WO2015029723A1 - 被接着物回収方法、被接着物回収装置、ガス発生膜および樹脂組成物 - Google Patents
被接着物回収方法、被接着物回収装置、ガス発生膜および樹脂組成物 Download PDFInfo
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- WO2015029723A1 WO2015029723A1 PCT/JP2014/070686 JP2014070686W WO2015029723A1 WO 2015029723 A1 WO2015029723 A1 WO 2015029723A1 JP 2014070686 W JP2014070686 W JP 2014070686W WO 2015029723 A1 WO2015029723 A1 WO 2015029723A1
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- 238000012258 culturing Methods 0.000 description 1
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Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
- C12N1/00—Microorganisms, e.g. protozoa; Compositions thereof; Processes of propagating, maintaining or preserving microorganisms or compositions thereof; Processes of preparing or isolating a composition containing a microorganism; Culture media therefor
- C12N1/02—Separating microorganisms from their culture media
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B43/00—Operations specially adapted for layered products and not otherwise provided for, e.g. repairing; Apparatus therefor
- B32B43/006—Delaminating
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/22—Compounds containing nitrogen bound to another nitrogen atom
- C08K5/23—Azo-compounds
- C08K5/235—Diazo and polyazo compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/22—Compounds containing nitrogen bound to another nitrogen atom
- C08K5/27—Compounds containing a nitrogen atom bound to two other nitrogen atoms, e.g. diazoamino-compounds
- C08K5/28—Azides
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12M—APPARATUS FOR ENZYMOLOGY OR MICROBIOLOGY; APPARATUS FOR CULTURING MICROORGANISMS FOR PRODUCING BIOMASS, FOR GROWING CELLS OR FOR OBTAINING FERMENTATION OR METABOLIC PRODUCTS, i.e. BIOREACTORS OR FERMENTERS
- C12M25/00—Means for supporting, enclosing or fixing the microorganisms, e.g. immunocoatings
- C12M25/06—Plates; Walls; Drawers; Multilayer plates
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12M—APPARATUS FOR ENZYMOLOGY OR MICROBIOLOGY; APPARATUS FOR CULTURING MICROORGANISMS FOR PRODUCING BIOMASS, FOR GROWING CELLS OR FOR OBTAINING FERMENTATION OR METABOLIC PRODUCTS, i.e. BIOREACTORS OR FERMENTERS
- C12M33/00—Means for introduction, transport, positioning, extraction, harvesting, peeling or sampling of biological material in or from the apparatus
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
- C12N5/00—Undifferentiated human, animal or plant cells, e.g. cell lines; Tissues; Cultivation or maintenance thereof; Culture media therefor
- C12N5/06—Animal cells or tissues; Human cells or tissues
- C12N5/0602—Vertebrate cells
- C12N5/0625—Epidermal cells, skin cells; Cells of the oral mucosa
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12M—APPARATUS FOR ENZYMOLOGY OR MICROBIOLOGY; APPARATUS FOR CULTURING MICROORGANISMS FOR PRODUCING BIOMASS, FOR GROWING CELLS OR FOR OBTAINING FERMENTATION OR METABOLIC PRODUCTS, i.e. BIOREACTORS OR FERMENTERS
- C12M23/00—Constructional details, e.g. recesses, hinges
- C12M23/20—Material Coatings
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T156/00—Adhesive bonding and miscellaneous chemical manufacture
- Y10T156/11—Methods of delaminating, per se; i.e., separating at bonding face
- Y10T156/1142—Changing dimension during delaminating [e.g., crushing, expanding, warping, etc.]
- Y10T156/1147—Using shrinking or swelling agent during delaminating
Definitions
- the present invention relates to an adherend collection method, an adherend collection apparatus, and a resin composition.
- iPS cells and ES cells are not uniform, and somatic cells cultured from them include various types. For this reason, techniques for selectively recovering cells have been studied.
- An object of the present invention is to provide a method for recovering an adherend that can recover the adherend regardless of the type of the adherend such as cells.
- the present invention includes, for example, the following [1] to [12].
- [1] A method for recovering an adherend from a support; Step (I) of exposing a laminated body having a photogas generating layer, an adhesive layer and an adherend in this order on the support, gas is generated from the photogas generating layer, and the support and the laminate are separated by the gas
- a method for recovering an adherend comprising the step (II) of recovering the adherend from the support by recovering the separated laminate.
- a plurality of the laminates are provided on a support, and a desired adherend is selectively recovered from the support by selectively exposing the desired laminate, [1] to [4] The method for recovering adherends.
- a resin composition comprising a polymer having a structural unit derived from (meth) acrylic acid, and at least one selected from an azide and a diazo compound.
- the resin composition according to [9] containing 5 to 20 parts by mass of at least one selected from the azide and the diazo compound with respect to 100 parts by mass of the polymer having a structural unit derived from (meth) acrylic acid. object.
- a gas generating film comprising a polymer having a structural unit derived from (meth) acrylic acid, and at least one selected from an azide and a diazo compound.
- the adherend can be collected regardless of the kind of the adherend such as cells.
