WO2019181447A1 - Procédé de production d'article traité et corps stratifié adhésif - Google Patents

Procédé de production d'article traité et corps stratifié adhésif Download PDF

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Publication number
WO2019181447A1
WO2019181447A1 PCT/JP2019/008260 JP2019008260W WO2019181447A1 WO 2019181447 A1 WO2019181447 A1 WO 2019181447A1 JP 2019008260 W JP2019008260 W JP 2019008260W WO 2019181447 A1 WO2019181447 A1 WO 2019181447A1
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WIPO (PCT)
Prior art keywords
pressure
sensitive adhesive
adhesive layer
adhesive sheet
layer
Prior art date
Application number
PCT/JP2019/008260
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English (en)
Japanese (ja)
Inventor
中山　武人
岡本　直也
高志 阿久津
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リンテック株式会社
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Application filed by リンテック株式会社 filed Critical リンテック株式会社
Priority to CN201980018435.XA priority Critical patent/CN111837219A/zh
Priority to JP2020508132A priority patent/JP7273792B2/ja
Priority to KR1020207023470A priority patent/KR20200133209A/ko
Publication of WO2019181447A1 publication Critical patent/WO2019181447A1/fr

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    • 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
    • H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
    • H01L21/77—Manufacture or treatment of devices consisting of a plurality of solid state components or integrated circuits formed in, or on, a common substrate
    • H01L21/78—Manufacture or treatment of devices consisting of a plurality of solid state components or integrated circuits formed in, or on, a common substrate with subsequent division of the substrate into plural individual devices
    • 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
    • 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
    • H01L21/56—Encapsulations, e.g. encapsulation layers, coatings
    • 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
    • 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
    • H01L21/6835—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 using temporarily an auxiliary support
    • H01L21/6836—Wafer tapes, e.g. grinding or dicing support tapes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2221/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof covered by H01L21/00
    • H01L2221/67—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere
    • H01L2221/683—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus 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
    • H01L2221/68304—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus 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 using temporarily an auxiliary support
    • H01L2221/68318—Auxiliary support including means facilitating the separation of a device or wafer from the auxiliary support
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2221/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof covered by H01L21/00
    • H01L2221/67—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere
    • H01L2221/683—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus 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
    • H01L2221/68304—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus 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 using temporarily an auxiliary support
    • H01L2221/68327—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus 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 using temporarily an auxiliary support used during dicing or grinding

Definitions

  • the present invention relates to a method for producing a processed product subjected to at least one of cutting and grinding, and an adhesive laminate used in the production method.
  • the pressure-sensitive adhesive sheet is not only used for semi-permanently fixing members, but also for temporary fixing for temporarily fixing target members when processing or inspecting building materials, interior materials, and electronic parts. May be used.
  • Such a pressure-sensitive adhesive sheet for temporarily fixing is required to satisfy both adhesiveness at the time of use and peelability after use.
  • Patent Document 1 discloses a heat-peelable pressure-sensitive adhesive sheet for temporary fixing at the time of cutting an electronic component, in which a heat-expandable pressure-sensitive adhesive layer containing heat-expandable microspheres is provided on at least one surface of a substrate. ing.
  • This heat-peelable pressure-sensitive adhesive sheet adjusts the maximum particle size of the heat-expandable microspheres with respect to the thickness of the heat-expandable pressure-sensitive adhesive layer, and calculates the center line average roughness of the surface of the heat-expandable pressure-sensitive adhesive layer before heating. It is adjusted to 0.4 ⁇ m or less.
  • the heat-peelable pressure-sensitive adhesive sheet can secure a contact area with an adherend when cutting an electronic component, it can exhibit adhesiveness that can prevent adhesion failure such as chip jumping, After use, there is a description that it can be easily peeled by heating to expand the thermally expandable microspheres to reduce the contact area with the adherend.
  • an object to be processed (hereinafter also referred to as “processing object”) using the pressure-sensitive adhesive sheet is temporarily fixed, and predetermined processing is performed on the processing object. After being applied, the processing object is separated from the adhesive sheet.
  • processing object is separated from the adhesive sheet.
  • a plurality of processing steps including at least one of a step of cutting a workpiece and a step of grinding are often performed. Therefore, for example, after the processing object temporarily fixed to the adhesive sheet is subjected to at least one of the cutting process and the grinding process, the processing object is removed from the adhesive sheet.
  • the separated workpiece is pasted on a new pressure-sensitive adhesive sheet and used for the next step.
  • the processing object is separated from the adhesive sheet and separated.
  • the processing object is affixed to a new pressure-sensitive adhesive sheet, and at least one of the processing steps of cutting and grinding the processing object is performed.
  • the workpiece after the workpiece is fixed to the support and the workpiece is processed, the workpiece can be easily separated from the support in a lump with a slight force.
  • the processing object separated from the support can be used for the next process as a state of being attached to the adhesive sheet, and the processing object is at least at any timing before and after the separation of the processing object from the support.
  • a method for manufacturing a processed product that has been subjected to at least one of cutting and grinding, and at least one of cutting and grinding has been performed. It aims at providing the adhesive laminated body for manufacture of a processed article.
  • the present inventors have a heat-expandable pressure-sensitive adhesive sheet (I) having a base material and a pressure-sensitive adhesive layer, and a layer containing heat-expandable particles in any layer, and a base material and a pressure-sensitive adhesive layer.
  • a pressure-sensitive adhesive laminate comprising the pressure-sensitive adhesive sheet (II) and directly laminated with the base material of the pressure-sensitive adhesive sheet (I) and the pressure-sensitive adhesive sheet (II) is subjected to at least one of cutting and grinding. It has been found that the above problem can be solved by manufacturing a processed product.
  • a method of manufacturing a processed product subjected to at least one of cutting and grinding using It has the following steps (1) to (3) in this order, Step (1): A step of sticking the surface of the pressure-sensitive adhesive layer (X1) of the pressure-sensitive adhesive laminate to a support and sticking a workpiece to the surface of the pressure-sensitive adhesive layer (X2) of the pressure-sensitive adhesive laminate. Step (2): Step of performing one or more processings on the workpiece. Step (3): Heating the thermal expandable particles at a thermal expansion start temperature (t) or higher, thereby sticking the workpiece to the adhesive.
  • the pressure-sensitive adhesive laminate is separated at the interface P between the pressure-sensitive adhesive sheet (I) and the base material (Y2) of the pressure-sensitive adhesive sheet (II) while maintaining the state of being stuck on the surface of the pressure-sensitive adhesive layer (X2).
  • the said process (4) is the following.
  • (X) The manufacturing method of the processed goods implemented in at least any one of (Y).
  • the first pressure-sensitive adhesive layer (X11) is a heat-expandable pressure-sensitive adhesive layer containing the heat-expandable particles
  • the second pressure-sensitive adhesive layer (X12) is a non-thermally expandable pressure-sensitive adhesive layer
  • the first pressure-sensitive adhesive layer (X11) of the pressure-sensitive adhesive sheet (I) and the base material (Y2) of the pressure-sensitive adhesive sheet (II) are directly The manufacturing method according to the above [1] or [2], wherein the surface of the second pressure-sensitive adhesive layer (X12) of the pressure-sensitive adhesive sheet (I) having a laminated structure is a surface to be attached to the support.
  • the storage elastic modulus G ′ (23 ° C.) of the pressure-sensitive adhesive layer (X2) is 0.1 MPa or more.
  • the workpiece is a semiconductor wafer
  • the one or more processes in the step (2) include the following step (2-A): Step (2-A): a step of forming a modified region serving as a division starting point on the semiconductor wafer.
  • the step (4) is the following step (4-A): Step (4-A): A step of grinding the surface of the semiconductor wafer opposite to the surface to be adhered to the adhesive layer (X2).
  • the step (4-A) includes the following (XA ) Or (YA), the production method according to any one of [1] to [12] above.
  • the object to be processed is a semiconductor chip
  • the one or more processes in the step (2) include the following step (2-B): Step (2-B): covering the semiconductor chip and the periphery of the semiconductor chip among the adhesive surfaces of the adhesive layer (X2) with a sealing material, and curing the sealing material; A step of obtaining a cured encapsulant in which the semiconductor chip is encapsulated in a cured encapsulant
  • the step (4) is performed in at least one of the following (XB) and (YB), [1] The production method according to [12].
  • the workpiece after the workpiece is fixed to the support and the workpiece is processed, the workpiece can be easily separated from the support with a slight force.
  • the object to be processed separated from the support can be applied to the next process as being attached to the adhesive sheet, and the process can be performed at least before or after the separation of the object to be processed from the support.
  • a method for manufacturing a workpiece that has been subjected to at least one of cutting and grinding, and at least one of cutting and grinding can be performed. It is possible to provide an adhesive laminate for producing a processed product.
  • whether the “layer” is a “non-thermally expandable layer” or a “thermally expandable layer” is determined as follows.
  • the target layer is heat-treated for 3 minutes at the expansion start temperature (t) of the heat-expandable particles contained in the layer containing the heat-expandable particles.
  • t expansion start temperature
  • Volume change rate (%) ⁇ (volume of the layer after heat treatment ⁇ volume of the layer before heat treatment) / volume of the layer before heat treatment ⁇ ⁇ 100
  • the layer not containing the thermally expandable particles is assumed to be a “non-thermally expandable layer”.
  • the “active ingredient” refers to a component excluding a diluent solvent among components contained in a target composition.
  • the mass average molecular weight (Mw) is a value in terms of standard polystyrene measured by a gel permeation chromatography (GPC) method, specifically a value measured based on the method described in Examples. It is.
  • 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 value and the upper limit value described in a stepwise manner can be independently combined for a preferable numerical range (for example, a range such as content). For example, from the description “preferably 10 to 90, more preferably 30 to 60”, “preferable lower limit (10)” and “more preferable upper limit (60)” are combined to obtain “10 to 60”. You can also.
  • the method for producing a processed product according to the present invention includes a base material (Y1) and a pressure-sensitive adhesive layer (X1), and one of the layers includes a heat-expandable pressure-sensitive adhesive containing heat-expandable particles having a thermal expansion start temperature (t).
  • a sheet (I) and a pressure-sensitive adhesive sheet (II) having a base material (Y2) and a pressure-sensitive adhesive layer (X2) are provided, and the pressure-sensitive adhesive sheet (I) and the base material (Y2) of the pressure-sensitive adhesive sheet (II) are directly laminated.
  • the pressure-sensitive adhesive laminate is separated at the interface P between the pressure-sensitive adhesive sheet (I) and the base material (Y2) of the pressure-sensitive adhesive sheet (II) while maintaining the state of being stuck on the surface of the pressure-sensitive adhesive layer (X2).
  • the said process (4) is the following. It is carried out in at least one of (X) and (Y).
  • the adhesive laminate used in the production method of the present invention will be described. Then, each manufacturing process including the steps (1) to (4) will be described.
  • the pressure-sensitive adhesive laminate used in the production method of the present invention has a base material (Y1) and a pressure-sensitive adhesive layer (X1), and includes a heat-expandable particle in any layer (I). And a pressure sensitive adhesive sheet (II) having a base material (Y2) and a pressure sensitive adhesive layer (X2), and the pressure sensitive adhesive sheet (I) and the base material (Y2) of the pressure sensitive adhesive sheet (II) are directly laminated.
  • the predetermined processing means the processing in step (2) in the production method of the present invention.
  • step (4) may be performed as one of the one or more processes in step (2). Therefore, the predetermined processing may include step (4) in the manufacturing method of the present invention.
  • the surface of the pressure-sensitive adhesive layer (X1) of the pressure-sensitive adhesive sheet (I) is a surface to which a support is attached.
  • the surface of the second pressure-sensitive adhesive layer (X12) is the surface to which the support is attached, and the first pressure-sensitive adhesive layer
  • the surface of the agent layer (X11) is a surface laminated on the base material (Y2) side of the pressure-sensitive adhesive sheet (II).
  • the surface of the pressure-sensitive adhesive layer (X2) of the pressure-sensitive adhesive sheet (II) is a surface on which a workpiece is pasted.
  • the adhesive laminated body used for the manufacturing method of this invention is the base material of adhesive sheet (I) and adhesive sheet (II) by heat processing at the temperature more than the expansion start temperature (t) of a thermally expansible particle. Separation is possible at the interface P with (Y2).
  • the heat treatment is also referred to as “separation heat treatment”. 1 to 3 are schematic cross-sectional views showing the structures of the first, second, and third embodiments of the pressure-sensitive adhesive laminate used in the production method of the present invention, respectively.
  • the pressure-sensitive adhesive laminates 1a and 1b include a pressure-sensitive adhesive sheet (I) having a base material (Y1) and a pressure-sensitive adhesive layer (X1), and a pressure-sensitive adhesive sheet (II) having a base material (Y2) and a pressure-sensitive adhesive layer (X2).
  • the base material (Y1) of the pressure-sensitive adhesive sheet (I) and the base material (Y2) of the pressure-sensitive adhesive sheet (II) are directly laminated.
  • any layer of the pressure-sensitive adhesive sheet (I) is a layer containing thermally expandable particles so that it can be separated at the interface P by the heat treatment for separation. .
  • the thermally expandable particles are expanded by the heat treatment for separation, and irregularities are generated on the surface of the layer containing the thermally expandable particles. Thereby, the contact area of the base material (Y2) of adhesive sheet (I) and adhesive sheet (II) reduces.
  • the processing object can be fixed to the support via the above-mentioned adhesive laminate and the predetermined processing can be performed, and the processing target subjected to the predetermined processing Objects can be easily separated from the support body with a slight force.
  • the object to be processed separated from the support can be used as it is in the next step as it is attached to the adhesive sheet (II). Therefore, it is not necessary to perform an operation of attaching the processed object after separation subjected to the predetermined processing to a new pressure-sensitive adhesive sheet, and workability and product productivity can be improved.
  • the substrate (Y1) has a thermally expandable substrate layer (Y1-1) containing thermally expandable particles like the adhesive laminates 1a and 1b shown in FIG. Is preferred.
  • the base material (Y1) has a single-layer structure having only a thermally expandable base material layer (Y1-1) containing heat-expandable particles, like the adhesive laminate 1a shown in FIG. 1 (a). May be.
  • the base material (Y1) is composed of a heat-expandable base material layer (Y1-1) and a non-heat-expandable base material layer (Y1-2) like the adhesive laminate 1b shown in FIG. 1 (b).
  • a multilayer structure having
  • the heat-expandable particles contained in the heat-expandable base material layer (Y1-1) constituting the base material (Y1) are expanded by the heat treatment for separation, Unevenness occurs on the surface of the base material (Y1) on the pressure-sensitive adhesive sheet (II) side, and the contact area between the base material (Y1) and the base material (Y2) of the pressure-sensitive adhesive sheet (II) decreases.
  • the adhesive layer (X1) which the adhesive laminated body 1a has is affixed with the support body, an unevenness
  • the adhesive laminate 1a can be easily separated by a slight force at the interface P between the base material (Y1) of the adhesive sheet (I) and the base material (Y2) of the adhesive sheet (II). It becomes.
  • the pressure-sensitive adhesive layer (X1) of the pressure-sensitive adhesive laminate 1a from a pressure-sensitive adhesive composition that increases the pressure-sensitive adhesive force to the support, it can be more easily separated at the interface P. It is also possible to design.
  • the thermally expandable particles contained in the thermally expandable substrate layer (Y1-1) constituting the substrate (Y1) are expanded by the heat treatment for separation. And the unevenness
  • the non-thermally expandable base material layer (Y1-2) constituting the base material (Y1) has a small degree of expansion due to heat treatment, and therefore the surface of the base material (Y1) on the pressure-sensitive adhesive layer (X1) side. It is difficult to form irregularities on the surface.
  • the adhesive laminate 1b can be easily separated by a slight force at the interface P between the base material (Y1) of the adhesive sheet (I) and the base material (Y2) of the adhesive sheet (II). It becomes.
  • the pressure-sensitive adhesive layer (X1) of the pressure-sensitive adhesive laminate 1b is formed from a pressure-sensitive adhesive composition that enhances the adhesive strength to the support, whereby the interface P Therefore, it is also possible to design so as to be more easily separable.
  • the base material (Y1) has a thermally expandable base material layer (Y1-1) on one surface side. And a non-thermally expandable base material layer (Y1-2) on the other surface side.
  • the adhesive laminates 1a and 1b are made of an adhesive sheet (I). It is preferable that the thermally expandable base material layer (Y1-1) of the base material (Y1) and the base material (Y2) of the pressure-sensitive adhesive sheet (II) are directly laminated.
