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WO2018181510A1 - Feuille adhésive - Google Patents

Feuille adhésive Download PDF

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Publication number
WO2018181510A1
WO2018181510A1 PCT/JP2018/012837 JP2018012837W WO2018181510A1 WO 2018181510 A1 WO2018181510 A1 WO 2018181510A1 JP 2018012837 W JP2018012837 W JP 2018012837W WO 2018181510 A1 WO2018181510 A1 WO 2018181510A1
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WO
WIPO (PCT)
Prior art keywords
pressure
sensitive adhesive
adhesive layer
adhesive sheet
meth
Prior art date
Application number
PCT/JP2018/012837
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English (en)
Japanese (ja)
Inventor
和恵 上村
Original Assignee
リンテック株式会社
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Filing date
Publication date
Application filed by リンテック株式会社 filed Critical リンテック株式会社
Publication of WO2018181510A1 publication Critical patent/WO2018181510A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • 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
    • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
    • 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
    • H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
    • H01L21/683—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping

Definitions

  • the present invention relates to a pressure-sensitive adhesive sheet that can reduce the adhesive strength at a desired timing and facilitates the peeling of the adherend.
  • an adhesive sheet may be used to temporarily fix a processing target such as an electronic member such as a semiconductor wafer or a display device constituent member (electronic member / optical member).
  • a pressure-sensitive adhesive sheet can reduce the pressure-sensitive adhesive force of the pressure-sensitive adhesive sheet at a desired timing by a method such as applying energy, thereby facilitating the separation of the object to be processed (the adherend).
  • it is subjected to a desired processing step in a state where an adherend such as an electronic member or an optical member is fixed to the adhesive sheet.
  • An object of the present invention is to provide a peeling method between an adhesive sheet and an adherend that can reduce the adhesive force at a desired timing by a novel action mechanism.
  • this invention is a peeling method of the adhesive sheet which peels an adhesive sheet provided with an adhesive layer at least, and the to-be-adhered body stuck on the adhesive surface of the said adhesive layer,
  • the said adhesive layer is The adhesive surface has a recess, and the adherend is attached to the adhesive sheet so that an independent space is formed by the recess of the adhesive layer, and at least the adherend is attached.
  • the pressure-sensitive adhesive sheet is peeled from the adherend by reducing the pressure-sensitive adhesive force of the pressure-sensitive adhesive layer by subjecting the pressure-sensitive adhesive sheet to a decompression process for expanding the gas in the space.
  • a method for peeling an adhesive sheet is provided (Invention 1).
  • the “sheet” in the present invention includes the concept of “tape”.
  • the adhesive force can be reduced at a desired timing by a novel action mechanism of expanding the gas in the space by a decompression process. Peeling of the sheet and the adherend can be facilitated.
  • the pressure reduction treatment is lower than the atmospheric pressure of the environment in which the adhesive sheet is attached to the adherend (Invention 2).
  • the adhesive composition which forms the said adhesive layer may not have active energy ray curability and thermosetting (invention 3), and this invention (invention) In 3), it is preferable that the pressure-sensitive adhesive composition contains a (meth) acrylic acid ester polymer (Invention 4).
  • the adhesive composition which forms the said adhesive layer may have active energy ray curability or thermosetting (invention 5), this invention (invention 5).
  • the active energy ray-curable pressure-sensitive adhesive composition preferably contains a (meth) acrylic acid ester polymer having an active energy ray-curable group in the side chain (Invention 6).
  • the said pressure reduction process may be performed (invention 7), and the said pressure reduction After the treatment, the pressure-sensitive adhesive layer may be cured by irradiating the pressure-sensitive adhesive layer with energy rays (Invention 8).
  • the pressure-sensitive adhesive sheet is preferably used for temporarily fixing the adherend (Invention 9).
  • the adherend is an electronic member or an optical member. It may be a member (Invention 10).
  • 2nd this invention is a manufacturing method of the workpiece obtained by processing a workpiece
  • the pressure-sensitive adhesive layer is placed in a reduced pressure environment and subjected to a pressure reduction treatment to expand the gas in the space, thereby reducing the adhesive strength of the pressure-sensitive adhesive layer, and the processed product and the pressure-sensitive adhesive sheet.
  • the manufacturing method of the workpiece characterized by providing the peeling process which peels is provided (invention 11).
  • the adhesive force can be reduced at a desired timing by a novel action mechanism, and the peeling between the pressure-sensitive adhesive sheet and the adherend is facilitated. be able to.
  • the peeling method of the adhesive sheet which concerns on this embodiment is a method of peeling an adhesive sheet provided with an adhesive layer at least, and the to-be-adhered body stuck on the adhesive surface of the said adhesive layer.
  • the pressure-sensitive adhesive layer has a concave portion on the pressure-sensitive adhesive surface, and the adherend and the pressure-sensitive adhesive sheet are bonded to each other so that an independent space is generated by the concave portion of the pressure-sensitive adhesive layer.
  • at least the pressure-sensitive adhesive sheet to which the adherend is adhered is subjected to a pressure reduction treatment for expanding the gas in the space generated by the recess and the adherend, thereby increasing the adhesive strength of the pressure-sensitive adhesive layer. Decrease and facilitate separation of the adhesive sheet and the adherend.
  • FIG. 1 is a sectional view of an adhesive sheet used in one embodiment of the present invention.
  • the pressure-sensitive adhesive sheet 1 according to the present embodiment includes a pressure-sensitive adhesive layer 2, and the pressure-sensitive adhesive layer 2 has a pressure-sensitive adhesive surface P; a concave portion 3 on a surface that contacts the adherend (the upper surface in FIG. 1). .
  • the adhesive sheet 1 which concerns on this embodiment may be further equipped with the base material 4 in the surface (lower surface in FIG. 1) on the opposite side to the adhesive surface P in an adhesive layer.
  • the pressure-sensitive adhesive sheet 1 according to this embodiment can be used for temporarily fixing an electronic member or an optical member, for example.
  • the case where it is used for temporarily fixing a semiconductor wafer will be mainly described.
  • the pressure-sensitive adhesive layer is formed from a pressure-sensitive adhesive composition that does not have active energy ray curability and thermosetting (hereinafter sometimes referred to as “non-curable” in the present specification). It may be a pressure-sensitive adhesive layer, or may be a pressure-sensitive adhesive layer formed from a pressure-sensitive adhesive composition having active energy ray curability or thermosetting. When the pressure-sensitive adhesive layer is composed of multiple layers, a combination of a non-curable pressure-sensitive adhesive layer and a curable pressure-sensitive adhesive layer may be used.
  • Non-curable pressure-sensitive adhesive compositions examples include acrylic pressure-sensitive adhesive compositions, rubber-based pressure-sensitive adhesive compositions, silicone-based pressure-sensitive adhesive compositions, and urethane-based pressure-sensitive adhesives. Examples thereof include a composition, a polyester-based pressure-sensitive adhesive composition, a polyvinyl ether-based pressure-sensitive adhesive composition, and among them, an acrylic pressure-sensitive adhesive composition is preferable.
  • an acrylic adhesive composition what contains a conventionally well-known (meth) acrylic acid ester polymer can be used. In the present specification, the term “polymer” includes the concept of “copolymer”.
  • the (meth) acrylic acid ester polymer (A) contained in the acrylic pressure-sensitive adhesive composition may be a homopolymer formed from one type of (meth) acrylic acid ester monomer, or a plurality of types of ( The copolymer may be a copolymer formed from a (meth) acrylate monomer, or a copolymer formed from one or more types of (meth) acrylate monomers and monomers other than (meth) acrylate monomers. It may be a polymer. Moreover, a (meth) acrylic acid ester polymer (A) may be used individually by 1 type, and may be used in combination of 2 or more type.
