WO2019188819A1 - Adhesive agent composition, adhesive sheet, and method for producing processed product - Google Patents

Adhesive agent composition, adhesive sheet, and method for producing processed product Download PDF

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Publication number
WO2019188819A1
WO2019188819A1 PCT/JP2019/012175 JP2019012175W WO2019188819A1 WO 2019188819 A1 WO2019188819 A1 WO 2019188819A1 JP 2019012175 W JP2019012175 W JP 2019012175W WO 2019188819 A1 WO2019188819 A1 WO 2019188819A1
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WO
WIPO (PCT)
Prior art keywords
pressure
sensitive adhesive
meth
acrylate
adhesive sheet
Prior art date
Application number
PCT/JP2019/012175
Other languages
French (fr)
Japanese (ja)
Inventor
慎弥 高岡
康彦 垣内
高志 阿久津
Original Assignee
リンテック株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by リンテック株式会社 filed Critical リンテック株式会社
Priority to KR1020207024194A priority Critical patent/KR102644545B1/en
Priority to CN201980014254.XA priority patent/CN111742027B/en
Priority to JP2020509981A priority patent/JP7304847B2/en
Publication of WO2019188819A1 publication Critical patent/WO2019188819A1/en

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/16—Layered products comprising a layer of synthetic resin specially treated, e.g. irradiated
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • 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
    • 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
    • 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
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • 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]
    • C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/385—Acrylic polymers
    • 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
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C09J2301/416—Additional features of adhesives in the form of films or foils characterized by the presence of essential components use of irradiation

Definitions

  • the present invention relates to a pressure-sensitive adhesive sheet that can be easily peeled off from an adherend, a pressure-sensitive adhesive composition that makes it possible to produce such a pressure-sensitive adhesive sheet, and a method for producing a workpiece using such a pressure-sensitive adhesive sheet. It is.
  • an adhesive sheet may be used to temporarily fix a processing target such as a semiconductor wafer or a ceramic green sheet laminate.
  • a processing target such as a semiconductor wafer or a ceramic green sheet laminate.
  • the above-mentioned pressure-sensitive adhesive sheet one that can reduce the adhesion between the pressure-sensitive adhesive sheet and the adherend at a desired timing is used. According to the pressure-sensitive adhesive sheet, after the cut piece is obtained, it is possible to easily separate the cut piece from the pressure-sensitive adhesive sheet by reducing the adhesion between the pressure-sensitive adhesive sheet and the adherend.
  • Patent Document 1 and Patent Document 2 include an acrylic containing a carboxy precursor group-containing monomer as a monomer unit constituting the polymer.
  • a pressure-sensitive adhesive sheet is disclosed in which a pressure-sensitive adhesive layer is formed of a pressure-sensitive adhesive composition containing a polymer and an acid catalyst or an acid generator.
  • a gas is generated from the carboxy precursor group-containing monomer described above by the action of the acid component generated from the acid catalyst or the acid generator, and the gas is accumulated at the interface between the pressure-sensitive adhesive sheet and the adherend. The sheet can be easily separated from the adherend.
  • the present invention has been made in view of the above circumstances, and is a pressure-sensitive adhesive sheet that can be easily peeled off from an adherend, a pressure-sensitive adhesive composition that enables the production of such a pressure-sensitive adhesive sheet, and such a pressure-sensitive adhesive. It aims at providing the manufacturing method of the processed material using a sheet
  • the present invention provides a (meth) acrylic acid alkyl ester (a1) having an alkyl group having 1 to 12 carbon atoms as a monomer unit constituting a polymer and a hydrocarbon-based polymer by heating.
  • a pressure-sensitive adhesive composition comprising: an acid generator (B) that generates an acid upon irradiation with active energy rays and / or heating; and a photoinitiator (C) (Invention 1). ).
  • a pressure-sensitive adhesive sheet comprising a pressure-sensitive adhesive layer formed using the pressure-sensitive adhesive composition of the invention (Invention 1)
  • the pressure-sensitive adhesive layer is heated in the presence of an acid derived from the acid generator (B) in the pressure-sensitive adhesive layer.
  • the adhesive force on the adherend decreases due to the curing of the adhesive layer by irradiation of active energy rays. This action is combined, and these actions combine to make it possible to peel the adhesive sheet from the adherend very easily.
  • the (meth) acrylic acid ester copolymer (A) preferably contains a hydroxy group-containing monomer (a3) as a monomer unit constituting the polymer (Invention 2).
  • the carboxy precursor group-containing monomer (a2) has a structure in which a secondary carbon atom of an alkyl group having a secondary carbon atom and a (meth) acryloyloxy group are bonded.
  • the carboxy precursor group-containing monomer (a2) is sec-butyl (meth) acrylate, isopropyl (meth) acrylate, sec-hexyl (meth) acrylate, sec-octyl (meth) acrylate.
  • the (meth) acrylic acid ester copolymer (A), as a monomer unit constituting the polymer, contains 1% by mass or more of the carboxy precursor group-containing monomer (a2), It is preferable to contain in the ratio of 75 mass% or less (invention 5).
  • the (meth) acrylic acid ester copolymer (A) preferably contains 2-ethylhexyl acrylate as at least one kind of the (meth) acrylic acid alkyl ester (a1). (Invention 6).
  • the present invention provides a pressure-sensitive adhesive sheet comprising a pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition (Invention 1 to 6) (Invention 7).
  • the thickness of the pressure-sensitive adhesive layer is preferably 1 ⁇ m or more and 60 ⁇ m or less (Invention 8).
  • the above inventions may be used for processing brittle members (Invention 9). After completion of the processing of the brittle member, it is preferable that the adhesive sheet can be easily peeled from the brittle member. From this viewpoint, the above inventions (Inventions 7 and 8) can be used for processing the brittle member. preferable.
  • the present invention includes a laminating step of laminating the pressure-sensitive adhesive sheet (Inventions 7 to 10) on a workpiece, a processing step of processing the workpiece on the pressure-sensitive adhesive sheet to obtain a workpiece, An irradiation step of irradiating active energy rays to the pressure-sensitive adhesive layer in the pressure-sensitive adhesive sheet laminated on the workpiece, and heating the pressure-sensitive adhesive layer in the pressure-sensitive adhesive layer laminated on the workpiece.
  • a manufacturing method of a workpiece including a heating step to be performed and a peeling step of peeling the pressure-sensitive adhesive sheet that has undergone the irradiation step and the heating step from the workpiece, wherein the heating step is performed after the irradiation step is completed.
  • the manufacturing method of the workpiece characterized by performing the said irradiation process and the said heating process simultaneously is provided (invention 11).
  • the workpiece is preferably a semiconductor device or a member of a semiconductor device (Invention 12).
  • the pressure-sensitive adhesive sheet according to the present invention can be easily peeled off from the adherend. Moreover, according to the adhesive composition which concerns on this invention, it is possible to manufacture such an adhesive sheet. Furthermore, in the manufacturing method of the workpiece which concerns on this invention, an adhesive sheet can be easily peeled from a to-be-adhered body.
  • the pressure-sensitive adhesive composition contains a (meth) acrylic acid ester copolymer (A), an acid generator (B), and a photoinitiator (C).
  • the (meth) acrylic acid ester copolymer (A) is a (meth) acrylic acid alkyl ester (a1) having an alkyl group having 1 to 12 carbon atoms as a monomer unit constituting the polymer and a hydrocarbon-based polymer by heating.
  • the said (meth) acrylic acid ester copolymer (A) has an active energy ray reactive group in a side chain.
  • the acid generator (B) generates an acid by at least one of irradiation with active energy rays and heating.
  • the (meth) acrylic acid ester copolymer (A) has an active energy ray-reactive group in the side chain
  • the pressure-sensitive adhesive composition is a photoinitiator ( C).
  • a (meth) acrylic acid ester copolymer (A) contains a carboxy precursor group containing monomer (a2) as a monomer unit which comprises a polymer as above-mentioned. Therefore, the (meth) acrylic acid ester copolymer (A) has a carboxy precursor group.
  • the pressure-sensitive adhesive composition contains an acid generator (B).
  • an acid is generated from the acid generator (B) by applying at least one stimulus of irradiation with active energy rays and heating to the pressure-sensitive adhesive layer formed using the pressure-sensitive adhesive composition.
  • a reaction occurs.
  • the released hydrocarbon-based gas accumulates at the interface between the pressure-sensitive adhesive layer and the adherend in the pressure-sensitive adhesive sheet, thereby reducing the contact area between the pressure-sensitive adhesive layer and the adherend, and the adhesion to the adherend. Will be further reduced.
  • the adhesive force is lowered by the curing of the pressure-sensitive adhesive layer by irradiation with active energy rays (hereinafter, May be referred to as “first action”) and the action of reducing the contact area between the pressure-sensitive adhesive layer and the adherend due to the generation of the hydrocarbon gas (hereinafter, referred to as “second action”). ) And the adhesive sheet can be easily peeled off from the adherend. Since these actions are both caused by external stimuli, the above-described peeling from the adherend can be caused at a desired timing.
  • the amount of carboxy groups present in the (meth) acrylic acid ester copolymer (A) increases as the amount of released hydrocarbon gas increases.
  • the pressure-sensitive adhesive force in the pressure-sensitive adhesive layer tends to increase. Therefore, when peeling from the adherend is caused only by the second action related to the generation of the hydrocarbon-based gas as in the case of the conventional pressure-sensitive adhesive sheet, the pressure-sensitive adhesive layer is adhered to the adhesive layer by the generated hydrocarbon-based gas.
  • the adhesive strength itself of the pressure-sensitive adhesive layer is hardly lowered.
  • the first effect that the adhesive force decreases due to the curing of the pressure-sensitive adhesive layer also occurs. Peeling from the body can be easily performed.
  • the hydrocarbon-based gas generated in the second action can easily separate the adhesive layer and the adherend. Further, since further hydrocarbon-based gas is likely to be accumulated in the part separated as such, separation of the pressure-sensitive adhesive layer and the adherend is promoted starting from the part. Therefore, in the pressure-sensitive adhesive sheet obtained using the pressure-sensitive adhesive composition according to this embodiment, the first action and the second action act synergistically to achieve very easy peeling from the adherend. can do.
  • the adhesiveness between the pressure-sensitive adhesive sheet and the adherend can be remarkably reduced, so that the pressure-sensitive adhesive sheet can be covered without applying a force to peel off the pressure-sensitive adhesive sheet. It can also be peeled off from the body.
  • the pressure-sensitive adhesive sheet can be peeled from the adherend by the weight of the pressure-sensitive adhesive sheet or the adherend.
  • the adhesive sheet can be peeled by dropping the adhesive sheet from the adherend by gravity with the adhesive sheet side facing downward.
  • self-peeling Such a property is called “self-peeling”.
  • the (meth) acrylic acid ester copolymer (A) is a monomer unit constituting the polymer, the (meth) acrylic acid alkyl ester (a1) having an alkyl group having 1 to 12 carbon atoms and heating.
  • the carboxy precursor group-containing monomer (a2) having a carboxy precursor group that changes to a carboxy group by releasing a hydrocarbon gas and has an active energy ray reactive group in the side chain, there is no particular limitation.
  • the (meth) acrylic acid ester copolymer (A) comprises the above-mentioned (meth) acrylic acid alkyl ester (a1) and carboxy precursor group-containing monomer (a2).
  • An acrylic copolymer (AP) obtained by copolymerizing a monomer containing), an active energy ray containing a functional group capable of reacting with the acrylic copolymer (AP) and an active energy ray reactive group It is preferable to react with a reactive group containing compound (AC).
  • a (meth) acrylic acid ester copolymer (A) is obtained by reaction of an acrylic copolymer (AP) and an active energy ray reactive group containing compound (AC) is demonstrated. .
  • Examples of the (meth) acrylic acid alkyl ester (a1) having 1 to 12 carbon atoms in the alkyl group include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and n-butyl (meth) acrylate. N-pentyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, n-decyl (meth) acrylate, n-dodecyl (meth) acrylate, and the like. .
  • Desirable pressure-sensitive adhesive is obtained when the acrylic copolymer (AP) contains a (meth) acrylic acid alkyl ester (a1) having an alkyl group having 1 to 12 carbon atoms as a monomer constituting the polymer.
  • the adhesiveness can be expressed.
  • (meth) acrylic acid alkyl esters it is preferable to use (meth) acrylic acid alkyl esters having an alkyl group having 1 to 8 carbon atoms, particularly n-butyl (meth) acrylate and 2
  • these may be used independently and may be used in combination of 2 or more type.
  • the acrylic copolymer (AP) preferably contains a monomer having a glass transition temperature (Tg) as a homopolymer of 0 ° C. or lower as at least one of the above-mentioned (meth) acrylic acid alkyl ester (a1).
  • a monomer having a glass transition temperature (Tg) as a homopolymer of ⁇ 40 ° C. or lower is preferably included, and a monomer having a glass transition temperature (Tg) as a homopolymer of ⁇ 60 ° C. or lower is further preferable.
  • the carboxy precursor group-containing monomer (a2) contained as a monomer of the acrylic copolymer (AP) tends to have a relatively high glass transition temperature (Tg) as a homopolymer
  • the acrylic copolymer (AP) Including a monomer having a glass transition temperature (Tg) of 0 ° C. or less as a homopolymer, the glass transition temperature (Tg) of the resulting (meth) acrylic acid ester copolymer (A) as a whole is adjusted to an appropriate temperature. It is easy to adjust.
  • the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition according to the present embodiment has a good pressure-sensitive adhesive force on the adherend (before irradiation and heating of active energy rays to the pressure-sensitive adhesive layer).
  • the adhesive force in a state where the first action and the second action described above are not generated; hereinafter may be referred to as “initial adhesive force”) is easily exhibited.
  • the acrylic copolymer (AP) preferably contains 10% by mass or more, particularly 20% by mass or more, of the above-mentioned (meth) acrylic acid alkyl ester (a1) as a monomer unit constituting the polymer. It is preferable to contain 30% by mass or more.
  • the acrylic copolymer (AP) preferably contains the above-mentioned (meth) acrylic acid alkyl ester (a1) as a monomer unit constituting the polymer at 90% by mass or less, particularly 80% by mass. % Or less, and more preferably 70% by mass or less. When the content of the (meth) acrylic acid alkyl ester (a1) is 10% by mass or more, the obtained pressure-sensitive adhesive layer easily exhibits a desired initial adhesive force.
  • the carboxy precursor group-containing monomer (a2) has a carboxy precursor group that is converted into a carboxy group by releasing a hydrocarbon gas by heating in the presence of an acid, and can constitute an acrylic copolymer (AP). If it is, it will not be specifically limited.
  • Preferred examples of the carboxy precursor group-containing monomer (a2) include a (meth) acrylic acid alkyl ester having a structure in which a secondary carbon atom of an alkyl group having a secondary carbon atom and a (meth) acryloyloxy group are bonded to each other. And at least one of (meth) acrylic acid alkyl ester having a structure in which a tertiary carbon atom of a alkyl group having a tertiary carbon atom and a (meth) acryloyloxy group are bonded, and benzyl (meth) acrylate. .
  • Preferred examples of the (meth) acrylic acid alkyl ester having a structure in which the secondary carbon atom of the alkyl group having a secondary carbon atom and the (meth) acryloyloxy group are bonded to each other include sec-butyl (meta ) Acrylate, isopropyl (meth) acrylate, sec-hexyl (meth) acrylate, sec-octyl (meth) acrylate, sec-nonyl (meth) acrylate, sec-decyl (meth) acrylate, bornyl (meth) acrylate, isobornyl (meth) ) Acrylate, cyclohexyl (meth) acrylate and the like.
  • the (meth) acrylic acid alkyl ester having the structure in which the tertiary carbon atom of the alkyl group having a tertiary carbon atom and the (meth) acryloyloxy group are bonded to each other include tert-butyl (meta ) Acrylate, tert-hexyl (meth) acrylate, tert-octyl (meth) acrylate, tert-nonyl (meth) acrylate, tert-decyl (meth) acrylate, 2-methyl-2-adamantyl (meth) acrylate, 2-ethyl -2-Adamantyl (meth) acrylate and the like.
  • carboxy precursor group-containing monomer (a2) sec-butyl (meth) acrylate, isopropyl (meth) acrylate, tert-butyl (meth) acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate and It is preferable to use at least one benzyl (meth) acrylate, and it is particularly preferable to use tert-butyl (meth) acrylate.
  • tert-butyl (meth) acrylate as the carboxy precursor group-containing monomer (a2), it becomes easy to release the hydrocarbon-based gas satisfactorily, so that the pressure-sensitive adhesive sheet according to this embodiment can be released from the adherend. Peeling can be performed more easily.
  • the preferable example of the above carboxy precursor group containing monomer (a2) may be used independently, and may be used in combination of 2 or more type.
  • the acrylic copolymer (AP) preferably contains 1% by mass or more of the carboxy precursor group-containing monomer (a2) as the monomer unit constituting the polymer, and more preferably contains 10% by mass or more. In particular, the content is preferably 35% by mass or more, and more preferably 40% by mass or more.
  • the acrylic copolymer (AP) preferably contains the carboxy precursor group-containing monomer (a2) as a monomer unit constituting the polymer in an amount of 75% by mass or less, particularly 65% by mass or less. It is preferable to contain it at 55 mass% or less.
  • the hydrocarbon gas is favorably generated from the pressure-sensitive adhesive layer during the second action described above, and this embodiment It becomes possible to peel the adhesive sheet from the adherend more easily. Moreover, it becomes easy to ensure fully content of the (meth) acrylic-acid alkylester (a1) mentioned above and other monomers because content of a carboxy precursor group containing monomer (a2) is 75 mass% or less.
  • desired adhesive force can be easily achieved, and the pressure-sensitive adhesive layer can be easily cured by the first action described above.
  • the acrylic copolymer (AP) includes a hydroxy group-containing monomer (a3) as a monomer unit constituting the polymer, together with the aforementioned (meth) acrylic acid alkyl ester (a1) and carboxy precursor group-containing monomer (a2). It is preferable to include.
  • the acrylic copolymer (AP) contains the hydroxy group-containing monomer (a3) as a monomer unit constituting the polymer
  • the acrylic copolymer (AP) contains a hydroxy group as a side chain.
  • the hydroxy group can function as a reaction point with the active energy ray-reactive group-containing compound (AC), whereby (meth) acrylic in which the active energy ray-reactive group has been sufficiently introduced.
  • the pressure-sensitive adhesive composition in the present embodiment contains a cross-linking agent (particularly a polyisocyanate compound) described later, the above-mentioned hydroxy group can function as a reaction point with the cross-linking agent, which is good. It becomes easy to obtain a cross-linked adhesive.
  • Preferred examples of the hydroxy group-containing monomer (a3) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3 Examples include (meth) acrylic acid hydroxyalkyl esters such as -hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyheptyl (meth) acrylate, and 8-hydroxyoctyl (meth) acrylate.
  • 2-hydroxyethyl (meth) acrylate is preferable from the viewpoint of excellent reactivity with the above-described crosslinking agent and active energy ray-reactive group-containing compound (AC). These may be used alone or in combination of two or more.
  • the acrylic copolymer (AP) preferably contains 1% by mass or more of the hydroxy group-containing monomer (a3) as a monomer unit constituting the polymer, and particularly preferably contains 5% by mass or more. Furthermore, it is preferable to contain 8 mass% or more.
  • the acrylic copolymer (AP) preferably contains the hydroxy group-containing monomer (a3) at 50% by mass or less, particularly 40% by mass or less, as a monomer unit constituting the polymer. It is preferable that it is contained in an amount of 25% by mass or less.
  • the content of the hydroxy group-containing monomer (a3) is 1% by mass or more, it is possible to cause the reaction with the crosslinking agent and the active energy ray-reactive group-containing compound (AC) as described above to occur more favorably. It becomes. Moreover, content of a hydroxy group containing monomer (a3) is 50 mass% or less, and content of the (meth) acrylic-acid alkylester (a1) mentioned above and a carboxy precursor group containing monomer (a2) is fully ensured. Therefore, the first action and the second action described above can be effectively generated.
  • the acrylic copolymer (AP) is, as desired, as a monomer unit constituting the copolymer, the (meth) acrylic acid alkyl ester (a1), the carboxy precursor group-containing monomer (a2), and the hydroxy group-containing monomer described above. You may contain other monomers other than (a3).
  • Examples of such other monomers include monomers having a reactive group capable of reacting with a crosslinking agent such as a carboxy group, an amino group, and an aziridinyl group.
  • examples of the monomer containing a carboxy group include ethylenically unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid, and citraconic acid.
  • examples of the monomer containing an amino group include aminoethyl (meth) acrylate and n-butylaminoethyl (meth) acrylate. These monomers can also be used individually by 1 type, and can also be used in combination of 2 or more type.
  • alkoxyalkyl group-containing (meth) acrylic acid such as methoxymethyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxymethyl (meth) acrylate, ethoxyethyl (meth) acrylate, etc.
  • esters (meth) acrylic acid esters having an aromatic ring such as phenyl (meth) acrylate; non-crosslinkable acrylamides such as acrylamide and methacrylamide; N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethyl (Meth) acrylic acid ester having a non-crosslinkable tertiary amino group such as aminopropyl (meth) acrylate; vinyl acetate; styrene. These may be used alone or in combination of two or more.
  • the polymerization mode of the acrylic copolymer (AP) may be a random copolymer or a block copolymer.
  • the acrylic copolymer (AP) can be obtained by copolymerizing the above-described monomers by a conventional method. For example, it can be produced by polymerization by emulsion polymerization, solution polymerization, suspension polymerization, bulk polymerization, aqueous solution polymerization, or the like. Especially, it is preferable to manufacture by the solution polymerization method performed in an organic solvent from a viewpoint of the stability at the time of superposition
  • An acrylic copolymer (AP) can be produced by radical polymerization by adding an azo polymerization initiator such as (cyanovaleric acid) or a peroxide polymerization initiator such as benzoyl peroxide.
  • an azo polymerization initiator such as (cyanovaleric acid) or a peroxide polymerization initiator such as benzoyl peroxide.
  • the mass average molecular weight of the acrylic copolymer (AP) is preferably 100,000 or more, particularly preferably 200,000 or more, and more preferably 300,000 or more. Further, the mass average molecular weight is preferably 2 million or less, particularly preferably 1 million or less, and more preferably 800,000 or less. When the mass average molecular weight of the acrylic copolymer (AP) is in the above range, it becomes easy to form a pressure-sensitive adhesive layer having a desired initial adhesive force.
  • the mass mean molecular weight in this specification is the value of standard polystyrene conversion measured by the gel permeation chromatography (GPC) method.
  • the active energy ray-reactive group-containing compound (AC) is not particularly limited as long as it has a functional group capable of reacting with the acrylic copolymer (AP) and contains an active energy ray-reactive group.
  • Examples of functional groups capable of reacting with the acrylic copolymer (AP) include isocyanate groups, epoxy groups, carboxy groups, and the like.
  • the acrylic copolymer (AP) contains the hydroxy group-containing monomer (a3) as a monomer constituting the polymer
  • the active energy ray-reactive group-containing compound (AC) is: It preferably has an isocyanate group excellent in reactivity with the hydroxy group derived from the monomer.
  • the active energy ray reactive group is preferably an energy ray curable carbon-carbon double bond, and particularly preferably a (meth) acryloyl group.
  • the active energy ray-reactive group-containing compound (AC) preferably has 1 to 5, more preferably 1 to 2 active energy ray-reactive groups in one molecule.
  • Examples of the active energy ray-reactive group-containing compound (AC) include 2-methacryloyloxyethyl isocyanate, meta-isopropenyl- ⁇ , ⁇ -dimethylbenzyl isocyanate, methacryloyl isocyanate, allyl isocyanate, 1,1- (bisacryloyloxy Methyl) ethyl isocyanate; acryloyl monoisocyanate compound obtained by reaction of diisocyanate compound or polyisocyanate compound with hydroxyethyl (meth) acrylate; diisocyanate compound or polyisocyanate compound, polyol compound, and hydroxyethyl (meth) acrylate Examples include acryloyl monoisocyanate compounds obtained by the reaction.
  • 2-methacryloyloxyethyl isocyanate is preferable from the viewpoint that it is easy to introduce an active energy ray-reactive group into an acrylic copolymer (AP), thereby easily causing the first action described above.
  • An active energy ray reactive group containing compound (AC) may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the (meth) acrylic acid ester copolymer (A) contains 10 mol% or more of the active energy ray-reactive group-containing compound (AC) with respect to the hydroxy group of the acrylic copolymer (AP). It is preferable that the reaction is performed at a rate of 40 mol% or more, and it is preferable that the reaction is performed at a rate of 70 mol% or more. Is preferred. Moreover, the (meth) acrylic acid ester copolymer (A) in this embodiment is 99 mol of active energy ray reactive group containing compound (AC) with respect to the hydroxy group which acrylic copolymer (AP) has.
  • the (meth) acrylic acid ester copolymer (A) is obtained by reacting the acrylic copolymer (AP) with the active energy ray-reactive group-containing compound (AC) at the above-described ratio.
  • the active energy ray-reactive group is sufficiently introduced, and the first action described above is easily generated.
  • the reaction between the acrylic copolymer (AP) and the active energy ray-reactive group-containing compound (AC) may be performed by a conventional method.
  • the hydroxyl group in the acrylic copolymer (AP) reacts with the functional group (for example, isocyanate group) in the active energy ray-reactive group-containing compound (AC) to react with the active energy ray reactivity.
  • a group is introduced as a side chain of the acrylic copolymer (AP) to obtain an energy ray-curable (meth) acrylic acid ester copolymer (A).
  • the mass average molecular weight of the (meth) acrylic acid ester copolymer (A) is preferably 200,000 or more, particularly preferably 300,000 or more, and more preferably 400,000 or more. Further, the mass average molecular weight is preferably 2 million or less, particularly preferably 1 million or less, and more preferably 800,000 or less.
  • the adhesive composition which concerns on this embodiment may contain 1 type of the (meth) acrylic acid ester copolymer (A) demonstrated above, or contains 2 or more types. Also good. Moreover, the adhesive composition which concerns on this embodiment may contain another (meth) acrylic acid ester copolymer with the (meth) acrylic acid ester copolymer (A) demonstrated above. .
  • Acid generator (B) As the acid generator (B), an acid is generated by at least one of irradiation with active energy rays and heating, and the carboxy precursor group-containing monomer (a2) in the (meth) acrylate copolymer (A) by the acid. There is no particular limitation as long as the hydrocarbon-based gas can be sufficiently released from the portion derived from the above.
  • examples of such an acid generator (B) include an ester compound of N-hydroxynaphthalimide and an acid component, or a compound thereof.
  • examples thereof include sulfonium salts, iodonium salts, diazonium salts, selenium salts, pyridinium salts, ferrocenium salts, phosphonium salts, thiopyrinium salts, and the like.
  • Examples of the acid component in the ester compound of N-hydroxynaphthalimide and an acid component described above or a derivative thereof include trifluoromethanesulfonic acid, methanesulfonic acid, benzenesulfonic acid, and the like.
  • anion component in the onium salt described above examples include CF 3 SO 3 ⁇ , (CF 3 SO 2 ) 2 N ⁇ , (CF 3 SO 2 ) 3 C ⁇ , BF 4 ⁇ , PF 6 ⁇ , AsF 6 ⁇ , SbF 6 ⁇ , B (C 6 F 5 ) 4 — and the like.
  • the acid generator (B) in this embodiment is preferably an ester compound of N-hydroxynaphthalimide and an acid component or a derivative thereof, more preferably N-hydroxy, from the viewpoint of easily generating an acid.
  • An ester compound of naphthalimide and trifluoromethanesulfonic acid or a derivative thereof is preferable, and 1,8-naphthalimide trifluoromethanesulfonic acid ester or a derivative thereof is particularly preferable.
  • the type of the active energy ray is preferably an ultraviolet ray, an electron beam or the like, and is particularly easy to handle. In addition, it is preferable to use ultraviolet rays that can effectively generate acid.
