WO2022196752A1 - Procédé de fabrication de dispositif semi-conducteur et appareil de fabrication de dispositif semi-conducteur - Google Patents

Procédé de fabrication de dispositif semi-conducteur et appareil de fabrication de dispositif semi-conducteur Download PDF

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Publication number
WO2022196752A1
WO2022196752A1 PCT/JP2022/012171 JP2022012171W WO2022196752A1 WO 2022196752 A1 WO2022196752 A1 WO 2022196752A1 JP 2022012171 W JP2022012171 W JP 2022012171W WO 2022196752 A1 WO2022196752 A1 WO 2022196752A1
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Prior art keywords
adhesive layer
layer
thermally expandable
sensitive adhesive
pressure
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PCT/JP2022/012171
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English (en)
Japanese (ja)
Inventor
康彦 垣内
智史 川田
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リンテック株式会社
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Publication of WO2022196752A1 publication Critical patent/WO2022196752A1/fr

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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
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/304—Mechanical treatment, e.g. grinding, polishing, cutting
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/50—Assembly of semiconductor devices using processes or apparatus not provided for in a single one of the subgroups H01L21/06 - H01L21/326, e.g. sealing of a cap to a base of a container
    • H01L21/52—Mounting semiconductor bodies in containers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
    • H01L21/683—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping

Definitions

  • the present invention relates to a semiconductor device manufacturing method and a semiconductor device manufacturing apparatus.
  • a semiconductor wafer is processed into semiconductor chips through a grinding process for reducing the thickness by grinding, a singulation process for cutting and separating into individual pieces, and the like.
  • the semiconductor wafer is subjected to a predetermined processing while being temporarily fixed to the temporary fixing sheet.
  • an expanding process is performed to widen the gap between the semiconductor chips, and a re-arrangement of a plurality of semiconductor chips with widened gaps is performed.
  • a reversing process of reversing the front and back of the semiconductor chip, and the like they are mounted on the substrate.
  • DAF die attach film
  • the DAF is attached to one surface of a semiconductor wafer or a plurality of singulated semiconductor chips, and is divided into the same shape as the semiconductor chips at the same time as the semiconductor wafer is singulated or after being attached to the semiconductor chips.
  • the semiconductor chip with the DAF obtained by singulation is attached (die attached) to the substrate from the DAF side, and then the semiconductor chip and the substrate are fixed by thermally curing the DAF. Therefore, the DAF must retain the property of being adhered by pressure or heat until it is attached to the substrate, and a process that enables this is required.
  • Patent Document 1 discloses a method of using a heat-peelable pressure-sensitive adhesive sheet for temporary fixing provided with a heat-expandable pressure-sensitive adhesive layer containing heat-expandable microspheres on at least one side of a base material for cutting electronic components. It is The document describes a method in which a ceramic sheet is temporarily fixed to the adhesive surface of a heat-peelable adhesive sheet, cut into chips, and then heat-treated on a hot plate to separate the adhesive sheet and the chips. It is
  • the present invention has been made in view of the above problems, and is a method for manufacturing a semiconductor device using a heat-peelable pressure-sensitive adhesive sheet, which suppresses thermal change of an adherend due to heating when the pressure-sensitive adhesive sheet is peeled off. It is an object of the present invention to provide a method for manufacturing a semiconductor device and a manufacturing apparatus for a semiconductor device.
  • the present inventors focused on the temperature control of the adherend when peeling the adhesive sheet, found that the above problems could be solved, and completed the present invention.
  • the present invention relates to the following [1] to [16].
  • [1] Having an adhesive layer (X1), a base layer (Y), and an adhesive layer (X2) in this order, the adhesive layer (X1) and the base layer (Y) At least one of them is a thermally expandable layer containing thermally expandable particles, and by expanding the thermally expandable layer, using a double-sided pressure-sensitive adhesive sheet in which irregularities are formed on the surface of the pressure-sensitive adhesive layer (X1), A method of manufacturing a semiconductor device including steps 1 to 3.
  • Step 1 A step of attaching an object to be processed (W) to the adhesive layer (X2) of the double-sided adhesive sheet, and attaching a support (S) to the adhesive layer (X1) of the double-sided adhesive sheet.
  • Step 3 While cooling the processed product (P), the thermally expandable layer is heated to the expansion start temperature (t) of the thermally expandable particles or higher.
  • Step 2-1 A step of subjecting the workpiece (W) to one or more processing treatments selected from grinding and singulation
  • Step 2-2 The workpiece (W) subjected to the processing treatment , the surface (W ⁇ ) opposite to the adhesive layer (X2) is subjected to one or more processes selected from application of a semiconductor adhesive and application of a semiconductor film to obtain a processed product (P)
  • Step [3] The method of manufacturing a semiconductor device according to the above [1] or [2], wherein the semiconductor adhesive is a thermosetting paste, and the semiconductor film is a thermosetting film.
  • the cooling treatment is a treatment for cooling the surface (P ⁇ ) of the processed product (P) opposite to the adhesive layer (X2).
  • a method of manufacturing the described semiconductor device [5] The above [4], wherein the cooling treatment is a treatment in which the cooled heat conductor is brought into contact with the surface (P ⁇ ) of the processed product (P) opposite to the adhesive layer (X2).
  • the heating of the thermally expandable layer in the step 3 is carried out by bringing a heated plate into contact with the surface (S ⁇ ) of the support (S) opposite to the pressure-sensitive adhesive layer (X1). , a method for manufacturing a semiconductor device according to any one of the above [1] to [6].
  • Step 4 A step of curing the pressure-sensitive adhesive layer (X2) by irradiating the pressure-sensitive adhesive layer (X2) with energy rays to separate the pressure-sensitive adhesive layer (X2) and the processed product (P) [ 10]
  • the substrate layer (Y) is a substrate laminate in which a thermally expandable substrate layer (Y1) containing thermally expandable particles and a non-thermally expandable substrate layer (Y2) are laminated. and the double-sided pressure-sensitive adhesive sheet comprises the pressure-sensitive adhesive layer (X1), the thermally expandable base layer (Y1), the non-thermally expandable base layer (Y2), and the pressure-sensitive adhesive layer (X2) , in this order.
  • a method for manufacturing a semiconductor device using a heat-peelable pressure-sensitive adhesive sheet a method for manufacturing a semiconductor device and a semiconductor device capable of suppressing thermal change of an adherend due to heating when the pressure-sensitive adhesive sheet is peeled off. manufacturing equipment can be provided.
  • FIG. 1 is a cross-sectional view showing an example of the configuration of a double-sided pressure-sensitive adhesive sheet used in the production method of the present invention
  • FIG. FIG. 4 is a cross-sectional view showing another example of the configuration of the double-sided pressure-sensitive adhesive sheet used in the production method of the present invention
  • It is a sectional view explaining an example of a process of a manufacturing method of a semiconductor device of the present invention. It is a sectional view explaining an example of a process of a manufacturing method of a semiconductor device of the present invention. It is a sectional view explaining an example of a process of a manufacturing method of a semiconductor device of the present invention. It is a sectional view explaining an example of a process of a manufacturing method of a semiconductor device of the present invention. It is a sectional view explaining an example of a process of a manufacturing method of a semiconductor device of the present invention.
  • the term “active ingredient” refers to the components contained in the target composition, excluding the diluent solvent.
  • Mw mass average molecular weight
  • GPC gel permeation chromatography
  • (meth)acrylic acid indicates both “acrylic acid” and “methacrylic acid”, and the same applies to other similar terms.
  • the lower limit and upper limit values described stepwise for preferred numerical ranges can be independently combined. For example, from the statement “preferably 10 to 90, more preferably 30 to 60", combining “preferred lower limit (10)” and “more preferred upper limit (60)” to “10 to 60” can also
  • the term "energy ray” means an electromagnetic wave or charged particle beam that has energy quanta, and examples thereof include ultraviolet rays, radiation, electron beams, and the like.
  • Ultraviolet rays can be applied 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 light source.
  • the electron beam can be generated by an electron beam accelerator or the like.
  • the term “energy ray polymerizable” means the property of polymerizing upon irradiation with an energy ray.
  • energy ray curability means the property of being cured by irradiation with an energy ray.
  • a "layer” is a "non-thermally expandable layer” or a “thermally expandable layer” is determined as follows.
  • the layer to be judged contains thermally expandable particles, the layer is heat-treated for 3 minutes at the expansion start temperature (t) of the thermally expandable particles. If the volume change rate calculated from the following formula is less than 5%, the layer is determined to be a "non-thermally expandable layer", and if it is 5% or more, the layer is a "thermally expandable layer”. judge 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 ⁇ x 100
  • a layer containing no thermally expandable particles is referred to as a "non-thermally expandable layer”.
  • the "front surface” of a semiconductor wafer and semiconductor chip refers to the surface on which circuits are formed (hereinafter also referred to as “circuit surface”)
  • the "back surface” of the semiconductor wafer and semiconductor chips refers to the surface on which circuits are formed. point to the side that is not
  • the thickness of each layer is the thickness at 23°C and means the value measured by the method described in Examples.
  • the adhesive strength of each layer means the adhesive strength to the mirror surface of the silicon mirror wafer, and in an environment of 23° C. and 50% RH (relative humidity), 180° peeling based on JIS Z0237:2000. means the adhesive force measured at a pulling speed of 300 mm/min according to the Law.
  • the term “heat peeling” refers to the pressure-sensitive adhesive layer (X1 ) to separate the pressure-sensitive adhesive layer (X1) from the support (S).
  • the object to be processed (W) means the object to be processed in step 2 of the manufacturing method of the present invention.
  • the adherend at the time and after separation from the pressure-sensitive adhesive layer (X2) after finishing the processing in step 2 is referred to as a "processed product (P)", and before or after processing in step 2.
  • An adherend that is in the process of being processed to a processed product (P) is referred to as a "processed object (W)".
  • a method for manufacturing a semiconductor device has an adhesive layer (X1), a base layer (Y), and an adhesive layer (X2) in this order, and the adhesive layer (X1 ) and the substrate layer (Y) is a thermally expandable layer containing thermally expandable particles, and by expanding the thermally expandable layer, the surface of the pressure-sensitive adhesive layer (X1) becomes uneven.
  • Step 1 A step of attaching an object to be processed (W) to the adhesive layer (X2) of the double-sided adhesive sheet, and attaching a support (S) to the adhesive layer (X1) of the double-sided adhesive sheet.
  • Step 3 While cooling the processed product (P), the thermally expandable layer is heated to the expansion start temperature (t) of the thermally expandable particles or higher. Heating to separate the adhesive layer (X1) and the support (S)
  • semiconductor device refers to all devices that can function by utilizing semiconductor characteristics.
  • a wafer comprising integrated circuits a thinned wafer comprising integrated circuits, a chip comprising integrated circuits, a thinned chip comprising integrated circuits, electronic components comprising these chips, and electronic equipment comprising such electronic components and the like.
  • the workpiece (W) to be processed by the method for manufacturing a semiconductor device according to one embodiment of the present invention typically includes a semiconductor wafer and a semiconductor chip, and the manufacturing method of the present invention can be applied. is not particularly limited.
  • the processed product (P) is subjected to a cooling process when the double-sided pressure-sensitive adhesive sheet is thermally peeled off. Therefore, the processed product (P) is less likely to be affected by heat applied to the double-sided pressure-sensitive adhesive sheet, and thermal changes in physical properties, shape, and the like are suppressed.
  • the processed product (P) has DAF
  • the progress of curing of DAF is suppressed when the double-sided pressure-sensitive adhesive sheet is peeled off by heating, so DAF retains good adhesive strength for mounting on a substrate.
  • the processed product (P) has an adhesive sheet such as a dicing tape
  • the adhesiveness of the adhesive sheet is suppressed from being changed by heat, and the intended function of the adhesive sheet is sufficiently exhibited. can be done.
  • the double-sided pressure-sensitive adhesive sheet used in the method for manufacturing a semiconductor device of one embodiment of the present invention will be described first, and then each step included in the method for manufacturing a semiconductor device of one embodiment of the present invention will be described in detail.
  • the double-sided pressure-sensitive adhesive sheet used in the method for manufacturing a semiconductor device of one embodiment of the present invention has a pressure-sensitive adhesive layer (X1), a base layer (Y), and a pressure-sensitive adhesive layer (X2) in this order, At least one of the adhesive layer (X1) and the substrate layer (Y) is a thermally expandable layer containing thermally expandable particles, and the adhesive layer (X1) is expanded by expanding the thermally expandable layer.
  • X1 is a double-sided pressure-sensitive adhesive sheet in which unevenness is formed on the surface.
  • the support (S) can be attached to the adhesive layer (X1), and the object to be processed (W) can be attached to the adhesive layer (X2).
  • the vibration and position of the workpiece (W) can be reduced when the workpiece (W) is processed. It is possible to suppress misalignment and damage when the workpiece (W) is fragile, and improve machining accuracy, machining speed, inspection accuracy, and the like.
  • the thermally expandable particles contained in the thermally expandable layer which is at least one of the adhesive layer (X1) and the base layer (Y) are heated at the expansion start temperature (t ) to form irregularities on the adhesive surface of the adhesive layer (X1) by heating to a temperature equal to or higher than the above temperature to form unevenness, and the support (S) attached to the adhesive surface of the adhesive layer (X1) and the adhesive It greatly reduces the contact area with the surface.
  • the adhesiveness between the adhesive surface of the adhesive layer (X1) and the support (S) can be significantly reduced, and the double-sided adhesive sheet and the support (S) can be easily separated.
  • the double-sided pressure-sensitive adhesive sheet of one aspect of the present invention may have the pressure-sensitive adhesive layer (X1), the base layer (Y), and the pressure-sensitive adhesive layer (X2) in this order.
  • X1), the substrate layer (Y), and the pressure-sensitive adhesive layer (X2) alone may be included, or other layers may be included as necessary.
  • one surface of the double-sided pressure-sensitive adhesive sheet of one embodiment of the present invention is the pressure-sensitive adhesive surface of the pressure-sensitive adhesive layer (X1)
  • the other surface of the double-sided pressure-sensitive adhesive sheet of one embodiment of the present invention is the pressure-sensitive adhesive layer (X2). is the surface.
  • the double-sided pressure-sensitive adhesive sheet of one embodiment of the present invention may have 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).
  • the PSA layer (X1) and the base layer (Y) may be a thermally expandable layer containing thermally expandable particles.
