WO2025005046A1 - 活性エネルギー線硬化型粘着剤組成物及び粘着シート - Google Patents

活性エネルギー線硬化型粘着剤組成物及び粘着シート Download PDF

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WO2025005046A1
WO2025005046A1 PCT/JP2024/022821 JP2024022821W WO2025005046A1 WO 2025005046 A1 WO2025005046 A1 WO 2025005046A1 JP 2024022821 W JP2024022821 W JP 2024022821W WO 2025005046 A1 WO2025005046 A1 WO 2025005046A1
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mass
acrylic
meth
adhesive
active energy
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English (en)
French (fr)
Japanese (ja)
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伸幸 竹谷
一樹 大房
祐介 橋本
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Toagosei Co Ltd
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Toagosei Co Ltd
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Priority to KR1020257041872A priority Critical patent/KR20260029440A/ko
Priority to CN202480039939.0A priority patent/CN121399220A/zh
Priority to JP2025530120A priority patent/JPWO2025005046A1/ja
Publication of WO2025005046A1 publication Critical patent/WO2025005046A1/ja
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • 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
    • C09J133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • 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
    • 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]

Definitions

  • Adhesives are processed into various forms such as tapes and labels, and are used in a wide range of applications.
  • adhesive sheets are also used in the semiconductor device manufacturing process to improve the ease of handling during semiconductor manufacturing and to further improve the performance of semiconductor elements (see, for example, Patent Document 1 and Patent Document 2).
  • Patent Document 1 discloses a heat-resistant temporary adhesive tape having an adhesive layer formed from an adhesive layer-forming material that contains an acrylic polymer, an energy ray-polymerizable oligomer, a polymerization initiator, and a crosslinking agent, and in which the weight loss rate of the polymerization initiator as determined by thermogravimetry is equal to or less than a predetermined value.
  • Patent Document 2 discloses an adhesive tape having an adhesive layer that contains a (meth)acrylic polymer and a photopolymerization initiator that has a molar absorption coefficient at a wavelength of 385 nm equal to or greater than a predetermined value. These adhesive tapes are used for the purposes of temporary fixing and surface protection of electronic components, and when fixing of electronic components and surface protection are no longer required, their adhesive strength is weakened by irradiation with active energy rays, making them easily peelable.
  • FOWLP Fluorescence Injection Layer
  • 3D-IC three-dimensional integrated semiconductor
  • an adhesive tape is attached to a support substrate such as glass, a semiconductor chip is placed on the adhesive layer of the adhesive tape to temporarily fix the semiconductor chip to the support substrate, and then various lamination processes are carried out to form a laminate on the support substrate, after which the laminate including the semiconductor chip is peeled off from the support substrate.
  • This method makes it possible to further reduce the thickness and improve the performance of semiconductor devices while improving the handleability during semiconductor manufacturing.
  • a method of peeling off a laminate including a semiconductor chip from a support substrate using active energy rays and weakening the adhesive strength of the adhesive layer by irradiating the active energy rays can simplify the peeling process and is also useful industrially.
  • Adhesive tapes used in the above-mentioned semiconductor manufacturing processes are required to exhibit high adhesion to the adherend when forming a laminate on a support substrate, while at the same time being required to be able to easily peel the laminate including the semiconductor chip from the support substrate when peeling the laminate from the support substrate.
  • the semiconductor manufacturing process may involve high-temperature heat treatment, for example at or above 200°C, and adhesive tapes used in the semiconductor manufacturing process are required to have excellent heat resistance, being resistant to lifting or foaming even during high-temperature heat treatment.
  • the present disclosure has been made in consideration of the above circumstances, and one of its objectives is to provide an active energy ray-curable adhesive composition that exhibits easy peelability when irradiated with active energy rays and is capable of forming an adhesive layer that has excellent heat resistance. Another objective is to provide an adhesive sheet that exhibits easy peelability when irradiated with active energy rays and has excellent heat resistance.
  • the present inventors have conducted extensive research to solve the above problems, and have focused on promoting the formation of a crosslinked structure by irradiation with active energy rays, thereby making the adhesive layer easier to peel. Based on this focus, they have discovered that when a specific structure is introduced into the polymer, it is possible to improve the ease of peeling while ensuring the heat resistance of the adhesive layer.
  • the present disclosure provides the following active energy ray-curable adhesive composition and adhesive sheet.
  • An active energy ray-curable pressure-sensitive adhesive composition comprising an acrylic adhesive polymer (A) that does not contain a compound having two or more reactive unsaturated bonds in one molecule, and has at least one group selected from the group consisting of an ether group, a hydroxyl group, an aliphatic tertiary carbon, a secondary amino group, and a tertiary amino group, in a side chain, wherein the acrylic adhesive polymer (A) contains a structural unit (U1) having a hydrogen abstraction type photopolymerization initiator structure, the content of the structural unit (U1) in the acrylic adhesive polymer (A) is 0.1 mass% or more and 50 mass% or less with respect to all structural units of the acrylic adhesive polymer (A), and the content of a crosslinking agent is 0 part by mass or more and 3 parts by mass or less with respect to 100 parts by mass of the content of the acrylic adhesive polymer (A).
  • the acrylic adhesive polymer (A) contains a structural unit (U2) derived from a (meth)acrylic monomer having at least one selected from the group consisting of an ether group, a hydroxyl group, an aliphatic tertiary carbon (excluding the carbon atom constituting the carbon-carbon double bond in a methacryloyl group), a secondary amino group, and a tertiary amino group, and the content of the structural unit (U2) in the acrylic adhesive polymer (A) is 10 mass% or more based on the total structural units of the acrylic adhesive polymer (A).
  • a structural unit (U2) derived from a (meth)acrylic monomer having at least one selected from the group consisting of an ether group, a hydroxyl group, an aliphatic tertiary carbon (excluding the carbon atom constituting the carbon-carbon double bond in a methacryloyl group), a secondary amino group, and a tertiary amino group and the content of the structural unit (U2) in
  • a pressure-sensitive adhesive sheet comprising a pressure-sensitive adhesive layer formed from the active energy ray-curable pressure-sensitive adhesive composition according to any one of [1] to [8].
  • the pressure-sensitive adhesive layer has a weight loss rate of 5% by weight or less at 200°C, as measured by thermogravimetry under conditions of a heating rate of 20°C/min and a heating range of 25 to 350°C.
  • an adhesive layer and adhesive sheet that can be easily peeled off from an adherend by irradiating it with active energy rays and that has excellent heat resistance.
  • FIG. 1 is a diagram showing an example of a pressure-sensitive adhesive sheet.
  • FIG. 2 is a diagram showing an example of a method of using the adhesive sheet.
  • (meth)acrylic means acrylic and/or methacrylic.
  • (meth)acrylate means acrylate and/or methacrylate.
  • the active energy ray curable pressure-sensitive adhesive composition of the present disclosure (hereinafter also referred to as "the composition") is a pressure-sensitive adhesive composition that contains an acrylic adhesive polymer (A) having a hydrogen abstraction type photopolymerization initiator structure, has a crosslinking agent content within a predetermined range, and does not contain a compound having two or more reactive unsaturated bonds in one molecule (hereinafter also referred to as "reactive unsaturated compound").
  • the pressure-sensitive adhesive layer formed by the composition has high adhesive strength when bonded to an adherend, but the adhesive strength is reduced by irradiating the pressure-sensitive adhesive layer with active energy rays after bonding the pressure-sensitive adhesive layer to the adherend, and the pressure-sensitive adhesive layer exhibits easy peelability.
  • the acrylic adhesive polymer (A) contained in the composition and the components blended as necessary will be described below.
  • the acrylic adhesive polymer (A) is a polymer mainly composed of structural units derived from (meth)acrylic monomers, and has adhesive properties.
  • the term "mainly composed of” the acrylic adhesive polymer (A) is used to mean that the proportion of structural units derived from (meth)acrylic monomers is preferably 50% by mass or more with respect to all structural units derived from monomers constituting the acrylic adhesive polymer (A) (hereinafter also referred to as "total structural units” or “total monomer units”).
  • the proportion of structural units derived from (meth)acrylic monomers is more preferably 60% by mass or more, even more preferably 70% by mass or more, and even more preferably 80% by mass or more.
