WO2022044441A1 - Member processing method - Google Patents

Member processing method Download PDF

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Publication number
WO2022044441A1
WO2022044441A1 PCT/JP2021/018010 JP2021018010W WO2022044441A1 WO 2022044441 A1 WO2022044441 A1 WO 2022044441A1 JP 2021018010 W JP2021018010 W JP 2021018010W WO 2022044441 A1 WO2022044441 A1 WO 2022044441A1
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WO
WIPO (PCT)
Prior art keywords
meth
acrylate
absorbing layer
ultraviolet absorbing
workpiece
Prior art date
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PCT/JP2021/018010
Other languages
French (fr)
Japanese (ja)
Inventor
周作 上野
高正 平山
Original Assignee
日東電工株式会社
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Publication date
Application filed by 日東電工株式会社 filed Critical 日東電工株式会社
Priority to KR1020237000517A priority Critical patent/KR20230056653A/en
Priority to CN202180055460.2A priority patent/CN116034144A/en
Publication of WO2022044441A1 publication Critical patent/WO2022044441A1/en

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/67—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
    • 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
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • 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 at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System 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
    • H01L21/02—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 at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/304—Mechanical treatment, e.g. grinding, polishing, cutting
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/67—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
    • 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
    • H01L2221/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof covered by H01L21/00
    • H01L2221/67—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere
    • H01L2221/683—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping
    • H01L2221/68304—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
    • H01L2221/68318—Auxiliary support including means facilitating the separation of a device or wafer from the auxiliary support
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2221/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof covered by H01L21/00
    • H01L2221/67—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere
    • H01L2221/683—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping
    • H01L2221/68304—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
    • H01L2221/68381—Details of chemical or physical process used for separating the auxiliary support from a device or wafer

Definitions

  • the present invention relates to a member processing method.
  • the members may be sandwiched between a set of substrates to process the members (for example, Patent Document 1).
  • a set of substrates for example, Patent Document 1
  • the member is temporarily placed on the terminal on the wiring circuit board, and a steel plate is laminated on the terminal via a double-sided adhesive sheet and added.
  • the member is held while being pressed, and heat treatment is performed to fix the terminal.
  • the pressure is released, the steel plate is peeled off from the member, and the member is fixed to the terminal on the wiring circuit board.
  • the members are sandwiched between a set of substrates (first substrate, second substrate), as typified by the process of thermally crimping the members on the wiring circuit board, and then one of the substrates (second substrate).
  • first substrate, second substrate a set of substrates
  • second substrate one of the substrates
  • the present invention has been made to solve the above-mentioned conventional problems, and an object thereof is to peel a hard substrate from a work piece (member or the like), but to damage the work piece. It is an object of the present invention to provide the member processing method which can prevent such a thing.
  • the member processing method of the present invention comprises a laminating step of laminating a hard substrate, an ultraviolet absorbing layer, and a workpiece in this order, a processing step of processing the workpiece, and then the ultraviolet absorbing layer. It includes a peeling step of irradiating a hard substrate with ultraviolet rays to peel the hard substrate from the workpiece.
  • the workpiece includes another rigid substrate and members disposed on at least one side of the rigid substrate.
  • the workpiece is a semiconductor wafer.
  • the rigid substrate has light transmission.
  • the UV absorbing layer has adhesiveness.
  • the UV absorbing layer comprises an active energy ray-curable pressure-sensitive adhesive.
  • the UV absorbing layer comprises a UV absorber.
  • the present invention it is possible to provide a member processing method capable of preventing damage to the workpiece while including peeling the hard substrate from the workpiece (member or the like).
  • FIG. 1 is a schematic diagram illustrating a member processing method according to one embodiment of the present invention.
  • the member processing method of the present invention comprises (i) a step of laminating a hard substrate 10, an ultraviolet absorbing layer 20, and a work piece 30 in this order (hereinafter, also referred to as a laminating step), and (ii) then the work.
  • the process includes a step of processing the body 30 (processing step), and (iii) a step of irradiating the ultraviolet absorbing layer 20 with ultraviolet rays to peel off the hard substrate 10 from the workpiece 30 (peeling step).
  • the laminating step is a step of laminating the hard substrate 10, the ultraviolet absorbing layer 20, and the workpiece 30 in this order.
  • the UV absorbing layer is sticky.
  • the workpiece 30 of the illustrated example includes another hard substrate 31 and a member 32 arranged on one side of the other hard substrate 31.
  • the base material 21 and the pressure-sensitive adhesive layer 22 may be further arranged between the ultraviolet absorbing layer 20 and the workpiece 30.
  • the ultraviolet absorbing layer 20, the base material 21, and the pressure-sensitive adhesive layer 22 may be arranged in this order.
  • the laminate composed of the ultraviolet absorbing layer 20, the base material 21, and the pressure-sensitive adhesive layer 22 can be a double-sided pressure-sensitive adhesive sheet A.
  • the rigid substrate and the workpiece may be arranged via an ultraviolet absorbing layer. More specifically, the rigid substrate is placed directly on one surface of the UV absorbing layer and the workpiece is placed directly on the other side of the UV absorbing layer.
  • the hard substrate refers to a molded body on a plate having a flexural modulus of 1 GPa or more.
  • the flexural modulus can be measured by a four-point bending test in accordance with JIS K7171 or JIS R1602, respectively, depending on the material constituting the hard substrate.
  • any suitable material can be used as the material constituting the hard substrate.
  • the hard substrate include a glass substrate, a metal substrate, a silicon substrate, a sapphire substrate, a plastic substrate, and the like.
  • the hard substrate has light transmission.
  • the ultraviolet (wavelength 360 nm) transmittance of the hard substrate is preferably 70% or more, and more preferably 80% to 99.9%. If the hard substrate has light transmission property, peeling in the peeling step can be preferably caused.
  • the ultraviolet absorbing layer may be a layer that has adhesiveness at the initial stage (that is, before irradiation with ultraviolet rays), and the adhesive strength decreases after irradiation with ultraviolet rays to exhibit peelability.
  • the UV absorbing layer can be a layer whose adhesive strength is partially reduced by partial UV irradiation (eg, UV laser light irradiation).
  • the UV absorbing layer comprises a UV absorber.
  • the UV absorbing layer further comprises an adhesive.
  • the pressure-sensitive adhesive include a pressure-sensitive pressure-sensitive adhesive and an active energy ray-curable pressure-sensitive adhesive.
  • the adherend can be peeled off by UV laser light irradiation. More specifically, the gas generated by decomposing the ultraviolet absorber by irradiating the ultraviolet absorbing layer with UV laser light, and / or the gas generated by decomposing the ultraviolet absorbing layer by generating heat of the ultraviolet absorber. As a result, the ultraviolet absorbing layer is deformed, and as a result, peelability is exhibited in the portion irradiated with the UV laser light.
  • the adhesive strength of the entire ultraviolet absorbing layer can be reduced by irradiating the active energy ray.
  • the entire ultraviolet absorbing layer is irradiated with active energy rays to reduce the adhesive force, and then the laser beam is irradiated as described above.
  • Examples of the active energy ray include gamma ray, ultraviolet ray, visible ray, infrared ray (heat ray), radio wave, alpha ray, beta ray, electron beam, plasma flow, ionization ray, particle beam and the like. Ultraviolet rays are preferable.
  • the light transmittance of the ultraviolet absorbing layer at a wavelength of 360 nm is preferably 50% or less. By lowering the light transmittance, the laser output at the time of peeling can be lowered.
  • the light transmittance of the ultraviolet absorbing layer at a wavelength of 355 nm is preferably 30% or less. Within such a range, the above effect becomes more remarkable.
  • the light transmittance of the ultraviolet absorbing layer at a wavelength of 380 nm is preferably 30% or more, more preferably 50% or more.
  • the initial adhesive force at 23 ° C. when the ultraviolet absorbing layer is attached to the stainless steel plate is preferably 0.1N / 20mm to 20N / 20mm, and more preferably 0.5N / 20mm to 15N / 20mm. Within such a range, it is possible to form an ultraviolet absorbing layer that can satisfactorily hold the workpiece. Adhesive strength is measured according to JIS Z 0237: 2000. Specifically, the ultraviolet absorbing layer was attached to a stainless steel plate (arithmetic mean surface roughness Ra: 50 ⁇ 25 nm) by one reciprocation of a 2 kg roller, left at 23 ° C for 30 minutes, and then peeled at an angle of 180 °.
  • the adhesive strength of the ultraviolet absorbing layer changes due to irradiation with active energy rays and laser light, but in the present specification, the "initial adhesive strength" means the adhesive strength before irradiation with active energy rays and laser light. ..
  • the adhesive strength at 23 ° C. after the ultraviolet absorbing layer is attached to a stainless steel plate and irradiated with ultraviolet rays of 460 mJ / cm 2 is preferably 0.01 N / 20 mm to 2 N / 20 mm. More preferably, it is 0.02N / 20mm to 1N / 20mm. Within such a range, it is possible to form an ultraviolet absorbing layer that can be peeled off with little adhesive residue.
  • ultraviolet irradiation for example, using an ultraviolet irradiation device (manufactured by Nitto Seiki Co., Ltd., trade name "UM-810"), ultraviolet rays of a high-pressure mercury lamp (characteristic wavelength: 365 nm, integrated light amount: 460 mJ / cm 2 , irradiation energy: 70 W. It is performed by irradiating the ultraviolet absorbing layer with / cm 2 , irradiation time: 6.6 seconds).
  • UM-810 ultraviolet rays of a high-pressure mercury lamp
  • the thickness of the ultraviolet absorbing layer is preferably 50 ⁇ m or less. Within such a range, it is possible to lower the laser output at the time of peeling.
  • the thickness of the ultraviolet absorbing layer is more preferably 40 ⁇ m or less, further preferably 30 ⁇ m or less, and more preferably 1 ⁇ m to 30 ⁇ m. Within such a range, the above effect becomes remarkable.
  • UV absorber any suitable ultraviolet absorber can be used as long as it is a compound that absorbs ultraviolet rays (for example, a wavelength of 355 nm).
  • the ultraviolet absorber include a benzotriazole-based ultraviolet absorber, a benzophenone-based ultraviolet absorber, a triazine-based ultraviolet absorber, a salicylate-based ultraviolet absorber, a cyanoacrylate-based ultraviolet absorber, and the like. Of these, a triazine-based ultraviolet absorber or a benzotriazole-based ultraviolet absorber is preferable, and a triazine-based ultraviolet absorber is particularly preferable.
  • a triazine-based ultraviolet absorber can be preferably used because the acrylic pressure-sensitive adhesive has high compatibility with the base polymer.
  • the triazine-based ultraviolet absorber is more preferably composed of a compound having a hydroxyl group, and particularly preferably an ultraviolet absorber composed of a hydroxyphenyltriazine-based compound (hydroxyphenyltriazine-based ultraviolet absorber).
  • hydroxyphenyltriazine-based ultraviolet absorber examples include 2- (4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine-2-yl) -5-hydroxyphenyl and [(C10). -C16 (mainly C12-C13) alkyloxy) methyl] Reaction product with oxylane (trade name "TINUVIN 400", manufactured by BASF), 2- [4,6-bis (2,4-dimethylphenyl) -1 , 3,5-Triazine-2-yl] -5- [3- (dodecyloxy) -2-hydroxypropoxy] phenol), 2- (2,4-dihydroxyphenyl) -4,6-bis- (2, Reaction product of 4-dimethylphenyl) -1,3,5-triazine and (2-ethylhexyl) -glycidate (trade name "TINUVIN 405", manufactured by BASF), 2,4-bis (2-hydroxy- 4-Butoxyphenyl) -6-
  • benzotriazole-based ultraviolet absorber examples include 2- (2-hydroxy-5-tert-butylphenyl) -2H-benzotriazole (trade name "TINUVIN PS", manufactured by BASF) and benzene.
  • Ester compounds of propanoic acid and 3- (2H-benzotriazole-2-yl) -5- (1,1-dimethylethyl) -4-hydroxy (C7-9 side chain and linear alkyl) (trade name "TINUVIN 384") -2 ", manufactured by BASF), Octyl 3- [3-tert-butyl-4-hydroxy-5- (5-chloro-2H-benzotriazole-2-yl) phenyl] propionate and 2-ethylhexyl-3- [ 3-tert-Butyl-4-hydroxy-5- (5-chloro-2H-benzotriazole-2yl) phenyl] propionate mixture (trade name "TINUVIN 109", manufactured by BASF), 2- (2H-benzotriazole) -2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol (trade name "TINUVIN 900", manufactured by BASF), 2- (2H-benzotriazole-2-yl) -6- (1-Met
  • the ultraviolet absorber may be a dye or a pigment.
  • the pigment include azo-based, phthalocyanine-based, anthraquinone-based, rake-based, perylene-based, perinone-based, quinacridone-based, thioindigo-based, dioxandine-based, isoindoleinone-based, and quinophthalone-based pigments.
  • the dye include azo dyes, phthalocyanine dyes, anthraquinone dyes, carbonyl dyes, indigo dyes, quinone imine dyes, methine dyes, quinoline dyes, and nitro dyes.
  • the molecular weight of the compound constituting the ultraviolet absorber is preferably 100 to 1500, more preferably 200 to 1200, and further preferably 200 to 1000. Within such a range, an ultraviolet absorbing layer capable of forming a better deformed portion can be formed by laser light irradiation.
  • the maximum absorption wavelength of the ultraviolet absorber is preferably 300 nm to 450 nm, more preferably 320 nm to 400 nm, and further preferably 330 nm to 380 nm.
  • the difference between the maximum absorption wavelength of the ultraviolet absorber and the maximum absorption wavelength of the photopolymerization initiator is preferably 10 nm or more, more preferably 25 nm or more.
  • the 5% weight loss temperature of the ultraviolet absorber is preferably 350 ° C. or lower, more preferably 330 ° C. or lower.
  • the lower limit of the 5% weight loss temperature of the UV absorber is, for example, 100 ° C. Within such a range, an ultraviolet absorbing layer capable of forming a better deformed portion can be formed by laser light irradiation.
  • the 5% weight loss temperature of the UV absorber means the temperature at the time when the weight of the UV absorber when the temperature of the UV absorber is raised is reduced by 5% by weight with respect to the weight before the temperature rise. do.
  • the 5% weight loss temperature is measured using a differential thermal analyzer under the measurement conditions of a temperature rise temperature of 10 ° C./min, an air atmosphere, and a flow rate of 25 ml / min.
  • the content ratio of the ultraviolet absorber is preferably 1 part by weight to 50 parts by weight, and more preferably 5 parts by weight to 20 parts by weight with respect to 100 parts by weight of the base polymer in the ultraviolet absorbing layer.
  • the content ratio of the ultraviolet absorber is preferably 1 part by weight to 50 parts by weight, and more preferably 5 parts by weight to 20 parts by weight with respect to 100 parts by weight of the base polymer in the ultraviolet absorbing layer.
  • Active energy ray-curable adhesive in one embodiment, as an active energy ray-curable pressure-sensitive adhesive, an active energy ray-curable type containing a base polymer as a base material and an active energy ray-reactive compound (monomer or oligomer) capable of binding to the base polymer.
  • the pressure-sensitive adhesive (A1) is used.
  • an active energy ray-curable pressure-sensitive adhesive (A2) containing an active energy ray-reactive polymer is used as a base polymer.
  • the base polymer has a functional group capable of reacting with the photopolymerization initiator. Examples of the functional group include a hydroxyl group and a carboxyl group.
  • Examples of the base polymer used in the pressure-sensitive adhesive (A1) include natural rubber, polyisobutylene rubber, styrene / butadiene rubber, styrene / isoprene / styrene block copolymer rubber, recycled rubber, butyl rubber, polyisobutylene rubber, and nitrile rubber.
  • Examples include rubber-based polymers such as (NBR); silicone-based polymers; acrylic-based polymers. These polymers may be used alone or in combination of two or more. Of these, an acrylic polymer is preferable.
  • acrylic polymer examples include a hydrocarbon group-containing (meth) acrylic acid ester homopolymer or copolymer such as (meth) acrylic acid alkyl ester, (meth) acrylic acid cycloalkyl ester, and (meth) acrylic acid aryl ester.
  • examples thereof include a copolymer of the hydrocarbon group-containing (meth) acrylic acid ester and another copolymerizable monomer.
  • Examples of the (meth) acrylic acid alkyl ester include methyl ester, ethyl ester, propyl ester, isopropyl ester, butyl ester, isobutyl ester, s-butyl ester, t-butyl ester, pentyl ester and iso of (meth) acrylic acid.
  • Examples include decyl esters, octadecyl esters, and eicosyl esters.
  • Examples of the (meth) acrylic acid cycloalkyl ester include cyclopentyl ester and cyclohexyl ester of (meth) acrylic acid.
  • Examples of the (meth) acrylic acid aryl ester include phenyl (meth) acrylic acid and benzyl (meth) acrylic acid.
  • the content ratio of the constituent unit derived from the hydrocarbon group-containing (meth) acrylic acid ester is preferably 40 parts by weight or more, and more preferably 60 parts by weight or more with respect to 100 parts by weight of the base polymer.
  • Examples of the other copolymerizable monomers include carboxy group-containing monomers, acid anhydride monomers, hydroxy group-containing monomers, glycidyl group-containing monomers, sulfonic acid group-containing monomers, phosphate group-containing monomers, acrylamide, and acrylonitrile.
  • Examples include functional group-containing monomers.
  • Examples of the carboxy group-containing monomer include acrylic acid, methacrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, itaconic acid, maleic acid, fumaric acid, and crotonic acid.
  • Examples of the acid anhydride monomer include maleic anhydride and itaconic anhydride.
  • Examples of the hydroxy group-containing monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 6-hydroxyhexyl (meth) acrylate. Examples include 8-hydroxyoctyl acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate, and (4-hydroxymethylcyclohexyl) methyl (meth) acrylate. Examples of the glycidyl group-containing monomer include glycidyl (meth) acrylate and methyl glycidyl (meth) acrylate.
  • Examples of the sulfonic acid group-containing monomer include styrene sulfonic acid, allyl sulfonic acid, 2- (meth) acrylamide-2-methyl propane sulfonic acid, (meth) acrylamide propane sulfonic acid, sulfopropyl (meth) acrylate, and (meth). ) Acryloyloxynaphthalene sulfonic acid can be mentioned.
  • Examples of the phosphoric acid group-containing monomer include 2-hydroxyethylacryloyl phosphate.
  • Examples of acrylamide include N-acryloyl morpholine. These may be used individually by 1 type, or may be used in combination of 2 or more type.
  • the content ratio of the structural unit derived from the copolymerizable monomer is preferably 60 parts by weight or less, and more preferably 40 parts by weight or less with respect to 100 parts by weight of the base polymer.
  • Acrylic polymers may contain structural units derived from polyfunctional monomers in order to form crosslinked structures in the polymer skeleton.
  • the polyfunctional monomer include hexanediol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and pentaerythritol di.
  • (Meta) Acrylate, Trimethylol Propanetri (Meta) Acrylate, Pentaerythritol Tri (Meta) Acrylate, Dipentaerythritol Hexa (Meta) Acrylate, Epoxy (Meta) Acrylate (ie, Polyglycidyl (Meta) Acrylate), Polyester (Meta) ) Acrylate and urethane (meth) acrylate can be mentioned. These may be used individually by 1 type, or may be used in combination of 2 or more type.