  • examples of the acid generator (B) include N- (4-methylbenzyl) 4′-pyridinium hexafluoroantimonate Hydrazine salts; phosphonium salts; sulfonium salts such as dimethylphenylsulfonium hexafluorophosphate; phosphonic acid esters; sulfonic acid esters such as cyclohexyl (4-methylphenyl) sulfonate and isopropyl (4-methylphenyl) sulfonate; And vinyl ether adduct derivatives of carboxylic acids such as propyl vinyl ether of 1,2,4-trimellitic acid.
  • the acid generator (B) described above can be used singly or in combination of two or more.
  • the content of the acid generator (B) in the pressure-sensitive adhesive composition according to the present embodiment is preferably 0.5 parts by mass or more with respect to 100 parts by mass of the (meth) acrylic acid ester copolymer (A).
  • the amount is preferably 1 part by mass or more, and more preferably 2 parts by mass or more.
  • the content is preferably 20 parts by mass or less, particularly preferably 15 parts by mass or less, and more preferably 10 parts by mass with respect to 100 parts by mass of the (meth) acrylic acid ester copolymer (A). Part or less.
  • the hydrocarbon-based gas can be generated satisfactorily from (A), and as a result, the pressure-sensitive adhesive sheet can be more easily peeled off from the adherend. Moreover, when content of an acid generator (B) is 20 mass parts or less, when forming a coating film using the adhesive composition which concerns on this embodiment, it becomes easy to maintain a favorable surface state. .
  • Photoinitiator (C) A photoinitiator (C) can accelerate
  • photoinitiators (C) examples include benzoin compounds, acetophenone compounds, acylphosphine oxide compounds, titanocene compounds, thioxanthone compounds, peroxide compounds, and the like, and specifically, 1-hydroxycyclohexylphenyl.
  • Ketone benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzyldiphenyl sulfide, tetramethylthiuram monosulfide, azobisisobutyronitrile, dibenzyl, diacetyl, ⁇ -chloranthraquinone, 2,4,6-trimethyl
  • Examples include benzoyldiphenylphosphine oxide.
  • an acetophenone compound is preferable and 1-hydroxycyclohexyl phenyl ketone is more preferable from the viewpoint that the reaction at the active energy ray-reactive group can be effectively promoted.
  • These photoinitiators (C) can be used individually by 1 type or in combination of 2 or more types.
  • content of the photoinitiator (C) in the adhesive composition which concerns on this embodiment is 0.1 mass part or more with respect to 100 mass parts of (meth) acrylic acid ester copolymers (A).
  • the amount is preferably 0.5 parts by mass or more, and more preferably 1.0 part by mass or more.
  • the content is preferably 10 parts by mass or less, particularly preferably 8 parts by mass or less, and more preferably 5 parts by mass with respect to 100 parts by mass of the (meth) acrylic acid ester copolymer (A). Part or less.
  • the reaction in the active energy ray-reactive group can be effectively promoted, and as a result, the pressure-sensitive adhesive sheet can be more easily detached from the adherend. It can be easily performed.
  • Cross-linking agent (D) The pressure-sensitive adhesive composition according to this embodiment preferably contains a crosslinking agent (D).
  • a cross-linking reaction between the (meth) acrylic acid ester copolymer (A) and the cross-linking agent (D) can occur, and the pressure-sensitive adhesive according to the present embodiment.
  • a three-dimensional network structure can be favorably formed. Thereby, it becomes easy to form the adhesive layer which has desired adhesive force.
  • the crosslinking agent (D) is not particularly limited as long as it can cause a crosslinking reaction with the (meth) acrylic acid ester copolymer (A), and is not limited to polyisocyanate compounds, epoxy compounds, Examples thereof include polyimine compounds such as metal chelate compounds and aziridine compounds, melamine resins, urea resins, dialdehydes, methylol polymers, metal alkoxides, and metal salts. Among these, a polyisocyanate compound or an epoxy compound is preferable because of easy control of the crosslinking reaction, and a polyisocyanate compound is particularly preferable.
  • the polyisocyanate compound is a compound having two or more isocyanate groups per molecule.
  • aromatic polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate and xylylene diisocyanate; aliphatic polyisocyanates such as hexamethylene diisocyanate; alicyclic polyisocyanates such as isophorone diisocyanate and hydrogenated diphenylmethane diisocyanate;
  • Examples thereof include biuret bodies, isocyanurate bodies, and adduct bodies that are reaction products with low molecular active hydrogen-containing compounds such as ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane, and castor oil.
  • trimethylolpropane-modified tolylene diisocyanate is preferable.
  • 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.
  • content of the said crosslinking agent (D) is 0 with respect to 100 mass parts of (meth) acrylic acid ester copolymers (A). It is preferably 1 part by mass or more, particularly preferably 0.2 part by mass or more, and further preferably 0.3 part by mass or more.
  • the content is preferably 20 parts by mass or less, particularly preferably 15 parts by mass or less, and more preferably 10 parts by mass with respect to 100 parts by mass of the (meth) acrylic acid ester copolymer (A). Part or less.
  • crosslinking agent (D) When the content of the crosslinking agent (D) is in the above-described range, a crosslinking reaction between the (meth) acrylic acid ester copolymer (A) and the crosslinking agent (D) is appropriately generated, and thereby a desired adhesion. It is easy to form a pressure-sensitive adhesive layer.
  • the pressure-sensitive adhesive composition according to the present embodiment may contain various additives such as coloring materials such as dyes and pigments, flame retardants, fillers, plasticizers, and antistatic agents in addition to the above components. However, it is preferable to use only those additives that do not inhibit the transmission of ultraviolet rays.
  • the pressure-sensitive adhesive composition according to the present embodiment produced a (meth) acrylic acid ester copolymer (A) and the obtained (meth) acrylic acid ester copolymer (A) and The acid generator (B), the photoinitiator (C), and, if desired, the crosslinking agent (D) and the additive can be mixed.
  • the mixing may be performed in a solvent, and in this case, a coating solution for the pressure-sensitive adhesive composition can be obtained.
  • the solvent examples include aliphatic hydrocarbons such as hexane, heptane, and cyclohexane; aromatic hydrocarbons such as toluene and xylene; halogenated hydrocarbons such as methylene chloride and ethylene chloride; methanol, ethanol, propanol, butanol, 1 Alcohols such as methoxy-2-propanol; ketones such as acetone, methyl ethyl ketone, 2-pentanone, isophorone and cyclohexanone; esters such as ethyl acetate and butyl acetate; cellosolv solvents such as ethyl cellosolve and the like.
  • aliphatic hydrocarbons such as hexane, heptane, and cyclohexane
  • aromatic hydrocarbons such as toluene and xylene
  • halogenated hydrocarbons such as methylene chloride and ethylene chloride
  • the concentration / viscosity of the coating solution prepared in this manner is not particularly limited as long as it is within a coatable range, and can be appropriately selected according to the situation. For example, it is diluted so that the concentration of the adhesive composition is 10% by mass or more and 60% by mass or less.
  • the addition of a solvent or the like is not necessary, and the solvent may not be added as long as the viscosity can be coated by the adhesive composition.
  • the pressure-sensitive adhesive sheet according to this embodiment includes a pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition according to this embodiment.
  • the pressure-sensitive adhesive sheet according to the present embodiment may be a single-sided pressure-sensitive adhesive sheet including a base material laminated on one side of the pressure-sensitive adhesive layer, and the base material obtained by laminating the pressure-sensitive adhesive layer on both surfaces of the base material.
  • a double-sided pressure-sensitive adhesive sheet may be used, or a double-sided double-sided pressure-sensitive adhesive sheet not provided with a base material may be used.
  • the pressure-sensitive adhesive sheet according to this embodiment is a surface (hereinafter referred to as “adhesive”) for the purpose of protecting the pressure-sensitive adhesive layer until the pressure-sensitive adhesive layer is applied to the adherend.
  • the release sheet may be laminated on the “surface” in some cases.
  • the pressure-sensitive adhesive sheet according to this embodiment is the above-mentioned single-sided pressure-sensitive adhesive sheet or double-sided pressure-sensitive adhesive sheet with a base material
  • the base material constituting the pressure-sensitive adhesive sheet can be laminated with a pressure-sensitive adhesive layer.
  • the constituent material is not particularly limited, and it is usually composed of a film mainly composed of a resin-based material.
  • Such films include ethylene-copolymer films such as ethylene-vinyl acetate copolymer films, ethylene- (meth) acrylic acid copolymer films, ethylene- (meth) acrylic acid ester copolymer films; Polyethylene film such as density 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 Polyurethane film; polyimide film; polyamide films; polystyrene films; polycarbonate films; Lev tallate film, polyester films such as polyethylene naphthalate film and a fluorine resin film. Further, modified films such as these cross
  • the substrate is preferably permeable to active energy rays.
  • the base material has such permeability, it becomes possible to effectively irradiate the adhesive layer with active energy rays through the base material. Thereby, it becomes easy to harden an adhesive layer favorably and peeling from the adherend of an adhesive sheet becomes easier.
  • an acid generator (B) when generating an acid by irradiation of an active energy ray, it becomes easy to generate an acid effectively, and as a result, peeling of an adhesive sheet from an adherend becomes easier. Become.
  • the base material preferably has heat resistance.
  • the release of the hydrocarbon-based gas described above is promoted by heating the pressure-sensitive adhesive layer.
  • produces an acid by heating as an acid generator (B) in this embodiment, it is necessary to heat an adhesive layer also for the generation
  • the pressure-sensitive adhesive sheet according to the present embodiment is used for dicing semiconductor wafers or the like, it is possible to effectively suppress the movement and scattering of the cut product obtained by dicing by suppressing the deformation of the pressure-sensitive adhesive sheet. It becomes possible.
  • the base material may contain various additives such as pigments, flame retardants, plasticizers, antistatic agents, lubricants, and fillers.
  • pigments include titanium dioxide and carbon black.
  • 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.
  • a primer treatment for the purpose of improving adhesion with a layer (such as a pressure-sensitive adhesive layer) provided on the surface, a primer treatment, an oxidation method, a concavo-convex method, etc., where a primer layer is provided on one or both sides as desired.
  • surface treatment can be performed.
  • synthetic resins such as a polyester type, a polyurethane type, a polyacryl type, are illustrated, for example, These can be used individually or in combination of 2 or more types.
  • Examples of the oxidation method include corona discharge treatment, chromic acid treatment, flame treatment, hot air treatment, ozone / ultraviolet treatment, and examples of the unevenness method include a sand blast method and a solvent treatment method. These surface treatment methods are appropriately selected according to the type of substrate. As an example, a resin film having a primer layer formed by primer treatment, particularly a polyethylene terephthalate film is preferably used.
  • the thickness of the substrate is not limited as long as the adhesive sheet can function properly in a desired process.
  • the thickness of the substrate is preferably 20 ⁇ m or more, particularly preferably 25 ⁇ m or more, and more preferably 50 ⁇ m or more.
  • the thickness is preferably 450 ⁇ m or less, particularly preferably 400 ⁇ m or less, and more preferably 350 ⁇ m or less.
  • the pressure-sensitive adhesive layer is formed from the pressure-sensitive adhesive composition described above.
  • the thickness of the pressure-sensitive adhesive layer is preferably 1 ⁇ m or more, more preferably 5 ⁇ m or more, particularly preferably 10 ⁇ m or more, and further preferably 15 ⁇ m or more.
  • the thickness of the pressure-sensitive adhesive layer is preferably 60 ⁇ m or less, more preferably 50 ⁇ m or less, particularly preferably 40 ⁇ m or less, and further preferably 30 ⁇ m or less.
  • the pressure-sensitive adhesive sheet When the gas is released, the amount of release of the hydrocarbon-based gas becomes sufficient, and the pressure-sensitive adhesive sheet can be easily peeled off from the adherend by the second action described above. Moreover, when the thickness of the pressure-sensitive adhesive layer is 60 ⁇ m or less, when the active energy ray is irradiated to the pressure-sensitive adhesive layer, the pressure-sensitive adhesive layer can be sufficiently cured, and by the first action described above, The adhesive sheet can be easily peeled off from the adherend.
  • the release sheet is not limited as long as the release sheet can be satisfactorily released from the pressure-sensitive adhesive layer.
  • the release sheet include paper substrates such as glassine paper, coated paper, high-quality paper, laminated paper obtained by laminating a resin such as polyethylene on these paper substrates, or polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, etc.
  • plastic films such as polyester films, polyolefin films such as polypropylene and polyethylene. It is preferable that a release treatment is performed on these release surfaces (surfaces in contact with the pressure-sensitive adhesive layer).
  • the release agent used for the release treatment include silicone-based, fluorine-based, and long-chain alkyl-based release agents.
  • the initial pressure-sensitive adhesive strength of the pressure-sensitive adhesive sheet according to the present embodiment is preferably 2N / 25 mm or more, particularly 4N / It is preferably 25 mm or more, and more preferably 6 N / 25 mm or more.
  • the initial adhesive strength is preferably 30 N / 25 mm or less, particularly preferably 25 N / 25 mm or less, and more preferably 20 N / 25 mm or less.
  • the initial adhesive strength basically refers to an adhesive strength measured by a 180 ° peeling method according to JIS Z0237: 2000, and the detailed measuring method is as shown in the examples described later.
  • the adhesive strength in (before) is 1 N / 25 mm or less, particularly 0.5 N / 25 mm or less, and more preferably 0.2 N / 25 mm or less.
  • the pressure-sensitive adhesive layer can be cured by irradiation with active energy rays, and thus the adhesive force can be reduced to 1 N / 25 mm or less.
  • the said adhesive force basically says the adhesive force measured by 180 degree peeling method according to JISZ0237: 2000, and a detailed measuring method is as showing in the Example mentioned later.
  • a pressure-sensitive adhesive composition constituting the pressure-sensitive adhesive layer and, if desired, a coating solution further containing a solvent or a dispersion medium are prepared, and on the release surface of the release sheet, a die coater, a curtain coater, a spray coater, a slit coater, An adhesive layer can be formed by applying the coating solution with a knife coater or the like to form a coating film and drying the coating film.
  • the laminated body of the pressure-sensitive adhesive layer and the release sheet thus obtained is in the state as it is, or in the state where another release sheet is further laminated on the surface on the release agent layer side of the laminate, and there is no substrate. It can be set as a double-sided adhesive sheet.
  • the surface on the pressure-sensitive adhesive layer side of the laminate of the pressure-sensitive adhesive layer and the release sheet obtained as described above is attached to one side of the substrate, thereby It can be set as the single-sided adhesive sheet provided with a material, an adhesive layer, and a peeling sheet.
  • a pressure-sensitive adhesive sheet comprising a base material and a pressure-sensitive adhesive layer is manufactured by applying the coating liquid described above to one side of the base material and drying the obtained coating film. May be.
  • a double-sided pressure-sensitive adhesive sheet with a substrate prepare two laminates of the pressure-sensitive adhesive layer and release sheet obtained as described above, and the surface on the pressure-sensitive adhesive layer side of one laminate is prepared. Laminating on one surface of the substrate and laminating the surface on the pressure-sensitive adhesive layer side in the other laminate on the other surface of the substrate, one release sheet, one adhesive layer, and the substrate A double-sided pressure-sensitive adhesive sheet with a substrate in which another pressure-sensitive adhesive layer and another release sheet are laminated in order can be obtained.
  • the above-mentioned coating solution is applied to both sides of the base material, and the obtained coating film is dried, whereby one adhesive layer and the base material You may manufacture an adhesive sheet provided with another adhesive layer.
  • the release sheet used for the production of the pressure-sensitive adhesive sheet may be peeled after the production of the pressure-sensitive adhesive sheet, or the pressure-sensitive adhesive layer may be protected until the pressure-sensitive adhesive sheet is applied to the adherend. .
  • the properties of the above-described coating solution are not particularly limited as long as it can be applied.
  • the component for forming the pressure-sensitive adhesive layer may be contained as a solute, or as a dispersoid. There is also.
  • the pressure-sensitive adhesive composition contains a crosslinking agent (D)
  • (meth) acrylic acid ester can be obtained by changing the drying conditions (temperature, time, etc.) or by separately providing a heat treatment. It is preferable to advance a crosslinking reaction between the copolymer (A) and the crosslinking agent (D) to form a crosslinked structure at a desired density in the pressure-sensitive adhesive layer. For example, after forming the pressure-sensitive adhesive layer, it is preferable to perform curing such as leaving for several days in an environment of 23 ° C. and 50% relative humidity.
  • the pressure-sensitive adhesive sheet according to the present embodiment is formed by using the pressure-sensitive adhesive composition described above. It can be peeled off from the adherend very easily. Therefore, the adhesive sheet according to the present embodiment can be suitably used for applications in which the adherend is peeled from the adhesive sheet after being attached to the adherend.
  • the pressure-sensitive adhesive sheet according to the present embodiment is preferably used for processing a predetermined member. Specifically, the pressure-sensitive adhesive sheet is attached to a workpiece as an adherend, and the workpiece is attached. After processing on an adhesive sheet, it is preferable to use it for the use which isolate
  • the above-described member to be processed is not particularly limited, and examples thereof include a brittle member.
  • the brittle member include glass, ceramic green sheet, ceramic green sheet laminate, resin film, thin film metal plate, and the like.
  • Such a brittle member is easily cracked or collapsed when a force is applied.
  • the pressure-sensitive adhesive sheet is peeled off from the brittle member attached to the conventional pressure-sensitive adhesive sheet, the brittle member is easily cracked or collapsed by the force applied for peeling.
  • the pressure-sensitive adhesive sheet according to the present embodiment can be peeled off very easily.
  • the pressure-sensitive adhesive sheet can be peeled off from the adherend by its own weight. It becomes possible to peel while suppressing.
  • the processing of a member includes forming the member on an adhesive sheet. Therefore, when the member is a ceramic green sheet, the processing of the ceramic green sheet includes not only the processing of cutting the already formed ceramic green sheet on the adhesive sheet, but also the ceramic green sheet on the adhesive sheet. It also includes forming a sheet.
  • the pressure-sensitive adhesive sheet according to this embodiment is preferably used for semiconductor processing.
  • it is preferably used for dicing or back surface polishing of a semiconductor wafer or semiconductor package.
  • dicing a large number of minute cuts obtained by cutting a semiconductor wafer or a semiconductor package are stacked on the adhesive sheet. These cut products are individually picked up from the adhesive sheet.
  • the pressure-sensitive adhesive sheet according to this embodiment can be peeled off from the adherend very easily by the first action and the second action described above. By using it, it becomes possible to pick up the cut material satisfactorily.
  • the pressure-sensitive adhesive sheet according to the present embodiment when used for back surface polishing, the pressure-sensitive adhesive sheet can be peeled off while suppressing the impact on the adherend that has been polished and thinned as much as possible.
  • the body can be effectively prevented from cracking or collapsing.
  • the adhesive sheet which concerns on this embodiment is a double-sided adhesive sheet
  • the pressure-sensitive adhesive sheet according to the present embodiment it is possible to peel from the adherend very easily by the first action and the second action described above, and thus the above-described destruction occurs. It is possible to separate hard adherends very easily without causing them to occur.
  • the adhesive sheet which concerns on this embodiment for the use mentioned above in order to produce the 1st effect
  • the adhesive sheet which concerns on this embodiment is with a base material provided with one adhesive layer formed from the adhesive composition which concerns on this embodiment, and the other adhesive layer comprised from a desired adhesive
  • the pressure-sensitive adhesive sheet according to this embodiment can exhibit excellent performance in various applications.
  • Examples of the pressure-sensitive adhesive constituting the other pressure-sensitive adhesive layer include, for example, an active energy ray-curable pressure-sensitive adhesive, a pressure-sensitive adhesive that hardly causes adhesive residue on the adherend, a pressure-sensitive adhesive having excellent heat resistance, and solvent resistance.
  • An excellent pressure-sensitive adhesive is exemplified.
  • the manufacturing method of the workpiece according to the present embodiment includes a laminating step of laminating the above-described pressure-sensitive adhesive sheet on a workpiece, a processing step of processing the workpiece on the pressure-sensitive adhesive sheet to obtain a workpiece, Irradiation step of irradiating active energy rays to the pressure-sensitive adhesive layer in the pressure-sensitive adhesive sheet laminated on the workpiece, and heating to heat the pressure-sensitive adhesive layer in the pressure-sensitive adhesive sheet laminated on the workpiece And a peeling step of peeling the pressure-sensitive adhesive sheet that has undergone the irradiation step and the heating step from the workpiece. And in the manufacturing method of the workpiece which concerns on this embodiment, a heating process is performed after completion of an irradiation process, or an irradiation process and a heating process are performed simultaneously.
  • the lamination process mentioned above laminates
  • the pressure-sensitive adhesive sheet includes a release sheet
  • the workpiece is laminated on the pressure-sensitive adhesive layer exposed by peeling the release sheet.
  • the workpiece is not particularly limited as long as it is processed on an adhesive sheet.
  • a semiconductor member such as a semiconductor wafer or a semiconductor package, glass, a ceramic green sheet laminate, a resin film, a thin film, or the like.
  • a brittle member such as a metal plate, a ceramic slurry, a coating solution for forming a member such as an uncured sealing resin, and the like.
  • the workpiece When the workpiece already has a predetermined shape, such as the semiconductor wafer described above, lamination is performed by sticking the adhesive surface of the adhesive sheet to the workpiece. In addition, when the workpiece is a liquid that does not yet have a predetermined shape like the ceramic slurry described above, the workpiece is applied to the adhesive surface of the adhesive sheet to form a coating film. By doing so, lamination is performed.
  • the pressure-sensitive adhesive sheet is a double-sided pressure-sensitive adhesive sheet, a pressure-sensitive adhesive surface opposite to the pressure-sensitive adhesive surface on which the workpieces in the double-sided pressure-sensitive adhesive sheet are laminated may be attached to a support or the like.
  • the workpiece is processed on an adhesive sheet to obtain a processed product.
  • the workpiece is a semiconductor wafer, a semiconductor package, glass, a ceramic green sheet laminate, etc.
  • processing, dicing, back surface polishing, circuit formation, sealing, etc. are performed, A member of a semiconductor device such as a semiconductor chip, a semiconductor device, a glass chip, and the like are obtained.
  • a to-be-processed object is a ceramic slurry
  • coating a ceramic slurry is dried as a process mentioned above, and a ceramic green sheet is obtained as a processed object.
  • the pressure-sensitive adhesive layer is formed of the above-described pressure-sensitive adhesive composition, so that before the pressure-sensitive adhesive layer is irradiated with active energy or heated, the workpiece and the processed material are processed. Good initial adhesive strength can be exhibited. Therefore, the workpiece and the workpiece are prevented from moving or scattering during the above-described processing, and the processing can be performed satisfactorily.
  • Irradiation process and heating process An irradiation process and a heating process are performed after a processing process.
  • the heating process may be performed after completion of the irradiation process, or the irradiation process and the heating process may be performed simultaneously.
  • active energy rays are irradiated to the pressure-sensitive adhesive layer in the pressure-sensitive adhesive sheet in a state where the workpiece is laminated on the pressure-sensitive adhesive sheet.
  • the irradiation of the active energy ray is preferably performed through a member having transparency to the active energy ray.
  • the pressure-sensitive adhesive sheet is a single-sided pressure-sensitive adhesive sheet including a base material that is permeable to active energy rays, it is preferable to irradiate the pressure-sensitive adhesive layer with the active energy rays through the base material.
  • the pressure-sensitive adhesive sheet is a double-sided pressure-sensitive adhesive sheet and one of the pressure-sensitive adhesive surfaces is affixed to a support that is permeable to active energy rays
  • the pressure-sensitive adhesive layer is activated via the support. It is preferable to irradiate energy rays.
  • the pressure-sensitive adhesive sheet is either a single-sided pressure-sensitive adhesive sheet or a double-sided pressure-sensitive adhesive sheet
  • the work piece laminated in the form of the pressure-sensitive adhesive sheet is permeable to active energy rays
  • the pressure-sensitive adhesive sheet is attached through the work piece.
  • the agent layer may be irradiated with active energy rays.
  • the reaction occurs at the active energy ray-reactive group present in the side chain of the (meth) acrylic acid ester copolymer (A) contained in the pressure-sensitive adhesive layer. proceed.
  • the pressure-sensitive adhesive layer is cured, and a first effect is produced in which the pressure-sensitive adhesive force of the pressure-sensitive adhesive layer on the workpiece is reduced.
  • the acid generator (B) contained in the pressure-sensitive adhesive layer by irradiation with active energy rays is used. Acid is generated. The acid promotes a reaction in which a hydrocarbon-based gas is released from the carboxy precursor group of the (meth) acrylic acid ester copolymer (A) during the heating step.
  • Examples of the active energy rays include ionizing radiation, that is, ultraviolet 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 are preferably used for ease of handling.
  • the amount of ultraviolet light is usually preferably 50 mJ / cm 2 or more, particularly preferably 100 mJ / cm 2 or more, and more preferably 200 mJ / cm 2 or more. Further, the amount of ultraviolet light, it is preferable to usually 2000 mJ / cm 2 or less, particularly preferably to 1700mJ / cm 2 or less, more preferably in a 1400mJ / cm 2 or less.
  • the illuminance of ultraviolet rays is usually preferably 50 mW / cm 2 or more, particularly preferably 100 mW / cm 2 or more, and more preferably 200 mW / cm 2 or more. Further, the illuminance of ultraviolet rays, it is preferable to usually 500 mW / cm 2 or less, particularly preferably to 450 mW / cm 2 or less, more preferably in a 400 mW / cm 2 or less.
  • the ultraviolet light source is not particularly limited, and for example, a high pressure mercury lamp, a metal halide lamp, a UV-LED, or the like is used.
  • the acceleration voltage is usually preferably 10 kV or more and 1000 kV or less. Moreover, it is preferable that irradiation dose is normally 0.1 kGy or more and 10 kGy or less.
  • the electron beam source is not particularly limited, and for example, various electron beam accelerators such as a Cockloft Walton type, a bandegraft type, a resonant transformer type, an insulated core transformer type, a linear type, a dynamitron type, and a high frequency type are used. be able to.
  • (3-2) Heating step In the heating step, the pressure-sensitive adhesive layer is heated in a state where the workpiece is laminated on the pressure-sensitive adhesive sheet.
  • a reaction in which the hydrocarbon gas is released from the carboxy precursor group of the (meth) acrylic acid ester copolymer (A) proceeds by heating.
  • the acid derived from the acid generator (B) acts as a catalyst to promote the reaction.
  • the acid generator (B) that generates acid by heating is used, the acid is supplied from the acid generator (B) by heating in the heating step.
  • the acid generator (B) when an acid generator (B) that generates an acid upon irradiation with active energy rays is used, as described above, the acid generator (B) generates an acid by irradiation with active energy rays in the irradiation step. Is supplied.
  • the hydrocarbon-based gas released from the pressure-sensitive adhesive layer accumulates at the interface between the pressure-sensitive adhesive layer and the adherend in the pressure-sensitive adhesive sheet, and this has the second effect of reducing the contact area between the pressure-sensitive adhesive layer and the workpiece. Will occur.
  • suitable means such as a hot plate, a hot air dryer, a near infrared lamp, and a heating roller can be employed.
  • heating conditions for example, it is preferable to heat at a temperature of 100 ° C. or higher and 250 ° C. or lower for a time of 5 seconds or longer and 30 minutes or shorter.
  • the pressure-sensitive adhesive sheet is peeled from the workpiece.
  • the pressure-sensitive adhesive sheet according to the present embodiment has a first action in which the pressure-sensitive adhesive layer is cured and the pressure-sensitive adhesive force is reduced, and a second action in which the contact area between the pressure-sensitive adhesive layer and the workpiece is reduced by the generation of the hydrocarbon-based gas.
  • the pressure-sensitive adhesive sheet can be peeled off from the workpiece very easily. Therefore, for example, when the workpiece is a semiconductor device (particularly a semiconductor chip) or a glass chip, the workpiece can be easily picked up using a general-purpose means such as a suction collet.