  • the acrylic adhesive polymer (A) is a polymer having a hydrogen abstraction type photopolymerization initiator structure in its side chain, and includes a structural unit having a hydrogen abstraction type photopolymerization initiator structure (hereinafter also referred to as "structural unit (U1)").
  • the hydrogen abstraction type photopolymerization initiator structure of the structural unit (U1) is a structure derived from a compound (i.e., a hydrogen abstraction type photopolymerization initiator) that generates radicals by abstracting hydrogen from other molecules when irradiated with active energy rays.
  • active energy rays include ultraviolet rays, visible rays, and electron beams, and ultraviolet rays or electron beams are preferred.
  • hydrogen abstraction type photopolymerization initiator structure possessed by the structural unit (U1) a structure derived from a known hydrogen abstraction type radical polymerization initiator can be adopted.
  • hydrogen abstraction type photopolymerization initiators include benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2,4,6-trimethylbenzophenone, 4-phenylbenzophenone, 4-(methylphenylthio)phenylphenylmethane, methyl-2-benzophenone, 1-[4-(4-benzoylphenylsulfanyl)phenyl]-2-methyl-2-(4-methylphenylsulfonyl)propan-1-one, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, and 4-methoxy-4' -Dimethylaminobenzophenone and the like benzophenones; thioxanthone, 2-
  • the structural unit (U1) may also have a structure derived from a commercially available hydrogen abstraction type photopolymerization initiator, for example, under the trade names OMNIPOL BP, OMNIPOL TX, OMNIRAD ASA, OMNIRAD 4PBZ, OMNIRAD 2702, OMBBB, OMNIRAD BMS, OMNIRAD EMK, OMNIRAD DETX, OMNIRAD ITX, OMNIRAD EDB, OMNIRAD EHA, OMNIRAD BP Flasks, OMNIRAD 4MBZ Flasks, and ESACURE 3644 (all manufactured by IGM RESINS).
  • a commercially available hydrogen abstraction type photopolymerization initiator for example, under the trade names OMNIPOL BP, OMNIPOL TX, OMNIRAD ASA, OMNIRAD 4PBZ, OMNIRAD 2702, OMBBB, OMNIRAD BMS, OMNIRAD EMK, OMNIRAD DETX,
  • the structural unit (U1) is preferably a structural unit having a benzophenone skeleton, in terms of high efficiency in generating radicals when irradiated with active energy rays and excellent heat resistance.
  • the structural unit (U1) can be a structural unit derived from a (meth)acrylic monomer having a hydrogen abstraction type photopolymerization initiator structure.
  • a (meth)acrylic monomer is available as a commercial product.
  • a specific example is the product name MBP (manufactured by Shinryo Corporation).
  • the content of the structural unit (U1) is 0.1% by mass or more and 50% by mass or less with respect to the total structural units of the acrylic adhesive polymer (A). If the content of the structural unit (U1) is less than 0.1% by mass, there is a concern that the crosslinked structure using the acrylic adhesive polymer (A) may not be sufficiently formed when irradiated with active energy rays. For this reason, the content of the structural unit (U1) is preferably 0.5% by mass or more, more preferably 1% by mass or more, with respect to the total structural units of the acrylic adhesive polymer (A).
  • the content of the structural unit (U1) is preferably 40 mass% or less, more preferably 35 mass% or less, even more preferably 30 mass% or less, even more preferably 20 mass% or less, and even more preferably 15 mass% or less, based on the total structural units of the acrylic adhesive polymer (A).
  • the structural unit (U1) one type may be used alone, or two or more types may be used in combination.
  • the acrylic adhesive polymer (A) has at least one group selected from the group consisting of an ether group, a hydroxyl group, an aliphatic tertiary carbon, a secondary amino group, and a tertiary amino group in the side chain, together with the structural unit (U1). It is believed that by forming an adhesive layer using such an acrylic adhesive polymer (A) and irradiating the adhesive layer with active energy rays, hydrogen is extracted from the side chain portion of the acrylic adhesive polymer (A), and a crosslinked structure is formed via the hydrogen extraction portion.
  • radicals are generated in the adhesive layer due to the hydrogen abstraction type photopolymerization initiator structure in the structural unit (U1).
  • These radicals abstract hydrogen from the side chain portion of the acrylic adhesive polymer (A) (more specifically, the ether group in the side chain, the C-H bond adjacent to the secondary amino group or tertiary amino group, the hydroxyl group, and the aliphatic tertiary carbon), generating carbon radicals and/or oxygen radicals. It is believed that the radicals thus generated couple with each other, thereby forming a crosslinked structure.
  • the crosslinking between the side chains forms a dense crosslinked structure in the adhesive layer, which can reduce the adhesive strength of the adhesive sheet.
  • the present adhesive sheet maintains high adhesive strength before being irradiated with active energy rays, and then, by being irradiated with active energy rays, a crosslinked structure is sufficiently formed between or within the molecules of the acrylic adhesive polymer (A), which is believed to result in easy peeling.
  • the acrylic adhesive polymer (A) preferably contains a structural unit (hereinafter also referred to as "structural unit (U2)") derived from a (meth)acrylic monomer having at least one selected from the group consisting of an ether group, a hydroxyl group, an aliphatic tertiary carbon (excluding the carbon atom constituting the carbon-carbon double bond in the methacryloyl group), a secondary amino group, and a tertiary amino group.
  • structural unit (U2) structural unit derived from a (meth)acrylic monomer having at least one selected from the group consisting of an ether group, a hydroxyl group, an aliphatic tertiary carbon (excluding the carbon atom constituting the carbon-carbon double bond in the methacryloyl group), a secondary amino group, and a tertiary amino group.
  • aliphatic tertiary carbon refers to a carbon having one hydrogen atom and three carbon atoms bonded thereto, at least one of the three bonded carbon atoms constituting an aliphatic hydrocarbon group.
  • An ether group refers to a group in which one or more hydrogen atoms are directly bonded to at least one of the two carbon atoms bonded to "-O-" in "hydrocarbon group-O-hydrocarbon group".
  • monomers constituting the structural unit (U2) include (meth)acrylic acid alkoxyalkyl esters, (meth)acrylic acid esters having an aliphatic tertiary carbon, (meth)acrylic acid hydroxyalkyl esters, polyalkylene glycol mono(meth)acrylates, and amino group-containing (meth)acrylic acid esters.
  • alkoxyalkyl (meth)acrylates such as methoxymethyl (meth)acrylate, ethoxymethyl (meth)acrylate, methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, n-propoxyethyl (meth)acrylate, n-butoxyethyl (meth)acrylate, methoxypropyl (meth)acrylate, ethoxypropyl (meth)acrylate, n-propoxypropyl (meth)acrylate, n-butoxypropyl (meth)acrylate, methoxybutyl (meth)acrylate, ethoxybutyl (meth)acrylate, n-propoxybutyl (meth)acrylate, and n-butoxybutyl (meth)acrylate.
  • alkoxyalkyl (meth)acrylates such as methoxymethyl (meth)acrylate, ethoxymethyl (meth)acrylate, meth
  • (meth)acrylic acid esters having an aliphatic tertiary carbon include isobutyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, isononyl (meth)acrylate, methylcyclohexyl (meth)acrylate, tert-butylcyclohexyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyl (meth)acrylate, and EO-modified 2-ethylhexyl (meth)acrylate.
  • (meth)acrylic acid hydroxyalkyl esters include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate.
  • a specific example of the polyalkylene glycol mono(meth)acrylate is a monomer represented by the following formula (1).
  • R 1 represents a hydrogen atom or a methyl group
  • R 2 represents a linear or branched alkylene group having 2 to 6 carbon atoms
  • R 3 represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms
  • n represents an integer of 2 to 100.
  • R3 in the above formula (1) is preferably an alkyl group or an aryl group.
  • n is preferably 2 to 50, more preferably 2 to 30, and even more preferably 2 to 10.
