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
• • 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
  • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
  • C09J133/04—Homopolymers or copolymers of esters
• • 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
  • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
  • C09J133/04—Homopolymers or copolymers of esters
  • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
  • C09J133/08—Homopolymers or copolymers of acrylic acid esters
• • 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
  • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
  • C09J133/04—Homopolymers or copolymers of esters
  • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
  • C09J133/10—Homopolymers or copolymers of methacrylic acid esters
• • 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
  • C09J7/00—Adhesives in the form of films or foils
  • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
  • C09J7/38—Pressure-sensitive adhesives [PSA]
• • 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
  • H10P52/00—Grinding, lapping or polishing of wafers, substrates or parts of devices
• • 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
• • 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
  • H10P95/00—Generic processes or apparatus for manufacture or treatments not covered by the other groups of this subclass

Definitions

• the present invention provides a protective tape that has excellent heat resistance and can reliably generate gas even when light is irradiated through a substrate to easily peel off an adherend such as a semiconductor device, and the protective tape. and a semiconductor device manufacturing method using the semiconductor protective tape.
• adhesive tapes are used to facilitate handling during processing of wafers and semiconductor chips and to prevent breakage. For example, when 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, grinding is performed after bonding an adhesive tape to the thick-film wafer.
• 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 gas upon stimulation such as an azo compound. It is In the wafer processing method described in Patent Document 1, first, the wafer is fixed to a support 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 support, and at least a portion of the tape is peeled off by the pressure.
• the wafer can be peeled off without damaging the wafer and leaving no adhesive residue.
• a process of subjecting the surface of a wafer to chemical treatment, heat treatment, or heat-generating treatment has come to be performed.
• the thin film wafer obtained by grinding is bumped, bumps are formed on the back surface, and reflow is performed during three-dimensional stacking.
• a pressure-sensitive adhesive containing a gas generating agent is used on a support such as glass.
• Each treatment is performed after laminating the layers and laminating a semiconductor device such as a wafer to the adhesive layer on the opposite side.
• ultraviolet light or the like is irradiated from the support side to generate gas from the gas generating agent to separate the support and the double-sided adhesive tape, and then the double-sided tape and the semiconductor device are separated.
• the conventional manufacturing process requires two peeling steps, so in order to reduce the number of steps, the adhesive layer containing the gas generating agent and the semiconductor device are laminated together, that is, the double-sided adhesive tape is conventionally used. On the contrary, it is considered that the semiconductor device is peeled off in one peeling process by sticking.
• the ultraviolet rays or the like irradiated to generate the gas cause the adhesive on the opposite side of the support. There is a problem that the gas is not sufficiently generated because it is absorbed while passing through the agent layer and the base material. Moreover, even when a sufficient amount of gas is generated, the heat resistance of the gas generating agent is insufficient, and there is also the problem that unintended peeling occurs during high-temperature processing of semiconductor devices.
• the present invention provides a protective tape that has excellent heat resistance and can reliably generate gas even when light is irradiated through a substrate to easily peel off an adherend such as a semiconductor device, and the protective tape. and a method for manufacturing a semiconductor device using the semiconductor protective tape.
• the present invention is a protective tape having a substrate, an adhesive layer A having an adhesive layer containing a gas generating agent on one surface of the substrate, and an adhesive layer B on the other surface,
• the pressure-sensitive adhesive layer containing the gas generating agent contains a photocurable pressure-sensitive adhesive, and the gas generating agent has a molar absorption coefficient of 10 L/( mol cm) or more, and a 5% weight loss temperature (T d5 ) of 200° C. or more measured at a temperature increase rate of 5° C./min using a simultaneous differential thermogravimetry device. .
• T d5 5% weight loss temperature
• the protective tape of the present invention comprises a substrate, an adhesive layer A having an adhesive layer containing a gas generating agent on one side of the substrate, and an adhesive layer B on the other side of the substrate.
