CN116018671A - Member transfer printing method - Google Patents

Member transfer printing method Download PDF

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Publication number
CN116018671A
CN116018671A CN202180055418.0A CN202180055418A CN116018671A CN 116018671 A CN116018671 A CN 116018671A CN 202180055418 A CN202180055418 A CN 202180055418A CN 116018671 A CN116018671 A CN 116018671A
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China
Prior art keywords
absorbing layer
ultraviolet
hard substrate
ultraviolet absorbing
meth
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CN202180055418.0A
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Chinese (zh)
Inventor
上野周作
平山高正
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Nitto Denko Corp
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Nitto Denko Corp
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Publication of CN116018671A publication Critical patent/CN116018671A/en
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    • 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
    • H01L21/02—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
    • 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

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  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Computer Hardware Design (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Optics & Photonics (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Plasma & Fusion (AREA)
  • Mechanical Engineering (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Dicing (AREA)
  • Laminated Bodies (AREA)
  • Laser Beam Processing (AREA)

Abstract

Provided is a member transfer method capable of transferring a member (a processed product) satisfactorily even when a hard substrate is used. The member transfer method of the present invention is a method of transferring a member disposed on a 1 st hard substrate to a 2 nd hard substrate, the method including: a step of forming a laminate A by laminating the 1 st hard substrate and the member with the 1 st ultraviolet absorbing layer interposed therebetween; thereafter, a step of fixing the laminate a to the 2 nd hard substrate so that the member becomes the 2 nd hard substrate side, thereby forming a laminate B; and then, irradiating the 1 st ultraviolet absorbing layer with ultraviolet rays to peel the 1 st hard substrate from the laminate B.

Description

Member transfer printing method
Technical Field
The present invention relates to a member transfer method.
Background
Conventionally, in processing of electronic components, a substrate is used as a carrier for transfer between steps and the like, and an operation of transferring the electronic components disposed on the substrate to another substrate is performed. In the case of transferring a very small chip such as a micro LED, a hard substrate may be used as a carrier in order to improve positional accuracy during transfer.
Prior art literature
Patent literature
Patent document 1: international publication No. 2012/01202
Disclosure of Invention
Problems to be solved by the invention
When the hard substrate is used as a carrier, more specifically, when an electronic component (for example, a micro LED) disposed on the 1 st hard substrate with a predetermined adhesive layer interposed therebetween is transferred onto the 2 nd hard substrate with the adhesive layer, the 1 st hard substrate is separated in a vertical direction with respect to the main surface of the substrate because the hard substrate is hard to flex. In this way, there are problems such as damage to the electronic component due to load applied to the electronic component, and defective transfer.
The present invention has been made to solve the above-described conventional problems, and an object of the present invention is to provide a member transfer method capable of transferring a member (a workpiece) satisfactorily even when a hard substrate is used.
Solution for solving the problem
The member transfer method of the present invention is a method of transferring a member disposed on a 1 st hard substrate to a 2 nd hard substrate, the method including: a step of laminating the 1 st hard substrate and the member with the 1 st ultraviolet absorbing layer interposed therebetween to form a laminate A; thereafter, a step of fixing the laminate a to the 2 nd hard substrate so that the member becomes the 2 nd hard substrate side, thereby forming a laminate B; and then, irradiating the 1 st ultraviolet absorbing layer with ultraviolet rays to peel the 1 st hard substrate from the laminate B.
In 1 embodiment, an adhesive layer is disposed between the 1 st hard substrate and the member.
In one embodiment, the 1 st ultraviolet absorbing layer is made of an organic material.
In one embodiment, the 1 st ultraviolet absorbing layer is made of an inorganic material.
In one embodiment, a 2 nd ultraviolet absorbing layer is formed on the 2 nd hard substrate, and the 2 nd ultraviolet absorbing layer is disposed between the member and the 2 nd hard substrate.
According to another aspect of the present invention, a laminate is provided. The laminate is provided with: a 1 st hard substrate, a 1 st ultraviolet absorbing layer, a member, and a 2 nd hard substrate, the laminate being used in the above-described member transfer method.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, a member transfer method can be provided that can satisfactorily transfer a member (workpiece) even when a hard substrate is used.
Drawings
Fig. 1 is a schematic diagram illustrating a member transfer method according to 1 embodiment of the present invention.
Fig. 2 is a schematic diagram illustrating a member transfer method according to another embodiment of the present invention.
Fig. 3 is a schematic diagram illustrating a member transfer method according to another embodiment of the present invention.
Detailed Description
A. Outline of Member transfer method
Fig. 1 is a schematic diagram illustrating a member transfer method according to 1 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 the member 30 disposed on the 1 st hard substrate 10 to the 2 nd hard substrate 20. The method comprises the following steps: a step of forming a laminate a by laminating the 1 st hard substrate 10 and the member 30 with the 1 st ultraviolet absorbing layer 40 interposed therebetween (hereinafter also referred to as a lamination step); thereafter, a step (hereinafter also referred to as a fixing step) of fixing the laminate a to the 2 nd hard substrate 20 so that the member 30 is on the 2 nd hard substrate 20 side, thereby forming a laminate B; thereafter, the 1 st ultraviolet absorbing layer 40 is irradiated with ultraviolet light, and the 1 st hard substrate 10 is peeled from the laminate B (the 2 nd hard substrate 20) (hereinafter also referred to as a peeling step). The ultraviolet light absorbing layer (1 st ultraviolet light absorbing layer 40, 2 nd ultraviolet light absorbing layer 50 (described later)) is a layer having a characteristic of absorbing ultraviolet light, and means a layer having a surface of which part or all of the surface exhibits peelability by irradiation of ultraviolet light (preferably UV laser light).
The member is not particularly limited, and for example, electronic components such as a semiconductor element and an optical semiconductor element can be used. The 1 st ultraviolet absorbing layer may be provided with a plurality of the above members or 1 st ultraviolet absorbing layer before the fixing step.
The average mounting area of each of the above members is, for example, 1 μm 2 ～1cm 2 . In the case where a plurality of members are arranged, the interval is, for example, 2 μm to 5mm.
In embodiment 1, the member 30 and the 1 st ultraviolet absorbing layer 40 are integrally used. As a constituent (for example, an electronic component) composed of the member 30/the 1 st ultraviolet absorbing layer 40, for example, the member 30 combined with the 1 st ultraviolet absorbing layer 40 as an inorganic substance, specifically, for example, an optical semiconductor element (LED) having a GaN (gallium nitride) -based compound crystal layer as the 1 st ultraviolet absorbing layer 40 is exemplified. In this embodiment, as shown in fig. 1, the structural body composed of the member 30/the 1 st ultraviolet absorbing layer 40 is transferred from the 1 st hard substrate 10 to the 2 nd hard substrate 20 by the above method.
