Classifications

• • 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
  • C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2/00—Processes of polymerisation
  • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2/00—Processes of polymerisation
  • C08F2/46—Polymerisation initiated by wave energy or particle radiation
  • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
  • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
• • 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
  • C09J109/00—Adhesives based on homopolymers or copolymers of conjugated diene hydrocarbons
• • 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
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
  • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
  • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
  • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
  • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
  • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
  • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
  • H01L21/304—Mechanical treatment, e.g. grinding, polishing, cutting
• • 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
  • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
  • C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors

Definitions

• the present invention relates to the provision of a composition excellent in heat resistance, low outgassing property, and peelability.
• the three-dimensional mounting technology is a semiconductor manufacturing technology in which one semiconductor chip is thinned and further laminated in multiple layers while being connected by a through silicon via (TSV).
• TSV through silicon via
• a back surface protective tape has been applied to the opposite side of the ground surface to prevent wafer damage during grinding.
• this tape uses an organic resin film as a base material and is flexible, but has insufficient strength and heat resistance, and is not suitable for performing a TSV forming process or a wiring layer forming process on the back surface.
• Necessary properties of the adhesive include viscosity suitable for coating, shear adhesive strength that can withstand grinding and polishing when thinning silicon, heat resistance that can withstand insulation film formation and solder reflow process, thinning and resist process Examples include chemical resistance that can be tolerated, easy peelability that allows the wafer to be easily peeled from the support, and easy cleaning properties.
• Patent Document 2 As an adhesive and its peeling method, the technique which peels an adhesive bond layer from a support body by irradiating the adhesive agent containing a light absorptive substance with high intensity
• the former technique requires an expensive apparatus such as a laser, and has a problem that the processing time per substrate becomes long.
• the latter technique is simple because it is controlled only by heating, but its application range is narrow because the thermal stability at a high temperature exceeding 200 ° C. is insufficient.
• a method of disassembling the adhesive body including the step of irradiating the excimer light having a center wavelength of 172 nm or 193 nm with respect to the adhesive body formed by the method, wherein at least one of the substrates is transparent to the excimer light.
• Patent Document 3 Patent Document 3
• Patent Document 3 there is no description that it is not necessary to use excimer light having high energy for the peeling method.
• Patent Documents 4 to 5 An acrylic adhesive to which a fluorine compound is added is disclosed (Patent Documents 4 to 5).
• fluorine compounds are limited to radically polymerizable monomers or oligomers, and there is no description about (meth) acrylates having a specific number average molecular weight.
• a photocurable resin composition comprising at least one acrylic monomer, a polymerization initiator, and a fluorosurfactant, and having a surface tension in the air of 28 mN / m or less.
• Patent Document 6 there is no description regarding the number average molecular weight.
• the present invention has been completed as a result of various investigations to solve the problems of, for example, improvement in heat resistance, low outgassing property, and peelability.
• the present invention is as follows.
• composition according to (1) wherein the component (E) contains 0.01 to 5 parts by mass with respect to 100 parts by mass in total of the components (A) to (C).
• Component (B) is (B-1) phenoxypolyalkylene glycol mono (meth) acrylate having an alkylene oxide chain, (B-2) alkyl (meth) having a linear or branched alkyl group One or more selected from acrylate, (B-3) monofunctional (meth) acrylate having an alicyclic alkyl group, and (B-4) silicone having one (meth) acryloyl group (1) to The composition according to one of (7).
• the component (C) is at least one selected from trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, and tricyclodecane dimethanol di (meth) acrylate.
• the component (D) is 2-dimethylamino-2- (4-methyl-benzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one, 2,2-dimethoxy- 11.
• the component (D) is contained in 0.5 to 4 parts by mass with respect to a total of 100 parts by mass of the components (A) to (C), (1) to (12) Composition.
• a temporary fixing adhesive for semiconductor production comprising the composition according to one of (1) to (13).
• the component (A) is a polyfunctional (meth) acrylate having a number average molecular weight of 1000 or more, and the component (B) is (B-1) a phenoxypolyalkylene glycol mono (meth) acrylate having an alkylene oxide chain.