• an adhesive layer containing a gas-generating agent on at least one surface of the double-sided adhesive tape having a substrate, by irradiating with ultraviolet rays or the like after the semiconductor device is processed, a gas is generated and the semiconductor device can be easily manufactured. can be peeled off.
• the pressure-sensitive adhesive layer A refers to the entire layer laminated on the surface of the substrate opposite to the surface on which the pressure-sensitive adhesive layer B is laminated, and does not contain an adhesive component. Also includes layers. Layers contained in the adhesive layer A other than the adhesive layer containing the gas generating agent include, for example, an easily peelable layer and a barrier layer, which will be described later.
• the pressure-sensitive adhesive layer containing the gas generating agent contains a photocurable pressure-sensitive adhesive.
• the pressure-sensitive adhesive layer containing the gas generating agent contains a photocurable pressure-sensitive adhesive
• the pressure-sensitive adhesive layer containing the gas generating agent can be cured before processing the semiconductor device, so that it can be cured by processing the semiconductor device such as high temperature processing. It can suppress hyperadhesion. As a result, the semiconductor device can be easily peeled off after finishing the processing.
• the photocurable pressure-sensitive adhesive include a photocurable pressure-sensitive adhesive containing a polymerizable polymer as a main component and a photopolymerization initiator as a polymerization initiator.
• the polymerizable polymer includes, for example, a (meth)acrylic polymer having a functional group in the molecule (hereinafter referred to as a (meth)acrylic polymer containing a functional group) and a functional group in the molecule that reacts with the functional group. and a compound having a radically polymerizable unsaturated bond (hereinafter referred to as a functional group-containing unsaturated compound).
• (meth)acrylate means acrylate or methacrylate
• (meth)acryl means acrylic or methacrylic.
• the above functional group-containing (meth)acrylic polymer is a polymer having adhesiveness at room temperature, as in the case of general (meth)acrylic polymers, the number of carbon atoms in the alkyl group is usually in the range of 2 to 18 acrylic
• an acid alkyl ester and/or a methacrylic acid alkyl ester as a main monomer and copolymerizing this with a functional group-containing monomer and, if necessary, another monomer for modification that can be copolymerized with them by a conventional method. It is what you get.
• 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 carboxyl group-containing monomers such as acrylic acid and methacrylic acid, hydroxyl group-containing monomers such as hydroxyethyl acrylate and hydroxyethyl methacrylate, and epoxy compounds such as glycidyl acrylate and glycidyl methacrylate.
• Examples include group-containing monomers, isocyanate group-containing monomers such as isocyanate ethyl acrylate and isocyanate ethyl methacrylate, and amino group-containing monomers such as aminoethyl acrylate and aminoethyl methacrylate.
• Examples of other copolymerizable modifying monomers include various monomers used in general (meth)acrylic polymers such as vinyl acetate, acrylonitrile, and styrene.
• the same functional group-containing monomer as described above is used according to the functional group of the functional group-containing (meth)acrylic polymer.
• 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 photopolymerization initiator examples include those activated by irradiation with light having a wavelength of 250 to 800 nm.
• the photocurable pressure-sensitive adhesive may contain a photopolymerization initiator having a molar absorption coefficient of 1 or more at 405 nm because it is easy to adjust so as not to overlap with the wavelength that activates the gas generating agent. More preferably, it contains a photopolymerization initiator having a molar extinction coefficient of 200 L/(mol ⁇ cm) or more at 405 nm.
• the upper limit of the molar extinction coefficient at 405 nm of the photopolymerization initiator is not particularly limited, it is, for example, 2000 L/(mol ⁇ cm) and 1500 L/(mol ⁇ cm).
