WO2010010900A1 - 部材の仮固定・剥離方法及びそれに好適な仮固定用接着剤 - Google Patents
部材の仮固定・剥離方法及びそれに好適な仮固定用接着剤 Download PDFInfo
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- WO2010010900A1 WO2010010900A1 PCT/JP2009/063119 JP2009063119W WO2010010900A1 WO 2010010900 A1 WO2010010900 A1 WO 2010010900A1 JP 2009063119 W JP2009063119 W JP 2009063119W WO 2010010900 A1 WO2010010900 A1 WO 2010010900A1
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- meth
- acrylate
- temporary fixing
- adhesive
- fixing method
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Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/08—Homopolymers or copolymers of acrylic acid esters
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
- C09J175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J201/00—Adhesives based on unspecified macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
- C09J2301/416—Additional features of adhesives in the form of films or foils characterized by the presence of essential components use of irradiation
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2433/00—Presence of (meth)acrylic polymer
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2475/00—Presence of polyurethane
Definitions
- the present invention relates to a temporary fixing / peeling method for processing various members, and also relates to a temporary fixing adhesive suitable for temporary fixing.
- the present invention relates to a method of temporarily fixing the member for processing an optical member, a peeling method, and a photocurable temporary fixing adhesive suitable for the application.
- double-sided tapes and hot melt adhesives are used, and members bonded or laminated with these adhesives, After cutting into a predetermined shape, the adhesive is removed and a processed member is manufactured.
- a processed member For example, in a semiconductor mounting component, after fixing these components to a base material with a double-sided tape, a desired part is cut, and further, the double-sided tape is irradiated with ultraviolet rays to be peeled off from the part.
- a hot-melt adhesive after joining the members, the adhesive is infiltrated into the gap by heating, and then the desired part is cut and the adhesive is peeled off in an organic solvent.
- a photo-curing or heating adhesive for temporary fixing containing a water-soluble compound such as a water-soluble vinyl monomer has been proposed.
- the peelability in water is solved, but there is a problem that the adhesive strength at the time of component fixing is low and the dimensional accuracy of the member after cutting is poor.
- an adhesive for temporary fixing has been proposed which has improved adhesion by using a specific (meth) acrylate having high hydrophilicity and improved peelability by swelling or partial dissolution.
- This temporary fixing adhesive generates frictional heat between a component and a cutting jig such as a blade or a diamond cutter at the time of cutting.
- the present invention has a pressure applied from one or both of the fixing member and the workpiece, and the pressure is applied and the irradiation is performed. At least for a certain period of time at the same time, it was possible to obtain excellent dimensional accuracy during processing and to obtain the knowledge that the present invention can be achieved.
- the present invention has the following configuration. (1) Applying a temporary fixing adhesive to the fixing member (hereinafter referred to as an application step), mounting a workpiece on the temporary fixing adhesive (hereinafter referred to as a mounting step), and temporary mounting after the mounting Including irradiating the fixing adhesive with at least one of visible light or ultraviolet light to increase the adhesive strength of the temporary fixing adhesive (hereinafter referred to as an irradiation step), and applying pressure from one or both of the fixing member and the workpiece It is a temporary fixing method including applying (hereinafter referred to as a pressure step), and applying the pressure and irradiating at the same time for at least a certain time.
- any one or more of the fixing member, the temporary fixing adhesive, and the workpiece are controlled to 0 ° C. or higher and 150 ° C. or lower.
- the temporary fixing adhesive is a composition containing (A) a polyfunctional (meth) acrylate, (B) a monofunctional (meth) acrylate, and (C) a photopolymerization initiator.
- the temporary fixing method as described in any one of (4).
- the temporary fixing method according to any one of (1) to (6), wherein the glass transition temperature of the temporary fixing adhesive is ⁇ 50 ° C. or higher and 50 ° C. or lower.
- the temporary fixing adhesive is 1 to 90 parts by mass of (A), 10 to 99 parts by mass of (B) in 100 parts by mass of the total amount of (A) and (B), and (A) The temporary fixing method according to any one of (5) to (7) above, wherein 0.1 to 30 parts by mass of (C) is contained with respect to 100 parts by mass of the total amount of (B).
- the granular material (D) in which the temporarily fixing adhesive does not dissolve in (A) to (C) is 0.1 to 20 parts by mass with respect to 100 parts by mass of the total amount of (A) and (B).
- the temporary fixing method according to the above (9), wherein the granular material (D) not dissolved in (A) to (C) has a spherical shape.
- the particulate material (D) that does not dissolve in (A) to (C) is any one of or a mixture of crosslinked polymethyl methacrylate particles, crosslinked polystyrene particles, and crosslinked polymethyl methacrylate polystyrene copolymer particles.
- the standard deviation of the particle volume distribution with respect to the particle diameter when the particle diameter ( ⁇ m) of the granular substance (D) not dissolved in (A) to (C) is logarithmically expressed is 0.0001 to 0
- the polyfunctional (meth) acrylate contains a polyfunctional (meth) acrylate oligomer / polymer and / or a bifunctional (meth) acrylate monomer.
- Temporary fixing method as described.
- the photopolymerization initiator is benzyldimethyl ketal, oxy-phenyl-acetic acid 2- [2-oxo-2-phenyl-acetoxy-ethoxy] -ethyl ester or oxy-phenyl-acetic acid 2
- the temporary fixing method according to any one of (5) to (13) above, which contains one or more selected from the group consisting of [2-hydroxy-ethoxy] -ethyl ester.
- the temporary fixing adhesive is applied to the fixing member or the workpiece to be temporarily fixed.
- any method can be used as long as it is a known coating process, but a process of coating an appropriate amount of an adhesive on the bonding surface of one fixing member or workpiece to be fixed is preferable.
- the application amount of the adhesive is preferably 0.00000001 to 0.1 mg / mm 2 , more preferably 0.000001 to 0.001 mg / mm 2 .
- the method for applying an appropriate amount is not particularly limited as long as it is a known method, but, for example, a method using an applicator is simple and accurate, and is preferable in terms of productivity.
- the mounting step in the present invention is a step of mounting the member to be processed or the fixing member on the fixing member to which the adhesive for temporary fixing is applied after the applying step or the adhesive for temporary fixing on the member to be processed.
- the mounting process is not particularly limited as long as it is a known method, but for example, a process of using an automatic mounting apparatus such as an industrial robot is preferable in terms of simplicity and accuracy and improving productivity.
- the flow of the temporary fixing adhesive is performed by controlling one or more of the fixing member, the temporary fixing adhesive, and the workpiece to be performed at 0 ° C. or more and 150 ° C. or less. Gender can be controlled.
- the fixing member, the temporary fixing adhesive, and the workpiece are at 0 ° C. or higher, the fluidity is excellent, and when the fixing member is 150 ° C. or lower, the temporary curing adhesive is not polymerized by thermal curing, and the dimensional accuracy is excellent.
- it is preferably 10 ° C. or higher and 100 ° C. or lower, and more preferably 20 ° C. or higher and 80 ° C. or lower. Still more preferably, it is 20 ° C. or higher and 60 ° C. or lower.
- the pressure step of the present invention is preferably a step of applying pressure from one or both of the fixing member and the workpiece, and more preferably a step of applying pressure from one or both of the fixing member and the workpiece to be uniform.
- a vacuum press machine or a pressurization press machine is preferable.