• component (B-2) alkyl (meth) acrylate having a linear or branched alkyl group, (B-3) monofunctional (meth) acrylate having an alicyclic alkyl group, (B-4) 1 piece And (C) component is trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, tricyclodecane dimethanol di
• Component (A) is at least one selected from (meth) acrylate, and in a total of 100 parts by mass of components (A) to (C) 0 to 80 parts by mass, (B) component 19.99 to 65 parts by mass, (C) component 0.01 to 50 parts by mass, and (D) component is a total of 100 components (A) to (C) 0.5 to 4 parts by mass with respect to parts by mass, and component (E) contains 0.01 to 5 parts by mass with respect to a total of 100 parts by mass of components (A) to (C) ( The temporary fixing adhesive for semiconductor
• (20) A method for producing a thin wafer using the temporary fixing adhesive for semiconductor production according to (16) or (17).
• (21) A method for temporarily fixing a substrate, wherein the substrate is bonded using the adhesive described in (14), the substrate is temporarily fixed, and then the substrate is peeled off.
• (22) A base material is bonded using the temporary fixing adhesive for semiconductor production described in (16), the temporary fixing adhesive for semiconductor manufacturing is cured, the base material is temporarily fixed, and the temporary fixed base material A method of temporarily fixing the base material, after removing the processed base material.
• a composition excellent in heat resistance, low outgassing property, and peelability can be obtained.
• the polyfunctional (meth) acrylate refers to a compound having two or more (meth) acryloyl groups.
• Monofunctional (meth) acrylate refers to a compound having one (meth) acryloyl group.
• a (meth) acrylate having a number average molecular weight of 1000 or more refers to a compound having one or more (meth) acryloyl groups having a number average molecular weight of 1000 or more.
• Examples of (A) include oligomer / polymer.
• polyfunctional (meth) acrylate (A) examples include polyfunctional (meth) acrylate oligomers / polymers that are two or more (meth) acryloylated at the end or side chain of the oligomer / polymer.
• polyfunctional (meth) acrylate oligomer / polymer examples include 1,2-polybutadiene-terminated urethane (meth) acrylate (for example, “TE-2000” and “TEA-1000” manufactured by Nippon Soda Co., Ltd.), hydrogenated products of the above ( For example, “TEAI-1000” manufactured by Nippon Soda Co., Ltd.), 1,4-polybutadiene terminated urethane (meth) acrylate (eg “BAC-45” manufactured by Osaka Organic Chemical Co., Ltd.), polyisoprene terminated (meth) acrylate, polyester urethane (Meth) acrylate (for example, “UV-2000B”, “UV-3000B”, “UV-7000B” manufactured by Nippon Gosei Co., Ltd., “KHP-11”, “KHP-17” manufactured by Negami Kogyo Co., Ltd.), polyether urethane (Meth) acrylate (for example, “UV-3
• a diene-based or hydrogenated diene-based skeleton having two or more (meth) acryloyl groups in the molecule and having excellent adhesion, heat resistance, and peelability.
• the diene skeleton include polybutadiene and polyisoprene.
• the hydrogenated diene-based skeleton include a polybutadiene hydrogenated product and a polyisoprene hydrogenated product. Of the diene or hydrogenated diene skeletons, polyisoprene is preferred.
• R represents a hydrogen atom or a methyl group
• Y represents an alkylene group.
• m and n are arbitrary positive integers.
• the number of functional groups is preferably 1 to 10, and the molecular weight is preferably 3000 to 50000.
• Y is preferably an alkylene group having 1 to 5 carbon atoms, more preferably an ethylene group.
• m is preferably from 100 to 1500.
• n is preferably 1-20.
• Urethane (meth) acrylate is a reaction (for example, polycondensation) of a polyol compound (hereinafter represented by X), an organic polyisocyanate compound (hereinafter represented by Y), and hydroxy (meth) acrylate (hereinafter represented by Z).
• reaction refers to urethane (meth) acrylate having a urethane bond in the molecule.
• Examples of (A) (meth) acrylates include silicones having at least one (meth) acryloyl group, macromonomers, and the like.
• the silicone having one or more (meth) acryloyl groups is a polyorganosiloxane having one or more (meth) acryloyl groups in the molecule.
• the silicone used as the base polymer of the silicone may be polysiloxane having a main chain composed of a siloxane bond, for example, all side chains, dimethyl silicone having a terminal methyl group, and a phenyl group in a part of the side chain. Examples thereof include methylphenyl silicone and methyl hydrogen silicone in which a part of the side chain is hydrogen. Of these, dimethyl silicone is preferred.
• the position at which the (meth) acryloyl group is introduced is not particularly limited, and may be present at one end (one end type) or both ends (both end types) of the main chain, or in the side chain (side chain type). You may have. Of these, polyorganosiloxanes having (meth) acryloyl groups at both ends are preferred.
