WO2023112427A1 - Method for producing semiconductor device, and semiconductor device - Google Patents

Method for producing semiconductor device, and semiconductor device Download PDF

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Publication number
WO2023112427A1
WO2023112427A1 PCT/JP2022/036826 JP2022036826W WO2023112427A1 WO 2023112427 A1 WO2023112427 A1 WO 2023112427A1 JP 2022036826 W JP2022036826 W JP 2022036826W WO 2023112427 A1 WO2023112427 A1 WO 2023112427A1
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WO
WIPO (PCT)
Prior art keywords
semiconductor device
resin
manufacturing
pressure
sensitive adhesive
Prior art date
Application number
PCT/JP2022/036826
Other languages
French (fr)
Japanese (ja)
Inventor
耕治 直田
健一 中西
一博 佐々木
敬太 湯本
Original Assignee
株式会社レゾナック
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 株式会社レゾナック filed Critical 株式会社レゾナック
Priority to KR1020247010432A priority Critical patent/KR20240055794A/en
Priority to CN202280082078.5A priority patent/CN118402041A/en
Priority to JP2023567551A priority patent/JPWO2023112427A1/ja
Publication of WO2023112427A1 publication Critical patent/WO2023112427A1/en

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Classifications

    • 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
    • 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
    • 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]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
    • H01L21/683—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
    • H01L21/683—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping
    • H01L21/6835—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
    • H01L21/6836—Wafer tapes, e.g. grinding or dicing support tapes
    • 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
    • C09J2301/40—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
    • 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
    • C09J2301/50—Additional features of adhesives in the form of films or foils characterized by process specific features
    • C09J2301/502—Additional features of adhesives in the form of films or foils characterized by process specific features process for debonding adherents
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/80—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected
    • H01L2224/86—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using tape automated bonding [TAB]
    • H01L2224/868—Bonding techniques
    • H01L2224/8685—Bonding techniques using a polymer adhesive, e.g. an adhesive based on silicone, epoxy, polyimide, polyester
    • H01L2224/86855—Hardening the adhesive by curing, i.e. thermosetting
    • H01L2224/86874—Ultraviolet [UV] curing

Definitions

  • the present invention relates to a semiconductor device manufacturing method and a semiconductor device.
  • Various adhesive sheets are used in the semiconductor manufacturing process. Specifically, there are a protective sheet for protecting the wafer in the back grinding process of the semiconductor wafer, and a fixing sheet used in the process of cutting and dividing the semiconductor wafer into element pieces (dicing). These pressure-sensitive adhesive sheets are re-peelable pressure-sensitive adhesive sheets that are attached to a semiconductor wafer, which is an adherend, and are peeled off from the adherend after a predetermined processing step is completed.
  • a semiconductor chip for example, a Through Silicon Via (TSV) chip
  • TSV Through Silicon Via
  • This semiconductor chip with bumps is electrically bonded and mounted to another semiconductor chip or substrate by a reflow process in which the solder is heated to a temperature higher than the melting temperature (usually 200° C. or higher).
  • a sputtering process may be performed in which a metal film is deposited (usually at a temperature of 150° C. or higher) as an electromagnetic wave shield on the periphery of the semiconductor chip.
  • a removable adhesive sheet is used to protect the bump surfaces.
  • a printed circuit board (PCB) with bumps is widely used in semiconductor devices. Adhesive tape is sometimes used to secure the bumped PCB to another substrate or housing. In the semiconductor chip mounting process, the bumped PCB may undergo a reflow process or a sputtering process.
  • Patent Document 1 an adhesive tape having an ultraviolet curable adhesive layer that can be used by applying ultraviolet rays to cure the adhesive layer after attaching it to a semiconductor chip with bumps and peeling off after a high temperature treatment process.
  • a pressure-sensitive adhesive tape is disclosed that satisfies the relational expression: -5 ⁇ B-exp(A/30).
  • the adhesive sheet accurately follows the irregularities during the processing process. must adhere.
  • the adhesive sheet is required to have high heat resistance so that outgassing is not generated during high-temperature processing such as a reflow process, and adhesive residue does not remain on the semiconductor chip when the adhesive sheet is peeled off.
  • Patent Document 1 since the pressure-sensitive adhesive layer is not flexible enough to follow the bumps, there are cases where the adhesiveness to the unevenness of the sheet attachment surface is insufficient. In addition, there are cases where outgassing is generated after the heating process due to the additive, and where adhesive remains when the adhesive sheet is peeled off.
  • the present invention has been made in view of the above circumstances, and an adhesive that can accurately follow the unevenness and adhere to it even during the processing of semiconductor devices having uneven surfaces such as semiconductor chips with bumps and PCBs with bumps. It is an object of the present invention to provide a method for manufacturing a semiconductor device, including the use of a sheet, which does not generate outgassing during high-temperature processing and does not leave adhesive residue on the surface of an adherend when an adhesive sheet is peeled off.
  • Another object of the present invention is to provide a semiconductor device manufactured by the above manufacturing method.
  • the present inventors have found a carboxy group-containing resin (b) obtained by polymerizing a carboxy group-containing ethylenically unsaturated monomer (a) as an essential monomer component, and an alicyclic epoxy group-containing ethylenically unsaturated monomer.
  • a pressure-sensitive adhesive composition containing, as essential components, a resin (A) having a weight average molecular weight of 50,000 to 550,000 and a photopolymerization initiator (B) obtained by an addition reaction with the compound (c)
  • the present inventors have found that the above problem can be solved by providing a protective step of attaching the adhesive sheet to be formed to the adherend surface with the bumps.
  • the present invention includes the following aspects.
  • a protective step of attaching an adhesive sheet having a sheet-like base material and an adhesive layer formed on the base material to a bumped adherend surface of a semiconductor device comprising a UV irradiation step of irradiating the adhesive sheet to cure the adhesive layer, and a peeling step of peeling and removing the adhesive sheet from the adherend surface with bumps, ,
  • the pressure-sensitive adhesive layer is a cured product of the pressure-sensitive adhesive composition
  • the adhesive composition contains a resin (A) represented by the following general formula (1-1) and a photopolymerization initiator (B), and the weight average molecular weight of the resin (A) is 50,000 to 550,000.
  • k is more than 0 to 92 or less.
  • l is 0 to 50.
  • m is greater than 0 to 90.
  • the sum of k, l and m is 65 to 95.
  • n is 5 to 35.
  • R 1 to R 4 are —H or —CH 3.
  • R 5 is carbon.
  • R 6 being an alicyclic hydrocarbon group having 3 to 30 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms
  • R 7 being -H or - (CH 2 ) j —COOH (in the formula, j is 1 or 2.)
  • R 8 is a group represented by the general formula (1-2) or (1-3). -2) and (1-3), p and q are any selected from 0, 1 and 2. s is 0 when p is 0 and 1 when p is 1 or 2 and R 9 is —H or —CH 3. ) [2] The method for manufacturing a semiconductor device according to [1], wherein n in the formula (1-1) is 7 to 33.
  • [3] The method for manufacturing a semiconductor device according to [1] or [2], wherein k is 45 to 90, l is 4 to 40, and m is 1 to 20 in the formula (1-1).
  • [4] The method for producing a semiconductor device according to any one of [1] to [3], wherein the pressure-sensitive adhesive composition further contains a cross-linking agent (C).
  • [5] The method for manufacturing a semiconductor device according to any one of [1] to [4], wherein the resin (A) has a glass transition temperature of -80 to 0°C.
  • [7] The method of manufacturing a semiconductor device according to any one of [1] to [6], including a processing step between the protection step and the peeling step.
  • a pressure-sensitive adhesive composition containing a resin (A) and a photopolymerization initiator (B) has good heat resistance because the resin (A) has a structure derived from an alicyclic compound. Further, since the resin (A) has a weight average molecular weight of 50,000 to 550,000, flexibility is imparted to the pressure-sensitive adhesive layer. Therefore, the pressure-sensitive adhesive composition can form a pressure-sensitive adhesive layer having good adhesion to electronic components such as semiconductor chips with bumps and PCBs with bumps having uneven surfaces. In addition, when the resin (A) has a weight average molecular weight of 50,000 to 550,000, it is possible to reduce outgassing generated from the pressure-sensitive adhesive layer during high-temperature treatment.
  • the adhesive strength of the adhesive layer containing the cured product of the adhesive composition is that the unsaturated bonds in the resin (A) form a three-dimensional crosslinked structure and cure by irradiating with ultraviolet rays (UV). change depending on Specifically, the pressure-sensitive adhesive composition exhibits sufficient adhesive strength to the adherend before UV irradiation, and the adhesive strength decreases after UV irradiation, resulting in excellent easy peelability. At the same time, it is possible to sufficiently prevent adhesive residue on the adherend after peeling.
  • a semiconductor device By using the method for manufacturing a semiconductor device according to the present invention, it is possible to adhere the adhesive sheet accurately following the unevenness even during the process of processing a semiconductor device having unevenness on the surface, such as a semiconductor chip with bumps or a PCB with bumps.
  • a semiconductor device can be manufactured without outgassing during high-temperature processing and without adhesive residue on the adherend surface with bumps when the adhesive sheet is peeled off.
  • a method for manufacturing a semiconductor device includes: A protective step of attaching an adhesive sheet having a sheet-like base material and an adhesive layer formed on the base material to the bumped adherend surface of the semiconductor device; The method includes a UV irradiation step of irradiating the adhesive sheet to cure the adhesive layer, and a peeling step of peeling and removing the adhesive sheet from the adherend surface with bumps.
  • an adhesive sheet is attached to the bump-attached surface of the semiconductor device provided with the bump electrode.
  • the semiconductor device include a semiconductor device having an uneven surface, such as a semiconductor chip with bumps, a printed wiring board (PCB) with bumps, and an FPC board with bumps.
  • PCB printed wiring board
  • FPC board FPC board with bumps.
  • an adhesive sheet is attached to some or all of the attachment surfaces with bumps in the protection process.
  • an adhesive sheet can be attached to the non-mounting surface of the bump-attached surface excluding the mounting surface.
  • a pressure-sensitive adhesive sheet of one embodiment has a sheet-like base material and a pressure-sensitive adhesive layer formed on the base material.
  • a release sheet is preferably provided on the surface of the pressure-sensitive adhesive layer opposite to the substrate.
  • the release sheet can protect the adhesive layer until use.
  • the work of peeling off the release sheet to expose the pressure-sensitive adhesive layer and press-bonding the pressure-sensitive adhesive layer (attachment surface) to the adherend can be performed efficiently.
  • the adhesive sheet may be used as an adhesive tape shaped according to the shape of the adherend by a punching method or the like.
  • the adhesive sheet may be used as a roll-shaped adhesive tape by winding and cutting.
  • the base material a known sheet-like material can be appropriately selected and used.
  • the substrate it is preferable to use a resin sheet made of a transparent resin material.
  • resin materials include polyolefins such as polyethylene (PE) and polypropylene (PP); polyesters such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT) and polyethylene naphthalate (PEN); polyvinyl chloride (PVC); polyimide (PI); polyphenylene sulfide (PPS); ethylene vinyl acetate (EVA); and polytetrafluoroethylene (PTFE).
  • PE polyethylene
  • PP polypropylene
  • PET polyethylene terephthalate
  • PBT polybutylene terephthalate
  • PEN polyethylene naphthalate
  • PVC polyvinyl chloride
  • PI polyimide
  • PPS polyphenylene sulfide
  • EVA ethylene vinyl acetate
  • PTFE polytetrafluoroethylene
  • the resin materials may be used alone or in combination of two or more.
  • the resin sheet When a resin sheet is used as the base material, the resin sheet may be a single layer or may have a multi-layer structure of two or more layers (for example, a three-layer structure). In the resin sheet having a multilayer structure, each layer may be composed of one type of resin material, or two or more types thereof may be included.
  • the thickness of the base material can be appropriately selected according to the application of the adhesive sheet, the material of the base material, etc.
  • the adhesive sheet protects a semiconductor chip with bumps or a flexible printed circuit board (FPC) with bumps when performing a reflow process or a sputtering process, and when a resin sheet is used as the base material, the base material
  • the thickness is preferably 5-1000 ⁇ m, more preferably 10-300 ⁇ m.
  • the pressure-sensitive adhesive sheet has high rigidity (strength). Therefore, when the adhesive sheet is attached to or peeled off from an adherend such as a semiconductor chip, the adhesive sheet tends to be less likely to wrinkle or lift.
  • the thickness of the substrate is 5 ⁇ m or more, the pressure-sensitive adhesive sheet attached to the adherend can be easily peeled off from the adherend, and good workability (handleability, handling) can be obtained.
  • the thickness of the base material is 1000 ⁇ m or less, it is possible to prevent the pressure-sensitive adhesive sheet from becoming too rigid (strong in stiffness) and reducing workability.
  • a conventionally known general sheet molding method e.g., extrusion molding, T-die molding, inflation molding, uniaxial or biaxial stretch molding, etc.
  • extrusion molding e.g., extrusion molding, T-die molding, inflation molding, uniaxial or biaxial stretch molding, etc.
  • the surface of the substrate that contacts the adhesive layer may be surface-treated to improve the adhesion between the substrate and the adhesive layer.
  • Examples of surface treatment include corona discharge treatment, acid treatment, ultraviolet irradiation treatment, plasma treatment, and primer application.
  • the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet of one embodiment contains a cured product of the pressure-sensitive adhesive composition described below.
  • the thickness of the pressure-sensitive adhesive layer is preferably 1-1000 ⁇ m, more preferably 5-750 ⁇ m, even more preferably 10-500 ⁇ m. When the thickness of the pressure-sensitive adhesive layer is 1 ⁇ m or more, the thickness uniformity of the pressure-sensitive adhesive layer is good. When the thickness of the pressure-sensitive adhesive layer is 1000 ⁇ m or less, the pressure-sensitive adhesive layer can be sufficiently adhered to the unevenness of the surface without floating.
  • a release sheet When a release sheet is provided on the surface of the pressure-sensitive adhesive layer opposite to the base material, a known sheet-like material can be appropriately selected and used as the release sheet.
  • the release sheet the same resin sheet as the base material can be used.
  • the thickness of the release sheet can be appropriately selected according to the application of the adhesive sheet, the material of the release sheet, and the like.
  • the thickness of the release sheet is preferably 5 to 300 ⁇ m, more preferably 10 to 200 ⁇ m, still more preferably 25 to 100 ⁇ m.
  • the release surface of the release sheet (the surface placed in contact with the pressure-sensitive adhesive layer) is subjected to a release treatment using a conventionally known release agent such as a silicone, long-chain alkyl, or fluorine release agent, if necessary.
  • a conventionally known release agent such as a silicone, long-chain alkyl, or fluorine release agent, if necessary.
  • the pressure-sensitive adhesive sheet of one embodiment can be produced, for example, by the method shown below.
  • an adhesive solution is prepared by dissolving or dispersing the adhesive composition described later in a solvent. You may use the adhesive composition mentioned above as an adhesive solution as it is.
  • an adhesive solution is applied to the substrate, and if it contains a solvent, it is dried by heating to remove the solvent, forming an adhesive layer. After that, a release sheet is pasted on the pressure-sensitive adhesive layer, if necessary. Furthermore, if necessary, the obtained sheet is cured in an oven for a certain period of time to form a crosslinked structure, whereby a pressure-sensitive adhesive sheet can be obtained.
  • Another method for producing an adhesive sheet is to apply the above adhesive solution on a release sheet, and if it contains a solvent, heat dry it to remove the solvent, and form an adhesive layer. Thereafter, a release sheet having an adhesive layer is placed on the substrate with the adhesive layer side facing the substrate, and the adhesive layer is transferred (transferred) onto the substrate.
  • a method of curing in an oven for a certain period of time to form a crosslinked structure can be used.
  • a known method can be used as a method for applying the above adhesive solution onto the substrate (or onto the release sheet).
  • Specific examples include a method of coating using a conventional coater such as gravure roll coater, reverse roll coater, kiss roll coater, dip roll coater, bar coater, knife coater, spray coater, comma coater, direct coater, and the like. be done.
  • the conditions for heat drying the applied adhesive solution are not particularly limited, but usually 25 to 180 ° C., preferably 60 to 150 ° C., usually 1 to 20 minutes, preferably 1 to 10 minutes. I do.
  • the solvent contained in the adhesive solution can be removed by performing heat drying under the above conditions.
  • the conditions for curing the pressure-sensitive adhesive sheet after heat drying in an oven for a certain period of time are not particularly limited, but the curing is usually carried out at 25 to 100° C., preferably 30 to 80° C., for usually 1 to 7 days, preferably 1 to 3 days. .
  • the resin (A) and the cross-linking agent (C) are cross-linked, and the gel fraction of the pressure-sensitive adhesive layer can be adjusted within a desired range.
  • the pressure-sensitive adhesive composition of one embodiment contains a resin (A) and a photoinitiator (B).
  • the resin (A) contained in the adhesive composition of one embodiment is a compound represented by the following general formula (1-1).
  • k is more than 0 to 92 or less.
  • l is 0 to 50.
  • m is greater than 0 to 90.
  • the sum of k, l and m is 65 to 95.
  • n is 5 to 35.
  • R 1 to R 4 are —H or —CH 3.
  • R 5 is carbon.
  • R 6 being an alicyclic hydrocarbon group having 3 to 30 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms
  • R 7 being -H or - (CH 2 ) j —COOH (in the formula, j is 1 or 2.)
  • R 8 is a group represented by the general formula (1-2) or (1-3). -2) and (1-3), p and q are any selected from 0, 1 and 2. s is 0 when p is 0 and 1 when p is 1 or 2 and R 9 is —H or —CH 3. )
  • k is greater than 0 to 92 or less.
  • l is 0-50.
  • m is from more than 0 to 90 or less.
  • the sum of k, l and m is 65-95.
  • a pressure-sensitive adhesive layer having sufficient adhesiveness to an adherend can be formed before UV irradiation.
  • the sum of k, l and m is preferably 70-94, more preferably 75-90.
  • repeating unit k the repeating unit shown in parentheses surrounded by k (hereinafter referred to as "repeating unit k") is an essential repeating unit.
  • the repeating unit k contributes to the adhesive strength of the adhesive composition before UV irradiation.
  • the repeating number k of the repeating unit k is from more than 0 to 92 or less, preferably from 45 to 90, more preferably from 60 to 88.
  • repeating unit l the repeating unit shown in parentheses enclosed by l (hereinafter referred to as "repeating unit l”) may be omitted. In other words, the repeating number of repeating unit l may be zero.
  • the repeating unit l contributes to the heat resistance of the pressure-sensitive adhesive composition.
  • the repeating number l of the repeating unit l is 0 to 50, preferably 4 to 40, more preferably 5 to 30.
  • repeating unit m the repeating unit shown in parentheses surrounded by m (hereinafter referred to as "repeating unit m") is an essential repeating unit.
  • the repeating unit m contributes to the adhesive strength and heat resistance of the adhesive composition before UV irradiation.
  • the repeating unit m reacts with the cross-linking agent to impart cohesion to the pressure-sensitive adhesive layer.
  • the repeating number m of the repeating unit m is from more than 0 to 90 or less, preferably from 1 to 20, more preferably from 1 to 10.
  • repeating unit n the repeating unit shown in parentheses surrounded by n (hereinafter referred to as "repeating unit n") is an essential repeating unit.
  • the repeating unit n contributes to heat resistance of the pressure-sensitive adhesive composition.
  • the repeating number n of repeating unit n is 5 to 35, preferably 7 to 33, more preferably 10 to 30.
  • the repeating unit n is 35 or less, the unsaturated bonds in the resin (A) are cured by UV irradiation to form a three-dimensional crosslinked structure, resulting in a pressure-sensitive adhesive layer whose adhesive strength is reduced to an appropriate range. can be formed.
  • n is 5 or more, the effect of improving heat resistance due to the structure derived from the alicyclic compound can be obtained.
  • the pressure-sensitive adhesive composition containing the resin (A) Due to the synergistic effect of the functions contributed by these repeating units, the pressure-sensitive adhesive composition containing the resin (A) has a better balance between the adhesive strength before ultraviolet (UV) irradiation and the adhesive strength after UV irradiation. Become. As a result, it is possible to obtain a pressure-sensitive adhesive composition that exhibits sufficient adhesive strength to an adherend before UV irradiation, and that exhibits reduced adhesive strength after UV irradiation, thereby providing superior easy peelability. .
  • this pressure-sensitive adhesive composition does not excessively increase its adhesive strength even when it is brought to a high temperature state before UV irradiation and then returned to room temperature, and excellent easy peelability can be obtained after UV irradiation, and the adhesive composition can be easily peeled off after peeling. Adhesive residue on the body is less likely to occur.
  • R 1 is -H or -CH 3 , preferably -H.
  • R 5 is an alkyl group having 1 to 16 carbon atoms, preferably an alkyl group having 1 to 8 carbon atoms, particularly preferably an alkyl group having 2, 4 or 8 carbon atoms.
  • Repeating unit k may be a plurality of repeating units with different R 1 and/or R 5 .
  • the repeating number k of the repeating unit k indicates the total number of repeating units of the multiple types of repeating units. For example, if repeating unit k contains repeating units A and B with different R 1 and/or R 5 , and contains two repeating units A and three repeating units B, then the number of repeating units k is the number of A and B The numbers add up to 5.
  • R 2 is -H or -CH 3 , preferably -H.
  • R 6 is an alicyclic hydrocarbon group having 3 to 30 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms, and an alicyclic hydrocarbon group having 6 to 20 carbon atoms or 6 carbon atoms ⁇ 12 aromatic hydrocarbon groups are preferred.
  • Repeating unit 1 may be a plurality of repeating units with different R 2 and/or R 6 .
  • the repeating number 1 of the repeating unit 1 indicates the sum of the repeating numbers of the multiple types of repeating units.
  • R 3 is -H or -CH 3 , preferably -H.
  • R 7 is -H or -(CH 2 ) j -COOH (where j is 1 or 2), preferably -H.
  • Repeating unit m may be a plurality of repeating units with different R 3 and/or R 7 .
  • the repeating number m of the repeating unit m indicates the total number of repeating units of the multiple types of repeating units.
  • R 4 is -H or -CH 3 , preferably -H.
  • R 8 is a group represented by formula (1-2) or (1-3). Each group represented by formula (1-2) or (1-3) contains a structure derived from an alicyclic compound and has the function of improving the heat resistance of the pressure-sensitive adhesive composition.
  • p and q are any selected from 0, 1 and 2.
  • s is 0 when p is 0 and 1 when p is 1 or 2;
  • R 9 is -H or -CH 3 .
  • Repeating unit n may be a plurality of repeating units with different R 4 and/or R 8 .
  • the repeating number n of the repeating unit n indicates the total number of repeating units of the multiple types of repeating units.
  • the resin (A) represented by formula (1-1) is a random copolymer, block copolymer, or alternating copolymer composed of repeating unit k, repeating unit l, repeating unit m, and repeating unit n. may be either.
  • the resin (A) represented by formula (1-1) may not contain the repeating unit l, and may be a random copolymer or a block copolymer consisting of a repeating unit k, a repeating unit m, and a repeating unit n. , alternating copolymers.
  • the weight average molecular weight of the resin (A) is 50,000 to 550,000, preferably 100,000 to 500,000, more preferably 260,000 to 450,000.
  • the weight average molecular weight of the resin (A) is 50,000 or more, when a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer containing a cured product of the pressure-sensitive adhesive composition is attached to an adherend and then peeled off, the pressure-sensitive adhesive layer is It becomes more difficult to remain on the adherend.
  • the weight average molecular weight of the resin (A) is 550,000 or less, the pressure-sensitive adhesive layer can be sufficiently adhered to uneven surfaces such as bumps without gaps.
  • the weight average molecular weight of resin (A) is a value measured by the method described in Examples.
  • the glass transition temperature (Tg) of the resin (A) is preferably -80 to 0°C, more preferably -60 to -10°C, still more preferably -50 to -10°C.
  • the Tg of resin (A) is a value measured by the method described in Examples.
  • the acid value of resin (A) is preferably greater than 0 to 25 mgKOH/g, more preferably 3 to 20 mgKOH/g.
  • the acid value of the resin (A) is in the range of more than 0 to 25 mgKOH/g, contamination of the adherend (adhesive residue) after heating can be reduced.
  • the pressure-sensitive adhesive composition contains a cross-linking agent, if the acid value of the resin (A) is within the above range, the resin (A) and the cross-linking agent react to effectively increase the cohesive strength of the pressure-sensitive adhesive composition. As a result, contamination of the adherend (adhesive residue) after heating can be further reduced.
  • the acid value of Resin (A) is a value measured by the method described in Examples.
  • Resin (A) can be produced, for example, by the method shown below.
  • raw material monomers containing a carboxy group-containing ethylenically unsaturated monomer (a) and an ethylenically unsaturated monomer (d) are polymerized to produce a carboxy group-containing resin (b).
  • the ethylenically unsaturated monomer (d) contains a monomer that forms the repeating unit k after polymerization, and may contain a monomer that forms the skeleton of the repeating unit l.
  • the resin (A) can be produced by an addition reaction between the carboxy group-containing resin (b) and the specific alicyclic epoxy group-containing ethylenically unsaturated compound (c).
  • the carboxy group-containing ethylenically unsaturated monomer (a) used when producing the carboxy group-containing resin (b) is a monomer that forms a skeleton of the repeating unit m by polymerizing.
  • the carboxy group-containing ethylenically unsaturated monomer (a) has one carboxy group.
  • Carboxy group-containing ethylenically unsaturated monomers (a) include, for example, (meth)acrylic acid, carboxymethyl (meth)acrylate, and ⁇ -carboxyethyl (meth)acrylate.
  • (meth)acrylic acid and/or ⁇ -carboxyethyl (meth)acrylate as the carboxy group-containing ethylenically unsaturated monomer (a) in terms of reactivity.
  • (meth)acryl means “acryl” or “methacryl”.
  • (Meth)acrylate means “acrylate” or “methacrylate”.
  • (Meth)acryloyl means “acryloyl” or “methacryloyl”.
  • the carboxy group-containing resin (b) is a carboxy group-containing ethylenically unsaturated monomer (a) and an ethylenically unsaturated monomer copolymerizable with the carboxy group-containing ethylenically unsaturated monomer (a) ( It is obtained by copolymerizing raw material monomers containing at least d).
  • the carboxy group-containing resin (b) is a component that forms the skeleton of the resin (A) represented by formula (1-1).
  • Repeating unit k, repeating unit l, and repeating unit m are all repeating units derived from the carboxy group-containing resin (b).
  • the ethylenically unsaturated monomer (d) one or more monomers that form a skeleton of the repeating unit k when polymerized are used.
  • the ethylenically unsaturated monomer (d) at least one monomer that forms the skeleton of the repeating unit k by polymerization and a monomer that forms the skeleton of the repeating unit l by polymerization are used. good too.
  • the ethylenically unsaturated monomer (d) that forms the skeleton of the repeating unit k by polymerization is an alkyl (meth)acrylate having 1 to 16 carbon atoms, from the viewpoint of adjusting the peel strength of the pressure-sensitive adhesive composition. Therefore, it preferably contains an alkyl (meth)acrylate having 2 to 16 carbon atoms, more preferably an alkyl (meth)acrylate having 4 to 12 carbon atoms.
  • alkyl (meth)acrylates having 1 to 16 carbon atoms include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, tert- Butyl (meth)acrylate, isobutyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isodecyl (meth)acrylate, n-hexyl (meth)acrylate, isooctyl (meth)acrylate, and lauryl (meth)acrylate.
  • methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and isooctyl (meth)acrylate are preferred.
  • the number of carbon atoms used for (meth)acrylate refers to the number of carbon atoms in the residue excluding the (meth)acryloyloxy group.
  • Examples of the ethylenically unsaturated monomer (d) that forms the skeleton of the repeating unit l by polymerization include (meth)acrylates containing a cyclic alkyl group having 3 to 30 carbon atoms, and 6 to 20 carbon atoms. of aromatic group-containing (meth)acrylates.