- “Uniform” in the present invention means that a difference obtained by subtracting the smallest part from the largest part between the fixed member and the workpiece to be processed is within a range of 40 ⁇ m or less. Within this range, good dimensional accuracy can be obtained when the workpiece is processed. From the viewpoint of dimensional accuracy, the difference obtained by subtracting the smallest part from the largest part between the fixing member and the workpiece is preferably within a range of 20 ⁇ m or less, and more preferably within a range of 10 ⁇ m or less. It is still more preferable that it is in the range of 5 ⁇ m or less.
- the pressure step of the present invention it is preferable to apply a pressure of 1 g / cm 2 or more and 1000 kg / cm 2 or less from one or both of the fixing member and the workpiece. If the distance between the fixing member and the workpiece is uniform, there is no problem even if pressure is locally applied to the fixing member and the workpiece. It is preferable from the viewpoint of the interval. When the applied pressure is 1 g / cm 2 or more, the distance between the fixing member and the workpiece can be made uniform, and when it is 1000 kg / cm 2 or less, the fixing member and the workpiece are not damaged.
- 3 g / cm 2 or more and 800 kg / cm 2 or less is preferable from the viewpoint of uniformity of the distance between the fixing member and the workpiece and damage, and 5 g / cm 2 or more and 500 kg / cm 2 or less is even more preferable, and 10 g / cm 2. More preferably, it is 300 kg / cm 2 or less.
- an irradiation step is required in which the temporary fixing adhesive is irradiated with at least one of visible light or ultraviolet light to increase the adhesive strength of the temporary fixing adhesive.
- the lamp used in the irradiation step and the re-irradiation step described later is not particularly limited as long as it increases the adhesive strength of the temporary fixing adhesive, but a black lamp or a metal halide lamp that can irradiate ultraviolet rays having a wavelength of 365 nm, High pressure mercury lamps, LED lamps and the like are preferable.
- the wavelength of ultraviolet light is preferably 10 to 430 nm, more preferably 200 to 420 nm, and most preferably 330 to 405 nm.
- the irradiation amount of visible light or ultraviolet light is preferably in the range of 1 mJ / cm 2 to 4000 mJ / cm 2 at a wavelength of 365 nm. Within this range, good dimensional accuracy can be obtained when the workpiece is processed. From the viewpoint of dimensional accuracy, it is preferably in the range of 10mJ / cm 2 ⁇ 3000mJ / cm 2, more preferably more to be in the range of 100mJ / cm 2 ⁇ 2000mJ / cm 2, 300mJ / cm 2 ⁇ 1000mJ / cm 2 It is still more preferable that it is in the range.
- the irradiation step it is preferable to simultaneously perform the irradiation step for at least a certain time during the pressure step.
- processing refers to, for example, cutting, grinding, polishing, drilling, or the like of a member to be processed into a desired shape.
- the certain time here is not particularly limited as long as it includes a period during which curing is performed. It is preferable to perform the pressure process and the irradiation process at the same time after the pressure process is performed in advance, because the distance between the fixing member and the workpiece can be made uniform.
- the material of the workpiece and the fixing member is not particularly limited, but a member made of a material that can transmit ultraviolet rays or visible rays is preferable.
- a material that can transmit ultraviolet rays or visible rays examples include a crystal member, a glass member, and a plastic member.
- (A) polyfunctional (meth) acrylate used in the present invention two or more (meth) acryloylated polyfunctional (meth) acrylate oligomer / polymer or two or more ( A monomer having a (meth) acryloyl group can be used.
- Examples of the polyfunctional (meth) acrylate oligomer / polymer include 1,2-polybutadiene-terminated urethane (meth) acrylate (for example, “TE-2000” and “TEA-1000” manufactured by Nippon Soda Co., Ltd.), the hydrogenated product (for example, "TEAI-1000” manufactured by Nippon Soda Co., Ltd.), 1,4-polybutadiene-terminated urethane (meth) acrylate (for example, "BAC-45” manufactured by Osaka Organic Chemical Co., Ltd.), polyisoprene-terminated (meth) acrylate, polyester-based urethane (meta) ) Acryte (for example, “UV-2000B”, “UV-3000B”, “UV-7000B” manufactured by Nippon Synthetic Co., Ltd.
- 1,2-polybutadiene-terminated urethane (meth) acrylate for example, “TE-2000” and “TEA-1000” manufactured
- polyester-based urethane (meth) acrylate and / or polyether-based urethane (meth) acrylate are preferable, and polyester-based urethane (meth) acrylate is more preferable because of its great effect.
- the weight average molecular weight of the polyfunctional (meth) acrylate oligomer / polymer is preferably 10,000 to 60,000, and more preferably 13,000 to 40,000. The weight average molecular weight was determined by preparing a calibration curve with commercially available standard polystyrene using a GPC system (SC-8010 manufactured by Tosoh Corporation).
- bifunctional (meth) acrylate monomer examples include 1,3-butylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexadiol di (meth) acrylate, 1,9- Nonanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, 2-ethyl-2-butyl-propanediol (meth) acrylate, neopentyl glycol modified trimethylolpropane di (Meth) acrylate, stearic acid-modified pentaerythritol diacrylate, polypropylene glycol di (meth) acrylate, 2,2-bis (4- (meth) acryloxydiethoxyphenyl) propane, 2,2-bis (4- ( (Meta) acryloxy propo Shifeniru) propane,
- 1,6-hexadiol di (meth) acrylate and / or dicyclopentanyl di (meth) acrylate is preferable, and dicyclopentanyl di (meth) acrylate is more preferable from the viewpoint of great effect.
- trifunctional (meth) acrylate monomer examples include trimethylolpropane tri (meth) acrylate, tris [(meth) acryloxyethyl] isocyanurate, and the like.
- tetrafunctional or higher (meth) acrylate monomers dimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol ethoxytetra (meth) acrylate, dipentaerystol penta (meth) acrylate, dipenta Examples include erythrole hexa (meth) acrylate.
- the polyfunctional (meth) acrylate is more preferably hydrophobic.
- hydrophobic refers to a property that is difficult to dissolve in water or a property that is difficult to mix with water.
- examples of the hydrophobic polyfunctional (meth) acrylate include 1,3-butylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexadiol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, 2-ethyl-2-butyl-propanediol (meth) acrylate, neopentyl glycol modified Trimethylolpropane di (meth) acrylate, stearic acid-modified pentaerythritol diacrylate,
- hydrophobic trifunctional (meth) acrylate monomer examples include trimethylolpropane tri (meth) acrylate and tris [(meth) acryloxyethyl] isocyanurate.
- Hydrophobic tetrafunctional or higher functional (meth) acrylate monomers include dimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol ethoxytetra (meth) acrylate, and dipentaerythritol penta (meth) acrylate. And dipentaerythrole hexa (meth) acrylate.
- the cured product of the resin composition swells at the time of cutting, so that the position shifts and the dimensional accuracy at the time of processing may be inferior. Even if it is hydrophilic, it can be used as long as the cured product of the composition is not greatly swollen or partially dissolved by water.
- the polyfunctional (meth) acrylates it is preferable to contain a polyfunctional (meth) acrylate oligomer / polymer and / or a bifunctional (meth) acrylate monomer in terms of high effect. It is more preferable to use a polymer and a bifunctional (meth) acrylate monomer in combination.
- the content ratio is 100 parts by mass in total of the polyfunctional (meth) acrylate oligomer / polymer and the bifunctional (meth) acrylate monomer.
- Multifunctional (meth) acrylate oligomer / polymer: bifunctional (meth) acrylate monomer 30 to 95: 5 to 70, preferably 40 to 90:60 to 10, more preferably 60 to 80:40 to 20 Is most preferred.