• Macromonomer means a polymerizable polymer / oligomer having one or more (meth) acryloyl groups in the molecule.
• the macromonomer is composed of a polymer chain portion and a (meth) acryloyl group portion.
• the polymerizable polymer / oligomer preferably has one (meth) acryloyl group moiety at the end of the polymer chain.
• Examples of the polymer chain portion include alkyl (meth) acrylate, styrene and derivatives thereof, (meth) acrylonitrile, vinyl acetate, and homopolymers or copolymers formed from one or more monomers selected from butadiene. preferable.
• the homopolymer of an alkyl (meth) acrylate is preferable.
• alkyl (meth) acrylates butyl (meth) acrylate is preferred.
• butyl (meth) acrylates n-butyl (meth) acrylate is preferred.
• macromonomer include terminal methacryl-modified-poly-n-butyl acrylate macromonomer (“AB-6” manufactured by Toagosei Co., Ltd.).
• AB-6 is a homopolymer having a polymer chain portion of n-butyl acrylate, a number average molecular weight of 6000, one (meth) acryloyl group portion, and a (meth) acryloyl group portion as methacryloyl. It is a group.
• the number average molecular weight of (A) (meth) acrylate is preferably 1000 or more, more preferably 5000 or more, most preferably 6000 or more, and still more preferably 10,000 or more.
• the number average molecular weight of (A) (meth) acrylate is preferably 200000 or less, more preferably 100000 or less, most preferably 60000 or less, and still more preferably 40000 or less.
• the number average molecular weight is determined by creating a calibration curve with commercially available standard polystyrene using tetrahydrofuran as a solvent under the following conditions, using a GPC system. Flow rate: 1.0 ml / min Setting temperature: 40 ° C.
• Sample injection volume 100 ⁇ l (sample solution concentration 1 mg / ml)
• Liquid feeding pressure 39 kg / cm 2
• the amount of (A) (meth) acrylate used is preferably 30 to 80 parts by mass, more preferably 45 to 65 parts by mass, out of a total of 100 parts by mass of (A) to (C). If it is 30 parts by mass or more, heat resistance and peelability are obtained, and if it is 80 parts by mass or less, curability is obtained.
• the number average molecular weight of the monofunctional (meth) acrylate is less than 1000, preferably 900 or less, more preferably 800 or less, and most preferably 700 or less.
• a monomer is preferable.
• (B-1) a phenoxypolyalkylene glycol mono (meth) acrylate having an alkylene oxide chain
• (B-2) an alkyl (meth) acrylate having a linear or branched alkyl group
• One or more selected from (B-3) monofunctional (meth) acrylate having an alicyclic alkyl group and (B-4) silicone having one (meth) acryloyl group are preferred.
• (B-1) As the phenoxy polyalkylene glycol mono (meth) acrylate having an alkylene oxide chain, a (meth) acrylate represented by the following formula (2) is preferable.
• R 1 is preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom.
• R 2 is preferably an alkylene group having 2 to 3 carbon atoms, more preferably an ethylene group having 2 carbon atoms.
• R 3 is preferably a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 20 carbon atoms, and most preferably a nonyl group having 9 carbon atoms.
• n is preferably 1 to 15, more preferably 1 to 3, and most preferably 1.
• One or more of these (meth) acrylates can be used.
• Examples of (meth) acrylates in which R 3 is a nonyl group include nonylphenol ethylene oxide modified (meth) acrylate, nonylphenol (ethylene oxide 4 mol modified) (meth) acrylate, nonylphenol (ethylene oxide 8 mol modified) (meth) acrylate, nonylphenol (Propylene oxide 2.5 mol modification) (meth) acrylate etc. are mentioned.
• (B-2) As the alkyl (meth) acrylate having a linear or branched alkyl group, a (meth) acrylate represented by the following formula (3) is preferable.
• R 4 preferably has 5 to 20 carbon atoms, more preferably 8 to 18 carbon atoms, most preferably 10 to 16 carbon atoms, still more preferably 11 to 14 carbon atoms, and still more preferably 12 carbon atoms.
• One or more of these (meth) acrylates can be used.
• alkyl (meth) acrylate having an alkyl group having 5 to 20 carbon atoms examples include hexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, Decyl (meth) acrylate, isodecyl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, pentadecyl (Meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, octadecyl (
• Monofunctional (meth) acrylates having an alicyclic alkyl group include adamantyl (meth) acrylate, dicyclopentenyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate Cyclohexyl (meth) acrylate, and 1- (1-adamantyl) -1-methylethyl (meth) acrylate.
