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
  • 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
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
  • B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
  • B32B37/30—Partial laminating
• • 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
  • C09J5/06—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving heating of the applied adhesive
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
  • H10P72/00—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof
  • H10P72/70—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof for supporting or gripping
  • H10P72/74—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof for supporting or gripping using temporarily an auxiliary support
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
  • H10W72/00—Interconnections or connectors in packages
  • H10W72/01—Manufacture or treatment
  • H10W72/0198—Manufacture or treatment batch processes
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
  • H10W72/00—Interconnections or connectors in packages
  • H10W72/071—Connecting or disconnecting
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
  • H10W72/00—Interconnections or connectors in packages
  • H10W72/071—Connecting or disconnecting
  • H10W72/073—Connecting or disconnecting of die-attach connectors
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
  • B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
  • B32B2037/1253—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives curable adhesive
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2310/00—Treatment by energy or chemical effects
  • B32B2310/08—Treatment by energy or chemical effects by wave energy or particle radiation
  • B32B2310/0806—Treatment by energy or chemical effects by wave energy or particle radiation using electromagnetic radiation
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2457/00—Electrical equipment
  • B32B2457/14—Semiconductor wafers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
  • B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
  • B32B37/1207—Heat-activated adhesive
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B43/00—Operations specially adapted for layered products and not otherwise provided for, e.g. repairing; Apparatus therefor
  • B32B43/006—Delaminating
• • 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
• • 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
• • 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
  • C09J2301/50—Additional features of adhesives in the form of films or foils characterized by process specific features
  • C09J2301/502—Additional features of adhesives in the form of films or foils characterized by process specific features process for debonding adherents
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
  • H10P72/00—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof
  • H10P72/70—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof for supporting or gripping
  • H10P72/74—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof for supporting or gripping using temporarily an auxiliary support
  • H10P72/7402—Wafer tapes, e.g. grinding or dicing support tapes
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
  • H10P72/00—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof
  • H10P72/70—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof for supporting or gripping
  • H10P72/74—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof for supporting or gripping using temporarily an auxiliary support
  • H10P72/7416—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof for supporting or gripping using temporarily an auxiliary support used during dicing or grinding
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
  • H10P72/00—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof
  • H10P72/70—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof for supporting or gripping
  • H10P72/74—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof for supporting or gripping using temporarily an auxiliary support
  • H10P72/7422—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof for supporting or gripping using temporarily an auxiliary support used to protect an active side of a device or wafer
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
  • H10P72/00—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof
  • H10P72/70—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof for supporting or gripping
  • H10P72/74—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof for supporting or gripping using temporarily an auxiliary support
  • H10P72/744—Details of chemical or physical process used for separating the auxiliary support from a device or a wafer

Definitions

• the present invention is a wafer processing method for processing a wafer in a state where the wafer is fixed to a support plate via an adhesive composition, and includes a wafer processing step for performing a chemical treatment, a heat treatment, or a process involving heat generation. Nevertheless, the present invention relates to a wafer processing method capable of maintaining a sufficient adhesive force during the wafer processing step and peeling the support plate from the wafer after the wafer processing step without damaging the wafer or leaving adhesive residue.
• the wafer is fixed to a support plate in order to facilitate handling during wafer processing and prevent damage.
• a thick film wafer cut from a high-purity silicon single crystal or the like is ground to a predetermined thickness to form a thin film wafer
• the thick film wafer can be bonded to a support plate via an adhesive composition. Done.
• Adhesive compositions that bond a wafer to a support plate are required to have high adhesive properties that can firmly fix the wafer during the processing step, and that the wafer can be peeled off without damaging the wafer after the end of the step (hereinafter referred to as “high”). Also referred to as “adhesive easy peeling”.)
• Patent Document 1 describes a wafer processing method using a double-sided adhesive tape having an adhesive layer containing a gas generating agent that generates a gas upon stimulation with an azo compound or the like. Has been. In the wafer processing method described in Patent Document 1, first, a wafer is fixed to a support plate via a double-sided adhesive tape.
• the gas generated from the gas generating agent is released to the interface between the surface of the tape and the wafer, and at least a part is peeled off by the pressure. If the double-sided adhesive tape of patent document 1 is used, it can peel, without damaging a wafer and without the adhesive residue.
• TSV Through Si via
• the adhesive composition is eroded and bonded in the step of performing chemical treatment on the surface of the wafer.
• the strength of the adhesive composition may be reduced, and conversely, the adhesive composition may be increased in adhesion due to a high temperature, resulting in a decrease in peelability.
• the present invention is a wafer processing method for processing a wafer in a state where the wafer is fixed to a support plate via an adhesive composition, and the wafer is subjected to a chemical treatment, a heat treatment or a heat generation treatment.
• a wafer that can maintain a sufficient adhesive force at the time of the wafer processing step and can peel the support plate from the wafer without damaging the wafer or leaving adhesive residue after the wafer processing step is completed.
• An object is to provide a processing method.
• the present invention includes a support plate fixing step of fixing a wafer to a support plate through an adhesive composition containing a curable adhesive component that is crosslinked and cured by light irradiation or heating, and irradiating the adhesive composition with light.
• an adhesive curing step for crosslinking and curing the curable adhesive component by heating a wafer processing step for subjecting the surface of the wafer fixed to the support plate to a chemical treatment, a heat treatment, or a process involving heat generation, and the treatment
• a support plate peeling step for peeling the support plate from the subsequent wafer.
• a support plate fixing step of fixing the wafer to the support plate is performed through an adhesive composition containing a curable adhesive component that is crosslinked and cured by light irradiation or heating.
• the support plate is not particularly limited as long as it has sufficient strength, excellent heat resistance and chemical resistance, and transmits or passes light, and examples thereof include a glass plate, a quartz plate, and a sapphire plate. It is done.
• the support plate for example, commercially available products such as AF32 (manufactured by Schott) and boronfloat 33 (manufactured by Schott) can be used.
• the adhesive composition contains a photocurable adhesive component that is crosslinked and cured by light irradiation, or a thermosetting adhesive component that is crosslinked and cured by heating.
• the photocurable adhesive component include a photocurable adhesive containing a polymerizable polymer as a main component and a photopolymerization initiator.
• the thermosetting adhesive component include a thermosetting adhesive containing a polymerizable polymer as a main component and a thermal polymerization initiator.