  • the pressure-sensitive adhesive laminates 1c and 1d have a configuration in which the pressure-sensitive adhesive sheet (I) has a substrate (Y1) sandwiched between the first pressure-sensitive adhesive layer (X11) and the second pressure-sensitive adhesive layer (X12).
  • the first pressure-sensitive adhesive layer (X11) of (I) and the base material (Y2) of the pressure-sensitive adhesive sheet (II) are directly laminated.
  • the surface of a 2nd adhesive layer (X12) turns into a surface affixed with a support body.
  • the substrate (Y1) has a thermally expandable substrate layer (Y1-1) containing thermally expandable particles like the adhesive laminates 1c and 1d shown in FIG. Is preferred.
  • the base material (Y1) has a single-layer structure having only a heat-expandable base material layer (Y1-1) containing heat-expandable particles, like the adhesive laminate 1c shown in FIG. 2 (a). May be.
  • the base material (Y1) is composed of a heat-expandable base material layer (Y1-1) and a non-heat-expandable base material layer (Y1-2) as in the adhesive laminate 1d shown in FIG. 2 (b).
  • the substrate (Y1) has a multi-layer structure having a thermally expandable substrate layer (Y1-1) and a non-thermally expandable substrate layer (Y1-2), the thermally expandable substrate layer (Y1-1) is preferably disposed on the pressure-sensitive adhesive sheet (II) side, and the non-thermally expandable base material layer (Y1-2) is preferably disposed on the second pressure-sensitive adhesive layer (X12) side.
  • the heat-expandable particles in the heat-expandable base material layer (Y1-1) constituting the base material (Y1) are expanded by the heat treatment for separation. Unevenness occurs on the surface of the material (Y1) on the first pressure-sensitive adhesive layer (X11) side. And the 1st adhesive layer (X11) is also pushed up by the unevenness which arose on the surface of substrate (Y1), and the unevenness is formed also in the surface at the side of adhesive sheet (II) of the 1st adhesive layer (X11). . Thereby, the contact area of the 1st adhesive layer (X11) and the base material (Y2) of adhesive sheet (II) reduces.
  • the second pressure-sensitive adhesive layer (X12) of the pressure-sensitive adhesive laminate 1c is formed from a pressure-sensitive adhesive composition that increases the pressure-sensitive adhesive force to the support so that it can be more easily separated at the interface P. It is also possible to design.
  • the thermally expandable particles contained in the thermally expandable substrate layer (Y1-1) constituting the substrate (Y1) are expanded by the heat treatment for separation.
  • corrugation arises in the surface at the side of the 1st adhesive layer (X11) of a base material (Y1).
  • the 1st adhesive layer (X11) is also pushed up by the unevenness which arose on the surface of substrate (Y1), and the unevenness is formed also in the surface at the side of adhesive sheet (II) of the 1st adhesive layer (X11). .
  • the contact area of the 1st adhesive layer (X11) and the base material (Y2) of adhesive sheet (II) reduces.
  • the non-thermally expandable base material layer (Y1-2) constituting the base material (Y1) has a small degree of expansion due to the heat treatment, and therefore the second pressure-sensitive adhesive layer (X12) side of the base material (Y1). It is difficult for irregularities to be formed on the surface. Thereby, an unevenness
  • corrugation can be efficiently formed in the surface at the side of the 1st adhesive layer (X11) of a base material (Y1). As a result, the adhesive laminate 1d can be easily separated by a slight force at the interface P between the base material (Y1) of the adhesive sheet (I) and the base material (Y2) of the adhesive sheet (II). It becomes.
  • the second pressure-sensitive adhesive layer (X12) of the pressure-sensitive adhesive laminate 1d from a pressure-sensitive adhesive composition that increases the adhesive strength to the support, It is also possible to design so as to be more easily separable at the interface P.
  • the adhesive laminates 1c and 1d are adhesive sheets (I) from the viewpoint of forming an adhesive laminate that can be easily separated at a slight force at the interface P. It is preferable that the thermally expandable base material layer (Y1-1) of the base material (Y1) and the first pressure-sensitive adhesive layer (X11) are directly laminated. In this case, it is more preferable that the first pressure-sensitive adhesive layer (X11) and the base material (Y2) of the resin film-forming sheet (II) are directly laminated.
  • ⁇ Adhesive laminate of the third aspect> The adhesive laminates 1a and 1b of the first embodiment and the adhesive laminates 1c and 1d of the second embodiment used in the production method of the present invention are all heated as one of the layers constituting the substrate (Y1). A layer containing expandable particles is included.
  • the adhesive laminate of the third aspect used in the production method of the present invention the thermally expandable adhesive containing the thermally expandable particles on the surface on the interface P side of the base material (Y1) of the adhesive sheet (I).
  • the structure which provided the agent layer and provided the non-heat-expandable adhesive layer in the other surface of a base material (Y1) may be sufficient.
  • the adhesive sheet (I) is made of a base material (Y1) by the first adhesive layer (X11) and the second adhesive layer (X12). ) Are sandwiched, the first pressure-sensitive adhesive layer (X11) is a heat-expandable pressure-sensitive adhesive layer containing heat-expandable particles, and the second pressure-sensitive adhesive layer (X12) is a non-heat-expandable pressure-sensitive adhesive layer.
  • the adhesive layer include a layer in which the first pressure-sensitive adhesive layer (X11) of the pressure-sensitive adhesive sheet (I) and the base material (Y2) of the pressure-sensitive adhesive sheet (II) are directly laminated.
  • the surface of a 2nd adhesive layer (X12) is a surface stuck with a support body.
  • a base material (Y1) is a non-thermally expansible base material.
  • the surface of the thermally expandable pressure-sensitive adhesive layer that is the first pressure-sensitive adhesive layer (X11) is uneven by the heat treatment for separation, and the first pressure-sensitive adhesive layer (X11) and The contact area between the adhesive sheet (II) and the base material (Y2) is reduced.
  • the surface of the first pressure-sensitive adhesive layer (X11) on the base material (Y1) side is not easily uneven because the base material (Y1) that is a non-thermally expandable base material is laminated. Therefore, unevenness is efficiently formed on the surface of the first pressure-sensitive adhesive layer (X11) on the pressure-sensitive adhesive sheet (II) side.
  • the pressure-sensitive adhesive laminate 2 can be easily collected with a slight force at the interface P between the first pressure-sensitive adhesive layer (X11) of the pressure-sensitive adhesive sheet (I) and the base material (Y2) of the pressure-sensitive adhesive sheet (II). Can be separated.
  • ⁇ Configuration of adhesive laminate having release material> In one embodiment of the pressure-sensitive adhesive laminate used in the production method of the present invention, one or both of the surface of the pressure-sensitive adhesive layer (X1) to which the support is stuck and the surface of the pressure-sensitive adhesive layer (X2) to which the workpiece is stuck are attached. Further, a configuration in which a release material is further laminated may be employed. For example, in the adhesive laminates 1a and 1b shown in FIGS. 1 (a) and 1 (b), one adhesive surface of the adhesive layer (X1) and the adhesive layer (X2) is subjected to a peeling treatment on both sides. It is good also as a structure which wound what the release material laminated
  • One embodiment of the pressure-sensitive adhesive laminate used in the production method of the present invention is based on the pressure-sensitive adhesive sheet (I) and the pressure-sensitive adhesive sheet (II) by heat treatment at a temperature equal to or higher than the expansion start temperature (t) of the thermally expandable particles.
  • the peeling force (F 1 ) when separating at the interface P by heat treatment at a temperature equal to or higher than the expansion start temperature (t) of the thermally expandable particles is as follows.
  • the release force (F 1) is in the case of 0 mN / 25 mm, even trying to measure the peel strength by the method described in Example, includes the case where the measurement impossible because peel strength is too small.
  • the layer between the pressure-sensitive adhesive sheet (I) and the base material (Y2) of the pressure-sensitive adhesive sheet (II) from the viewpoint of sufficiently fixing the object to be processed and not adversely affecting the processing work before the heat treatment. It is preferable that the adhesiveness is high.
  • the peeling force (F 0 ) when separating at the interface P before performing the heat treatment is preferably 100 mN / 25 mm or more, More preferably, it is 300 mN / 25 mm or more, More preferably, it is 500 mN / 25 mm or more, Preferably it is 50000 mN / 25 mm or less.
  • the peel force (F 0 ) is greater than the peel force (F 1 ).
  • the ratio [(F 1 ) / (F 0 )] between the peel force (F 1 ) and the peel force (F 0 ) is preferably 0 to 0.9, more preferably 0 to 0.8. More preferably, it is 0 to 0.5, and still more preferably 0 to 0.2.
  • thermally expandable particles may be any temperature at which expansion.
  • the temperature conditions used for measuring the peel force (F 0) but may be less than the expansion start temperature (t), is basically a room temperature (23 ° C.).
  • more specific measurement conditions and measurement methods for the peel force (F 1 ) and the peel force (F 0 ) are based on the methods described in the examples.
  • the pressure-sensitive adhesive layer (X1) (first pressure-sensitive adhesive layer (X11) and second pressure-sensitive adhesive) of the pressure-sensitive adhesive sheet (I) at room temperature (23 ° C.)
  • the pressure-sensitive adhesive strength of the layer (X12) and the pressure-sensitive adhesive strength of the pressure-sensitive adhesive layer (X2) of the pressure-sensitive adhesive sheet (II) are each independently preferably 0.1 to 10.0 N / 25 mm, more preferably 0.
  • the range is from 0.2 to 8.0 N / 25 mm, more preferably from 0.4 to 6.0 N / 25 mm, still more preferably from 0.5 to 4.0 N / 25 mm.
  • the adhesive strengths of the first pressure-sensitive adhesive layer (X11) and the second pressure-sensitive adhesive layer (X12) are respectively The above-mentioned range is preferable, but from the viewpoint of improving the adhesion with the support and enabling easy separation at the interface P all at once, the second pressure-sensitive adhesive layer (X12) to be attached to the support is used. More preferably, the adhesive strength is higher than the adhesive strength of the first adhesive layer (X11).
  • the base material (Y1) included in the pressure-sensitive adhesive sheet (I) and the base material (Y2) included in the pressure-sensitive adhesive sheet (II) are non-adhesive base materials.
  • whether or not the non-adhesive substrate is determined if the probe tack value measured in accordance with JIS Z0237: 1991 is less than 50 mN / 5 mm ⁇ with respect to the surface of the target substrate.
  • the said base material is judged as a "non-adhesive base material".
  • the probe tack values on the surface of the base material (Y1) of the pressure-sensitive adhesive sheet (I) and the base material (Y2) of the pressure-sensitive adhesive sheet (II) used in one embodiment of the present invention are each independently usually less than 50 mN / 5 mm ⁇ . However, it is preferably less than 30 mN / 5 mm ⁇ , more preferably less than 10 mN / 5 mm ⁇ , and even more preferably less than 5 mN / 5 mm ⁇ .
  • the specific measuring method of the probe tack value on the surface of a thermally expansible base material is based on the method as described in an Example.
  • the pressure-sensitive adhesive sheet (I) of the pressure-sensitive adhesive laminate used in the production method of the present invention has a base material (Y1) and a pressure-sensitive adhesive layer (X1), and the base material of the pressure-sensitive adhesive sheet (II) by heat treatment for separation. It is a heat-expandable pressure-sensitive adhesive sheet containing heat-expandable particles in any layer so that it can be separated at the interface with (Y2).
  • the thermal expansion start temperature (t) of the thermally expandable particles is preferably 60 to 270 ° C.
  • -Pressure-sensitive adhesive sheet (I) of the first aspect Pressure-sensitive adhesive sheet (I) having a heat-expandable base material layer (Y1-1) containing heat-expandable particles as the base material (Y1).
  • -Adhesive sheet (I) of 2nd aspect 1st adhesive layer (X11) which is a thermally expansible adhesive layer containing a thermally expansible particle on both surfaces of a base material (Y1), and non-thermally expandable adhesive Adhesive sheet (I) which has the 2nd adhesive layer (X12) which is an agent layer.
  • -Adhesive sheet (I) whose base material (Y1) is a non-thermally expandable base material.
  • the substrate (Y1) has a thermally expandable substrate layer (Y1-1) containing thermally expandable particles. It is done.
  • the pressure-sensitive adhesive sheet (I) of the first embodiment is adhesive from the viewpoint that it can be easily separated with a slight force at the interface P between the pressure-sensitive adhesive sheet (I) and the base material (Y2) of the pressure-sensitive adhesive sheet (II).
  • the agent layer (X1) is preferably a non-thermally expandable pressure-sensitive adhesive layer.
  • the pressure-sensitive adhesive layer (X1) is preferably a non-thermally expandable pressure-sensitive adhesive layer.
  • both the first pressure-sensitive adhesive layer (X11) and the second pressure-sensitive adhesive layer (X12) are non-thermally expandable pressure-sensitive adhesives.
  • An agent layer is preferred.
  • the thickness of the base material (Y1) before the heat treatment for separation of the pressure-sensitive adhesive sheet (I) of the first aspect is preferably 10 to 1000 ⁇ m, more preferably 20 to 700 ⁇ m, still more preferably 25 to 500 ⁇ m, and still more preferably. 30 to 300 ⁇ m.
  • the thickness of the pressure-sensitive adhesive layer (X1) before separation heat treatment of the pressure-sensitive adhesive sheet (I) of the first aspect is preferably 1 to 60 ⁇ m, more preferably 2 to 50 ⁇ m, still more preferably 3 to 40 ⁇ m, and still more preferably. Is 5 to 30 ⁇ m.
  • the above “thickness of the pressure-sensitive adhesive layer (X1)” It means the thickness of the agent layer (in FIG. 2, the thickness of each of the adhesive layers (X11) and (X12)).
  • the thickness of each layer which comprises an adhesive laminated body means the value measured by the method as described in an Example.
  • the thickness ratio [(Y1-1) / (X1) between the heat-expandable base material layer (Y1-1) and the pressure-sensitive adhesive layer (X1) before the heat treatment for separation. ]] Is preferably 1000 or less, more preferably 200 or less, still more preferably 60 or less, and still more preferably 30 or less. If the thickness ratio is 1000 or less, it can be easily separated by a heat treatment at the interface P between the pressure sensitive adhesive sheet (I) and the base material (Y2) of the pressure sensitive adhesive sheet (II). It can be set as an adhesive laminated body.
  • the thickness ratio is preferably 0.2 or more, more preferably 0.5 or more, still more preferably 1.0 or more, and still more preferably 5.0 or more.
  • the base material (Y1) is composed only of the thermally expandable base material layer (Y1-1) as shown in FIG. 1 (a). As shown in FIG. 1B, it has a heat-expandable base material layer (Y1-1) on the pressure-sensitive adhesive sheet (II) side, and a non-heat-expandable base material layer on the pressure-sensitive adhesive layer (X1) side. It may have (Y1-2).
  • the thickness ratio between the thermally expandable substrate layer (Y1-1) and the non-thermally expandable substrate layer (Y1-2) [(Y1 -1) / (Y1-2)] is preferably 0.02 to 200, more preferably 0.03 to 150, and still more preferably 0.05 to 100.
  • the pressure-sensitive adhesive sheet (I) of the second embodiment is a first pressure-sensitive adhesive layer that is a heat-expandable pressure-sensitive adhesive layer containing heat-expandable particles on both sides of the base material (Y1).
  • (X11) and what has the 2nd adhesive layer (X12) which is a non-thermally expandable adhesive layer are mentioned.
  • the 1st adhesive layer (X11) which is a thermally expansible adhesive layer, and the base material (Y2) of adhesive sheet (II) contact directly.
  • a base material (Y1) is a non-thermally expandable base material layer.
  • the first pressure-sensitive adhesive layer (X11) which is a thermally expandable pressure-sensitive adhesive layer and the second pressure-sensitive adhesive layer which is a non-thermally expandable pressure-sensitive adhesive layer before the heat treatment for separation.
  • the thickness ratio [(X11) / (X12)] to (X12) is preferably 0.1 to 80, more preferably 0.3 to 50, and still more preferably 0.5 to 15.
  • the thickness ratio between the first pressure-sensitive adhesive layer (X11) which is a thermally expandable pressure-sensitive adhesive layer and the base material (Y1) before the heat treatment for separation [( X11) / (Y1)] is preferably 0.05 to 20, more preferably 0.1 to 10, and still more preferably 0.2 to 3.