  • Specific types of the compound that becomes the (meth) acrylic acid ester monomer are not particularly limited, and specific examples include (meth) acrylic acid, (meth) acrylic acid ester, and derivatives thereof (acrylonitrile, itaconic acid, and the like).
  • Specific examples of (meth) acrylic acid esters include chain skeletons such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate.
  • (meth) acrylate Having Dorokishi group (meth) acrylate; glycidyl (meth) acrylate, (meth) acrylates having reactive functional groups other than hydroxy group, such as N- methylaminoethyl (meth) acrylate.
  • monomers other than (meth) acrylic acid ester monomers include olefins such as ethylene and norbornene, vinyl acetate, and styrene.
  • the (meth) acrylic acid ester monomer is an alkyl (meth) acrylate, the alkyl group preferably has 1 to 18 carbon atoms.
  • (meth) acrylic acid means both acrylic acid and methacrylic acid. The same applies to other similar terms.
  • the (meth) acrylic acid ester polymer (A) is directly contained in the pressure-sensitive adhesive composition.
  • at least a part thereof may be contained as a crosslinked product by performing a crosslinking reaction with a crosslinking agent.
  • the (meth) acrylic acid ester polymer (A) preferably has a reactive functional group that reacts with the crosslinking agent.
  • the type of the reactive functional group is not particularly limited, and may be appropriately determined based on the type of the crosslinking agent.
  • examples of the reactive functional group of the (meth) acrylic acid ester polymer (A) include a hydroxy group, a carboxyl group, and an amino group. These highly reactive hydroxy groups are preferred.
  • examples of the reactive functional group of the (meth) acrylic acid ester polymer (A) include a carboxyl group, an amino group, an amide group, etc. These highly reactive carboxyl groups are preferred.
  • the method for introducing the reactive functional group into the (meth) acrylic acid ester polymer (A) is not particularly limited.
  • the (meth) acrylic acid ester polymer (A) using a monomer having a reactive functional group is used.
  • a constitutional unit based on a monomer having a reactive functional group is contained in the polymer skeleton.
  • a carboxyl group is introduced into the (meth) acrylic acid ester polymer (A)
  • a (meth) acrylic acid ester polymer (A) is formed using a monomer having a carboxyl group such as (meth) acrylic acid. do it.
  • the (meth) acrylic acid ester polymer (A) When the (meth) acrylic acid ester polymer (A) has a reactive functional group, it accounts for the total mass of the (meth) acrylic acid ester polymer (A) from the viewpoint of making the degree of crosslinking a good range.
  • the proportion of the mass of the structural portion derived from the monomer having a reactive functional group is preferably about 1 to 20% by mass, and more preferably 2 to 10% by mass.
  • the weight average molecular weight (Mw) of the (meth) acrylic acid ester polymer (A) is preferably 10,000 to 2,000,000, and more preferably 100,000 to 1,500,000 from the viewpoint of film forming properties at the time of coating. preferable.
  • the weight average molecular weights of the (meth) acrylic acid ester polymer (A) and the (meth) acrylic acid ester polymers (B1) and (B3) described later are gel permeation chromatography (GPC). It is a value in terms of standard polystyrene measured by the method, and details of the measuring method are shown in the examples described later.
  • the glass transition temperature Tg of the (meth) acrylic acid ester polymer (A) is preferably in the range of ⁇ 70 ° C. to 30 ° C., more preferably in the range of ⁇ 60 ° C. to 20 ° C.
  • the glass transition temperature can be calculated from the Fox equation.
  • the active energy ray-curable pressure-sensitive adhesive composition has an active energy ray-curable compound (B2) and an active energy ray-curable group introduced into the side chain ( It is preferable that at least one of the (meth) acrylic acid ester polymer (B3) is contained.
  • the active energy ray-curable pressure-sensitive adhesive composition is composed of the active energy ray-curable compound (B2) and the (meth) acrylic acid ester polymer (B3) in which an active energy ray-curable group is introduced into the side chain.
  • the active energy ray-curable pressure-sensitive adhesive composition may further contain a (meth) acrylic acid ester polymer (B1) having no active energy ray curability.
  • (1-2-1) (Meth) acrylic acid ester polymer having no active energy ray curability (B1)
  • the adhesive composition which forms the adhesive layer in this embodiment contains the (meth) acrylic acid ester polymer (B1) which does not have active energy ray curability
  • the said (meth) acrylic acid ester polymer (B1) ) May be contained in the pressure-sensitive adhesive composition as it is, or at least a part thereof may be contained as a crosslinked product by performing a crosslinking reaction with a crosslinking agent described later.
  • (meth) acrylic acid ester polymer (B1) the same thing as the (meth) acrylic acid ester polymer (A) mentioned above regarding the non-curable adhesive composition can be used.
  • the active energy ray curable compound (B2) is a compound having an active energy ray curable group and polymerized when irradiated with active energy rays such as ultraviolet rays and electron beams.
  • the active energy ray-curable group possessed by the active energy ray-curable compound (B2) is, for example, a group containing an active energy ray-curable carbon-carbon double bond, and specifically includes a (meth) acryloyl group, vinyl Examples include groups.
  • Examples of the active energy ray-curable compound (B2) are not particularly limited as long as the active energy ray-curable group has the above-mentioned active energy ray-curable group.
  • low molecular weight compounds monofunctional and polyfunctional monomers and Oligomer
  • Specific examples of the low molecular weight active energy ray-curable compound (B2) include trimethylolpropane tri (meth) acrylate, tetramethylolmethanetetra (meth) acrylate, pentaerythritol tri (meth) acrylate, and dipentaerythritol monohydroxypenta.
  • the active energy ray-curable compound (B2) usually has a molecular weight of 100 to 30,000, preferably about 300 to 10,000.
  • the content of the active energy ray-curable compound (B2) in the active energy ray-curable adhesive composition and the content ratio with other components are not particularly limited, but the active energy ray-curable adhesive composition is active energy.
  • the active energy ray-curable adhesive composition is active energy.
  • the active energy ray curable compound (B2) is the above (meth) acrylic acid.
  • the amount is preferably 10 to 400 parts by mass, more preferably about 30 to 350 parts by mass with respect to 100 parts by mass of the ester polymer (B1).
  • the active energy ray-curable compound (B2) when it contains the active energy ray-curable compound (B2) and the (meth) acrylic acid ester polymer (B3) in which an active energy ray-curable group is introduced in the side chain described later, )
  • the content of the active energy ray-curable compound (B2) is preferably in the above range with respect to 100 parts by mass of the acrylic ester polymer (B3).
  • the active energy ray-curable pressure-sensitive adhesive composition has the active energy ray-curable compound (B2), the (meth) acrylic acid ester polymer (B1), and the active energy ray-curable group introduced into the side chain.
  • the total amount of the (meth) acrylic acid ester polymer (B1) and the (meth) acrylic acid ester polymer (B3) is 100 parts by mass.
  • the content of the active energy ray-curable compound (B2) is preferably in the above range.
  • (1-2-3) (Meth) acrylic acid ester polymer (B3) having an active energy ray-curable group introduced in the side chain
  • the active energy ray-curable pressure-sensitive adhesive composition in the present embodiment contains a (meth) acrylic acid ester polymer (B3) having an active energy ray-curable group introduced in the side chain, such (meth) acrylic acid ester
  • the polymer (B3) may be contained in the pressure-sensitive adhesive composition as it is, or at least a part thereof may be contained as a crosslinked product by performing a crosslinking reaction with a crosslinking agent described later.