  • the (meth)acrylate containing a cyclic alkyl group having 3 to 30 carbon atoms used as the ethylenically unsaturated monomer (d) that forms the skeleton of the repeating unit l by polymerization includes, for example, cyclohexyl (meth)acrylate , norbornyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, dicyclopentanyl (meth)acrylate, and dicyclopentanyloxyethyl (meth)acrylate Acrylates are mentioned.
  • the pressure-sensitive adhesive composition containing the resin (A) produced using the carboxy group-containing resin (b) It can increase the heat resistance of the object.
  • the aromatic group-containing (meth)acrylate having 6 to 20 carbon atoms used as the ethylenically unsaturated monomer (d) that forms the skeleton of the repeating unit l by polymerization includes, for example, benzyl (meth)acrylate , phenoxyethyl (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate, phenoxypropyl (meth)acrylate, and phenoxypolypropylene glycol (meth)acrylate.
  • the pressure-sensitive adhesive composition containing the resin (A) produced using the carboxy group-containing resin (b) It can increase the heat resistance of the object.
  • the raw material monomers of the carboxy group-containing resin (b) not only the above carboxy group-containing ethylenically unsaturated monomer (a) and the above ethylenically unsaturated monomer (d), but also the above A monomer copolymerizable with the carboxy group-containing ethylenically unsaturated monomer (a) other than the ethylenically unsaturated monomer (d) may also be included.
  • Examples of the ethylenically unsaturated monomer copolymerizable with the carboxy group-containing ethylenically unsaturated monomer (a) other than the above ethylenically unsaturated monomer (d) include, for example, alkoxyalkyl (meth) Acrylates, alkoxy(poly)alkylene glycol (meth)acrylates, hydroxy group-containing (meth)acrylates, fluorinated alkyl (meth)acrylates, dialkylaminoalkyl (meth)acrylates, and (meth)acrylamide compounds.
  • Alkoxyalkyl (meth)acrylates include, for example, ethoxyethyl (meth)acrylate, methoxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, 2-methoxyethoxyethyl (meth)acrylate, and 2-ethoxyethoxyethyl (meth)acrylate. ) acrylates.
  • Alkoxy (poly) alkylene glycol (meth) acrylates include, for example, methoxydiethylene glycol (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, and methoxydipropylene glycol (meth) acrylate.
  • hydroxy group-containing (meth)acrylates examples include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 1,3-butanediol (meth)acrylate, 1,4-butanediol (meth)acrylate, 1,6-hexanediol (meth)acrylate, and 3-methylpentanediol (meth)acrylate.
  • fluorinated alkyl (meth)acrylates examples include octafluoropentyl (meth)acrylate.
  • dialkylaminoalkyl (meth)acrylates examples include N,N-dimethylaminoethyl (meth)acrylate and N,N-diethylaminoethyl (meth)acrylate.
  • (Meth)acrylamide compounds include, for example, (meth)acrylamide, N-methyl(meth)acrylamide, N-ethyl(meth)acrylamide, N-propyl(meth)acrylamide, N-isopropyl(meth)acrylamide, N-hexyl (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, (meth)acryloylmorpholine, and diacetoneacrylamide.
  • the monomer copolymerizable with the carboxy group-containing ethylenically unsaturated monomer (a) other than the ethylenically unsaturated monomer (d) include acrylonitrile, methacrylonitrile, styrene, ⁇ -methylstyrene, vinyl acetate, vinyl propionate, vinyl stearate, vinyl chloride, vinylidene chloride, alkyl vinyl ether, vinyl toluene, N-vinylpyridine, N-vinylpyrrolidone, dialkyl itaconate, dialkyl fumarate, allyl alcohol , hydroxybutyl vinyl ether, hydroxyethyl vinyl ether, 4-hydroxymethylcyclohexylmethyl vinyl ether, triethylene glycol monovinyl ether, diethylene glycol monovinyl ether, methyl vinyl ketone, allyltrimethylammonium chloride, and dimethyl allyl vinyl ketone.
  • the method for producing the carboxy group-containing resin (b) is not particularly limited.
  • raw material monomers containing a carboxy group-containing ethylenically unsaturated monomer (a) and an ethylenically unsaturated monomer (d), which are constituent components of the carboxy group-containing resin (b), are subjected to known polymerization.
  • Carboxy group-containing resin (b) can be obtained by copolymerizing according to the method.
  • a solution polymerization method, an emulsion polymerization method, a bulk polymerization method, a suspension polymerization method, an alternating copolymerization method, or the like can be used.
  • the radical polymerization initiator is not particularly limited, and can be appropriately selected from known ones and used.
  • radical polymerization initiators examples include 2,2′-azobis(isobutyronitrile), 2,2′-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis(2 ,4-dimethylvaleronitrile), 2,2′-azobis(2-methylbutyronitrile), 1,1′-azobis(cyclohexane-1-carbonitrile), 2,2′-azobis(2,4,4 -trimethylpentane), dimethyl-2,2'-azobis (2-methylpropionate) and other azo polymerization initiators; and benzoyl peroxide, t-butyl hydroperoxide, di-t-butyl peroxide, t -butyl peroxybenzoate, dicumyl peroxide, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(t-butylperoxy)cyclododecane, etc.
  • examples include
  • radical polymerization initiators may be used alone or in combination of two or more.
  • the amount of the radical polymerization initiator to be used is preferably 0.01 to 5 parts by mass, more preferably 0.02 to 4 parts by mass, with respect to the total 100 parts by mass of the raw material monomers of the carboxy group-containing resin (b). and more preferably 0.03 to 3 parts by mass.
  • solvents can be used as the solvent for polymerization used when producing the carboxy group-containing resin (b).
  • solvents include esters such as ethyl acetate, n-propyl acetate and n-butyl acetate; aromatic hydrocarbons such as toluene, xylene and benzene; aliphatic hydrocarbons such as n-hexane and n-heptane; alicyclic hydrocarbons such as methylcyclohexane; ketones such as methyl ethyl ketone and methyl isobutyl ketone; glycols such as ethylene glycol, propylene glycol and dipropylene glycol; glycol ethers such as methyl cellosolve, propylene glycol monomethyl ether and dipropylene glycol monomethyl ether; and glycol esters such as ethylene glycol diacetate and propylene glycol monomethyl ether acetate.
  • solvents may be used alone or in combination of two or more.
  • the carboxy group-containing resin (b) When producing the carboxy group-containing resin (b), the carboxy group-containing ethylenically unsaturated monomer (a), the ethylenically unsaturated monomer (d), and other optionally contained
  • the content of the carboxy group-containing ethylenically unsaturated monomer (a) in the raw material monomer containing the monomer is preferably 5 to 40% by mass, and may be 7 to 30% by mass. More preferably, it is 10 to 25% by mass.
  • the carboxy group-containing resin (b) and the alicyclic epoxy group-containing ethylenically unsaturated compound By setting the content of the carboxy group-containing ethylenically unsaturated monomer (a) in the raw material monomer to the above range, the carboxy group-containing resin (b) and the alicyclic epoxy group-containing ethylenically unsaturated compound (
  • the pressure-sensitive adhesive layer obtained from the pressure-sensitive adhesive composition containing the resin (A) produced by the addition reaction with c) has good adhesive strength before UV irradiation.
  • the alicyclic epoxy group-containing ethylenically unsaturated compound (c) is an ethylenically unsaturated group-containing compound having an alicyclic epoxy group and represented by general formula (1-2) or general formula (1-3). It is the compound that gives the structure.
  • An alicyclic epoxy group in the present disclosure refers to an epoxy group formed by bonding one oxygen to two adjacent carbon atoms on the ring of an alicyclic hydrocarbon compound.
  • the alicyclic epoxy group-containing ethylenically unsaturated compound (c) has the following partial structural formula (1-2') or (1-3') in the repeating unit n of the resin (A) represented by formula (1-1). ) is used to add Partial structural formula (1-2') or (1-3') in repeating unit n in formula (1-1) is a group derived from an alicyclic epoxy group-containing ethylenically unsaturated compound (c). .
  • q is any one selected from 0, 1 and 2.
  • R 9 is —H or —CH 3.
  • Examples of the alicyclic epoxy group-containing ethylenically unsaturated compound (c) include compounds represented by the following formula (1) or (2).
  • R 9 is —H or —CH 3. q is any one selected from 0, 1 and 2.
  • R 9 is —H or —CH 3. q is any one selected from 0, 1 and 2.
  • R 9 is -H or -CH 3 .
  • q is any one selected from 0, 1 and 2, preferably q is 1;
  • R 9 is -H or -CH 3 .
  • q is any one selected from 0, 1 and 2, preferably q is 1;
  • the alicyclic epoxy group-containing ethylenically unsaturated compound (c) is preferably a compound represented by formula (1), and particularly preferably 3,4-epoxycyclohexylmethyl (meth)acrylate.
  • the alicyclic epoxy group-containing ethylenically unsaturated compound (c) may be used alone or in combination of two or more.
  • the resin (A) can be produced by subjecting the carboxy group of the carboxy group-containing resin (b) to an addition reaction with the alicyclic epoxy group of the alicyclic epoxy group-containing ethylenically unsaturated compound (c).
  • the amount of the resin (A) is preferably 0.2 to 0.99 mol, more preferably 0.3 to 0.95 mol, still more preferably 0.6 to 0.99 mol, per 1 mol of the carboxy group of the carboxy group-containing resin (b). It is preferably produced by addition reaction of 95 mol of the alicyclic epoxy group-containing ethylenically unsaturated compound (c).
  • this pressure-sensitive adhesive composition does not easily increase its adhesive strength even when it is brought to a high temperature state before UV irradiation and then returned to room temperature, and excellent easy peelability can be obtained after UV irradiation. The adhesive residue can be prevented more effectively.
  • the temperature of the addition reaction when producing the resin (A) is preferably 80 to 130°C, particularly preferably 90 to 120°C.
  • the addition reaction temperature is 80° C. or higher, a sufficient reaction rate can be obtained.
  • the temperature of the addition reaction is 130° C. or lower, it is possible to prevent the formation of a gelled product due to cross-linking of double bonds due to thermal radical polymerization.
  • a known catalyst can be used, if necessary, for the addition reaction during the production of the resin (A).
  • catalysts include primary amines such as n-butylamine, n-hexylamine and benzylamine; triethylamine, tributylamine, dimethylbenzylamine, 1,8-diazabicyclo[5.4.0]undec-7-ene, Tertiary amines such as 1,5-diazabicyclo[4.3.0]non-5-ene, 1,4-diazabicyclo[2.2.2]octane; aniline, toluidine, phenylenediamine, 1,8-diaminonaphthalene aromatic amines such as; pyridine, 2,6-lutidine, 4-N,N-dimethylaminopyridine and other pyridine compounds; Alkyl ureas such as methyl urea; Alkyl guanidines such as tetramethyl guanidine; Phosphines
  • a tertiary amine a pyridine compound, or a phosphine compound in terms of reactivity.
  • the amount of the catalyst used in the addition reaction is preferably 0.01 to 20 parts by mass with respect to a total of 100 parts by mass of the carboxy group-containing resin (b) and the alicyclic epoxy group-containing ethylenically unsaturated compound (c). , more preferably 0.05 to 10 parts by mass, most preferably 0.1 to 5 parts by mass.
  • a gas having a polymerization inhibitory effect may be introduced into the reaction system, or a polymerization inhibitor may be added. Gelation during the addition reaction can be prevented by introducing a gas having a polymerization inhibitory effect into the reaction system or by adding a polymerization inhibitor.
  • Gases that have the effect of inhibiting polymerization include gases that contain oxygen to the extent that they do not fall within the explosion range of substances in the system, such as air.
  • polymerization inhibitor known ones can be used without particular limitation. 4-methyl-6-t-butylphenol), and phenothiazine. These polymerization inhibitors may be used alone or in combination of two or more.
  • the amount of the polymerization inhibitor used is preferably 0.005 to 5 parts by mass with respect to a total of 100 parts by mass of the carboxy group-containing resin (b) and the alicyclic epoxy group-containing ethylenically unsaturated compound (c). More preferably 0.03 to 3 parts by mass, most preferably 0.05 to 1.5 parts by mass. If the amount of polymerization inhibitor is too small, the effect of inhibiting polymerization may not be sufficient. On the other hand, if the amount of the polymerization inhibitor is too large, the exposure sensitivity of the resin (A) during UV irradiation may decrease.
  • Examples of the photopolymerization initiator (B) contained in the adhesive composition include benzophenone, benzyl, benzoin, ⁇ -bromoacetophenone, chloroacetone, acetophenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2 -phenylacetophenone, p-dimethylaminoacetophenone, p-dimethylaminopropiophenone, 2-chlorobenzophenone, 4,4'-dichlorobenzophenone, 4,4'-bisdiethylaminobenzophenone, Michler's ketone, benzoin methyl ether, benzoin isobutyl ether, Benzoin-n-butyl ether, benzyl methyl ketal, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2- methylpropan-1-
  • Examples of the photopolymerization initiator (B) include sulfide photopolymerization initiators such as diphenyl disulfide, dibenzyl disulfide, tetraethylthiuram disulfide, and tetramethylammonium monosulfide; 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4 Acylphosphine oxides such as ,6-trimethylbenzoylphenylethoxyphosphine oxide; quinone photopolymerization initiators such as benzoquinone and anthraquinone; sulfochloride photopolymerization initiators; A photoinitiator may also be used.
  • sulfide photopolymerization initiators such as diphenyl disulfide, dibenzyl disulfide, tetraethylthiuram disulfide, and tetramethylammonium monosulfide
  • photopolymerization initiators (B) it is preferable to use 1-hydroxycyclohexylphenyl ketone and/or 2,4,6-trimethylbenzoyldiphenylphosphine oxide from the viewpoint of solubility in the adhesive composition.
  • photopolymerization initiators (B) may be used alone or in combination of two or more.
  • the photopolymerization initiator (B) contained in the adhesive composition is preferably 0.1 to 5.0 parts by mass, and 0.5 to 2.0 parts by mass, relative to 100 parts by mass of the resin (A). Part is more preferred.
  • the adhesive composition can be cured at a sufficiently high curing rate by UV irradiation. , so that the adhesive strength of the adhesive composition after UV irradiation can be sufficiently reduced.
  • the content of the photopolymerization initiator (B) is 5.0 parts by mass or less with respect to 100 parts by mass of the resin (A)
  • the adhesive sheet having the adhesive layer containing the adhesive composition is attached to the adherend.
  • the adhesive layer When the adhesive layer is peeled off after application, the adhesive layer is less likely to remain on the adherend. Even if the content of the photoinitiator (B) with respect to 100 parts by mass of the resin (A) exceeds 5.0 parts by mass, the effect corresponding to the content of the photoinitiator (B) is not seen, so the same content By setting the amount to 5.0 parts by mass or less, the pressure-sensitive adhesive composition can be produced economically.
  • the pressure-sensitive adhesive composition may contain not only the resin (A) and the photoinitiator (B) but also the cross-linking agent (C). By containing the cross-linking agent (C), it is possible to obtain a pressure-sensitive adhesive composition having a better balance between the adhesive strength before UV irradiation and the adhesive strength after UV irradiation.
  • the cross-linking agent (C) is not particularly limited, but is preferably a compound having two or more functional groups reactive with the hydroxyl group of repeating unit n, or the hydroxyl group of repeating unit n and the carboxy group of repeating unit m.
  • cross-linking agent (C) examples include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hydrogenated tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, diphenylmethane- 4,4-diisocyanate, isophorone diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, isocyanurate of hexamethylene diisocyanate, tetramethylxylylene diisocyanate, 1,5-naphthalene diisocyanate, tolylene diisocyanate addition of trimethylolpropane xylylene diisocyanate adduct of trimethylolpropane, triphenylmethane triisocyanate, isocyanate compounds such as methylenebis(4-phenylmethane) triisocyanate; 1,3-bis(N,N'-
  • cross-linking agents (C) it is preferable to use epoxy-based compounds and/or isocyanate-based compounds because they have good reactivity with the resin (A).
  • cross-linking agents (C) may be used alone or in combination of two or more.
  • the cross-linking agent (C) contained in the adhesive composition is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, with respect to 100 parts by mass of the resin (A). It is preferably 0.1 to 1.0 parts by mass, more preferably.
  • the content of the cross-linking agent (C) is 0.05 parts by mass or more relative to 100 parts by mass of the resin (A)
  • a three-dimensional cross-linked structure is sufficiently formed in the pressure-sensitive adhesive composition.
  • the adhesive strength of the adhesive composition after UV irradiation can be sufficiently reduced.
  • the content of the cross-linking agent (C) is 10 parts by mass or less with respect to 100 parts by mass of the resin (A)
  • the adhesive strength of the pressure-sensitive adhesive composition before UV irradiation is good.
  • the pressure-sensitive adhesive composition may contain components other than the resin (A), the photopolymerization initiator (B), and the cross-linking agent (C) described above, if necessary.
  • Other ingredients include, for example, tackifiers, solvents, and various additives.
  • tackifier As the tackifier, conventionally known ones can be used without particular limitation.
  • tackifiers include terpene-based tackifying resins, phenol-based tackifying resins, rosin-based tackifying resins, aliphatic petroleum resins, aromatic petroleum resins, copolymer petroleum resins, and alicyclic petroleum resins. , xylene resins, epoxy tackifier resins, polyamide tackifier resins, ketone tackifier resins, and elastomer tackifier resins. These tackifiers may be used alone or in combination of two or more.
  • the content thereof is preferably 30 parts by mass or less, more preferably 5 to 20 parts by mass, based on 100 parts by mass of the resin (A).
  • solvent A solvent can be used to dilute the adhesive composition for the purpose of adjusting the viscosity of the adhesive composition when the adhesive composition is applied.
  • the solvent examples include organic solvents such as methyl ethyl ketone, methyl isobutyl ketone, acetone, ethyl acetate, n-propyl acetate, tetrahydrofuran, dioxane, cyclohexanone, n-hexane, toluene, xylene, n-propanol and isopropanol. can. These solvents may be used alone or in combination of two or more.
  • Additives include, for example, plasticizers, surface lubricants, leveling agents, softeners, antioxidants, anti-aging agents, light stabilizers, ultraviolet absorbers, polymerization inhibitors, light stabilizers such as benzotriazoles, phosphorus Acid ester and other flame retardants, surfactants, and antistatic agents are included.
  • An adhesive composition can be manufactured by a conventionally well-known method.
  • the resin (A) and the photopolymerization initiator (B) described above, a cross-linking agent (C) contained as necessary, and other components such as a tackifier, a solvent, and various additives are conventionally It can be produced by mixing and stirring using a known method.
  • the pressure-sensitive adhesive composition of one embodiment is suitable as a material for forming the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet, and is particularly preferable as the material for forming the pressure-sensitive adhesive layer of the removable pressure-sensitive adhesive sheet.
  • the pressure-sensitive adhesive composition of one embodiment contains the resin (A) represented by formula (1-1) and the photopolymerization initiator (B), it can be used as a material for forming the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet.
  • a pressure-sensitive adhesive sheet having sufficient adhesive strength to an adherend can be obtained.
  • the adherend to which the adhesive sheet is attached is heated to a high temperature and then returned to room temperature and then peeled off, the adhesive sheet exhibits excellent easy peelability after UV irradiation and hardly leaves adhesive residue.
  • the method for manufacturing a semiconductor device may have a processing step between the protection step and the peeling step described below.
  • processing steps conventionally known processing steps used in the manufacture of semiconductor devices can be applied without particular limitations.
  • the adhesive sheet used in the protection process is used as a wafer dicing tape
  • the wafer is cut into individual pieces as a processing process.
  • a dicing process is performed to cut (dicing) into parts to obtain element pieces (chips).
  • a semiconductor chip lamination process is performed as a processing process, only the non-mounting surface of the bumped adherend surface is protected by a protective process, and the mounting surfaces to which the adhesive sheet is not attached are brought into contact with each other and electrically connected while laminating. Connecting.
  • the method for manufacturing a semiconductor device may have a heating step between the protection step and the peeling step described below.
  • the order of the processing step and the heating step is not limited, but the protective function and temporary fixing function of the adhesive sheet, that is, the adhesion performance is maximized. From the point of view, it is preferable that the processing step and the heating step are performed at the same time, or that the processing step is performed before the heating step.
  • the heating process a conventionally known heating process used for manufacturing semiconductor devices can be applied without particular limitation.
  • the heating process include a PCB after-curing process with bumps, a semiconductor chip sputtering process, and a reflow process after semiconductor chip lamination.
  • the conditions for the heating process are not particularly limited. By carrying out the protection step before the heating step, even when high temperature treatment such as 150° C. or higher, 180° C. or higher, or 200° C. or higher is performed, the adherend surface with bumps can be well protected.
  • the upper limit temperature of the heating step is not particularly limited, but is preferably 300° C. or lower, more preferably 270° C. or lower from the viewpoint of heat resistance of the adhesive sheet.
  • the heating time is not particularly limited, but is, for example, 1 minute to 180 minutes, preferably 1 minute to 120 minutes, more preferably 1 minute to 60 minutes.
  • UV irradiation process UV is usually irradiated from the substrate side of the adhesive sheet.
  • the adhesive sheet may be irradiated with UV from the adherend side.
  • the adhesive layer can be cross-linked and cured, and the heat resistance of the adhesive sheet can be increased, or the adhesive sheet can be imparted with light release properties.
  • the UV irradiation step may be performed between the protecting step and the later-described peeling step, and the order of the processing step and the heating step is not limited.
  • Examples of the light source used for UV irradiation to the adhesive sheet before peeling attached to the adherend include LED lamps, high pressure mercury lamps, ultra-high pressure mercury lamps, carbon arc lamps, xenon lamps, metal halide lamps, chemical lamps, and black lights. It is preferable to use an LED lamp, a high-pressure mercury lamp, or a metal halide lamp for UV irradiation.
  • the amount of UV irradiation applied to the adhesive sheet is preferably 50-3000 mJ/cm 2 , more preferably 100-600 mJ/cm 2 .
  • the adhesive layer can be cured at a sufficiently high curing speed by UV irradiation, thereby improving the adhesion of the adhesive layer after UV irradiation.
  • the force can be made sufficiently small. Even if the amount of UV irradiation applied to the adhesive sheet exceeds 3000 mJ/cm 2 , the corresponding effect cannot be obtained .
  • the pressure-sensitive adhesive sheet can be removed economically while reducing the effects of UV irradiation.
  • the processing step may be performed between the protection step and the UV irradiation step, or may be performed between the UV irradiation step and the peeling step.
  • the heating step may be performed between the protection step and the UV irradiation step, or may be performed between the UV irradiation step and the peeling step.
  • the semiconductor device manufacturing method of one embodiment even when the heating step is performed, the semiconductor device can be obtained in a state where no outgassing occurs and no adhesive residue remains on the surface of the adherend with bumps. Therefore, the subsequent mounting process can be carried out without any problem on the semiconductor device obtained.
  • ⁇ Preparation of second mixed solution> As shown in Table 1, 59.8 parts by mass of 3,4-epoxycyclohexylmethyl methacrylate, which is an alicyclic epoxy group-containing ethylenically unsaturated compound (c), and a carboxy group-containing solution obtained using the first mixed solution 1.5 parts by mass of tris(4-methylphenyl)phosphine (TPTP) as a catalyst with respect to a total of 100 parts by mass of the resin (b) and the alicyclic epoxy group-containing ethylenically unsaturated compound (c), and a solvent
  • TPTP tris(4-methylphenyl)phosphine
  • a second mixed solution was prepared containing 100.0 parts by weight of n-butyl acetate and 91.1 parts by weight of toluene.
  • a four-necked flask equipped with a stirrer, a dropping funnel, a condenser tube and a nitrogen inlet tube was charged with 175.6 parts by mass of n-butyl acetate as a solvent, and heated to 80°C under a nitrogen gas atmosphere. Then, while maintaining the reaction temperature at 80 ° C. ⁇ 2 ° C., the first mixed solution is uniformly added dropwise to the four-necked flask over 4 hours. Polymerization was carried out while stirring to obtain a carboxy group-containing resin (b).
  • the temperature of the reaction system to which 4-methoxyphenol was added was raised to 100° C., and the second mixed solution was added dropwise over 0.5 hours, followed by continued stirring at a temperature of 100° C. for 8 hours to obtain resin (A-1). was synthesized and cooled to room temperature (23° C.).
  • Resin (A-1) was identified by a nuclear magnetic resonance method (NMR method) and found to be a compound represented by general formula (2-1).
  • the repeating unit k of the compound represented by the general formula (2-1) is two kinds of repeating units (k-1, k-2) with different R5 .
  • resin (A-1) the weight average molecular weight and glass transition temperature were examined by the methods shown below.
  • the acid value of resin (A-1) was measured according to JIS K 0070:1992.
  • Tg ⁇ Glass transition temperature
  • a 10 mg sample was taken from resin (A-1).
  • Differential scanning calorimetry was performed using a differential scanning calorimeter (DSC) while changing the temperature of the sample from -100°C to 200°C at a heating rate of 10°C/min. was taken as Tg.
  • DSC differential scanning calorimeter
  • Tg was taken as a simple average value of two or more endothermic start temperatures.
  • a second mixed solution was prepared in the same manner as in Production Example 1, except that the content (parts by mass) shown in Table 1 and the alicyclic epoxy group-containing ethylenically unsaturated compound (c) and the catalyst were used. bottom.
  • Resins (A-2) to (A-12) were obtained in the same manner as in Production Example 1, except that the first mixed solution and the second mixed solution were used.
  • Resins (A-2) to (A-12) were identified in the same manner as in Production Example 1, and were found to be compounds represented by general formulas (2-2) to (2-12).
  • the repeating units k of the compounds represented by general formulas (2-2) to (2-7) and (2-10) are two types of repeating units in which R 5 is different or both R 1 and R 5 are different.
  • the unit is (k-1, k-2).
  • the resin (A-2) is a compound represented by the following general formula (2-2).
  • the resin (A-3) is a compound represented by the following general formula (2-3).
  • the resin (A-4) is a compound represented by the following general formula (2-4).
  • the resin (A-5) is a compound represented by the above general formula (2-5).
  • the resin (A-6) is a compound represented by the following general formula (2-6).
  • the resin (A-7) is a compound represented by the following general formula (2-7).
  • the resin (A-8) is a compound represented by the following general formula (2-8).
  • the resin (A-9) is a compound represented by the following general formula (2-9).
  • the resin (A-10) is a compound represented by the following general formula (2-10).
  • the resin (A-11) is a compound represented by the following general formula (2-11).
  • the resin (A-12) is a compound represented by the following general formula (2-12).
  • k-1 is 69.7
  • k-2 is 16.0
  • m is 1.2
  • the sum of k-1, k-2 and m is 86 .9 and n is 13.1.
  • k-1 is 10.6, k-2 is 51.7, m is 4.4, and the sum of k-1, k-2 and m is 66 .7 and n is 33.3.
  • k-1 is 14.4, k-2 is 72.2, m is 1.1, and the sum of k-1, k-2 and m is 87 .7 and n is 12.3.
  • Table 1 shows the carboxyl group-containing ethylenically unsaturated monomer (a) used in the production of resins (A-1) to (A-12), and the ethylenically unsaturated monomer copolymerizable with (a) above.
  • the types and amounts (mass parts) of the monomer (d), polymerization initiator, alicyclic epoxy group-containing ethylenically unsaturated compound (c), catalyst, polymerization inhibitor and solvent are shown.
  • Ethyl acetate as a diluent solvent was added to the reaction solution of the resins (A-1) to (A-12) synthesized in Production Examples 1 to 12, and the contents of the resins (A-1) to (A-12) were determined. was adjusted to 30% by mass.
  • a resin (A-1) to (A-12) solution having a resin (A-1) to (A-12) content of 30% by mass a pressure-sensitive adhesive composition was obtained by the method shown below. .
  • Resin (A) shown in Tables 3 and 4 are contained in a plastic container in a room shielded from active rays. The amount (parts by mass) was added and stirred to obtain pressure-sensitive adhesive compositions of Examples 1 to 11 and Comparative Examples 1 to 6.
  • the numerical values of resins (A-1) to (A-12) in Tables 3 and 4 are resin (A-1) in which the content of resins (A-1) to (A-12) is 30% by mass.