- the amount of (A) polyfunctional (meth) acrylate used is preferably 1 to 90 parts by weight, more preferably 30 to 85 parts by weight, in a total of 100 parts by weight of (A) and (B). If it is 1 part by mass or more, the property that the cured product peels from the adherend when the cured product of the composition is immersed in warm water (hereinafter simply referred to as “peelability”) is sufficiently promoted. It can be ensured that the cured body peels into a film. Moreover, if it is 90 mass parts or less, there is no possibility that initial adhesiveness may fall.
- a monofunctional (meth) acrylate monomer can be used as the monofunctional (meth) acrylate.
- Single tube (meth) acrylate monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, isodecyl (Meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, phenyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopenteni Roxyethyl (meth) acrylate, isobornyl (meth) acrylate, methoxylated cyclodecatriene
- Hydrophobic monofunctional (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, Isodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, phenyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopent Tenyloxyethy
- the cured product of the resin composition swells during cutting, which may cause displacement and deteriorate processing accuracy. Even if it is hydrophilic, it can be used if the cured product of the resin composition does not swell or partially dissolve with water.
- phenol-ethylene oxide 2 mol-modified (meth) acrylate and / or 2- (1,2-cyclohexacarboximido) ethyl (meth) acrylate is contained because of its great effect. It is more preferable to use phenol ethylene oxide 2 mol modified (meth) acrylate in combination with 2- (1,2-cyclohexacarboximido) ethyl (meth) acrylate.
- the amount of (B) monofunctional (meth) acrylate used is preferably 10 to 99 parts by mass, more preferably 15 to 70 parts by mass, out of a total of 100 parts by mass of (A) and (B). If it is 10 parts by mass or more, there is no fear that the initial adhesiveness is lowered.
- the blended composition of (A) and (B) described above may contain (meth) acryloyloxyethyl acid phosphate, dibutyl 2- (meth) acryloyloxyethyl acid phosphate, dioctyl 2- (meth) acryloyloxyethyl phosphate.
- Adhesion to a metal surface by using a phosphate ester having a vinyl group or (meth) acrylic group such as diphenyl 2- (meth) acryloyloxyethyl phosphate, (meth) acryloyloxyethyl polyethylene glycol acid phosphate
- the property can be further improved.
- the photopolymerization initiator is blended for sensitization with visible light or ultraviolet active light to promote photocuring of the resin composition, and various known photopolymerization initiators can be used.
- the photopolymerization initiator include benzophenone and derivatives thereof, benzyl and derivatives thereof, entraquinone and derivatives thereof, benzoin derivatives such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isobutyl ether, and benzyl dimethyl ketal.
- Acetophenone derivatives such as ethoxyacetophenone and 4-t-butyltrichloroacetophenone, 2-dimethylaminoethylbenzoate, p-dimethylaminoethylbenzoate, diphenyldisulfide, thioxanthone and its derivatives, camphorquinone, 7,7-dimethyl-2,3- Dioxobicyclo [2.2.1] heptane-1-carboxylic acid, 7,7-dimethyl-2,3-dioxobicyclo [2.2.1] heptane-1-ca Boxy-2-bromoethyl ester, 7,7-dimethyl-2,3-dioxobicyclo [2.2.1] heptane-1-carboxy-2-methyl ester, 7,7-dimethyl-2,3-di Camphorquinone derivatives such as oxobicyclo [2.2.1] heptane-1-carboxylic acid chloride, 2-methyl-1
- a photoinitiator can be used 1 type or in combination of 2 or more types.
- 1 benzyl dimethyl ketal, oxy-phenyl-acetic acid 2- [2-oxo-2-phenyl-acetoxy-ethoxy] -ethyl ester and oxy-phenyl-acetic acid 2 are particularly effective.
- One or more selected from the group consisting of-[2-hydroxy-ethoxy] -ethyl ester is preferred.
- the photopolymerization initiator is preferably used in an amount of 0.1 to 30 parts by mass with respect to 100 parts by mass in total of (A) and (B). 0.5 to 25 parts by mass is more preferable. If it is 0.1 mass part or more, the effect of hardening acceleration
- the composition can be cured without depending on the amount of light irradiation, and further, the cross-linking density of the cured product of the composition is increased, so that no misalignment or the like occurs during cutting. In terms of improving peelability, it is more preferable.
- the glass transition temperature of the cured product obtained from the temporary fixing adhesive is preferably in the range of ⁇ 50 ° C. to 50 ° C.
- the member is temporarily bonded, and the temporarily fixed member is processed, and then the processed member is 100 ° C. or lower.
- the cured body of the temporary fixing adhesive itself undergoes large thermal expansion. As a result, the reduction of the bonding area is achieved and the bonding strength is reduced, so that only the member can be easily recovered.
- the glass transition temperature of the cured product obtained from the temporary fixing adhesive is ⁇ 50 ° C.
- the temporary fixed member is less likely to be displaced during processing, and the dimensional accuracy is excellent.
- the hot water peelability is excellent.
- the glass transition temperature of the cured product obtained from the temporary fixing adhesive is more preferably ⁇ 25 ° C. to 45 ° C., further preferably ⁇ 20 ° C. to 42 ° C., Still more preferably, it is 0 ° C to 40 ° C.
- the method for measuring the glass transition temperature of the cured product obtained from the temporary fixing adhesive used in the present invention is not particularly limited, but is measured by a known method such as DSC or dynamic viscoelastic spectrum.
- a preferable method is a method using a dynamic viscoelastic spectrum.
- the adhesive composition is used to temporarily bond the member, After processing the fixed member, when the processed member is immersed in warm water of 100 ° C. or less, a wavy or three-dimensional deformation occurs at the interface between the member and the cured body of the temporary fixing adhesive, and as a result, Reduction of the adhesion area is achieved, and the peelability is further improved.
- the material of the particulate material that does not dissolve in (A) to (C) may be either generally used organic or inorganic particles.
- organic particles include polyethylene particles, polypolypropylene particles, crosslinked polymethyl methacrylate particles, and crosslinked polystyrene particles
- inorganic particles include ceramic particles such as glass, silica, alumina, and titanium.
- the granular material not dissolved in (A) to (C) is preferably spherical in order to improve the dimensional accuracy when processing, that is, to control the film thickness of the adhesive.
- organic particles include methyl methacrylate monomers, crosslinked polymethyl methacrylate particles, crosslinked polystyrene particles and crosslinked polymethyl methacrylate polystyrene copolymers obtained as monodisperse particles by a known emulsion polymerization method of a styrene monomer and a crosslinkable monomer. Particles are preferred.
- spherical silica is preferable because the deformation of the particles is small and the variation in the film thickness of the composition after curing due to the variation in the particle size is small.
- crosslinked polymethyl methacrylate particles, crosslinked polystyrene particles, crosslinked polymethyl methacrylate polystyrene copolymer particles, crosslinked polymethyl methacrylate are used. Any one of particles, crosslinked polystyrene particles, crosslinked polymethyl methacrylate polystyrene copolymer particles, or a mixture thereof is more preferable. Any one of a crosslinked polymethyl methacrylate particle, a crosslinked polystyrene particle, a crosslinked polymethyl methacrylate polystyrene copolymer particle, or a mixture thereof is more preferable.
- the average particle diameter of the granular material not dissolved in (A) to (C) by the laser method is preferably in the range of 5 ⁇ m to 200 ⁇ m.