• photopolymerization initiators include acetophenone derivative compounds such as methoxyacetophenone, benzoin ether compounds such as benzoin propyl ether and benzoin isobutyl ether, ketal derivative compounds such as benzyl dimethyl ketal and acetophenone diethyl ketal, Phosphine oxide derivative compounds, bis( ⁇ 5-cyclopentadienyl) titanocene derivative compounds, benzophenone, Michler's ketone, chlorothioxanthone, todecylthioxanthone, dimethylthioxanthone, diethylthioxanthone, ⁇ -hydroxycyclohexylphenyl ketone, 2-hydroxymethylphenylpropane and other
• the photocurable pressure-sensitive adhesive preferably contains a radically polymerizable polyfunctional oligomer or monomer.
• a radically polymerizable polyfunctional oligomer or monomer By containing a radically polymerizable polyfunctional oligomer or monomer, the photocurability is further improved.
• the polyfunctional oligomer or monomer preferably has a molecular weight of 10,000 or less, and more preferably has a molecular weight of 5,000 so that the photocurable pressure-sensitive adhesive can be efficiently formed into a three-dimensional network by heating or light irradiation. and 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 a methacrylate similar to the above. and the like.
• These polyfunctional oligomers or monomers may be used alone or in combination of two or more.
• the gas generating agent is not particularly limited as long as it satisfies the ranges of the molar extinction coefficient and the 5% weight loss temperature (T d5 ) described later, but since it easily satisfies these ranges and has excellent heat resistance, Azo compounds are preferred.
• the tetrazole compound or the azo compound is more preferably a tetrazole compound represented by the following formula (1) because it easily satisfies the ranges of the molar extinction coefficient and the 5% weight loss temperature (T d5 ) described later.
• R 1 and R 2 represents a nitrogen- or oxygen-containing aryl group or a nitrogen- or oxygen-containing heterocyclic group.
• the other is not particularly limited, and may be hydrogen, a hydrocarbon group, an aromatic group, or the like. , preferably hydrogen.
• the aryl group include a phenyl group and a naphthyl group.
• the aryl group containing nitrogen or oxygen, or the heterocyclic group containing nitrogen or oxygen easily satisfies the molar extinction coefficient and the 5% weight loss temperature (T d5 ) described later, so a hydroxyl group, an alkoxy group, At least one functional group selected from the group consisting of a phenyl group having a carbonyl group, a cyano group, an amino group, a thiol group, a vinyl group, an aldehyde group, an aromatic group or a nitro group, and a pyridine group, more preferably An aryl group having a nitro group or an amino group, or a pyridine group is more preferable.
• Examples of the gas generating agent include 5-(4-nitrophenyl)-1H-tetrazole, 2-(1H-tetrazol-5-yl)pyridine, 4-(1H-tetrazol-1-yl)-1,2-benzene Diamine, 5-(3-phenoxyphenyl)-1H-tetrazole, azodicarbonamide and the like can be preferably used, and 5-(4-nitrophenyl)-1H-tetrazole, 2-(1H-tetrazol-5-yl ) pyridine, 4-(1H-tetrazol-1-yl)-1,2-benzenediamine, and 5-(3-phenoxyphenyl)-1H-tetrazole can be used more preferably.
• the gas generating agent has a molar absorption coefficient (hereinafter simply referred to as molar absorption coefficient) of 10 L/(mol ⁇ cm) or more at any wavelength at which the light transmittance of the base material is 50% or more.
• the molar absorption coefficient of the gas generating agent is within the above range, that is, the wavelength of light for causing the gas generating agent to generate gas is a wavelength that sufficiently penetrates the base material, so that the pressure-sensitive adhesive layer A side can be used as a semiconductor device. , the pressure-sensitive adhesive layer B side is attached to the support, and light is irradiated from the support side, a sufficient amount of light can reach the gas generating agent.
• the wavelength at which the light transmittance of the base material is 50% or more varies depending on the type of base material.
• the wavelength at which the light transmittance is 50% or more is 310 to 320 nm or more.
• the molar extinction coefficient of the gas generating agent should be within the above range in any one of these wavelength regions. The molar extinction coefficient can be adjusted by a combination of the type of gas generating agent and the base material.
• the molar extinction coefficient is preferably 45 L/(mol ⁇ cm) or more, more preferably 50 L/(mol ⁇ cm) or more, and even more preferably 80 L/(mol ⁇ cm) or more.
