WO2022038844A1 - Method for transferring member - Google Patents

Method for transferring member Download PDF

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Publication number
WO2022038844A1
WO2022038844A1 PCT/JP2021/018004 JP2021018004W WO2022038844A1 WO 2022038844 A1 WO2022038844 A1 WO 2022038844A1 JP 2021018004 W JP2021018004 W JP 2021018004W WO 2022038844 A1 WO2022038844 A1 WO 2022038844A1
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WO
WIPO (PCT)
Prior art keywords
absorbing layer
hard substrate
ultraviolet absorbing
ultraviolet
sensitive adhesive
Prior art date
Application number
PCT/JP2021/018004
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
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 日東電工株式会社 filed Critical 日東電工株式会社
Priority to CN202180055418.0A priority Critical patent/CN116018671A/en
Priority to KR1020237000514A priority patent/KR20230050312A/en
Publication of WO2022038844A1 publication Critical patent/WO2022038844A1/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
    • H01L21/02—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
    • H01L21/50—Assembly of semiconductor devices using processes or apparatus not provided for in a single one of the subgroups H01L21/06 - H01L21/326, e.g. sealing of a cap to a base of a container
    • H01L21/52—Mounting semiconductor bodies in containers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K26/00—Working by laser beam, e.g. welding, cutting or boring
    • B23K26/50—Working by transmitting the laser beam through or within the workpiece
    • B23K26/57—Working by transmitting the laser beam through or within the workpiece the laser beam entering a face of the workpiece from which it is transmitted through the workpiece material to work on a different workpiece face, e.g. for effecting removal, fusion splicing, modifying or reforming
    • 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
    • H01L21/50—Assembly of semiconductor devices using processes or apparatus not provided for in a single one of the subgroups H01L21/06 - H01L21/326, e.g. sealing of a cap to a base of a container
    • 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
    • H01L21/677—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 conveying, e.g. between different workstations
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • H01L24/93—Batch processes
    • H01L24/95—Batch processes at chip-level, i.e. with connecting carried out on a plurality of singulated devices, i.e. on diced chips
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L25/00—Assemblies consisting of a plurality of individual semiconductor or other solid state devices ; Multistep manufacturing processes thereof
    • H01L25/03—Assemblies consisting of a plurality of individual semiconductor or other solid state devices ; Multistep manufacturing processes thereof all the devices being of a type provided for in the same subgroup of groups H01L27/00 - H01L33/00, or in a single subclass of H10K, H10N, e.g. assemblies of rectifier diodes
    • H01L25/04—Assemblies consisting of a plurality of individual semiconductor or other solid state devices ; Multistep manufacturing processes thereof all the devices being of a type provided for in the same subgroup of groups H01L27/00 - H01L33/00, or in a single subclass of H10K, H10N, e.g. assemblies of rectifier diodes the devices not having separate containers
    • H01L25/075—Assemblies consisting of a plurality of individual semiconductor or other solid state devices ; Multistep manufacturing processes thereof all the devices being of a type provided for in the same subgroup of groups H01L27/00 - H01L33/00, or in a single subclass of H10K, H10N, e.g. assemblies of rectifier diodes the devices not having separate containers the devices being of a type provided for in group H01L33/00
    • H01L25/0753—Assemblies consisting of a plurality of individual semiconductor or other solid state devices ; Multistep manufacturing processes thereof all the devices being of a type provided for in the same subgroup of groups H01L27/00 - H01L33/00, or in a single subclass of H10K, H10N, e.g. assemblies of rectifier diodes the devices not having separate containers the devices being of a type provided for in group H01L33/00 the devices being arranged next to each other
    • 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
    • H01L2221/68322—Auxiliary support including means facilitating the selective separation of some of a plurality of devices 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
    • H01L2221/68368—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 used in a transfer process involving at least two transfer steps, i.e. including an intermediate handle substrate
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/93—Batch processes
    • H01L2224/95—Batch processes at chip-level, i.e. with connecting carried out on a plurality of singulated devices, i.e. on diced chips
    • H01L2224/95001—Batch processes at chip-level, i.e. with connecting carried out on a plurality of singulated devices, i.e. on diced chips involving a temporary auxiliary member not forming part of the bonding apparatus, e.g. removable or sacrificial coating, film or substrate

Definitions

  • the present invention relates to a member transfer method.
  • a substrate is used as a carrier for transfer between processes, and the electronic components arranged on the substrate are transferred to another substrate.
  • a hard substrate may be used as a carrier from the viewpoint of improving the position accuracy at the time of transfer.
  • an electronic component for example, a micro LED
  • a predetermined adhesive layer is provided with a second adhesive layer.
  • the first hard substrate is separated in the direction perpendicular to the main surface of the substrate. Then, a load is applied to the electronic component, and problems such as damage to the electronic component and transfer failure occur.
  • the present invention has been made to solve the above-mentioned conventional problems, and an object thereof is a member transfer method capable of satisfactorily transferring a member (workpiece) while using a hard substrate. Is to provide.
  • the member transfer method of the present invention is a method of transferring a member arranged on a first hard substrate to a second hard substrate, and the member is transferred to the first hard substrate via a first ultraviolet absorbing layer.
  • the pressure-sensitive adhesive layer is arranged between the first hard substrate and the member.
  • the first UV absorbing layer is composed of organic matter.
  • the first UV absorbing layer is composed of an inorganic substance.
  • a second ultraviolet absorbing layer is formed on the second hard substrate, and the second ultraviolet absorbing layer is arranged between the member and the second hard substrate.
  • a laminate is provided. This laminated body includes a first hard substrate, a first ultraviolet absorbing layer, a member, and a second hard substrate in this order, and is used in the member transfer method.
  • FIG. 1 is a schematic diagram illustrating a member transfer method according to one embodiment of the present invention.
  • FIG. 2 is a schematic diagram illustrating a member transfer method according to another embodiment of the present invention.
  • the member transfer method of the present invention is a method of transferring a member 30 arranged on a first hard substrate 10 to a second hard substrate 20.
  • the method comprises a step of laminating a first hard substrate 10 and a member 30 via a first ultraviolet absorbing layer 40 to form a laminated body A (hereinafter, also referred to as a laminating step), and then a laminated body A.
  • a step of irradiating the ultraviolet absorbing layer 40 with ultraviolet rays to peel off the first hard substrate 10 from the laminated body B (second hard substrate 20) (hereinafter, also referred to as a peeling step) is included.
  • the ultraviolet absorbing layer (first ultraviolet absorbing layer 40, second ultraviolet absorbing layer 50 (described later)) is a layer having a property of being able to absorb ultraviolet rays, and is irradiated with ultraviolet rays (preferably UV laser light). Refers to a layer that exhibits peelability on a part or all of its surface.
  • the above member is not particularly limited, and for example, an electronic component such as a semiconductor element or an optical semiconductor element can be used. Before the fixing step, a plurality of the above members may be arranged on the first ultraviolet absorbing layer, or one may be arranged.
  • the mounting area per member is, for example, 1 ⁇ m 2 to 1 cm 2 .
  • the interval is, for example, 2 ⁇ m to 5 mm.
  • the member 30 and the first ultraviolet absorbing layer 40 are used integrally.
  • the component for example, an electronic component
  • the component composed of the member 30 / the first ultraviolet absorbing layer 40 include a member 30 combined with the first ultraviolet absorbing layer 40 which is an inorganic substance, and specific examples thereof include the member 30.
  • the first ultraviolet absorbing layer 40 an optical semiconductor device (LED) provided with a GaN (gallium nitride) -based compound crystal layer can be mentioned.
  • LED optical semiconductor device
  • GaN gallium nitride
  • the laminated body including the first hard substrate 10 and the first ultraviolet absorbing layer 40 is the laminated body B (first hard substrate 10). Therefore, the member 30 and the first ultraviolet absorbing layer 40 are separated from each other by the above transfer method.
  • the first ultraviolet absorbing layer 40 which is an organic substance, can be formed as the first ultraviolet absorbing layer 40.
  • the transfer of the member can be completed without applying an unnecessary load to the member.
  • any appropriate process for processing a member may be performed between the laminating process and the fixing process.
  • the hard substrate (first hard substrate, second rigid substrate) refers to a molded body on a plate having a flexural modulus of 1 GPa or more.
  • the bending elasticity 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 material constituting the hard substrate include glass, metal, silicon, sapphire, and plastic.
  • a hard substrate made of polyethylene terephthalate is used as the hard substrate.
  • the thickness of the hard substrate made of polyethylene terephthalate is, for example, 100 ⁇ m or more.
  • 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 first hard substrate and the second rigid substrate may have the same configuration or different configurations.
  • the first ultraviolet absorbing layer is composed of an organic substance. In another embodiment, the first UV absorbing layer is composed of an inorganic substance.