• the polymerizable polymer is prepared by, for example, previously synthesizing a (meth) acrylic polymer having a functional group in the molecule (hereinafter referred to as a functional group-containing (meth) acrylic polymer) and reacting with the functional group in the molecule. It can obtain by making it react with the compound (henceforth a functional group containing unsaturated compound) which has a functional group to perform and a radically polymerizable unsaturated bond.
• the functional group-containing (meth) acrylic polymer is an acrylic polymer having an alkyl group usually in the range of 2 to 18 as a polymer having adhesiveness at room temperature, as in the case of general (meth) acrylic polymers.
• a functional group-containing monomer, and, if necessary, another modifying monomer copolymerizable therewith by a conventional method It is obtained.
• the weight average molecular weight of the functional group-containing (meth) acrylic polymer is usually about 200,000 to 2,000,000.
• Examples of the functional group-containing monomer include a carboxyl group-containing monomer such as acrylic acid and methacrylic acid; a hydroxyl group-containing monomer such as hydroxyethyl acrylate and hydroxyethyl methacrylate; and an epoxy group containing glycidyl acrylate and glycidyl methacrylate.
• Examples of other modifying monomers that can be copolymerized include various monomers used in general (meth) acrylic polymers such as vinyl acetate, acrylonitrile, and styrene.
• the functional group-containing unsaturated compound to be reacted with the functional group-containing (meth) acrylic polymer is the same as the functional group-containing monomer described above according to the functional group of the functional group-containing (meth) acrylic polymer. it can.
• the functional group of the functional group-containing (meth) acrylic polymer is a carboxyl group
• an epoxy group-containing monomer or an isocyanate group-containing monomer is used
• the functional group is a hydroxyl group
• an isocyanate group-containing monomer is used.
• the functional group is an epoxy group
• a carboxyl group-containing monomer or an amide group-containing monomer such as acrylamide is used
• the functional group is an amino group
• an epoxy group-containing monomer is used.
• the polymerizable polymer preferably has a lower limit of the content of the radical polymerizable unsaturated bond of 0.01 meq / g and a preferable upper limit of 2.0 meq / g.
• the adhesive composition is irradiated or heated in the adhesive curing step to crosslink and cure the curable adhesive component.
• the adhesive composition after being subjected to a storage shear modulus at 25 ° C. of 2.0 ⁇ 10 5 to 10 measured under the condition of continuous temperature increase from ⁇ 50 ° C. to 300 ° C. in the shear mode of dynamic viscoelasticity measurement. It can be adjusted to a range of about 8 Pa.
• the minimum with more preferable content of the radically polymerizable unsaturated bond of the said polymeric polymer is 0.05 meq / g, and a more preferable upper limit is 1.0 meq / g.
• Examples of the photopolymerization initiator include those activated by irradiation with light having a wavelength of 250 to 800 nm.
• Examples of such a photopolymerization initiator include acetophenone derivative compounds such as methoxyacetophenone; Benzoin ether compounds such as benzoinpropyl ether and benzoin isobutyl ether; ketal derivative compounds such as benzyldimethyl ketal and acetophenone diethyl ketal; phosphine oxide derivative compounds; bis ( ⁇ 5-cyclopentadienyl) titanocene derivative compounds, benzophenone, Michler's ketone, Chlorothioxanthone, todecylthioxanthone, dimethylthioxanthone, diethylthioxanthone, ⁇ -hydroxycyclohexyl phenyl ketone, 2-hydroxymethylphenylpropane, etc.
• These radical photopolymerization initiators These
• thermal polymerization initiator examples include those that decompose by heat and generate active radicals that initiate polymerization, such as dicumyl peroxide, di-t-butyl peroxide, t-butyl peroxybenzoate, t- Examples thereof include butyl hydroperoxide, benzoyl peroxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, paramentane hydroperoxide, and di-t-butyl peroxide. These thermal polymerization initiators may be used independently and 2 or more types may be used together.
• the photocurable adhesive or thermosetting adhesive preferably further contains a radical polymerizable polyfunctional oligomer or monomer.
• a radical polymerizable polyfunctional oligomer or monomer By containing a radically polymerizable polyfunctional oligomer or monomer, photocurability or thermosetting is improved.
• the polyfunctional oligomer or monomer preferably has a molecular weight of 10,000 or less, and more preferably has a molecular weight of 5000 or less so that the three-dimensional network of the adhesive layer can be efficiently formed by heating or light irradiation.
• the number of radically polymerizable unsaturated bonds in the molecule is 2 to 20.
• the polyfunctional oligomer or monomer is, for example, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol monohydroxypentaacrylate, dipentaerythritol hexaacrylate, or the same methacrylate as described above. And the like.
• Examples include 1,4-butylene glycol diacrylate, 1,6-hexanediol diacrylate, polypropylene glycol # 700 diacrylate, polyethylene glycol diacrylate, commercially available oligoester acrylate, and methacrylates similar to those described above. These polyfunctional oligomers or monomers may be used alone or in combination of two or more.
• the photocurable adhesive or thermosetting adhesive may contain a gas generating agent that generates a gas by stimulation.
• the photo-curing adhesive or thermosetting adhesive contains the gas generating agent, in the support plate peeling step described later, the processed wafer is stimulated to generate gas from the gas generating agent. As a result, the support plate can be peeled off from the wafer more easily and without adhesive residue.
• the photocurable adhesive component or thermosetting adhesive component and the gas generating agent include light or heat for crosslinking and curing the photocurable adhesive component or thermosetting adhesive component, and gas generation.
• a combination of qualitatively or quantitatively different stimuli for generating gas from the agent is selected. By selecting such a combination, it is possible to prevent the wafer from which the gas is generated from the gas generating agent and the support plate from being peeled off by light irradiation or heating in the adhesive curing step described later.
• a gas generating agent that generates gas by a stimulus other than light such as heat is selected.
• the photocurable adhesive component A gas generating agent that requires a larger amount of light than the amount of light that crosslinks and cures is selected.
• the photocurable adhesive component it is possible to select a gas generating agent that generates gas by a stimulus other than light such as heat.
• a gas generating agent that generates gas by a stimulus other than light such as heat.
• the photocurable adhesive component A gas generating agent that requires a larger amount of light than the amount of light that crosslinks and cures is selected.
• the photocurable adhesive component that is crosslinked and cured by light irradiation contains a polymer having an unsaturated double bond such as a vinyl group in the side chain and a photopolymerization initiator that is activated at a wavelength of 250 to 800 nm.