  • thermally expandable substrate layer (Y1-1) constituting the substrate (Y1) non-thermally expanded
  • the adhesive base layer (Y1-2) and the pressure-sensitive adhesive layer (X1) will be described in detail.
  • the thermally expandable particles used in the present invention may be particles that expand by heating, but are preferably particles whose expansion start temperature (t) is adjusted to 60 to 270 ° C. Expansion start temperature (t) is suitably selected according to the use of an adhesive layered product. For example, in the manufacturing method of the present invention, when the adhesive laminate is not exposed to a high temperature environment in the steps (1) and (2) (for example, a modified region is formed as a division starting point in the semiconductor wafer) The expansion start temperature of the thermally expandable particles is preferably as low as possible within the above temperature range.
  • separating an adhesive sheet (I) and an adhesive sheet (1I) can be made into a small thing, and the manufacturing cost of a cut material and / or a ground material can be reduced. Further, the pressure-sensitive adhesive sheet (I) and the pressure-sensitive adhesive sheet (1I) can be separated without giving an excessive heat history to the workpiece.
  • the expansion start temperature (t) of the 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 composed of a thermoplastic resin and an encapsulated component encapsulated in the outer shell and vaporized when heated to a predetermined temperature.
  • a thermoplastic resin constituting the outer shell of the microencapsulated foaming agent include vinylidene chloride-acrylonitrile copolymer, polyvinyl alcohol, polyvinyl butyral, polymethyl methacrylate, polyacrylonitrile, polyvinylidene chloride, and polysulfone.
  • Examples of the inclusion component contained in the outer shell include propane, butane, pentane, hexane, heptane, octane, nonane, decane, isobutane, isopentane, isohexane, isoheptane, isooctane, isononane, isodecane, cyclopropane, cyclobutane, cyclopentane.
  • the average particle diameter of the thermally expandable particles before expansion at 23 ° C. used in one embodiment of the present invention is preferably 3 to 100 ⁇ m, more preferably 4 to 70 ⁇ m, still more preferably 6 to 60 ⁇ m, still more preferably 10 to 50 ⁇ m.
  • the average particle diameter of the thermally expandable particles before expansion is the volume-median particle diameter (D 50 ), and is a laser diffraction particle size distribution measuring device (for example, product name “Mastersizer 3000” manufactured by Malvern).
  • the cumulative volume frequency calculated from the smaller particle diameter of the heat-expandable particles before expansion means a particle diameter corresponding to 50%.
  • the 90% particle diameter (D 90 ) before expansion at 23 ° C. of the thermally expandable particles used in one embodiment of the present invention is preferably 10 to 150 ⁇ m, more preferably 20 to 100 ⁇ m, still more preferably 25 to 90 ⁇ m, More preferably, it is 30 to 80 ⁇ m.
  • grain is expansion
  • the particle diameter corresponding to 90% of the cumulative volume frequency calculated from the smaller particle diameter of the thermally expandable particles before expansion is meant.
  • 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 embodiment of the present invention is preferably 1.5 to 100 times, more preferably 2 to 80 times, Preferably it is 2.5 to 60 times, and more preferably 3 to 40 times.
  • Thermal expansion base material layer (Y1-1) preferably satisfies the following requirement (1).
  • the storage elastic modulus E ′ (t) of the thermally expandable base material layer (Y1-1) at the expansion start temperature (t) of the thermally expandable particles is 1.0 ⁇ 10 7 Pa or less. is there.
  • the storage elastic modulus E ′ of the thermally expandable base material layer (Y1-1) at a predetermined temperature means a value measured by the method described in the examples.
  • the requirement (1) can be said to be an index indicating the rigidity of the thermally expandable substrate layer (Y1-1) immediately before the thermally expandable particles expand.
  • the storage elastic modulus E ′ of the thermally expandable base material layer (Y1-1) decreases as the temperature rises.
  • the thermally expandable particles start to expand before and after reaching the expansion start temperature (t) of the thermally expandable particles, the storage elastic modulus E ′ of the thermally expandable base material layer (Y1-1) is decreased. It is suppressed.
  • the temperature is higher than the expansion start temperature (t). It is necessary to make it easy to form unevenness on the surface of the pressure-sensitive adhesive sheet (I) on the side laminated with the base material (Y2) by heating. That is, the thermally expandable substrate layer (Y1-1) satisfying the above requirement (1) becomes sufficiently large by expansion of the thermally expandable particles at the expansion start temperature (t), and the substrate of the pressure-sensitive adhesive sheet (II) Unevenness is easily formed on the surface of the pressure-sensitive adhesive sheet (I) on the side laminated with (Y2). As a result, it can be an adhesive laminate that can be easily and collectively separated with a slight force at the interface P between the adhesive sheet (I) and the base material (Y2) of the adhesive sheet (II).
  • the storage elastic modulus E ′ (t) defined by the requirement (1) of the thermally expandable substrate layer (Y1-1) used in the present invention is preferably 9.0 ⁇ 10 6 Pa or less, more preferably Is 8.0 ⁇ 10 6 Pa or less, more preferably 6.0 ⁇ 10 6 Pa or less, and still more preferably 4.0 ⁇ 10 6 Pa or less. Moreover, the flow of the expanded thermally expandable particles is suppressed, and the shape maintaining property of the unevenness formed on the surface of the pressure-sensitive adhesive sheet (I) on the side laminated with the base material (Y2) of the pressure-sensitive adhesive sheet (II) is improved.
  • the storage elastic modulus E ′ (t) defined by the requirement (1) of the thermally expandable base material layer (Y1-1) is preferably It is 1.0 ⁇ 10 3 Pa or more, more preferably 1.0 ⁇ 10 4 Pa or more, and further preferably 1.0 ⁇ 10 5 Pa or more.
  • the content of the heat-expandable particles in the heat-expandable base material layer (Y1-1) Preferably, it is 1 to 40% by mass, more preferably 5 to 35% by mass, still more preferably 10 to 30% by mass, and still more preferably 15 to 30% by mass with respect to the total mass (100% by mass) of the layer (Y1-1). 25% by mass.
  • the surface of the heat-expandable base material layer (Y1-1) is oxidized or You may perform surface treatment by an uneven
  • the oxidation method include corona discharge treatment, plasma discharge treatment, chromic acid treatment (wet), hot air treatment, ozone, and ultraviolet irradiation treatment.
  • the unevenness method include sand blast method and solvent treatment method. Etc.
  • the thermally expandable substrate layer (Y1-1) is preferably formed from a resin composition (y) containing a resin and thermally expandable particles.
  • the additive for base materials in the resin composition (y) in the range which does not impair the effect of this invention as needed.
  • the substrate additive include an ultraviolet absorber, a light stabilizer, an antioxidant, an antistatic agent, a slip agent, an antiblocking agent, and a colorant.
  • These base material additives may be used alone or in combination of two or more. When these base material additives are contained, the content of each base material additive is preferably 0.0001 to 20 parts by mass, more preferably 0.001 to about 100 parts by mass of the resin. 10 parts by mass.
  • the thermally expandable particles contained in the resin composition (y), which is a material for forming the thermally expandable base material layer (Y1-1), are as described above.
  • the content of the heat-expandable particles is preferably 1 to 40% by mass, more preferably 5 to 35% by mass, and still more preferably 10% with respect to the total amount (100% by mass) of the active ingredients of the resin composition (y). To 30% by mass, and more preferably 15 to 25% by mass.
  • the resin contained in the resin composition (y) that is a material for forming the thermally expandable base material layer (Y1-1) may be a non-adhesive resin or an adhesive resin. That is, even if the resin contained in the resin composition (y) is an adhesive resin, in the process of forming the thermally expandable substrate layer (Y1-1) from the resin composition (y), the adhesive resin
  • the resin obtained by polymerization reaction with the polymerizable compound may be a non-adhesive resin, and the thermally expandable base material layer (Y1-1) containing the resin may be non-adhesive.
  • the mass average molecular weight (Mw) of the resin contained in the resin composition (y) is preferably 1,000 to 1,000,000, more preferably 1,000 to 700,000, and still more preferably 1,000 to 500,000. Further, when the resin is a copolymer having two or more kinds of structural units, the form of the copolymer is not particularly limited, and any of a block copolymer, a random copolymer, and a graft copolymer It may be.
  • the content of the resin is preferably 50 to 99% by mass, more preferably 60 to 95% by mass, and still more preferably 65 to 90% by mass with respect to the total amount (100% by mass) of the active ingredients of the resin composition (y). %, More preferably 70 to 85% by mass.
  • the resin contained in the resin composition (y) is selected from acrylic urethane resins and olefin resins. It is preferable that 1 or more types included are included. Moreover, as said acrylic urethane type resin, the following resin (U1) is preferable.
  • urethane prepolymer (UP) serving as the main chain of the acrylic urethane resin (U1) include a reaction product of a polyol and a polyvalent isocyanate.
  • the urethane prepolymer (UP) is preferably obtained by further performing a chain extension reaction using a chain extender.
  • Examples of the polyol used as a raw material for the urethane prepolymer (UP) include alkylene type polyols, ether type polyols, ester type polyols, ester amide type polyols, ester / ether type polyols, and carbonate type polyols. These polyols may be used independently and may use 2 or more types together.
  • the polyol used in one embodiment of the present invention is preferably a diol, more preferably an ester diol, an alkylene diol, and a carbonate diol, and even more preferably an ester diol and a carbonate diol.
  • ester type diols include alkane diols such as 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol; ethylene glycol, propylene glycol, One or more selected from diols such as alkylene glycols such as diethylene glycol and dipropylene glycol; phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, 4,4-diphenyldicarboxylic acid, diphenylmethane-4 , 4'-dicarboxylic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, het acid, maleic acid, fumaric acid, itaconic acid, cyclohexane-1,3-dicarboxylic acid, cyclohexane-1,4-dicarbox
  • alkylene type diol examples include alkane diols such as 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol; ethylene glycol, propylene glycol, And alkylene glycols such as diethylene glycol and dipropylene glycol; polyalkylene glycols such as polyethylene glycol, polypropylene glycol, and polybutylene glycol; polyoxyalkylene glycols such as polytetramethylene glycol; and the like.
  • alkane diols such as 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol
  • ethylene glycol, propylene glycol And alkylene glycols such as diethylene glycol and dipropylene glycol
  • Examples of the carbonate type diol include 1,4-tetramethylene carbonate diol, 1,5-pentamethylene carbonate diol, 1,6-hexamethylene carbonate diol, 1,2-propylene carbonate diol, and 1,3-propylene carbonate diol. 2,2-dimethylpropylene carbonate diol, 1,7-heptamethylene carbonate diol, 1,8-octamethylene carbonate diol, 1,4-cyclohexane carbonate diol, and the like.
  • polyvalent isocyanate used as a raw material for the urethane prepolymer (UP) examples include aromatic polyisocyanates, aliphatic polyisocyanates, and alicyclic polyisocyanates. These polyvalent isocyanates may be used alone or in combination of two or more. These polyisocyanates may be a trimethylolpropane adduct type modified product, a burette type modified product reacted with water, or an isocyanurate type modified product containing an isocyanurate ring.
  • the polyisocyanate used in one embodiment of the present invention is preferably diisocyanate, and 4,4′-diphenylmethane diisocyanate (MDI), 2,4-tolylene diisocyanate (2,4-TDI), 2,6 More preferred is at least one selected from tolylene diisocyanate (2,6-TDI), hexamethylene diisocyanate (HMDI), and alicyclic diisocyanate.
  • MDI 4,4′-diphenylmethane diisocyanate
  • 2,4-TDI 2,4-tolylene diisocyanate
  • 2,6 More preferred is at least one selected from tolylene diisocyanate (2,6-TDI), hexamethylene diisocyanate (HMDI), and alicyclic diisocyanate.
  • alicyclic diisocyanate examples include 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate, IPDI), 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane.
  • IPDI isophorone diisocyanate
  • Examples include diisocyanate, methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, and isophorone diisocyanate (IPDI) is preferred.
  • the urethane prepolymer (UP) serving as the main chain of the acrylic urethane resin (U1) is a reaction product of a diol and a diisocyanate, and is a straight chain having ethylenically unsaturated groups at both ends.
  • a urethane prepolymer is preferred.
  • an NCO group at the end of the linear urethane prepolymer obtained by reacting a diol and a diisocyanate compound, and a hydroxyalkyl (meth) acrylate And a method of reacting with.
  • hydroxyalkyl (meth) acrylate examples include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 3-hydroxy Examples thereof include butyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate.
  • the (meth) acrylic acid ester is preferably one or more selected from alkyl (meth) acrylates and hydroxyalkyl (meth) acrylates, and more preferably used in combination with alkyl (meth) acrylates and hydroxyalkyl (meth) acrylates.
  • the proportion of hydroxyalkyl (meth) acrylate to 100 parts by mass of alkyl (meth) acrylate is preferably 0.1 to 100 parts by mass, The amount is preferably 0.5 to 30 parts by mass, more preferably 1.0 to 20 parts by mass, and still more preferably 1.5 to 10 parts by mass.
  • the carbon number of the alkyl group of the alkyl (meth) acrylate is preferably 1 to 24, more preferably 1 to 12, still more preferably 1 to 8, and still more preferably 1 to 3.
  • hydroxyalkyl (meth) acrylate the same thing as the hydroxyalkyl (meth) acrylate used in order to introduce
  • vinyl compounds other than (meth) acrylic acid esters include aromatic hydrocarbon vinyl compounds such as styrene, ⁇ -methylstyrene, and vinyl toluene; vinyl ethers such as methyl vinyl ether and ethyl vinyl ether; vinyl acetate and vinyl propionate.
  • Polar group-containing monomers such as (meth) acrylonitrile, N-vinylpyrrolidone, (meth) acrylic acid, maleic acid, fumaric acid, itaconic acid, and meta (acrylamide). These may be used alone or in combination of two or more.
  • the content of the (meth) acrylic acid ester in the vinyl compound is preferably 40 to 100% by mass, more preferably 65 to 100% by mass, and still more preferably based on the total amount (100% by mass) of the vinyl compound. It is 80 to 100% by mass, more preferably 90 to 100% by mass.
  • the total content of alkyl (meth) acrylate and hydroxyalkyl (meth) acrylate in the vinyl compound is preferably 40 to 100% by mass, more preferably 65 to 100% by mass with respect to the total amount (100% by mass) of the vinyl compound.
  • the amount is 100% by mass, more preferably 80 to 100% by mass, and still more preferably 90 to 100% by mass.
  • the acrylic urethane-based resin (U1) used in one embodiment of the present invention is obtained by mixing a urethane prepolymer (UP) and a vinyl compound containing a (meth) acrylic acid ester and polymerizing both.
  • the polymerization is preferably performed by adding a radical initiator.
  • the content ratio of the structural unit (u11) derived from the urethane prepolymer (UP) and the structural unit (u12) derived from the vinyl compound [(u11 ) / (U12)] is preferably 10/90 to 80/20, more preferably 20/80 to 70/30, still more preferably 30/70 to 60/40, and still more preferably 35 by mass ratio. / 65 to 55/45.
  • the olefin resin suitable as the resin contained in the resin composition (y) is a polymer having at least a structural unit derived from an olefin monomer.
  • the olefin monomer is preferably an ⁇ -olefin having 2 to 8 carbon atoms, and specifically includes ethylene, propylene, butylene, isobutylene, 1-hexene and the like. Among these, ethylene and propylene are preferable.
  • olefinic resins for example, ultra low density polyethylene (VLDPE, density: 880 kg / m 3 or more 910 kg / m less than 3), low density polyethylene (LDPE, density: 910 kg / m 3 or more 915 kg / m less than 3 ), Medium density polyethylene (MDPE, density: 915 kg / m 3 or more and less than 942 kg / m 3 ), high density polyethylene (HDPE, density: 942 kg / m 3 or more), linear low density polyethylene, etc .; polypropylene resin (PP); polybutene resin (PB); ethylene-propylene copolymer; olefin elastomer (TPO); poly (4-methyl-1-pentene) (PMP); ethylene-vinyl acetate copolymer (EVA); ethylene -Vinyl alcohol copolymer (EVOH); ethylene-propylene Olefinic terpolymers such as-(5-ethylid)
  • the olefin resin may be a modified olefin resin further modified by one or more selected from acid modification, hydroxyl group modification, and acrylic modification.
  • an acid-modified olefin resin obtained by subjecting an olefin resin to acid modification a modified polymer obtained by graft polymerization of the above-mentioned unmodified olefin resin with an unsaturated carboxylic acid or its anhydride.