• the upper limit of the molar absorbance is not particularly limited, and the higher the better.
• any wavelength at which the light transmittance of the substrate becomes 50% or more preferably does not overlap with the wavelength for activating the photopolymerization initiator. By doing so, it becomes easier to adjust so that the wavelength for activating the gas generating agent and the wavelength for activating the photopolymerization initiator do not overlap.
• the wavelength region where the light transmittance of the substrate is 50% or more it is preferable to have a wavelength that does not overlap with the wavelength that activates the photopolymerization initiator in the wavelength region of 405 nm or less, and 380 nm. It is more preferable to have it in the following wavelength regions.
• the molar extinction coefficient can be measured by the following method. First, only the base material is measured using a spectrophotometer (for example, U-3000 manufactured by Hitachi Ltd. or equivalent) to specify the wavelength range in which the light transmittance is 50% or more. Next, the gas generating agent is weighed so that it becomes 1 to 3 ⁇ 10 -4 mol / L, and the solvent (solvent in which the gas generating agent is soluble: acetonitrile, dimethyl sulfoxide, methyl alcohol and sodium hydroxide aqueous solution mixed solvent, water etc.). After that, using a spectrophotometer (for example, U-3000 manufactured by Hitachi Ltd.
• the gas generating agent preferably has a molar extinction coefficient of less than 100 L/(mol ⁇ cm) at 405 nm.
• Light with a wavelength of 405 nm is a widely used light for activating common photoinitiators.
• the molar absorption coefficient at 405 nm of the gas generating agent is more preferably less than 50 L/(mol ⁇ cm), still more preferably less than 10 L/(mol ⁇ cm).
• the lower limit of the molar extinction coefficient at 405 nm of the gas generating agent is not particularly limited.
• the molar extinction coefficient at 405 nm of the gas generating agent can be adjusted according to the type of gas generating agent.
• the molar extinction coefficient of the gas generating agent at 405 nm can be measured in the same manner as the molar extinction coefficient.
• the gas generating agent has a 5% weight loss temperature (T d5 ) of 200° C. or higher measured at a temperature elevation rate of 5° C./min using a simultaneous differential thermal thermogravimetric measurement device.
• T d5 5% weight loss temperature
• the 5% weight loss temperature is preferably 210° C. or higher, more preferably 220° C. or higher.
• the upper limit of the 5% weight loss temperature is not particularly limited, and the higher the temperature, the better.
• the 5% weight loss temperature can be adjusted depending on the type of gas generating agent.
• the 5% weight loss temperature can be measured by the following method. 5 to 10 mg of the gas generating agent is weighed into an aluminum pan of a thermobalance (TG/DTA6200 or its equivalent manufactured by SII), in an air flow (flow rate of 200 mL/min) under the conditions of a temperature increase rate of 5°C/min. It can be obtained by heating from room temperature (30° C.) to 400° C. and measuring the temperature when the weight is reduced by 5%.
• TG/DTA6200 or its equivalent manufactured by SII thermobalance
• the content of the gas generating agent is not particularly limited, it is preferably 5 parts by weight or more and 50 parts by weight or less with respect to 100 parts by weight of the polymerizable polymer.
• the content of the gas generating agent is more preferably 15 parts by weight or more, and more preferably 45 parts by weight or less.
• the pressure-sensitive adhesive layer containing the gas generating agent may further contain a photosensitizer. Since the photosensitizer has the effect of amplifying the stimulation of the gas generating agent by light, the gas can be released with less light irradiation. In addition, gas can be emitted by light in a wider wavelength range.
• the photosensitizer is not particularly limited as long as it has excellent heat resistance.
• the photosensitizer include thioxanthone compounds such as 2,4-diethylthioxanthone, anthracene compounds such as dibutylanthracene and dipropylanthracene, and 2,2-dimethoxy-1,2-diphenylethan-1-one.