• a photo-curable adhesive component is combined with a gas generating agent that generates gas by irradiating light with a wavelength of 300 nm or less, light with a wavelength of 365 nm or more is irradiated in the adhesive curing step. And it becomes possible to irradiate the light of a wavelength of 300 nm or less in a support plate peeling process.
• thermosetting type adhesive component selecting the gas generating agent which generate
• the temperature condition for crosslinking and curing the thermosetting adhesive component is lower than the temperature condition for generating gas from the gas generating agent.
• produces gas by stimuli other than heat, such as light is mentioned.
• the temperature condition for crosslinking and curing the thermosetting adhesive component is lower than the temperature condition for generating gas from the gas generating agent.
• Select For example, heating at 200 ° C. or higher for a thermosetting adhesive containing a polymer having an unsaturated double bond such as a vinyl group in the side chain and a thermal polymerization initiator activated by heating at about 50 to 150 ° C. If a gas generating agent that generates gas is combined, it is possible to heat at 50 to 150 ° C. in the adhesive curing step and to heat at 200 ° C. or higher in the support plate peeling step.
• the said gas generating agent is not specifically limited, For example, conventionally well-known gas generating agents, such as an azo compound and an azide compound, can be used.
• the carboxylic acid compound represented by the following general formula (1) or a salt thereof is also suitable because it does not peel off even by chemical treatment, heat treatment or heat generation treatment, that is, it has excellent resistance to these treatments.
• Such a gas generating agent generates gas (carbon dioxide gas) by irradiating light such as ultraviolet rays, and has high heat resistance that does not decompose even at a high temperature of about 200 ° C. Moreover, it is excellent also in the tolerance with respect to chemical
• R 1 to R 7 each represents hydrogen or an organic group.
• R 1 to R 7 may be the same or different.
• Two of R 1 to R 7 may be bonded to each other to form a cyclic structure.
• Examples of the organic group in the general formula (1) include an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, and an isobutyl group, an alkoxy group such as a methoxy group and an ethoxy group, a carboxyl group, a hydroxyl group, , Aromatic groups such as nitro groups and phenyl groups, polycyclic hydrocarbon groups such as naphthyl groups, fluorenyl groups and pyrenyl groups, ring-assembled hydrocarbon groups such as biphenyl groups, and heterocyclic groups such as xanthenyl groups Etc.
• an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, and an isobutyl group
• an alkoxy group such as a methoxy group and an ethoxy group
• a carboxyl group such as a hydroxyl group
• R 3 to R 7 in the above formula (1) is an organic group represented by the following formula (2), or R 3 to R 7 in the above formula (1). It is preferable that two adjacent ones are bonded to each other to form a cyclic structure represented by the following formula (3).
• R 8 to R 12 each represent hydrogen or an organic group.
• R 8 to R 12 may be the same or different.
• Two of R 8 to R 12 may be bonded to each other to form a cyclic structure.
• R 13 to R 16 each represent hydrogen or an organic group.
• R 13 to R 16 may be the same or different.
• Two of R 13 to R 16 may be bonded to each other to form a cyclic structure.
• R 1 in the above formula (1) is preferably a methyl group.
• carboxylic acid compound represented by the above formula (1) include, for example, phenylacetic acid, diphenylacetic acid, triphenylacetic acid, 2-phenylpropionic acid, 2,2-diphenylpropionic acid, 2,2,2- Triphenylpropionic acid, 2-phenylbutyric acid, ⁇ -methoxyphenylacetic acid, mandelic acid, atrolactone acid, benzylic acid, tropic acid, phenylmalonic acid, phenylsuccinic acid, 3-methyl-2-phenylbutyric acid, orthotoluylacetic acid , Metatoluylacetic acid, 4-isobutyl- ⁇ -methylphenylacetic acid, p-toluylacetic acid, 1,2-phenylenediacetic acid, 1,3-phenylenediacetic acid, 1,4-phenylenediacetic acid, 2-methoxyphenylacetic acid, 2-hydroxy Phenylacetic acid, 2-nitrophenylacetic acid, 3-nitro
• the carboxylic acid compound represented by the above formula (1) is ketoprofen represented by the following formula (1-1) or 2-xanthone acetic acid represented by the following formula (1-2). preferable.
• the salt of the carboxylic acid compound represented by the above formula (1) also has a skeleton derived from the carboxylic acid compound represented by the above formula (1), decarboxylation easily occurs when irradiated with light, Carbon dioxide gas can be generated.
• the salt of the carboxylic acid compound represented by the above formula (1) can be obtained by simply mixing the carboxylic acid compound represented by the above formula (1) and the basic compound in a container without going through a complicated synthesis route. Easy to prepare.
• the basic compound is not particularly limited, and examples thereof include amines, hydrazine compounds, quaternary ammonium hydroxide salts, and phosphine compounds.
• the amine is not particularly limited, and any of primary amines, secondary amines, and tertiary amines can be used. Among these, the basic compound is preferably a monoalkylamine or a dialkylamine.
• the polarity of the obtained salt of the carboxylic acid compound represented by the formula (1) can be reduced, and the solubility with the adhesive component can be increased. More preferably, it is a monoalkylamine or dialkylamine having 6 to 12 carbon atoms.
• gas generating agent a tetrazole compound represented by the following general formula (4), general formula (5) or general formula (6) or a salt thereof is also suitable.
• gas generating agents also generate gas (nitrogen gas) by irradiating light such as ultraviolet rays, and have high heat resistance that does not decompose even at a high temperature of about 200 ° C. Moreover, it is excellent also in tolerance with respect to chemical
• R 21 and R 22 represent hydrogen, an alkyl group having 1 to 7 carbon atoms, an alkylene group, a phenyl group, a mercapto group, a hydroxyl group, or an amino group.
• the salt of the tetrazole compound represented by the general formulas (4) to (6) also has a skeleton derived from the tetrazole compound represented by the general formula (4) to (6), light is irradiated. And nitrogen gas can be generated.
• the salt of the tetrazole compound represented by the general formulas (4) to (6) is not particularly limited, and examples thereof include a sodium salt, a potassium salt, and an ammonium salt.
• the salt of the tetrazole compound represented by the general formulas (4) to (6) can be obtained by simply mixing the tetrazole compound and the basic compound represented by the general formulas (4) to (6) in a container. It can be easily prepared without going through a complicated synthetic route.
• the basic compound is not particularly limited, and examples thereof include amines, hydrazine compounds, quaternary ammonium hydroxide salts, and phosphine compounds.
• the amine is not particularly limited, and any of primary amines, secondary amines, and tertiary amines can be used. Among these, the basic compound is preferably a monoalkylamine or a dialkylamine.