- the average particle size of the granular material is 5 ⁇ m or more, the peelability is excellent, and when the average particle size is 200 ⁇ m or less, the temporarily fixed member is hardly displaced during processing, and the dimensional accuracy is excellent.
- a more preferable average particle diameter is 8 ⁇ m to 150 ⁇ m, and further preferably 9 ⁇ m to 120 ⁇ m.
- the standard deviation of the particle size and particle size distribution was measured by “Laser Diffraction Particle Size Distribution Analyzer SALD-2200” manufactured by Shimadzu Corporation. The particle diameter is based on volume.
- the standard deviation of the particle volume distribution with respect to the particle diameter when the particle diameter ( ⁇ m) of the granular material not dissolved in (A) to (C) is logarithmically expressed is 0.0001 to It is preferable to be in the range of 0.25. If there is a standard deviation of the particle size of the granular material within this range, the variation in the film thickness of the composition after curing due to the variation in the particle size will be reduced, and deviation during processing of the temporarily fixed member will not occur easily, which is excellent in terms of dimensional accuracy. Not only the releasability is remarkably improved.
- the standard deviation of the particle size of the granular material is more preferably 0.0001 to 0.15, even more preferably 0.0001 to 0.1, and 0.0001 to 0.00. 08 is even more preferable, and 0.0001 to 0.072 is extremely preferable.
- the amount of the particulate material not dissolved in (A) to (C) is 0 with respect to the total amount of 100 parts by mass of (A) and (B) in terms of adhesive strength, processing accuracy, and peelability.
- the amount is preferably 1 to 20 parts by mass, more preferably 0.2 to 10 parts by mass, and still more preferably 0.2 to 6 parts by mass.
- a small amount of a polymerization inhibitor can be used for improving the storage stability.
- Polymerization inhibitors include methyl hydroquinone, hydroquinone, 2,2-methylene-bis (4-methyl-6-tertiary butylphenol), catechol, hydroquinone monomethyl ether, monotertiary butyl hydroquinone, 2,5-ditertiary butyl hydroquinone.
- P-benzoquinone 2,5-diphenyl-p-benzoquinone, 2,5-ditertiarybutyl-p-benzoquinone, picric acid, citric acid, phenothiazine, tertiary butylcatechol, 2-butyl-4-hydroxyanisole and 2 , 6-ditertiary butyl-p-cresol and the like.
- the amount of these polymerization inhibitors used is preferably 0.001 to 3 parts by mass, more preferably 0.01 to 2 parts by mass with respect to 100 parts by mass of the total amount of (A) and (B). Storage stability is ensured at 0.001 part by mass or more, good adhesiveness is obtained at 3 parts by mass or less, and it does not become uncured.
- a polar organic solvent may be used together.
- the adhesive for temporary fixing of the present invention includes various elastomers such as commonly used acrylic rubber, urethane rubber, acrylonitrile-butadiene-styrene rubber, inorganic filler, solvent, extender, and the like within a range not to impair the purpose of the present invention.
- Additives such as reinforcing materials, plasticizers, thickeners, dyes, pigments, flame retardants, silane coupling agents and surfactants may be used.
- the present invention provides a temporary fixing member for removing a temporary fixing adhesive that has been cured by immersing the processed member in warm water at 100 ° C. or lower after processing the temporary fixing member by using the temporary fixing adhesive. Fixing and peeling method. According to the present invention, the processing accuracy of various members such as optical members can be increased without using an organic solvent.
- the temporary fixing adhesive is cured by irradiating the temporary fixing adhesive with visible light or ultraviolet rays when the workpiece is removed from the cured body of the temporary fixing adhesive. It is possible to shorten the time for removing the temporarily fixing adhesive that has been cured by immersing the body in warm water of 100 ° C. or less.
- the visible light or ultraviolet irradiation amount to the temporary fixing adhesive is 1000 mJ / cm 2 or more and 40000 mJ at 365 nm.
- Irradiation dose is more preferably 2000 mJ / cm 2 or more 38000mJ / cm 2 or less, even more preferably not more than 4000 mJ / cm 2 or more 36000mJ / cm 2.
- moderately heated hot water for example, hot water of 100 ° C. or lower, because the releasability in water can be achieved in a short time and the productivity is improved.
- hot water preferably 30 ° C. to 100 ° C., more preferably 40 to 99 ° C.
- the cured product of the adhesive is thermally expanded in a short time and the residual strain stress generated when the composition is cured is released.
- the adhesive composition is used to bond and temporarily fix the member, and after processing the temporarily fixed member, the processing When the formed member is immersed in hot water of 100 ° C.
- Example 1 (Preparation of temporary fixing adhesive) A temporary fixing adhesive was prepared according to the procedure described below.
- A As a polyfunctional (meth) acrylate, “UV-3000B” manufactured by Nippon Gosei Co., Ltd. (polyester urethane acrylate, hereinafter abbreviated as “UV-3000B”, hydrophobic (meth) acrylate, weight average molecular weight 15000) 30 15 parts by mass of dicyclopentanyl diacrylate (“KAYARAD R-684” manufactured by Nippon Kayaku Co., Ltd., hereinafter abbreviated as “R-684”)
- B monofunctional 2- (1,2-cyclohexacarboximido) ethyl acrylate (“Aronix M-140” manufactured by Toagosei Co., Ltd., hereinafter abbreviated as “M-140”), is a hydrophobic (meth) acrylate as (meth) acrylate ) 20 parts by mass, phenol ethylene oxide 2
- Glass transition temperature The resin composition was sandwiched between PET films using a 1 mm thick silicon sheet as a mold. The resin composition was cured from the upper surface under the condition of an integrated light amount of 2000 mJ / cm 2 with a wavelength of 365 nm by a curing device manufactured by Fusion Corporation using an electrodeless discharge lamp, and further, an integrated light amount of 2000 mJ with a wavelength of 365 nm from the bottom. A cured product of a resin composition having a thickness of 1 mm was produced by curing under the conditions of / cm 2 . The produced cured body was cut into a length of 50 mm and a width of 5 mm with a cutter to obtain a cured body for measuring a glass transition temperature.
- the obtained cured body was subjected to stress and strain in a tensile direction of 1 Hz to the cured body in a nitrogen atmosphere by a dynamic viscoelasticity measuring device “DMS210” manufactured by Seiko Electronics Industry Co., Ltd. Tan ⁇ was measured while the temperature was raised at a rate of, and the temperature at the peak top of the tan ⁇ was taken as the glass transition temperature.
- DMS210 dynamic viscoelasticity measuring device manufactured by Seiko Electronics Industry Co., Ltd. Tan ⁇ was measured while the temperature was raised at a rate of, and the temperature at the peak top of the tan ⁇ was taken as the glass transition temperature.
- Tensile shear adhesive strength (“Adhesive strength” in the table): Measured according to JIS K 6850. Specifically, using heat-resistant glass (25 mm ⁇ 25 mm ⁇ thickness 2.0 mm) as an adherend, the bonded portion was 8 mm in diameter, and two heat-resistant glasses were bonded together with the produced resin composition, A tensile shear bond strength test piece was prepared by curing with a curing device manufactured by Fusion Corporation using an electrodeless discharge lamp under conditions of an integrated light quantity of 2000 mJ / cm 2 with a wavelength of 365 nm. The prepared test piece was measured for tensile shear bond strength at a tensile rate of 10 mm / min in an environment of a temperature of 23 ° C. and a humidity of 50% using a universal testing machine.