• 1-adamantyl (meth) acrylate is preferable from the viewpoint of heat resistance.
• Silicone having one (meth) acryloyl group is a polyorganosiloxane having one (meth) acryloyl group in the molecule.
• the silicone used as the base polymer of the silicone may be polysiloxane having a main chain composed of a siloxane bond, for example, all side chains, dimethyl silicone having a terminal methyl group, and a phenyl group in a part of the side chain. Examples thereof include methylphenyl silicone and methyl hydrogen silicone in which a part of the side chain is hydrogen. Of these, dimethyl silicone is preferred.
• the position at which the (meth) acryloyl group is introduced is not particularly limited, and may be at one end (one end type) of the main chain or at the side chain (side chain type). Among these, polyorganosiloxane having a (meth) acryloyl group at one end is preferable.
• the amount of the monofunctional (meth) acrylate used is preferably 19.99 to 65 parts by mass, more preferably 35 to 55 parts by mass, out of a total of 100 parts by mass of (A) to (C). If it is 19.99 mass parts or more, favorable sclerosis
• the polyfunctional (meth) acrylate has a number average molecular weight of less than 1000, preferably 900 or less, more preferably 800 or less, and most preferably 700 or less.
• Examples of the (C) polyfunctional (meth) acrylate include bifunctional (meth) acrylate, trifunctional (meth) acrylate, and tetrafunctional or higher (meth) acrylate.
• bifunctional (meth) acrylate examples include 1,3-adamantyl dimethanol di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, and 1,4-butane Diol di (meth) acrylate, 1,6-hexadiol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, Neopentyl glycol-modified trimethylolpropane di (meth) acrylate, stearic acid-modified pentaerythritol di (meth) acrylate, tripropylene glycol di (meth) acrylate, 2,2-bis (4- (meth) acryloxydiethoxyphenyl )propane 2,2-bis (4- (meth)
• trifunctional (meth) acrylates examples include isocyanuric acid ethylene oxide-modified tri (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, tris [(meth) acryloyloxyethyl] isocyanurate, etc. Is mentioned.
• Examples of tetrafunctional or higher (meth) acrylates include ditrimethylolpropane tetra (meth) acrylate, dimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol ethoxytetra (meth) acrylate, and dipentaerythritol penta.
• Method (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc. are mentioned.
• One or more selected from acrylates are preferred, and trimethylolpropane tri (meth) acrylate and ditrimethylolpropane tetra (meth) acrylic. Over DOO, more preferably one or more selected from tricyclode
• the amount of polyfunctional (meth) acrylate used is preferably 0.01 to 50 parts by mass, more preferably 0.1 to 10 parts by mass, out of a total of 100 parts by mass of (A) to (C). Most preferred is ⁇ 5 parts by weight. If it is 0.01 mass part or more, favorable peelability will be obtained, and if it is 50 mass parts or less, there is no possibility that heat resistance will fall.
• the radical photopolymerization initiator is 2-hydroxy-1- ⁇ 4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl ⁇ in terms of heat resistance and low outgassing properties.
• 2-Methyl-propan-1-one 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1,2-dimethylamino-2- (4-methyl-benzyl) -1- ( 4-morpholin-4-yl-phenyl) -butan-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, oxy-phenyl-acetic acid 2- [2-oxo-2-phenyl-acetoxy One or more members selected from the group consisting of ethoxy] -ethyl ester
• the amount of radical photopolymerization initiator used is 0.5 to 4 parts by mass with respect to a total of 100 parts by mass of (A) to (C) in terms of curability, low outgassing properties and heat resistance. It is preferably 1 to 3 parts by mass. When the amount of the radical photopolymerization initiator used is 0.5 parts by mass or more, sufficient curability is obtained, and when it is 4 parts by mass or less, low outgassing properties and heat resistance are excellent.
• non-radically polymerizable compounds selected from a fluorine compound, a non-radically polymerizable silicone compound and an olefin compound are preferable, and a fluorine compound is more preferable. These may be used in combination.
• the fluorine-based compound refers to a compound having fluorine.
• the fluorine-based compound include a fluorine-based surfactant and a fluorine-based polymer. In these, a fluorochemical surfactant is preferable.
• a surfactant having a perfluoroalkyl group is preferable.