• benzophenone compounds such as diphenyl sulfide.
• the wavelength region of light activated by the photosensitizer overlaps with the wavelength region of light activated by the gas generating agent. Since such a photosensitizer has the effect of further amplifying the stimulation of the gas generating agent by light, the gas can be more sufficiently released even with less light irradiation. Further, in the photosensitizer, it is more preferable that the wavelength region of light activated by the photosensitizer and the wavelength region of light activated by the photopolymerization initiator do not overlap. Such a photosensitizer can further suppress the generation of unintended gas due to light irradiation for curing the pressure-sensitive adhesive layer containing the gas generating agent.
• the pressure-sensitive adhesive layer containing the gas generating agent may contain a silicone compound. Since the silicone compound has excellent heat resistance, it prevents the adhesive from burning even after a treatment involving heating at 200° C. or higher, and bleeds out to the adherend interface during peeling to facilitate peeling.
• the silicone compound is preferably a silicone compound having a functional group crosslinkable with the polymerizable polymer. When the silicone compound has a functional group that can be crosslinked with the polymerizable polymer, the silicone compound chemically reacts with the polymerizable polymer and is incorporated into the photocurable pressure-sensitive adhesive by light irradiation. Silicone compounds will not adhere to and contaminate the surface. In addition, the addition of a silicone compound exhibits the effect of preventing adhesive residue on semiconductor devices.
• the pressure-sensitive adhesive layer containing the above-mentioned gas-generating agent may optionally contain various cross-linking agents such as isocyanate compounds, melamine compounds, and epoxy compounds that are blended in general pressure-sensitive adhesives for the purpose of adjusting the cohesive force of the pressure-sensitive adhesive. It may be contained as appropriate.
• the pressure-sensitive adhesive layer A may contain known additives such as inorganic fillers such as fumed silica, plasticizers, resins, surfactants, waxes and fine particle fillers.
• the pressure-sensitive adhesive layer containing the gas generating agent preferably has a shear storage modulus G′ of 1.0 ⁇ 10 2 Pa or more and 2.0 ⁇ 10 5 Pa or less before curing.
• G′ shear storage modulus
• the protective tape can be attached to the adherend more reliably.
• the pressure-sensitive adhesive layer containing the gas generating agent preferably has a shear storage elastic modulus G′ of 2.0 ⁇ 10 5 Pa or more and 1.0 ⁇ 10 9 Pa or less after curing.
• G′ a shear storage elastic modulus
• the shear storage elastic modulus of the adhesive layer containing the gas generating agent can be measured by the following method. First, a measurement sample consisting of only an adhesive layer containing a gas generating agent is produced. For the obtained measurement sample, using a viscoelastic spectrometer (manufactured by IT Keisoku Co., Ltd., DVA-200, or equivalent), under the conditions of 5 ° C./min and 1 Hz in the slow heating shear deformation mode, -50 The storage elastic modulus at 23°C is measured when the dynamic viscoelasticity spectrum is measured from °C to 200°C. Let this be the storage elastic modulus G' before hardening.
• a viscoelastic spectrometer manufactured by IT Keisoku Co., Ltd., DVA-200, or equivalent
• Another measurement sample was irradiated with ultraviolet rays of 365 nm using a high-pressure mercury ultraviolet irradiation device (GWSM-300R, manufactured by Takatori Co., Ltd., or equivalent) so that the cumulative irradiation amount was 3000 mJ / cm 2 to generate gas.
• the adhesive layer containing the agent is cured.
• the irradiation intensity at this time is not particularly limited as long as the pressure-sensitive adhesive layer containing the gas generating agent can be completely cured, but is preferably 50 to 100 mW/cm 2 .
• the storage elastic modulus G′ before curing is measured in the same manner, and the obtained storage elastic modulus is taken as the storage elastic modulus G′ after curing.