- UV light having a wavelength of 365 nm was irradiated with 300 mJ / cm 2 from blue plate glass as a fixing member (the irradiation step was performed simultaneously with the pressure step). (30 seconds)). Only the blue plate glass which is a workpiece of the obtained adhesion test specimen was cut into a 10 mm square using a dicing apparatus. During cutting, the blue plate glass, which is a workpiece, did not fall off, and good workability was exhibited.
- a metal halide lamp was used for the adhesion test piece obtained by cutting only the blue plate glass that was the workpiece, and after irradiation with 16000 mJ / cm 2 of UV light having a wavelength of 365 nm (re-irradiation step (40 seconds)), it was heated to 80 ° C. hot water. When immersed, all peeled in 1 minute (hot water peeling time). In addition, 10 pieces of the peeled test specimens were taken out arbitrarily, and each side of the back face (the face temporarily fixed with the temporary fixing adhesive) was observed using an optical microscope. The maximum width of the location was measured, and the average value and standard deviation were obtained.
- Examples 2 to 7, Comparative Examples 1 and 2 Except that the temporary fixing / peeling method was performed under the conditions shown in Tables 1 to 2 and 4, the same as in Example 1, the average value and standard deviation of the maximum width of the portion where the glass on each side was missing, and temporary fixing The average value and the standard deviation of the cured product film thickness of the adhesive were measured. The measurement results are shown in Tables 1 to 2 and 4.
- Examples 8 to 11 In the same manner as in Example 1 except that the raw materials of the types shown in Tables 2 and 3 were used in the compositions shown in Tables 2 and 3, the average value and standard deviation of the maximum width of the portions where the glass on each side was missing, and The average value and standard deviation of the cured film thickness of the temporary fixing adhesive were measured. The measurement results are shown in Tables 2 and 3.
- Example 12 As a granular substance not dissolved in (A) to (C), a spherical cross-linked polymer having an average particle diameter of 140 ⁇ m and a particle volume distribution ( ⁇ m) expressed in logarithm with a standard deviation of the particle volume distribution relative to the particle diameter of 0.086 Using methyl methacrylate particles (manufactured by sieving “GM-5003” manufactured by Gantz Kasei Co., Ltd. using a 150 ⁇ m sieve and a 125 ⁇ m sieve), the raw materials of the types shown in Table 3 have the compositions shown in Table 3. A temporary fixing adhesive was produced in the same manner as in Example 1 except that it was used.
- Example 13 (D) Spherical cross-linked polystyrene particles having an average particle size of 40 ⁇ m as a granular material not dissolved in (A) to (C) and a standard deviation of the particle volume distribution with respect to the particle size when the particle size ( ⁇ m) is logarithmically expressed as 0.062
- a temporary fixing adhesive was prepared in the same manner as in Example 1 except that (GS-240 manufactured by Sekisui Chemical Co., Ltd.) was used and the raw materials of the type shown in Table 3 were used in the composition shown in Table 3. About the obtained adhesive for temporary fixing, the glass transition temperature, the tensile shear adhesive strength, and the peeling test were done like Example 1.
- Example 14 (D) Spherical cross-linked polystyrene particles having an average particle diameter of 20 ⁇ m as a granular material not dissolved in (A) to (C) and a standard deviation of the particle volume distribution with respect to the particle diameter when the particle diameter ( ⁇ m) is logarithmically expressed as 0.061
- a temporary fixing adhesive was prepared in the same manner as in Example 1 except that (GS-220 manufactured by Sekisui Chemical Co., Ltd.) was used and the raw materials of the type shown in Table 3 were used in the composition shown in Table 3. About the obtained adhesive for temporary fixing, the glass transition temperature, the tensile shear adhesive strength, and the peeling test were done like Example 1.
- FIG. 1 The obtained adhesive for temporary fixing, the glass transition temperature, the tensile shear adhesive strength, and the peeling test were done like Example 1.
- Example 15 (D) Spherical cross-linked polystyrene particles having an average particle diameter of 10 ⁇ m as a granular material not dissolved in (A) to (C) and a standard deviation of particle volume distribution with respect to the particle diameter when the particle diameter ( ⁇ m) is expressed in logarithm (SP-210, manufactured by Sekisui Chemical Co., Ltd.) was used, and a temporary fixing adhesive was produced in the same manner as in Example 1 except that the raw materials of the type shown in Table 3 were used in the composition shown in Table 3. About the obtained adhesive for temporary fixing, the glass transition temperature, the tensile shear adhesive strength, and the peeling test were done like Example 1. FIG.
- UV-3700B polyether urethane acrylate (“UV-3700B” manufactured by Nippon Synthetic Chemical Co., Ltd.), hydrophobic (meth) acrylate, weight average molecular weight 38000
- 1.6-XA Hexanediol diacrylate (“Light acrylate 1.6-HX-A” manufactured by Kyoeisha Chemical Co., Ltd.)
- hydrophobic (meth) acrylate I-754 oxy-phenyl-acetic acid 2- Mixture of [2-oxo-2-phenyl-acetoxy-ethoxy] -ethyl ester and oxy-phenyl-acetic acid 2- [2-hydroxy-ethoxy] -ethyl ester (“IRGACURE754” manufactured by Ciba Japan)
- the present invention has a pressure process in which a pressure of 1 g / cm 2 or more and 1000 kg / cm 2 or less is applied from one or both so that the distance between the fixing member and the workpiece is uniform, and the pressure process and the irradiation process are performed. By carrying out simultaneously, the outstanding dimensional accuracy at the time of a process can be obtained.
- a specific hydrophobic (meth) acrylic monomer is used and a temporary fixing adhesive having a specific composition in combination with this is used. Since the strength can be expressed, it is difficult to cause a deviation during the processing of the member, and a member to be processed that is superior in terms of dimensional accuracy can be easily obtained.
- the fixing member and the workpiece are immersed in warm water after being processed, whereby the adhesive strength is reduced, the adhesive force between the fixing member and the workpiece is reduced, and the workpiece can be easily recovered.
- the present invention has photocurability because of the composition of the temporary fixing adhesive, and is cured by visible light or ultraviolet light. For this reason, as compared with the conventional hot melt adhesive, a remarkable effect is obtained in terms of labor saving, energy saving, and work shortening.
- a remarkable effect can be obtained in terms of dimensional accuracy of the workpiece by performing the irradiation process during the pressure process. That is, by performing the irradiation step during the pressure step, it is possible to easily control the thickness of the temporary fixing adhesive.
- more preferable dimensional accuracy can be obtained by using a temporary fixing adhesive containing a particulate material having a small standard deviation of the particle volume distribution.
- the cured body temporarily fixed according to the present invention reduces the adhesive strength by contacting with warm water of 100 ° C. or less, and reduces the adhesive force between the members or between the member and the jig.
- the cured product comes into contact with warm water of 100 ° C. or less and can be recovered from the member in the form of a film, so that an effect of excellent workability can be obtained.
- the temporary fixing method of the present invention is industrially useful as an adhesive for temporarily fixing optical lenses, prisms, arrays, silicon wafers, semiconductor mounting parts and the like.