  • the first ultraviolet absorbing layer composed of an organic substance may be a layer that has adhesiveness at an initial stage (that is, before irradiation with ultraviolet rays), and the adhesive strength decreases after irradiation with ultraviolet rays to exhibit peelability.
  • the first UV absorbing layer may be a layer whose adhesive strength is partially reduced by partial UV irradiation (eg, UV laser light irradiation).
  • the first UV absorbing layer composed of organic matter contains a UV absorber.
  • the first UV-absorbing layer composed of an organic substance further contains an active energy ray-curable pressure-sensitive adhesive.
  • the adherend can be peeled off by irradiation with UV laser light. More specifically, by irradiating the first ultraviolet absorbing layer with UV laser light, the gas generated by the decomposition of the ultraviolet absorber and / or the heat of the ultraviolet absorber causes the first ultraviolet absorbing layer to generate heat. The gas generated by decomposition causes deformation of the first ultraviolet absorbing layer, and as a result, peelability is exhibited in the portion irradiated with the UV laser light.
  • the adhesive strength of the entire first ultraviolet absorbing layer is lowered by irradiating with the active energy rays.
  • 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 first ultraviolet absorbing layer composed of the above organic substances at a wavelength of 355 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 first ultraviolet absorbing layer at a wavelength of 355 nm is more preferably 40% or less, still more preferably 30% or less. Within such a range, the above effect becomes more remarkable.
  • the initial adhesive force at 23 ° C. when the first ultraviolet absorbing layer composed of an organic substance is attached to a stainless steel plate is preferably 0.1 N / 20 mm to 20 N / 20 mm, more preferably 0.5 N / 20 mm. It is ⁇ 15N / 20mm. Within such a range, it is possible to form an ultraviolet absorbing layer that can hold the member well. Adhesive strength is measured according to JIS Z 0237: 2000. Specifically, the first ultraviolet absorbing layer is 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 the peeling angle.
  • the measurement is performed by peeling off the first ultraviolet absorbing layer under the conditions of 180 ° and a 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. ..
  • the first ultraviolet absorbing layer composed of an organic substance is attached to a stainless steel plate, and the adhesive strength at 23 ° C. after irradiation with ultraviolet rays of 460 mJ / cm 2 is preferably 0.01 N /. It is 20 mm to 2N / 20 mm, more preferably 0.02N / 20 mm to 1N / 20 mm. Within such a range, the member can be transferred with less 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 first 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 first ultraviolet absorbing layer composed of organic substances 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 first 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, more preferably 5 parts by weight to 20 parts by weight, based on 100 parts by weight of the base polymer in the first 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 peelability is obtained by laser light irradiation. It is possible to form an ultraviolet absorbing layer showing the above.
  • 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 a 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 first ultraviolet absorbing layer and the peeling by the ultraviolet absorber 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.
  • the first ultraviolet absorbing layer made of an inorganic substance and the above-mentioned member can be used in combination to form one component (for example, an electronic component). That is, the first ultraviolet absorbing layer made of an inorganic substance can be a part of the above-mentioned constituent (for example, an electronic component).
  • the first ultraviolet absorbing layer composed of the above-mentioned inorganic substances may be an epitaxial layer.
  • Examples of the first ultraviolet absorbing layer made of the above-mentioned inorganic substances include a layer made of a group III nitride such as a GaN (gallium nitride) compound crystal layer.
  • the first ultraviolet absorbing layer composed of an inorganic substance exhibits peelability by a so-called laser lift-off method.
  • the first ultraviolet absorbing layer made of an inorganic substance is decomposed, and as a result, the first ultraviolet absorbing layer and the first hard substrate are separated from each other. Details of the laser lift-off are described, for example, in International Publication No. 2012/011202, and the description in this publication is incorporated herein by reference.
  • Adhesive layer The laminate A may include an adhesive layer.
  • an adhesive layer may be placed between the first rigid substrate and the member.
  • an adhesive layer may be arranged between the first rigid substrate and the first UV absorbing layer.
  • the pressure-sensitive adhesive layer and the first ultraviolet absorbing layer may be laminated via any suitable base material.
  • the base material a base material composed of any suitable resin can be used.
  • the pressure-sensitive adhesive layer contains a UV curable pressure-sensitive adhesive.
  • the pressure-sensitive adhesive layer may be a pressure-sensitive adhesive layer whose adhesive strength is improved by irradiation with ultraviolet rays, or may be a pressure-sensitive adhesive layer whose adhesive strength is reduced by irradiation with ultraviolet rays.
  • the pressure-sensitive adhesive for example, the above-mentioned active energy ray-curable pressure-sensitive adhesive can be used.
  • the pressure-sensitive adhesive layer comprises a pressure-sensitive pressure-sensitive adhesive.
  • a commonly used pressure-sensitive adhesive may be used.
  • the hard substrate described in Section B-1 can be used as the second hard substrate.
  • a second ultraviolet absorbing layer 50 or an adhesive layer may be formed on the second hard substrate 20.
  • the second ultraviolet absorbing layer 50 may be arranged between the member 30 and the second hard substrate 20.
  • the second ultraviolet absorbing layer 50 is preferably a layer composed of an organic substance. Examples of such an ultraviolet absorbing layer include the ultraviolet absorbing layer described in the section “First ultraviolet absorbing layer composed of organic substances”, that is, the second ultraviolet absorbing layer 50 is initially (that is,).
  • the layer may have adhesiveness (before irradiation with ultraviolet rays), and the adhesive strength may decrease after irradiation with ultraviolet rays to exhibit peelability.
  • the laminate C including the second hard substrate 20 / the second ultraviolet absorbing layer 50 / member 30 is subjected to a further transfer step, and laser light is applied.
  • the member can be easily peeled off from the laminated body C by irradiation, and the transfer efficiency can be improved.
  • the pressure-sensitive adhesive layer comprises a UV curable pressure-sensitive adhesive.
  • the pressure-sensitive adhesive layer may be a pressure-sensitive adhesive layer whose adhesive strength is improved by irradiation with ultraviolet rays, or may be a pressure-sensitive adhesive layer whose adhesive strength is reduced by irradiation with ultraviolet rays.
  • the pressure-sensitive adhesive for example, the above-mentioned active energy ray-curable pressure-sensitive adhesive can be used.
  • the laminate B formed by the fixing step (first hard substrate 10 / first ultraviolet absorbing layer 40 / member 30 / (second ultraviolet absorbing layer 50) / second
  • the first ultraviolet absorbing layer 40 of the hard substrate 20 is irradiated with ultraviolet rays (preferably UV laser light) to peel off the member 30 from the first hard substrate 10.
  • the conditions of ultraviolet irradiation can be any appropriate conditions depending on the configuration of the first ultraviolet absorbing layer 40, as long as the first ultraviolet absorbing layer 40 can be peeled off.
  • the first UV absorbing layer is composed of organic material (preferably containing a UV absorber), it will emit any suitable output of laser light with a wavelength of 200 nm to 380 nm (eg, 0.
  • the gas generated by the decomposition of the ultraviolet absorbing agent and / or the ultraviolet absorbing agent generates heat, so that the pressure-sensitive adhesive layer is generated.
  • the gas generated by decomposition causes deformation of the first ultraviolet absorbing layer, and as a result, peelability is exhibited in the portion irradiated with the laser beam.
  • the first ultraviolet absorbing layer is composed of an organic substance (preferably containing an ultraviolet absorbing agent) and the first ultraviolet absorbing layer contains an active energy ray-curable pressure-sensitive adhesive, the above-mentioned case.
  • the entire first ultraviolet absorbing layer may be irradiated with active energy rays to reduce the adhesive strength of the first 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 . In this way, if the active energy ray is irradiated before the laser light irradiation, the adhesive residue can be prevented and the member can be transferred.
  • the first UV absorbing layer when the first UV absorbing layer is composed of an inorganic substance, it is shorter than the absorption edge wavelength of the material constituting the first UV absorption layer and higher than the absorption edge wavelength of the first hard substrate.
  • a laser beam having a long wavelength is applied to the first ultraviolet absorbing layer.
  • the first ultraviolet absorbing layer when the first ultraviolet absorbing layer is a GaN (gallium nitride) -based compound crystal layer, it has a wavelength shorter than the absorption edge wavelength (365 nm) of GaN and longer than the absorption edge wavelength (180 nm) of the sapphire substrate.
  • an excimer laser having a wavelength of 248 nm is used.
  • the first hard substrate 10 is peeled from the laminated body B, and the member 30 (substantially, the first ultraviolet absorbing) is absorbed.
  • a structure composed of the layer 40 and the member 30) can be transferred onto the second rigid substrate 20.
  • the first hard substrate 10 and the first ultraviolet absorbing layer 40 can be peeled off from the laminated body B, and the member 30 can be transferred onto the second hard substrate 20.
  • the partial transfer method can be repeated a plurality of times, and the members can be transferred one after another.
  • the second ultraviolet absorbing layer is formed on the second hard substrate.