In another embodiment, as shown in fig. 2, in the peeling step, the laminate including the 1 st hard substrate 10 and the 1 st ultraviolet absorbing layer 40 is peeled from the laminate B (1 st hard substrate 10), and therefore, the member 30 is separated from the 1 st ultraviolet absorbing layer 40 by the transfer method described above. In the present embodiment, the 1 st ultraviolet absorbing layer 40 is formed as the 1 st ultraviolet absorbing layer 40, which is an organic material.
According to the present invention, since the hard substrate can be peeled off by irradiation with ultraviolet rays, transfer of the member can be completed without applying an excessive load to the member. Any suitable process for processing the member may be performed between the lamination process and the fixing process.
B. Lamination step
B-1. Hard substrate
The hard substrate (1 st hard substrate, 2 nd hard substrate) is a plate-like molded article having a flexural modulus of elasticity of 1GPa or more. The flexural modulus can be measured by a 4-point bending test according to JIS K7171 or JIS R1602, respectively, depending on the material constituting the hard substrate.
Any suitable material may 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.
The ultraviolet ray (wavelength of 360 nm) transmittance of the hard substrate is preferably 70% or more, more preferably 80% to 99.9%. If the hard substrate has light transmittance, peeling in the peeling step can be preferably performed.
The 1 st hard substrate and the 2 nd hard substrate may have the same or different structures.
B-2. 1 st ultraviolet absorbing layer
In one embodiment, the 1 st ultraviolet absorbing layer is made of an organic material. In another embodiment, the 1 st ultraviolet absorbing layer is made of an inorganic material.
(1 st ultraviolet light-absorbing layer comprising organic matter)
The 1 st ultraviolet absorbing layer made of an organic material may be a layer having adhesion at an initial stage (i.e., before ultraviolet irradiation) and exhibiting peelability by lowering adhesion after ultraviolet irradiation. In 1 embodiment, the 1 st ultraviolet absorbing layer may be a layer whose local adhesive force is reduced by local ultraviolet irradiation (e.g., UV laser irradiation).
In 1 embodiment, the 1 st ultraviolet absorbing layer made of an organic material contains an ultraviolet absorber. The 1 st ultraviolet absorbing layer preferably made of an organic material further contains an active energy ray-curable adhesive.
The release of the adherend by UV laser irradiation can be achieved by including the 1 st ultraviolet absorbing layer with an ultraviolet absorber. More specifically, the 1 st ultraviolet absorbing layer is irradiated with UV laser light to decompose the ultraviolet absorber to generate gas, and/or the ultraviolet absorber generates heat to decompose the 1 st ultraviolet absorbing layer to generate gas, which deforms the 1 st ultraviolet absorbing layer, so that the portion irradiated with UV laser light exhibits peelability.
In addition, if the 1 st ultraviolet absorbing layer contains an active energy ray curable adhesive, the adhesive force of the 1 st ultraviolet absorbing layer as a whole is lowered by irradiation of active energy rays. After the adhesive force is reduced by irradiation of active energy rays to the entire 1 st ultraviolet absorbing layer to which the member is attached, the adhesive residue after peeling can be prevented by irradiation of laser light as described above. Examples of the active energy ray include gamma rays, ultraviolet rays, visible rays, infrared rays (heat rays), radio waves, alpha rays, beta rays, electron beams, plasma streams, ionizing radiation rays, and particle rays. Preferably ultraviolet light.
The 1 st ultraviolet absorbing layer composed of an organic material preferably has a light transmittance of 50% or less at a wavelength of 355 nm. By reducing the light transmittance, the laser output at the time of peeling can be reduced. The 1 st ultraviolet absorbing layer has a light transmittance of 355nm of more preferably 40% or less, and still more preferably 30% or less. When the range is within this range, the above-mentioned effect becomes more remarkable.
The initial adhesion at 23℃of the 1 st ultraviolet absorbing layer composed of an organic substance to be adhered to the stainless steel plate is preferably 0.1N/20 to 20N/20mm, more preferably 0.5N/20 to 15N/20mm. When the amount is within this range, an ultraviolet absorbing layer that can satisfactorily hold the member can be formed. Adhesion according to JIS Z0237: 2000. Specifically, the 1 st ultraviolet absorbing layer was attached to a stainless steel plate (arithmetic average surface roughness Ra: 50.+ -. 25 nm) by reciprocating a 2kg roller 1 time, and after leaving at 23℃for 30 minutes, the 1 st ultraviolet absorbing layer was peeled off and measured under conditions of a peeling angle of 180℃and a peeling speed (stretching speed) of 300 mm/min. The adhesive force of the ultraviolet absorbing layer is changed by irradiation with active energy rays and irradiation with laser light, and in this specification, "initial adhesive force" means adhesive force before irradiation with active energy rays and laser light.
In embodiment 1, the 1 st ultraviolet absorbing layer made of an organic material is adhered to a stainless steel plate, and irradiated with 460mJ/cm 2 The adhesive strength at 23℃after ultraviolet rays of (C) is preferably 0.01N/20mm to 2N/20mm, more preferably 0.02N/20mm to 1N/20mm. When the amount is within this range, transfer of the member can be performed with less residual adhesive. The above ultraviolet irradiation is performed by irradiating the 1 st ultraviolet absorption layer with ultraviolet rays (characteristic wavelength: 365nm, cumulative light amount: 460 mJ/cm) of a high-pressure mercury lamp using an ultraviolet irradiation device (trade name: UM-810, manufactured by Nito Seiyaku Co., ltd.) 2 Irradiation energy: 70W/cm 2 Irradiation time: 6.6 seconds).
The 1 st ultraviolet absorbing layer made of an organic material preferably has a thickness of 50 μm or less. When the laser beam is within this range, the laser beam output at the time of peeling can be further reduced. The thickness of the 1 st ultraviolet absorbing layer is more preferably 40 μm or less, still more preferably 30 μm or less, still more preferably 1 μm to 30 μm. When the content is within such a range, the above-mentioned effects become remarkable.
Ultraviolet absorber:
as the ultraviolet absorber, any suitable ultraviolet absorber may be used as long as it is a compound that absorbs ultraviolet light (for example, has a wavelength of 355 nm). Examples of the ultraviolet absorber include benzotriazole-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, triazine-based ultraviolet absorbers, salicylate-based ultraviolet absorbers, and cyanoacrylate-based ultraviolet absorbers. Among them, 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 adhesive is used as the adhesive a, a triazine-based ultraviolet absorber is preferably used in view of high compatibility with the base polymer of the acrylic adhesive. The triazine ultraviolet light absorber is more preferably composed of a compound having a hydroxyl group, and particularly preferably an ultraviolet light absorber composed of a hydroxyphenyl triazine compound (hydroxyphenyl triazine ultraviolet light absorber).