• the surfactant having a perfluoroalkyl group examples include a fluorine-based oligomer having a perfluoroalkyl group (for example, “F-553” manufactured by DIC), and a fluorine-based compound of a non-radically polymerizable compound having a perfluoroalkyl group (for example, One or more selected from “FC-4430” manufactured by 3M, “S-386” manufactured by AGC Seimi Chemical Co., Ltd.) are preferred, and fluorine-based compounds of non-radically polymerizable compounds having a perfluoroalkyl group are more preferred.
• a fluorine-based oligomer having a perfluoroalkyl group for example, “F-553” manufactured by DIC
• a fluorine-based compound of a non-radically polymerizable compound having a perfluoroalkyl group for example, One or more selected from “FC-4430” manufactured by 3M, “S-386” manufactured by AGC Seimi Chemical Co
• fluorine-based compounds of a non-radically polymerizable compound having a perfluoroalkyl group perfluoroalkylsulfonic acid and / or a salt thereof (for example, “FC-4430” manufactured by 3M) is preferable.
• the non-radically polymerizable silicone compound is preferably a non-radically polymerizable compound.
• a siloxane compound is preferable.
• Non-radically polymerizable compounds include non-modified silicone oil (non-modified polydimethylsiloxane, etc., for example, “KF-96-100cs”, “KF-96-1000cs”, “KF-96H-10000cs” manufactured by Shin-Etsu Chemical Co., Ltd.)
• Non-reactive modified silicones modified with non-radically polymerizable functional groups for example, polyether-modified silicone oils “X-22-4515”, “X-22-2516” manufactured by Shin-Etsu Chemical Co., Ltd.
• One or more selected from a modified silicone oil “FL-100-1000cs” and a polypropylene oxide-modified silicone “TSF4446” manufactured by Momentive, Inc. is preferable.
• the olefin compound is preferably a non-radically polymerizable olefin compound having a number average molecular weight of 1000 to 10,000.
• the non-radically polymerizable olefin compounds one or more selected from polyethylene polymers, polypropylene polymers, and ethylene-propylene copolymers are preferable, and ethylene-propylene copolymers are more preferable.
• Examples of the ethylene-propylene copolymer include “Lucant HC-600” (viscosity: 14,000 mPa ⁇ s) manufactured by Mitsui Chemicals, “Lucanto HC-2000” (viscosity: 89,000 mPa ⁇ s) manufactured by Mitsui Chemicals, and the like. Can be mentioned.
• the amount of the releasing property-imparting compound used is preferably 0.01 to 5 parts by mass with respect to 100 parts by mass in total of (A) to (C).
• the fluorine compound is more preferably 0.01 to 2 parts by mass, and most preferably 0.05 to 1 part by mass.
• the silicone compound and the olefin compound are more preferably 0.1 to 3 parts by mass. If it is 0.01 parts by mass or more, peelability is secured, and if it is 5 parts by mass or less, good adhesiveness is obtained, and it does not become uncured.
• the composition of the present invention may use an antioxidant in order to maintain the peelability after being exposed to a high temperature.
• Antioxidants 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, 2 , 6-ditertiarybutyl-p-cresol, 4-[[4,6-bis (octylthio) -1,3,5-triazin-2-yl] amino] -2,6-ditertiarybutylphenol, and the like.
• the amount of the antioxidant used is preferably 0.001 to 3 parts by mass with respect to 100 parts by mass in total of (A) to (C). When it is 0.001 part by mass or more, it is possible to maintain the peelability after being exposed to a high temperature, and when it is 3 parts by mass or less, good adhesiveness is obtained, and it is not uncured.
• composition of the present invention may contain an antifoaming agent in order to suppress foaming during production and use.
• composition of the present invention includes various elastomers such as acrylic rubber, urethane rubber, acrylonitrile-butadiene-styrene rubber, inorganic fillers, solvents, fillers, reinforcing materials, Additives such as plasticizers, thickeners, dyes, pigments, flame retardants, silane coupling agents and surfactants may be used.
• elastomers such as acrylic rubber, urethane rubber, acrylonitrile-butadiene-styrene rubber, inorganic fillers, solvents, fillers, reinforcing materials.
• Additives such as plasticizers, thickeners, dyes, pigments, flame retardants, silane coupling agents and surfactants may be used.
• composition of the present invention can be used as an adhesive.
• the adhesive of the present invention can be used as a temporary fixing adhesive.