  • the substrate layer (Y) is a thermally expandable substrate layer containing thermally expandable particles ( Y1) and a non-thermally expandable substrate layer (Y2) are laminated to form a substrate laminate comprising an adhesive layer (X1), a thermally expandable substrate layer (Y1), and a non-thermally expandable substrate.
  • a double-sided pressure-sensitive adhesive sheet having a layer (Y2) and a pressure-sensitive adhesive layer (X2) in this order is exemplified.
  • the double-sided pressure-sensitive adhesive sheet having such a configuration may be referred to as "the double-sided pressure-sensitive adhesive sheet of the first aspect".
  • the double-sided pressure-sensitive adhesive sheet of one embodiment of the present invention when the pressure-sensitive adhesive layer (X1) is a heat-expandable layer containing heat-expandable particles, the double-sided pressure-sensitive adhesive sheet, which is a heat-expandable layer, A double-sided pressure-sensitive adhesive sheet having (X1), a substrate layer (Y), and a pressure-sensitive adhesive layer (X2) in this order is exemplified.
  • the double-sided pressure-sensitive adhesive sheet having such a configuration may be referred to as "the double-sided pressure-sensitive adhesive sheet of the second aspect”.
  • the double-sided pressure-sensitive adhesive sheet of the first aspect of the present invention includes, for example, a pressure-sensitive adhesive layer (X1), a thermally expandable substrate layer (Y1), and a non-thermally expandable substrate shown in FIG.
  • a double-sided pressure-sensitive adhesive sheet 1a having a layer (Y2) and a pressure-sensitive adhesive layer (X2) in this order is exemplified.
  • the double-sided pressure-sensitive adhesive sheet 1b shown in FIG. 10b may be provided.
  • the double-sided pressure-sensitive adhesive sheet of the second aspect of the present invention includes, for example, a heat-expandable pressure-sensitive adhesive layer (X1), a substrate layer (Y), and a pressure-sensitive adhesive layer shown in FIG. and (X2) in this order. Moreover, like the double-sided pressure-sensitive adhesive sheet 2b shown in FIG. 10b may be provided.
  • double-sided pressure-sensitive adhesive sheet of another embodiment in the double-sided pressure-sensitive adhesive sheet 1a shown in FIG. 1(a) and the double-sided pressure-sensitive adhesive sheet 2a shown in FIG. It may be a double-sided pressure-sensitive adhesive sheet having a structure in which a release material having both sides subjected to a release treatment is laminated on the pressure-sensitive adhesive surface of the sheet and wound into a roll.
  • the double-sided pressure-sensitive adhesive sheet used in one aspect of the present invention may or may not have another layer between the base layer (Y) and the pressure-sensitive adhesive layer (X1). good too.
  • the double-sided pressure-sensitive adhesive sheet used in one aspect of the present invention may have another layer between the base layer (Y) and the pressure-sensitive adhesive layer (X2). It doesn't have to be.
  • the surface of the thermally expandable substrate layer (Y1) opposite to the pressure-sensitive adhesive layer (X1) has a non-thermally expandable It is preferable that the flexible substrate layer (Y2) is directly laminated.
  • a layer capable of suppressing expansion on the surface opposite to the pressure-sensitive adhesive surface of the pressure-sensitive adhesive layer (X1) is directly laminated. More preferably, the material layer (Y) is directly laminated.
  • the expansion start temperature (t) of the thermally expandable particles is preferably less than 125°C, from the viewpoint of suppressing thermal change of the processed product (P) during heat peeling. It is more preferably 120° C. or lower, still more preferably 115° C. or lower, still more preferably 110° C. or lower, and even more preferably 105° C. or lower.
  • the thermally expansible particles expand due to a temperature rise such as when the workpiece (W) is ground. Sometimes I end up Such unintended expansion of the thermally expandable particles leads to a decrease in adhesion between the support (S) and the pressure-sensitive adhesive layer (X1), leading to displacement of the workpiece (W), etc., and is thus suppressed. is desirable.
  • the expansion initiation temperature (t) of the thermally expandable particles is preferably 50° C. or higher, more preferably 55° C. or higher, still more preferably 60° C. or higher. Preferably, it is 70°C or higher.
  • the expansion start temperature (t) of thermally expandable particles 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 encapsulated component that is encapsulated in the outer shell and vaporizes when heated to a predetermined temperature.
  • the thermoplastic resin constituting the outer shell of the microencapsulated foaming agent includes, for example, polyvinyl alcohol, polyvinyl butyral, polymethyl methacrylate, polyacrylonitrile, polyvinylidene chloride, polysulfone, or structural units contained in these thermoplastic resins. Examples thereof include copolymers obtained by polymerizing two or more of the monomers to be formed.
  • Examples of encapsulated components that are encapsulated in the outer shell of the microencapsulated foaming agent include propane, propylene, butene, n-butane, isobutane, isopentane, neopentane, n-pentane, n-hexane, isohexane, n- Low boiling point liquids such as heptane, n-octane, cyclopropane, cyclobutane, and petroleum ether are included. Among these, it suppresses the thermal change of the workpiece (P) when thermally peeling, and suppresses the unintended expansion of the thermally expandable particles due to the temperature rise when grinding the workpiece (W).
  • the expansion start temperature (t) of the thermally expandable particles is 50° C. or more and less than 125° C.
  • propane, isobutane, n-pentane, and cyclopropane are preferable as the encapsulated component.
  • These inclusion components may be used individually by 1 type, and may use 2 or more types together.
  • the expansion start temperature (t) of the thermally expandable particles can be adjusted by appropriately selecting the type of inclusion component.
  • the average particle size of the thermally expandable particles used in one aspect of the present invention before expansion at 23° C. is preferably 3 to 100 ⁇ m, more preferably 4 to 70 ⁇ m, even more preferably 6 to 60 ⁇ m, still more preferably 10 to 10 ⁇ m. 50 ⁇ m.
  • the average particle size of the thermally expandable particles before expansion is the volume-median particle size (D 50 ), and is measured by a laser diffraction particle size distribution analyzer (for example, manufactured by Malvern, product name "Mastersizer 3000").
  • D 50 volume-median particle size
  • a laser diffraction particle size distribution analyzer for example, manufactured by Malvern, product name "Mastersizer 3000"
  • the 90% particle diameter (D 90 ) before expansion at 23° C. of the thermally expandable particles used in one aspect of the present invention 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 diameter (D 90 ) of the thermally expandable particles before expansion is measured using a laser diffraction particle size distribution analyzer (for example, manufactured by Malvern, product name “Mastersizer 3000”). In the particle distribution of the thermally expandable particles before expansion, it means a particle size corresponding to a cumulative volume frequency of 90% calculated from the smallest particle size of the thermally expandable particles before expansion.
  • the maximum volume expansion coefficient when heated to a temperature equal to or higher than the expansion start temperature (t) of the thermally expandable particles used in one aspect of the present invention is preferably 1.5 to 200 times, more preferably 2 to 150 times, and further It is preferably 2.5 to 120 times, and more preferably 3 to 100 times.
  • the content of the thermally expandable particles in the thermally expandable layer is preferably 1% by mass or more, more preferably 3% by mass or more, still more preferably 7% by mass, relative to the total mass (100% by mass) of the thermally expandable layer. It is at least 10% by mass, more preferably at least 10% by mass.
  • the content of the thermally expandable particles in the thermally expandable layer is preferably 25% by mass or less, more preferably 20% by mass or less, and still more preferably, based on the total mass (100% by mass) of the thermally expandable layer. is 16% by mass or less, more preferably 14% by mass or less.
  • the content of the thermally expandable particles is 1% by mass or more, there is a tendency that the peelability at the time of heat peeling is improved. Further, when the content of the thermally expandable particles is 25% by mass or less, the generation of irregularities due to the thermally expandable particles before thermal expansion is suppressed, and good adhesion tends to be obtained.
  • the thickness of the thermally expandable layer before thermal expansion is preferably 10-200 ⁇ m, more preferably 20-150 ⁇ m, even more preferably 25-120 ⁇ m.
  • the thickness of the thermally expandable layer before thermal expansion is 10 ⁇ m or more, it is possible to suppress the formation of irregularities due to the thermally expandable particles before thermal expansion.
  • the thickness of the thermally expandable layer before thermal expansion is 200 ⁇ m or less, the double-sided pressure-sensitive adhesive sheet tends to be easy to handle.
  • the thickness of the entire double-sided pressure-sensitive adhesive sheet of one embodiment of the present invention before thermal expansion is preferably 90 to 300 ⁇ m, more preferably 100 to 250 ⁇ m, still more preferably 130 to 200 ⁇ m.
  • the total thickness of the double-sided pressure-sensitive adhesive sheet is 90 ⁇ m or more, the mechanical strength of the double-sided pressure-sensitive adhesive sheet will be good, and it will be easy to handle.
  • the thickness of the entire double-sided pressure-sensitive adhesive sheet is 300 ⁇ m or less, the handling of the double-sided pressure-sensitive adhesive sheet tends to be easy.
  • the double-sided pressure-sensitive adhesive sheet of the first aspect comprises a pressure-sensitive adhesive layer (X1), a thermally expandable substrate layer (Y1), a non-thermally expandable substrate layer (Y2), and an adhesive layer (X2), It is a double-sided pressure-sensitive adhesive sheet having in this order.
  • the pressure-sensitive adhesive layer (X1) of the double-sided pressure-sensitive adhesive sheet of the first aspect may be either a thermally expandable layer or a non-thermally expandable layer, but is preferably a non-thermally 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%, more Preferably less than 1%, more preferably less than 0.1%, even more preferably less than 0.01%.
  • the pressure-sensitive adhesive layer (X1) preferably does not contain heat-expandable particles, but may contain heat-expandable particles as long as the object of the present invention is not compromised.
  • the content thereof is preferably as small as possible, and preferably less than 3% by mass, more than It is preferably less than 1% by mass, more preferably less than 0.1% by mass, even more preferably less than 0.01% by mass, and even more preferably less than 0.001% by mass.
  • the pressure-sensitive adhesive layer (X1) of the double-sided pressure-sensitive adhesive sheet of the first aspect can be formed from a pressure-sensitive adhesive composition (x-1) containing a pressure-sensitive adhesive resin. Each component contained in the adhesive composition (x-1) is described below.
  • the adhesive resin examples include 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 2,000,000, more preferably 20,000 to 1,500,000, and still more preferably 30,000 to 100, from the viewpoint of improving the adhesive strength of the adhesive layer (X1). Ten thousand.
  • adhesive resins include acrylic resins, urethane resins, rubber resins such as polyisobutylene resins, polyester resins, olefin resins, silicone resins, and polyvinyl ether resins. These adhesive resins may be used alone or in combination of two or more. In addition, when these adhesive resins are copolymers having two or more structural units, the form of the copolymer is not particularly limited, and may be block copolymers, random copolymers, and graft copolymers. Any polymer may be used.
  • the adhesive resin preferably contains an acrylic resin from the viewpoint of exhibiting excellent adhesive strength in the adhesive layer (X1).
  • 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). ⁇ 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, a cyclic structure
  • examples include polymers containing structural units derived from (meth)acrylates having
  • the mass average molecular weight (Mw) of the acrylic resin is preferably 100,000 to 1,500,000, more preferably 200,000 to 1,300,000, still more preferably 350,000 to 1,200,000, and even more preferably 500,000 to 1,100,000. .
  • the acrylic resin used in one embodiment of the present invention includes structural units (a1) derived from alkyl (meth)acrylate (a1′) (hereinafter also referred to as “monomer (a1′)”) and functional group-containing monomers (a2 ') (hereinafter also referred to as “monomer (a2')”).
  • the number of carbon atoms in the alkyl group of the monomer (a1′) is preferably 1 to 24, more preferably 1 to 12, still more preferably 2, from the viewpoint of exhibiting excellent adhesive strength in the pressure-sensitive adhesive layer (X1). ⁇ 10, more preferably 4-8.
  • the alkyl group possessed by the monomer (a1') may be a linear alkyl group or a branched alkyl group.
  • Examples of the monomer (a1′) include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, iso-butyl (meth)acrylate, Acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate, stearyl (meth)acrylate and the like.
  • These monomers (a1') may be used alone or in combination of two or more.
  • Preferred monomers (a1′) are n-butyl acrylate and 2-ethylhexyl acrylate.
  • 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 units (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 functional groups possessed by the monomer (a2′) include hydroxyl groups, carboxyl groups, amino groups, epoxy groups and the like. That is, examples of the monomer (a2′) include hydroxyl group-containing monomers, carboxy group-containing monomers, amino group-containing monomers, epoxy group-containing monomers, and the like. These monomers (a2') may be used alone or in combination of two or more. Among these, as the monomer (a2'), hydroxyl group-containing monomers and carboxy group-containing monomers are preferable, and hydroxyl group-containing monomers are more preferable.
  • hydroxyl group-containing monomers examples include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, ) hydroxyalkyl (meth)acrylates such as acrylate and 4-hydroxybutyl (meth)acrylate; and hydroxyl group-containing compounds such as unsaturated alcohols such as vinyl alcohol and allyl alcohol.
  • Carboxy group-containing monomers include, for example, 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.
  • monocarboxylic acids such as (meth)acrylic acid and crotonic acid
  • 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 units (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 70 to 100% by mass, more preferably 80 to 100% by mass, still more preferably 90 to 100% by mass, still 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; Having a cyclic structure such as benzyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, imide (meth)acrylate, etc.
  • olefins such as ethylene, propylene and isobutylene
  • halogenated olefins such as vinyl chloride and vinylidene chloride
  • diene monomers such as butadiene, isoprene and chloroprene
  • Having a cyclic structure such as benzyl
  • the content of the adhesive resin in the adhesive composition (x-1) is preferably 35 to 100% by mass with respect to the total amount (100% by mass) of the active ingredients in the adhesive composition (x-1), More preferably 50 to 100% by mass, still more preferably 60 to 100% by mass, still more preferably 70 to 99.5% by mass.
  • the cross-linking agent reacts with the adhesive resin having a functional group to cross-link the adhesive resins with each other using the functional group as a cross-linking starting point.
  • cross-linking agents 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 crosslinking agents may be used alone, or two or more thereof may be used in combination.
  • isocyanate-based cross-linking agents are preferable from the viewpoints of increasing cohesive strength and improving adhesive strength, and from the viewpoints of availability, and the like.