  • ⁇ (A-12) is the solid content of the solution, that is, the amount (parts by mass) of the resins (A-1) ⁇ (A-12) used.
  • the numerical value of the photopolymerization initiator (B) is the amount (parts by mass) of the photopolymerization initiator (B) used with respect to 100 parts by mass of the resin (A).
  • the numerical value of the cross-linking agent (C) is the amount (parts by mass) of the cross-linking agent (C) used with respect to 100 parts by mass of the resin (A).
  • TTRAD-C 1,3-bis(N,N'-diglycidylaminomethyl)cyclohexane (manufactured by Mitsubishi Gas Chemical Company, Inc., trade name: TETRAD-C)
  • TETRAD-C 1,3-bis(N,N'-diglycidylaminomethyl)cyclohexane
  • TETRAD-X N,N′-[1,3-phenylenebis(methylene)]bis[bis(oxiran-2-ylmethyl)amine]
  • TETRAD-X isocyanurate form of hexamethylene diisocyanate
  • Coronate registered trademark
  • HX 2,4,6-trimethylbenzoyldiphenylphosphine oxide
  • Adhesive Sheet for Adhesion Measurement The adhesive compositions of Examples 1 to 11 and Comparative Examples 1 to 6 are directly coated on a substrate so that the film thickness after drying is 20 ⁇ m, and dried by heating at 100 ° C. for 2 minutes to obtain an adhesive. formed a layer. Thereafter, a release sheet was laminated on the adhesive layer to obtain adhesive sheets of Examples 1 to 11 and Comparative Examples 1 to 6.
  • a polyamide (PA) film having a thickness of 25 ⁇ m was used as the base material.
  • PET polyethylene terephthalate
  • the pressure-sensitive adhesive sheet for measuring the pressure-sensitive adhesive strength was cut into a size of 25 mm long and 100 mm wide, and the release sheet was peeled off to expose the pressure-sensitive adhesive layer.
  • the adhesive sheet is attached to the glass plate so that the exposed adhesive layer (measurement surface) is in contact with the glass plate, and a 2 kg rubber roller (width: about 50 mm) is reciprocated once to measure the peel strength before UV irradiation. A sample for measurement was obtained.
  • the obtained measurement sample was left for 24 hours in an environment with a temperature of 23°C and a humidity of 50%. After that, according to JIS Z 0237:2009, a tensile test was performed in a 180° direction at a peel speed of 300 mm/min to measure the peel strength (N/25 mm) of the adhesive sheet to the glass plate.
  • UV irradiation Prepare the same sample for measuring the peel strength before UV irradiation, and irradiate ultraviolet rays (UV) from the adhesive sheet side at a dose of 1000 mJ/cm 2 to obtain a sample for measuring the peel strength after UV irradiation. rice field.
  • UV irradiation a conveyor type ultraviolet irradiation device (manufactured by Eye Graphics, 2 KW lamp, 80 W/cm) was used.
  • the peel strength (N/25 mm) of the adhesive sheet to the glass plate was measured in the same manner as the “peeling strength before UV irradiation".
  • a conveyor type ultraviolet irradiation device manufactured by Eye Graphics, 2 KW lamp, 80 W/cm was used. After that, the adhesive sheet was peeled off, and the PCB with bumps was observed with an optical microscope. If the area of the adhesive residue was 5% or less of the entire PCB with bumps, "A” was applied. The adhesive residue was evaluated as "B” when it was less than 20%, and as "C” when it was 20% or more.
  • Step fillability 2 A blade ("SDC200 R100 NMR” manufactured by Tokyo Seimitsu Co., Ltd., kerf width: 0.3 mm, blade rotation speed: Dicing was performed at 28000 rpm, cutting speed: 30 mm/sec, depth of cut: 100 ⁇ m).
  • the PCB with bumps cut into small pieces by dicing is observed with an optical microscope from the side of the bump protection adhesive sheet, and "A” is given when the area containing air bubbles is 1% or less of the entire PCB with bumps. % and less than 10% were evaluated as "B" and 10% or more as "C".
  • Step fillability 3 A heat treatment was performed at 200° C. for 2 hours on the PCB with bumps to which the pressure-sensitive adhesive sheet for protecting bumps was adhered, which was cut into small pieces by the operation of step filling property 2 . After allowing the PCB with bumps to cool, observe with an optical microscope from the side of the adhesive sheet for bump protection, and if the area containing air bubbles is 1% or less of the entire PCB with bumps, "A" is higher than 1%. Level difference fillability 3 was evaluated as "B” when it was largely less than 10%, and "C" when it was 10% or more.
  • the adhesive sheets of Examples 1 to 11 all had A or B in "adhesive residue after heating test".
  • these pressure-sensitive adhesive sheets were rated A in all of the evaluations of "step-filling property 1," “step-filling property 2,” and “step-filling property 3,” indicating good adhesion to PCBs with bumps. .
  • “step-filling property 1”, “step-filling property 2”, and “step-filling property 3” were B or C, and the adhesion to the bumped PCB was insufficient.

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Abstract

The present invention provides a method for producing a semiconductor device, the method using an adhesive sheet that is capable of accurately following and adhering to recesses and projections in the surface during a processing step of a semiconductor device that has recesses and projections in the surface, such as a semiconductor chip with a bump and a PCB with a bump, while being free from the generation of an outgas during a high temperature treatment or an adhesive residue on the surface of an adherend from which the adhesive sheet is removed. A method for producing a semiconductor device according to the present invention comprises: a protection step in which an adhesive sheet that has a sheet-like base material and an adhesive layer that is formed on the base material is bonded to an adherend surface of a semiconductor device, the adherend surface having a bump; a UV irradiation step in which the adhesive sheet is irradiated with UV light, thereby curing the adhesive layer; and a separation step in which the adhesive sheet is separated and removed from the adherend surface having a bump. With respect to this method for producing a semiconductor device, the adhesive layer is a cured product of an adhesive composition; the adhesive composition contains a resin (A) that is represented by general formula (1-1) and a photopolymerization initiator (B); and the resin (A) has a weight average molecular weight of 50,000 to 550,000.

Description

半導体デバイスの製造方法及び半導体デバイスSemiconductor device manufacturing method and semiconductor device
　本発明は、半導体デバイスの製造方法及び半導体デバイスに関する。 The present invention relates to a semiconductor device manufacturing method and a semiconductor device.
　半導体の製造工程において、様々な粘着シートが用いられている。具体的には、半導体ウエハの裏面研削（バックグラインド）工程においてウエハを保護するための保護シート、半導体ウエハから素子小片への切断分割（ダイシング）工程において用いられる固定用シートなどがある。これらの粘着シートは、被着体である半導体ウエハに貼付され、所定の加工工程が終了した後に被着体から剥離される再剥離型の粘着シートである。 Various adhesive sheets are used in the semiconductor manufacturing process. Specifically, there are a protective sheet for protecting the wafer in the back grinding process of the semiconductor wafer, and a fixing sheet used in the process of cutting and dividing the semiconductor wafer into element pieces (dicing). These pressure-sensitive adhesive sheets are re-peelable pressure-sensitive adhesive sheets that are attached to a semiconductor wafer, which is an adherend, and are peeled off from the adherend after a predetermined processing step is completed.
　近年では、電子機器の小型化及び高密度化に伴い、半導体素子を最小の面積で実装可能な方法として、フリップチップ実装が主流となりつつある。フリップチップ実装においては、チップ間の接合を図るために半田からなる先端部を有する突起電極（バンプ）を有する半導体チップ（例えば、Through Silicon Via（ＴＳＶ）チップ）が使用される。このバンプ付き半導体チップは、他の半導体チップ又は基板と、半田の溶融温度以上の温度（通常は２００℃以上）に加熱するリフロー工程により電気的に接合されて実装される。また、通信用の電子機器に半導体チップを実装する場合は、チップ内部から生じる電磁波により通信障害が発生する場合がある。これを防止するために、半導体チップ外周部に電磁波遮蔽シールドとして、金属膜を蒸着させる（通常は１５０℃以上）スパッタリング工程を経る場合もある。リフロー工程又はスパッタリング工程においては、バンプ表面を保護するために再剥離型の粘着シートが使用される。 In recent years, with the miniaturization and increasing density of electronic devices, flip-chip mounting is becoming the mainstream as a method that allows semiconductor elements to be mounted in the smallest possible area. In flip-chip mounting, a semiconductor chip (for example, a Through Silicon Via (TSV) chip) having protruding electrodes (bumps) having tip portions made of solder is used for bonding between chips. This semiconductor chip with bumps is electrically bonded and mounted to another semiconductor chip or substrate by a reflow process in which the solder is heated to a temperature higher than the melting temperature (usually 200° C. or higher). Further, when a semiconductor chip is mounted on an electronic device for communication, electromagnetic waves generated from inside the chip may cause communication failure. In order to prevent this, a sputtering process may be performed in which a metal film is deposited (usually at a temperature of 150° C. or higher) as an electromagnetic wave shield on the periphery of the semiconductor chip. In the reflow process or sputtering process, a removable adhesive sheet is used to protect the bump surfaces.
　半導体装置にバンプ付き配線回路基板（ＰＣＢ）が広く利用されている。バンプ付きＰＣＢを別の基板又は筐体に固定する場合に、粘着テープが使用されることがある。半導体チップの実装工程で、このバンプ付きＰＣＢがリフロー工程又はスパッタリング工程を経ることがある。 A printed circuit board (PCB) with bumps is widely used in semiconductor devices. Adhesive tape is sometimes used to secure the bumped PCB to another substrate or housing. In the semiconductor chip mounting process, the bumped PCB may undergo a reflow process or a sputtering process.
　特許文献１には、バンプ付き半導体チップに貼り付けた後に紫外線を照射し粘着剤層を硬化させて、高温処理工程後に剥離するという使用法により運用可能な紫外線硬化型粘着剤層を有する粘着テープであって、前記粘着剤層の硬化前のゲル分率をＡ（％）、３０００ｍＪ／ｃｍ２の光照射した後の前記粘着剤層の引張弾性率をＢ（ＭＰａ）としたときに以下の関係式：－５≦Ｂ－ｅｘｐ（Ａ／３０）を満たす、粘着テープが開示されている。 In Patent Document 1, an adhesive tape having an ultraviolet curable adhesive layer that can be used by applying ultraviolet rays to cure the adhesive layer after attaching it to a semiconductor chip with bumps and peeling off after a high temperature treatment process. When the gel fraction of the pressure-sensitive adhesive layer before curing is A (%) and the tensile elastic modulus of the pressure-sensitive adhesive layer after irradiation with light of 3000 mJ/cm 2 is B (MPa), the following is obtained. A pressure-sensitive adhesive tape is disclosed that satisfies the relational expression: -5≦B-exp(A/30).
特開２０２０－９４１９９号公報JP 2020-94199 A
　バンプ付き半導体チップ及びバンプ付きＰＣＢは、その表面に大きな凹凸形状を有しているため、再剥離型の粘着シートで保護する場合、粘着シートは加工工程中に正確にその凹凸形状に追従して密着しなければならない。また、粘着シートには、リフロー工程などの高温処理中にアウトガスが発生したり、粘着シート剥離時に半導体チップに糊残りすることのない、高い耐熱性が要求される。 Since semiconductor chips with bumps and PCBs with bumps have large irregularities on their surfaces, when protected with a removable adhesive sheet, the adhesive sheet accurately follows the irregularities during the processing process. must adhere. In addition, the adhesive sheet is required to have high heat resistance so that outgassing is not generated during high-temperature processing such as a reflow process, and adhesive residue does not remain on the semiconductor chip when the adhesive sheet is peeled off.
　しかしながら、従来の粘着シートは上記の条件を全て満足するものではなかった。特許文献１では、粘着剤層がバンプに追従できるほど柔軟ではないため、シート貼り付け面の凹凸への密着性が不十分である場合があった。また、添加剤に起因して加熱工程後にアウトガスが発生する場合や、粘着シート剥離時に糊残りする場合があった。 However, conventional adhesive sheets did not satisfy all of the above conditions. In Patent Document 1, since the pressure-sensitive adhesive layer is not flexible enough to follow the bumps, there are cases where the adhesiveness to the unevenness of the sheet attachment surface is insufficient. In addition, there are cases where outgassing is generated after the heating process due to the additive, and where adhesive remains when the adhesive sheet is peeled off.
　本発明は、上記事情を鑑みてなされたものであり、バンプ付き半導体チップ、バンプ付きＰＣＢ等の表面に凹凸を有する半導体デバイスの加工工程中でも正確に凹凸に追従して密着することが可能な粘着シートを用いることを含む、高温処理中のアウトガスの発生及び粘着シート剥離時の被着体表面の糊残りがない半導体デバイスの製造方法を提供することを課題とする。 The present invention has been made in view of the above circumstances, and an adhesive that can accurately follow the unevenness and adhere to it even during the processing of semiconductor devices having uneven surfaces such as semiconductor chips with bumps and PCBs with bumps. It is an object of the present invention to provide a method for manufacturing a semiconductor device, including the use of a sheet, which does not generate outgassing during high-temperature processing and does not leave adhesive residue on the surface of an adherend when an adhesive sheet is peeled off.
　また、本発明は、上記製造方法により製造された半導体デバイスを提供することを課題とする。 Another object of the present invention is to provide a semiconductor device manufactured by the above manufacturing method.
　本発明者らは、カルボキシ基含有エチレン性不飽和単量体（ａ）を必須単量体成分として重合して得られるカルボキシ基含有樹脂（ｂ）と、脂環式エポキシ基含有エチレン性不飽和化合物（ｃ）との付加反応により得られる、重量平均分子量が５万～５５万である樹脂（Ａ）と、光重合開始剤（Ｂ）とを必須成分として含有する粘着剤組成物を用いて形成される粘着シートをバンプ付き被着面に貼り付ける保護工程を設けることで、上記課題を解決できることを見出した。 The present inventors have found a carboxy group-containing resin (b) obtained by polymerizing a carboxy group-containing ethylenically unsaturated monomer (a) as an essential monomer component, and an alicyclic epoxy group-containing ethylenically unsaturated monomer. Using a pressure-sensitive adhesive composition containing, as essential components, a resin (A) having a weight average molecular weight of 50,000 to 550,000 and a photopolymerization initiator (B) obtained by an addition reaction with the compound (c) The present inventors have found that the above problem can be solved by providing a protective step of attaching the adhesive sheet to be formed to the adherend surface with the bumps.
　本発明は以下の態様を含む。
［１］
　シート状の基材と前記基材上に形成された粘着剤層とを有する粘着シートを半導体デバイスのバンプ付き被着面に貼り付ける保護工程、
　前記粘着シートに対してＵＶ照射を行い、前記粘着剤層を硬化させるＵＶ照射工程、及び
　前記粘着シートを前記バンプ付き被着面から剥離除去する剥離工程
を含む、半導体デバイスの製造方法であって、
　前記粘着剤層が、粘着剤組成物の硬化物であり、
　前記粘着剤組成物が、下記一般式（１－１）で示される樹脂（Ａ）と、光重合開始剤（Ｂ）とを含み、前記樹脂（Ａ）の重量平均分子量が５万～５５万である半導体デバイスの製造方法。
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000004
 （式（１－１）において、ｋ、ｌ、ｍ及びｎは、ｋ＋ｌ＋ｍ＋ｎ＝１００としたときのモル組成比を示す。ｋは０超～９２以下である。ｌは０～５０である。ｍは０超～９０以下である。ｋ、ｌ及びｍの合計は６５～９５である。ｎは５～３５である。Ｒ１～Ｒ４は－Ｈ又は－ＣＨ３である。Ｒ５は炭素原子数１～１６のアルキル基である。Ｒ６は炭素原子数３～３０の脂環式炭化水素基又は炭素原子数６～２０の芳香族炭化水素基である。Ｒ７は－Ｈ又は－（ＣＨ２）ｊ－ＣＯＯＨ（式中のｊは１又は２である。）である。Ｒ８は上記一般式（１－２）又は（１－３）で示される基である。式（１－２）及び（１－３）において、ｐ及びｑは０、１及び２から選ばれるいずれかである。ｓはｐが０のときは０であり、ｐが１又は２のときは１である。Ｒ９は－Ｈ又は－ＣＨ３である。）
［２］
　前記式（１－１）におけるｎが７～３３である［１］に記載の半導体デバイスの製造方法。
［３］
　前記式（１－１）におけるｋが４５～９０であり、ｌが４～４０であり、ｍが１～２０である［１］又は［２］に記載の半導体デバイスの製造方法。
［４］
　前記粘着剤組成物が架橋剤（Ｃ）を更に含有する［１］～［３］のいずれかに記載の半導体デバイスの製造方法。
［５］
　前記樹脂（Ａ）のガラス転移温度が－８０～０℃である［１］～［４］のいずれかに記載の半導体デバイスの製造方法。
［６］
　前記保護工程と前記剥離工程の間に、１５０℃以上の加熱工程を有する［１］～［５］のいずれかに記載の半導体デバイスの製造方法。
［７］
　前記保護工程と前記剥離工程の間に、加工工程を有する［１］～［６］のいずれかに記載の半導体デバイスの製造方法。
［８］
　前記保護工程と前記ＵＶ照射工程の間に、１５０℃以上の加熱工程を有する［１］～［５］のいずれかに記載の半導体デバイスの製造方法。
［９］
　前記保護工程と前記ＵＶ照射工程の間に、加工工程を有する［１］～［６］のいずれかに記載の半導体デバイスの製造方法。
［１０］
　前記ＵＶ照射工程と前記剥離工程の間に、１５０℃以上の加熱工程を有する［１］～［５］のいずれかに記載の半導体デバイスの製造方法。
［１１］
　前記ＵＶ照射工程と前記剥離工程の間に、加工工程を有する［１］～［６］のいずれかに記載の半導体デバイスの製造方法。
［１２］
　［１］～［１１］のいずれかに記載の方法により製造された半導体デバイス。 The present invention includes the following aspects.
[1]
A protective step of attaching an adhesive sheet having a sheet-like base material and an adhesive layer formed on the base material to a bumped adherend surface of a semiconductor device;
A method for manufacturing a semiconductor device, comprising a UV irradiation step of irradiating the adhesive sheet to cure the adhesive layer, and a peeling step of peeling and removing the adhesive sheet from the adherend surface with bumps, ,
The pressure-sensitive adhesive layer is a cured product of the pressure-sensitive adhesive composition,
The adhesive composition contains a resin (A) represented by the following general formula (1-1) and a photopolymerization initiator (B), and the weight average molecular weight of the resin (A) is 50,000 to 550,000. A method of manufacturing a semiconductor device.
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000004
 (In formula (1-1), k, l, m and n represent the molar composition ratio when k + l + m + n = 100. k is more than 0 to 92 or less. l is 0 to 50. m is greater than 0 to 90. The sum of k, l and m is 65 to 95. n is 5 to 35. R 1 to R 4 are —H or —CH 3. R 5 is carbon. an alkyl group having 1 to 16 atoms, R 6 being an alicyclic hydrocarbon group having 3 to 30 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms, and R 7 being -H or - (CH 2 ) j —COOH (in the formula, j is 1 or 2.) R 8 is a group represented by the general formula (1-2) or (1-3). -2) and (1-3), p and q are any selected from 0, 1 and 2. s is 0 when p is 0 and 1 when p is 1 or 2 and R 9 is —H or —CH 3. )
[2]
The method for manufacturing a semiconductor device according to [1], wherein n in the formula (1-1) is 7 to 33.
[3]
The method for manufacturing a semiconductor device according to [1] or [2], wherein k is 45 to 90, l is 4 to 40, and m is 1 to 20 in the formula (1-1).
[4]
The method for producing a semiconductor device according to any one of [1] to [3], wherein the pressure-sensitive adhesive composition further contains a cross-linking agent (C).
[5]
The method for manufacturing a semiconductor device according to any one of [1] to [4], wherein the resin (A) has a glass transition temperature of -80 to 0°C.
[6]
The method of manufacturing a semiconductor device according to any one of [1] to [5], including a heating step of 150° C. or higher between the protecting step and the peeling step.
[7]
The method of manufacturing a semiconductor device according to any one of [1] to [6], including a processing step between the protection step and the peeling step.
[8]
The method for manufacturing a semiconductor device according to any one of [1] to [5], including a heating step of 150° C. or higher between the protection step and the UV irradiation step.
[9]
The method of manufacturing a semiconductor device according to any one of [1] to [6], including a processing step between the protection step and the UV irradiation step.
[10]
The method of manufacturing a semiconductor device according to any one of [1] to [5], including a heating step of 150° C. or higher between the UV irradiation step and the peeling step.
[11]
The method of manufacturing a semiconductor device according to any one of [1] to [6], further comprising a processing step between the UV irradiation step and the peeling step.
[12]
A semiconductor device manufactured by the method according to any one of [1] to [11].
　樹脂（Ａ）と光重合開始剤（Ｂ）とを含有する粘着剤組成物は、樹脂（Ａ）が脂環式化合物に由来する構造を有するため、良好な耐熱性を有する。また、樹脂（Ａ）の重量平均分子量が５万～５５万であるため、粘着剤層に柔軟性が付与される。そのため、粘着剤組成物は、表面に凹凸のあるバンプ付き半導体チップ、バンプ付きＰＣＢ等の電子部品に対して良好な密着性を有する粘着剤層を形成することができる。また、樹脂（Ａ）の重量平均分子量が５万～５５万であることにより、高温処理中に粘着剤層から発生するアウトガスを低減することができる。更に、上記粘着剤組成物の硬化物を含む粘着剤層の粘着力は、紫外線（ＵＶ）を照射することにより樹脂（Ａ）中の不飽和結合が三次元架橋構造を形成して硬化することにより変化する。具体的には、粘着剤組成物にＵＶを照射する前には被着体に対して十分な粘着力を示し、ＵＶを照射した後には粘着力が低下して優れた易剥離性が得られるとともに、剥離後の被着体への糊残りを十分に防止することができる。 A pressure-sensitive adhesive composition containing a resin (A) and a photopolymerization initiator (B) has good heat resistance because the resin (A) has a structure derived from an alicyclic compound. Further, since the resin (A) has a weight average molecular weight of 50,000 to 550,000, flexibility is imparted to the pressure-sensitive adhesive layer. Therefore, the pressure-sensitive adhesive composition can form a pressure-sensitive adhesive layer having good adhesion to electronic components such as semiconductor chips with bumps and PCBs with bumps having uneven surfaces. In addition, when the resin (A) has a weight average molecular weight of 50,000 to 550,000, it is possible to reduce outgassing generated from the pressure-sensitive adhesive layer during high-temperature treatment. Furthermore, the adhesive strength of the adhesive layer containing the cured product of the adhesive composition is that the unsaturated bonds in the resin (A) form a three-dimensional crosslinked structure and cure by irradiating with ultraviolet rays (UV). change depending on Specifically, the pressure-sensitive adhesive composition exhibits sufficient adhesive strength to the adherend before UV irradiation, and the adhesive strength decreases after UV irradiation, resulting in excellent easy peelability. At the same time, it is possible to sufficiently prevent adhesive residue on the adherend after peeling.
　本発明の半導体デバイスの製造方法を用いることで、バンプ付き半導体チップ、バンプ付きＰＣＢ等の表面に凹凸を有する半導体デバイスの加工工程中でも粘着シートを正確に凹凸に追従させて密着させることができ、高温処理中のアウトガス及び粘着シート剥離時のバンプ付き被着面上での糊残りを生じさせずに半導体デバイスを製造することができる。 By using the method for manufacturing a semiconductor device according to the present invention, it is possible to adhere the adhesive sheet accurately following the unevenness even during the process of processing a semiconductor device having unevenness on the surface, such as a semiconductor chip with bumps or a PCB with bumps. A semiconductor device can be manufactured without outgassing during high-temperature processing and without adhesive residue on the adherend surface with bumps when the adhesive sheet is peeled off.
　以下、本発明の半導体デバイスの製造方法及び半導体デバイスについて詳細に説明する。ただし、本発明は、以下に示す実施形態に限定されるものではない。 The method for manufacturing a semiconductor device and the semiconductor device of the present invention will be described in detail below. However, the present invention is not limited to the embodiments shown below.
［半導体デバイスの製造方法］
　一実施形態の半導体デバイスの製造方法は、
　シート状の基材と基材上に形成された粘着剤層とを有する粘着シートを半導体デバイスのバンプ付き被着面に貼り付ける保護工程、
　前記粘着シートに対してＵＶ照射を行い、粘着剤層を硬化させるＵＶ照射工程、及び
　粘着シートをバンプ付き被着面から剥離除去する剥離工程
を含む。 [Method for manufacturing a semiconductor device]
A method for manufacturing a semiconductor device according to one embodiment includes:
A protective step of attaching an adhesive sheet having a sheet-like base material and an adhesive layer formed on the base material to the bumped adherend surface of the semiconductor device;
The method includes a UV irradiation step of irradiating the adhesive sheet to cure the adhesive layer, and a peeling step of peeling and removing the adhesive sheet from the adherend surface with bumps.
［保護工程］
　保護工程では、バンプ電極を設けた半導体デバイスのバンプ付き被着面に粘着シートを貼り付ける。このことにより、半導体デバイスのバンプ付き被着面が保護される。前記半導体デバイスとしては、バンプ付き半導体チップ、バンプ付きプリント配線基板（ＰＣＢ）、バンプ付きＦＰＣ基板等の表面に凹凸を持った半導体デバイスが挙げられる。これらの半導体デバイスは、バンプ電極を他の電子デバイスに接続する実装工程までの製造工程において、種々の加工工程に付される。バンプ付き被着面が前記加工工程中に保護されることで、バンプ付き被着面の傷つき、破損、汚染等を防止することができる。保護工程は、続く加工工程を行うための半導体デバイスの仮固定の機能を兼ねることもできる。 [Protection process]
In the protection step, an adhesive sheet is attached to the bump-attached surface of the semiconductor device provided with the bump electrode. This protects the bumped attachment surface of the semiconductor device. Examples of the semiconductor device include a semiconductor device having an uneven surface, such as a semiconductor chip with bumps, a printed wiring board (PCB) with bumps, and an FPC board with bumps. These semiconductor devices are subjected to various processing steps in the manufacturing process up to the mounting step for connecting the bump electrodes to other electronic devices. By protecting the bumped attachment surface during the processing steps, it is possible to prevent the bumped attachment surface from being scratched, damaged, contaminated, and the like. The protection process can also serve as temporary fixing of the semiconductor device for the subsequent processing process.
　半導体デバイスがバンプ付き被着面を複数有する場合、保護工程においては、一部又は全てのバンプ付き被着面に粘着シートを貼り付ける。例えば、特開２０１４－２２５５４６号公報等に開示される半導体チップの積層を行う場合、バンプ付き被着面の実装面を除く非実装面に粘着シートを貼り付けることができる。 When a semiconductor device has multiple attachment surfaces with bumps, an adhesive sheet is attached to some or all of the attachment surfaces with bumps in the protection process. For example, when stacking semiconductor chips as disclosed in Japanese Patent Application Laid-Open No. 2014-225546, an adhesive sheet can be attached to the non-mounting surface of the bump-attached surface excluding the mounting surface.
［粘着シート］
　一実施形態の粘着シートは、シート状の基材と、基材上に形成された粘着剤層とを有する。 [Adhesive sheet]
A pressure-sensitive adhesive sheet of one embodiment has a sheet-like base material and a pressure-sensitive adhesive layer formed on the base material.
　粘着剤層の基材と反対側の表面には、剥離シート（セパレーター）が設けられていることが好ましい。粘着剤層上に剥離シートが設けられている場合、剥離シートによって使用時まで粘着剤層を保護することができる。粘着剤層上に剥離シートが設けられている場合、剥離シートを剥がして粘着剤層を露出させ、粘着剤層（貼付面）を被着体に圧着する作業を効率よく行うことができる。 A release sheet (separator) is preferably provided on the surface of the pressure-sensitive adhesive layer opposite to the substrate. When a release sheet is provided on the adhesive layer, the release sheet can protect the adhesive layer until use. When a release sheet is provided on the pressure-sensitive adhesive layer, the work of peeling off the release sheet to expose the pressure-sensitive adhesive layer and press-bonding the pressure-sensitive adhesive layer (attachment surface) to the adherend can be performed efficiently.