- recovery method of this invention The schematic diagram which shows an example of a support body.
- the adherend recovery method of the present invention is an adherend recovery method for recovering an adherend from a support, A laminated body having a photogas generating layer, an adhesive layer and an adherend in this order on the support is exposed (step (1)), gas is generated from the photogas generating layer, and the support is laminated with the gas. The body is separated (step (2)), and the separated laminate is collected to recover the adherend from the support (step (3)).
- a schematic diagram of the adherend collection method is shown in FIG.
- the adhesive layer that adheres the adherend has both the function of adhering the adherend and the function of chemically changing the light, so that the adherend is damaged by the chemical change.
- the present invention forms a photogas generation layer having a function of chemically changing the function of adhering an object to be adhered together with the adhesive layer, and therefore there is no fear of damaging the object to be adhered due to the chemical change.
- the adhesive layer can be appropriately selected according to the type of the adherend, for example, when the adherent is a biologically related substance such as a cell having an anchorage dependency, the adhesive layer is limited. Is also applicable.
- the phenomenon caused by the chemical change is the generation of gas, and the layer affected by the gas is between the substrate and the photogas generation layer and is separated from the adherend and the adhesive layer. Does not damage the adherend.
- Step (1) is a step of exposing the laminated body 200 having the optical gas generation layer 20, the adhesive layer 30, and the adherend 40 on the support 100 in this order.
- the support 100 may be hard or soft as long as the laminate 200 can be held, and may be any material.
- examples of the support 100 include those containing materials such as silicon, glass, quartz, silicon carbide, silicon nitride, acrylic resin, polycarbonate, polycycloolefin, polyimide, and polystyrene.
- those containing a material having high transparency with respect to the exposure light 300 such as glass, quartz, silicon carbide, acrylic resin, polycarbonate, polycycloolefin, and polystyrene are preferable.
- the shape of the support 100 only needs to have a surface 101 on which the stacked body 200 can be placed, and the surface may or may not be flat.
- Examples of the support include a flat plate shape and a shape having a recess as shown in FIG.
- the thickness of the support is usually 1 ⁇ m to 1 mm, and can be appropriately selected depending on the intended use.
- the support 100 may be provided with a connection port to an external member such as a supply / discharge port.
- the surface 101 of the support 100 on which the stacked body 200 is placed may have a surface modification layer.
- the surface modification layer include cups such as 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, and hexamethyldisilazane in order to improve the adhesion between the support 100 and the laminate 200.
- the laminated body 200 has the optical gas generating layer 20, the adhesive layer 30, and the adherend 40 in this order.
- the thickness of the laminate 200 is normally 1 ⁇ m to 1 cm, and can be appropriately selected depending on the type of the adherend 40.
- the photogas generating layer 20, the adhesive layer 30, and the adherend 40 are placed in this order on the surface 101 on which the laminate 200 of the support 100 is placed. Can be formed.
- a gas barrier layer 50 may be provided between the photogas generation layer 20 and the adhesive layer 30.
- the gas barrier layer 50 is a layer formed for the purpose of discharging the gas 21 generated from the optical gas generation layer 20 to the support 100 side.
- the gas barrier layer 50 include those containing materials such as polyacryl, polyolefin, polycarbonate, vinyl chloride resin, ABS resin, polyethylene terephthalate resin, nylon resin, urethane resin, polyimide resin, and glass.
- the thickness of the gas barrier layer 50 is usually 1 ⁇ m to 1 mm, and can be appropriately selected depending on the material of the gas barrier layer 50, the type of the gas 21, and the like.
- the exposure light 300 usually includes ultraviolet rays and visible rays.
- the exposure light 300 is light having a wavelength of 200 to 500 nm (eg, i-line (365 nm)), and can be appropriately selected depending on the type of the photogas generating layer 20.
- the exposure light may be laser light or light including a plurality of wavelengths.
- the irradiation amount of the actinic ray can be appropriately selected depending on the type and thickness of the photogas generation layer 20, but when using i-ray for exposure light, the exposure amount is usually 100 to 1500 mJ / cm 2 . .
- each laminated body 200 may be individually exposed. For example, as shown in FIG. You may expose via the mask 301 which has an opening part only in the area
- the exposure is performed using, for example, a contact aligner, a stepper, or a scanner.
- the exposure to the laminate 200 may be performed from any direction, whether from the adherend 40 side or the support 100 side. Among these, it is preferable to expose the laminated body 200 from the support 100 side because there is no fear of damaging the adherend 40 by the exposure light 300.
- the support body 100 is preferably made of a material that is highly transparent to the exposure light 300.
- the photogas generation layer 20 contains a photogas generating agent that generates gas by light. Further, the photogas generating layer 20 may include a binder resin or the like for supplementing the photogas generating agent in addition to the photogas generating agent.
- the photogas generating agent is a substance that generates a gas by photoreaction or oxidative decomposition when irradiated with light having a desired wavelength.
- the photogas generating agent that generates gas by oxidative decomposition is used together with a photocatalyst such as titanium oxide, and is a substance that decomposes by the oxidizing action of the photocatalyst to generate gas.