Examples of the hydroxyphenyl triazine ultraviolet light absorber include a reaction product of 2- (4, 6-bis (2, 4-dimethylphenyl) -1,3, 5-triazin-2-yl) -5-hydroxyphenyl with [ (C10-C16 (mainly C12-C13) alkyloxy) methyl ] ethylene oxide (trade name "TINUVIN 400", manufactured by BASF corporation), a reaction product of 2- [4, 6-bis (2, 4-dimethylphenyl) -1,3, 5-triazin-2-yl ] -5- [3- (dodecyloxy) -2-hydroxypropoxy ] phenol), a reaction product of 2- (2, 4-dihydroxyphenyl) -4, 6-bis- (2, 4-dimethylphenyl) -1,3, 5-triazine with (2-ethylhexyl) -glycidic acid ester (trade name "TINU405", manufactured by BASF corporation), a reaction product of 2, 4-bis (2-hydroxy-4-butoxyphenyl) -6- (2, 4-dibutoxyphenyl) -1,3, 5-triazine (trade name "TINU460", manufactured by BASF corporation), a reaction product of 2- (2, 4-dihydroxyphenyl) -4, 6-bis- (2, 4-dimethylphenyl) -1,3, 5-triazine with (2-ethylhexyl) -glycidic acid ester (trade name "TINUVIN", manufactured by BASF corporation), and a reaction product of 2, 4-bis (2-hydroxy-4-butoxyphenyl) -6- (2-butoxyphenyl) -6-dibutyryl group-glycidic acid ester (trade name "product of BASF (N-methyl group), 2- (4, 6-diphenyl-1, 3, 5-triazin-2-yl) -5- [2- (2-ethylhexanoyloxy) ethoxy ] -phenol (trade name "ADK STAB 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 the like.
Examples of benzotriazole-based ultraviolet absorbers (benzotriazole-based compounds) include 2- (2-hydroxy-5-tert-butylphenyl) -2H-benzotriazole (trade name "TINUVIN PS", manufactured by BASF), phenylpropionic acid, and 3- (2H-benzotriazol-2-yl) -5- (1, 1-dimethylethyl) -4-hydroxy (C7-9 side chain and linear alkyl) ester compounds (trade name "TINUVIN 384-2", manufactured by BASF), octyl 3- [ 3-tert-butyl-4-hydroxy-5- (5-chloro-2H-benzotriazol-2-yl) phenyl ] propionate, and a mixture of 2-ethylhexyl-3- [ 3-tert-butyl-4-hydroxy-5- (5-chloro-2H-benzotriazol-2-yl) phenyl ] propionate (trade name "TINUVIN 109", manufactured by BASF), 2- (2H-benzotriazol-2-yl) -4, 6-bis (1-methyl-1-phenylethyl) phenol (trade name "TINUVIN 384-2", manufactured by BASF), 2- (2H-benzotriazol-2-yl) -4, 6-bis (1-methyl-phenylethyl) phenol (trade name "TINUVIN" 3", manufactured by BASF 900", and 4-methyl-phenyl) phenyl ] propionate, BASF), methyl 3- (3- (2H-benzotriazol-2-yl) -5-tert-butyl-4-hydroxyphenyl) propionate/polyethylene glycol 300 (trade name "TINUVIN1130", BASF), 2- (2H-benzotriazol-2-yl) -P-cresol (trade name "TINUVIN P", BASF), 2- (2H-benzotriazol-2-yl) -4, 6-bis (1-methyl-1-phenylethyl) phenol (trade name "TINUVIN 234", BASF), a process for preparing the same, and a process for preparing the same 2- [ 5-chloro-2H-benzotriazol-2-yl ] -4-methyl-6- (tert-butyl) phenol (trade name "TINUVIN 326", manufactured by BASF), 2- (2H-benzotriazol-2-yl) -4, 6-di-tert-pentylphenol (trade name "TINUVIN 328", manufactured by BASF), 2- (2H-benzotriazol-2-yl) -4- (1, 3-tetramethylbutyl) phenol (trade name "TINUVIN 329", manufactured by BASF), 2' -methylenebis [6- (2H-benzotriazol-2-yl) -4- (1, 3-tetramethylbutyl) phenol ] (trade name "TINUVIN 360", manufactured by BASF), reaction product of methyl 3- (3- (2H-benzotriazol-2-yl) -5-tert-butyl-4-hydroxyphenyl) propionate with polyethylene glycol 300 (trade name "TINUVIN 213", manufactured by BASF corporation), 2- (2H-benzotriazol-2-yl) -6-dodecyl-4-methylphenol (trade name "TINUVIN 571", manufactured by BASF corporation), 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 SHIPKARO SEI SE), 2- (2H-benzotriazol-2-yl) -4-methyl-6- (3, 4,5, 6-tetrahydrophthalimide-methyl) phenol (trade name "SEESORB706", manufactured by SHIPSEI SEI-4-hydroxy-2-hydroxy-5-methylphenyl) -5-benzotriazole (trade name "SEI-12. Manufactured by SHIPSEI-2-hydroxy-phenyl) -5-chloro-2H-benzotriazole (trade name" SEESESORB 703", manufactured by SHIPKARO SEI-Co., ltd.) 2-tert-butyl-6- (5-chloro-2H-benzotriazol-2-yl) -4-methylphenol (trade name "KEMISORB 73", manufactured by Chemipro Kasei Co., ltd.), 2' -methylenebis [6- (2H-benzotriazol-2-yl) -4-tert-octylphenol ] (trade name "ADK STAB LA-31", manufactured by ADEKA Co., ltd.), 2- (2H-benzotriazol-2-yl) -p-cellulose (trade name "ADK STAB LA-32", manufactured by ADEKA Co., ltd.), 2- (5-chloro-2H-benzotriazol-2-yl) -6-tert-butyl-4-methylphenol (trade name "ADK STAB LA-36", manufactured by ADEKA Co., ltd.), and the like.
The ultraviolet absorber may be a dye or a pigment. Examples of pigments include azo pigments, phthalocyanine pigments, anthraquinone pigments, lake pigments, perylene pigments, pyrenone pigments, quinacridone pigments, thioindigo pigments, dioxazine pigments, isoindolone pigments, quinophthalone pigments, and the like. 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.