　粘着シートは、打ち抜き法などにより被着体の形状に応じた形状とされた粘着テープとして用いてもよい。粘着シートは、巻き取って切断することにより、ロール形状とされた粘着テープとして用いてもよい。 The adhesive sheet may be used as an adhesive tape shaped according to the shape of the adherend by a punching method or the like. The adhesive sheet may be used as a roll-shaped adhesive tape by winding and cutting.
　基材としては、公知のシート状の材料を適宜選択して使用することができる。基材としては、透明な樹脂材料からなる樹脂シートを用いることが好ましい。 As the base material, a known sheet-like material can be appropriately selected and used. As the substrate, it is preferable to use a resin sheet made of a transparent resin material.
　樹脂材料としては、例えば、ポリエチレン（ＰＥ）、ポリプロピレン（ＰＰ）等のポリオレフィン；ポリエチレンテレフタレート（ＰＥＴ）、ポリブチレンテレフタレート（ＰＢＴ）、ポリエチレンナフタレート（ＰＥＮ）等のポリエステル；ポリ塩化ビニル（ＰＶＣ）；ポリアミド（ＰＡ）；ポリイミド（ＰＩ）；ポリフェニレンサルファイド（ＰＰＳ）；エチレン酢酸ビニル（ＥＶＡ）；及びポリテトラフルオロエチレン（ＰＴＦＥ）が挙げられる。これらの樹脂材料の中でも、適度な可撓性を有するシートが得られるため、ＰＥ、ＰＰ、又はＰＥＴを用いることが好ましい。樹脂材料は、単独で使用してもよいし、２種以上を混合して使用してもよい。 Examples of resin materials include polyolefins such as polyethylene (PE) and polypropylene (PP); polyesters such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT) and polyethylene naphthalate (PEN); polyvinyl chloride (PVC); polyimide (PI); polyphenylene sulfide (PPS); ethylene vinyl acetate (EVA); and polytetrafluoroethylene (PTFE). Among these resin materials, it is preferable to use PE, PP, or PET because a sheet having appropriate flexibility can be obtained. The resin materials may be used alone or in combination of two or more.
　基材として樹脂シートを用いる場合、樹脂シートは、単層であってもよいし、二層以上の多層構造（例えば三層構造）であってもよい。多層構造を有する樹脂シートにおいて、各層を構成する樹脂材料は、１種であってもよいし、２種以上を含んでもよい。 When a resin sheet is used as the base material, the resin sheet may be a single layer or may have a multi-layer structure of two or more layers (for example, a three-layer structure). In the resin sheet having a multilayer structure, each layer may be composed of one type of resin material, or two or more types thereof may be included.
　基材の厚さは、粘着シートの用途、基材の材料等に応じて適宜選択することができる。粘着シートが、リフロー工程又はスパッタリング処理を行う際にバンプ付き半導体チップ又はバンプ付きフレキシブル配線回路基板（ＦＰＣ）を保護するものであって、基材として樹脂シートが用いられている場合、基材の厚さは、好ましくは５～１０００μｍ、より好ましくは１０～３００μｍである。基材の厚さが５μｍ以上であると、粘着シートの剛性が高く（コシが強く）なる。そのため、粘着シートを、半導体チップなどの被着体に貼り付けたり、被着体から剥離したりする際に、粘着シートにしわ及び浮きが生じ難くなる傾向がある。また、基材の厚さが５μｍ以上であると、被着体に貼り付けた粘着シートを被着体から剥離しやすくなり、良好な作業性（取扱い性、ハンドリング）が得られる。基材の厚さが１０００μｍ以下であると、粘着シートの剛性が高く（コシが強く）なりすぎて作業性が低下することを防止できる。 The thickness of the base material can be appropriately selected according to the application of the adhesive sheet, the material of the base material, etc. The adhesive sheet protects a semiconductor chip with bumps or a flexible printed circuit board (FPC) with bumps when performing a reflow process or a sputtering process, and when a resin sheet is used as the base material, the base material The thickness is preferably 5-1000 μm, more preferably 10-300 μm. When the thickness of the substrate is 5 μm or more, the pressure-sensitive adhesive sheet has high rigidity (strength). Therefore, when the adhesive sheet is attached to or peeled off from an adherend such as a semiconductor chip, the adhesive sheet tends to be less likely to wrinkle or lift. Further, when the thickness of the substrate is 5 μm or more, the pressure-sensitive adhesive sheet attached to the adherend can be easily peeled off from the adherend, and good workability (handleability, handling) can be obtained. When the thickness of the base material is 1000 μm or less, it is possible to prevent the pressure-sensitive adhesive sheet from becoming too rigid (strong in stiffness) and reducing workability.
　基材として、樹脂シートを用いる場合、従来公知の一般的なシート成形方法（例えば押出成形、Ｔダイ成形、インフレーション成形、単軸又は２軸延伸成形等）を適宜採用して、基材を製造することができる。 When a resin sheet is used as the substrate, a conventionally known general sheet molding method (e.g., extrusion molding, T-die molding, inflation molding, uniaxial or biaxial stretch molding, etc.) is appropriately employed to produce the substrate. can do.
　基材の粘着剤層と接する側の表面には、基材と粘着剤層との接着性を向上させるための表面処理が施されていてもよい。 The surface of the substrate that contacts the adhesive layer may be surface-treated to improve the adhesion between the substrate and the adhesive layer.
　表面処理としては、例えば、コロナ放電処理、酸処理、紫外線照射処理、プラズマ処理、及び下塗剤（プライマー）塗付が挙げられる。 Examples of surface treatment include corona discharge treatment, acid treatment, ultraviolet irradiation treatment, plasma treatment, and primer application.
　一実施形態の粘着シートの粘着剤層は、後述する粘着剤組成物の硬化物を含む。 The pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet of one embodiment contains a cured product of the pressure-sensitive adhesive composition described below.
　粘着剤層の厚さは、１～１０００μｍであることが好ましく、５～７５０μｍであることがより好ましく、１０～５００μｍであることが更に好ましい。粘着剤層の厚さが１μｍ以上であると、粘着剤層の厚さの均一性が良好である。粘着剤層の厚さが１０００μｍ以下であると、粘着剤層を表面の凹凸に対して浮きが無い状態で十分に密着させることができる。 The thickness of the pressure-sensitive adhesive layer is preferably 1-1000 μm, more preferably 5-750 μm, even more preferably 10-500 μm. When the thickness of the pressure-sensitive adhesive layer is 1 μm or more, the thickness uniformity of the pressure-sensitive adhesive layer is good. When the thickness of the pressure-sensitive adhesive layer is 1000 μm or less, the pressure-sensitive adhesive layer can be sufficiently adhered to the unevenness of the surface without floating.
　粘着剤層の基材と反対側の表面に剥離シートが設けられている場合、剥離シートとして、公知のシート状の材料を適宜選択して使用することができる。剥離シートとしては、基材として使用される上述した樹脂シートと同様のものを用いることができる。 When a release sheet is provided on the surface of the pressure-sensitive adhesive layer opposite to the base material, a known sheet-like material can be appropriately selected and used as the release sheet. As the release sheet, the same resin sheet as the base material can be used.
　剥離シートの厚さは、粘着シートの用途、剥離シートの材料等に応じて適宜選択することができる。剥離シートとして樹脂シートを用いる場合、剥離シートの厚さは、好ましくは５～３００μｍ、より好ましくは１０～２００μｍ、更に好ましくは２５～１００μｍである。 The thickness of the release sheet can be appropriately selected according to the application of the adhesive sheet, the material of the release sheet, and the like. When a resin sheet is used as the release sheet, the thickness of the release sheet is preferably 5 to 300 μm, more preferably 10 to 200 μm, still more preferably 25 to 100 μm.
　剥離シートの剥離面（粘着剤層に接して配置される面）には、必要に応じてシリコーン系、長鎖アルキル系、フッ素系等の従来公知の剥離剤を用いて剥離処理が施されていてもよい。 The release surface of the release sheet (the surface placed in contact with the pressure-sensitive adhesive layer) is subjected to a release treatment using a conventionally known release agent such as a silicone, long-chain alkyl, or fluorine release agent, if necessary. may
［粘着シートの製造方法］
　一実施形態の粘着シートは、例えば、以下に示す方法により製造することができる。 [Method for producing adhesive sheet]
The pressure-sensitive adhesive sheet of one embodiment can be produced, for example, by the method shown below.
　まず、後述する粘着剤組成物を溶媒に溶解又は分散させた粘着剤溶液を調製する。上述した粘着剤組成物を、そのまま粘着剤溶液として使用してもよい。 First, an adhesive solution is prepared by dissolving or dispersing the adhesive composition described later in a solvent. You may use the adhesive composition mentioned above as an adhesive solution as it is.
　次に、基材上に粘着剤溶液を塗布し、溶媒を含む場合は加熱乾燥して溶媒を除去し、粘着剤層を形成する。その後、粘着剤層上に、必要に応じて剥離シートを貼り合せる。更に、得られたシートを必要に応じて、オーブンで一定時間養生し、架橋構造を形成させることにより、粘着シートを得ることができる。 Next, an adhesive solution is applied to the substrate, and if it contains a solvent, it is dried by heating to remove the solvent, forming an adhesive layer. After that, a release sheet is pasted on the pressure-sensitive adhesive layer, if necessary. Furthermore, if necessary, the obtained sheet is cured in an oven for a certain period of time to form a crosslinked structure, whereby a pressure-sensitive adhesive sheet can be obtained.
　粘着シートを製造する別の方法としては、剥離シート上に上記の粘着剤溶液を塗布し、溶媒を含む場合は加熱乾燥して溶媒を除去し、粘着剤層を形成する。その後、粘着剤層を有する剥離シートを基材上に、粘着剤層側の面を基材に向けて設置し、基材上に粘着剤層を転写（移着）し、必要に応じて、オーブンで一定時間養生し、架橋構造を形成させる方法が挙げられる。 Another method for producing an adhesive sheet is to apply the above adhesive solution on a release sheet, and if it contains a solvent, heat dry it to remove the solvent, and form an adhesive layer. Thereafter, a release sheet having an adhesive layer is placed on the substrate with the adhesive layer side facing the substrate, and the adhesive layer is transferred (transferred) onto the substrate. A method of curing in an oven for a certain period of time to form a crosslinked structure can be used.
　上記の粘着剤溶液を基材上に（又は剥離シート上に）塗布する方法としては、公知の方法を用いることができる。具体的には、慣用のコーター、例えば、グラビヤロールコーター、リバースロールコーター、キスロールコーター、ディップロールコーター、バーコーター、ナイフコーター、スプレーコーター、コンマコーター、ダイレクトコーター等を用いて塗布する方法が挙げられる。 A known method can be used as a method for applying the above adhesive solution onto the substrate (or onto the release sheet). Specific examples include a method of coating using a conventional coater such as gravure roll coater, reverse roll coater, kiss roll coater, dip roll coater, bar coater, knife coater, spray coater, comma coater, direct coater, and the like. be done.
　上記の塗布した粘着剤溶液を加熱乾燥する際の条件は、特に制限されないが、通常２５～１８０℃、好ましくは６０～１５０℃にて、通常１～２０分、好ましくは１～１０分加熱乾燥を行う。上記条件で加熱乾燥を行うことにより、粘着剤溶液に含まれる溶媒を除去することができる。加熱乾燥後の粘着シートをオーブンで一定時間養生する条件は、特に制限されないが、通常２５～１００℃、好ましくは３０～８０℃にて通常１～７日間、好ましくは１～３日間養生を行う。上記条件で養生を行うことにより、樹脂（Ａ）と架橋剤（Ｃ）を架橋させて、粘着剤層のゲル分率を所望の範囲に調整することができる。 The conditions for heat drying the applied adhesive solution are not particularly limited, but usually 25 to 180 ° C., preferably 60 to 150 ° C., usually 1 to 20 minutes, preferably 1 to 10 minutes. I do. The solvent contained in the adhesive solution can be removed by performing heat drying under the above conditions. The conditions for curing the pressure-sensitive adhesive sheet after heat drying in an oven for a certain period of time are not particularly limited, but the curing is usually carried out at 25 to 100° C., preferably 30 to 80° C., for usually 1 to 7 days, preferably 1 to 3 days. . By curing under the above conditions, the resin (A) and the cross-linking agent (C) are cross-linked, and the gel fraction of the pressure-sensitive adhesive layer can be adjusted within a desired range.
［粘着剤組成物］
　一実施形態の粘着剤組成物は、樹脂（Ａ）と、光重合開始剤（Ｂ）とを含む。 [Adhesive composition]
The pressure-sensitive adhesive composition of one embodiment contains a resin (A) and a photoinitiator (B).
〈樹脂（Ａ）〉
　一実施形態の粘着剤組成物に含まれる樹脂（Ａ）は、下記一般式（１－１）で示される化合物である。 <Resin (A)>
The resin (A) contained in the adhesive composition of one embodiment is a compound represented by the following general formula (1-1).
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000006
 （式（１－１）において、ｋ、ｌ、ｍ及びｎは、ｋ＋ｌ＋ｍ＋ｎ＝１００としたときのモル組成比を示す。ｋは０超～９２以下である。ｌは０～５０である。ｍは０超～９０以下である。ｋ、ｌ及びｍの合計は６５～９５である。ｎは５～３５である。Ｒ１～Ｒ４は－Ｈ又は－ＣＨ３である。Ｒ５は炭素原子数１～１６のアルキル基である。Ｒ６は炭素原子数３～３０の脂環式炭化水素基又は炭素原子数６～２０の芳香族炭化水素基である。Ｒ７は－Ｈ又は－（ＣＨ２）ｊ－ＣＯＯＨ（式中のｊは１又は２である。）である。Ｒ８は上記一般式（１－２）又は（１－３）で示される基である。式（１－２）及び（１－３）において、ｐ及びｑは０、１及び２から選ばれるいずれかである。ｓはｐが０のときは０であり、ｐが１又は２のときは１である。Ｒ９は－Ｈ又は－ＣＨ３である。）
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000006
 (In formula (1-1), k, l, m and n represent the molar composition ratio when k + l + m + n = 100. k is more than 0 to 92 or less. l is 0 to 50. m is greater than 0 to 90. The sum of k, l and m is 65 to 95. n is 5 to 35. R 1 to R 4 are —H or —CH 3. R 5 is carbon. an alkyl group having 1 to 16 atoms, R 6 being an alicyclic hydrocarbon group having 3 to 30 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms, and R 7 being -H or - (CH 2 ) j —COOH (in the formula, j is 1 or 2.) R 8 is a group represented by the general formula (1-2) or (1-3). -2) and (1-3), p and q are any selected from 0, 1 and 2. s is 0 when p is 0 and 1 when p is 1 or 2 and R 9 is —H or —CH 3. )
　式（１－１）において、ｋ、ｌ、ｍ及びｎは、ｋ＋ｌ＋ｍ＋ｎ＝１００としたときのモル組成比を示す。ｋは０超～９２以下である。ｌは０～５０である。ｍは０超～９０以下である。ｋ、ｌ及びｍの合計は６５～９５である。ｋ、ｌ及びｍの合計が６５以上であると、ＵＶ照射前に被着体に対して十分な粘着性を有する粘着剤層を形成することができる。ｋ、ｌ及びｍの合計は７０～９４であることが好ましく、７５～９０であることがより好ましい。 In the formula (1-1), k, l, m and n represent molar composition ratios when k+l+m+n=100. k is greater than 0 to 92 or less. l is 0-50. m is from more than 0 to 90 or less. The sum of k, l and m is 65-95. When the sum of k, l and m is 65 or more, a pressure-sensitive adhesive layer having sufficient adhesiveness to an adherend can be formed before UV irradiation. The sum of k, l and m is preferably 70-94, more preferably 75-90.
　式（１－１）において、ｋでくくられる括弧内で示される繰り返し単位（以下、「繰り返し単位ｋ」という。）は、必須の繰り返し単位である。繰り返し単位ｋは、ＵＶ照射前の粘着剤組成物の粘着力に寄与する。繰り返し単位ｋの繰り返し数ｋは、０超～９２以下であり、４５～９０であることが好ましく、６０～８８であることがより好ましい。 In formula (1-1), the repeating unit shown in parentheses surrounded by k (hereinafter referred to as "repeating unit k") is an essential repeating unit. The repeating unit k contributes to the adhesive strength of the adhesive composition before UV irradiation. The repeating number k of the repeating unit k is from more than 0 to 92 or less, preferably from 45 to 90, more preferably from 60 to 88.
　式（１－１）においては、ｌでくくられる括弧内で示される繰り返し単位（以下、「繰り返し単位ｌ」という。）はなくてもよい。言い換えると、繰り返し単位ｌの繰り返し数は０でもよい。繰り返し単位ｌは、粘着剤組成物の耐熱性に寄与する。繰り返し単位ｌの繰り返し数ｌは、０～５０であり、４～４０であることが好ましく、５～３０であることがより好ましい。 In formula (1-1), the repeating unit shown in parentheses enclosed by l (hereinafter referred to as "repeating unit l") may be omitted. In other words, the repeating number of repeating unit l may be zero. The repeating unit l contributes to the heat resistance of the pressure-sensitive adhesive composition. The repeating number l of the repeating unit l is 0 to 50, preferably 4 to 40, more preferably 5 to 30.
　式（１－１）において、ｍでくくられる括弧内で示される繰り返し単位（以下、「繰り返し単位ｍ」という。）は、必須の繰り返し単位である。繰り返し単位ｍは、ＵＶ照射前の粘着剤組成物の粘着力及び耐熱性に寄与する。また、粘着剤組成物がカルボキシ基と反応する官能基を有する架橋剤を含む場合、繰り返し単位ｍは、架橋剤と反応して粘着剤層に凝集力を付与する。繰り返し単位ｍの繰り返し数ｍは、０超～９０以下であり、１～２０であることが好ましく、１～１０であることがより好ましい。 In formula (1-1), the repeating unit shown in parentheses surrounded by m (hereinafter referred to as "repeating unit m") is an essential repeating unit. The repeating unit m contributes to the adhesive strength and heat resistance of the adhesive composition before UV irradiation. Moreover, when the pressure-sensitive adhesive composition contains a cross-linking agent having a functional group that reacts with a carboxyl group, the repeating unit m reacts with the cross-linking agent to impart cohesion to the pressure-sensitive adhesive layer. The repeating number m of the repeating unit m is from more than 0 to 90 or less, preferably from 1 to 20, more preferably from 1 to 10.
　式（１－１）において、ｎでくくられる括弧内で示される繰り返し単位（以下、「繰り返し単位ｎ」という。）は、必須の繰り返し単位である。繰り返し単位ｎは、粘着剤組成物の耐熱性に寄与する。繰り返し単位ｎの繰り返し数ｎは５～３５であり、７～３３であることが好ましく、１０～３０であることがより好ましい。繰り返し単位ｎが３５以下であると、ＵＶ照射することにより樹脂（Ａ）中の不飽和結合が三次元架橋構造を形成して硬化して、粘着力が適切な範囲に低下する粘着剤層を形成することができる。ｎが５以上であると、脂環式化合物に由来する構造に起因する耐熱性向上効果を得ることができる。 In formula (1-1), the repeating unit shown in parentheses surrounded by n (hereinafter referred to as "repeating unit n") is an essential repeating unit. The repeating unit n contributes to heat resistance of the pressure-sensitive adhesive composition. The repeating number n of repeating unit n is 5 to 35, preferably 7 to 33, more preferably 10 to 30. When the repeating unit n is 35 or less, the unsaturated bonds in the resin (A) are cured by UV irradiation to form a three-dimensional crosslinked structure, resulting in a pressure-sensitive adhesive layer whose adhesive strength is reduced to an appropriate range. can be formed. When n is 5 or more, the effect of improving heat resistance due to the structure derived from the alicyclic compound can be obtained.
　これらの各繰り返し単位が寄与する機能の相乗効果により、樹脂（Ａ）を含む粘着剤組成物は、紫外線（ＵＶ）照射前の粘着力とＵＶ照射後の粘着力とのバランスがより一層良好となる。その結果、ＵＶ照射前には被着体に対して十分な粘着力が得られ、ＵＶ照射後には粘着力が低下してより優れた易剥離性が得られる粘着剤組成物を得ることができる。しかも、この粘着剤組成物は、ＵＶ照射前に高温状態にしてから室温に戻しても粘着力が高くなり過ぎることがなく、ＵＶ照射後に優れた易剥離性が得られるとともに、剥離後の被着体への糊残りが生じにくい。 Due to the synergistic effect of the functions contributed by these repeating units, the pressure-sensitive adhesive composition containing the resin (A) has a better balance between the adhesive strength before ultraviolet (UV) irradiation and the adhesive strength after UV irradiation. Become. As a result, it is possible to obtain a pressure-sensitive adhesive composition that exhibits sufficient adhesive strength to an adherend before UV irradiation, and that exhibits reduced adhesive strength after UV irradiation, thereby providing superior easy peelability. . Moreover, this pressure-sensitive adhesive composition does not excessively increase its adhesive strength even when it is brought to a high temperature state before UV irradiation and then returned to room temperature, and excellent easy peelability can be obtained after UV irradiation, and the adhesive composition can be easily peeled off after peeling. Adhesive residue on the body is less likely to occur.
　繰り返し単位ｋにおいて、Ｒ１は－Ｈ又は－ＣＨ３であり、－Ｈであることが好ましい。Ｒ５は炭素原子数１～１６のアルキル基であり、炭素原子数１～８のアルキル基であることが好ましく、炭素原子数２、４又は８のアルキル基であることが特に好ましい。 In repeating unit k, R 1 is -H or -CH 3 , preferably -H. R 5 is an alkyl group having 1 to 16 carbon atoms, preferably an alkyl group having 1 to 8 carbon atoms, particularly preferably an alkyl group having 2, 4 or 8 carbon atoms.
　繰り返し単位ｋは、Ｒ１及び／又はＲ５の異なる複数種の繰り返し単位であってもよい。繰り返し単位ｋが、複数種の繰り返し単位を含む場合、繰り返し単位ｋの繰り返し数ｋは、複数種の繰り返し単位の繰り返し数の合計を示す。例えば、繰り返し単位ｋが、Ｒ１及び／又はＲ５の異なる繰り返し単位Ａ及びＢを含み、繰り返し単位Ａを２つ、繰り返し単位Ｂを３つ含む場合、繰り返し数ｋはＡの数とＢの数を合計して「５」となる。 Repeating unit k may be a plurality of repeating units with different R 1 and/or R 5 . When the repeating unit k contains multiple types of repeating units, the repeating number k of the repeating unit k indicates the total number of repeating units of the multiple types of repeating units. For example, if repeating unit k contains repeating units A and B with different R 1 and/or R 5 , and contains two repeating units A and three repeating units B, then the number of repeating units k is the number of A and B The numbers add up to 5.
　繰り返し単位ｌにおいて、Ｒ２は－Ｈ又は－ＣＨ３であり、－Ｈであることが好ましい。Ｒ６は炭素原子数３～３０の脂環式炭化水素基又は炭素原子数６～２０の芳香族炭化水素基であり、炭素原子数６～２０の脂環式炭化水素基又は炭素原子数６～１２の芳香族炭化水素基であることが好ましい。 In repeating unit l, R 2 is -H or -CH 3 , preferably -H. R 6 is an alicyclic hydrocarbon group having 3 to 30 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms, and an alicyclic hydrocarbon group having 6 to 20 carbon atoms or 6 carbon atoms ~12 aromatic hydrocarbon groups are preferred.
　繰り返し単位ｌは、Ｒ２及び／又はＲ６の異なる複数種の繰り返し単位であってもよい。繰り返し単位ｌが、複数種の繰り返し単位を含む場合、繰り返し単位ｌの繰り返し数ｌは、複数種の繰り返し単位の繰り返し数の合計を示す。 Repeating unit 1 may be a plurality of repeating units with different R 2 and/or R 6 . When the repeating unit 1 contains multiple types of repeating units, the repeating number 1 of the repeating unit 1 indicates the sum of the repeating numbers of the multiple types of repeating units.
　繰り返し単位ｍにおいて、Ｒ３は－Ｈ又は－ＣＨ３であり、－Ｈであることが好ましい。Ｒ７は－Ｈ又は－（ＣＨ２）ｊ－ＣＯＯＨ（式中のｊは１又は２である。）であり、－Ｈであることが好ましい。 In repeating unit m, R 3 is -H or -CH 3 , preferably -H. R 7 is -H or -(CH 2 ) j -COOH (where j is 1 or 2), preferably -H.
　繰り返し単位ｍは、Ｒ３及び／又はＲ７の異なる複数種の繰り返し単位であってもよい。繰り返し単位ｍが、複数種の繰り返し単位を含む場合、繰り返し単位ｍの繰り返し数ｍは、複数種の繰り返し単位の繰り返し数の合計を示す。 Repeating unit m may be a plurality of repeating units with different R 3 and/or R 7 . When the repeating unit m contains multiple types of repeating units, the repeating number m of the repeating unit m indicates the total number of repeating units of the multiple types of repeating units.
　繰り返し単位ｎにおいて、Ｒ４は－Ｈ又は－ＣＨ３であり、－Ｈであることが好ましい。Ｒ８は式（１－２）又は（１－３）で示される基である。式（１－２）又は（１－３）で示される基は、いずれも脂環式化合物に由来する構造を含み、粘着剤組成物の耐熱性を向上させる機能を有する。式（１－２）又は（１－３）において、ｐ及びｑは０、１及び２から選ばれるいずれかである。ｓはｐが０のときは０であり、ｐが１又は２のときは１である。Ｒ９は－Ｈ又は－ＣＨ３である。 In repeating unit n, R 4 is -H or -CH 3 , preferably -H. R 8 is a group represented by formula (1-2) or (1-3). Each group represented by formula (1-2) or (1-3) contains a structure derived from an alicyclic compound and has the function of improving the heat resistance of the pressure-sensitive adhesive composition. In formula (1-2) or (1-3), p and q are any selected from 0, 1 and 2. s is 0 when p is 0 and 1 when p is 1 or 2; R 9 is -H or -CH 3 .
　繰り返し単位ｎは、Ｒ４及び／又はＲ８の異なる複数種の繰り返し単位であってもよい。繰り返し単位ｎが、複数種の繰り返し単位を含む場合、繰り返し単位ｎの繰り返し数ｎは、複数種の繰り返し単位の繰り返し数の合計を示す。 Repeating unit n may be a plurality of repeating units with different R 4 and/or R 8 . When the repeating unit n contains multiple types of repeating units, the repeating number n of the repeating unit n indicates the total number of repeating units of the multiple types of repeating units.
　式（１－１）で示される樹脂（Ａ）は、繰り返し単位ｋと、繰り返し単位ｌと、繰り返し単位ｍと、繰り返し単位ｎとからなるランダム共重合体、ブロック共重合体、交互共重合体のいずれであってもよい。式（１－１）で示される樹脂（Ａ）は、繰り返し単位ｌを含まなくてもよく、繰り返し単位ｋと、繰り返し単位ｍと、繰り返し単位ｎとからなるランダム共重合体、ブロック共重合体、交互共重合体のいずれであってもよい。 The resin (A) represented by formula (1-1) is a random copolymer, block copolymer, or alternating copolymer composed of repeating unit k, repeating unit l, repeating unit m, and repeating unit n. may be either. The resin (A) represented by formula (1-1) may not contain the repeating unit l, and may be a random copolymer or a block copolymer consisting of a repeating unit k, a repeating unit m, and a repeating unit n. , alternating copolymers.
