,000, and the above-mentioned adhesive resin. Is distinct from.
  • the mass average molecular weight (Mw) of the tackifier is less than 10,000, preferably 400 to 9000, more preferably 500 to 8000, and even more preferably 800 to 5000.
  • the tackifier for example, it is obtained by copolymerizing a C5 distillate such as rosin resin, terpene resin, styrene resin, penten, isoprene, piperin, 1,3-pentadiene produced by thermal decomposition of petroleum naphtha.
  • a C5 distillate such as rosin resin, terpene resin, styrene resin, penten, isoprene, piperin, 1,3-pentadiene produced by thermal decomposition of petroleum naphtha.
  • C5-based petroleum resins C9-based petroleum resins obtained by copolymerizing C9 distillates such as inden and vinyl toluene produced by thermal decomposition of petroleum naphtha
  • hydrides obtained by hydrogenating these.
  • the softening point of the tackifier is preferably 60 to 170 ° C, more preferably 65 to 160 ° C, and even more preferably 70 to 150 ° C.
  • the "softening point" of the tackifier means a value measured in accordance with JIS K 2531.
  • the tackifier one type may be used alone, or two or more types having different softening points, structures, etc. may be used in combination.
  • the weighted average of the softening points of the plurality of tackifiers belongs to the above range.
  • the content of the tackifier is preferably 0.01 to 65% by mass, more preferably 0.1 to 50% by mass, based on the total amount (100% by mass) of the active ingredient of the pressure-sensitive adhesive composition (x-1). %, More preferably 1 to 40% by mass, still more preferably 2 to 30% by mass.
  • the pressure-sensitive adhesive composition (x-1) contains an energy ray-curable pressure-sensitive adhesive resin as the pressure-sensitive adhesive resin, it preferably further contains a photopolymerization initiator.
  • a photopolymerization initiator By preparing a pressure-sensitive adhesive composition containing an energy ray-curable pressure-sensitive adhesive resin and a photopolymerization initiator, the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition can be subjected to irradiation with relatively low-energy energy rays. The curing reaction can be sufficiently advanced, and the adhesive strength can be adjusted to a desired range.
  • Examples of the photopolymerization initiator used in one embodiment of the present invention include 1-hydroxy-cyclohexyl-phenylketone, benzoin, benzoinmethyl ether, benzoin ethyl ether, benzoin propyl ether, benzylphenyl sulfide, and tetramethylthium. Examples thereof include monosulfide, azobisisobutyrolnitrile, dibenzyl, diacetyl, 8-chloranthraquinone and the like. One of these photopolymerization initiators may be used alone, or two or more thereof may be used in combination.
  • the content of the photopolymerization initiator is preferably 0.01 to 10 parts by mass, more preferably 0.03 to 5 parts by mass, and further preferably 0.% by mass with respect to 100 parts by mass of the energy ray-curable adhesive resin. It is 05 to 2 parts by mass.
  • the pressure-sensitive adhesive composition (x-1) is an additive for a pressure-sensitive adhesive used in a general pressure-sensitive adhesive in addition to the above-mentioned additives as long as the effect of the present invention is not impaired. May be contained.
  • additives for adhesives include antioxidants, softeners (plasticizers), rust inhibitors, pigments, dyes, retarders, reaction accelerators (catalysts), ultraviolet absorbers and the like. These adhesive additives may be used alone or in combination of two or more.
  • each additive for adhesive is independently, preferably 0.0001 to 20 parts by mass, based on 100 parts by mass of the adhesive resin. It is preferably 0.001 to 10 parts by mass.
  • the thickness of the pressure-sensitive adhesive layer (X1) at 23 ° C. exhibits good adhesive strength, and when the heat-expandable particles are expanded by heating, the thickness of the pressure-sensitive adhesive layer (X1) is increased. From the viewpoint of satisfactorily forming irregularities on the adhesive surface, it is preferably 3 to 10 ⁇ m, more preferably 3 to 8 ⁇ m, and even more preferably 3 to 7 ⁇ m.
  • the thickness of the pressure-sensitive adhesive layer (X1) at 23 ° C. is a value measured by the method described in Examples described later.
  • the product of the Young's modulus of the pressure-sensitive adhesive layer (X1) at 23 ° C. and the thickness of the pressure-sensitive adhesive layer (X1) at 23 ° C. is thermally expandable.
  • the content is preferably 0.3 to 50, more preferably 1.0 to 30. It is more preferably 1.5 to 20, and even more preferably 2.0 to 10.
  • the heat-expandable base material layer (Y1) is a base material layer having heat-expandable particles, and is provided between the pressure-sensitive adhesive layer (X1) and the non-heat-expandable base material layer (Y2).
  • the heat-expandable base material layer (Y1) preferably satisfies the following requirement (1).
  • the storage elastic modulus E'of the heat-expandable base material layer (Y1) at a predetermined temperature means a value measured by the method described in Examples.
  • the above requirement (1) can be said to be an index showing the rigidity of the heat-expandable base material layer (Y1) immediately before the heat-expandable particles expand.
  • the storage elastic modulus E'of the thermally expandable base material layer (Y1) decreases as the temperature rises.
  • the thermally expandable particles start to expand, so that the decrease in the storage elastic modulus E'of the thermally expandable base material layer (Y1) is suppressed.
  • the heat-expandable base material layer (Y1) is adhered by heating to a temperature equal to or higher than the expansion start temperature (t). It is necessary to make it easy for irregularities to be formed on the surface on the agent layer (X1) side.
  • the heat-expandable base layer (Y1) that satisfies the above requirement (1), the heat-expandable particles expand at the expansion start temperature (t) to become sufficiently large, and the pressure-sensitive adhesive of the heat-expandable base layer (Y1). Unevenness is likely to be formed on the surface on the layer (X1) side. Therefore, unevenness is likely to be formed on the adhesive surface of the adhesive layer (X1).
  • the storage elastic modulus E'(t) defined in the requirement (1) of the heat-expandable base material layer (Y1) is preferably 9.0 ⁇ 10 6 Pa or less from the above viewpoint. It is preferably 8.0 ⁇ 10 6 Pa or less, more preferably 6.0 ⁇ 10 6 Pa or less, and even more preferably 4.0 ⁇ 10 6 Pa or less.
  • the storage elastic modulus E'(t) specified in the requirement (1) of the thermally expandable base material layer (Y1) is preferably 1.0 ⁇ . It is 10 3 Pa or more, more preferably 1.0 ⁇ 10 4 Pa or more, and further preferably 1.0 ⁇ 10 5 Pa or more.
  • the content of the heat-expandable particles in the heat-expandable base material layer (Y1) is the heat-expandable base material layer (Y1). It is preferably 1 to 40% by mass, more preferably 5 to 35% by mass, still more preferably 10 to 30% by mass, still more preferably 15 to 25% by mass, based on the total mass (100% by mass) of the above.
  • the Young's modulus of the heat-expandable base material layer (Y1) at 23 ° C. is larger than the Young's modulus of the pressure-sensitive adhesive layer (X1) at 23 ° C., and the non-heat-expandable base material layer. It is preferably larger than the Young's modulus of (Y2) at 23 ° C.
  • the Young's modulus of the heat-expandable base material layer (Y1) at 23 ° C. is preferably 100 MPa or more, more preferably 200 MPa or more, still more preferably 300 MPa or more. Further, it is usually 600 MPa or less, preferably 500 MPa or less.
  • the surface of the heat-expandable base material layer (Y1) is subjected to an oxidation method, an unevenness method, or the like.
  • Surface treatment, easy adhesion treatment, or primer treatment may be performed.
  • the oxidation method include corona discharge treatment, plasma discharge treatment, chromic acid treatment (wet), hot air treatment, ozone, and ultraviolet irradiation treatment
  • the unevenness method include sandblasting method and solvent treatment method. And so on.
  • the heat-expandable base material layer (Y1) is preferably formed from a resin composition (y-1) containing a resin and heat-expandable particles.
  • the resin composition (y-1) may contain an additive for a base material, if necessary, as long as the effects of the present invention are not impaired.
  • the base material additive include an ultraviolet absorber, a light stabilizer, an antioxidant, an antistatic agent, a slip agent, an antiblocking agent, and a colorant. These base material additives may be used alone or in combination of two or more. When these base material additives are contained, the content of each base material additive is independently, preferably 0.0001 to 20 parts by mass, more preferably 0.0001 to 20 parts by mass with respect to 100 parts by mass of the resin. Is 0.001 to 10 parts by mass.
  • the heat-expandable particles contained in the resin composition (y-1), which is a material for forming the heat-expandable base material layer (Y1), are as described above.
  • the content of the heat-expandable particles is preferably 1 to 40% by mass, more preferably 5 to 35% by mass, still more preferably, with respect to the total amount (100% by mass) of the active ingredient of the resin composition (y-1). Is 10 to 30% by mass, more preferably 15 to 25% by mass.
  • the resin contained in the resin composition (y-1) which is the material for forming the heat-expandable base material layer (Y1) may be a non-adhesive resin or an adhesive resin. That is, even if the resin contained in the resin composition (y-1) is an adhesive resin, the adhesiveness is obtained in the process of forming the heat-expandable base material layer (Y1) from the resin composition (y-1). It is sufficient that the resin polymerizes with the polymerizable compound, the obtained resin becomes a non-adhesive resin, and the heat-expandable base material layer (Y1) containing the resin becomes non-adhesive.
  • the mass average molecular weight (Mw) of the resin contained in the resin composition (y-1) is preferably 10 to 1,000,000, more preferably 10 to 700,000, and even more preferably 10 to 500,000.