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Abstract
Description
又、特定の親水性の高い(メタ)アクリレートの使用により接着性向上させるとともに、膨潤や一部溶解によって剥離性を向上させた仮固定用接着剤が提案された。この仮固定用接着剤は、切削加工時には、部品とブレードやダイヤモンドカッター等の切削治具との摩擦熱を発生するため、大量の水で冷却させて行う必要があった。上記の親水性の高い組成物では、切削時に硬化物が膨潤し柔軟になるため、より高い寸法精度に到達できないという課題があった。又、剥離した部材に一部溶解した硬化物が糊残りするため、外観上問題となっていた(特許文献1、2、3参照)。
(1) 固定部材に仮固定用接着剤を塗布することと(以下、塗布工程という)、仮固定用接着剤に被加工部材を搭載することと(以下、搭載工程という)、当該搭載後に仮固定用接着剤に可視光線又は紫外線の少なくとも一方を照射して仮固定用接着剤の接着力を高めること(以下、照射工程という)を含み、固定部材と被加工部材の一方又は双方から圧力をかけること(以下、圧力工程という)を含む仮固定方法であり、当該圧力をかけることと当該照射することを少なくとも一定時間同時に行う、仮固定方法。
(5) 仮固定用接着剤が、(A)多官能(メタ)アクリレート、(B)単官能(メタ)アクリレート、及び(C)光重合開始剤を含有する組成物である上記(1)乃至(4)のいずれか一項に記載の仮固定方法。
(6) (A)及び(B)がいずれも疎水性である上記(5)に記載の部材の仮固定方法。
(7) 仮固定用接着剤のガラス転移温度が-50℃以上50℃以下である上記(1)乃至(6)のいずれか一項に記載の仮固定方法。
(9) 仮固定用接着剤が(A)~(C)に溶解しない粒状物質(D)を、(A)及び(B)の合計量100質量部に対して、0.1~20質量部含有する上記(5)乃至(8)のいずれか一項に記載の仮固定方法。
(10) (A)~(C)に溶解しない粒状物質(D)の形状が球状である上記(9)記載の仮固定方法。
(12) (A)~(C)に溶解しない粒状物質(D)の平均粒径が5μm~200μmである上記(9)乃至(11)のいずれか一項に記載の仮固定方法。
(13) (A)~(C)に溶解しない粒状物質(D)のレーザー回折法による粒径(μm)を対数で表示したときの粒径に対する粒子体積分布の標準偏差が0.0001~0.25の範囲にある上記(9)乃至(12)のいずれか一項に記載の仮固定方法。
(15) 上記(1)乃至(13)のいずれか一項に記載の仮固定方法を用い、該仮固定された部材を加工後、可視光線若しくは紫外線を仮固定用接着剤に照射し該加工された部材を100℃以下の温水に浸漬して、前記組成物の硬化体を取り外すことを含む部材の仮固定・剥離方法。
(17) 当該仮固定された部材を加工後に照射する可視光線若しくは紫外線の照射量が波長365nmにおいて1000mJ/cm2~40000mJ/cm2の範囲であることを特徴とする上記(15)に記載の仮固定・剥離方法。
(19) (A)多官能(メタ)アクリレートが、多官能(メタ)アクリレートオリゴマー/ポリマー及び2官能(メタ)アクリレートモノマーを含有する上記(5)乃至(13)のいずれか一項に記載の仮固定方法。
(20) 多官能(メタ)アクリレートオリゴマー/ポリマーがポリエステル系ウレタン(メタ)アクリート及び/又はポリエーテル系ウレタン(メタ)アクリレートを含有する上記(18)又は(19)に記載の仮固定方法。
(21) 2官能(メタ)アクリレートモノマーが1,6-ヘキサジオールジ(メタ)アクリレート及び/又はジシクロペンタニルジ(メタ)アクリレートを含有する上記(18)又は(19)に記載の仮固定方法。
(23) (B)単官能(メタ)アクリレートが、フェノールエチレンオキサイド2モル変成(メタ)アクリレート及び2-(1,2-シクロヘキサカルボキシイミド)エチル(メタ)アクリレートを含有する上記(5)乃至(13)のいずれか一項に記載の仮固定方法。
(24)(C)光重合開始剤が、ベンジルジメチルケタール、オキシ-フェニル-アセチックアシッド2-[2-オキソ-2-フェニル-アセトキシ-エトキシ]-エチルエステル及びオキシ-フェニル-アセチックアシッド2-[2-ヒドロキシ-エトキシ]-エチルエステルからなる群より選択される1種又は2種以上を含有する上記(5)乃至(13)のいずれか一項に記載の仮固定方法。
多官能(メタ)アクリレートオリゴマー/ポリマーの重量平均分子量は、10000~60000が好ましく、13000~40000がより好ましい。重量平均分子量は、GPCシステム(東ソ-社製 SC-8010)等を使用し、市販の標準ポリスチレンで検量線を作成して求めた。
多官能(メタ)アクリレートの中では、効果が大きい点で、多官能(メタ)アクリレートオリゴマー/ポリマー及び/又は2官能(メタ)アクリレートモノマーを含有することが好ましく、多官能(メタ)アクリレートオリゴマー/ポリマーと2官能(メタ)アクリレートモノマーを併用することがより好ましい。
(仮固定用接着剤の作製)
以下に記す手順により仮固定用接着剤を作製した。(A)多官能(メタ)アクリレートとして、日本合成社製「UV-3000B」(ポリエステル系ウレタンアクリレート以下「UV-3000B」と略す、疎水性の(メタ)アクリレートである、重量平均分子量15000)30質量部、ジシクロペンタニルジアクリレート(日本化薬社製「KAYARAD R-684」、以下「R-684」と略す、疎水性の(メタ)アクリレートである)15質量部、(B)単官能(メタ)アクリレートとして、2-(1,2-シクロヘキサカルボキシイミド)エチルアクリレート(東亜合成社製「アロニックスM-140」、以下「M-140」と略す、疎水性の(メタ)アクリレートである)20質量部、フェノールエチレンオキサイド2モル変成アクリレート(東亜合成社製「アロニックスM-101A」、疎水性の(メタ)アクリレートである)35質量部、(C)光重合開始剤としてベンジルジメチルケタール(チバ・スペシャルティ・ケミカルズ社製「IRGACURE651」、以下「BDK」と略す)10質量部、(D)(A)~(C)に溶解しない粒状物質として平均粒径100μm、粒径(μm)を対数で表示したときの粒径に対する粒子体積分布の標準偏差0.063、の球状架橋ポリスチレン粒子(ガンツ化成社製「GS-100S」)1質量部、重合禁止剤として2,2-メチレン-ビス(4-メチル-6-ターシャリーブチルフェノール)(住友化学工業社製「スミライザーMDP-S」、以下「MDP」と略す)0.1質量部使用して樹脂組成物を作製した。
得られた樹脂組成物を使用して、以下に示す評価方法にてガラス転移温度、引張せん断接着強さ、剥離試験を行った。それらの結果を表1に示す。又、(D)(A)~(C)に溶解しない粒状物質の平均粒径及び粒径(μm)を対数で表示したときの粒径に対する粒子体積分布の標準偏差も測定した。
ガラス転移温度:樹脂組成物を、1mm厚のシリコンシートを型枠とし、PETフィルムに挟み込んだ。樹脂組成物を、無電極放電ランプを使用したフュージョン社製硬化装置により、365nmの波長の積算光量2000mJ/cm2の条件にて上面から硬化させた後、更に下から365nmの波長の積算光量2000mJ/cm2の条件にて硬化させ、厚さ1mmの樹脂組成物の硬化体を作製した。作製した硬化体をカッターにて長さ50mm幅5mmに切断しガラス転移温度測定用硬化体とした。得られた硬化体をセイコー電子産業社製、動的粘弾性測定装置「DMS210」により、窒素雰囲気中にて前記硬化体に1Hzの引張方向の応力及び歪みを加え、昇温速度毎分2℃の割合で昇温しながらtanδを測定し、該tanδのピークトップの温度をガラス転移温度とした。