- Examples of the photogas generator by photoreaction include azides, diazo compounds, azo compounds, diazonium salts, sulfohydrazide compounds, hydrazo compounds, nitrobenzyl carbamate compounds, benzoin carbamate compounds, and diazomethane sulfonate compounds. .
- the gas 21 an azide that generates nitrogen, which is an inert gas that does not damage the adherend 40 and the adhesive layer 30, a diazo compound, a nitrobenzyl carbamate compound that generates carbon dioxide, and a benzoin carbamate compound Is preferred.
- an azide when combined with an elastomer as a binder resin described later, an azide is selected from azide and a diazo compound when combined with a polymer containing a monomer unit derived from (meth) acrylic acid as a binder resin. At least one of these is preferred.
- a gas having a volume approximately 2 to 100 times that of the photogas generating agent can be generated, so that the support 100 and the laminate 200 can be efficiently separated. it can.
- azide examples include compounds described in JP2013-071847A and JP2010-153774A, specifically, 4,4′-diazidodiphenylsulfone, 3,3 '-Diazidodiphenylsulfone, 3,4'-diazidodiphenylsulfone, 4,4'-diazidostilbene, 1,3-bis- (4'-azidobenzal) -acetone, 1,3-bis- (4' -Azidocinnamilidene) -2-propanone, 4,4'-diazidochalcone, 2,6-bis- (4'-azidobenzal) -cyclohexanone, 2,6-bis- (4'-azidobenzal) -4- Methylcyclohexanone, 2,6-bis- (4′-azidobenzal) -4-tert-butylcyclohexanone, 4-azidoacetophenone, 4-azido
- diazo compound examples include diazomethane, diazodinitrophenol, bis (trifluoromethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (phenylsulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane, and methylsulfonyl-p.
- Examples of the photogas generator by oxidative decomposition include compounds having a functional group such as carboxylic acid, aldehyde, and primary alcohol that are easily oxidized by the action of a photocatalyst. These compounds generate carbon dioxide as a gas by oxidation.
- a photogas generating agent may be used by 1 type and may use 2 or more types together.
- the photogas generating layer 20 may include a binder resin or the like for fixing the photogas generating agent to the photogas generating layer 29.
- the binder resin is used to supplement the photogas generating agent and fix it to the photogas generating layer 20.
- binder resin examples include cycloolefin polymer, polyether, polycarbonate, polystyrene, polyimide, phenol resin, petroleum resin, elastomer, and acrylic resin.
- the elastomer is preferable because it contracts due to stress and wraps the adherend 40.
- an acrylic resin is preferable because gas permeability is low and generated gas can be efficiently captured.
- Examples of the elastomer include natural rubber, styrene isoprene rubber, styrene butadiene rubber, butadiene rubber, ethylene propylene rubber, urethane rubber, and cyclized rubber having a ring structure in these rubbers.
- Examples of the cyclized rubber include cyclized natural rubber, cyclized polyisoprene, cyclized polyisobutylene, and cyclized polybutadiene.
- the acrylic resin refers to a polymer obtained using at least one monomer selected from (meth) acrylic acid and (meth) acrylic acid ester.
- the (meth) acrylic acid ester include phenoxydiethylene glycol (meth) acrylate, phenoxytriethylene glycol (meth) acrylate, phenoxytetraethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, and phenoxydipropylene glycol (meth).
- the content ratio of the photogas generating agent is 0.1 to 1000 parts by mass, preferably 0.5 to 100 parts by mass with respect to 100 parts by mass of the binder resin.
- the amount is 100 parts by mass, more preferably 1 to 50 parts by mass, and still more preferably 5 to 20 parts by mass.
- the laminate 200 can be separated from the support 100 well.
- the content ratio of the photogas generating agent and the binder resin contained in the photogas generating layer 20 is 1 to 99% by weight, preferably 50 to 99% by weight.
- the laminate 200 can be separated from the 100.
- the most preferable combination of the photogas generator and the binder resin is a combination of an azide and an elastomer, a combination of an azide and an acrylic resin, or a combination of a diazo compound and an acrylic resin.
- the azide generates gas upon exposure, and reacts with the elastomer to form a crosslinked structure, so that the photogas generation layer 20 contracts upon exposure.
- the laminate 200 has a structure that shrinks and encloses the adherend 40. With such a structure, the adherend 40 can be efficiently recovered from the support 100.
- the acrylic resin has a low gas permeability and can efficiently capture the generated gas, the adherend can be efficiently recovered from the support.
- the light gas generating layer 30 is provided with additives such as a leveling agent, a plasticizer, a surfactant, an antifoaming agent, a sensitizer, an antihalation agent, and a storage stabilizer as long as the functions of the light gas generating layer 30 are not impaired. Can be contained.
- additives such as a leveling agent, a plasticizer, a surfactant, an antifoaming agent, a sensitizer, an antihalation agent, and a storage stabilizer as long as the functions of the light gas generating layer 30 are not impaired. Can be contained.