  • polyalkylene glycol mono(meth)acrylates include polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, polyethylene glycol-polypropylene glycol mono(meth)acrylate, polyethylene glycol-polytetraethylene glycol mono(meth)acrylate, methoxypolyethylene glycol mono(meth)acrylate, lauroxypolyethylene glycol mono(meth)acrylate, stearoxypolyethylene glycol mono(meth)acrylate, octoxypolyethylene glycol-polypropylene glycol mono(meth)acrylate, phenoxypolyethylene glycol mono(meth)acrylate, phenoxypolyethylene glycol-polypropylene glycol mono(meth)acrylate, nonylphenoxypolyethylene glycol mono(meth)acrylate, nonylphenoxypolyethylene glycol mono(meth)acrylate, and nonylphenoxypolyethylene glycol-polypropylene glycol
  • polyalkylene glycol mono(meth)acrylate products include, by product name, Aronix M-101A, M-102, M-113, M-120, and M-140 (all manufactured by Toagosei Co., Ltd.); Blenmar PP series, AP series, PME series, and AME series (all manufactured by NOF Corporation).
  • amino group-containing (meth)acrylic acid esters include dimethylaminomethyl (meth)acrylate, diethylaminomethyl (meth)acrylate, 2-dimethylaminoethyl (meth)acrylate, 2-diethylaminoethyl (meth)acrylate, 2-(di-n-propylamino)ethyl (meth)acrylate, 2-dimethylaminopropyl (meth)acrylate, 2-diethylaminopropyl (meth)acrylate, 2-(di-n-propylamino)propyl (meth)acrylate, 3-dimethylaminopropyl (meth)acrylate, 3-diethylaminopropyl (meth)acrylate, and 3-(di-n-propylamino)propyl (meth)acrylate.
  • the (meth)acrylic adhesive polymer (A) preferably contains a structural unit derived from at least one selected from the group consisting of (meth)acrylic acid alkoxyalkyl esters, (meth)acrylic acid hydroxyalkyl esters, and monomers represented by the above formula (1), and more preferably contains at least a structural unit derived from a monomer represented by the above formula (1).
  • the content of the structural unit (U2) is preferably 10% by mass or more relative to the total structural units of the acrylic adhesive polymer (A) from the viewpoint of facilitating the formation of a crosslinked structure by irradiation with active energy rays.
  • the content of the structural unit (U2) is more preferably 15% by mass or more, even more preferably 20% by mass or more, and even more preferably 25% by mass or more relative to the total structural units of the acrylic adhesive polymer (A).
  • the content of the structural unit (U2) is preferably 90% by mass or less relative to the total structural units of the acrylic adhesive polymer (A), more preferably 85% by mass or less, even more preferably 80% by mass or less, even more preferably 75% by mass or less, and even more preferably 70% by mass or less.
  • the acrylic adhesive polymer (A) may further contain structural units (hereinafter also referred to as "other structural units") different from the structural units (U1) and (U2).
  • other structural units include (meth)acrylic acid alkyl esters, aliphatic cyclic esters of (meth)acrylic acid, aromatic esters of (meth)acrylic acid, epoxy group-containing (meth)acrylic acid esters, silyl group-containing (meth)acrylic acid esters, unsaturated acid anhydrides, (meth)acrylamide or derivatives thereof, nitrile group-containing (meth)acrylic acid esters, aromatic vinyl compounds and imide group-containing vinyl compounds, unsaturated carboxylic acids, etc.
  • aliphatic cyclic esters of (meth)acrylic acid include cyclohexyl (meth)acrylate, cyclododecyl (meth)acrylate, etc.
  • aromatic esters of (meth)acrylic acid include phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxymethyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, and 3-phenoxypropyl (meth)acrylate, etc.
  • epoxy group-containing (meth)acrylic acid esters include glycidyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, 3,4-epoxycyclohexylmethyl (meth)acrylate, etc.
  • silyl group-containing (meth)acrylic acid esters include trimethoxysilylpropyl (meth)acrylate, triethoxysilylpropyl (meth)acrylate, methyldimethoxysilylpropyl (meth)acrylate, and dimethylmethoxysilylpropyl (meth)acrylate, etc.
  • unsaturated acid anhydrides include maleic anhydride, itaconic anhydride, citraconic anhydride, etc.
  • (meth)acrylamide or its derivatives include (meth)acrylamide, tert-butyl(meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, N,N-dimethylaminopropyl(meth)acrylamide, and (meth)acryloylmorpholine.
  • nitrile group-containing (meth)acrylic acid esters include cyanomethyl (meth)acrylate, 1-cyanoethyl (meth)acrylate, 2-cyanoethyl (meth)acrylate, 1-cyanopropyl (meth)acrylate, 2-cyanopropyl (meth)acrylate, 3-cyanopropyl (meth)acrylate, 4-cyanobutyl (meth)acrylate, 6-cyanohexyl (meth)acrylate, 2-ethyl-6-cyanohexyl (meth)acrylate, and 8-cyanooctyl (meth)acrylate.
  • aromatic vinyl compounds include styrene, ⁇ -methylstyrene, ⁇ -methylstyrene, vinylxylene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene, p-n-butylstyrene, p-isobutylstyrene, p-t-butylstyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, p-hydroxystyrene, m-hydroxystyrene, o-hydroxystyrene, p-isopropenyl
  • imide group-containing vinyl compounds include maleimide compounds such as maleimide and N-substituted maleimide compounds; itaconimide compounds such as N-methylitaconimide, N-ethylitaconimide, N-butylitaconimide, N-octylitaconimide, N-2-ethylhexylitaconimide, N-cyclohexylitaconimide, and N-laurylitaconimide; N-methylcitraconimide, N-ethylcitraconimide, N-butylcitraconimide, N-octylcitraconimide, N-2-ethylhexylcitraconimide, Examples of the citraconimide compounds include N-cyclohexylcitraconimide and N-laurylcitraconimide; and (meth)acrylamide compounds such as N-(2-(meth)acryloyloxyethyl)
  • unsaturated carboxylic acids include (meth)acrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, citraconic acid, cinnamic acid, and monoalkyl esters of unsaturated dicarboxylic acids (monoalkyl esters of maleic acid, fumaric acid, itaconic acid, citraconic acid, etc.).
  • the acrylic adhesive polymer (A) contains a structural unit derived from an alkyl (meth)acrylate.
  • the monomer constituting the structural unit derived from an alkyl (meth)acrylate is preferably an alkyl (meth)acrylate having an alkyl moiety with 1 to 8 carbon atoms, and more preferably an alkyl (meth)acrylate having an alkyl moiety with 1 to 4 carbon atoms.
  • the proportion of structural units derived from (meth)acrylic acid alkyl ester is preferably 3% by mass or more, more preferably 5% by mass or more, and even more preferably 10% by mass or more, based on the total structural units of the acrylic adhesive polymer (A), from the viewpoint of improving the adhesive performance of the acrylic adhesive polymer (A).
  • the upper limit of the proportion of structural units derived from (meth)acrylic acid alkyl ester is not particularly limited, but from the viewpoint of sufficiently performing crosslinking formation by irradiation with active energy rays, it is preferably 95% by mass or less, more preferably 90% by mass or less, and even more preferably 80% by mass or less, based on the total structural units of the acrylic adhesive polymer (A).
  • the acrylic adhesive polymer (A) contains a structural unit (hereinafter also referred to as "structural unit (W)") derived from at least one monomer selected from the group consisting of (meth)acrylic monomers having a boiling point of 150°C or less and (meth)acrylic monomers having a boiling point of 200°C or more.
  • structural unit (W) structural unit derived from at least one monomer selected from the group consisting of (meth)acrylic monomers having a boiling point of 150°C or less and (meth)acrylic monomers having a boiling point of 200°C or more.
  • the proportion of the structural unit (W) is preferably 30% by mass or more, more preferably 40% by mass or more, even more preferably 50% by mass or more, even more preferably 60% by mass or more, even more preferably 70% by mass or more, and even more preferably 80% by mass or more, based on the total structural units of the acrylic adhesive polymer (A).
  • the boiling point of the monomer is a predicted value calculated by Fujitsu Limited's scientific research information management solution (ACD/Labs). In this specification, the boiling point is a value under atmospheric pressure.
  • the acrylic adhesive polymer (A) preferably contains a structural unit derived from a (meth)acrylic monomer having a boiling point of 150°C or less (hereinafter also referred to as "structural unit (W1)"), in that it can increase the elastic modulus of the acrylic adhesive polymer (A) and improve its heat resistance, and that it is easily volatilized during the manufacturing process of the adhesive sheet, thereby suppressing foaming from the adhesive sheet.
  • structural unit (W1) is preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 30% by mass or more, based on the total structural units of the acrylic adhesive polymer (A).