  • unsaturated carboxylic acid or anhydride thereof include maleic acid, fumaric acid, itaconic acid, citraconic acid, glutaconic acid, tetrahydrophthalic acid, aconitic acid, (meth) acrylic acid, maleic anhydride, itaconic anhydride.
  • Glutaconic anhydride citraconic anhydride, aconitic anhydride, norbornene dicarboxylic anhydride, tetrahydrophthalic anhydride, and the like.
  • unsaturated carboxylic acid or its anhydride may be used independently, and may use 2 or more types together.
  • An acrylic modified olefin resin obtained by subjecting an olefin resin to acrylic modification is a modification obtained by graft polymerization of an alkyl (meth) acrylate as a side chain to the above-mentioned unmodified olefin resin that is a main chain.
  • a polymer is mentioned.
  • the number of carbon atoms in the alkyl group of the alkyl (meth) acrylate is preferably 1-20, more preferably 1-16, and still more preferably 1-12.
  • As said alkyl (meth) acrylate the same thing as the compound which can be selected as a below-mentioned monomer (a1 ') is mentioned, for example.
  • Examples of the hydroxyl group-modified olefin resin obtained by subjecting an olefin resin to hydroxyl group modification include a modified polymer obtained by graft-polymerizing a hydroxyl group-containing compound to the above-mentioned unmodified olefin resin as the main chain.
  • Examples of the hydroxyl group-containing compound include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 3-hydroxybutyl.
  • Examples thereof include hydroxyalkyl (meth) acrylates such as (meth) acrylate and 4-hydroxybutyl (meth) acrylate; unsaturated alcohols such as vinyl alcohol and allyl alcohol.
  • the resin composition (y) may contain a resin other than the acrylic urethane-based resin and the olefin-based resin as long as the effects of the present invention are not impaired.
  • 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 Polycarbonate; Polyurethane; Polyetheretherketone; Polyethersulfone; Polyphenylenesulfide; Polyimide resin such as polyetherimide and polyimide; Polyamide resin; Acrylic resin; Fluorine resin etc. are mentioned.
  • vinyl resins such as polyvinyl chloride, polyvinylidene chloride, and polyvinyl alcohol
  • polyester resins such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate
  • polystyrene acrylonitrile-butadiene-styrene copolymer
  • Polycarbonate Polyurethane
  • the content ratio of the resin other than the acrylic urethane-based resin and the olefin-based resin in the resin composition (y) is: Less is preferable.
  • the content ratio of the resin other than the acrylic urethane-based resin and the olefin-based resin is preferably less than 30 parts by mass, more preferably 20 parts by mass with respect to 100 parts by mass of the total amount of the resin contained in the resin composition (y). Less than, more preferably less than 10 parts by mass, still more preferably less than 5 parts by mass, and even more preferably less than 1 part by mass.
  • solvent-free resin composition (y1) As one embodiment of the resin composition (y) used in one embodiment of the present invention, an oligomer having an ethylenically unsaturated group having a mass average molecular weight (Mw) of 50000 or less, an energy ray polymerizable monomer, and the above-described thermal expansibility A solvent-free resin composition (y1) that includes particles and does not contain a solvent is exemplified. In the solventless resin composition (y1), no solvent is blended, but the energy beam polymerizable monomer contributes to the improvement of the plasticity of the oligomer. By irradiating the coating film formed from the solventless resin composition (y1) with energy rays, it is easy to form the thermally expandable base material layer (Y1-1) satisfying the requirement (1).
  • Mw mass average molecular weight
  • the mass average molecular weight (Mw) of the oligomer contained in the solventless resin composition (y1) is 50000 or less, preferably 1000 to 50000, more preferably 2000 to 40000, and still more preferably 3000 to 35000. More preferably, it is 4000-30000.
  • oligomer As said oligomer, what is necessary is just to have an ethylenically unsaturated group whose mass mean molecular weight is 50000 or less among resin contained in the above-mentioned resin composition (y), but the above-mentioned urethane prepolymer (UP ) Is preferred.
  • a modified olefin resin having an ethylenically unsaturated group can also be used.
  • the total content of the oligomer and the energy beam polymerizable monomer in the solventless resin composition (y1) is preferably 50 to 100% with respect to the total amount (100% by mass) of the solventless resin composition (y1). It is 99% by mass, more preferably 60 to 95% by mass, still more preferably 65 to 90% by mass, and still more preferably 70 to 85% by mass.
  • Examples of the energy ray polymerizable monomer include isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyloxy (meth) acrylate, cyclohexyl (meth) acrylate, adamantane ( Cycloaliphatic polymerizable compounds such as (meth) acrylate and tricyclodecane acrylate; Aromatic polymerizable compounds such as phenylhydroxypropyl acrylate, benzyl acrylate and phenol ethylene oxide modified acrylate; Tetrahydrofurfuryl (meth) acrylate, morpholine acrylate, N- And heterocyclic polymerizable compounds such as vinylpyrrolidone and N-vinylcaprolactam. These energy beam polymerizable monomers may be used independently and may use 2 or more types together.
  • the content ratio [oligomer / energy ray polymerizable monomer] of the oligomer and the energy ray polymerizable monomer in the solventless resin composition (y1) is preferably 20/80 to 90 / in mass ratio. 10, more preferably 30/70 to 85/15, still more preferably 35/65 to 80/20.
  • the solventless resin composition (y1) is further blended with a photopolymerization initiator.
  • a photopolymerization initiator By containing the photopolymerization initiator, the curing reaction can be sufficiently advanced even by irradiation with a relatively low energy beam.
  • photopolymerization initiator examples include 1-hydroxy-cyclohexyl-phenyl-ketone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzyl phenyl sulfide, tetramethylthiuram monosulfide, azobisisobutyrol. Nitrile, dibenzyl, diacetyl, 8-chloroanthraquinone and the like can be mentioned. These photoinitiators may be used independently and may use 2 or more types together.
  • the blending amount of the photopolymerization initiator is preferably 0.01 to 5 parts by mass, more preferably 0.01 to 4 parts by mass with respect to the total amount (100 parts by mass) of the oligomer and the energy ray polymerizable monomer.
  • the amount is preferably 0.02 to 3 parts by mass.
  • Non-thermally expandable substrate layer (Y1-2) Examples of the material for forming the non-thermally expandable base material layer (Y1-2) constituting the base material (Y1) include paper materials, resins, metals, and the like. It can select suitably according to a use.
  • Examples of the paper material include thin paper, medium quality paper, high quality paper, impregnated paper, coated paper, art paper, sulfate paper, glassine paper, and the like.
  • Examples of the resin include polyolefin resins such as polyethylene and polypropylene; vinyl resins such as polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl acetate copolymer, and ethylene-vinyl alcohol copolymer; polyethylene terephthalate, poly Polyester resins such as butylene terephthalate and polyethylene naphthalate; polystyrene; acrylonitrile-butadiene-styrene copolymer; cellulose triacetate; polycarbonate; urethane resin such as polyurethane and acrylic modified polyurethane; polymethylpentene; polysulfone; polyether ether ketone; Polyethersulfone; Polyphenylene sulfide; Polyimide resin such as poly
  • These forming materials may be composed of one kind or in combination of two or more kinds.
  • 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.
  • non-thermally expandable base material layer (Y1-2) contains a resin
  • it may contain the above-mentioned base material additive that can be contained in the resin composition (y) together with the resin.
  • the non-thermally expandable base material layer (Y1-2) is a non-thermally expandable layer that is determined based on the above-described method. Therefore, the volume change rate (%) of the non-thermally expandable substrate layer (Y1-2) calculated from the above formula is less than 5%, preferably less than 2%, more preferably less than 1%. More preferably, it is less than 0.1%, and still more preferably less than 0.01%.
  • the non-thermally expandable substrate layer (Y1-2) may contain thermally expandable particles as long as the volume change rate is in the above range.
  • the volume change rate can be adjusted to the above range even if the thermally expandable particles are included.
  • the specific content of the heat-expandable particles is usually less than 3% by weight, preferably less than 1% by weight, based on the total weight (100% by weight) of the non-heat-expandable base material layer (Y1-2).
  • the heat-expandable particles are not contained in the non-heat-expandable base material layer (Y1-2).
  • the pressure-sensitive adhesive layer (X1) of the pressure-sensitive adhesive sheet (I) used in the first aspect of the present invention can be formed from a pressure-sensitive adhesive composition (x1) containing a pressure-sensitive adhesive resin.
  • the pressure-sensitive adhesive composition (x1) may contain pressure-sensitive adhesive additives such as a crosslinking agent, a tackifier, a polymerizable compound, and a polymerization initiator as necessary.
  • pressure-sensitive adhesive additives such as a crosslinking agent, a tackifier, a polymerizable compound, and a polymerization initiator as necessary.
  • the pressure-sensitive adhesive sheet (I) has the first pressure-sensitive adhesive layer (X11) and the second pressure-sensitive adhesive layer (X12), the first pressure-sensitive adhesive layer (X11) and the second pressure-sensitive adhesive layer (X12) are also used. It can be formed from a pressure-sensitive adhesive composition (x1) containing the following components.
  • any polymer may be used as long as the resin has adhesiveness and has a mass average molecular weight (Mw) of 10,000 or more.
  • the mass average molecular weight (Mw) of the adhesive resin used in one embodiment of the present invention is preferably 10,000 to 2,000,000, more preferably 20,000 to 1,500,000, and even more preferably 30,000, from the viewpoint of improving the adhesive strength. ⁇ 1 million.
  • the adhesive resin examples include rubber resins such as acrylic resins, urethane resins, and polyisobutylene resins, polyester resins, olefin resins, silicone resins, and polyvinyl ether resins. These adhesive resins may be used independently and may use 2 or more types together. In addition, when these adhesive resins are copolymers having two or more kinds of structural units, the form of the copolymer is not particularly limited, and a block copolymer, a random copolymer, and a graft copolymer are not limited. Any of polymers may be used.
  • the adhesive resin used in one embodiment of the present invention may be an energy ray curable adhesive resin in which a polymerizable functional group is introduced into the side chain of the above-mentioned adhesive resin.
  • a polymerizable functional group include a (meth) acryloyl group and a vinyl group.
  • energy rays include ultraviolet rays and electron beams, but ultraviolet rays are preferred.
  • the adhesive resin contains an acrylic resin from the viewpoint of developing excellent adhesive force.
  • the first pressure-sensitive adhesive layer (X11) in contact with the resin film-forming sheet (II) Includes an acrylic resin, it is possible to easily form irregularities on the surface of the first pressure-sensitive adhesive layer.
  • the content of the acrylic resin in the adhesive resin is preferably 30 to 100 with respect to the total amount (100% by mass) of the adhesive resin contained in the adhesive composition (x1) or the adhesive layer (X1). % By mass, more preferably 50 to 100% by mass, still more preferably 70 to 100% by mass, and still more preferably 85 to 100% by mass.
  • the acrylic resin that can be used as the adhesive resin includes, for example, a polymer including a structural unit derived from an alkyl (meth) acrylate having a linear or branched alkyl group, a cyclic structure And a polymer containing a structural unit derived from a (meth) acrylate having a hydrogen atom.
  • the mass average molecular weight (Mw) of the acrylic resin is preferably 100,000 to 1,500,000, more preferably 200,000 to 1,300,000, still more preferably 350,000 to 1,200,000, still more preferably 500,000 to 1,100,000. .
  • a structural unit (a1) derived from an alkyl (meth) acrylate (a1 ′) (hereinafter also referred to as “monomer (a1 ′)”) and a functional group-containing monomer (a2).
  • An acrylic copolymer (A1) having a structural unit (a2) derived from ') (hereinafter also referred to as “monomer (a2')") is more preferred.
  • the number of carbon atoms of the alkyl group contained in the monomer (a1 ′) is preferably 1 to 24, more preferably 1 to 12, still more preferably 2 to 10, and still more preferably 4 to 8 from the viewpoint of improving adhesive properties. It is.
  • the alkyl group contained in the monomer (a1 ′) may be a linear alkyl group or a branched alkyl group.
  • Examples of the monomer (a1 ′) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, tridecyl ( Examples include meth) acrylate and stearyl (meth) acrylate. These monomers (a1 ′) may be used alone or in combination of two or more. As the monomer (a1 ′), butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate are preferable.
  • the content of the structural unit (a1) is preferably 50 to 99.9% by mass, more preferably 60 to 99.0% by mass with respect to the total structural unit (100% by mass) of the acrylic copolymer (A1). %, More preferably 70 to 97.0% by mass, and still more preferably 80 to 95.0% by mass.
  • a hydroxyl group, a carboxy group, an amino group, an epoxy group etc. examples include a hydroxyl group-containing monomer, a carboxy group-containing monomer, an amino group-containing monomer, and an epoxy group-containing monomer. These monomers (a2 ′) may be used alone or in combination of two or more. Among these, as the monomer (a2 ′), a hydroxyl group-containing monomer and a carboxy group-containing monomer are preferable.
  • Examples of the hydroxyl group-containing monomer include the same hydroxyl group-containing compounds as described above.
  • carboxy group-containing monomer examples include ethylenically unsaturated monocarboxylic acids such as (meth) acrylic acid and crotonic acid; ethylenically unsaturated dicarboxylic acids such as fumaric acid, itaconic acid, maleic acid and citraconic acid, and anhydrides thereof.
  • ethylenically unsaturated monocarboxylic acids such as (meth) acrylic acid and crotonic acid
  • dicarboxylic acids such as fumaric acid, itaconic acid, maleic acid and citraconic acid, and anhydrides thereof.
  • the content of the structural unit (a2) is preferably 0.1 to 40% by weight, more preferably 0.5 to 35% by weight with respect to all the structural units (100% by weight) of the acrylic copolymer (A1). %, More preferably 1.0 to 30% by mass, and still more preferably 3.0 to 25% by mass.
  • the acrylic copolymer (A1) may further have a structural unit (a3) derived from another monomer (a3 ′) other than the monomers (a1 ′) and (a2 ′).
  • the content of the structural units (a1) and (a2) is preferably 70 with respect to the total structural units (100% by mass) of the acrylic copolymer (A1).
  • To 100% by mass more preferably 80 to 100% by mass, still more preferably 90 to 100% by mass, and still more preferably 95 to 100% by mass.
  • Examples of the monomer (a3 ′) include olefins such as ethylene, propylene, and isobutylene; halogenated olefins such as vinyl chloride and vinylidene chloride; diene monomers such as butadiene, isoprene, and chloroprene; cyclohexyl (meth) acrylate, It has a cyclic structure such as benzyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, imide (meth) acrylate, etc.
  • olefins such as ethylene, propylene, and isobutylene
  • halogenated olefins such as vinyl chloride and vinylidene chloride
  • diene monomers such as butadiene, iso
  • the acrylic copolymer (A1) may be an energy ray curable acrylic copolymer having a polymerizable functional group introduced into the main chain and / or side chain.
  • the polymerizable functional group and the energy ray are as described above.
  • the polymerizable functional group includes an acrylic copolymer having the above structural units (a1) and (a2), and a substituent that can be bonded to the functional group of the structural unit (a2) of the acrylic copolymer.
  • a polymerizable compound (Xa) having a polymerizable functional group can be introduced.
  • Examples of the polymerizable compound (Xa) include (meth) acryloyloxyethyl isocyanate, meta-isopropenyl- ⁇ , ⁇ -dimethylbenzyl isocyanate, (meth) acryloyl isocyanate, allyl isocyanate, glycidyl (meth) acrylate, (meth) Acrylic acid etc. are mentioned.
  • the adhesive composition (x1) contains the adhesive resin which has a functional group like the above-mentioned acrylic copolymer (A1), it may contain a crosslinking agent further. preferable.
  • the said crosslinking agent reacts with the adhesive resin which has a functional group, and bridge
  • crosslinking agent examples include an isocyanate crosslinking agent, an epoxy crosslinking agent, an aziridine crosslinking agent, and a metal chelate crosslinking agent. These crosslinking agents may be used independently and may use 2 or more types together. Among these crosslinking agents, an isocyanate-based crosslinking agent is preferable from the viewpoints of increasing cohesive force and improving adhesive force, and availability.
  • the content of the crosslinking agent is appropriately adjusted depending on the number of functional groups that the adhesive resin has, but is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the adhesive resin having a functional group, The amount is more preferably 0.03 to 7 parts by mass, still more preferably 0.05 to 5 parts by mass.