  • the content ratio of the structural unit derived from the polyfunctional monomer is preferably 40 parts by weight or less, more preferably 30 parts by weight or less, based on 100 parts by weight of the base polymer.
  • the weight average molecular weight of the acrylic polymer is preferably 100,000 to 3 million, more preferably 200,000 to 2 million.
  • the weight average molecular weight can be measured by GPC (solvent: THF).
  • Examples of the active energy ray-reactive compound that can be used in the pressure-sensitive adhesive (A1) include functional groups having a polymerizable carbon-carbon multiple bond such as an acryloyl group, a methacryloyl group, a vinyl group, an allyl group, and an acetylene group.
  • Examples thereof include photoreactive monomers or oligomers having.
  • Specific examples of the photoreactive monomer include trimethylol propanetri (meth) acrylate, tetramethylol methanetetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and dipentaerythritol mono.
  • monomers such as methacryloisocyanate, 2-methacryloyloxyethyl isocyanate (2-isocyanatoethyl methacrylate), m-isopropenyl- ⁇ , and ⁇ -dimethylbenzylisocyanate may be used.
  • Specific examples of the photoreactive oligomer include 2 to pentamers of the above-mentioned monomers.
  • the molecular weight of the photoreactive oligomer is preferably 100 to 3000.
  • the active energy ray-reactive compound a monomer such as epoxidized butadiene, glycidyl methacrylate, acrylamide, vinyl siloxane; or an oligomer composed of the monomer may be used.
  • the active energy ray-reactive compound a mixture of an organic salt such as an onium salt and a compound having a plurality of heterocycles in the molecule may be used.
  • the organic salt is cleaved by irradiation with active energy rays (for example, ultraviolet rays and electron beams) to generate ions, which act as a starting species to induce a ring-opening reaction of a heterocycle to form a three-dimensional network structure.
  • active energy rays for example, ultraviolet rays and electron beams
  • examples of the organic salts include iodonium salt, phosphonium salt, antimonium salt, sulfonium salt, borate salt and the like.
  • the heterocycle in the compound having a plurality of heterocycles in the molecule include oxylan, oxetane, oxolane, thiirane, and aziridine.
  • the content ratio of the active energy ray-reactive compound is preferably 0.1 part by weight to 500 parts by weight, and more preferably 5 parts by weight to 300 parts by weight with respect to 100 parts by weight of the base polymer. It is a part by weight, more preferably 40 parts by weight to 150 parts by weight.
  • the active energy ray-reactive polymer (base polymer) contained in the pressure-sensitive adhesive (A2) for example, a functional group having a carbon-carbon multiple bond such as an acryloyl group, a methacryloyl group, a vinyl group, an allyl group, or an acetylene group can be used.
  • a functional group having a carbon-carbon multiple bond such as an acryloyl group, a methacryloyl group, a vinyl group, an allyl group, or an acetylene group
  • examples include the polymer having.
  • Specific examples of the active energy ray-reactive polymer include a polymer composed of a polyfunctional (meth) acrylate; a photocationically polymerized polymer; a cinnamoyl group-containing polymer such as polyvinyl cinnamate; a diazotized aminonovolac resin; polyacrylamide. ; Etc. can be mentioned.
  • an active energy ray-reactive polymer configured by introducing an active energy ray-polymerizable carbon-carbon multiple bond into the side chain, main chain and / or main chain end of the acrylic polymer.
  • a method for introducing a radiation-polymerizable carbon-carbon double bond into an acrylic polymer for example, a raw material monomer containing a monomer having a predetermined functional group (first functional group) is copolymerized to obtain an acrylic polymer. After obtaining the compound, a compound having a predetermined functional group (second functional group) capable of reacting with the first functional group and having a radiopolymerizable carbon-carbon double bond can be obtained as carbon-carbon. Examples thereof include a method of subjecting an acrylic polymer to a condensation reaction or an addition reaction while maintaining the radiation polymerizable property of the double bond.
  • Examples of the combination of the first functional group and the second functional group include a carboxy group and an epoxy group, an epoxy group and a carboxy group, a carboxy group and an aziridyl group, an aziridyl group and a carboxy group, a hydroxy group and an isocyanate group, and an isocyanate group. And hydroxy groups.
  • a combination of a hydroxy group and an isocyanate group or a combination of an isocyanate group and a hydroxy group is preferable from the viewpoint of ease of reaction tracking.
  • it is technically difficult to prepare a polymer having a highly reactive isocyanate group but from the viewpoint of easy preparation or availability of an acrylic polymer, the first functionality on the acrylic polymer side is described above.
  • the group is a hydroxy group and the second functional group is an isocyanate group.
  • the isocyanate compound having both a radiopolymerizable carbon-carbon double bond and an isocyanate group as a second functional group include methacryloyl isocyanate, 2-methacryloyloxyethyl isocyanate, and m-isopropenyl- ⁇ . Examples include ⁇ -dimethylbenzyl isocyanate.
  • the acrylic polymer having the first functional group preferably contains the above-mentioned structural unit derived from the hydroxy group-containing monomer, such as 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, and diethylene glucol monovinyl ether. Those containing a structural unit derived from the ether-based compound of the above are also preferable.
  • the pressure-sensitive adhesive (A2) may further contain the active energy ray-reactive compound (monomer or oligomer).
  • the active energy ray-curable pressure-sensitive adhesive may contain a photopolymerization initiator.
  • any suitable initiator can be used as the photopolymerization initiator.
  • the photopolymerization initiator include 4- (2-hydroxyethoxy) phenyl (2-hydroxy-2-propyl) ketone, ⁇ -hydroxy- ⁇ , ⁇ '-dimethylacetophenone, and 2-methyl-2-hydroxypropio.
  • ⁇ -Ketol compounds such as phenone and 1-hydroxycyclohexylphenyl ketone; methoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 2-methyl-1- [4- (methylthio) -Phenyl] -2-Acetphenone compounds such as morpholinopropane-1, benzoin ether compounds such as benzoin ethyl ether, benzoin isopropyl ether and anisoin methyl ether; ketal compounds such as benzyl dimethyl ketal; 2-naphthalene sulfonyl chloride and the like.
  • Aromatic sulfonyl chloride compounds such as 1-phenone-1,1-propanedione-2- (o-ethoxycarbonyl) oxime; benzophenone, benzoylbenzoic acid, 3,3'-dimethyl-4 -Benzophenone compounds such as methoxybenzophenone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4 -Tioxane compounds such as diethylthioxanson and 2,4-diisopropylthioxanson; camphorquinone; halogenated ketone; acylphosphinoxide; acylphosphonate and the like can be mentioned.
  • the amount of the photopolymerization initiator used can be set to any suitable amount.
  • a photopolymerization initiator having a maximum absorption wavelength in the range of 400 nm or less preferably 380 nm or less, more preferably 340 nm or less
  • the curing reaction of the adhesive preferably occurs, and an ultraviolet absorbing layer having a particularly small amount of adhesive residue is formed. be able to.
  • a commercially available product may be used as the photopolymerization initiator.
  • a photopolymerization initiator having a maximum absorption wavelength in the range of 400 nm or less BASF's trade names "Irgacure 127", “Irgacure 369", “Irgacure 369E”, “Irgacure 379”, “Irgacure 379EG”, “Irgacure 379EG”
  • Examples thereof include “Irgacure 819", “Irgacure TOP", “Irgacure 784", and "Irgacure OXE01".
  • the active energy ray-curable pressure-sensitive adhesive may contain a photosensitizer.
  • the photosensitizer can be used in combination with the photopolymerization initiator. Since the photosensitizer can generate radicals from the photopolymerization initiator by passing the energy obtained by absorbing light to the photopolymerization initiator, the absorption peak of the photopolymerization initiator itself is high. The polymerization can proceed with light on the long wavelength side. Therefore, by containing the photosensitizer, it is possible to increase the difference between the absorption wavelength of the ultraviolet absorber and the wavelength at which radicals can be generated from the photopolymerization initiator. As a result, the photopolymerization of the ultraviolet absorbing layer and the peeling by the ultraviolet absorbing agent can be performed without affecting each other.
  • 2,2-dimethoxy-1,2-diphenylethane-1-one (for example, manufactured by BASF, trade name "Irgacure 651") as a photopolymerization initiator and a photosensitizer are used. Is used together. Examples of such a photosensitizer include the product name "UVS-581” manufactured by Kawasaki Kasei Chemicals Co., Ltd. and 9,10-diethoxyanthracene (for example, the product name "UVS1101” manufactured by Kawasaki Kasei Chemicals Co., Ltd.). Be done.
  • photosensitizer examples include 9,10-dibutoxyanthracene (for example, manufactured by Kawasaki Kasei Chemicals, trade name "UVS-1331”), 2-isopropylthioxanthone, benzophenone, thioxanthone derivative, 4,4. '-Bis (dimethylamino) benzophenone and the like can be mentioned.
  • thioxanthone derivative examples include ethoxycarbonylthioxanthone and isopropylthioxanthone.
  • the content ratio of the photosensitizer is preferably 0.01 parts by weight to 2 parts by weight, and more preferably 0.5 parts by weight to 2 parts by weight with respect to 100 parts by weight of the base polymer.
  • the active energy ray-curable pressure-sensitive adhesive contains a cross-linking agent.
  • the cross-linking agent include isocyanate-based cross-linking agents, epoxy-based cross-linking agents, oxazoline-based cross-linking agents, aziridine-based cross-linking agents, melamine-based cross-linking agents, peroxide-based cross-linking agents, urea-based cross-linking agents, and metal alkoxide-based cross-linking agents.
  • examples thereof include a metal chelate-based cross-linking agent, a metal salt-based cross-linking agent, a carbodiimide-based cross-linking agent, and an amine-based cross-linking agent.
  • the content ratio of the cross-linking agent is preferably 0.5 parts by weight to 10 parts by weight, and more preferably 1 part by weight to 8 parts by weight with respect to 100 parts by weight of the base polymer of the pressure-sensitive adhesive.
  • an isocyanate-based cross-linking agent is preferably used.
  • Isocyanate-based cross-linking agents are preferable because they can react with various functional groups.
  • Specific examples of the isocyanate-based cross-linking agent include lower aliphatic polyisocyanates such as butylene diisocyanate and hexamethylene diisocyanate; alicyclic isocyanates such as cyclopentylene diisocyanate, cyclohexylene diisocyanate, and isophorone diisocyanate; 2,4-.
  • Aromatic isocyanates such as tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate; trimethylolpropane / tolylene diisocyanate trimer adduct (manufactured by Nippon Polyurethane Industry Co., Ltd., trade name "Coronate L”), tri Methylolpropane / hexamethylene diisocyanate trimeric adduct (manufactured by Nippon Polyurethane Industry Co., Ltd., trade name "Coronate HL”), isocyanurate of hexamethylene diisocyanate (manufactured by Japan Polyurethane Industry Co., Ltd., trade name "Coronate HX”), etc. Isocyanate adduct; etc.
  • a cross-linking agent having 3 or more isocyanate groups is used.
  • the active energy ray-curable pressure-sensitive adhesive may further contain any suitable additive, if necessary.
  • the additive include an active energy ray polymerization accelerator, a radical trapping agent, an antistatic agent, a plasticizer (for example, a trimellitic acid ester-based plasticizer, a pyromellitic acid ester-based plasticizer, etc.), a pigment, a dye, and a filling.
  • the additive include agents, antioxidants, conductive materials, antistatic agents, ultraviolet absorbers, light stabilizers, release modifiers, softeners, surfactants, flame retardants, antioxidants and the like.
  • Pressure-sensitive adhesive examples include acrylic adhesives, rubber adhesives, vinyl alkyl ether adhesives, silicone adhesives, polyester adhesives, polyamide adhesives, urethane adhesives, and styrene-diene blocks. Copolymerization system adhesives, etc. may be mentioned. Of these, an acrylic pressure-sensitive adhesive or a rubber-based pressure-sensitive adhesive is preferable, and an acrylic-based pressure-sensitive adhesive is more preferable.
  • the pressure-sensitive adhesive may be used alone or in combination of two or more.
  • an acrylic pressure-sensitive adhesive for example, an acrylic pressure-sensitive adhesive using an acrylic polymer (homoromer or copolymer) using one or more (meth) acrylic acid alkyl esters as a monomer component as a base polymer.
  • the (meth) acrylic acid alkyl ester include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, and (meth).
  • the acrylic polymer is a unit corresponding to other monomer components copolymerizable with the (meth) acrylic acid alkyl ester, if necessary, for the purpose of modifying cohesive force, heat resistance, crosslinkability and the like. May include.
  • monomer components include carboxyl group-containing monomers such as acrylic acid, methacrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid, and crotonic acid; maleic anhydride and icotanic anhydride.
  • Acid Anhydromer Monomers such as (meth) hydroxyethyl acrylate, (meth) hydroxypropyl acrylate, (meth) hydroxybutyl acrylate, (meth) hydroxyhexyl acrylate, (meth) hydroxyoctyl acrylate, (meth) Hydromer group-containing monomers such as hydroxydecyl acrylate, hydroxylauryl (meth) acrylate, and (4-hydroxymethylcyclohexyl) methylmethacrylate; styrene sulfonic acid, allyl sulfonic acid, 2- (meth) acrylamide-2-methyl propane sulfonic acid.
  • Maleimide-based monomers such as N-cyclohexyl maleimide, N-isopropylmaleimide, N-laurylmaleimide, N-phenylmaleimide; N-methylitaconimide, N-ethylitaconimide, N-butylitaconimide, N-octylitaconimide , N-2-ethylhexylitaconimide, N-cyclohexylitaconimide, N-laurylitaconimide and other itaconeimide-based monomers; Succinimide-based monomers such as N- (meth) acryloyl-8-oxyoctamethylene succinimide; vinyl acetate, vinyl propionate, N-vinylpyrrolidone, methylvinylpyrro Vinyls such as lidone, vinylpyridine, vinylpiperidone, vinylpyrimidine, vinylpiperazin, vinylpyrazine, vinylpyrrole, vinylimidazole,
  • Acrylate-based monomers Cyanoacrylate monomers such as acrylonitrile and methacrylonitrile; Epoxy group-containing acrylic monomers such as glycidyl (meth) acrylate; Polyethylene glycol (meth) acrylate, Polypropylene glycol (meth) acrylate, (meth) acrylic acid Glycol-based acrylic ester monomers such as methoxyethylene glycol and methoxypolypropylene glycol (meth) acrylate; heterocycles such as tetrahydrofurfuryl (meth) acrylate, fluorine (meth) acrylate and silicone (meth) acrylate, halogen atoms and silicon atoms.
  • Acrylate-based monomers having such as; hexanediol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol.
  • Polyfunctional monomers such as di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, epoxy acrylate, polyester acrylate, urethane acrylate; isoprene, butadiene, Olefin-based monomers such as isobutylene; vinyl ether-based monomers such as vinyl ether and the like can be mentioned. These monomer components may be used alone or in combination of two or more.
  • the rubber-based pressure-sensitive adhesive examples include natural rubber; polyisoprene rubber, styrene / butadiene (SB) rubber, styrene / isoprene (SI) rubber, styrene / isoprene / styrene block copolymer (SIS) rubber, and styrene / butadiene.
  • SBS -Sterethane block copolymer
  • SEBS styrene / ethylene / butylene / styrene block copolymer
  • SEPS styrene / ethylene / propylene / styrene block copolymer
  • SEP rubber-based pressure-sensitive adhesives using polymer
  • the pressure sensitive pressure-sensitive adhesive may contain any suitable additive, if necessary.
  • the additive include a cross-linking agent, a tackifier (for example, a rosin-based tackifier, a terpene-based tackifier, a hydrocarbon-based tackifier, etc.), and a plasticizer (for example, a trimellitic acid ester-based plasticizer).
  • a tackifier for example, a rosin-based tackifier, a terpene-based tackifier, a hydrocarbon-based tackifier, etc.
  • plasticizer for example, a trimellitic acid ester-based plasticizer
  • Piromellitic acid ester plasticizer pigments, dyes, anti-aging agents, conductive materials, antistatic agents, light stabilizers, release modifiers, softeners, surfactants, flame retardants, antioxidants, etc. ..
  • any suitable workpiece can be used.
  • electronic components are used as the workpiece.
  • the workpiece 30 includes another hard substrate 31 and a member 32 arranged on at least one side of the other hard substrate 31.
  • the rigid substrate described in Section B-1 can be used.
  • a rigid wiring circuit board or the like may be used.
  • the member include electronic components such as semiconductor devices and optical semiconductor devices.
  • Specific examples of the workpiece include a terminal on a rigid wiring circuit board in which a plurality of semiconductor elements for connecting to the terminal are arranged side by side, and a semiconductor element is mounted on a glass carrier with a double-sided adhesive sheet. Examples include those placed.
  • a semiconductor wafer is used as the work piece.
  • the semiconductor wafer may be, for example, an optical semiconductor wafer such as an LED or a light receiving element.
  • a plurality of the workpieces may be arranged, or one piece may be arranged.
  • the interval is, for example, 2 ⁇ m to 10 mm.
  • the substrate 21 and the pressure-sensitive adhesive layer 22 may be further arranged between the ultraviolet absorbing layer 20 and the workpiece 30.
  • the laminate composed of the ultraviolet absorbing layer 20, the base material 21, and the pressure-sensitive adhesive layer 22 can be a double-sided pressure-sensitive adhesive sheet A.
  • the double-sided pressure-sensitive adhesive sheet A can be peeled off in a post-process, and the adhesive residue due to coagulation fracture can be suppressed. Since the adhesive residue can be remarkably suppressed, the load of the cleaning process for removing the scorched residue, which is a problem in the existing varnish method, can be reduced. Further, by providing the base material, the base material functions as a protective material, and damage to the workpiece can be prevented.
  • the base material may be composed of any suitable resin.
  • the resin include polyolefin resins such as polyethylene resins, polypropylene resins, polybutene resins, and polymethylpentene resins, polyurethane resins, polyester resins, polyimide resins, polyether ketone resins, and polystyrene resins.
  • polyolefin resins such as polyethylene resins, polypropylene resins, polybutene resins, and polymethylpentene resins, polyurethane resins, polyester resins, polyimide resins, polyether ketone resins, and polystyrene resins.
  • resins polyvinyl chloride resins, polyvinylidene chloride resins, fluororesins, silicon resins, cellulose resins, ionomer resins and the like. Of these, a polyimide resin is preferable.
  • the above effect becomes remarkable, and it is possible to efficiently prevent the workpiece (device) from being damaged by the laser beam incident from the glass substrate side, and the glass. It can be selectively peeled off only from the substrate side.
  • the thickness of the base material is preferably 1 ⁇ m to 300 ⁇ m, more preferably 1 ⁇ m to 100 ⁇ m, and further preferably 1 ⁇ m to 50 ⁇ m.
  • the light transmittance of the base material at a wavelength of 355 nm is preferably 90% or less, more preferably 85% or less, further preferably 50% or less, and particularly preferably 15% or less. If the light transmittance is small, the damage to the adherend can be reduced, which is preferable.
  • the lower limit of the light transmittance of the substrate at a wavelength of 355 nm is, for example, 0%, and in one embodiment, 10%.