  • isocyanate-based cross-linking agents include aromatic polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate and xylylene diisocyanate; Alicyclic polyisocyanates such as methylcyclohexylene diisocyanate, methylenebis(cyclohexyl isocyanate), 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate, hydrogenated xylylene diisocyanate; hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate acyclic aliphatic polyisocyanates such as; polyvalent isocyanate compounds such as; Examples of the isocyanate-based cross-linking agent include trimethylolpropane adduct-type modified products of the polyvalent isocyanate compounds, biuret-type modified products reacted with water, and isocyanurate-type modified products
  • an isocyanurate-type modified product containing an isocyanurate ring, and an isocyanurate of an acyclic aliphatic polyisocyanate it is preferable to use an isocyanurate-type modified product containing an isocyanurate ring, and an isocyanurate of an acyclic aliphatic polyisocyanate. It is more preferable to use a type modified product, and it is even more preferable to 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 possessed by the adhesive resin. More preferably 0.03 to 7 parts by mass, still more preferably 0.05 to 5 parts by mass.
  • the pressure-sensitive adhesive composition (x-1) may further contain a tackifier from the viewpoint of further improving the adhesive strength.
  • tackifier refers to a component that supplementarily improves the adhesive strength of the adhesive resin and has a weight average molecular weight (Mw) of less than 10,000. is distinguished from The weight average molecular weight (Mw) of the tackifier is less than 10,000, preferably 400 to 9,000, more preferably 500 to 8,000, still more preferably 800 to 5,000.
  • tackifiers include rosin-based resins, terpene-based resins, styrene-based resins, pentene produced by thermal decomposition of petroleum naphtha, isoprene, piperine, obtained by copolymerizing C5 fractions such as 1,3-pentadiene. and C9 petroleum resins obtained by copolymerizing C9 fractions such as indene and vinyl toluene produced by thermal decomposition of petroleum naphtha, and hydrogenated resins obtained by hydrogenating these.
  • the softening point of the tackifier is preferably 60 to 170°C, more preferably 65 to 160°C, still more preferably 70 to 150°C.
  • the "softening point" of a tackifier means the value measured based on JISK2531.
  • a single tackifier may be used alone, or two or more different softening points, structures, and the like may be used in combination.
  • the weighted average of the softening points of the tackifiers preferably falls within the above range.
  • the content of the tackifier is preferably 0.01 to 65% by mass, more preferably 0.1 to 50% by mass, relative to the total amount (100% by mass) of the active ingredients of the adhesive composition (x-1). %, more preferably 1 to 40% by mass, and even more preferably 2 to 30% by mass.
  • the pressure-sensitive adhesive composition (x-1) includes, in addition to the above-described additives, additives for pressure-sensitive adhesives that are commonly used in pressure-sensitive adhesives, as long as the effects of the present invention are not impaired. may contain.
  • adhesive additives include antioxidants, softeners (plasticizers), rust inhibitors, pigments, dyes, retarders, reaction accelerators (catalysts), ultraviolet absorbers, and energy rays described later.
  • a curable compound, a photopolymerization initiator, and the like are included.
  • these additives for pressure-sensitive adhesives may be used alone, respectively, or two or more of them may be used in combination.
  • each adhesive additive is independently preferably 0.0001 to 20 parts by mass, more than 100 parts by mass of the adhesive resin. It is preferably 0.001 to 10 parts by mass.
  • the adhesive strength of the adhesive layer (X1) before thermally expanding the thermally expandable substrate layer (Y1) is preferably 0.1 to 12.0 N/25 mm, more preferably 0.5 to 9.0 N/25 mm. , more preferably 1.0 to 8.0 N/25 mm, still more preferably 1.2 to 7.5 N/25 mm. If the adhesive strength of the adhesive layer (X1) before thermally expanding the thermally expandable base material layer (Y1) is 0.1 N/25 mm or more, unintended peeling from the support (S) during temporary fixing can be prevented. It is possible to suppress the displacement of the workpiece (W) and the like more effectively. On the other hand, if the adhesive strength is 12.0 N/25 mm or less, the peelability during heat peeling can be further improved.
  • the adhesive strength of the pressure-sensitive adhesive layer (X1) after thermally expanding the thermally expandable substrate layer (Y1) is preferably 1.5 N/25 mm or less, more preferably 0.05 N/25 mm or less, still more preferably 0 .01 N/25 mm or less, more preferably 0 N/25 mm.
  • the adhesive force of 0 N/25 mm means an adhesive force below the measurable limit in the adhesive force measurement method. It also includes the case where the film is peeled off.
  • the thickness of the pressure-sensitive adhesive layer (X1) of the double-sided pressure-sensitive adhesive sheet of the first aspect allows the expression of good adhesive strength, and the thickness of the pressure-sensitive adhesive layer (X1) when the thermally expandable particles are expanded by heating. From the viewpoint of forming unevenness on the adhesive surface, the thickness is preferably 3 to 10 ⁇ m, more preferably 3 to 8 ⁇ m, and still more preferably 3 to 7 ⁇ m.
  • the thickness of the pressure-sensitive adhesive layer (X1) can be easily formed, and the adhesive surface of the pressure-sensitive adhesive layer (X1) can be satisfactorily uneven. You can make it easier.
  • the thermally expandable substrate layer (Y1) of the double-sided pressure-sensitive adhesive sheet of the first aspect is a thermally expandable layer containing thermally expandable particles in a resin material. It is a layer provided between the substrate layer (Y2).
  • the thermally expandable substrate layer (Y1) is preferably a non-adhesive substrate.
  • the probe tack value on the surface of the thermally expandable substrate layer (Y1) is usually less than 50 mN/5 mm ⁇ , preferably less than 30 mN/5 mm ⁇ , more preferably less than 10 mN/5 mm ⁇ , still more preferably less than 5 mN/5 mm ⁇ .
  • the probe tack value on the surface of the substrate means the value measured by the following method. ⁇ Probe tack value> After cutting the base material to be measured into a square with a side of 10 mm, a test sample was left to stand in an environment of 23 ° C. and 50% RH (relative humidity) for 24 hours.
  • the probe tack value on the surface of the test sample is measured in accordance with JIS Z0237: 1991. be able to. Specifically, a stainless steel probe with a diameter of 5 mm is brought into contact with the surface of the test sample for 1 second with a contact load of 0.98 N/cm 2 , and then the probe is moved at a speed of 10 mm/second to the test sample. The force required to remove it from the surface can be measured and the resulting value taken as the probe tack value for that test sample.
  • a tacking tester product name “NTS-4800” manufactured by Nippon Tokushu Sokki Co., Ltd.
  • the surface of the thermally expandable substrate layer (Y1) is subjected to an oxidation method, a roughening method, or the like.
  • a treatment, an easy-adhesion treatment, or a primer treatment may be applied.
  • oxidation methods include corona discharge treatment, plasma discharge treatment, chromic acid treatment (wet), hot air treatment, ozone, and ultraviolet irradiation treatment.
  • roughening methods include sandblasting, solvent treatment, and the like. are mentioned.
  • the thermally expandable substrate layer (Y1) is preferably formed from a resin composition (y-1) containing a resin and thermally expandable particles. Preferred embodiments of the resin composition (y-1) are described below. Preferred aspects of the thermally expandable particles are as described above.
  • the resin contained in the resin composition (y-1) may be a non-adhesive resin or a tacky resin. That is, even if the resin contained in the resin composition (y-1) is an adhesive resin, in the process of forming the thermally expandable base layer (Y1) from the resin composition (y-1), the adhesive It is sufficient that the resin undergoes a polymerization reaction with the polymerizable compound, the resulting resin becomes a non-tacky resin, and the thermally expandable substrate layer (Y1) containing the resin becomes non-tacky.
  • the mass average molecular weight (Mw) of the resin contained in the resin composition (y-1) is preferably 1,000 to 1,000,000, more preferably 1,000 to 700,000, and still more preferably 1,000 to 50. Ten thousand. Further, when the resin is a copolymer having two or more structural units, the form of the copolymer is not particularly limited, and may be a block copolymer, a random copolymer, or a graft copolymer. 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 95% by mass, relative to the total amount (100% by mass) of the active ingredients of the resin composition (y-1) 90% by mass, more preferably 70 to 85% by mass.
  • the resin contained in the resin composition (y-1) from the viewpoint of facilitating the formation of unevenness on the adhesive surface of the pressure-sensitive adhesive layer (X1) and from the viewpoint of improving the sheet shape retention after thermal expansion, It preferably contains one or more selected from the group consisting of acrylic urethane resins and olefin resins. That is, the thermally expandable base layer (Y1) preferably contains one or more selected from the group consisting of acrylic urethane resins and olefin resins. Moreover, as the acrylic urethane-based resin, the following resin (U1) is preferable.
  • An acrylic urethane resin (U1) obtained by polymerizing a urethane prepolymer (UP) and a vinyl compound containing a (meth)acrylic acid ester.
  • prepolymer means a compound obtained by polymerizing a monomer and capable of forming a polymer by further polymerization.
  • urethane prepolymer (UP1) examples include reaction products of polyols and polyvalent isocyanates.
  • the urethane prepolymer (UP) is obtained by subjecting the urethane prepolymer (UP) to a chain extension reaction using a chain extension agent.
  • polyols used as raw materials for urethane prepolymers include alkylene-type polyols, ether-type polyols, ester-type polyols, esteramide-type polyols, ester/ether-type polyols, and carbonate-type polyols. These polyols may be used alone or in combination of two or more.
  • the polyol used in one aspect of the present invention is preferably a diol, more preferably an ester-type diol, an alkylene-type diol or a carbonate-type diol, and still more preferably an ester-type diol or a carbonate-type diol.
  • ester diols include alkanediols such as 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol and 1,6-hexanediol; ethylene glycol, propylene glycol, 1 or 2 or more selected from diols such as alkylene glycols such as diethylene glycol and dipropylene glycol; ,4'-dicarboxylic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, het acid, maleic acid, fumaric acid, itaconic acid, cyclohexane-1,3-dicarboxylic acid, cyclohexane-1,4-dicarboxylic acid, hexa Condensation products of one or more selected from dicarboxylic acids such as hydrophthalic acid, hexahydroisophthalic acid, hexahydro
  • alkylene type diols examples include alkanediols such as 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol and 1,6-hexanediol; ethylene glycol, propylene glycol, 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;
  • carbonate-type diols examples 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.
  • Aromatic polyisocyanates, aliphatic polyisocyanates, alicyclic polyisocyanates, and the like are examples of polyvalent isocyanates that are raw materials for urethane prepolymers (UP).
  • 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 trimethylolpropane adduct-type modified products, biuret-type modified products reacted with water, and isocyanurate-type modified products containing an isocyanurate ring.
  • diisocyanates are preferable as the polyvalent isocyanate used in one embodiment of the present invention, and 4,4′-diphenylmethane diisocyanate (MDI), 2,4-tolylene diisocyanate (2,4-TDI), 2,6 At least one selected from -tolylene diisocyanate (2,6-TDI), hexamethylene diisocyanate (HMDI), and alicyclic diisocyanate is more preferred.
  • MDI 4,4′-diphenylmethane diisocyanate
  • 2,4-TDI 2,4-tolylene diisocyanate
  • 2,6 At least one selected from -tolylene diisocyanate (2,6-TDI), hexamethylene diisocyanate (HMDI), and alicyclic diisocyanate is more preferred.
  • Alicyclic diisocyanates include, for example, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate, IPDI), 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane Examples include diisocyanate, methyl-2,4-cyclohexanediisocyanate, methyl-2,6-cyclohexanediisocyanate, and isophorone diisocyanate (IPDI) is preferred.
  • IPDI isophorone diisocyanate
  • the urethane prepolymer (UP) that forms 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.
  • Hydroxyalkyl (meth)acrylates include, for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxy Butyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate and the like can be mentioned.
  • At least (meth)acrylic acid ester is included as the vinyl compound that becomes the side chain of the acrylic urethane resin (U1).
  • the (meth)acrylic acid ester one or more selected from alkyl (meth)acrylates and hydroxyalkyl (meth)acrylates is preferable, and it is more preferable to use alkyl (meth)acrylates and hydroxyalkyl (meth)acrylates together.
  • the ratio of hydroxyalkyl (meth)acrylate to 100 parts by mass of alkyl (meth)acrylate is preferably 0.1 to 100 parts by mass, more 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 number of carbon atoms in the alkyl group of the alkyl (meth)acrylate is preferably 1-24, more preferably 1-12, even more preferably 1-8, and even more preferably 1-3.
  • hydroxyalkyl (meth)acrylates include the same hydroxyalkyl (meth)acrylates used for introducing ethylenically unsaturated groups to both ends of the linear urethane prepolymer described above.
  • vinyl compounds other than (meth)acrylic esters 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. , (meth)acrylonitrile, N-vinylpyrrolidone, (meth)acrylic acid, maleic acid, fumaric acid, itaconic acid, meth (acrylamide) and other polar group-containing monomers; These may be used individually by 1 type, and may use 2 or more types together.
  • the content of the (meth)acrylic acid ester in the vinyl compound is preferably 40 to 100% by mass, more preferably 65 to 100% by mass, and still more preferably 80 to 100% by mass, more preferably 90 to 100% by mass.
  • the total content of alkyl (meth)acrylate and hydroxyalkyl (meth)acrylate in the vinyl compound is preferably 40 to 100% by mass, more preferably 65 to 100% by mass, based on the total amount (100% by mass) of the vinyl compound. 100% by mass, more preferably 80 to 100% by mass, even more preferably 90 to 100% by mass.
  • the acrylic urethane resin (U1) used in one aspect of the present invention is obtained by mixing a urethane prepolymer (UP) and a vinyl compound containing a (meth)acrylic acid ester and polymerizing the two. In the polymerization, it is preferable to further add a radical initiator.
  • the content ratio of the structural unit (u11) derived from the urethane prepolymer (UP) and the structural unit (u12) derived from the vinyl compound [(u11 )/(u12)] is preferably 10/90 to 80/20, more preferably 20/80 to 70/30, still more preferably 30/70 to 60/40, still more preferably 35 /65 to 55/45.
  • 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.
  • ⁇ -olefins having 2 to 8 carbon atoms are preferable, and specific examples include ethylene, propylene, butylene, isobutylene, 1-hexene, and the like. Among these, ethylene and propylene are preferred.
  • olefin resins include, for example, ultra-low density polyethylene (VLDPE, density: 880 kg/m 3 or more and less than 910 kg/m 3 ), low density polyethylene (LDPE, density: 910 kg/m 3 or more and less than 915 kg/m 3 ), medium density polyethylene (MDPE, density: 915 kg/m 3 or more and less than 942 kg/m 3 ), high density polyethylene (HDPE, density: 942 kg/m 3 or more), polyethylene resin such as linear low density polyethylene; polypropylene resin (PP); polybutene resin (PB); ethylene-propylene copolymer; olefin elastomer (TPO); poly (4-methyl-1-pentene) (PMP); ethylene-vinyl acetate copolymer (EVA); -vinyl alcohol copolymer (EVOH); olefinic terpolymers such as ethylene-propylene-(5-ethylidene-2-norbornene);
  • the olefin-based resin may be a modified olefin-based resin further subjected to one or more modifications selected from acid modification, hydroxyl modification, and acrylic modification.