  • the form of the copolymer is not particularly limited, and any of a block copolymer, a random copolymer, and a graft copolymer can be used. It may be.
  • the content of the resin is preferably 50 to 99% by mass, more preferably 60 to 95% by mass, still more preferably 65 to 65% by mass, based on the total amount (100% by mass) of the active ingredient of the resin composition (y-1). It is 90% by mass, more preferably 70 to 85% by mass.
  • the resin contained in the resin composition (y-1) is selected from acrylic urethane-based resin and olefin-based resin. It is preferable to include one or more of these. Further, as the acrylic urethane resin, the following resin (U1) is preferable. -Acrylic urethane resin (U1) obtained by polymerizing a urethane prepolymer (UP) and a vinyl compound containing a (meth) acrylic acid ester.
  • urethane prepolymer (UP) that serves as the main chain of the acrylic urethane resin (U1) include a reaction product of a polyol and a multivalent isocyanate.
  • the urethane prepolymer (UP) is preferably obtained by further performing a chain extension reaction using a chain extender.
  • Examples of the polyol which is a raw material of the urethane prepolymer (UP) include an alkylene type polyol, an ether type polyol, an ester type polyol, an ester amide type polyol, an ester ether type polyol, and a carbonate type polyol.
  • One of these polyols may be used alone, or two or more thereof may be used in combination.
  • a diol is preferable, an ester type diol, an alkylene type diol and a carbonate type diol are more preferable, and an ester type diol and a carbonate type diol are further preferable.
  • ester-type diol examples include alkanediols such as 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, and 1,6-hexanediol; ethylene glycol, propylene glycol, and the like.
  • diols such as diethylene glycol, alkylene glycol such as dipropylene glycol; and 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, hetic acid, maleic acid, fumaric acid, itaconic acid, cyclohexane-1,3-dicarboxylic acid, cyclohexane-1,4-dicarboxylic acid, hexa
  • dicarboxylic acids such as hydrophthalic acid, hexahydroisophthalic acid, hexahydroterephthalic acid, and methylhexahydrophthalic acid, and one or more selected from these anhydrides.
  • alkylene-type diol examples include alkanediols such as 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, and 1,6-hexanediol; ethylene glycol, propylene glycol, and the like.
  • 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.
  • 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.
  • polyisocyanate used as a raw material for the urethane prepolymer (UP) examples include aromatic polyisocyanates, aliphatic polyisocyanates, and alicyclic polyisocyanates.
  • aromatic polyisocyanates aliphatic polyisocyanates
  • alicyclic polyisocyanates One of these polyvalent isocyanates may be used alone, or two or more thereof may be used in combination. Further, these polyvalent isocyanates may be a trimethylolpropane adduct-type modified product, a biuret-type modified product reacted with water, or an isocyanurate-type modified product containing an isocyanurate ring.
  • diisocyanate is preferable as the polyvalent isocyanate used in one embodiment of the present invention
  • diisocyanate 4,4'-diphenylmethane diisocyanate (MDI), 2,4-tolylene diisocyanate (2,4-TDI), 2,6.
  • MDI 4,4'-diphenylmethane diisocyanate
  • 2,4-TDI 2,4-tolylene diisocyanate
  • 2,6 2,6.
  • -One or more selected from tolylene diisocyanate (2,6-TDI), hexamethylene diisocyanate (HMDI), and alicyclic diisocyanate are more preferable.
  • alicyclic diisocyanate examples include 3-isocyanate methyl-3,5,5-trimethylcyclohexylisocyanate (isophorone diisocyanate, IPDI), 1,3-cyclopentane diisocyanate, 1,3-cyclohexanediisocyanate, and 1,4-cyclohexane.
  • IPDI isophorone diisocyanate
  • Examples thereof include diisocyanate, methyl-2,4-cyclohexanediisocyanate and methyl-2,6-cyclohexanediisocyanate, but isophorone diisocyanate (IPDI) is preferable.
  • 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.
  • Urethane prepolymers are preferred.
  • an NCO group at the terminal of the linear urethane prepolymer formed by reacting a diol and a diisocyanate compound and a hydroxyalkyl (meth) acrylate There is 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 vinyl compound that forms the side chain of the acrylic urethane resin (U1) contains at least (meth) acrylic acid ester.
  • the (meth) acrylic acid ester one or more selected from alkyl (meth) acrylate and hydroxyalkyl (meth) acrylate is preferable, and alkyl (meth) acrylate and hydroxyalkyl (meth) acrylate are more preferably used in combination.
  • the blending ratio of hydroxyalkyl (meth) acrylate to 100 parts by mass of alkyl (meth) acrylate is preferably 0.1 to 100 parts by mass. It is preferably 0.5 to 30 parts by mass, more preferably 1.0 to 20 parts by mass, and even more preferably 1.5 to 10 parts by mass.
  • the alkyl group of the alkyl (meth) acrylate has preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 1 to 8 carbon atoms, and even more preferably 1 to 3 carbon atoms.
  • hydroxyalkyl (meth) acrylate the same hydroxyalkyl (meth) acrylate used for introducing an ethylenically unsaturated group into both ends of the above-mentioned linear urethane prepolymer can be mentioned.
  • vinyl compounds other than (meth) acrylic acid ester include aromatic hydrocarbon-based vinyl compounds such as styrene, ⁇ -methylstyrene and vinyltoluene; vinyl ethers such as methyl vinyl ether and ethyl vinyl ether; vinyl acetate and vinyl propionate. , (Meta) acrylonitrile, N-vinylpyrrolidone, (meth) acrylic acid, maleic acid, fumaric acid, itaconic acid, polar group-containing monomers such as meta (acrylamide); and the like. One of these may be used alone, or two or more thereof may be used in combination.
  • 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, 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 the alkyl (meth) acrylate and the hydroxyalkyl (meth) acrylate in the vinyl compound is preferably 40 to 100% by mass, more preferably 65 to 100% by mass, based on the total amount (100% by mass) of the vinyl compound. It is 100% by mass, more preferably 80 to 100% by mass, and even more preferably 90 to 100% by mass.
  • the acrylic urethane 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. In the polymerization, it is preferable to further add a radical initiator.
  • the olefin-based resin suitable as the resin contained in the resin composition (y-1) 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 specific examples thereof include ethylene, propylene, butylene, isobutylene, and 1-hexene. Among these, ethylene and propylene are preferable.
  • VLDPE ultra low density polyethylene
  • LDPE low density polyethylene
  • MDPE Medium density polyethylene
  • HDPE high density polyethylene
  • PP polypropylene resin
  • PB Polybutene resin
  • Ethylene-propylene copolymer Olefin-based elastomer
  • PMP Poly (4-methyl-1-pentene)
  • Ethylene-vinyl acetate copolymer Ethylene -Vinyl alcohol copolymer (EVOH); olefin-based ternary copolymer such as
  • the olefin resin may be a modified olefin resin further subjected to one or more modifications selected from acid modification, hydroxyl group modification, and acrylic modification.
  • the acid-modified olefin-based resin obtained by acid-modifying an olefin-based resin is a modified polymer obtained by graft-polymerizing an unsaturated carboxylic acid or an anhydride thereof with the above-mentioned non-modified olefin-based resin.
  • the unsaturated carboxylic acid or its anhydride include maleic acid, fumaric acid, itaconic acid, citraconic acid, glutaconic acid, tetrahydrophthalic acid, aconitic acid, (meth) acrylic acid, maleic anhydride, and itaconic anhydride.
  • the unsaturated carboxylic acid or its anhydride may be used alone or in combination of two or more.
  • the acrylic-modified olefin-based resin obtained by subjecting the olefin-based resin to acrylic modification is a modification obtained by graft-polymerizing an alkyl (meth) acrylate as a side chain to the above-mentioned non-modified olefin-based resin which is the main chain.
  • the alkyl group of the above alkyl (meth) acrylate has preferably 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, and further preferably 1 to 12 carbon atoms.
  • Examples of the above-mentioned alkyl (meth) acrylate include the same compounds as those that can be selected as the monomer (a1') described later.
  • Examples of the hydroxyl group-modified olefin resin obtained by subjecting the olefin resin to hydroxyl group modification include a modified polymer obtained by graft-polymerizing a hydroxyl group-containing compound on the above-mentioned non-modified olefin resin which is the main chain.
  • Examples of the above-mentioned hydroxyl group-containing compound include the same as the above-mentioned hydroxyl group-containing compound.
  • the resin composition (y-1) 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.
  • 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 co-weight.
  • cellulose triacetate polycarbonate; polyurethane not applicable to acrylic urethane resin; polysulfone; polyether ether ketone; polyether sulfone; polyphenylene sulfide; polyimide resin such as polyetherimide and polyimide; polyamide resin; acrylic resin; Fluorine-based resin and the like can be mentioned.
  • the content of the acrylic urethane resin and the resin other than the olefin resin in the resin composition (y-1) is determined. Less is preferable.
  • the content of the resin other than the acrylic urethane resin and the olefin resin is preferably less than 30 parts by mass, more preferably 20 parts by mass with respect to 100 parts by mass of the total amount of the resin contained in the resin composition (y-1). It is less than parts by mass, more preferably less than 10 parts by mass, still more preferably less than 5 parts by mass, and even more preferably less than 1 part by mass.