  • Adhesive layer contains any suitable adhesive.
  • the pressure-sensitive pressure-sensitive adhesive is included.
  • a heat-resistant adhesive is used as the adhesive contained in the adhesive layer.
  • the heat-resistant adhesive means a pressure-sensitive adhesive having a predetermined adhesive strength in an environment of 260 ° C. It is preferable that the heat-resistant adhesive can be used in an environment of 260 ° C. without adhesive residue.
  • the heat-resistant pressure-sensitive adhesive contains an acrylic resin, a silicone-based resin, or the like as the base polymer.
  • the processing process the workpiece arranged on the hard substrate is processed as described above.
  • the processing in this step can be any suitable processing.
  • a heating process a back grind process, a dicing process, a mounting (reflow) process, a circuit forming (RDL) process, and the like can be mentioned.
  • a press machine provided with an upper plate 100 and a lower plate 200 is used to process (heat) the laminate while pressing (or after pressing) the laminate formed in the lamination step.
  • the ultraviolet absorbing layer when the ultraviolet absorbing layer contains an active energy ray-curable pressure-sensitive adhesive, the ultraviolet absorbing layer is irradiated with active energy rays (for example, ultraviolet rays) before the processing to obtain the ultraviolet absorbing layer.
  • active energy rays for example, ultraviolet rays
  • the adhesive strength may be increased.
  • the ultraviolet absorbing layer is irradiated with ultraviolet rays to peel the hard substrate from the workpiece.
  • the ultraviolet absorbing layer 20 is peeled.
  • the double-sided pressure-sensitive adhesive sheet A is composed of the ultraviolet absorbing layer 20, the base material 21, and the pressure-sensitive adhesive layer 22, the double-sided pressure-sensitive adhesive sheet A is peeled off after the ultraviolet-absorbing layer 20 is peeled off.
  • the hard substrate and the ultraviolet absorbing layer are integrally peeled off.
  • the conditions of ultraviolet irradiation can be any appropriate conditions depending on the configuration of the ultraviolet absorbing layer as long as the ultraviolet absorbing layer can be peeled off.
  • UV laser light eg, wavelength: 200 nm to 380 nm
  • any suitable output eg, 0.01 W to 6 W, preferably 0.05 W to 5 W
  • the gas generated by the decomposition of the UV absorber and / or The gas generated by the decomposition of the pressure-sensitive adhesive layer due to the heat generation of the ultraviolet absorber causes deformation of the ultraviolet absorbing layer, and as a result, peelability is exhibited in the portion irradiated with the laser beam.
  • the wavelength of the UV laser light is preferably 360 nm or less.
  • the entire ultraviolet absorbing layer may be irradiated with active energy rays to reduce the adhesive strength of the ultraviolet absorbing layer.
  • the entire ultraviolet absorbing layer may be irradiated with active energy rays to reduce the adhesive strength of the ultraviolet absorbing layer.
  • the active energy ray include gamma ray, ultraviolet ray, visible ray, infrared ray (heat ray), radio wave, alpha ray, beta ray, electron beam, plasma flow, ionization ray, particle beam and the like. Ultraviolet rays are preferable.
  • the wavelength of ultraviolet rays is preferably 300 nm to 400 nm.
  • the irradiation amount is, for example, an integrated light amount of 300 mJ / cm 2 to 1500 mJ / cm 2 . As described above, if the active energy ray is irradiated before the laser light irradiation, the reattachment can be prevented and the hard substrate can be peeled off.
  • the hard substrate can be peeled off by irradiating the ultraviolet absorbing layer with ultraviolet rays, and the peeling force at that time is low, so that the load applied to the workpiece can be reduced, and as a result, the workpiece is processed. It can prevent damage to the body.
  • a semiconductor element 32 (member 32) was placed on a terminal on a rigid wiring circuit board 31 (another rigid board 31) to prepare a workpiece 30.
  • the glass substrate 10 (hard substrate 10) was laminated and fixed on the semiconductor element 32 using a double-sided adhesive sheet containing an ultraviolet absorbing layer 20.
  • a double-sided adhesive sheet a sheet in which an ultraviolet absorbing layer 20 containing an ultraviolet curable adhesive was formed on one surface of the PI base material 21 and an adhesive layer 22 was formed on the other surface was used.
  • the laminate obtained in the above laminating step was sandwiched between presses, and the semiconductor element 32 was embedded in the pressure-sensitive adhesive layer 22 and held.
  • the upper plate of the press machine is removed, and the ultraviolet absorbing layer 20 is irradiated with ultraviolet rays (wavelength: 355 nm to 365 nm, integrated light amount: 1380 mJ / cm 2 ) through the glass substrate 10 (hard substrate 10) to cure the ultraviolet absorbing layer.
  • the adhesive force of the ultraviolet absorbing layer to the glass substrate 10 (hard substrate 10) was reduced.
  • the semiconductor element 32 (member 32) was fixed to the terminal on the rigid wiring circuit board 31 (another rigid substrate 31) by heating in a state of being crimped by a press machine.
  • metal bonding such as solder, ACF (anisotropic conductive film), ACP (anisotropic paste) and the like can be used.
  • the upper plate of the press machine is removed, and the ultraviolet laser beam (wavelength: 355 nm, irradiation energy: 10 J / cm 2 ) is irradiated to the ultraviolet absorbing layer through the glass substrate 10 (hard substrate 10) to irradiate the glass substrate 10 (hard substrate 10). 10) was peeled off. Then, the double-sided adhesive sheet was peeled off. There was no damage to the semiconductor element 32 (member 32). Further, the semiconductor element 32 (member 32) did not separate from the rigid wiring circuit board 31 (another rigid substrate 31).

Abstract

Provided is a member processing method capable of preventing damage, etc., to the workpiece while including detachment of a hard substrate from a workpiece (member, etc.).　The member processing method of the present invention includes a lamination step for laminating a hard substrate, a UV-absorbing layer, and a workpiece in that order, followed by a processing step for processing the workpiece, followed by a detachment step for irradiating the UV-absorbing layer with UV rays to detach the hard substrate from the workpiece.

Description

部材加工方法Member processing method
　本発明は、部材加工方法に関する。 The present invention relates to a member processing method.
　電子部品（部材）の加工においては、工程間のハンドリング性を考慮して、部材を一組の基板で挟持して、当該部材を加工する場合がある（例えば、特許文献１）。例えば、配線回路基板上の端子に部材を熱圧着して接続する工程においては、部材を配線回路基板上の端子に仮置きした状態で、その上から鋼板を両面粘着シートを介して重ね、加圧しながら当該部材を保持し、熱処理して当該端子を固着させることが行われている。そして、熱処理後、加圧を解放し、鋼板を部材から剥離して、配線回路基板上の端子に上記部材が固着される。 In the processing of electronic parts (members), in consideration of handleability between processes, the members may be sandwiched between a set of substrates to process the members (for example, Patent Document 1). For example, in the process of thermocompression-bonding a member to a terminal on a wiring circuit board, the member is temporarily placed on the terminal on the wiring circuit board, and a steel plate is laminated on the terminal via a double-sided adhesive sheet and added. The member is held while being pressed, and heat treatment is performed to fix the terminal. Then, after the heat treatment, the pressure is released, the steel plate is peeled off from the member, and the member is fixed to the terminal on the wiring circuit board.
特許第６６９１１８４号Patent No. 6691184
　上記の配線回路基板上の部材を熱圧着する工程に代表されるような、部材を一組の基板（第１の基板、第２の基板）で挟持し、その後に、一方の基板（第２の基板）を部材から剥離させる工程においては、剥離される第２の基板が硬質である場合、当該第２の基板（硬質基板）がしなりにくいために、当該第２の基板（硬質基板）を垂直方向に離間させることとなる。そうすると、部材に負荷がかかり当該部材が破損したり、部材が第１の基板から不要に脱離する等の問題がある。 The members are sandwiched between a set of substrates (first substrate, second substrate), as typified by the process of thermally crimping the members on the wiring circuit board, and then one of the substrates (second substrate). In the step of peeling the second substrate (hard substrate) from the member, when the second substrate to be peeled is hard, the second substrate (hard substrate) is difficult to bend, so that the second substrate (hard substrate) Will be separated in the vertical direction. Then, there is a problem that a load is applied to the member and the member is damaged, or the member is unnecessarily detached from the first substrate.
　本発明は上記従来の課題を解決するためになされたものであり、その目的とするところは、硬質基板を被加工体（部材等）から剥離することを含みつつも、当該被加工体の破損等を防止することができる部材加工方法を提供することにある。 The present invention has been made to solve the above-mentioned conventional problems, and an object thereof is to peel a hard substrate from a work piece (member or the like), but to damage the work piece. It is an object of the present invention to provide the member processing method which can prevent such a thing.
　本発明の部材加工方法は、硬質基板と、紫外線吸収層と、被加工体とをこの順に積層する積層工程と、その後、該被加工体を加工する加工工程と、その後、該紫外線吸収層に紫外線を照射して、硬質基板を被加工体から剥離する剥離工程とを含む。
　１つの実施形態においては、上記被加工体が、別の硬質基板と、該硬質基板の少なくとも片側に配置された部材とを含む。
　１つの実施形態においては、上記被加工体が、半導体ウエハである。
　１つの実施形態においては、上記硬質基板が、光透過性を有する。
　１つの実施形態においては、上記紫外線吸収層が、粘着性を有する。
　１つの実施形態においては、上記紫外線吸収層が、活性エネルギー線硬化型粘着剤を含む。
　１つの実施形態においては、上記紫外線吸収層が、紫外線吸収剤を含む。 The member processing method of the present invention comprises a laminating step of laminating a hard substrate, an ultraviolet absorbing layer, and a workpiece in this order, a processing step of processing the workpiece, and then the ultraviolet absorbing layer. It includes a peeling step of irradiating a hard substrate with ultraviolet rays to peel the hard substrate from the workpiece.
In one embodiment, the workpiece includes another rigid substrate and members disposed on at least one side of the rigid substrate.
In one embodiment, the workpiece is a semiconductor wafer.
In one embodiment, the rigid substrate has light transmission.
In one embodiment, the UV absorbing layer has adhesiveness.
In one embodiment, the UV absorbing layer comprises an active energy ray-curable pressure-sensitive adhesive.
In one embodiment, the UV absorbing layer comprises a UV absorber.
　本発明によれば、硬質基板を被加工体（部材等）から剥離することを含みつつも、当該被加工体の破損等を防止することができる部材加工方法を提供することができる。 According to the present invention, it is possible to provide a member processing method capable of preventing damage to the workpiece while including peeling the hard substrate from the workpiece (member or the like).
本発明の１つの実施形態による部材加工方法を説明する概略図である。It is a schematic diagram explaining the member processing method by one Embodiment of this invention.
Ａ．部材加工方法の概要
　図１は、本発明の１つの実施形態による部材加工方法を説明する概略図である。本発明の部材加工方法は、（ｉ）硬質基板１０と、紫外線吸収層２０と、被加工体３０とをこの順に積層する工程（以下、積層工程ともいう）、（ｉｉ）その後、該被加工体３０を加工する工程（加工工程）、および（ｉｉｉ）その後、該紫外線吸収層２０に紫外線を照射して、硬質基板１０を被加工体３０から剥離する工程（剥離工程）を含む。 A. Outline of Member Processing Method FIG. 1 is a schematic diagram illustrating a member processing method according to one embodiment of the present invention. The member processing method of the present invention comprises (i) a step of laminating a hard substrate 10, an ultraviolet absorbing layer 20, and a work piece 30 in this order (hereinafter, also referred to as a laminating step), and (ii) then the work. The process includes a step of processing the body 30 (processing step), and (iii) a step of irradiating the ultraviolet absorbing layer 20 with ultraviolet rays to peel off the hard substrate 10 from the workpiece 30 (peeling step).
Ｂ．積層工程
　上記のとおり、積層工程は、硬質基板１０と、紫外線吸収層２０と、被加工体３０とをこの順に積層する工程である。１つの実施形態において、紫外線吸収層は、粘着性を有する。図示例の被加工体３０は、別の硬質基板３１と別の硬質基板３１の片側に配置された部材３２とを備えている。 B. Laminating Step As described above, the laminating step is a step of laminating the hard substrate 10, the ultraviolet absorbing layer 20, and the workpiece 30 in this order. In one embodiment, the UV absorbing layer is sticky. The workpiece 30 of the illustrated example includes another hard substrate 31 and a member 32 arranged on one side of the other hard substrate 31.
　１つの実施形態において、紫外線吸収層２０と被加工体３０との間には、基材２１と粘着剤層２２とがさらに配置され得る。紫外線吸収層２０と基材２１と粘着剤層２２とはこの順に配置され得る。１つの実施形態において、紫外線吸収層２０と基材２１と粘着剤層２２とから構成される積層体は、両面粘着シートＡであり得る。 In one embodiment, the base material 21 and the pressure-sensitive adhesive layer 22 may be further arranged between the ultraviolet absorbing layer 20 and the workpiece 30. The ultraviolet absorbing layer 20, the base material 21, and the pressure-sensitive adhesive layer 22 may be arranged in this order. In one embodiment, the laminate composed of the ultraviolet absorbing layer 20, the base material 21, and the pressure-sensitive adhesive layer 22 can be a double-sided pressure-sensitive adhesive sheet A.
　別の実施形態においては、硬質基板と被加工体とは紫外線吸収層を介して、配置され得る。より詳細には、硬質基板は、紫外線吸収層の一方の面に直接配置され、被加工体は、紫外線吸収層の他方の面に直接配置される。 In another embodiment, the rigid substrate and the workpiece may be arranged via an ultraviolet absorbing layer. More specifically, the rigid substrate is placed directly on one surface of the UV absorbing layer and the workpiece is placed directly on the other side of the UV absorbing layer.
Ｂ－１．硬質基板
　上記硬質基板とは、曲げ弾性率が、１ＧＰａ以上である板上の成形体をいう。曲げ弾性率は、硬質基板を構成する材料に応じて、ＪＩＳ　Ｋ７１７１またはＪＩＳ　Ｒ１６０２にそれぞれ準拠して、４点曲げ試験により測定することができる B-1. Hard substrate The hard substrate refers to a molded body on a plate having a flexural modulus of 1 GPa or more. The flexural modulus can be measured by a four-point bending test in accordance with JIS K7171 or JIS R1602, respectively, depending on the material constituting the hard substrate.
　上記硬質基板を構成する材料としては、任意の適切な材料が用いられ得る。硬質基板としては、例えば、ガラス基板、金属基板、シリコン基板、サファイア基板、プラスチック基板等が挙げられる。 Any suitable material can be used as the material constituting the hard substrate. Examples of the hard substrate include a glass substrate, a metal substrate, a silicon substrate, a sapphire substrate, a plastic substrate, and the like.
　好ましくは、上記硬質基板は、光透過性を有する。上記硬質基板の紫外線（波長３６０ｎｍ）透過率は、好ましくは７０％以上であり、より好ましくは８０％～９９．９％である。硬質基板が光透過性を有していれば、剥離工程における剥離を好ましく生じさせることができる。 Preferably, the hard substrate has light transmission. The ultraviolet (wavelength 360 nm) transmittance of the hard substrate is preferably 70% or more, and more preferably 80% to 99.9%. If the hard substrate has light transmission property, peeling in the peeling step can be preferably caused.
Ｂ－２．紫外線吸収層
　紫外線吸収層は、初期には（すなわち、紫外線照射前には）粘着性を有し、紫外線照射後に粘着力が低下して剥離性を示す層であり得る。１つの実施形態においては、紫外線吸収層は、部分的な紫外線照射（例えば、ＵＶレーザー光照射）により、部分的に粘着力が低下する層であり得る。 B-2. Ultraviolet absorbing layer The ultraviolet absorbing layer may be a layer that has adhesiveness at the initial stage (that is, before irradiation with ultraviolet rays), and the adhesive strength decreases after irradiation with ultraviolet rays to exhibit peelability. In one embodiment, the UV absorbing layer can be a layer whose adhesive strength is partially reduced by partial UV irradiation (eg, UV laser light irradiation).
　１つの実施形態において、紫外線吸収層は、紫外線吸収剤を含む。好ましくは、紫外線吸収層は、粘着剤をさらに含む。粘着剤としては、例えば、感圧粘着剤、活性エネルギー線硬化型粘着剤が挙げられる。 In one embodiment, the UV absorbing layer comprises a UV absorber. Preferably, the UV absorbing layer further comprises an adhesive. Examples of the pressure-sensitive adhesive include a pressure-sensitive pressure-sensitive adhesive and an active energy ray-curable pressure-sensitive adhesive.
　紫外線吸収層が紫外線吸収剤を含むことにより、ＵＶレーザー光照射による被着体の剥離が可能となる。より詳細には、紫外線吸収層にＵＶレーザー光を照射することで、紫外線吸収剤が分解して発生するガス、および／または紫外線吸収剤が発熱することにより紫外線吸収層が分解して発生するガスにより、紫外線吸収層に変形が生じ、その結果、ＵＶレーザー光が照射された部分において、剥離性が発現する。 Since the ultraviolet absorbing layer contains an ultraviolet absorber, the adherend can be peeled off by UV laser light irradiation. More specifically, the gas generated by decomposing the ultraviolet absorber by irradiating the ultraviolet absorbing layer with UV laser light, and / or the gas generated by decomposing the ultraviolet absorbing layer by generating heat of the ultraviolet absorber. As a result, the ultraviolet absorbing layer is deformed, and as a result, peelability is exhibited in the portion irradiated with the UV laser light.
　また、紫外線吸収層が、活性エネルギー線硬化型粘着剤を含んでいれば、活性エネルギー線を照射することにより、紫外線吸収層全体の粘着力を低下させることができる。１つの実施形態においては、紫外線吸収層の全体に活性エネルギー線を照射して、粘着力を低下させた後に、上記のようにレーザー光を照射する。このようにすれば、剥離後の糊残りや硬質基板への再付着を顕著に防止することができ、例えば、ワニスを用いた従来の方法と比較しても汚染防止の観点から有利である。活性エネルギー線としては、例えば、ガンマ線、紫外線、可視光線、赤外線（熱線）、ラジオ波、アルファ線、ベータ線、電子線、プラズマ流、電離線、粒子線等が挙げられる。好ましくは、紫外線である。 Further, if the ultraviolet absorbing layer contains an active energy ray-curable pressure-sensitive adhesive, the adhesive strength of the entire ultraviolet absorbing layer can be reduced by irradiating the active energy ray. In one embodiment, the entire ultraviolet absorbing layer is irradiated with active energy rays to reduce the adhesive force, and then the laser beam is irradiated as described above. By doing so, it is possible to remarkably prevent the adhesive residue after peeling and the reattachment to the hard substrate, which is advantageous from the viewpoint of contamination prevention as compared with the conventional method using varnish, for example. Examples of the active energy ray include gamma ray, ultraviolet ray, visible ray, infrared ray (heat ray), radio wave, alpha ray, beta ray, electron beam, plasma flow, ionization ray, particle beam and the like. Ultraviolet rays are preferable.