• the polarity of the resulting salt of the tetrazole compound represented by the general formulas (4) to (6) can be reduced, so that it can be dissolved in a photocurable adhesive component.
• a photocurable adhesive component Can increase the sex. More preferably, it is a monoalkylamine or dialkylamine having 6 to 12 carbon atoms.
• the tetrazole compound represented by the above general formula (4) or a salt thereof is not particularly limited. Specifically, for example, 1H-tetrazole, 5-phenyl-1H-tetrazole, 5,5-azobis-1H-tetrazole, 5 -Amino-1H-tetrazole, 5-methyl-1H-tetrazole, 1-methyl-5-mercapto-1H-tetrazole, 1-methyl-5-ethyl-1H-tetrazole, 1- (dimethylaminoethyl) -5-mercapto -1H-tetrazole and the like.
• the tetrazole compound represented by the general formula (5) or a salt thereof is not particularly limited, and specific examples include 5,5'-bistetrazole diammonium salt.
• the tetrazole compound represented by the general formula (6) or a salt thereof is not particularly limited, and specific examples include 5,5'-bistetrazoleamine monoammonium salt.
• the content of the gas generating agent is such that a preferable lower limit with respect to 100 parts by weight of the photocurable adhesive component or the thermosetting adhesive component is 5 parts by weight, and a preferable upper limit is 50 parts by weight.
• a preferable lower limit with respect to 100 parts by weight of the photocurable adhesive component or the thermosetting adhesive component is 5 parts by weight
• a preferable upper limit is 50 parts by weight.
• the content of the gas generating agent is less than 5 parts by weight, the generation of carbon dioxide gas or nitrogen gas due to stimulation may be reduced and sufficient peeling may not be performed.
• the content exceeds 50 parts by weight photocuring is performed.
• the adhesive cannot be dissolved in the mold adhesive component or the thermosetting adhesive component, resulting in a decrease in adhesive strength.
• the minimum with more preferable content of the said gas generating agent is 10 weight part, and a more preferable upper limit is 30 weight part.
• the adhesive composition may further contain a photosensitizer. Since the photosensitizer has an effect of amplifying stimulation by light on the gas generating agent, gas can be released by irradiation with less light. In addition, gas can be emitted by light in a wider wavelength region.
• the photosensitizer is not particularly limited as long as it has excellent heat resistance.
• the photosensitizer excellent in heat resistance include polycyclic aromatic compounds having at least one alkoxy group.
• a substituted alkoxy polycyclic aromatic compound having an alkoxy group partially substituted with a glycidyl group or a hydroxyl group is preferable.
• These photosensitizers have high resistance to sublimation and can be used at high temperatures.
• the solubility in the photocurable adhesive component is increased, and bleeding out can be prevented.
• the polycyclic aromatic compound is preferably an anthracene derivative.
• the alkoxy group preferably has 1 to 18 carbon atoms, and more preferably has 1 to 8 carbon atoms.
• polycyclic aromatic compound having at least one alkoxy group examples include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 2-tbutyl-9,10-dimethoxyanthracene, 2, 3-dimethyl-9,10-dimethoxyanthracene, 9-methoxy-10-methylanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 2-tbutyl-9,10-di Ethoxyanthracene, 2,3-dimethyl-9,10-diethoxyanthracene, 9-ethoxy-10-methylanthracene, 9,10-dipropoxyanthracene, 2-ethyl-9,10-dipropoxyanthracene, 2-tbutyl -9,10-dipropoxyanthracene, 2,3-dimethyl-9, 0-dipropoxyanthracene
• the substituted alkoxy polycyclic aromatic compound having an alkoxy group partially substituted with a glycidyl group or a hydroxyl group includes, for example, 9,10-di (glycidyloxy) anthracene, 2-ethyl-9,10-di (glycidyloxy) ) Anthracene, 2-tbutyl-9,10-di (glycidyloxy) anthracene, 2,3-dimethyl-9,10-di (glycidyloxy) anthracene, 9- (glycidyloxy) -10-methylanthracene, 9, 10-di (2-vinyloxyethoxy) anthracene, 2-ethyl-9,10-di (2-vinyloxyethoxy) anthracene, 2-tbutyl-9,10-di (2-vinyloxyethoxy) anthracene, 2 , 3-Dimethyl-9,10-di (2-vinyloxyeth
• a preferable lower limit with respect to 100 parts by weight of the photocurable adhesive component or the thermosetting adhesive component is 0.05 parts by weight, and a preferable upper limit is 10 parts by weight.
• a preferable upper limit is 10 parts by weight.
• the content of the photosensitizer is less than 0.05 parts by weight, a sufficient sensitizing effect may not be obtained.
• the content exceeds 10 parts by weight the residue derived from the photosensitizer increases. , Sufficient peeling may not be performed.
• the minimum with more preferable content of the said photosensitizer is 0.1 weight part, and a more preferable upper limit is 5 weight part.
• the adhesive composition may contain fumed silica.
• fumed silica By blending fumed silica, the cohesive strength of the adhesive composition is increased. For this reason, the adhesive composition can be made uniform without separation even when additives having different polarities are mixed with the functional group-containing (meth) acrylic polymer. Further, since the tensile strength is remarkably improved, the adhesive is not broken by the stress at the time of peeling and can be peeled without any adhesive residue even after being subjected to a chemical treatment or a high temperature treatment of 200 ° C. or higher.
• the lower limit of the average particle diameter of the fumed silica is 0.05 ⁇ m, and the upper limit is 3 ⁇ m.
• the preferable lower limit of the average particle diameter of the fumed silica is 0.06 ⁇ m, the preferable upper limit is 2 ⁇ m, the more preferable lower limit is 0.07 ⁇ m, and the more preferable upper limit is 1 ⁇ m.
• the average particle diameter of fumed silica is determined by using any of the laser scattering / diffraction method or the dynamic light scattering method, methyl ethyl ketone, methyl ethyl ketone / toluene (60:40) solution before blending, or the like.
• the particle diameter of fumed silica dispersed in the medium is measured.
• the compounding quantity of 40 weight part or less is preferable with respect to 100 weight part of said photocurable adhesive components or thermosetting adhesive components. With a blending amount of 40 parts by weight or less, the effect of improving the cohesive force to make the adhesive composition uniform and the effect of improving the non-glue residue can be exhibited.