  • the proportion of the structural unit (W1) is preferably 80% by mass or less, more preferably 70% by mass or less, and even more preferably 65% by mass or less, based on the total structural units of the acrylic adhesive polymer (A).
  • the acrylic adhesive polymer (A) preferably contains a structural unit derived from a (meth)acrylic monomer having a boiling point of 200° C. or more (hereinafter also referred to as "structural unit (W2)”), in terms of exhibiting excellent peelability by irradiation with active energy rays and being able to suppress the volatilization of monomers (i.e., unreacted monomers) contained in the adhesive layer when a thermal load is applied.
  • the proportion of the structural unit (W2) is preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 30% by mass or more, based on the total structural units of the acrylic adhesive polymer (A).
  • the proportion of the structural unit (W2) is preferably 80% by mass or less, more preferably 70% by mass or less, and even more preferably 65% by mass or less, based on the total structural units of the acrylic adhesive polymer (A).
  • a monomer having a crosslinkable functional group (hereinafter also referred to as a "crosslinkable group-containing monomer”) may be used so that the acrylic adhesive polymer (A) contains a structural unit having a crosslinkable functional group.
  • crosslinkable group-containing monomer By introducing a structural unit having a crosslinkable functional group into the acrylic adhesive polymer (A), it is possible to easily adjust the gel fraction of the adhesive layer.
  • the crosslinkable group-containing monomer used in the production of the acrylic adhesive polymer (A) is not particularly limited.
  • the crosslinkable group-containing monomer is preferably at least one selected from the group consisting of (meth)acrylic acid, a (meth)acrylic acid hydroxyalkyl compound, an epoxy group-containing (meth)acrylic acid ester compound, and a reactive silyl group-containing (meth)acrylic acid ester compound.
  • At least one selected from the group consisting of (meth)acrylic acid and a (meth)acrylic acid hydroxyalkyl compound is preferred, since it tends to increase the adhesive strength of the acrylic adhesive polymer (A), and at least one selected from the group consisting of (meth)acrylic acid and a (meth)acrylic acid hydroxyalkyl compound having a hydroxyalkyl group having 2 to 8 carbon atoms is more preferred.
  • the content ratio of the structural unit having a crosslinkable functional group is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1% by mass or more, based on the total structural units of the acrylic adhesive polymer (A).
  • the upper limit of the content ratio of the structural unit having a crosslinkable functional group is not particularly limited, but from the viewpoint of ensuring the adhesive performance of the obtained adhesive layer, it is preferably 30% by mass or less, more preferably 20% by mass or less, even more preferably 15% by mass or less, and particularly preferably 10% by mass or less, based on the total structural units of the acrylic adhesive polymer (A).
  • the acrylic adhesive polymer (A) is not particularly limited in the production method, and can be obtained by a known production method.
  • the acrylic adhesive polymer (A) can be obtained by polymerizing the above-mentioned monomers by adopting a known radical polymerization method such as a solution polymerization method, a suspension polymerization method, an emulsion polymerization method, or a bulk polymerization method.
  • the manufacturing method involves charging an organic solvent and monomers into a reactor, adding a polymerization initiator, and heating to 50 to 300°C to polymerize.
  • the method of feeding each raw material including the monomer may be a batch-type initial lump-sum feeding in which all raw materials are fed at once, a semi-continuous feeding in which at least some of the raw materials are fed continuously into the reactor, or a continuous polymerization method in which all raw materials are fed continuously and the resulting resin is simultaneously continuously removed from the reactor.
  • organic solvents used in the solution polymerization method include cyclic ethers such as tetrahydrofuran and dioxane, aromatic hydrocarbon compounds such as benzene, toluene and xylene, esters such as ethyl acetate and butyl acetate, ketones such as acetone, methyl ethyl ketone and cyclohexanone, and alcohols such as methyl orthoformate, methyl orthoacetate, methanol, ethanol and isopropanol.
  • cyclic ethers such as tetrahydrofuran and dioxane
  • aromatic hydrocarbon compounds such as benzene, toluene and xylene
  • esters such as ethyl acetate and butyl acetate
  • ketones such as acetone, methyl ethyl ketone and cyclohexanone
  • alcohols such as methyl orthoformate, methyl orthoacetate, methanol,
  • known radical polymerization initiators such as azo compounds, organic peroxides, inorganic peroxides, etc. can be used, and are not particularly limited. Among these, azo compounds are preferred because they are safe and easy to handle, and side reactions are less likely to occur during radical polymerization. Azo compounds are preferred.
  • a redox type polymerization initiator consisting of a known oxidizing agent and reducing agent may also be used. Furthermore, a known chain transfer agent can be used in combination with the polymerization initiator.
  • polymerization initiators include azo compounds such as 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 4,4'-azobis(4-cyanovaleric acid), 2-(tert-butylazo)-2-cyanopropane, 2,2'-azobis(2,4,4-trimethylpentane), 2,2'-azobis(2-methylpropane), and dimethyl 2,2'-azobis(2-methylpropionate).
  • azo compounds such as 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 4,4'-azobis(4-cyanovaleric acid), 2-(tert-butylazo)-2-cyanopropane, 2,2'-azobis(2,4,4-trimethylpentane), 2,2'-azobis(
  • organic peroxides examples include cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, diisopropylbenzene peroxide, and 2,5-dimethyl-2,5-di(benzoylperoxy)hexane.
  • inorganic peroxides include potassium persulfate and sodium persulfate.
  • redox type polymerization initiators include those using sodium sulfite, sodium thiosulfate, sodium formaldehyde sulfoxylate, ascorbic acid, ferrous sulfate, etc. as a reducing agent and potassium peroxodisulfate, hydrogen peroxide, tert-butyl hydroperoxide, etc. as an oxidizing agent.
  • the amount of polymerization initiator used is, for example, 0.01 to 20 parts by mass per 100 parts by mass of the total monomers used in the polymerization.
  • the glass transition temperature (Tg) of the acrylic adhesive polymer (A) is preferably in the range of -80°C or more and 10°C or less. If the Tg of the acrylic adhesive polymer (A) is -80°C or more, it is preferable in that the cohesive force of the adhesive layer can be sufficiently increased and sufficient adhesiveness can be ensured. From the viewpoint of increasing the adhesiveness of the adhesive layer, the Tg of the acrylic adhesive polymer (A) is more preferably -70°C or more, even more preferably -60°C or more, and even more preferably -55°C or more.
  • the Tg of the acrylic adhesive polymer (A) is 10°C or less, it is preferable because an adhesive sheet with good conformability to the adherend can be obtained.
  • the upper limit of the Tg of the acrylic adhesive polymer (A) is more preferably 5°C or less, even more preferably 0°C or less, even more preferably -5°C or less, and particularly preferably -10°C or less.
  • the preferred range of the Tg of the acrylic adhesive polymer (A) is more preferably from -80°C to 5°C, even more preferably from -70°C to 0°C.
  • the Tg of a polymer is a value determined from the intersection of the baseline of a heat flux curve obtained using a differential scanning calorimeter (DSC) and the tangent point at the inflection point. Details of the measurement conditions are as described in the examples below.
  • the Tg of a polymer can be selected arbitrarily by changing the type and composition of the constituent monomers.
  • the weight average molecular weight (Mw) of the acrylic adhesive polymer (A) is preferably 100,000 or more in order to exhibit sufficient cohesive strength and good adhesiveness. When the Mw of the acrylic adhesive polymer (A) is 100,000 or more, sufficient adhesiveness and solvent resistance can be ensured.
  • the Mw of the acrylic adhesive polymer (A) is more preferably 120,000 or more, even more preferably 150,000 or more, and even more preferably 200,000 or more.
  • the upper limit of the Mw of the acrylic adhesive polymer (A) is not particularly limited, but from the viewpoint of ensuring good coating and handling properties when forming an adhesive sheet and further ensuring ease of manufacture, it is preferably 3,000,000 or less, more preferably 2,000,000 or less, and even more preferably 1,500,000 or less.
  • the Mw range of the acrylic adhesive polymer (A) is preferably 100,000 or more and 3,000,000 or less, more preferably 150,000 or more and 2,000,000 or less, and even more preferably 200,000 or more and 1,500,000 or less.
  • the molecular weight of the polymer is a polystyrene-equivalent value measured by gel permeation chromatography (GPC).