• the thickness of the pressure-sensitive adhesive layer containing the gas generating agent is not particularly limited, it is preferably 10 ⁇ m or more and 200 ⁇ m or less. When the pressure-sensitive adhesive layer containing the gas generating agent has a thickness within this range, it can be adhered to the semiconductor device with sufficient adhesive strength, and the semiconductor device can be protected during processing.
• the thickness of the pressure-sensitive adhesive layer containing the gas generating agent is more preferably 20 ⁇ m or more, and more preferably 150 ⁇ m or less.
• the pressure-sensitive adhesive layer A preferably has an easily peelable layer containing a photocurable pressure-sensitive adhesive on the side opposite to the base material. That is, it is preferable to have an easily peelable layer on the surface of the pressure-sensitive adhesive layer containing the gas generating agent on the side opposite to the substrate side.
• an easy peeling layer on the surface of the adhesive layer A on the adherend side, that is, on the surface on the adherend side, the adherend can be more easily peeled off.
• the photocurable pressure-sensitive adhesive constituting the easy peeling layer is not particularly limited, and may be the same as or different from the photocurable pressure-sensitive adhesive contained in the pressure-sensitive adhesive layer containing the gas generating agent. good too.
• the thickness of the easy peeling layer is not particularly limited, it is preferably 5 ⁇ m or more and 30 ⁇ m or less. By setting the thickness of the easily peelable layer within the above range, the deformation of the pressure-sensitive adhesive layer containing the gas generating agent due to gas generation can be easily propagated, and the semiconductor device can be more easily peeled off.
• the thickness of the easily peelable layer is more preferably 10 ⁇ m or more, and more preferably 20 ⁇ m or less.
• the protective tape of the present invention further has a gas barrier layer, and the pressure-sensitive adhesive layer B, the base material, the pressure-sensitive adhesive layer containing the gas generating agent, the gas barrier layer, and the easily peelable layer are preferably laminated in this order.
• the pressure-sensitive adhesive layer A further has a gas barrier layer.
• the gas barrier layer is not particularly limited, it preferably has properties that make it difficult for the gas generated from the pressure-sensitive adhesive layer containing the gas generating agent to permeate. /m 2 ⁇ 24 h or less is more preferable.
• Water vapor transmission rate is within the above range, gas permeation is suppressed, and even if the amount of generated gas is small, deformation occurs efficiently. Further, the deformation is maintained even after the elapse of time after the generation of gas, and the film can be easily peeled off.
• Water vapor permeability can be measured using a water vapor permeability measuring device (Swiss Lissi L80-4000J or equivalent) in an atmosphere of 40°C and 90% humidity in accordance with JIS K7129A. can.
• the gas barrier layer preferably has a tensile elastic modulus E′ at 100° C. of 1.0 ⁇ 10 9 Pa or more and 1.0 ⁇ 10 10 Pa or less.
• a more preferable lower limit of the tensile modulus E′ at 100° C. is 1.6 ⁇ 10 9 Pa
• a more preferable upper limit is 4.5 ⁇ 10 9 Pa
• a still more preferable lower limit is 1.8 ⁇ 10 9 Pa, still more preferable.
• the upper limit is 4.0 ⁇ 10 9 Pa.
• the tensile elastic modulus E' of the gas barrier layer at 100°C can be measured by the following method.
• the base material is immersed in liquid nitrogen and cooled to -50 ° C., then using a viscoelastic spectrometer (DVA-200, manufactured by IT Instrument Control Co., Ltd., or its equivalent), constant rate heating tensile mode, The temperature is raised to 300° C. under the conditions of a heating rate of 10° C./min, a frequency of 10 Hz, and a static/power ratio of 1.5, and the storage elastic modulus is measured.
• the storage elastic modulus at 100 degreeC be the said tensile elastic modulus from the result of the obtained storage elastic modulus.
• the gas barrier layer has a plurality of layers, it means the tensile modulus of the entire gas barrier layer.
• the material constituting the gas barrier layer is not particularly limited. Since it may be applied, those having heat resistance are preferable.