  • solvent-free resin composition (y-1a) As one aspect of the resin composition (y-1) used in one aspect of the present invention, an oligomer having an ethylenically unsaturated group having a mass average molecular weight (Mw) of 50,000 or less, an energy ray-polymerizable monomer, and the above-mentioned heat. Examples thereof include a solvent-free resin composition (y-1a) containing expandable particles and not containing a solvent. In the solvent-free resin composition (y-1a), no solvent is blended, but the energy ray-polymerizable monomer contributes to the improvement of the plasticity of the oligomer. By irradiating the coating film formed from the solvent-free resin composition (y-1a) with energy rays, it is easy to form a heat-expandable base material layer (Y1) satisfying the above requirement (1).
  • the types and shapes of the heat-expandable particles to be blended in the solvent-free resin composition (y-1a) and the blending amount (content) are as described above.
  • the mass average molecular weight (Mw) of the oligomer contained in the solvent-free resin composition (y-1a) is 50,000 or less, preferably 1000 to 50,000, more preferably 2000 to 40,000, still more preferably 3000 to 35,000. , Even more preferably 4000 to 30,000.
  • the oligomer may be any resin contained in the above-mentioned resin composition (y-1) having an ethylenically unsaturated group having a mass average molecular weight of 50,000 or less, and the above-mentioned urethane prepolymer. (UP) is preferable.
  • UP urethane prepolymer
  • a modified olefin resin having an ethylenically unsaturated group can also be used.
  • the total content of the oligomer and the energy ray-polymerizable monomer in the solvent-free resin composition (y-1a) is based on the total amount (100% by mass) of the solvent-free resin composition (y-1a). It is preferably 50 to 99% by mass, more preferably 60 to 95% by mass, still more preferably 65 to 90% by mass, and even more preferably 70 to 85% by mass.
  • Examples of the energy ray-polymerizable monomer include isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyloxy (meth) acrylate, cyclohexyl (meth) acrylate, and adamantan ().
  • Alicyclic polymerizable compounds such as meta) acrylates and tricyclodecane acrylates; aromatic polymerizable compounds such as phenylhydroxypropyl acrylates, benzyl acrylates and phenolethylene oxide modified acrylates; tetrahydrofurfuryl (meth) acrylates, morpholine acrylates, N- Examples thereof include heterocyclic polymerizable compounds such as vinylpyrrolidone and N-vinylcaprolactam.
  • One of these energy ray-polymerizable monomers may be used alone, or two or more thereof may be used in combination.
  • the content ratio [oligomer / energy ray-polymerizable monomer] of the oligomer to the energy ray-polymerizable monomer in the solvent-free resin composition (y-1a) is preferably 20/80 to 20/80 in mass ratio. It is 90/10, more preferably 30/70 to 85/15, and even more preferably 35/65 to 80/20.
  • the solvent-free resin composition (y-1a) is preferably further blended with a photopolymerization initiator.
  • a photopolymerization initiator By containing the photopolymerization initiator, the curing reaction can be sufficiently advanced even by irradiation with relatively low energy energy rays.
  • photopolymerization initiator examples include the same photopolymerization initiators that the pressure-sensitive adhesive composition (x-1) may contain. One of these photopolymerization initiators may be used alone, or two or more thereof may be used in combination.
  • the blending amount of the photopolymerization initiator is preferably 0.01 to 5 parts by mass, more preferably 0.01 to 4 parts by mass, and further, based on the total amount (100 parts by mass) of the oligomer and the energy ray-polymerizable monomer. It is preferably 0.02 to 3 parts by mass.
  • the thickness of the heat-expandable substrate layer (Y1) is preferably 10 to 1000 ⁇ m, more preferably 20 to 500 ⁇ m, still more preferably 25 to 400 ⁇ m, still more preferably 30 to 300 ⁇ m. ..
  • Non-thermally expandable base material layer (Y2) contained in the pressure-sensitive adhesive sheet of the present invention is provided on the surface of the heat-expandable base material layer (Y1) opposite to the laminated surface of the pressure-sensitive adhesive layer (X1).
  • the Young's modulus of the non-thermally expandable base material layer (Y2) at 23 ° C. is higher than the Young's modulus of the pressure-sensitive adhesive layer (X1) at 23 ° C.
  • the heat-expandable base layer (Y1) is more adherent than the surface of the heat-expandable base layer (Y1) on the non-heat-expandable base layer (Y2) side. Unevenness is likely to be formed on the surface of the agent layer (X1) side. Therefore, unevenness is satisfactorily formed on the adhesive surface of the adhesive layer (X1).
  • the Young's modulus of the non-thermally expandable base material layer (Y2) at 23 ° C. is preferably 700 MPa or more, more preferably 1000 MPa or more, still more preferably 1300 MPa or more, still more preferably 1600 MPa or more, still more preferably. It is 1800 MPa or more. In addition, it is usually 10,000 MPa or less.
  • Examples of the material for forming the non-thermally expandable base material layer (Y2) include resins, metals, and paper materials, which can be appropriately selected depending on the use of the pressure-sensitive adhesive sheet according to one aspect of the present invention.
  • the resin examples include polyolefin resins such as polyethylene and polypropylene; vinyl resins such as polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl acetate copolymer, and ethylene-vinyl alcohol copolymer; polyethylene terephthalate and poly.
  • polyolefin resins such as polyethylene and polypropylene
  • vinyl resins such as polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl acetate copolymer, and ethylene-vinyl alcohol copolymer
  • polyethylene terephthalate and poly examples include polyethylene terephthalate and poly.
  • Polyimide-based resins such as butylene terephthalate and polyethylene naphthalate; polystyrene; acrylonitrile-butadiene-styrene copolymer; cellulose triacetate; polycarbonate; urethane resins such as polyurethane and acrylic-modified polyurethane; polymethylpentene; polysulfone; polyether ether ketone; Polyether sulfone; polyphenylene sulfide; polyimide resin such as polyetherimide and polyimide; polyamide resin; acrylic resin; fluorine resin and the like can be mentioned.
  • the metal include aluminum, tin, chromium, titanium and the like.
  • the paper material examples include thin-leaf paper, medium-quality paper, high-quality paper, impregnated paper, coated paper, art paper, parchment paper, and glassin paper.
  • polyester resins such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate are preferable.
  • forming materials may be composed of one kind, or two or more kinds may be used in combination.
  • a paper material laminated with a thermoplastic resin such as polyethylene, or a metal film is formed on the surface of a resin film or sheet containing the resin. Examples thereof include those formed.
  • a method for forming the metal layer for example, a method of vapor-depositing the metal by a PVD method such as vacuum vapor deposition, sputtering, or ion plating, or a method of attaching a metal foil made of the metal by using a general adhesive. The method of doing this can be mentioned.
  • the non-thermally expandable base material layer (Y2) contains a resin
  • it is a non-thermally expandable group from the viewpoint of improving the interlayer adhesion between the non-thermally expandable base material layer (Y2) and other layers to be laminated.
  • the surface of the material layer (Y2) may also be subjected to surface treatment, easy adhesion treatment, or primer treatment by an oxidation method, an unevenness method, or the like, similarly to the above-mentioned thermal expansion base material layer (Y1). ..
  • the non-thermally expandable base material layer (Y2) contains a resin
  • the above-mentioned base material additive which can be contained in the resin composition (y-1) may be contained together with the resin.
  • the non-thermally expandable base material layer (Y2) is a non-thermally expandable layer determined based on the above method. Therefore, the volume change rate (%) of the non-thermally expandable base material layer (Y2) calculated from the above formula is less than 5%, but preferably less than 2%, more preferably less than 1%, and further. It is preferably less than 0.1%, and even more preferably less than 0.01%.
  • the non-thermally expandable base material layer (Y2) may contain thermally expandable particles as long as the volume change rate is within the above range.
  • the resin contained in the non-thermally expandable base material layer (Y2) it is possible to adjust the volume change rate within the above range even if the thermally expandable particles are contained.
  • the smaller the content of the heat-expandable particles in the non-heat-expandable base material layer (Y2) the more preferable.
  • the specific content of the heat-expandable particles is usually less than 3% by mass, preferably less than 1% by mass, more preferably with respect to the total mass (100% by mass) of the non-heat-expandable base material layer (Y2). Is less than 0.1% by mass, more preferably less than 0.01% by mass, and even more preferably less than 0.001% by mass. Even more preferably, it does not contain thermally expandable particles.
  • the storage elastic modulus E'(23) of the non-thermally expandable substrate layer (Y2) at 23 ° C. is preferably 5.0 ⁇ 10 7 to 5.0 ⁇ 10 9 Pa, more preferably 5.0 ⁇ 10 8. It is ⁇ 4.5 ⁇ 10 9 Pa, more preferably 1.0 ⁇ 10 9 to 4.0 ⁇ 10 9 Pa.
  • the storage elastic modulus E of the non-heat-expandable base material layer (Y2) '(23) is 5.0 ⁇ 10 7 Pa or more, heat-expandable base layer non-intumescent base material layer (Y1) ( It is easy to effectively suppress the expansion of the surface on the Y2) side, and it is easy to improve the deformation resistance of the adhesive sheet.
  • non-heat-expandable base material layer (Y2) of the storage modulus E '(23) is less than 5.0 ⁇ 10 9 Pa, to improve the handling properties of the pressure-sensitive adhesive sheet easily.
  • the storage elastic modulus E'(23) of the non-thermally expandable base material layer (Y2) means a value measured by the method described in Examples.
  • the coefficient of thermal expansion E'(t) at the expansion start temperature (t) of the thermally expandable particles of the non-thermally expandable substrate layer (Y2) is preferably 5.0 ⁇ 10 7 to 3.0 ⁇ 10 9 Pa. It is more preferably 2.0 ⁇ 10 8 to 2.5 ⁇ 10 9 Pa, and even more preferably 5.0 ⁇ 10 8 to 2.0 ⁇ 10 9 Pa.