  • the pressure-sensitive adhesive composition (x1) may further contain a tackifier from the viewpoint of further improving the adhesive strength.
  • the “tackifier” is a component that assists in improving the adhesive strength of the above-mentioned adhesive resin, and refers to an oligomer having a mass average molecular weight (Mw) of less than 10,000. It is distinguished from a functional resin.
  • the mass average molecular weight (Mw) of the tackifier is preferably 400 to 10000, more preferably 500 to 8000, and still more preferably 800 to 5000.
  • Examples of the tackifier are obtained by copolymerizing C5 fractions such as rosin resin, terpene resin, styrene resin, pentene, isoprene, piperine, 1,3-pentadiene generated by thermal decomposition of petroleum naphtha.
  • C9 petroleum resin obtained by copolymerizing C9 fractions such as indene generated by thermal decomposition of petroleum naphtha and vinyltoluene, 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, and still more preferably 70 to 150 ° C.
  • the “softening point” of the tackifier means a value measured according to JIS K2531.
  • a tackifier may be used independently and may use 2 or more types from which a softening point and a structure differ. And when using 2 or more types of several tackifier, it is preferable that the weighted average of the softening point of these several tackifier belongs to the said range.
  • the content of the tackifier is preferably 0.01 to the total amount (100% by mass) of the active ingredient in the adhesive composition (x1) or the total mass (100% by mass) of the adhesive layer (X1). 65% by mass, more preferably 0.05 to 55% by mass, still more preferably 0.1 to 50% by mass, still more preferably 0.5 to 45% by mass, still more preferably 1.0 to 40% by mass. is there.
  • the pressure-sensitive adhesive composition (x1) includes an energy ray-curable pressure-sensitive adhesive resin as the pressure-sensitive adhesive resin
  • a pressure-sensitive polymerization initiator is further contained.
  • the adhesive layer formed from the adhesive composition can be irradiated with a relatively low energy energy beam. It is possible to sufficiently advance the curing reaction and adjust the adhesive strength to a desired range.
  • mode of this invention the same thing as what is mix
  • the content of the photopolymerization initiator is preferably 0.01 to 10 parts by mass, more preferably 0.03 to 5 parts by mass, and still more preferably 0.001 parts by mass with respect to 100 parts by mass of the energy ray curable adhesive resin. 05 to 2 parts by mass.
  • the pressure-sensitive adhesive composition (x1) contains additives for pressure-sensitive adhesives used for general pressure-sensitive adhesives in addition to the above-mentioned additives, as long as the effects of the present invention are not impaired. You may do it.
  • an adhesive additive include antioxidants, softeners (plasticizers), rust inhibitors, pigments, dyes, retarders, reaction accelerators (catalysts), ultraviolet absorbers, and the like. These pressure-sensitive adhesive additives may be used alone or in combination of two or more.
  • each pressure-sensitive adhesive additive is preferably 0.0001 to 20 parts by mass, more preferably 0.001 to 100 parts by mass of the adhesive resin. ⁇ 10 parts by mass.
  • the 1st adhesive layer (X11) which is a thermally expansible adhesive layer is further It is formed from a heat-expandable pressure-sensitive adhesive composition (x11) containing heat-expandable particles.
  • the thermally expandable particles are as described above.
  • the content of the heat-expandable particles is preferably based on the total amount (100% by mass) of the active ingredient of the heat-expandable pressure-sensitive adhesive composition (x11) or the total mass (100% by mass) of the heat-expandable pressure-sensitive adhesive layer. Is 1 to 70% by mass, more preferably 2 to 60% by mass, still more preferably 3 to 50% by mass, and still more preferably 5 to 40% by mass.
  • the content of the heat-expandable particles in the non-heat-expandable pressure-sensitive adhesive composition that is a material for forming the non-heat-expandable pressure-sensitive adhesive layer is The less it is, the better.
  • the content of the heat-expandable particles is preferably based on the total amount (100% by mass) of the active ingredients of the non-thermally expandable pressure-sensitive adhesive composition or the total mass (100% by mass) of the non-heat-expandable pressure-sensitive adhesive layer.
  • the heat-expandable particles are not contained in the non-heat-expandable pressure-sensitive adhesive composition or the non-heat-expandable pressure-sensitive adhesive layer.
  • the storage shear modulus G ′ (23) of the first pressure-sensitive adhesive layer (X11) which is a non-thermally expandable pressure-sensitive adhesive layer at 23 ° C. is preferably 1.0 ⁇ 10 8 Pa or less. Preferably it is 5.0 * 10 ⁇ 7 > Pa or less, More preferably, it is 1.0 * 10 ⁇ 7 > Pa or less.
  • the storage shear modulus G ′ (23) of the first pressure-sensitive adhesive layer (X11) which is a non-thermally expandable pressure-sensitive adhesive layer is 1.0 ⁇ 10 8 Pa or less, for example, the pressure-sensitive adhesive laminate shown in FIG.
  • the first is in contact with the pressure-sensitive adhesive sheet (II) due to the expansion of the thermally expandable particles in the thermally expandable substrate layer (Y1-1) by the heat treatment for separation. Unevenness is easily formed on the surface of the pressure-sensitive adhesive layer (X11).
  • the storage shear modulus G ′ (23) of the first pressure-sensitive adhesive layer (X11), which is a non-thermally expandable pressure-sensitive adhesive layer, at 23 ° C. is preferably 1.0 ⁇ 10 4 Pa or more, more preferably 5 0.0 ⁇ 10 4 Pa or more, more preferably 1.0 ⁇ 10 5 Pa or more.
  • the storage shear elastic modulus G '(23) of an adhesive layer means the value measured by the method as described in an Example.
  • the pressure-sensitive adhesive sheet (II) of the pressure-sensitive adhesive laminate used in the production method of the present invention has a base material (Y2) and a pressure-sensitive adhesive layer (X2), and the base material (Y2) is directly laminated with the pressure-sensitive adhesive sheet (I). To do.
  • the above-described oxidation method or unevenness method is applied to the surface of the base material (Y2) on the side where the pressure-sensitive adhesive layer is laminated.
  • the surface treatment by such as, easy adhesion treatment, or primer treatment may be performed.
  • the surface of the adhesive layer (X2) such as a semiconductor wafer having bumps, from the viewpoint of suppressing the residue of the adhesive layer (X2) from adhering to the cut object and / or the ground object.
  • the adhesive sheet (II) is based on the viewpoint that the followability is excellent with respect to the workpiece having large irregularities and the temporal stability of the adhesive force of the adhesive layer (X2) is excellent.
  • the surface of the base material (Y2) on the pressure-sensitive adhesive layer (X2) side may be subjected to antistatic treatment. When it has an intermediate
  • the substrate (Y2) is preferably a non-thermally expandable substrate.
  • the pressure-sensitive adhesive layer (X2) is also a non-thermally expandable pressure-sensitive adhesive layer from the viewpoint of maintaining good adhesion to the adherend before and after the heat treatment.
  • the intermediate layer (Z2) is also preferably a non-thermally expandable layer.
  • the volume change rate (%) of the base material (Y2), the pressure-sensitive adhesive layer (X2), and the intermediate layer (Z2) calculated from the above formulas is independently less than 5%, preferably Is less than 2%, more preferably less than 1%, still more preferably less than 0.1%, still more preferably less than 0.01%. More preferably, the base material (Y2), the pressure-sensitive adhesive layer (X2), and the intermediate layer (Z2) are free from thermally expandable particles.
  • the substrate (Y2), the pressure-sensitive adhesive layer (X2), and the intermediate layer (Z2) will be described.
  • Base material (Y2) examples include the same materials as those for forming the non-thermally expandable base material layer (Y1-2) described above.
  • a base material (Y2) contains resin, and it is more preferable that the resin layer containing resin is formed in the surface of the base material (Y2) at the side of laminating
  • the base material (Y2) is more preferably a resin film or a resin sheet. Further, among the resin film or resin sheet, the grinding of the workpiece in the step (4) has the property of stably holding the workpiece even when the workpiece is ground extremely thin.
  • a polyethylene film, a polypropylene film, an ethylene-vinyl acetate copolymer (EVA) film, and a polyethylene terephthalate film are preferable, and an ethylene-vinyl acetate copolymer (EVA) film is more preferable.
  • the above-mentioned resin film or resin sheet may contain a well-known filler, a coloring agent, an antistatic agent, antioxidant, an organic lubricant, a catalyst, etc.
  • coloring or metal may be vapor-deposited as desired.
  • the surface of the base material (Y2) to be laminated on the pressure-sensitive adhesive sheet (I) has been subjected to a peeling treatment from the viewpoint of enabling easy separation with a slight force at the interface P after the heat treatment for separation. Also good.
  • the base material (Y2) has a viewpoint that it is easy to prevent positional displacement when the processing object is applied to the adhesive layer (X2), and the adhesive layer ( From the viewpoint of easily preventing excessive subsidence in X2), the storage elastic modulus E ′ (23) at 23 ° C. is preferably 1.0 ⁇ 10 6 Pa or more.
  • the base material (Y2) may contain thermally expandable particles as long as the volume change rate is in the above range. From the above viewpoint, the content of the thermally expandable particles in the base material (Y2) is Less is preferable.
  • the content of the heat-expandable particles in the substrate (Y2) is usually less than 3% by mass, preferably less than 1% by mass, more preferably relative to the total mass (100% by mass) of the substrate (Y2). It is less than 0.1% by mass, more preferably less than 0.01% by mass, and still more preferably less than 0.001% by mass. More preferably, the thermally expandable particles are not contained in the base material (Y2).
  • the thickness of the substrate (Y2) is preferably 5 to 500 ⁇ m, more preferably 15 to 300 ⁇ m, and still more preferably 20 to 200 ⁇ m. If the thickness of the substrate (Y2) is 5 ⁇ m or more, it is easy to make it excellent in deformation resistance (dimensional stability) at high temperatures. On the other hand, when the thickness of the base material is 500 ⁇ m or less, the pressure-sensitive adhesive sheet (II) due to vibration is applied when at least one of cutting and grinding is performed on the workpiece attached to the pressure-sensitive adhesive sheet (II). Therefore, it is easy to improve processing accuracy such as film thickness accuracy.
  • the pressure-sensitive adhesive layer (X2) of the resin film-forming sheet (II) can be formed by using the above-mentioned pressure-sensitive adhesive composition (x1). It is the same as the pressure-sensitive adhesive composition (x1).
  • the pressure-sensitive adhesive layer (X2) is a pressure-sensitive adhesive composition containing an energy ray-curable pressure-sensitive adhesive resin having a polymerizable functional group introduced in the side chain as a pressure-sensitive adhesive resin.
  • the pressure-sensitive adhesive composition is preferably a formed layer and contains an energy ray-curable acrylic polymer (B) (hereinafter also referred to as “acrylic polymer (B)” or “component (B)”). More preferably, the layer is formed from.
  • the pressure-sensitive adhesive layer (X2) formed from the pressure-sensitive adhesive composition has excellent adhesive strength that can sufficiently hold the object to be processed before irradiation with energy rays, but the adhesive strength decreases after irradiation with energy rays. To do. Therefore, the processed product can be easily separated from the pressure-sensitive adhesive sheet (II).
  • the content of the component (B) in the pressure-sensitive adhesive composition is preferably 70% by mass or more, more preferably 80% by mass or more, and still more preferably 90% by mass with respect to the total amount (100% by mass) of the pressure-sensitive adhesive composition. % Or more, preferably 99.9% by mass or less, more preferably 99.0% by mass or less, and still more preferably 98.0% by mass or less.
  • the thickness of the pressure-sensitive adhesive layer (X2) has a good adhesive force and has good followability to a workpiece to be processed such as a semiconductor wafer having bumps and the like having a large surface unevenness difference.
  • the thickness is preferably 1 to 100 ⁇ m, more preferably 1 to 75 ⁇ m, and still more preferably 1 to 50 ⁇ m.
  • the pressure-sensitive adhesive composition which is a material for forming the pressure-sensitive adhesive layer (X2)
  • contains an energy ray-curable pressure-sensitive adhesive resin such as an energy ray-curable acrylic polymer (B), a crosslinking agent or It is preferable to contain a photopolymerization initiator.
  • the crosslinking agent include those similar to those blended in the above-mentioned acrylic resin, and the content range is also as described above, but the gel fraction of the pressure-sensitive adhesive layer (X2) is increased and processed.
  • the amount is preferably 0.1 to 20 parts by mass, more preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the adhesive resin having a functional group. 5 to 15 parts by mass, more preferably 1.0 to 10 parts by mass.
  • a photoinitiator the thing similar to what is mix
  • the energy ray-curable acrylic polymer (B) contained in the pressure-sensitive adhesive composition will be described.
  • the energy ray-curable acrylic polymer (B) used in one embodiment of the present invention is an acrylic in which a polymerizable functional group is introduced into the side chain and / or main chain of the non-energy ray-curable acrylic polymer.
  • Copolymer Non-energy ray curable acrylic polymers include, for example, acrylic polymers having structural units derived from alkyl (meth) acrylates having linear or branched alkyl groups, and (meth) acrylates having a cyclic structure. An acrylic polymer having a derived structural unit can be used.
  • the polymerizable functional group is as described above, a (meth) acryloyl group is preferable from the viewpoint of easy introduction into a non-energy ray curable acrylic polymer.
  • the weight average molecular weight (Mw) of the component (B) is preferably 100,000 to 1,500,000, more preferably 200,000 to 1,200,000, more preferably 250,000 to 1,000,000, still more preferably 300,000 to 900,000. Preferably, it is 350,000 to 800,000.
  • an alkyl (meth) acrylate (b1 ′) having an alkyl group having 1 to 18 carbon atoms (b1 ′) (hereinafter referred to as “adhesive sheet”) whose adhesive strength can be effectively reduced by irradiation with energy rays
  • a structural unit (b2) derived from a structural unit (b1) derived from a monomer (b1 ′) and a functional group-containing monomer (b2 ′) hereinafter also referred to as “monomer (b2 ′)”.
  • the form of copolymerization of the acrylic copolymers (B0) and (B1) is not particularly limited, and may be any of a block copolymer, a random copolymer, and a graft copolymer.
  • the content of the acrylic copolymer (B1) is preferably 70 to 100% by mass, more preferably 80 to 100%, based on the total amount (100% by mass) of the component (B) contained in the pressure-sensitive adhesive composition. % By mass, more preferably 90 to 100% by mass, and still more preferably 100% by mass.
  • the number of carbon atoms of the alkyl group contained in the monomer (b1 ′) is preferably 1 to 18, more preferably 1 to 12, still more preferably 1 to 8, and still more preferably 1 to 6.
  • Examples of the monomer (b1 ′) include those exemplified as the above-described monomer (a1 ′), but butyl (meth) acrylate or 2-ethylhexyl (meth) acrylate is preferable, and butyl (meth) acrylate is more preferable.
  • the content of the structural unit (b1) in the acrylic copolymer (B0) is the total structural unit (100 mass) of the acrylic copolymer (B0) from the viewpoint of improving the adhesive strength of the pressure-sensitive adhesive layer to be formed. %) Is preferably 50 to 99.5% by mass, more preferably 60 to 99% by mass, still more preferably 70 to 98% by mass, and still more preferably 80 to 96% by mass.
  • Examples of the monomer (b2 ′) include those exemplified as the above-mentioned monomer (a2 ′), but one or more selected from a hydroxyl group-containing monomer, a carboxy group-containing monomer, and an epoxy group-containing monomer are preferable. Is more preferable, and 2-hydroxyethyl (meth) acrylate is still more preferable.
  • the content of the structural unit (b2) in the acrylic copolymer (B0) is preferably 0.5 to 40% by weight with respect to the total structural unit (100% by weight) of the acrylic copolymer (B0). More preferably, it is 1 to 30% by mass, still more preferably 2 to 25% by mass, and still more preferably 3 to 15% by mass.
  • content of a structural unit (b2) is 0.5 mass% or more, content of the structural unit (b2) which has a functional group used as a reaction point with polymeric compound (Xb) can fully be ensured, and energy Since a highly curable pressure-sensitive adhesive layer (X2) can be formed by irradiation with a line, when the cut and / or ground material is peeled from the pressure-sensitive adhesive layer (X2), the cut and / or ground material It can peel, preventing generation
  • the polymerizable compound (Xb) is a substituent that can be bonded to a functional group in the structural unit (b2) of the acrylic copolymer (B0) (hereinafter also referred to as “reactive functional group”) and polymerizable.
  • a compound having a functional group is meant.