  • the molecular weight distribution (Mw/Mn) of the acrylic adhesive polymer (A), which is expressed as the ratio of Mw to the number average molecular weight (Mn), is preferably 10.0 or less, and more preferably 9.0 or less, from the viewpoint of easily obtaining good adhesion and suppressing the increase in viscosity of the adhesive composition.
  • the lower limit of Mw/Mn of the acrylic adhesive polymer (A) is not particularly limited, and can be 1.0 or more.
  • the Mw and Mn of the polymer are standard polystyrene equivalent values obtained using gel permeation chromatography (GPC).
  • the present composition does not substantially contain a compound having two or more reactive unsaturated bonds in one molecule (reactive unsaturated compound).
  • the reactive unsaturated compound has two or more unsaturated bonds (specifically, carbon-carbon unsaturated bonds) in one molecule that react when irradiated with active energy rays, and when irradiated with active energy rays, the reactive unsaturated compounds react with each other to form a crosslinked structure in the adhesive layer.
  • Examples of reactive unsaturated compounds include compounds having two or more carbon-carbon unsaturated bonds in the molecule, and specific examples thereof include polyfunctional (meth)acrylic compounds and polyfunctional vinyl compounds.
  • a reactive unsaturated compound When a reactive unsaturated compound is further blended into the present composition, when a heat load (for example, about 200° C.) is applied to an adhesive sheet having an adhesive layer formed from this composition, the reaction of the reactive unsaturated compound in the adhesive layer proceeds, and a crosslinked structure is formed, which leads to an unintended decrease in strength of the adhesive layer, or the reactive unsaturated compound itself volatilizes, resulting in a decrease in heat resistance.
  • "free of reactive unsaturated compounds” does not exclude the reactive unsaturated compounds being contained in the composition in a small amount to such an extent that the effect of the present disclosure is not impaired.
  • the content of the reactive unsaturated compounds in the composition is preferably 0.2% by mass or less, more preferably 0.1% by mass or less, and even more preferably 0.05% by mass or less, based on the total amount of the composition.
  • this composition differs from so-called syrup-type active energy ray-curable adhesive compositions in that it does not contain a reactive unsaturated compound.
  • the syrup-type active energy ray-curable adhesive composition contains a polymer component that will form part of the acrylic adhesive polymer in the adhesive layer and a monomer component that will form the remainder, and the active energy ray-curable adhesive composition is irradiated with active energy rays to produce the acrylic adhesive polymer that is the main component of the adhesive layer.
  • At least one of the monomer components contained in such a syrup-type active energy ray-curable adhesive composition corresponds to the "reactive unsaturated compound" in this disclosure.
  • the composition may further contain components other than the acrylic adhesive polymer (A) (hereinafter also referred to as "other components") within the scope of not impairing the effects of the present disclosure.
  • other components include a hydrogen abstraction type photopolymerization initiator, a solvent, a crosslinking agent, a tackifier, a plasticizer, etc.
  • Hydrogen abstraction type photopolymerization initiator In order to further increase the crosslinking efficiency in the pressure-sensitive adhesive layer, a hydrogen abstraction type photopolymerization initiator may be added to the composition in addition to the acrylic adhesive polymer (A).
  • a hydrogen abstraction type photopolymerization initiator a known hydrogen abstraction type radical polymerization initiator can be used.
  • Specific examples of the hydrogen abstraction type photopolymerization initiator include the specific examples of the hydrogen abstraction type photopolymerization initiator exemplified in the explanation of the structural unit (U1) and the same as commercially available products.
  • the content of the hydrogen abstraction type photopolymerization initiator is preferably 30 parts by mass or less per 100 parts by mass of the acrylic adhesive polymer (A).
  • the amount of the hydrogen abstraction type photopolymerization initiator is more preferably 20 parts by mass or less, and even more preferably 15 parts by mass or less, per 100 parts by mass of the acrylic adhesive polymer (A).
  • the hydrogen abstraction type photopolymerization initiator one type may be used alone, or two or more types may be used in combination.
  • the present composition is preferably a solvent-based adhesive composition further containing a solvent.
  • the solvent contained in the present composition is preferably an organic solvent capable of dissolving the acrylic adhesive polymer (A).
  • the organic solvent include aprotic polar solvents, phenolic solvents, alcoholic solvents, ester solvents, ketone solvents, ether solvents, and hydrocarbon solvents.
  • the organic solvent may be one of these, or a mixed solvent of two or more of them.
  • the solvent contained in the present composition is preferably at least one selected from the group consisting of ethyl acetate, butyl acetate, ethyl methyl ketone, and toluene.
  • crosslinking agent capable of reacting with the crosslinkable functional group
  • a crosslinking agent capable of reacting with the crosslinkable functional group
  • examples of the crosslinkable functional group include a hydroxyl group, a carboxyl group, and the like, and preferably a hydroxyl group.
  • crosslinking agent examples include a compound that does not have a reactive unsaturated bond, and specifically include a glycidyl-based compound having two or more glycidyl groups, an isocyanate-based compound having two or more isocyanate groups, an aziridine-based compound having two or more aziridinyl groups, an oxazoline-based compound having an oxazoline group, a metal chelate compound, and a butylated melamine compound.
  • an isocyanate-based compound is preferred in that it can form an adhesive layer with a higher cohesive force.
  • cross-linking agents include glycidyl compounds such as polyfunctional glycidyl compounds, such as ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, tetraglycidylxylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, and trimethylolpropane polyglycidyl ether.
  • polyfunctional glycidyl compounds such as ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, tetraglycidylxylenediamine, 1,3
  • Isocyanate compounds include aromatic isocyanate compounds such as diphenylmethane diisocyanate (MDI), tolylene diisocyanate (TDI), naphthalene diisocyanate (NDI), p-phenylene diisocyanate (PPDI), xylene diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI), and tolidine diisocyanate (TODI); hexamethylene diisocyanate (HDI), and lysine diisocyanate (LYS).
  • MDI diphenylmethane diisocyanate
  • TDI tolylene diisocyanate
  • NDI naphthalene diisocyanate
  • PPDI p-phenylene diisocyanate
  • XDI xylene diisocyanate
  • TMXDI tetramethylxylylene diisocyanate
  • TODI tol
  • Aliphatic isocyanate compounds such as isophorone diisocyanate (IPDI), cyclohexyl diisocyanate (CHDI), hydrogenated XDI (H6XDI), and hydrogenated MDI (H12MDI); modified isocyanate compounds such as urethane modified products, dimers, trimers, carbodiimide modified products, urea modified products, isocyanurate modified products, oxazolidone modified products, and isocyanate group-terminated prepolymers.
  • IPDI isophorone diisocyanate
  • CHDI cyclohexyl diisocyanate
  • H6XDI hydrogenated XDI
  • H12MDI hydrogenated MDI
  • modified isocyanate compounds such as urethane modified products, dimers, trimers, carbodiimide modified products, urea modified products, isocyanurate modified products, oxazolidone modified products, and isocyanate group-terminated prepolymers.
  • Aziridine compounds include 1,6-bis(1-aziridinylcarbonylamino)hexane, 1,1'-(methylene-di-p-phenylene)bis-3,3-aziridyl urea, ethylene bis-(2-aziridinyl propionate), 2,4,6-triaziridinyl-1,3,5-triazine, trimethylolpropane-tris(2-aziridinyl propionate), etc.
  • the content of the crosslinking agent in the present composition is preferably 0 to 5 parts by mass, more preferably 0 to 3 parts by mass, even more preferably 0 to 2 parts by mass, still more preferably 0 to 1 part by mass, and even more preferably 0 to 0.8 parts by mass, relative to 100 parts by mass of the acrylic adhesive polymer (A), from the viewpoint of achieving a well-balanced improvement in the adhesive performance and tracking ability of the adhesive layer formed using the present composition.
  • the present composition may further contain a tackifier.
  • tackifiers include rosin derivatives such as rosin ester, gum rosin, tall oil rosin, hydrogenated rosin ester, maleic rosin, and disproportionated rosin ester; terpene-based resins mainly composed of terpene phenol resins, ⁇ -pinene, ⁇ -pinene, or limonene; coumarone-indene resins, hydrogenated aromatic copolymers, and phenolic resins.
  • the tackifier may be used alone or in combination of two or more kinds.
  • the content of the tackifier is preferably 0 to 20 parts by mass, more preferably 0 to 10 parts by mass, and even more preferably 0 to 5 parts by mass, relative to 100 parts by mass of the acrylic adhesive polymer (A).