• heat-resistant substrates include polyesters such as polyethylene terephthalate and polyethylene naphthalate, polyacetals, polyamides, polycarbonates, polyphenylene ethers, polybutylene terephthalates, ultra-high molecular weight polyethylenes, syndiotactic polystyrenes, polyarylates, and polysulfones. , polyether sulfone, polyphenylene sulfide, polyether ether ketone, polyimide, polyether imide, fluororesin, and liquid crystal polymer.
• polyester resins, polyether resins and polyimide resins are preferable, and polyethylene terephthalate, polyethylene naphthalate, polyether ether ketone (PEEK) and polyimide are more preferable from the viewpoint of heat resistance and light transmittance.
• PEEK polyether ether ketone
• the gas barrier layer has an inorganic layer.
• the inorganic layer is preferably provided on the surface facing the adhesive layer containing the gas generating agent.
• the material constituting the inorganic layer is not particularly limited, but examples include silicon, hydrogenated carbon, aluminum, magnesium, zinc, tin, nickel, titanium, oxides, carbides, nitrides thereof, or mixtures and alloys thereof. is mentioned. Among them, it preferably contains at least one selected from the group consisting of aluminum, aluminum oxide, silica, and titania.
• the thickness of the inorganic layer is not particularly limited, the thickness of the inorganic layer is preferably 3 nm or more and 10 ⁇ m or less, more preferably 5 nm or more and 1 ⁇ m or less, from the viewpoint of adjusting water vapor permeability and light transmission.
• a more preferable upper limit of the inorganic layer is 20 nm, and a still more preferable upper limit is 10 nm.
• the thickness of the gas barrier layer is preferably 0.1 ⁇ m or more and 40 ⁇ m or less. With the above thickness, deformation of the pressure-sensitive adhesive layer containing the gas generating agent due to gas generation can be easily propagated, and the semiconductor device can be more easily peeled off. Furthermore, it becomes easier to adjust the water vapor transmission rate.
• a more preferable lower limit of the thickness of the gas barrier layer is 0.5 ⁇ m, and a further preferable lower limit is 1 ⁇ m.
• a more preferable upper limit of the thickness of the gas barrier layer is 30 ⁇ m, and a further preferable upper limit is 15 ⁇ m.
• the thickness of the gas barrier layer means the total thickness when the gas barrier layer has the resin and the inorganic layer.
• the substrate is not particularly limited as long as it can transmit light that activates the gas generating agent and light that activates the photopolymerization initiator. is preferred.
• heat-resistant substrates include polyethylene terephthalate, polyethylene naphthalate, polyacetal, polyamide, polycarbonate, polyphenylene ether, polybutylene terephthalate, ultra-high molecular weight polyethylene, syndiotactic polystyrene, polyarylate, polysulfone, and polyether.
• Examples include sulfone, polyphenylene sulfide, polyetheretherketone, polyimide, polyetherimide, fluororesin, and liquid crystal polymer.
• polyethylene terephthalate and polyethylene naphthalate are preferable because of their excellent heat resistance.
• the shape of the substrate is not particularly limited, and examples thereof include a sheet shape, a sheet shape having a mesh structure, a sheet shape with holes, and the like.
• the thickness of the substrate is not particularly limited, but the preferred lower limit is 5 ⁇ m and the preferred upper limit is 100 ⁇ m. When the thickness of the base material is within this range, the protective tape can have appropriate stiffness and be excellent in handleability. A more preferable lower limit of the thickness of the substrate is 10 ⁇ m, and a more preferable upper limit thereof is 50 ⁇ m.
• the base material has a transmittance of 50% or more in at least any wavelength region of 300 nm or more and 400 nm or less. If there is a wavelength in the above wavelength range for which the transmittance of the substrate is greater than 50%, a sufficient amount of light to generate a gas even through the substrate to the light-activated gas generating agent in the above wavelength range. can be reached. In addition, since the light in the above wavelength range does not overlap with the wavelength of light that activates a general photopolymerization initiator, if a gas generating agent that is activated by light in the above wavelength range can be used, the pressure-sensitive adhesive layer Unintended generation of gas due to irradiation of light for curing A can be further suppressed. Examples of the substrate having a transmittance of 50% or more in the above wavelength region include polyethylene terephthalate.