- the photogas generating layer 20 As a method for forming the photogas generating layer 20, for example, a composition containing the photogas generating material and, if necessary, a solvent is applied to the surface 101 on which the stacked body 200 of the support 100 is placed by spin coating, What is necessary is just to form using the apply
- the resin composition used for forming the photogas generating layer 20 according to the present invention is at least one selected from the above-mentioned polymer having a structural unit derived from (meth) acrylic acid, and an azide and a diazo compound. Containing.
- the thickness of the gas generating layer is appropriately selected according to the coating method, the content of the photogas generating agent, and the like, but it may usually be 1 ⁇ m or more. Moreover, after apply
- the heating conditions are usually 20 to 200 ° C. and 1 to 600 seconds.
- the solvent may be any solvent as long as it can efficiently dissolve other components contained in the composition.
- an ether such as tetrahydrofuran, diethyl ether, or diethylene glycol diethyl ether is used.
- Preferred solvents are aromatic solvents such as toluene, benzene, or xylene, or ketone solvents such as methyl ethyl ketone, methyl amyl ketone, cyclopentanone, or cyclohexanone.
- ketone solvents such as methyl ethyl ketone, methyl amyl ketone, cyclopentanone, or cyclohexanone.
- the composition contains a diazo compound, ethyl lactate, Ester solvents such as ethyl acetate or propylene glycol monomethyl ether acetate are preferred.
- the optical gas generation layer can be applied as a gas generation film.
- a gas generating film contains a polymer having a structural unit derived from (meth) acrylic acid, and at least one selected from an azide and a diazo compound as described above.
- the film thickness is not particularly limited and is appropriately selected according to the application.
- it may be formed in the peeling base material surface, and what can be transcribe
- the adhesive layer adhesive layer 30 is used for adhering the adherend 40.
- the adhesive layer 30 can be appropriately selected depending on the type of the adherend 40.
- the adhesive layer 30 only needs to contain a material having adhesiveness to the adherend 40.
- examples of the material having adhesiveness include materials generally used for bonding with inorganic materials such as epoxy resins, acrylic resins, and phenol resins.
- a biological substance is used as the adherend 40, a material that exhibits adhesiveness to a desired biological substance, for example, a general biological substance is cultured as the adhesive material. A culture medium is mentioned.
- Materials that exhibit adhesion to biological materials include various materials such as glass, aluminum oxide, quartz, gold, and plasma-treated polystyrene; hydrophilic polystyrene, polylysine, aminopropyltriethoxysilane, N- ( 2-aminoethyl) -3-aminopropyltrimethoxysilane and other basic substances, and condensates of these basic substances; fibronectin, laminin, tenascin, vitronectin, peptide, collagen, atelocollagen, gelatin, fibrous protein, glycoprotein , Glucosaminoglycan, proteoglycan, fibronectin, hyaluronic acid, entactin, chondroitin sulfate proteoglycan and other biological substances, and these complexes such as extracellular matrix.
- the adhesive layer 30 is an additive such as a leveling agent, a plasticizer, a surfactant, an antifoaming agent, a sensitizer, a polyvinyl alcohol, an unsaturated polyester, an acrylic resin as long as the adhesiveness to the adherend 40 is not impaired.
- Polyethylene diallyl phthalate, ethylene propylene diene monomer, epoxy resin, phenol resin, polyurethane, melamine resin, polycarbonate, polyvinyl chloride, polyamide, polyimide, styrene butadiene rubber, chloroprene rubber, polypropylene, polybutylene, polystyrene, polyvinyl acetate, nylon May contain binder resins such as polyester, polybutadiene, polybenzimidazole, polyacrylonitrile, epichlorohydrin, polysulfide, polyisoprene, and polyethylene glycol. Kill.
- binder resins such as polyester, polybutadiene, polybenzimidazole, polyacrylonitrile, epichlorohydrin, polysulfide, polyisoprene, and polyethylene glycol. Kill.
- the adhesive layer 30 may provide a gas barrier function to the gas 21 in the same manner as the gas barrier layer 50.
- the adhesive layer 30 can contain a material used for the gas barrier layer 50.
- the adhesive layer 30 can be formed by applying the adhesive material and, if necessary, a composition containing a solvent onto the photogas generating layer 20. Moreover, after apply
- the heating conditions are usually 20 to 200 ° C. and 1 to 600 seconds.
- the thickness of the adhesive layer is appropriately selected according to the size and type of the adherend, but if it is thin, the adhesiveness may be insufficient. Therefore, the lower limit is usually 10 ⁇ m or more.
- an upper limit should just be 1 mm or less normally.
- adherend 40 examples include stem cells such as iPS cells and ES cells, somatic cells derived therefrom, nucleic acids, proteins, sugar chains, peptides, and biologically related substances such as these groups (colony).
- stem cells such as iPS cells and ES cells
- somatic cells derived therefrom nucleic acids, proteins, sugar chains, peptides, and biologically related substances such as these groups (colony).
- a semiconductor chip having a semiconductor element or the like can be given.
- the method for placing the adherend 40 on the adhesive layer 30 can be appropriately selected depending on the type of the adherend 40.