  • the main skeleton of the (meth) acrylic acid ester polymer (B3) in which the active energy ray-curable group is introduced into the side chain is not particularly limited, and is the same as that of the aforementioned (meth) acrylic acid ester polymer (B1). Are illustrated.
  • the active energy ray-curable group introduced into the side chain of the (meth) acrylate polymer (B3) is, for example, a group containing an active energy ray-curable carbon-carbon double bond.
  • a meth) acryloyl group etc. can be illustrated.
  • the active energy ray-curable group may be bonded to the (meth) acrylic acid ester polymer (B3) via an alkylene group, an alkyleneoxy group, a polyalkyleneoxy group, or the like.
  • the (meth) acrylic acid ester polymer (B3) in which an active energy ray-curable group is introduced into the side chain contains, for example, a functional group such as a hydroxy group, a carboxyl group, an amino group, a substituted amino group, and an epoxy group.
  • a (meth) acrylic acid ester polymer is reacted with a substituent that reacts with the functional group and a curable group-containing compound having 1 to 5 active energy ray-curable carbon-carbon double bonds per molecule. Obtained.
  • Such a (meth) acrylic acid ester polymer includes a (meth) acrylic acid ester monomer or a derivative thereof having a functional group such as a hydroxy group, a carboxyl group, an amino group, a substituted amino group, and an epoxy group, and the component (B1) described above. It can be obtained by copolymerizing with a monomer that constitutes.
  • curable group-containing compound examples include (meth) acryloyloxyethyl isocyanate, meta-isopropenyl- ⁇ , ⁇ -dimethylbenzyl isocyanate, (meth) acryloyl isocyanate, allyl isocyanate, glycidyl (meth) acrylate, (meth) Acrylic acid etc. are mentioned, These can be used individually by 1 type or in combination of 2 or more types.
  • the active energy ray hardening group was introduce
  • the kind of the reactive functional group is not particularly limited, and the (meth) acrylic acid ester polymer (B1) described above (and the (meth) acrylic acid ester polymer (A) described above with respect to the non-curable pressure-sensitive adhesive composition) and The same thing can be illustrated.
  • the weight average molecular weight (Mw) of the (meth) acrylic acid ester polymer (B3) having an active energy ray-curable group introduced in the side chain is preferably 100,000 to 2,000,000, and 300,000 to 1,500,000. More preferably.
  • the glass transition temperature (Tg) of the (meth) acrylic acid ester polymer (B3) is preferably in the range of ⁇ 70 to 30 ° C., more preferably in the range of ⁇ 60 to 20 ° C.
  • the glass transition temperature (Tg) of the (meth) acrylic acid ester polymer (B3) refers to that of the (meth) acrylic acid ester polymer before being reacted with the curable group-containing compound.
  • thermosetting pressure-sensitive adhesive composition examples include those containing an epoxy resin, a phenol resin, and the like.
  • the adhesive composition forming the adhesive layer in this embodiment may contain a crosslinking agent capable of reacting with the polymer contained in the above-mentioned adhesive composition.
  • the pressure-sensitive adhesive layer in this embodiment comprises a polymer ((meth) acrylic acid ester polymer (A), (B1), (B3), etc.) contained in the pressure-sensitive adhesive composition and a crosslinking agent. Contains a cross-linked product obtained by a cross-linking reaction.
  • crosslinking agent examples include polyimine compounds such as polyisocyanate compounds, epoxy compounds, metal chelate compounds, and aziridine compounds, melamine resins, urea resins, dialdehydes, methylol polymers, metal alkoxides, metal salts, and the like. 1 type can be used individually or in combination of 2 or more types. Among these, an epoxy compound or a polyisocyanate compound is preferable because it is easy to control the crosslinking reaction.
  • a polyisocyanate compound is a compound having two or more isocyanate groups per molecule.
  • aromatic polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, aliphatic polyisocyanates such as hexamethylene diisocyanate, alicyclic polyisocyanates such as isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, and the like
  • epoxy compound examples include 1,3-bis (N, N′-diglycidylaminomethyl) cyclohexane, N, N, N ′, N′-tetraglycidyl-m-xylylenediamine, ethylene glycol diglycidyl ether. 1,6-hexanediol diglycidyl ether, trimethylolpropane diglycidyl ether, diglycidylaniline, diglycidylamine and the like.
  • the content of the crosslinking agent in the pressure-sensitive adhesive composition that forms the pressure-sensitive adhesive layer is the polymer contained in the pressure-sensitive adhesive composition (for example, (meth) acrylic acid ester polymers (A), (B1) and (B3)). Is preferably 0.01 to 50 parts by mass, more preferably 0.02 to 10 parts by mass, and more preferably 0.03 to 5 parts by mass with respect to 100 parts by mass of the total amount of Part is more preferable, and 0.08 to 0.5 part by mass is particularly preferable.
  • the pressure-sensitive adhesive composition forming the pressure-sensitive adhesive layer in the present embodiment contains a crosslinking agent
  • an appropriate crosslinking accelerator may be contained depending on the type of the crosslinking agent.
  • the pressure-sensitive adhesive composition forming the pressure-sensitive adhesive layer in the present embodiment includes, in addition to the above components, a photopolymerization initiator, a photosensitizer, a crosslinking accelerator, a dye, a pigment, and the like. You may contain various additives, such as a coloring material, a flame retardant, a filler, a heat conductive agent, a tackifier, a plasticizer, and an antistatic agent.
  • the pressure-sensitive adhesive composition when the pressure-sensitive adhesive composition has active energy ray curability that is cured by active energy rays such as ultraviolet rays, the pressure-sensitive adhesive composition preferably contains a photopolymerization initiator.
  • photopolymerization initiators examples include photoinitiators such as benzoin compounds, acetophenone compounds, acylphosphine oxide compounds, titanocene compounds, thioxanthone compounds, and peroxide compounds, and photosensitizers such as amines and quinones.
  • 1-hydroxycyclohexyl phenyl ketone benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzyldiphenyl sulfide, tetramethylthiuram monosulfide, azobisisobutyronitrile, dibenzyl, diacetyl, ⁇ -chloranthraquinone 2,4,6-trimethylbenzoyldiphenylphosphine oxide and the like, and these can be used alone or in combination of two or more.
  • ultraviolet rays When ultraviolet rays are used as energy rays, the irradiation time and irradiation amount can be reduced by blending a photopolymerization initiator.
  • the adhesive layer 2 has the concave part 3 in the adhesive surface P. As shown in FIG. As will be described later, in the pressure-sensitive adhesive sheet peeling method according to the present embodiment, the adherend is adhered to the pressure-sensitive adhesive sheet 1 (the pressure-sensitive adhesive surface P) so that a space is generated by the concave portion 3 of the pressure-sensitive adhesive layer 2.
  • the pressure-sensitive adhesive layer 2 preferably has an independent recess 3.
  • that the concave portion 3 is independent means that the entire outer edge of the concave portion 3 is surrounded by a flat surface portion (sometimes referred to as a non-recessed portion) constituting the adhesive surface P, in other words, the concave portion 3. Means that it does not communicate with the end of the pressure-sensitive adhesive sheet 1.
  • the pressure-sensitive adhesive layer 2 has the independent recess 3, it becomes easy to make the space generated by the adherend and the recess 3 of the pressure-sensitive adhesive layer 2 an independent space.