• the energy amount is in the range of 1 to 20000 mJ / cm 2 at a wavelength of 365 nm.
• the energy amount is 1 mJ / cm 2 or more, sufficient adhesiveness is obtained, and when it is 20000 mJ / cm 2 or less, productivity is excellent, decomposition products from the photo radical polymerization initiator are hardly generated, and outgas is generated. Is also suppressed. From the viewpoint of productivity, adhesion, outgassing, and easy peelability, it is more preferably in the range of 2000 to 10000 mJ / cm 2 .
• the substrate to be bonded by the composition of the present invention is preferably a transparent substrate that transmits light.
• the transparent substrate include inorganic substrates such as quartz, glass, quartz, and calcium fluoride, and organic substrates such as plastic. Among these, at least one selected from glass and quartz is preferable because of its versatility and great effects.
• the composition of the present invention is photocurable, and the cured product can have excellent heat resistance and peelability.
• the cured product of the composition of the present invention has a low outgas amount even when exposed at high temperatures, and is suitable for bonding, sealing, and coating of various optical components, optical devices, and electronic components.
• it can be used for temporary fixing agents, adhesives, protective sheets, low birefringence optical films, interlayer stress relaxation agents, etc., especially in a wide range of solvent resistance, heat resistance, adhesion, etc. as in the semiconductor manufacturing process. Suitable for applications that require durability.
• the cured product of the composition of the present invention can be used from room temperature to high temperatures.
• the heating temperature during the process is preferably 350 ° C. or lower, more preferably 300 ° C. or lower, and most preferably 250 ° C. or lower.
• Adhesives bonded with a temporary fixing adhesive using the composition of the present invention have a high shear adhesive strength and can withstand a thinning process, etc. easily after a heating process such as insulation film formation. Can peel.
• the cured product of the composition of the present invention can be used at a high temperature of preferably 200 ° C. or higher, more preferably 250 ° C. or higher.
• it can be peeled off by applying an external force to an adhesive body having a base material bonded with an adhesive.
• an adhesive body having a base material bonded with an adhesive For example, it can be peeled by inserting a blade, a sheet or a wire.
• the thin wafer manufacturing method of the present invention is characterized in that a temporary fixing adhesive is used as an adhesive layer between a wafer having a semiconductor circuit or the like and a support.
• the thin wafer manufacturing method of the present invention includes the following steps (a) to (e).
• Step (a) In the step (a), when the circuit forming surface of the wafer having a circuit forming surface on the front surface and a circuit non-forming surface on the back surface is bonded to the support through an adhesive, In this step, an adhesive is applied by spin coating and bonded to the other support or wafer with circuit under vacuum. At this time, the (E) releasability-imparting compound is dissolved in an appropriate solvent as the first agent, and the adhesive composed of components other than the (E) releasability-imparting compound is used as the second agent.
• a two-agent type temporary fixing agent in which one agent and a second agent are mixed may be used.
• the first agent is applied to the circuit forming surface of the wafer, the solvent is distilled off, a release layer made of a release property-imparting compound is formed, and the second agent is applied to the support side.
• the wafer and the support may be bonded and photocured.
• a wafer having a circuit formation surface and a circuit non-formation surface is a wafer in which one surface is a circuit formation surface and the other surface is a circuit non-formation surface.
• a wafer to which the present invention is applicable is usually a semiconductor wafer.
• the semiconductor wafer include not only a silicon wafer but also a germanium wafer, a gallium-arsenic wafer, a gallium-phosphorus wafer, a gallium-arsenic-aluminum wafer, and the like.
• the thickness of the wafer is not particularly limited, but is preferably 600 to 800 ⁇ m, more preferably 625 to 775 ⁇ m.
• As the support for example, a transparent substrate that transmits light is used.
• Step (b) is a step of photocuring the adhesive.
• the wafer processed body laminate substrate
• the energy amount is 1 mJ / cm 2 or more, sufficient adhesiveness is obtained, and when it is 20000 mJ / cm 2 or less, productivity is excellent, decomposition products from the photo radical polymerization initiator are hardly generated, and outgas is generated. Is also suppressed. From the viewpoint of productivity, adhesion, outgassing, and easy peelability, it is more preferably in the range of 2000 to 10000 mJ / cm 2 .
• the step (c) is a step of grinding or polishing the non-circuit-formed surface of the wafer bonded to the support, that is, grinding the wafer back surface side of the wafer processed body obtained by bonding in the step (a), This is a step of reducing the thickness of the wafer.