The molecular weight of the compound constituting the ultraviolet absorber is preferably 100 to 1500, more preferably 200 to 1200, and even more preferably 200 to 1000. In such a range, an ultraviolet absorbing layer capable of forming a more favorable deformed portion by laser irradiation can be formed.
The maximum absorption wavelength of the ultraviolet absorber is preferably 300nm to 450nm, more preferably 320nm to 400nm, and still more preferably 330nm to 380nm. The difference between the maximum absorption wavelength of the ultraviolet absorber and the maximum absorption wavelength of the photopolymerization initiator is preferably 10nm or more, more preferably 25nm or more.
The weight reduction temperature of the ultraviolet absorber is preferably 350 ℃ or less, more preferably 330 ℃ or less. The lower limit of the 5% weight loss temperature of the ultraviolet absorber is, for example, 100 ℃. In such a range, an ultraviolet absorbing layer capable of forming a more favorable deformed portion by laser irradiation can be formed. The 5% weight reduction temperature of the ultraviolet absorber means a temperature at which the weight of the ultraviolet absorber is reduced by 5% by weight relative to the weight before the temperature rise when the ultraviolet absorber is heated. The weight loss temperature of 5% was measured using a differential thermal analyzer under conditions of a temperature rise of 10℃per minute and a flow rate of 25 ml/min under an air atmosphere.
The content ratio of the ultraviolet absorber is preferably 1 to 50 parts by weight, more preferably 5 to 20 parts by weight, based on 100 parts by weight of the base polymer in the 1 st ultraviolet absorbing layer. In such a range, the ultraviolet absorbing layer can be formed so that the curing of the ultraviolet absorbing layer is satisfactorily performed when the adhesive force of the entire ultraviolet absorbing layer is satisfactorily reduced by irradiation with active energy rays, and the ultraviolet absorbing layer exhibits satisfactory peelability by laser irradiation.
Active energy ray-curable adhesive:
in the 1 embodiment, as the active energy ray-curable adhesive, an active energy ray-curable adhesive (A1) containing a base polymer as a parent agent and an active energy ray-reactive compound (monomer or oligomer) capable of bonding to the base polymer is used. In another embodiment, an active energy ray-curable adhesive (A2) containing an active energy ray-reactive polymer as a base polymer is used. Preferably, the base polymer has a functional group capable of reacting with the photopolymerization initiator. Examples of the functional group include a hydroxyl group and a carboxyl group.
Examples of the base polymer used for the adhesive (A1) include rubber-based polymers such as natural rubber, polyisobutylene rubber, styrene-butadiene rubber, styrene-isoprene-styrene block copolymer rubber, reclaimed rubber, butyl rubber, polyisobutylene rubber, and nitrile rubber (NBR); an organosilicon-based polymer; acrylic polymers, and the like. These polymers may be used singly or in combination of 2 or more. Among them, acrylic polymers are preferable.
Examples of the acrylic polymer include homopolymers and copolymers of hydrocarbon group-containing (meth) acrylates such as alkyl (meth) acrylates, cycloalkyl (meth) acrylates, aryl (meth) acrylates, and the like; copolymers of the hydrocarbon group-containing (meth) acrylate with other copolymerizable monomers, and the like. Examples of the alkyl (meth) acrylate include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, hexyl, heptyl, octyl, 2-ethylhexyl, isooctyl, nonyl, decyl, isodecyl, undecyl, dodecyl, i.e., lauryl, tridecyl, tetradecyl, hexadecyl, octadecyl, and eicosyl esters of (meth) acrylic acid. Examples of cycloalkyl (meth) acrylate include cyclopentyl (meth) acrylate and cyclohexyl (meth) acrylate. Examples of the aryl (meth) acrylate include phenyl (meth) acrylate and benzyl (meth) acrylate. The content of the structural unit derived from the above-mentioned hydrocarbon group-containing (meth) acrylate is preferably 40 parts by weight or more, more preferably 60 parts by weight or more, based on 100 parts by weight of the base polymer.
Examples of the other copolymerizable monomer include carboxyl group-containing monomers, acid anhydride monomers, hydroxyl group-containing monomers, glycidyl group-containing monomers, sulfonic acid group-containing monomers, phosphoric acid group-containing monomers, acrylamide, and functional group-containing monomers such as acrylonitrile. Examples of the carboxyl 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 hydroxyl group-containing monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) 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-methylpropanesulfonic acid, (meth) acrylamide propane sulfonic acid, sulfopropyl (meth) acrylate, and (meth) acryloxynaphthalene sulfonic acid. Examples of the phosphoric acid-containing monomer include 2-hydroxyethyl acryloyl phosphate. As the acrylamide, for example, N-acryloylmorpholine may be mentioned. These may be used alone or in combination of 1 or more than 2. The content of the structural unit derived from the above-mentioned copolymerizable monomer is preferably 60 parts by weight or less, more preferably 40 parts by weight or less, based on 100 parts by weight of the base polymer.
The acrylic polymer contains structural units derived from a polyfunctional monomer in order to form a crosslinked structure in its polymer backbone. 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, pentaerythritol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, epoxy (meth) acrylate (i.e., poly (meth) glycidyl acrylate), polyester (meth) acrylate, and urethane (meth) acrylate. These may be used alone or in combination of 1 or more than 2. The content of the structural unit derived from the above-mentioned 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 10 to 300 tens of thousands, more preferably 20 to 200 tens of thousands. The weight average molecular weight can be determined by GPC (solvent: THF).
Examples of the active energy ray-reactive compound that can be used for the binder (A1) include photoreactive monomers or oligomers having a functional group having a polymerizable carbon-carbon multiple bond such as an acryl group, a methacryl group, a vinyl group, an allyl group, and an acetylene group. Specific examples of the photoreactive monomer include esters of (meth) acrylic acid and polyhydric alcohols such as trimethylolpropane tri (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol monohydroxypenta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1, 4-butanediol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, polyethylene glycol di (meth) acrylate, and the like; multifunctional urethane (meth) acrylates; epoxy (meth) acrylates; oligomeric ester (meth) acrylates, and the like. Monomers such as methacryloyl isocyanate, 2-methacryloyloxyethyl isocyanate (2-isocyanatoethyl methacrylate), and m-isopropenyl- α, α -dimethylbenzyl isocyanate can also be used. Specific examples of the photoreactive oligomer include 2 to 5 polymers of the above monomers. The molecular weight of the photoreactive oligomer is preferably 100 to 3000.
Further, as the active energy ray-reactive compound, monomers such as epoxidized butadiene, glycidyl methacrylate, acrylamide, vinyl siloxane, and the like can be used; or an oligomer composed of the monomer.