  • the pressure-sensitive adhesive layer 2 preferably has a plurality of recesses 3. Since the pressure-sensitive adhesive layer 2 has a plurality of recesses 3, it is easy to make the space generated by the adherend and the recesses 3 of the pressure-sensitive adhesive layer 2 independent spaces. Furthermore, it is particularly preferable that the pressure-sensitive adhesive layer 2 has a plurality of independent recesses 3. In addition, when the adhesive layer 2 has two or more recessed parts, all the recessed parts 3 do not necessarily need to be independent, and the one part may be connected with the edge part of the adhesive sheet 1. FIG.
  • each recess 3 may have the same shape or may have a different shape.
  • the concave portion 3 has a circular shape (including an elliptical shape or an oval shape) (FIG. 2A), a rectangular shape when the shape of the concave portion 3 on the adhesive surface P is viewed in plan view.
  • a convex polygonal shape (the same (b)
  • a concave polygonal shape such as a star shape (the same (c)), etc.
  • these are combined and arranged in a predetermined pattern (the same (d), (e)) It may also be an irregular shape (same (f)).
  • a plurality of rectangular concave portions 31 are arranged in parallel in the long side direction to form one repeating unit U, and the length of the rectangular concave portion 31 constituting the repeating unit U is long.
  • a plurality of repeating units U are repeatedly arranged vertically and horizontally so that the side directions are alternated.
  • a plurality of rectangular recesses 32 and two right-angled triangular recesses 33 form one repeating unit U ′, and the repeating units U ′ are arranged vertically and horizontally. Yes.
  • one side forming a right angle in the right triangular recess 33 is parallel to the long side of the rectangular recess 32, and the oblique side of the right triangular recess 33 faces the short side of the rectangular recess 32.
  • the rectangular recess 32 and the right triangle recess 33 are arranged.
  • the plurality of rectangular recesses 32 have long sides that become longer as they move away from the right triangle recess 33.
  • the recess 34 has an irregular shape, and the size (length, width, depth, etc.) of the recess 34 is not limited to a specific value. Further, the width and direction of one concave portion 34 are continuously or intermittently changed, and may have a branched shape.
  • the embossed pattern may be a polygon such as a regular triangle, a right triangle, a square, a rectangle, a rhombus, etc.
  • a star-shaped polygon such as a pentagram or a hexagon; a circle; an ellipse; a regular repetitive pattern provided with a plurality of shapes such as a polygon having a curved shape such as a fan shape or a heart shape.
  • emboss pattern is not particularly limited as long as it can form a recess 3 that creates an independent space with the adherend. However, it is preferable that the emboss pattern can form an independent recess 3. Those not communicating with the portion are preferred, and it is particularly preferred that a plurality of independent recesses 3 can be formed.
  • the cross-sectional shape of the recess 3 is semicircular (FIG. 3A), quadrangular (same (b)), trapezoid (same (c)), triangular (same (d)). ) And the like.
  • the recessed part 3 expands the gas in the space produced by the recessed part 3 and a to-be-adhered body by performing a pressure reduction process, and a viewpoint which reduces the adhesive force of the adhesive layer 2 effectively. Therefore, it is preferable that the expanded gas has a shape that tends to concentrate locally.
  • the shape of the concave portion 3 on the adhesive surface P is preferably a convex polygonal shape, a concave polygonal shape, or an irregular shape.
  • the height of the recess 3 is preferably 2 ⁇ m or more and not more than the thickness of the pressure-sensitive adhesive layer 2, particularly preferably 5 ⁇ m or more and not more than the thickness of the pressure-sensitive adhesive layer 2, and 10 ⁇ m or more and the thickness of the pressure-sensitive adhesive layer 2 or less. It is more preferable that the thickness is 20 ⁇ m or more and not more than the thickness of the pressure-sensitive adhesive layer 2.
  • the lower limit of the ratio of the recessed area to the total area of the adhesive surface P (hereinafter also referred to as recessed area ratio) is preferably 3% or more, particularly preferably 10% or more, and 25% or more. More preferably. Further, the upper limit value of the recessed area ratio is preferably 90% or less, particularly preferably 75% or less, and further preferably 60% or less.
  • the area ratio of the recess is 3% or more, a sufficient space is generated between the recess 3 and the adherend. Therefore, when decompression processing is performed, the pressure due to gas expansion becomes large in the space, and the adhesive strength Can be effectively reduced.
  • the recess area ratio is 90% or less, a sufficient contact area with the adherend can be ensured, so that a desired adhesive force can be secured.
  • the concave area ratio is obtained by obtaining an image of the adhesive surface P at a photographing magnification of 20 to 100 times using a digital microscope and imaging the concave surface when the adhesive surface P is viewed in plan. It can be measured by performing (binarization processing) and automatically measuring the total area of the recessed areas. Specifically, a value calculated based on the following formula in a predetermined region D arbitrarily selected on the adhesive surface P can be regarded as a recess area ratio. A detailed measurement method will be described in Examples described later.
  • Examples of the method for forming the recess 3 include embossing in which an emboss pattern is transferred to an adhesive layer.
  • the convex portion in the emboss pattern is transferred to the pressure-sensitive adhesive layer and becomes the concave portion 3 on the pressure-sensitive adhesive surface.
  • the ratio of the convex area to the total area of the surface (embossed surface) on which the embossed pattern is formed (hereinafter also referred to as convex area ratio) is preferably 30% or more as a lower limit, and 50%. It is particularly preferable that the ratio is 70% or more.
  • the upper limit value of the convex area ratio is preferably 98% or less, particularly preferably 95% or less, and further preferably 90% or less.
  • the convex area ratio on the embossed surface does not necessarily coincide with the concave area ratio of the adhesive surface P when embossing is performed on a relatively soft adhesive layer. However, even in such a case, when the convex area ratio on the embossed surface is in the above range, it is easy to keep the concave area ratio in the above-described preferable range on the adhesive surface P to which the embossed pattern is transferred. Become.
  • the convex area ratio on the embossed surface is obtained by obtaining an image of the embossed surface when the embossed surface is viewed in plan using a digital microscope, a laser microscope, or an electron microscope with a shooting magnification of 20 to 1000 times. Then, image processing (binarization processing) is performed on the image, and the total value of the convex area can be measured by automatic area measurement. Specifically, a value calculated based on the following formula in a predetermined region T arbitrarily selected on the embossed surface can be regarded as a convex area ratio. A detailed measurement method will be described in Examples described later.
  • a pattern printing method may be used so that the recesses 3 are formed.
  • the recesses 3 are formed by laser thermal processing for irradiating a laser to the adhesive layer. May be.
  • the method described in International Publication No. 2015/152347 can also be illustrated as a method of forming the recess 3 having an irregular shape.
  • a coating film made of a composition having a high content of fine particles and a small content of resin and a coating film made of a composition containing a resin as a main component are separately formed. The method of drying a coating film simultaneously is mentioned. According to this method, the shrinkage stress difference caused by the fine particles is generated inside the coating film, causing cracking of the coating film, and the peripheral resin flows into the cracking of the coating film, thereby forming the recess 3. it is conceivable that.
  • the thickness of the pressure-sensitive adhesive layer in this embodiment is preferably 5 to 100 ⁇ m, particularly preferably 10 to 50 ⁇ m, and 15 to 30 ⁇ m. More preferably. It is preferable that the pressure-sensitive adhesive layer has a thickness of 5 ⁇ m or more because more space can be secured during decompression. It is preferable for the thickness of the pressure-sensitive adhesive layer to be 100 ⁇ m or less because the film thickness accuracy during application can be ensured.
  • the adhesive strength of the adhesive sheet is preferably 0.5 to 50 N / 25 mm, more preferably 2 to 40 N / 25 mm, and particularly preferably 5 to 30 N / 25 mm. .
  • the adherend can be reliably fixed. For example, it is very useful for temporarily fixing the adherend in the processing step of the adherend.