  • the pressure-sensitive adhesive sheet in this embodiment can be self-peeled without performing a process of actively peeling off the pressure-sensitive adhesive sheet, for example, a process such as turning the pressure-sensitive adhesive sheet upside down is performed.
  • the pressure-sensitive adhesive sheet can be dropped from the workpiece by the weight of the pressure-sensitive adhesive sheet, or the workpiece can be dropped from the pressure-sensitive adhesive sheet by the weight of the workpiece.
  • the pressure-sensitive adhesive sheet is a double-sided pressure-sensitive adhesive sheet, and one of the pressure-sensitive adhesive surfaces is affixed to the support, the pressure-sensitive adhesive sheet is peeled off from the workpiece and peeled off from the support. Also good.
  • the order of peeling from the workpiece and peeling from the support is not particularly limited, and may be performed simultaneously. According to the pressure-sensitive adhesive sheet according to this embodiment, peeling from the support can be performed very easily, as is peeling from the workpiece. Peeling from the support of the pressure-sensitive adhesive sheet may be performed by removing the pressure-sensitive adhesive sheet from the support using manual or general-purpose means, or, as described above, by dropping from the support due to the weight of the pressure-sensitive adhesive sheet. You may go.
  • the method for manufacturing a workpiece according to the present embodiment has excellent performance because the adhesive sheet can be peeled off from the workpiece very easily by irradiation with active energy rays and heating. A workpiece can be efficiently manufactured.
  • Example 1 10 parts by mass of n-butyl acrylate, 35 parts by mass of 2-ethylhexyl acrylate, 45 parts by mass of tert-butyl acrylate, and 10 parts by mass of 2-hydroxyethyl acrylate were copolymerized to obtain an acrylic copolymer (AP). Obtained.
  • This acrylic copolymer (AP) and methacryloyloxyethyl isocyanate (MOI) as the active energy ray-reactive group-containing compound (AC) are mixed at a rate of MOI of 10.7 g per 100 g of acrylic copolymer (MOI).
  • (Meth) acrylic acid ester copolymer (A) was obtained by reacting to 80 mol (80 mol%) per 100 mol of 2-hydroxyethyl acrylate units in the acrylic copolymer (AP). . In addition, it was 500,000 when the mass mean molecular weight of the (meth) acrylic acid ester copolymer (A) was measured by the method mentioned later.
  • the obtained coating solution was applied onto the release-treated surface of a release sheet (product name “SP-PET381031” manufactured by Lintec Corporation) in which one main surface of the polyethylene terephthalate film was release-treated with a silicone-based release agent. And dried by heating at 100 ° C. for 2 minutes to form an adhesive layer having a thickness of 25 ⁇ m.
  • a release sheet product name “SP-PET381031” manufactured by Lintec Corporation
  • the above-mentioned mass average molecular weight (Mw) is a polystyrene-reduced mass average molecular weight measured under the following conditions (GPC measurement) using gel permeation chromatography (GPC).
  • GPC measuring device HLC-8020 manufactured by Tosoh Corporation
  • Developing solvent Tetrahydrofuran
  • Flow rate 1.0 mL / min
  • Detector Differential refractometer
  • Standard sample Polystyrene
  • Examples 4-7, Comparative Example 4 A pressure-sensitive adhesive sheet was obtained in the same manner as in Example 1 except that the composition of the monomer constituting the acrylic copolymer (AP) was changed as shown in Table 2.
  • Test Example 1 Measurement of adhesive strength
  • the pressure-sensitive adhesive sheets produced in the examples and comparative examples were cut to obtain test pieces having a width of 25 mm and a length of 100 mm.
  • the release sheet was peeled from the test piece, and the exposed adhesive surface was affixed to the polished surface of a stainless steel plate (SUS304 polished SUS304) in an environment of 23 ° C. and 50% RH (relative humidity). It was left to stand for 24 hours. Thereby, a sample for measurement was obtained.
  • This measurement sample was made of stainless steel according to JIS Z0237; 2000 using a universal tensile tester (Orientec Co., Ltd., TENSILON / UTM-4-100) at a peeling speed of 300 mm / min and a peeling angle of 180 °.
  • the adhesive sheet was peeled from the plate, and the adhesive strength measured at that time was defined as the adhesive strength before UV irradiation (N / 25 mm). The results are shown in Tables 1 and 2.
  • the measurement sample produced in the same manner as above was irradiated with ultraviolet (UV) light on the adhesive layer through the substrate using an ultraviolet irradiation device (product name “RAD-2000” manufactured by Lintec Corporation).
  • UV ultraviolet
  • UV-2000 ultraviolet irradiation device
  • the adhesive force of the adhesive sheet was measured on the same conditions as the above, and this was made into the adhesive force (N / 25mm) after UV irradiation.
  • Tables 1 and 2 The results are shown in Tables 1 and 2.
  • Test Example 2 Evaluation of self-peeling property
  • UV ultraviolet rays
  • the measurement sample was heated in an oven at 150 ° C. for 10 minutes and then left in a room temperature environment.
  • the measurement sample was handled so that the surface on the pressure-sensitive adhesive sheet side was always on the upper side.
  • the pressure-sensitive adhesive sheets obtained in the examples exhibit excellent self-peelability by irradiation with active energy rays and heating, and can be peeled off very easily. there were.
  • the pressure-sensitive adhesive sheet according to the present invention can be used for processing brittle members and semiconductor members.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Adhesive Tapes (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Dicing (AREA)

Abstract

An adhesive agent composition which contains, as polymer-constituting monomer units, a (meth)acrylic acid alkyl ester (a1) that has an alkyl group having 1 to 12 carbon atoms and a carboxy precursor group-containing monomer (a2) that has a carboxy precursor group and can release a hydrocarbon-based gas upon heating to convert the carboxy precursor group to a carboxy group, and which also contains, in a side chain, a (meth)acrylic acid ester copolymer (A) having an active energy ray-reactive group, an acid generator (B) capable of generating an acid upon at least one of irradiation with an active energy ray and heating, and a photoinitiator (C). The adhesive agent composition enables the production of an adhesive sheet that can be detached easily from an adherend.

Description

粘着剤組成物、粘着シートおよび加工物の製造方法Pressure-sensitive adhesive composition, pressure-sensitive adhesive sheet, and processed product
　本発明は、被着体から容易に剥離することができる粘着シート、そのような粘着シートの製造を可能にする粘着剤組成物、およびそのような粘着シートを用いた加工物の製造方法に関するものである。 The present invention relates to a pressure-sensitive adhesive sheet that can be easily peeled off from an adherend, a pressure-sensitive adhesive composition that makes it possible to produce such a pressure-sensitive adhesive sheet, and a method for producing a workpiece using such a pressure-sensitive adhesive sheet. It is.
　半導体チップや積層セラミックコンデンサといった電子部品の製造工程においては、半導体ウエハやセラミックグリーンシート積層体といった加工対象を仮固定するために粘着シートが用いられることがある。このような製造工程においては、例えば、半導体ウエハやセラミックグリーンシート積層体等の被着体を粘着シートに固定した状態で、これらを所定の大きさに切断し、その後得られた切断片を粘着シートから分離することが行われている。 In an electronic component manufacturing process such as a semiconductor chip or a multilayer ceramic capacitor, an adhesive sheet may be used to temporarily fix a processing target such as a semiconductor wafer or a ceramic green sheet laminate. In such a manufacturing process, for example, in a state where an adherend such as a semiconductor wafer or a ceramic green sheet laminate is fixed to an adhesive sheet, these are cut into a predetermined size, and then the obtained cut pieces are adhered. Separation from the sheet is performed.
　ここで、上述した粘着シートとしては、所望のタイミングで粘着シートと被着体との密着性を低下させることができるものが使用される。当該粘着シートによれば、切断片を得た後に、粘着シートと被着体との密着性を低下させることで、当該切断片の粘着シートからの分離を容易に行うことが可能となる。 Here, as the above-mentioned pressure-sensitive adhesive sheet, one that can reduce the adhesion between the pressure-sensitive adhesive sheet and the adherend at a desired timing is used. According to the pressure-sensitive adhesive sheet, after the cut piece is obtained, it is possible to easily separate the cut piece from the pressure-sensitive adhesive sheet by reducing the adhesion between the pressure-sensitive adhesive sheet and the adherend.
　このような所望のタイミングで被着体との密着性を低下させることができる粘着シートとして、特許文献１および特許文献２には、重合体を構成するモノマー単位としてカルボキシ前駆基含有モノマーを含むアクリル系重合体と、酸触媒または酸発生剤とを含有する粘着剤組成物によって粘着剤層が形成されてなる粘着シートが開示されている。当該粘着シートでは、酸触媒または酸発生剤から生じる酸成分の作用によって、上述したカルボキシ前駆基含有モノマーからガスが発生し、当該ガスが粘着シートと被着体との界面に溜まることで、粘着シートを被着体から容易に分離できるものとなっている。 As pressure-sensitive adhesive sheets that can lower the adhesion to the adherend at such a desired timing, Patent Document 1 and Patent Document 2 include an acrylic containing a carboxy precursor group-containing monomer as a monomer unit constituting the polymer. A pressure-sensitive adhesive sheet is disclosed in which a pressure-sensitive adhesive layer is formed of a pressure-sensitive adhesive composition containing a polymer and an acid catalyst or an acid generator. In the pressure-sensitive adhesive sheet, a gas is generated from the carboxy precursor group-containing monomer described above by the action of the acid component generated from the acid catalyst or the acid generator, and the gas is accumulated at the interface between the pressure-sensitive adhesive sheet and the adherend. The sheet can be easily separated from the adherend.
特許第５５７７４６１号Japanese Patent No. 5577461 特許第５１７４２１７号Japanese Patent No. 5174217
　しかしながら、上述したような電子部品の製造方法では、より工程を簡略化して、生産効率を上昇させる観点から、被着体からの粘着シートの分離をさらに容易に行うことが求められている。そこで、本発明者らは、粘着シートを引き剥がす力を印加することなく、被着体から粘着シートを分離する手法について検討したものの、特許文献１および特許文献２に開示されるような従来の粘着シートは、そのような手法に用いることはできず、被着体からの分離の際に、引き剥がす力の印加を要するものであった。そのため、より容易に剥離できる粘着シートが望まれている。 However, in the method for manufacturing an electronic component as described above, it is required to further easily separate the adhesive sheet from the adherend from the viewpoint of further simplifying the process and increasing the production efficiency. Therefore, the present inventors have studied a method for separating the pressure-sensitive adhesive sheet from the adherend without applying a force to peel off the pressure-sensitive adhesive sheet, but the conventional techniques disclosed in Patent Document 1 and Patent Document 2 are disclosed. The pressure-sensitive adhesive sheet cannot be used in such a method, and requires application of a peeling force when separated from the adherend. Therefore, an adhesive sheet that can be more easily peeled is desired.
　本発明は、上記のような実状に鑑みてなされたものであり、被着体から容易に剥離できる粘着シート、そのような粘着シートの製造を可能にする粘着剤組成物、およびそのような粘着シートを用いた加工物の製造方法を提供することを目的とする。 The present invention has been made in view of the above circumstances, and is a pressure-sensitive adhesive sheet that can be easily peeled off from an adherend, a pressure-sensitive adhesive composition that enables the production of such a pressure-sensitive adhesive sheet, and such a pressure-sensitive adhesive. It aims at providing the manufacturing method of the processed material using a sheet | seat.
　上記目的を達成するために、第一に本発明は、重合体を構成するモノマー単位として、アルキル基の炭素数が１～１２の（メタ）アクリル酸アルキルエステル（ａ１）および加熱により炭化水素系ガスを放出してカルボキシ基に変化するカルボキシ前駆基を有するカルボキシ前駆基含有モノマー（ａ２）を含むとともに、側鎖に活性エネルギー線反応性基を有する（メタ）アクリル酸エステル共重合体（Ａ）と、活性エネルギー線の照射および加熱の少なくとも一方により酸を発生する酸発生剤（Ｂ）と、光開始剤（Ｃ）とを含有することを特徴とする粘着剤組成物を提供する（発明１）。 In order to achieve the above object, first, the present invention provides a (meth) acrylic acid alkyl ester (a1) having an alkyl group having 1 to 12 carbon atoms as a monomer unit constituting a polymer and a hydrocarbon-based polymer by heating. A (meth) acrylic acid ester copolymer (A) having a carboxy precursor group-containing monomer (a2) having a carboxy precursor group that changes into a carboxy group by releasing gas and having an active energy ray reactive group in the side chain A pressure-sensitive adhesive composition comprising: an acid generator (B) that generates an acid upon irradiation with active energy rays and / or heating; and a photoinitiator (C) (Invention 1). ).
　上記発明（発明１）の粘着剤組成物を用いて形成された粘着剤層を備える粘着シートでは、粘着剤層中に酸発生剤（Ｂ）に由来する酸の存在下、粘着剤層が加熱されることにより放出される炭化水素系ガスによって、粘着シートと被着体との接触面積が減少する作用とともに、活性エネルギー線の照射による粘着剤層の硬化によって、被着体に対する粘着力が低下する作用が生じ、これらの作用が相まって被着体から粘着シートを非常に容易に剥離することが可能となる。 In a pressure-sensitive adhesive sheet comprising a pressure-sensitive adhesive layer formed using the pressure-sensitive adhesive composition of the invention (Invention 1), the pressure-sensitive adhesive layer is heated in the presence of an acid derived from the acid generator (B) in the pressure-sensitive adhesive layer. In addition to the action of reducing the contact area between the pressure-sensitive adhesive sheet and the adherend due to the released hydrocarbon gas, the adhesive force on the adherend decreases due to the curing of the adhesive layer by irradiation of active energy rays. This action is combined, and these actions combine to make it possible to peel the adhesive sheet from the adherend very easily.
　上記発明（発明１）において、前記（メタ）アクリル酸エステル共重合体（Ａ）は、重合体を構成するモノマー単位として、ヒドロキシ基含有モノマー（ａ３）を含むことが好ましい（発明２）。 In the above invention (Invention 1), the (meth) acrylic acid ester copolymer (A) preferably contains a hydroxy group-containing monomer (a3) as a monomer unit constituting the polymer (Invention 2).
　上記発明（発明１，２）において、前記カルボキシ前駆基含有モノマー（ａ２）は、第二級炭素原子を有するアルキル基の第二級炭素原子と（メタ）アクリロイルオキシ基とが結合した構造を有する（メタ）アクリル酸アルキルエステル、第三級炭素原子を有するアルキル基の第三級炭素原子と（メタ）アクリロイルオキシ基とが結合した構造を有する（メタ）アクリル酸アルキルエステル、およびベンジル（メタ）アクリレートの少なくとも一種であることが好ましい（発明３）。 In the above inventions (Inventions 1 and 2), the carboxy precursor group-containing monomer (a2) has a structure in which a secondary carbon atom of an alkyl group having a secondary carbon atom and a (meth) acryloyloxy group are bonded. (Meth) acrylic acid alkyl ester, (meth) acrylic acid alkyl ester having a structure in which a tertiary carbon atom of an alkyl group having a tertiary carbon atom and a (meth) acryloyloxy group are bonded, and benzyl (meth) It is preferably at least one acrylate (Invention 3).
　上記発明（発明１～３）において、前記カルボキシ前駆基含有モノマー（ａ２）は、ｓｅｃ－ブチル（メタ）アクリレート、イソプロピル（メタ）アクリレート、ｓｅｃ－ヘキシル（メタ）アクリレート、ｓｅｃ－オクチル（メタ）アクリレート、ｓｅｃ－ノニル（メタ）アクリレート、ｓｅｃ－デシル（メタ）アクリレート、ボルニル（メタ）アクリレート、イソボルニル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、ｔｅｒｔ－ブチル（メタ）アクリレート、ｔｅｒｔ－ヘキシル（メタ）アクリレート、ｔｅｒｔ－オクチル（メタ）アクリレート、ｔｅｒｔ－ノニル（メタ）アクリレート、ｔｅｒｔ－デシル（メタ）アクリレート、２－メチル－２－アダマンチル（メタ）アクリレート、２－エチル－２－アダマンチル（メタ）アクリレート、およびベンジル（メタ）アクリレートからなる群から選択される少なくとも一種であることが好ましい（発明４）。 In the above inventions (Inventions 1 to 3), the carboxy precursor group-containing monomer (a2) is sec-butyl (meth) acrylate, isopropyl (meth) acrylate, sec-hexyl (meth) acrylate, sec-octyl (meth) acrylate. , Sec-nonyl (meth) acrylate, sec-decyl (meth) acrylate, bornyl (meth) acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, tert-butyl (meth) acrylate, tert-hexyl (meth) acrylate , Tert-octyl (meth) acrylate, tert-nonyl (meth) acrylate, tert-decyl (meth) acrylate, 2-methyl-2-adamantyl (meth) acrylate, 2-ethyl-2-adamanchi (Meth) acrylate, and is preferably at least one selected from the group consisting of benzyl (meth) acrylate (invention 4).
　上記発明（発明１～４）において、前記（メタ）アクリル酸エステル共重合体（Ａ）は、当該重合体を構成するモノマー単位として、前記カルボキシ前駆基含有モノマー（ａ２）を１質量％以上、７５質量％以下の割合で含有することが好ましい（発明５）。 In the above inventions (Inventions 1 to 4), the (meth) acrylic acid ester copolymer (A), as a monomer unit constituting the polymer, contains 1% by mass or more of the carboxy precursor group-containing monomer (a2), It is preferable to contain in the ratio of 75 mass% or less (invention 5).
　上記発明（発明１～５）において、前記（メタ）アクリル酸エステル共重合体（Ａ）は、前記（メタ）アクリル酸アルキルエステル（ａ１）の少なくとも一種として、２－エチルヘキシルアクリレートを含むことが好ましい（発明６）。 In the above inventions (Inventions 1 to 5), the (meth) acrylic acid ester copolymer (A) preferably contains 2-ethylhexyl acrylate as at least one kind of the (meth) acrylic acid alkyl ester (a1). (Invention 6).
　第２に本発明は、前記粘着剤組成物（発明１～６）から形成された粘着剤層を備えることを特徴とする粘着シートを提供する（発明７）。 Second, the present invention provides a pressure-sensitive adhesive sheet comprising a pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition (Invention 1 to 6) (Invention 7).
　上記発明（発明７）において、前記粘着剤層の厚さは、１μｍ以上、６０μｍ以下であることが好ましい（発明８）。 In the above invention (Invention 7), the thickness of the pressure-sensitive adhesive layer is preferably 1 μm or more and 60 μm or less (Invention 8).
　上記発明（発明７，８）は、脆質部材の加工のために使用されるものであってもよい（発明９）。脆質部材の加工の完了後には、脆質部材から粘着シートを容易に剥離できることが好ましく、この観点から、脆質部材の加工のためには上記発明（発明７，８）を使用することが好ましい。 The above inventions (Inventions 7 and 8) may be used for processing brittle members (Invention 9). After completion of the processing of the brittle member, it is preferable that the adhesive sheet can be easily peeled from the brittle member. From this viewpoint, the above inventions (Inventions 7 and 8) can be used for processing the brittle member. preferable.
　上記発明（発明７～９）においては、半導体加工のために使用されることが好ましい（発明１０）。 In the above inventions (Inventions 7 to 9), it is preferably used for semiconductor processing (Invention 10).
　第３に本発明は、前記粘着シート（発明７～１０）を被加工物に積層する積層工程と、前記被加工物を前記粘着シート上で加工して、加工物を得る加工工程と、前記加工物に積層された前記粘着シートにおける前記粘着剤層に対して、活性エネルギー線の照射を行う照射工程と、前記加工物に積層された前記粘着シートにおける前記粘着剤層に対して、加熱を行う加熱工程と、前記照射工程および前記加熱工程を経た前記粘着シートを、前記加工物から剥離する剥離工程とを含む加工物の製造方法であって、前記加熱工程を前記照射工程の完了後に行うか、あるいは前記照射工程と前記加熱工程とを同時に行うことを特徴とする加工物の製造方法を提供する（発明１１）。 Thirdly, the present invention includes a laminating step of laminating the pressure-sensitive adhesive sheet (Inventions 7 to 10) on a workpiece, a processing step of processing the workpiece on the pressure-sensitive adhesive sheet to obtain a workpiece, An irradiation step of irradiating active energy rays to the pressure-sensitive adhesive layer in the pressure-sensitive adhesive sheet laminated on the workpiece, and heating the pressure-sensitive adhesive layer in the pressure-sensitive adhesive layer laminated on the workpiece. A manufacturing method of a workpiece including a heating step to be performed and a peeling step of peeling the pressure-sensitive adhesive sheet that has undergone the irradiation step and the heating step from the workpiece, wherein the heating step is performed after the irradiation step is completed. Or the manufacturing method of the workpiece characterized by performing the said irradiation process and the said heating process simultaneously is provided (invention 11).
　上記発明（発明１１）において、前記加工物は、半導体装置または半導体装置の一部材であることが好ましい（発明１２）。 In the above invention (Invention 11), the workpiece is preferably a semiconductor device or a member of a semiconductor device (Invention 12).
　本発明に係る粘着シートは、被着体から容易に剥離することができる。また、本発明に係る粘着剤組成物によれば、そのような粘着シートを製造することが可能である。さらに、本発明に係る加工物の製造方法では、粘着シートを被着体から容易に剥離することができる。 The pressure-sensitive adhesive sheet according to the present invention can be easily peeled off from the adherend. Moreover, according to the adhesive composition which concerns on this invention, it is possible to manufacture such an adhesive sheet. Furthermore, in the manufacturing method of the workpiece which concerns on this invention, an adhesive sheet can be easily peeled from a to-be-adhered body.
　以下、本発明の実施形態について説明する。
〔粘着剤組成物〕
　本実施形態に係る粘着剤組成物は、（メタ）アクリル酸エステル共重合体（Ａ）と、酸発生剤（Ｂ）と、光開始剤（Ｃ）とを含有する。 Hereinafter, embodiments of the present invention will be described.
[Adhesive composition]
The pressure-sensitive adhesive composition according to this embodiment contains a (meth) acrylic acid ester copolymer (A), an acid generator (B), and a photoinitiator (C).
　上記（メタ）アクリル酸エステル共重合体（Ａ）は、重合体を構成するモノマー単位として、アルキル基の炭素数が１～１２の（メタ）アクリル酸アルキルエステル（ａ１）および加熱により炭化水素系ガスを放出してカルボキシ基に変化するカルボキシ前駆基を有するカルボキシ前駆基含有モノマー（ａ２）を含む。さらに、上記（メタ）アクリル酸エステル共重合体（Ａ）は、側鎖に活性エネルギー線反応性基を有する。 The (meth) acrylic acid ester copolymer (A) is a (meth) acrylic acid alkyl ester (a1) having an alkyl group having 1 to 12 carbon atoms as a monomer unit constituting the polymer and a hydrocarbon-based polymer by heating. A carboxy precursor group-containing monomer (a2) having a carboxy precursor group that releases a gas and changes to a carboxy group. Furthermore, the said (meth) acrylic acid ester copolymer (A) has an active energy ray reactive group in a side chain.
　また、上記酸発生剤（Ｂ）は、活性エネルギー線の照射および加熱の少なくとも一方により酸を発生するものである。 The acid generator (B) generates an acid by at least one of irradiation with active energy rays and heating.
　本実施形態に係る粘着剤組成物では、上述の通り、（メタ）アクリル酸エステル共重合体（Ａ）が側鎖に活性エネルギー線反応性基を有するとともに、粘着剤組成物が光開始剤（Ｃ）を含んでいる。これらにより、当該粘着剤組成物を用いて形成される粘着剤層に対して活性エネルギー線を照射することで、活性エネルギー線反応性基同士が結合する反応を進行させることができ、それにより粘着剤層を硬化させることができる。その結果、当該粘着剤層を備える粘着シートでは、被着体に対する粘着力が低下する。 In the pressure-sensitive adhesive composition according to this embodiment, as described above, the (meth) acrylic acid ester copolymer (A) has an active energy ray-reactive group in the side chain, and the pressure-sensitive adhesive composition is a photoinitiator ( C). By irradiating an active energy ray with respect to the adhesive layer formed using the said adhesive composition by these, the reaction which active energy ray reactive group couple | bonds can be advanced, and, thereby, adhesion The agent layer can be cured. As a result, in the pressure-sensitive adhesive sheet having the pressure-sensitive adhesive layer, the adhesive force to the adherend is reduced.
　また、本実施形態に係る粘着剤組成物では、上述の通り（メタ）アクリル酸エステル共重合体（Ａ）が、重合体を構成するモノマー単位として、カルボキシ前駆基含有モノマー（ａ２）を含むことにより、（メタ）アクリル酸エステル共重合体（Ａ）がカルボキシ前駆基を有するものとなっている。さらに、粘着剤組成物が酸発生剤（Ｂ）を含んでいる。これらにより、当該粘着剤組成物を用いて形成される粘着剤層に対して、活性エネルギー線の照射および加熱の少なくとも一方の刺激を与えることで、酸発生剤（Ｂ）から酸が生じ、さらに当該酸の存在下において粘着剤層を加熱することで、（メタ）アクリル酸エステル共重合体（Ａ）が有するカルボキシ前駆基において、炭化水素系ガスが放出されるとともにカルボキシ基が残留するという分解反応が生じる。放出された炭化水素系ガスは、粘着シートにおける粘着剤層と被着体との界面に溜まり、これにより、粘着剤層と被着体との接触面積が減少するとともに、被着体に対する粘着力がさらに低下することとなる。 Moreover, in the adhesive composition which concerns on this embodiment, a (meth) acrylic acid ester copolymer (A) contains a carboxy precursor group containing monomer (a2) as a monomer unit which comprises a polymer as above-mentioned. Therefore, the (meth) acrylic acid ester copolymer (A) has a carboxy precursor group. Furthermore, the pressure-sensitive adhesive composition contains an acid generator (B). Thus, an acid is generated from the acid generator (B) by applying at least one stimulus of irradiation with active energy rays and heating to the pressure-sensitive adhesive layer formed using the pressure-sensitive adhesive composition. Decomposition of heating the pressure-sensitive adhesive layer in the presence of the acid to release the hydrocarbon gas and leave the carboxy group in the carboxy precursor group of the (meth) acrylic acid ester copolymer (A). A reaction occurs. The released hydrocarbon-based gas accumulates at the interface between the pressure-sensitive adhesive layer and the adherend in the pressure-sensitive adhesive sheet, thereby reducing the contact area between the pressure-sensitive adhesive layer and the adherend, and the adhesion to the adherend. Will be further reduced.
　以上のように、本実施形態に係る粘着剤組成物を用いて形成される粘着剤層を備える粘着シートでは、活性エネルギー線の照射による粘着剤層の硬化によって粘着力が低下する作用（以下、「第一の作用」という場合がある。）と、炭化水素系ガスの発生によって粘着剤層と被着体との接触面積が減少する作用（以下、「第二の作用」という場合がある。）とが相まって、粘着シートを被着体から容易に剥離することが可能となる。これらの作用は、ともに外部からの刺激によって生じるものであるため、上述したような被着体からの剥離は所望のタイミングで生じさせることができる。 As described above, in the pressure-sensitive adhesive sheet including the pressure-sensitive adhesive layer formed using the pressure-sensitive adhesive composition according to the present embodiment, the adhesive force is lowered by the curing of the pressure-sensitive adhesive layer by irradiation with active energy rays (hereinafter, May be referred to as “first action”) and the action of reducing the contact area between the pressure-sensitive adhesive layer and the adherend due to the generation of the hydrocarbon gas (hereinafter, referred to as “second action”). ) And the adhesive sheet can be easily peeled off from the adherend. Since these actions are both caused by external stimuli, the above-described peeling from the adherend can be caused at a desired timing.