　紫外線吸収層の波長３６０ｎｍの光透過率は、好ましくは５０％以下である。当該光透過率を低くすることにより、剥離の際のレーザー出力を低くすることができる。紫外線吸収層の波長３５５ｎｍの光透過率は、好ましくは３０％以下である。このような範囲であれば、上記効果はより顕著となる。また、紫外線吸収層の波長３８０ｎｍの光透過率は、好ましくは３０％以上であり、より好ましくは５０％以上である。 The light transmittance of the ultraviolet absorbing layer at a wavelength of 360 nm is preferably 50% or less. By lowering the light transmittance, the laser output at the time of peeling can be lowered. The light transmittance of the ultraviolet absorbing layer at a wavelength of 355 nm is preferably 30% or less. Within such a range, the above effect becomes more remarkable. The light transmittance of the ultraviolet absorbing layer at a wavelength of 380 nm is preferably 30% or more, more preferably 50% or more.
　紫外線吸収層をステンレス板に貼着した際の２３℃における初期粘着力は、好ましくは０．１Ｎ／２０ｍｍ～２０Ｎ／２０ｍｍであり、より好ましくは０．５Ｎ／２０ｍｍ～１５Ｎ／２０ｍｍである。このような範囲であれば、良好に被加工体を保持し得る紫外線吸収層を形成することができる。粘着力は、ＪＩＳ　Ｚ　０２３７：２０００に準じて測定される。具体的には、２ｋｇのローラーを１往復により紫外線吸収層をステンレス板（算術平均表面粗さＲａ：５０±２５ｎｍ）に貼着し、２３℃下で３０分間放置した後、剥離角度１８０°、剥離速度（引張速度）３００ｍｍ／ｍｉｎの条件で、紫外線吸収層を引きはがして測定される。紫外線吸収層は、活性エネルギー線照射およびレーザー光照射により粘着力が変化するが、本明細書において、「初期粘着力」とは、活性エネルギー線およびレーザー光を照射する前の粘着力を意味する。 The initial adhesive force at 23 ° C. when the ultraviolet absorbing layer is attached to the stainless steel plate is preferably 0.1N / 20mm to 20N / 20mm, and more preferably 0.5N / 20mm to 15N / 20mm. Within such a range, it is possible to form an ultraviolet absorbing layer that can satisfactorily hold the workpiece. Adhesive strength is measured according to JIS Z 0237: 2000. Specifically, the ultraviolet absorbing layer was attached to a stainless steel plate (arithmetic mean surface roughness Ra: 50 ± 25 nm) by one reciprocation of a 2 kg roller, left at 23 ° C for 30 minutes, and then peeled at an angle of 180 °. It is measured by peeling off the ultraviolet absorbing layer under the condition of peeling speed (tensile speed) of 300 mm / min. The adhesive strength of the ultraviolet absorbing layer changes due to irradiation with active energy rays and laser light, but in the present specification, the "initial adhesive strength" means the adhesive strength before irradiation with active energy rays and laser light. ..
　１つの実施形態においては、紫外線吸収層をステンレス板に貼着し、４６０ｍＪ／ｃｍ２の紫外線を照射した後の２３℃における粘着力は、好ましくは０．０１Ｎ／２０ｍｍ～２Ｎ／２０ｍｍであり、より好ましくは０．０２Ｎ／２０ｍｍ～１Ｎ／２０ｍｍである。このような範囲であれば、糊残り少なく剥離可能な紫外線吸収層を形成することができる。上記紫外線照射は、例えば、紫外線照射装置（日東精機社製、商品名「ＵＭ－８１０」）を用いて、高圧水銀灯の紫外線（特性波長：３６５ｎｍ、積算光量：４６０ｍＪ／ｃｍ２、照射エネルギー：７０Ｗ／ｃｍ２、照射時間：６．６秒）を紫外線吸収層に照射して行われる。 In one embodiment, the adhesive strength at 23 ° C. after the ultraviolet absorbing layer is attached to a stainless steel plate and irradiated with ultraviolet rays of 460 mJ / cm 2 is preferably 0.01 N / 20 mm to 2 N / 20 mm. More preferably, it is 0.02N / 20mm to 1N / 20mm. Within such a range, it is possible to form an ultraviolet absorbing layer that can be peeled off with little adhesive residue. For the above ultraviolet irradiation, for example, using an ultraviolet irradiation device (manufactured by Nitto Seiki Co., Ltd., trade name "UM-810"), ultraviolet rays of a high-pressure mercury lamp (characteristic wavelength: 365 nm, integrated light amount: 460 mJ / cm 2 , irradiation energy: 70 W. It is performed by irradiating the ultraviolet absorbing layer with / cm 2 , irradiation time: 6.6 seconds).
　紫外線吸収層の厚みは、好ましくは５０μｍ以下である。このような範囲であれば、剥離の際のレーザー出力をより低くすることが可能となる。紫外線吸収層の厚みは、４０μｍ以下であることがより好ましく、３０μｍ以下であることがさらに好ましく、１μｍ～３０μｍであることより好ましい。このような範囲であれば、上記効果が顕著となる。 The thickness of the ultraviolet absorbing layer is preferably 50 μm or less. Within such a range, it is possible to lower the laser output at the time of peeling. The thickness of the ultraviolet absorbing layer is more preferably 40 μm or less, further preferably 30 μm or less, and more preferably 1 μm to 30 μm. Within such a range, the above effect becomes remarkable.
・紫外線吸収剤：
　紫外線吸収剤としては、紫外線（例えば、波長３５５ｎｍ）を吸収する化合物であれば、任意の適切な紫外線吸収剤が用いられ得る。紫外線吸収剤としては、例えば、ベンゾトリアゾール系紫外線吸収剤、ベンゾフェノン系紫外線吸収剤、トリアジン系紫外線吸収剤、サリチレート系紫外線吸収剤、シアノアクリレート系紫外線吸収剤等が挙げられる。なかでも好ましくは、トリアジン系紫外線吸収剤またはベンゾトリアゾール系紫外線吸収剤であり、特に好ましくはトリアジン系紫外線吸収剤である。特に、粘着剤Ａとしてアクリル系粘着剤を用いる場合に、当該アクリル系粘着剤のベースポリマーとの相溶性が高いことから、トリアジン系紫外線吸収剤は好ましく用いられ得る。トリアジン系紫外線吸収剤は、水酸基を有する化合物から構成されていることがより好ましく、ヒドロキシフェニルトリアジン系化合物から構成された紫外線吸収剤（ヒドロキシフェニルトリアジン系紫外線吸収剤）であることが特に好ましい。 ・ UV absorber:
As the ultraviolet absorber, any suitable ultraviolet absorber can be used as long as it is a compound that absorbs ultraviolet rays (for example, a wavelength of 355 nm). Examples of the ultraviolet absorber include a benzotriazole-based ultraviolet absorber, a benzophenone-based ultraviolet absorber, a triazine-based ultraviolet absorber, a salicylate-based ultraviolet absorber, a cyanoacrylate-based ultraviolet absorber, and the like. Of these, a triazine-based ultraviolet absorber or a benzotriazole-based ultraviolet absorber is preferable, and a triazine-based ultraviolet absorber is particularly preferable. In particular, when an acrylic pressure-sensitive adhesive is used as the pressure-sensitive adhesive A, a triazine-based ultraviolet absorber can be preferably used because the acrylic pressure-sensitive adhesive has high compatibility with the base polymer. The triazine-based ultraviolet absorber is more preferably composed of a compound having a hydroxyl group, and particularly preferably an ultraviolet absorber composed of a hydroxyphenyltriazine-based compound (hydroxyphenyltriazine-based ultraviolet absorber).
　ヒドロキシフェニルトリアジン系紫外線吸収剤としては、例えば、２－（４，６－ビス（２，４－ジメチルフェニル）－１，３，５－トリアジン－２－イル）－５－ヒドロキシフェニルと［（Ｃ１０－Ｃ１６（主としてＣ１２－Ｃ１３）アルキルオキシ）メチル］オキシランとの反応生成物（商品名「ＴＩＮＵＶＩＮ　４００」、ＢＡＳＦ社製）、２－［４，６－ビス（２，４－ジメチルフェニル）－１，３，５－トリアジン－２－イル］－５－［３－（ドデシルオキシ）－２－ヒドロキシプロポキシ］フェノール）、２－（２，４－ジヒドロキシフェニル）－４，６－ビス－（２，４－ジメチルフェニル）－１，３，５－トリアジンと（２－エチルヘキシル）－グリシド酸エステルの反応生成物（商品名「ＴＩＮＵＶＩＮ　４０５」、ＢＡＳＦ社製）、２，４－ビス（２－ヒドロキシ－４－ブトキシフェニル）－６－（２，４－ジブトキシフェニル）－１，３，５－トリアジン（商品名「ＴＩＮＵＶＩＮ　４６０」、ＢＡＳＦ社製）、２－（４，６－ジフェニル－１，３，５－トリアジン－２－イル）－５－［（ヘキシル）オキシ］－フェノール（商品名「ＴＩＮＵＶＩＮ　１５７７」、ＢＡＳＦ社製）、２－（４，６－ジフェニル－１，３，５－トリアジン－２－イル）－５－［２－（２－エチルヘキサノイルオキシ）エトキシ］－フェノール（商品名「アデカスタブ　ＬＡ－４６」、（株）ＡＤＥＫＡ製）、２－（２－ヒドロキシ－４－［１－オクチルオキシカルボニルエトキシ］フェニル）－４，６－ビス（４－フェニルフェニル）－１，３，５－トリアジン（商品名「ＴＩＮＵＶＩＮ　４７９」、ＢＡＳＦ社製）、ＢＡＳＦ社製の商品名「ＴＩＮＵＶＩＮ　４７７」などが挙げられる。 Examples of the hydroxyphenyltriazine-based ultraviolet absorber include 2- (4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine-2-yl) -5-hydroxyphenyl and [(C10). -C16 (mainly C12-C13) alkyloxy) methyl] Reaction product with oxylane (trade name "TINUVIN 400", manufactured by BASF), 2- [4,6-bis (2,4-dimethylphenyl) -1 , 3,5-Triazine-2-yl] -5- [3- (dodecyloxy) -2-hydroxypropoxy] phenol), 2- (2,4-dihydroxyphenyl) -4,6-bis- (2, Reaction product of 4-dimethylphenyl) -1,3,5-triazine and (2-ethylhexyl) -glycidate (trade name "TINUVIN 405", manufactured by BASF), 2,4-bis (2-hydroxy- 4-Butoxyphenyl) -6- (2,4-dibutoxyphenyl) -1,3,5-triazine (trade name "TINUVIN 460", manufactured by BASF), 2- (4,6-diphenyl-1,3) , 5-Triazine-2-yl) -5-[(hexyl) oxy] -phenol (trade name "TINUVIN 1577", manufactured by BASF), 2- (4,6-diphenyl-1,3,5-triazine- 2-Il) -5- [2- (2-ethylhexanoyloxy) ethoxy] -phenol (trade name "Adecastab LA-46", manufactured by ADEKA Co., Ltd.), 2- (2-hydroxy-4- [1 -Octyloxycarbonylethoxy] phenyl) -4,6-bis (4-phenylphenyl) -1,3,5-triazine (trade name "TINUVIN 479", manufactured by BASF), trade name "TINUVIN 477" manufactured by BASF "And so on.
　ベンゾトリアゾール系紫外線吸収剤（ベンゾトリアゾール系化合物）としては、例えば、２－（２－ヒドロキシ－５－ｔｅｒｔ－ブチルフェニル）－２Ｈ－ベンゾトリアゾール（商品名「ＴＩＮＵＶＩＮ　ＰＳ」、ＢＡＳＦ社製）、ベンゼンプロパン酸および３－（２Ｈ－ベンゾトリアゾール－２－イル）－５－（１，１－ジメチルエチル）－４－ヒドロキシ（Ｃ７－９側鎖および直鎖アルキル）のエステル化合物（商品名「ＴＩＮＵＶＩＮ　３８４－２」、ＢＡＳＦ社製）、オクチル３－［３－ｔｅｒｔ－ブチル－４－ヒドロキシ－５－（５－クロロ－２Ｈ－ベンゾトリアゾール－２－イル）フェニル］プロピオネートおよび２－エチルヘキシル－３－［３－ｔｅｒｔ－ブチル－４－ヒドロキシ－５－（５－クロロ－２Ｈ－ベンゾトリアゾール－２イル）フェニル］プロピオネートの混合物（商品名「ＴＩＮＵＶＩＮ　１０９」、ＢＡＳＦ社製）、２－（２Ｈ－ベンゾトリアゾール－２－イル）－４，６－ビス（１－メチル－１－フェニルエチル）フェノール（商品名「ＴＩＮＵＶＩＮ　９００」、ＢＡＳＦ社製）、２－（２Ｈ－ベンゾトリアゾール－２－イル）－６－（１－メチル－１－フェニルエチル）－４－（１，１，３，３－テトラメチルブチル）フェノール（商品名「ＴＩＮＵＶＩＮ　９２８」、ＢＡＳＦ製）、メチル３－（３－（２Ｈ－ベンゾトリアゾール－２－イル）－５－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオネート／ポリエチレングリコール３００の反応生成物（商品名「ＴＩＮＵＶＩＮ　１１３０」、ＢＡＳＦ社製）、２－（２Ｈ－ベンゾトリアゾール－２－イル）－ｐ－クレゾール（商品名「ＴＩＮＵＶＩＮ　Ｐ」、ＢＡＳＦ社製）、２－（２Ｈ－ベンゾトリアゾール－２－イル）－４，６－ビス（１－メチル－１－フェニルエチル）フェノール（商品名「ＴＩＮＵＶＩＮ　２３４」、ＢＡＳＦ社製）、２－［５－クロロ－２Ｈ－ベンゾトリアゾール－２－イル］－４－メチル－６－（ｔｅｒｔ－ブチル）フェノール（商品名「ＴＩＮＵＶＩＮ　３２６」、ＢＡＳＦ社製）、２－（２Ｈ－ベンゾトリアゾール－２－イル）－４，６－ジ－ｔｅｒｔ－ペンチルフェノール（商品名「ＴＩＮＵＶＩＮ　３２８」、ＢＡＳＦ社製）、２－（２Ｈ－ベンゾトリアゾール－２－イル）－４－（１，１，３，３－テトラメチルブチル）フェノール（商品名「ＴＩＮＵＶＩＮ　３２９」、ＢＡＳＦ社製）、２，２’－メチレンビス［６－（２Ｈ－ベンゾトリアゾール－２－イル）－４－（１，１，３，３－テトラメチルブチル）フェノール］（商品名「ＴＩＮＵＶＩＮ　３６０」、ＢＡＳＦ社製）、メチル３－（３－（２Ｈ－ベンゾトリアゾール－２－イル）－５－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオネートとポリエチレングリコール３００との反応生成物（商品名「ＴＩＮＵＶＩＮ　２１３」、ＢＡＳＦ社製）、２－（２Ｈ－ベンゾトリアゾール－２－イル）－６－ドデシル－４－メチルフェノール（商品名「ＴＩＮＵＶＩＮ　５７１」、ＢＡＳＦ社製）、２－［２－ヒドロキシ－３－（３，４，５，６－テトラヒドロフタルイミド－メチル）－５－メチルフェニル］ベンゾトリアゾール（商品名「Ｓｕｍｉｓｏｒｂ　２５０」、住友化学（株）製）、２－（３－ｔｅｒｔ－ブチル－２－ヒドロキシ－５－メチルフェニル）－５－クロロ－２Ｈ－ベンゾトリアゾール（商品名「ＳＥＥＳＯＲＢ　７０３」、シプロ化成社製）、２－（２Ｈ－ベンゾトリアゾール－２－イル）－４－メチル－６－（３，４，５，６－テトラヒドロフタルイミジルメチル）フェノール（商品名「ＳＥＥＳＯＲＢ　７０６」、シプロ化成社製）、２－（４－ベンゾイルオキシ－２－ヒドロキシフェニル）－５－クロロ－２Ｈ－ベンゾトリアゾール（シプロ化成社製の商品名「ＳＥＥＳＯＲＢ　７０１２ＢＡ」）、２－ｔｅｒｔ－ブチル－６－（５－クロロ－２Ｈ－ベンゾトリアゾール－２－イル）－４－メチルフェノール（商品名「ＫＥＭＩＳＯＲＢ　７３」、ケミプロ化成社製）、２，２’－メチレンビス［６－（２Ｈ－ベンゾトリアゾール－２－イル）－４－ｔｅｒｔ－オクチルフェノール］（商品名「アデカスタブ　ＬＡ－３１」、（株）ＡＤＥＫＡ製）、２－（２Ｈ－ベンゾトリアゾール－２－イル）－ｐ－セルロース（商品名「アデカスタブ　ＬＡ－３２」、（株）ＡＤＥＫＡ製）、２－（５－クロロ－２Ｈ－ベンゾトリアゾール－２－イル）－６－ｔｅｒｔ－ブチル－４－メチルフェノール（商品名「アデカスタブ　ＬＡ－３６」、（株）ＡＤＥＫＡ製）などが挙げられる。 Examples of the benzotriazole-based ultraviolet absorber (benzotriazole-based compound) include 2- (2-hydroxy-5-tert-butylphenyl) -2H-benzotriazole (trade name "TINUVIN PS", manufactured by BASF) and benzene. Ester compounds of propanoic acid and 3- (2H-benzotriazole-2-yl) -5- (1,1-dimethylethyl) -4-hydroxy (C7-9 side chain and linear alkyl) (trade name "TINUVIN 384") -2 ", manufactured by BASF), Octyl 3- [3-tert-butyl-4-hydroxy-5- (5-chloro-2H-benzotriazole-2-yl) phenyl] propionate and 2-ethylhexyl-3- [ 3-tert-Butyl-4-hydroxy-5- (5-chloro-2H-benzotriazole-2yl) phenyl] propionate mixture (trade name "TINUVIN 109", manufactured by BASF), 2- (2H-benzotriazole) -2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol (trade name "TINUVIN 900", manufactured by BASF), 2- (2H-benzotriazole-2-yl) -6- (1-Methyl-1-phenylethyl) -4- (1,1,3,3-tetramethylbutyl) phenol (trade name "TINUVIN 928", manufactured by BASF), methyl 3- (3- (2H-benzotriazole) -2-Il) -5-tert-Butyl-4-hydroxyphenyl) propionate / polyethylene glycol 300 reaction product (trade name "TINUVIN 1130", manufactured by BASF), 2- (2H-benzotriazole-2-yl) ) -P-Cresol (trade name "TINUVIN P", manufactured by BASF), 2- (2H-benzotriazole-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol (trade name) "TINUVIN 234", manufactured by BASF), 2- [5-chloro-2H-benzotriazole-2-yl] -4-methyl-6- (tert-butyl) phenol (trade name "TINUVIN 326", manufactured by BASF) ), 2- (2H-benzotriazole-2-yl) -4,6-di-tert-pentylphenol (trade name "TINUVIN 328", manufactured by BASF), 2- (2H-benzotriazole-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol (trade name "TINUVIN 329", BA (Manufactured by SF), 2,2'-methylenebis [6- (2H-benzotriazole-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol] (trade name "TINUVIN 360", A reaction product of methyl 3- (3- (2H-benzotriazole-2-yl) -5-tert-butyl-4-hydroxyphenyl) propionate and polyethylene glycol 300 (trade name "TINUVIN 213") manufactured by BASF. , BASF), 2- (2H-benzotriazole-2-yl) -6-dodecyl-4-methylphenol (trade name "TINUVIN 571", BASF), 2- [2-hydroxy-3-( 3,4,5,6-Tetrahydrophthalimide-methyl) -5-methylphenyl] Benzotriazole (trade name "Sumisorb 250", manufactured by Sumitomo Chemical Co., Ltd.), 2- (3-tert-butyl-2-hydroxy- 5-Methylphenyl) -5-Chloro-2H-benzotriazole (trade name "SEESORB 703", manufactured by Cipro Kasei Co., Ltd.), 2- (2H-benzotriazole-2-yl) -4-methyl-6- (3, 4,5,6-Tetrahydrophthalimidylmethyl) phenol (trade name "SEESORB 706", manufactured by Cipro Chemical Co., Ltd.), 2- (4-benzoyloxy-2-hydroxyphenyl) -5-chloro-2H-benzotriazole (4,5,6-tetrahydrophthalimidylmethyl) Cipro Kasei Co., Ltd. trade name "SEESORB 7012BA"), 2-tert-butyl-6- (5-chloro-2H-benzotriazole-2-yl) -4-methylphenol (trade name "KEMISORB 73", Chemipro Kasei , 2,2'-Methylenebis [6- (2H-benzotriazole-2-yl) -4-tert-octylphenol] (trade name "Adecastab LA-31", manufactured by ADEKA Co., Ltd.), 2- ( 2H-benzotriazole-2-yl) -p-cellulose (trade name "Adecastab LA-32", manufactured by ADEKA Co., Ltd.), 2- (5-chloro-2H-benzotriazole-2-yl) -6-tert -Butyl-4-methylphenol (trade name "Adecastab LA-36", manufactured by ADEKA Co., Ltd.) and the like can be mentioned.