  • the storage elastic modulus E of the non-heat-expandable base material layer (Y2) '(t) is 5.0 ⁇ 10 7 Pa or more, heat-expandable base layer non-intumescent base material layer (Y1) ( It is easy to effectively suppress the expansion of the surface on the Y2) side, and it is easy to improve the deformation resistance of the adhesive sheet.
  • heat-expandable base layer non-intumescent base material layer (Y1) It is easy to effectively suppress the expansion of the surface on the Y2) side, and it is easy to improve the deformation resistance of the adhesive sheet.
  • non-heat-expandable base material layer (Y2) storage modulus E '(t) is 3.0 ⁇ 10 9 Pa or less, to improve the handling properties of the pressure-sensitive adhesive sheet easily.
  • the storage elastic modulus E'(t) of the non-thermally expandable base material layer (Y2) means a value measured by the method described in Examples.
  • the thickness of the non-thermally expandable base material layer (Y2) is preferably 5 to 500 ⁇ m, more preferably 15 to 300 ⁇ m, and even more preferably 20 to 200 ⁇ m.
  • the thickness of the non-thermally expandable base material layer (Y2) is 5 ⁇ m or more, the deformation resistance of the pressure-sensitive adhesive sheet can be easily improved.
  • the thickness of the non-thermally expandable base material layer (Y2) is 500 ⁇ m or less, the handleability of the pressure-sensitive adhesive sheet can be easily improved.
  • the thickness of the non-thermally expandable base material layer (Y2) means the value measured by the method described in Example.
  • the pressure-sensitive adhesive layer (X2) is a layer arbitrarily provided on a surface of the non-thermally expandable base material layer (Y2) opposite to the laminated surface of the heat-expandable base material layer (Y1).
  • the pressure-sensitive adhesive layer (X2) may be a thermally expandable layer or a non-thermally expandable layer, but is preferably a non-thermally expandable layer.
  • the pressure-sensitive adhesive layer (X1) and the pressure-sensitive adhesive layer (X2) have different action mechanisms for reducing the adhesive strength of the pressure-sensitive adhesive layer, whereby the treatment for reducing the adhesive strength of one of the pressure-sensitive adhesive layers is performed. When doing so, it is possible to prevent the adhesive strength of the other adhesive layer from being unintentionally reduced.
  • the volume change rate (%) of the pressure-sensitive adhesive layer (X2) calculated from the above formula is less than 5%, preferably less than 2%. It is preferably less than 1%, more preferably less than 0.1%, and even more preferably less than 0.01%.
  • the pressure-sensitive adhesive layer (X2) preferably does not contain heat-expandable particles, but may contain heat-expandable particles within a range not contrary to the object of the present invention.
  • the pressure-sensitive adhesive layer (X2) contains thermally expandable particles, the smaller the content is, the more preferable, and the content is preferably less than 3% by mass, based on the total mass (100% by mass) of the pressure-sensitive adhesive layer (X2). It is preferably less than 1% by mass, more preferably less than 0.1% by mass, still more preferably less than 0.01% by mass, and even more preferably less than 0.001% by mass.
  • the pressure-sensitive adhesive layer (X2) is preferably formed from the pressure-sensitive adhesive composition (x-2) containing a pressure-sensitive adhesive resin.
  • a pressure-sensitive adhesive resin containing a pressure-sensitive adhesive resin.
  • the pressure-sensitive adhesive composition (x-2) contains a pressure-sensitive resin, and if necessary, a cross-linking agent, a pressure-sensitive adhesive, a polymerizable compound, a polymerization initiator, and general pressure-sensitive adhesive other than the above-mentioned components. It may contain an additive for a pressure-sensitive adhesive used in the agent.
  • the adhesive resin may be a polymer having adhesiveness by itself and having a mass average molecular weight (Mw) of 10,000 or more.
  • the mass average molecular weight (Mw) of the adhesive resin is preferably 10,000 to 2 million, more preferably 20,000 to 1.5 million, and further preferably 30,000 from the viewpoint of further improving the adhesive strength of the pressure-sensitive adhesive layer (X2). ⁇ 1 million.
  • Examples of the adhesive resin include those similar to the adhesive composition contained in the adhesive composition (x-1). One type of these adhesive resins may be used alone, or two or more types may be used in combination. When these adhesive resins are copolymers having two or more kinds of structural units, the form of the copolymer may be any of a block copolymer, a random copolymer, and a graft copolymer. There may be.
  • the adhesive resin contained in the pressure-sensitive adhesive composition (x-2) has a pressure-sensitive adhesive composition containing the pressure-sensitive adhesive resin from the viewpoint of differentiating the mechanism of action of reducing the adhesive strength with the pressure-sensitive adhesive layer (X1).
  • x-2) is preferably a pressure-sensitive adhesive composition that is cured by irradiation with energy rays, and more preferably a pressure-sensitive adhesive composition having an energy ray-polymerizable functional group in the side chain.
  • the pressure-sensitive adhesive layer (X2) can be made into a pressure-sensitive adhesive layer that is cured by energy ray irradiation and whose adhesive strength is reduced.
  • the adhesive surface of the pressure-sensitive adhesive layer (X1) can be in a mode in which the adhesive strength is reduced by heating, and the adhesive surface of the pressure-sensitive adhesive layer (X2) can be in a mode in which the adhesive strength is reduced by irradiation with energy rays.
  • the mechanism of action that reduces the adhesive strength of the pressure-sensitive adhesive layer can be different. Therefore, it is possible to prevent the adhesive strength of one of the pressure-sensitive adhesive layers from being unintentionally reduced when the treatment is performed to reduce the adhesive strength of the other pressure-sensitive adhesive layer.
  • the energy ray-polymerizable functional group include those having a carbon-carbon double bond such as a (meth) acryloyl group, a vinyl group, and an allyl group.
  • ultraviolet rays ultraviolet rays, which are easy to handle, are preferable.
  • the pressure-sensitive adhesive composition (x-2) is a pressure-sensitive adhesive composition that is cured by irradiation with energy rays
  • the pressure-sensitive adhesive composition preferably further contains a photopolymerization initiator.
  • the photopolymerization initiator include the same photopolymerization initiators that may be contained in the pressure-sensitive adhesive composition (x-1).
  • the content of the photopolymerization initiator is preferably 0.01 to 10 parts by mass, more preferably 0.03 to 5 parts by mass, based on 100 parts by mass of the total amount of the adhesive resin having an energy ray-polymerizable functional group. More preferably, it is 0.05 to 2 parts by mass.
  • the adhesive resin preferably contains an acrylic resin from the viewpoint of exhibiting excellent adhesive strength.
  • the content of the acrylic resin in the pressure-sensitive adhesive composition (x-2) is preferably 30 to 30% with respect to the total amount (100% by mass) of the pressure-sensitive resin contained in the pressure-sensitive adhesive composition (x-2). It is 100% by mass, more preferably 50 to 100% by mass, still more preferably 70 to 100% by mass, and even more preferably 85 to 100% by mass.
  • the content of the pressure-sensitive resin in the pressure-sensitive adhesive composition (x-2) is preferably 35 to 100% by mass, based on the total amount (100% by mass) of the active ingredients of the pressure-sensitive adhesive composition (x-2). It is more preferably 50 to 100% by mass, further preferably 60 to 98% by mass, and even more preferably 70 to 95% by mass.
  • the pressure-sensitive adhesive composition (x-2) when the pressure-sensitive adhesive composition (x-2) contains a pressure-sensitive adhesive resin having a functional group, the pressure-sensitive adhesive composition (x-2) preferably further contains a cross-linking agent.
  • the cross-linking agent reacts with a tacky resin having a functional group to cross-link the tacky resins with the functional group as a cross-linking starting point.
  • Examples of the cross-linking agent that may be contained in the pressure-sensitive adhesive composition (x-2) include those equivalent to the cross-linking agent that may be contained in the pressure-sensitive adhesive composition (x-1), but have a cohesive force.
  • An isocyanate-based cross-linking agent is preferable from the viewpoint of increasing the adhesive strength and improving the adhesive strength, and from the viewpoint of easy availability.
  • the content of the cross-linking agent is appropriately adjusted according to the number of functional groups of the adhesive resin, and is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the adhesive resin having functional groups. It is more preferably 0.03 to 7 parts by mass, and further preferably 0.05 to 5 parts by mass.
  • the pressure-sensitive adhesive composition (x-2) may further contain a pressure-sensitive adhesive from the viewpoint of further improving the adhesive strength.
  • a pressure-sensitive adhesive from the viewpoint of further improving the adhesive strength.
  • the same pressure-imparting agent that may be contained in the pressure-sensitive adhesive composition (x-1) may be used. it can.
  • Examples of the pressure-sensitive adhesive additive include the same pressure-sensitive adhesive additives that the pressure-sensitive adhesive composition (x-1) may contain.
  • the pressure-sensitive adhesive composition (x-2) can be produced by mixing a pressure-sensitive resin, a cross-linking agent used as necessary, a pressure-sensitive adhesive, an additive for pressure-sensitive adhesive, and the like.
  • the thickness of the pressure-sensitive adhesive layer (X2) at 23 ° C. is preferably 5 to 150 ⁇ m, more preferably 8 to 100 ⁇ m, still more preferably 12 to 70 ⁇ m, and even more preferably 15 to 50 ⁇ m. If the thickness of the pressure-sensitive adhesive layer (X2) at 23 ° C. is 5 ⁇ m or more, sufficient adhesive strength can be easily obtained, and unintentional peeling from the adherend during temporary fixing, misalignment of the adherend, etc. can occur. It tends to be suppressed. On the other hand, if the thickness of the pressure-sensitive adhesive layer (X2) at 23 ° C. is 150 ⁇ m or less, the pressure-sensitive adhesive sheet tends to be easy to handle.