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 heterocyclic rings in the molecule can be used. The mixture is irradiated with active energy rays (e.g., ultraviolet rays, electron beams) to cleave the organic salt and generate ions, which serve as starting species, causing a ring-opening reaction of the heterocycle, thereby forming a three-dimensional network structure. Examples of the organic salts include iodonium salts, phosphonium salts, antimony salts, sulfonium salts, and borates. Examples of the heterocycle in the compound having a plurality of heterocycles in the molecule include ethylene oxide, oxetane, oxolane, thiirane, and aziridine.
In the adhesive (A1), the content of the active energy ray-reactive compound is preferably 0.1 to 500 parts by weight, more preferably 5 to 300 parts by weight, and still more preferably 40 to 150 parts by weight, based on 100 parts by weight of the base polymer.
Examples of the active energy ray-reactive polymer (base polymer) included in the binder (A2) include polymers having a functional group having a carbon-carbon multiple bond such as an acryl group, a methacryl group, a vinyl group, an allyl group, and an acetylene group. Specific examples of the active energy ray-reactive polymer include polymers composed of polyfunctional (meth) acrylates; a photocationic polymerizable polymer; cinnamoyl-containing polymers such as polyvinyl cinnamate; diazotized amino novolac resins; polyacrylamide; etc.
In one embodiment, an active energy ray-reactive polymer is used, which is formed by introducing an active energy ray-polymerizable carbon-carbon multiple bond into a side chain, a main chain and/or a main chain end of the acrylic polymer. Examples of the method for introducing a radiation-polymerizable carbon-carbon double bond into an acrylic polymer include the following methods: after copolymerizing a raw material monomer including a monomer having a predetermined functional group (functional group 1), a compound having a predetermined functional group (functional group 2) capable of reacting with and bonding to the functional group 1 and a radiation polymerizable carbon-carbon double bond is subjected to a condensation reaction or an addition reaction with the acrylic polymer while maintaining the radiation polymerization property of the carbon-carbon double bond.
Examples of the combination of the 1 st functional group and the 2 nd functional group include a carboxyl group and an epoxy group, an epoxy group and a carboxyl group, a carboxyl group and an aziridine group, an aziridine group and a carboxyl group, a hydroxyl group and an isocyanate group, and an isocyanate group and a hydroxyl group. Among these combinations, a combination of a hydroxyl group and an isocyanate group and a combination of an isocyanate group and a hydroxyl group are preferable from the viewpoint of ease of reaction tracking. In addition, since it is technically difficult to produce a polymer having an isocyanate group with high reactivity, it is more preferable that the 1 st functional group on the acrylic polymer side is a hydroxyl group and the 2 nd functional group is an isocyanate group from the viewpoint of ease of production or obtaining of the acrylic polymer. In this case, examples of the isocyanate compound having both a radiation polymerizable carbon-carbon double bond and an isocyanate group as the 2 nd functional group include methacryloyl isocyanate, 2-methacryloyloxyethyl isocyanate, and m-isopropenyl- α, α -dimethylbenzyl isocyanate. The acrylic polymer having the 1 st functional group preferably contains a structural unit derived from the above-mentioned hydroxyl group-containing monomer, and also preferably contains a structural unit derived from an ether compound such as 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, diethylene glycol monovinyl ether, and the like.
The binder (A2) may further contain the active energy ray-reactive compound (monomer or oligomer).
The active energy ray-curable adhesive may contain a photopolymerization initiator.
As the photopolymerization initiator, any appropriate initiator may be used. Examples of the photopolymerization initiator include α -ketol compounds such as 4- (2-hydroxyethoxy) phenyl (2-hydroxy-2-propyl) ketone, α -hydroxy- α, α' -dimethyl acetophenone, 2-methyl-2-hydroxy propiophenone, and 1-hydroxycyclohexyl phenyl ketone; acetophenone compounds such as methoxyacetophenone, 2-dimethoxy-2-phenylacetophenone, 2-diethoxyacetophenone, and 2-methyl-1- [4- (methylthio) -phenyl ] -2-morpholinopropane-1; benzoin ether compounds such as benzoin ethyl ether, benzoin isopropyl ether, anisoin methyl ether, and the like; ketal compounds such as benzil dimethyl ketal; aromatic sulfonyl chloride compounds such as 2-naphthalenesulfonyl chloride; photoactive oxime-based compounds such as 1-benzophenone-1, 1-propanedione-2- (o-ethoxycarbonyl) oxime; benzophenone-based compounds such as benzophenone, benzoylbenzoic acid, and 3,3' -dimethyl-4-methoxybenzophenone; thioxanthone compounds such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2, 4-dimethylthioxanthone, isopropylthioxanthone, 2, 4-dichlorothioxanthone, 2, 4-diethylthioxanthone, and 2, 4-diisopropylthioxanthone; camphorquinone; halogenated ketones; acyl phosphine oxides; acyl phosphonates and the like. The amount of the photopolymerization initiator to be used may be set to any appropriate amount.
In 1 embodiment, a photopolymerization initiator having a maximum absorption wavelength in a range of 400nm or less (preferably 380nm or less, more preferably 340nm or less) is used. When such a photopolymerization initiator is used, it is preferable that the curing reaction of the adhesive occurs when the adhesive force of the entire ultraviolet absorbing layer is lowered by irradiation of active energy rays, and an ultraviolet absorbing layer having particularly little residual adhesive can be formed.
As the photopolymerization initiator, commercially available ones can be used. For example, examples of photopolymerization initiators having a maximum absorption wavelength in a range of 400nm or less include trade names "Irgacure 127", "Irgacure 369E", "Irgacure379EG", "Irgacure 819", "Irgacure TOP", "Irgacure 784", "Irgacure OXE01" manufactured by BASF corporation.
In one embodiment, the active energy ray-curable adhesive may contain a photosensitizer.
In 1 embodiment, the above-mentioned photosensitizer may be used in combination with the above-mentioned photopolymerization initiator. Since the photosensitizer transmits energy obtained by itself absorbing light to the photopolymerization initiator, and radicals can be generated by the photopolymerization initiator, polymerization can be performed by light on the long wavelength side where the photopolymerization initiator itself does not have an absorption peak. Therefore, by containing the photosensitizer, the difference between the absorption wavelength of the ultraviolet absorber and the wavelength at which radicals can be generated by the photopolymerization initiator can be increased. As a result, photopolymerization of the 1 st ultraviolet absorbing layer and peeling by the ultraviolet absorber can be performed without affecting each other. In one embodiment, 2-dimethoxy-1, 2-diphenylethan-1-one (for example, trade name "Irgacure 651", manufactured by BASF corporation) and a photosensitizer are used in combination as a photopolymerization initiator. Examples of such a photosensitizer include "UVS-581" which is a product of Kawasaki chemical industry Co., ltd., 9, 10-diethoxyanthracene (for example, "UVS1101" which is a product of Kawasaki chemical industry Co., ltd.).