　ここで、第二の作用においては、前述した通り、炭化水素系ガスの発生と同時に、（メタ）アクリル酸エステル共重合体（Ａ）にカルボキシ基が生じることとなる。そのため、炭化水素系ガスの放出量が増えるほど、（メタ）アクリル酸エステル共重合体（Ａ）に存在するカルボキシ基の量が増大することとなる。ここで、一般的に、粘着剤層中におけるカルボキシ基の量が増大するほど、当該粘着剤層における粘着力が上昇し易いものとなる。したがって、従来の粘着シートのように、炭化水素系ガスの発生に係る第二の作用のみによって被着体からの剥離を生じさせる場合には、生じた炭化水素系ガスによって粘着剤層と被着体との接触面積が減少して剥離が促される一方で、粘着剤層の粘着力自体が十分に低下し難い。しかしながら、本願実施形態に係る粘着剤組成物によれば、炭化水素系ガスの発生に係る第二の作用とともに、粘着剤層の硬化により粘着力が低下する第一の作用も生じるため、被着体から剥離を容易に行うことが可能となる。 Here, in the second action, as described above, a carboxy group is generated in the (meth) acrylic acid ester copolymer (A) simultaneously with the generation of the hydrocarbon-based gas. Therefore, the amount of carboxy groups present in the (meth) acrylic acid ester copolymer (A) increases as the amount of released hydrocarbon gas increases. Here, generally, as the amount of the carboxy group in the pressure-sensitive adhesive layer increases, the pressure-sensitive adhesive force in the pressure-sensitive adhesive layer tends to increase. Therefore, when peeling from the adherend is caused only by the second action related to the generation of the hydrocarbon-based gas as in the case of the conventional pressure-sensitive adhesive sheet, the pressure-sensitive adhesive layer is adhered to the adhesive layer by the generated hydrocarbon-based gas. While the contact area with the body is reduced and peeling is promoted, the adhesive strength itself of the pressure-sensitive adhesive layer is hardly lowered. However, according to the pressure-sensitive adhesive composition according to the embodiment of the present application, in addition to the second effect related to the generation of hydrocarbon-based gas, the first effect that the adhesive force decreases due to the curing of the pressure-sensitive adhesive layer also occurs. Peeling from the body can be easily performed.
　また、第一の作用によって被着体に対する粘着力が低下することにより、第二の作用において生じる炭化水素系ガスが、粘着剤層と被着体とを引き離し易くなる。また、そのように引き離された部位には、さらなる炭化水素系ガスが溜まり易くなるため、当該部位を起点として、粘着剤層と被着体との分離が促進されるものとなる。そのため、本実施形態に係る粘着剤組成物を用いて得られる粘着シートでは、第一の作用と第二の作用とが相乗的に作用することで、被着体から非常に容易な剥離を達成することができる。 In addition, since the adhesive force to the adherend is reduced by the first action, the hydrocarbon-based gas generated in the second action can easily separate the adhesive layer and the adherend. Further, since further hydrocarbon-based gas is likely to be accumulated in the part separated as such, separation of the pressure-sensitive adhesive layer and the adherend is promoted starting from the part. Therefore, in the pressure-sensitive adhesive sheet obtained using the pressure-sensitive adhesive composition according to this embodiment, the first action and the second action act synergistically to achieve very easy peeling from the adherend. can do.
　なお、本実施形態に係る粘着剤組成物によれば、粘着シートと被着体との密着性を著しく低下させることができるため、粘着シートを引き剥がす力を印加することなく、粘着シートを被着体から剥離させることもできる。例えば、粘着シートまたは被着体の自重により、粘着シートを被着体から剥離させることができる。具体的には、被着体に粘着シートが貼付されてなる積層体において、粘着シート側を下側に向け、重力により粘着シートを被着体から落下させることで剥離させることができる。なお、本明細書では、粘着シートを引き剥がす力を印加することなく、粘着シートが被着体から剥がれている状態となったり、剥がれ落ちたりすることを「自己剥離」というものとし、また、そのような性質を「自己剥離性」というものとする。 In addition, according to the pressure-sensitive adhesive composition according to the present embodiment, the adhesiveness between the pressure-sensitive adhesive sheet and the adherend can be remarkably reduced, so that the pressure-sensitive adhesive sheet can be covered without applying a force to peel off the pressure-sensitive adhesive sheet. It can also be peeled off from the body. For example, the pressure-sensitive adhesive sheet can be peeled from the adherend by the weight of the pressure-sensitive adhesive sheet or the adherend. Specifically, in a laminate in which an adhesive sheet is attached to an adherend, the adhesive sheet can be peeled by dropping the adhesive sheet from the adherend by gravity with the adhesive sheet side facing downward. In this specification, without applying a force to peel off the pressure-sensitive adhesive sheet, the pressure-sensitive adhesive sheet is peeled off from the adherend or is referred to as “self-peeling”. Such a property is called “self-peeling”.
１．（メタ）アクリル酸エステル共重合体（Ａ）
　本実施形態における（メタ）アクリル酸エステル共重合体（Ａ）は、重合体を構成するモノマー単位として、アルキル基の炭素数が１～１２の（メタ）アクリル酸アルキルエステル（ａ１）および加熱により炭化水素系ガスを放出してカルボキシ基に変化するカルボキシ前駆基を有するカルボキシ前駆基含有モノマー（ａ２）を含むとともに、側鎖に活性エネルギー線反応性基を有するものである限り、特に制限されない。 1. (Meth) acrylic acid ester copolymer (A)
In the present embodiment, the (meth) acrylic acid ester copolymer (A) is a monomer unit constituting the polymer, the (meth) acrylic acid alkyl ester (a1) having an alkyl group having 1 to 12 carbon atoms and heating. As long as it contains the carboxy precursor group-containing monomer (a2) having a carboxy precursor group that changes to a carboxy group by releasing a hydrocarbon gas and has an active energy ray reactive group in the side chain, there is no particular limitation.
　作製し易いとともに、所望の性能を達成し易いという観点から、（メタ）アクリル酸エステル共重合体（Ａ）は、上述した（メタ）アクリル酸アルキルエステル（ａ１）およびカルボキシ前駆基含有モノマー（ａ２）を含むモノマーを共重合体して得られるアクリル系共重合体（ＡＰ）と、当該アクリル系共重合体（ＡＰ）と反応可能な官能基および活性エネルギー線反応性基を含有する活性エネルギー線反応性基含有化合物（ＡＣ）とを反応させてなるものであることが好ましい。以下では、（メタ）アクリル酸エステル共重合体（Ａ）がアクリル系共重合体（ＡＰ）と活性エネルギー線反応性基含有化合物（ＡＣ）との反応により得られたものである場合について説明する。 From the viewpoint of easy production and easy achievement of desired performance, the (meth) acrylic acid ester copolymer (A) comprises the above-mentioned (meth) acrylic acid alkyl ester (a1) and carboxy precursor group-containing monomer (a2). ) An acrylic copolymer (AP) obtained by copolymerizing a monomer containing), an active energy ray containing a functional group capable of reacting with the acrylic copolymer (AP) and an active energy ray reactive group It is preferable to react with a reactive group containing compound (AC). Below, the case where a (meth) acrylic acid ester copolymer (A) is obtained by reaction of an acrylic copolymer (AP) and an active energy ray reactive group containing compound (AC) is demonstrated. .
　アルキル基の炭素数が１～１２の（メタ）アクリル酸アルキルエステル（ａ１）としては、例えば、メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、ｎ－ブチル（メタ）アクリレート、ｎ－ペンチル（メタ）アクリレート、ｎ－ヘキシル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、イソオクチル（メタ）アクリレート、ｎ－デシル（メタ）アクリレート、ｎ－ドデシル（メタ）アクリレート等が挙げられる。アクリル系共重合体（ＡＰ）が、重合体を構成するモノマーとして、アルキル基の炭素数が１～１２の（メタ）アクリル酸アルキルエステル（ａ１）を含有することで、得られる粘着剤が所望の粘着性を発現することができる。この観点から、上述した（メタ）アクリル酸アルキルエステルの中でも、アルキル基の炭素数が１～８の（メタ）アクリル酸アルキルエステルを使用することが好ましく、特にｎ－ブチル（メタ）アクリレートおよび２－エチルヘキシル（メタ）アクリレートの少なくとも一方を使用することが好ましく、さらには２－エチルヘキシル（メタ）アクリレートを使用することが好ましい。なお、これらは単独で用いてもよいし、２種以上を組み合わせて用いてもよい。 Examples of the (meth) acrylic acid alkyl ester (a1) having 1 to 12 carbon atoms in the alkyl group include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and n-butyl (meth) acrylate. N-pentyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, n-decyl (meth) acrylate, n-dodecyl (meth) acrylate, and the like. . Desirable pressure-sensitive adhesive is obtained when the acrylic copolymer (AP) contains a (meth) acrylic acid alkyl ester (a1) having an alkyl group having 1 to 12 carbon atoms as a monomer constituting the polymer. The adhesiveness can be expressed. From this viewpoint, among the above-mentioned (meth) acrylic acid alkyl esters, it is preferable to use (meth) acrylic acid alkyl esters having an alkyl group having 1 to 8 carbon atoms, particularly n-butyl (meth) acrylate and 2 It is preferable to use at least one of ethylhexyl (meth) acrylate, more preferably 2-ethylhexyl (meth) acrylate. In addition, these may be used independently and may be used in combination of 2 or more type.
　なお、アクリル系共重合体（ＡＰ）は、上述した（メタ）アクリル酸アルキルエステル（ａ１）の少なくとも一種として、ホモポリマーとしてのガラス転移温度（Ｔｇ）が０℃以下のモノマーを含むことが好ましく、特にホモポリマーとしてのガラス転移温度（Ｔｇ）が－４０℃以下のモノマーを含むことが好ましく、さらにはホモポリマーとしてのガラス転移温度（Ｔｇ）が－６０℃以下のモノマーを含むことが好ましい。アクリル系共重合体（ＡＰ）のモノマーとして含まれるカルボキシ前駆基含有モノマー（ａ２）は、ホモポリマーとしてのガラス転移温度（Ｔｇ）が比較的高い傾向にあるため、アクリル系共重合体（ＡＰ）がホモポリマーとしてのガラス転移温度（Ｔｇ）が０℃以下のモノマーも含むことで、得られる（メタ）アクリル酸エステル共重合体（Ａ）全体としてのガラス転移温度（Ｔｇ）を適度な温度に調整することが容易となる。それにより、本実施形態に係る粘着剤組成物から形成される粘着剤層が、被着体に対して良好な粘着力（粘着剤層に対して活性エネルギー線の照射および加熱を行う前であって、前述した第一の作用および第二の作用が生じていない状態における粘着力；以下「初期粘着力」という場合がある。）を発揮し易いものとなる。このような観点からも、上述した（メタ）アクリル酸アルキルエステル（ａ１）としては、ｎ－ブチル（メタ）アクリレートおよび２－エチルヘキシル（メタ）アクリレートの少なくとも一方を使用することが好ましく、特に２－エチルヘキシル（メタ）アクリレートを使用することが好ましい。 The acrylic copolymer (AP) preferably contains a monomer having a glass transition temperature (Tg) as a homopolymer of 0 ° C. or lower as at least one of the above-mentioned (meth) acrylic acid alkyl ester (a1). In particular, a monomer having a glass transition temperature (Tg) as a homopolymer of −40 ° C. or lower is preferably included, and a monomer having a glass transition temperature (Tg) as a homopolymer of −60 ° C. or lower is further preferable. Since the carboxy precursor group-containing monomer (a2) contained as a monomer of the acrylic copolymer (AP) tends to have a relatively high glass transition temperature (Tg) as a homopolymer, the acrylic copolymer (AP) Including a monomer having a glass transition temperature (Tg) of 0 ° C. or less as a homopolymer, the glass transition temperature (Tg) of the resulting (meth) acrylic acid ester copolymer (A) as a whole is adjusted to an appropriate temperature. It is easy to adjust. As a result, the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition according to the present embodiment has a good pressure-sensitive adhesive force on the adherend (before irradiation and heating of active energy rays to the pressure-sensitive adhesive layer). Thus, the adhesive force in a state where the first action and the second action described above are not generated; hereinafter may be referred to as “initial adhesive force”) is easily exhibited. From this point of view, it is preferable to use at least one of n-butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate as the above-mentioned (meth) acrylic acid alkyl ester (a1). Preference is given to using ethylhexyl (meth) acrylate.
　アクリル系共重合体（ＡＰ）は、当該重合体を構成するモノマー単位として、上述した（メタ）アクリル酸アルキルエステル（ａ１）を、１０質量％以上含有することが好ましく、特に２０質量％以上含有することが好ましく、さらには３０質量％以上含有することが好ましい。また、アクリル系共重合体（ＡＰ）は、当該重合体を構成するモノマー単位として、上述した（メタ）アクリル酸アルキルエステル（ａ１）を、９０質量％以下で含有することが好ましく、特に８０質量％以下で含有することが好ましく、さらには７０質量％以下で含有することが好ましい。（メタ）アクリル酸アルキルエステル（ａ１）の含有量が１０質量％以上であることで、得られる粘着剤層が所望の初期粘着力を発揮し易いものとなる。また、（メタ）アクリル酸アルキルエステル（ａ１）の含有量が９０質量％以下であることで、得られる粘着剤層に対して活性エネルギー線を照射した際に、粘着力を良好に低下させ易いものとなる。 The acrylic copolymer (AP) preferably contains 10% by mass or more, particularly 20% by mass or more, of the above-mentioned (meth) acrylic acid alkyl ester (a1) as a monomer unit constituting the polymer. It is preferable to contain 30% by mass or more. The acrylic copolymer (AP) preferably contains the above-mentioned (meth) acrylic acid alkyl ester (a1) as a monomer unit constituting the polymer at 90% by mass or less, particularly 80% by mass. % Or less, and more preferably 70% by mass or less. When the content of the (meth) acrylic acid alkyl ester (a1) is 10% by mass or more, the obtained pressure-sensitive adhesive layer easily exhibits a desired initial adhesive force. Moreover, when the content of the (meth) acrylic acid alkyl ester (a1) is 90% by mass or less, it is easy to satisfactorily lower the adhesive strength when the obtained adhesive layer is irradiated with active energy rays. It will be a thing.
　カルボキシ前駆基含有モノマー（ａ２）としては、酸の存在下において加熱により炭化水素系ガスを放出してカルボキシ基に変化するカルボキシ前駆基を有するとともに、アクリル系共重合体（ＡＰ）を構成できるものであれば、特に限定されない。 The carboxy precursor group-containing monomer (a2) has a carboxy precursor group that is converted into a carboxy group by releasing a hydrocarbon gas by heating in the presence of an acid, and can constitute an acrylic copolymer (AP). If it is, it will not be specifically limited.
　カルボキシ前駆基含有モノマー（ａ２）の好ましい例としては、第二級炭素原子を有するアルキル基の第二級炭素原子と（メタ）アクリロイルオキシ基とが結合した構造を有する（メタ）アクリル酸アルキルエステル、第三級炭素原子を有するアルキル基の第三級炭素原子と（メタ）アクリロイルオキシ基とが結合した構造を有する（メタ）アクリル酸アルキルエステル、およびベンジル（メタ）アクリレートの少なくとも一種が挙げられる。 Preferred examples of the carboxy precursor group-containing monomer (a2) include a (meth) acrylic acid alkyl ester having a structure in which a secondary carbon atom of an alkyl group having a secondary carbon atom and a (meth) acryloyloxy group are bonded to each other. And at least one of (meth) acrylic acid alkyl ester having a structure in which a tertiary carbon atom of a alkyl group having a tertiary carbon atom and a (meth) acryloyloxy group are bonded, and benzyl (meth) acrylate. .
　上述した、第二級炭素原子を有するアルキル基の第二級炭素原子と（メタ）アクリロイルオキシ基とが結合した構造を有する（メタ）アクリル酸アルキルエステルの好ましい例としては、ｓｅｃ－ブチル（メタ）アクリレート、イソプロピル（メタ）アクリレート、ｓｅｃ－ヘキシル（メタ）アクリレート、ｓｅｃ－オクチル（メタ）アクリレート、ｓｅｃ－ノニル（メタ）アクリレート、ｓｅｃ－デシル（メタ）アクリレート、ボルニル（メタ）アクリレート、イソボルニル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート等が挙げられる。 Preferred examples of the (meth) acrylic acid alkyl ester having a structure in which the secondary carbon atom of the alkyl group having a secondary carbon atom and the (meth) acryloyloxy group are bonded to each other include sec-butyl (meta ) Acrylate, isopropyl (meth) acrylate, sec-hexyl (meth) acrylate, sec-octyl (meth) acrylate, sec-nonyl (meth) acrylate, sec-decyl (meth) acrylate, bornyl (meth) acrylate, isobornyl (meth) ) Acrylate, cyclohexyl (meth) acrylate and the like.
　上述した、第三級炭素原子を有するアルキル基の第三級炭素原子と（メタ）アクリロイルオキシ基とが結合した構造を有する（メタ）アクリル酸アルキルエステルの好ましい例としては、ｔｅｒｔ－ブチル（メタ）アクリレート、ｔｅｒｔ－ヘキシル（メタ）アクリレート、ｔｅｒｔ－オクチル（メタ）アクリレート、ｔｅｒｔ－ノニル（メタ）アクリレート、ｔｅｒｔ－デシル（メタ）アクリレート、２－メチル－２－アダマンチル（メタ）アクリレート、２－エチル－２－アダマンチル（メタ）アクリレート等が挙げられる。 Preferable examples of the (meth) acrylic acid alkyl ester having the structure in which the tertiary carbon atom of the alkyl group having a tertiary carbon atom and the (meth) acryloyloxy group are bonded to each other include tert-butyl (meta ) Acrylate, tert-hexyl (meth) acrylate, tert-octyl (meth) acrylate, tert-nonyl (meth) acrylate, tert-decyl (meth) acrylate, 2-methyl-2-adamantyl (meth) acrylate, 2-ethyl -2-Adamantyl (meth) acrylate and the like.
　以上のカルボキシ前駆基含有モノマー（ａ２）の好ましい例の中でも、ｓｅｃ－ブチル（メタ）アクリレート、イソプロピル（メタ）アクリレート、ｔｅｒｔ－ブチル（メタ）アクリレート、イソボルニル（メタ）アクリレート、シクロヘキシル（メタ）アクリレートおよびベンジル（メタ）アクリレートの少なくとも１種を使用することが好ましく、特にｔｅｒｔ－ブチル（メタ）アクリレートを使用することが好ましい。カルボキシ前駆基含有モノマー（ａ２）としてｔｅｒｔ－ブチル（メタ）アクリレートを使用することで、良好に炭化水素系ガスを放出し易くなり、それにより、本実施形態に係る粘着シートの被着体からの剥離をより容易に行うことが可能となる。 Among the preferred examples of the carboxy precursor group-containing monomer (a2), sec-butyl (meth) acrylate, isopropyl (meth) acrylate, tert-butyl (meth) acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate and It is preferable to use at least one benzyl (meth) acrylate, and it is particularly preferable to use tert-butyl (meth) acrylate. By using tert-butyl (meth) acrylate as the carboxy precursor group-containing monomer (a2), it becomes easy to release the hydrocarbon-based gas satisfactorily, so that the pressure-sensitive adhesive sheet according to this embodiment can be released from the adherend. Peeling can be performed more easily.
　なお、以上のカルボキシ前駆基含有モノマー（ａ２）の好ましい例は、単独で用いてもよいし、２種以上を組み合わせて用いてもよい。 In addition, the preferable example of the above carboxy precursor group containing monomer (a2) may be used independently, and may be used in combination of 2 or more type.
　アクリル系共重合体（ＡＰ）は、当該重合体を構成するモノマー単位として、カルボキシ前駆基含有モノマー（ａ２）を、１質量％以上含有することが好ましく、１０質量％以上含有することがより好ましく、特に３５質量％以上含有することが好ましく、さらには４０質量％以上含有することが好ましい。また、アクリル系共重合体（ＡＰ）は、当該重合体を構成するモノマー単位として、カルボキシ前駆基含有モノマー（ａ２）を、７５質量％以下で含有することが好ましく、特に６５質量％以下で含有することが好ましく、さらには５５質量％以下で含有することが好ましい。カルボキシ前駆基含有モノマー（ａ２）の含有量が１質量％以上であることで、前述した第二の作用の際に、粘着剤層から炭化水素系ガスが良好に発生するものとなり、本実施形態に係る粘着シートの被着体からの剥離をより容易に行うことが可能となる。また、カルボキシ前駆基含有モノマー（ａ２）の含有量が７５質量％以下であることで、前述した（メタ）アクリル酸アルキルエステル（ａ１）やそのほかのモノマーの含有量を十分に確保し易いものとなり、本実施形態に係る粘着シートにおいて所望の粘着力を達成し易くなるとともに、前述した第一の作用による粘着剤層の硬化を生じさせ易くなる。 The acrylic copolymer (AP) preferably contains 1% by mass or more of the carboxy precursor group-containing monomer (a2) as the monomer unit constituting the polymer, and more preferably contains 10% by mass or more. In particular, the content is preferably 35% by mass or more, and more preferably 40% by mass or more. The acrylic copolymer (AP) preferably contains the carboxy precursor group-containing monomer (a2) as a monomer unit constituting the polymer in an amount of 75% by mass or less, particularly 65% by mass or less. It is preferable to contain it at 55 mass% or less. When the content of the carboxy precursor group-containing monomer (a2) is 1% by mass or more, the hydrocarbon gas is favorably generated from the pressure-sensitive adhesive layer during the second action described above, and this embodiment It becomes possible to peel the adhesive sheet from the adherend more easily. Moreover, it becomes easy to ensure fully content of the (meth) acrylic-acid alkylester (a1) mentioned above and other monomers because content of a carboxy precursor group containing monomer (a2) is 75 mass% or less. In the pressure-sensitive adhesive sheet according to this embodiment, desired adhesive force can be easily achieved, and the pressure-sensitive adhesive layer can be easily cured by the first action described above.
　アクリル系共重合体（ＡＰ）は、重合体を構成するモノマー単位として、前述した（メタ）アクリル酸アルキルエステル（ａ１）およびカルボキシ前駆基含有モノマー（ａ２）とともに、ヒドロキシ基含有モノマー（ａ３）を含むことが好ましい。アクリル系共重合体（ＡＰ）が、重合体を構成するモノマー単位としてヒドロキシ基含有モノマー（ａ３）を含むことで、アクリル系共重合体（ＡＰ）が側鎖としてヒドロキシ基を含有するものとなる。ここで、当該ヒドロキシ基は、活性エネルギー線反応性基含有化合物（ＡＣ）との反応点として機能することが可能となり、それにより、活性エネルギー線反応性基が十分に導入された（メタ）アクリル酸エステル共重合体（Ａ）を得ることが容易となる。また、本実施形態における粘着剤組成物が後述する架橋剤（特にポリイソシアネート系化合物）を含有する場合には、上述のヒドロキシ基が架橋剤との反応点としても機能することが可能となり、良好に架橋した粘着剤を得ることが容易となる。 The acrylic copolymer (AP) includes a hydroxy group-containing monomer (a3) as a monomer unit constituting the polymer, together with the aforementioned (meth) acrylic acid alkyl ester (a1) and carboxy precursor group-containing monomer (a2). It is preferable to include. When the acrylic copolymer (AP) contains the hydroxy group-containing monomer (a3) as a monomer unit constituting the polymer, the acrylic copolymer (AP) contains a hydroxy group as a side chain. . Here, the hydroxy group can function as a reaction point with the active energy ray-reactive group-containing compound (AC), whereby (meth) acrylic in which the active energy ray-reactive group has been sufficiently introduced. It becomes easy to obtain the acid ester copolymer (A). In addition, when the pressure-sensitive adhesive composition in the present embodiment contains a cross-linking agent (particularly a polyisocyanate compound) described later, the above-mentioned hydroxy group can function as a reaction point with the cross-linking agent, which is good. It becomes easy to obtain a cross-linked adhesive.
　ヒドロキシ基含有モノマー（ａ３）の好ましい例としては、２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート、３－ヒドロキシプロピル（メタ）アクリレート、２－ヒドロキシブチル（メタ）アクリレート、３－ヒドロキシブチル（メタ）アクリレート、４－ヒドロキシブチル（メタ）アクリレート、６－ヒドロキシへプチル（メタ）アクリレート、８－ヒドロキシオクチル（メタ）アクリレート等の（メタ）アクリル酸ヒドロキシアルキルエステルが挙げられる。これらの中でも、上述した架橋剤や活性エネルギー線反応性基含有化合物（ＡＣ）との反応性に優れる観点から、２－ヒドロキシエチル（メタ）アクリレートが好ましい。これらは単独で用いてもよいし、２種以上を組み合わせて用いてもよい。 Preferred examples of the hydroxy group-containing monomer (a3) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3 Examples include (meth) acrylic acid hydroxyalkyl esters such as -hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyheptyl (meth) acrylate, and 8-hydroxyoctyl (meth) acrylate. Among these, 2-hydroxyethyl (meth) acrylate is preferable from the viewpoint of excellent reactivity with the above-described crosslinking agent and active energy ray-reactive group-containing compound (AC). These may be used alone or in combination of two or more.
　アクリル系共重合体（ＡＰ）は、当該重合体を構成するモノマー単位として、ヒドロキシ基含有モノマー（ａ３）を、１質量％以上含有することが好ましく、特に５質量％以上含有することが好ましく、さらには８質量％以上含有することが好ましい。また、アクリル系共重合体（ＡＰ）は、当該重合体を構成するモノマー単位として、ヒドロキシ基含有モノマー（ａ３）を、５０質量％以下で含有することが好ましく、特に４０質量％以下で含有することが好ましく、さらには２５質量％以下で含有することが好ましい。ヒドロキシ基含有モノマー（ａ３）の含有量が１質量％以上であることで、上述したような架橋剤や活性エネルギー線反応性基含有化合物（ＡＣ）との反応をより良好に生じさせることが可能となる。また、ヒドロキシ基含有モノマー（ａ３）の含有量が５０質量％以下であることで、前述した（メタ）アクリル酸アルキルエステル（ａ１）およびカルボキシ前駆基含有モノマー（ａ２）の含有量を十分に確保し易いもとなり、前述した第一の作用および第二の作用を効果的に生じさせることが可能となる。 The acrylic copolymer (AP) preferably contains 1% by mass or more of the hydroxy group-containing monomer (a3) as a monomer unit constituting the polymer, and particularly preferably contains 5% by mass or more. Furthermore, it is preferable to contain 8 mass% or more. The acrylic copolymer (AP) preferably contains the hydroxy group-containing monomer (a3) at 50% by mass or less, particularly 40% by mass or less, as a monomer unit constituting the polymer. It is preferable that it is contained in an amount of 25% by mass or less. When the content of the hydroxy group-containing monomer (a3) is 1% by mass or more, it is possible to cause the reaction with the crosslinking agent and the active energy ray-reactive group-containing compound (AC) as described above to occur more favorably. It becomes. Moreover, content of a hydroxy group containing monomer (a3) is 50 mass% or less, and content of the (meth) acrylic-acid alkylester (a1) mentioned above and a carboxy precursor group containing monomer (a2) is fully ensured. Therefore, the first action and the second action described above can be effectively generated.
　アクリル系共重合体（ＡＰ）は、所望により、当該共重合体を構成するモノマー単位として、前述した（メタ）アクリル酸アルキルエステル（ａ１）、カルボキシ前駆基含有モノマー（ａ２）およびヒドロキシ基含有モノマー（ａ３）以外の他のモノマーを含有してもよい。 The acrylic copolymer (AP) is, as desired, as a monomer unit constituting the copolymer, the (meth) acrylic acid alkyl ester (a1), the carboxy precursor group-containing monomer (a2), and the hydroxy group-containing monomer described above. You may contain other monomers other than (a3).