固定部材である青板硝子(150mm×150mm×厚さ1.7mm)をホットプレート上で80℃に加熱し、作製した仮固定用接着剤を1g塗布した(塗布工程)。その後、被加工部材である青板硝子(80mm×80mm×厚さ1.1mm)を上方から搭載した(搭載工程)。次に、被加工部材である青板硝子上に厚さ50mmの石英ガラス(80mm×80mm×厚さ5mm)を上方より搭載し、前記石英ガラスの上から荷重を加え、石英ガラスの重量分と合計で12.5g/cm2の圧力をかけ、5分放置した(圧力工程)。固定部材と被加工部材の間隔は、最も大きいところから最も小さいところを引いた差分において、5μm以下であった。
仮固定・剥離方法を表1~2、4に示す条件で行ったこと以外は実施例1と同様にして、各辺の硝子が欠けている箇所の最大幅の平均値と標準偏差及び仮固定用接着剤の硬化物フィルム膜厚の平均値と標準偏差を測定した。その測定結果を表1~2、4に示した。
表2、3に示す種類の原材料を表2、3に示す組成で使用したこと以外は実施例1と同様にして、各辺の硝子が欠けている箇所の最大幅の平均値と標準偏差及び仮固定用接着剤の硬化物フィルム膜厚の平均値と標準偏差を測定した。その測定結果を表2、3に示した。
(D)(A)~(C)に溶解しない粒状物質として、平均粒子径140μm、粒径(μm)を対数で表示したときの粒径に対する粒子体積分布の標準偏差0.086の球状架橋ポリメチルメタクリレート粒子(ガンツ化成社製「GM-5003」を目開き150μmの篩と125μmの篩を用いて篩分けして作製)を使用し、表3に示す種類の原材料を表3に示す組成で使用したこと以外は実施例1と同様にして、仮固定用接着剤を作製した。得られた仮固定用接着剤について、実施例1と同様にガラス転移温度、引張せん断接着強さ、剥離試験を行った。又、(D)(A)~(C)に溶解しない粒状物質の平均粒径及び粒径(μm)を対数で表示したときの粒径に対する粒子体積分布の標準偏差も測定した。それらの結果を表3に示した。
この仮固定用接着剤を用いて、仮固定・剥離方法を表3に示す条件で行ったこと以外は実施例1と同様にして、各辺の硝子が欠けている箇所の最大幅の平均値と標準偏差及び仮固定用接着剤の硬化物フィルム膜厚の平均値と標準偏差を測定した。その測定結果を表3に示した。
(D)(A)~(C)に溶解しない粒状物質として平均粒子径40μm、粒径(μm)を対数で表示したときの粒径に対する粒子体積分布の標準偏差0.062の球状架橋ポリスチレン粒子(積水化学社製「GS-240」)を使用し、表3に示す種類の原材料を表3に示す組成で使用したこと以外は実施例1と同様にして仮固定用接着剤を作製した。得られた仮固定用接着剤について、実施例1と同様にガラス転移温度、引張せん断接着強さ、剥離試験を行った。又、(D)(A)~(C)に溶解しない粒状物質の平均粒径及び粒径(μm)を対数で表示したときの粒径に対する粒子体積分布の標準偏差も測定した。それらの結果を表3に示した。
この仮固定用接着剤を用いて、仮固定・剥離方法を表3に示す条件で行ったこと以外は実施例1と同様にして、各辺の硝子が欠けている箇所の最大幅の平均値と標準偏差及び仮固定用接着剤の硬化物フィルム膜厚の平均値と標準偏差を測定した。その測定結果を表3に示した。
(D)(A)~(C)に溶解しない粒状物質として平均粒子径20μm、粒径(μm)を対数で表示したときの粒径に対する粒子体積分布の標準偏差0.061の球状架橋ポリスチレン粒子(積水化学社製「GS-220」)を使用し、表3に示す種類の原材料を表3に示す組成で使用したこと以外は実施例1と同様にして仮固定用接着剤を作製した。得られた仮固定用接着剤について、実施例1と同様にガラス転移温度、引張せん断接着強さ、剥離試験を行った。又、(D)(A)~(C)に溶解しない粒状物質の平均粒径及び粒径(μm)を対数で表示したときの粒径に対する粒子体積分布の標準偏差も測定した。それらの結果を表3に示した。
この仮固定用接着剤を用いて、仮固定・剥離方法を表3に示す条件で行ったこと以外は実施例1と同様にして、各辺の硝子が欠けている箇所の最大幅の平均値と標準偏差及び仮固定用接着剤の硬化物フィルム膜厚の平均値と標準偏差を測定した。その測定結果を表3に示した。
(D)(A)~(C)に溶解しない粒状物質として平均粒子径10μm、粒径(μm)を対数で表示したときの粒径に対する粒子体積分布の標準偏差0.058の球状架橋ポリスチレン粒子(積水化学社製「SP-210」)を使用し、表3に示す種類の原材料を表3に示す組成で使用したこと以外は実施例1と同様にして仮固定用接着剤を作製した。得られた仮固定用接着剤について、実施例1と同様にガラス転移温度、引張せん断接着強さ、剥離試験を行った。又、(D)(A)~(C)に溶解しない粒状物質の平均粒径及び粒径(μm)を対数で表示したときの粒径に対する粒子体積分布の標準偏差も測定した。それらの結果を表3に示した。
この仮固定用接着剤を用いて、仮固定・剥離方法を表3に示す条件で行ったこと以外は実施例1と同様にして、各辺の硝子が欠けている箇所の最大幅の平均値と標準偏差及び仮固定用接着剤の硬化物フィルム膜厚の平均値と標準偏差を測定した。その測定結果を表3に示した。
UV-3700B:ポリエーテル系ウレタンアクリレート(日本合成化学社製「UV-3700B」)、疎水性の(メタ)アクリレート、重量平均分子量38000
1.6-X-A:ヘキサンジオールジアクリレート(共栄社化学社製「ライトアクリレート1.6-HX-A」)、疎水性の(メタ)アクリレート
I-754:オキシ-フェニル-アセチックアシッド2-[2-オキソ-2-フェニル-アセトキシ-エトキシ]-エチルエステルとオキシ-フェニル-アセチックアシッド2-[2-ヒドロキシ-エトキシ]-エチルエステルの混合物(チバ・ジャパン社製「IRGACURE754」)
本出願は、2008年7月22日出願の日本特許出願(特願2008-188295)に基づくものであり、その内容はここに参照として取り込まれる。
Claims (24)
- 固定部材に仮固定用接着剤を塗布することと、仮固定用接着剤に被加工部材を搭載することと、当該搭載後に仮固定用接着剤に可視光線又は紫外線の少なくとも一方を照射して仮固定用接着剤の接着力を高めることを含み、固定部材と被加工部材の一方又は双方から圧力をかけることを含む仮固定方法であり、当該圧力をかけることと当該照射することを少なくとも一定時間同時に行う、仮固定方法。
- 被加工部材に仮固定用接着剤を塗布することと、仮固定用接着剤に固定部材を搭載することと、当該搭載後に仮固定用接着剤に可視光線又は紫外線の少なくとも一方を照射して仮固定用接着剤の接着力を高めることを含み、固定部材と被加工部材の一方又は双方から圧力をかけることを含む仮固定方法であり、当該圧力をかけることと当該照射することを少なくとも一定時間同時に行う、仮固定方法。
- 固定部材と被加工部材の一方又は双方からかける圧力が1g/cm2以上1000kg/cm2以下に制御する請求項1又は2に記載の仮固定方法。
- 固定部材、仮固定用接着剤、被加工部材の内いずれか1つ以上を0℃以上150℃以下に制御する請求項1乃至3に記載の仮固定方法。
- 仮固定用接着剤が、(A)多官能(メタ)アクリレート、(B)単官能(メタ)アクリレート、及び(C)光重合開始剤を含有する組成物である請求項1乃至4のいずれか一項に記載の仮固定方法。
- (A)及び(B)がいずれも疎水性である請求項5に記載の部材の仮固定方法。
- 仮固定用接着剤のガラス転移温度が-50℃以上50℃以下である請求項1乃至6のいずれか一項に記載の仮固定方法。