　上記紫外線吸収剤は、染料または顔料であってもよい。顔料としては、例えば、アゾ系、フタロシアニン系、アントラキノン系、レーキ系、ペリレン系、ペリノン系、キナクリドン系、チオインジゴ系、ジオキサンジン系、イソインドリノン系、キノフタロン系等の顔料が挙げられる。染料としては、アゾ系、フタロシアニン系、アントラキノン系、カルボニル系、インジゴ系、キノンイミン系、メチン系、キノリン系、ニトロ系等の染料が挙げられる。 The ultraviolet absorber may be a dye or a pigment. Examples of the pigment include azo-based, phthalocyanine-based, anthraquinone-based, rake-based, perylene-based, perinone-based, quinacridone-based, thioindigo-based, dioxandine-based, isoindoleinone-based, and quinophthalone-based pigments. Examples of the dye include azo dyes, phthalocyanine dyes, anthraquinone dyes, carbonyl dyes, indigo dyes, quinone imine dyes, methine dyes, quinoline dyes, and nitro dyes.
　上記紫外線吸収剤を構成する化合物の分子量は、好ましくは１００～１５００であり、より好ましくは２００～１２００であり、さらに好ましくは２００～１０００である。このような範囲であれば、レーザー光照射により、より良好な変形部を形成し得る紫外線吸収層を形成することができる。 The molecular weight of the compound constituting the ultraviolet absorber is preferably 100 to 1500, more preferably 200 to 1200, and further preferably 200 to 1000. Within such a range, an ultraviolet absorbing layer capable of forming a better deformed portion can be formed by laser light irradiation.
　上記紫外線吸収剤の最大吸収波長は、好ましくは３００ｎｍ～４５０ｎｍであり、より好ましくは３２０ｎｍ～４００ｎｍであり、さらに好ましくは３３０ｎｍ～３８０ｎｍである。紫外線吸収剤の最大吸収波長と上記光重合開始剤の最大吸収波長との差は、好ましく１０ｎｍ以上であり、より好ましくは２５ｎｍ以上である。 The maximum absorption wavelength of the ultraviolet absorber is preferably 300 nm to 450 nm, more preferably 320 nm to 400 nm, and further preferably 330 nm to 380 nm. The difference between the maximum absorption wavelength of the ultraviolet absorber and the maximum absorption wavelength of the photopolymerization initiator is preferably 10 nm or more, more preferably 25 nm or more.
　上記紫外線吸収剤の５％重量減少温度は、好ましくは３５０℃以下であり、より好ましくは３３０℃以下である。紫外線吸収剤の５％重量減少温度の下限は、例えば、１００℃である。このような範囲であれば、レーザー光照射により、より良好な変形部を形成し得る紫外線吸収層を形成することができる。紫外線吸収剤の５％重量減少温度とは、紫外線吸収剤を昇温させた際の当該紫外線吸収剤の重量が、昇温前の重量に対して、５重量％減少した時点での温度を意味する。５％重量減少温度は、示差熱分析装置を用いて、昇温温度１０℃／分、空気雰囲気下、流量２５ｍｌ／分の測定条件で測定される。 The 5% weight loss temperature of the ultraviolet absorber is preferably 350 ° C. or lower, more preferably 330 ° C. or lower. The lower limit of the 5% weight loss temperature of the UV absorber is, for example, 100 ° C. Within such a range, an ultraviolet absorbing layer capable of forming a better deformed portion can be formed by laser light irradiation. The 5% weight loss temperature of the UV absorber means the temperature at the time when the weight of the UV absorber when the temperature of the UV absorber is raised is reduced by 5% by weight with respect to the weight before the temperature rise. do. The 5% weight loss temperature is measured using a differential thermal analyzer under the measurement conditions of a temperature rise temperature of 10 ° C./min, an air atmosphere, and a flow rate of 25 ml / min.
　上記紫外線吸収剤の含有割合は、紫外線吸収層中のベースポリマー１００重量部に対して、好ましくは１重量部～５０重量部であり、より好ましくは５重量部～２０重量部である。このような範囲であれば、活性エネルギー線の照射により紫外線吸収層全体の粘着力を良好に低下させる際に、紫外線吸収層の硬化が良好に進み、かつ、レーザー光照射により、良好な剥離性を示す紫外線吸収層を形成することができる。 The content ratio of the ultraviolet absorber is preferably 1 part by weight to 50 parts by weight, and more preferably 5 parts by weight to 20 parts by weight with respect to 100 parts by weight of the base polymer in the ultraviolet absorbing layer. Within such a range, when the adhesive strength of the entire ultraviolet absorbing layer is satisfactorily lowered by irradiation with active energy rays, the curing of the ultraviolet absorbing layer proceeds satisfactorily, and good peeling property is obtained by laser light irradiation. It is possible to form an ultraviolet absorbing layer showing the above.
・活性エネルギー線硬化型粘着剤：
　１つの実施形態においては、活性エネルギー線硬化型粘着剤として、母剤となるベースポリマーと、該ベースポリマーと結合可能な活性エネルギー線反応性化合物（モノマーまたはオリゴマー）とを含む活性エネルギー線硬化型粘着剤（Ａ１）が用いられる。別の実施形態においては、ベースポリマーとして活性エネルギー線反応性ポリマーを含む活性エネルギー線硬化型粘着剤（Ａ２）が用いられる。好ましくは、上記ベースポリマーは、光重合開始剤と反応し得る官能基を有する。該官能基としては、例えば、ヒドロキシル基、カルボキシル基等が挙げられる。 ・ Active energy ray-curable adhesive:
In one embodiment, as an active energy ray-curable pressure-sensitive adhesive, an active energy ray-curable type containing a base polymer as a base material and an active energy ray-reactive compound (monomer or oligomer) capable of binding to the base polymer. The pressure-sensitive adhesive (A1) is used. In another embodiment, an active energy ray-curable pressure-sensitive adhesive (A2) containing an active energy ray-reactive polymer is used as a base polymer. Preferably, the base polymer has a functional group capable of reacting with the photopolymerization initiator. Examples of the functional group include a hydroxyl group and a carboxyl group.
　上記粘着剤（Ａ１）において用いられるベースポリマーとしては、例えば、天然ゴム、ポリイソブチレンゴム、スチレン・ブタジエンゴム、スチレン・イソプレン・スチレンブロック共重合体ゴム、再生ゴム、ブチルゴム、ポリイソブチレンゴム、ニトリルゴム（ＮＢＲ）等のゴム系ポリマー；シリコーン系ポリマー；アクリル系ポリマー等が挙げられる。これらのポリマーは、単独で、または２種以上組み合わせて用いてもよい。なかでも好ましくは、アクリル系ポリマーである。 Examples of the base polymer used in the pressure-sensitive adhesive (A1) include natural rubber, polyisobutylene rubber, styrene / butadiene rubber, styrene / isoprene / styrene block copolymer rubber, recycled rubber, butyl rubber, polyisobutylene rubber, and nitrile rubber. Examples include rubber-based polymers such as (NBR); silicone-based polymers; acrylic-based polymers. These polymers may be used alone or in combination of two or more. Of these, an acrylic polymer is preferable.
　アクリル系ポリマーとしては、（メタ）アクリル酸アルキルエステル、（メタ）アクリル酸シクロアルキルエステル、（メタ）アクリル酸アリールエステルなどの炭化水素基含有（メタ）アクリル酸エステルの単重合体または共重合体；該炭化水素基含有（メタ）アクリル酸エステルと他の共重合性モノマーとの共重合体等が挙げられる。（メタ）アクリル酸アルキルエステルとしては、例えば、（メタ）アクリル酸のメチルエステル、エチルエステル、プロピルエステル、イソプロピルエステル、ブチルエステル、イソブチルエステル、ｓ－ブチルエステル、ｔ－ブチルエステル、ペンチルエステル、イソペンチルエステル、ヘキシルエステル、ヘプチルエステル、オクチルエステル、２－エチルヘキシルエステル、イソオクチルエステル、ノニルエステル、デシルエステル、イソデシルエステル、ウンデシルエステル、ドデシルエステルすなわちラウリルエステル、トリデシルエステル、テトラデシルエステル、ヘキサデシルエステル、オクタデシルエステル、およびエイコシルエステルが挙げられる。（メタ）アクリル酸シクロアルキルエステルとしては、例えば、（メタ）アクリル酸のシクロペンチルエステルおよびシクロヘキシルエステルが挙げられる。（メタ）アクリル酸アリールエステルとしては、例えば、（メタ）アクリル酸フェニルおよび（メタ）アクリル酸ベンジルが挙げられる。上記炭化水素基含有（メタ）アクリル酸エステル由来の構成単位の含有割合は、ベースポリマー１００重量部に対して、好ましくは４０重量部以上であり、より好ましくは６０重量部以上である。 Examples of the acrylic polymer include a hydrocarbon group-containing (meth) acrylic acid ester homopolymer or copolymer such as (meth) acrylic acid alkyl ester, (meth) acrylic acid cycloalkyl ester, and (meth) acrylic acid aryl ester. Examples thereof include a copolymer of the hydrocarbon group-containing (meth) acrylic acid ester and another copolymerizable monomer. Examples of the (meth) acrylic acid alkyl ester include methyl ester, ethyl ester, propyl ester, isopropyl ester, butyl ester, isobutyl ester, s-butyl ester, t-butyl ester, pentyl ester and iso of (meth) acrylic acid. Pentyl ester, hexyl ester, heptyl ester, octyl ester, 2-ethylhexyl ester, isooctyl ester, nonyl ester, decyl ester, isodecyl ester, undecyl ester, dodecyl ester, that is, lauryl ester, tridecyl ester, tetradecyl ester, hexa. Examples include decyl esters, octadecyl esters, and eicosyl esters. Examples of the (meth) acrylic acid cycloalkyl ester include cyclopentyl ester and cyclohexyl ester of (meth) acrylic acid. Examples of the (meth) acrylic acid aryl ester include phenyl (meth) acrylic acid and benzyl (meth) acrylic acid. The content ratio of the constituent unit derived from the hydrocarbon group-containing (meth) acrylic acid ester is preferably 40 parts by weight or more, and more preferably 60 parts by weight or more with respect to 100 parts by weight of the base polymer.
　上記他の共重合性モノマーとしては、例えば、カルボキシ基含有モノマー、酸無水物モノマー、ヒドロキシ基含有モノマー、グリシジル基含有モノマー、スルホン酸基含有モノマー、リン酸基含有モノマー、アクリルアミド、およびアクリロニトリルなどの官能基含有モノマー等が挙げられる。カルボキシ基含有モノマーとしては、例えば、アクリル酸、メタクリル酸、カルボキシエチル（メタ）アクリレート、カルボキシペンチル（メタ）アクリレート、イタコン酸、マレイン酸、フマル酸、およびクロトン酸が挙げられる。酸無水物モノマーとしては、例えば、無水マレイン酸および無水イタコン酸が挙げられる。ヒドロキシ基含有モノマーとしては、例えば、（メタ）アクリル酸２－ヒドロキシエチル、（メタ）アクリル酸２－ヒドロキシプロピル、（メタ）アクリル酸４－ヒドロキシブチル、（メタ）アクリル酸６－ヒドロキシヘキシル、（メタ）アクリル酸８－ヒドロキシオクチル、（メタ）アクリル酸１０－ヒドロキシデシル、（メタ）アクリル酸１２－ヒドロキシラウリル、および（４－ヒドロキシメチルシクロヘキシル）メチル（メタ）アクリレートが挙げられる。グリシジル基含有モノマーとしては、例えば、（メタ）アクリル酸グリシジルおよび（メタ）アクリル酸メチルグリシジルが挙げられる。スルホン酸基含有モノマーとしては、例えば、スチレンスルホン酸、アリルスルホン酸、２－（メタ）アクリルアミド－２－メチルプロパンスルホン酸、（メタ）アクリルアミドプロパンスルホン酸、スルホプロピル（メタ）アクリレート、および（メタ）アクリロイルオキシナフタレンスルホン酸が挙げられる。リン酸基含有モノマーとしては、例えば、２－ヒドロキシエチルアクリロイルホスフェートが挙げられる。アクリルアミドとしては、例えばＮ－アクリロイルモルホリンが挙げられる。これらは、１種を単独で用いてもよいし、２種以上を組み合わせて用いてもよい。上記共重合性モノマー由来の構成単位の含有割合は、ベースポリマー１００重量部に対して、好ましくは６０重量部以下であり、より好ましくは４０重量部以下である。 Examples of the other copolymerizable monomers include carboxy group-containing monomers, acid anhydride monomers, hydroxy group-containing monomers, glycidyl group-containing monomers, sulfonic acid group-containing monomers, phosphate group-containing monomers, acrylamide, and acrylonitrile. Examples include functional group-containing monomers. Examples of the carboxy group-containing monomer include acrylic acid, methacrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, itaconic acid, maleic acid, fumaric acid, and crotonic acid. Examples of the acid anhydride monomer include maleic anhydride and itaconic anhydride. Examples of the hydroxy group-containing monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 6-hydroxyhexyl (meth) acrylate. Examples include 8-hydroxyoctyl acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate, and (4-hydroxymethylcyclohexyl) methyl (meth) acrylate. Examples of the glycidyl group-containing monomer include glycidyl (meth) acrylate and methyl glycidyl (meth) acrylate. Examples of the sulfonic acid group-containing monomer include styrene sulfonic acid, allyl sulfonic acid, 2- (meth) acrylamide-2-methyl propane sulfonic acid, (meth) acrylamide propane sulfonic acid, sulfopropyl (meth) acrylate, and (meth). ) Acryloyloxynaphthalene sulfonic acid can be mentioned. Examples of the phosphoric acid group-containing monomer include 2-hydroxyethylacryloyl phosphate. Examples of acrylamide include N-acryloyl morpholine. These may be used individually by 1 type, or may be used in combination of 2 or more type. The content ratio of the structural unit derived from the copolymerizable monomer is preferably 60 parts by weight or less, and more preferably 40 parts by weight or less with respect to 100 parts by weight of the base polymer.
　アクリル系ポリマーは、そのポリマー骨格中に架橋構造を形成するために、多官能性モノマー由来の構成単位を含み得る。多官能性モノマーとして、例えば、ヘキサンジオールジ（メタ）アクリレート、（ポリ）エチレングリコールジ（メタ）アクリレート、（ポリ）プロピレングリコールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、ペンタエリスリトールジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、エポキシ（メタ）アクリレート（すなわち、ポリグリシジル（メタ）アクリレート）、ポリエステル（メタ）アクリレート、およびウレタン（メタ）アクリレートが挙げられる。これらは、１種を単独で用いてもよいし、２種以上を組み合わせて用いてもよい。上記多官能性モノマー由来の構成単位の含有割合は、ベースポリマー１００重量部に対して、好ましくは４０重量部以下であり、より好ましくは３０重量部以下である。 Acrylic polymers may contain structural units derived from polyfunctional monomers in order to form crosslinked structures in the polymer skeleton. Examples of the polyfunctional monomer include hexanediol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and pentaerythritol di. (Meta) Acrylate, Trimethylol Propanetri (Meta) Acrylate, Pentaerythritol Tri (Meta) Acrylate, Dipentaerythritol Hexa (Meta) Acrylate, Epoxy (Meta) Acrylate (ie, Polyglycidyl (Meta) Acrylate), Polyester (Meta) ) Acrylate and urethane (meth) acrylate can be mentioned. These may be used individually by 1 type, or may be used in combination of 2 or more type. The content ratio of the structural unit derived from the polyfunctional monomer is preferably 40 parts by weight or less, more preferably 30 parts by weight or less, based on 100 parts by weight of the base polymer.
　上記アクリル系ポリマーの重量平均分子量は、好ましくは１０万～３００万であり、より好ましくは２０万～２００万である。重量平均分子量は、ＧＰＣ（溶媒：ＴＨＦ）により測定され得る。 The weight average molecular weight of the acrylic polymer is preferably 100,000 to 3 million, more preferably 200,000 to 2 million. The weight average molecular weight can be measured by GPC (solvent: THF).
　上記粘着剤（Ａ１）に用いられ得る上記活性エネルギー線反応性化合物としては、例えば、アクリロイル基、メタクリロイル基、ビニル基、アリル基、アセチレン基等の重合性炭素－炭素多重結合を有する官能基を有する光反応性のモノマーまたはオリゴマーが挙げられる。該光反応性のモノマーの具体例としては、トリメチロールプロパントリ（メタ）アクリレート、テトラメチロールメタンテトラ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールモノヒドロキシペンタ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、１，４－ブタンジオールジ（メタ）アクリレート、１，６－ヘキサンジオールジ（メタ）アクリレート、ポリエチレングリコールジ（メタ）アクリレート等の（メタ）アクリル酸と多価アルコールとのエステル化物；多官能ウレタン（メタ）アクリレート；エポキシ（メタ）アクリレート；オリゴエステル（メタ）アクリレート等が挙げられる。また、メタクリロイソシアネート、２－メタクリロイルオキシエチルイソシアネート（２－イソシアナトエチルメタクリレート）、ｍ－イソプロペニル－α，α－ジメチルベンジルイソシアネート等のモノマーを用いてもよい。光反応性のオリゴマーの具体例としては、上記モノマーの２～５量体等が挙げられる。光反応性のオリゴマーの分子量は、好ましくは１００～３０００である。 Examples of the active energy ray-reactive compound that can be used in the pressure-sensitive adhesive (A1) include functional groups having a polymerizable carbon-carbon multiple bond such as an acryloyl group, a methacryloyl group, a vinyl group, an allyl group, and an acetylene group. Examples thereof include photoreactive monomers or oligomers having. Specific examples of the photoreactive monomer include trimethylol propanetri (meth) acrylate, tetramethylol methanetetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and dipentaerythritol mono. (Hydroxypenta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, polyethylene glycol di (meth) acrylate, etc. Examples thereof include esterified products of meth) acrylic acid and polyhydric alcohol; polyfunctional urethane (meth) acrylate; epoxy (meth) acrylate; oligoester (meth) acrylate and the like. Further, monomers such as methacryloisocyanate, 2-methacryloyloxyethyl isocyanate (2-isocyanatoethyl methacrylate), m-isopropenyl-α, and α-dimethylbenzylisocyanate may be used. Specific examples of the photoreactive oligomer include 2 to pentamers of the above-mentioned monomers. The molecular weight of the photoreactive oligomer is preferably 100 to 3000.