  • the acid-modified olefin resin obtained by subjecting an olefin resin to acid modification is a modified polymer obtained by graft-polymerizing an unsaturated carboxylic acid or its anhydride to the above-described unmodified olefin resin.
  • unsaturated carboxylic acids or anhydrides thereof include maleic acid, fumaric acid, itaconic acid, citraconic acid, glutaconic acid, tetrahydrophthalic acid, aconitic acid, (meth)acrylic acid, maleic anhydride, and itaconic anhydride.
  • unsaturated carboxylic acid or its anhydride may be used individually by 1 type, and may use 2 or more types together.
  • the acrylic-modified olefin-based resin obtained by subjecting an olefin-based resin to acrylic modification includes modification obtained by graft-polymerizing an alkyl (meth)acrylate as a side chain to the above-described unmodified olefin-based resin that is the main chain. polymers.
  • the number of carbon atoms in the alkyl group of the alkyl (meth)acrylate is preferably 1-20, more preferably 1-16, and still more preferably 1-12.
  • Examples of the above alkyl (meth)acrylates include the same compounds as the above-described compounds that can be selected as the monomer (a1′).
  • the hydroxyl group-modified olefin resin obtained by modifying the olefin resin with hydroxyl groups includes a modified polymer obtained by graft polymerizing a hydroxyl group-containing compound to the above-mentioned unmodified olefin resin which is the main chain.
  • Examples of the hydroxyl group-containing compound include those similar to the hydroxyl group-containing compound described above.
  • the resin composition (y-1) may contain a resin other than the acrylic urethane-based resin and the olefin-based resin within a range that does not impair the effects of the present invention.
  • resins examples include vinyl resins such as polyvinyl chloride, polyvinylidene chloride and polyvinyl alcohol; polyester resins such as polyethylene terephthalate, polybutylene terephthalate and polyethylene naphthalate; polystyrene; acrylonitrile-butadiene-styrene copolymer; Coalescence; cellulose triacetate; polycarbonate; polyurethane not applicable to acrylic urethane resins; polysulfone; polyetheretherketone; polyethersulfone; polyphenylene sulfide; Fluorinated resins and the like are included.
  • vinyl resins such as polyvinyl chloride, polyvinylidene chloride and polyvinyl alcohol
  • polyester resins such as polyethylene terephthalate, polybutylene terephthalate and polyethylene naphthalate
  • polystyrene acrylonitrile-butadiene-styrene copolymer
  • Coalescence
  • the acrylic urethane resin in the resin composition (y-1) and the content of resins other than olefinic resins is preferably as small as possible.
  • 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 resin contained in the resin composition (y-1). Less than 10 parts by weight, more preferably less than 5 parts by weight, and even more preferably less than 1 part by weight.
  • the resin composition (y-1) may contain a base material additive within a range that does not impair the effects of the present invention.
  • base material additives include ultraviolet absorbers, light stabilizers, antioxidants, antistatic agents, slip agents, antiblocking agents, and colorants. These base material additives may be used alone, or two or more of them may be used in combination.
  • the content of each base material additive is preferably 0.0001 to 20 parts by mass, more preferably 0.0001 to 20 parts by mass, based on 100 parts by mass of the resin. is 0.001 to 10 parts 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 and a solvent-free resin composition (y-1a) containing no solvent. In the solvent-free resin composition (y-1a), no solvent is blended, but the energy ray-polymerizable monomer contributes to improving the plasticity of the oligomer.
  • Mw mass average molecular weight
  • the weight average molecular weight (Mw) of the oligomer contained in the solventless resin composition (y-1a) is 50,000 or less, preferably 1,000 to 50,000, more preferably 2,000 to 40,000, more preferably 3,000 to 35,000, even more preferably 4,000 to 30,000.
  • the oligomer among the resins contained in the resin composition (y-1) described above, those having an ethylenically unsaturated group having a mass average molecular weight of 50,000 or less may be used. (UP) is preferable, and a linear urethane prepolymer having ethylenically unsaturated groups at both ends is more preferable. A modified olefinic resin having an ethylenically unsaturated group can also be used as the oligomer.
  • 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 mass%) of the solvent-free resin composition (y-1a), It is preferably 50 to 99% by mass, more preferably 60 to 95% by mass, even more preferably 65 to 90% by mass, still more preferably 70 to 85% by mass.
  • Energy beam-polymerizable monomers include, for example, isobornyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyloxy (meth)acrylate, cyclohexyl (meth)acrylate, adamantane ( Alicyclic polymerizable compounds such as meth) acrylate and tricyclodecane acrylate; Aromatic polymerizable compounds such as phenylhydroxypropyl acrylate, benzyl acrylate, and phenol ethylene oxide-modified acrylate; Examples include heterocyclic polymerizable compounds such as vinylpyrrolidone and N-vinylcaprolactam. Among these, isobornyl (meth)acrylate and phenylhydroxypropyl acrylate are preferred. 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 and the energy ray-polymerizable monomer in the solvent-free resin composition (y-1a) is preferably from 20/80 by mass. 90/10, more preferably 30/70 to 85/15, still more preferably 35/65 to 80/20.
  • the solvent-free resin composition (y-1a) preferably further contains a photopolymerization initiator.
  • a photopolymerization initiator By containing a photopolymerization initiator, the curing reaction can be sufficiently advanced even by irradiation with relatively low-energy energy rays.
  • Photopolymerization initiators include, for example, 1-hydroxycyclohexylphenyl ketone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzylphenyl sulfide, tetramethylthiuram monosulfide, azobisisobutyronitrile, dibenzyl , diacetyl, ⁇ -chloroanthraquinone, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and the like.
  • One of these photopolymerization initiators may be used alone, or two or more thereof may be used in combination.
  • the 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 preferably 0.01 to 5 parts by mass, 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 thermally expandable substrate layer (Y1) before thermal expansion is preferably 10 to 200 ⁇ m, more preferably 20 to 150 ⁇ m, still more preferably 25 to 120 ⁇ m.
  • the thickness of the thermally expandable base layer (Y1) before thermal expansion is 10 ⁇ m or more, it is possible to suppress the formation of unevenness due to the thermally expandable particles before thermal expansion, and the pressure-sensitive adhesive layer (X1). The adhesive strength of can be improved.
  • the thickness of the thermally expandable substrate layer (Y1) before thermal expansion is 200 ⁇ m or less, the double-sided PSA sheet tends to be easy to handle.
  • Non-thermally expandable base layer (Y2) ⁇ Non-thermally expandable base layer (Y2)>
  • the non-thermally expandable substrate layer (Y2) of the double-sided pressure-sensitive adhesive sheet of the first aspect is provided on the surface of the thermally expandable substrate layer (Y1) opposite to the surface on which the pressure-sensitive adhesive layer (X1) is laminated. .
  • the non-thermally expandable base material layer (Y2) is preferably a non-adhesive base material.
  • the probe tack value on the surface of the non-thermally expandable base material layer (Y2) is usually less than 50 mN/5 mm ⁇ , preferably less than 30 mN/5 mm ⁇ , more preferably less than 10 mN/5 mm ⁇ , still more preferably less than 5 mN/5 mm ⁇ . be.
  • Non-thermally expandable base layer (Y2) includes, for example, resins, metals, and paper materials, which can be appropriately selected according to the application of the double-sided pressure-sensitive adhesive sheet.
  • resins 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; polyester resins such as butylene terephthalate and polyethylene naphthalate; polystyrene; acrylonitrile-butadiene-styrene copolymer; cellulose triacetate; polycarbonate; polyether sulfone; polyphenylene sulfide; polyimide-based resins such as polyetherimide and polyimide; polyamide-based resins; acrylic resins; Examples of metals include aluminum, tin, chromium, and titanium.
  • the paper material examples include thin paper, medium quality paper, fine paper, impregnated paper, coated paper, art paper, parchment paper, and glassine paper.
  • polyester resins such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate are preferred.
  • the non-thermally expandable base layer (Y2) using two or more forming materials in combination includes a paper material laminated with a thermoplastic resin such as polyethylene, a resin film or sheet containing a resin, and a metal film formed on the surface of the sheet. and the like.
  • a method for forming the metal layer for example, the above metal is deposited by a PVD method such as vacuum deposition, sputtering, or ion plating, or a metal foil made of the above metal is attached using a general adhesive. and the like.
  • the non-thermally expandable group may also be subjected to a surface treatment such as an oxidation method or roughening method, an easy-adhesion treatment, or a primer treatment in the same manner as the thermally expandable base layer (Y1) described above. .
  • non-thermally expandable base material layer (Y2) contains a resin
  • it may contain the above base material additives that can also be contained in the resin composition (y-1) together with the resin.
  • the non-thermally expandable base layer (Y2) is a non-thermally expandable layer determined based on the method described above. Therefore, the volume change rate (%) of the non-thermally expandable base layer (Y2) calculated from the above formula is less than 5%, preferably less than 2%, more preferably less than 1%, and further Preferably less than 0.1%, even more preferably less than 0.01%.
  • the non-thermally expandable base layer (Y2) may contain thermally expandable particles as long as the volume change rate is within the above range.
  • the content of the thermally expandable particles in the non-thermally expandable base layer (Y2) is preferably as small as possible.
  • a specific content of the thermally expandable particles is usually less than 3% by mass, preferably less than 1% by mass, more preferably less than the total mass (100% by mass) of the non-thermally expandable base material layer (Y2). is less than 0.1 wt%, more preferably less than 0.01 wt%, even more preferably less than 0.001 wt%. Even more preferably, it does not contain heat-expandable particles.
  • the storage 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 to 4.5 ⁇ 10 9 Pa, more preferably 1.0 ⁇ 10 9 to 4.0 ⁇ 10 9 Pa.
  • the storage elastic modulus E′(23) of the non-thermally expandable base layer (Y2) is 5.0 ⁇ 10 7 Pa or more, the deformation resistance of the double-sided PSA sheet can be easily improved.
  • the storage elastic modulus E′(23) of the non-thermally expandable base layer (Y2) is 5.0 ⁇ 10 9 Pa or less, the handleability of the double-sided PSA sheet can be easily improved.
  • the storage elastic modulus E'(23) of the non-thermally expandable base layer (Y2) means a value measured by the method described in Examples.
  • the thickness of the non-thermally expandable substrate layer (Y2) is preferably 5-500 ⁇ m, more preferably 15-300 ⁇ m, and still more preferably 20-200 ⁇ m. If the thickness of the non-thermally expandable base layer (Y2) is 5 ⁇ m or more, the deformation resistance of the double-sided PSA sheet can be easily improved. On the other hand, if the thickness of the non-thermally expandable base material layer (Y2) is 500 ⁇ m or less, it becomes easier to improve the handleability of the double-sided pressure-sensitive adhesive sheet.
  • the pressure-sensitive adhesive layer (X2) of the double-sided pressure-sensitive adhesive sheet of the first aspect is provided on the surface of the non-thermally expandable substrate layer (Y2) opposite to the lamination surface of the thermally expandable substrate layer (Y1). layer.
  • the pressure-sensitive adhesive layer (X2) is preferably an energy ray-curable pressure-sensitive adhesive layer that is cured by irradiation with an energy ray to reduce the adhesive strength, and more preferably is cured by irradiation with an ultraviolet ray to reduce the adhesive strength. is a pressure-sensitive adhesive layer in which the
  • the adhesive layer (X2) is preferably a non-thermally expandable layer.
  • the volume change rate (%) of the pressure-sensitive adhesive layer (X2) calculated from the above formula is less than 5%, preferably less than 2%, more Preferably less than 1%, more preferably less than 0.1%, 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 as long as the object of the present invention is not compromised.
  • the content is preferably as small as possible, and preferably less than 3% by mass, more than It is preferably less than 1% by mass, more preferably less than 0.1% by mass, even more preferably less than 0.01% by mass, and even more preferably less than 0.001% by mass.
  • the adhesive layer (X2) is preferably formed from an adhesive composition (x-2) containing an adhesive resin. Each component contained in the adhesive composition (x-2) is described below.
  • the adhesive composition (x-2) contains an adhesive resin, and if necessary, a cross-linking agent, a tackifier, a polymerizable compound, a polymerization initiator, a general adhesive other than the above components It may contain additives for pressure-sensitive adhesives and the like used in agents.
  • the tacky resin As the tacky resin, a polymer having tackiness by itself and having a mass average molecular weight (Mw) of 10,000 or more may be used.
  • the mass average molecular weight (Mw) of the adhesive resin is preferably 10,000 to 2,000,000, more preferably 20,000 to 1,500,000, and still more preferably 30,000, from the viewpoint of further improving the adhesive strength of the adhesive layer (X2). ⁇ 1 million.
  • the adhesive resin examples include those similar to the adhesive resin contained in the adhesive composition (x-1). These adhesive resins may be used alone or in combination of two or more. In addition, when these adhesive resins are copolymers having two or more structural units, the form of the copolymer is any of a block copolymer, a random copolymer, and a graft copolymer. There may be.
  • the pressure-sensitive adhesive resin contained in the pressure-sensitive adhesive composition (x-2) is a pressure-sensitive adhesive layer in which the pressure-sensitive adhesive layer (X2) obtained is cured by energy ray irradiation to reduce the pressure-sensitive adhesive strength.
  • a tacky resin having an energy ray-polymerizable functional group is preferred.
  • the energy ray polymerizable functional group include those having a carbon-carbon double bond such as (meth)acryloyl group, vinyl group and allyl group.
  • the adhesive resin preferably contains an acrylic resin from the viewpoint of exhibiting excellent adhesive strength.
  • the content of the acrylic resin in the adhesive composition (x-2) is preferably 30 to 100 mass %, more preferably 50 to 100 mass %, still more preferably 70 to 100 mass %, still more preferably 85 to 100 mass %.
  • the content of the adhesive resin in the adhesive composition (x-2) is preferably 35 to 100% by mass with respect to the total amount (100% by mass) of the active ingredients in the adhesive composition (x-2), More preferably 50 to 100% by mass, still more preferably 60 to 98% by mass, still more preferably 70 to 95% by mass.