  • the second 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. If the second ultraviolet absorbing layer 50 is formed, the transfer efficiency can be improved.
  • the laminated body C (FIGS. 3A to 3B) obtained through the peeling step is laminated on the third hard substrate 60 (FIG. 3 (FIG. 3). c) to (d)), and then the second ultraviolet absorbing layer 50 is irradiated with ultraviolet rays (FIG. 3 (e)) to peel off the member 30 from the second hard substrate 20 (FIG. 3 (f)).
  • the laminate C has a structure of a second hard substrate / second ultraviolet absorbing layer / member or a second hard substrate / second ultraviolet absorbing layer / member / first ultraviolet absorbing layer. It can be taken.
  • the laminated body C is laminated on the third hard substrate 60, the surface of the laminated body C opposite to the second hard substrate 20 (member 30 in the illustrated example) is on the third hard substrate 60 side.
  • the laminated body C is arranged so as to be.
  • the rigid substrate described in Section B-1 can be used as the third rigid substrate.
  • a third ultraviolet absorbing layer 70 or an adhesive layer may be formed on the third hard substrate 60.
  • the third ultraviolet absorbing layer 70 may be arranged between the member 30 and the third hard substrate 60.
  • the third ultraviolet absorbing layer 70 is preferably a layer composed of an organic substance. Examples of such an ultraviolet absorbing layer include the ultraviolet absorbing layer described in the section “First ultraviolet absorbing layer composed of organic substances”, that is, the third ultraviolet absorbing layer 70 is initially (that is,).
  • the layer may have adhesiveness (before irradiation with ultraviolet rays), and the adhesive strength may decrease after irradiation with ultraviolet rays to exhibit peelability.
  • the laminate D including the third hard substrate 60 / the third ultraviolet absorbing layer 70 / member 30 is subjected to a further transfer step, and laser light is applied.
  • the member 30 can be easily peeled off from the laminated body D by irradiation, and the transfer efficiency can be improved.
  • the pressure-sensitive adhesive layer may be arranged between the third hard substrate and the third ultraviolet absorbing layer.
  • the pressure-sensitive adhesive layer comprises a UV curable pressure-sensitive adhesive.
  • the pressure-sensitive adhesive layer may be a pressure-sensitive adhesive layer whose adhesive strength is improved by irradiation with ultraviolet rays, or may be a pressure-sensitive adhesive layer whose adhesive strength is reduced by irradiation with ultraviolet rays.
  • the pressure-sensitive adhesive for example, the above-mentioned active energy ray-curable pressure-sensitive adhesive can be used.
  • the second ultraviolet absorbing layer is a layer containing an ultraviolet curable pressure-sensitive adhesive, and the second ultraviolet absorbing layer is used before the laminated body C is laminated on the third hard substrate. Is irradiated with ultraviolet rays to reduce the adhesive strength of the second ultraviolet absorbing layer.
  • the conditions for ultraviolet irradiation are, for example, an ultraviolet wavelength of 300 nm to 400 nm, and an irradiation amount of an integrated light amount of 300 mJ / cm 2 to 1500 mJ / cm 2 . As described above, if the member is irradiated with active energy rays before being laminated on the third hard substrate, the transferability of the member can be improved.
  • the above members can be transferred one after another.
  • a sapphire substrate 10 (first rigid substrate 10) having an optical semiconductor element 30 (member 30) formed on the surface thereof via an epitaxial layer 40 (first ultraviolet absorbing layer 40) is prepared. did.
  • the optical semiconductor element 30 (member 30) is placed on a glass substrate 20 (second hard substrate 20) on which an ultraviolet curable pressure-sensitive adhesive layer 50 (second ultraviolet absorbing layer 50) containing an ultraviolet absorber is laminated.
  • an ultraviolet curable pressure-sensitive adhesive layer 50 second ultraviolet absorbing layer 50
  • the optical semiconductor element 30 (member 30) was transferred from the sapphire substrate 10 (first hard substrate 10) to the glass substrate 20 (second hard substrate 20). According to this method, it was possible to transfer without destroying the member.
  • Example 1-2 The same process as in Example 1 was performed, and the optical semiconductor element 30 (member 30) arranged on the second hard substrate 20 via the ultraviolet curable pressure-sensitive adhesive layer 50 (second ultraviolet absorbing layer 50) was formed. A laminated body C configured by being arranged was obtained. Next, the ultraviolet curable adhesive layer 50 (second ultraviolet absorbing layer 50) is irradiated with ultraviolet rays (wavelength: 355 nm to 365 nm, integrated light amount: 1380 mJ / cm 2 ) through the glass substrate 20 (second hard substrate 20). Then, the pressure-sensitive adhesive layer was cured, and the pressure-sensitive adhesive force of the pressure-sensitive adhesive layer on the optical semiconductor element 30 (member 30) was reduced (not shown). Next, as described with reference to FIG.
  • the glass substrate 60 (third hard substrate 60) on which the ultraviolet curable pressure-sensitive adhesive layer 70 (third ultraviolet absorbing layer 70) containing an ultraviolet absorber is laminated is placed on the glass substrate 60 (third hard substrate 60).
  • the optical semiconductor element 30 (member 30) was bonded.
  • the ultraviolet curable pressure-sensitive adhesive layer 50 (second ultraviolet absorbing layer 50) is irradiated with ultraviolet laser light (wavelength: 355 nm, irradiation energy: 10 J / cm 2 ) to generate the optical semiconductor element 30 (member 30).
  • ultraviolet laser light wavelength: 355 nm, irradiation energy: 10 J / cm 2
  • Examples 2-1 and -2 Instead of forming the UV-curable pressure-sensitive adhesive layer 50 (second UV-absorbing layer 50) as a single layer, the UV-curable pressure-sensitive adhesive layer 50 (second UV-absorbing layer 50), a PET substrate, and pressure-sensitive. Instead of using a double-sided pressure-sensitive adhesive sheet composed of a pressure-sensitive adhesive layer and forming the UV-curable pressure-sensitive adhesive layer 70 (third UV-absorbing layer 70) as a single layer, the UV-curable pressure-sensitive adhesive layer 70 (third). Transfer of the member 30 in the same manner as in Examples 1-1 and 1-2, except that the double-sided pressure-sensitive adhesive sheet composed of the ultraviolet absorbing layer 70) of 3), the PET base material, and the pressure-sensitive pressure-sensitive adhesive layer was used. Was done. Even by this method, it was possible to transfer the member without destroying the member.

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Abstract

The present invention provides a method for transferring a member, said method being capable of reliably transferring a member (an article to be processed), while using a hard substrate.　A method for transferring a member according to the present invention transfers a member, which is arranged on a first hard substrate, to a second hard substrate. This method for transferring a member comprises: a step for forming a multilayer body A by stacking the first hard substrate and the member, with a first ultraviolet absorption layer being interposed therebetween; a step for forming a multilayer body B by subsequently affixing the multilayer body A to the second hard substrate in such a manner that the member is positioned on the second hard substrate side; and a step for subsequently separating the first hard substrate from the multilayer body B by irradiating the first ultraviolet absorption layer with ultraviolet light.

Description

部材転写方法Member transfer method
　本発明は、部材転写方法に関する。 The present invention relates to a member transfer method.
　従来より、電子部品の加工においては、工程間の移送等のため、基板をキャリアとして用い、当該基板上に配置された電子部品を他の基板に転写することが行われている。マイクロＬＥＤ等の超小型チップを転写する際には、転写の際の位置精度をよくする観点から、硬質基板をキャリアとして用いることがある。 Conventionally, in the processing of electronic components, a substrate is used as a carrier for transfer between processes, and the electronic components arranged on the substrate are transferred to another substrate. When transferring an ultra-small chip such as a micro LED, a hard substrate may be used as a carrier from the viewpoint of improving the position accuracy at the time of transfer.
国際公開第２０１２／０１１２０２号International Publication No. 2012/011202
　硬質基板をキャリアとした場合、より具体的には、第１の硬質基板上に所定の粘着剤層を介して配置された電子部品（例えば、マイクロＬＥＤ）を、粘着剤層付の第２の硬質基板上に転写する場合、しなりにくい硬質基板を用いているため、第１の硬質基板を基板の主面に対して垂直方向に離間させることとなる。そうすると、電子部品に負荷がかかり当該電子部品が破損したり、転写不良が生じたり等の問題が生じる。 When a hard substrate is used as a carrier, more specifically, an electronic component (for example, a micro LED) arranged on the first hard substrate via a predetermined adhesive layer is provided with a second adhesive layer. When transferring onto a hard substrate, since a hard substrate that is difficult to bend is used, the first hard substrate is separated in the direction perpendicular to the main surface of the substrate. Then, a load is applied to the electronic component, and problems such as damage to the electronic component and transfer failure occur.