　また、上記活性エネルギー線反応性化合物として、エポキシ化ブタジエン、グリシジルメタクリレート、アクリルアミド、ビニルシロキサン等のモノマー；または該モノマーから構成されるオリゴマーを用いてもよい。 Further, as the active energy ray-reactive compound, a monomer such as epoxidized butadiene, glycidyl methacrylate, acrylamide, vinyl siloxane; or an oligomer composed of the monomer may be used.
　さらに、上記活性エネルギー線反応性化合物として、オニウム塩等の有機塩類と、分子内に複数の複素環を有する化合物との混合物を用いてもよい。該混合物は、活性エネルギー線（例えば、紫外線、電子線）の照射により有機塩が開裂してイオンを生成し、これが開始種となって複素環の開環反応を引き起こして３次元網目構造を形成し得る。上記有機塩類としては、例えば、ヨードニウム塩、フォスフォニウム塩、アンチモニウム塩、スルホニウム塩、ボレート塩等が挙げられる。上記分子内に複数の複素環を有する化合物における複素環としては、オキシラン、オキセタン、オキソラン、チイラン、アジリジン等が挙げられる。 Further, as the active energy ray-reactive compound, a mixture of an organic salt such as an onium salt and a compound having a plurality of heterocycles in the molecule may be used. In the mixture, the organic salt is cleaved by irradiation with active energy rays (for example, ultraviolet rays and electron beams) to generate ions, which act as a starting species to induce a ring-opening reaction of a heterocycle to form a three-dimensional network structure. Can be. Examples of the organic salts include iodonium salt, phosphonium salt, antimonium salt, sulfonium salt, borate salt and the like. Examples of the heterocycle in the compound having a plurality of heterocycles in the molecule include oxylan, oxetane, oxolane, thiirane, and aziridine.
　上記粘着剤（Ａ１）において、活性エネルギー線反応性化合物の含有割合は、ベースポリマー１００重量部に対して、好ましくは０．１重量部～５００重量部であり、より好ましくは５重量部～３００重量部であり、さらに好ましくは４０重量部～１５０重量部である。 In the pressure-sensitive adhesive (A1), the content ratio of the active energy ray-reactive compound is preferably 0.1 part by weight to 500 parts by weight, and more preferably 5 parts by weight to 300 parts by weight with respect to 100 parts by weight of the base polymer. It is a part by weight, more preferably 40 parts by weight to 150 parts by weight.
　上記粘着剤（Ａ２）に含まれる活性エネルギー線反応性ポリマー（ベースポリマー）としては、例えば、アクリロイル基、メタクリロイル基、ビニル基、アリル基、アセチレン基等の炭素－炭素多重結合を有する官能基を有するポリマーが挙げられる。活性エネルギー線反応性ポリマーの具体例としては、多官能（メタ）アクリレートから構成されるポリマー；光カチオン重合型ポリマー；ポリビニルシンナマート等のシンナモイル基含有ポリマー；ジアゾ化されたアミノノボラック樹脂；ポリアクリルアミド；等が挙げられる。 As the active energy ray-reactive polymer (base polymer) contained in the pressure-sensitive adhesive (A2), for example, a functional group having a carbon-carbon multiple bond such as an acryloyl group, a methacryloyl group, a vinyl group, an allyl group, or an acetylene group can be used. Examples include the polymer having. Specific examples of the active energy ray-reactive polymer include a polymer composed of a polyfunctional (meth) acrylate; a photocationically polymerized polymer; a cinnamoyl group-containing polymer such as polyvinyl cinnamate; a diazotized aminonovolac resin; polyacrylamide. ; Etc. can be mentioned.
　１つの実施形態においては、上記アクリル系ポリマーの側鎖、主鎖および／または主鎖末端に、活性エネルギー線重合性の炭素－炭素多重結合が導入されて構成された活性エネルギー線反応性ポリマーが用いられる。アクリル系ポリマーへの放射線重合性の炭素－炭素二重結合の導入手法としては、例えば、所定の官能基（第１の官能基）を有するモノマーを含む原料モノマーを共重合させてアクリル系ポリマーを得た後、第１の官能基との間で反応を生じて結合しうる所定の官能基（第２の官能基）と放射線重合性炭素－炭素二重結合とを有する化合物を、炭素－炭素二重結合の放射線重合性を維持したままアクリル系ポリマーに対して縮合反応または付加反応させる方法が、挙げられる。 In one embodiment, an active energy ray-reactive polymer configured by introducing an active energy ray-polymerizable carbon-carbon multiple bond into the side chain, main chain and / or main chain end of the acrylic polymer. Used. As a method for introducing a radiation-polymerizable carbon-carbon double bond into an acrylic polymer, for example, a raw material monomer containing a monomer having a predetermined functional group (first functional group) is copolymerized to obtain an acrylic polymer. After obtaining the compound, a compound having a predetermined functional group (second functional group) capable of reacting with the first functional group and having a radiopolymerizable carbon-carbon double bond can be obtained as carbon-carbon. Examples thereof include a method of subjecting an acrylic polymer to a condensation reaction or an addition reaction while maintaining the radiation polymerizable property of the double bond.
　第１の官能基と第２の官能基の組み合わせとしては、例えば、カルボキシ基とエポキシ基、エポキシ基とカルボキシ基、カルボキシ基とアジリジル基、アジリジル基とカルボキシ基、ヒドロキシ基とイソシアネート基、イソシアネート基とヒドロキシ基が挙げられる。これら組み合わせのうち、反応追跡の容易さの観点からは、ヒドロキシ基とイソシアネート基の組み合わせや、イソシアネート基とヒドロキシ基の組み合わせが、好ましい。また、反応性の高いイソシアネート基を有するポリマーを作製するのは技術的難易度が高いところ、アクリル系ポリマーの作製または入手のしやすさの観点からは、アクリル系ポリマー側の上記第１の官能基がヒドロキシ基であり且つ上記第２の官能基がイソシアネート基である場合が、より好ましい。この場合、放射線重合性炭素－炭素二重結合と第２の官能基たるイソシアネート基とを併有するイソシアネート化合物としては、例えば、メタクリロイルイソシアネート、２－メタクリロイルオキシエチルイソシアネート、およびｍ－イソプロペニル－α，α－ジメチルベンジルイソシアネートが挙げられる。また、第１の官能基を有するアクリル系ポリマーとしては、上記のヒドロキシ基含有モノマー由来の構成単位を含むものが好ましく、２－ヒドロキシエチルビニルエーテルや、４－ヒドロキシブチルビニルエーテル、ジエチレングルコールモノビニルエーテルなどのエーテル系化合物由来の構成単位を含むものも好ましい。 Examples of the combination of the first functional group and the second functional group include a carboxy group and an epoxy group, an epoxy group and a carboxy group, a carboxy group and an aziridyl group, an aziridyl group and a carboxy group, a hydroxy group and an isocyanate group, and an isocyanate group. And hydroxy groups. Of these combinations, a combination of a hydroxy group and an isocyanate group or a combination of an isocyanate group and a hydroxy group is preferable from the viewpoint of ease of reaction tracking. Further, it is technically difficult to prepare a polymer having a highly reactive isocyanate group, but from the viewpoint of easy preparation or availability of an acrylic polymer, the first functionality on the acrylic polymer side is described above. It is more preferable that the group is a hydroxy group and the second functional group is an isocyanate group. In this case, examples of the isocyanate compound having both a radiopolymerizable carbon-carbon double bond and an isocyanate group as a second functional group include methacryloyl isocyanate, 2-methacryloyloxyethyl isocyanate, and m-isopropenyl-α. Examples include α-dimethylbenzyl isocyanate. The acrylic polymer having the first functional group preferably contains the above-mentioned structural unit derived from the hydroxy group-containing monomer, such as 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, and diethylene glucol monovinyl ether. Those containing a structural unit derived from the ether-based compound of the above are also preferable.
　上記粘着剤（Ａ２）は、上記活性エネルギー線反応性化合物（モノマーまたはオリゴマー）をさらに含んでいてもよい。 The pressure-sensitive adhesive (A2) may further contain the active energy ray-reactive compound (monomer or oligomer).
　上記活性エネルギー線硬化型粘着剤は、光重合開始剤を含み得る。 The active energy ray-curable pressure-sensitive adhesive may contain a photopolymerization initiator.
　光重合開始剤としては、任意の適切な開始剤を用いることができる。光重合開始剤としては、例えば、４－（２－ヒドロキシエトキシ）フェニル（２－ヒドロキシ－２－プロピル）ケトン、α－ヒドロキシ－α，α’－ジメチルアセトフェノン、２－メチル－２－ヒドロキシプロピオフェノン、１－ヒドロキシシクロヘキシルフェニルケトン等のα－ケトール系化合物；メ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、２，２－ジエトキシアセトフェノン、２－メチル－１－［４－（メチルチオ）－フェニル］－２－モルホリノプロパン－１等のアセトフェノン系化合物；ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル、アニソインメチルエーテル等のベンゾインエーテル系化合物；ベンジルジメチルケタール等のケタール系化合物；２－ナフタレンスルホニルクロリド等の芳香族スルホニルクロリド系化合物；１－フェノン－１，１―プロパンジオン－２－（ｏ－エトキシカルボニル）オキシム等の光活性オキシム系化合物；ベンゾフェノン、ベンゾイル安息香酸、３，３’－ジメチル－４－メトキシベンゾフェノン等のベンゾフェノン系化合物；チオキサンソン、２－クロロチオキサンソン、２－メチルチオキサンソン、２，４－ジメチルチオキサンソン、イソプロピルチオキサンソン、２，４－ジクロロチオキサンソン、２，４－ジエチルチオキサンソン、２，４－ジイソプロピルチオキサンソン等のチオキサンソン系化合物；カンファーキノン；ハロゲン化ケトン；アシルホスフィノキシド；アシルホスフォナート等が挙げられる。光重合開始剤の使用量は、任意の適切な量に設定され得る。 Any suitable initiator can be used as the photopolymerization initiator. Examples of the photopolymerization initiator include 4- (2-hydroxyethoxy) phenyl (2-hydroxy-2-propyl) ketone, α-hydroxy-α, α'-dimethylacetophenone, and 2-methyl-2-hydroxypropio. Α-Ketol compounds such as phenone and 1-hydroxycyclohexylphenyl ketone; methoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 2-methyl-1- [4- (methylthio) -Phenyl] -2-Acetphenone compounds such as morpholinopropane-1, benzoin ether compounds such as benzoin ethyl ether, benzoin isopropyl ether and anisoin methyl ether; ketal compounds such as benzyl dimethyl ketal; 2-naphthalene sulfonyl chloride and the like. Aromatic sulfonyl chloride compounds; photoactive oxime compounds such as 1-phenone-1,1-propanedione-2- (o-ethoxycarbonyl) oxime; benzophenone, benzoylbenzoic acid, 3,3'-dimethyl-4 -Benzophenone compounds such as methoxybenzophenone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4 -Tioxane compounds such as diethylthioxanson and 2,4-diisopropylthioxanson; camphorquinone; halogenated ketone; acylphosphinoxide; acylphosphonate and the like can be mentioned. The amount of the photopolymerization initiator used can be set to any suitable amount.
　１つの実施形態においては、４００ｎｍ以下（好ましくは３８０ｎｍ以下、より好ましくは３４０ｎｍ以下）の範囲に最大吸収波長を有する光重合開始剤が用いられる。このような光重合開始剤を用いれば、活性エネルギー線を照射することにより紫外線吸収層全体の粘着力低下させる際、粘着剤の硬化反応が好ましく生じ、糊残りの特に少ない紫外線吸収層を形成することができる。 In one embodiment, a photopolymerization initiator having a maximum absorption wavelength in the range of 400 nm or less (preferably 380 nm or less, more preferably 340 nm or less) is used. When such a photopolymerization initiator is used, when the adhesive strength of the entire ultraviolet absorbing layer is lowered by irradiating with active energy rays, the curing reaction of the adhesive preferably occurs, and an ultraviolet absorbing layer having a particularly small amount of adhesive residue is formed. be able to.
　上記光重合開始剤として、市販品を用いてもよい。例えば、４００ｎｍ以下の範囲に最大吸収波長を有する光重合開始剤として、ＢＡＳＦ社製の商品名「イルガキュア１２７」、「イルガキュア３６９」、「イルガキュア３６９Ｅ」、「イルガキュア３７９」、「イルガキュア３７９ＥＧ」、「イルガキュア８１９」、「イルガキュアＴＯＰ」、「イルガキュア７８４」、「イルガキュアＯＸＥ０１」等が挙げられる。 A commercially available product may be used as the photopolymerization initiator. For example, as a photopolymerization initiator having a maximum absorption wavelength in the range of 400 nm or less, BASF's trade names "Irgacure 127", "Irgacure 369", "Irgacure 369E", "Irgacure 379", "Irgacure 379EG", "Irgacure 379EG" Examples thereof include "Irgacure 819", "Irgacure TOP", "Irgacure 784", and "Irgacure OXE01".
　１つの実施形態においては、上記活性エネルギー線硬化型粘着剤は、光増感剤を含み得る。 In one embodiment, the active energy ray-curable pressure-sensitive adhesive may contain a photosensitizer.
　１つの実施形態においては、上記光増感剤は、上記光重合開始剤と併用され得る。当該光増感剤は、自らが光を吸収して得たエネルギーを光重合開始剤に渡すことで、光重合開始剤からラジカルを発生させることができるため、光重合開始剤自身の吸収ピークが無い長波長側の光で重合を進行させることができる。このため、光増感剤を含有させることにより、上記紫外線吸収剤の吸収波長と光重合開始剤からラジカルを発生させることが可能な波長との差を大きくすることが可能となる。その結果、紫外線吸収層の光重合と紫外線吸収剤による剥離を互いに影響せずに行うことができる。１つの実施形態においては、光重合開始剤としての２，２－ジメトキシ－１，２－ジフェニルエタン－１－オン（例えば、ＢＡＳＦ社製、商品名「イルガキュア６５１」）と、光増感剤とが併用される。このような光増感剤としては、川崎化成工業株式会社製の商品名「ＵＶＳ－５８１」、９，１０－ジエトキシアントラセン（例えば、川崎化成工業社製、商品名「ＵＶＳ１１０１」）等が挙げられる。 In one embodiment, the photosensitizer can be used in combination with the photopolymerization initiator. Since the photosensitizer can generate radicals from the photopolymerization initiator by passing the energy obtained by absorbing light to the photopolymerization initiator, the absorption peak of the photopolymerization initiator itself is high. The polymerization can proceed with light on the long wavelength side. Therefore, by containing the photosensitizer, it is possible to increase the difference between the absorption wavelength of the ultraviolet absorber and the wavelength at which radicals can be generated from the photopolymerization initiator. As a result, the photopolymerization of the ultraviolet absorbing layer and the peeling by the ultraviolet absorbing agent can be performed without affecting each other. In one embodiment, 2,2-dimethoxy-1,2-diphenylethane-1-one (for example, manufactured by BASF, trade name "Irgacure 651") as a photopolymerization initiator and a photosensitizer are used. Is used together. Examples of such a photosensitizer include the product name "UVS-581" manufactured by Kawasaki Kasei Chemicals Co., Ltd. and 9,10-diethoxyanthracene (for example, the product name "UVS1101" manufactured by Kawasaki Kasei Chemicals Co., Ltd.). Be done.
　上記光増感剤のその他の例としては、９，１０－ジブトキシアントラセン（例えば、川崎化成工業社製、商品名「ＵＶＳ－１３３１」）、２－イソプロピルチオキサントン、ベンゾフェノン、チオキサントン誘導体、４，４’－ビス（ジメチルアミノ）ベンゾフェノン等が挙げられる。チオキサントン誘導体としては、例えば、エトキシカルボニルチオキサントン、イソプロピルチオキサントン等が挙げられる。 Other examples of the above photosensitizer include 9,10-dibutoxyanthracene (for example, manufactured by Kawasaki Kasei Chemicals, trade name "UVS-1331"), 2-isopropylthioxanthone, benzophenone, thioxanthone derivative, 4,4. '-Bis (dimethylamino) benzophenone and the like can be mentioned. Examples of the thioxanthone derivative include ethoxycarbonylthioxanthone and isopropylthioxanthone.
　上記光増感剤の含有割合は、ベースポリマー１００重量部に対して、好ましくは０．０１重量部～２重量部であり、より好ましくは０．５重量部～２重量部である。 The content ratio of the photosensitizer is preferably 0.01 parts by weight to 2 parts by weight, and more preferably 0.5 parts by weight to 2 parts by weight with respect to 100 parts by weight of the base polymer.
　好ましくは、上記活性エネルギー線硬化型粘着剤は、架橋剤を含む。架橋剤としては、例えば、イソシアネート系架橋剤、エポキシ系架橋剤、オキサゾリン系架橋剤、アジリジン系架橋剤、メラミン系架橋剤、過酸化物系架橋剤、尿素系架橋剤、金属アルコキシド系架橋剤、金属キレート系架橋剤、金属塩系架橋剤、カルボジイミド系架橋剤、アミン系架橋剤等が挙げられる。 Preferably, the active energy ray-curable pressure-sensitive adhesive contains a cross-linking agent. Examples of the cross-linking agent include isocyanate-based cross-linking agents, epoxy-based cross-linking agents, oxazoline-based cross-linking agents, aziridine-based cross-linking agents, melamine-based cross-linking agents, peroxide-based cross-linking agents, urea-based cross-linking agents, and metal alkoxide-based cross-linking agents. Examples thereof include a metal chelate-based cross-linking agent, a metal salt-based cross-linking agent, a carbodiimide-based cross-linking agent, and an amine-based cross-linking agent.
　上記架橋剤の含有割合は、粘着剤のベースポリマー１００重量部に対して、好ましくは０．５重量部～１０重量部であり、より好ましくは１重量部～８重量部である。 The content ratio of the cross-linking agent is preferably 0.5 parts by weight to 10 parts by weight, and more preferably 1 part by weight to 8 parts by weight with respect to 100 parts by weight of the base polymer of the pressure-sensitive adhesive.