- the adherend 40 when it is a biological substance, it can be placed with a medium such as water, a buffer solution, or gas through a connection port to an external member, such as a supply port in a support.
- various treatments may be applied to the adherend 40.
- the various treatments include general semiconductor processing means such as culture when the adherend is a biological substance, and photofabrication when the adherend is a semiconductor chip.
- Step (2) is a step of generating a gas 21 from the optical gas generation layer 200 by exposure and separating the support 100 and the laminate 200 by the gas 21.
- the support 100 and the laminate 200 are separated by floating the laminate 200 from the support 100 by the buoyancy of the gas 21 generated from the photogas generation layer 200 by exposure.
- Step (2) may be performed simultaneously with the exposure of step (1) or after step (1).
- the separation of the support 100 and the laminate 200 includes separation of a part of the laminate as shown in FIG.
- the laminate 200 can be heated with a hot plate or the like. This heating condition is usually 10 to 600 seconds at 20 to 100 ° C. when the adherend 40 is a biological substance, and 30 to 300 usually 70 to 180 ° C. when the adherend 40 is a semiconductor chip. Seconds. Further, in order to improve the buoyancy of the gas 21, the support 100 and the laminate 200 may be vibrated by ultrasonic waves or the like.
- Process (3) is a step of recovering the adherend 40 from the support 100 by recovering the stacked body 200. Recovery of the adherend 40 is performed by recovering the laminate 200 separated from the support 100 in the step (2). Since the adherend 40 is performed by collecting the laminate 200, the adherend can be efficiently collected from the support 100. Furthermore, reattachment of the adherend 40 to the support 100 can be prevented.
- recovery can be suitably selected with the kind of to-be-adhered thing 40.
- FIG. When the adherend 40 is a biological material, it can be collected through a connection port to an external member such as a discharge port in the support together with a medium such as water, buffer solution, or gas. Step (3) may be performed simultaneously with the separation of step (2), after step (2), or may be performed simultaneously with step (1) and step (2).
- the adherend 40 can be isolated by separating the adherend 40 and the adhesive layer 30 from each other.
- the separation method can be appropriately selected depending on the type of the adherend 40.
- the adherend 40 is a biological substance
- the molecules involved in the bonding between the adhesive layer 30 and the adherend 40 and the adhesive layer 30 are decomposed using enzymes such as proteolytic enzymes and collagen degrading enzymes.
- the adherend 40 can be isolated.
- the adherend can be recovered by an apparatus (adherent recovery apparatus) including the following means (1) to (6).
- a base material hereinafter, also referred to as “a substrate for collecting an adherend” having a laminate having a support, a photogas generation layer, and an adhesive layer in this order, (2) a stage on which the base material is placed, (3) Means for supplying the adherend to the substrate, (4) Detection means for obtaining position information of the adherend, (5) Exposure means for exposing the photogas generating layer, (6) Control means for controlling the means (1) to (5).
- a means for identifying the adherend may be provided.
- the means for identifying for example, when the adherend is a biological substance, an irradiation unit that irradiates light having a wavelength that does not damage the biological substance, and fluorescence obtained from the biological substance by the light Means including an image sensor for acquiring an image may be mentioned.
- the method for selectively recovering an adherend is a method for selectively recovering an adherend using the method for recovering an adherend of the present invention. That is, this is an adherend recovery method in which there are a plurality of the laminates, and the desired laminate is selectively exposed to selectively recover the desired adherend from the support.
- FIG. 7 is a schematic diagram showing a method for selectively recovering the adherend.
- “There are a plurality of stacked bodies 200” means that there are at least two stacked bodies 200.
- the stacked body 200 may be arranged in any form. For example, a form in which the stacked body 200 is arranged in a lattice shape as shown in FIG.
- the desired adherend 41 can be collected by selectively exposing the laminate 200 having the desired adherend 41 from the plurality of laminates 200.
- the exposure light usually include ultraviolet rays and visible rays.
- the exposure light is light having a wavelength of 200 to 500 nm (eg, i-line (365 nm)), and can be appropriately selected depending on the type of the photogas generating layer.
- the exposure light may be laser light or light including a plurality of wavelengths.
- the dose of active ray is and the type of the light gas generating layer, but can be appropriately selected depending on the thickness, when using the i-line as exposure light, the exposure dose is usually 100 ⁇ 1500mJ / cm 2.
- each stacked body 200 may be individually exposed, for example, through a mask having an opening only in a region where the desired stacked body 200 is placed. May be exposed.
- the exposure is performed using, for example, a contact aligner, a stepper, or a scanner.
- the recovered adherend 41 can be isolated by separating the adherend 41 and the adhesive layer as described above.
- the adherend 40 that has not been collected by the selective recovery method of the adherend is separated from the adherend 40 and the adhesive layer in the same manner as the collected adherend. Can be separated.
- the laminate 200 remaining on the support 100 by the selective recovery method of the adherend can be used as a substrate in which the adherend 40 is disposed at an appropriate position of the support 100.
- the adherend 40 is a biological material, it can be used as a cell sensor substrate.