  • the pressure-sensitive adhesive composition (x-2) may contain, together with the pressure-sensitive adhesive resin, a monomer or oligomer capable of being polymerized and cured by energy ray irradiation as an energy ray-curable compound.
  • Examples of such energy ray-curable compounds include trimethylolpropane tri(meth)acrylate, pentaerythritol (meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 1,4- Polyvalent (meth)acrylate monomers such as butylene glycol di(meth)acrylate, 1,6-hexanediol (meth)acrylate; polyfunctional urethane (meth)acrylate, polyfunctional polyester (meth)acrylate, polyfunctional polyether ( Examples include oligomers such as meth)acrylates and polyfunctional epoxy (meth)acrylates.
  • polyfunctional urethane (meth)acrylate oligomers are preferable because they have relatively high molecular weights and are less likely to lower the elastic modulus of the pressure-sensitive adhesive layer (X2).
  • the molecular weight of the energy ray-curable compound is preferably 100 to 12,000, more preferably 200 to 10,000, still more preferably 400 to 8,000, even more preferably. is between 600 and 6,000.
  • the adhesive composition (x-2) preferably further contains a photopolymerization initiator.
  • a photopolymerization initiator By containing a photopolymerization initiator, the polymerization of the energy ray-polymerizable component can proceed more efficiently.
  • the photopolymerization initiator include those exemplified in the description of the solvent-free resin composition (y-1a). Among these, 1-hydroxycyclohexylphenyl ketone is preferred.
  • the content of the photopolymerization initiator is preferably 0.01 to 10 parts by mass, more preferably 0.03 to 5 parts by mass, with respect to 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 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 the adhesive resin having a functional group to cross-link the adhesive resins with each other using 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 the same or equivalent cross-linking agents that may be contained in the pressure-sensitive adhesive composition (x-1).
  • An isocyanate-based cross-linking agent is preferred from the viewpoints of increasing cohesive strength and improving adhesive strength, as well as from the viewpoint of availability.
  • the content of the cross-linking agent is appropriately adjusted according to the number of functional groups possessed by the adhesive resin. More preferably 0.03 to 7 parts by mass, still more preferably 0.05 to 5 parts by mass.
  • the pressure-sensitive adhesive composition (x-2) may further contain a tackifier from the viewpoint of further improving the adhesive strength.
  • a tackifier from the viewpoint of further improving the adhesive strength.
  • the same tackifier that may be contained in the pressure-sensitive adhesive composition (x-1) may be used. can.
  • Adhesive additive examples of the adhesive additive include the same additives as the adhesive additive that may be contained in the adhesive composition (x-1).
  • the adhesive composition (x-2) can be produced by mixing an adhesive resin, optionally used cross-linking agent, tackifier, adhesive additive, and the like.
  • the adhesive strength of the pressure-sensitive adhesive layer (X2) before energy beam irradiation is preferably 1.1 to 30.0 N/25 mm, more preferably 3.0 to 25.0 N/25 mm, still more preferably 5.0 to 20.0 N/25 mm. 0 N/25 mm. If the adhesive strength of the adhesive layer (X2) before energy beam irradiation is 1.1 N/25 mm or more, unintended peeling of the workpiece (W) is suppressed, and positional displacement of the workpiece (W) is prevented. It can be suppressed more effectively. On the other hand, when the adhesive strength is 30.0 N/25 mm or less, the peelability after energy ray irradiation can be further improved.
  • the adhesive strength of the adhesive layer (X2) after energy beam irradiation is preferably 1.0 N/25 mm or less, more preferably 0.9 N/25 mm or less, still more preferably 0.8 N/25 mm or less, and even more preferably 0 .7 N/25 mm or less.
  • the lower limit of the pressure-sensitive adhesive layer (X2) after irradiation with energy rays is not particularly limited, and may be 0 N/25 mm or more. If the adhesive strength of the pressure-sensitive adhesive layer (X2) after energy ray irradiation is 1.0 N/25 mm or less, the peelability from the processed product (P) will be excellent.
  • the thickness of the pressure-sensitive adhesive layer (X2) of the double-sided pressure-sensitive adhesive sheet of the first aspect is preferably 5 to 150 ⁇ m, more preferably 8 to 100 ⁇ m, even more preferably 12 to 70 ⁇ m, still more preferably 15 to 50 ⁇ m. . If the thickness of the pressure-sensitive adhesive layer (X2) is 5 ⁇ m or more, it becomes easy to obtain sufficient adhesive strength, and there is a tendency that unintended peeling of the workpiece (W) during temporary fixing, positional displacement, etc. can be suppressed. . On the other hand, when the thickness of the pressure-sensitive adhesive layer (X2) is 150 ⁇ m or less, the double-sided pressure-sensitive adhesive sheet tends to be easy to handle.
  • the pressure-sensitive adhesive layer (X1), the thermally expandable base layer (Y1), the non-thermally expandable base layer (Y2), and the pressure-sensitive adhesive layer (X2) before thermal expansion is preferably 90 to 300 ⁇ m, more preferably 100 to 250 ⁇ m, still more preferably 130 to 200 ⁇ m.
  • the double-sided pressure-sensitive adhesive sheet has good mechanical strength and the like and is easy to handle. Further, when the total thickness is 300 ⁇ m or less, the double-sided pressure-sensitive adhesive sheet tends to be easy to handle.
  • the method for producing the double-sided pressure-sensitive adhesive sheet of the first aspect is not particularly limited, and includes, for example, a method for producing a double-sided pressure-sensitive adhesive sheet having the following steps (1a) to (5a).
  • Step (1a) A step of applying an adhesive composition (x-1) onto the release-treated surface of a release material to form an adhesive layer (X1).
  • 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.
  • coating methods include spin coating, spray coating, bar coating, knife coating, roll coating, blade coating, die coating, and gravure coating.
  • the step of drying the coating film formed from the resin composition (y-1), the adhesive composition (x-1), and the adhesive composition (x-2) causes expansion of the thermally expandable particles.
  • the drying temperature is preferably lower than the expansion start temperature (t) of the thermally expandable particles.
  • the double-sided pressure-sensitive adhesive sheet of the second aspect is a double-sided pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer (X1) which is a thermally expandable layer, a substrate layer (Y), and a pressure-sensitive adhesive layer (X2) in this order. .
  • the description of the base layer (Y) of the double-sided pressure-sensitive adhesive sheet of the second aspect is the same as the description of the non-thermally expandable base layer (Y2) of the double-sided pressure-sensitive adhesive sheet of the first aspect.
  • the description of the pressure-sensitive adhesive layer (X2) of the double-sided pressure-sensitive adhesive sheet of aspect 1 is the same as the description of the pressure-sensitive adhesive layer (X2) of the double-sided pressure-sensitive adhesive sheet of aspect 1.
  • the pressure-sensitive adhesive layer (X1) of the second aspect is a thermally expandable layer containing thermally expandable particles, and preferably contains an energy ray-polymerizable component polymer and thermally expandable particles.
  • the polymer comprises, as the energy ray-polymerizable components, a monomer (b1) having an energy ray-polymerizable functional group (hereinafter also referred to as "(b1) component") and a prepolymer (b2) having an energy ray-polymerizable functional group.
  • polymerizable composition (x-1′) (hereinafter also referred to as “(b2) component”) (hereinafter also referred to as “polymerizable composition (x-1′)”) is irradiated with energy rays.
  • prepolymer means a compound obtained by polymerizing a monomer and capable of forming a polymer by further polymerization.
  • the energy ray-polymerizable component contained in the polymerizable composition (x-1′) is a component that polymerizes upon exposure to energy rays, and has an energy ray-polymerizable functional group.
  • the energy ray polymerizable functional group include those having a carbon-carbon double bond such as (meth)acryloyl group, vinyl group and allyl group.
  • a functional group partially containing a vinyl group or a substituted vinyl group such as a (meth)acryloyl group or an allyl group, and a vinyl group or a substituted vinyl group itself are referred to as a "vinyl group-containing group.”
  • a vinyl group-containing group may be collectively referred to as Each component contained in the polymerizable composition (x-1′) will be described below.
  • the monomer having an energy ray-polymerizable functional group (b1) may be a monomer having an energy ray-polymerizable functional group, and in addition to the energy ray-polymerizable functional group, a hydrocarbon group and an energy ray-polymerizable functional group. You may have a functional group etc. other than.
  • hydrocarbon group of the component (b1) examples include an aliphatic hydrocarbon group, an aromatic hydrocarbon group, a combination of these groups, and the like.
  • the aliphatic hydrocarbon group may be a linear or branched aliphatic hydrocarbon group, or an alicyclic hydrocarbon group.
  • Linear or branched aliphatic hydrocarbon groups include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, tert-butyl group, sec-butyl group, n-pentyl group, n-hexyl group, 2-ethylhexyl group, n-octyl group, isooctyl group, n-decyl group, n-dodecyl group, n-myristyl group, n-palmityl group, n-stearyl group, etc. Twenty aliphatic hydrocarbon groups are mentioned.
  • the alicyclic hydrocarbon group includes, for example, alicyclic hydrocarbon groups having 3 to 20 carbon atoms such as cyclopentyl group, cyclohexyl group and isobornyl group.
  • Aromatic hydrocarbon groups include, for example, a phenyl group.
  • Groups in which an aliphatic hydrocarbon group and an aromatic hydrocarbon group are combined include, for example, a phenoxyethyl group and a benzyl group.
  • the component (b1) has an energy ray-polymerizable functional group and a linear or branched aliphatic hydrocarbon group from the viewpoint of further improving the adhesive strength of the pressure-sensitive adhesive layer (X1).
  • Monomer (b1-1) (hereinafter also referred to as “(b1-1) component”), monomer (b1-2) having an energy ray-polymerizable functional group and an alicyclic hydrocarbon group (hereinafter referred to as “(b1- 2) Also referred to as “component”) and the like are preferably contained.
  • component (b1) contains component (b1-1)
  • its content is preferably 20 to 80% by mass, more preferably 40 to 80% by mass, relative to the total (100% by mass) of component (b1) 70% by mass, more preferably 50 to 60% by mass.
  • component (b1) contains component (b1-2)
  • its content is preferably 5 to 60% by mass, more preferably 10 to 60% by mass, relative to the total (100% by mass) of component (b1) 40% by mass, more preferably 20 to 30% by mass.
  • the (b1) component is a monomer (b1-3) having an energy ray-polymerizable functional group and a hydroxy group (hereinafter referred to as "(b1 -3) (also referred to as "component”) is preferably contained.
  • component (b1) contains component (b1-3)
  • its content is preferably 1 to 60% by mass, more preferably 5 to 60% by mass, relative to the total (100% by mass) of component (b1) 30% by mass, more preferably 10 to 20% by mass.
  • the number of energy ray-polymerizable functional groups possessed by the component (b1) may be one, or two or more.
  • the component (b1) is a monomer (b1-4) having three or more energy ray-polymerizable functional groups (hereinafter referred to as "(b1-4) (also referred to as "component”).
  • component (b1) contains component (b1-4)
  • its content is preferably 1 to 20% by mass, more preferably 2 to 15% by mass, more preferably 3 to 10% by mass.
  • a monomer having one energy ray-polymerizable functional group a monomer having one vinyl group-containing group (hereinafter also referred to as “polymerizable vinyl monomer”) is preferred.
  • a monomer having two or more energy ray-polymerizable functional groups a monomer having two or more (meth)acryloyl groups (hereinafter also referred to as “polyfunctional (meth)acrylate monomer”) is preferable.
  • the component (b1) contains the above compounds, the cohesive force of the adhesive obtained by polymerizing these is improved, and the adhesive layer (X1) with less contamination of the processed product (P) after peeling is formed. be able to.
  • the polymerizable vinyl monomer is not particularly limited as long as it has a vinyl group-containing group, and conventionally known monomers can be appropriately used. Polymerizable vinyl monomers may be used singly or in combination of two or more.
  • polymerizable vinyl monomers examples include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, ) acrylate, isooctyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, myristyl (meth)acrylate, palmityl (meth)acrylate, stearyl (meth)acrylate, etc.
  • the polymerizable vinyl monomer may further have functional groups other than the vinyl group-containing group in the molecule.
  • the functional group include a hydroxy group, a carboxyl group, a thiol group, a primary or secondary amino group, and the like.
  • a polymerizable vinyl monomer having a hydroxy group corresponding to the above component (b1-3) is preferred.
  • Polymerizable vinyl monomers having a hydroxy group include, for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3 -hydroxyalkyl (meth)acrylates such as hydroxybutyl (meth)acrylate and 4-hydroxybutyl (meth)acrylate; and hydroxy group-containing acrylamides such as N-methylol acrylamide and N-methylol methacrylamide.
  • polymerizable vinyl monomers having a carboxy group examples include ethylenically unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid and citraconic acid. Among these, 2-hydroxyethyl acrylate and 4-hydroxybutyl acrylate are preferred.
  • Examples of other polymerizable vinyl monomers include vinyl esters such as vinyl acetate and vinyl propionate; olefins such as ethylene, propylene and isobutylene; halogenated olefins such as vinyl chloride and vinylidene chloride; -Styrenic monomers such as methylstyrene; Diene monomers such as butadiene, isoprene and chloroprene; Acrylonitrile, nitrile monomers such as methacrylonitrile; Acrylamide, methacrylamide, N-methylacrylamide, N-methyl Amide-based monomers such as methacrylamide, N,N-dimethyl (meth)acrylamide, N,N-diethyl (meth)acrylamide, N-vinylpyrrolidone; N,N-diethylaminoethyl (meth)acrylate, N-( Tertiary amino group-containing monomers such as meth)acryloylmorpholine and the like
  • the polyfunctional (meth)acrylate monomer is not particularly limited as long as it is a monomer having two or more (meth)acryloyl groups in one molecule, and conventionally known monomers can be appropriately used. Polyfunctional (meth)acrylate monomers may be used alone or in combination of two or more.
  • Polyfunctional (meth)acrylate monomers include, for example, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate.
  • acrylate neopentyl glycol adipate di(meth)acrylate, neopentyl glycol hydroxypivalate di(meth)acrylate, dicyclopentanyl di(meth)acrylate, caprolactone-modified dicyclopentenyl di(meth)acrylate, ethylene oxide-modified phosphoric acid Bifunctional (meth)acrylate monomers such as di(meth)acrylate, di(acryloxyethyl)isocyanurate, allylated cyclohexyl di(meth)acrylate, isocyanurate ethylene oxide-modified diacrylate; trimethylolpropane tri(meth)acrylate, dipentaerythritol tri(meth)acrylate, propionic acid-modified dipentaerythritol tri(meth)acrylate, pentaerythritol tri(meth)acrylate, propylene oxide-modified trimethylolpropane tri(meth)
  • the total content of the polymerizable vinyl monomers in the polymerizable composition (x-1') is preferably 10 with respect to the total amount (100% by mass) of the active ingredients in the polymerizable composition (x-1'). ⁇ 80% by mass, more preferably 30 to 75% by mass, still more preferably 50 to 70% by mass.