• the thickness of the thinned wafer is preferably 10 to 300 ⁇ m, more preferably 30 to 100 ⁇ m.
• There is no particular limitation on the method of grinding the back surface of the wafer and a known grinding method is adopted.
• the grinding is preferably performed while cooling the wafer and a grindstone (such as diamond) with water.
• Step (d) is a step of processing the wafer non-circuited surface of the non-circuit-formed surface, that is, the non-circuit-formed surface of the wafer processed body thinned by back surface grinding.
• This process includes various processes used at the wafer level. For example, electrode formation, metal wiring formation, protective film formation, etc. are mentioned.
• metal sputtering for forming electrodes, etc. wet etching for etching metal sputtering layers
• application of resist for use as a mask for metal wiring formation pattern formation by exposure and development
• resist Conventionally known processes such as peeling of silicon, dry etching, formation of metal plating, silicon etching for TSV formation, and formation of an oxide film on the silicon surface can be mentioned.
• step (e) the wafer processed in step (c) is peeled off from the wafer processed body, that is, after various processing is performed on the thinned wafer, it is peeled off from the wafer processed body before dicing. It is a process.
• This peeling process is generally performed under a relatively low temperature condition from room temperature to about 60 ° C., one of the wafer and the support of the wafer processed body is fixed horizontally, and the other is attached at a certain angle from the horizontal direction. Lift up.
• This peeling method is applicable to the present invention. At this time, after fixing one of the wafer and the support of the wafer processed body horizontally and putting a knife or swelling the outer periphery of the adhesive layer with a solvent (for example, mesitylene) to create a trigger for peeling It is also preferable to lift the other at a certain angle from the horizontal direction.
• a solvent for example, mesitylene
• These peeling methods are usually carried out at room temperature, but it is also preferable to heat at an upper limit of about 90 ° C.
• step (E) After passing through the process of peeling the processed wafer from the support, it is preferable to perform the process of (i) removing the adhesive remaining on the circuit forming surface of the peeled wafer. Part of the adhesive may remain on the circuit forming surface of the wafer peeled off from the support in step (e).
• the peeled support is preferably washed and reused, but an adhesive residue may adhere to the support surface. Examples of the method for removing the adhesive residue include a method in which an adhesive tape is attached to the adhesive residue and peeled in a direction of 180 °, and a method in which the adhesive residue is immersed in a chemical solution.
• (A) The following compounds were selected as (meth) acrylates having a number average molecular weight of 1000 or more.
• (A-1) Isoprene oligomer (“UC-102” manufactured by Kuraray Co., Ltd.) (Number average molecular weight of 17,000 in terms of polystyrene by GPC, esterified oligomer of maleic anhydride adduct of isoprene polymer and 2-hydroxyethyl methacrylate, formula In (1), Y is an ethylene group, and R is a methyl group)
• (A-2) Terminal methacryl-modified poly-n-butyl acrylate macromonomer (“AB-6” manufactured by Toagosei Co., Ltd., number average molecular weight 6000)
• (A-3) Acrylic-modified organosiloxane at both ends (X-22-1602, Shin-Etsu Chemical Co., Ltd., number average molecular weight 1200)
• (B) The following compounds were selected as monofunctional (meth) acrylates having a number average molecular weight of less than 1000.
• (B-1) Nonylphenol ethylene oxide modified acrylate (“M-111” manufactured by Toagosei Co., Ltd., the structure is represented by formula (2), R 1 is a hydrogen atom, R 2 is an ethylene group, and R 3 is nonyl.
• n is 1) (B-2) Lauryl acrylate (“LA” manufactured by Osaka Organic Chemical Co., Ltd.) (B-3) 1-adamantyl methacrylate (“ADMA” manufactured by Osaka Organic Chemical Co., Ltd.) (B-4) One-end methacryl-modified polyorganosiloxane (“X-22-2475” manufactured by Shin-Etsu Chemical Co., Ltd., number average molecular weight 420)
• C The following compounds were selected as polyfunctional (meth) acrylates having a number average molecular weight of less than 1000.
• C-1 Trimethylolpropane trimethacrylate (“TMPTM” manufactured by Shin-Nakamura Chemical Co., Ltd.)
• C-2) Ditrimethylolpropane tetramethacrylate (“D-TMP” manufactured by Shin-Nakamura Chemical Co., Ltd.)
• (D) The following compounds were selected as radical photopolymerization initiators.