　そのような他のモノマーの例としては、カルボキシ基、アミノ基、アジリジニル基といった架橋剤との反応が可能な反応基を有するモノマーが挙げられる。特に、カルボキシ基を含有するモノマーとしては、例えば、アクリル酸、メタクリル酸、クロトン酸、マレイン酸、イタコン酸、シトラコン酸等のエチレン性不飽和カルボン酸が挙げられる。また、アミノ基を含有するモノマーとしては、例えば、アミノエチル（メタ）アクリレート、ｎ－ブチルアミノエチル（メタ）アクリレート等が挙げられる。これらのモノマーは、１種を単独で使用することもできるし、２種以上を組み合わせて使用することもできる。 Examples of such other monomers include monomers having a reactive group capable of reacting with a crosslinking agent such as a carboxy group, an amino group, and an aziridinyl group. In particular, examples of the monomer containing a carboxy group include ethylenically unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid, and citraconic acid. Examples of the monomer containing an amino group include aminoethyl (meth) acrylate and n-butylaminoethyl (meth) acrylate. These monomers can also be used individually by 1 type, and can also be used in combination of 2 or more type.
　上述した他のモノマーの更なる例としては、メトキシメチル（メタ）アクリレート、メトキシエチル（メタ）アクリレート、エトキシメチル（メタ）アクリレート、エトキシエチル（メタ）アクリレート等のアルコキシアルキル基含有（メタ）アクリル酸エステル；フェニル（メタ）アクリレート等の芳香族環を有する（メタ）アクリル酸エステル；アクリルアミド、メタクリルアミド等の非架橋性のアクリルアミド；Ｎ，Ｎ－ジメチルアミノエチル（メタ）アクリレート、Ｎ，Ｎ－ジメチルアミノプロピル（メタ）アクリレート等の非架橋性の３級アミノ基を有する（メタ）アクリル酸エステル；酢酸ビニル；スチレンなどが挙げられる。これらは単独で用いてもよいし、２種以上を組み合わせて用いてもよい。 Further examples of the other monomers mentioned above include alkoxyalkyl group-containing (meth) acrylic acid such as methoxymethyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxymethyl (meth) acrylate, ethoxyethyl (meth) acrylate, etc. Esters; (meth) acrylic acid esters having an aromatic ring such as phenyl (meth) acrylate; non-crosslinkable acrylamides such as acrylamide and methacrylamide; N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethyl (Meth) acrylic acid ester having a non-crosslinkable tertiary amino group such as aminopropyl (meth) acrylate; vinyl acetate; styrene. These may be used alone or in combination of two or more.
　アクリル系共重合体（ＡＰ）の重合態様は、ランダム共重合体であってもよいし、ブロック共重合体であってもよい。また、アクリル系共重合体（ＡＰ）は、上述した各モノマーを常法によって共重合することにより得ることができる。例えば、乳化重合法、溶液重合法、懸濁重合法、塊状重合法、水溶液重合法などにより重合して製造することができる。中でも、重合時の安定性および使用時の取り扱い易さの観点から、有機溶媒中で行う溶液重合法で製造するのが好ましい。 The polymerization mode of the acrylic copolymer (AP) may be a random copolymer or a block copolymer. The acrylic copolymer (AP) can be obtained by copolymerizing the above-described monomers by a conventional method. For example, it can be produced by polymerization by emulsion polymerization, solution polymerization, suspension polymerization, bulk polymerization, aqueous solution polymerization, or the like. Especially, it is preferable to manufacture by the solution polymerization method performed in an organic solvent from a viewpoint of the stability at the time of superposition | polymerization and the ease of handling at the time of use.
　例えば、有機溶媒中にモノマー成分の混合物を溶解した後、従来公知のアゾビスイソブチロニトリル、２，２’－アゾビス（２－アミノジプロパン）二塩酸塩、４，４’－アゾビス（４－シアノ吉草酸）等のアゾ系重合開始剤またはベンゾイルパーオキシド等の過酸化物系重合開始剤を添加してラジカル重合させることにより、アクリル系共重合体（ＡＰ）を製造することができる。 For example, after a mixture of monomer components is dissolved in an organic solvent, conventionally known azobisisobutyronitrile, 2,2′-azobis (2-aminodipropane) dihydrochloride, 4,4′-azobis (4 An acrylic copolymer (AP) can be produced by radical polymerization by adding an azo polymerization initiator such as (cyanovaleric acid) or a peroxide polymerization initiator such as benzoyl peroxide.
　アクリル系共重合体（ＡＰ）の質量平均分子量は、１０万以上であることが好ましく、特に２０万以上であることが好ましく、さらには３０万以上であることが好ましい。また、当該質量平均分子量は、２００万以下であることが好ましく、特に１００万以下であることが好ましく、さらには８０万以下であることが好ましい。アクリル系共重合体（ＡＰ）の質量平均分子量が上記範囲であることで、所望の初期粘着力を有する粘着剤層を形成し易いものとなる。なお、本明細書における質量平均分子量は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）法により測定した標準ポリスチレン換算の値である。 The mass average molecular weight of the acrylic copolymer (AP) is preferably 100,000 or more, particularly preferably 200,000 or more, and more preferably 300,000 or more. Further, the mass average molecular weight is preferably 2 million or less, particularly preferably 1 million or less, and more preferably 800,000 or less. When the mass average molecular weight of the acrylic copolymer (AP) is in the above range, it becomes easy to form a pressure-sensitive adhesive layer having a desired initial adhesive force. In addition, the mass mean molecular weight in this specification is the value of standard polystyrene conversion measured by the gel permeation chromatography (GPC) method.
　活性エネルギー線反応性基含有化合物（ＡＣ）としては、アクリル系共重合体（ＡＰ）と反応可能な官能基を有するともに、活性エネルギー線反応性基を含有するものであれば、特に限定されない。 The active energy ray-reactive group-containing compound (AC) is not particularly limited as long as it has a functional group capable of reacting with the acrylic copolymer (AP) and contains an active energy ray-reactive group.
　アクリル系共重合体（ＡＰ）と反応可能な官能基の例としては、イソシアネート基、エポキシ基、カルボキシ基等が挙げられる。ここで、アクリル系共重合体（ＡＰ）が、重合体を構成するモノマーとして、前述したヒドロキシ基含有モノマー（ａ３）を含有する場合には、活性エネルギー線反応性基含有化合物（ＡＣ）は、当該モノマーに由来するヒドロキシ基との反応性に優れたイソシアネート基を有することが好ましい。 Examples of functional groups capable of reacting with the acrylic copolymer (AP) include isocyanate groups, epoxy groups, carboxy groups, and the like. Here, when the acrylic copolymer (AP) contains the hydroxy group-containing monomer (a3) as a monomer constituting the polymer, the active energy ray-reactive group-containing compound (AC) is: It preferably has an isocyanate group excellent in reactivity with the hydroxy group derived from the monomer.
　また、活性エネルギー線反応性基は、エネルギー線硬化性の炭素－炭素二重結合であることが好ましく、特に（メタ）アクリロイル基であることが好ましい。活性エネルギー線反応性基含有化合物（ＡＣ）は、１分子中に、活性エネルギー線反応性基を１～５個有することが好ましく、特に１～２個有することが好ましい。 Further, the active energy ray reactive group is preferably an energy ray curable carbon-carbon double bond, and particularly preferably a (meth) acryloyl group. The active energy ray-reactive group-containing compound (AC) preferably has 1 to 5, more preferably 1 to 2 active energy ray-reactive groups in one molecule.
　活性エネルギー線反応性基含有化合物（ＡＣ）の例としては、２－メタクリロイルオキシエチルイソシアネート、メタ－イソプロペニル－α，α－ジメチルベンジルイソシアネート、メタクリロイルイソシアネート、アリルイソシアネート、１，１－（ビスアクリロイルオキシメチル）エチルイソシアネート；ジイソシアネート化合物またはポリイソシアネート化合物と、ヒドロキシエチル（メタ）アクリレートとの反応により得られるアクリロイルモノイソシアネート化合物；ジイソシアネート化合物またはポリイソシアネート化合物と、ポリオール化合物と、ヒドロキシエチル（メタ）アクリレートとの反応により得られるアクリロイルモノイソシアネート化合物などが挙げられる。これらの中でも、アクリル系共重合体（ＡＰ）に対して活性エネルギー線反応性基を導入し易く、それにより、前述した第一の作用を生じさせ易いという観点から、２－メタクリロイルオキシエチルイソシアネートが好ましい。活性エネルギー線反応性基含有化合物（ＡＣ）は、１種を単独で使用してもよく、２種以上を組み合わせて使用してもよい。 Examples of the active energy ray-reactive group-containing compound (AC) include 2-methacryloyloxyethyl isocyanate, meta-isopropenyl-α, α-dimethylbenzyl isocyanate, methacryloyl isocyanate, allyl isocyanate, 1,1- (bisacryloyloxy Methyl) ethyl isocyanate; acryloyl monoisocyanate compound obtained by reaction of diisocyanate compound or polyisocyanate compound with hydroxyethyl (meth) acrylate; diisocyanate compound or polyisocyanate compound, polyol compound, and hydroxyethyl (meth) acrylate Examples include acryloyl monoisocyanate compounds obtained by the reaction. Among these, 2-methacryloyloxyethyl isocyanate is preferable from the viewpoint that it is easy to introduce an active energy ray-reactive group into an acrylic copolymer (AP), thereby easily causing the first action described above. preferable. An active energy ray reactive group containing compound (AC) may be used individually by 1 type, and may be used in combination of 2 or more type.
　本実施形態における（メタ）アクリル酸エステル共重合体（Ａ）は、アクリル系共重合体（ＡＰ）が有するヒドロキシ基に対して、活性エネルギー線反応性基含有化合物（ＡＣ）が１０モル％以上の割合で反応してなるものであることが好ましく、特に４０モル％以上の割合で反応してなるものであることが好ましく、さらには７０モル％以上の割合で反応してなるものであることが好ましい。また、本実施形態における（メタ）アクリル酸エステル共重合体（Ａ）は、アクリル系共重合体（ＡＰ）が有するヒドロキシ基に対して、活性エネルギー線反応性基含有化合物（ＡＣ）が９９モル％以下の割合で反応してなるものであることが好ましく、特に９０モル％以下の割合で反応してなるものであることが好ましく、さらには８５モル％以下の割合で反応してなるものであることが好ましい。（メタ）アクリル酸エステル共重合体（Ａ）が、アクリル系共重合体（ＡＰ）と活性エネルギー線反応性基含有化合物（ＡＣ）とが上述した割合で反応してなるものであることで、活性エネルギー線反応性基が十分に導入されたものとなり、前述した第一の作用を生じさせ易いものとなる。 In the present embodiment, the (meth) acrylic acid ester copolymer (A) contains 10 mol% or more of the active energy ray-reactive group-containing compound (AC) with respect to the hydroxy group of the acrylic copolymer (AP). It is preferable that the reaction is performed at a rate of 40 mol% or more, and it is preferable that the reaction is performed at a rate of 70 mol% or more. Is preferred. Moreover, the (meth) acrylic acid ester copolymer (A) in this embodiment is 99 mol of active energy ray reactive group containing compound (AC) with respect to the hydroxy group which acrylic copolymer (AP) has. %, Preferably at a rate of 90 mol% or less, more preferably at a rate of 85 mol% or less. Preferably there is. The (meth) acrylic acid ester copolymer (A) is obtained by reacting the acrylic copolymer (AP) with the active energy ray-reactive group-containing compound (AC) at the above-described ratio. The active energy ray-reactive group is sufficiently introduced, and the first action described above is easily generated.
　アクリル系共重合体（ＡＰ）と活性エネルギー線反応性基含有化合物（ＡＣ）との反応は、常法によって行えばよい。この反応工程により、アクリル系共重合体（ＡＰ）中のヒドロキシ基と、活性エネルギー線反応性基含有化合物（ＡＣ）中の官能基（例えばイソシアネート基）とが反応して、活性エネルギー線反応性基がアクリル系共重合体（ＡＰ）の側鎖として導入され、エネルギー線硬化性の（メタ）アクリル酸エステル共重合体（Ａ）が得られる。 The reaction between the acrylic copolymer (AP) and the active energy ray-reactive group-containing compound (AC) may be performed by a conventional method. By this reaction step, the hydroxyl group in the acrylic copolymer (AP) reacts with the functional group (for example, isocyanate group) in the active energy ray-reactive group-containing compound (AC) to react with the active energy ray reactivity. A group is introduced as a side chain of the acrylic copolymer (AP) to obtain an energy ray-curable (meth) acrylic acid ester copolymer (A).
　（メタ）アクリル酸エステル共重合体（Ａ）の質量平均分子量は、２０万以上であることが好ましく、特に３０万以上であることが好ましく、さらには４０万以上であることが好ましい。また、当該質量平均分子量は、２００万以下であることが好ましく、特に１００万以下であることが好ましく、さらには８０万以下であることが好ましい。 The mass average molecular weight of the (meth) acrylic acid ester copolymer (A) is preferably 200,000 or more, particularly preferably 300,000 or more, and more preferably 400,000 or more. Further, the mass average molecular weight is preferably 2 million or less, particularly preferably 1 million or less, and more preferably 800,000 or less.
　なお、本実施形態に係る粘着剤組成物は、以上説明した（メタ）アクリル酸エステル共重合体（Ａ）を１種含有するものであってもよく、または２種以上含有するものであってもよい。また、本実施形態に係る粘着剤組成物は、以上説明した（メタ）アクリル酸エステル共重合体（Ａ）とともに、別の（メタ）アクリル酸エステル共重合体を含有するものであってもよい。 In addition, the adhesive composition which concerns on this embodiment may contain 1 type of the (meth) acrylic acid ester copolymer (A) demonstrated above, or contains 2 or more types. Also good. Moreover, the adhesive composition which concerns on this embodiment may contain another (meth) acrylic acid ester copolymer with the (meth) acrylic acid ester copolymer (A) demonstrated above. .
２．酸発生剤（Ｂ）
　酸発生剤（Ｂ）としては、活性エネルギー線の照射および加熱の少なくとも一方により酸を発生し、当該酸によって、（メタ）アクリル酸エステル共重合体（Ａ）におけるカルボキシ前駆基含有モノマー（ａ２）に由来する部分から炭化水素系ガスが十分に放出させることが可能である限り、特に限定されない。 2. Acid generator (B)
As the acid generator (B), an acid is generated by at least one of irradiation with active energy rays and heating, and the carboxy precursor group-containing monomer (a2) in the (meth) acrylate copolymer (A) by the acid. There is no particular limitation as long as the hydrocarbon-based gas can be sufficiently released from the portion derived from the above.
　酸発生剤（Ｂ）が活性エネルギー線の照射により酸を発生するものである場合、そのような酸発生剤（Ｂ）の例としては、Ｎ－ヒドロキシナフタルイミドと酸成分とのエステル化合物またはその誘導体や、オニウム塩等が挙げられ、当該オニウム塩の例としては、スルホニウム塩、ヨードニウム塩、ジアゾニウム塩、セレニウム塩、ピリジニウム塩、フェロセニウム塩、ホスホニウム塩、チオピリニウム塩等が挙げられる。 When the acid generator (B) generates an acid upon irradiation with active energy rays, examples of such an acid generator (B) include an ester compound of N-hydroxynaphthalimide and an acid component, or a compound thereof. Examples thereof include sulfonium salts, iodonium salts, diazonium salts, selenium salts, pyridinium salts, ferrocenium salts, phosphonium salts, thiopyrinium salts, and the like.
　上述したＮ－ヒドロキシナフタルイミドと酸成分とのエステル化合物またはその誘導体における酸成分の例としては、トリフルオロメタンスルホン酸、メタンスルホン酸、ベンゼンスルホン酸等が挙げられる。 Examples of the acid component in the ester compound of N-hydroxynaphthalimide and an acid component described above or a derivative thereof include trifluoromethanesulfonic acid, methanesulfonic acid, benzenesulfonic acid, and the like.
　上述したオニウム塩におけるアニオン成分の例としては、ＣＦ３ＳＯ３ －、（ＣＦ３ＳＯ２）２Ｎ－、（ＣＦ３ＳＯ２）３Ｃ－、ＢＦ４ －、ＰＦ６ －、ＡｓＦ６ －、ＳｂＦ６ －、Ｂ（Ｃ６Ｆ５）４ －等が挙げられる。 Examples of the anion component in the onium salt described above include CF 3 SO 3 − , (CF 3 SO 2 ) 2 N − , (CF 3 SO 2 ) 3 C − , BF 4 − , PF 6 − , AsF 6 − , SbF 6 − , B (C 6 F 5 ) 4 — and the like.
　特に、本実施形態における酸発生剤（Ｂ）としては、良好に酸を発生させ易いという観点から、Ｎ－ヒドロキシナフタルイミドと酸成分とのエステル化合物またはその誘導体が好ましく、より好ましくはＮ－ヒドロキシナフタルイミドとトリフルオロメタンスルホン酸のエステル化合物またはその誘導体が好ましく、１，８－ナフタルイミドトリフルオロメタンスルホン酸エステルまたはその誘導体が特に好ましい。 In particular, the acid generator (B) in this embodiment is preferably an ester compound of N-hydroxynaphthalimide and an acid component or a derivative thereof, more preferably N-hydroxy, from the viewpoint of easily generating an acid. An ester compound of naphthalimide and trifluoromethanesulfonic acid or a derivative thereof is preferable, and 1,8-naphthalimide trifluoromethanesulfonic acid ester or a derivative thereof is particularly preferable.
　また、酸発生剤（Ｂ）が活性エネルギー線の照射により酸を発生するものである場合、当該活性エネルギー線の種類としては、紫外線、電子線等であることが好ましく、特に、取り扱いが容易であるとともに、酸の効果的に発生させることができる紫外線であることが好ましい。 In addition, when the acid generator (B) generates an acid upon irradiation with an active energy ray, the type of the active energy ray is preferably an ultraviolet ray, an electron beam or the like, and is particularly easy to handle. In addition, it is preferable to use ultraviolet rays that can effectively generate acid.
　一方、酸発生剤（Ｂ）が加熱により酸を発生するものである場合、当該酸発生剤（Ｂ）の例としては、Ｎ－（４－メチルベンジル）４’－ピリジニウム・ヘキサフルオロアンチモネートなどのピリジニウム塩誘導体；ヒドラジニウム塩；ホスホニウム塩；ジメチルフェニルスルホニウム・ヘキサフルオロホスフェートなどのスルホニウム塩；ホスホン酸エステル；シクロヘキシル（４－メチルフェニル）スルホネート、イソプロピル（４－メチルフェニル）スルホネートなどのスルホン酸エステル；１，２，４－トリメリット酸のプロピルビニルエーテルなどのカルボン酸のビニルエーテル付加物誘導体等が挙げられる。 On the other hand, when the acid generator (B) generates an acid by heating, examples of the acid generator (B) include N- (4-methylbenzyl) 4′-pyridinium hexafluoroantimonate Hydrazine salts; phosphonium salts; sulfonium salts such as dimethylphenylsulfonium hexafluorophosphate; phosphonic acid esters; sulfonic acid esters such as cyclohexyl (4-methylphenyl) sulfonate and isopropyl (4-methylphenyl) sulfonate; And vinyl ether adduct derivatives of carboxylic acids such as propyl vinyl ether of 1,2,4-trimellitic acid.
　以上説明した酸発生剤（Ｂ）は、１種を単独でまたは２種以上を組み合わせて使用することができる。 The acid generator (B) described above can be used singly or in combination of two or more.
　本実施形態に係る粘着剤組成物における酸発生剤（Ｂ）の含有量は、（メタ）アクリル酸エステル共重合体（Ａ）１００質量部に対し、０．５質量部以上であることが好ましく、特に１質量部以上であることが好ましく、さらには２質量部以上であることが好ましい。また、当該含有量は、（メタ）アクリル酸エステル共重合体（Ａ）１００質量部に対し、２０質量部以下であることが好ましく、特に１５質量部以下であることが好ましく、さらには１０質量部以下であることが好ましい。酸発生剤（Ｂ）の含有量が０．５質量部以上であることで、得られる粘着剤層において効果的に酸を発生させることができ、それにより、（メタ）アクリル酸エステル共重合体（Ａ）から炭化水素系ガスを良好に発生させることができ、その結果、粘着シートの被着体からの剥離をより容易に行うことが可能となる。また、酸発生剤（Ｂ）の含有量が２０質量部以下であることで、本実施形態に係る粘着剤組成物を用いて塗膜を形成する際に、良好な面状態を維持し易くなる。 The content of the acid generator (B) in the pressure-sensitive adhesive composition according to the present embodiment is preferably 0.5 parts by mass or more with respect to 100 parts by mass of the (meth) acrylic acid ester copolymer (A). In particular, the amount is preferably 1 part by mass or more, and more preferably 2 parts by mass or more. The content is preferably 20 parts by mass or less, particularly preferably 15 parts by mass or less, and more preferably 10 parts by mass with respect to 100 parts by mass of the (meth) acrylic acid ester copolymer (A). Part or less. When the content of the acid generator (B) is 0.5 parts by mass or more, an acid can be effectively generated in the obtained pressure-sensitive adhesive layer, and thereby a (meth) acrylic acid ester copolymer. The hydrocarbon-based gas can be generated satisfactorily from (A), and as a result, the pressure-sensitive adhesive sheet can be more easily peeled off from the adherend. Moreover, when content of an acid generator (B) is 20 mass parts or less, when forming a coating film using the adhesive composition which concerns on this embodiment, it becomes easy to maintain a favorable surface state. .
３．光開始剤（Ｃ）
　光開始剤（Ｃ）は、活性エネルギー線の照射によって生じる、（メタ）アクリル酸エステル共重合体（Ａ）の活性エネルギー線反応性基における反応を促進することができるものである。これにより、本実施形態に係る粘着剤組成物から形成される粘着剤層の硬化を促進することが可能である限り、特に限定されないが、光ラジカル重合開始剤であることが、反応性の面から好ましい。 3. Photoinitiator (C)
A photoinitiator (C) can accelerate | stimulate reaction in the active energy ray reactive group of the (meth) acrylic acid ester copolymer (A) produced by irradiation of an active energy ray. This is not particularly limited as long as it can accelerate the curing of the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition according to the present embodiment, but it is a reactive surface that is a radical photopolymerization initiator. To preferred.
　このような光開始剤（Ｃ）の例としては、ベンゾイン化合物、アセトフェノン化合物、アシルフォスフィンオキサイド化合物、チタノセン化合物、チオキサントン化合物、パーオキサイド化合物等が挙げられ、具体的には、１－ヒドロキシシクロヘキシルフェニルケトン、ベンゾイン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル、ベンジルジフェニルサルファイド、テトラメチルチウラムモノサルファイド、アゾビスイソブチロニトリル、ジベンジル、ジアセチル、β－クロールアンスラキノン、２,４,６－トリメチルベンゾイルジフェニルフォスフィンオキサイドなどが例示される。これらの中でも、活性エネルギー線反応性基における反応を効果的に促進することができるという観点から、アセトフェノン化合物が好ましく、１－ヒドロキシシクロヘキシルフェニルケトンがより好ましい。これらの光開始剤（Ｃ）は、１種を単独でまたは２種以上を組み合わせて使用することができる。 Examples of such photoinitiators (C) include benzoin compounds, acetophenone compounds, acylphosphine oxide compounds, titanocene compounds, thioxanthone compounds, peroxide compounds, and the like, and specifically, 1-hydroxycyclohexylphenyl. Ketone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzyldiphenyl sulfide, tetramethylthiuram monosulfide, azobisisobutyronitrile, dibenzyl, diacetyl, β-chloranthraquinone, 2,4,6-trimethyl Examples include benzoyldiphenylphosphine oxide. Among these, an acetophenone compound is preferable and 1-hydroxycyclohexyl phenyl ketone is more preferable from the viewpoint that the reaction at the active energy ray-reactive group can be effectively promoted. These photoinitiators (C) can be used individually by 1 type or in combination of 2 or more types.
　本実施形態に係る粘着剤組成物における光開始剤（Ｃ）の含有量は、（メタ）アクリル酸エステル共重合体（Ａ）１００質量部に対し、０．１質量部以上であることが好ましく、特に０．５質量部以上であることが好ましく、さらには１．０質量部以上であることが好ましい。また、当該含有量は、（メタ）アクリル酸エステル共重合体（Ａ）１００質量部に対し、１０質量部以下であることが好ましく、特に８質量部以下であることが好ましく、さらには５質量部以下であることが好ましい。光開始剤（Ｃ）の含有量が上述した範囲であることで、活性エネルギー線反応性基における反応を効果的に促進することができ、その結果、粘着シートの被着体からの剥離をより容易に行うことが可能となる。 It is preferable that content of the photoinitiator (C) in the adhesive composition which concerns on this embodiment is 0.1 mass part or more with respect to 100 mass parts of (meth) acrylic acid ester copolymers (A). In particular, the amount is preferably 0.5 parts by mass or more, and more preferably 1.0 part by mass or more. In addition, the content is preferably 10 parts by mass or less, particularly preferably 8 parts by mass or less, and more preferably 5 parts by mass with respect to 100 parts by mass of the (meth) acrylic acid ester copolymer (A). Part or less. When the content of the photoinitiator (C) is in the above-described range, the reaction in the active energy ray-reactive group can be effectively promoted, and as a result, the pressure-sensitive adhesive sheet can be more easily detached from the adherend. It can be easily performed.
４．架橋剤（Ｄ）
　本実施形態に係る粘着剤組成物は、架橋剤（Ｄ）を含むことが好ましい。粘着剤組成物が架橋剤（Ｄ）を含むことにより、（メタ）アクリル酸エステル共重合体（Ａ）と架橋剤（Ｄ）との架橋反応が生じることが可能となり、本実施形態に係る粘着剤組成物から形成される粘着剤層において、三次元網目構造を良好に形成することが可能となる。これにより、所望の粘着力を有する粘着剤層を形成することが容易となる。 4). Cross-linking agent (D)
The pressure-sensitive adhesive composition according to this embodiment preferably contains a crosslinking agent (D). When the pressure-sensitive adhesive composition contains the cross-linking agent (D), a cross-linking reaction between the (meth) acrylic acid ester copolymer (A) and the cross-linking agent (D) can occur, and the pressure-sensitive adhesive according to the present embodiment. In the pressure-sensitive adhesive layer formed from the agent composition, a three-dimensional network structure can be favorably formed. Thereby, it becomes easy to form the adhesive layer which has desired adhesive force.
　架橋剤（Ｄ）としては、（メタ）アクリル酸エステル共重合体（Ａ）との間で架橋反応を生じることができるものである限り、特に限定されず、ポリイソシアネート系化合物、エポキシ系化合物、金属キレート系化合物、アジリジン系化合物等のポリイミン化合物、メラミン樹脂、尿素樹脂、ジアルデヒド類、メチロールポリマー、金属アルコキシド、金属塩等が挙げられる。これらの中でも、架橋反応を制御し易いことなどの理由により、ポリイソシアネート系化合物またはエポキシ系化合物であることが好ましく、特にポリイソシアネート系化合物であることが好ましい。 The crosslinking agent (D) is not particularly limited as long as it can cause a crosslinking reaction with the (meth) acrylic acid ester copolymer (A), and is not limited to polyisocyanate compounds, epoxy compounds, Examples thereof include polyimine compounds such as metal chelate compounds and aziridine compounds, melamine resins, urea resins, dialdehydes, methylol polymers, metal alkoxides, and metal salts. Among these, a polyisocyanate compound or an epoxy compound is preferable because of easy control of the crosslinking reaction, and a polyisocyanate compound is particularly preferable.