• the minimum of the compounding quantity of the said fumed silica is not specifically limited, In order to fully exhibit the effect of the uniformity of the said adhesive composition, and non-adhesive residue improvement, it is preferable to mix
• the adhesive composition may contain a silicone compound having a functional group capable of crosslinking with the photocurable adhesive component or the thermosetting adhesive component (hereinafter also simply referred to as “silicone compound A”).
• Silicone compounds are excellent in chemical resistance and heat resistance, so that even after chemical treatment or high-temperature treatment at 200 ° C or higher, the adhesive is not burnt. make it easier.
• the silicone compound has a functional group capable of cross-linking with the photocurable adhesive component or the thermosetting adhesive component
• the photocurable adhesive component or the thermosetting adhesive component can be obtained by light irradiation or heating. Since it is chemically reacted and taken into the photocurable adhesive component or the thermosetting adhesive component, the silicone compound does not adhere to and adhere to the adherend. Further, by blending the silicone compound, the affinity for the support plate is improved, and the effect of preventing adhesive residue on the wafer is also exhibited.
• the silicone skeleton of the silicone compound A is not particularly limited, and may be either D-form or DT-form.
• the silicone compound A preferably has the functional group at the side chain or terminal of the silicone skeleton.
• a silicone compound having a D-form silicone skeleton and having a functional group capable of cross-linking with the photocurable adhesive component or the thermosetting adhesive component at the terminal is used, a high initial adhesive force and a chemical solution are obtained. It is more preferable because it is easy to achieve both the treatment and the peeling force after high-temperature treatment at 200 ° C or higher.
• photocurable adhesive component or thermosetting adhesive component is mainly composed of (meth) acrylic acid alkyl ester polymerizable polymer having radical polymerizable unsaturated bond in the molecule.
• a functional group capable of crosslinking with a (meth) acryl group is selected.
• the functional group capable of crosslinking with the (meth) acryl group is a functional group having an unsaturated double bond, and specific examples include a vinyl group, a (meth) acryl group, an allyl group, and a maleimide group. .
• the functional group equivalent of the silicone compound A is not particularly limited, but the preferred lower limit is 1, and the preferred upper limit is 20. When the functional group equivalent is less than 1, the silicone compound A is not sufficiently taken into the photocurable adhesive component when the resulting adhesive composition is cured, and the adherend is contaminated or peelable. In some cases, sufficient adhesion may not be achieved, and when it exceeds 20, sufficient adhesive strength may not be obtained.
• a more preferable upper limit of the functional group equivalent is 10, a more preferable lower limit is 2, and a more preferable upper limit is 6.
• the molecular weight of the silicone compound A is not particularly limited, but a preferred lower limit is 300 and a preferred upper limit is 50000. When the molecular weight is less than 300, chemical resistance and heat resistance of the resulting adhesive composition may be insufficient, and when it exceeds 50,000, the photocurable adhesive component or the thermosetting adhesive component. May be difficult to mix with.
• the more preferable lower limit of the molecular weight is 400, the more preferable upper limit is 10,000, the still more preferable lower limit is 500, and the more preferable upper limit is 5000.
• the method for synthesizing the silicone compound A is not particularly limited.
• a silicone resin having a SiH group and a vinyl compound having a functional group capable of crosslinking with the photocurable adhesive component or the thermosetting adhesive component A method of introducing a functional group capable of crosslinking with the photocurable adhesive component or thermosetting adhesive component into a silicone resin by reacting with a hydrosilylation reaction, a siloxane compound, and the photocurable adhesive component.
• silicone compounds A include, for example, X-22-164, X-22-164AS, X-22-164A, X-22-164B, X-22-164C manufactured by Shin-Etsu Chemical Co., Ltd. , X-22-164E and other silicone compounds having methacrylic groups at both ends, and X-22-174DX, X-22-2426, X-22-2475 manufactured by Shin-Etsu Chemical Co., Ltd.
• a silicone compound having an acrylic group such as EBECRYL350 and EBECRYL1360 manufactured by Daicel Cytec, a silicone compound having an acrylic group such as AC-SQ TA-100 and AC-SQ SI-20 manufactured by Toagosei Co., Ltd. MAC-SQ TM-100, MAC-SQ SI-20, MAC-, manufactured by Toagosei Co., Ltd. Silicone compounds having a methacryl group such as Q HDM like.
• the said silicone compound A has especially high chemical resistance and heat resistance, and since it has high polarity, it is easy to bleed out from an adhesive composition. Therefore, the following general formula (I), general formula (II) ), A silicone compound having a (meth) acryl group in the siloxane skeleton represented by the general formula (III) is preferable.
• X and Y represent an integer of 0 to 1200 (except when X and Y are both 0), and R represents a functional group having an unsaturated double bond.
• silicone compounds having a (meth) acryl group in the siloxane skeleton represented by the above general formula (I), general formula (II), or general formula (III) commercially available products are, for example, manufactured by Daicel Cytec Co., Ltd. EBECRYL350, EBECRYL1360 (both of which R is an acrylic group) and the like.
• the content of the silicone compound A is preferably 0.5 parts by weight and preferably 50 parts by weight with respect to 100 parts by weight of the photocurable adhesive component or the thermosetting adhesive component.
• the adhesive force may not be sufficiently reduced even when irradiated with light or heated, and may not be peeled off from the adherend. May cause contamination of the adherend.
• the more preferable lower limit of the content of the silicone compound A is 1 part by weight, and the more preferable upper limit is 40 parts by weight.
• the adhesive composition suitably contains various polyfunctional compounds that are blended in general adhesives such as isocyanate compounds, melamine compounds, and epoxy compounds as needed for the purpose of adjusting the cohesive force as an adhesive. May be.
• the adhesive composition may contain known additives such as a plasticizer, a resin, a surfactant, a wax, and a fine particle filler.
• the wafer and the support plate may be bonded directly by the adhesive composition, or a double-sided adhesive tape having an adhesive layer made of the adhesive composition on at least one surface. May be used for bonding.
• the double-sided adhesive tape may be a support tape having an adhesive layer on both sides of the base material, or a non-support tape having no base material.
• the base material is, for example, a sheet or mesh made of a transparent resin such as acrylic, olefin, polycarbonate, vinyl chloride, ABS, polyethylene terephthalate (PET), nylon, urethane, or polyimide. And a sheet having a hole-like structure, a sheet having holes, and the like.
• an adhesive curing step is then performed in which the adhesive composition is irradiated or heated to crosslink and cure the curable adhesive component.