  • Examples of the release material include a release sheet that has undergone double-sided release treatment, a release sheet that has undergone single-sided release treatment, and the like, in which a release agent is applied onto a base material for the release material.
  • Examples of the base material for the release material include plastic films and papers.
  • Examples of the plastic film include polyester resin films such as polyethylene terephthalate resin, polybutylene terephthalate resin and polyethylene naphthalate resin; and olefin resin films such as polypropylene resin and polyethylene resin.
  • Examples of papers include high-quality paper. , Glassin paper, kraft paper, etc.
  • the release agent examples include rubber-based elastomers such as silicone-based resins, olefin-based resins, isoprene-based resins, and butadiene-based resins; long-chain alkyl-based resins, alkyd-based resins, and fluorine-based resins.
  • rubber-based elastomers such as silicone-based resins, olefin-based resins, isoprene-based resins, and butadiene-based resins
  • long-chain alkyl-based resins alkyd-based resins
  • fluorine-based resins fluorine-based resins
  • the thickness of the release material is preferably 10 to 200 ⁇ m, more preferably 20 to 150 ⁇ m, and even more preferably 35 to 80 ⁇ m.
  • the method for producing the pressure-sensitive adhesive sheet of the present invention is not particularly limited, and examples thereof include a method for manufacturing a pressure-sensitive adhesive sheet having the following steps (1a) to (3a).
  • Step (1a) A step of applying the pressure-sensitive adhesive composition (x-1) on the peeling-treated surface of the release material to form the pressure-sensitive adhesive layer (X1).
  • Step (4a) A step of applying the pressure-sensitive adhesive composition (x-2) on the peeling-treated surface of the release material to form the pressure-sensitive adhesive layer (X2).
  • Step (5a) A step of adhering the adhesive surface of the pressure-sensitive adhesive layer (X2) formed in step (4a) to the surface of the non-thermally expandable base material layer (Y2) of the pressure-sensitive adhesive sheet formed in step (3a).
  • the resin composition (y-1), the pressure-sensitive adhesive composition (x-1), and the pressure-sensitive adhesive composition (x-2) are further blended with a diluting solvent to form a solution.
  • a diluting solvent to form a solution.
  • the coating method include a spin coating method, a spray coating method, a bar coating method, a knife coating method, a roll coating method, a blade coating method, a die coating method, and a gravure coating method.
  • the step of drying the coating film formed from the resin composition (y-1), the pressure-sensitive adhesive composition (x-1), and the pressure-sensitive adhesive composition (x-2) causes the expansion of the heat-expandable particles.
  • the drying temperature is lower than the expansion start temperature (t) of the thermally expandable particles.
  • the pressure-sensitive adhesive sheet according to one aspect of the present invention can be easily peeled off by heating the temporarily fixed adherend, and can suppress contamination of the adherend surface after peeling, and is applicable to various applications. It is possible. Specifically, for example, a dicing sheet used when dicing an adherend such as a semiconductor wafer, a back grind sheet used in a process of grinding an adherend, a substrate such as a semiconductor chip individualized by dicing. Expanding tape used to increase the distance between wafers, transfer tape used to invert the front and back of adherends such as semiconductor chips, and temporary fixing used to temporarily fix an object to be inspected. Suitable for fixing sheets and the like.
  • the adherend of the pressure-sensitive adhesive sheet according to one aspect of the present invention is not particularly limited, and examples thereof include semiconductor chips, semiconductor wafers, compound semiconductors, semiconductor packages, electronic components, sapphire substrates, displays, and panel substrates.
  • the expansion start temperature (t) of the heat-expandable particles is set to less than 125 ° C. as in the pressure-sensitive adhesive sheet of one aspect of the present invention, heat peeling is possible at a low temperature, so that heat of a semiconductor chip with DAF or the like can be obtained. It is suitable for temporarily fixing a variable adherend. Further, when the expansion start temperature (t) of the heat-expandable particles is set to 50 ° C.
  • thermal expansion due to temperature rise such as when grinding the adherend is performed. Since it can suppress the unintended expansion of the sex particles, it is suitable for use as a back grind sheet used in the process of grinding an adherend.
  • the heating temperature at which the pressure-sensitive adhesive sheet according to one aspect of the present invention is heat-peeled from the adherend is equal to or higher than the expansion start temperature (t) of the heat-expandable particles, and is preferably “a temperature higher than the expansion start temperature (t)”. , More preferably “expansion start temperature (t) + 2 ° C.” or higher, further preferably “expansion start temperature (t) + 4 ° C.” or higher, and even more preferably "expansion start temperature (t) + 5 ° C.” or higher.
  • the heating temperature at the time of heat peeling is preferably less than 125 ° C., more preferably 120 ° C. or lower, and further, within the range of the expansion start temperature (t) or higher, from the viewpoint of suppressing the thermal change of the adherend. It is preferably 115 ° C. or lower, more preferably 110 ° C. or lower, and even more preferably 105 ° C. or lower.
  • the heating method is not particularly limited as long as it can be heated to a temperature higher than the temperature at which the thermally expandable particles expand, and for example, an electric heater; dielectric heating; magnetic heating; near infrared rays, mid infrared rays, and far infrared rays. It is possible to appropriately use heating by electromagnetic waves such as infrared rays.
  • the heating method may be any of a contact type heating method such as a heating roller and a heating press, and a non-contact type heating method such as an atmosphere heating device and infrared irradiation.
  • the present invention also provides a method for manufacturing a semiconductor device using the pressure-sensitive adhesive sheet according to one aspect of the present invention.
  • the adhesive sheet of one aspect of the present invention is used as a temporary fixing sheet for performing at least one of processing and inspection of an adherend (hereinafter referred to as an aspect).
  • a method for manufacturing a semiconductor device of the first aspect also referred to as "a method for manufacturing a semiconductor device of the first aspect”.
  • a semiconductor device refers to a device in general that can function by utilizing semiconductor characteristics. For example, wafers with integrated circuits, thinned wafers with integrated circuits, chips with integrated circuits, thinned chips with integrated circuits, electronic components including these chips, and electronic components with the electronic components. kind and the like.
  • a processing inspection object is attached to the pressure-sensitive adhesive sheet of one aspect of the present invention, and the processing inspection object is selected from processing and inspection.
  • a method for manufacturing a semiconductor device which includes a step of heating the pressure-sensitive adhesive sheet to the expansion start temperature (t) or higher after applying the above-mentioned one or more.
  • the processing inspection object include semiconductor chips, semiconductor wafers, compound semiconductors, semiconductor packages, electronic components, LED elements, sapphire substrates, displays, panel substrates, and the like.
  • the processing performed on the object to be inspected is not particularly limited, and examples thereof include grinding processing and individualization processing.
  • the inspection performed on the object to be processed is not particularly limited, but for example, defect inspection using an optical microscope or laser (for example, dust inspection, surface scratch inspection, wiring pattern inspection, etc.), visual surface inspection, etc. Can be mentioned.
  • the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet to which the processing inspection object is attached may be the pressure-sensitive adhesive layer (X1), and when the pressure-sensitive adhesive sheet is a double-sided pressure-sensitive adhesive sheet, it is pressure-sensitive. It may be an agent layer (X2).
  • the pressure-sensitive adhesive sheet is a double-sided pressure-sensitive adhesive sheet, it is preferable that the object to be processed and inspected is attached to one of the pressure-sensitive adhesive layers and the support is attached to the other pressure-sensitive adhesive layer.
  • the support may be attached to the pressure-sensitive adhesive layer (X1) and the object to be processed and inspected may be attached to the pressure-sensitive adhesive layer (X2), or the object to be processed and inspected may be attached to the pressure-sensitive adhesive layer (X1).
  • the support may be attached to the pressure-sensitive adhesive layer (X2).
  • the pressure-sensitive adhesive layer (X1) has excellent peelability after heat treatment.
  • the adhesive sheet and the support can be heat-peeled without bending.
  • the composition of the pressure-sensitive adhesive layer (X2) may be appropriately selected according to the type of the object to be processed and inspected.
  • the pressure-sensitive adhesive layer (X2) may be a pressure-sensitive adhesive layer whose adhesive strength is reduced by irradiation with energy rays. Then, the object to be processed can be peeled off without being contaminated by the residue derived from the thermal expansion particles.
  • the object to be processed and inspected is attached to the pressure-sensitive adhesive layer (X1) and the support is attached to the pressure-sensitive adhesive layer (X2)
  • the object to be processed and inspected is an adhesive having excellent peelability after heat treatment.
  • the layer (X1) when heat peeling is performed after processing, it is not necessary to pick up the objects to be processed and inspected individually, and the objects can be easily peeled at once, so that the productivity of the semiconductor device is excellent. ..
  • the pressure-sensitive adhesive sheet according to one aspect of the present invention is used as a temporary fixing sheet for inspecting a processing inspection object as part of a manufacturing process, a plurality of processing inspections are performed on the pressure-sensitive adhesive layer (X1) of the pressure-sensitive adhesive sheet.
  • the inspection can be carried out with the object attached.
  • a part of the adhesive sheet to which the plurality of processing inspection objects are attached is locally heated to selectively select a specific processing inspection object attached to the portion. It can also be peeled off by heating.
  • the pressure-sensitive adhesive sheet according to one aspect of the present invention can be heat-peeled at a low temperature, it is excellent in workability and energy saving of the heat-peeling work, and the object to be processed and inspected is easily changed by heat. However, it is possible to suppress the thermal change of the processing inspection object due to heating at the time of heat peeling.