- Preparation Examples 1 to 15 The binder resins shown in Table 1 and the photogas generating agent were dissolved in an amount such that the solid content was 10% by mass with the solvents shown in Table 1 to prepare compositions of Preparation Examples 1 to 15.
- “parts” represents parts by mass.
- the details of each component in Table 1 are as follows.
- PMMA polymethacrylic acid
- weight average molecular weight 120,000 RB810 Butadiene rubber, trade name “RB810”, manufactured by JSR Corporation, weight average molecular weight 230,000
- Azide compound 1 a condensate of 1 mol of the compound represented by the following formula (1) and 2.5 mol of 1,2-naphthoquinonediazide-5-sulfonic acid
- Azide compound 2 Condensation product of 1 mol of the compound represented by the above formula (1) and 4 mol of 1,2-naphthoquinonediazide-5-sulfonic acid
- Azide compound 3 1 mol of the compound represented by the following formula (2) and 1,2- Condensate with 3.5 mol of naphthoquinonediazide-5-sulfonic acid
- Azide compound 4 Condensation product of 1 mol of the compound represented by the above formula (2) and 4 mol of 1,2-naphthoquinonediazide-5-sulfonic acid.
- Azide 1 Compound represented by the following formula (3)
- Example 1 The composition of Preparation Example 1 was spin-coated on a glass substrate and heated on a hot plate at 110 ° C. for 5 minutes to form a coating film (photogas generation layer) having a thickness of 10 ⁇ m.
- a vitronectin film having a thickness of 50 ⁇ m is formed as an adhesive layer on the photogas generation layer, and normal human skin fibroblasts (manufactured by Dainippon Pharmaceutical Co., Ltd.) are placed on the adhesive layer as an adherend,
- the laminate was exposed on the entire surface of the laminate from the glass substrate side (high pressure mercury lamp).
- the exposure was performed so that the exposure at a wavelength of 430 nm was 2,000 mJ / cm 2 . After the exposure, the glass substrate and the laminate were immersed in water. It was confirmed that the laminate was peeled off from the glass substrate after immersion. A photograph showing the laminate peeled from the glass substrate is shown in FIG.
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Abstract
Description
本発明は、細胞などの被接着物の種類を問わずに、どのような被接着物であっても被接着物を回収することができる被接着物回収方法を提供することを目的とする。
[1]支持体から、被接着物を回収する被接着物回収方法であって、
支持体上の光ガス発生層、接着層および被接着物をこの順に有する積層体を、露光する工程(I)、光ガス発生層からガスを発生させ、前記ガスにより支持体と積層体を分離する工程(II)、分離した積層体を回収することで、支持体から被接着物を回収する工程(III)を有することを特徴とする被接着物回収方法。
[2]前記光ガス発生層が、アジ化物およびジアゾ化合物から選ばれる少なくとも一種を含有する光ガス発生層である[1]に記載の被接着物回収方法。
[3]前記光ガス発生層が、エラストマーを含有する[1]または[2]の被接着物回収方法。