  • the composition may contain a plasticizer.
  • the plasticizer include phthalates such as di-n-butyl phthalate, di-n-octyl phthalate, bis(2-ethylhexyl) phthalate, and di-n-decyl phthalate; adipates such as bis(2-ethylhexyl) adipate and di-n-octyl adipate; sebacic acid esters; azelaic acid esters; paraffins such as chlorinated paraffin; glycols such as polypropylene glycol; epoxy-modified vegetable oils such as epoxidized soybean oil and epoxidized linseed oil; phosphates such as trioctyl phosphate and triphenyl phosphate; phosphites such as triphenyl phosphite; ester oligomers such as esters of adipic acid and 1,3-butylene glycol; low molecular weight polymers such as
  • the content of the plasticizer is preferably 0 to 20 parts by mass, more preferably 0 to 10 parts by mass, and even more preferably 0 to 5 parts by mass, per 100 parts by mass of the acrylic adhesive polymer (A).
  • additives that may be incorporated into the composition include, for example, an intramolecular cleavage-type photopolymerization initiator, an antioxidant, an ultraviolet absorber, an antiaging agent, a flame retardant, an antifungal agent, a silane coupling agent, a filler, a colorant, etc.
  • the content of the additives can be appropriately set according to the various compounds within a range that does not impair the effects of the present disclosure.
  • the solids concentration in the adhesive composition is not particularly limited, but is preferably 1 to 70 mass%.
  • the solids concentration is 1 mass% or more, an adhesive layer with sufficient thickness can be formed.
  • the solids concentration is 70 mass% or less, good coating properties can be ensured, and an adhesive layer with uniform thickness can be easily formed.
  • the solids concentration in the present composition is more preferably 5 to 50 mass%, and even more preferably 10 to 45 mass%.
  • the viscosity of the composition is preferably 500 to 10,000 mPa ⁇ s. If the viscosity is 10,000 mPa ⁇ s or less, good coatability can be ensured. In addition, the composition can be used as is without diluting it to a viscosity suitable for coating, and handleability is good. From this viewpoint, the viscosity of the composition is more preferably 8,000 mPa ⁇ s or less, and even more preferably 6,000 mPa ⁇ s or less. In addition, the lower limit of the viscosity of the composition is more preferably 1,000 mPa ⁇ s or more, and even more preferably 1,500 mPa ⁇ s or more, from the viewpoint of preventing the film thickness from becoming too thin.
  • the viscosity of the adhesive composition is a value measured at 25°C using a B-type viscometer for an adhesive composition with a solids concentration of 25%.
  • the pressure-sensitive adhesive sheet of the present disclosure (hereinafter also referred to as “the pressure-sensitive adhesive sheet”) comprises a pressure-sensitive adhesive layer formed from an active energy ray-curable pressure-sensitive adhesive composition containing the above-mentioned acrylic pressure-sensitive adhesive polymer (A).
  • the adhesive layer in the adhesive sheet can be formed by applying the above-mentioned composition to a separator or the like, and then performing a drying process as necessary.
  • a resin film made of various resin materials can be used as the separator.
  • resin materials that make up the resin film include polyester-based resins such as polyethylene terephthalate, polyethersulfone-based resins, acetate-based resins, polycarbonate-based resins, polyolefin-based resins, etc.
  • the composition When forming an adhesive layer using a solvent-based adhesive composition, the composition is first applied to a separator by a known coating method, and the solvent is preferably removed by a drying treatment such as heating.
  • the heating temperature and heating time when forming the adhesive layer may be set as appropriate depending on the type of solvent contained in the composition, the solids concentration, etc., as long as the solvent can be removed.
  • the thickness of the adhesive layer is, for example, 2 to 150 ⁇ m, preferably 2 to 100 ⁇ m, and more preferably 2 to 75 ⁇ m.
  • the adhesive layer may be formed by laminating multiple thin films to obtain the desired thickness.
  • the present composition may be applied to a separator or the like, and the adhesive layer after removing the solvent as necessary may be irradiated with active energy rays to perform pre-crosslinking.
  • the irradiation dose of the active energy rays is appropriately set so that the gel fraction based on the acrylic adhesive polymer (A) in the adhesive layer is 90% or less, preferably 80% or less, and more preferably 70% or less.
  • the adhesive sheet 10 in FIG. 1 is a laminate in which a first separator 11, an adhesive layer 12, and a second separator 13 are laminated in this order. It is preferable that the first separator 11 and the second separator 13 have different release properties.
  • the first separator 11 may be a heavy release film
  • the second separator 13 may be a light release film.
  • the adhesive sheet may have a structure in which a substrate is disposed on one side of the adhesive layer and a separator is disposed on the other side.
  • the adhesive sheet may be, for example, in the form of a sheet, in the form of a roll, or cut into strips. It may also have any shape depending on the location of adhesion.
  • One embodiment of the adhesive sheet is an adhesive tape.
  • the adhesive layer of the adhesive sheet preferably has a gel fraction based on the acrylic adhesive polymer (A) in the range of 90% or less.
  • A acrylic adhesive polymer
  • the adhesive strength of the adhesive layer can be sufficiently ensured.
  • the adhesive layer is irradiated with active energy rays after bonding to the adherend, the difference in peel strength before and after irradiation with active energy rays can be ensured, and the adhesive layer can be easily peeled off.
  • the gel fraction of the adhesive layer in the adhesive sheet before lamination with an adherend is more preferably 85% or less, even more preferably 80% or less, and even more preferably 75% or less.
  • the lower limit of the gel fraction of the adhesive layer in the adhesive sheet before being bonded to the adherend is not particularly limited.
  • the gel fraction of the adhesive layer in the adhesive sheet before being bonded to the adherend is preferably 1% or more, more preferably 3% or more, and even more preferably 4% or more.
  • the preferred range of the gel fraction of the adhesive layer in the adhesive sheet before being bonded to the adherend can be determined by appropriately combining the above-mentioned upper and lower limit values. Specifically, 1 to 90% is more preferable, 2 to 85% is more preferable, and 4 to 80% is even more preferable. Details of the measurement method follow the method described in the examples below.
  • Weight loss rate The weight loss rate at 200°C measured by thermogravimetry at a temperature rise rate of 20°C/min and a temperature rise range of 25 to 350°C is preferably 5% by weight or less. If the weight loss rate is 5% by weight or less, the adhesive layer is less likely to volatilize components when a thermal load is applied to the adhesive sheet, and the adhesive sheet can be made to have high heat resistance in which foaming and lifting due to thermal load are suppressed. From the viewpoint of improving the heat resistance of the adhesive sheet, the weight loss rate measured under the above conditions is more preferably 4% by weight or less, and even more preferably 3% by weight or less. In this specification, the method for measuring the weight loss rate of the adhesive layer by thermogravimetry follows the method described in the Examples below.
  • Peel strength The adhesive sheet is irradiated with active energy rays after bonding the adhesive layer to the adherend, and crosslinks or further crosslinks the acrylic adhesive polymer (A), thereby reducing the adhesive strength, and thus exhibiting easy peelability.
  • the adhesive strength before irradiating the adhesive sheet preferably an adhesive sheet with a gel fraction of the adhesive layer of 90% or less
  • the adhesive strength after irradiating the adhesive sheet attached to the adherend it is preferable that the adhesive strength before irradiation with active energy rays is high, thereby suppressing peeling from the adherend.
  • the adhesive strength after irradiation with active energy rays is lower than that before irradiation with active energy rays.
  • the ratio (S2/S1) of the peel strength (referred to as "S1") before the present adhesive sheet (preferably an adhesive sheet having a gel fraction of 90% or less in the adhesive layer) attached to the adherend is irradiated with active energy rays to the present adhesive sheet attached to the adherend
  • the peel strength (referred to as "S2") after the gel fraction based on the acrylic adhesive polymer (A) of the adhesive layer is increased to more than 90% by irradiating the present adhesive sheet attached to the adherend with active energy rays
  • the ratio (S2/S1) is preferably 0.7 or less.
  • the ratio (S2/S1) is more preferably 0.65 or less, even more preferably 0.6 or less, and even more preferably 0.5 or less.
  • the peel strength is a value measured in accordance with JIS Z-0237. Details of the measurement method are as described in the examples below.