　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、硬質基板を用いつつも、良好に部材（被加工品）の転写を行うことができる部材転写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 a member transfer method capable of satisfactorily transferring a member (workpiece) while using a hard substrate. Is to provide.
　本発明の部材転写方法は、第１の硬質基板上に配置された部材を第２の硬質基板に転写する方法であって、第１の紫外線吸収層を介して、該第１の硬質基板と該部材とを積層して、積層体Ａを形成する工程と、その後、該積層体Ａを、該部材が該第２の硬質基板側となるようにして、該第２の硬質基板に固定し、積層体Ｂを形成する工程と、その後、該第１の紫外線吸収層に紫外線を照射して、該積層体Ｂから該第１の硬質基板を剥離する工程とを含む。
　１つの実施形態において、上記第１の硬質基板と、上記部材との間に、粘着剤層が配置されている。
　１つの実施形態において、上記第１の紫外線吸収層が、有機物から構成される。
　１つの実施形態において、上記第１の紫外線吸収層が、無機物から構成される。
　１つの実施形態において、上記第２の硬質基板上に、第２の紫外線吸収層が形成され、該第２の紫外線吸収層が、前記部材と前記第２の硬質基板との間に配置されている。
　本発明の別の局面によれば、積層体が提供される。この積層体は、第１の硬質基板と、第１の紫外線吸収層と、部材と、第２の硬質基板とをこの順に備え、上記部材転写方法に用いられる。 The member transfer method of the present invention is a method of transferring a member arranged on a first hard substrate to a second hard substrate, and the member is transferred to the first hard substrate via a first ultraviolet absorbing layer. A step of laminating the member to form a laminated body A, and then fixing the laminated body A to the second hard substrate so that the member is on the second hard substrate side. , A step of forming the laminated body B, and then a step of irradiating the first ultraviolet absorbing layer with ultraviolet rays to peel off the first hard substrate from the laminated body B.
In one embodiment, the pressure-sensitive adhesive layer is arranged between the first hard substrate and the member.
In one embodiment, the first UV absorbing layer is composed of organic matter.
In one embodiment, the first UV absorbing layer is composed of an inorganic substance.
In one embodiment, a second ultraviolet absorbing layer is formed on the second hard substrate, and the second ultraviolet absorbing layer is arranged between the member and the second hard substrate. There is.
According to another aspect of the invention, a laminate is provided. This laminated body includes a first hard substrate, a first ultraviolet absorbing layer, a member, and a second hard substrate in this order, and is used in the member transfer method.
　本発明によれば、硬質基板を用いつつも、良好に部材（被加工品）の転写を行うことができる部材転写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 transfer method capable of satisfactorily transferring a member (workpiece) while using a hard substrate.
本発明の１つの実施形態による部材転写方法を説明する概略図である。It is a schematic diagram explaining the member transfer method by one Embodiment of this invention. 本発明の別の実施形態による部材転写方法を説明する概略図である。It is a schematic diagram explaining the member transfer method by another embodiment of this invention. 本発明の別の実施形態による部材転写方法を説明する概略図である。It is a schematic diagram explaining the member transfer method by another embodiment of this invention.
Ａ．部材転写法の概要
　図１は、本発明の１つの実施形態による部材転写方法を説明する概略図である。図２は、本発明の別の実施形態による部材転写方法を説明する概略図である。本発明の部材転写方は、第１の硬質基板１０上に配置された部材３０を第２の硬質基板２０に転写する方法である。当該方法は、第１の紫外線吸収層４０を介して第１の硬質基板１０と部材３０とを積層して積層体Ａを形成する工程（以下、積層工程ともいう）と、その後、積層体Ａを、部材３０が第２の硬質基板２０側となるようにして、第２の硬質基板２０に固定し、積層体Ｂを形成する工程（以下、固定工程ともいう）と、その後、第１の紫外線吸収層４０に紫外線を照射して、上記積層体Ｂ（第２の硬質基板２０）から第１の硬質基板１０を剥離する工程（以下、剥離工程ともいう）を含む。紫外線吸収層（第１の紫外線吸収層４０、第２の紫外線吸収層５０（後述））とは、紫外線を吸収し得る特性を有する層であって、紫外線（好ましくは、ＵＶレーザー光）の照射により、その表面の一部または全部において、剥離性を示す層をいう。 A. Outline of Member Transfer Method FIG. 1 is a schematic diagram illustrating a member transfer method according to one embodiment of the present invention. FIG. 2 is a schematic diagram illustrating a member transfer method according to another embodiment of the present invention. The member transfer method of the present invention is a method of transferring a member 30 arranged on a first hard substrate 10 to a second hard substrate 20. The method comprises a step of laminating a first hard substrate 10 and a member 30 via a first ultraviolet absorbing layer 40 to form a laminated body A (hereinafter, also referred to as a laminating step), and then a laminated body A. Is fixed to the second hard substrate 20 so that the member 30 is on the second hard substrate 20 side to form the laminated body B (hereinafter, also referred to as a fixing step), and then the first step. A step of irradiating the ultraviolet absorbing layer 40 with ultraviolet rays to peel off the first hard substrate 10 from the laminated body B (second hard substrate 20) (hereinafter, also referred to as a peeling step) is included. The ultraviolet absorbing layer (first ultraviolet absorbing layer 40, second ultraviolet absorbing layer 50 (described later)) is a layer having a property of being able to absorb ultraviolet rays, and is irradiated with ultraviolet rays (preferably UV laser light). Refers to a layer that exhibits peelability on a part or all of its surface.
　上記部材は、特に限定されず、例えば、半導体素子、光半導体素子などの電子部品が、用いられ得る。固定工程前、上記部材は、第１の紫外線吸収層上に複数配置されていてもよく、１個配置されていてもよい。 The above member is not particularly limited, and for example, an electronic component such as a semiconductor element or an optical semiconductor element can be used. Before the fixing step, a plurality of the above members may be arranged on the first ultraviolet absorbing layer, or one may be arranged.
　上記部材ひとつあたりの載置面積は、例えば、１μｍ２～１ｃｍ２である。また、複数の部材が配置される場合、その間隔は、例えば、２μｍ～５ｍｍである。 The mounting area per member is, for example, 1 μm 2 to 1 cm 2 . When a plurality of members are arranged, the interval is, for example, 2 μm to 5 mm.
　１つの実施形態において、上記部材３０と上記第１の紫外線吸収層４０とは一体で用いられる。部材３０／第１の紫外線吸収層４０とから構成される構成体（例えば、電子部品）としては、例えば、無機物である第１の紫外線吸収層４０と組み合わされた部材３０が挙げられ、具体的には、例えば、第１の紫外線吸収層４０として、ＧａＮ（窒化ガリウム）系化合物結晶層を備える光半導体素子（ＬＥＤ）が挙げられる。この実施形態においては、図１に示すように、上記方法により、部材３０／第１の紫外線吸収層４０とから構成される構成体が、第１の硬質基板１０から第２の硬質基板２０に転写される。 In one embodiment, the member 30 and the first ultraviolet absorbing layer 40 are used integrally. Examples of the component (for example, an electronic component) composed of the member 30 / the first ultraviolet absorbing layer 40 include a member 30 combined with the first ultraviolet absorbing layer 40 which is an inorganic substance, and specific examples thereof include the member 30. For example, as the first ultraviolet absorbing layer 40, an optical semiconductor device (LED) provided with a GaN (gallium nitride) -based compound crystal layer can be mentioned. In this embodiment, as shown in FIG. 1, by the above method, the structure composed of the member 30 / the first ultraviolet absorbing layer 40 is changed from the first hard substrate 10 to the second hard substrate 20. Transferred.
　別の実施形態においては、図２に示すように、剥離工程において、第１の硬質基板１０と第１の紫外線吸収層４０とを含む積層体が、積層体Ｂ（第１の硬質基板１０）から剥離され、したがって、上記転写方法により、部材３０と第１の紫外線吸収層４０とは離間する。本実施形態においては、第１の紫外線吸収層４０として、有機物である第１の紫外線吸収層４０が形成され得る。 In another embodiment, as shown in FIG. 2, in the peeling step, the laminated body including the first hard substrate 10 and the first ultraviolet absorbing layer 40 is the laminated body B (first hard substrate 10). Therefore, the member 30 and the first ultraviolet absorbing layer 40 are separated from each other by the above transfer method. In the present embodiment, the first ultraviolet absorbing layer 40, which is an organic substance, can be formed as the first ultraviolet absorbing layer 40.
　本発明によれば、紫外線の照射により、硬質基板の剥離が実現できるため、部材に不要な負荷をかけることなく、当該部材の転写を完了させることができる。なお、積層工程と固定工程との間において、部材を加工する任意の適切な工程を行ってもよい。 According to the present invention, since the hard substrate can be peeled off by irradiation with ultraviolet rays, the transfer of the member can be completed without applying an unnecessary load to the member. In addition, any appropriate process for processing a member may be performed between the laminating process and the fixing process.