  • the adhesive force here does not perform the pressure reduction process mentioned later (When the adhesive composition has active energy ray curable property or thermosetting property, irradiation and heating of the active energy ray are not further performed).
  • a silicon mirror wafer be a to-be-adhered body, stick an adhesive sheet on the mirror surface, and let it be the adhesive force (mN / 25mm) measured by 180 degree peeling method according to JISZ0237: 2009.
  • the adhesive strength reduction rate of the adhesive sheet is preferably 10% or more, more preferably 20% or more, and particularly preferably 30% or more. When the adhesive strength of the adhesive sheet is within the above range, in this embodiment, the adhesive sheet and the adherend are more easily separated.
  • the adhesive force decreasing rate here is before performing the pressure reduction process mentioned later (When the adhesive composition has active energy ray curable or thermosetting, after irradiation or heating of active energy rays)
  • the adhesive strength is measured as described above, and is calculated by the following formula based on the obtained value.
  • Adhesive strength reduction rate (%) (adhesive strength before decompression ⁇ adhesive strength after decompression) / (adhesive strength before decompression) ⁇ 100
  • the irradiation or heating of the active energy ray when the pressure-sensitive adhesive composition has active energy ray curable property or thermosetting property may be before or after the decompression treatment, Even in this case, the adhesive strength reduction rate is calculated by the above formula.
  • the lower limit value of the stress relaxation rate of the pressure-sensitive adhesive layer is preferably 40% or more, particularly preferably 50% or more, and 55% or more. Is more preferable.
  • the upper limit of the stress relaxation rate of the pressure-sensitive adhesive layer is preferably 90% or less, particularly preferably 85% or less, and further preferably 80% or less.
  • the stress relaxation rate of an adhesive layer here is not performing the pressure reduction process mentioned later (When an adhesive composition has active energy ray sclerosis
  • the pressure-sensitive adhesive layer is the stress relaxation rate after being stretched by 10% in a tensile test and held for 300 seconds. Specifically, the tensile test was performed at a speed of 200 mm / min with an adhesive formed into a thickness of 50 ⁇ m, a width of 15 mm, and a length of 120 mm (of which the measurement range is 100 mm) in an environment of 23 ° C. and 50% RH. And 10% elongation.
  • the lower limit of the breaking elongation of the pressure-sensitive adhesive layer is preferably 110% or more, particularly preferably 120% or more, and preferably 130% or more. Is more preferable.
  • the upper limit of the elongation at break of the pressure-sensitive adhesive layer is preferably 300% or less, particularly preferably 200% or less, and further preferably 150% or less.
  • the pressure-sensitive adhesive layer was measured as a single pressure-sensitive adhesive layer without a substrate or the like. Specifically, the pressure-sensitive adhesive layer was formed into a thickness of 50 ⁇ m, a width of 15 mm, and a length of 120 mm (of which the measurement range was 100 mm) The pressure-sensitive adhesive is stretched at a speed of 200 mm / min in an environment of 23 ° C. and 50% RH.
  • the lower limit of the gel fraction of the pressure-sensitive adhesive layer is preferably 2% or more, particularly preferably 4% or more, and 6% or more. Is more preferable.
  • the upper limit of the gel fraction of the pressure-sensitive adhesive layer is preferably 90% or less, particularly preferably 40% or less, and further preferably 15% or less.
  • the stability of the pressure-sensitive adhesive sheet can be ensured by the reaction between the pressure-sensitive adhesives due to crosslinking.
  • the upper limit of the gel fraction of the pressure-sensitive adhesive layer is 90% or less, it is easy to impart tack to the pressure-sensitive adhesive sheet, and good temporary fixability can be obtained.
  • the gel fraction of an adhesive layer here is not performing the pressure reduction process mentioned later (When an adhesive composition has active energy ray sclerosis
  • the pressure-sensitive adhesive sheet according to this embodiment may include a base material in addition to the pressure-sensitive adhesive layer.
  • the base material is not particularly limited as long as the pressure-sensitive adhesive sheet can appropriately function in a desired process such as an adherend processing process.
  • a paper base material, a resin film or sheet, a paper base The base material etc. which laminated the material with resin are mentioned, According to the use of the adhesive sheet of 1 aspect of this embodiment, it can select suitably.
  • the film is composed of a film mainly composed of a resin-based material because of its advantage for the decompression effect.
  • Such films include ethylene-copolymer films such as ethylene-vinyl acetate copolymer films, ethylene- (meth) acrylic acid copolymer films, and ethylene- (meth) acrylic acid ester copolymer films; low density Polyethylene films such as polyethylene (LDPE) film, linear low density polyethylene (LLDPE) film, high density polyethylene (HDPE) film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, ethylene-norbornene copolymer film, Polyolefin film such as norbornene resin film; Polyvinyl chloride film such as polyvinyl chloride film and vinyl chloride copolymer film; Polyethylene terephthalate film, Polybutylene tele Polyester film of tallate films; polyurethane film; polyimide film; polystyrene films; polycarbonate films; and fluorine resin film. Further, modified films such as these crosslinked films and ionomer films are also used
  • the film constituting the base material preferably includes at least one of an ethylene copolymer film and a polyolefin film. It is easy to control the mechanical characteristics of an ethylene copolymer film in a wide range by changing the copolymerization ratio. For this reason, the base material provided with the ethylene-based copolymer film easily satisfies the mechanical properties required as the base material of the pressure-sensitive adhesive sheet according to this embodiment. Moreover, since the ethylene copolymer film has relatively high adhesion to the pressure-sensitive adhesive layer, peeling at the interface between the base material and the pressure-sensitive adhesive layer hardly occurs when used as a pressure-sensitive adhesive sheet.
  • the base material used in the present embodiment contains various additives such as pigments, dyes, flame retardants, plasticizers, antistatic agents, lubricants, fillers, etc., in the film mainly composed of the above-mentioned resin-based material. May be.
  • the pigment include titanium dioxide and carbon black.
  • the filler include organic materials such as melamine resin, inorganic materials such as fumed silica, and metal materials such as nickel particles. The content of such an additive is not particularly limited, but should be within a range where the substrate exhibits a desired function and does not lose smoothness and flexibility.
  • the substrate is preferably permeable to ultraviolet rays.
  • the base material has the transparency of an electron beam.
  • the adherend has energy ray permeability and the energy beam is irradiated from the adherend side, the substrate does not need to have energy ray permeability.
  • a component having one or more kinds selected from the group consisting of a carboxyl group and its ions and salts is provided on the surface of the substrate on the side of the pressure-sensitive adhesive layer (hereinafter also referred to as “substrate-coated surface”). Is preferably present.
  • substrate-coated surface a component having one or more kinds selected from the group consisting of a carboxyl group and its ions and salts.
  • the base material itself is an ethylene- (meth) acrylic acid copolymer film, an ionomer resin film, etc., and the resin constituting the base material is selected from the group consisting of carboxyl groups, ions and salts thereof. Or you may have 2 or more types.
  • the substrate is, for example, a polyolefin film, and the substrate-adhered surface side is subjected to corona treatment or a primer layer is provided. May be.
  • Various coating films may be provided on the surface of the substrate opposite to the substrate deposition surface.
  • the thickness of the substrate is not limited as long as the pressure-sensitive adhesive sheet can function properly in a desired process, but it is preferably 5 to 1000 ⁇ m, more preferably 10 to 500 ⁇ m, and still more preferably 12 to 12 from the viewpoint of handleability and economy.
  • the thickness is 250 ⁇ m, more preferably 15 to 150 ⁇ m.
  • the release sheet is laminated on the adhesive surface of the adhesive layer for the purpose of protecting the adhesive layer until the adhesive layer is applied to the adherend. It may be.