　樹脂（Ａ）の重量平均分子量は、５万～５５万であり、１０万～５０万であることが好ましく、２６万～４５万であることがより好ましい。樹脂（Ａ）の重量平均分子量が５万以上であると、粘着剤組成物の硬化物を含む粘着剤層を有する粘着シートを被着体に貼り付けた後に剥離した場合に、粘着剤層が被着体によりいっそう残存しにくくなる。樹脂（Ａ）の重量平均分子量が５５万以下であると、バンプ等の表面の凹凸に対して、粘着剤層を隙間なく十分に密着させることができる。樹脂（Ａ）の重量平均分子量は、実施例に記載の方法で測定した値である。 The weight average molecular weight of the resin (A) is 50,000 to 550,000, preferably 100,000 to 500,000, more preferably 260,000 to 450,000. When the weight average molecular weight of the resin (A) is 50,000 or more, when a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer containing a cured product of the pressure-sensitive adhesive composition is attached to an adherend and then peeled off, the pressure-sensitive adhesive layer is It becomes more difficult to remain on the adherend. When the weight average molecular weight of the resin (A) is 550,000 or less, the pressure-sensitive adhesive layer can be sufficiently adhered to uneven surfaces such as bumps without gaps. The weight average molecular weight of resin (A) is a value measured by the method described in Examples.
　樹脂（Ａ）のガラス転移温度（Ｔｇ）は、好ましくは－８０～０℃、より好ましくは－６０～－１０℃、更に好ましくは－５０～－１０℃である。樹脂（Ａ）のガラス転移温度が－８０℃～０℃の範囲であると、ＵＶ照射前の粘着剤組成物の粘着力が良好である。樹脂（Ａ）のＴｇは、実施例に記載の方法で測定した値である。 The glass transition temperature (Tg) of the resin (A) is preferably -80 to 0°C, more preferably -60 to -10°C, still more preferably -50 to -10°C. When the glass transition temperature of the resin (A) is in the range of -80°C to 0°C, the adhesive strength of the adhesive composition before UV irradiation is good. The Tg of resin (A) is a value measured by the method described in Examples.
　樹脂（Ａ）の酸価は、０超～２５ｍｇＫＯＨ／ｇであることが好ましく、３～２０ｍｇＫＯＨ／ｇであることがより好ましい。樹脂（Ａ）の酸価が０超～２５ｍｇＫＯＨ／ｇの範囲内であると、加熱後の被着体汚染（糊残り）を低減することができる。粘着剤組成物が架橋剤を含む場合、樹脂（Ａ）の酸価が上記範囲内であると、樹脂（Ａ）と架橋剤とが反応して粘着剤組成物の凝集力を効果的に高めることができ、これにより加熱後の被着体汚染（糊残り）をいっそう低減することができる。樹脂（Ａ）の酸価は、実施例に記載の方法で測定した値である。 The acid value of resin (A) is preferably greater than 0 to 25 mgKOH/g, more preferably 3 to 20 mgKOH/g. When the acid value of the resin (A) is in the range of more than 0 to 25 mgKOH/g, contamination of the adherend (adhesive residue) after heating can be reduced. When the pressure-sensitive adhesive composition contains a cross-linking agent, if the acid value of the resin (A) is within the above range, the resin (A) and the cross-linking agent react to effectively increase the cohesive strength of the pressure-sensitive adhesive composition. As a result, contamination of the adherend (adhesive residue) after heating can be further reduced. The acid value of Resin (A) is a value measured by the method described in Examples.
（樹脂（Ａ）の製造方法）
　樹脂（Ａ）は、例えば、以下に示す方法により製造することができる。 (Method for producing resin (A))
Resin (A) can be produced, for example, by the method shown below.
　まず、カルボキシ基含有エチレン性不飽和単量体（ａ）と、エチレン性不飽和単量体（ｄ）とを含む原料単量体を重合し、カルボキシ基含有樹脂（ｂ）を製造する。エチレン性不飽和単量体（ｄ）は、重合後に、繰り返し単位ｋを形成する単量体を含み、繰り返し単位ｌの骨格を形成する単量体を含むものであってもよい。 First, raw material monomers containing a carboxy group-containing ethylenically unsaturated monomer (a) and an ethylenically unsaturated monomer (d) are polymerized to produce a carboxy group-containing resin (b). The ethylenically unsaturated monomer (d) contains a monomer that forms the repeating unit k after polymerization, and may contain a monomer that forms the skeleton of the repeating unit l.
　次に、カルボキシ基含有樹脂（ｂ）と、特定の脂環式エポキシ基含有エチレン性不飽和化合物（ｃ）との付加反応により、樹脂（Ａ）を製造することができる。 Next, the resin (A) can be produced by an addition reaction between the carboxy group-containing resin (b) and the specific alicyclic epoxy group-containing ethylenically unsaturated compound (c).
（カルボキシ基含有エチレン性不飽和単量体（ａ））
　カルボキシ基含有樹脂（ｂ）を製造する際に使用するカルボキシ基含有エチレン性不飽和単量体（ａ）は、重合することで繰り返し単位ｍの骨格を形成する単量体である。カルボキシ基含有エチレン性不飽和単量体（ａ）は、１個のカルボキシ基を有する。 (Carboxy group-containing ethylenically unsaturated monomer (a))
The carboxy group-containing ethylenically unsaturated monomer (a) used when producing the carboxy group-containing resin (b) is a monomer that forms a skeleton of the repeating unit m by polymerizing. The carboxy group-containing ethylenically unsaturated monomer (a) has one carboxy group.
　カルボキシ基含有エチレン性不飽和単量体（ａ）としては、例えば、（メタ）アクリル酸、カルボキシメチル（メタ）アクリレート、及びβ－カルボキシエチル（メタ）アクリレートが挙げられる。 Carboxy group-containing ethylenically unsaturated monomers (a) include, for example, (meth)acrylic acid, carboxymethyl (meth)acrylate, and β-carboxyethyl (meth)acrylate.
　これらの中でも、カルボキシ基含有エチレン性不飽和単量体（ａ）としては、反応性の点で、（メタ）アクリル酸及び／又はβ－カルボキシエチル（メタ）アクリレートを用いることが好ましい。 Among these, it is preferable to use (meth)acrylic acid and/or β-carboxyethyl (meth)acrylate as the carboxy group-containing ethylenically unsaturated monomer (a) in terms of reactivity.
　本開示において、（メタ）アクリルとは、「アクリル」又は「メタクリル」を意味する。（メタ）アクリレートとは、「アクリレート」又は「メタクリレート」を意味する。（メタ）アクリロイルとは、「アクリロイル」又は「メタクリロイル」を意味する。 In the present disclosure, (meth)acryl means "acryl" or "methacryl". (Meth)acrylate means "acrylate" or "methacrylate". (Meth)acryloyl means "acryloyl" or "methacryloyl".
（カルボキシ基含有樹脂（ｂ））
　カルボキシ基含有樹脂（ｂ）は、カルボキシ基含有エチレン性不飽和単量体（ａ）と、カルボキシ基含有エチレン性不飽和単量体（ａ）と共重合可能なエチレン性不飽和単量体（ｄ）とを少なくとも含む原料単量体を共重合したものである。 (Carboxy group-containing resin (b))
The carboxy group-containing resin (b) is a carboxy group-containing ethylenically unsaturated monomer (a) and an ethylenically unsaturated monomer copolymerizable with the carboxy group-containing ethylenically unsaturated monomer (a) ( It is obtained by copolymerizing raw material monomers containing at least d).
　カルボキシ基含有樹脂（ｂ）は、式（１－１）で示される樹脂（Ａ）の骨格となる成分である。繰り返し単位ｋ、繰り返し単位ｌ、及び繰り返し単位ｍは、いずれもカルボキシ基含有樹脂（ｂ）に由来する繰り返し単位である。 The carboxy group-containing resin (b) is a component that forms the skeleton of the resin (A) represented by formula (1-1). Repeating unit k, repeating unit l, and repeating unit m are all repeating units derived from the carboxy group-containing resin (b).
　エチレン性不飽和単量体（ｄ）としては、重合することで繰り返し単位ｋの骨格を形成する単量体を１種以上用いる。エチレン性不飽和単量体（ｄ）として、重合することで繰り返し単位ｋの骨格を形成する単量体とともに、重合することで繰り返し単位ｌの骨格を形成する単量体を１種以上用いてもよい。 As the ethylenically unsaturated monomer (d), one or more monomers that form a skeleton of the repeating unit k when polymerized are used. As the ethylenically unsaturated monomer (d), at least one monomer that forms the skeleton of the repeating unit k by polymerization and a monomer that forms the skeleton of the repeating unit l by polymerization are used. good too.
　重合することで繰り返し単位ｋの骨格を形成するエチレン性不飽和単量体（ｄ）は、炭素原子数１～１６のアルキル（メタ）アクリレートであり、粘着剤組成物の剥離強度の調整の観点から、炭素原子数２～１６のアルキル（メタ）アクリレートを含むことが好ましく、炭素原子数４～１２のアルキル（メタ）アクリレートを含むことがより好ましい。炭素原子数１～１６のアルキル（メタ）アクリレートとしては、具体的には、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ－プロピル（メタ）アクリレート、ｎ－ブチル（メタ）アクリレート、ｔｅｒｔ－ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、イソデシル（メタ）アクリレート、ｎ－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、及びラウリル（メタ）アクリレートが挙げられる。これらの中でも、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ－ブチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、及びイソオクチル（メタ）アクリレートが好ましい。本開示において、（メタ）アクリレートに関して用いられる炭素原子数は、（メタ）アクリロイルオキシ基を除く残基の炭素原子数を指す。 The ethylenically unsaturated monomer (d) that forms the skeleton of the repeating unit k by polymerization is an alkyl (meth)acrylate having 1 to 16 carbon atoms, from the viewpoint of adjusting the peel strength of the pressure-sensitive adhesive composition. Therefore, it preferably contains an alkyl (meth)acrylate having 2 to 16 carbon atoms, more preferably an alkyl (meth)acrylate having 4 to 12 carbon atoms. Specific examples of alkyl (meth)acrylates having 1 to 16 carbon atoms include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, tert- Butyl (meth)acrylate, isobutyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isodecyl (meth)acrylate, n-hexyl (meth)acrylate, isooctyl (meth)acrylate, and lauryl (meth)acrylate. Among these, methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and isooctyl (meth)acrylate are preferred. In this disclosure, the number of carbon atoms used for (meth)acrylate refers to the number of carbon atoms in the residue excluding the (meth)acryloyloxy group.
　重合することで繰り返し単位ｌの骨格を形成するエチレン性不飽和単量体（ｄ）としては、例えば、炭素原子数３～３０の環状アルキル基含有（メタ）アクリレート、及び炭素原子数６～２０の芳香族基含有（メタ）アクリレートが挙げられる。 Examples of the ethylenically unsaturated monomer (d) that forms the skeleton of the repeating unit l by polymerization include (meth)acrylates containing a cyclic alkyl group having 3 to 30 carbon atoms, and 6 to 20 carbon atoms. of aromatic group-containing (meth)acrylates.
　重合することで繰り返し単位ｌの骨格を形成するエチレン性不飽和単量体（ｄ）として用いられる炭素原子数３～３０の環状アルキル基含有（メタ）アクリレートとしては、例えば、シクロヘキシル（メタ）アクリレート、ノルボルニル（メタ）アクリレート、イソボルニル（メタ）アクリレート、ジシクロペンテニル（メタ）アクリレート、ジシクロペンテニルオキシエチル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート、及びジシクロペンタニルオキシエチル（メタ）アクリレートが挙げられる。これらの中でも、イソボルニル（メタ）アクリレートを用いることが特に好ましい。カルボキシ基含有樹脂（ｂ）の原料単量体中に環状アルキル基含有（メタ）アクリレートが含まれていると、カルボキシ基含有樹脂（ｂ）を用いて製造した樹脂（Ａ）を含む粘着剤組成物の耐熱性を高めることができる。 The (meth)acrylate containing a cyclic alkyl group having 3 to 30 carbon atoms used as the ethylenically unsaturated monomer (d) that forms the skeleton of the repeating unit l by polymerization includes, for example, cyclohexyl (meth)acrylate , norbornyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, dicyclopentanyl (meth)acrylate, and dicyclopentanyloxyethyl (meth)acrylate Acrylates are mentioned. Among these, it is particularly preferable to use isobornyl (meth)acrylate. When a cyclic alkyl group-containing (meth)acrylate is contained in the raw material monomer of the carboxy group-containing resin (b), the pressure-sensitive adhesive composition containing the resin (A) produced using the carboxy group-containing resin (b) It can increase the heat resistance of the object.
　重合することで繰り返し単位ｌの骨格を形成するエチレン性不飽和単量体（ｄ）として用いられる炭素原子数６～２０の芳香族基含有（メタ）アクリレートとしては、例えば、ベンジル（メタ）アクリレート、フェノキシエチル（メタ）アクリレート、フェノキシポリエチレングリコール（メタ）アクリレート、フェノキシプロピル（メタ）アクリレート、及びフェノキシポリプロピレングリコール（メタ）アクリレートが挙げられる。これらの中でも、ベンジル（メタ）アクリレートを用いることが特に好ましい。カルボキシ基含有樹脂（ｂ）の原料単量体中に芳香族基含有（メタ）アクリレートが含まれていると、カルボキシ基含有樹脂（ｂ）を用いて製造した樹脂（Ａ）を含む粘着剤組成物の耐熱性を高めることができる。 The aromatic group-containing (meth)acrylate having 6 to 20 carbon atoms used as the ethylenically unsaturated monomer (d) that forms the skeleton of the repeating unit l by polymerization includes, for example, benzyl (meth)acrylate , phenoxyethyl (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate, phenoxypropyl (meth)acrylate, and phenoxypolypropylene glycol (meth)acrylate. Among these, it is particularly preferable to use benzyl (meth)acrylate. When aromatic group-containing (meth)acrylate is contained in the raw material monomer of the carboxy group-containing resin (b), the pressure-sensitive adhesive composition containing the resin (A) produced using the carboxy group-containing resin (b) It can increase the heat resistance of the object.
　カルボキシ基含有樹脂（ｂ）の原料単量体中には、上記のカルボキシ基含有エチレン性不飽和単量体（ａ）及び上記のエチレン性不飽和単量体（ｄ）だけでなく、上記のエチレン性不飽和単量体（ｄ）以外の、カルボキシ基含有エチレン性不飽和単量体（ａ）と共重合可能な単量体が含まれていてもよい。 Among the raw material monomers of the carboxy group-containing resin (b), not only the above carboxy group-containing ethylenically unsaturated monomer (a) and the above ethylenically unsaturated monomer (d), but also the above A monomer copolymerizable with the carboxy group-containing ethylenically unsaturated monomer (a) other than the ethylenically unsaturated monomer (d) may also be included.
　上記のエチレン性不飽和単量体（ｄ）以外の、カルボキシ基含有エチレン性不飽和単量体（ａ）と共重合可能なエチレン性不飽和単量体としては、例えば、アルコキシアルキル（メタ）アクリレート、アルコキシ（ポリ）アルキレングリコール（メタ）アクリレート、ヒドロキシ基含有（メタ）アクリレート、フッ素化アルキル（メタ）アクリレート、ジアルキルアミノアルキル（メタ）アクリレート、及び（メタ）アクリルアミド化合物が挙げられる。 Examples of the ethylenically unsaturated monomer copolymerizable with the carboxy group-containing ethylenically unsaturated monomer (a) other than the above ethylenically unsaturated monomer (d) include, for example, alkoxyalkyl (meth) Acrylates, alkoxy(poly)alkylene glycol (meth)acrylates, hydroxy group-containing (meth)acrylates, fluorinated alkyl (meth)acrylates, dialkylaminoalkyl (meth)acrylates, and (meth)acrylamide compounds.
　アルコキシアルキル（メタ）アクリレートとしては、例えば、エトキシエチル（メタ）アクリレート、メトキシエチル（メタ）アクリレート、ブトキシエチル（メタ）アクリレート、２－メトキシエトキシエチル（メタ）アクリレート、及び２－エトキシエトキシエチル（メタ）アクリレートが挙げられる。 Alkoxyalkyl (meth)acrylates include, for example, ethoxyethyl (meth)acrylate, methoxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, 2-methoxyethoxyethyl (meth)acrylate, and 2-ethoxyethoxyethyl (meth)acrylate. ) acrylates.
　アルコキシ（ポリ）アルキレングリコール（メタ）アクリレートとしては、例えば、メトキシジエチレングリコール（メタ）アクリレート、エトキシジエチレングリコール（メタ）アクリレート、及びメトキシジプロピレングリコール（メタ）アクリレートが挙げられる。 Alkoxy (poly) alkylene glycol (meth) acrylates include, for example, methoxydiethylene glycol (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, and methoxydipropylene glycol (meth) acrylate.
　ヒドロキシ基含有（メタ）アクリレートとしては、例えば、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、４－ヒドロキシブチル（メタ）アクリレート、１，３－ブタンジオール（メタ）アクリレート、１，４－ブタンジオール（メタ）アクリレート、１，６－ヘキサンジオール（メタ）アクリレート、及び３－メチルペンタンジオール（メタ）アクリレートが挙げられる。 Examples of hydroxy group-containing (meth)acrylates include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 1,3-butanediol (meth)acrylate, 1,4-butanediol (meth)acrylate, 1,6-hexanediol (meth)acrylate, and 3-methylpentanediol (meth)acrylate.
　フッ素化アルキル（メタ）アクリレートとしては、例えば、オクタフルオロペンチル（メタ）アクリレートが挙げられる。 Examples of fluorinated alkyl (meth)acrylates include octafluoropentyl (meth)acrylate.
　ジアルキルアミノアルキル（メタ）アクリレートとしては、例えば、Ｎ，Ｎ－ジメチルアミノエチル（メタ）アクリレート、及びＮ，Ｎ－ジエチルアミノエチル（メタ）アクリレートが挙げられる。 Examples of dialkylaminoalkyl (meth)acrylates include N,N-dimethylaminoethyl (meth)acrylate and N,N-diethylaminoethyl (meth)acrylate.
　（メタ）アクリルアミド化合物としては、例えば、（メタ）アクリルアミド、Ｎ－メチル（メタ）アクリルアミド、Ｎ－エチル（メタ）アクリルアミド、Ｎ－プロピル（メタ）アクリルアミド、Ｎ－イソプロピル（メタ）アクリルアミド、Ｎ－ヘキシル（メタ）アクリルアミド、Ｎ，Ｎ－ジメチル（メタ）アクリルアミド、Ｎ，Ｎ－ジエチル（メタ）アクリルアミド、（メタ）アクリロイルモルホリン、及びジアセトンアクリルアミドが挙げられる。 (Meth)acrylamide compounds include, for example, (meth)acrylamide, N-methyl(meth)acrylamide, N-ethyl(meth)acrylamide, N-propyl(meth)acrylamide, N-isopropyl(meth)acrylamide, N-hexyl (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, (meth)acryloylmorpholine, and diacetoneacrylamide.
　エチレン性不飽和単量体（ｄ）以外の、カルボキシ基含有エチレン性不飽和単量体（ａ）と共重合可能な単量体の上記以外の具体例として、アクリロニトリル、メタクリロニトリル、スチレン、α－メチルスチレン、酢酸ビニル、プロピオン酸ビニル、ステアリン酸ビニル、塩化ビニル、塩化ビニリデン、アルキルビニルエーテル、ビニルトルエン、Ｎ－ビニルピリジン、Ｎ－ビニルピロリドン、イタコン酸ジアルキルエステル、フマル酸ジアルキルエステル、アリルアルコール、ヒドロキシブチルビニルエーテル、ヒドロキシエチルビニルエーテル、４－ヒドロキシメチルシクロヘキシルメチルビニルエーテル、トリエチレングリコールモノビニルエーテル、ジエチレングリコールモノビニルエーテル、メチルビニルケトン、アリルトリメチルアンモニウムクロライド、及びジメチルアリルビニルケトンが挙げられる。 Specific examples of the monomer copolymerizable with the carboxy group-containing ethylenically unsaturated monomer (a) other than the ethylenically unsaturated monomer (d) include acrylonitrile, methacrylonitrile, styrene, α-methylstyrene, vinyl acetate, vinyl propionate, vinyl stearate, vinyl chloride, vinylidene chloride, alkyl vinyl ether, vinyl toluene, N-vinylpyridine, N-vinylpyrrolidone, dialkyl itaconate, dialkyl fumarate, allyl alcohol , hydroxybutyl vinyl ether, hydroxyethyl vinyl ether, 4-hydroxymethylcyclohexylmethyl vinyl ether, triethylene glycol monovinyl ether, diethylene glycol monovinyl ether, methyl vinyl ketone, allyltrimethylammonium chloride, and dimethyl allyl vinyl ketone.
　カルボキシ基含有樹脂（ｂ）を製造する方法としては、特に限定されない。例えば、カルボキシ基含有樹脂（ｂ）の構成成分となるカルボキシ基含有エチレン性不飽和単量体（ａ）とエチレン性不飽和単量体（ｄ）とを含む原料単量体を、公知の重合方法により共重合することによりカルボキシ基含有樹脂（ｂ）を得ることができる。具体的には、重合方法として、溶液重合法、乳化重合法、塊状重合法、懸濁重合法、交互共重合法などを用いることができる。これらの重合方法の中でも、重合後に得られるカルボキシ基含有樹脂（ｂ）と脂環式エポキシ基含有エチレン性不飽和化合物（ｃ）との付加反応を考慮すると、反応の容易さの点で溶液重合法を用いることが好ましい。 The method for producing the carboxy group-containing resin (b) is not particularly limited. For example, raw material monomers containing a carboxy group-containing ethylenically unsaturated monomer (a) and an ethylenically unsaturated monomer (d), which are constituent components of the carboxy group-containing resin (b), are subjected to known polymerization. Carboxy group-containing resin (b) can be obtained by copolymerizing according to the method. Specifically, as the polymerization method, a solution polymerization method, an emulsion polymerization method, a bulk polymerization method, a suspension polymerization method, an alternating copolymerization method, or the like can be used. Among these polymerization methods, considering the addition reaction between the carboxy group-containing resin (b) obtained after polymerization and the alicyclic epoxy group-containing ethylenically unsaturated compound (c), solution polymerization is preferred in terms of ease of reaction. It is preferred to use law.
　溶液重合法によりカルボキシ基含有樹脂（ｂ）を製造する際には、必要に応じて、ラジカル重合開始剤及び／又は溶媒を用いる。 When producing the carboxy group-containing resin (b) by solution polymerization, a radical polymerization initiator and/or solvent are used as necessary.
　ラジカル重合開始剤としては、特に限定されず、公知のものの中から適宜選択して使用することができる。 The radical polymerization initiator is not particularly limited, and can be appropriately selected from known ones and used.
　ラジカル重合開始剤としては、例えば、２，２’－アゾビス（イソブチロニトリル）、２，２’－アゾビス（４－メトキシ－２，４－ジメチルバレロニトリル）、２，２’－アゾビス（２，４－ジメチルバレロニトリル）、２，２’－アゾビス（２－メチルブチロニトリル）、１，１’－アゾビス（シクロヘキサン－１－カルボニトリル）、２，２’－アゾビス（２，４，４－トリメチルペンタン）、ジメチル－２，２’－アゾビス（２－メチルプロピオネート）等のアゾ系重合開始剤；及びベンゾイルパーオキサイド、ｔ－ブチルハイドロパーオキサイド、ジ－ｔ－ブチルパーオキサイド、ｔ－ブチルパーオキシベンゾエート、ジクミルパーオキサイド、１，１－ビス（ｔ－ブチルパーオキシ）－３，３，５－トリメチルシクロヘキサン、１，１－ビス（ｔ－ブチルパーオキシ）シクロドデカン等の過酸化物系重合開始剤などの油溶性重合開始剤が挙げられる。 Examples of radical polymerization initiators include 2,2′-azobis(isobutyronitrile), 2,2′-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis(2 ,4-dimethylvaleronitrile), 2,2′-azobis(2-methylbutyronitrile), 1,1′-azobis(cyclohexane-1-carbonitrile), 2,2′-azobis(2,4,4 -trimethylpentane), dimethyl-2,2'-azobis (2-methylpropionate) and other azo polymerization initiators; and benzoyl peroxide, t-butyl hydroperoxide, di-t-butyl peroxide, t -butyl peroxybenzoate, dicumyl peroxide, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(t-butylperoxy)cyclododecane, etc. Examples include oil-soluble polymerization initiators such as oxide polymerization initiators.
　これらのラジカル重合開始剤は、単独で使用してもよいし、２種以上を組み合わせて使用してもよい。 These radical polymerization initiators may be used alone or in combination of two or more.
　ラジカル重合開始剤の使用量は、カルボキシ基含有樹脂（ｂ）の原料単量体の合計１００質量部に対して、０．０１～５質量部であることが好ましく、０．０２～４質量部であることがより好ましく、０．０３～３質量部であることが更に好ましい。 The amount of the radical polymerization initiator to be used is preferably 0.01 to 5 parts by mass, more preferably 0.02 to 4 parts by mass, with respect to the total 100 parts by mass of the raw material monomers of the carboxy group-containing resin (b). and more preferably 0.03 to 3 parts by mass.
　カルボキシ基含有樹脂（ｂ）を製造する際に用いる重合用の溶媒としては、一般的な各種の溶媒を用いることができる。溶媒としては、例えば、酢酸エチル、酢酸ｎ－プロピル、酢酸ｎ－ブチル等のエステル；トルエン、キシレン、ベンゼン等の芳香族炭化水素；ｎ－ヘキサン、ｎ－ヘプタン等の脂肪族炭化水素；シクロヘキサン、メチルシクロヘキサン等の脂環式炭化水素；メチルエチルケトン、メチルイソブチルケトン等のケトン；エチレングリコール、プロピレングリコール、ジプロピレングリコール等のグリコール；メチルセロソルブ、プロピレングリコールモノメチルエーテル、ジプロピレングリコールモノメチルエーテル等のグリコールエーテル；及びエチレングリコールジアセテート、プロピレングリコールモノメチルエーテルアセテート等のグリコールエステルが挙げられる。 Various general solvents can be used as the solvent for polymerization used when producing the carboxy group-containing resin (b). Examples of solvents include esters such as ethyl acetate, n-propyl acetate and n-butyl acetate; aromatic hydrocarbons such as toluene, xylene and benzene; aliphatic hydrocarbons such as n-hexane and n-heptane; alicyclic hydrocarbons such as methylcyclohexane; ketones such as methyl ethyl ketone and methyl isobutyl ketone; glycols such as ethylene glycol, propylene glycol and dipropylene glycol; glycol ethers such as methyl cellosolve, propylene glycol monomethyl ether and dipropylene glycol monomethyl ether; and glycol esters such as ethylene glycol diacetate and propylene glycol monomethyl ether acetate.
　これらの溶媒は、単独で使用してもよいし、２種以上を組み合わせて使用してもよい。 These solvents may be used alone or in combination of two or more.
　カルボキシ基含有樹脂（ｂ）を製造する際には、カルボキシ基含有エチレン性不飽和単量体（ａ）と、エチレン性不飽和単量体（ｄ）と、必要に応じて含有されるその他の単量体とを含む原料単量体中におけるカルボキシ基含有エチレン性不飽和単量体（ａ）の含有量を、５～４０質量％とすることが好ましく、７～３０質量％とすることがより好ましく、１０～２５質量％とすることが更に好ましい。原料単量体中におけるカルボキシ基含有エチレン性不飽和単量体（ａ）の含有量を上記範囲とすることで、カルボキシ基含有樹脂（ｂ）と脂環式エポキシ基含有エチレン性不飽和化合物（ｃ）との付加反応により製造した樹脂（Ａ）を含む粘着剤組成物から得られる粘着剤層のＵＶ照射前の粘着力が良好である。 When producing the carboxy group-containing resin (b), the carboxy group-containing ethylenically unsaturated monomer (a), the ethylenically unsaturated monomer (d), and other optionally contained The content of the carboxy group-containing ethylenically unsaturated monomer (a) in the raw material monomer containing the monomer is preferably 5 to 40% by mass, and may be 7 to 30% by mass. More preferably, it is 10 to 25% by mass. By setting the content of the carboxy group-containing ethylenically unsaturated monomer (a) in the raw material monomer to the above range, the carboxy group-containing resin (b) and the alicyclic epoxy group-containing ethylenically unsaturated compound ( The pressure-sensitive adhesive layer obtained from the pressure-sensitive adhesive composition containing the resin (A) produced by the addition reaction with c) has good adhesive strength before UV irradiation.