As other examples of the above-mentioned photosensitizer, 9, 10-dibutoxyanthracene (for example, manufactured by Kawasaki chemical Co., ltd., trade name "UVS-1331"), 2-isopropylthioxanthone, benzophenone, thioxanthone derivatives, 4' -bis (dimethylamino) benzophenone, and the like are given. Examples of thioxanthone derivatives include ethoxycarbonyl thioxanthone and isopropyl thioxanthone.
The content ratio of the photosensitizer is preferably 0.01 to 2 parts by weight, more preferably 0.5 to 2 parts by weight, based on 100 parts by weight of the base polymer.
Preferably, the active energy ray-curable adhesive contains a crosslinking agent. Examples of the crosslinking agent include isocyanate-based crosslinking agents, epoxy-based crosslinking agents, oxazoline-based crosslinking agents, aziridine-based crosslinking agents, melamine-based crosslinking agents, peroxide-based crosslinking agents, urea-based crosslinking agents, metal alkoxide-based crosslinking agents, metal chelate-based crosslinking agents, metal salt-based crosslinking agents, carbodiimide-based crosslinking agents, and amine-based crosslinking agents.
The content ratio of the crosslinking agent is preferably 0.5 to 10 parts by weight, more preferably 1 to 8 parts by weight, based on 100 parts by weight of the base polymer of the adhesive.
In one embodiment, an isocyanate-based crosslinking agent is preferably used. The isocyanate-based crosslinking agent is preferable in that it can react with various functional groups. Specific examples of the isocyanate-based crosslinking agent include lower aliphatic polyisocyanates such as butylene diisocyanate and hexamethylene diisocyanate; alicyclic isocyanates such as cyclopentylene diisocyanate, cyclohexylene diisocyanate and isophorone diisocyanate; aromatic isocyanates such as 2, 4-toluene diisocyanate, 4' -diphenylmethane diisocyanate, and xylylene diisocyanate; isocyanate adducts such as trimethylolpropane/toluene diisocyanate trimer adduct (Nippon Polyurethane Industry co., ltd., trade name "cor onate L"), trimethylolpropane/hexamethylene diisocyanate trimer adduct (Nippon Polyurethane Industry co., ltd., trade name "cor onate HL"), isocyanurate body of hexamethylene diisocyanate (Nippon Polyurethane Industry co., ltd., trade name "cor onate HX"); etc. It is preferable to use a crosslinking agent having 3 or more isocyanate groups.
The active energy ray-curable adhesive may further contain any appropriate additive as needed. Examples of the additives include active energy ray polymerization accelerators, radical scavengers, tackifiers, plasticizers (e.g., trimellitate plasticizers, pyromellitic acid plasticizers, etc.), pigments, dyes, fillers, antioxidants, conductive materials, antistatic agents, ultraviolet absorbers, light stabilizers, peeling regulators, softeners, surfactants, flame retardants, antioxidants, and the like.
(1 st ultraviolet light-absorbing layer made of inorganic substance)
As described above, the 1 st ultraviolet absorbing layer made of an inorganic material and the above-described member can be used in combination, and thus one constituent (for example, an electronic component) can be constituted. That is, the 1 st ultraviolet absorbing layer made of an inorganic material may be a part of the above-described constituent body (for example, an electronic component).
The 1 st ultraviolet absorbing layer made of an inorganic material as described above may be an epitaxial layer. As the 1 st ultraviolet absorbing layer made of an inorganic material as described above, for example, a layer containing a group III nitride such as a GaN (gallium nitride) based compound crystal layer can be cited.
The 1 st ultraviolet absorbing layer made of an inorganic material exhibits peelability by a method called laser peeling. For example, the 1 st ultraviolet absorbing layer made of an inorganic material is decomposed by irradiation with a high-density UV laser light, and as a result, the 1 st ultraviolet absorbing layer is separated from the 1 st hard substrate. Details of laser lift-off are described in, for example, international publication No. 2012/011012, the description of which is incorporated by reference into the present specification.
B-3 adhesive layer
The laminate a may include an adhesive layer. In 1 embodiment, an adhesive layer may be disposed between the 1 st rigid substrate and the member. For example, an adhesive layer may be disposed between the 1 st hard substrate and the 1 st ultraviolet absorbing layer. The pressure-sensitive adhesive layer and the 1 st ultraviolet absorbing layer may be laminated via any appropriate substrate. As the base material, a base material composed of any appropriate resin can be used.
In one embodiment, the adhesive layer includes an ultraviolet curable adhesive. The adhesive layer may be an adhesive layer whose adhesive force is improved by ultraviolet irradiation, or an adhesive layer whose adhesive force is reduced by ultraviolet irradiation. As the adhesive, for example, the above active energy ray-curable adhesive can be used. In another embodiment, the adhesive layer comprises a pressure sensitive adhesive. As the pressure-sensitive adhesive, a conventional adhesive can be used.
C. Fixing step
After the laminate a (1 st hard substrate 10/1 st ultraviolet absorbing layer 40/member 30) is formed in the above-described lamination step, the laminate a is fixed to the 2 nd hard substrate 20 in a fixing step.
(2 nd hard substrate)
As the 2 nd hard substrate, the hard substrate described in item B-1 can be used.
As shown in fig. 1 and 2, a 2 nd ultraviolet absorbing layer 50 or an adhesive layer may be formed on the 2 nd hard substrate 20. The 2 nd ultraviolet absorbing layer 50 may be disposed between the member 30 and the 2 nd rigid substrate 20. The 2 nd ultraviolet absorbing layer 50 is preferably a layer made of an organic material. As such an ultraviolet absorbing layer, the ultraviolet absorbing layer described in the item "1 st ultraviolet absorbing layer made of an organic material", that is, the 2 nd ultraviolet absorbing layer 50 may be a layer having adhesiveness at an initial stage (that is, before ultraviolet irradiation) and exhibiting peelability by lowering adhesive force after ultraviolet irradiation. If the 2 nd ultraviolet absorbing layer 50 is formed, the laminate C including the 2 nd hard substrate 20/the 2 nd ultraviolet absorbing layer 50/the member 30 is subjected to a further transfer step after the peeling step, and the member can be easily peeled from the laminate C by laser irradiation, so that transfer efficiency can be improved.