  • the acrylic copolymer (B0) may have a structural unit (b3) derived from a monomer (b3 ′) other than the monomers (b1 ′) and (b2 ′).
  • Examples of the other monomer (b3 ′) include those exemplified as the monomer (a3 ′) described above.
  • the content of the structural unit (b3) in the acrylic copolymer (B0) is preferably 0 to 20% by weight, based on the total structural units (100% by weight) of the acrylic copolymer (B0).
  • the content is preferably 0 to 10% by mass, more preferably 0 to 5% by mass, and still more preferably 0 to 1% by mass.
  • the monomers (b1 ′) to (b3 ′) described above may be used alone or in combination of two or more.
  • the energy ray curable acrylic copolymer (B1) is obtained by reacting the acrylic copolymer (B0) having the structural units (b1) and (b2) with the polymerizable compound (Xb). It is done.
  • the polymerizable compound (Xb) include those exemplified as the above-described polymerizable compound (Xa). Among them, the polymerizable compound (Xb) has a reactive functional group and 1 to 5 polymerizable functional groups per molecule. It is preferable that it is a compound which has.
  • an isocyanate group, a carboxyl group, an epoxy group etc. are mentioned, for example, An isocyanate group is preferable.
  • polymerizable functional group (meth) acryloyl group, a vinyl group, etc. are mentioned as above-mentioned, (meth) acryloyl group is preferable.
  • polymerizable compound (Xb) (meth) acryloyloxyethyl isocyanate is preferable.
  • the relationship between the number of functional groups of the acrylic copolymer (B0) and the blending amount of the polymerizable compound (Xb) has an appropriate adhesive force before irradiation with energy rays.
  • the value of ⁇ calculated from the following formula (1) is preferably 0.5 to 50, more preferably 1. It is 0 to 40, more preferably 1.2 to 35, and still more preferably 1.5 to 30.
  • the value ⁇ corresponds to the number of polymerizable functional groups that the acrylic copolymer (B1) has.
  • Formula (1): ⁇ [P B ] ⁇ [Q B ] ⁇ [R B ] / 100
  • [P B ] represents the content of the structural unit (b2) with respect to 100 parts by mass of all the structural units of the acrylic copolymer (B0).
  • [Q B ] represents the acrylic copolymer. for functional group 100 equivalents from the functional group-containing monomer polymer of (B0) has,. shows the equivalent weight of the polymerizable compound (Xb)
  • R B] shows the polymerizable functional groups of the polymerizable compound (Xb) has .
  • the intermediate layer (Z2) is a composition for forming an intermediate layer (z2) comprising a non-energy ray curable acrylic polymer (C) and an energy ray curable acrylic polymer (D). ).
  • the pressure-sensitive adhesive sheet (II) is excellent in followability with respect to an object to be processed having large surface irregularities such as a semiconductor wafer having bumps.
  • middle layer (Z2) may have adhesiveness and does not need to have adhesiveness.
  • the thickness of the intermediate layer (Z2) is appropriately selected depending on the degree of unevenness of the workpiece, for example, when the workpiece is a semiconductor wafer or semiconductor chip, the height of the bumps of the semiconductor wafer or semiconductor chip. However, it is preferably 10 to 800 ⁇ m, more preferably 15 to 600 ⁇ m, and still more preferably 20 to 400 ⁇ m. If the thickness of the intermediate layer (Z2) is 10 ⁇ m or more, it is possible to improve the followability with respect to the workpiece having a large unevenness difference. On the other hand, if the thickness of the intermediate layer is 800 ⁇ m or less, the deformation of the pressure-sensitive adhesive sheet (II) can be easily suppressed.
  • the intermediate layer forming layer composition (z2) which is a material for forming the intermediate layer (Z2), provides adhesion between the intermediate layer (Z2) and the adhesive layer (X2) of the adhesive sheet (II) after irradiation with energy rays.
  • the intermediate layer forming layer composition (z2) which is a material for forming the intermediate layer (Z2), provides adhesion between the intermediate layer (Z2) and the adhesive layer (X2) of the adhesive sheet (II) after irradiation with energy rays.
  • a non-energy ray curable acrylic polymer (C) (hereinafter also referred to as “acrylic polymer (C)” or “(C) component”), and a mass average molecular weight
  • acrylic polymer (C) (hereinafter also referred to as “acrylic polymer (C)” or “(D) component”)
  • mass average molecular weight Preferably contains 50,000 to 250,000 energy ray-curable acrylic polymer (D) (hereinafter also referred to as “acrylic polymer (D)” or “(D) component”).
  • the content of the component (D) in the intermediate layer forming composition (z2) is , (C)
  • the amount is preferably 25 parts by mass or more, more preferably 30 parts by mass or more, still more preferably 37 parts by mass or more, and still more preferably 40 parts by mass or more with respect to 100 parts by mass of the component (C).
  • the content of the component is preferably 150 parts by mass or less, more preferably 140 parts by mass or less, and still more preferably 130 parts by mass or less with respect to 100 parts by mass of the component (C).
  • the total content of the component (C) and the component (D) in the intermediate layer forming composition (z2) is preferably 70% by mass with respect to the total amount (100% by mass) of the intermediate layer forming composition (z2). % Or more, more preferably 80% by weight or more, still more preferably 90% by weight or more, preferably 99.9% by weight or less, more preferably 99.0% by weight or less, still more preferably 98.0% by weight. It is as follows.
  • middle layer formation contains a photoinitiator and a crosslinking agent further in addition to the said (C) component and (D) component.
  • a crosslinking agent the thing similar to what is mix
  • a photoinitiator the thing similar to what is mix
  • the non-energy ray curable acrylic polymer (C) and the energy ray curable acrylic polymer (D) contained in the intermediate layer forming composition (z2) will be described.
  • non-energy ray curable acrylic polymer (C) examples include a polymer having a structural unit derived from an alkyl (meth) acrylate having a linear or branched alkyl group, and a cyclic structure (meth). Examples thereof include a polymer having a structural unit derived from acrylate.
  • the mass average molecular weight (Mw) of the component (C) is preferably 300,000 to 1,500,000, more preferably 350,000 to 1,300,000, more preferably 400,000 to 1,200,000, still more preferably 400,000 to 1,100,000, and even more It is preferably 450,000 to 900,000.
  • an alkyl (meth) acrylate (c1 ′) having an alkyl group having 1 to 18 carbon atoms hereinafter also referred to as “monomer (c1 ′)”.
  • an acrylic copolymer (C1) having a structural unit (c2) derived from a structural unit (c1) derived from a functional group-containing monomer (c2 ′) hereinafter also referred to as “monomer (c2 ′)
  • the form of copolymerization of the acrylic copolymer (C1) is not particularly limited, and may be any of a block copolymer, a random copolymer, and a graft copolymer.
  • the content of the acrylic copolymer (C1) is preferably 70 to 100% by mass with respect to the total amount (100% by mass) of the component (C) contained in the intermediate layer forming composition (z2).
  • the amount is preferably 80 to 100% by mass, more preferably 90 to 100% by mass, and still more preferably 100% by mass.
  • the number of carbon atoms of the alkyl group contained in the monomer (c1 ′) is more preferably 4 to 12, further preferably 4 to 8, and still more preferably 4 to 6, from the viewpoint of compatibility with the component (D). .
  • Examples of the monomer (c1 ′) include the same as the monomer (a1 ′) described above. Among these, butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate are preferable, and butyl (meth) acrylate is more preferable.
  • the content of the structural unit (c1) in the acrylic copolymer (C1) is preferably 50 to 99.5 mass% with respect to the total structural units (100 mass%) of the acrylic copolymer (C1). More preferably, it is 60 to 99% by mass, still more preferably 70 to 95% by mass, and still more preferably 80 to 93% by mass. If the content of the structural unit (c1) is 50% by mass or more, it is preferable because the pressure-sensitive adhesive sheet has a good followability with respect to a workpiece with a large unevenness difference. Moreover, if content of a structural unit (c1) is 99.5 mass% or less, content of a structural unit (c2) can fully be ensured, and compatibility with (D) component can be made favorable. Therefore, it is preferable.
  • the acrylic copolymer (C1) is an alkyl group having an alkyl group having 4 or more carbon atoms (preferably 4 to 12, more preferably 4 to 8, more preferably 4 to 6) as the structural unit (c1). It is preferable to have a structural unit (c11) derived from (meth) acrylate.
  • the content ratio of the structural unit (c11) in the structural unit (c1) is preferably 60% by weight or more with respect to the total amount (100% by weight) of the structural unit (c1) included in the acrylic copolymer (C1). More preferably, it is 70 mass% or more, More preferably, it is 80 mass% or more, More preferably, it is 85 mass% or more, Preferably it is 100 mass% or less.
  • a functional group which a monomer (c2 ') has As a functional group which a monomer (c2 ') has, the thing similar to the functional group which the monomer (a2') mentioned above has is mentioned.
  • Specific examples of the monomer (c2 ′) include those similar to the monomer (a2 ′) described above. Among these, 1 or more types chosen from a hydroxyl group containing monomer, a carboxy group containing monomer, and an epoxy group containing monomer are preferable, and a carboxy group containing monomer is more preferable. Specific examples of the hydroxyl group-containing monomer, the carboxy group-containing monomer, and the epoxy group-containing monomer are the same as those of the monomer (a2 ′) described above.
  • the content of the structural unit (c2) in the acrylic copolymer (C1) is preferably 0.5 to 50% by weight with respect to all the structural units (100% by weight) of the acrylic copolymer (C1). More preferably, it is 1 to 40% by mass, still more preferably 5 to 30% by mass, and still more preferably 7 to 20% by mass. If content of a structural unit (c2) is 0.5 mass% or more, since compatibility with (D) component can be made favorable, it is preferable. Moreover, if content of a structural unit (c2) is 50 mass% or less, since it can be set as an adhesive sheet with the favorable followable
  • the acrylic copolymer (C1) may have a structural unit (c3) derived from a monomer (c3 ′) other than the monomers (c1 ′) and (c2 ′).
  • Examples of the other monomer (c3 ′) include those similar to the monomer (a3 ′) described above.
  • the content of the structural unit (c3) in the acrylic copolymer (C1) is preferably 0 to 30% by mass, more preferably 0 to 30% by mass, based on the total structural unit (100% by mass) of the acrylic copolymer (C1).
  • the content is preferably 0 to 20% by mass, more preferably 0 to 10% by mass, and still more preferably 0 to 5% by mass.
  • the monomers (c1 ′) to (c3 ′) described above may be used alone or in combination of two or more.
  • the energy ray curable acrylic polymer (D) is an acrylic polymer in which a polymerizable functional group is introduced to a non-energy ray curable acrylic polymer.
  • the polymerizable functional group is introduced into the main chain and / or side chain of the non-energy ray curable acrylic polymer.
  • the adhesive layer (X2) and the intermediate layer (Z2) are hardened and adhesive residue can be suppressed. Therefore, the adhesion of the pressure-sensitive adhesive layer (X2) can be suppressed when the cut and / or ground material is peeled from the pressure-sensitive adhesive sheet (II).
  • non-energy ray curable acrylic polymers include acrylic polymers having structural units derived from alkyl (meth) acrylates having linear or branched alkyl groups, and (meth) acrylates having a cyclic structure.
  • An acrylic polymer having a derived structural unit can be used.
  • the polymerizable functional group may be any group containing an energy beam polymerizable carbon-carbon double bond, and examples thereof include a (meth) acryloyl group and a vinyl group. From the viewpoint of being present, a (meth) acryloyl group is preferred.
  • the energy beam polymerizable group may be bonded to the main chain or side chain of the non-energy beam curable acrylic polymer via an alkylene group, an alkyleneoxy group, a polyalkyleneoxy group, or the like.
  • the weight average molecular weight (Mw) of the component (D) is preferably 50,000 to 250,000, more preferably 60,000 to 220,000, still more preferably 70,000 to 200,000, still more preferably 80,000 to 180,000. More preferably, it is 850,000 to 150,000.
  • Mw of the component (D) is less than 50,000, the stability of the obtained pressure-sensitive adhesive sheet tends to be poor. That is, when the pressure-sensitive adhesive sheet is stored for a long time, a part of the component (D) moves into the pressure-sensitive adhesive layer, the pressure-sensitive adhesive force of the pressure-sensitive adhesive sheet becomes unstable, and the pressure-sensitive adhesive layer ( X2) tends to harden excessively.
  • the pressure-sensitive adhesive sheet when used after long-term storage, or when left for a long time with the object to be processed attached, the adhesion between the intermediate layer (Z2) and the pressure-sensitive adhesive layer (X2) after irradiation with energy rays Since the property becomes insufficient, when the pressure-sensitive adhesive sheet is peeled off, the pressure-sensitive adhesive layer (X2) may be broken or the residue of the pressure-sensitive adhesive layer (X2) may adhere to the cut and / or ground material.
  • the adhesion between the intermediate layer (Z2) and the pressure-sensitive adhesive layer (X2) after irradiation with energy rays tends to be inferior, and the cut or searched material is removed from the pressure-sensitive adhesive sheet (II ),
  • the adhesive layer (X2) may break or the residue of the adhesive layer (X2) may adhere to the cut product and / or the ground product.
  • a pressure-sensitive adhesive sheet having excellent temporal stability, and a pressure-sensitive adhesive with improved adhesion after irradiation with energy rays between the formed intermediate layer (Z2) and pressure-sensitive adhesive layer (X2)
  • component (D) contains a structural unit (d1) derived from an alkyl (meth) acrylate (d1 ′) having an alkyl group having 1 to 18 carbon atoms (hereinafter also referred to as “monomer (d1 ′)”) and a functional group.
  • the energy beam-curable acrylic copolymer (D1) is included, and more preferable is the energy beam-curable acrylic copolymer (D1).
  • the form of copolymerization of the acrylic copolymers (D0) and (D1) is not particularly limited, and may be any of a block copolymer, a random copolymer, and a graft copolymer.
  • the content of the acrylic copolymer (D1) is preferably 70 to 100% by mass with respect to the total amount (100% by mass) of the component (D) contained in the intermediate layer forming composition (z2).
  • the amount is preferably 80 to 100% by mass, more preferably 90 to 100% by mass, and still more preferably 100% by mass.
  • the number of carbon atoms of the alkyl group contained in the monomer (d1 ′) is more preferably 4 to 12, still more preferably 4 to 8, and still more preferably 4 to 6.
  • the monomer (d1 ′) those exemplified as the aforementioned monomer (a1 ′) can be mentioned.
  • butyl (meth) acrylate or 2-ethylhexyl (meth) acrylate is preferable, and butyl (meth) acrylate is more preferable.
  • the content of the structural unit (d1) in the acrylic copolymer (D0) is preferably 50 to 99% by weight, based on the total structural unit (100% by weight) of the acrylic copolymer (D0).
  • the amount is preferably 55 to 95% by mass, more preferably 60 to 90% by mass, and still more preferably 65 to 85% by mass.
  • a content of the structural unit (d1) of 50% by mass or more is preferable because the shape of the intermediate layer (Z2) to be formed can be sufficiently maintained.
  • content of a structural unit (d1) is 99 mass% or less
  • content of the structural unit (d2) which has a functional group used as a reaction point with polymeric compound (Xd) can fully be ensured, and formation
  • the intermediate layer (Z2) and the pressure-sensitive adhesive layer (X2) to be adhered can be improved since the adhesion after irradiation with energy rays can be improved.
  • Examples of the monomer (d2 ′) include those exemplified as the above-mentioned monomer (a2 ′), but one or more selected from a hydroxyl group-containing monomer, a carboxy group-containing monomer, and an epoxy group-containing monomer are preferable. Is more preferable, hydroxyacryl (meth) acrylate is more preferable, and 2-hydroxyethyl (meth) acrylate is still more preferable.
  • the content of the structural unit (d2) in the acrylic copolymer (D0) is preferably 1 to 50% by weight, based on the total structural unit (100% by weight) of the acrylic copolymer (D0).
  • the amount is preferably 5 to 45% by mass, more preferably 10 to 40% by mass, and still more preferably 15 to 35% by mass.
  • the content of the structural unit (d2) is 1% by mass or more, sufficient polymerizability to improve the adhesion between the intermediate layer (Z2) to be formed and the pressure-sensitive adhesive layer (X2) after irradiation with energy rays. It is preferable because a reaction point with the compound (Xd) can be secured.
  • content of a structural unit (d2) is 50 mass% or less, since the shape of the intermediate
  • the acrylic copolymer (D0) may have a structural unit (b3) derived from another monomer (d3 ′) other than the monomers (d1 ′) and (d2 ′).