[4]前記光ガス発生層が、(メタ)アクリル酸由来の構造単位を有する重合体を含有する[1]または[2]の被接着物回収方法。
[5]前記光ガス発生層が、(メタ)アクリル酸由来の構造単位を有する重合体を100質量部に対して、アジ化物およびジアゾ化合物から選ばれる少なくとも一種を5~20質量部含有する[1]の被接着物回収方法。
[6]前記被接着物が細胞である[1]~[5]の被接着物回収方法。
[7]支持体上に、前記積層体が複数あって、所望の積層体を選択的に露光することで、支持体から所望の被接着物を選択的に回収する、[1]~[4]の被接着物回収方法。
[8](1)支持体、光ガス発生層、および接着層をこの順に有する積層体を有する基材、
(2)前記基材を載せるステージ、
(3)被接着物を前記基材に供給するための手段、
(4)被接着物の位置情報を得るための検出手段、
(5)前記、光ガス発生層を露光するための露光手段、
(6)前記(1)~(5)の手段を制御するための制御手段
を有することを特徴とする被接着物回収装置。
[9](メタ)アクリル酸由来の構造単位を有する重合体、およびアジ化物およびジアゾ化合物から選ばれる少なくとも一種を含有することを特徴とする樹脂組成物。
[10]前記(メタ)アクリル酸由来の構造単位を有する重合体を100質量部に対して、前記アジ化物およびジアゾ化合物から選ばれる少なくとも一種を5~20質量部含有する[9]の樹脂組成物。
[11](メタ)アクリル酸由来の構造単位を有する重合体、およびアジ化物およびジアゾ化合物から選ばれる少なくとも一種を含有することを特徴とするガス発生膜。
[12]前記(メタ)アクリル酸由来の構造単位を有する重合体を100質量部に対して、前記アジ化物およびジアゾ化合物から選ばれる少なくとも一種を5~20質量部含有する[11]に記載のガス発生膜。
支持体上の光ガス発生層、接着層および被接着物をこの順に有する積層体を、露光すること(工程(1))、光ガス発生層からガスを発生させ、前記ガスにより支持体と積層体を分離させる(工程(2))、分離した積層体を回収することで、支持体から被接着物を回収する(工程(3))を有することを特徴とする。
被着物回収方法の模式図を図1に示す。
工程(1)は、支持体100上の光ガス発生層20、接着層30および被接着物40をこの順に有する積層体200を、露光する工程である。
前記支持体100としては、積層体200を保持できれば、硬質であっても軟質であってもよく、また、どのような材質であってもよい。例えば、支持体100としては、シリコン、ガラス、石英、炭化珪素、窒化珪素、アクリル樹脂、ポリカーボネート、ポリシクロオレフィン、ポリイミド、ポリスチレン等の材料を含むものが挙げられる。これらの中でも、ガラス、石英、炭化珪素、アクリル樹脂、ポリカーボネート、ポリシクロオレフィン、ポリスチレン等の、露光光300に対して透明性の高い材料を含むものが好ましい。
支持体100上に、積層体200を載置する方法としては、支持体100の積層体200を載置する面101に、光ガス発生層20、接着層30および被接着物40の順に載置することにより形成できる。
光ガス発生層20は、光によりガスを発生させる光ガス発生剤を含む。また、光ガス発生層20は、光ガス発生剤の他に、光ガス発生剤を補足するためのバインダー樹脂等を含んでもよい。光ガス発生剤は、所望の波長の光を照射することで光反応、または酸化分解を起こし、ガスを発生する物質を示す。酸化分解によりガスを発生する光ガス発生剤は、酸化チタンなどの光触媒と共に用いるものであり、光触媒の酸化作用により分解してガスを発生させる物質である。
光ガス発生剤は、1種で用いてもよく、2種以上を併用してもよい。
環化ゴムとしては、環化天然ゴム、環化ポリイソプレン、環化ポリイソブチレン、環化ポリブタジエン等が挙げられる。
アクリル樹脂中に含まれる(メタ)アクリレート単量体由来の構造単位の含有割合は、ガス透過率が向上することから、50質量%以上、好ましくは70質量%以上、より好ましくは90質量%以上である。
なお、光ガス発生層は、ガス発生膜として、応用することが可能である。かかるガス発生膜は、前記したように(メタ)アクリル酸由来の構造単位を有する重合体、およびアジ化物およびジアゾ化合物から選ばれる少なくとも一種を含有する。膜厚は特に制限されず、く用途に応じて適宜選択される。なお、膜として、自立できるものであっても、剥離基材表面に形成され、被形成物に対し、転写しうるものであってもよい。
接着層30は、被接着物40を接着するために用いるものである。接着層30としては、被接着物40の種類により、適宜選択可能である。接着層30としては、被接着物40に対して接着性を有する材料を含有していればよい。被接着物40として半導体素子などの無機材料を用いる場合、接着性を有する材料としては、エポキシ樹脂、アクリル樹脂、およびフェノール樹脂等の一般的に無機材料との接着に用いられる材料が挙げられる。また、被接着物40として生体関連物質を用いる場合には、接着性を有する材料としては、所望の生体関連物質に対して接着性を発揮する材料、例えば、一般的な生体関連物質を培養する培地が挙げられる。
また、前記組成物を塗布した後は、例えば、ホットプレート等で加熱することができる。加熱条件は、通常、20~200℃で1~600秒である。
接着層の厚さは、被接着物の大きさや種類に応じて適宜選択されるが、薄いと接着性が不十分となることがあるため、下限は、通常10μm以上であればよい。また、接着層が厚すぎると、被接着物の単離が難しくなることがあるので、上限は、通常1mm以下であればよい。
被接着物40としては、iPS細胞やES細胞などの幹細胞、そこから分化誘導した体細胞、核酸、タンパク、糖鎖、並びにペプチド、およびこれらの群(コロニー)等の生体関連物質の他に、半導体素子等を有する半導体チップが挙げられる。
工程(2)は、露光により光ガス発生層200からガス21を発生させ、前記ガス21により支持体100と積層体200を分離させる工程である。
支持体100と積層体200との分離は、露光により光ガス発生層200から発生したガス21の浮力により、支持体100から積層体200を浮かせることにより、分離する。