When the 2 nd ultraviolet absorbing layer 50 is formed on the 2 nd hard substrate 20, an adhesive layer may be disposed between the 2 nd hard substrate 20 and the 2 nd ultraviolet absorbing layer 50. In one embodiment, the adhesive layer includes an ultraviolet curable adhesive. The adhesive layer may be an adhesive layer whose adhesive force is improved by ultraviolet irradiation, or an adhesive layer whose adhesive force is reduced by ultraviolet irradiation. As the adhesive, for example, the above active energy ray-curable adhesive can be used.
D. Stripping process
In the peeling step, ultraviolet rays (preferably UV laser light) are irradiated to the 1 st ultraviolet absorbing layer 40 of the laminate B (1 st hard substrate 10/1 st ultraviolet absorbing layer 40/member 30/(2 nd ultraviolet absorbing layer 50)/2 nd hard substrate 20) formed in the fixing step, and the member 30 is peeled from the 1 st hard substrate 10. As for each condition of ultraviolet irradiation, any suitable condition may be set depending on the configuration of the 1 st ultraviolet absorbing layer 40, as long as the 1 st ultraviolet absorbing layer 40 can be made releasable.
In the 1 st embodiment, when the 1 st ultraviolet absorbing layer is made of an organic material (preferably, when the 1 st ultraviolet absorbing layer contains an ultraviolet absorber), laser light having a wavelength of 200nm to 380nm is irradiated to the 1 st ultraviolet absorbing layer at an arbitrary appropriate output (for example, 0.01W to 6W, preferably 0.05W to 5W), and the ultraviolet absorber is decomposed to generate gas, and/or the ultraviolet absorber generates heat to decompose the adhesive layer to generate gas, and the gas deforms the 1 st ultraviolet absorbing layer, so that the portion irradiated with the laser light exhibits peelability.
In the case where the 1 st ultraviolet light absorbing layer is made of an organic material (preferably, in the case where the ultraviolet light absorbing agent is contained), and in the case where the 1 st ultraviolet light absorbing layer contains an active energy ray-curable adhesive, the adhesive force of the 1 st ultraviolet light absorbing layer may be reduced by irradiation of active energy rays to the entire 1 st ultraviolet light absorbing layer before irradiation of UV laser light as described above. Examples of the active energy ray include gamma rays, ultraviolet rays, visible rays, infrared rays (heat rays), radio waves, alpha rays, beta rays, electron beams, plasma streams, ionizing radiation rays, and particle rays. Preferably ultraviolet light. The wavelength of ultraviolet light is preferably 300nm to 400nm. The irradiation amount is, for example, 300mJ/cm of the cumulative light amount 2 ～1500mJ/cm 2 . In this way, if the active energy ray is irradiated before the laser irradiation, the transfer member of the resist residue can be prevented.
In the 1 st embodiment, when the 1 st ultraviolet absorbing layer is made of an inorganic material, the 1 st ultraviolet absorbing layer is irradiated with a laser beam (excimer laser beam) having a wavelength shorter than the absorption edge wavelength of the material constituting the 1 st ultraviolet absorbing layer and longer than the absorption edge wavelength of the 1 st hard substrate. For example, when the 1 st ultraviolet absorbing layer is a GaN (gallium nitride) compound crystal layer, an excimer laser having 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, a wavelength 248nm is used.
As described above, the 1 st hard substrate 10 can be peeled from the laminate B by imparting peelability to the 1 st ultraviolet absorbing layer, and the member 30 (the structure consisting essentially of the 1 st ultraviolet absorbing layer 40 and the member 30) can be transferred onto the 2 nd hard substrate 20. Alternatively, the 1 st hard substrate 10 and the 1 st ultraviolet absorbing layer 40 may be peeled off from the laminate B, and the member 30 may be transferred onto the 2 nd hard substrate 20.
E. Application of component transfer printing method
In 1 embodiment, the above-described partial transfer method is repeated a plurality of times, whereby the above-described member is continuously transferred. In this embodiment, the 2 nd ultraviolet absorbing layer is preferably formed on the 2 nd hard substrate. As described above, the 2 nd ultraviolet absorbing layer may be a layer having adhesiveness at an initial stage (i.e., before ultraviolet irradiation) and having adhesiveness reduced after ultraviolet irradiation, thereby exhibiting peelability. If the 2 nd ultraviolet absorbing layer 50 is formed, transfer efficiency can be improved.
Specifically, as shown in fig. 3, the laminate C (fig. 3 (a) to (b)) obtained through the peeling step is laminated on the 3 rd hard substrate 60 (fig. 3 (C) to (d)), and thereafter, the 2 nd ultraviolet absorbing layer 50 is irradiated with ultraviolet light (fig. 3 (e)), and the member 30 is peeled from the 2 nd hard substrate 20 (fig. 3 (f)). As described above, the laminate C may be configured of the 2 nd hard substrate/the 2 nd ultraviolet absorbing layer/the member, or the 2 nd hard substrate/the 2 nd ultraviolet absorbing layer/the member/the 1 st ultraviolet absorbing layer. When the laminated body C is laminated on the 3 rd hard substrate 60, the laminated body C is arranged such that the surface (the member 30 in the example shown in the figure) of the laminated body C on the opposite side to the 2 nd hard substrate 20 is the 3 rd hard substrate 60 side.
As the 3 rd hard substrate, the hard substrate described in item B-1 can be used.
The 3 rd ultraviolet absorbing layer 70 or the adhesive layer may be formed on the 3 rd hard substrate 60. The 3 rd ultraviolet absorbing layer 70 may be disposed between the member 30 and the 3 rd rigid substrate 60. The 3 rd ultraviolet absorbing layer 70 is preferably a layer made of an organic material. As such an ultraviolet absorbing layer, the ultraviolet absorbing layer described in the item "1 st ultraviolet absorbing layer made of an organic material", that is, the 3 rd ultraviolet absorbing layer 70 may be a layer having adhesiveness at an initial stage (that is, before ultraviolet irradiation) and exhibiting peelability by lowering adhesive force after ultraviolet irradiation. If the 3 rd ultraviolet absorbing layer 70 is formed, the laminate D including the 3 rd hard substrate 60/the 3 rd ultraviolet absorbing layer 70/the member 30 is subjected to a further transfer step after the peeling step, and the member 30 can be easily peeled from the laminate D by laser irradiation, so that transfer efficiency can be improved.
When the 3 rd ultraviolet absorbing layer is formed on the 3 rd hard substrate, an adhesive layer may be disposed between the 3 rd hard substrate and the 3 rd ultraviolet absorbing layer. In one embodiment, the adhesive layer includes an ultraviolet curable adhesive. The adhesive layer may be an adhesive layer whose adhesive force is improved by ultraviolet irradiation, or an adhesive layer whose adhesive force is reduced by ultraviolet irradiation. As the adhesive, for example, the above active energy ray-curable adhesive can be used.