  • Examples of the other monomer (d3 ′) include those exemplified as the monomer (a3 ′) described above.
  • the content of the structural unit (d3) in the acrylic copolymer (D0) is preferably 0 to 30% by weight, based on the total structural unit (100% by weight) of the acrylic copolymer (D0).
  • the content is preferably 0 to 20% by mass, more preferably 0 to 10% by mass, and still more preferably 0 to 5% by mass.
  • the monomers (d1 ′) to (d3 ′) described above may be used alone or in combination of two or more.
  • the energy ray-curable acrylic copolymer (D1) is obtained by reacting the functional group in the structural unit (d2) of the acrylic copolymer (D0) with the polymerizable compound (Xd).
  • the polymerizable functional group possessed by (Xd) is introduced into at least one of the main chain and the side chain of the acrylic copolymer (D0).
  • the polymerizable compound (Xd) is a compound having a polymerizable functional group and is not particularly limited as long as it is a compound having a reactive functional group.
  • a compound having the above-described reactive substituent and having 1 to 5 polymerizable functional groups per molecule is preferable.
  • an isocyanate group, a carboxyl group, an epoxy group etc. are mentioned, for example, An isocyanate group is preferable.
  • As said polymerizable functional group (meth) acryloyl group, a vinyl group, etc. are mentioned as above-mentioned, (meth) acryloyl group is preferable.
  • polymerizable compound (Xd) examples include the same compounds as the polymerizable compound (Xb) described above.
  • the polymerizable compound (Xd) may be used alone or in combination of two or more.
  • (Meth) acryloyloxyethyl isocyanate is preferred.
  • the intermediate layer (Z2) and the pressure-sensitive adhesive layer (X2) are formed with respect to the relationship between the number of functional groups of the acrylic copolymer (D0) and the blending amount of the polymerizable compound (Xd).
  • the value of ⁇ calculated from the following formula (2) is preferably 1 to 50, more preferably 2 to 40, still more preferably 3 to 35, More preferably, it is 5-30.
  • the value of ⁇ corresponds to the number of energy ray polymerizable groups possessed by the acrylic copolymer (D1).
  • the intermediate layer forming composition (z2) may contain other additives as long as the effects of the present invention are not impaired.
  • other additives include antioxidants, softeners (plasticizers), fillers, rust inhibitors, pigments, dyes, tackifiers, and the like.
  • the content of each additive is preferably 0.01 to 6 parts by mass, more preferably 0.01 to 2 parts by mass with respect to 100 parts by mass of component (A). is there.
  • a release material may be further laminated on the surfaces of the pressure-sensitive adhesive layers (X1) and (X2) to be attached to the workpiece.
  • a release material a release sheet that has been subjected to a double-sided release process, a release sheet that has been subjected to a single-sided release process, or the like is used. Examples include a release material coated on a release material substrate.
  • Examples of the base material for the release material include papers such as high-quality paper, glassine paper, and kraft paper; polyester resin films such as polyethylene terephthalate resin, polybutylene terephthalate resin, and polyethylene naphthalate resin; and olefins such as polypropylene resin and polyethylene resin.
  • a plastic film such as a resin film;
  • release agent examples include silicone-based resins, olefin-based resins, isoprene-based resins, rubber-based elastomers such as butadiene-based resins, long-chain alkyl-based resins, alkyd-based resins, and fluorine-based resins.
  • the thickness of the release material is not particularly limited, but is preferably 10 to 200 ⁇ m, more preferably 25 to 170 ⁇ m, and still more preferably 35 to 80 ⁇ m.
  • the pressure-sensitive adhesive sheet (II) preferably satisfies one or more of the following requirements ( ⁇ ) to ( ⁇ ). It is more preferable to satisfy any two of ( ⁇ ) to ( ⁇ ), and it is further preferable to satisfy all of the requirements ( ⁇ ) to ( ⁇ ).
  • -Requirement ((alpha)) Young's modulus of a base material (Y2) is 1.0 Mpa or more.
  • -Requirement ((beta)) The thickness of a base material (Y2) is 5 micrometers or more.
  • the storage elastic modulus G ′ (23 ° C.) of the pressure-sensitive adhesive layer (X2) is 0.10 MPa or more.
  • the Young's modulus of the base material (Y2) defined by the requirement ( ⁇ ) is preferably 1.0 to 1000 MPa, preferably 1.5 to 800 MPa is more preferable, and 2.0 to 500 MPa is still more preferable.
  • the thickness of the base material (Y2) defined by the requirement ( ⁇ ) is preferably 5 to 250 ⁇ m, and preferably 10 to 230 ⁇ m. Is more preferably 20 to 210 ⁇ m.
  • the storage elastic modulus G ′ (23 ° C.) of the pressure-sensitive adhesive layer (X2) defined by the requirement ( ⁇ ) is 0.10 to 1 MPa. It is preferably 0.12 to 0.9 MPa, more preferably 0.14 to 0.8 MPa.
  • the method for producing a processed product according to the present invention includes a base material (Y1) and a pressure-sensitive adhesive layer (X1), and one of the layers includes a heat-expandable pressure-sensitive adhesive containing heat-expandable particles having a thermal expansion start temperature (t).
  • a sheet (I) and a pressure-sensitive adhesive sheet (II) having a base material (Y2) and a pressure-sensitive adhesive layer (X2) are provided, and the pressure-sensitive adhesive sheet (I) and the base material (Y2) of the pressure-sensitive adhesive sheet (II) are directly laminated.
  • Step (4) a step of performing at least one of cutting and grinding on the surface opposite to the surface of the workpiece to be adhered to the adhesive layer (X2). It is carried out in at least one of the following (X) and (Y).
  • the above-mentioned adhesive laminate is used. Specifically, the surface of the adhesive layer (X1) of the adhesive sheet (I) of the adhesive laminate is affixed to the support, and the adhesive layer (X2) of the adhesive sheet (II) of the adhesive laminate is An object to be processed is attached to the surface for use. Therefore, a predetermined process can be performed in a state where the object to be processed is fixed to the support. Moreover, after the predetermined processing is performed, the adhesive sheet (II) to which the processing object subjected to the predetermined processing is pasted can be easily separated from the adhesive sheet (I) in a lump with a slight force. can do.
  • the pressure-sensitive adhesive sheet (II) to which the processing object subjected to the predetermined processing is attached can be easily separated from the support. Therefore, it can use for the following process, without sticking the processing target object which performed the said predetermined process to a new adhesive sheet.
  • FIG.4 and FIG.5 each process of the manufacturing method of this invention is demonstrated, referring FIG.4 and FIG.5 suitably.
  • FIG. 4A and FIG. 5A are schematic cross-sectional views showing a state where a processing object is attached to a support via an adhesive laminate.
  • step (1) as shown in FIGS. 4 (a) and 5 (a), the workpieces 60 and 70 are affixed to the support 50 via the adhesive laminate 1a of the first aspect, The support, the adhesive laminate, and the workpiece are laminated in this order.
  • FIG.4 and FIG.5 although the example using the adhesive laminated body 1a shown to Fig.1 (a) is shown, also when using the adhesive laminated body of this invention which has another structure, Similarly, the support, the adhesive laminate, and the workpiece are laminated in this order.
  • the processing objects 60 and 70 are affixed on the adhesive layer (X2) of the adhesive sheet (II) which the said adhesive laminated body has. And the adhesive layer (X1) of the adhesive sheet (I) which the said adhesive laminated body has and the support body 50 are stuck.
  • the object to be processed may be a semiconductor wafer or the like having a cut groove formed on the surface, and the surface on which the cut groove is formed may be bonded to the pressure-sensitive adhesive layer (X2) of the pressure-sensitive adhesive sheet (II).
  • the object to be processed may be a semiconductor wafer or the like in which a modified region is previously formed inside by laser beam irradiation.
  • the cut groove or the modified region serves as a division starting point, and the workpiece can be divided. That is, when the workpiece is a semiconductor wafer having a cut groove formed on the surface, in the manufacturing method of one embodiment of the present invention, the step (1) is the following step (1-C), and the step (4) ) Is the following step (4-C).
  • Step / step (4-C) for attaching a surface having a groove a step of grinding the surface of the semiconductor wafer opposite to the adhesive layer (X2) to be attached.
  • step (4) is the following step (4-A).
  • the support is used for fixing the object to be processed in step (2) and increasing the processing accuracy. It is preferable that the said support body is affixed on the whole adhesive surface of the adhesive layer (X1) of an adhesive laminated body. Therefore, the support is preferably plate-shaped. Moreover, as shown in FIG.4 and FIG.5, the area of the surface of the support body 50 by which the adhesive surface 122a of the adhesive layer (X1) is stuck is more than the area of the adhesive surface 122a of an adhesive layer (X1). It is preferable that
  • the material constituting the support is appropriately selected in consideration of required properties such as mechanical strength and heat resistance according to the type of the object to be processed and the processing performed in step (2).
  • Specific materials constituting the support include, for example, metal 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, Examples thereof include resin materials such as polyamideimide resin; composite materials such as glass epoxy resin, and among these, SUS, glass, silicon wafer and the like are preferable.
  • Examples of engineering plastics include nylon, polycarbonate (PC), and polyethylene terephthalate (PET).
  • Examples of super engineering plastics include polyphenylene sulfide (PPS), polyether sulfone (PES), and polyether ether ketone (PEEK).
  • the thickness of the support is appropriately selected in consideration of required characteristics and the like, but is preferably 20 ⁇ m or more and 50 mm or less, more preferably 60 ⁇ m or more and 20 mm or less.
  • the temperature condition in the step (1) may be less than the expansion start temperature (t) of the thermally expandable particles.
  • ⁇ Step (2)> one or more processes are performed with respect to the said process target object stuck on the adhesive layer (X2) of the adhesive laminated body of this invention at the process (1).
  • the processing performed in the step (2) include, for example, a sealing process using a resin for the processing target, a process for forming a modified region serving as a division starting point on the processing target, a circuit forming process, an etching process, and a plating process. , Sputtering treatment, vapor deposition treatment, protective film formation treatment, laminating treatment using a separately prepared adhesive sheet, and the like.
  • the processing applied in the step (2) may be at least one of cutting and grinding for the workpiece.
  • the processing performed in the step (2) may be processing including at least one of the step of cutting the workpiece and the step of grinding, or the step of cutting the workpiece and the step of grinding Processing that does not include Similarly to the step (1), the temperature condition in the step (2) may be less than the expansion start temperature (t) of the thermally expandable particles.
  • the sealing process using the resin for the processing object (process (2) -B)) will be described as an example.
  • Step (2-A) is a step in which the object to be processed is a semiconductor wafer, and a modified region serving as a division starting point is formed on the semiconductor wafer.
  • the surface opposite to the surface of the semiconductor wafer attached to the adhesive sheet (II) is the laser light incident surface, and the condensing point of the laser light is the semiconductor wafer.
  • a modified region 71 by multiphoton absorption or the like is formed.
  • the modified region 71 functions as a starting point for dividing the semiconductor wafer by grinding in the step (4).
  • FIG. 4B the surface opposite to the surface of the semiconductor wafer attached to the adhesive sheet (II) is the laser light incident surface, and the condensing point of the laser light is the semiconductor wafer.
  • step (4) is performed after step (3), but one of one or more processes in step (2) is performed after step (2-A).
  • the grinding in the step (4) may be performed.
  • the separated semiconductor wafer can be subjected to the next process while being attached to the adhesive sheet (II) without separating the separated semiconductor wafer from the adhesive sheet (II).
  • the workpiece is a semiconductor wafer
  • the one or more processes in the step (2) include the following step (2-A): Step (2-A): A step of forming a modified region serving as a division starting point on the semiconductor wafer.
  • Step (4) is the following step (4-A): Step (4-A): A step of grinding the surface of the semiconductor wafer opposite to the surface to which the adhesive layer (X2) is attached Step (4-A) is the following (XA) Or (YA). (XA): Implemented after step (2-A) as one or more processes (YA): Implemented after step (3)
  • the object to be processed is a semiconductor chip, and the semiconductor chip and a peripheral portion of the semiconductor chip in the adhesive surface of the adhesive layer (X2) are covered with a sealing material,
  • This is a step of curing the encapsulant to obtain a cured encapsulant in which the semiconductor chip is encapsulated with a cured encapsulant.
  • the semiconductor chip 60 is used as a processing object.
  • a conventionally known semiconductor chip 60 can be used, and an integrated circuit composed of circuit elements such as transistors, resistors, and capacitors is formed on the circuit surface. And it is preferable to mount so that the circuit surface of the semiconductor chip 60 may be covered with the adhesive surface of the adhesive layer (X2) of adhesive sheet (II).
  • a known device such as a flip chip bonder or a die bonder can be used. The layout, number of arrangements, etc. of the semiconductor chip 60 may be appropriately determined according to the target package form, the number of production, etc.
  • the semiconductor chip 60 is covered with a sealing material in a region larger than the chip size, such as FOWLP and FOPLP, and not only the circuit surface of the semiconductor chip 60 but also the sealing. It is preferable to be applied to a package for forming a rewiring layer also in the surface region of the stopper. Therefore, the semiconductor chip 60 is placed on a part of the adhesive surface of the adhesive layer (X2), and the plurality of semiconductor chips 60 are arranged in a state of being spaced apart at a certain interval.
  • a sealing material in a region larger than the chip size, such as FOWLP and FOPLP, and not only the circuit surface of the semiconductor chip 60 but also the sealing. It is preferable to be applied to a package for forming a rewiring layer also in the surface region of the stopper. Therefore, the semiconductor chip 60 is placed on a part of the adhesive surface of the adhesive layer (X2), and the plurality of semiconductor chips 60 are arranged in a state of being spaced apart at a certain interval.
  • the plurality of semiconductor chips 60 be mounted on the adhesive surface in a state of being arranged in a matrix of a plurality of rows and a plurality of columns with a certain interval.
  • the interval between the semiconductor chips 60 may be appropriately determined according to the target package form and the like.
  • the semiconductor chip 60 and the adhesive surface of the adhesive layer (X1) at least in the peripheral portion of the semiconductor chip 60 are covered with a sealing material (hereinafter referred to as “coating step”). Also, the sealing material is cured to obtain a cured sealing body 61 in which the semiconductor chip 60 is sealed with the cured sealing material (hereinafter also referred to as a “curing step”).
  • the semiconductor chip 60 is placed on a part of the pressure-sensitive adhesive surface of the pressure-sensitive adhesive layer (X2), so that the peripheral portion of the semiconductor chip 60 is formed on the pressure-sensitive adhesive surface of the pressure-sensitive adhesive layer (X2). That is, the peripheral portion of the semiconductor chip 60 refers to the adhesive surface of the adhesive layer (X2) corresponding to the gap between the adjacent semiconductor chips 60 among the plurality of semiconductor chips 60.
  • the semiconductor chip 60 and the peripheral portion of the semiconductor chip 60 on the adhesive surface of the adhesive layer (X2) are covered with a sealing material.
  • the sealing material fills the gaps between the plurality of semiconductor chips CP while covering the entire exposed surface of the semiconductor chip CP.
  • the sealing material has a function of protecting the semiconductor chip CP and its accompanying elements from the external environment.
  • any material used as a semiconductor sealing material can be appropriately selected and used.
  • a sealing material containing a thermosetting resin or an energy ray curable resin can be used. And the like.
  • the sealing material may be a solid such as a granule or a sheet at room temperature, or a liquid in the form of a composition. From the viewpoint of workability, the sealing material is in the form of a sheet. Is preferred.
  • a method of covering the semiconductor chip 60 and its peripheral part using the sealing material it is appropriately selected and applied according to the type of the sealing material from methods conventionally used in the semiconductor sealing process. For example, a roll laminating method, a vacuum pressing method, a vacuum laminating method, a spin coating method, a die coating method, a transfer molding method, a compression molding mold method, or the like can be applied.
  • the sealing material can be hardened and the hardening sealing body 61 by which the semiconductor chip 60 is sealed with the hardening sealing material can be obtained.
  • the covering step and the curing step in step (2-B) are preferably performed under a temperature condition that is lower than the expansion start temperature (t) of the thermally expandable particles.
  • the coating step and the curing step may be performed separately. However, when the sealing material is heated in the coating step, the sealing material is cured as it is by the heating, and the coating step and the curing step are performed. May be performed simultaneously. In the manufacturing example shown in FIG. 5, step (4) is performed after step (3), but one of one or more processes in step (2) is performed after step (2-B).