Ｂ.積層工程
Ｂ－１．硬質基板
　上記硬質基板（第１の硬質基板、第２の硬質基板）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. Laminating process B-1. Hard substrate The hard substrate (first hard substrate, second rigid substrate) refers to a molded body on a plate having a flexural modulus of 1 GPa or more. The bending elasticity 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。硬質基板を構成する材料としては、例えば、ガラス、金属、シリコン、サファイア、プラスチック等が挙げられる。１つの実施形態においては、硬質基板としてポリエチレンテレフタレートから構成された硬質基板が用いられる。ポリエチレンテレフタレートから構成された硬質基板の厚みは、例えば、１００μｍ以上である。 Any suitable material can be used as the material constituting the hard substrate. Examples of the material constituting the hard substrate include glass, metal, silicon, sapphire, and plastic. In one embodiment, a hard substrate made of polyethylene terephthalate is used as the hard substrate. The thickness of the hard substrate made of polyethylene terephthalate is, for example, 100 μm or more.
　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。 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.
　第１の硬質基板と第２の硬質基板は、同じ構成であってもよく、異なる構成であってもよい。 The first hard substrate and the second rigid substrate may have the same configuration or different configurations.
Ｂ－２．第１の紫外線吸収層
　１つの実施形態において、上記第１の紫外線吸収層は、有機物から構成される。別の実施形態においては、上記第１の紫外線吸収層は、無機物から構成される。 B-2. First Ultraviolet Absorbing Layer In one embodiment, the first ultraviolet absorbing layer is composed of an organic substance. In another embodiment, the first UV absorbing layer is composed of an inorganic substance.
（有機物から構成される第１の紫外線吸収層）
　有機物から構成される第１の紫外線吸収層は、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、第１の紫外線吸収層は、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。 (First ultraviolet absorbing layer composed of organic substances)
The first ultraviolet absorbing layer composed of an organic substance may be a layer that has adhesiveness at an 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 first UV absorbing layer may 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、有機物から構成される第１の紫外線吸収層は、紫外線吸収剤を含む。好ましくは、有機物から構成される第１の紫外線吸収層は、活性エネルギー線硬化型粘着剤をさらに含む。 In one embodiment, the first UV absorbing layer composed of organic matter contains a UV absorber. Preferably, the first UV-absorbing layer composed of an organic substance further contains an active energy ray-curable pressure-sensitive adhesive.
　第１の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、第１の紫外線吸収層にＵＶレーザー光を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第１の紫外線吸収層が分解して発生するガスにより、第１の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 first ultraviolet absorbing layer contains an ultraviolet absorber, the adherend can be peeled off by irradiation with UV laser light. More specifically, by irradiating the first ultraviolet absorbing layer with UV laser light, the gas generated by the decomposition of the ultraviolet absorber and / or the heat of the ultraviolet absorber causes the first ultraviolet absorbing layer to generate heat. The gas generated by decomposition causes deformation of the first ultraviolet absorbing layer, and as a result, peelability is exhibited in the portion irradiated with the UV laser light.
　また、第１の紫外線吸収層が、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、第１の紫外線吸収層全体の粘着力が低下する。部材が貼着された第１の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とにより、剥離後の糊残りを防止することができる。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 first ultraviolet absorbing layer contains an active energy ray-curable pressure-sensitive adhesive, the adhesive strength of the entire first ultraviolet absorbing layer is lowered by irradiating with the active energy rays. By irradiating the entire first ultraviolet absorbing layer to which the member is attached with active energy rays to reduce the adhesive strength, and then irradiating with laser light as described above, adhesive residue after peeling is prevented. can do. 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.
　上記有機物から構成される第１の紫外線吸収層の波長３５５ｎｍ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。第１の紫外線吸収層の波長３５５ｎｍの光透過率は、より好ましくは４０％以下であり、さらに好ましくは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。 The light transmittance of the first ultraviolet absorbing layer composed of the above organic substances at a wavelength of 355 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 first ultraviolet absorbing layer at a wavelength of 355 nm is more preferably 40% or less, still more preferably 30% or less. Within such a range, the above effect becomes more remarkable.
　有機物から構成される第１の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、良好に部材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往復により第１の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、第１の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 first ultraviolet absorbing layer composed of an organic substance is attached to a stainless steel plate is preferably 0.1 N / 20 mm to 20 N / 20 mm, more preferably 0.5 N / 20 mm. It is ~ 15N / 20mm. Within such a range, it is possible to form an ultraviolet absorbing layer that can hold the member well. Adhesive strength is measured according to JIS Z 0237: 2000. Specifically, the first ultraviolet absorbing layer is 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 the peeling angle. The measurement is performed by peeling off the first ultraviolet absorbing layer under the conditions of 180 ° and a 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、有機物から構成される第１の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、糊残り少なく部材の転写を行うことができる。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）を第１の紫外線吸収層に照射して行われる。 In one embodiment, the first ultraviolet absorbing layer composed of an organic substance is attached to a stainless steel plate, and the adhesive strength at 23 ° C. after irradiation with ultraviolet rays of 460 mJ / cm 2 is preferably 0.01 N /. It is 20 mm to 2N / 20 mm, more preferably 0.02N / 20 mm to 1N / 20 mm. Within such a range, the member can be transferred with less 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 first ultraviolet absorbing layer with / cm 2 , irradiation time: 6.6 seconds).
　有機物から構成される第１の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。第１の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 first ultraviolet absorbing layer composed of organic substances 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 first 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、第１の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, more preferably 5 parts by weight to 20 parts by weight, based on 100 parts by weight of the base polymer in the first 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 peelability 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 a 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、第１の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 first ultraviolet absorbing layer and the peeling by the ultraviolet absorber 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.
（無機物から構成される第１の紫外線吸収層）
　上記のとおり、無機物から構成される第１の紫外線吸収層と上記部材とは、組み合わせて用いられ得、ひとつの構成体（例えば、電子部品）を構成し得る。すなわち、無機物から構成される第１の紫外線吸収層は、上記構成体（例えば、電子部品）の一部であり得る。 (First UV absorbing layer composed of inorganic substances)
As described above, the first ultraviolet absorbing layer made of an inorganic substance and the above-mentioned member can be used in combination to form one component (for example, an electronic component). That is, the first ultraviolet absorbing layer made of an inorganic substance can be a part of the above-mentioned constituent (for example, an electronic component).
　上記のような無機物から構成される第１の紫外線吸収層は、エピタキシャル層であり得る。上記のような無機物から構成される第１の紫外線吸収層としては、例えば、ＧａＮ（窒化ガリウム）系化合物結晶層等のIII族の窒化物からなる層が挙げられる。 The first ultraviolet absorbing layer composed of the above-mentioned inorganic substances may be an epitaxial layer. Examples of the first ultraviolet absorbing layer made of the above-mentioned inorganic substances include a layer made of a group III nitride such as a GaN (gallium nitride) compound crystal layer.
　無機物から構成される第１の紫外線吸収層は、いわゆるレーザーリフトオフの手法により剥離性を発現する。例えば、高密度ＵＶレーザー光が照射されることにより、無機物から構成される第１の紫外線吸収層が分解して、その結果、第１の紫外線吸収層と第１の硬質基板とが離間する。レーザーリフトオフの詳細は、例えば、国際公開第２０１２／０１１２０２号に記載されており、当該公報の記載は本明細書に参考として援用される。 The first ultraviolet absorbing layer composed of an inorganic substance exhibits peelability by a so-called laser lift-off method. For example, when irradiated with high-density UV laser light, the first ultraviolet absorbing layer made of an inorganic substance is decomposed, and as a result, the first ultraviolet absorbing layer and the first hard substrate are separated from each other. Details of the laser lift-off are described, for example, in International Publication No. 2012/011202, and the description in this publication is incorporated herein by reference.
Ｂ－３．粘着剤層
　上記積層体Ａは、粘着剤層を備えていてもよい。１つの実施形態においては、第１の硬質基板と部材との間に粘着剤層が配置され得る。例えば、第１の硬質基板と第１の紫外線吸収層との間に、粘着剤層が配置され得る。また、粘着剤層と第１の紫外線吸収層とは、任意の適切な基材を介して、積層されていてもよい。基材としては、任意の適切な樹脂から構成された基材が用いられ得る。 B-3. Adhesive layer The laminate A may include an adhesive layer. In one embodiment, an adhesive layer may be placed between the first rigid substrate and the member. For example, an adhesive layer may be arranged between the first rigid substrate and the first UV absorbing layer. Further, the pressure-sensitive adhesive layer and the first ultraviolet absorbing layer may be laminated via any suitable base material. As the base material, a base material composed of any suitable resin can be used.