  • ⁇ Manufacturing method of semiconductor device of the second aspect> As a method for manufacturing the semiconductor device of the second aspect, as the adhesive sheet of one aspect of the present invention, a double-sided adhesive sheet in which the expansion start temperature (t) of the heat-expandable particles is 50 ° C. or higher and lower than 125 ° C. is used, and the following steps are taken. Examples thereof include 1A to 3A, a manufacturing method including the following first separation step and the following second separation step (hereinafter, also referred to as “manufacturing method A”). Step 1A: Attaching the object to be processed to the pressure-sensitive adhesive layer (X2) and attaching the support to the adhesive layer (X1) Step 2A: Select from grinding and individualizing the object to be processed.
  • Step 3A A step of sticking a thermosetting film on the surface of the processed object to be treated, which is opposite to the adhesive layer (X2).
  • First separation step The above. Step of separating the pressure-sensitive adhesive layer (X1) from the support by heating the pressure-sensitive adhesive sheet to the expansion start temperature (t) or more and less than 125 ° C. Second separation step: The pressure-sensitive adhesive layer (X2) and the processing target The process of separating things
  • Step 1A is a step of attaching the object to be processed to the pressure-sensitive adhesive layer (X2) of the pressure-sensitive adhesive sheet and attaching the support to the pressure-sensitive adhesive layer (X1).
  • FIG. 3 is a cross-sectional view illustrating a step of attaching the semiconductor wafer W to the adhesive layer (X2) of the adhesive sheet 2b and attaching the support 3 to the adhesive layer (X1). The semiconductor wafer W is attached so that the surface W1 which is the circuit surface is on the adhesive layer (X2) side.
  • the semiconductor wafer W may be a silicon wafer, a wafer such as gallium arsenide, silicon carbide, sapphire, lithium tantalate, lithium niobate, gallium nitride, indium phosphorus, or a glass wafer.
  • the thickness of the semiconductor wafer W before grinding is usually 500 to 1000 ⁇ m.
  • the circuit included in the surface W1 of the semiconductor wafer W can be formed by, for example, a conventionally used general-purpose method such as an etching method or a lift-off method.
  • the material of the support 3 may be appropriately selected in consideration of required characteristics such as mechanical strength and heat resistance according to the type of the object to be processed, the content of processing, and the like.
  • Examples of the material of the support 3 include metal materials such as SUS; non-metallic inorganic materials such as glass and silicon wafers; epoxy resin, ABS resin, acrylic resin, engineering plastic, super engineering plastic, polyimide resin, polyamideimide resin and the like.
  • Resin materials Composite materials such as glass epoxy resin, and among these, SUS, glass, and silicon wafers are preferable.
  • the engineering plastic include nylon, polycarbonate (PC), polyethylene terephthalate (PET), and the like.
  • Examples of the super engineering plastic include polyphenylene sulfide (PPS), polyethersulfone (PES), and polyetheretherketone (PEEK).
  • the support 3 is preferably attached to the entire surface of the adhesive surface of the adhesive layer (X1). Therefore, the area of the surface of the support 3 on the side to be attached to the adhesive surface of the adhesive layer (X1) is preferably equal to or larger than the area of the adhesive surface of the adhesive layer (X1). Further, it is preferable that the surface of the support 3 on the side to be attached to the adhesive surface of the adhesive layer (X1) is flat.
  • the shape of the support 3 is not particularly limited, but is preferably plate-shaped.
  • the thickness of the support 3 may be appropriately selected in consideration of the required characteristics, but is preferably 20 ⁇ m or more and 50 mm or less, and more preferably 60 ⁇ m or more and 20 mm or less.
  • Step 2A is a step of performing one or more processes selected from a grinding process and an individualizing process on the object to be processed.
  • One or more processes selected from the grinding process and the individualizing process include, for example, a grinding process using a grinder or the like; an individualizing process by a blade dicing method, a laser dicing method, a stealth dicing (registered trademark) method; a blade tip. Grinding process and individualization process by dicing method, stealth tip dicing method; etc. can be mentioned.
  • individualization treatment by stealth dicing method, grinding treatment and individualization treatment by blade tip dicing method, grinding treatment and individualization treatment by stealth tip dicing method are preferable, and grinding treatment by blade tip dicing method. And individualization treatment, grinding treatment by stealth tip dicing method and individualization treatment are more preferable.
  • the stealth dicing method is a method in which a modified region is formed inside a semiconductor wafer by irradiation with laser light, and the semiconductor wafer is individualized using the modified region as a division starting point.
  • the modified region formed on the semiconductor wafer is a portion brittled by multiphoton absorption, and the modified region is applied by applying stress in the direction in which the semiconductor wafer is parallel to the wafer surface and the wafer is expanded by expanding.
  • the cracks extend toward the front surface and the back surface of the semiconductor wafer starting from the above, and are separated into semiconductor chips. That is, the modified region is formed along the dividing line when it is individualized.
  • the modified region is formed inside the semiconductor wafer by irradiation with a laser beam focused on the inside of the semiconductor wafer.
  • the incident surface of the laser beam may be the front surface or the back surface of the semiconductor wafer. Further, the laser beam incident surface may be a surface to which the adhesive sheet is attached, in which case the laser beam is applied to the semiconductor wafer
  • the blade tip dicing method is also called the DBG method (Dicing Before Grinding).
  • DBG method Diing Before Grinding
  • a groove is formed in the semiconductor wafer in advance along the line to be divided at a depth shallower than the thickness, and then the semiconductor wafer is back-ground to be thin until the ground surface reaches at least the groove. It is a method of individualizing while making it.
  • the groove reached by the ground surface becomes a notch penetrating the semiconductor wafer, and the semiconductor wafer is divided by the notch and separated into semiconductor chips.
  • the pre-formed groove is usually provided on the surface (circuit surface) of the semiconductor wafer, and can be formed by dicing using, for example, a conventionally known wafer dicing apparatus provided with a dicing blade.
  • the stealth dicing method is also called the SDBG method (Stealth Dicing Before Grinding). Similar to the stealth dicing method, the stealth dicing method is a kind of method in which a modified region is formed inside the semiconductor wafer by irradiation with laser light, and the semiconductor wafer is individualized using the modified region as a division starting point. However, it differs from the stealth dicing method in that the semiconductor wafer is fragmented into semiconductor chips while thinning the semiconductor wafer by grinding. Specifically, while the semiconductor wafer having the modified region is back-ground to be thinned, the pressure applied to the semiconductor wafer at that time causes the modified region as a starting point to be directed toward the surface to be attached to the pressure-sensitive adhesive layer of the semiconductor wafer.
  • the cracks are extended and the semiconductor wafer is separated into semiconductor chips.
  • the grinding thickness after the reformed region is formed may be the thickness reaching the reformed region, but even if it does not reach the reformed region strictly, it is ground to a position close to the reformed region. Then, it may be split by the processing pressure of a grinding wheel or the like.
  • the semiconductor wafer W is individualized by the blade tip dicing method, it is preferable that a groove is formed in advance on the surface W1 of the semiconductor wafer W to be attached to the pressure-sensitive adhesive layer (X2) in step 1A.
  • the semiconductor wafer W to be attached to the pressure-sensitive adhesive layer (X2) is irradiated with laser light in step 1A to form a modified region in advance.
  • the semiconductor wafer W attached to the pressure-sensitive adhesive layer (X2) may be irradiated with a laser beam to form a modified region.
  • FIG. 4 shows a cross-sectional view illustrating a step of forming a plurality of reformed regions 5 on the semiconductor wafer W attached to the pressure-sensitive adhesive layer (X2) by using the laser light irradiation device 4.
  • the laser beam is irradiated from the back surface W2 side of the semiconductor wafer W, and a plurality of modified regions 5 are formed inside the semiconductor wafer W at substantially equal intervals.
  • FIG. 5 a plurality of semiconductor chip CPs are shown while thinning the semiconductor wafer W by grinding the back surface W2 of the semiconductor wafer W on which the modified region 5 is formed by a grinder 6 and dividing the semiconductor wafer W starting from the modified region 5.
  • a cross-sectional view illustrating the process of individualizing is shown.
  • the back surface W2 of the semiconductor wafer W is ground in a state where the support 3 supporting the semiconductor wafer W is fixed on a fixed table such as a chuck table.
  • the thickness of the semiconductor chip CP after grinding is preferably 5 to 100 ⁇ m, more preferably 10 to 45 ⁇ m. Further, when the grinding process and the individualization process are performed by the stealth tip dicing method, the thickness of the semiconductor chip CP obtained by grinding can be easily set to 50 ⁇ m or less, more preferably 10 to 45 ⁇ m.
  • the size of the semiconductor chip CP after grinding in a plan view is preferably less than 600 mm 2 , more preferably less than 400 mm 2 , and even more preferably less than 300 mm 2 .
  • the plan view means to see in the thickness direction.
  • the shape of the semiconductor chip CP after fragmentation in a plan view may be a rectangular shape or an elongated shape such as a rectangle.
  • the pressure-sensitive adhesive sheet used in the method for manufacturing the semiconductor device of the second aspect has an expansion start temperature (t) of the thermally expandable particles of 50 ° C. or higher, it is thermally expandable due to a temperature rise such as when grinding is performed. It is possible to avoid a situation in which the particles unintentionally expand. Therefore, unintended separation and misalignment of the object to be processed are suppressed.
  • Step 3A is a step of attaching a thermosetting film to the surface of the processed object to be processed, which is opposite to the pressure-sensitive adhesive layer (X2).