  • the configuration of the release sheet is arbitrary, and examples include a release film of a plastic film with a release agent.
  • Specific examples of the plastic film include polyester films such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate, and polyolefin films such as polypropylene and polyethylene.
  • the release agent silicone-based, fluorine-based, long-chain alkyl-based, and the like can be used, and among these, a silicone-based material that is inexpensive and provides stable performance is preferable.
  • the thickness of the release sheet is not particularly limited, but is usually about 20 to 250 ⁇ m.
  • a release sheet may be a release sheet on which an emboss pattern for forming a recess is formed, and the release surface is flat, and the adhesive layer is protected after the recess is formed. It may be a release sheet laminated on the substrate.
  • the manufacturing method of an adhesive sheet is a method which can form the adhesive layer formed from the above-mentioned adhesive composition, and can form a recessed part in the adhesive surface of an adhesive layer. If there is, the detailed method is not particularly limited. As an example, first, a sheet on which an emboss pattern corresponding to the concave portion is formed is prepared, and a release sheet on which the emboss pattern is formed is obtained by performing a release process on the surface of the sheet.
  • a coating composition containing the pressure-sensitive adhesive composition described above and, if desired, further containing a solvent or a dispersion medium is prepared, and on the release-treated surface of the release sheet having an emboss pattern obtained as described above, a die coater Applying the coating composition by a curtain coater, spray coater, slit coater, knife coater, etc. to form a coating film, and drying the coating film forms a laminate composed of an adhesive layer and a release sheet can do.
  • a surface of the pressure-sensitive adhesive layer of the laminate that is opposite to the surface on the side of the release sheet may be attached to a substrate to obtain a laminate of the pressure-sensitive adhesive sheet and the release sheet.
  • the release sheet in this laminate may be peeled off as a process material, or the adhesive layer may be protected until being attached to an adherend such as an electronic member or an optical member.
  • the properties of the coating composition are not particularly limited as long as it can be applied, and may contain a component for forming the pressure-sensitive adhesive layer as a solute or a dispersoid. There is also a case.
  • the coating composition contains a crosslinking agent, (meth) acrylic acid in the coating film can be obtained by changing the drying conditions (temperature, time, etc.) or by separately providing a heat treatment. What is necessary is just to advance the crosslinking reaction of ester polymer (A), (B1) or (B3), and a crosslinking agent, and to form a crosslinked structure in a desired presence density in an adhesive layer.
  • crosslinking of the pressure-sensitive adhesive refers to a reaction performed before sticking the pressure-sensitive adhesive sheet to the adherend, and before sticking to the adherend is, for example, the pressure-sensitive adhesive described above. A step of forming a layer may be mentioned. Therefore, “crosslinking” of the pressure-sensitive adhesive is clearly distinguished from “curing” described later.
  • the pressure-sensitive adhesive sheet may be performed by laser thermal processing by laser irradiation instead of embossing.
  • a laser is irradiated from the pressure-sensitive adhesive side of the pressure-sensitive adhesive layer to form a recess.
  • the laser used for laser thermal processing include carbon dioxide (CO 2 ) laser, TEA-CO 2 laser, YAG laser, UV-YAG laser, YVO 4 laser, YLF laser, etc. From the viewpoint of cost and the like, a carbon dioxide laser is preferable.
  • burst processing burst mode
  • laser light is continuously irradiated to one place until one through-hole is formed, and laser light is sequentially irradiated to a plurality of places.
  • burst processing burst mode
  • the former is superior in terms of thermal efficiency
  • the latter is superior in terms of reducing the thermal effect on the workpiece.
  • Thermal processing may be performed in any mode.
  • Examples of the workpiece W to be subjected to the peeling method according to this embodiment include electronic members such as a semiconductor wafer, a semiconductor package, a multilayer substrate, a ceramic green sheet laminate, a batch sealing module; a liquid crystal display member, and an organic EL display member. And optical members such as an optical filter, a polarizing plate, and a retardation plate.
  • the attachment of the workpiece W and the pressure-sensitive adhesive sheet 1 may be performed under atmospheric pressure, or may be performed in a chamber in which the atmospheric pressure is controlled by the pressure control device 10 described later.
  • the atmospheric pressure in which the sticking process is performed or the atmospheric pressure in the chamber corresponds to the pressure of the gas in the space C in the subsequent process, and after performing the sticking process after appropriately adjusting the atmospheric pressure, It becomes easy to control the amount of gas expansion in the decompression process.
  • work W stuck on the adhesive sheet 1 by the sticking process can be attached
  • processing steps include a back grinding process, a circuit forming process, a dicing process, a die sort process, and the like if the work W is a semiconductor wafer, and a laminating process and a transfer process if the work W is a display device component. Etc.
  • the workpiece W is processed into a workpiece W ′.
  • the adhesive sheet 1 is peeled from the workpiece W as described later after the processing step of the workpiece W, it can be said that it is used for temporarily fixing the workpiece W during the processing step.
  • At least the space C is given a pressure in a direction in which it expands in a direction along the vertical direction (the normal direction of the adhesive surface P of the adhesive layer 2).
  • the lateral direction applied to one space C (the pressure-sensitive adhesive surface P in the pressure-sensitive adhesive layer 2).
  • Force in the vertical direction of the space C the pressure in the vertical direction remains without being canceled, and the pressure in the space C adjacent to the space C cancels the pressure in the vertical direction. Is more preferable because it becomes more prominent.
  • the pressure reduction treatment is preferably lower than the atmospheric pressure of the pasting environment, more preferably lower so that the atmospheric pressure in the chamber has a difference of 10 kPa or more than the atmospheric pressure of the pasting environment.
  • the difference is more preferably 30 kPa or more, still more preferably 50 kPa or more, further preferably 80 kPa or more, and particularly preferably 90 kPa or more.
  • the lower limit value of the pressure in the chamber is not particularly limited, but is usually 10 ⁇ 7 Pa or more, preferably 10 ⁇ 5 Pa or more, more preferably 10 ⁇ 1 Pa or more, and even more, from a technical viewpoint.
  • it is 10 Pa or more, More preferably, it is 100 Pa or more, Especially preferably, it is 1000 Pa or more.
  • the adhesive is applied from that location.
  • the agent layer 2 is partially or entirely peeled from the workpiece W ′ (FIG. 4E). Since the pressure-sensitive adhesive layer 2 has a plurality of recesses 3, a plurality of spaces C are formed, and therefore, the number of expanding portions increases, resulting in an increase in the number of locations that cause peeling.
  • the pressure-sensitive adhesive layer 2 may be hard or soft. When the pressure-sensitive adhesive layer 2 is relatively hard, as shown in FIG.
  • the pressure-sensitive adhesive layer 2 and the workpiece W ′ The peeling of the interface proceeds from the space C side. This is because the pressure due to the expansion of the gas is an interface between the pressure-sensitive adhesive layer 2 and the workpiece W ′, which is a relatively fragile portion of the inner wall of the space C constituted by the pressure-sensitive adhesive layer 2 and the workpiece W ′. This is thought to be easier to concentrate on.
  • the pressure-sensitive adhesive layer 2 is relatively soft, after the space C and the pressure-sensitive adhesive layer 2 are deformed in the vertical direction, the pressure-sensitive adhesive layer 2 and the workpiece W ′ are formed as shown in FIG. Peel off. In this way, the adhesive strength of the pressure-sensitive adhesive layer 2 to the workpiece W ′ is reduced.
  • the adhesive sheet 1 and the workpiece W ′ can be easily peeled off.