• the curable adhesive component that has been crosslinked and cured by irradiation with light or heating has drastically improved chemical resistance, and the adhesive does not dissolve into the chemical even in the step of chemical treatment on the wafer surface.
• the elastic modulus of the cured and cured curable adhesive component is increased, adhesion is not easily increased even at a high temperature, and the peelability in the support plate peeling process is not lowered.
• the adhesive curing step is performed before the wafer processing step, so that the wafer processing step is sufficient even though the wafer processing step performs the chemical treatment, the heat treatment, or the heat generation treatment.
• the support plate can be peeled from the wafer without damaging the wafer or leaving glue remaining after the wafer processing step is completed.
• the photocurable adhesive component that is crosslinked and cured by light irradiation contains a polymer having an unsaturated double bond such as a vinyl group in the side chain and a photopolymerization initiator that is activated at a wavelength of 250 to 800 nm.
• the photocurable adhesive component can be crosslinked and cured by irradiating light having a wavelength of 365 nm or more.
• irradiate with an illuminance of 50 mW or more It is more preferable to irradiate with an illuminance of 50 mW or more.
• thermosetting adhesive component that is crosslinked and cured by heating
• a polymer having an unsaturated double bond such as a vinyl group in the side chain and a thermal polymerization initiator that is activated by heating at about 50 to 150 ° C.
• the thermosetting adhesive component can be crosslinked and cured by heating to a temperature of about 50 to 150 ° C.
• the preferred lower limit of the storage shear modulus at 25 ° C. measured at a continuous temperature rise from ⁇ 50 ° C. to 300 ° C. in the shear mode of dynamic viscoelasticity measurement is 2. 0.0 ⁇ 10 5 Pa, and the preferred upper limit is 10 8 Pa. If the elastic modulus is within this range, the wafer and the support plate will not be unintentionally separated in the wafer processing step, while the wafer is removed when the support plate is removed from the wafer in the support plate peeling step. It is possible to prevent the occurrence of adhesive residue on the surface.
• a more preferable lower limit of the elastic modulus is 1.0 ⁇ 10 6 Pa, and a more preferable upper limit is 5.0 ⁇ 10 7 Pa.
• the surface of the wafer fixed to the support plate is subjected to a chemical solution process, a heat process or a process involving heat generation.
• medical solution process will not be specifically limited if it is a process using an acid, an alkali, or an organic solvent,
• plating processing such as electrolytic plating and electroless plating, hydrofluoric acid, tetramethylammonium hydroxide aqueous solution (TMAH) etc.
• TMAH tetramethylammonium hydroxide aqueous solution
• Examples include a wet etching process, a resist stripping process using N-methyl-2-pyrrolidone, monoethanolamine, DMSO, and a cleaning process using concentrated sulfuric acid, ammonia water, hydrogen peroxide water, and the like.
• Examples of the heat treatment or treatment accompanied by heat generation include sputtering, vapor deposition, etching, chemical vapor deposition (CVD), physical vapor deposition (PVD), resist coating / patterning, and reflow.
• the wafer processing step of the present invention may include a dicing tape attaching step of attaching a dicing tape to the processed surface of the wafer after the processing, prior to a support plate peeling step described later.
• a dicing tape attaching step of attaching a dicing tape to the processed surface of the wafer after the processing, prior to a support plate peeling step described later.
• the wafer processing method of the present invention includes a support plate peeling step for peeling the support plate from the processed wafer. Since the curable adhesive component is crosslinked and cured in the adhesive curing step, peeling of the support plate from the wafer can be performed relatively easily and without adhesive residue.
• the support plate is more easily supported from the wafer by generating a gas from the gas generating agent by stimulating the processed wafer in the support plate peeling step. Can be peeled off.
• gas is emitted from the gas generating agent by irradiating light with a wavelength of 300 nm or less.
• the support plate can be easily peeled off from the wafer.
• light with a wavelength of 254 nm is preferably irradiated with an illuminance of 5 mW or more, more preferably with an illuminance of 10 mW or more, and irradiation with an illuminance of 20 mW or more.
• irradiation with an illuminance of 50 mW or more is particularly preferable.
• the gas when a gas generating agent that generates gas by heating at 200 ° C. or higher is used as the gas generating agent, the gas is generated from the gas generating agent by heating to a temperature of 200 ° C. or higher,
• the support plate can be easily peeled from the wafer.
• a wafer processing method for processing a wafer in a state in which the wafer is fixed to a support plate via an adhesive composition, the wafer processing step for performing a chemical treatment, a heat treatment or a process involving heat generation.
• a wafer processing method that maintains a sufficient adhesive force during the wafer processing step and can peel the support plate from the wafer without damaging the wafer or leaving adhesive residue after the wafer processing step is completed. Can be provided.
• Resins B to L were synthesized in the same manner as in the case of Resin A, except that the (meth) acrylic acid alkyl ester, the functional group-containing monomer, and the functional group-containing unsaturated compound described in Table 1 were used.
• resin I 5 parts by weight of pentaerythritol triacrylate was used in combination as a polyfunctional oligomer to initiate polymerization.
• Example 1 Manufacture of adhesive tape 1 part by weight of a photopolymerization initiator (Esacure One, manufactured by Nippon Sebel Hegner) was mixed with 100 parts by weight of the resin solid content of the obtained ethyl acetate solution of resin A.
• the coating solution was dried by heating at 110 ° C. for 5 minutes. Thereafter, static curing was performed at 40 ° C. for 3 days to obtain an adhesive tape.
• the adhesive component was cross-linked and cured by irradiating with ultraviolet rays of 365 nm for 2 minutes while adjusting the illuminance so that the irradiation intensity on the tape surface was 80 mW / cm 2 .
• the cured sample for evaluation was measured at a shear mode angular frequency of 10 Hz for dynamic viscoelasticity measurement, and the storage elastic modulus at 25 ° C of the measured value continuously raised from -50 ° C to 300 ° C. Got.
• the obtained adhesive tape was cut into a circle having a diameter of 20 cm and attached to a silicon wafer having a diameter of 20 cm and a thickness of about 750 ⁇ m in a vacuum.
• a quartz glass plate having a diameter of 20 cm and a thickness of 1 mm was attached to the surface opposite to the surface attached to the silicon wafer in a vacuum to obtain a laminate.
• the wafer side of the obtained laminate was ground and polished to a thickness of 50 ⁇ m.
• the obtained adhesive tape was cut into a circle having a diameter of 20 cm, and attached to a silicon wafer having a diameter of 20 cm and a thickness of about 750 ⁇ m in a vacuum.