　１つの実施形態において、上記粘着剤層は、紫外線硬化型の粘着剤を含む。当該粘着剤層は、紫外線照射により粘着力が向上する粘着剤層であってもよく、紫外線照射により粘着力が低下する粘着剤層であってもよい。粘着剤としては、例えば、上記活性エネルギー線硬化型粘着剤が用いられ得る。別の実施形態においては、上記粘着剤層は、感圧粘着剤を含む。感圧粘着剤としては、常用の粘着剤が用いられ得る。 In one embodiment, the pressure-sensitive adhesive layer contains a UV curable pressure-sensitive adhesive. The pressure-sensitive adhesive layer may be a pressure-sensitive adhesive layer whose adhesive strength is improved by irradiation with ultraviolet rays, or may be a pressure-sensitive adhesive layer whose adhesive strength is reduced by irradiation with ultraviolet rays. As the pressure-sensitive adhesive, for example, the above-mentioned active energy ray-curable pressure-sensitive adhesive can be used. In another embodiment, the pressure-sensitive adhesive layer comprises a pressure-sensitive pressure-sensitive adhesive. As the pressure-sensitive pressure-sensitive adhesive, a commonly used pressure-sensitive adhesive may be used.
Ｃ.固定工程
　上記積層工程により、積層体Ａ（第１の硬質基板１０／第１の紫外線吸収層４０／部材３０）を形成した後、固定工程において、当該積層体Ａを第２の硬質基板２０上に固定する。 C. Fixing step After forming the laminated body A (first hard substrate 10 / first ultraviolet absorbing layer 40 / member 30) by the above laminating step, the laminated body A is used as a second hard substrate in the fixing step. Fix on 20.
（第２の硬質基板）
　第２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。 (Second hard substrate)
As the second hard substrate, the hard substrate described in Section B-1 can be used.
　図１および図２に示すように、第２の硬質基板２０上には、第２の紫外線吸収層５０または粘着剤層が形成され得る。第２の紫外線吸収層５０は、部材３０と第２の硬質基板２０との間に配置され得る。第２の紫外線吸収層５０としては、有機物から構成される層であることが好ましい。このような紫外線吸収層としては、「有機物から構成される第１の紫外線吸収層」の項で説明した紫外線吸収層が挙げられ、すなわち、第２の紫外線吸収層５０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。第２の紫外線吸収層５０が形成されていれば、剥離工程の後に、第２の硬質基板２０／第２の紫外線吸収層５０／部材３０を含む積層体Ｃをさらなる移送工程に供し、レーザー光照射により積層体Ｃから容易に部材を剥離することができ、転写効率を向上させることができる。 As shown in FIGS. 1 and 2, a second ultraviolet absorbing layer 50 or an adhesive layer may be formed on the second hard substrate 20. The second ultraviolet absorbing layer 50 may be arranged between the member 30 and the second hard substrate 20. The second ultraviolet absorbing layer 50 is preferably a layer composed of an organic substance. Examples of such an ultraviolet absorbing layer include the ultraviolet absorbing layer described in the section “First ultraviolet absorbing layer composed of organic substances”, that is, the second ultraviolet absorbing layer 50 is initially (that is,). The layer may have adhesiveness (before irradiation with ultraviolet rays), and the adhesive strength may decrease after irradiation with ultraviolet rays to exhibit peelability. If the second ultraviolet absorbing layer 50 is formed, after the peeling step, the laminate C including the second hard substrate 20 / the second ultraviolet absorbing layer 50 / member 30 is subjected to a further transfer step, and laser light is applied. The member can be easily peeled off from the laminated body C by irradiation, and the transfer efficiency can be improved.
　第２の硬質基板２０上に第２の紫外線吸収層５０が形成される場合、当該第２の硬質基板２０と第２の紫外線吸収層５０との間に、粘着剤層が配置されていてもよい。１つの実施形態において、上記粘着剤層は、紫外線硬化型の粘着剤を含む。当該粘着剤層は、紫外線照射により粘着力が向上する粘着剤層であってもよく、紫外線照射により粘着力が低下する粘着剤層であってもよい。粘着剤としては、例えば、上記活性エネルギー線硬化型粘着剤が用いられ得る。 When the second ultraviolet absorbing layer 50 is formed on the second hard substrate 20, even if the pressure-sensitive adhesive layer is arranged between the second hard substrate 20 and the second ultraviolet absorbing layer 50. good. In one embodiment, the pressure-sensitive adhesive layer comprises a UV curable pressure-sensitive adhesive. The pressure-sensitive adhesive layer may be a pressure-sensitive adhesive layer whose adhesive strength is improved by irradiation with ultraviolet rays, or may be a pressure-sensitive adhesive layer whose adhesive strength is reduced by irradiation with ultraviolet rays. As the pressure-sensitive adhesive, for example, the above-mentioned active energy ray-curable pressure-sensitive adhesive can be used.
Ｄ.剥離工程
　剥離工程においては、上記固定工程により形成された積層体Ｂ（第１の硬質基板１０／第１の紫外線吸収層４０／部材３０／（第２の紫外線吸収層５０）／第２の硬質基板２０）の第１の紫外線吸収層４０に紫外線（好ましくは、ＵＶレーザー光）を照射して、第１の硬質基板１０から部材３０を剥離する。紫外線照射の諸条件は、第１の紫外線吸収層４０に剥離性を生じさせ得る限り、第１の紫外線吸収層４０の構成に応じて、任意の適切条件とすることができる。 D. Peeling step In the peeling step, the laminate B formed by the fixing step (first hard substrate 10 / first ultraviolet absorbing layer 40 / member 30 / (second ultraviolet absorbing layer 50) / second The first ultraviolet absorbing layer 40 of the hard substrate 20) is irradiated with ultraviolet rays (preferably UV laser light) to peel off the member 30 from the first hard substrate 10. The conditions of ultraviolet irradiation can be any appropriate conditions depending on the configuration of the first ultraviolet absorbing layer 40, as long as the first ultraviolet absorbing layer 40 can be peeled off.
　１つの実施形態において、第１の紫外線吸収層が、有機物から構成される場合（好ましくは、紫外線吸収剤を含む場合）、波長２００ｎｍ～３８０ｎｍの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）で第１の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、第１の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。 In one embodiment, if the first UV absorbing layer is composed of organic material (preferably containing a UV absorber), it will emit any suitable output of laser light with a wavelength of 200 nm to 380 nm (eg, 0. By irradiating the first ultraviolet absorbing layer with 01W to 6W, preferably 0.05W to 5W), the gas generated by the decomposition of the ultraviolet absorbing agent and / or the ultraviolet absorbing agent generates heat, so that the pressure-sensitive adhesive layer is generated. The gas generated by decomposition causes deformation of the first ultraviolet absorbing layer, and as a result, peelability is exhibited in the portion irradiated with the laser beam.
　第１の紫外線吸収層が、有機物から構成される場合（好ましくは、紫外線吸収剤を含む場合）であって、当該第１の紫外線吸収層が、活性エネルギー線硬化型粘着剤を含む場合、上記のようにＵＶレーザー光を照射する前に、活性エネルギー線を第１の紫外線吸収層の全体に照射して、第１の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、糊残りを防止して、部材を転写することができる。 When the first ultraviolet absorbing layer is composed of an organic substance (preferably containing an ultraviolet absorbing agent) and the first ultraviolet absorbing layer contains an active energy ray-curable pressure-sensitive adhesive, the above-mentioned case. Before irradiating the UV laser light as described above, the entire first ultraviolet absorbing layer may be irradiated with active energy rays to reduce the adhesive strength of the first 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 . In this way, if the active energy ray is irradiated before the laser light irradiation, the adhesive residue can be prevented and the member can be transferred.
　１つの実施形態において、第１の紫外線吸収層が、無機物から構成される場合、第１の紫外線吸収層を構成する材料の吸収端波長よりも短く、第１の硬質基板の吸収端波長よりも長い波長を有するレーザー光（エキシマレーザー光）が、第１の紫外線吸収層に照射される。例えば、第１の紫外線吸収層が、ＧａＮ（窒化ガリウム）系化合物結晶層である場合、ＧａＮの吸収端波長（３６５ｎｍ）よりも短く、サファイア基板の吸収端波長（１８０ｎｍ）よりも長い波長を有する、例えば、波長２４８ｎｍのエキシマレーザーが利用される。 In one embodiment, when the first UV absorbing layer is composed of an inorganic substance, it is shorter than the absorption edge wavelength of the material constituting the first UV absorption layer and higher than the absorption edge wavelength of the first hard substrate. A laser beam having a long wavelength (excimer laser beam) is applied to the first ultraviolet absorbing layer. For example, when the first ultraviolet absorbing layer is a GaN (gallium nitride) -based compound crystal layer, it has a wavelength shorter than the absorption edge wavelength (365 nm) of GaN and longer than the absorption edge wavelength (180 nm) of the sapphire substrate. For example, an excimer laser having a wavelength of 248 nm is used.