　ポリイソシアネート系化合物は、１分子当たりイソシアネート基を２個以上有する化合物である。具体的には、トリレンジイソシアネート、ジフェニルメタンジイソシアネート、キシリレンジイソシアネート等の芳香族ポリイソシアネート；ヘキサメチレンジイソシアネート等の脂肪族ポリイソシアネート；イソホロンジイソシアネート、水素添加ジフェニルメタンジイソシアネート等の脂環式ポリイソシアネート；など、およびそれらのビウレット体、イソシアヌレート体、さらにはエチレングリコール、プロピレングリコール、ネオペンチルグリコール、トリメチロールプロパン、ヒマシ油等の低分子活性水素含有化合物との反応物であるアダクト体などが挙げられる。これらの中でも、トリメチロールプロパン変性トリレンジイソシアネートが好ましい。 The polyisocyanate compound is a compound having two or more isocyanate groups per molecule. Specifically, aromatic polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate and xylylene diisocyanate; aliphatic polyisocyanates such as hexamethylene diisocyanate; alicyclic polyisocyanates such as isophorone diisocyanate and hydrogenated diphenylmethane diisocyanate; Examples thereof include biuret bodies, isocyanurate bodies, and adduct bodies that are reaction products with low molecular active hydrogen-containing compounds such as ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane, and castor oil. Among these, trimethylolpropane-modified tolylene diisocyanate is preferable.
　エポキシ系化合物としては、例えば、１，３－ビス（Ｎ，Ｎ’－ジグリシジルアミノメチル）シクロヘキサン、Ｎ，Ｎ，Ｎ’，Ｎ’－テトラグリシジル－ｍ－キシリレンジアミン、エチレングリコールジグリシジルエーテル、１，６－ヘキサンジオールジグリシジルエーテル、トリメチロールプロパンジグリシジルエーテル、ジグリシジルアニリン、ジグリシジルアミン等が挙げられる。 Examples of the epoxy compound 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.
　本実施形態に係る粘着剤組成物が架橋剤（Ｄ）を含有する場合、当該架橋剤（Ｄ）の含有量は、（メタ）アクリル酸エステル共重合体（Ａ）１００質量部に対し、０．１質量部以上であることが好ましく、特に０．２質量部以上であることが好ましく、さらには０．３質量部以上であることが好ましい。また、当該含有量は、（メタ）アクリル酸エステル共重合体（Ａ）１００質量部に対し、２０質量部以下であることが好ましく、特に１５質量部以下であることが好ましく、さらには１０質量部以下であることが好ましい。架橋剤（Ｄ）の含有量が上述した範囲であることで、（メタ）アクリル酸エステル共重合体（Ａ）と架橋剤（Ｄ）との架橋反応が適度に生じ、それにより、所望の粘着力を有する粘着剤層を形成することが容易となる。 When the adhesive composition which concerns on this embodiment contains a crosslinking agent (D), content of the said crosslinking agent (D) is 0 with respect to 100 mass parts of (meth) acrylic acid ester copolymers (A). It is preferably 1 part by mass or more, particularly preferably 0.2 part by mass or more, and further preferably 0.3 part by mass or more. The content is preferably 20 parts by mass or less, particularly preferably 15 parts by mass or less, and more preferably 10 parts by mass with respect to 100 parts by mass of the (meth) acrylic acid ester copolymer (A). Part or less. When the content of the crosslinking agent (D) is in the above-described range, a crosslinking reaction between the (meth) acrylic acid ester copolymer (A) and the crosslinking agent (D) is appropriately generated, and thereby a desired adhesion. It is easy to form a pressure-sensitive adhesive layer.
５．その他の成分
　本実施形態に係る粘着剤組成物は、上記の成分に加えて、染料や顔料等の着色材料、難燃剤、フィラー、可塑剤、帯電防止剤などの各種添加剤を含有してもよいが、当該添加剤としては、紫外線の透過を阻害しないもののみを使用することが好ましい。 5. Other Components The pressure-sensitive adhesive composition according to the present embodiment may contain various additives such as coloring materials such as dyes and pigments, flame retardants, fillers, plasticizers, and antistatic agents in addition to the above components. However, it is preferable to use only those additives that do not inhibit the transmission of ultraviolet rays.
６．粘着剤組成物の製造方法
　本実施形態に係る粘着剤組成物は、（メタ）アクリル酸エステル共重合体（Ａ）を製造し、得られた（メタ）アクリル酸エステル共重合体（Ａ）と、酸発生剤（Ｂ）と、光開始剤（Ｃ）と、所望により、架橋剤（Ｄ）と、添加剤とを混合することで製造することができる。当該混合は、溶剤中で行ってもよく、この場合、粘着剤組成物の塗布液を得ることができる。 6). Production method of pressure-sensitive adhesive composition The pressure-sensitive adhesive composition according to the present embodiment produced a (meth) acrylic acid ester copolymer (A) and the obtained (meth) acrylic acid ester copolymer (A) and The acid generator (B), the photoinitiator (C), and, if desired, the crosslinking agent (D) and the additive can be mixed. The mixing may be performed in a solvent, and in this case, a coating solution for the pressure-sensitive adhesive composition can be obtained.
　上記溶剤としては、例えば、ヘキサン、ヘプタン、シクロヘキサン等の脂肪族炭化水素；トルエン、キシレン等の芳香族炭化水素；塩化メチレン、塩化エチレン等のハロゲン化炭化水素；メタノール、エタノール、プロパノール、ブタノール、１－メトキシ－２－プロパノール等のアルコール；アセトン、メチルエチルケトン、２－ペンタノン、イソホロン、シクロヘキサノン等のケトン；酢酸エチル、酢酸ブチル等のエステル；エチルセロソルブ等のセロソルブ系溶剤などが用いられる。 Examples of the solvent include aliphatic hydrocarbons such as hexane, heptane, and cyclohexane; aromatic hydrocarbons such as toluene and xylene; halogenated hydrocarbons such as methylene chloride and ethylene chloride; methanol, ethanol, propanol, butanol, 1 Alcohols such as methoxy-2-propanol; ketones such as acetone, methyl ethyl ketone, 2-pentanone, isophorone and cyclohexanone; esters such as ethyl acetate and butyl acetate; cellosolv solvents such as ethyl cellosolve and the like.
　このようにして調製された塗布液の濃度・粘度としては、コーティング可能な範囲であればよく、特に制限されず、状況に応じて適宜選定することができる。例えば、粘着性組成物の濃度が１０質量％以上、６０質量％以下となるように希釈する。なお、塗布液を得るに際して、溶剤等の添加は必要ではなく、粘着性組成物がコーティング可能な粘度等であれば、溶剤を添加しなくてもよい。 The concentration / viscosity of the coating solution prepared in this manner is not particularly limited as long as it is within a coatable range, and can be appropriately selected according to the situation. For example, it is diluted so that the concentration of the adhesive composition is 10% by mass or more and 60% by mass or less. In addition, when obtaining a coating liquid, the addition of a solvent or the like is not necessary, and the solvent may not be added as long as the viscosity can be coated by the adhesive composition.
〔粘着シート〕
　本実施形態に係る粘着シートは、本実施形態に係る粘着剤組成物から形成された粘着剤層を備えたものである。本実施形態に係る粘着シートは、当該粘着剤層の片面側に積層された基材を備える片面粘着シートであってもよく、当該粘着剤層が基材の両面にそれぞれ積層されてなる基材付き両面粘着シートであってもよく、または、基材を備えていない基材無し両面粘着シートであってもよい。基材付き両面粘着シートの場合は、片方の粘着剤層のみが本実施形態に係る粘着剤組成物から形成されていてもよいし、両方の粘着剤層が本実施形態に係る粘着剤組成物から形成されたものであってもよい。また、本実施形態に係る粘着シートは、粘着剤層を被着体に貼付するまでの間、粘着剤層を保護する目的で、粘着剤層における被着体に貼付される面（以下「粘着面」という場合がある。）に剥離シートが積層されていてもよい。 [Adhesive sheet]
The pressure-sensitive adhesive sheet according to this embodiment includes a pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition according to this embodiment. The pressure-sensitive adhesive sheet according to the present embodiment may be a single-sided pressure-sensitive adhesive sheet including a base material laminated on one side of the pressure-sensitive adhesive layer, and the base material obtained by laminating the pressure-sensitive adhesive layer on both surfaces of the base material. A double-sided pressure-sensitive adhesive sheet may be used, or a double-sided double-sided pressure-sensitive adhesive sheet not provided with a base material may be used. In the case of a double-sided pressure-sensitive adhesive sheet with a substrate, only one pressure-sensitive adhesive layer may be formed from the pressure-sensitive adhesive composition according to this embodiment, or both pressure-sensitive adhesive layers according to this embodiment. It may be formed from. In addition, the pressure-sensitive adhesive sheet according to this embodiment is a surface (hereinafter referred to as “adhesive”) for the purpose of protecting the pressure-sensitive adhesive layer until the pressure-sensitive adhesive layer is applied to the adherend. The release sheet may be laminated on the “surface” in some cases.
１．粘着シートの構成
（１）基材
　本実施形態に係る粘着シートが上述した片面粘着シート、または基材付き両面粘着シートである場合、当該粘着シートを構成する基材は、粘着剤層を積層可能である限り、その構成材料は特に限定されず、通常は樹脂系の材料を主材とするフィルムから構成される。 1. Configuration of pressure-sensitive adhesive sheet (1) base material When the pressure-sensitive adhesive sheet according to this embodiment is the above-mentioned single-sided pressure-sensitive adhesive sheet or double-sided pressure-sensitive adhesive sheet with a base material, the base material constituting the pressure-sensitive adhesive sheet can be laminated with a pressure-sensitive adhesive layer. As long as it is, the constituent material is not particularly limited, and it is usually composed of a film mainly composed of a resin-based material.
　そのフィルムの具体例としては、エチレン－酢酸ビニル共重合体フィルム、エチレン－（メタ）アクリル酸共重合体フィルム、エチレン－（メタ）アクリル酸エステル共重合体フィルム等のエチレン系共重合フィルム；低密度ポリエチレン（ＬＤＰＥ）フィルム、直鎖低密度ポリエチレン（ＬＬＤＰＥ）フィルム、高密度ポリエチレン（ＨＤＰＥ）フィルム等のポリエチレンフィルム、ポリプロピレンフィルム、ポリブテンフィルム、ポリブタジエンフィルム、ポリメチルペンテンフィルム、エチレン－ノルボルネン共重合体フィルム、ノルボルネン樹脂フィルム等のポリオレフィン系フィルム；ポリ塩化ビニルフィルム、塩化ビニル共重合体フィルム等のポリ塩化ビニル系フィルム；ポリエチレンテレフタレートフィルム、ポリブチレンテレフタレートフィルム、ポリエチレンナフタレートフィルム等のポリエステル系フィルム；ポリウレタンフィルム；ポリイミドフィルム；ポリアミドフィルム；ポリスチレンフィルム；ポリカーボネートフィルム；フッ素樹脂フィルムなどが挙げられる。またこれらの架橋フィルム、アイオノマーフィルムのような変性フィルムも用いられる。上記の基材はこれらの１種からなるフィルムでもよいし、さらにこれらを２種類以上組み合わせた積層フィルムであってもよい。 Specific examples of such films include ethylene-copolymer films such as ethylene-vinyl acetate copolymer films, ethylene- (meth) acrylic acid copolymer films, ethylene- (meth) acrylic acid ester copolymer films; Polyethylene film such as density 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 Polyurethane film; polyimide film; polyamide films; polystyrene films; polycarbonate films; Lev tallate film, polyester films such as polyethylene naphthalate film and a fluorine resin film. Further, modified films such as these crosslinked films and ionomer films are also used. The substrate may be a film made of one of these, or may be a laminated film in which two or more of these are combined.
　基材は、活性エネルギー線に対して透過性を有することが好ましい。基材がこのような透過性を有することにより、粘着剤層に対し、基材を介して活性エネルギー線を効果的に照射することが可能となる。これにより、粘着剤層を良好に硬化させ易くなり、粘着シートの被着体からの剥離がより容易となる。また、酸発生剤（Ｂ）として、活性エネルギー線の照射により酸を発生する場合には、効果的に酸を発生させ易くなり、その結果、粘着シートの被着体からの剥離がより容易となる。 The substrate is preferably permeable to active energy rays. When the base material has such permeability, it becomes possible to effectively irradiate the adhesive layer with active energy rays through the base material. Thereby, it becomes easy to harden an adhesive layer favorably and peeling from the adherend of an adhesive sheet becomes easier. Moreover, as an acid generator (B), when generating an acid by irradiation of an active energy ray, it becomes easy to generate an acid effectively, and as a result, peeling of an adhesive sheet from an adherend becomes easier. Become.
　また、基材は、耐熱性を有することが好ましい。本実施形態に係る粘着シートでは、粘着剤層を加熱することで前述した炭化水素系ガスの放出が促進される。また、本実施形態における酸発生剤（Ｂ）として、加熱によって酸を発生する酸発生剤（Ｂ）を使用する場合には、当該酸の発生のためにも粘着剤層を加熱する必要がある。そのため、基材として耐熱性を有するものを使用することで、このような加熱を行った場合であっても、粘着シートの変形を抑制することが可能となる。特に、本実施形態に係る粘着シートを、半導体ウエハ等のダイシングに使用する場合には、粘着シートの変形を抑制することで、ダイシングにより得られた切断物の移動や飛び散りを効果的に抑制することが可能となる。 Further, the base material preferably has heat resistance. In the pressure-sensitive adhesive sheet according to this embodiment, the release of the hydrocarbon-based gas described above is promoted by heating the pressure-sensitive adhesive layer. Moreover, when using the acid generator (B) which generate | occur | produces an acid by heating as an acid generator (B) in this embodiment, it is necessary to heat an adhesive layer also for the generation | occurrence | production of the said acid. . Therefore, by using a heat-resistant material as the base material, it is possible to suppress deformation of the pressure-sensitive adhesive sheet even when such heating is performed. In particular, when the pressure-sensitive adhesive sheet according to the present embodiment is used for dicing semiconductor wafers or the like, it is possible to effectively suppress the movement and scattering of the cut product obtained by dicing by suppressing the deformation of the pressure-sensitive adhesive sheet. It becomes possible.
　基材には、顔料、難燃剤、可塑剤、帯電防止剤、滑剤、フィラー等の各種添加剤が含まれていてもよい。顔料としては、例えば、二酸化チタン、カーボンブラック等が挙げられる。また、フィラーとしては、メラミン樹脂のような有機系材料、ヒュームドシリカのような無機系材料およびニッケル粒子のような金属系材料が例示される。こうした添加剤の含有量は特に限定されないが、基材が所望の機能を発揮し、平滑性や柔軟性を失わない範囲に留めるべきである。 The base material may contain various additives such as pigments, flame retardants, plasticizers, antistatic agents, lubricants, and fillers. Examples of the pigment include titanium dioxide and carbon black. Examples of 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.
　また、基材においては、その表面に設けられる層（粘着剤層等）との密着性を向上させる目的で、所望により片面または両面に、プライマー層を設けるプライマー処理、酸化法、凹凸化法等により表面処理を施すことができる。上記プライマー処理においてプライマー層を構成する成分としては、例えば、ポリエステル系、ポリウレタン系、ポリアクリル系などの合成樹脂が例示され、これらを単独でまたは２種以上を組み合わせて用いることができる。酸化法としては、例えばコロナ放電処理、クロム酸処理、火炎処理、熱風処理、オゾン・紫外線処理等が挙げられ、凹凸化法としては、例えばサンドブラスト法、溶剤処理法等が挙げられる。これらの表面処理法は基材の種類に応じて適宜選ばれる。一例として、プライマー処理によりプライマー層を形成した樹脂フィルム、特にポリエチレンテレフタレートフィルムが好ましく用いられる。 In addition, in the base material, for the purpose of improving adhesion with a layer (such as a pressure-sensitive adhesive layer) provided on the surface, a primer treatment, an oxidation method, a concavo-convex method, etc., where a primer layer is provided on one or both sides as desired. Thus, surface treatment can be performed. As a component which comprises a primer layer in the said primer process, synthetic resins, such as a polyester type, a polyurethane type, a polyacryl type, are illustrated, for example, These can be used individually or in combination of 2 or more types. Examples of the oxidation method include corona discharge treatment, chromic acid treatment, flame treatment, hot air treatment, ozone / ultraviolet treatment, and examples of the unevenness method include a sand blast method and a solvent treatment method. These surface treatment methods are appropriately selected according to the type of substrate. As an example, a resin film having a primer layer formed by primer treatment, particularly a polyethylene terephthalate film is preferably used.
　基材の厚さは、粘着シートが所望の工程において適切に機能できる限り、限定されない。例えば、基材の厚さは、２０μｍ以上であることが好ましく、特に２５μｍ以上であることが好ましく、さらには５０μｍ以上であることが好ましい。また、当該厚さは、４５０μｍ以下であることが好ましく、特に４００μｍ以下であることが好ましく、さらには３５０μｍ以下であることが好ましい。 The thickness of the substrate is not limited as long as the adhesive sheet can function properly in a desired process. For example, the thickness of the substrate is preferably 20 μm or more, particularly preferably 25 μm or more, and more preferably 50 μm or more. The thickness is preferably 450 μm or less, particularly preferably 400 μm or less, and more preferably 350 μm or less.
（２）粘着剤層
　粘着剤層は、前述した粘着剤組成物から形成されるものである。当該粘着剤層の厚さは１μｍ以上であることが好ましく、５μｍ以上であることがより好ましく、特に１０μｍ以上であることが好ましく、さらには１５μｍ以上であることが好ましい。また、粘着剤層の厚さは６０μｍ以下であることが好ましく、５０μｍ以下であることがより好ましく、特に４０μｍ以下であることが好ましく、さらには３０μｍ以下であることが好ましい。粘着剤層の厚さが１μｍ以上であることで、被着体に対する初期粘着力が十分なものとなり、被着体をより良好に固定することが可能となるとともに、粘着剤層から炭化水素系ガスを放出させる際には、当該炭化水素系ガスの放出量が十分なものとなり、前述した第二の作用によって、粘着シートの被着体からの剥離を容易に行い易くなる。また、粘着剤層の厚さが６０μｍ以下であることで、粘着剤層に対して活性エネルギー線を照射した場合に、粘着剤層を十分に硬化させ易くなり、前述した第一の作用によって、粘着シートの被着体からの剥離を容易に行い易くなる。 (2) Pressure-sensitive adhesive layer The pressure-sensitive adhesive layer is formed from the pressure-sensitive adhesive composition described above. The thickness of the pressure-sensitive adhesive layer is preferably 1 μm or more, more preferably 5 μm or more, particularly preferably 10 μm or more, and further preferably 15 μm or more. The thickness of the pressure-sensitive adhesive layer is preferably 60 μm or less, more preferably 50 μm or less, particularly preferably 40 μm or less, and further preferably 30 μm or less. When the thickness of the pressure-sensitive adhesive layer is 1 μm or more, the initial adhesive force to the adherend becomes sufficient, and the adherend can be fixed more favorably. When the gas is released, the amount of release of the hydrocarbon-based gas becomes sufficient, and the pressure-sensitive adhesive sheet can be easily peeled off from the adherend by the second action described above. Moreover, when the thickness of the pressure-sensitive adhesive layer is 60 μm or less, when the active energy ray is irradiated to the pressure-sensitive adhesive layer, the pressure-sensitive adhesive layer can be sufficiently cured, and by the first action described above, The adhesive sheet can be easily peeled off from the adherend.
（３）剥離シート
　本実施形態に係る粘着シートが剥離シートを備えるものである場合、当該剥離シートとしては、粘着剤層から剥離シートを良好に剥離できるものである限り限定されない。当該剥離シートの例としては、グラシン紙、コート紙、上質紙等の紙基材、これらの紙基材にポリエチレン等の樹脂をラミネートしたラミネート紙、またはポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリエチレンナフタレート等のポリエステルフィルム、ポリプロピレン、ポリエチレン等のポリオレフィンフィルムなどのプラスチックフィルムが挙げられる。これらの剥離面（粘着剤層と接する面）には、剥離処理が施されていることが好ましい。剥離処理に使用される剥離剤としては、例えば、シリコーン系、フッ素系、長鎖アルキル系等の剥離剤が挙げられる。 (3) Release sheet When the pressure-sensitive adhesive sheet according to this embodiment includes a release sheet, the release sheet is not limited as long as the release sheet can be satisfactorily released from the pressure-sensitive adhesive layer. Examples of the release sheet include paper substrates such as glassine paper, coated paper, high-quality paper, laminated paper obtained by laminating a resin such as polyethylene on these paper substrates, or polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, etc. Examples thereof include plastic films such as polyester films, polyolefin films such as polypropylene and polyethylene. It is preferable that a release treatment is performed on these release surfaces (surfaces in contact with the pressure-sensitive adhesive layer). Examples of the release agent used for the release treatment include silicone-based, fluorine-based, and long-chain alkyl-based release agents.
　剥離シートの厚さについては特に制限はないが、通常２０μｍ以上、２５０μｍ以下である。 Although there is no restriction | limiting in particular about the thickness of a peeling sheet, Usually, they are 20 micrometers or more and 250 micrometers or less.
２．粘着シートの物性
　本実施形態に係る粘着シートの初期粘着力（前述した第一の作用および第二の作用を生じさせる前の粘着力）は、２Ｎ／２５ｍｍ以上であることが好ましく、特に４Ｎ／２５ｍｍ以上であることが好ましく、さらには６Ｎ／２５ｍｍ以上であることが好ましい。また、当該初期粘着力は、３０Ｎ／２５ｍｍ以下であることが好ましく、特に２５Ｎ／２５ｍｍ以下であることが好ましく、さらには２０Ｎ／２５ｍｍ以下であることが好ましい。上記粘着力が２Ｎ／２５ｍｍ以上であることで、被着体を加工する工程において、被着体を粘着シート上に保持し易くなり、良好な加工を行い易くなる。また、上記粘着力が３０Ｎ／２５ｍｍ以下であることで、活性エネルギー線を照射することで粘着剤層を硬化させた後における粘着力を後述する範囲に調整し易くなる。なお、上記初期粘着力は、基本的にはＪＩＳ　Ｚ０２３７：２０００に準じた１８０°引き剥がし法により測定した粘着力をいい、詳細な測定方法は後述する実施例に示す通りである。 2. Physical properties of the pressure-sensitive adhesive sheet The initial pressure-sensitive adhesive strength of the pressure-sensitive adhesive sheet according to the present embodiment (the pressure-sensitive adhesive strength before causing the first action and the second action described above) is preferably 2N / 25 mm or more, particularly 4N / It is preferably 25 mm or more, and more preferably 6 N / 25 mm or more. The initial adhesive strength is preferably 30 N / 25 mm or less, particularly preferably 25 N / 25 mm or less, and more preferably 20 N / 25 mm or less. When the adhesive force is 2 N / 25 mm or more, in the step of processing the adherend, the adherend is easily held on the adhesive sheet, and good processing is easily performed. Moreover, it becomes easy to adjust the adhesive force after hardening an adhesive layer by irradiating an active energy ray to the range mentioned later because the said adhesive force is 30 N / 25mm or less. The initial adhesive strength basically refers to an adhesive strength measured by a 180 ° peeling method according to JIS Z0237: 2000, and the detailed measuring method is as shown in the examples described later.
　また、本実施形態に係る粘着シートでは、活性エネルギー線を照射することで粘着剤層を硬化させた後且つ加熱を行う前（すなわち、前述した第二の作用に係る炭化水素系ガスの放出が生じる前）における粘着力が、１Ｎ／２５ｍｍ以下であることが好ましく、特に０．５Ｎ／２５ｍｍ以下であることが好ましく、さらには０．２Ｎ／２５ｍｍ以下であることが好ましい。本実施形態に係る粘着シートでは、活性エネルギー線の照射によって粘着剤層を硬化させることが可能であるため、粘着力を１Ｎ／２５ｍｍ以下に低下させることが可能である。そして、上記粘着力を１Ｎ／２５ｍｍ以下に低下させることにより、粘着シートを被着体からより容易に剥離することが可能となる。なお、上記粘着力の下限値については特に限定されないものの、０．００１Ｎ／２５ｍｍ以上であることが好ましく、特に０．００５Ｎ／２５ｍｍ以上であることが好ましく、さらには０．０１Ｎ／２５ｍｍ以上であることが好ましい。また、上記粘着力は、基本的にはＪＩＳ　Ｚ０２３７：２０００に準じた１８０°引き剥がし法により測定した粘着力をいい、詳細な測定方法は後述する実施例に示す通りである。 In the pressure-sensitive adhesive sheet according to this embodiment, after the pressure-sensitive adhesive layer is cured by irradiating active energy rays and before heating (that is, the release of the hydrocarbon-based gas according to the second action described above is performed). It is preferable that the adhesive strength in (before) is 1 N / 25 mm or less, particularly 0.5 N / 25 mm or less, and more preferably 0.2 N / 25 mm or less. In the pressure-sensitive adhesive sheet according to this embodiment, the pressure-sensitive adhesive layer can be cured by irradiation with active energy rays, and thus the adhesive force can be reduced to 1 N / 25 mm or less. And it becomes possible to peel an adhesive sheet more easily from a to-be-adhered body by reducing the said adhesive force to 1 N / 25mm or less. In addition, although it does not specifically limit about the lower limit of the said adhesive force, It is preferable that it is 0.001 N / 25mm or more, It is especially preferable that it is 0.005 N / 25mm or more, Furthermore, it is 0.01 N / 25mm or more. It is preferable. Moreover, the said adhesive force basically says the adhesive force measured by 180 degree peeling method according to JISZ0237: 2000, and a detailed measuring method is as showing in the Example mentioned later.
３．粘着シートの製造方法
　本実施形態に係る粘着シートの製造方法は特に限定されず、従来の粘着シートと同様に製造することができる。 3. Manufacturing method of adhesive sheet The manufacturing method of the adhesive sheet which concerns on this embodiment is not specifically limited, It can manufacture similarly to the conventional adhesive sheet.
　例えば、粘着剤層を構成する粘着剤組成物、および所望によりさらに溶媒または分散媒を含有する塗布液を調製し、剥離シートの剥離面上に、ダイコーター、カーテンコーター、スプレーコーター、スリットコーター、ナイフコーター等によりその塗布液を塗布して塗膜を形成し、当該塗膜を乾燥させることにより、粘着剤層を形成することができる。 For example, a pressure-sensitive adhesive composition constituting the pressure-sensitive adhesive layer and, if desired, a coating solution further containing a solvent or a dispersion medium are prepared, and on the release surface of the release sheet, a die coater, a curtain coater, a spray coater, a slit coater, An adhesive layer can be formed by applying the coating solution with a knife coater or the like to form a coating film and drying the coating film.
　このように得られた粘着剤層と剥離シートとの積層体は、そのままの状態で、または、当該積層体における剥離剤層側の面に他の剥離シートをさらに積層した状態で、基材無し両面粘着シートとすることができる。 The laminated body of the pressure-sensitive adhesive layer and the release sheet thus obtained is in the state as it is, or in the state where another release sheet is further laminated on the surface on the release agent layer side of the laminate, and there is no substrate. It can be set as a double-sided adhesive sheet.
　また、片面粘着シートを製造する場合には、上述のように得られた粘着剤層と剥離シートとの積層体における粘着剤層側の面を、基材の片面側に貼付することで、基材と粘着剤層と剥離シートとを備える片面粘着シートとすることができる。 In the case of producing a single-sided pressure-sensitive adhesive sheet, the surface on the pressure-sensitive adhesive layer side of the laminate of the pressure-sensitive adhesive layer and the release sheet obtained as described above is attached to one side of the substrate, thereby It can be set as the single-sided adhesive sheet provided with a material, an adhesive layer, and a peeling sheet.
　片面粘着シートの別の製造方法としては、上述した塗布液を基材の片面側に塗布し、得られた塗膜を乾燥させることで、基材と粘着剤層とを備える粘着シートを製造してもよい。 As another manufacturing method of a single-sided pressure-sensitive adhesive sheet, a pressure-sensitive adhesive sheet comprising a base material and a pressure-sensitive adhesive layer is manufactured by applying the coating liquid described above to one side of the base material and drying the obtained coating film. May be.