  • FIG. 6 illustrates a step of attaching a thermosetting film 7 provided with a support sheet 8 to a surface of a plurality of semiconductor chip CPs obtained by performing the above treatment on a surface opposite to the pressure-sensitive adhesive layer (X2). A cross-sectional view is shown.
  • the thermosetting film 7 is a film having thermosetting property obtained by forming a resin composition containing at least a thermosetting resin, and is used as an adhesive when mounting a semiconductor chip CP on a substrate.
  • the thermosetting film 7 may contain a curing agent for the thermosetting resin, a thermoplastic resin, an inorganic filler, a curing accelerator, and the like, if necessary.
  • a thermosetting film generally used as a die bonding film, a die attach film, or the like can be used as the thermosetting film 7, for example.
  • the thickness of the thermosetting film 7 is not particularly limited, but is usually 1 to 200 ⁇ m, preferably 3 to 100 ⁇ m, and more preferably 5 to 50 ⁇ m.
  • the support sheet 8 may be any as long as it can support the thermosetting film 7.
  • the resin, metal, and the resin, metal, and the resin, metal, and the non-thermally expandable base material layer (Y2) of the pressure-sensitive adhesive sheet of one aspect of the present invention examples include paper materials.
  • Examples of the method of attaching the thermosetting film 7 to a plurality of semiconductor chip CPs include a method of laminating. Laminating may be performed while heating or may be performed without heating.
  • the heating temperature is preferably "a temperature lower than the expansion start temperature (t)" from the viewpoint of suppressing the expansion of the thermally expandable particles and suppressing the thermal change of the adherend. It is preferably "expansion start temperature (t) -5 ° C.” or less, more preferably “expansion start temperature (t) -10 ° C.” or less, and even more preferably “expansion start temperature (t) -15 ° C.” or less.
  • the first separation step is a step of heating the pressure-sensitive adhesive sheet to a temperature equal to or higher than the expansion start temperature (t) and lower than 125 ° C. to separate the pressure-sensitive adhesive layer (X1) from the support.
  • FIG. 7 is a cross-sectional view illustrating a step of heating the pressure-sensitive adhesive sheet 2b to separate the pressure-sensitive adhesive layer (X1) and the support 3.
  • the heating temperature in the first separation step is equal to or higher than the expansion start temperature (t) of the thermally expandable particles, and is preferably "a temperature higher than the expansion start temperature (t)", more preferably “expansion” in the range of 120 ° C. or lower.
  • the heating temperature in the first separation step is preferably "expansion start temperature (t) + 50 ° C.” or less in the range of less than 125 ° C. from the viewpoint of energy saving and suppressing the thermal change of the adherend during heat peeling.
  • the heating temperature in the first separation step is preferably 120 ° C. or lower, more preferably 115 ° C. or lower, still more preferably 115 ° C. or lower, within the range of the expansion start temperature (t) or higher, from the viewpoint of suppressing the thermal change of the adherend. It is 110 ° C. or lower, more preferably 105 ° C. or lower.
  • the second separation step is a step of separating the pressure-sensitive adhesive layer (X2) from the object to be processed.
  • FIG. 8 shows a cross-sectional view illustrating a step of separating the pressure-sensitive adhesive layer (X2) and the plurality of semiconductor chip CPs.
  • the method for separating the pressure-sensitive adhesive layer (X2) and the plurality of semiconductor chip CPs may be appropriately selected according to the type of the pressure-sensitive adhesive layer (X2). For example, when the pressure-sensitive adhesive layer (X2) is a pressure-sensitive adhesive layer whose adhesive strength is reduced by irradiation with energy rays, the pressure-sensitive adhesive layer (X2) is irradiated with energy rays to reduce the pressure-sensitive adhesive strength. It should be separated.
  • thermosetting film 7 a plurality of semiconductor chip CPs attached on the thermosetting film 7 are obtained.
  • a method for dividing the thermosetting film 7 for example, a method such as laser dicing with laser light, expanding, or fusing can be applied.
  • FIG. 9 shows a semiconductor chip CP with a thermosetting film 7 divided into the same shape as the semiconductor chip CP.
  • the semiconductor chip CP with the thermosetting film 7 further includes an expanding step of widening the distance between the semiconductor chip CPs, a rearrangement step of arranging a plurality of semiconductor chip CPs having a wide distance, and a plurality of semiconductor chip CPs, if necessary. After an appropriate inversion step of inverting the front and back of the above, the thermosetting film 7 is attached (diatached) to the substrate from the side. After that, the semiconductor chip and the substrate can be fixed by thermosetting the thermosetting film.
  • the method for manufacturing a semiconductor device may not include step 3A in the manufacturing method A.
  • the first separation step may be a step of heating the pressure-sensitive adhesive sheet to the expansion start temperature (t) or higher to separate the pressure-sensitive adhesive layer (X1) from the support. ..
  • the method for manufacturing the semiconductor device of the second aspect may be a manufacturing method including the following steps 1B to 3B, the following first separation step, and the following second separation step (hereinafter, also referred to as “manufacturing method B”).
  • Manufacturing method B also referred to as “manufacturing method B”.
  • Step 1B A process of attaching the object to be processed to the pressure-sensitive adhesive layer (X1) of the pressure-sensitive adhesive sheet, and attaching a support to the pressure-sensitive adhesive layer (X2) of the pressure-sensitive adhesive sheet
  • Step 2B The process of attaching the support to the object to be processed.
  • Step 3B Thermosetting is applied to the surface of the processed object to which the treatment has been performed, which is opposite to the adhesive layer (X1).
  • Step of attaching the thermosetting film to be provided First separation step: The pressure-sensitive adhesive sheet is heated to a temperature equal to or higher than the expansion start temperature (t) and lower than 125 ° C. to separate the pressure-sensitive adhesive layer (X1) from the object to be processed.
  • Step Second separation step A step of separating the pressure-sensitive adhesive layer (X2) from the support.
  • Steps 1B to 3B are described by replacing the pressure-sensitive adhesive layer (X1) with the pressure-sensitive adhesive layer (X2) and the pressure-sensitive adhesive layer (X2) with the pressure-sensitive adhesive layer (X1) in the description of steps 1A to 3A. ..
  • the first separation step is a step of heating the pressure-sensitive adhesive sheet to a temperature equal to or higher than the expansion start temperature (t) and lower than 125 ° C. to separate the pressure-sensitive adhesive layer (X1) from the object to be processed.
  • the heating conditions such as the heating temperature of the pressure-sensitive adhesive sheet in the first separation step are the same as those described in the manufacturing method A.
  • the second separation step is a step of separating the pressure-sensitive adhesive layer (X2) from the support.
  • the method for separating the pressure-sensitive adhesive layer (X2) and the support may be appropriately selected according to the type of the pressure-sensitive adhesive layer (X2). For example, when the pressure-sensitive adhesive layer (X2) is a pressure-sensitive adhesive layer whose adhesive strength is reduced by irradiation with energy rays, the pressure-sensitive adhesive layer (X2) is irradiated with energy rays to reduce the pressure-sensitive adhesive strength. It should be separated.
  • the method for manufacturing a semiconductor device may not include step 3B in the manufacturing method B.
  • the first separation step is a step of heating the pressure-sensitive adhesive sheet to the expansion start temperature (t) or higher to separate the pressure-sensitive adhesive layer (X1) from the object to be processed. Good.
  • the method for manufacturing a semiconductor device of the present invention is not limited to the method for manufacturing a semiconductor device according to the first aspect described above, and may be a method for manufacturing a semiconductor device according to another aspect from the first aspect.
  • the method for manufacturing a semiconductor device of another aspect there is a method of separating an object to be processed attached to another sheet from the other sheet by using the adhesive sheet of one aspect of the present invention.
  • a plurality of semiconductor chips that are spaced apart on the expanding tape are attached to the adhesive surface of the expanding tape, but the work of picking up these chips one by one is complicated.
  • the pressure-sensitive adhesive layer (X1) of the pressure-sensitive adhesive sheet according to one aspect of the present invention is attached to the exposed surface of a plurality of semiconductor chips attached on the expanding tape, and then.
  • the plurality of semiconductor chips By peeling the expanding tape from the plurality of semiconductor chips, the plurality of semiconductor chips can be separated from the expanding tape at once.
  • a plurality of semiconductor chips attached on the pressure-sensitive adhesive sheet according to one aspect of the present invention can be obtained.
  • the plurality of semiconductor chips can be easily separated by subsequently heating the pressure-sensitive adhesive sheet to a temperature (t) or higher at which the heat-expandable particles start to expand.
  • t temperature
  • the pressure-sensitive adhesive sheet according to one aspect of the present invention can be heat-peeled at a low temperature, it is excellent in workability and energy saving of heat-peeling work, and even if the object to be processed is easily thermally changed.
  • the plurality of separated semiconductor chips may be transferred to another pressure-sensitive adhesive sheet, or may be subjected to a rearrangement step of aligning the plurality of semiconductor chips after being separated once.
  • [Storage modulus of substrate E'] A dynamic viscoelasticity measuring device (manufactured by TA Instruments, product name) using a heat-expandable base material layer (Y1) and a non-heat-expandable base material layer (Y2) cut into a length of 5 mm and a width of 30 mm as test samples. Using "DMAQ800”), the storage elastic modulus E'at a predetermined temperature was measured under the conditions of a test start temperature of 0 ° C., a test end temperature of 200 ° C., a temperature rise rate of 3 ° C./min, a frequency of 1 Hz, and an amplitude of 20 ⁇ m. ..