工程(2)は、工程(1)の露光と同時に行っても、工程(1)の後に行ってもよい。
工程(3)は、積層体200を回収することで、支持体100から被接着物40を回収する工程である。
被接着物40の回収は、前記工程(2)により支持体100から分離した積層体200を回収することで行う。被接着物40は、積層体200を回収することで行うことから、被接着物は、効率よく支持体100から回収することができる。さらに、被接着物40の支持体100への再付着を防止することができる。
工程(3)は、工程(2)の分離と同時に行っても、工程(2)の後に行っても、工程(1)及び工程(2)と同時に行ってもよい。
(1)支持体、光ガス発生層、および接着層をこの順に有する積層体を有する基材(以下、「被接着物回収用基材」ともいう)、(2)前記基材を載せるステージ、(3)被接着物を前記基材に供給するための手段、(4)被接着物の位置情報を得るための検出手段、(5)前記、光ガス発生層を露光するための露光手段、(6)前記(1)~(5)の手段を制御するための制御手段。
被接着物の選択的回収方法とは、本発明の被接着物回収方法を利用した被接着物の選択的回収方法である。つまり、前記積層体が複数あって、所望の積層体を選択的に露光することで、支持体から所望の被接着物を選択的に回収する被接着物回収方法である。被接着物の選択的回収方法を示す模式図を図7に示す。
また、被接着物の選択的回収方法により回収しなかった被接着物40についても、回収した被接着物と同様に、被接着物40と接着層を、分離することで被接着物40を単離することができる。
表1に示すバインダー樹脂、および光ガス発生剤を、表1に示す溶剤で固形分が10質量%となる量に溶解させ、調製例1~15の組成物を調製した。なお、表1中「部」は質量部を示す。また、表1中の各成分の詳細は以下のとおりである。
PMMA:ポリメタクリル酸、重量平均分子量120,000
RB810:ブタジエンゴム、商品名「RB810」、JSR株式会社製、重量平均分子量230、000
アジド化合物1:下記式(1)に示す化合物1molと、1,2-ナフトキノンジアジド-5-スルホン酸2.5molとの縮合物
アジド化合物3:下記式(2)に示す化合物1molと、1,2-ナフトキノンジアジド-5-スルホン酸3.5molとの縮合物
アジ化物1:下記式(3)に示す化合物
ガラス基板上に、前記調製例1の組成物をスピンコートし、ホットプレートにて110℃で5分間加熱し、膜厚10μmの塗膜(光ガス発生層)を形成した。前記光ガス発生層上に、接着層として膜厚50μmのビトロネクチン膜を形成し、前記接着層上に被接着物として、正常ヒト皮膚繊維芽細胞(大日本製薬株式会社製)を載置し、ガラス基板上に、光ガス発生層、接着層および被接着物の順に積層した積層体を形成した。ガラス基板側から前記積層体を積層体全面に露光(高圧水銀ランプ)した。露光量は波長430nmにおける露光量が2,000mJ/cm2となるように行った。露光後、ガラス基板および積層体を水に浸漬した。浸漬後ガラス基板から積層体が剥がれることを確認した。ガラス基板から剥がれた積層体を示す写真を図8に示す。
下記表2に示す条件を変更する以外は、前記[実験例1]と同様の操作を行い、ガラス基板から積層体が剥がれるかどうかを確認した。結果を表2に併記する。
Claims (12)
- 支持体から、被接着物を回収する被接着物回収方法であって、
支持体上の光ガス発生層、接着層および被接着物をこの順に有する積層体を、露光する工程(I)、光ガス発生層からガスを発生させ、前記ガスにより支持体と積層体を分離する工程(II)、分離した積層体を回収することで、支持体から被接着物を回収する工程(III)を有することを特徴とする被接着物回収方法。 - 前記光ガス発生層が、アジ化物およびジアゾ化合物から選ばれる少なくとも一種を含有する光ガス発生層である請求項1に記載の被接着物回収方法。
- 前記光ガス発生層が、エラストマーを含有する請求項1または2に記載の被接着物回収方法。
- 前記光ガス発生層が、(メタ)アクリル酸由来の構造単位を有する重合体を含有する請求項1または2に記載の被接着物回収方法。
- 前記光ガス発生層が、(メタ)アクリル酸由来の構造単位を有する重合体を100質量部に対して、アジ化物およびジアゾ化合物から選ばれる少なくとも一種を5~20質量部含有する請求項1に記載の被接着物回収方法。
- 前記被接着物が細胞である請求項1~5のいずれかに記載の被接着物回収方法。
- 支持体上に、前記積層体が複数あって、所望の積層体を選択的に露光することで、支持体から所望の被接着物を選択的に回収する、請求項1~4のいずれかに記載の被接着物回収方法。
- (1)支持体、光ガス発生層、および接着層をこの順に有する積層体を有する基材、
(2)前記基材を載せるステージ、
(3)被接着物を前記基材に供給するための手段、
(4)被接着物の位置情報を得るための検出手段、
(5)前記、光ガス発生層を露光するための露光手段、
(6)前記(1)~(5)の手段を制御するための制御手段
を有することを特徴とする被接着物回収装置。 - (メタ)アクリル酸由来の構造単位を有する重合体、およびアジ化物およびジアゾ化合物から選ばれる少なくとも一種を含有することを特徴とする樹脂組成物。
- 前記(メタ)アクリル酸由来の構造単位を有する重合体を100質量部に対して、前記アジ化物およびジアゾ化合物から選ばれる少なくとも一種を5~20質量部含有する請求項9に記載の樹脂組成物。
- (メタ)アクリル酸由来の構造単位を有する重合体、およびアジ化物およびジアゾ化合物から選ばれる少なくとも一種を含有することを特徴とするガス発生膜。
- 前記(メタ)アクリル酸由来の構造単位を有する重合体を100質量部に対して、前記アジ化物およびジアゾ化合物から選ばれる少なくとも一種を5~20質量部含有する請求項11に記載のガス発生膜。
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