• a quartz glass plate having a diameter of 20 cm and a thickness of 1 mm was attached to the surface opposite to the surface attached to the silicon wafer in a vacuum to obtain a laminate.
• the wafer side of the obtained laminate was ground and polished to a thickness of 50 ⁇ m.
• Example 2 Examples 2 to 25, Comparative Example 1
• silicone compound having a (meth) acrylic group manufactured by Daicel Cytec, EBECRYL350 (acrylic equivalent 2), EBECRYL1360 (acrylic equivalent) 6
• plasticizers manufactured by Negami Kogyo Co., Ltd., UN-2600, UN-5500, UN-7700
• I got a tape Evaluation similar to Example 1 was performed using the obtained adhesive tape.
• Comparative Example 1 in the chemical resistance, heat resistance evaluation and adhesive residue evaluation, the adhesive component was not crosslinked and cured by irradiating with ultraviolet rays. The results are shown in Table 2.
• Example 26 (1) Manufacture of adhesive tape For 100 parts by weight of resin solid content of the obtained resin A in ethyl acetate solution, 1 part by weight of photopolymerization initiator (Esacure One, manufactured by Nippon Sebel Hegner), silicone compound (EBECRYL350, Daicel Cytec) 5 parts by weight), 20 parts by weight of a plasticizer (UN-5500, manufactured by Negami Kogyo Co., Ltd.), and 10 parts by weight of 5-phenyl-1H-tetrazole as a gas generating agent were mixed.
• photopolymerization initiator Esacure One, manufactured by Nippon Sebel Hegner
• silicone compound EBECRYL350, Daicel Cytec
• a plasticizer manufactured by Negami Kogyo Co., Ltd.
• the coating solution was dried by heating at 110 ° C. for 5 minutes. Thereafter, static curing was performed at 40 ° C. for 3 days to obtain an adhesive tape.
• the adhesive component was cross-linked and cured by irradiating with ultraviolet rays of 365 nm for 2 minutes while adjusting the illuminance so that the irradiation intensity on the tape surface was 80 mW / cm 2 .
• the cured sample for evaluation was measured at a shear mode angular frequency of 10 Hz for dynamic viscoelasticity measurement, and the storage elastic modulus at 25 ° C of the measured value continuously raised from -50 ° C to 300 ° C. Got.
• the obtained adhesive tape was cut into a circle having a diameter of 20 cm and attached to a silicon wafer having a diameter of 20 cm and a thickness of about 750 ⁇ m in a vacuum.
• a quartz glass plate having a diameter of 20 cm and a thickness of 1 mm was attached to the surface opposite to the surface attached to the silicon wafer in a vacuum to obtain a laminate.
• the wafer side of the obtained laminate was ground and polished to a thickness of 50 ⁇ m.
• the obtained adhesive tape was cut into a circle having a diameter of 20 cm, and attached to a silicon wafer having a diameter of 20 cm and a thickness of about 750 ⁇ m in a vacuum.
• a quartz glass plate having a diameter of 20 cm and a thickness of 1 mm was attached to the surface opposite to the surface attached to the silicon wafer in a vacuum to obtain a laminate.
• the wafer side of the obtained laminate was ground and polished to a thickness of 50 ⁇ m.
• Examples 27 to 45 Adhesive composition and adhesive tape were obtained in the same manner as in Example 26 except that the type of resin and the type and amount of gas generating agent blended in the adhesive composition were as shown in Table 3, and the obtained adhesive was obtained. Evaluation similar to Example 26 was performed using a tape. In Comparative Example 2, in the chemical resistance, heat resistance evaluation and adhesive residue evaluation, the adhesive component was not crosslinked and cured by irradiating with ultraviolet rays.
• Example 46 (1) Manufacture of adhesive tape 1 part by weight of a thermal polymerization initiator (Perhexyl O, manufactured by NOF Corporation) was mixed with 100 parts by weight of resin solid content of the obtained ethyl acetate solution of resin A. A doctor knife with an ethyl acetate solution of the obtained adhesive composition on the corona-treated surface of a transparent polyethylene naphthalate film having a thickness of 50 ⁇ m and subjected to corona treatment on one side so that the thickness of the dry film becomes 30 ⁇ m. The coating solution was dried by heating at 80 ° C. for 5 minutes. Thereafter, static curing was performed at 40 ° C. for 3 days to obtain an adhesive tape.
• a thermal polymerization initiator Perhexyl O, manufactured by NOF Corporation
• an ethyl acetate solution of the adhesive composition is subjected to corona treatment on one side and is a transparent polyethylenena having a thickness of 50 ⁇ m.
• corona treatment On the corona-treated surface of the phthalate film, coating was performed with a doctor knife so that the thickness of the dried film was 500 ⁇ m, and the coating solution was dried by heating at 110 ° C. for 5 minutes. The incubator was performed.
• the obtained adhesive tape was cut into a rectangular shape having a length of 0.6 cm and a width of 1.0 cm, and this was used as a sample for evaluation. Next, heat treatment was performed at 100 ° C.
• the cured sample for evaluation was measured at a shear mode angular frequency of 10 Hz for dynamic viscoelasticity measurement, and the storage elastic modulus at 25 ° C of the measured value continuously raised from -50 ° C to 300 ° C. Got.
• the obtained adhesive tape was cut into a circle having a diameter of 20 cm and attached to a silicon wafer having a diameter of 20 cm and a thickness of about 750 ⁇ m in a vacuum.
• a quartz glass plate having a diameter of 20 cm and a thickness of 1 mm was attached to the surface opposite to the surface attached to the silicon wafer in a vacuum to obtain a laminate.
• the wafer side of the obtained laminate was ground and polished to a thickness of 50 ⁇ m.
• heat treatment was performed at 100 ° C. for 1 hour to crosslink and cure the adhesive component.
• the obtained adhesive tape was cut into a circle having a diameter of 20 cm and adhered to a silicon wafer having a diameter of 20 cm and a thickness of about 750 ⁇ m in a vacuum.
• a quartz glass plate having a diameter of 20 cm and a thickness of 1 mm was attached to the surface opposite to the surface attached to the silicon wafer in a vacuum to obtain a laminate.
• the wafer side of the obtained laminate was ground and polished to a thickness of 50 ⁇ m.
• heat treatment was performed at 100 ° C. for 1 hour to crosslink and cure the adhesive component.
• the laminate after the adhesive component was crosslinked and cured was subjected to heat treatment at 200 ° C. for 2 hours.