（脂環式エポキシ基含有エチレン性不飽和化合物（ｃ））
　脂環式エポキシ基含有エチレン性不飽和化合物（ｃ）は、脂環式エポキシ基を有するエチレン性不飽和基含有化合物であって、一般式（１－２）又は一般式（１－３）の構造を与える化合物である。本開示における脂環式エポキシ基とは、脂環式炭化水素化合物の環上の隣接する２個の炭素原子に１個の酸素が結合して形成されるエポキシ基をいう。 (Alicyclic epoxy group-containing ethylenically unsaturated compound (c))
The alicyclic epoxy group-containing ethylenically unsaturated compound (c) is an ethylenically unsaturated group-containing compound having an alicyclic epoxy group and represented by general formula (1-2) or general formula (1-3). It is the compound that gives the structure. An alicyclic epoxy group in the present disclosure refers to an epoxy group formed by bonding one oxygen to two adjacent carbon atoms on the ring of an alicyclic hydrocarbon compound.
　脂環式エポキシ基含有エチレン性不飽和化合物（ｃ）は、式（１－１）で示される樹脂（Ａ）の繰り返し単位ｎにおける下記部分構造式（１－２’）又は（１－３’）を付加するために用いられる。式（１－１）中の繰り返し単位ｎにおける部分構造式（１－２’）又は（１－３’）は、脂環式エポキシ基含有エチレン性不飽和化合物（ｃ）に由来する基である。 The alicyclic epoxy group-containing ethylenically unsaturated compound (c) has the following partial structural formula (1-2') or (1-3') in the repeating unit n of the resin (A) represented by formula (1-1). ) is used to add Partial structural formula (1-2') or (1-3') in repeating unit n in formula (1-1) is a group derived from an alicyclic epoxy group-containing ethylenically unsaturated compound (c). .
Figure JPOXMLDOC01-appb-C000007
 （式（１－２’）及び（１－３’）において、ｑは０、１及び２から選ばれるいずれかである。Ｒ９は－Ｈ又は－ＣＨ３である。）
Figure JPOXMLDOC01-appb-C000007
 (In formulas (1-2′) and (1-3′), q is any one selected from 0, 1 and 2. R 9 is —H or —CH 3. )
　脂環式エポキシ基含有エチレン性不飽和化合物（ｃ）としては、例えば、下記式（１）又は（２）で示される化合物が挙げられる。 Examples of the alicyclic epoxy group-containing ethylenically unsaturated compound (c) include compounds represented by the following formula (1) or (2).
Figure JPOXMLDOC01-appb-C000008
 （式（１）において、Ｒ９は－Ｈ又は－ＣＨ３である。ｑは０、１及び２から選ばれるいずれかである。）
（式（２）において、Ｒ９は－Ｈ又は－ＣＨ３である。ｑは０、１及び２から選ばれるいずれかである。）
Figure JPOXMLDOC01-appb-C000008
 (In formula (1), R 9 is —H or —CH 3. q is any one selected from 0, 1 and 2.)
(In formula (2), R 9 is —H or —CH 3. q is any one selected from 0, 1 and 2.)
　式（１）において、Ｒ９は－Ｈ又は－ＣＨ３である。ｑは０、１及び２から選ばれるいずれかであり、ｑが１であることが好ましい。 In formula (1), R 9 is -H or -CH 3 . q is any one selected from 0, 1 and 2, preferably q is 1;
　式（２）において、Ｒ９は－Ｈ又は－ＣＨ３である。ｑは０、１及び２から選ばれるいずれかであり、ｑが１であることが好ましい。 In formula (2), R 9 is -H or -CH 3 . q is any one selected from 0, 1 and 2, preferably q is 1;
　脂環式エポキシ基含有エチレン性不飽和化合物（ｃ）は、式（１）で示される化合物であることが好ましく、３，４－エポキシシクロヘキシルメチル（メタ）アクリレートであることが特に好ましい。 The alicyclic epoxy group-containing ethylenically unsaturated compound (c) is preferably a compound represented by formula (1), and particularly preferably 3,4-epoxycyclohexylmethyl (meth)acrylate.
　脂環式エポキシ基含有エチレン性不飽和化合物（ｃ）は、単独で使用してもよいし、２種以上組み合わせて使用してもよい。 The alicyclic epoxy group-containing ethylenically unsaturated compound (c) may be used alone or in combination of two or more.
　樹脂（Ａ）は、カルボキシ基含有樹脂（ｂ）のカルボキシ基に、脂環式エポキシ基含有エチレン性不飽和化合物（ｃ）の脂環式エポキシ基を付加反応させることによって製造することができる。 The resin (A) can be produced by subjecting the carboxy group of the carboxy group-containing resin (b) to an addition reaction with the alicyclic epoxy group of the alicyclic epoxy group-containing ethylenically unsaturated compound (c).
　樹脂（Ａ）は、カルボキシ基含有樹脂（ｂ）のカルボキシ基１ｍｏｌに対して好ましくは０．２～０．９９ｍｏｌ、より好ましくは０．３～０．９５ｍｏｌ、更に好ましくは０．６～０．９５ｍｏｌの脂環式エポキシ基含有エチレン性不飽和化合物（ｃ）を付加反応させて製造することが好ましい。カルボキシ基含有樹脂（ｂ）と脂環式エポキシ基含有エチレン性不飽和化合物（ｃ）とを上記の割合で用いて得られた樹脂（Ａ）を含む粘着剤組成物は、ＵＶ照射前には被着体に対して十分な粘着性を示し、ＵＶ照射後には粘着力が低下してより優れた易剥離性が得られる。しかも、この粘着剤組成物は、ＵＶ照射前に高温状態にしてから室温に戻しても粘着力が高くなりにくく、ＵＶ照射後に優れた易剥離性が得られるとともに、剥離後の被着体への糊残りをより効果的に防止することができる。 The amount of the resin (A) is preferably 0.2 to 0.99 mol, more preferably 0.3 to 0.95 mol, still more preferably 0.6 to 0.99 mol, per 1 mol of the carboxy group of the carboxy group-containing resin (b). It is preferably produced by addition reaction of 95 mol of the alicyclic epoxy group-containing ethylenically unsaturated compound (c). The pressure-sensitive adhesive composition containing the resin (A) obtained by using the carboxyl group-containing resin (b) and the alicyclic epoxy group-containing ethylenically unsaturated compound (c) in the above ratio, before UV irradiation It exhibits sufficient adhesiveness to adherends, and its adhesive strength decreases after UV irradiation, resulting in more excellent easy peelability. In addition, this pressure-sensitive adhesive composition does not easily increase its adhesive strength even when it is brought to a high temperature state before UV irradiation and then returned to room temperature, and excellent easy peelability can be obtained after UV irradiation. The adhesive residue can be prevented more effectively.
　樹脂（Ａ）を製造する際における付加反応の温度は、８０～１３０℃であることが好ましく、９０～１２０℃であることが特に好ましい。付加反応の温度が８０℃以上であると、十分な反応速度を得ることができる。付加反応の温度が１３０℃以下であると、熱によるラジカル重合によって二重結合部が架橋し、ゲル化物が生じることを防止できる。 The temperature of the addition reaction when producing the resin (A) is preferably 80 to 130°C, particularly preferably 90 to 120°C. When the addition reaction temperature is 80° C. or higher, a sufficient reaction rate can be obtained. When the temperature of the addition reaction is 130° C. or lower, it is possible to prevent the formation of a gelled product due to cross-linking of double bonds due to thermal radical polymerization.
　樹脂（Ａ）を製造する際における付加反応には、必要に応じて、公知の触媒を使用することができる。触媒としては、例えば、ｎ－ブチルアミン、ｎ－ヘキシルアミン、ベンジルアミン等の１級アミン；トリエチルアミン、トリブチルアミン、ジメチルベンジルアミン、１，８－ジアザビシクロ［５．４．０］ウンデカ－７－エン、１，５－ジアザビシクロ［４．３．０］ノナ－５－エン、１，４－ジアザビシクロ［２．２．２］オクタン等の３級アミン；アニリン、トルイジン、フェニレンジアミン、１，８－ジアミノナフタレン等の芳香族アミン；ピリジン、２，６－ルチジン、４－Ｎ，Ｎ－ジメチルアミノピリジン等のピリジン化合物；テトラメチルアンモニウムクロライド、テトラメチルアンモニウムブロマイド、テトラブチルアンモニウムブロマイド等の４級アンモニウム塩；テトラメチル尿素等のアルキル尿素；テトラメチルグアニジン等のアルキルグアニジン；及びトリフェニルホスフィン、ジメチルフェニルホスフィン、トリシクロヘキシルホスフィン、トリブチルホスフィン、トリス（４－メチルフェニル）ホスフィン、トリス（４－メトキシフェニル）ホスフィン、トリス（２，６－ジメチルフェニル）ホスフィン、トリス（２，６－ジメトキシフェニル）ホスフィン、トリス（２，４，６－トリメチルフェニル）ホスフィン、トリス（２，４，６－トリメトキシフェニル）ホスフィン等のホスフィン化合物が挙げられる。 A known catalyst can be used, if necessary, for the addition reaction during the production of the resin (A). Examples of catalysts include primary amines such as n-butylamine, n-hexylamine and benzylamine; triethylamine, tributylamine, dimethylbenzylamine, 1,8-diazabicyclo[5.4.0]undec-7-ene, Tertiary amines such as 1,5-diazabicyclo[4.3.0]non-5-ene, 1,4-diazabicyclo[2.2.2]octane; aniline, toluidine, phenylenediamine, 1,8-diaminonaphthalene aromatic amines such as; pyridine, 2,6-lutidine, 4-N,N-dimethylaminopyridine and other pyridine compounds; Alkyl ureas such as methyl urea; Alkyl guanidines such as tetramethyl guanidine; Phosphines such as (2,6-dimethylphenyl)phosphine, tris(2,6-dimethoxyphenyl)phosphine, tris(2,4,6-trimethylphenyl)phosphine and tris(2,4,6-trimethoxyphenyl)phosphine compound.
　付加反応の触媒としては、上記の中でも、反応性の点で３級アミン、ピリジン化合物、又はホスフィン化合物を用いることが好ましい。 Among the above catalysts for the addition reaction, it is preferable to use a tertiary amine, a pyridine compound, or a phosphine compound in terms of reactivity.
　付加反応における触媒の使用量は、カルボキシ基含有樹脂（ｂ）と脂環式エポキシ基含有エチレン性不飽和化合物（ｃ）との合計１００質量部に対して、０．０１～２０質量部が好ましく、０．０５～１０質量部が更に好ましく、０．１～５質量部が最も好ましい。 The amount of the catalyst used in the addition reaction is preferably 0.01 to 20 parts by mass with respect to a total of 100 parts by mass of the carboxy group-containing resin (b) and the alicyclic epoxy group-containing ethylenically unsaturated compound (c). , more preferably 0.05 to 10 parts by mass, most preferably 0.1 to 5 parts by mass.
　更に、付加反応時には、重合禁止効果のあるガスを反応系中に導入したり、重合禁止剤を添加したりしてもよい。重合禁止効果のあるガスを反応系中に導入したり、重合禁止剤を添加したりすることにより、付加反応時のゲル化を防ぐことができる。 Furthermore, during the addition reaction, a gas having a polymerization inhibitory effect may be introduced into the reaction system, or a polymerization inhibitor may be added. Gelation during the addition reaction can be prevented by introducing a gas having a polymerization inhibitory effect into the reaction system or by adding a polymerization inhibitor.
　重合禁止効果のあるガスとしては、系内物質の爆発範囲に入らない程度の酸素を含むガス、例えば、空気などが挙げられる。 Gases that have the effect of inhibiting polymerization include gases that contain oxygen to the extent that they do not fall within the explosion range of substances in the system, such as air.
　重合禁止剤としては、公知のものを使用することができ、特に制限はされないが、例えば、４－メトキシフェノール、ヒドロキノン、メトキノン、２，６－ジ－ｔ－ブチルフェノール、２，２’－メチレンビス（４－メチル－６－ｔ－ブチルフェノール）、及びフェノチアジンが挙げられる。これらの重合禁止剤は、単独で使用してもよいし、２種以上を組み合わせて使用してもよい。 As the polymerization inhibitor, known ones can be used without particular limitation. 4-methyl-6-t-butylphenol), and phenothiazine. These polymerization inhibitors may be used alone or in combination of two or more.
　重合禁止剤の使用量は、カルボキシ基含有樹脂（ｂ）と脂環式エポキシ基含有エチレン性不飽和化合物（ｃ）との合計１００質量部に対して、０．００５～５質量部が好ましく、０．０３～３質量部が更に好ましく、０．０５～１．５質量部が最も好ましい。重合禁止剤の量が少なすぎると、重合禁止効果が十分でない場合がある。一方、重合禁止剤の量が多すぎると、ＵＶ照射時の樹脂（Ａ）の露光感度が低下するおそれがある。 The amount of the polymerization inhibitor used is preferably 0.005 to 5 parts by mass with respect to a total of 100 parts by mass of the carboxy group-containing resin (b) and the alicyclic epoxy group-containing ethylenically unsaturated compound (c). More preferably 0.03 to 3 parts by mass, most preferably 0.05 to 1.5 parts by mass. If the amount of polymerization inhibitor is too small, the effect of inhibiting polymerization may not be sufficient. On the other hand, if the amount of the polymerization inhibitor is too large, the exposure sensitivity of the resin (A) during UV irradiation may decrease.
　重合禁止効果のあるガスと重合禁止剤とを併用すると、使用する重合禁止剤の量を低減したり、重合禁止効果を高めたりできるのでより好ましい。 It is more preferable to use a gas having a polymerization-inhibiting effect in combination with a polymerization inhibitor because the amount of the polymerization inhibitor to be used can be reduced and the polymerization-inhibiting effect can be enhanced.
粘着剤組成物に含まれる光重合開始剤（Ｂ）としては、例えば、ベンゾフェノン、ベンジル、ベンゾイン、ω－ブロモアセトフェノン、クロロアセトン、アセトフェノン、２，２－ジエトキシアセトフェノン、２，２－ジメトキシ－２－フェニルアセトフェノン、ｐ－ジメチルアミノアセトフェノン、ｐ－ジメチルアミノプロピオフェノン、２－クロロベンゾフェノン、４，４’－ジクロロベンゾフェノン、４，４’－ビスジエチルアミノベンゾフェノン、ミヒラーケトン、ベンゾインメチルエーテル、ベンゾインイソブチルエーテル、ベンゾイン－ｎ－ブチルエーテル、ベンジルメチルケタール、１－ヒドロキシシクロヘキシルフェニルケトン、２－ヒドロキシ－２－メチル－１－フェニル－プロパン－１－オン、１－（４－イソプロピルフェニル）－２－ヒドロキシ－２－メチルプロパン－１－オン、メチルベンゾイルホルメート、２，２－ジエトキシアセトフェノン、４－Ｎ，Ｎ’－ジメチルアセトフェノン、２－メチル－１－［４－（メチルチオ）フェニル］－２－モルフォリノプロパン－１－オン等のカルボニル系光重合開始剤が挙げられる。 Examples of the photopolymerization initiator (B) contained in the adhesive composition include benzophenone, benzyl, benzoin, ω-bromoacetophenone, chloroacetone, acetophenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2 -phenylacetophenone, p-dimethylaminoacetophenone, p-dimethylaminopropiophenone, 2-chlorobenzophenone, 4,4'-dichlorobenzophenone, 4,4'-bisdiethylaminobenzophenone, Michler's ketone, benzoin methyl ether, benzoin isobutyl ether, Benzoin-n-butyl ether, benzyl methyl ketal, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2- methylpropan-1-one, methylbenzoylformate, 2,2-diethoxyacetophenone, 4-N,N'-dimethylacetophenone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane Carbonyl-based photopolymerization initiators such as -1-one can be mentioned.
　光重合開始剤（Ｂ）としては、ジフェニルジスルフィド、ジベンジルジスルフィド、テトラエチルチウラムジスルフィド、テトラメチルアンモニウムモノスルフィド等のスルフィド系光重合開始剤；２，４，６－トリメチルベンゾイルジフェニルホスフィンオキサイド、２，４，６－トリメチルベンゾイルフェニルエトキシホスフィンオキサイド等のアシルホスフィンオキサイド；ベンゾキノン、アントラキノン等のキノン系光重合開始剤；スルホクロリド系光重合開始剤；又はチオキサントン、２－クロロチオキサントン、２－メチルチオキサントン等のチオキサントン系光重合開始剤を用いてもよい。 Examples of the photopolymerization initiator (B) include sulfide photopolymerization initiators such as diphenyl disulfide, dibenzyl disulfide, tetraethylthiuram disulfide, and tetramethylammonium monosulfide; 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4 Acylphosphine oxides such as ,6-trimethylbenzoylphenylethoxyphosphine oxide; quinone photopolymerization initiators such as benzoquinone and anthraquinone; sulfochloride photopolymerization initiators; A photoinitiator may also be used.
　これらの光重合開始剤（Ｂ）の中でも、粘着剤組成物への溶解性の点から、１－ヒドロキシシクロヘキシルフェニルケトン及び／又は２，４，６－トリメチルベンゾイルジフェニルホスフィンオキサイドを用いることが好ましい。 Among these photopolymerization initiators (B), it is preferable to use 1-hydroxycyclohexylphenyl ketone and/or 2,4,6-trimethylbenzoyldiphenylphosphine oxide from the viewpoint of solubility in the adhesive composition.
　これらの光重合開始剤（Ｂ）は、単独で使用してもよいし、２種以上を組み合わせて使用してもよい。 These photopolymerization initiators (B) may be used alone or in combination of two or more.
　粘着剤組成物に含まれる光重合開始剤（Ｂ）は、樹脂（Ａ）１００質量部に対して、０．１～５．０質量部であることが好ましく、０．５～２．０質量部であることがより好ましい。樹脂（Ａ）１００質量部に対する光重合開始剤（Ｂ）の含有量が０．１質量部以上であると、ＵＶ照射することにより十分に速い硬化速度で粘着剤組成物を硬化させることができ、これによりＵＶ照射後の粘着剤組成物の粘着力を十分に小さくすることができる。樹脂（Ａ）１００質量部に対する光重合開始剤（Ｂ）の含有量が５．０質量部以下であると、粘着剤組成物を含む粘着剤層を有する粘着シートを、被着体に貼り付けた後に剥離した場合に、粘着剤層が被着体に残存しにくくなる。樹脂（Ａ）１００質量部に対する光重合開始剤（Ｂ）の含有量が５．０質量部を超えても、光重合開始剤（Ｂ）の含有量に見合う効果が見られないため、同含有量を５．０質量部以下とすることで、経済的に粘着剤組成物を製造することができる。 The photopolymerization initiator (B) contained in the adhesive composition is preferably 0.1 to 5.0 parts by mass, and 0.5 to 2.0 parts by mass, relative to 100 parts by mass of the resin (A). Part is more preferred. When the content of the photopolymerization initiator (B) with respect to 100 parts by mass of the resin (A) is 0.1 parts by mass or more, the adhesive composition can be cured at a sufficiently high curing rate by UV irradiation. , so that the adhesive strength of the adhesive composition after UV irradiation can be sufficiently reduced. When the content of the photopolymerization initiator (B) is 5.0 parts by mass or less with respect to 100 parts by mass of the resin (A), the adhesive sheet having the adhesive layer containing the adhesive composition is attached to the adherend. When the adhesive layer is peeled off after application, the adhesive layer is less likely to remain on the adherend. Even if the content of the photoinitiator (B) with respect to 100 parts by mass of the resin (A) exceeds 5.0 parts by mass, the effect corresponding to the content of the photoinitiator (B) is not seen, so the same content By setting the amount to 5.0 parts by mass or less, the pressure-sensitive adhesive composition can be produced economically.
〈架橋剤（Ｃ）〉
　粘着剤組成物は、樹脂（Ａ）と光重合開始剤（Ｂ）だけでなく、架橋剤（Ｃ）を含有していてもよい。架橋剤（Ｃ）を含有することで、ＵＶ照射前の粘着力とＵＶ照射後の粘着力とのバランスがよりいっそう良好な粘着剤組成物を得ることができる。 <Crosslinking agent (C)>
The pressure-sensitive adhesive composition may contain not only the resin (A) and the photoinitiator (B) but also the cross-linking agent (C). By containing the cross-linking agent (C), it is possible to obtain a pressure-sensitive adhesive composition having a better balance between the adhesive strength before UV irradiation and the adhesive strength after UV irradiation.
　架橋剤（Ｃ）としては、特に限定されないが、繰り返し単位ｎの水酸基、又は繰り返し単位ｎの水酸基及び繰り返し単位ｍのカルボキシ基に対して反応性を有する官能基を２つ以上有する化合物が好ましい。 The cross-linking agent (C) is not particularly limited, but is preferably a compound having two or more functional groups reactive with the hydroxyl group of repeating unit n, or the hydroxyl group of repeating unit n and the carboxy group of repeating unit m.
　架橋剤（Ｃ）としては、例えば、２，４－トリレンジイソシアネート、２，６－トリレンジイソシアネート、水素化トリレンジイソシアネート、１，３－キシリレンジイソシアネート、１，４－キシリレンジイソシアネート、ジフェニルメタン－４，４－ジイソシアネート、イソホロンジイソシアネート、１，３－ビス（イソシアナトメチル）シクロヘキサン、ヘキサメチレンジイソシアネートのイソシアヌレート体、テトラメチルキシリレンジイソシアネート、１，５－ナフタレンジイソシアネート、トリメチロールプロパンのトリレンジイソシアネート付加物、トリメチロールプロパンのキシリレンジイソシアネート付加物、トリフェニルメタントリイソシアネート、メチレンビス（４－フェニルメタン）トリイソシアネート等のイソシアネート系化合物；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、ビスフェノールＡ・エピクロルヒドリン型のエポキシ樹脂、Ｎ，Ｎ’－［１，３－フェニレンビス（メチレン）］ビス［ビス（オキシラン－２－イルメチル）アミン］、エチレングリコールジグリシジルエーテル、ポリエチレングリコールジグリシジルエーテル、グリセリンジグリシジルエーテル、グリセリントリ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トリグリシジルエーテル、ソルビトールポリグリシジルエーテル、ポリグリセロールポリグリシジルエーテル、ペンタエリスリトールポリグリシジルエーテル、ジグリセロールポリグリシジルエーテル等のエポキシ系化合物；テトラメチロールメタン－トリ－β－アジリジニルプロピオネート、トリメチロールプロパン－トリ－β－アジリジニルプロピオネート、Ｎ，Ｎ’－ジフェニルメタン－４，４’－ビス（１－アジリジンカルボキシアミド）、Ｎ，Ｎ’－ヘキサメチレン－１，６－ビス（１－アジリジンカルボキシアミド）等のアジリジン系化合物；及びヘキサメトキシメチルメラミン、ヘキサエトキシメチルメラミン、ヘキサプロポキシメチルメラミン、ヘキサブトキシメチルメラミン、ヘキサペンチルオキシメチルメラミン、ヘキサヘキシルオキシメチルメラミン等のメラミン系化合物が挙げられる。 Examples of the cross-linking agent (C) include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hydrogenated tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, diphenylmethane- 4,4-diisocyanate, isophorone diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, isocyanurate of hexamethylene diisocyanate, tetramethylxylylene diisocyanate, 1,5-naphthalene diisocyanate, tolylene diisocyanate addition of trimethylolpropane xylylene diisocyanate adduct of trimethylolpropane, triphenylmethane triisocyanate, isocyanate compounds such as methylenebis(4-phenylmethane) triisocyanate; 1,3-bis(N,N'-diglycidylaminomethyl)cyclohexane , bisphenol A/epichlorohydrin type epoxy resin, N,N'-[1,3-phenylenebis(methylene)]bis[bis(oxiran-2-ylmethyl)amine], ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether , glycerin diglycidyl ether, glycerin triglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, diglycerol polyglycidyl ether epoxy-based compounds such as; 1-aziridinecarboxamide), N,N'-hexamethylene-1,6-bis(1-aziridinecarboxamide) and other aziridine compounds; and hexamethoxymethylmelamine, hexaethoxymethylmelamine, hexapropoxymethylmelamine, hexa Melamine-based compounds such as butoxymethylmelamine, hexapentyloxymethylmelamine, and hexahexyloxymethylmelamine are included.
　これらの架橋剤（Ｃ）の中でも、樹脂（Ａ）との反応性が良好であることから、エポキシ系化合物、及び／又はイソシアネート系化合物を用いることが好ましい。 Among these cross-linking agents (C), it is preferable to use epoxy-based compounds and/or isocyanate-based compounds because they have good reactivity with the resin (A).
　これらの架橋剤（Ｃ）は、単独で使用してもよいし、２種以上を組み合わせて使用してもよい。 These cross-linking agents (C) may be used alone or in combination of two or more.
　粘着剤組成物に含まれる架橋剤（Ｃ）は、樹脂（Ａ）１００質量部に対して、０．０５～１０質量部であることが好ましく、０．１～５質量部であることがより好ましく、０．１～１．０質量部であることが更に好ましい。樹脂（Ａ）１００質量部に対する架橋剤（Ｃ）の含有量が０．０５質量部以上であると、粘着剤組成物に三次元架橋構造が十分に形成される。その結果、ＵＶ照射後の粘着剤組成物の粘着力を十分に小さくすることができる。樹脂（Ａ）１００質量部に対する架橋剤（Ｃ）の含有量が１０質量部以下であると、ＵＶ照射前の粘着剤組成物の粘着力が良好である。 The cross-linking agent (C) contained in the adhesive composition is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, with respect to 100 parts by mass of the resin (A). It is preferably 0.1 to 1.0 parts by mass, more preferably. When the content of the cross-linking agent (C) is 0.05 parts by mass or more relative to 100 parts by mass of the resin (A), a three-dimensional cross-linked structure is sufficiently formed in the pressure-sensitive adhesive composition. As a result, the adhesive strength of the adhesive composition after UV irradiation can be sufficiently reduced. When the content of the cross-linking agent (C) is 10 parts by mass or less with respect to 100 parts by mass of the resin (A), the adhesive strength of the pressure-sensitive adhesive composition before UV irradiation is good.
〈他の成分〉
　粘着剤組成物は、必要に応じて、上述した樹脂（Ａ）、光重合開始剤（Ｂ）、及び架橋剤（Ｃ）以外の他の成分を含有していてもよい。他の成分としては、例えば、粘着付与剤、溶媒、及び各種添加剤が挙げられる。 <Other ingredients>
The pressure-sensitive adhesive composition may contain components other than the resin (A), the photopolymerization initiator (B), and the cross-linking agent (C) described above, if necessary. Other ingredients include, for example, tackifiers, solvents, and various additives.
（粘着付与剤）
　粘着付与剤としては、従来公知のものを特に限定なく使用できる。粘着付与剤としては、例えば、テルペン系粘着付与樹脂、フェノール系粘着付与樹脂、ロジン系粘着付与樹脂、脂肪族系石油樹脂、芳香族系石油樹脂、共重合系石油樹脂、脂環族系石油樹脂、キシレン樹脂、エポキシ系粘着付与樹脂、ポリアミド系粘着付与樹脂、ケトン系粘着付与樹脂、及びエラストマー系粘着付与樹脂が挙げられる。これらの粘着付与剤は、単独で使用してもよいし、２種以上を組み合わせて使用してもよい。 (Tackifier)
As the tackifier, conventionally known ones can be used without particular limitation. Examples of tackifiers include terpene-based tackifying resins, phenol-based tackifying resins, rosin-based tackifying resins, aliphatic petroleum resins, aromatic petroleum resins, copolymer petroleum resins, and alicyclic petroleum resins. , xylene resins, epoxy tackifier resins, polyamide tackifier resins, ketone tackifier resins, and elastomer tackifier resins. These tackifiers may be used alone or in combination of two or more.
　粘着剤組成物が粘着付与剤を含む場合、その含有量は、樹脂（Ａ）１００質量部に対して、３０質量部以下であることが好ましく、５～２０質量部であることがより好ましい。 When the adhesive composition contains a tackifier, the content thereof is preferably 30 parts by mass or less, more preferably 5 to 20 parts by mass, based on 100 parts by mass of the resin (A).