  • the pressure-sensitive adhesive sheet 1 and the workpiece W ′ can be peeled as they are in the state shown in FIG. 4E.
  • the pressure-sensitive adhesive sheet 1 is placed in the chamber so that the workpiece W ′ is on the upper side of the pressure-sensitive adhesive sheet 1.
  • the pressure-sensitive adhesive sheet 1 and the workpiece W ′ are peeled off by the weight of the workpiece W ′. You can also.
  • the pressure-sensitive adhesive composition forming the pressure-sensitive adhesive layer 2 has active energy ray curable or thermosetting property
  • the active energy ray irradiation or after the above-described processing step and before or after the decompression treatment It is preferable to cure the pressure-sensitive adhesive layer 2 by heating.
  • the pressure-sensitive adhesive layer 2 is cured before the pressure reduction treatment, the pressure-sensitive adhesive layer 2 is relatively hard at the stage of the pressure reduction treatment. Peeling of the interface between the pressure-sensitive adhesive layer 2 and the workpiece W ′ progresses from the space C side almost without causing the pressure-sensitive adhesive layer 2 and the workpiece W ′ and the adhesive force to be reduced.
  • the pressure-sensitive adhesive layer 2 is cured after the pressure reduction treatment, the space C and the pressure-sensitive adhesive layer 2 are deformed (FIG. 4D) because the pressure-sensitive adhesive layer 2 is relatively soft at the stage of the pressure reduction treatment. Thereafter, the pressure-sensitive adhesive layer 2 can be cured to further reduce the adhesive force, and the pressure-sensitive adhesive layer 2 and the workpiece W ′ can be easily separated from each other.
  • “curing” of the pressure-sensitive adhesive refers to a reaction performed after the pressure-sensitive adhesive sheet 1 is adhered to an adherend (work W, workpiece W ′). Therefore, for example, it is clearly distinguished from the above-mentioned “crosslinking” of the pressure-sensitive adhesive.
  • examples of the active energy ray for curing the pressure-sensitive adhesive composition include ionizing radiation, that is, ultraviolet rays, X-rays, and electron beams. Among these, ultraviolet rays that are relatively easy to introduce irradiation equipment are preferable.
  • near ultraviolet rays including ultraviolet rays having a wavelength of about 200 to 380 nm may be used for ease of handling.
  • the amount of light may be appropriately selected according to the type of active energy ray-curable group possessed by the active energy ray-curable pressure-sensitive adhesive composition and the thickness of the pressure-sensitive adhesive layer 2, and is usually about 50 to 1500 mJ / cm 2 . 200 to 1000 mJ / cm 2 is preferable, and 300 to 800 mJ / cm 2 is more preferable.
  • the ultraviolet illumination is usually 50 ⁇ 1500mW / cm 2 or so, preferably 200 ⁇ 1000mW / cm 2, more preferably 300 ⁇ 800mW / cm 2.
  • the ultraviolet light source is not particularly limited, and for example, an electrodeless lamp, a high-pressure mercury lamp, a metal halide lamp, a UV-LED, or the like is used.
  • the acceleration voltage is appropriately selected according to the type of active energy ray-curable group possessed by the active energy ray-curable adhesive composition and the thickness of the adhesive layer 2. Usually, the acceleration voltage is preferably about 10 to 1000 kV.
  • the irradiation dose may be set within a range where the active energy ray-curable pressure-sensitive adhesive composition is appropriately cured, and is usually selected within a range of 10 to 1000 krad.
  • the electron beam source is not particularly limited.
  • various electron beam accelerators such as a cockcroft Walton type, a bandegraph type, a resonant transformer type, an insulated core transformer type, a linear type, a dynamitron type, and a high frequency type may be used. it can.
  • these active energy rays may be irradiated from the surface opposite to the pressure-sensitive adhesive surface P (the surface on which the workpiece W ′ is adhered) in the pressure-sensitive adhesive sheet 1. preferable.
  • the pressure-sensitive adhesive composition has thermosetting properties
  • a heating means for curing the pressure-sensitive adhesive composition for example, an appropriate means such as a hot plate, a hot air dryer, or a near infrared lamp can be adopted. It can.
  • the heating conditions are appropriately set depending on the heating temperature required for the thermosetting of the pressure-sensitive adhesive layer 2, the desired peelability, the heat resistance of the workpiece W and the workpiece W ', the heating means, and the like.
  • As general heating conditions for example, when a hot plate is used, a temperature of 80 to 250 ° C., a heating time of 5 seconds to 60 seconds, and the like are exemplified.
  • the pressure-sensitive adhesive treatment of the pressure-sensitive adhesive sheet 1 to the adherend is reduced by a decompression process that forms a space C in the space C and expands the gas in the space C.
  • the adhesive force can be reduced at a desired timing by a novel mechanism of expanding the gas by the decompression process, thereby facilitating the peeling between the adhesive sheet and the adherend. Can do.
  • the adhesive force of the pressure-sensitive adhesive layer 2 is reduced using only active energy ray curable or thermosetting, the selection of materials is limited because the curing reaction (that is, chemical reaction) is sufficiently advanced. End up.
  • the adhesive force can be reduced by the expansion of the gas due to the decompression process, so that the active energy ray curable property or thermosetting property is not used at all or only partially used. Therefore, the freedom degree of the material which comprises the adhesive layer 2 can be made large.
  • the adhesive strength of the adhesive layer 2 decreases.
  • thermosetting property is not used at all or only partially used. Even if a heating process is included in the workpiece, the workpiece W can be sufficiently temporarily fixed.
  • another layer may be interposed between the base material 4 and the pressure-sensitive adhesive layer 2 in the pressure-sensitive adhesive sheet 1.
  • the pressure-sensitive adhesive sheet may be a double-sided pressure-sensitive adhesive sheet comprising only a pressure-sensitive adhesive layer without a base material.
  • a method of peeling a double-sided pressure-sensitive adhesive sheet having a first pressure-sensitive adhesive surface and a second pressure-sensitive adhesive surface, and a first adherend adhered to the first pressure-sensitive adhesive surface can do.
  • a second adherend may be attached to the second adhesive surface.
  • the first adhesive surface has a recess, and the first adherend is adhered to the adhesive layer so that an independent space is created by the recess.
  • the gas in the space expands, and the adhesive force of the double-sided pressure-sensitive adhesive sheet on the first adherend is increased.
  • the first adherend and the pressure-sensitive adhesive sheet can be peeled off.
  • An embossed film (1) is obtained by embossing a polyethylene terephthalate film (manufactured by Toray Industries, Inc., product name “Lumirror”, thickness 75 ⁇ m) to the pattern of FIG. It was.
  • a release agent on the embossed surface of the embossed film (1) a release agent having the same composition as the release agent of the release sheet (product name “SP-PET381130”, manufactured by Lintec Corporation) is 0.1 ⁇ m in thickness after drying.
  • the release sheet (1) having an embossed pattern on the surface was prepared by coating with a Meyer bar so that
  • polystyrene equivalent weight average molecular weight is a standard polystyrene equivalent value measured (GPC measurement) under the following conditions using a gel permeation chromatograph (manufactured by Tosoh Corporation, product name “HLC-8020”).
  • An embossed film (2) was obtained by embossing a polyethylene terephthalate film (manufactured by Toray Industries, Inc., product name “Lumirror”, thickness 75 ⁇ m) so as to have the pattern of FIG.
  • a release agent having the same composition as the release agent of the release sheet (product name “SP-PET381130”, manufactured by Lintec Corporation) is 0.1 ⁇ m in thickness after drying.
  • the release sheet (2) having an embossed pattern on the surface was prepared by applying with a Meyer bar so as to become and drying at 130 ° C. for 30 seconds.