  • step (4) may be performed.
  • the cured encapsulant can be subjected to the next step without being separated from the adhesive sheet (II) while being adhered to the adhesive sheet (II).
  • the object to be processed is a semiconductor chip
  • the one or more processes in the step (2) include the following step (2-B): Step (2-B): covering the semiconductor chip and the periphery of the semiconductor chip among the adhesive surfaces of the adhesive layer (X2) with a sealing material, and curing the sealing material; Step (4) of obtaining a cured sealing body in which the semiconductor chip is sealed with a curing sealing material is performed in at least one of the following (XB) and (YB).
  • Step (3) the adhesive sheet (I) of the adhesive laminate and the base material (Y2) of the adhesive sheet (II) by heat treatment (separation heat treatment) at a temperature equal to or higher than the expansion start temperature (t).
  • FIG. 4C and FIG. 5C are schematic cross-sectional views showing a state separated at the interface P by the heat treatment for separation. 4 (c) and 5 (c) show a state in which the object to be processed that has been subjected to the predetermined processing is separated in a state of being stacked on the pressure-sensitive adhesive sheet (II) by the heat treatment for separation.
  • the “temperature higher than the expansion start temperature (t)” in the separation heat treatment is “expansion start temperature (t) + 10 ° C.” or higher and “expansion start temperature (t) + 60 ° C.” or lower. It is preferable that it is “expansion start temperature (t) + 15 ° C.” or more and “expansion start temperature (t) + 40 ° C.” or less.
  • the pressure-sensitive adhesive sheet (II) is separated from the pressure-sensitive adhesive sheet (I) and separated from the support in a state where the processing objects subjected to the predetermined processing in the step (2) are laminated (attached). Therefore, it is possible to omit the work of attaching the processed object after separation to the adhesive sheet and use it for the next step.
  • the step (4) at least one of cutting and grinding is performed on the surface of the object to be processed which is opposite to the surface to be adhered to the adhesive layer (X2).
  • the workpiece can be divided into a desired size by cutting the workpiece.
  • the said workpiece can be adjusted to desired thickness by performing grinding. It is also possible to perform both cutting and grinding, and to divide the workpiece and adjust the thickness.
  • the surface of the semiconductor wafer in which the modified region serving as the division starting point is formed by laser light irradiation is opposite to the surface to which the adhesive sheet (II) is attached.
  • a gap 72 is generated with the modified region 71 as a division starting point by a processing pressure of a grinding wheel or the like, so that the semiconductor wafer has a predetermined size. It can be separated into a semiconductor chip.
  • the cured sealing body 61a obtained by separating the cured sealing body 61 into individual semiconductor chip CP units is obtained. Can do.
  • the cutting method for dividing the cured sealing body 61 into individual pieces is not particularly limited, and examples thereof include cutting means such as a dicing saw.
  • the cured sealing body 61 may be ground for the purpose of exposing the circuit surface of the semiconductor chip.
  • process (1)-(4) you may have another process between process (1)-(4), before process (1), and after process (4).
  • a rewiring forming process may be included.
  • step (4) may be performed as one of one or more processes in step (2), or may be performed after step (3). Furthermore, the step (4) may be performed as one of the one or more processes in the step (2) and may be performed after the step (3).
  • grinding is performed on the surface of the object to be processed which is opposite to the sticking surface to the adhesive layer (X2), and the cutting is performed after the process (3). It is also possible to perform.
  • one direction of the surface opposite to the surface to be adhered to the pressure-sensitive adhesive layer (X2) of the object to be processed (for example, of the XY plane of the object to be processed)
  • the workpiece is cut into strips by cutting only in the X-axis direction, and the strip is cut only in another direction (for example, the Y-axis direction in the XY plane of the workpiece) after step (3).
  • the particle distribution of the thermally expandable particles before expansion at 23 ° C. was measured using a laser diffraction particle size distribution measuring apparatus (for example, product name “Mastersizer 3000” manufactured by Malvern).
  • the particle diameters corresponding to 50% and 90% of the cumulative volume frequency calculated from the smaller particle diameter of the particle distribution are expressed as “average particle diameter (D 50 ) of thermally expandable particles” and “thermally expandable particles”, respectively. 90% particle diameter (D 90 ) ”.
  • the formed heat-expandable base material layer (Y1-1) was 5 mm long ⁇ 30 mm wide ⁇ 200 ⁇ m thick, and the test piece was prepared by removing the release material.
  • a dynamic viscoelasticity measuring apparatus TA Instruments, product name “DMAQ800”
  • a test start temperature 0 ° C.
  • a test end temperature of 300 ° C. a temperature increase rate of 3 ° C./min
  • a frequency of 1 Hz and an amplitude of 20 ⁇ m
  • the storage elastic modulus E ′ of the test sample at a predetermined temperature was measured.
  • a torsional shear method under conditions of a test start temperature of 0 ° C., a test end temperature of 300 ° C., a heating rate of 3 ° C./min, and a frequency of 1 Hz was used to measure the storage shear modulus G ′ of the test sample at a given temperature.
  • ⁇ Probe tack value> A substrate to be measured was cut into a square with a side of 10 mm, and then allowed to stand for 24 hours in an environment of 23 ° C. and 50% RH (relative humidity) as a test sample. Using a tacking tester (manufactured by NIPPON SPECIAL INSTRUMENTS CO., LTD., Product name “NTS-4800”) in an environment of 23 ° C. and 50% RH (relative humidity), the probe tack value on the surface of the test sample is measured according to JIS. It measured based on Z0237: 1991.
  • a stainless steel probe having a diameter of 5 mm is brought into contact with the surface of the test sample at a contact load of 0.98 N / cm 2 for 1 second, and then the probe is moved at a speed of 10 mm / sec. The force required to separate from the surface was measured, and the value obtained was used as the probe tack value of the test sample.
  • Acrylic copolymer (i): having a structural unit derived from a raw material monomer consisting of 2-ethylhexyl acrylate (2EHA) / 2-hydroxyethyl acrylate (HEA) 80.0 / 20.0 (mass ratio), An acrylic copolymer having a Mw of 600,000.
  • Acrylic copolymer (ii): n-butyl acrylate (BA) / methyl methacrylate (MMA) / 2-hydroxyethyl acrylate (HEA) / acrylic acid 86.0 / 8.0 / 5.0 / 1.
  • Isocyanate crosslinking agent (i): manufactured by Tosoh Corporation, product name “Coronate L”, solid content concentration: 75 mass%.
  • Photopolymerization initiator (i): manufactured by BASF, product name “Irgacure 184”, 1-hydroxy-cyclohexyl-phenyl-ketone.
  • Heavy release film manufactured by Lintec Corporation, product name “SP-PET382150”, a polyethylene terephthalate (PET) film provided with a release agent layer formed from a silicone release agent on one side, thickness: 38 ⁇ m.
  • Light release film manufactured by Lintec Co., Ltd., product name “SP-PET381031”, a PET film provided with a release agent layer formed from a silicone release agent on one side, thickness: 38 ⁇ m.
  • Example 1 In the adhesive laminate 1d shown in FIG. 2B, a release material was further laminated on the second adhesive layer (X12) of the adhesive sheet (I) and the adhesive layer (X2) of the adhesive sheet (II).
  • a pressure-sensitive adhesive laminate having a configuration and having an intermediate layer (Z2) provided between the base material (Y2) and the pressure-sensitive adhesive layer (X2) of the pressure-sensitive adhesive sheet (II) was produced by the following procedure.
  • the 1st adhesive layer (X11) which is an adhesive layer was formed.
  • the storage shear modulus G ′ (23) of the first pressure-sensitive adhesive layer (X11) at 23 ° C. was 2.5 ⁇ 10 5 Pa.
  • the adhesive force of the 1st adhesive layer (X11) measured based on the said method was 0.3 N / 25mm.
  • Second Adhesive Layer 100 parts by mass of the acrylic copolymer (ii), which is an adhesive resin, is added to the isocyanate crosslinking agent (i) 0.8 mass. Parts (solid content ratio) were mixed, diluted with toluene, and stirred uniformly to prepare a PSA composition having a solid content concentration (active ingredient concentration) of 25% by mass. And the said adhesive composition is apply
  • the storage shear modulus G ′ (23) of the second pressure-sensitive adhesive layer (X12) at 23 ° C. was 9.0 ⁇ 10 4 Pa.
  • the adhesive force of the 2nd adhesive layer (X12) measured based on the said method was 1.0 N / 25mm.
  • an ultraviolet irradiation device product name “ECS-401GX” manufactured by Eye Graphics Co., Ltd.
  • a high-pressure mercury lamp product name “H04-L41” manufactured by Eye Graphics Co., Ltd.
  • the coating film was cured by irradiating with ultraviolet rays under conditions of cm 2 to form a thermally expandable substrate (Y-1) having a thickness of 50 ⁇ m.
  • the above illuminance and light intensity during ultraviolet irradiation are values measured using an illuminance / light meter (product name “UV Power Pack II” manufactured by EIT).
  • the PET film as the non-thermally expandable substrate corresponds to the non-thermally expandable substrate layer (Y1-2).
  • the resin composition is applied to the surface of the release agent layer of the light release film to form a coating film, The membrane was dried at 100 ° C. for 120 seconds to similarly form a 50 ⁇ m thick thermally expandable substrate layer (Y1-1).
  • the storage elastic modulus and probe tack value at each temperature of the thermally expandable substrate layer (Y1-1) were measured. The measurement results were as follows. -Storage elastic modulus E '(23) at 23 ° C.
  • the substrate (Y2) was a polyethylene terephthalate (PET) film having a thickness of 50 ⁇ m (manufactured by Toyobo Co., Ltd., product name “Cosmo Shine A4300”, probe tack value: 0 mN / 5 mm ⁇ ).
  • PET polyethylene terephthalate
  • Intermediate layer (Z2) (1) Preparation of intermediate layer forming composition 100 parts by mass of non-energy ray curable acrylic copolymer C1, 68 parts by mass of energy ray curable acrylic copolymer D1, tolylene diisocyanate crosslinking agent (product) Name: BHS 8515, manufactured by Toyochem Co., Ltd. (2.8 parts by mass) and 2.7 parts by mass of the above photopolymerization initiator (i) were added and diluted with ethyl acetate to obtain a solid content concentration (active ingredient concentration). A 35% by mass solution of the intermediate layer forming composition was prepared.
  • non-energy ray-curable acrylic copolymer C1 90 parts by mass of butyl acrylate (BA) and 10 parts by mass of acrylic acid (AAc) are added to an ethyl acetate solvent, and azo is used as a polymerization initiator. 1.0 part by mass of bisisobutyronitrile (AIBN) was added and the solution polymerization proceeded to obtain a non-energy ray curable acrylic copolymer C1 (Mw: 500,000).
  • AIBN bisisobutyronitrile
  • methacryloyloxyethyl isocyanate is added to the acrylic copolymer in an amount such that the number of isocyanate groups is 80 equivalents relative to the total number of hydroxyl groups in the added HEA of 100 equivalents.
  • An energy ray-curable acrylic copolymer D1 (Mw: 100,000) having a group was obtained.
  • the value of ⁇ calculated from the above formula (2) is 22.4.
  • peeling force (F 0 ) the peeling force measured when peeling at the interface P at a pulling speed of 300 mm / min by the 180 ° peeling method based on JIS Z0237: 2000 is referred to as “peeling force (F 0 )”.
  • peeling force (F 1 ) The peeling force measured when peeling at the interface P was defined as “peeling force (F 1 )”.
  • peel force (F 1 ) when the adhesive sheet (I) of the adhesive laminate was fixed with the upper chuck of the universal tensile testing machine, the adhesive sheet (I) was completely separated at the interface P. Therefore, when the fixing was not possible, the measurement was terminated, and the peeling force (F 1 ) at that time was set to “0 mN / 25 mm”.
  • Example 2 The pressure-sensitive adhesive sheet (II) in a state where the object to be processed was affixed was produced by the following procedure. (1) Fixing of semiconductor wafer The light release film of the pressure-sensitive adhesive laminate produced in Example 1 was removed, and the pressure-sensitive adhesive surface of the second pressure-sensitive adhesive layer (X12) of the pressure-sensitive adhesive sheet (I) exposed was a support ( Glass). And the surface by the side of the circuit surface of the semiconductor wafer which has the circuit surface in which the pattern was formed, and the pressure-sensitive adhesive layer (X2) of the pressure-sensitive adhesive sheet (II) are bonded to each other through the pressure-sensitive adhesive laminate produced in Example 1. A semiconductor wafer was fixed to the support.
  • the adhesive laminate was subjected to a heat treatment at 120 ° C. for 3 minutes, which is higher than the expansion start temperature (90 ° C.) of the thermally expandable particles. And it was able to be easily separated collectively at the interface P between the first pressure-sensitive adhesive layer (X11) of the pressure-sensitive adhesive sheet (I) and the base material (Y2) of the pressure-sensitive adhesive sheet (II). Then, after separation, an adhesive sheet (II) was obtained in which a semiconductor wafer having a modified region formed therein was affixed.
  • Adhesive laminate (I) Adhesive sheet (X1) Adhesive layer (X11) First adhesive layer (X12) Second adhesive layer (Y1) Base material (Y1-1) Thermally expandable substrate layer (Y1-2) Non-thermally expandable substrate layer (II) Adhesive sheet (X2) Adhesive layer (Z2) Intermediate layer (Y2) Substrate 50 Supports 60, 70 Workpiece 61 Curing Sealed body 61a Separated product 71 of cured sealed body Modified region 72 Gap

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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)
  • Adhesives Or Adhesive Processes (AREA)
  • Laminated Bodies (AREA)
  • Dicing (AREA)
  • Container, Conveyance, Adherence, Positioning, Of Wafer (AREA)
  • Mechanical Treatment Of Semiconductor (AREA)

Abstract

L'invention concerne un procédé de production d'un article traité à l'aide d'un corps stratifié adhésif qui comprend une feuille adhésive à expansion thermique (I) ayant un substrat (Y1) et une couche adhésive (X1) et contenant des particules à expansion thermique dans l'une ou l'autre des couches et une feuille adhésive (II) ayant un substrat (Y2) et une couche adhésive (X2), le substrat (Y2) de la feuille adhésive (II) étant directement stratifié sur la feuille adhésive (I), ledit procédé comprenant séquentiellement l'étape (1) d'application de la surface de la couche adhésive (X1) du corps stratifié adhésif sur un support et l'application d'un article à traiter sur la surface de la couche adhésive (X2) du corps stratifié adhésif, l'étape (2) consistant à soumettre l'article à un ou plusieurs traitements, et l'étape (3) de chauffage à la température de début d'expansion thermique des particules d'expansion thermique ou plus pour séparer le corps stratifié adhésif au niveau de l'interface entre la feuille adhésive (I) et le substrat (Y2) de la feuille adhésive (II) tout en maintenant l'article appliqué à la surface de la couche adhésive (X2) du corps stratifié adhésif, ledit procédé comprenant en outre la réalisation au cours de l'étape (2) ou après l'étape (3) de l'étape (4) de découpe et/ou de meulage de la surface de l'article sur le côté opposé à la surface appliquée sur la couche adhésive (X2).
PCT/JP2019/008260 2018-03-20 2019-03-04 Procédé de production d'article traité et corps stratifié adhésif WO2019181447A1 (fr)

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CN201980018435.XA CN111837219A (zh) 2018-03-20 2019-03-04 加工品的制造方法及粘合性层叠体
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KR1020207023470A KR20200133209A (ko) 2018-03-20 2019-03-04 가공품의 제조 방법 및 점착성 적층체

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WO2021193910A1 (fr) * 2020-03-27 2021-09-30 リンテック株式会社 Feuille de fabrication de dispositif à semi-conducteur
WO2022196752A1 (fr) * 2021-03-17 2022-09-22 リンテック株式会社 Procédé de fabrication de dispositif semi-conducteur et appareil de fabrication de dispositif semi-conducteur

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WO2021193910A1 (fr) * 2020-03-27 2021-09-30 リンテック株式会社 Feuille de fabrication de dispositif à semi-conducteur
WO2022196752A1 (fr) * 2021-03-17 2022-09-22 リンテック株式会社 Procédé de fabrication de dispositif semi-conducteur et appareil de fabrication de dispositif semi-conducteur

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CN111837219A (zh) 2020-10-27
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JPWO2019181447A1 (ja) 2021-04-08
TW201940347A (zh) 2019-10-16

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