• (D-1) 2,2-dimethoxy-1,2-diphenylethane-1-one (“Irgacure 651” manufactured by BASF, hereinafter abbreviated as “I-651”)
• (D-2) 2-dimethylamino-2- (4-methyl-benzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one (“Irgacure 379” manufactured by BASF, hereinafter “I Abbreviated to "-379”)
• E The following compounds were selected as the releasability imparting compound.
• E-1 Fluorine-containing oligomer (“F-553” manufactured by DIC, including perfluoroalkyl group)
• E-4) Polyether-modified organosiloxane (“X-22-2516” manufactured by Shin-Etsu Chemical Co., Ltd.)
• IRGANOX565 4-[[4,6-Bis (octylthio) -1,3,5-triazin-2-yl] amino] -2,6-ditertiarybutylphenol (“IRGANOX565” manufactured by BASF, hereinafter abbreviated as “IRGANOX565”)
• Heated mass reduction rate of cured body (“1% heated mass reduction temperature of cured body” in the table): The produced resin composition was sandwiched between PET films. The resin composition was cured with black light under the condition of an integrated light amount of 3000 mJ / cm 2 with a wavelength of 365 nm to prepare a cured body. 10 mg of the resulting cured product was increased from 30 ° C. to 350 ° C. at a rate of 10 ° C./min under a nitrogen stream using a simultaneous differential thermal / thermal mass measuring device “TG-DTA2000SA” manufactured by Bruker AXS. The resulting cured product was heated and the mass reduction rate was measured. The 1 mass% heating mass decreasing temperature of the cured product was shown.
• the temperature at which the heating mass reduction rate is 1% by mass is preferably 230 ° C. or more from the viewpoint of high-temperature process compatibility in semiconductor manufacturing.
• Tensile shear adhesive strength (“Adhesive strength” in the table): a resin composition prepared using a slide glass (25 mm ⁇ 75 mm ⁇ thickness 1.3 mm) as an adherend and an adhesive site of 25 mm ⁇ 40 mm Two slide glasses were bonded together and cured with a black light under the condition of an integrated light quantity of 365 nm wavelength of 3000 mJ / cm 2 to prepare a tensile shear bond strength test piece. The produced test piece was measured for tensile shear adhesive strength at a tensile speed of 10 mm / min in an environment of a temperature of 23 ° C. and a humidity of 50% using a universal testing machine in accordance with JIS K 6850.
• Peeling / disassembling test (1) (“Peelability” in the table): 4 inch silicon wafer (diameter 10 mm ⁇ thickness 0.47 mm) and 4 inch glass wafer (diameter 10 mm ⁇ thickness 0) using the prepared resin composition 0.7 mm) was bonded together, and cured with black light under the condition of an integrated light quantity of 3000 nm wavelength of 3000 mJ / cm 2 to prepare a peel / disassemble test piece. The adhesive was applied to the entire bonded surface. The black light was irradiated from the surface of the 4-inch glass wafer. A pet sheet was inserted between the obtained specimens to evaluate the peelability.
• Peeling / disassembling test (2) (“peeling force" in the table): a resin composition prepared using a silicon wafer (25 mm x 75 mm x thickness 0.725 mm) as an adherent and having an adhesion site of 5 mm x 75 mm Then, the silicon wafer and the PET film were bonded to each other and cured with a black light under the condition of an integrated light amount of 3000 mJ / cm 2 with a wavelength of 365 nm, to prepare a peel strength test piece. The black light was irradiated from the surface of the PET film.
• the prepared test piece was peeled off using a variable angle peeling device (VERSATILE PEEL ANALYZER VPA-3 manufactured by Kyowa Interface Science Co., Ltd.) in an environment of a temperature of 23 ° C. and a humidity of 50% at a tensile speed of 40 mm / min and a peeling angle of 15 degrees. The strength was measured. The smaller the peel strength, the greater the peelability.
• VERSATILE PEEL ANALYZER VPA-3 manufactured by Kyowa Interface Science Co., Ltd.
• the composition of the present invention is excellent in workability and productivity because, in the production of various electronic components, optical components and optical devices, strong adhesiveness can be easily expressed simply by irradiating with ultraviolet rays or visible rays.
• the cured product of the composition of the present invention has a very small amount of outgas even at a high temperature of 250 ° C. Therefore, various electronic components, optical components, and optical devices bonded using the composition of the present invention can be applied even when vapor deposition at a high temperature exceeding 200 ° C. or baking coating at a high temperature is performed. Is possible.

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