  • ⁇ Adhesive resin> -Acrylic copolymer (A1): n-butyl acrylate (BA) / methyl methacrylate (MMA) / acrylic acid (AA) / 2-hydroxyethyl acrylate (HEA) 86/8/1/5 (mass ratio)
  • Solution containing an acrylic copolymer of Mw 600,000 having a structural unit derived from, diluting solvent: ethyl acetate, solid content concentration: 35% by mass -Acrylic copolymer (A3): manufactured by Nippon Synthetic Chemical Industry Co., Ltd., product name "Corponil N-9177", adhesive solution containing acrylic copolymer-Acrylic copolymer (A4): 2- An acrylic copolymer of Mw60 having a structural unit derived from a raw material monomer composed of ethylhexyl acrylate (2EHA) / methyl methacrylate (MMA) / 2-hydroxyethyl acrylate (HEA) 60/30/10 (mass ratio).
  • Containing solution, diluting polymer: ethyl acetate, solid content concentration: 40% by mass -Acrylic copolymer (A5): A composition derived from a raw material monomer composed of n-butyl acrylate (BA) / methyl methacrylate (MMA) / 2-hydroxyethyl acrylate (HEA) 52/20/28 (mass ratio).
  • Acrylic copolymer having a unit was reacted with 2-methacryloyloxyethyl isocyanate (MOI) so that the addition rate with respect to all the hydroxyl groups in the acrylic copolymer was 80% based on the number of moles.
  • -Isocyanate-based cross-linking agent (i): manufactured by Tosoh Corporation, product name "Coronate HX”, solution containing isocyanurate-type modified hexamethylene diisocyanate, solid content concentration: 75% by mass -Isocyanate-based cross-linking agent (ii): manufactured by Tosoh Corporation, product name "Coronate L”, solution containing trimethylolpropane-modified tolylene diisocyanate, solid content concentration: 75% by mass -Energy ray-curable compound: manufactured by Nippon Synthetic Chemical Industry Co., Ltd., product name "Shikou UT-4332", polyfunctional urethane acrylate-photopolymerization initiator (i): bis (2,4,6-trimethylbenzoyl) phenylphos Finoxide / Photopolymerization Initiator (ii): 1-Hydroxycyclohexylphenylketone /
  • Adhesive Layer (X1-A1) 0.74 parts by mass (solid content ratio) of the isocyanate-based cross-linking agent (i) is added to 100 parts by mass of the solid content of the acrylic copolymer (A1).
  • a pressure-sensitive adhesive composition (x-1-A1) having a solid content concentration (active ingredient concentration) of 25% by mass was prepared by blending, diluting with toluene, and stirring uniformly. Then, the prepared pressure-sensitive adhesive composition (x-1-A1) is applied onto the peeling surface of the light release film to form a coating film, and the coating film is dried at 100 ° C. for 60 seconds to have a thickness of 5 ⁇ m. Adhesive layer (X1-A1) was formed.
  • Production Example 1-2 Formation of Adhesive Layer (X1-A2)
  • the acrylic copolymer (A1) is changed to the acrylic copolymer (A2), and the blending amount of the isocyanate-based cross-linking agent (i) is the same.
  • a pressure-sensitive adhesive composition (x-1-A2) having a component concentration of 25% by mass was prepared to form a pressure-sensitive adhesive layer (X1-A2) having a thickness of 5 ⁇ m.
  • Production Example 1-3 Formation of Adhesive Layer (X1-A3)
  • the acrylic copolymer (A1) is changed to the acrylic copolymer (A3), and the blending amount of the isocyanate-based cross-linking agent (i) is the same.
  • a pressure-sensitive adhesive composition (x-1-A3) having a component concentration of 25% by mass was prepared, and a pressure-sensitive adhesive layer (X1-A3) having a thickness of 5 ⁇ m was formed.
  • Production Example 1-4 Formation of Adhesive Layer (X1-A4)
  • the acrylic copolymer (A1) is changed to the acrylic copolymer (A4), and the blending amount of the isocyanate-based cross-linking agent (i) is the same.
  • a pressure-sensitive adhesive composition (x-1-A4) having a component concentration of 25% by mass was prepared, and a pressure-sensitive adhesive layer (X1-A4) having a thickness of 5 ⁇ m was formed.
  • Adhesive Layer An energy ray-curable compound is added to 100 parts by mass of the solid content of the acrylic copolymer (A5), which is an energy ray-curable adhesive resin, by 4.2 parts by mass. 0.74 parts by mass of the isocyanate-based cross-linking agent (ii) and 1 part by mass of the photopolymerization initiator (i) are mixed, diluted with toluene, and uniformly stirred to obtain a solid content concentration (active ingredient concentration) of 30% by mass.
  • the pressure-sensitive adhesive composition (x-2-A5) of the above was prepared.
  • the prepared pressure-sensitive adhesive composition (x-2-A5) is applied onto the peeling surface of the heavy-release film to form a coating film, and the coating film is dried at 100 ° C. for 60 seconds to have a thickness of 20 ⁇ m.
  • Adhesive layer (X2-A5) was formed.
  • Production Example 3 Formation of a base material laminate in which a heat-expandable base material layer (Y1) and a non-heat-expandable base material layer (Y2) are laminated (1)
  • a solvent-free resin composition (y-1a) 2-Hydroxyethyl acrylate is reacted with the terminal isocyanate urethane prepolymer obtained by reacting the ester-type diol with isophorone diisocyanate (IPDI) to obtain a bifunctional acrylic urethane-based oligomer having a mass average molecular weight (Mw) of 5000. Obtained.
  • the heat-expandable particles (i) were blended with the energy ray-curable composition to prepare a solvent-free resin composition (y-1a) containing no solvent.
  • the content of the heat-expandable particles (i) was 20% by mass with respect to the total amount (100% by mass) of the solvent-free resin composition (y-1a).
  • an ultraviolet irradiation device manufactured by Eye Graphics Co., Ltd., product name "ECS-401GX”
  • a high-pressure mercury lamp manufactured by Eye Graphics Co., Ltd., product name "H04-L41”
  • an illuminance of 160 mW / cm 2 The coating film is cured by irradiating with ultraviolet rays under the condition of a light amount of 500 mJ / cm 2 , and a heat-expandable base layer (Y1) having a thickness of 100 ⁇ m is placed on a PET film as a non-heat-expandable base layer (Y2). Formed.
  • the above-mentioned illuminance and light intensity at the time of ultraviolet irradiation are values measured using an illuminance / light intensity meter (manufactured by EIT, product name "UV Power Pack II").
  • the storage elastic modulus E at 23 ° C. of the heat-expandable base layer (Y1) ' was 5.0 ⁇ 10 8 Pa.
  • the Young's modulus of the heat-expandable substrate layer (Y1) at 23 ° C. was 330 MPa, and the Young's modulus of the non-thermally expandable substrate layer (Y2) at 23 ° C. was 2000 MPa.
  • Example 1 The adhesive surface of the pressure-sensitive adhesive layer (X1-A1) formed in Production Example 1-1 and the surface of the heat-expandable base material layer (Y1) of the base material laminate formed in Production Example 3 were bonded together. Next, the adhesive surface of the pressure-sensitive adhesive layer (X2-A5) formed in Production Example 2 and the PET film surface of the base material laminate were bonded together. As a result, an adhesive sheet having the following structure was produced.
  • Example 2 A pressure-sensitive adhesive sheet having the following constitution was produced in the same manner as in Example 1 except that the pressure-sensitive adhesive layer (X1-A2) formed in Production Example 1-2 was used.
  • Comparative Example 1 A pressure-sensitive adhesive sheet having the following constitution was produced in the same manner as in Example 1 except that the pressure-sensitive adhesive layer (X1-A3) formed in Production Example 1-3 was used.
  • Comparative Example 2 A pressure-sensitive adhesive sheet having the following constitution was produced in the same manner as in Example 1 except that the pressure-sensitive adhesive layer (X1-A4) formed in Production Example 1-4 was used.
  • any of the pressure-sensitive adhesive layers (X1-A1, X1-A2, X1-A3, and X1-A4) of the pressure-sensitive adhesive sheets in Examples 1 and 2 and Comparative Examples 1 and 2 are soda lime glass as an adherend. It was confirmed that the board was attached to a level where it would not come off under its own weight.
  • a vacuum laminator manufactured by Nikko Materials Co., Ltd.
  • a test sample was prepared by pressing at 60 ° C. under the condition of 0.2 MPa for 30 seconds under the name “V-130”). Then, the test sample was placed on a hot plate and heated at 100 ° C., which is equal to or higher than the expansion start temperature of the heat-expandable particles, for 5 minutes. The test sample was placed on the hot plate so that the glass plate G2 side was on the side in contact with the hot plate and the adhesive sheet side was on the side not in contact with the hot plate.
  • the peeling state of the glass plate G1 from the adhesive sheet was visually confirmed, and the self-peeling property was evaluated according to the following criteria.
  • the Young's modulus of the pressure-sensitive adhesive layer (X1) at 23 ° C. is 5.0 MPa or less, and the Young's modulus of the non-thermally expandable base material layer (Y2) at 23 ° C. Since the coefficient is higher than the Young's modulus of the pressure-sensitive adhesive layer (X1) at 23 ° C., it can be seen that the self-peeling property is good.
  • the Young's modulus of the pressure-sensitive adhesive layer (X1) at 23 ° C. is larger than 5.0 MPa, it can be seen that the self-peeling property is deteriorated.

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PCT/JP2020/011177 2019-03-15 2020-03-13 粘着シート及び半導体装置の製造方法 WO2020189568A1 (ja)

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