  • the pressure-sensitive adhesive sheet is excellent in heat resistance, being unlikely to foam or lift off from the adherend even when heated at high temperatures (e.g., 200°C or higher). Therefore, the pressure-sensitive adhesive sheet is suitable as a pressure-sensitive adhesive sheet used in semiconductor manufacturing processes (i.e., a pressure-sensitive adhesive sheet for semiconductor manufacturing processes). In addition, the pressure-sensitive adhesive sheet exhibits easy peelability when irradiated with active energy rays after being attached to an adherend.
  • Such a pressure-sensitive adhesive sheet is used for the purpose of temporarily fixing an adherend or protecting the adherend surface in semiconductor manufacturing processes, and is suitable for applications in which the pressure-sensitive adhesive layer is required to be peeled off by irradiating the pressure-sensitive adhesive layer with active energy rays when the pressure-sensitive adhesive layer is no longer required for temporary fixation and surface protection.
  • an adhesive tape is attached to a support substrate (e.g., a glass substrate), a semiconductor chip is placed on the adhesive layer of the adhesive tape attached to the support substrate, and the semiconductor chip is temporarily fixed to the support substrate.
  • a support substrate e.g., a glass substrate
  • a semiconductor chip is placed on the adhesive layer of the adhesive tape attached to the support substrate
  • the semiconductor chip is temporarily fixed to the support substrate.
  • Various lamination processes are then carried out to form a laminate on the support substrate, and the support substrate and adhesive layer are then peeled off.
  • This adhesive sheet can be preferably used as the adhesive tape in such manufacturing processes.
  • the active energy rays irradiated to the adhesive sheet when peeling it off include ultraviolet light, visible light, and electron beams. Of these, ultraviolet light or electron beams are preferred.
  • the irradiation energy of the active energy rays can be set appropriately depending on the type of active energy rays, the compounding composition of the adhesive layer, etc.
  • the wavelength is, for example, 250 to 400 nm.
  • ultraviolet light irradiation devices include high-pressure mercury lamps, metal halide lamps, ultraviolet electrodeless lamps, and ultraviolet light-emitting diodes (UV-LEDs).
  • the integrated light amount of ultraviolet light having a wavelength of 365 nm is preferably 500 mJ/cm 2 or more, more preferably 1,000 mJ/cm 2 or more, and even more preferably 1,500 mJ/cm 2 or more.
  • the upper limit of the integrated light amount is preferably 100,000 mJ/cm 2 or less, more preferably 50,000 mJ/cm 2 or less, from the viewpoint of minimizing the influence on each component in the pressure-sensitive adhesive layer and from the viewpoint of reducing energy.
  • the illuminance and irradiation time of the ultraviolet light can be appropriately set so that the cumulative light amount is the desired amount.
  • the illuminance of ultraviolet light with a wavelength of 365 nm is preferably 1.0 mW/ cm2 or more, more preferably 2.0 mW/cm2 or more , and even more preferably 3.0 mW/ cm2 or more.
  • the upper limit of the illuminance is preferably 3,000 mW/cm2 or less, more preferably 2,000 mW/cm2 or less , and even more preferably 1,000 mW/cm2 or less .
  • the electron beam irradiation device is not particularly limited, but examples include Cockcroft-Walton type, Van de Graaff type, and resonant transformer type devices.
  • the absorbed dose of the electron beam is preferably 1 to 200 kGy, more preferably 10 to 100 kGy.
  • the acceleration voltage of the electron beam may be appropriately set in the range of 80 to 300 kV depending on the film thickness of the substrate.
  • the oxygen concentration of the electron beam irradiation atmosphere is preferably 500 ppm or less, more preferably 300 ppm or less.
  • Figure 2 shows an example of a case where a laminate is manufactured using this adhesive sheet in a semiconductor manufacturing process.
  • a semiconductor encapsulation body comprising a semiconductor chip and an encapsulation layer is manufactured as a laminate.
  • the first separator 11 is peeled off from the adhesive sheet 10 shown in FIG. 1, and the adhesive sheet 10 is attached to the glass substrate 21 so that the surface of the adhesive layer 12 of the adhesive sheet 10 is in contact with the surface of the glass substrate 21.
  • the second separator 13 is peeled off to expose the surface of the adhesive layer 12 (see FIG. 2(a)).
  • the semiconductor chip 22 is placed on the adhesive layer 12, and the semiconductor chip 22 is temporarily fixed on the glass substrate 21 (see FIG. 2(b)).
  • a sealing layer 23 is formed so as to cover the surface of the glass substrate 21 and the semiconductor chip 22.
  • a semiconductor sealed body 24 is obtained in which the semiconductor chip 22 is sealed by the sealing layer 23 on the glass substrate 21 (see FIG. 2(c)).
  • the material for forming the sealing layer 23 is not particularly limited, and for example, an epoxy resin or the like is used.
  • the laminate of the glass substrate 21 and the semiconductor encapsulant 24 is irradiated with active energy rays. This reduces the adhesive strength of the adhesive layer 12, and the semiconductor encapsulant 24 can be peeled off from the glass substrate 21 at the interface 25 between the semiconductor encapsulant 24 and the adhesive layer 12 (see Figures 2(c) and (d)).
  • the glass transition temperature (Tg) of the polymer was determined from the intersection of the baseline of a heat flux curve obtained using a differential scanning calorimeter and the tangent at the inflection point.
  • the heat flux curve was obtained by heating about 10 mg of a sample from room temperature (25°C) to 150°C at 10°C/min, subsequently cooling to -100°C, holding for 5 minutes, and then heating to 150°C at 10°C/min.
  • the monomer composition of the polymer was calculated from the charged amounts and the consumed amounts of monomers measured by gas chromatography (GC).
  • the obtained polymer A-1 was composed of 5% by mass of BPMA, 45% by mass of MA, 45% by mass of M-120, and 5% by mass of 4HBA, and had an Mw of 590,000, an Mw/Mn of 4.7, and a Tg of -30°C.
  • the obtained polymer A-2 consisted of 10% by mass of BPMA, 55% by mass of MA, 30% by mass of M-120, and 5% by mass of 4HBA, and had an Mw of 560,000, an Mw/Mn of 4.1, and a Tg of -14°C.
  • the obtained polymer A-3 consisted of 5% by mass of BPMA, 45% by mass of BA, 45% by mass of M-120, and 5% by mass of 4HBA, and had an Mw of 550,000, an Mw/Mn of 4.2, and a Tg of -54°C.
  • polymer A-4 was obtained.
  • the obtained polymer A-4 consisted of 17% by mass of BA, 78% by mass of C1, and 5% by mass of HEA, and had Mw of 570,000, Mw/Mn of 3.6, and Tg of -35°C.
  • the adhesive sheet sample was transferred to a polyimide film (Apical (registered trademark), 25 ⁇ m thick, manufactured by Kaneka Corporation) to obtain a first adhesive sheet for evaluation.
  • a glass plate (Fabritech FL11A, 1 mm thick, manufactured by AGC Corporation) was used as an adherend, and the first adhesive sheet for evaluation was attached to the glass plate to obtain a laminate of glass plate/adhesive layer/polyimide film.
  • the 180-degree peel strength of the first adhesive sheet for evaluation was measured at 23 ° C. using a tensile tester (Autograph AGS, manufactured by Shimadzu Corporation) in accordance with JIS Z-0237 "Test method for adhesive tape and adhesive sheet".
  • the peel speed was 300 mm / min. This measured value was taken as the peel strength S1 before UV irradiation.
  • the adhesive sheet sample was transferred to a polyimide film (Apical (registered trademark), 25 ⁇ m thick, manufactured by Kaneka Corporation) to obtain a second adhesive sheet for evaluation.
  • a glass plate (Fabritech FL11A, 1 mm thick, manufactured by AGC Corporation) was used as an adherend, and the second adhesive sheet for evaluation was laminated to the glass plate to obtain a glass plate/adhesive layer/polyimide film laminate.
  • UV irradiator Mini Grandage ECS-1511U, with metal halide lamp, manufactured by iGraphics Co., Ltd.
  • the 180-degree peel strength of the second adhesive sheet for evaluation was measured in the same manner as above, and this was defined as the peel strength S2 after UV irradiation.
  • the gel fraction of the second adhesive sheet for evaluation after UV irradiation was measured by the above method, and was found to be more than 90%.