• Example 47 to 70 Comparative Example 3
• a silicone compound having a (meth) acrylic group manufactured by Daicel Cytec, EBECRYL350 (acrylic equivalent 2), EBECRYL1360 (acrylic equivalent) 6
• an adhesive composition and an adhesive tape in the same manner as in Example 46 except that a plasticizer (UN-2600, UN-5500, UN-7700 manufactured by Negami Kogyo Co., Ltd.) was added as shown in Table 4.
• a plasticizer UN-2600, UN-5500, UN-7700 manufactured by Negami Kogyo Co., Ltd.
• Comparative Example 3 in the chemical resistance, heat resistance evaluation, and adhesive residue evaluation, heating was not performed to crosslink and cure the adhesive component. The results are shown in Table 4.
• Example 71 (1) Manufacture of adhesive tape For 100 parts by weight of resin solid content of the obtained resin A in ethyl acetate solution, 1 part by weight of thermal polymerization initiator (Perhexyl O, manufactured by NOF Corporation), silicone compound (EBECRYL350, Daicel) 5 parts by weight of Cytec Co., Ltd., 20 parts by weight of plasticizer (UN-5500, Negami Kogyo Co., Ltd.) and 10 parts by weight of 5-phenyl-1H-tetrazole as a gas generating agent were mixed.
• thermal polymerization initiator Perhexyl O, manufactured by NOF Corporation
• silicone compound EBECRYL350, Daicel
• plasticizer Un-5500, Negami Kogyo Co., Ltd.
• the coating solution was dried by heating at 80 ° C. for 5 minutes. Thereafter, static curing was performed at 40 ° C. for 3 days to obtain an adhesive tape.
• an ethyl acetate solution of the adhesive composition is subjected to corona treatment on one side and is a transparent polyethylenena having a thickness of 50 ⁇ m.
• corona treatment On the corona-treated surface of the phthalate film, coating was performed with a doctor knife so that the thickness of the dried film was 500 ⁇ m, and the coating solution was dried by heating at 110 ° C. for 5 minutes. The incubator was performed.
• the obtained adhesive tape was cut into a rectangular shape having a length of 0.6 cm and a width of 1.0 cm, and this was used as a sample for evaluation. Next, heat treatment was performed at 100 ° C.
• the cured sample for evaluation was measured at a shear mode angular frequency of 10 Hz for dynamic viscoelasticity measurement, and the storage elastic modulus at 25 ° C of the measured value continuously raised from -50 ° C to 300 ° C. Got.
• the obtained adhesive tape was cut into a circle having a diameter of 20 cm and attached to a silicon wafer having a diameter of 20 cm and a thickness of about 750 ⁇ m in a vacuum.
• a quartz glass plate having a diameter of 20 cm and a thickness of 1 mm was attached to the surface opposite to the surface attached to the silicon wafer in a vacuum to obtain a laminate.
• the wafer side of the obtained laminate was ground and polished to a thickness of 50 ⁇ m.
• heat treatment was performed at 100 ° C. for 1 hour to crosslink and cure the adhesive component.
• the obtained adhesive tape was cut into a circle having a diameter of 20 cm and adhered to a silicon wafer having a diameter of 20 cm and a thickness of about 750 ⁇ m in a vacuum.
• a quartz glass plate having a diameter of 20 cm and a thickness of 1 mm was attached to the surface opposite to the surface attached to the silicon wafer in a vacuum to obtain a laminate.
• the wafer side of the obtained laminate was ground and polished to a thickness of 50 ⁇ m.
• heat treatment was performed at 100 ° C. for 1 hour to crosslink and cure the adhesive component.
• the laminate after the adhesive component was crosslinked and cured was subjected to heat treatment at 200 ° C. for 2 hours.
• a dicing tape is attached to the surface of the silicon wafer that is not bonded to the adhesive tape, adsorbed and fixed, and light with an illuminance of 254 nm and an intensity of 70 mW / cm 2 is applied from the Tempax glass side using an ultra-high pressure mercury lamp. Irradiated for 150 seconds. Thereafter, the quartz glass plate and the adhesive tape were peeled off. When the surface of the silicon wafer from which the adhesive tape has been peeled is visually observed, “ ⁇ ” indicates that no adhesive residue is present, and “ ⁇ ” indicates that the adhesive residue is less than 5% of the total area. The case where it was 5% or more of the entire remaining area was evaluated as “x”.
• Example 72 to 90 Adhesive composition and adhesive tape were obtained in the same manner as in Example 71 except that the types of resin and the types and amounts of the gas generating agents blended in the adhesive composition were as shown in Table 5. Evaluation similar to Example 71 was performed using a tape. In Comparative Example 4, in the chemical resistance, heat resistance evaluation, and adhesive residue evaluation, heating was not performed to crosslink and cure the adhesive component.
• Example 91 to 93 Comparative Example 5
• fumed silica in which fumed silica was further dispersed in methyl ethyl ketone using a homogenizer, and the average particle size was adjusted to 0.1 ⁇ m.
• Table shows silica dispersion solution (Tokuyama, Leolosil MT-10), silicone compound having (meth) acrylic group (Daicel Cytec, EBECRYL350 (acrylic equivalent 2)), plasticizer (UN-5500, manufactured by Negami Industrial Co., Ltd.)
• An adhesive composition and an adhesive tape were obtained in the same manner as in Example 1 except for adding as shown in FIG. Evaluation similar to Example 1 was performed using the obtained adhesive tape.
• Comparative Example 5 in the chemical resistance, heat resistance evaluation and adhesive residue evaluation, the adhesive component was not crosslinked and cured by irradiating with ultraviolet rays. The results are shown in Table 6.
• a wafer processing method for processing a wafer in a state in which the wafer is fixed to a support plate via an adhesive composition, the wafer processing step for performing a chemical treatment, a heat treatment or a process involving heat generation.
• a wafer processing method that maintains a sufficient adhesive force during the wafer processing step and can peel the support plate from the wafer without damaging the wafer or leaving adhesive residue after the wafer processing step is completed. Can be provided.

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• 2013
  • 2013-08-06 US US14/420,450 patent/US9855734B2/en active Active
  • 2013-08-06 CN CN201380042206.4A patent/CN104520974B/zh active Active
  • 2013-08-06 WO PCT/JP2013/071208 patent/WO2014024861A1/ja not_active Ceased
  • 2013-08-06 JP JP2013538746A patent/JP5639280B2/ja active Active
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  • 2013-08-07 TW TW102128236A patent/TWI539535B/zh active
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