　上記のようにして、第１の紫外線吸収層に剥離性を生じさせることにより、積層体Ｂから第１の硬質基板１０を剥離して、上記部材３０（実質的には、第１の紫外線吸収層４０と部材３０とから構成される構成体）を第２の硬質基板２０上に転写することができる。あるいは、積層体Ｂから、第１の硬質基板１０および第１の紫外線吸収層４０を剥離して、上記部材３０を第２の硬質基板２０上に転写することができる。 By causing the first ultraviolet absorbing layer to have peelability as described above, the first hard substrate 10 is peeled from the laminated body B, and the member 30 (substantially, the first ultraviolet absorbing) is absorbed. A structure composed of the layer 40 and the member 30) can be transferred onto the second rigid substrate 20. Alternatively, the first hard substrate 10 and the first ultraviolet absorbing layer 40 can be peeled off from the laminated body B, and the member 30 can be transferred onto the second hard substrate 20.
Ｅ．部材転写法の応用
　１つの実施形態において、上記部分転写方法を複数回繰り返して、上記部材は、次々に転写され得る。この実施形態においては、上記第２の硬質基板上に第２の紫外線吸収層が形成されていることが好ましい。第２の紫外線吸収層は、上記のとおり、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。第２の紫外線吸収層５０が形成されていれば、転写効率を向上させることができる。 E. Application of member transfer method In one embodiment, the partial transfer method can be repeated a plurality of times, and the members can be transferred one after another. In this embodiment, it is preferable that the second ultraviolet absorbing layer is formed on the second hard substrate. As described above, the second 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. If the second ultraviolet absorbing layer 50 is formed, the transfer efficiency can be improved.
　具体的には、図３に示すように、上記剥離工程を経て得られた積層体Ｃ（図３（ａ）～（ｂ））を、第３の硬質基板６０上に積層し（図３（ｃ）～（ｄ））、その後、第２の紫外線吸収層５０に紫外線を照射して（図３（ｅ））、上記第２の硬質基板２０から部材３０を剥離する（図３（ｆ））。上記のとおり、積層体Ｃは、第２の硬質基板／第２の紫外線吸収層／部材、または、第２の硬質基板／第２の紫外線吸収層／部材／第１の紫外線吸収層の構成をとりうる。積層体Ｃを第３の硬質基板６０に積層する際には、積層体Ｃの第２の硬質基板２０とは反対側の面（図示例では、部材３０）が、第３の硬質基板６０側となるように、当該積層体Ｃが配置される。 Specifically, as shown in FIG. 3, the laminated body C (FIGS. 3A to 3B) obtained through the peeling step is laminated on the third hard substrate 60 (FIG. 3 (FIG. 3). c) to (d)), and then the second ultraviolet absorbing layer 50 is irradiated with ultraviolet rays (FIG. 3 (e)) to peel off the member 30 from the second hard substrate 20 (FIG. 3 (f)). ). As described above, the laminate C has a structure of a second hard substrate / second ultraviolet absorbing layer / member or a second hard substrate / second ultraviolet absorbing layer / member / first ultraviolet absorbing layer. It can be taken. When the laminated body C is laminated on the third hard substrate 60, the surface of the laminated body C opposite to the second hard substrate 20 (member 30 in the illustrated example) is on the third hard substrate 60 side. The laminated body C is arranged so as to be.
　第３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。 As the third rigid substrate, the rigid substrate described in Section B-1 can be used.
　第３の硬質基板６０上には、第３の紫外線吸収層７０または粘着剤層が形成され得る。第３の紫外線吸収層７０は、部材３０と第３の硬質基板６０との間に配置され得る。第３の紫外線吸収層７０としては、有機物から構成される層であることが好ましい。このような紫外線吸収層としては、「有機物から構成される第１の紫外線吸収層」の項で説明した紫外線吸収層が挙げられ、すなわち、第３の紫外線吸収層７０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。第３の紫外線吸収層７０が形成されていれば、剥離工程の後に、第３の硬質基板６０／第３の紫外線吸収層７０／部材３０を含む積層体Ｄをさらなる移送工程に供し、レーザー光照射により積層体Ｄから容易に部材３０を剥離することができ、転写効率を向上させることができる。 A third ultraviolet absorbing layer 70 or an adhesive layer may be formed on the third hard substrate 60. The third ultraviolet absorbing layer 70 may be arranged between the member 30 and the third hard substrate 60. The third ultraviolet absorbing layer 70 is preferably a layer composed of an organic substance. Examples of such an ultraviolet absorbing layer include the ultraviolet absorbing layer described in the section “First ultraviolet absorbing layer composed of organic substances”, that is, the third ultraviolet absorbing layer 70 is initially (that is,). The layer may have adhesiveness (before irradiation with ultraviolet rays), and the adhesive strength may decrease after irradiation with ultraviolet rays to exhibit peelability. If the third ultraviolet absorbing layer 70 is formed, after the peeling step, the laminate D including the third hard substrate 60 / the third ultraviolet absorbing layer 70 / member 30 is subjected to a further transfer step, and laser light is applied. The member 30 can be easily peeled off from the laminated body D by irradiation, and the transfer efficiency can be improved.
　第３の硬質基板上に第３の紫外線吸収層が形成される場合、当該第３の硬質基板と第３の紫外線吸収層との間に、粘着剤層が配置されていてもよい。１つの実施形態において、上記粘着剤層は、紫外線硬化型の粘着剤を含む。当該粘着剤層は、紫外線照射により粘着力が向上する粘着剤層であってもよく、紫外線照射により粘着力が低下する粘着剤層であってもよい。粘着剤としては、例えば、上記活性エネルギー線硬化型粘着剤が用いられ得る。 When the third ultraviolet absorbing layer is formed on the third hard substrate, the pressure-sensitive adhesive layer may be arranged between the third hard substrate and the third ultraviolet absorbing layer. In one embodiment, the pressure-sensitive adhesive layer comprises a UV curable pressure-sensitive adhesive. The pressure-sensitive adhesive layer may be a pressure-sensitive adhesive layer whose adhesive strength is improved by irradiation with ultraviolet rays, or may be a pressure-sensitive adhesive layer whose adhesive strength is reduced by irradiation with ultraviolet rays. As the pressure-sensitive adhesive, for example, the above-mentioned active energy ray-curable pressure-sensitive adhesive can be used.
　１つの実施形態においては、上記第２の紫外線吸収層が紫外線硬化型粘着剤を含む層であって、上記積層体Ｃを第３の硬質基板に積層する前に、当該第２の紫外線吸収層に紫外線を照射して、当該第２の紫外線吸収層の粘着力を低下させる。紫外線照射の条件としては、例えば、紫外線の波長３００ｎｍ～４００ｎｍで、照射量は、積算光量３００ｍＪ／ｃｍ２～１５００ｍＪ／ｃｍ２である。このように、第３の硬質基板に積層する前に、活性エネルギー線を照射すれば、部材を転写性を向上することができる。 In one embodiment, the second ultraviolet absorbing layer is a layer containing an ultraviolet curable pressure-sensitive adhesive, and the second ultraviolet absorbing layer is used before the laminated body C is laminated on the third hard substrate. Is irradiated with ultraviolet rays to reduce the adhesive strength of the second ultraviolet absorbing layer. The conditions for ultraviolet irradiation are, for example, an ultraviolet wavelength of 300 nm to 400 nm, and an irradiation amount of an integrated light amount of 300 mJ / cm 2 to 1500 mJ / cm 2 . As described above, if the member is irradiated with active energy rays before being laminated on the third hard substrate, the transferability of the member can be improved.
　上記の操作を繰り返すことに、上記部材を、次々に転写することができる。 By repeating the above operation, the above members can be transferred one after another.
［実施例１－１］
　図２で説明されるように、エピタキシャル層４０（第１の紫外線吸収層４０）を介して表面に光半導体素子３０（部材３０）を形成したサファイア基板１０（第１の硬質基板１０）を用意した。
　次いで、紫外線吸収剤を含む紫外線硬化型粘着剤層５０（第２の紫外線吸収層５０）が積層されたガラス基板２０（第２の硬質基板２０）上に、上記光半導体素子３０（部材３０）を接合した。
　エピタキシャル層４０（第１の紫外線吸収層４０）に紫外線レーザー光（波長：２４８ｎｍ、照射エネルギー：１０００Ｊ／ｃｍ２）を照射して、サファイア基板１０（第１の硬質基板１０）を剥離することによって、光半導体素子３０（部材３０）をサファイア基板１０（第１硬質基板１０）から、ガラス基板２０（第２の硬質基板２０）に転写した。当該方法によれば、部材を破壊することなく、転写することが可能であった。 [Example 1-1]
As described with reference to FIG. 2, a sapphire substrate 10 (first rigid substrate 10) having an optical semiconductor element 30 (member 30) formed on the surface thereof via an epitaxial layer 40 (first ultraviolet absorbing layer 40) is prepared. did.