　さらに、基材付き両面粘着シートを製造する場合には、上述のように得られた粘着剤層と剥離シートとの積層体を２枚用意し、一の積層体における粘着剤層側の面を基材の一方の面に積層するとともに、他の積層体における粘着剤層側の面を上記基材の他方の面に積層することで、一の剥離シートと一の粘着剤層と基材と他の粘着剤層と他の剥離シートとが順に積層されてなる基材付き両面粘着シートを得ることができる。 Furthermore, when manufacturing a double-sided pressure-sensitive adhesive sheet with a substrate, prepare two laminates of the pressure-sensitive adhesive layer and release sheet obtained as described above, and the surface on the pressure-sensitive adhesive layer side of one laminate is prepared. Laminating on one surface of the substrate and laminating the surface on the pressure-sensitive adhesive layer side in the other laminate on the other surface of the substrate, one release sheet, one adhesive layer, and the substrate A double-sided pressure-sensitive adhesive sheet with a substrate in which another pressure-sensitive adhesive layer and another release sheet are laminated in order can be obtained.
　基材付き両面粘着シートの別の製造方法としては、上述した塗布液を基材の両面側にそれぞれ塗布し、得られた塗膜をそれぞれ乾燥させることで、一の粘着剤層と基材と他の粘着剤層とを備える粘着シートを製造してもよい。 As another manufacturing method of the double-sided pressure-sensitive adhesive sheet with a base material, the above-mentioned coating solution is applied to both sides of the base material, and the obtained coating film is dried, whereby one adhesive layer and the base material You may manufacture an adhesive sheet provided with another adhesive layer.
　なお、粘着シートの製造のために使用した剥離シートは、粘着シートの製造後に剥離してもよいし、粘着シートを被着体に貼付するまでの間、粘着剤層を保護していてもよい。 The release sheet used for the production of the pressure-sensitive adhesive sheet may be peeled after the production of the pressure-sensitive adhesive sheet, or the pressure-sensitive adhesive layer may be protected until the pressure-sensitive adhesive sheet is applied to the adherend. .
　また、上述した塗布液は、塗布を行うことが可能であればその性状は特に限定されず、粘着剤層を形成するための成分を溶質として含有する場合もあれば、分散質として含有する場合もある。 In addition, the properties of the above-described coating solution are not particularly limited as long as it can be applied. In some cases, the component for forming the pressure-sensitive adhesive layer may be contained as a solute, or as a dispersoid. There is also.
　なお、粘着剤組成物が架橋剤（Ｄ）を含有する場合には、上記の乾燥の条件（温度、時間など）を変えることにより、または加熱処理を別途設けることにより、（メタ）アクリル酸エステル共重合体（Ａ）と架橋剤（Ｄ）との間における架橋反応を進行させ、粘着剤層内に所望の存在密度で架橋構造を形成させることが好ましい。例えば、粘着剤層を形成した後に、２３℃、相対湿度５０％の環境に数日間静置するといった養生を行うことが好ましい。 When the pressure-sensitive adhesive composition contains a crosslinking agent (D), (meth) acrylic acid ester can be obtained by changing the drying conditions (temperature, time, etc.) or by separately providing a heat treatment. It is preferable to advance a crosslinking reaction between the copolymer (A) and the crosslinking agent (D) to form a crosslinked structure at a desired density in the pressure-sensitive adhesive layer. For example, after forming the pressure-sensitive adhesive layer, it is preferable to perform curing such as leaving for several days in an environment of 23 ° C. and 50% relative humidity.
４．粘着シートの使用
　本実施形態に係る粘着シートは、粘着剤層が前述した粘着剤組成物を用いて形成されたものであるため、前述した第一の作用および第二の作用により、粘着シートを被着体から非常に容易に剥離することができる。そのため、本実施形態に係る粘着シートは、被着体に貼付した後に、当該被着体が粘着シートから剥離される用途に好適に使用することができる。特に、本実施形態に係る粘着シートは、所定の部材の加工のために使用することが好ましく、具体的には、粘着シートを被着体としての被加工物に貼付し、当該被加工物を粘着シート上で加工した後、得られた加工物を粘着シートから分離する用途に使用することが好ましい。このような用途の詳細については後述する。 4). Use of pressure-sensitive adhesive sheet The pressure-sensitive adhesive sheet according to the present embodiment is formed by using the pressure-sensitive adhesive composition described above. It can be peeled off from the adherend very easily. Therefore, the adhesive sheet according to the present embodiment can be suitably used for applications in which the adherend is peeled from the adhesive sheet after being attached to the adherend. In particular, the pressure-sensitive adhesive sheet according to the present embodiment is preferably used for processing a predetermined member. Specifically, the pressure-sensitive adhesive sheet is attached to a workpiece as an adherend, and the workpiece is attached. After processing on an adhesive sheet, it is preferable to use it for the use which isolate | separates the obtained processed material from an adhesive sheet. Details of such applications will be described later.
　上述した加工される部材としては、特に制限されないものの、例えば脆質部材が挙げられる。当該脆質部材の例としては、ガラス、セラミックグリーンシート、セラミックグリーンシート積層体、樹脂フィルム、薄膜金属板等が挙げられる。このような脆質部材は、力が印加されることで割れたり、崩壊したりし易い。特に、従来の粘着シートに貼付された脆質部材から当該粘着シートを剥離する際、剥離のために印加される力によって脆質部材が割れたり、崩壊したりし易い。しかしながら、本実施形態に係る粘着シートは、非常に容易に剥離することが可能であり、例えば粘着シートの自重により被着体から剥離することも可能であるため、脆質部材の割れや崩壊を抑制しながら、剥離することが可能となる。そのため、脆質部材の加工には、本実施形態に係る粘着シートを用いることが好ましい。なお、本明細書において、部材の加工とは、当該部材を粘着シート上で形成することを含むものとする。そのため、部材がセラミックグリーンシートである場合、当該セラミックグリーンシートの加工とは、既に形成されているセラミックグリーンシートを粘着シート上で切断等の処理を行うだけでなく、粘着シート上にてセラミックグリーンシートを形成することも含むものとする。 The above-described member to be processed is not particularly limited, and examples thereof include a brittle member. Examples of the brittle member include glass, ceramic green sheet, ceramic green sheet laminate, resin film, thin film metal plate, and the like. Such a brittle member is easily cracked or collapsed when a force is applied. In particular, when the pressure-sensitive adhesive sheet is peeled off from the brittle member attached to the conventional pressure-sensitive adhesive sheet, the brittle member is easily cracked or collapsed by the force applied for peeling. However, the pressure-sensitive adhesive sheet according to the present embodiment can be peeled off very easily. For example, the pressure-sensitive adhesive sheet can be peeled off from the adherend by its own weight. It becomes possible to peel while suppressing. Therefore, it is preferable to use the adhesive sheet according to the present embodiment for processing the brittle member. In the present specification, the processing of a member includes forming the member on an adhesive sheet. Therefore, when the member is a ceramic green sheet, the processing of the ceramic green sheet includes not only the processing of cutting the already formed ceramic green sheet on the adhesive sheet, but also the ceramic green sheet on the adhesive sheet. It also includes forming a sheet.
　また、本実施形態に係る粘着シートは、半導体加工のために使用することが好ましい。特に、半導体ウエハや半導体パッケージのダイシングや裏面研磨に使用することが好ましい。このようなダイシングを行うと、粘着シート上には、半導体ウエハや半導体パッケージが切断されてなる微小な切断物が多数積層された状態となる。これらの切断物は、粘着シートから個々にピックアップされることとなる。ここで、本実施形態に係る粘着シートは、前述した第一の作用および第二の作用によって、被着体から非常に容易に剥離することが可能であるため、当該粘着シートを上述したダイシングに使用することで、切断物のピックアップを良好に行うことが可能となる。また、本実施形態に係る粘着シートを裏面研磨に使用する場合には、研磨されて非常に薄くなった被着体に与える衝撃を極力抑制しながら、粘着シートを剥離することができ、被着体の割れや崩壊を効果的に抑制することができる。 Also, the pressure-sensitive adhesive sheet according to this embodiment is preferably used for semiconductor processing. In particular, it is preferably used for dicing or back surface polishing of a semiconductor wafer or semiconductor package. When such dicing is performed, a large number of minute cuts obtained by cutting a semiconductor wafer or a semiconductor package are stacked on the adhesive sheet. These cut products are individually picked up from the adhesive sheet. Here, the pressure-sensitive adhesive sheet according to this embodiment can be peeled off from the adherend very easily by the first action and the second action described above. By using it, it becomes possible to pick up the cut material satisfactorily. Further, when the pressure-sensitive adhesive sheet according to the present embodiment is used for back surface polishing, the pressure-sensitive adhesive sheet can be peeled off while suppressing the impact on the adherend that has been polished and thinned as much as possible. The body can be effectively prevented from cracking or collapsing.
　また、本実施形態に係る粘着シートが両面粘着シートである場合、当該両面粘着シートは、硬質の被着体同士を貼合し、所望により加工等を行った後に、被着体同士を分離する用途に使用することが好ましい。このような貼合の例としては、半導体ウエハやガラス板と硬質の支持体との貼合等が挙げられる。貼合された硬質の被着体同士の分離は、被着体同士を引き離す力を印加した際に、当該力を受けても被着体がしなりにくいために、非常に困難となることがある。特に、被着体同士が粘着剤層を介して過度に密着している場合には、分離の際に被着体が破壊される可能性もある。しかしながら、本実施形態に係る粘着シートによれば、前述した第一の作用および第二の作用によって、被着体から非常に容易に剥離することが可能であるため、上述のような破壊を生じさせることなく、非常に容易に硬質の被着体同士を分離することができる。なお、本実施形態に係る粘着シートを上述した用途に使用する場合には、前述した第一の作用を効果的に生じさせるために、被着体のいずれか一方が、活性エネルギー線に対して透過性を有するものであることが好ましい。 Moreover, when the adhesive sheet which concerns on this embodiment is a double-sided adhesive sheet, the said double-sided adhesive sheet isolate | separates adherends, after bonding hard adherends and processing etc. as needed. It is preferable to use for an application. Examples of such bonding include bonding between a semiconductor wafer or glass plate and a hard support. Separation of bonded adherends can be very difficult when applying a force to separate the adherends and the adherends are difficult to bend even when the force is applied. is there. In particular, when the adherends are in close contact with each other via the pressure-sensitive adhesive layer, the adherends may be destroyed during the separation. However, according to the pressure-sensitive adhesive sheet according to the present embodiment, it is possible to peel from the adherend very easily by the first action and the second action described above, and thus the above-described destruction occurs. It is possible to separate hard adherends very easily without causing them to occur. In addition, when using the adhesive sheet which concerns on this embodiment for the use mentioned above, in order to produce the 1st effect | action mentioned above effectively, either one of a to-be-adhered body is with respect to an active energy ray. It is preferable that it has permeability.
　また、本実施形態に係る粘着シートが、本実施形態に係る粘着剤組成物から形成された一の粘着剤層と、所望の粘着剤から構成される他の粘着剤層とを備える基材付き両面粘着シートである場合には、当該一の粘着剤層による、被着体から非常に容易に剥離することができるという効果と、当該他の粘着剤層による、所望の効果とを両立することもできる。このように、他の粘着剤層として種々の粘着剤層を組み合わせることにより、本実施形態に係る粘着シートは、様々な用途において優れた性能を発揮することが可能となる。上述した他の粘着剤層を構成する粘着剤としては、例えば、活性エネルギー線硬化性の粘着剤、被着体への糊残りが生じ難い粘着剤、耐熱性に優れる粘着剤、耐溶剤性に優れる粘着剤等が挙げられる。 Moreover, the adhesive sheet which concerns on this embodiment is with a base material provided with one adhesive layer formed from the adhesive composition which concerns on this embodiment, and the other adhesive layer comprised from a desired adhesive In the case of a double-sided PSA sheet, both the effect of being able to peel off from the adherend by the one PSA layer very easily and the desired effect of the other PSA layer are compatible. You can also. Thus, by combining various pressure-sensitive adhesive layers as other pressure-sensitive adhesive layers, the pressure-sensitive adhesive sheet according to this embodiment can exhibit excellent performance in various applications. Examples of the pressure-sensitive adhesive constituting the other pressure-sensitive adhesive layer include, for example, an active energy ray-curable pressure-sensitive adhesive, a pressure-sensitive adhesive that hardly causes adhesive residue on the adherend, a pressure-sensitive adhesive having excellent heat resistance, and solvent resistance. An excellent pressure-sensitive adhesive is exemplified.
〔加工物の製造方法〕
　本実施形態に係る加工物の製造方法は、前述した粘着シートを被加工物に積層する積層工程と、当該被加工物を当該粘着シート上で加工して、加工物を得る加工工程と、当該加工物に積層された当該粘着シートにおける粘着剤層に対して、活性エネルギー線の照射を行う照射工程と、当該加工物に積層された当該粘着シートにおける粘着剤層に対して、加熱を行う加熱工程と、当該照射工程および当該加熱工程を経た粘着シートを、当該加工物から剥離する剥離工程とを含む。そして、本実施形態に係る加工物の製造方法では、加熱工程を照射工程の完了後に行うか、あるいは照射工程と加熱工程とを同時に行う。 [Production method]
The manufacturing method of the workpiece according to the present embodiment includes a laminating step of laminating the above-described pressure-sensitive adhesive sheet on a workpiece, a processing step of processing the workpiece on the pressure-sensitive adhesive sheet to obtain a workpiece, Irradiation step of irradiating active energy rays to the pressure-sensitive adhesive layer in the pressure-sensitive adhesive sheet laminated on the workpiece, and heating to heat the pressure-sensitive adhesive layer in the pressure-sensitive adhesive sheet laminated on the workpiece And a peeling step of peeling the pressure-sensitive adhesive sheet that has undergone the irradiation step and the heating step from the workpiece. And in the manufacturing method of the workpiece which concerns on this embodiment, a heating process is performed after completion of an irradiation process, or an irradiation process and a heating process are performed simultaneously.
（１）積層工程
　上述した積層工程では、前述した粘着シートにおける粘着面に対し、被加工物に積層する。粘着シートが剥離シートを備える場合には、当該剥離シートを剥離して露出した粘着剤層の粘着面に対し、被加工物を積層する。ここで、被加工物としては、粘着シート上で加工されるものであれば特に限定されず、例えば、半導体ウエハ、半導体パッケージ等の半導体部材や、ガラス、セラミックグリーンシート積層体、樹脂フィルム、薄膜金属板等の脆質部材、セラミックスラリー、未硬化の封止樹脂等のような、部材を形成するための塗布液等が挙げられる。上述した半導体ウエハ等のように、被加工物が既に所定の形状を有するものである場合には、粘着シートにおける粘着面を当該被加工物に貼付することで、積層を行う。また、上述したセラミックスラリーのように、被加工物が所定の形状を未だ有していない液状のものである場合には、当該被加工物を粘着シートにおける粘着面に塗布して塗膜を形成することで、積層を行う。また、粘着シートが両面粘着シートである場合には、当該両面粘着シートにおける被加工物を積層した粘着面と反対の粘着面を支持体等に貼付してもよい。 (1) Lamination process In the lamination process mentioned above, it laminates | stacks on a to-be-processed object with respect to the adhesive surface in the adhesive sheet mentioned above. When the pressure-sensitive adhesive sheet includes a release sheet, the workpiece is laminated on the pressure-sensitive adhesive layer exposed by peeling the release sheet. Here, the workpiece is not particularly limited as long as it is processed on an adhesive sheet. For example, a semiconductor member such as a semiconductor wafer or a semiconductor package, glass, a ceramic green sheet laminate, a resin film, a thin film, or the like. Examples thereof include a brittle member such as a metal plate, a ceramic slurry, a coating solution for forming a member such as an uncured sealing resin, and the like. When the workpiece already has a predetermined shape, such as the semiconductor wafer described above, lamination is performed by sticking the adhesive surface of the adhesive sheet to the workpiece. In addition, when the workpiece is a liquid that does not yet have a predetermined shape like the ceramic slurry described above, the workpiece is applied to the adhesive surface of the adhesive sheet to form a coating film. By doing so, lamination is performed. When the pressure-sensitive adhesive sheet is a double-sided pressure-sensitive adhesive sheet, a pressure-sensitive adhesive surface opposite to the pressure-sensitive adhesive surface on which the workpieces in the double-sided pressure-sensitive adhesive sheet are laminated may be attached to a support or the like.
（２）加工工程
　貼付工程に続き、加工工程として、被加工物を粘着シート上で加工して、加工物を得る。ここで、被加工物が、半導体ウエハ、半導体パッケージ、ガラス、セラミックグリーンシート積層体等である場合には、上述した加工として、ダイシング、裏面研磨、回路形成、封止等を行い、加工物として、半導体チップといった半導体装置の一部材、半導体装置、ガラスチップ等を得る。また、被加工物が、セラミックスラリーである場合には、上述した加工として、セラミックスラリーを塗布して得られる塗膜を乾燥し、加工物としてセラミックグリーンシートを得る。 (2) Processing step Following the sticking step, as a processing step, the workpiece is processed on an adhesive sheet to obtain a processed product. Here, when the workpiece is a semiconductor wafer, a semiconductor package, glass, a ceramic green sheet laminate, etc., as the above-mentioned processing, dicing, back surface polishing, circuit formation, sealing, etc. are performed, A member of a semiconductor device such as a semiconductor chip, a semiconductor device, a glass chip, and the like are obtained. Moreover, when a to-be-processed object is a ceramic slurry, the coating film obtained by apply | coating a ceramic slurry is dried as a process mentioned above, and a ceramic green sheet is obtained as a processed object.
　本実施形態における粘着シートでは、前述した粘着剤組成物により粘着剤層が形成されていることにより、粘着剤層に対して活性エネルギーの照射や加熱を行う前においては、被加工物および加工物に対して良好な初期粘着力を発揮することができる。そのため、上述した加工の際に被加工物や加工物が移動したり、飛び散ることが抑制され、良好に加工を行うことができる。 In the pressure-sensitive adhesive sheet according to the present embodiment, the pressure-sensitive adhesive layer is formed of the above-described pressure-sensitive adhesive composition, so that before the pressure-sensitive adhesive layer is irradiated with active energy or heated, the workpiece and the processed material are processed. Good initial adhesive strength can be exhibited. Therefore, the workpiece and the workpiece are prevented from moving or scattering during the above-described processing, and the processing can be performed satisfactorily.
（３）照射工程および加熱工程
　加工工程の後、照射工程および加熱工程を行う。ここで、加熱工程は、照射工程の完了後に行ってもよく、または照射工程と加熱工程とを同時に行ってもよい。 (3) Irradiation process and heating process An irradiation process and a heating process are performed after a processing process. Here, the heating process may be performed after completion of the irradiation process, or the irradiation process and the heating process may be performed simultaneously.
（３－１）照射工程
　照射工程では、粘着シート上に加工物が積層された状態で、当該粘着シートにおける粘着剤層に対して活性エネルギー線の照射を行う。ここで、活性エネルギー線の照射は、当該活性エネルギー線に対して透過性を有する部材を介して行うことが好ましい。例えば、粘着シートが、活性エネルギー線に対して透過性を有する基材を備える片面粘着シートである場合には、当該基材を介して粘着剤層に活性エネルギー線を照射することが好ましい。また、粘着シートが両面粘着シートであり、その片方の粘着面が、活性エネルギー線に対して透過性を有する支持体に貼付されている場合には、当該支持体を介して粘着剤層に活性エネルギー線を照射することが好ましい。さらに、粘着シートが片面粘着シートおよび両面粘着シートのいずれの場合においても、当該粘着シート状に積層された加工物が活性エネルギー線に対して透過性を有する場合には、加工物を介して粘着剤層に活性エネルギー線を照射してもよい。 (3-1) Irradiation Step In the irradiation step, active energy rays are irradiated to the pressure-sensitive adhesive layer in the pressure-sensitive adhesive sheet in a state where the workpiece is laminated on the pressure-sensitive adhesive sheet. Here, the irradiation of the active energy ray is preferably performed through a member having transparency to the active energy ray. For example, when the pressure-sensitive adhesive sheet is a single-sided pressure-sensitive adhesive sheet including a base material that is permeable to active energy rays, it is preferable to irradiate the pressure-sensitive adhesive layer with the active energy rays through the base material. In addition, when the pressure-sensitive adhesive sheet is a double-sided pressure-sensitive adhesive sheet and one of the pressure-sensitive adhesive surfaces is affixed to a support that is permeable to active energy rays, the pressure-sensitive adhesive layer is activated via the support. It is preferable to irradiate energy rays. Furthermore, in the case where the pressure-sensitive adhesive sheet is either a single-sided pressure-sensitive adhesive sheet or a double-sided pressure-sensitive adhesive sheet, if the work piece laminated in the form of the pressure-sensitive adhesive sheet is permeable to active energy rays, the pressure-sensitive adhesive sheet is attached through the work piece. The agent layer may be irradiated with active energy rays.
　粘着剤層に対して活性エネルギー線を照射することで、粘着剤層中に含有される（メタ）アクリル酸エステル共重合体（Ａ）の側鎖に存在する活性エネルギー線反応性基において反応が進行する。これにより、粘着剤層が硬化し、粘着剤層の加工物に対する粘着力が低下する第一の作用が生じることとなる。 By irradiating active energy rays to the pressure-sensitive adhesive layer, the reaction occurs at the active energy ray-reactive group present in the side chain of the (meth) acrylic acid ester copolymer (A) contained in the pressure-sensitive adhesive layer. proceed. As a result, the pressure-sensitive adhesive layer is cured, and a first effect is produced in which the pressure-sensitive adhesive force of the pressure-sensitive adhesive layer on the workpiece is reduced.
　酸発生剤（Ｂ）として、活性エネルギー線の照射により酸を発生するものを使用している場合には、活性エネルギー線の照射によって、粘着剤層中に含有される酸発生剤（Ｂ）から酸が発生する。当該酸は、加熱工程の際に、（メタ）アクリル酸エステル共重合体（Ａ）が有するカルボキシ前駆基から炭化水素系ガスが放出される反応を促進する。 When an acid generator (B) that generates an acid upon irradiation with active energy rays is used, the acid generator (B) contained in the pressure-sensitive adhesive layer by irradiation with active energy rays is used. Acid is generated. The acid promotes a reaction in which a hydrocarbon-based gas is released from the carboxy precursor group of the (meth) acrylic acid ester copolymer (A) during the heating step.
　上記活性エネルギー線としては、電離放射線、すなわち紫外線、電子線などが挙げられる。これらのうちでも、比較的照射設備の導入の容易な紫外線が好ましい。 Examples of the active energy rays include ionizing radiation, that is, ultraviolet rays and electron beams. Among these, ultraviolet rays that are relatively easy to introduce irradiation equipment are preferable.
　電離放射線として紫外線を用いる場合には、取り扱いの容易さから波長２００～３８０ｎｍ程度の紫外線を含む近紫外線を用いることが好ましい。紫外線の光量は、通常５０ｍＪ／ｃｍ２以上とすることが好ましく、特に１００ｍＪ／ｃｍ２以上とすることが好ましく、さらには２００ｍＪ／ｃｍ２以上とすることが好ましい。また、紫外線の光量は、通常２０００ｍＪ／ｃｍ２以下とすることが好ましく、特に１７００ｍＪ／ｃｍ２以下とすることが好ましく、さらには１４００ｍＪ／ｃｍ２以下とすることが好ましい。紫外線の照度は、通常５０ｍＷ／ｃｍ２以上とすることが好ましく、特に１００ｍＷ／ｃｍ２以上とすることが好ましく、さらには２００ｍＷ／ｃｍ２以上とすることが好ましい。また、紫外線の照度は、通常５００ｍＷ／ｃｍ２以下とすることが好ましく、特に４５０ｍＷ／ｃｍ２以下とすることが好ましく、さらには４００ｍＷ／ｃｍ２以下とすることが好ましい。紫外線源としては特に制限はなく、例えば高圧水銀ランプ、メタルハライドランプ、ＵＶ－ＬＥＤなどが用いられる。 When ultraviolet rays are used as the ionizing radiation, near ultraviolet rays including ultraviolet rays having a wavelength of about 200 to 380 nm are preferably used for ease of handling. The amount of ultraviolet light is usually preferably 50 mJ / cm 2 or more, particularly preferably 100 mJ / cm 2 or more, and more preferably 200 mJ / cm 2 or more. Further, the amount of ultraviolet light, it is preferable to usually 2000 mJ / cm 2 or less, particularly preferably to 1700mJ / cm 2 or less, more preferably in a 1400mJ / cm 2 or less. The illuminance of ultraviolet rays is usually preferably 50 mW / cm 2 or more, particularly preferably 100 mW / cm 2 or more, and more preferably 200 mW / cm 2 or more. Further, the illuminance of ultraviolet rays, it is preferable to usually 500 mW / cm 2 or less, particularly preferably to 450 mW / cm 2 or less, more preferably in a 400 mW / cm 2 or less. The ultraviolet light source is not particularly limited, and for example, a high pressure mercury lamp, a metal halide lamp, a UV-LED, or the like is used.
　電離放射線として電子線を用いる場合、その加速電圧については、通常１０ｋＶ以上、１０００ｋＶ以下であることが好ましい。また、照射線量は、通常０．１ｋＧｙ以上、１０ｋＧｙ以下であることが好ましい。電子線源としては、特に制限はなく、例えばコックロフトワルトン型、バンデグラフト型、共振変圧器型、絶縁コア変圧器型、あるいは直線型、ダイナミトロン型、高周波型などの各種電子線加速器を用いることができる。 When an electron beam is used as the ionizing radiation, the acceleration voltage is usually preferably 10 kV or more and 1000 kV or less. Moreover, it is preferable that irradiation dose is normally 0.1 kGy or more and 10 kGy or less. The electron beam source is not particularly limited, and for example, various electron beam accelerators such as a Cockloft Walton type, a bandegraft type, a resonant transformer type, an insulated core transformer type, a linear type, a dynamitron type, and a high frequency type are used. be able to.
（３－２）加熱工程
　加熱工程では、粘着シート上に加工物が積層された状態で、粘着剤層を加熱する。加熱工程では、粘着剤層中において、（メタ）アクリル酸エステル共重合体（Ａ）が有するカルボキシ前駆基から炭化水素系ガスが放出する反応が加熱により進行する。この反応において、酸発生剤（Ｂ）に由来する酸が触媒として作用し、当該反応を促進する。ここで、酸発生剤（Ｂ）として加熱により酸を発生するものを使用している場合には、加熱工程における加熱によって、酸発生剤（Ｂ）から酸が供給される。一方、酸発生剤（Ｂ）として活性エネルギー線の照射により酸を発生するものを使用している場合には、前述の通り、照射工程における活性エネルギー線の照射により酸発生剤（Ｂ）から酸が供給される。粘着剤層から放出された炭化水素系ガスは、粘着シートにおける粘着剤層と被着体との界面に溜まり、これにより、粘着剤層と加工物との接触面積が減少する第二の作用が生じることとなる。 (3-2) Heating step In the heating step, the pressure-sensitive adhesive layer is heated in a state where the workpiece is laminated on the pressure-sensitive adhesive sheet. In the heating step, in the pressure-sensitive adhesive layer, a reaction in which the hydrocarbon gas is released from the carboxy precursor group of the (meth) acrylic acid ester copolymer (A) proceeds by heating. In this reaction, the acid derived from the acid generator (B) acts as a catalyst to promote the reaction. Here, when the acid generator (B) that generates acid by heating is used, the acid is supplied from the acid generator (B) by heating in the heating step. On the other hand, when an acid generator (B) that generates an acid upon irradiation with active energy rays is used, as described above, the acid generator (B) generates an acid by irradiation with active energy rays in the irradiation step. Is supplied. The hydrocarbon-based gas released from the pressure-sensitive adhesive layer accumulates at the interface between the pressure-sensitive adhesive layer and the adherend in the pressure-sensitive adhesive sheet, and this has the second effect of reducing the contact area between the pressure-sensitive adhesive layer and the workpiece. Will occur.