  • the total content of polyfunctional (meth)acrylate monomers in the polymerizable composition (x-1') is preferably based on the total amount (100% by mass) of the active ingredients in the polymerizable composition (x-1'). is 0.5 to 15 mass %, more preferably 1 to 10 mass %, still more preferably 2 to 5 mass %.
  • the total content of the component (b1) in the polymerizable composition (x-1') is preferably 15 to 90% by mass, more preferably 35 to 80% by mass, still more preferably 55 to 75% by mass.
  • prepolymer (b2) having an energy ray-polymerizable functional group examples include a prepolymer having one energy ray-polymerizable functional group, a prepolymer having two or more energy ray-polymerizable functional groups, and the like.
  • the component (b2) is a prepolymer having two or more energy ray-polymerizable functional groups from the viewpoint of forming a pressure-sensitive adhesive layer that has excellent releasability and less contamination of the processed product (P) after delamination.
  • It preferably contains a prepolymer having two energy ray-polymerizable functional groups, more preferably contains two energy ray-polymerizable functional groups, and has the energy ray-polymerizable functional groups at both ends. More preferably it contains a prepolymer.
  • the component (b2) preferably contains a prepolymer having two or more (meth)acryloyl groups as energy ray-polymerizable functional groups (hereinafter also referred to as "polyfunctional (meth)acrylate prepolymer").
  • polyfunctional (meth)acrylate prepolymer By containing the above compounds in the component (b2), the cohesive force of the adhesive obtained by polymerizing these is improved, and the adhesive layer has excellent peelability and less contamination of the processed product (P) after peeling.
  • (X1) can be formed.
  • the polyfunctional (meth)acrylate prepolymer is not particularly limited as long as it is a prepolymer having two or more (meth)acryloyl groups in one molecule, and conventionally known ones can be appropriately used. Polyfunctional (meth)acrylate prepolymer may be used alone or in combination of two or more.
  • Polyfunctional (meth)acrylate prepolymers include, for example, urethane acrylate prepolymers, polyester acrylate prepolymers, epoxy acrylate prepolymers, polyether acrylate prepolymers, polybutadiene acrylate prepolymers, silicone acrylate prepolymers, A polyacrylic acrylate-based prepolymer and the like are included.
  • Urethane acrylate prepolymers are obtained by reacting compounds such as polyalkylene polyols, polyether polyols, polyester polyols, hydrogenated isoprene having a terminal hydroxyl group, and hydrogenated butadiene having a terminal hydroxyl group with polyisocyanate.
  • a polyurethane prepolymer can be obtained by esterification with (meth)acrylic acid or a (meth)acrylic acid derivative.
  • polyalkylene polyols used for producing urethane acrylate prepolymers include polypropylene glycol, polyethylene glycol, polybutylene glycol, and polyhexylene glycol, among which polypropylene glycol is preferred.
  • the number of functional groups of the obtained urethane acrylate prepolymer is 3 or more, for example, glycerin, trimethylolpropane, triethanolamine, pentaerythritol, ethylenediamine, diethylenetriamine, sorbitol, sucrose, etc. may be appropriately combined.
  • polyisocyanates used in the production of urethane acrylate prepolymers include aliphatic diisocyanates such as hexamethylene diisocyanate and trimethylene diisocyanate; aromatic diisocyanates such as tolylene diisocyanate, xylylene diisocyanate and diphenyl diisocyanate; and dicyclohexylmethane diisocyanate. and alicyclic diisocyanate such as isophorone diisocyanate. Among these, aliphatic diisocyanate is preferred, and hexamethylene diisocyanate is more preferred.
  • the polyisocyanate is not limited to bifunctional, and trifunctional or higher functional polyisocyanate can also be used.
  • (Meth)acrylic acid derivatives used in the production of urethane acrylate prepolymers include, for example, hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl acrylate and 4-hydroxybutyl acrylate; Examples include isocyanatoethyl methacrylate, 1,1-bis(acryloxymethyl)ethyl isocyanate, etc. Among these, 2-isocyanatoethyl acrylate is preferred.
  • a hydroxy group possessed by a compound such as a polyalkylene polyol, a polyether polyol, a polyester polyol, a hydrogenated isoprene having a hydroxyl group terminal, a hydrogenated butadiene having a hydroxyl group terminal, and an isocyanate
  • a method of reacting with the —N ⁇ C ⁇ O portion possessed by the alkyl (meth)acrylate can be exemplified.
  • isocyanate alkyl (meth)acrylate for example, the above 2-isocyanate ethyl acrylate, 2-isocyanate ethyl methacrylate, 1,1-bis(acryloxymethyl)ethyl isocyanate, etc. can be used.
  • the polyester acrylate prepolymer can be obtained, for example, by esterifying the hydroxy groups of a polyester prepolymer having hydroxy groups at both ends thereof with (meth)acrylic acid obtained by condensation of a polycarboxylic acid and a polyhydric alcohol. can be done. It can also be obtained by esterifying the terminal hydroxy group of a prepolymer obtained by adding an alkylene oxide to a polyvalent carboxylic acid with (meth)acrylic acid.
  • Epoxy acrylate-based prepolymers can be obtained, for example, by reacting (meth)acrylic acid with oxirane rings of relatively low-molecular-weight bisphenol-type epoxy resins, novolac-type epoxy resins, etc. to esterify them.
  • a carboxy-modified epoxy acrylate prepolymer obtained by partially modifying an epoxy acrylate prepolymer with a dibasic carboxylic acid anhydride can also be used.
  • a polyether acrylate-based prepolymer can be obtained, for example, by esterifying the hydroxy groups of a polyether polyol with (meth)acrylic acid.
  • the polyacrylic acrylate-based prepolymer may have acryloyl groups on the side chains, or may have acryloyl groups on both ends or one end.
  • a polyacrylic acrylate-based prepolymer having acryloyl groups in side chains can be obtained, for example, by adding glycidyl methacrylate to the carboxy group of polyacrylic acid.
  • acryloyl groups are introduced at both ends using the polymer growth terminal structure of polyacrylate prepolymers synthesized by the ATRP (Atom Transfer Radical Polymerization) method. can be obtained by doing
  • the mass average molecular weight (Mw) of component (b2) is preferably 10,000 to 350,000, more preferably 15,000 to 200,000, still more preferably 20,000 to 50,000.
  • the total content of the polyfunctional (meth)acrylate prepolymer in the polymerizable composition (x-1 ') is based on the total amount (100% by mass) of the active ingredients in the polymerizable composition (x-1 '), It is preferably 10 to 60% by mass, more preferably 15 to 55% by mass, still more preferably 20 to 30% by mass.
  • the total content of the component (b2) in the polymerizable composition (x-1') is preferably 10 to 60% by mass, more preferably 15 to 55% by mass, still more preferably 20 to 30% by mass.
  • the content ratio [(b2)/(b1)] of the component (b2) and the component (b1) in the polymerizable composition (x-1′) is preferably 10/90 to 70/30 on a mass basis. , more preferably 20/80 to 50/50, still more preferably 25/75 to 40/60.
  • the polymerizable composition (x-1′) preferably contains a polymerizable vinyl monomer, a polyfunctional (meth)acrylate monomer and a polyfunctional (meth)acrylate prepolymer.
  • the total content of the polymerizable vinyl monomer, the polyfunctional (meth)acrylate monomer and the polyfunctional (meth)acrylate prepolymer in the energy ray polymerizable component contained in the polymerizable composition (x-1′) is the energy ray With respect to the total amount (100% by mass) of the polymerizable component, preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, still more preferably 99% by mass or more, and 100% by mass %.
  • the total content of the energy ray-polymerizable components in the polymerizable composition (x-1′) is preferably 70 with respect to the total amount (100% by mass) of the active ingredients in the polymerizable composition (x-1′). ⁇ 98% by mass, more preferably 75 to 97% by mass, still more preferably 80 to 96% by mass, still more preferably 82 to 95% by mass.
  • the polymerizable composition (x-1') may contain components other than the energy ray-polymerizable component and the thermally expandable particles.
  • components other than the energy ray-polymerizable component and the thermally expandable particles include photopolymerization initiators, tackifiers, additives for pressure-sensitive adhesives used in general pressure-sensitive adhesives other than the above components, and the like. These components are the same as those explained in the double-sided pressure-sensitive adhesive sheet of the first aspect.
  • the polymerizable composition (x-1′) may contain a solvent such as a diluent within the scope of the object of the present invention, but preferably does not contain a solvent. That is, the polymerizable composition (x-1') is preferably a solventless polymerizable composition. Since the polymerizable composition (x-1 ') is a solvent-free polymerizable composition, when forming the pressure-sensitive adhesive layer (X1), the heat drying of the solvent can be omitted.
  • the content is preferably as small as possible, relative to the total amount (100% by mass) of the active ingredients of the polymerizable composition (x-1 '), preferably is 10% by mass or less, more preferably 1% by mass or less, still more preferably 0.1% by mass or less, and even more preferably 0.01% by mass or less.
  • the polymerizable composition (x-1') can be produced by mixing the energy ray-polymerizable component, thermally expandable particles, and optionally other components. Since the resulting polymerizable composition (x-1′) is to have a high molecular weight by the subsequent energy beam polymerization, when forming a layer, the low molecular weight energy beam polymerizable component is used to achieve an appropriate viscosity. Adjustable. Therefore, the polymerizable composition (x-1') can be used as it is as a coating solution for forming the pressure-sensitive adhesive layer (X1) without adding a solvent such as a diluent.
  • the pressure-sensitive adhesive layer (X1) formed by irradiating the polymerizable composition (x-1′) with an energy ray includes a wide variety of polymers obtained by polymerizing the energy ray-polymerizable component and the polymer. Circumstances exist in which thermally expandable particles dispersed during coalescence are involved, but it is not possible or even nearly impractical to directly characterize them by structure and physical properties.
  • Adhesive strength of adhesive layer (X1) The adhesive strength before thermal expansion and the adhesive strength after thermal expansion of the pressure-sensitive adhesive layer (X1) in the double-sided pressure-sensitive adhesive sheet of the second aspect are the same as in the description of the double-sided pressure-sensitive adhesive sheet of the first aspect. Description of the adhesive strength of the adhesive layer (X1) before thermally expanding the material layer (Y1) and the adhesive strength of the adhesive layer (X1) after thermally expanding the thermally expandable base layer (Y1) are the same.
  • the thickness of the pressure-sensitive adhesive layer (X1) of the double-sided pressure-sensitive adhesive sheet of the second aspect before thermal expansion is preferably 10 to 200 ⁇ m, more preferably 20 to 150 ⁇ m, still more preferably 25 to 120 ⁇ m. If the thickness of the pressure-sensitive adhesive layer (X1) before thermal expansion is 10 ⁇ m or more, sufficient adhesive strength is easily obtained, unintended peeling from the support (S) during temporary fixing is suppressed, and the target to be processed is It tends to be possible to suppress the positional deviation of the object (W).
  • the thickness of the pressure-sensitive adhesive layer (X1) before thermal expansion is 200 ⁇ m or less, the peelability during heat peeling is improved, and the double-sided pressure-sensitive adhesive sheet is prevented from curling during heat peeling, thereby improving handling properties. It tends to improve.
  • the method for forming the pressure-sensitive adhesive layer (X1) is the polymerizable composition (x-1′) containing the energy ray-polymerizable component and the thermally expandable particles. It is preferable that the method for producing a double-sided pressure-sensitive adhesive sheet includes a step of irradiating an energy beam to form a polymer of the energy beam-polymerizable component, specifically, the following steps (1b) to (3b).
  • the manufacturing method includes Step (1b): Step of forming a polymerizable composition layer composed of the polymerizable composition (x-1′) on one side of the base material Step (2b): Applying an energy ray to the polymerizable composition layer A pressure-sensitive adhesive layer (X1) formed by irradiation to form a polymer of the energy ray-polymerizable component and containing the polymer and the thermally expandable particles on one side of the substrate layer (Y) Step (3b): Step of forming an adhesive layer (X2) on the other surface side of the base layer (Y)
  • the polymerizable composition (x-1′) is applied onto the release-treated surface of the release material to form a polymerizable composition layer, and the polymerizable composition layer is:
  • a method of applying a first energy ray to prepolymerize the energy ray-polymerizable component in the polymerizable composition layer and then attaching a substrate to the polymerizable composition layer after prepolymerization can be used.
  • the polymerizable composition (x-1') is preferably a solventless polymerizable composition.
  • the step of drying the solvent by heating may not be performed in this step, and expansion of the thermally expandable particles can be suppressed. .
  • the step (2b) comprises irradiating the polymerizable composition layer formed in the step (1b) with an energy ray to form a polymer of the energy ray-polymerizable component, and containing the polymer and thermally expandable particles.
  • This is a step of forming the pressure-sensitive adhesive layer (X1) to be applied.
  • the energy beam irradiation in step (2b) is the second energy beam irradiation performed on the polymerizable composition layer after prepolymerization.
  • the energy ray irradiation in step (2b) is preferably carried out to such an extent that the energy ray-polymerizable component does not substantially proceed with the polymerization even if the energy ray is further irradiated.
  • polymerization of the energy ray-polymerizable component proceeds to form a polymer of the energy ray-polymerizable component that constitutes the pressure-sensitive adhesive layer (X1).
  • step (3b) the pressure-sensitive adhesive composition (x-2) is applied to one surface of the release material to form the pressure-sensitive adhesive layer (X2), and the pressure-sensitive adhesive layer (X2) is applied to the base layer (Y ) can be attached to the other surface side.
  • none of the steps included in the steps (1b) and (2b) includes a step of heating the polymerizable composition.
  • heating means intentionally heating, for example, during drying, lamination, etc., and the heat given to the polymerizable composition by energy beam irradiation, the energy beam polymerizable composition A temperature rise due to heat of polymerization or the like generated by polymerization is not included.
  • a release sheet subjected to double-sided release treatment As the release material that the double-sided pressure-sensitive adhesive sheet of one embodiment of the present invention may have, a release sheet subjected to double-sided release treatment, a release sheet subjected to single-sided release treatment, or the like is used. Examples include those to which a release agent is applied.