Next, the optical semiconductor element 30 (member 30) is placed on a glass substrate 20 (second hard substrate 20) on which an ultraviolet curable pressure-sensitive adhesive layer 50 (second ultraviolet absorbing layer 50) containing an ultraviolet absorber is laminated. Was joined.
By irradiating the epitaxial layer 40 (first ultraviolet absorbing layer 40) with ultraviolet laser light (wavelength: 248 nm, irradiation energy: 1000 J / cm 2 ) to peel off the sapphire substrate 10 (first hard substrate 10). , The optical semiconductor element 30 (member 30) was transferred from the sapphire substrate 10 (first hard substrate 10) to the glass substrate 20 (second hard substrate 20). According to this method, it was possible to transfer without destroying the member.
［実施例１－２］
　実施例１と同様の工程を行い、第２の硬質基板２０上に、紫外線硬化型粘着剤層５０（第２の紫外線吸収層５０）を介して配置された光半導体素子３０（部材３０）が配置されて構成された積層体Ｃを得た。
　次いで、ガラス基板２０（第２の硬質基板２０）を通して紫外線（波長：３５５ｎｍ～３６５ｎｍ、積算光量：１３８０ｍＪ／ｃｍ２）を、紫外線硬化型粘着剤層５０（第２の紫外線吸収層５０）に照射し、当該粘着剤層を硬化し、当該粘着剤層の光半導体素子３０（部材３０）に対する粘着力を低下させた（図示せず）。
　次いで、図３で説明されるように、紫外線吸収剤を含む紫外線硬化型粘着剤層７０（第３の紫外線吸収層７０）が積層されたガラス基板６０（第３の硬質基板６０）上に、上記光半導体素子３０（部材３０）を接合した。
　次いで、紫外線硬化型粘着剤層５０（第２の紫外線吸収層５０）に、紫外線レーザー光（波長：３５５ｎｍ、照射エネルギー：１０Ｊ／ｃｍ２）を照射して、光半導体素子３０（部材３０）を剥離することによって、光半導体素子（部材）をガラス基板（第２の硬質基板）から、ガラス基板（第３の硬質基板）に転写した。当該方法によれば、部材を破壊することなく、転写することが可能であった。 [Example 1-2]
The same process as in Example 1 was performed, and the optical semiconductor element 30 (member 30) arranged on the second hard substrate 20 via the ultraviolet curable pressure-sensitive adhesive layer 50 (second ultraviolet absorbing layer 50) was formed. A laminated body C configured by being arranged was obtained.
Next, the ultraviolet curable adhesive layer 50 (second ultraviolet absorbing layer 50) is irradiated with ultraviolet rays (wavelength: 355 nm to 365 nm, integrated light amount: 1380 mJ / cm 2 ) through the glass substrate 20 (second hard substrate 20). Then, the pressure-sensitive adhesive layer was cured, and the pressure-sensitive adhesive force of the pressure-sensitive adhesive layer on the optical semiconductor element 30 (member 30) was reduced (not shown).
Next, as described with reference to FIG. 3, the glass substrate 60 (third hard substrate 60) on which the ultraviolet curable pressure-sensitive adhesive layer 70 (third ultraviolet absorbing layer 70) containing an ultraviolet absorber is laminated is placed on the glass substrate 60 (third hard substrate 60). The optical semiconductor element 30 (member 30) was bonded.
Next, the ultraviolet curable pressure-sensitive adhesive layer 50 (second ultraviolet absorbing layer 50) is irradiated with ultraviolet laser light (wavelength: 355 nm, irradiation energy: 10 J / cm 2 ) to generate the optical semiconductor element 30 (member 30). By peeling off, the optical semiconductor element (member) was transferred from the glass substrate (second hard substrate) to the glass substrate (third hard substrate). According to this method, it was possible to transfer without destroying the member.
［実施例２－１、－２］
　紫外線硬化型粘着剤層５０（第２の紫外線吸収層５０）を単層で構成したことに代えて、紫外線硬化型粘着剤層５０（第２の紫外線吸収層５０）とＰＥＴ基材と感圧粘着剤層とから構成される両面粘着シートを用い、紫外線硬化型粘着剤層７０（第３の紫外線吸収層７０）を単層で構成したことに代えて、紫外線硬化型粘着剤層７０（第３の紫外線吸収層７０）とＰＥＴ基材と感圧粘着剤層とから構成される両面粘着シートを用いたこと以外は、実施例１－１および１－２と同様にして、部材３０の転写を行った。当該方法によっても、部材を破壊することなく、転写することが可能であった。 [Examples 2-1 and -2]
Instead of forming the UV-curable pressure-sensitive adhesive layer 50 (second UV-absorbing layer 50) as a single layer, the UV-curable pressure-sensitive adhesive layer 50 (second UV-absorbing layer 50), a PET substrate, and pressure-sensitive. Instead of using a double-sided pressure-sensitive adhesive sheet composed of a pressure-sensitive adhesive layer and forming the UV-curable pressure-sensitive adhesive layer 70 (third UV-absorbing layer 70) as a single layer, the UV-curable pressure-sensitive adhesive layer 70 (third). Transfer of the member 30 in the same manner as in Examples 1-1 and 1-2, except that the double-sided pressure-sensitive adhesive sheet composed of the ultraviolet absorbing layer 70) of 3), the PET base material, and the pressure-sensitive pressure-sensitive adhesive layer was used. Was done. Even by this method, it was possible to transfer the member without destroying the member.
　１０　　　　　　　第１の硬質基板
　２０　　　　　　　第２の硬質基板
　３０　　　　　　　部材
　４０　　　　　　　第１の紫外線吸収層
　５０　　　　　　　第２の紫外線吸収層
　６０　　　　　　　第３の硬質基板
　７０　　　　　　　第３の紫外線吸収層 10 1st hard substrate 20 2nd hard substrate 30 Member 40 1st UV absorbing layer 50 2nd UV absorbing layer 60 3rd hard substrate 70 3rd UV absorbing layer

Claims (6)

  1. 　第１の硬質基板上に配置された部材を第２の硬質基板に転写する方法であって、
    　第１の紫外線吸収層を介して、該第１の硬質基板と該部材とを積層して、積層体Ａを形成する工程と、その後、
    　該積層体Ａを、該部材が該第２の硬質基板側となるようにして、該第２の硬質基板に固定し、積層体Ｂを形成する工程と、その後、
    　該第１の紫外線吸収層に紫外線を照射して、該積層体Ｂから該第１の硬質基板を剥離する工程とを含む、
    　部材転写方法。     A method of transferring a member arranged on a first hard substrate to a second hard substrate.
    A step of laminating the first hard substrate and the member via the first ultraviolet absorbing layer to form a laminated body A, and thereafter.
    A step of fixing the laminated body A to the second hard substrate so that the member is on the second hard substrate side to form the laminated body B, and thereafter.
    A step of irradiating the first ultraviolet absorbing layer with ultraviolet rays to peel off the first hard substrate from the laminated body B.
    Member transfer method.
  2. 　前記第１の硬質基板と、前記部材との間に、粘着剤層が配置されている、請求項１に記載の部材転写方法。 The member transfer method according to claim 1, wherein an adhesive layer is arranged between the first hard substrate and the member.
  3. 　前記第１の紫外線吸収層が、有機物から構成される、請求項１または２に記載の部材転写方法。 The member transfer method according to claim 1 or 2, wherein the first ultraviolet absorbing layer is composed of an organic substance.
  4. 　前記第１の紫外線吸収層が、無機物から構成される、請求項１または２に記載の部材転写方法。 The member transfer method according to claim 1 or 2, wherein the first ultraviolet absorbing layer is composed of an inorganic substance.
  5. 　前記第２の硬質基板上に、第２の紫外線吸収層が形成され、
    　該第２の紫外線吸収層が、前記部材と前記第２の硬質基板との間に配置されている、
    　請求項１から４のいずれかに記載の部材転写方法。     A second ultraviolet absorbing layer is formed on the second hard substrate, and the second ultraviolet absorbing layer is formed.
    The second ultraviolet absorbing layer is arranged between the member and the second hard substrate.
    The member transfer method according to any one of claims 1 to 4.
  6. 　第１の硬質基板と、第１の紫外線吸収層と、部材と、第２の硬質基板とをこの順に備え、
    　請求項１から５のいずれかに記載の部材転写方法に用いられる、
    　積層体。
          A first hard substrate, a first ultraviolet absorbing layer, a member, and a second hard substrate are provided in this order.
    The member transfer method according to any one of claims 1 to 5.
    Laminated body.
PCT/JP2021/018004 2020-08-18 2021-05-12 Method for transferring member WO2022038844A1 (en)

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Citations (1)

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JP2003077940A (en) * 2001-09-06 2003-03-14 Sony Corp Method of transferring device, method of arranging device using same, and method of manufacturing image display device unit

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