　上述した加熱のための手段としては、例えば、ホットプレート、熱風乾燥機、近赤外線ランプ、加熱ローラーなどの適当な手段を採用することができる。加熱条件としては、例えば、１００℃以上、２５０℃以下の温度で、５秒以上、３０分以下の時間加熱することが好ましい。 As the means for heating described above, suitable means such as a hot plate, a hot air dryer, a near infrared lamp, and a heating roller can be employed. As heating conditions, for example, it is preferable to heat at a temperature of 100 ° C. or higher and 250 ° C. or lower for a time of 5 seconds or longer and 30 minutes or shorter.
（４）剥離工程
　照射工程および加熱工程の完了に続き、粘着シートを加工物から剥離する。本実施形態における粘着シートは、粘着剤層が硬化して粘着力が低下する第一の作用と、炭化水素系ガスの発生によって粘着剤層と加工物との接触面積が減少する第二の作用とが相まって生じることにより、加工物から粘着シートを非常に容易に剥離することが可能となる。そのため、例えば、加工物が半導体装置（特に半導体チップ）やガラスチップである場合には、吸引コレット等の汎用手段を用いて、当該加工物を容易にピックアップすることができる。さらに、本実施形態における粘着シートは、積極的に粘着シートを引き剥がすような処理を行うことなく、自己剥離させることも可能であるため、例えば、粘着シートを上下反転させる等の処理を行って、粘着シートの自重により加工物から粘着シートを落下させたり、加工物の自重により粘着シートから加工物を落下させることもできる。 (4) Peeling process Following the completion of the irradiation process and the heating process, the pressure-sensitive adhesive sheet is peeled from the workpiece. The pressure-sensitive adhesive sheet according to the present embodiment has a first action in which the pressure-sensitive adhesive layer is cured and the pressure-sensitive adhesive force is reduced, and a second action in which the contact area between the pressure-sensitive adhesive layer and the workpiece is reduced by the generation of the hydrocarbon-based gas. When combined with the above, the pressure-sensitive adhesive sheet can be peeled off from the workpiece very easily. Therefore, for example, when the workpiece is a semiconductor device (particularly a semiconductor chip) or a glass chip, the workpiece can be easily picked up using a general-purpose means such as a suction collet. Furthermore, since the pressure-sensitive adhesive sheet in this embodiment can be self-peeled without performing a process of actively peeling off the pressure-sensitive adhesive sheet, for example, a process such as turning the pressure-sensitive adhesive sheet upside down is performed. The pressure-sensitive adhesive sheet can be dropped from the workpiece by the weight of the pressure-sensitive adhesive sheet, or the workpiece can be dropped from the pressure-sensitive adhesive sheet by the weight of the workpiece.
　また、粘着シートが両面粘着シートであり、その片方の粘着面が支持体に貼付されている場合には、粘着シートの加工物からの剥離とともに、当該粘着シートの支持体からの剥離を行ってもよい。ここで、加工物からの剥離および支持体からの剥離を行う順番としては特に限定されず、また同時に行ってもよい。本実施形態に係る粘着シートによれば、支持体からの剥離も、加工物からの剥離と同様に、非常に容易に行うことができる。粘着シートの支持体から剥離は、手動または汎用手段を用いて、支持体から粘着シートを取り除くことで行ってもよく、あるいは、上述したように、粘着シートの自重により支持体から落下させることで行ってもよい。 In addition, when the pressure-sensitive adhesive sheet is a double-sided pressure-sensitive adhesive sheet, and one of the pressure-sensitive adhesive surfaces is affixed to the support, the pressure-sensitive adhesive sheet is peeled off from the workpiece and peeled off from the support. Also good. Here, the order of peeling from the workpiece and peeling from the support is not particularly limited, and may be performed simultaneously. According to the pressure-sensitive adhesive sheet according to this embodiment, peeling from the support can be performed very easily, as is peeling from the workpiece. Peeling from the support of the pressure-sensitive adhesive sheet may be performed by removing the pressure-sensitive adhesive sheet from the support using manual or general-purpose means, or, as described above, by dropping from the support due to the weight of the pressure-sensitive adhesive sheet. You may go.
　以上のように、本実施形態に係る加工物の製造方法では、活性エネルギー線の照射および加熱によって、粘着シートを加工物から非常に容易に剥離することが可能であるため、優れた性能を有する加工物を効率的に製造することが可能となる。 As described above, the method for manufacturing a workpiece according to the present embodiment has excellent performance because the adhesive sheet can be peeled off from the workpiece very easily by irradiation with active energy rays and heating. A workpiece can be efficiently manufactured.
　以上説明した実施形態は、本発明の理解を容易にするために記載されたものであって、本発明を限定するために記載されたものではない。したがって、上記実施形態に開示された各要素は、本発明の技術的範囲に属する全ての設計変更や均等物をも含む趣旨である。 The embodiment described above is described for facilitating understanding of the present invention, and is not described for limiting the present invention. Therefore, each element disclosed in the above embodiment is intended to include all design changes and equivalents belonging to the technical scope of the present invention.
　以下、実施例等により本発明をさらに具体的に説明するが、本発明の範囲はこれらの実施例等に限定されるものではない。 Hereinafter, the present invention will be described more specifically with reference to examples and the like, but the scope of the present invention is not limited to these examples and the like.
〔実施例１〕
　ｎ－ブチルアクリレート１０質量部と、２－エチルヘキシルアクリレート３５質量部と、ｔｅｒｔ－ブチルアクリレート４５質量部と、２－ヒドロキシエチルアクリレート１０質量部とを共重合し、アクリル系共重合体（ＡＰ）を得た。このアクリル系共重合体（ＡＰ）と、活性エネルギー線反応性基含有化合物（ＡＣ）としてのメタクリロイルオキシエチルイソシアネート（ＭＯＩ）とを、ＭＯＩの反応量がアクリル系共重合体１００ｇ当たり１０．７ｇ（アクリル系共重合体（ＡＰ）中の２－ヒドロキシエチルアクリレート単位１００モル当たり８０モル（８０モル％））となるように反応させて、（メタ）アクリル酸エステル共重合体（Ａ）を得た。なお、（メタ）アクリル酸エステル共重合体（Ａ）の質量平均分子量を、後述する方法にて測定したところ、５０万であった。 [Example 1]
10 parts by mass of n-butyl acrylate, 35 parts by mass of 2-ethylhexyl acrylate, 45 parts by mass of tert-butyl acrylate, and 10 parts by mass of 2-hydroxyethyl acrylate were copolymerized to obtain an acrylic copolymer (AP). Obtained. This acrylic copolymer (AP) and methacryloyloxyethyl isocyanate (MOI) as the active energy ray-reactive group-containing compound (AC) are mixed at a rate of MOI of 10.7 g per 100 g of acrylic copolymer (MOI). (Meth) acrylic acid ester copolymer (A) was obtained by reacting to 80 mol (80 mol%) per 100 mol of 2-hydroxyethyl acrylate units in the acrylic copolymer (AP). . In addition, it was 500,000 when the mass mean molecular weight of the (meth) acrylic acid ester copolymer (A) was measured by the method mentioned later.
　得られた（メタ）アクリル酸エステル共重合体（Ａ）１００質量部（固形分換算；以下同じ）と、酸発生剤（Ｂ）としての１，８－ナフタルイミドトリフルオロメタンスルホン酸エステル３質量部と、光開始剤（Ｃ）としての１－ヒドロキシシクロヘキシルフェニルケトン（ＢＡＳＦ社製，製品名「イルガキュア１８４」）３質量部と、架橋剤（Ｄ）としてのトリメチロールプロパン変性トリレンジイソシアネート（東ソー株式会社製，製品名「コロネートＬ」）０．５質量部とを溶媒としてのメチルエチルケトン中で混合し、粘着剤組成物の塗布液を得た。 100 parts by mass of the (meth) acrylic acid ester copolymer (A) obtained (in terms of solid content; the same shall apply hereinafter) and 3 parts by mass of 1,8-naphthalimide trifluoromethanesulfonic acid ester as the acid generator (B) 3 parts by mass of 1-hydroxycyclohexyl phenyl ketone (product name “Irgacure 184” manufactured by BASF) as a photoinitiator (C), and trimethylolpropane-modified tolylene diisocyanate (Tosoh Corporation) as a crosslinking agent (D) 0.5 parts by mass of a product manufactured by the company, product name “Coronate L”) was mixed in methyl ethyl ketone as a solvent to obtain a coating solution of the pressure-sensitive adhesive composition.
　得られた塗布液を、ポリエチレンテレフタレートフィルムの一方の主面がシリコーン系剥離剤によって剥離処理されてなる剥離シート（リンテック株式会社製，製品名「ＳＰ－ＰＥＴ３８１０３１」）の剥離処理面上に塗布し、１００℃で２分間加熱することで乾燥させて、厚さ２５μｍの粘着剤層を形成した。 The obtained coating solution was applied onto the release-treated surface of a release sheet (product name “SP-PET381031” manufactured by Lintec Corporation) in which one main surface of the polyethylene terephthalate film was release-treated with a silicone-based release agent. And dried by heating at 100 ° C. for 2 minutes to form an adhesive layer having a thickness of 25 μm.
　次に、上記粘着剤層における剥離シートとは反対側の面と、基材としての易接着層付きポリエステルフィルム（東洋紡株式会社製，製品名「コスモシャインＡ４３００」，厚さ：５０μｍ）の易接着層側の面とを貼合した後、温度２３℃、相対湿度５０％の環境下で１６８時間シーズニングを行うことで、基材、粘着剤層および剥離シートが順に積層してなる粘着シートを得た。 Next, easy adhesion of the surface of the pressure-sensitive adhesive layer opposite to the release sheet and a polyester film with an easy-adhesion layer as a substrate (product name “Cosmo Shine A4300”, thickness: 50 μm, manufactured by Toyobo Co., Ltd.) After laminating the surface on the layer side, by performing seasoning for 168 hours in an environment of a temperature of 23 ° C. and a relative humidity of 50%, a pressure-sensitive adhesive sheet in which a base material, a pressure-sensitive adhesive layer, and a release sheet are sequentially laminated is obtained. It was.
　ここで、上述した質量平均分子量（Ｍｗ）は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）を用いて以下の条件で測定（ＧＰＣ測定）したポリスチレン換算の質量平均分子量である。
＜測定条件＞
・ＧＰＣ測定装置：東ソー株式会社製，ＨＬＣ－８０２０
・カラム　　：「ＴＳＫ　ｇｕａｒｄ　ｃｏｌｕｍｎ　ＨＸＬ－Ｌ」、「ＴＳＫ　ｇｅｌ　Ｇ２５００ＨＸＬ」、「ＴＳＫ　ｇｅｌ　Ｇ２０００ＨＸＬ」、「ＴＳＫ　ｇｅｌ　Ｇ１０００ＨＸＬ」（いずれも東ソー株式会社製）を順次連結したもの
・カラム温度：４０℃
・展開溶媒　：テトラヒドロフラン
・流速　　　：１．０ｍＬ／ｍｉｎ
・検出器　　：示差屈折計
・標準試料　：ポリスチレン Here, the above-mentioned mass average molecular weight (Mw) is a polystyrene-reduced mass average molecular weight measured under the following conditions (GPC measurement) using gel permeation chromatography (GPC).
<Measurement conditions>
・ GPC measuring device: HLC-8020 manufactured by Tosoh Corporation
Column: “TSK guard column HXL-L”, “TSK gel G2500HXL”, “TSK gel G2000HXL”, “TSK gel G1000HXL” (all manufactured by Tosoh Corporation) • Column temperature: 40 ° C.
・ Developing solvent: Tetrahydrofuran ・ Flow rate: 1.0 mL / min
・ Detector: Differential refractometer ・ Standard sample: Polystyrene
〔実施例２～３，比較例１～３〕
　アクリル系共重合体（ＡＰ）を構成するモノマーの割合、活性エネルギー線反応性基含有化合物（ＡＣ）の使用量、ならびに酸発生剤（Ｂ）、光開始剤（Ｃ）および架橋剤（Ｄ）の含有量を表１に示すように変更したこと以外、実施例１と同様にして粘着シートを得た。 [Examples 2 to 3, Comparative Examples 1 to 3]
Ratio of monomer constituting acrylic copolymer (AP), amount of active energy ray-reactive group-containing compound (AC) used, and acid generator (B), photoinitiator (C) and crosslinking agent (D) A pressure-sensitive adhesive sheet was obtained in the same manner as in Example 1 except that the content of was changed as shown in Table 1.
〔実施例４～７，比較例４〕
　アクリル系共重合体（ＡＰ）を構成するモノマーの組成を表２に示すように変更したこと以外、実施例１と同様にして粘着シートを得た。 [Examples 4-7, Comparative Example 4]
A pressure-sensitive adhesive sheet was obtained in the same manner as in Example 1 except that the composition of the monomer constituting the acrylic copolymer (AP) was changed as shown in Table 2.
〔試験例１〕（粘着力の測定）
　実施例および比較例で製造した粘着シートを裁断し、幅２５ｍｍ×長さ１００ｍｍの試験片を得た。当該試験片から剥離シートを剥離し、露出した粘着面を、２３℃、５０％ＲＨ（相対湿度）の環境下で、ステンレス板（３６０番研磨済みのＳＵＳ３０４）における研磨面に貼付し、同環境下に２４時間静置した。これにより、測定用サンプルを得た。 [Test Example 1] (Measurement of adhesive strength)
The pressure-sensitive adhesive sheets produced in the examples and comparative examples were cut to obtain test pieces having a width of 25 mm and a length of 100 mm. The release sheet was peeled from the test piece, and the exposed adhesive surface was affixed to the polished surface of a stainless steel plate (SUS304 polished SUS304) in an environment of 23 ° C. and 50% RH (relative humidity). It was left to stand for 24 hours. Thereby, a sample for measurement was obtained.
　この測定用サンプルについて、ＪＩＳ　Ｚ０２３７；２０００に準じ、万能型引張試験機（オリエンテック株式会社製，ＴＥＮＳＩＬＯＮ／ＵＴＭ－４－１００）を用いて、剥離速度３００ｍｍ／分、剥離角度１８０°にてステンレス板から粘着シートを剥離し、そのときに測定される粘着力をＵＶ照射前の粘着力（Ｎ／２５ｍｍ）とした。結果を表１および表２に示す。 This measurement sample was made of stainless steel according to JIS Z0237; 2000 using a universal tensile tester (Orientec Co., Ltd., TENSILON / UTM-4-100) at a peeling speed of 300 mm / min and a peeling angle of 180 °. The adhesive sheet was peeled from the plate, and the adhesive strength measured at that time was defined as the adhesive strength before UV irradiation (N / 25 mm). The results are shown in Tables 1 and 2.
　また、上記と同様に作製した測定用サンプルについて、紫外線照射装置（リンテック株式会社製，製品名「ＲＡＤ－２０００」）を用いて、基材を介して粘着剤層に対して紫外線（ＵＶ）照射（照度：３００ｍＷ／ｃｍ２，光量：１２００ｍＪ／ｃｍ２）を行い、粘着剤層を硬化させた。そして、上記同様の条件にて、粘着シートの粘着力を測定し、これをＵＶ照射後の粘着力（Ｎ／２５ｍｍ）とした。結果を表１および表２に示す。 In addition, the measurement sample produced in the same manner as above was irradiated with ultraviolet (UV) light on the adhesive layer through the substrate using an ultraviolet irradiation device (product name “RAD-2000” manufactured by Lintec Corporation). (Illuminance: 300 mW / cm 2 , light quantity: 1200 mJ / cm 2 ) was performed to cure the pressure-sensitive adhesive layer. And the adhesive force of the adhesive sheet was measured on the same conditions as the above, and this was made into the adhesive force (N / 25mm) after UV irradiation. The results are shown in Tables 1 and 2.
〔試験例２〕（自己剥離性の評価）
　試験例１と同様に作製した測定用サンプルについて、紫外線照射装置（リンテック株式会社製，製品名「ＲＡＤ－２０００」）を用いて、基材を介して粘着剤層に対して紫外線（ＵＶ）照射（照度：３００ｍＷ／ｃｍ２，光量：１２００ｍＪ／ｃｍ２）を行い、粘着剤層を硬化させた。 [Test Example 2] (Evaluation of self-peeling property)
The measurement sample produced in the same manner as in Test Example 1 was irradiated with ultraviolet rays (UV) to the adhesive layer through the substrate using an ultraviolet irradiation device (product name “RAD-2000” manufactured by Lintec Corporation). (Illuminance: 300 mW / cm 2 , light quantity: 1200 mJ / cm 2 ) was performed to cure the pressure-sensitive adhesive layer.
　続いて、測定用サンプルを、オーブン内にて１５０℃で１０分間加熱した後、室温環境下に放置した。なお、オーブンでの加熱および放置の際には、測定用サンプルにおける粘着シート側の面が常に上側となるように取り扱った。 Subsequently, the measurement sample was heated in an oven at 150 ° C. for 10 minutes and then left in a room temperature environment. In addition, when heating and leaving in an oven, the measurement sample was handled so that the surface on the pressure-sensitive adhesive sheet side was always on the upper side.
　測定用サンプルが室温まで冷却した後、測定用サンプルを持ち上げ、さらにステンレス板を支えた状態で、粘着シート側の面とステンレス板側の面とを反転させて、粘着シート側の面が下側となるようにした。その際の粘着シートの状態について、以下の基準に基づいて、粘着シートの自己剥離性を評価した。結果を表１および表２に示す。
　Ａ：粘着シートが落下した。
　Ｂ：粘着シートが落下しなかったものの、粘着シートとステンレス板との界面において、気泡による浮きおよび剥がれの少なくとも一方が生じた。
　Ｆ：粘着シートが落下せず、且つ、粘着シートとステンレス板との界面において、気泡による浮きおよび剥がれの両方が生じなかった。 After the measurement sample is cooled to room temperature, lift the measurement sample and support the stainless steel plate. Invert the surface on the adhesive sheet side and the surface on the stainless steel plate side. It was made to become. About the state of the adhesive sheet in that case, self-peelability of the adhesive sheet was evaluated based on the following criteria. The results are shown in Tables 1 and 2.
A: The adhesive sheet fell.
B: Although the adhesive sheet did not fall, at least one of floating and peeling due to bubbles occurred at the interface between the adhesive sheet and the stainless steel plate.
F: The pressure-sensitive adhesive sheet did not fall, and neither floating nor peeling due to bubbles occurred at the interface between the pressure-sensitive adhesive sheet and the stainless steel plate.
　なお、表１および表２に記載の略号等の詳細は以下の通りである。
　ＢＡ：ｎ－ブチルアクリレート
　２ＥＨＡ：２－エチルヘキシルアクリレート
　ｔ－ＢＡ：ｔｅｒｔ－ブチルアクリレート
　ＨＥＡ：２－ヒドロキシエチルアクリレート
　ＭＯＩ：２－メタクリロイルオキシエチルイソシアネート Details of the abbreviations described in Table 1 and Table 2 are as follows.
BA: n-butyl acrylate 2EHA: 2-ethylhexyl acrylate t-BA: tert-butyl acrylate HEA: 2-hydroxyethyl acrylate MOI: 2-methacryloyloxyethyl isocyanate
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　表１および表２から分かるように、実施例で得られた粘着シートは、活性エネルギー線の照射および加熱によって、優れた自己剥離性を発揮するものとなり、非常に簡単に剥離することが可能であった。 As can be seen from Table 1 and Table 2, the pressure-sensitive adhesive sheets obtained in the examples exhibit excellent self-peelability by irradiation with active energy rays and heating, and can be peeled off very easily. there were.
　本発明に係る粘着シートは、脆質部材や半導体部材等の加工のために使用することができる。 The pressure-sensitive adhesive sheet according to the present invention can be used for processing brittle members and semiconductor members.

Claims (12)

  1. 　重合体を構成するモノマー単位として、アルキル基の炭素数が１～１２の（メタ）アクリル酸アルキルエステル（ａ１）および加熱により炭化水素系ガスを放出してカルボキシ基に変化するカルボキシ前駆基を有するカルボキシ前駆基含有モノマー（ａ２）を含むとともに、側鎖に活性エネルギー線反応性基を有する（メタ）アクリル酸エステル共重合体（Ａ）と、
    　活性エネルギー線の照射および加熱の少なくとも一方により酸を発生する酸発生剤（Ｂ）と、
    　光開始剤（Ｃ）と
    を含有することを特徴とする粘着剤組成物。     The monomer unit constituting the polymer has a (meth) acrylic acid alkyl ester (a1) having 1 to 12 carbon atoms in the alkyl group and a carboxy precursor group that changes into a carboxy group by releasing a hydrocarbon-based gas upon heating. A (meth) acrylic acid ester copolymer (A) having a carboxy precursor group-containing monomer (a2) and having an active energy ray-reactive group in the side chain;
    An acid generator (B) that generates an acid by at least one of irradiation with active energy rays and heating;
    A pressure-sensitive adhesive composition comprising a photoinitiator (C).
  2. 　前記（メタ）アクリル酸エステル共重合体（Ａ）は、重合体を構成するモノマー単位として、ヒドロキシ基含有モノマー（ａ３）を含むことを特徴とする請求項１に記載の粘着剤組成物。 The pressure-sensitive adhesive composition according to claim 1, wherein the (meth) acrylic acid ester copolymer (A) includes a hydroxy group-containing monomer (a3) as a monomer unit constituting the polymer.
  3. 　前記カルボキシ前駆基含有モノマー（ａ２）は、第二級炭素原子を有するアルキル基の第二級炭素原子と（メタ）アクリロイルオキシ基とが結合した構造を有する（メタ）アクリル酸アルキルエステル、第三級炭素原子を有するアルキル基の第三級炭素原子と（メタ）アクリロイルオキシ基とが結合した構造を有する（メタ）アクリル酸アルキルエステル、およびベンジル（メタ）アクリレートの少なくとも一種であることを特徴とする請求項１または２に記載の粘着剤組成物。 The carboxy precursor group-containing monomer (a2) is a (meth) acrylic acid alkyl ester having a structure in which a secondary carbon atom of an alkyl group having a secondary carbon atom and a (meth) acryloyloxy group are bonded. It is at least one of (meth) acrylic acid alkyl ester having a structure in which a tertiary carbon atom of a alkyl group having a secondary carbon atom and a (meth) acryloyloxy group are bonded, and benzyl (meth) acrylate The pressure-sensitive adhesive composition according to claim 1 or 2.
  4. 　前記カルボキシ前駆基含有モノマー（ａ２）は、ｓｅｃ－ブチル（メタ）アクリレート、イソプロピル（メタ）アクリレート、ｓｅｃ－ヘキシル（メタ）アクリレート、ｓｅｃ－オクチル（メタ）アクリレート、ｓｅｃ－ノニル（メタ）アクリレート、ｓｅｃ－デシル（メタ）アクリレート、ボルニル（メタ）アクリレート、イソボルニル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、ｔｅｒｔ－ブチル（メタ）アクリレート、ｔｅｒｔ－ヘキシル（メタ）アクリレート、ｔｅｒｔ－オクチル（メタ）アクリレート、ｔｅｒｔ－ノニル（メタ）アクリレート、ｔｅｒｔ－デシル（メタ）アクリレート、２－メチル－２－アダマンチル（メタ）アクリレート、２－エチル－２－アダマンチル（メタ）アクリレート、およびベンジル（メタ）アクリレートからなる群から選択される少なくとも一種であることを特徴とする請求項１～３のいずれか一項に記載の粘着剤組成物。 The carboxy precursor group-containing monomer (a2) includes sec-butyl (meth) acrylate, isopropyl (meth) acrylate, sec-hexyl (meth) acrylate, sec-octyl (meth) acrylate, sec-nonyl (meth) acrylate, sec -Decyl (meth) acrylate, bornyl (meth) acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, tert-butyl (meth) acrylate, tert-hexyl (meth) acrylate, tert-octyl (meth) acrylate, tert Nonyl (meth) acrylate, tert-decyl (meth) acrylate, 2-methyl-2-adamantyl (meth) acrylate, 2-ethyl-2-adamantyl (meth) acrylate, and Jill (meth) pressure-sensitive adhesive composition according to any one of claims 1 to 3, characterized in that at least one selected from the group consisting of acrylate.
  5. 　前記（メタ）アクリル酸エステル共重合体（Ａ）は、当該重合体を構成するモノマー単位として、前記カルボキシ前駆基含有モノマー（ａ２）を１質量％以上、７５質量％以下の割合で含有することを特徴とする請求項１～４のいずれか一項に記載の粘着剤組成物。 The (meth) acrylic acid ester copolymer (A) contains the carboxy precursor group-containing monomer (a2) as a monomer unit constituting the polymer in a proportion of 1% by mass to 75% by mass. The pressure-sensitive adhesive composition according to any one of claims 1 to 4, wherein:
  6. 　前記（メタ）アクリル酸エステル共重合体（Ａ）は、前記（メタ）アクリル酸アルキルエステル（ａ１）の少なくとも一種として、２－エチルヘキシルアクリレートを含むことを特徴とする請求項１～５のいずれか一項に記載の粘着剤組成物。 6. The (meth) acrylic acid ester copolymer (A) contains 2-ethylhexyl acrylate as at least one of the (meth) acrylic acid alkyl ester (a1). The pressure-sensitive adhesive composition according to one item.
  7. 　請求項１～６のいずれか一項に記載の粘着剤組成物から形成された粘着剤層を備えることを特徴とする粘着シート。 A pressure-sensitive adhesive sheet comprising a pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition according to any one of claims 1 to 6.
  8. 　前記粘着剤層の厚さは、１μｍ以上、６０μｍ以下であることを特徴とする請求項７に記載の粘着シート。 The pressure-sensitive adhesive sheet according to claim 7, wherein the pressure-sensitive adhesive layer has a thickness of 1 µm or more and 60 µm or less.
  9. 　脆質部材の加工のために使用されることを特徴とする請求項７または８に記載の粘着シート。 The pressure-sensitive adhesive sheet according to claim 7 or 8, which is used for processing a brittle member.
  10. 　半導体加工のために使用されることを特徴とする請求項７～９のいずれか一項に記載の粘着シート。 The pressure-sensitive adhesive sheet according to any one of claims 7 to 9, wherein the pressure-sensitive adhesive sheet is used for semiconductor processing.
  11. 　請求項７～１０のいずれか一項に記載の粘着シートを被加工物に積層する積層工程と、
    　前記被加工物を前記粘着シート上で加工して、加工物を得る加工工程と、
    　前記加工物に積層された前記粘着シートにおける前記粘着剤層に対して、活性エネルギー線の照射を行う照射工程と、
    　前記加工物に積層された前記粘着シートにおける前記粘着剤層に対して、加熱を行う加熱工程と、
    　前記照射工程および前記加熱工程を経た前記粘着シートを、前記加工物から剥離する剥離工程と
    を含む加工物の製造方法であって、
    　前記加熱工程を前記照射工程の完了後に行うか、あるいは前記照射工程と前記加熱工程とを同時に行うことを特徴とする加工物の製造方法。     A laminating step of laminating the pressure-sensitive adhesive sheet according to any one of claims 7 to 10 on a workpiece;
    Processing the workpiece on the pressure-sensitive adhesive sheet to obtain a workpiece; and
    An irradiation step of irradiating active energy rays to the pressure-sensitive adhesive layer in the pressure-sensitive adhesive sheet laminated on the workpiece,
    A heating step of heating the pressure-sensitive adhesive layer in the pressure-sensitive adhesive sheet laminated on the workpiece;
    A process for producing a workpiece including a peeling step of peeling the pressure-sensitive adhesive sheet that has undergone the irradiation step and the heating step from the workpiece,
    The method for manufacturing a workpiece, wherein the heating step is performed after the irradiation step is completed, or the irradiation step and the heating step are performed simultaneously.
  12. 　前記加工物は、半導体装置または半導体装置の一部材であることを特徴とする請求項１１に記載の加工物の製造方法。 12. The method of manufacturing a workpiece according to claim 11, wherein the workpiece is a semiconductor device or a member of a semiconductor device.
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