- 仮固定用接着剤が、(A)及び(B)の合計量100質量部中、(A)を1~90質量部、(B)を10~99質量部、及び、(A)及び(B)の合計量100質量部に対して、(C)を0.1~30質量部を含有する請求項5乃至7のいずれか一項に記載の仮固定方法。
- 仮固定用接着剤が(A)~(C)に溶解しない粒状物質(D)を、(A)及び(B)の合計量100質量部に対して、0.1~20質量部含有する請求項5乃至8のいずれか一項に記載の仮固定方法。
- (A)~(C)に溶解しない粒状物質(D)の形状が球状である請求項9記載の仮固定方法。
- (A)~(C)に溶解しない粒状物質(D)が架橋ポリメタクリル酸メチル粒子、架橋ポリスチレン粒子、及び架橋ポリメタクリル酸メチルポリスチレン共重合体粒子のいずれか若しくはこれらの混合物である請求項9又は10に記載の仮固定方法。
- (A)~(C)に溶解しない粒状物質(D)の平均粒径が5μm~200μmである請求項9乃至11のいずれか一項に記載の仮固定方法。
- (A)~(C)に溶解しない粒状物質(D)のレーザー回折法による粒径(μm)を対数で表示したときの粒径に対する粒子体積分布の標準偏差が0.0001~0.25の範囲にある請求項9乃至12のいずれか一項に記載の仮固定方法。
- 請求項1乃至13いずれか一項に記載の仮固定方法を用い、該仮固定された部材を加工後、該加工された部材を100℃以下の温水に浸漬して、前記組成物の硬化体を取り外すことを含む部材の仮固定・剥離方法。
- 請求項1乃至13いずれか一項に記載の仮固定方法を用い、該仮固定された部材を加工後、可視光線若しくは紫外線を仮固定用接着剤に照射し該加工された部材を100℃以下の温水に浸漬して、前記組成物の硬化体を取り外すことを含む部材の仮固定・剥離方法。
- 可視光線若しくは紫外線の照射量が波長365nmにおいて1mJ/cm2~4000mJ/cm2の範囲である請求項1乃至13いずれか一項に記載の仮固定方法。
- 当該仮固定された部材を加工後に照射する可視光線若しくは紫外線の照射量が波長365nmにおいて1000mJ/cm2~40000mJ/cm2の範囲であることを特徴とする請求項15に記載の仮固定・剥離方法。
- (A)多官能(メタ)アクリレートが、多官能(メタ)アクリレートオリゴマー/ポリマー及び/又は2官能(メタ)アクリレートモノマーを含有する請求項5乃至13のいずれか一項に記載の仮固定方法。
- (A)多官能(メタ)アクリレートが、多官能(メタ)アクリレートオリゴマー/ポリマー及び2官能(メタ)アクリレートモノマーを含有する請求項5乃至13のいずれか一項に記載の仮固定方法。
- 多官能(メタ)アクリレートオリゴマー/ポリマーがポリエステル系ウレタン(メタ)アクリート及び/又はポリエーテル系ウレタン(メタ)アクリレートを含有する請求項18又は19に記載の仮固定方法。
- 2官能(メタ)アクリレートモノマーが1,6-ヘキサジオールジ(メタ)アクリレート及び/又はジシクロペンタニルジ(メタ)アクリレートを含有する請求項18又は19に記載の仮固定方法。
- (B)単官能(メタ)アクリレートが、フェノールエチレンオキサイド2モル変成(メタ)アクリレート及び/又は2-(1,2-シクロヘキサカルボキシイミド)エチル(メタ)アクリレートを含有する請求項5乃至13のいずれか一項に記載の仮固定方法。
- (B)単官能(メタ)アクリレートが、フェノールエチレンオキサイド2モル変成(メタ)アクリレート及び2-(1,2-シクロヘキサカルボキシイミド)エチル(メタ)アクリレートを含有する請求項5乃至13のいずれか一項に記載の仮固定方法。
- (C)光重合開始剤が、ベンジルジメチルケタール、オキシ-フェニル-アセチックアシッド2-[2-オキソ-2-フェニル-アセトキシ-エトキシ]-エチルエステル及びオキシ-フェニル-アセチックアシッド2-[2-ヒドロキシ-エトキシ]-エチルエステルからなる群より選択される1種又は2種以上を含有する請求項5乃至13のいずれか一項に記載の仮固定方法。
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- 2009-07-22 CN CN200980128706.3A patent/CN102105546B/zh active Active
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JP2010248352A (ja) * | 2009-04-14 | 2010-11-04 | Denki Kagaku Kogyo Kk | 接着剤用(メタ)アクリル系樹脂組成物 |
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CN103228450A (zh) * | 2010-11-30 | 2013-07-31 | 电气化学工业株式会社 | 透光性硬质基板层叠体的加工方法及使用它的板状制品的制造方法 |
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JPWO2013011970A1 (ja) * | 2011-07-15 | 2015-02-23 | 電気化学工業株式会社 | 透光性硬質基板積層体の製造方法及び透光性硬質基板貼り合わせ装置 |
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US9381727B2 (en) | 2011-07-15 | 2016-07-05 | Denka Company Limited | Method of manufacturing translucent rigid substrate laminate and translucent rigid substrate bonding apparatus |
JPWO2013084953A1 (ja) * | 2011-12-05 | 2015-04-27 | 電気化学工業株式会社 | 透光性硬質基板積層体の製造方法 |
WO2013084953A1 (ja) * | 2011-12-05 | 2013-06-13 | 電気化学工業株式会社 | 透光性硬質基板積層体の製造方法 |
EP2975098A4 (en) * | 2013-03-11 | 2016-11-30 | Lintec Corp | ADHESIVE FOIL AND MANUFACTURING METHOD FOR PROCESSED DEVICE-RELATED ELEMENTS |
JP2017179125A (ja) * | 2016-03-30 | 2017-10-05 | デンカ株式会社 | 薄厚基板用組成物及び仮固定方法 |
WO2022230874A1 (ja) * | 2021-04-26 | 2022-11-03 | デンカ株式会社 | 組成物 |
JP7434666B2 (ja) | 2021-04-26 | 2024-02-20 | デンカ株式会社 | 組成物 |
Also Published As
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JPWO2010010900A1 (ja) | 2012-01-05 |
KR101660056B1 (ko) | 2016-09-30 |
CN102105546B (zh) | 2016-12-07 |
CN102105546A (zh) | 2011-06-22 |
JP5675355B2 (ja) | 2015-02-25 |
MY162000A (en) | 2017-05-31 |
KR20110031347A (ko) | 2011-03-25 |
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