（溶媒）
　溶媒は、粘着剤組成物を塗工する場合に、粘着剤組成物の粘度の調整を目的として粘着剤組成物を希釈するために用いることができる。 (solvent)
A solvent can be used to dilute the adhesive composition for the purpose of adjusting the viscosity of the adhesive composition when the adhesive composition is applied.
　溶媒としては、例えば、メチルエチルケトン、メチルイソブチルケトン、アセトン、酢酸エチル、酢酸ｎ－プロピル、テトラヒドロフラン、ジオキサン、シクロヘキサノン、ｎ－へキサン、トルエン、キシレン、ｎ－プロパノール、イソプロパノール等の有機溶媒を用いることができる。これらの溶媒は、単独で使用してもよいし、２種以上を混合して使用してもよい。 Examples of the solvent include organic solvents such as methyl ethyl ketone, methyl isobutyl ketone, acetone, ethyl acetate, n-propyl acetate, tetrahydrofuran, dioxane, cyclohexanone, n-hexane, toluene, xylene, n-propanol and isopropanol. can. These solvents may be used alone or in combination of two or more.
（添加剤）
　添加剤としては、例えば、可塑剤、表面潤滑剤、レベリング剤、軟化剤、酸化防止剤、老化防止剤、光安定剤、紫外線吸収剤、重合禁止剤、ベンゾトリアゾール系等の光安定剤、リン酸エステル系及びその他の難燃剤、界面活性剤、並びに帯電防止剤が挙げられる。 (Additive)
Additives include, for example, plasticizers, surface lubricants, leveling agents, softeners, antioxidants, anti-aging agents, light stabilizers, ultraviolet absorbers, polymerization inhibitors, light stabilizers such as benzotriazoles, phosphorus Acid ester and other flame retardants, surfactants, and antistatic agents are included.
［粘着剤組成物の製造方法］
　粘着剤組成物は、従来公知の方法により製造することができる。 [Method for producing pressure-sensitive adhesive composition]
An adhesive composition can be manufactured by a conventionally well-known method.
　例えば、上述した樹脂（Ａ）及び光重合開始剤（Ｂ）と、必要に応じて含有される架橋剤（Ｃ）と、粘着付与剤、溶媒、各種添加剤等の他の成分とを、従来公知の方法を用いて混合し、攪拌することにより製造することができる。 For example, the resin (A) and the photopolymerization initiator (B) described above, a cross-linking agent (C) contained as necessary, and other components such as a tackifier, a solvent, and various additives are conventionally It can be produced by mixing and stirring using a known method.
　一実施形態の粘着剤組成物は、粘着シートの粘着剤層を形成する材料として好適であり、再剥離型の粘着シートの粘着剤層を形成する材料として特に好ましい。 The pressure-sensitive adhesive composition of one embodiment is suitable as a material for forming the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet, and is particularly preferable as the material for forming the pressure-sensitive adhesive layer of the removable pressure-sensitive adhesive sheet.
　一実施形態の粘着剤組成物は、式（１－１）で示される樹脂（Ａ）と、光重合開始剤（Ｂ）とを含むため、粘着シートの粘着剤層を形成する材料として用いることで、被着体に対して十分な粘着力を有する粘着シートを得ることができる。しかも、この粘着シートは、粘着シートを貼付した被着体を高温状態にしてから室温に戻して剥離しても、ＵＶ照射後に優れた易剥離性が得られるとともに、糊残りが発生しにくい。 Since the pressure-sensitive adhesive composition of one embodiment contains the resin (A) represented by formula (1-1) and the photopolymerization initiator (B), it can be used as a material for forming the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet. Thus, a pressure-sensitive adhesive sheet having sufficient adhesive strength to an adherend can be obtained. Moreover, even if the adherend to which the adhesive sheet is attached is heated to a high temperature and then returned to room temperature and then peeled off, the adhesive sheet exhibits excellent easy peelability after UV irradiation and hardly leaves adhesive residue.
［加工工程］
　半導体デバイスの製造方法は、前記保護工程と後述する剥離工程との間に加工工程を有してもよい。 [Process]
The method for manufacturing a semiconductor device may have a processing step between the protection step and the peeling step described below.
　加工工程としては、従来公知の半導体デバイスの製造に用いられる加工工程を特に制限なく適用することができる。例えば、保護工程に用いる粘着シートをウエハのダイシングテープとして用いる場合、保護工程により複数の部品が形成されているウエハに粘着シートを貼り付けた後、加工工程として、ウエハを切断して、個々の部品に切り分け（ダイシングして）、素子小片（チップ）とするダイシング工程を実施する。加工工程として半導体チップの積層工程を実施する場合、バンプ付き被着面の非実装面のみ保護工程で保護し、粘着シートが貼り付けられていない実装面同士を接触させて積層しながら電気的に接続する。 As the processing steps, conventionally known processing steps used in the manufacture of semiconductor devices can be applied without particular limitations. For example, when the adhesive sheet used in the protection process is used as a wafer dicing tape, after the adhesive sheet is attached to the wafer on which a plurality of parts are formed in the protection process, the wafer is cut into individual pieces as a processing process. A dicing process is performed to cut (dicing) into parts to obtain element pieces (chips). When a semiconductor chip lamination process is performed as a processing process, only the non-mounting surface of the bumped adherend surface is protected by a protective process, and the mounting surfaces to which the adhesive sheet is not attached are brought into contact with each other and electrically connected while laminating. Connecting.
［加熱工程］
　半導体デバイスの製造方法は、前記保護工程と後述する剥離工程との間に加熱工程を有してもよい。半導体デバイスの製造方法が保護工程の後に加工工程を有する場合には、前記加工工程と加熱工程の順序は限定されないが、粘着シートの保護機能及び仮固定機能、すなわち密着性能を最大限に発揮させる観点からは、加工工程と加熱工程が同時に実施されること、あるいは加工工程が加熱工程の前に実施されることが好ましい。 [Heating process]
The method for manufacturing a semiconductor device may have a heating step between the protection step and the peeling step described below. When the semiconductor device manufacturing method has a processing step after the protection step, the order of the processing step and the heating step is not limited, but the protective function and temporary fixing function of the adhesive sheet, that is, the adhesion performance is maximized. From the point of view, it is preferable that the processing step and the heating step are performed at the same time, or that the processing step is performed before the heating step.
　加熱工程としては、従来公知の半導体デバイスの製造に用いられる加熱工程を特に制限なく適用することができる。加熱工程としては、例えば、バンプ付きＰＣＢのアフターキュア工程、半導体チップのスパッタリング工程、及び半導体チップ積層後のリフロー工程が挙げられる。 As the heating process, a conventionally known heating process used for manufacturing semiconductor devices can be applied without particular limitation. Examples of the heating process include a PCB after-curing process with bumps, a semiconductor chip sputtering process, and a reflow process after semiconductor chip lamination.
　加熱工程の条件は特に制限されない。前記保護工程を加熱工程の前に実施することにより、例えば１５０℃以上、１８０℃以上、又は２００℃以上といった高温処理を行った場合でも、バンプ付き被着面を良好に保護することができる。加熱工程の上限温度は、特に限定されないが、粘着シートの耐熱性の観点から、好ましくは３００℃以下、より好ましくは２７０℃以下である。加熱時間は特に制限されないが、例えば１分～１８０分、好ましくは１分～１２０分、より好ましくは１分～６０分である。 The conditions for the heating process are not particularly limited. By carrying out the protection step before the heating step, even when high temperature treatment such as 150° C. or higher, 180° C. or higher, or 200° C. or higher is performed, the adherend surface with bumps can be well protected. The upper limit temperature of the heating step is not particularly limited, but is preferably 300° C. or lower, more preferably 270° C. or lower from the viewpoint of heat resistance of the adhesive sheet. The heating time is not particularly limited, but is, for example, 1 minute to 180 minutes, preferably 1 minute to 120 minutes, more preferably 1 minute to 60 minutes.
[ＵＶ照射工程]
　ＵＶ照射工程では、通常、粘着シートの基材側からＵＶを照射する。被着体が光透過性を有する場合は被着体側から粘着シートに向けてＵＶを照射してもよい。ＵＶ照射により粘着剤層を架橋硬化させることができ、粘着シートの耐熱性を上げる、あるいは粘着シートに軽剥離性を付与することができる。ＵＶ照射工程は、前記保護工程と後述する剥離工程の間に行えばよく、前記加工工程及び前記加熱工程との順序は限定されない。 [UV irradiation process]
In the UV irradiation step, UV is usually irradiated from the substrate side of the adhesive sheet. When the adherend has optical transparency, the adhesive sheet may be irradiated with UV from the adherend side. By UV irradiation, the adhesive layer can be cross-linked and cured, and the heat resistance of the adhesive sheet can be increased, or the adhesive sheet can be imparted with light release properties. The UV irradiation step may be performed between the protecting step and the later-described peeling step, and the order of the processing step and the heating step is not limited.
　被着体に貼り付けられた剥離前の粘着シートに、ＵＶ照射を行う際に使用される光源としては、例えば、ＬＥＤランプ、高圧水銀灯、超高圧水銀灯カーボンアーク灯、キセノン灯、メタルハライドランプ、ケミカルランプ、及びブラックライトが挙げられる。ＵＶ照射には、ＬＥＤランプ、高圧水銀灯又はメタルハライドランプを用いることが好ましい。 Examples of the light source used for UV irradiation to the adhesive sheet before peeling attached to the adherend include LED lamps, high pressure mercury lamps, ultra-high pressure mercury lamps, carbon arc lamps, xenon lamps, metal halide lamps, chemical lamps, and black lights. It is preferable to use an LED lamp, a high-pressure mercury lamp, or a metal halide lamp for UV irradiation.
　粘着シートに照射するＵＶ照射量は、５０～３０００ｍＪ／ｃｍ２であることが好ましく、１００～６００ｍＪ／ｃｍ２であることがより好ましい。粘着シートに照射するＵＶ照射量が５０ｍＪ／ｃｍ２以上であると、ＵＶ照射することにより十分に速い硬化速度で粘着剤層を硬化させることができ、これによりＵＶ照射後の粘着剤層の粘着力を十分に小さくすることができる。粘着シートに照射するＵＶ照射量を３０００ｍＪ／ｃｍ２超にしても、それに見合う効果が得られないため、粘着シートに照射するＵＶ照射量を３０００ｍＪ／ｃｍ２以下とすることで、被着体に対するＵＶ照射の影響を軽減しながら、経済的に粘着シートを剥離することができる。 The amount of UV irradiation applied to the adhesive sheet is preferably 50-3000 mJ/cm 2 , more preferably 100-600 mJ/cm 2 . When the amount of UV irradiation applied to the adhesive sheet is 50 mJ/cm 2 or more, the adhesive layer can be cured at a sufficiently high curing speed by UV irradiation, thereby improving the adhesion of the adhesive layer after UV irradiation. The force can be made sufficiently small. Even if the amount of UV irradiation applied to the adhesive sheet exceeds 3000 mJ/cm 2 , the corresponding effect cannot be obtained . The pressure-sensitive adhesive sheet can be removed economically while reducing the effects of UV irradiation.
［剥離工程］
　剥離工程では、ＵＶ照射を行い粘着剤層を硬化させた後で、前記粘着シートを前記バンプ付き被着面から剥離除去する。ＵＶが照射されることにより、粘着剤中の不飽和結合が三次元架橋構造を形成して硬化する。その結果、粘着剤層の粘着力が低下する。その後、半導体デバイスから粘着シートを剥離する。 [Peeling process]
In the peeling step, after the adhesive layer is cured by UV irradiation, the adhesive sheet is peeled off from the adherend surface with the bumps. By UV irradiation, unsaturated bonds in the adhesive form a three-dimensional crosslinked structure and cure. As a result, the adhesive strength of the adhesive layer is lowered. After that, the adhesive sheet is peeled off from the semiconductor device.
　前記加工工程は、前記保護工程と前記ＵＶ照射工程の間に行ってもよく、前記ＵＶ照射工程と前記剥離工程の間に行ってもよい。前記加熱工程は、前記保護工程と前記ＵＶ照射工程の間に行ってもよく、前記ＵＶ照射工程と前記剥離工程の間に行ってもよい。 The processing step may be performed between the protection step and the UV irradiation step, or may be performed between the UV irradiation step and the peeling step. The heating step may be performed between the protection step and the UV irradiation step, or may be performed between the UV irradiation step and the peeling step.
　一実施形態の半導体デバイスの製造方法によれば、加熱工程を実施した場合であっても、アウトガスの発生がなく、バンプ付き被着体表面上での糊残りがない状態で半導体デバイスを得ることができるため、得られた半導体デバイスに対して問題なく続く実装工程を実施することができる。 According to the semiconductor device manufacturing method of one embodiment, even when the heating step is performed, the semiconductor device can be obtained in a state where no outgassing occurs and no adhesive residue remains on the surface of the adherend with bumps. Therefore, the subsequent mounting process can be carried out without any problem on the semiconductor device obtained.
　以下、実施例及び比較例により本発明を更に具体的に説明する。なお、本発明は、以下の実施例のみに限定されない。 Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. In addition, the present invention is not limited only to the following examples.
［製造例１：樹脂（Ａ）の製造］
〈第１混合溶液の調製〉
　表１に示すように、カルボキシ基含有エチレン性不飽和単量体（ａ）であるアクリル酸２３．９質量部と、上記（ａ）と共重合可能なエチレン性不飽和単量体（ｄ）であるｎ－ブチルアクリレート７１．８質量部及び２－エチルヘキシルアクリレート１４３．６質量部とを含有する原料単量体と、カルボキシ基含有樹脂（ｂ）の原料単量体の合計１００質量部に対して重合開始剤である２，２’－アゾビス（イソブチロニトリル）２．３９質量部とを含有する第１混合溶液を調製した。 [Production Example 1: Production of resin (A)]
<Preparation of first mixed solution>
As shown in Table 1, 23.9 parts by mass of acrylic acid, which is a carboxy group-containing ethylenically unsaturated monomer (a), and an ethylenically unsaturated monomer (d) copolymerizable with the above (a) A raw material monomer containing 71.8 parts by mass of n-butyl acrylate and 143.6 parts by mass of 2-ethylhexyl acrylate, and a total of 100 parts by mass of the raw material monomer of the carboxy group-containing resin (b) A first mixed solution containing 2.39 parts by mass of 2,2'-azobis(isobutyronitrile) as a polymerization initiator was prepared.
〈第２混合溶液の調製〉
　表１に示すように、脂環式エポキシ基含有エチレン性不飽和化合物（ｃ）である３，４－エポキシシクロヘキシルメチルメタクリレート５９．８質量部と、第１混合溶液を用いて得られるカルボキシ基含有樹脂（ｂ）と脂環式エポキシ基含有エチレン性不飽和化合物（ｃ）との合計１００質量部に対して触媒としてのトリス（４－メチルフェニル）ホスフィン（ＴＰＴＰ）１．５質量部と、溶媒としての酢酸ｎ－ブチル１００．０質量部及びトルエン９１．１質量部とを含有する第２混合溶液を調製した。 <Preparation of second mixed solution>
As shown in Table 1, 59.8 parts by mass of 3,4-epoxycyclohexylmethyl methacrylate, which is an alicyclic epoxy group-containing ethylenically unsaturated compound (c), and a carboxy group-containing solution obtained using the first mixed solution 1.5 parts by mass of tris(4-methylphenyl)phosphine (TPTP) as a catalyst with respect to a total of 100 parts by mass of the resin (b) and the alicyclic epoxy group-containing ethylenically unsaturated compound (c), and a solvent A second mixed solution was prepared containing 100.0 parts by weight of n-butyl acetate and 91.1 parts by weight of toluene.
　攪拌機、滴下ロート、冷却管及び窒素導入管を備えた四ツ口フラスコに、溶媒として酢酸ｎ－ブチルを１７５．６質量部仕込み、窒素ガス雰囲気下で８０℃に昇温した。そして、反応温度を８０℃±２℃に保ちながら、上記四ツ口フラスコに上記第１混合溶液を４時間かけて均一に滴下し、滴下完了後、８０℃±２℃の温度で更に６時間攪拌を続けて重合を行い、カルボキシ基含有樹脂（ｂ）を得た。その後、反応系に、カルボキシ基含有樹脂（ｂ）と脂環式エポキシ基含有エチレン性不飽和化合物（ｃ）との合計１００質量部に対して重合禁止剤として４－メトキシフェノール０．１５質量部を添加した。 A four-necked flask equipped with a stirrer, a dropping funnel, a condenser tube and a nitrogen inlet tube was charged with 175.6 parts by mass of n-butyl acetate as a solvent, and heated to 80°C under a nitrogen gas atmosphere. Then, while maintaining the reaction temperature at 80 ° C. ± 2 ° C., the first mixed solution is uniformly added dropwise to the four-necked flask over 4 hours. Polymerization was carried out while stirring to obtain a carboxy group-containing resin (b). Then, 0.15 parts by mass of 4-methoxyphenol as a polymerization inhibitor is added to the reaction system with respect to a total of 100 parts by mass of the carboxy group-containing resin (b) and the alicyclic epoxy group-containing ethylenically unsaturated compound (c). was added.
　４－メトキシフェノールを添加した反応系を１００℃に昇温し、上記第２混合溶液を０．５時間かけて滴下した後、１００℃の温度で８時間攪拌を続け、樹脂（Ａ－１）を合成し、室温（２３℃）に冷却した。 The temperature of the reaction system to which 4-methoxyphenol was added was raised to 100° C., and the second mixed solution was added dropwise over 0.5 hours, followed by continued stirring at a temperature of 100° C. for 8 hours to obtain resin (A-1). was synthesized and cooled to room temperature (23° C.).
　樹脂（Ａ－１）を核磁気共鳴法（ＮＭＲ法）により同定した結果、一般式（２－１）で示される化合物であった。一般式（２－１）で示される化合物の繰り返し単位ｋは、Ｒ５の異なる２種の繰り返し単位（ｋ－１、ｋ－２）である。 Resin (A-1) was identified by a nuclear magnetic resonance method (NMR method) and found to be a compound represented by general formula (2-1). The repeating unit k of the compound represented by the general formula (2-1) is two kinds of repeating units (k-1, k-2) with different R5 .
Figure JPOXMLDOC01-appb-C000009
 （式（２－１）において、ｋ－１は３３．６であり、ｋ－２は４６．６であり、ｍは１．６であり、ｋ－１、ｋ－２及びｍの合計は８１．８である。ｎは１８.２である。）
Figure JPOXMLDOC01-appb-C000009
 (In formula (2-1), k-1 is 33.6, k-2 is 46.6, m is 1.6, and the sum of k-1, k-2 and m is 81 .8 and n is 18.2.)
　樹脂（Ａ－１）について、以下に示す方法により、重量平均分子量とガラス転移温度とを調べた。樹脂（Ａ－１）の酸価を、ＪＩＳ　Ｋ　００７０：１９９２に従って測定した。 For the resin (A-1), the weight average molecular weight and glass transition temperature were examined by the methods shown below. The acid value of resin (A-1) was measured according to JIS K 0070:1992.
〈重量平均分子量（Ｍｗ）〉
　ゲル・パーミエーション・クロマトグラフィー（昭和電工株式会社製、ショウデックス（登録商標）ＧＰＣ－１０１）を用いて、下記条件にて常温で測定し、ポリスチレン換算にて算出した。
　カラム：昭和電工株式会社製、ショウデックス（登録商標）ＬＦ－８０４
　カラム温度：４０℃
　試料：樹脂（Ａ）の０．２質量％テトラヒドロフラン溶液
　流量：１ｍＬ／分
　溶離液：テトラヒドロフラン
　検出器：ＲＩ検出器 <Weight average molecular weight (Mw)>
Using gel permeation chromatography (Showdex (registered trademark) GPC-101, manufactured by Showa Denko KK), measurement was performed at room temperature under the following conditions, and the values were calculated in terms of polystyrene.
Column: Showdex (registered trademark) LF-804 manufactured by Showa Denko K.K.
Column temperature: 40°C
Sample: 0.2% by mass tetrahydrofuran solution of resin (A) Flow rate: 1 mL/min Eluent: Tetrahydrofuran Detector: RI detector
〈ガラス転移温度（Ｔｇ）〉
　樹脂（Ａ－１）から１０ｍｇの試料を採取した。示差走査熱量計（ＤＳＣ）を用いて、１０℃／分の昇温速度で－１００℃から２００℃まで試料の温度を変化させて示差走査熱量測定を行い、観察されたガラス転移による吸熱開始温度をＴｇとした。吸熱開始温度が２つ以上観察された場合は、Ｔｇは２つ以上の吸熱開始温度の単純平均値とした。 <Glass transition temperature (Tg)>
A 10 mg sample was taken from resin (A-1). Differential scanning calorimetry was performed using a differential scanning calorimeter (DSC) while changing the temperature of the sample from -100°C to 200°C at a heating rate of 10°C/min. was taken as Tg. When two or more endothermic start temperatures were observed, Tg was taken as a simple average value of two or more endothermic start temperatures.
［製造例２～１２］
　表１に示す含有量（質量部）で、カルボキシ基含有エチレン性不飽和単量体（ａ）と、エチレン性不飽和単量体（ｄ）と、重合開始剤とを用いたこと以外は、製造例１と同様にして第１混合溶液を調製した。 [Production Examples 2 to 12]
The content (parts by mass) shown in Table 1, except for using a carboxyl group-containing ethylenically unsaturated monomer (a), an ethylenically unsaturated monomer (d), and a polymerization initiator, A first mixed solution was prepared in the same manner as in Production Example 1.
　表１に示す含有量（質量部）で、脂環式エポキシ基含有エチレン性不飽和化合物（ｃ）と、触媒とを用いたこと以外は、製造例１と同様にして第２混合溶液を調製した。 A second mixed solution was prepared in the same manner as in Production Example 1, except that the content (parts by mass) shown in Table 1 and the alicyclic epoxy group-containing ethylenically unsaturated compound (c) and the catalyst were used. bottom.
　上記第１混合溶液及び上記第２混合溶液を用いたこと以外は、製造例１と同様にして樹脂（Ａ－２）～（Ａ－１２）を得た。 Resins (A-2) to (A-12) were obtained in the same manner as in Production Example 1, except that the first mixed solution and the second mixed solution were used.
　樹脂（Ａ－２）～（Ａ－１２）をそれぞれ製造例１と同様にして同定した結果、一般式（２－２）～（２－１２）で示される化合物であった。一般式（２－２）～（２－７）、及び（２－１０）で示される化合物の繰り返し単位ｋは、Ｒ５が異なる、又はＲ１とＲ５の両方が異なる、２種の繰り返し単位（ｋ－１、ｋ－２）である。 Resins (A-2) to (A-12) were identified in the same manner as in Production Example 1, and were found to be compounds represented by general formulas (2-2) to (2-12). The repeating units k of the compounds represented by general formulas (2-2) to (2-7) and (2-10) are two types of repeating units in which R 5 is different or both R 1 and R 5 are different. The unit is (k-1, k-2).
　樹脂（Ａ－２）は、下記一般式（２－２）で示される化合物である。 The resin (A-2) is a compound represented by the following general formula (2-2).
　樹脂（Ａ－３）は、下記一般式（２－３）で示される化合物である。 The resin (A-3) is a compound represented by the following general formula (2-3).
　樹脂（Ａ－４）は、下記一般式（２－４）で示される化合物である。 The resin (A-4) is a compound represented by the following general formula (2-4).
　樹脂（Ａ－５）は、上記一般式（２－５）で示される化合物である。 The resin (A-5) is a compound represented by the above general formula (2-5).
　樹脂（Ａ－６）は、下記一般式（２－６）で示される化合物である。 The resin (A-6) is a compound represented by the following general formula (2-6).
　樹脂（Ａ－７）は、下記一般式（２－７）で示される化合物である。 The resin (A-7) is a compound represented by the following general formula (2-7).
　樹脂（Ａ－８）は、下記一般式（２－８）で示される化合物である。 The resin (A-8) is a compound represented by the following general formula (2-8).
　樹脂（Ａ－９）は、下記一般式（２－９）で示される化合物である。 The resin (A-9) is a compound represented by the following general formula (2-9).
　樹脂（Ａ－１０）は、下記一般式（２－１０）で示される化合物である。 The resin (A-10) is a compound represented by the following general formula (2-10).
　樹脂（Ａ－１１）は、下記一般式（２－１１）で示される化合物である。 The resin (A-11) is a compound represented by the following general formula (2-11).
　樹脂（Ａ－１２）は、下記一般式（２－１２）で示される化合物である。 The resin (A-12) is a compound represented by the following general formula (2-12).
Figure JPOXMLDOC01-appb-C000010
 （式（２－２）において、ｋ－１は３１．９であり、ｋ－２は４７．６であり、ｍは１．８であり、ｋ－１、ｋ－２及びｍの合計は８１．３である。ｎは１８．７である。）
Figure JPOXMLDOC01-appb-C000010
 (In formula (2-2), k-1 is 31.9, k-2 is 47.6, m is 1.8, and the sum of k-1, k-2 and m is 81 .3 and n is 18.7.)
Figure JPOXMLDOC01-appb-C000011
 （式（２－３）において、ｋ－１は６９．７であり、ｋ－２は１６．０であり、ｍは１．２であり、ｋ－１、ｋ－２及びｍの合計は８６．９である。ｎは１３．１である。）
Figure JPOXMLDOC01-appb-C000011
 (In formula (2-3), k-1 is 69.7, k-2 is 16.0, m is 1.2, and the sum of k-1, k-2 and m is 86 .9 and n is 13.1.)
Figure JPOXMLDOC01-appb-C000012
 （式（２－４）において、ｋ－１は５２．３であり、ｋ－２は３４．１であり、ｍは２．９であり、ｋ－１、ｋ－２及びｍの合計は８９．３である。ｎは１０．７である。）
Figure JPOXMLDOC01-appb-C000012
 (In formula (2-4), k-1 is 52.3, k-2 is 34.1, m is 2.9, and the sum of k-1, k-2 and m is 89 .3 and n is 10.7.)
Figure JPOXMLDOC01-appb-C000013
 （式（２－５）において、ｋ－１は１０．６であり、ｋ－２は５１．７であり、ｍは４．４であり、ｋ－１、ｋ－２及びｍの合計は６６．７であり、ｎは３３．３である。）
Figure JPOXMLDOC01-appb-C000013
 (In formula (2-5), k-1 is 10.6, k-2 is 51.7, m is 4.4, and the sum of k-1, k-2 and m is 66 .7 and n is 33.3.)
Figure JPOXMLDOC01-appb-C000014
 （式（２－６）において、ｋ－１は５６．４であり、ｋ－２は２３．６であり、ｍは０．２であり、ｋ－１、ｋ－２及びｍの合計は８０．２である。ｎは１９．８である。）
Figure JPOXMLDOC01-appb-C000014
 (In formula (2-6), k-1 is 56.4, k-2 is 23.6, m is 0.2, and the sum of k-1, k-2 and m is 80 .2 and n is 19.8.)
Figure JPOXMLDOC01-appb-C000015
 （式（２－７）において、ｋ－１は１４．４であり、ｋ－２は７２．２であり、ｍは１．１であり、ｋ－１、ｋ－２及びｍの合計は８７．７である。ｎは１２．３である。）
Figure JPOXMLDOC01-appb-C000015
 (In formula (2-7), k-1 is 14.4, k-2 is 72.2, m is 1.1, and the sum of k-1, k-2 and m is 87 .7 and n is 12.3.)
Figure JPOXMLDOC01-appb-C000016
 （式（２－８）において、ｋは７６．４であり、ｍは３．５であり、ｋ及びｍの合計は７９．９である。ｎは２０．１である。）
Figure JPOXMLDOC01-appb-C000016
 (In formula (2-8), k is 76.4, m is 3.5, and the sum of k and m is 79.9. n is 20.1.)