　１つの実施形態においては、イソシアネート系架橋剤が好ましく用いられる。イソシアネート系架橋剤は、多種の官能基と反応し得る点で好ましい。上記イソシアネート系架橋剤の具体例としては、ブチレンジイソシアネート、ヘキサメチレンジイソシアネート等の低級脂肪族ポリイソシアネート類；シクロペンチレンジイソシアネート、シクロへキシレンジイソシアネート、イソホロンジイソシアネート等の脂環族イソシアネート類；２，４－トリレンジイソシアネート、４，４’－ジフェニルメタンジイソシアネート、キシリレンジイソシアネート等の芳香族イソシアネート類；トリメチロールプロパン／トリレンジイソシアネート３量体付加物（日本ポリウレタン工業社製、商品名「コロネートＬ」）、トリメチロールプロパン／へキサメチレンジイソシアネート３量体付加物（日本ポリウレタン工業社製、商品名「コロネートＨＬ」）、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（日本ポリウレタン工業社製、商品名「コロネートＨＸ」）等のイソシアネート付加物；等が挙げられる。好ましくは、イソシアネート基を３個以上有する架橋剤が用いられる。 In one embodiment, an isocyanate-based cross-linking agent is preferably used. Isocyanate-based cross-linking agents are preferable because they can react with various functional groups. Specific examples of the isocyanate-based cross-linking agent include lower aliphatic polyisocyanates such as butylene diisocyanate and hexamethylene diisocyanate; alicyclic isocyanates such as cyclopentylene diisocyanate, cyclohexylene diisocyanate, and isophorone diisocyanate; 2,4-. Aromatic isocyanates such as tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate; trimethylolpropane / tolylene diisocyanate trimer adduct (manufactured by Nippon Polyurethane Industry Co., Ltd., trade name "Coronate L"), tri Methylolpropane / hexamethylene diisocyanate trimeric adduct (manufactured by Nippon Polyurethane Industry Co., Ltd., trade name "Coronate HL"), isocyanurate of hexamethylene diisocyanate (manufactured by Japan Polyurethane Industry Co., Ltd., trade name "Coronate HX"), etc. Isocyanate adduct; etc. Preferably, a cross-linking agent having 3 or more isocyanate groups is used.
　活性エネルギー線硬化型粘着剤は、必要に応じて、任意の適切な添加剤をさらに含み得る。添加剤としては、例えば、活性エネルギー線重合促進剤、ラジカル捕捉剤、粘着付与剤、可塑剤（例えば、トリメリット酸エステル系可塑剤、ピロメリット酸エステル系可塑剤等）、顔料、染料、充填剤、老化防止剤、導電材、帯電防止剤、紫外線吸収剤、光安定剤、剥離調整剤、軟化剤、界面活性剤、難燃剤、酸化防止剤等が挙げられる。 The active energy ray-curable pressure-sensitive adhesive may further contain any suitable additive, if necessary. Examples of the additive include an active energy ray polymerization accelerator, a radical trapping agent, an antistatic agent, a plasticizer (for example, a trimellitic acid ester-based plasticizer, a pyromellitic acid ester-based plasticizer, etc.), a pigment, a dye, and a filling. Examples thereof include agents, antioxidants, conductive materials, antistatic agents, ultraviolet absorbers, light stabilizers, release modifiers, softeners, surfactants, flame retardants, antioxidants and the like.
・感圧粘着剤：
　感圧粘着剤としては、例えば、アクリル系粘着剤、ゴム系粘着剤、ビニルアルキルエーテル系粘着剤、シリコーン系粘着剤、ポリエステル系粘着剤、ポリアミド系粘着剤、ウレタン系粘着剤、スチレン－ジエンブロック共重合体系粘着剤、等が挙げられる。なかでも好ましくは、アクリル系粘着剤またはゴム系粘着剤であり、より好ましくはアクリル系粘着剤である。なお、上記粘着剤は、単独で、または２種以上組み合わせて用いてもよい。 ・ Pressure-sensitive adhesive:
Examples of the pressure-sensitive adhesive include acrylic adhesives, rubber adhesives, vinyl alkyl ether adhesives, silicone adhesives, polyester adhesives, polyamide adhesives, urethane adhesives, and styrene-diene blocks. Copolymerization system adhesives, etc. may be mentioned. Of these, an acrylic pressure-sensitive adhesive or a rubber-based pressure-sensitive adhesive is preferable, and an acrylic-based pressure-sensitive adhesive is more preferable. The pressure-sensitive adhesive may be used alone or in combination of two or more.
　上記アクリル系粘着剤としては、例えば、（メタ）アクリル酸アルキルエステルの１種または２種以上を単量体成分として用いたアクリル系ポリマー（ホモポリマーまたはコポリマー）をベースポリマーとするアクリル系粘着剤等が挙げられる。（メタ）アクリル酸アルキルエステルの具体例としては、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸プロピル、（メタ）アクリル酸イソプロピル、（メタ）アクリル酸ブチル、（メタ）アクリル酸イソブチル、（メタ）アクリル酸ｓ－ブチル、（メタ）アクリル酸ｔ－ブチル、（メタ）アクリル酸ペンチル、（メタ）アクリル酸ヘキシル、（メタ）アクリル酸ヘプチル、（メタ）アクリル酸オクチル、（メタ）アクリル酸２－エチルヘキシル、（メタ）アクリル酸イソオクチル、（メタ）アクリル酸ノニル、（メタ）アクリル酸イソノニル、（メタ）アクリル酸デシル、（メタ）アクリル酸イソデシル、（メタ）アクリル酸ウンデシル、（メタ）アクリル酸ドデシル、（メタ）アクリル酸トリデシル、（メタ）アクリル酸テトラデシル、（メタ）アクリル酸ペンタデシル、（メタ）アクリル酸ヘキサデシル、（メタ）アクリル酸ヘプタデシル、（メタ）アクリル酸オクタデシル、（メタ）アクリル酸ノナデシル、（メタ）アクリル酸エイコシル等の（メタ）アクリル酸Ｃ１－２０アルキルエステルが挙げられる。なかでも、炭素数が４～１８の直鎖状もしくは分岐状のアルキル基を有する（メタ）アクリル酸アルキルエステルが好ましく用いられ得る。 As the acrylic pressure-sensitive adhesive, for example, an acrylic pressure-sensitive adhesive using an acrylic polymer (homoromer or copolymer) using one or more (meth) acrylic acid alkyl esters as a monomer component as a base polymer. And so on. Specific examples of the (meth) acrylic acid alkyl ester include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, and (meth). ) Isobutyl acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate , (Meta) 2-ethylhexyl acrylate, (meth) isooctyl acrylate, (meth) nonyl acrylate, (meth) isononyl acrylate, (meth) decyl acrylate, (meth) isodecyl acrylate, (meth) acrylate Undecyl, (meth) dodecyl acrylate, (meth) tridecyl acrylate, (meth) tetradecyl acrylate, (meth) pentadecyl acrylate, (meth) hexadecyl acrylate, (meth) heptadecyl acrylate, octadecyl (meth) acrylate , (Meta) acrylic acid nonadecil, (meth) acrylic acid eicosyl and the like (meth) acrylic acid C1-20 alkyl esters. Among them, a (meth) acrylic acid alkyl ester having a linear or branched alkyl group having 4 to 18 carbon atoms can be preferably used.
　上記アクリル系ポリマーは、凝集力、耐熱性、架橋性等の改質を目的として、必要に応じて、上記（メタ）アクリル酸アルキルエステルと共重合可能な他の単量体成分に対応する単位を含んでいてもよい。このような単量体成分として、例えば、アクリル酸、メタクリル酸、カルボキシエチルアクリレート、カルボキシペンチルアクリレート、イタコン酸、マレイン酸、フマル酸、クロトン酸等のカルボキシル基含有モノマー；無水マレイン酸、無水イコタン酸等の酸無水物モノマー；（メタ）アクリル酸ヒドロキシエチル、（メタ）アクリル酸ヒドロキシプロピル、（メタ）アクリル酸ヒドロキシブチル、（メタ）アクリル酸ヒドロキシヘキシル、（メタ）アクリル酸ヒドロキシオクチル、（メタ）アクリル酸ヒドロキシデシル、（メタ）アクリル酸ヒドロキシラウリル、（４－ヒドロキシメチルシクロヘキシル）メチルメタクリレート等のヒドロキシル基含有モノマー；スチレンスルホン酸、アリルスルホン酸、２－（メタ）アクリルアミド－２－メチルプロパンスルホン酸、（メタ）アクリルアミドプロパンスルホン酸、スルホプロピル（メタ）アクリレート、（メタ）アクリロイルオキシナフタレンスルホン酸等のスルホン酸基含有モノマー；（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－ブチル（メタ）アクリルアミド、Ｎ－メチロール（メタ）アクリルアミド、Ｎ－メチロールプロパン（メタ）アクリルアミド等の（Ｎ－置換）アミド系モノマー；（メタ）アクリル酸アミノエチル、（メタ）アクリル酸Ｎ，Ｎ－ジメチルアミノエチル、（メタ）アクリル酸ｔ－ブチルアミノエチル等の（メタ）アクリル酸アミノアルキル系モノマー；（メタ）アクリル酸メトキシエチル、（メタ）アクリル酸エトキシエチル等の（メタ）アクリル酸アルコキシアルキル系モノマー；Ｎ－シクロヘキシルマレイミド、Ｎ－イソプロピルマレイミド、Ｎ－ラウリルマレイミド、Ｎ－フェニルマレイミド等のマレイミド系モノマー；Ｎ－メチルイタコンイミド、Ｎ－エチルイタコンイミド、Ｎ－ブチルイタコンイミド、Ｎ－オクチルイタコンイミド、Ｎ－２－エチルヘキシルイタコンイミド、Ｎ－シクロヘキシルイタコンイミド、Ｎ－ラウリルイタコンイミド等のイタコンイミド系モノマー；Ｎ－（メタ）アクリロイルオキシメチレンスクシンイミド、Ｎ－（メタ）アクルロイル－６－オキシヘキサメチレンスクシンイミド、Ｎ－（メタ）アクリロイル－８－オキシオクタメチレンスクシンイミド等のスクシンイミド系モノマー；酢酸ビニル、プロピオン酸ビニル、Ｎ－ビニルピロリドン、メチルビニルピロリドン、ビニルピリジン、ビニルピペリドン、ビニルピリミジン、ビニルピペラジン、ビニルピラジン、ビニルピロール、ビニルイミダゾール、ビニルオキサゾール、ビニルモルホリン、Ｎ－ビニルカルボン酸アミド類、スチレン、α－メチルスチレン、Ｎ－ビニルカプロラクタム等のビニル系モノマー；アクリロニトリル、メタクリロニトリル等のシアノアクリレートモノマー；（メタ）アクリル酸グリシジル等のエポキシ基含有アクリル系モノマー；（メタ）アクリル酸ポリエチレングリコール、（メタ）アクリル酸ポリプロピレングリコール、（メタ）アクリル酸メトキシエチレングリコール、（メタ）アクリル酸メトキシポリプロピレングリコール等のグリコール系アクリルエステルモノマー；（メタ）アクリル酸テトラヒドロフルフリル、フッ素（メタ）アクリレート、シリコーン（メタ）アクリレート等の複素環、ハロゲン原子、ケイ素原子等を有するアクリル酸エステル系モノマー；ヘキサンジオールジ（メタ）アクリレート、（ポリ）エチレングリコールジ（メタ）アクリレート、（ポリ）プロピレングリコールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、ペンタエリスリトールジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、エポキシアクリレート、ポリエステルアクリレート、ウレタンアクリレート等の多官能モノマー；イソプレン、ブタジエン、イソブチレン等のオレフィン系モノマー；ビニルエーテル等のビニルエーテル系モノマー等が挙げられる。これらの単量体成分は、単独で、または２種以上組み合わせて用いてもよい。 The acrylic polymer is a unit corresponding to other monomer components copolymerizable with the (meth) acrylic acid alkyl ester, if necessary, for the purpose of modifying cohesive force, heat resistance, crosslinkability and the like. May include. Examples of such monomer components include carboxyl group-containing monomers such as acrylic acid, methacrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid, and crotonic acid; maleic anhydride and icotanic anhydride. Acid Anhydromer Monomers such as (meth) hydroxyethyl acrylate, (meth) hydroxypropyl acrylate, (meth) hydroxybutyl acrylate, (meth) hydroxyhexyl acrylate, (meth) hydroxyoctyl acrylate, (meth) Hydromer group-containing monomers such as hydroxydecyl acrylate, hydroxylauryl (meth) acrylate, and (4-hydroxymethylcyclohexyl) methylmethacrylate; styrene sulfonic acid, allyl sulfonic acid, 2- (meth) acrylamide-2-methyl propane sulfonic acid. , (Meta) acrylamide propanesulfonic acid, sulfopropyl (meth) acrylate, (meth) acryloyloxynaphthalene sulfonic acid and other sulfonic acid group-containing monomers; (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-butyl (N-substituted) amide-based monomers such as (meth) acrylamide, N-methylol (meth) acrylamide, N-methylolpropane (meth) acrylamide; aminoethyl (meth) acrylate, N, N-dimethyl (meth) acrylate (Meta) Aminoalkyl-based monomers such as t-butylaminoethyl (meth) acrylate; (Meta) alkoxyalkyl-based (meth) acrylates such as methoxyethyl (meth) acrylate and ethoxyethyl (meth) acrylate. Monomers; Maleimide-based monomers such as N-cyclohexyl maleimide, N-isopropylmaleimide, N-laurylmaleimide, N-phenylmaleimide; N-methylitaconimide, N-ethylitaconimide, N-butylitaconimide, N-octylitaconimide , N-2-ethylhexylitaconimide, N-cyclohexylitaconimide, N-laurylitaconimide and other itaconeimide-based monomers; Succinimide-based monomers such as N- (meth) acryloyl-8-oxyoctamethylene succinimide; vinyl acetate, vinyl propionate, N-vinylpyrrolidone, methylvinylpyrro Vinyls such as lidone, vinylpyridine, vinylpiperidone, vinylpyrimidine, vinylpiperazin, vinylpyrazine, vinylpyrrole, vinylimidazole, vinyloxazole, vinylmorpholin, N-vinylcarboxylic acid amides, styrene, α-methylstyrene, N-vinylcaprolactam, etc. Acrylate-based monomers; Cyanoacrylate monomers such as acrylonitrile and methacrylonitrile; Epoxy group-containing acrylic monomers such as glycidyl (meth) acrylate; Polyethylene glycol (meth) acrylate, Polypropylene glycol (meth) acrylate, (meth) acrylic acid Glycol-based acrylic ester monomers such as methoxyethylene glycol and methoxypolypropylene glycol (meth) acrylate; heterocycles such as tetrahydrofurfuryl (meth) acrylate, fluorine (meth) acrylate and silicone (meth) acrylate, halogen atoms and silicon atoms. Acrylate-based monomers having such as; hexanediol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol. Polyfunctional monomers such as di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, epoxy acrylate, polyester acrylate, urethane acrylate; isoprene, butadiene, Olefin-based monomers such as isobutylene; vinyl ether-based monomers such as vinyl ether and the like can be mentioned. These monomer components may be used alone or in combination of two or more.
　上記ゴム系粘着剤としては、例えば、天然ゴム；ポリイソプレンゴム、スチレン・ブタジエン（ＳＢ）ゴム、スチレン・イソプレン（ＳＩ）ゴム、スチレン・イソプレン・スチレンブロック共重合体（ＳＩＳ）ゴム、スチレン・ブタジエン・スチレンブロック共重合体（ＳＢＳ）ゴム、スチレン・エチレン・ブチレン・スチレンブロック共重合体（ＳＥＢＳ）ゴム、スチレン・エチレン・プロピレン・スチレンブロック共重合体（ＳＥＰＳ）ゴム、スチレン・エチレン・プロピレンブロック共重合体（ＳＥＰ）ゴム、再生ゴム、ブチルゴム、ポリイソブチレン、これらの変性体等の合成ゴム；等をベースポリマーとするゴム系粘着剤が挙げられる。 Examples of the rubber-based pressure-sensitive adhesive include natural rubber; polyisoprene rubber, styrene / butadiene (SB) rubber, styrene / isoprene (SI) rubber, styrene / isoprene / styrene block copolymer (SIS) rubber, and styrene / butadiene. -Sterethane block copolymer (SBS) rubber, styrene / ethylene / butylene / styrene block copolymer (SEBS) rubber, styrene / ethylene / propylene / styrene block copolymer (SEPS) rubber, styrene / ethylene / propylene block Examples thereof include rubber-based pressure-sensitive adhesives using polymer (SEP) rubber, recycled rubber, butyl rubber, polyisobutylene, synthetic rubber such as modified products thereof; and the like as a base polymer.
　上記感圧粘着剤は、必要に応じて、任意の適切な添加剤を含み得る。該添加剤としては、例えば、架橋剤、粘着付与剤（例えば、ロジン系粘着付与剤、テルペン系粘着付与剤、炭化水素系粘着付与剤等）、可塑剤（例えば、トリメリット酸エステル系可塑剤、ピロメリット酸エステル系可塑剤）、顔料、染料、老化防止剤、導電材、帯電防止剤、光安定剤、剥離調整剤、軟化剤、界面活性剤、難燃剤、酸化防止剤等が挙げられる。 The pressure sensitive pressure-sensitive adhesive may contain any suitable additive, if necessary. Examples of the additive include a cross-linking agent, a tackifier (for example, a rosin-based tackifier, a terpene-based tackifier, a hydrocarbon-based tackifier, etc.), and a plasticizer (for example, a trimellitic acid ester-based plasticizer). , Piromellitic acid ester plasticizer), pigments, dyes, anti-aging agents, conductive materials, antistatic agents, light stabilizers, release modifiers, softeners, surfactants, flame retardants, antioxidants, etc. ..
Ｂ－３．被加工体
　被加工体としては、任意の適切な被加工体が用いられ得る。１つの実施形態においては、被加工体として電子部品が用いられる。 B-3. As the workpiece, any suitable workpiece can be used. In one embodiment, electronic components are used as the workpiece.
　１つの実施形態においては、図１に示すように、被加工体３０は、別の硬質基板３１と、該別の硬質基板３１の少なくとも片側に配置された部材３２を備える。別の硬質基板としては、Ｂ－１項で説明した硬質基板が用いられ得る。また、別の硬質基板として、リジッド配線回路基板等を用いてもよい。上記部材としては、例えば、半導体素子、光半導体素子等の電子部品が挙げられる。被加工体の具体例としては、えば、リジッド配線回路基板上の端子に、その端子に接続するための複数の半導体素子を並べて載置したもの、ガラスキャリア上に両面粘着シートで半導体素子を載置したものなどが挙げられる。 In one embodiment, as shown in FIG. 1, the workpiece 30 includes another hard substrate 31 and a member 32 arranged on at least one side of the other hard substrate 31. As another rigid substrate, the rigid substrate described in Section B-1 can be used. Further, as another rigid substrate, a rigid wiring circuit board or the like may be used. Examples of the member include electronic components such as semiconductor devices and optical semiconductor devices. Specific examples of the workpiece include a terminal on a rigid wiring circuit board in which a plurality of semiconductor elements for connecting to the terminal are arranged side by side, and a semiconductor element is mounted on a glass carrier with a double-sided adhesive sheet. Examples include those placed.
　別の実施形態においては、上記被加工体として、半導体ウエハが用いられる。半導体ウエハは、例えば、ＬＥＤ、受光素子等の光半導体ウエハであってもよい。 In another embodiment, a semiconductor wafer is used as the work piece. The semiconductor wafer may be, for example, an optical semiconductor wafer such as an LED or a light receiving element.