  • Base materials for the release material include, for example, plastic films and papers.
  • plastic films include polyester resin films such as polyethylene terephthalate resin, polybutylene terephthalate resin, and polyethylene naphthalate resin; olefin resin films such as polypropylene resin and polyethylene resin; , glassine paper, kraft paper, and the like.
  • release agents 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, fluorine-based resins, and the like.
  • the release agent may be used alone or in combination of two or more.
  • the thickness of the release material is preferably 10-200 ⁇ m, more preferably 20-150 ⁇ m, still more preferably 35-80 ⁇ m.
  • Step 1 is a step of attaching the workpiece (W) to the adhesive layer (X2) of the double-sided adhesive sheet, and attaching the support (S) to the adhesive layer (X1) of the double-sided adhesive sheet.
  • FIG. 3 shows a cross-sectional view for explaining the steps of attaching the semiconductor wafer W to the adhesive layer (X2) of the double-sided adhesive sheet 1a and attaching the support (S) to the adhesive layer (X1). there is The semiconductor wafer W is attached such that the front surface W ⁇ , which is the circuit surface, faces the adhesive layer (X2).
  • the semiconductor wafer W may be a silicon wafer, a wafer of gallium arsenide, silicon carbide, sapphire, lithium tantalate, lithium niobate, gallium nitride, indium phosphide, or the like, or a glass wafer.
  • the thickness of the semiconductor wafer W before grinding is usually 500 to 1,000 ⁇ m.
  • the circuit on the surface W ⁇ of the semiconductor wafer W can be formed by conventional methods such as etching and lift-off.
  • the material of the support (S) may be appropriately selected according to the type of object to be processed, details of processing, etc., taking into consideration the required properties such as mechanical strength and heat resistance.
  • Materials for the support (S) include, for example, metallic materials such as SUS; non-metallic inorganic materials such as glass and silicon wafers; epoxy resins, ABS resins, acrylic resins, engineering plastics, super engineering plastics, polyimide resins, and polyamideimide. Resin materials such as resins; composite materials such as glass epoxy resins; among others, 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 plastics include polyphenylene sulfide (PPS), polyethersulfone (PES), polyetheretherketone (PEEK), and the like.
  • the support (S) is preferably attached to the entire adhesive surface of the adhesive layer (X1). Therefore, the area of the surface of the support (S) that is attached to the adhesive surface of the adhesive layer (X1) is preferably equal to or greater than the area of the adhesive surface of the adhesive layer (X1). Further, the surface of the support (S) on the side to be attached to the adhesive surface of the adhesive layer (X1) is preferably planar. Although the shape of the support (S) is not particularly limited, it is preferably plate-like. The thickness of the support (S) may be appropriately selected in consideration of required properties, but is preferably 20 ⁇ m to 50 mm, more preferably 60 ⁇ m to 20 mm.
  • Step 2 is selected from applying a semiconductor adhesive and attaching a semiconductor film to the surface (W ⁇ ) of the object (W) opposite to the adhesive layer (X2) 1 This is a step of obtaining a processed product (P) by performing the above processing.
  • Step 2 preferably includes steps 2-1 and 2-2 below.
  • Step 2-1 A step of subjecting the object to be processed (W) to one or more processing treatments selected from grinding treatment and singulation treatment
  • Step 2-2 The object to be processed (W ), the surface (W ⁇ ) opposite to the adhesive layer (X2) is subjected to one or more processes selected from application of a semiconductor adhesive and application of a semiconductor film to obtain a processed product (P )
  • Step 2-1 is a step of subjecting the workpiece (W) to one or more processing processes selected from grinding and singulation.
  • One or more processing treatments selected from grinding treatment and singulation treatment include, for example, grinding treatment using a grinder; blade dicing method, laser dicing method, stealth dicing (registered trademark) method, blade tip dicing method, stealth Singulation processing by a pre-dicing method or the like can be mentioned.
  • singulation processing by the stealth dicing method, grinding processing and singulation processing by the blade tip dicing method, grinding processing and singulation processing by the stealth tip dicing method are preferable, and grinding processing by the blade tip dicing method and singulation processing, grinding processing and singulation processing by the stealth tip dicing method are more preferable.
  • the stealth dicing method is a method in which a modified region is formed inside a semiconductor wafer by irradiating a laser beam, and the semiconductor wafer is singulated using the modified region as a division starting point.
  • the modified region formed in the semiconductor wafer is a portion embrittled by multiphoton absorption, and stress is applied to the semiconductor wafer in the direction parallel to the wafer surface and in the direction in which the wafer is expanded by expanding the modified region.
  • the crack extends toward the front surface and the back surface of the semiconductor wafer from the starting point, thereby singulating into semiconductor chips. That is, the modified regions are formed along the parting lines when singulated.
  • the modified region is formed inside the semiconductor wafer by irradiating laser light 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.
  • the laser beam incident surface may be a surface to which a double-sided adhesive sheet is attached, in which case the semiconductor wafer is irradiated with the laser beam via the double-sided adhesive sheet.
  • the blade tip dicing method is also called the DBG method (Dicing Before Grinding).
  • DBG method Dynamic Bit Bit Rate (Dicing Before Grinding).
  • the blade-tip dicing method grooves are formed in advance in a semiconductor wafer to a depth shallower than the thickness of the semiconductor wafer along lines to be divided, and then the semiconductor wafer is ground back until the ground surface reaches at least the grooves. It is a method of individualizing while separating.
  • the grooves reached by the ground surface form cuts penetrating the semiconductor wafer, and the semiconductor wafer is divided by the cuts into individual semiconductor chips.
  • the grooves formed in advance are usually provided on the surface (circuit surface) of the semiconductor wafer, and can be formed, for example, by dicing using a conventionally known wafer dicing apparatus equipped with a dicing blade.
  • the stealth dicing method is also called the SDBG method (Stealth Dicing Before Grinding).
  • the stealth dicing method is a type of method in which a modified region is formed inside a semiconductor wafer by irradiation with a laser beam, and the semiconductor wafer is singulated using the modified region as a starting point for division.
  • the stealth dicing method differs from the stealth dicing method in that the semiconductor wafer is divided into semiconductor chips while being thinned by grinding. Specifically, while thinning the semiconductor wafer having the modified region by back grinding, the pressure applied to the semiconductor wafer at that time is applied to the surface of the semiconductor wafer to be attached to the adhesive layer with the modified region as a starting point.
  • the grinding thickness after forming the modified region may be a thickness that reaches the modified region. Then, it may be cleaved by a processing pressure such as a grinding wheel.
  • a processing pressure such as a grinding wheel.
  • Semiconductor chips separated into individual pieces by the SDBG process are in a state of being in contact with each other, and are likely to cause a so-called chipping phenomenon in which the outer edge is chipped finely due to vibration. Therefore, the method for manufacturing a semiconductor device according to one embodiment of the present invention, in which vibration can be suppressed by being firmly fixed to the support (S), is particularly suitable for the SDBG method.
  • the semiconductor wafer W When the semiconductor wafer W is diced by the blade tip dicing method, it is preferable to previously form grooves on the surface W ⁇ of the semiconductor wafer W to be adhered to the adhesive layer (X2) in step 1 .
  • the semiconductor wafer W attached to the adhesive layer (X2) in step 1 is irradiated with a laser beam to form a modified region in advance.
  • the modified region may be formed by irradiating the semiconductor wafer W attached to the adhesive layer (X2) with a laser beam.
  • FIG. 4 shows a cross-sectional view for explaining the process of forming a plurality of modified regions 4 on the semiconductor wafer W adhered to the adhesive layer (X2) using the laser beam irradiation device 3.
  • a laser beam is irradiated from the back surface W ⁇ side of the semiconductor wafer W, and a plurality of modified regions 4 are formed inside the semiconductor wafer W at substantially equal intervals.
  • FIG. 5A and 5(b) show cross-sectional views for explaining the process of separating the semiconductor wafer W into a plurality of semiconductor chips CP while thinning it.
  • the rear surface W ⁇ of the semiconductor wafer W on which the modified region 4 is formed is ground by a grinder 5.
  • the pressure applied to the semiconductor wafer W causes the modified region 4 to be a starting point. give rise to
  • FIG. 5B a plurality of semiconductor chips CP obtained by thinning and singulating the semiconductor wafer W are obtained.
  • the back surface W ⁇ of the semiconductor wafer W formed with the modified region 4 is ground while the support (S) 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 singulation process are performed by the stealth 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 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 .
  • planar view means seeing in a thickness direction.
  • the shape of the semiconductor chip CP after singulation in plan view may be a square or an elongated shape such as a rectangle.
  • Step 2-2 a semiconductor adhesive is applied and a semiconductor film is applied to the surface (W ⁇ ) opposite to the adhesive layer (X2) of the object (W) subjected to the processing treatment.
  • This is a step of obtaining a processed product (P) by applying one or more processes selected from lamination.
  • examples of the semiconductor film to be attached to the object (W) include a thermosetting film and an adhesive sheet.
  • Thermosetting films include, for example, die attach films for mounting semiconductor chips on substrates.
  • the adhesive sheet for example, a dicing sheet used when dicing an object (W) such as a semiconductor wafer, or a dicing sheet that enlarges the distance between the objects (W) such as semiconductor chips separated into individual pieces by dicing. Expanding tape used for this purpose, transfer tape used for reversing the front and back of the workpiece (W) such as a semiconductor chip, temporary fixing sheet used for temporarily fixing the inspection object for inspection, etc. mentioned.
  • examples of the semiconductor adhesive applied to the workpiece (W) include a die attach paste used for the purpose of mounting a semiconductor chip on a substrate.
  • the semiconductor adhesive applied to the processed object (W) is a thermosetting adhesive such as a die attach paste.
  • the paste is a flexible paste
  • the semiconductor film to be attached to the workpiece (W) is preferably a thermosetting film such as a die attach film.
  • thermosetting film 6 provided with a support sheet 7 is attached to the surface W ⁇ of the plurality of semiconductor chips CP obtained by performing the above-described processing, on the side opposite to the adhesive layer (X2). Then, a cross-sectional view for explaining a process of obtaining a semiconductor chip CP to which a thermosetting film 6 having a support sheet 7 is attached as a processed product (P) is shown.
  • the thermosetting film 6 is a thermosetting film obtained by forming a resin composition containing at least a thermosetting resin, and is used as an adhesive when mounting the semiconductor chip CP on the substrate.
  • the thermosetting film 6 may contain a curing agent for the thermosetting resin, a thermoplastic resin, an inorganic filler, a curing accelerator, etc., if necessary.
  • the thickness of the thermosetting film 6 is not particularly limited, but is usually 1-200 ⁇ m, preferably 3-100 ⁇ m, more preferably 5-50 ⁇ m.
  • the support sheet 7 may be any material as long as it can support the thermosetting film 6.
  • the resins, metals, paper materials, etc. listed as the base material layer (Y) of the double-sided pressure-sensitive adhesive sheet used in one embodiment of the present invention are used. is mentioned.
  • Lamination may be performed with heating or without heating.
  • the heating temperature in the case of laminating while heating is preferably "a temperature lower than the expansion start temperature (t)" from the viewpoint of suppressing the expansion of the thermally expandable particles and the viewpoint of suppressing the thermal change of the adherend. It is preferably "expansion start temperature (t) -5°C” or lower, more preferably “expansion start temperature (t) -10°C” or lower, still more preferably “expansion start temperature (t) -15°C” or lower.
  • Step 3 While the processed product (P) is subjected to a cooling treatment, the thermally expandable layer is heated to a temperature (t) at which the thermally expandable particles start to expand, thereby forming the adhesive layer (X1). and the support (S).
  • the cooling treatment performed on the processed product (P) includes, for example, a method of contacting a cooled thermal conductor with the processed product (P), a method of air-cooling the processed product (P), and a method of air cooling the processed product (P).
  • Examples include a method of contacting (P) with a coolant, a method of exposing the processed product (P) to a cooled atmosphere, and the like.
  • the method of bringing a cooled heat conductor into contact with the processed product (P) is preferable from the viewpoint of facilitating the control of the location to be cooled and the cooling temperature.
  • the cooling treatment is preferably a treatment for cooling the surface (P ⁇ ) of the processed product (P) opposite to the adhesive layer (X2).
  • the cooled heat conductor is preferably a heat conductor cooled by a refrigerant.
  • a heat conductor cooled by a coolant for example, the heat conductor has a through hole inside, and the coolant is filled, circulated, or circulated in the through hole to cool the surface of the heat conductor. things are mentioned.
  • the coolant filled or circulated inside the heat conductor is not particularly limited, but water is preferable from the viewpoint of economy.
  • the process of bringing the cooled thermal conductor into contact is preferably a process of bringing the cooled thermal conductor into contact with the surface (P ⁇ ) of the workpiece (P) to uniformly cool the workpiece (P).
  • a method of contacting a plate with a smooth surface such as a cooled plate (hereinafter also referred to as a “cooling plate”) to the surface (P ⁇ ) of the workpiece (P) is preferred.
  • the cooling plate include a metal plate cooled by a coolant, a ceramic plate cooled by a coolant, and the like.
  • the surface temperature of the cooled heat conductor that contacts the surface (P ⁇ ) of the workpiece (P) is preferably 1-45°C, more preferably 3-40°C, and even more preferably 5-35°C.
  • the surface temperature of the cooled heat conductor is 1° C. or higher, the cooling temperature becomes appropriate, and problems such as deterioration of adhesiveness of the semiconductor film due to excessive cooling tend to occur less easily.
  • the surface temperature of the cooled heat conductor is 45° C. or less, there is a tendency that a sufficient cooling effect on the processed product (P) can be easily obtained.
  • the method of heating the thermally expandable layer includes, for example, a method of bringing a heated thermal conductor into contact with the surface (S ⁇ ) of the support (S) opposite to the pressure-sensitive adhesive layer (X1), Examples include a method of irradiating the thermally expandable layer with energy rays, a method of exposing the thermally expandable layer to a heated atmosphere, and the like. Among these methods, from the viewpoint of facilitating control of the heating point and the heating temperature, the surface (S ⁇ ) of the support (S) opposite to the pressure-sensitive adhesive layer (X1) is brought into contact with a heated heat conductor.
  • the preferred method is to
  • a preferred method is to bring a plate with a smooth surface such as a heated plate (hereinafter also referred to as a "heating plate") into contact with the surface (S ⁇ ) of the support (S).
  • a heated plate hereinafter also referred to as a "heating plate”
  • the heating plate include metal plates and ceramic plates.