Figure JPOXMLDOC01-appb-C000017
 （式（２－９）において、ｋは７９．９であり、ｍは１１．５であり、ｋ及びｍの合計は９１．４である。ｎは８．６である。）
Figure JPOXMLDOC01-appb-C000017
 (In formula (2-9), k is 79.9, m is 11.5, and the sum of k and m is 91.4. n is 8.6.)
Figure JPOXMLDOC01-appb-C000018
 （式（２－１０）において、ｋ－１は３３．５であり、ｋ－２は４６．６であり、ｍは４．４であり、ｋ－１、ｋ－２及びｍの合計は８４．５である。ｎは１５．５である。）
Figure JPOXMLDOC01-appb-C000018
 (In formula (2-10), k-1 is 33.5, k-2 is 46.6, m is 4.4, and the sum of k-1, k-2 and m is 84 .5 and n is 15.5.)
Figure JPOXMLDOC01-appb-C000019
 （式（２－１１）において、ｋは６５．９であり、ｌは１１．７であり、ｍは１．８であり、ｋ、ｌ及びｍの合計は７９．４である。ｎは２０．６である。）
Figure JPOXMLDOC01-appb-C000019
 (In formula (2-11), k is 65.9, l is 11.7, m is 1.8, and the sum of k, l and m is 79.4. n is 20 .6.)
Figure JPOXMLDOC01-appb-C000020
 （式（２－１２）において、ｋは５５．５であり、ｌは２３．０であり、ｍは１．７であり、ｋ、ｌ及びｍの合計は８０．２である。ｎは１９．８である。）
Figure JPOXMLDOC01-appb-C000020
 (In formula (2-12), k is 55.5, l is 23.0, m is 1.7, and the sum of k, l and m is 80.2. n is 19 .8.)
　樹脂（Ａ－２）～（Ａ－１２）について、それぞれ樹脂（Ａ－１）と同様にして、重量平均分子量、ガラス転移温度、及び酸価を調べた。結果を表２に示す。 For resins (A-2) to (A-12), the weight average molecular weight, glass transition temperature, and acid value were examined in the same manner as for resin (A-1). Table 2 shows the results.
　表１には、樹脂（Ａ－１）～（Ａ－１２）の製造に使用したカルボキシ基含有エチレン性不飽和単量体（ａ）、上記（ａ）と共重合可能なエチレン性不飽和単量体（ｄ）、重合開始剤、脂環式エポキシ基含有エチレン性不飽和化合物（ｃ）、触媒、重合禁止剤及び溶媒の種類及び使用量（質量部）をそれぞれ示す。 Table 1 shows the carboxyl group-containing ethylenically unsaturated monomer (a) used in the production of resins (A-1) to (A-12), and the ethylenically unsaturated monomer copolymerizable with (a) above. The types and amounts (mass parts) of the monomer (d), polymerization initiator, alicyclic epoxy group-containing ethylenically unsaturated compound (c), catalyst, polymerization inhibitor and solvent are shown.
Figure JPOXMLDOC01-appb-T000021
Figure JPOXMLDOC01-appb-T000021
Figure JPOXMLDOC01-appb-T000022
Figure JPOXMLDOC01-appb-T000022
Figure JPOXMLDOC01-appb-T000023
Figure JPOXMLDOC01-appb-T000023
製造例１～１２で合成した樹脂（Ａ－１）～（Ａ－１２）の反応溶液に、希釈溶媒である酢酸エチルを加え、それぞれ樹脂（Ａ－１）～（Ａ－１２）の含有量が３０質量％となるように調整した。樹脂（Ａ－１）～（Ａ－１２）の含有量が３０質量％である樹脂（Ａ－１）～（Ａ－１２）溶液を用いて、以下に示す方法により粘着剤組成物を得た。 Ethyl acetate as a diluent solvent was added to the reaction solution of the resins (A-1) to (A-12) synthesized in Production Examples 1 to 12, and the contents of the resins (A-1) to (A-12) were determined. was adjusted to 30% by mass. Using a resin (A-1) to (A-12) solution having a resin (A-1) to (A-12) content of 30% by mass, a pressure-sensitive adhesive composition was obtained by the method shown below. .
　活性線の遮断された室内でプラスチック製容器に、表３及び表４に示す樹脂（Ａ）と光重合開始剤（Ｂ）と架橋剤（Ｃ）とを、それぞれ表３及び表４に示す含有量（質量部）で加えて攪拌し、実施例１～１１、比較例１～６の粘着剤組成物を得た。 Resin (A) shown in Tables 3 and 4, photoinitiator (B) and cross-linking agent (C) shown in Tables 3 and 4 are contained in a plastic container in a room shielded from active rays. The amount (parts by mass) was added and stirred to obtain pressure-sensitive adhesive compositions of Examples 1 to 11 and Comparative Examples 1 to 6.
　表３及び表４中の樹脂（Ａ－１）～（Ａ－１２）の数値は、樹脂（Ａ－１）～（Ａ－１２）の含有量が３０質量％である樹脂（Ａ－１）～（Ａ－１２）溶液の固形分、すなわち樹脂（Ａ－１）～（Ａ－１２）の使用量（質量部）である。光重合開始剤（Ｂ）の数値は、樹脂（Ａ）１００質量部に対する光重合開始剤（Ｂ）の使用量（質量部）である。架橋剤（Ｃ）の数値は、樹脂（Ａ）１００質量部に対する架橋剤（Ｃ）の使用量（質量部）である。 The numerical values of resins (A-1) to (A-12) in Tables 3 and 4 are resin (A-1) in which the content of resins (A-1) to (A-12) is 30% by mass. ~ (A-12) is the solid content of the solution, that is, the amount (parts by mass) of the resins (A-1) ~ (A-12) used. The numerical value of the photopolymerization initiator (B) is the amount (parts by mass) of the photopolymerization initiator (B) used with respect to 100 parts by mass of the resin (A). The numerical value of the cross-linking agent (C) is the amount (parts by mass) of the cross-linking agent (C) used with respect to 100 parts by mass of the resin (A).
　表３及び表４における「ＴＥＴＲＡＤ－Ｃ」、「ＴＥＴＲＡＤ－Ｘ」、「ＨＸ」及び「ＴＰＯ」は、それぞれ以下に示すものである。
「ＴＥＴＲＡＤ－Ｃ」：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（三菱ガス化学株式会社製、商品名：ＴＥＴＲＡＤ－Ｃ）
「ＴＥＴＲＡＤ－Ｘ」：Ｎ，Ｎ’－［１，３－フェニレンビス（メチレン）］ビス［ビス（オキシラン－２－イルメチル）アミン］（三菱ガス化学株式会社製、商品名：ＴＥＴＲＡＤ－Ｘ）
「ＨＸ」：ヘキサメチレンジイソシアネートのイソシアヌレート体（東ソー株式会社製、商品名：コロネート（登録商標）ＨＸ）
「ＴＰＯ」：２，４，６－トリメチルベンゾイルジフェニルホスフィンオキサイド（ＢＡＳＦ社製、商品名：Ｌ－ＴＰＯ） "TETRAD-C", "TETRAD-X", "HX" and "TPO" in Tables 3 and 4 are as follows.
"TETRAD-C": 1,3-bis(N,N'-diglycidylaminomethyl)cyclohexane (manufactured by Mitsubishi Gas Chemical Company, Inc., trade name: TETRAD-C)
“TETRAD-X”: N,N′-[1,3-phenylenebis(methylene)]bis[bis(oxiran-2-ylmethyl)amine] (manufactured by Mitsubishi Gas Chemical Company, Inc., trade name: TETRAD-X)
"HX": isocyanurate form of hexamethylene diisocyanate (manufactured by Tosoh Corporation, trade name: Coronate (registered trademark) HX)
"TPO": 2,4,6-trimethylbenzoyldiphenylphosphine oxide (manufactured by BASF, trade name: L-TPO)
［粘着力測定用粘着シートの製造］
　実施例１～１１及び比較例１～６の粘着剤組成物をそのまま、乾燥後の膜厚が２０μｍになるように基材上に塗工し、１００℃で２分間、加熱乾燥させて粘着剤層を形成した。その後、粘着剤層上に剥離シートを貼り合せることにより、実施例１～１１及び比較例１～６の粘着シートを得た。基材としては、厚さ２５μｍのポリアミド（ＰＡ）フィルムを用いた。剥離シートとしては厚さ２５μｍのポリエチレンテレフタレート（ＰＥＴ）フィルムを用いた。 [Production of Adhesive Sheet for Adhesion Measurement]
The adhesive compositions of Examples 1 to 11 and Comparative Examples 1 to 6 are directly coated on a substrate so that the film thickness after drying is 20 μm, and dried by heating at 100 ° C. for 2 minutes to obtain an adhesive. formed a layer. Thereafter, a release sheet was laminated on the adhesive layer to obtain adhesive sheets of Examples 1 to 11 and Comparative Examples 1 to 6. A polyamide (PA) film having a thickness of 25 μm was used as the base material. A polyethylene terephthalate (PET) film having a thickness of 25 μm was used as the release sheet.
［バンプ保護用粘着シートの製造］
　実施例１～１１及び比較例１～６の粘着剤組成物をそのまま、乾燥後の膜厚が１００μｍになるように基材上に塗工し、１００℃で２分間、加熱乾燥させて粘着剤層を形成した。その後、粘着剤層上に剥離シートを貼り合せて、４０℃で３日間、オーブンで養生し、粘着剤層を架橋硬化させることにより、実施例１～１１及び比較例１～６の粘着シートを得た。基材としては、厚さ２５μｍのポリアミド（ＰＡ）フィルムを用いた。剥離シートとしては厚さ２５μｍのポリエチレンテレフタレート（ＰＥＴ）フィルムを用いた。 [Manufacturing of adhesive sheet for bump protection]
The pressure-sensitive adhesive compositions of Examples 1 to 11 and Comparative Examples 1 to 6 are directly coated on a substrate so that the film thickness after drying is 100 μm, and dried by heating at 100 ° C. for 2 minutes. formed a layer. After that, a release sheet is attached to the adhesive layer, cured in an oven at 40° C. for 3 days, and the adhesive layer is crosslinked and cured to obtain the adhesive sheets of Examples 1 to 11 and Comparative Examples 1 to 6. Obtained. A polyamide (PA) film having a thickness of 25 μm was used as the base material. A polyethylene terephthalate (PET) film having a thickness of 25 μm was used as the release sheet.
　このようにして得られた実施例１～１１及び比較例１～６の粘着シートについて、以下に示す方法により、以下に示す項目の評価を行った。結果を表３及び表４に示す。 The adhesive sheets of Examples 1 to 11 and Comparative Examples 1 to 6 thus obtained were evaluated for the items shown below by the methods shown below. Tables 3 and 4 show the results.
粘着力測定用粘着シートを縦２５ｍｍ、横１００ｍｍの大きさに切り取り、剥離シートを剥がして粘着剤層を露出させた。次に、露出させた粘着剤層（測定面）がガラス板に接するように、粘着シートをガラス板に貼付し、２ｋｇのゴムローラー（幅：約５０ｍｍ）を１往復させ、ＵＶ照射前剥離強度の測定用サンプルを得た。 The pressure-sensitive adhesive sheet for measuring the pressure-sensitive adhesive strength was cut into a size of 25 mm long and 100 mm wide, and the release sheet was peeled off to expose the pressure-sensitive adhesive layer. Next, the adhesive sheet is attached to the glass plate so that the exposed adhesive layer (measurement surface) is in contact with the glass plate, and a 2 kg rubber roller (width: about 50 mm) is reciprocated once to measure the peel strength before UV irradiation. A sample for measurement was obtained.
　得られた測定用サンプルを、温度２３℃、湿度５０％の環境下で２４時間放置した。その後、ＪＩＳ　Ｚ　０２３７：２００９に準じて、剥離速度３００ｍｍ／分で１８０°方向の引張試験を行い、粘着シートのガラス板に対する剥離強度（Ｎ／２５ｍｍ）を測定した。 The obtained measurement sample was left for 24 hours in an environment with a temperature of 23°C and a humidity of 50%. After that, according to JIS Z 0237:2009, a tensile test was performed in a 180° direction at a peel speed of 300 mm/min to measure the peel strength (N/25 mm) of the adhesive sheet to the glass plate.
ＵＶ照射前剥離強度の測定用サンプルと同じものを作製し、粘着シート側の面から照射量１０００ｍＪ／ｃｍ２の条件で紫外線（ＵＶ）を照射し、ＵＶ照射後剥離強度の測定用サンプルを得た。ＵＶ照射には、コンベヤー型紫外線照射装置（アイグラフィックス社製、２ＫＷランプ、８０Ｗ／ｃｍ）を用いた。 Prepare the same sample for measuring the peel strength before UV irradiation, and irradiate ultraviolet rays (UV) from the adhesive sheet side at a dose of 1000 mJ/cm 2 to obtain a sample for measuring the peel strength after UV irradiation. rice field. For UV irradiation, a conveyor type ultraviolet irradiation device (manufactured by Eye Graphics, 2 KW lamp, 80 W/cm) was used.
　得られた測定用サンプルについて「ＵＶ照射前剥離強度」と同様にして、粘着シートのガラス板に対する剥離強度（Ｎ／２５ｍｍ）を測定した。 For the obtained measurement sample, the peel strength (N/25 mm) of the adhesive sheet to the glass plate was measured in the same manner as the "peeling strength before UV irradiation".
［加熱試験後の糊残り］
　バンプ保護用粘着シートの剥離シートを剥がして粘着剤層を露出させた。次に、露出させた粘着剤層とバンプ付きＰＣＢ（バンプ径φ＝２０μｍ、バンプ間距離３０μｍ、バンプ高さ４５μｍ）とを、マウンター（ヒューグルエレクトロニクス社　ＨＳ７８００）を用いて、４０℃で１０分間処理して貼り付けを行った。次いで、２００℃、２時間の熱処理を行い、放冷した後に粘着シートの基材側から照射量１０００ｍＪ／ｃｍ２の条件で紫外線（ＵＶ）を照射した。ＵＶ照射には、コンベヤー型紫外線照射装置（アイグラフィックス社製、２ＫＷランプ、８０Ｗ／ｃｍ）を用いた。その後、粘着シートを剥離し、バンプ付きＰＣＢを光学顕微鏡にて観察し、糊残りの面積がバンプ付きＰＣＢ全体の５％以下であった場合を「Ａ」、５％より大きく２０％未満であった場合を「Ｂ」、２０％以上であった場合を「Ｃ」として糊残りを評価した。 [Adhesive residue after heating test]
The release sheet of the pressure-sensitive adhesive sheet for bump protection was peeled off to expose the pressure-sensitive adhesive layer. Next, the exposed adhesive layer and PCB with bumps (bump diameter φ = 20 µm, distance between bumps 30 µm, height of bumps 45 µm) were placed at 40°C for 10 minutes using a mounter (HS7800, Hugle Electronics). processed and pasted. Next, heat treatment was performed at 200° C. for 2 hours, and after allowing to cool, ultraviolet rays (UV) were irradiated from the substrate side of the pressure-sensitive adhesive sheet at an irradiation dose of 1000 mJ/cm 2 . For UV irradiation, a conveyor type ultraviolet irradiation device (manufactured by Eye Graphics, 2 KW lamp, 80 W/cm) was used. After that, the adhesive sheet was peeled off, and the PCB with bumps was observed with an optical microscope. If the area of the adhesive residue was 5% or less of the entire PCB with bumps, "A" was applied. The adhesive residue was evaluated as "B" when it was less than 20%, and as "C" when it was 20% or more.
［段差埋め性１］
　バンプ保護用粘着シートの剥離シートを剥がして粘着剤層を露出させた。次に、露出させた粘着剤層とバンプ付きＰＣＢ（バンプ径φ＝２０μｍ、バンプ間距離３０μｍ、バンプ高さ４５μｍ）とを、マウンター（ヒューグルエレクトロニクス社製　ＨＳ７８００）を用いて、４０℃で５分間処理して貼り付けを行った。バンプ保護用粘着シート側から光学顕微鏡にて観察し、気泡が混入している面積がバンプ付きＰＣＢ全体の１％以下であった場合を「Ａ」、１％より大きく１０％未満であった場合を「Ｂ」、１０％以上であった場合を「Ｃ」として段差埋め性１を評価した。 [Step fillability 1]
The release sheet of the pressure-sensitive adhesive sheet for bump protection was peeled off to expose the pressure-sensitive adhesive layer. Next, the exposed adhesive layer and PCB with bumps (bump diameter φ = 20 µm, distance between bumps 30 µm, height of bumps 45 µm) were bonded together at 40°C for 5 minutes using a mounter (HS7800 manufactured by Hugle Electronics). Affixing was performed after processing for 1 minute. Observation with an optical microscope from the bump protection adhesive sheet side, "A" when the area where air bubbles are mixed in the entire PCB with bumps is 1% or less, and when it is more than 1% and less than 10% was evaluated as "B", and the case where it was 10% or more was evaluated as "C".
［段差埋め性２］
　段差埋め性１の操作により得られた、バンプ保護用粘着シートが貼りつけられたバンプ付きＰＣＢに対して、ブレード（東京精密社製「ＳＤＣ２００　Ｒ１００ＮＭＲ」、カーフ幅：０．３ｍｍ、ブレード回転数：２８０００ｒｐｍ、切削速度：３０ｍｍ／ｓｅｃ、切込深さ：１００μｍ）にてダイシングを行った。ダイシングにより小片化されたバンプ付きＰＣＢをバンプ保護用粘着シート側から光学顕微鏡にて観察し、気泡が混入している面積がバンプ付きＰＣＢ全体の１％以下であった場合を「Ａ」、１％より大きく１０％未満であった場合を「Ｂ」、１０％以上であった場合を「Ｃ」として段差埋め性２を評価した。 [Step fillability 2]
A blade ("SDC200 R100 NMR" manufactured by Tokyo Seimitsu Co., Ltd., kerf width: 0.3 mm, blade rotation speed: Dicing was performed at 28000 rpm, cutting speed: 30 mm/sec, depth of cut: 100 μm). The PCB with bumps cut into small pieces by dicing is observed with an optical microscope from the side of the bump protection adhesive sheet, and "A" is given when the area containing air bubbles is 1% or less of the entire PCB with bumps. % and less than 10% were evaluated as "B" and 10% or more as "C".
［段差埋め性３］
　段差埋め性２の操作により小片化された、バンプ保護用粘着シートが貼りつけられたバンプ付きＰＣＢに対して２００℃、２時間の熱処理を行った。バンプ付きＰＣＢを放冷した後にバンプ保護用粘着シート側から光学顕微鏡にて観察し、気泡が混入している面積がバンプ付きＰＣＢ全体の１％以下であった場合を「Ａ」、１％より大きく１０％未満であった場合を「Ｂ」、１０％以上であった場合を「Ｃ」として段差埋め性３を評価した。 [Step fillability 3]
A heat treatment was performed at 200° C. for 2 hours on the PCB with bumps to which the pressure-sensitive adhesive sheet for protecting bumps was adhered, which was cut into small pieces by the operation of step filling property 2 . After allowing the PCB with bumps to cool, observe with an optical microscope from the side of the adhesive sheet for bump protection, and if the area containing air bubbles is 1% or less of the entire PCB with bumps, "A" is higher than 1%. Level difference fillability 3 was evaluated as "B" when it was largely less than 10%, and "C" when it was 10% or more.
　表３に示すように、実施例１～１１の粘着シートは、いずれも「加熱試験後の糊残り」がＡ又はＢであった。また、これらの粘着シートは、「段差埋め性１」、「段差埋め性２」、「段差埋め性３」のいずれの評価においてもＡであり、バンプ付きＰＣＢへの密着性が良好であった。 As shown in Table 3, the adhesive sheets of Examples 1 to 11 all had A or B in "adhesive residue after heating test". In addition, these pressure-sensitive adhesive sheets were rated A in all of the evaluations of "step-filling property 1," "step-filling property 2," and "step-filling property 3," indicating good adhesion to PCBs with bumps. .
　これに対し、表４に示すように、樹脂（Ａ）の分子量が５５万を超えている比較例１～６の粘着シートは、「加熱試験後の糊残り」はいずれもＡであったが、「段差埋め性１」、「段差埋め性２」、「段差埋め性３」に関してはＢ又はＣであり、バンプ付きＰＣＢへの密着性が不十分であった。 On the other hand, as shown in Table 4, the pressure-sensitive adhesive sheets of Comparative Examples 1 to 6, in which the resin (A) had a molecular weight of more than 550,000, had an "adhesive residue after the heating test" of A. , “step-filling property 1”, “step-filling property 2”, and “step-filling property 3” were B or C, and the adhesion to the bumped PCB was insufficient.
Figure JPOXMLDOC01-appb-T000024
Figure JPOXMLDOC01-appb-T000024
Figure JPOXMLDOC01-appb-T000025
Figure JPOXMLDOC01-appb-T000025
Figure JPOXMLDOC01-appb-T000026
Figure JPOXMLDOC01-appb-T000026

Claims (12)

  1. 　シート状の基材と前記基材上に形成された粘着剤層とを有する粘着シートを半導体デバイスのバンプ付き被着面に貼り付ける保護工程、
    　前記粘着シートに対してＵＶ照射を行い、前記粘着剤層を硬化させるＵＶ照射工程、及び
    　前記粘着シートを前記バンプ付き被着面から剥離除去する剥離工程
    を含む、半導体デバイスの製造方法であって、
    　前記粘着剤層が、粘着剤組成物の硬化物であり、
    　前記粘着剤組成物が、下記一般式（１－１）で示される樹脂（Ａ）と、光重合開始剤（Ｂ）とを含み、前記樹脂（Ａ）の重量平均分子量が５万～５５万である半導体デバイスの製造方法。
    Figure JPOXMLDOC01-appb-C000001
    Figure JPOXMLDOC01-appb-C000002
     （式（１－１）において、ｋ、ｌ、ｍ及びｎは、ｋ＋ｌ＋ｍ＋ｎ＝１００としたときのモル組成比を示す。ｋは０超～９２以下である。ｌは０～５０である。ｍは０超～９０以下である。ｋ、ｌ及びｍの合計は６５～９５である。ｎは５～３５である。Ｒ１～Ｒ４は－Ｈ又は－ＣＨ３である。Ｒ５は炭素原子数１～１６のアルキル基である。Ｒ６は炭素原子数３～３０の脂環式炭化水素基又は炭素原子数６～２０の芳香族炭化水素基である。Ｒ７は－Ｈ又は－（ＣＨ２）ｊ－ＣＯＯＨ（式中のｊは１又は２である。）である。Ｒ８は上記一般式（１－２）又は（１－３）で示される基である。式（１－２）及び（１－３）において、ｐ及びｑは０、１及び２から選ばれるいずれかである。ｓはｐが０のときは０であり、ｐが１又は２のときは１である。Ｒ９は－Ｈ又は－ＣＨ３である。）     A protective step of attaching an adhesive sheet having a sheet-like base material and an adhesive layer formed on the base material to a bumped adherend surface of a semiconductor device;
    A method for manufacturing a semiconductor device, comprising a UV irradiation step of irradiating the adhesive sheet to cure the adhesive layer, and a peeling step of peeling and removing the adhesive sheet from the adherend surface with bumps, ,
    The pressure-sensitive adhesive layer is a cured product of the pressure-sensitive adhesive composition,
    The adhesive composition contains a resin (A) represented by the following general formula (1-1) and a photopolymerization initiator (B), and the weight average molecular weight of the resin (A) is 50,000 to 550,000. A method for manufacturing a semiconductor device.
    Figure JPOXMLDOC01-appb-C000001
    Figure JPOXMLDOC01-appb-C000002
     (In formula (1-1), k, l, m and n represent the molar composition ratio when k + l + m + n = 100. k is more than 0 to 92 or less. l is 0 to 50. m is greater than 0 to 90. The sum of k, l and m is 65 to 95. n is 5 to 35. R 1 to R 4 are —H or —CH 3. R 5 is carbon. an alkyl group having 1 to 16 atoms, R 6 being an alicyclic hydrocarbon group having 3 to 30 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms, and R 7 being -H or - (CH 2 ) j —COOH (in the formula, j is 1 or 2.) R 8 is a group represented by the general formula (1-2) or (1-3). -2) and (1-3), p and q are any selected from 0, 1 and 2. s is 0 when p is 0 and 1 when p is 1 or 2 and R 9 is —H or —CH 3. )
  2. 　前記式（１－１）におけるｎが７～３３である請求項１に記載の半導体デバイスの製造方法。 The method for manufacturing a semiconductor device according to claim 1, wherein n in the formula (1-1) is 7 to 33.
  3. 　前記式（１－１）におけるｋが４５～９０であり、ｌが４～４０であり、ｍが１～２０である請求項１又は２に記載の半導体デバイスの製造方法。 The method of manufacturing a semiconductor device according to claim 1 or 2, wherein k is 45 to 90, l is 4 to 40, and m is 1 to 20 in the formula (1-1).
  4. 　前記粘着剤組成物が架橋剤（Ｃ）を更に含有する請求項１又は２に記載の半導体デバイスの製造方法。 The method for manufacturing a semiconductor device according to claim 1 or 2, wherein the pressure-sensitive adhesive composition further contains a cross-linking agent (C).
  5. 　前記樹脂（Ａ）のガラス転移温度が－８０～０℃である請求項１又は２に記載の半導体デバイスの製造方法。 The method for manufacturing a semiconductor device according to claim 1 or 2, wherein the resin (A) has a glass transition temperature of -80 to 0°C.
  6. 　前記保護工程と前記剥離工程の間に、１５０℃以上の加熱工程を有する請求項１又は２に記載の半導体デバイスの製造方法。 The method for manufacturing a semiconductor device according to claim 1 or 2, further comprising a heating step of 150°C or higher between the protecting step and the peeling step.
  7. 　前記保護工程と前記剥離工程の間に、加工工程を有する請求項１又は２に記載の半導体デバイスの製造方法。 The method for manufacturing a semiconductor device according to claim 1 or 2, further comprising a processing step between the protecting step and the peeling step.
  8. 　前記保護工程と前記ＵＶ照射工程の間に、１５０℃以上の加熱工程を有する請求項１又は２に記載の半導体デバイスの製造方法。 The method of manufacturing a semiconductor device according to claim 1 or 2, further comprising a heating step of 150°C or higher between the protection step and the UV irradiation step.
  9. 　前記保護工程と前記ＵＶ照射工程の間に、加工工程を有する請求項１又は２に記載の半導体デバイスの製造方法。 The method of manufacturing a semiconductor device according to claim 1 or 2, further comprising a processing step between the protection step and the UV irradiation step.
  10. 　前記ＵＶ照射工程と前記剥離工程の間に、１５０℃以上の加熱工程を有する請求項１又は２に記載の半導体デバイスの製造方法。 The method for manufacturing a semiconductor device according to claim 1 or 2, further comprising a heating step of 150°C or higher between the UV irradiation step and the peeling step.
  11. 　前記ＵＶ照射工程と前記剥離工程の間に、加工工程を有する請求項１又は２に記載の半導体デバイスの製造方法。 The method for manufacturing a semiconductor device according to claim 1 or 2, further comprising a processing step between the UV irradiation step and the peeling step.
  12. 　請求項１又は２に記載の方法により製造された半導体デバイス。 A semiconductor device manufactured by the method according to claim 1 or 2.
PCT/JP2022/036826 2021-12-14 2022-09-30 Method for producing semiconductor device, and semiconductor device WO2023112427A1 (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020049829A1 (en) * 2018-09-03 2020-03-12 昭和電工株式会社 Pressure-sensitive adhesive composition and pressure-sensitive adhesive sheet
JP2020094199A (en) * 2018-11-28 2020-06-18 積水化学工業株式会社 Adhesive tape
WO2020217793A1 (en) * 2019-04-26 2020-10-29 積水化学工業株式会社 Adhesive tape

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020049829A1 (en) * 2018-09-03 2020-03-12 昭和電工株式会社 Pressure-sensitive adhesive composition and pressure-sensitive adhesive sheet
JP2020094199A (en) * 2018-11-28 2020-06-18 積水化学工業株式会社 Adhesive tape
WO2020217793A1 (en) * 2019-04-26 2020-10-29 積水化学工業株式会社 Adhesive tape

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