  • a pressure-sensitive adhesive sheet was produced in the same manner as in Example 1 except that the obtained release sheet (2) was used.
  • Example 3 An embossed film (3) was obtained by embossing a polyethylene terephthalate film (manufactured by Toray Industries, Inc., product name “Lumirror”, thickness 75 ⁇ m) so as to have the pattern of FIG.
  • a release agent having the same composition as the release agent of the release sheet (product name “SP-PET381130”, manufactured by Lintec Corporation) is 0.1 ⁇ m in thickness after drying.
  • the release sheet (3) having an embossed pattern on the surface was prepared by coating with a Meyer bar so that A pressure-sensitive adhesive sheet was produced in the same manner as in Example 1 except that the obtained release sheet (3) was used.
  • the release sheet (1) is 4 mm long x 5 mm wide
  • the release sheet (2) is 8 mm long x 10 mm wide
  • the release sheet (3) 2 mm long ⁇ 2.5 mm wide were selected.
  • the photographing conditions of the digital microscope are as follows.
  • Convex part area ratio [convex part area in region T / total area of region T] ⁇ 100
  • FIGS. 5B, 6B, and 7B The binarized images obtained for the embossed surfaces of the release sheets of Examples 1 to 3 are shown in FIGS. 5B, 6B, and 7B, respectively.
  • the pressure-sensitive adhesive surface of the pressure-sensitive adhesive sheet obtained in each example was bonded to a glass plate (Corning Co., Ltd., product name “Eagle XG”), and the adhesive surface was passed through the glass plate with a digital microscope (magnification 20 to 50 times). Using, an arbitrarily selected range on the adhesive surface was photographed vertically from the upper surface, and an image was acquired. The obtained images are shown in FIGS. 8 (a), 9 (a), and 10 (a). In this case, more specifically, the focal point was sequentially moved from above the portion that was visually determined to be a non-recessed portion from the vertical direction, and the first focused portion was photographed as a non-recessed portion. Then, in the obtained connected image, a region D surrounded by a rectangle 6 mm long ⁇ 8 mm wide is arbitrarily selected as one region, and this is defined as an “image of region D”.
  • the photographing conditions of the digital microscope are as follows.
  • the ultraviolet irradiation conditions are an illuminance of 700 mW / cm 2 and a light amount of 700 mJ / cm 2 in a wavelength range of 200 to 380 nm.
  • the illuminance and light amount are determined by an illuminance / light meter (product name “UV Power Pack II” manufactured by EIT). Used to measure illuminance and light intensity.
  • Adhesive strength reduction rate (%) (Adhesive strength after UV irradiation ⁇ Adhesive strength after reduced pressure) / (Adhesive strength after UV irradiation) ⁇ 100
  • ⁇ Stress relaxation rate> the embossed film was changed to a heavy release sheet (manufactured by Lintec Co., Ltd., product name “SP-PET 382050”, thickness 38 ⁇ m, polyethylene terephthalate film coated with a silicone release agent), and the substrate was lightly released. Change to a sheet (manufactured by Lintec Corporation, product name “SP-PET 381031”, thickness 38 ⁇ m, polyethylene terephthalate film coated with silicone release agent), so that the thickness of the adhesive layer after drying is 50 ⁇ m A substrate-less double-sided pressure-sensitive adhesive sheet sandwiched between two release sheets was prepared in the same manner as described in the Examples except that it was applied.
  • the substrate-less double-sided pressure-sensitive adhesive sheet is allowed to stand for 2 weeks in an atmosphere of 23 ° C. and 50% RH, and is irradiated with ultraviolet rays using an irradiation ultraviolet irradiation device (product name “Light Hammer 10 MARK II”, electrodeless lamp) manufactured by Heraeus. Was irradiated.
  • the ultraviolet irradiation conditions are an illuminance of 700 mW / cm 2 and a light amount of 700 mJ / cm 2 in a wavelength range of 200 to 380 nm.
  • the illuminance and light amount are determined by an illuminance / light meter (product name “UV Power Pack II” manufactured by EIT). Used to measure illuminance and light intensity.
  • a 15 mm wide ⁇ 120 mm long sample is cut out from the pressure sensitive adhesive sheet in which a plurality of the pressure sensitive adhesive layers are laminated, and the release sheet laminated on the outermost layer of the laminate is peeled off so that the sample measurement range becomes 15 mm wide ⁇ 100 mm long.
  • the sample was set in a universal tensile testing machine (manufactured by Shimadzu Corporation, Autograph AG-10kNIS). Then, in an environment of 23 ° C. and 50% RH (relative humidity), the sample was stretched at a pulling rate of 200 mm / min, a stress A (Pa) at the time of 10% elongation, and a stress B after 300 seconds from the elongation stop. (Pa) was measured.
  • the pressure-sensitive adhesive sheet obtained in the examples was cut into a size of 80 mm ⁇ 80 mm, and the pressure-sensitive adhesive layer from which the release sheet was removed was wrapped in a polyester mesh (number of meshes: 200 mesh / inch). Weighed with a precision balance. The mass at this time is M1.
  • the pressure-sensitive adhesive sample was immersed in an ethyl acetate solvent at room temperature (23 ° C.) for 24 hours. Thereafter, the pressure-sensitive adhesive was taken out and air-dried for 24 hours in an environment of a temperature of 23 ° C. and 50% RH, and further dried in an oven at 80 ° C. for 12 hours. The mass of only the pressure-sensitive adhesive after drying was weighed with a precision balance. The mass at this time is M2.
  • the gel fraction (%) is represented by (M2 / M1) ⁇ 100.
  • the measurement results are shown in Table 1.

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Abstract

La présente invention concerne un procédé de délaminage de la feuille adhésive (1) permettant le délaminage de la feuille adhésive (1) pourvue d'au moins une couche adhésive (2) et le délaminage des corps de fixation (W, W') fixés à la surface adhésive (P) de la couche adhésive (2), le procédé étant caractérisé en ce que : la couche adhésive (2) comporte une partie évidée (3) dans la surface adhésive (P) ; les corps de fixation (W, W') sont fixés à la feuille adhésive (1) de telle sorte qu'un espace indépendant (C) est formé par la partie évidée (3) de la couche adhésive (2) ; un processus de dépressurisation servant à dilater un gaz à l'intérieur de l'espace (C) est réalisé sur la feuille adhésive (1), à laquelle au moins les corps de fixation (W, W') est fixé, pour ainsi réduire l'adhérence de la couche adhésive (2) et délaminer la feuille adhésive (1) et les corps de fixation (W, W'). Grâce à ce procédé, l'adhérence peut être réduite à un moment souhaité au moyen d'un nouveau mécanisme d'action.
PCT/JP2018/012837 2017-03-31 2018-03-28 Feuille adhésive WO2018181510A1 (fr)

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KR102811494B1 (ko) 2019-09-25 2025-05-22 맥셀 주식회사 점착 테이프

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CN110854057B (zh) * 2019-11-14 2022-07-12 京东方科技集团股份有限公司 一种转移基板及其制作方法、转移方法

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JP2009035660A (ja) * 2007-08-03 2009-02-19 Nippon Zeon Co Ltd 発泡粘着シートの剥離方法
JP2010129701A (ja) * 2008-11-26 2010-06-10 Nitto Denko Corp ダイシング・ダイボンドフィルム及び半導体装置の製造方法
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JP2009035660A (ja) * 2007-08-03 2009-02-19 Nippon Zeon Co Ltd 発泡粘着シートの剥離方法
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102811494B1 (ko) 2019-09-25 2025-05-22 맥셀 주식회사 점착 테이프

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