WO2022044441A1 - 部材加工方法 - Google Patents

部材加工方法 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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Prior art keywords
meth
acrylate
absorbing layer
ultraviolet absorbing
workpiece
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PCT/JP2021/018010
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English (en)
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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Application filed by 日東電工株式会社 filed Critical 日東電工株式会社
Priority to CN202180055460.2A priority Critical patent/CN116034144A/zh
Priority to KR1020237000517A priority patent/KR20230056653A/ko
Publication of WO2022044441A1 publication Critical patent/WO2022044441A1/ja

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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 potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • 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).

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