  • the surface temperature of the heated heat conductor that is brought into contact with the surface (S ⁇ ) of the support (S) is equal to or higher than the expansion start temperature (t) of the thermally expandable particles, preferably "higher than the expansion start temperature (t) temperature”, more preferably “expansion start temperature (t) + 2°C” or higher, still more preferably “expansion start temperature (t) + 4°C” or higher, still more preferably “expansion start temperature (t) + 5°C” or higher .
  • the surface temperature of the heated heat conductor is preferably "expansion start temperature (t) + 50 ° C.” or less from the viewpoint of energy saving and suppressing thermal change of the processed product (P) during heat peeling.
  • the surface temperature of the heated heat conductor brought into contact with the surface (S ⁇ ) of the support (S) is in the range of the expansion start temperature (t) or higher from the viewpoint of suppressing the thermal change of the processed product (P).
  • the temperature is preferably 130° C. or lower, more preferably 120° C. or lower, and still more preferably 115° C. or lower.
  • a heated heat conductor is brought into contact with the surface (S ⁇ ) of the support (S) opposite to the adhesive layer (X1) to form the adhesive layer (X2) of the processed product (P).
  • the temperature difference [T S ⁇ T P ] is 20° C.
  • FIG. 7( a ) A cross-sectional view for explaining the step of separating the pressure-sensitive adhesive layer (X1) and the support (S) by heating to .
  • a cooling plate 8 is brought into contact with the surface (P ⁇ ) of the support sheet 7 of the thermosetting film 6 opposite to the pressure-sensitive adhesive layer (X2) for thermosetting.
  • the heat-expandable base layer (Y1) is formed by bringing a heating plate 9 into contact with the surface (S ⁇ ) of the support (S) opposite to the pressure-sensitive adhesive layer (X1). is heated to the expansion start temperature (t) of the thermally expandable particles or higher.
  • the pressure-sensitive adhesive layer (X1) and the support (S) are separated as shown in FIG. 7(b) while suppressing thermal change of the processed product (P).
  • the method for manufacturing a semiconductor device preferably further includes step 4 below.
  • Step 4 is a step of irradiating the adhesive layer (X2) with energy rays to separate the adhesive layer (X2) and the processed product (P).
  • FIG. 8 shows a cross-sectional view for explaining the step of separating the adhesive layer (X2) and the processed product (P). Since the pressure-sensitive adhesive layer (X2) is cured by irradiation with energy rays to reduce its adhesive force, the processed product (P) and the pressure-sensitive adhesive layer (X2) can be easily separated by irradiation with energy rays. can.
  • the energy beam used for the energy beam irradiation in step 4 among the above-described energy beams, ultraviolet rays, which are easy to handle, are preferable.
  • the illuminance and light amount of ultraviolet rays may be such that the adhesion between the adhesive layer (X2) and the processed product (P) is sufficiently low.
  • the illuminance of ultraviolet rays is preferably 100 to 400 mW. /cm 2 , more preferably 150 to 350 mW/cm 2 , more preferably 180 to 300 mW/cm 2
  • the amount of ultraviolet light is preferably 100 to 2,000 mJ/cm 2 , more preferably 200 to 1,000 mJ. /cm 2 , more preferably 300 to 500 mJ/cm 2 .
  • Energy rays may be irradiated from any direction as long as the adhesive layer (X2) can be cured, but from the viewpoint of efficient curing, irradiation from the adhesive layer (X1) side is preferred.
  • the substrate layer (Y) and the pressure-sensitive adhesive layer (X1) preferably have energy ray transparency from the viewpoint of enabling sufficient energy ray irradiation to the pressure-sensitive adhesive layer (X2).
  • thermosetting film 6 A plurality of semiconductor chips CP attached to the thermosetting film 6 is obtained through the above steps 1 to 4. Next, it is preferable to obtain semiconductor chips CP with thermosetting films 6 by dividing the thermosetting film 6 to which a plurality of semiconductor chips CP are attached in the same shape as the semiconductor chips CP.
  • a method for dividing the thermosetting film 6 for example, a method such as laser dicing using a laser beam, expansion, or fusion cutting can be applied.
  • FIG. 9 shows a semiconductor chip CP with a thermosetting film 6 divided into the same shape as the semiconductor chip CP.
  • the semiconductor chips CP with the thermosetting film 6 are further subjected to an expansion step of widening the gap between the semiconductor chips CP, a rearrangement step of arranging a plurality of semiconductor chips CP with widened gaps, and a plurality of semiconductor chips CP.
  • the film is attached (die attached) to the substrate from the thermosetting film 6 side. After that, the semiconductor chip and the substrate can be fixed by thermosetting the thermosetting film 6 .
  • a semiconductor device manufacturing apparatus of one embodiment of the present invention is a semiconductor device manufacturing apparatus used in step 3 of the semiconductor device manufacturing method of one embodiment of the present invention, a cooling mechanism for cooling the processed product (P); and a heating mechanism for heating the thermally expandable layer to an expansion start temperature (t) of the thermally expandable particles or higher.
  • the cooling mechanism is preferably a mechanism for cooling the surface (P ⁇ ) of the processed product (P) opposite to the adhesive layer (X2).
  • the cooling mechanism for example, a mechanism for contacting the processed product (P) with a cooled heat conductor, a mechanism for air-cooling the processed product (P), a mechanism for contacting the processed product (P) with a coolant, a processed product ( and a mechanism for exposing P) to a cooled atmosphere.
  • a mechanism that brings the cooled heat conductor into contact with the workpiece (P) is preferable from the viewpoint of facilitating control of the cooling location and the cooling temperature. ) on the side opposite to the pressure-sensitive adhesive layer (X2) (P ⁇ ).
  • a preferred embodiment of the cooled thermal conductor and the method for contacting the cooled thermal conductor is as described in step 3 of the method for manufacturing a semiconductor device of one embodiment of the present invention.
  • the cooled thermal conductor is preferably a cooled plate.
  • the heating mechanism is preferably a mechanism that heats the surface (S ⁇ ) of the support (S) opposite to the pressure-sensitive adhesive layer (X1).
  • the heating mechanism includes a mechanism for bringing a heated thermal conductor into contact with the surface (S ⁇ ) of the support (S) opposite to the pressure-sensitive adhesive layer (X1), and irradiating the thermally expandable layer with energy rays.
  • mechanism a mechanism for exposing the thermally expandable layer to a heated atmosphere, and the like.
  • the surface (S ⁇ ) of the support (S) opposite to the pressure-sensitive adhesive layer (X1) is brought into contact with a heated heat conductor.
  • a mechanism that allows A preferred embodiment of the heated thermal conductor and the method for contacting the heated thermal conductor is as described in Step 3 of the method for manufacturing a semiconductor device of one embodiment of the present invention.
  • the heated thermal conductor is preferably a heated plate.
  • the present invention will be specifically described by the following examples, but the present invention is not limited to the following examples.
  • the physical property values in each production example and working example are values measured by the following methods.
  • MOI 2-methacryloyl
  • Isocyanate-based cross-linking agent manufactured by Tosoh Corporation, product name "Coronate HX”, isocyanurate-type modified form of hexamethylene diisocyanate, solid content concentration: 100% by mass
  • Photoinitiator > - Photoinitiator (i): bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide - Photoinitiator (ii): 1-hydroxycyclohexylphenyl ketone
  • Production example 1 Formation of pressure-sensitive adhesive layer (X1) 0.74 parts by mass of isocyanate cross-linking agent (i) (solid content ratio) was blended with 100 parts by mass of the solid content of the acrylic copolymer (A1). The mixture was diluted and uniformly stirred to prepare a pressure-sensitive adhesive composition (x-1) having a solid content concentration (active ingredient concentration) of 25% by mass. Then, on the release surface of the heavy release film, the prepared adhesive composition (x-1) is applied to form a coating film, and the coating film is dried at 100 ° C. for 60 seconds to obtain an adhesive with a thickness of 5 ⁇ m. An agent layer (X1) was formed.
  • a solvent-free resin composition (y-1a) was prepared by blending as follows and containing no solvent.
  • a substrate laminate by laminating a thermally expandable substrate layer (Y1) and a non-thermally expandable substrate layer (Y2)
  • a PET film Toyobo Co., Ltd. company's product name "Cosmo Shine A4300", thickness: 50 ⁇ m
  • the non-solvent resin composition (y-1a) is applied to one side of the PET film so that the thermally expandable base layer (Y1) to be formed has a thickness of 100 ⁇ m to form a coating film. did.
  • Examples 1-3 A semiconductor wafer W having a diameter of 12 inches and a thickness of 730 ⁇ m and a circuit surface on which a pattern is formed is prepared as an object (W) to be processed. Co., Ltd., device name "RAD-3510F / 12"), on a table at room temperature (25 ° C.), the release film was removed from the adhesive layer (X2) of the double-sided adhesive sheet prepared above. , the adhesive layer (X2) and the circuit surface of the semiconductor wafer W were laminated so as to be in contact with each other.
  • a silicon mirror wafer (12 inches in diameter, 750 ⁇ m in thickness) was placed as a support (S) on the adhesive layer (X1) exposed by removing the release film from the adhesive layer (X1) of the double-sided adhesive sheet. By sticking, a laminate was obtained in which the support (S), the double-sided adhesive sheet and the semiconductor wafer W were laminated in this order.
  • Step 2-1 Next, using a stealth laser irradiation device (manufactured by Disco Co., Ltd., device name “DFL7361”), a stealth laser is irradiated from the back surface of the semiconductor wafer W opposite to the circuit formation surface, and the inside of the semiconductor wafer W is irradiated with a stealth laser. A modified region was formed. Then, using a grinder/polisher (manufactured by Disco Co., Ltd., device name “DGP8761”), the back surface of the semiconductor wafer W is subjected to grinding while being exposed to ultrapure water, and at the same time it is singulated to a thickness of 20 ⁇ m. A semiconductor chip CP was obtained. During these processes, vibration and displacement of the semiconductor wafer W, which is the object to be processed (W), due to insufficient adhesion between the double-sided adhesive sheet and the support (S) were sufficiently suppressed.
  • a stealth laser irradiation device manufactured by Disco Co.,
  • Step 2-2 Subsequently, a die attach film with a support sheet (manufactured by Lintec Corporation, product name: "Adwill LD01D-7") is mounted on the back side of the semiconductor chip CP using a mounter (manufactured by Lintec Corporation, product name: "RAD2700"). At 50° C., the back surface of the semiconductor chip CP and the DAF were attached so as to be in contact with each other to obtain a laminate having the support (S), the double-sided adhesive sheet, the semiconductor chip CP, the DAF and the support sheet in this order. .
  • Step 3 the laminate obtained above was brought into contact with a hot plate (made of stainless steel) having a surface temperature of 110° C. on the side of the support (S), and the surface on the side of the support sheet of the DAF was brought into contact with the surface temperature shown in Table 1.
  • a water-cooling plate ceramics with a surface treated with Teflon (registered trademark) and having through-holes in which water of a predetermined temperature is circulated through the through-holes
  • the treatment was performed for 1 minute to expand the thermally expandable base layer (Y1) and separate the pressure-sensitive adhesive layer (X1) of the double-sided pressure-sensitive adhesive sheet from the support (S).
  • the adhesiveness between the pressure-sensitive adhesive layer (X1) and the support (S) after heating is such that the support (S) faces upward and the double-sided pressure-sensitive adhesive sheet to which the semiconductor chip CP is attached faces downward.
  • the weight of the double-sided pressure-sensitive adhesive sheet to which the CP was attached fell to such an extent that it fell.
  • Step 4 the pressure-sensitive adhesive layer (X1) side of the double-sided pressure-sensitive adhesive sheet separated from the support (S) was irradiated with ultraviolet rays under the conditions of an illuminance of 230 mW/cm 2 and a light amount of 380 mJ/cm 2 , and the pressure-sensitive adhesive layer ( After X2) was cured to reduce adhesion, the adhesive layer (X2) and the semiconductor chip CP with DAF were separated. When the surface of the semiconductor chip CP with the DAF separated from the adhesive layer (X2) was visually checked, no contamination or adhesive residue was found.
  • Comparative example 1 A semiconductor chip CP with a DAF was obtained in the same manner as in Example 1, except that in Step 3 of Example 1, the surface of the DAF on the support sheet side was not cooled.
  • the DAF contained in the processed products obtained in Examples 1 to 3, which are the production methods of the present embodiment has a low storage elastic modulus E' at 23 ° C., and when the support (S) is thermally peeled It can be seen that the curing of DAF in is suppressed.
  • the storage elastic modulus E' of DAF at 23 ° C. was high, and the DAF during heat peeling of the support (S) Suppression of hardening was not sufficient.

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  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Adhesive Tapes (AREA)
  • Die Bonding (AREA)

Abstract

La présente invention concerne un procédé de fabrication de dispositif semi-conducteur comprenant les étapes 1 à 3, ledit procédé utilisant une feuille adhésive double face qui comporte une couche adhésive (X1), une couche de matériau de base (Y) et une couche adhésive (X2), dans cet ordre ; dans lequel au moins l'une parmi la couche adhésive (X1) et la couche de matériau de base (Y) est une couche thermiquement expansible contenant des particules thermiquement expansibles ; et dans lequel des irrégularités sont formées sur la surface de la couche adhésive (X1) suite à l'expansion de la couche thermiquement expansible.
PCT/JP2022/012171 2021-03-17 2022-03-17 Procédé de fabrication de dispositif semi-conducteur et appareil de fabrication de dispositif semi-conducteur WO2022196752A1 (fr)

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JP2021-043516 2021-03-17

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005116679A (ja) * 2003-10-06 2005-04-28 Nitto Denko Corp 半導体ウエハの支持材からの剥離方法およびこれを用いた装置
WO2019181447A1 (fr) * 2018-03-20 2019-09-26 リンテック株式会社 Procédé de production d'article traité et corps stratifié adhésif
WO2020196756A1 (fr) * 2019-03-28 2020-10-01 リンテック株式会社 Procédé de fabrication de feuille adhésive, procédé de fabrication de dispositif à semi-conducteur et feuille adhésive

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005116679A (ja) * 2003-10-06 2005-04-28 Nitto Denko Corp 半導体ウエハの支持材からの剥離方法およびこれを用いた装置
WO2019181447A1 (fr) * 2018-03-20 2019-09-26 リンテック株式会社 Procédé de production d'article traité et corps stratifié adhésif
WO2020196756A1 (fr) * 2019-03-28 2020-10-01 リンテック株式会社 Procédé de fabrication de feuille adhésive, procédé de fabrication de dispositif à semi-conducteur et feuille adhésive

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