　上記被加工体は、複数配置されていてもよく、１個配置されていてもよい。 A plurality of the workpieces may be arranged, or one piece may be arranged.
　複数の被加工体が配置される場合、その間隔は、例えば、２μｍ～１０ｍｍである。 When a plurality of workpieces are arranged, the interval is, for example, 2 μm to 10 mm.
Ｂ－４．基材
　上記のとおり、１つの実施形態においては、紫外線吸収層２０と被加工体３０との間には、基材２１と粘着剤層２２とがさらに配置され得る。１つの実施形態において、紫外線吸収層２０と基材２１と粘着剤層２２とから構成される積層体は、両面粘着シートＡであり得る。このような構成とすることにより、後工程において、両面粘着シートＡをピール剥離することが可能となり、凝集破壊による糊残りを抑制することができる。糊残りを顕著に抑制できる為、既存のワニス工法等で課題となる焦げ付き残渣を除去する為の洗浄工程負荷を削減できる。また、基材を備えることにより、当該基材が保護材として機能し、被加工体の破損を防止することができる。 B-4. Substrate As described above, in one embodiment, the substrate 21 and the pressure-sensitive adhesive layer 22 may be further arranged between the ultraviolet absorbing layer 20 and the workpiece 30. In one embodiment, the laminate composed of the ultraviolet absorbing layer 20, the base material 21, and the pressure-sensitive adhesive layer 22 can be a double-sided pressure-sensitive adhesive sheet A. With such a configuration, the double-sided pressure-sensitive adhesive sheet A can be peeled off in a post-process, and the adhesive residue due to coagulation fracture can be suppressed. Since the adhesive residue can be remarkably suppressed, the load of the cleaning process for removing the scorched residue, which is a problem in the existing varnish method, can be reduced. Further, by providing the base material, the base material functions as a protective material, and damage to the workpiece can be prevented.
　上記基材は、任意の適切な樹脂から構成され得る。該樹脂としては、例えば、ポリエチレン系樹脂、ポリプロピレン系樹脂、ポリブテン系樹脂、ポリメチルペンテン系樹脂等のポリオレフィン系樹脂、ポリウレタン系樹脂、ポリエステル系樹脂、ポリイミド系樹脂、ポリエーテルケトン系樹脂、ポリスチレン系樹脂、ポリ塩化ビニル系樹脂、ポリ塩化ビニリデン系樹脂、フッ素系樹脂、シリコン系樹脂、セルロース系樹脂、アイオノマー樹脂等が挙げられる。なかでも好ましくはポリイミド系樹脂である。ポリイミド系樹脂から構成される基材を用いれば、上記効果が顕著となり、かつ、ガラス基板側から入射したレーザー光によって被加工体（デバイス）が破損することを効率的に防ぐことができ、ガラス基板側からのみ選択的に剥離することができる。 The base material may be composed of any suitable resin. Examples of the resin include polyolefin resins such as polyethylene resins, polypropylene resins, polybutene resins, and polymethylpentene resins, polyurethane resins, polyester resins, polyimide resins, polyether ketone resins, and polystyrene resins. Examples thereof include resins, polyvinyl chloride resins, polyvinylidene chloride resins, fluororesins, silicon resins, cellulose resins, ionomer resins and the like. Of these, a polyimide resin is preferable. If a base material made of a polyimide resin is used, the above effect becomes remarkable, and it is possible to efficiently prevent the workpiece (device) from being damaged by the laser beam incident from the glass substrate side, and the glass. It can be selectively peeled off only from the substrate side.
　上記基材の厚みは、好ましくは１μｍ～３００μｍであり、より好ましくは１μｍ～１００μｍであり、さらに好ましくは１μｍ～５０μｍである。 The thickness of the base material is preferably 1 μm to 300 μm, more preferably 1 μm to 100 μm, and further preferably 1 μm to 50 μm.
　基材の波長３５５ｎｍの光透過率は、好ましくは９０％以下であり、より好ましくは８５％以下であり、さらに好ましくは５０％以下であり、特に好ましくは１５％以下である。当該光透過率が小さければ、被着体ダメージが低減し得る点で好ましい。基材の波長３５５ｎｍの光透過率の下限は、例えば、０％であり、１つの実施形態においては、１０％である。 The light transmittance of the base material at a wavelength of 355 nm is preferably 90% or less, more preferably 85% or less, further preferably 50% or less, and particularly preferably 15% or less. If the light transmittance is small, the damage to the adherend can be reduced, which is preferable. The lower limit of the light transmittance of the substrate at a wavelength of 355 nm is, for example, 0%, and in one embodiment, 10%.
Ｂ－５．粘着剤層
　粘着剤層は、任意の適切な粘着剤を含む。例えば、上記感圧粘着剤を含む。 B-5. Adhesive layer The adhesive layer contains any suitable adhesive. For example, the pressure-sensitive pressure-sensitive adhesive is included.
　１つの実施形態においては、粘着剤層に含まれる粘着剤として、耐熱粘着剤が用いられる。耐熱粘着剤から構成された粘着剤層を備えることにより、レーザー光を照射した際に被加工体（デバイス）への焦げ付き（糊残り）を抑制することができる。本明細書において、耐熱粘着剤とは、２６０℃の環境下で、所定の粘着力を有する粘着剤を意味する。耐熱粘着剤は、２６０℃の環境下で、糊残りなく使用し得ることが好ましい。好ましくは、耐熱粘着剤は、ベースポリマーとして、アクリル系樹脂、シリコーン系樹脂等を含む。 In one embodiment, a heat-resistant adhesive is used as the adhesive contained in the adhesive layer. By providing the pressure-sensitive adhesive layer composed of the heat-resistant pressure-sensitive adhesive, it is possible to suppress the scorching (glue residue) on the workpiece (device) when irradiated with the laser beam. In the present specification, the heat-resistant adhesive means a pressure-sensitive adhesive having a predetermined adhesive strength in an environment of 260 ° C. It is preferable that the heat-resistant adhesive can be used in an environment of 260 ° C. without adhesive residue. Preferably, the heat-resistant pressure-sensitive adhesive contains an acrylic resin, a silicone-based resin, or the like as the base polymer.
Ｃ．加工工程
　加工工程においては、上記のようにして硬質基板上に配置された被加工体を加工する。本工程における加工は、任意の適切な加工であり得る。例えば、加熱工程、バックグラインド工程、ダイシング工程、実装（リフロー）工程、回路形成（ＲＤＬ）工程等が挙げられる。図１においては、上板１００と下板２００を備えるプレス機により、積層工程で形成された積層体をプレスしながら（またはプレスの後）、当該積層体を加工（加熱）している。 C. Processing process In the processing process, the workpiece arranged on the hard substrate is processed as described above. The processing in this step can be any suitable processing. For example, a heating process, a back grind process, a dicing process, a mounting (reflow) process, a circuit forming (RDL) process, and the like can be mentioned. In FIG. 1, a press machine provided with an upper plate 100 and a lower plate 200 is used to process (heat) the laminate while pressing (or after pressing) the laminate formed in the lamination step.
　１つの実施形態においては上記紫外線吸収層が活性エネルギー線硬化型粘着剤を含む場合、上記加工の前に、当該紫外線吸収層に活性エネルギー線（例えば、紫外線）照射して、当該紫外線吸収層の粘着力を高めてもよい。 In one embodiment, when the ultraviolet absorbing layer contains an active energy ray-curable pressure-sensitive adhesive, the ultraviolet absorbing layer is irradiated with active energy rays (for example, ultraviolet rays) before the processing to obtain the ultraviolet absorbing layer. The adhesive strength may be increased.
Ｄ．剥離工程
　剥離工程においては、紫外線吸収層に紫外線を照射して、硬質基板を被加工体から剥離する。 D. Peeling step In the peeling step, the ultraviolet absorbing layer is irradiated with ultraviolet rays to peel the hard substrate from the workpiece.
　１つの実施形態においては、図１に示すように、硬質基板１０を紫外線吸収層２０から剥離した後、紫外線吸収層２０が剥離される。紫外線吸収層２０と基材２１と粘着剤層２２とから両面粘着シートＡが構成されている場合、紫外線吸収層２０の剥離の後、当該両面粘着シートＡが剥離される。 In one embodiment, as shown in FIG. 1, after the hard substrate 10 is peeled from the ultraviolet absorbing layer 20, the ultraviolet absorbing layer 20 is peeled. When the double-sided pressure-sensitive adhesive sheet A is composed of the ultraviolet absorbing layer 20, the base material 21, and the pressure-sensitive adhesive layer 22, the double-sided pressure-sensitive adhesive sheet A is peeled off after the ultraviolet-absorbing layer 20 is peeled off.
　別の実施形態においては、上記硬質基板と上記紫外線吸収層とが一体で、剥離される。 In another embodiment, the hard substrate and the ultraviolet absorbing layer are integrally peeled off.
　紫外線照射の諸条件は、紫外線吸収層に剥離性を生じさせ得る限り、紫外線吸収層の構成に応じて、任意の適切条件とすることができる。１つの実施形態において、ＵＶレーザー光（例えば、波長：２００ｎｍ～３８０ｎｍ）が紫外線吸収層に照射される。ＵＶレーザー光を任意の適切な出力（例えば、０．０１Ｗ～６Ｗ、好ましくは０．０５Ｗ～５Ｗ）で紫外線吸収層に照射することにより、紫外線吸収剤が分解して発生するガス、および／または紫外線吸収剤が発熱することにより粘着剤層が分解して発生するガスにより、紫外線吸収層に変形が生じ、その結果、レーザー光が照射された部分において、剥離性が発現する。ＵＶレーザー光の波長は、好ましくは３６０ｎｍ以下である。硬質基板が紫外線吸収層の一方の面に直接配置され、被加工体が、紫外線吸収層の他方の面に直接配置される場合、ＵＶレーザー光照射による剥離が好ましく行われる。 The conditions of ultraviolet irradiation can be any appropriate conditions depending on the configuration of the ultraviolet absorbing layer as long as the ultraviolet absorbing layer can be peeled off. In one embodiment, UV laser light (eg, wavelength: 200 nm to 380 nm) is applied to the UV absorption layer. By irradiating the UV absorber layer with UV laser light at any suitable output (eg, 0.01 W to 6 W, preferably 0.05 W to 5 W), the gas generated by the decomposition of the UV absorber and / or The gas generated by the decomposition of the pressure-sensitive adhesive layer due to the heat generation of the ultraviolet absorber causes deformation of the ultraviolet absorbing layer, and as a result, peelability is exhibited in the portion irradiated with the laser beam. The wavelength of the UV laser light is preferably 360 nm or less. When the hard substrate is directly arranged on one surface of the ultraviolet absorbing layer and the workpiece is directly arranged on the other surface of the ultraviolet absorbing layer, peeling by UV laser light irradiation is preferably performed.
　紫外線吸収層が、活性エネルギー線硬化型粘着剤を含む場合、活性エネルギー線を紫外線吸収層の全体に照射して、紫外線吸収層の粘着力を低下させてもよい。１つの実施形態においては、ＵＶレーザー光を照射した後に、活性エネルギー線を紫外線吸収層の全体に照射して、紫外線吸収層の粘着力を低下させてもよい。活性エネルギー線としては、例えば、ガンマ線、紫外線、可視光線、赤外線（熱線）、ラジオ波、アルファ線、ベータ線、電子線、プラズマ流、電離線、粒子線等が挙げられる。好ましくは、紫外線である。紫外線の波長としては、好ましくは３００ｎｍ～４００ｎｍである。照射量は、例えば、積算光量３００ｍＪ／ｃｍ２～１５００ｍＪ／ｃｍ２である。このように、レーザー光照射の前に、活性エネルギー線を照射すれば、再付着を防止して、硬質基板を剥離することができる。 When the ultraviolet absorbing layer contains an active energy ray-curable pressure-sensitive adhesive, the entire ultraviolet absorbing layer may be irradiated with active energy rays to reduce the adhesive strength of the ultraviolet absorbing layer. In one embodiment, after irradiating with UV laser light, the entire ultraviolet absorbing layer may be irradiated with active energy rays to reduce the adhesive strength of the ultraviolet absorbing layer. Examples of the active energy ray include gamma ray, ultraviolet ray, visible ray, infrared ray (heat ray), radio wave, alpha ray, beta ray, electron beam, plasma flow, ionization ray, particle beam and the like. Ultraviolet rays are preferable. The wavelength of ultraviolet rays is preferably 300 nm to 400 nm. The irradiation amount is, for example, an integrated light amount of 300 mJ / cm 2 to 1500 mJ / cm 2 . As described above, if the active energy ray is irradiated before the laser light irradiation, the reattachment can be prevented and the hard substrate can be peeled off.
　上記のようにして、被加工体の加工が完了する。本発明においては、紫外線吸収層への紫外線照射により硬質基板を剥離することができ、その際の剥離力が低いため、被加工体にかかる負荷を低減することができ、その結果、当該被加工体の損傷を防止することができる。 As described above, the processing of the workpiece is completed. In the present invention, the hard substrate can be peeled off by irradiating the ultraviolet absorbing layer with ultraviolet rays, and the peeling force at that time is low, so that the load applied to the workpiece can be reduced, and as a result, the workpiece is processed. It can prevent damage to the body.
（積層工程）
　リジッド配線回路基板３１（別の硬質基板３１）上の端子に、半導体素子３２（部材３２）を載置して、被加工体３０を用意した。
　紫外線吸収層２０を含む両面粘着シートを用いてガラス基板１０（硬質基板１０）を半導体素子３２の上に重ねて固定した。
　両面粘着シートとしては、ＰＩ基材２１の一方の面に紫外線硬化型粘着剤を含む紫外線吸収層２０を形成し、他方の面に粘着剤層２２を形成したものを用いた。
（加工工程）
　上記積層工程で得られた積層体を、プレス機で挟んで、半導体素子３２を粘着剤層２２に埋没させ、ホールドした。
　プレス機の上板を外して、ガラス基板１０（硬質基板１０）を通して、紫外線（波長：３５５ｎｍ～３６５ｎｍ、積算光量：１３８０ｍＪ／ｃｍ２）を紫外線吸収層２０に照射して、紫外線吸収層を硬化させ、紫外線吸収層のガラス基板１０（硬質基板１０）に対する粘着力を低減させた。
　プレス機で圧着した状態で、加熱し、半導体素子３２（部材３２）をリジッド配線回路基板３１（別の硬質基板３１）上の端子に固着した。固着手段としては、ハンダなどの金属接合、ＡＣＦ（異方導電性フィルム）、ＡＣＰ（異方導電性ペースト）などを利用することができる。
（剥離工程）
　プレス機の上板を外して、ガラス基板１０（硬質基板１０）を通して、紫外線レーザー光（波長：３５５ｎｍ、照射エネルギー：１０Ｊ／ｃｍ２）を紫外線吸収層に照射して、ガラス基板１０（硬質基板１０）を剥離した。
　次いで、両面粘着シートをピール剥離した。半導体素子３２（部材３２）の損傷はなかった。また、半導体素子３２（部材３２）が、リジッド配線回路基板３１（別の硬質基板３１）から、脱離することはなかった。 (Laminating process)
A semiconductor element 32 (member 32) was placed on a terminal on a rigid wiring circuit board 31 (another rigid board 31) to prepare a workpiece 30.
The glass substrate 10 (hard substrate 10) was laminated and fixed on the semiconductor element 32 using a double-sided adhesive sheet containing an ultraviolet absorbing layer 20.
As the double-sided adhesive sheet, a sheet in which an ultraviolet absorbing layer 20 containing an ultraviolet curable adhesive was formed on one surface of the PI base material 21 and an adhesive layer 22 was formed on the other surface was used.
(Processing process)
The laminate obtained in the above laminating step was sandwiched between presses, and the semiconductor element 32 was embedded in the pressure-sensitive adhesive layer 22 and held.
The upper plate of the press machine is removed, and the ultraviolet absorbing layer 20 is irradiated with ultraviolet rays (wavelength: 355 nm to 365 nm, integrated light amount: 1380 mJ / cm 2 ) through the glass substrate 10 (hard substrate 10) to cure the ultraviolet absorbing layer. The adhesive force of the ultraviolet absorbing layer to the glass substrate 10 (hard substrate 10) was reduced.
The semiconductor element 32 (member 32) was fixed to the terminal on the rigid wiring circuit board 31 (another rigid substrate 31) by heating in a state of being crimped by a press machine. As the fixing means, metal bonding such as solder, ACF (anisotropic conductive film), ACP (anisotropic paste) and the like can be used.
(Peeling process)
The upper plate of the press machine is removed, and the ultraviolet laser beam (wavelength: 355 nm, irradiation energy: 10 J / cm 2 ) is irradiated to the ultraviolet absorbing layer through the glass substrate 10 (hard substrate 10) to irradiate the glass substrate 10 (hard substrate 10). 10) was peeled off.
Then, the double-sided adhesive sheet was peeled off. There was no damage to the semiconductor element 32 (member 32). Further, the semiconductor element 32 (member 32) did not separate from the rigid wiring circuit board 31 (another rigid substrate 31).
　１０　　　　　　　硬質基板
　２０　　　　　　　紫外線吸収層
　３０　　　　　　　被加工体 10 Hard substrate 20 UV absorbing layer 30 Work piece

Claims (7)

  1. 　硬質基板と、紫外線吸収層と、被加工体とをこの順に積層する積層工程と、その後、
    　該被加工体を加工する加工工程と、その後、
    　該紫外線吸収層に紫外線を照射して、硬質基板を被加工体から剥離する剥離工程とを含む、
    　部材加工方法。     A laminating process in which a hard substrate, an ultraviolet absorbing layer, and a workpiece are laminated in this order, and then
    A processing process for processing the workpiece, followed by
    A peeling step of irradiating the ultraviolet absorbing layer with ultraviolet rays to peel the hard substrate from the workpiece is included.
    Member processing method.
  2. 　前記被加工体が、別の硬質基板と、該硬質基板の少なくとも片側に配置された部材とを含む、請求項１の部材加工方法。 The member processing method according to claim 1, wherein the workpiece includes another hard substrate and a member arranged on at least one side of the hard substrate.
  3. 　前記被加工体が、半導体ウエハである、請求項１に記載の部材加工方法。 The member processing method according to claim 1, wherein the workpiece is a semiconductor wafer.
  4. 　前記硬質基板が、光透過性を有する、請求項１から３のいずれかに記載の部材加工方法。 The member processing method according to any one of claims 1 to 3, wherein the hard substrate has light transmission.
  5. 　前記紫外線吸収層が、粘着性を有する、請求項１から４のいずれかに記載の部材加工方法。 The member processing method according to any one of claims 1 to 4, wherein the ultraviolet absorbing layer has adhesiveness.
  6. 　前記紫外線吸収層が、活性エネルギー線硬化型粘着剤を含む、請求項１から５のいずれかに記載の部材加工方法。 The member processing method according to any one of claims 1 to 5, wherein the ultraviolet absorbing layer contains an active energy ray-curable pressure-sensitive adhesive.
  7. 　前記紫外線吸収層が、紫外線吸収剤を含む、請求項１から６のいずれかに記載の部材加工方法。 The member processing method according to any one of claims 1 to 6, wherein the ultraviolet absorbing layer contains an ultraviolet absorbing agent.
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