  • the ratio (S2/S1) of the peel strength S2 after UV irradiation to the peel strength S1 before UV irradiation was determined, and the ease of peeling was evaluated according to the following criteria. ⁇ : S2/S1 is 0.7 or less ⁇ : S2/S1 is more than 0.7
  • thermogravimetric analyzer TG/DTA, STA2500Regulus type, manufactured by NETZSCH.
  • the measurement sample was heated from 25°C to 350°C at a heating rate of 20°C/min in a nitrogen atmosphere using the thermogravimetric analyzer, and the weight loss rate at 200°C was measured.
  • the heat resistance of the pressure-sensitive adhesive layer was evaluated according to the following criteria based on the measured weight loss rate. The smaller the weight loss rate, the less foaming occurred when the pressure-sensitive adhesive layer was subjected to a heat load, indicating better heat resistance.
  • ⁇ Weight loss rate is 5% by weight or less
  • ⁇ Weight loss rate is more than 5% by weight
  • Example 2 A pressure-sensitive adhesive composition was produced in the same manner as in Example 1, except that the amount of the crosslinking agent "Takenate D-110N" added was 0.4 parts by mass per 100 parts by mass of the acrylic adhesive polymer, and various evaluations were performed in the same manner as in Example 1.
  • Example 3 The ethyl acetate solution of polymer A-1 obtained in Synthesis Example 1 was used as a pressure-sensitive adhesive composition, and this pressure-sensitive adhesive composition was applied to a PET separator having a thickness of 38 ⁇ m so that the thickness after drying was 40 ⁇ m. The pressure-sensitive adhesive composition was dried at 120° C. for 4 minutes to remove ethyl acetate.
  • a UV irradiator Mini Grandage ECS-1511U, with metal halide lamp, manufactured by iGraphics Co., Ltd.
  • Example 4 A pressure-sensitive adhesive composition was produced by the same operation as in Example 1, except that the polymer A-2 obtained in Synthesis Example 2 was used instead of the polymer A-1, and the amount of the crosslinking agent "Takenate D-110N" added was 0.4 parts by mass relative to 100 parts by mass of the acrylic pressure-sensitive adhesive polymer, and various evaluations were performed in the same manner as in Example 1.
  • Example 5 A pressure-sensitive adhesive composition was produced by the same operation as in Example 1, except that the polymer A-3 obtained in Synthesis Example 3 was used instead of the polymer A-1, and the amount of the crosslinking agent "Takenate D-110N" added was 0.4 parts by mass relative to 100 parts by mass of the acrylic pressure-sensitive adhesive polymer, and various evaluations were performed in the same manner as in Example 1.
  • Example 6 A pressure-sensitive adhesive composition was produced by the same procedure as in Example 1, except that the amount of the crosslinking agent "Takenate D-110N" added was 0.04 parts by mass per 100 parts by mass of the acrylic adhesive polymer, and various evaluations were performed in the same manner as in Example 1.
  • Example 1 A pressure-sensitive adhesive composition was produced by the same procedure as in Example 1, except that the amount of the crosslinking agent "Takenate D-110N" added was 4 parts by mass per 100 parts by mass of the acrylic pressure-sensitive adhesive polymer, and various evaluations were performed in the same manner as in Example 1.
  • Example 2 A pressure-sensitive adhesive composition was produced by the same operation as in Example 1, except that the amount of the crosslinking agent "Takenate D-110N” added was 0.4 parts by mass relative to 100 parts by mass of the acrylic adhesive polymer, 30 parts by mass of a polyfunctional acrylate with the trade name "Aronix M-402" (manufactured by Toagosei Co., Ltd.) was added relative to 100 parts by mass of the acrylic adhesive polymer, and 3 parts by mass of a photoinitiator "OMNIRAD 184" was added relative to 100 parts by mass of the acrylic adhesive polymer.
  • Various evaluations were performed in the same manner as in Example 1.
  • Example 3 A pressure-sensitive adhesive composition was produced by the same operation as in Example 1, except that the polymer A-4 obtained in Synthesis Example 4 was used instead of the polymer A-1, and the amount of the crosslinking agent "Takenate D-110N" added was 0.4 parts by mass relative to 100 parts by mass of the acrylic pressure-sensitive adhesive polymer, and various evaluations were performed in the same manner as in Example 1.
  • compositions and evaluation results of the adhesive compositions of Examples 1 to 6 and Comparative Examples 1 to 3 are shown in Table 1.
  • BPMA 4-benzoylphenyl methacrylate (boiling point 418°C)
  • MA Methyl acrylate (boiling point 80°C)
  • M-120 2-ethylhexyl EO-modified (n ⁇ 2) acrylate, trade name "Aronix M-120", manufactured by Toagosei Co., Ltd.
  • OMNIRAD intramolecular cleavage type photopolymerization initiator, trade name "OMNIRAD 184", manufactured by IGM RESINS Co., Ltd.
  • the blending amounts of the crosslinking agent, multifunctional acrylate and photopolymerization initiator are blending amounts relative to 100 parts by mass of the acrylic adhesive polymer.
  • the boiling points of the monomers are predicted values under atmospheric pressure calculated by Fujitsu Limited's scientific research information management solution (ACD/Labs). The boiling points (predicted values) of each monomer are also shown in Table 1.
  • the adhesive sheet formed using an adhesive composition in which the content of the crosslinking agent was 4 parts by mass per 100 parts by mass of the acrylic adhesive polymer was rated as "x" for ease of peeling (Comparative Example 1).
  • the adhesive sheet in which an adhesive layer was formed using an adhesive composition containing a multifunctional acrylate was rated as "x” for heat resistance (Comparative Example 2).
  • the adhesive sheet formed using an adhesive composition containing polymer A-4 as the acrylic adhesive polymer was rated as "x” for both ease of peeling and heat resistance (Comparative Example 3).

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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JPH0597934A (ja) * 1991-08-09 1993-04-20 Nok Corp 透明性アクリルゴム組成物の製造法
JP2011184582A (ja) * 2010-03-09 2011-09-22 Three M Innovative Properties Co 光学用粘着シート
JP2012031316A (ja) 2010-07-30 2012-02-16 Dainippon Printing Co Ltd 耐熱仮着用粘着テープ
JP2016089045A (ja) 2014-11-05 2016-05-23 日東電工株式会社 粘着テープ
WO2018047903A1 (ja) * 2016-09-09 2018-03-15 日本合成化学工業株式会社 アクリル系粘着剤組成物、粘着剤及び粘着シート
JP2021510394A (ja) * 2018-04-12 2021-04-22 エルジー・ケム・リミテッド 臨時固定用粘着シートおよびこれを使用した半導体装置の製造方法
WO2023013489A1 (ja) * 2021-08-02 2023-02-09 三菱ケミカル株式会社 粘着剤組成物、粘着剤、及び粘着シート
WO2023112512A1 (ja) * 2021-12-17 2023-06-22 キヤノン株式会社 膜形成方法、および物品の製造方法
WO2024176580A1 (ja) * 2023-02-24 2024-08-29 リンテック株式会社 ワーク加工用シートおよびその使用方法

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0597934A (ja) * 1991-08-09 1993-04-20 Nok Corp 透明性アクリルゴム組成物の製造法
JP2011184582A (ja) * 2010-03-09 2011-09-22 Three M Innovative Properties Co 光学用粘着シート
JP2012031316A (ja) 2010-07-30 2012-02-16 Dainippon Printing Co Ltd 耐熱仮着用粘着テープ
JP2016089045A (ja) 2014-11-05 2016-05-23 日東電工株式会社 粘着テープ
WO2018047903A1 (ja) * 2016-09-09 2018-03-15 日本合成化学工業株式会社 アクリル系粘着剤組成物、粘着剤及び粘着シート
JP2021510394A (ja) * 2018-04-12 2021-04-22 エルジー・ケム・リミテッド 臨時固定用粘着シートおよびこれを使用した半導体装置の製造方法
WO2023013489A1 (ja) * 2021-08-02 2023-02-09 三菱ケミカル株式会社 粘着剤組成物、粘着剤、及び粘着シート
WO2023112512A1 (ja) * 2021-12-17 2023-06-22 キヤノン株式会社 膜形成方法、および物品の製造方法
WO2024176580A1 (ja) * 2023-02-24 2024-08-29 リンテック株式会社 ワーク加工用シートおよびその使用方法

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