In the 1 st embodiment, the 2 nd ultraviolet absorbing layer is a layer containing an ultraviolet curable adhesive, and the adhesive force of the 2 nd ultraviolet absorbing layer is reduced by irradiating ultraviolet rays to the 2 nd ultraviolet absorbing layer before the laminate C is laminated on the 3 rd hard substrate. As the condition of ultraviolet irradiation, for example, the wavelength of ultraviolet is 300nm to 400nm, and the irradiation amount is 300mJ/cm of the accumulated light amount 2 ～1500mJ/cm 2 . In this way, when the active energy ray is irradiated before being laminated on the 3 rd hard substrate, the transferability of the member can be improved.
By repeating the above operation, the above member can be continuously transferred.
Examples
Examples 1 to 1
As illustrated in fig. 2, a sapphire substrate 10 (1 st hard substrate 10) having an optical semiconductor element 30 (member 30) formed on the surface thereof via an epitaxial layer 40 (1 st ultraviolet absorbing layer 40) is prepared.
Next, the optical semiconductor element 30 (member 30) is bonded to the glass substrate 20 (the 2 nd hard substrate 20) on which the ultraviolet curable adhesive layer 50 (the 2 nd ultraviolet absorbing layer 50) containing an ultraviolet absorber is laminated.
Ultraviolet laser (wavelength: 248nm, irradiation energy: 1000J/cm) is irradiated to the epitaxial layer 40 (1 st ultraviolet absorbing layer 40) 2 ) The sapphire substrate 10 (1 st hard substrate 10) is peeled off, whereby the optical semiconductor element 30 (member 30) is transferred from the sapphire substrate 10 (1 st hard substrate 10) to the glass substrate 20 (2 nd hard substrate 20). According to this method, the operation can be performed without damaging the memberAnd (5) transferring.
Examples 1 to 2
The same procedure as in example 1 was performed to obtain a laminate C in which the optical semiconductor element 30 (member 30) was disposed on the 2 nd hard substrate 20 with the ultraviolet curable adhesive layer 50 (2 nd ultraviolet absorbing layer 50) interposed therebetween.
Next, ultraviolet rays (wavelength: 355nm to 365nm, accumulated light amount: 1380 mJ/cm) are irradiated to the ultraviolet-curable adhesive layer 50 (the 2 nd ultraviolet absorbing layer 50) through the glass substrate 20 (the 2 nd hard substrate 20) 2 ) The adhesive layer is cured to reduce the adhesive force of the adhesive layer to the optical semiconductor element 30 (member 30) (not shown).
Next, as described with reference to fig. 3, the optical semiconductor element 30 (member 30) is bonded to the glass substrate 60 (the 3 rd hard substrate 60) on which the ultraviolet curable adhesive layer 70 (the 3 rd ultraviolet absorbing layer 70) containing an ultraviolet absorber is laminated.
Next, the ultraviolet curable adhesive layer 50 (the 2 nd ultraviolet absorbing layer 50) was irradiated with ultraviolet laser (wavelength: 355nm, irradiation energy: 10J/cm) 2 ) The optical semiconductor element 30 (member 30) is peeled off, whereby the optical semiconductor element (member) is transferred from the glass substrate (the 2 nd hard substrate) to the glass substrate (the 3 rd hard substrate). According to this method, transfer can be performed without damaging the member.
Examples 2-1 and 2
The transfer of the member 30 was performed in the same manner as in examples 1-1 and 1-2, except that the double-sided adhesive sheet composed of the ultraviolet-curable adhesive layer 50 (the 2 nd ultraviolet-absorbing layer 50), the PET substrate, and the pressure-sensitive adhesive layer was used instead of the ultraviolet-curable adhesive layer 50 (the 2 nd ultraviolet-absorbing layer 50) composed of a single layer, and the double-sided adhesive sheet composed of the ultraviolet-curable adhesive layer 70 (the 3 rd ultraviolet-absorbing layer 70), the PET substrate, and the pressure-sensitive adhesive layer was used instead of the ultraviolet-curable adhesive layer 70 (the 3 rd ultraviolet-absorbing layer 70) composed of a single layer. By this method, transfer can be performed without damaging the member.
Description of the reference numerals
10 st hard substrate
20 nd hard substrate
30 component parts
40 st ultraviolet light absorbing layer 1
50 nd ultraviolet absorbing layer
60 rd 3 rd hard substrate
70 rd ultraviolet absorbing layer

Claims (6)

1. A member transfer method of transferring a member disposed on a 1 st hard substrate to a 2 nd hard substrate, the method comprising:
A step of forming a laminate A by laminating the 1 st hard substrate and the member with the 1 st ultraviolet absorbing layer interposed therebetween; thereafter, the process is carried out,
a step of forming a laminate B by fixing the laminate a to the 2 nd hard substrate so that the member is on the 2 nd hard substrate side; thereafter, the process is carried out,
and a step of irradiating the 1 st ultraviolet absorbing layer with ultraviolet rays and peeling the 1 st hard substrate from the laminate B.
2. The member transfer method according to claim 1, wherein an adhesive layer is disposed between the 1 st hard substrate and the member.
3. The member transfer method according to claim 1 or 2, wherein the 1 st ultraviolet absorbing layer is composed of an organic substance.
4. The member transfer method according to claim 1 or 2, wherein the 1 st ultraviolet absorbing layer is composed of an inorganic substance.
5. The member transfer method according to any one of claims 1 to 4, wherein a 2 nd ultraviolet absorbing layer is formed on the 2 nd hard substrate,
the 2 nd ultraviolet absorbing layer is disposed between the member and the 2 nd hard substrate.
6. A laminated body is provided with: a 1 st hard substrate, a 1 st ultraviolet absorbing layer, a member, and a 2 nd hard substrate,
The laminate is used in the member transfer method according to any one of claims 1 to 5.
CN202180055418.0A 2020-08-18 2021-05-12 Member transfer printing method Pending CN116018671A (en)

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JP2020138133A JP2022034374A (en) 2020-08-18 2020-08-18 Member transfer method
JP2020-138133 2020-08-18
PCT/JP2021/018004 WO2022038844A1 (en) 2020-08-18 2021-05-12 Method for transferring member

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CN116018671A true CN116018671A (en) 2023-04-25

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WO (1) WO2022038844A1 (en)

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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
JP4948629B2 (en) 2010-07-20 2012-06-06 ウシオ電機株式会社 Laser lift-off method

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