• the pressure-sensitive adhesive layer B is not particularly limited as long as it can transmit light for activating the gas generating agent and light for activating the photopolymerization initiator, and may be of a curable type or a non-curable type. . Above all, the pressure-sensitive adhesive layer B preferably contains a photocurable pressure-sensitive adhesive from the viewpoint of facilitating separation from the support. When the pressure-sensitive adhesive layer B contains a photocurable pressure-sensitive adhesive, the same photocurable pressure-sensitive adhesive as used for the pressure-sensitive adhesive layer A can be used.
• the adhesive constituting the adhesive layer B may be, for example, a rubber-based adhesive, an acrylic adhesive, a vinyl alkyl ether-based adhesive, Silicone-based adhesives, polyester-based adhesives, polyamide-based adhesives, urethane-based adhesives, styrene/diene block copolymer-based adhesives, and the like can be used.
• the thickness of the pressure-sensitive adhesive layer B is not particularly limited, it is preferably 5 ⁇ m or more, more preferably 10 ⁇ m or more, more preferably 100 ⁇ m or less, and 30 ⁇ m or less from the viewpoint of strength and handleability. is more preferable.
• the pressure-sensitive adhesive layer B preferably has a transmittance of 50% or more in at least one of the wavelength regions of 300 nm or more and 400 nm or less, and the wavelength at which the transmittance is 50% or more is common to the base material. is preferred.
• the wavelength region of 300 nm or more and 400 nm or less is common to the base material, so that even when light is irradiated from the adhesive layer B side, the adhesive More light can reach the gas generant in layer A.
• the adhesive that constitutes the adhesive layer B can be mentioned.
• the protective tape of the present invention preferably has a light transmittance of 0.1% or more at a wavelength of 405 nm.
• the light transmittance at a wavelength of 405 nm is 0.1% or more, the easy peeling layer containing the photocurable pressure-sensitive adhesive can be cured more sufficiently.
• a more preferable lower limit of the light transmittance at a wavelength of 405 nm is 0.3%, a still more preferable lower limit is 0.4%, and a still more preferable lower limit is 0.5%.
• the upper limit of the light transmittance at a wavelength of 405 nm is not particularly limited, and the higher the better.
• the light transmittance at a wavelength of 405 nm can be measured using a spectrophotometer (U-3900, manufactured by Hitachi Ltd., or equivalent). More specifically, the transmittance at 405 nm can be measured in the region of 800 to 200 nm at a scan speed of 300 nm/min and a slit interval of 4 nm.
• the method for producing the masking tape of the present invention is not particularly limited, and for example, it can be produced by the following method. First, a polymerizable polymer, a photopolymerization initiator, a gas generating agent, and, if necessary, other components are mixed in a solvent to prepare a solution of an adhesive layer (adhesive layer A) containing a gas generating agent. Prepare. On the other hand, the adhesive and additives constituting the adhesive layer B are mixed in a solvent to prepare a solution of the adhesive layer B. Next, the adhesive layer A and the adhesive layer B are formed by coating the adhesive layer A solution and the adhesive layer B solution on the release-treated surfaces of the two release films, respectively, and drying them, It is then laminated to each side of the substrate.
• a polymerizable polymer, a photopolymerization initiator, a gas generating agent, and, if necessary, other components are mixed in a solvent to prepare a solution of an adhesive layer (adhesive layer A) containing a
• the adhesive layer A can also be produced by a method in which the solution of the pressure-sensitive adhesive layer A and the solution of the pressure-sensitive adhesive layer B are directly applied onto the substrate layer and then dried.
• the adhesive layer A further has an easily peelable layer
• it can be produced by the following method.
• Manufactured by forming an easy peeling layer by coating and drying the solution of the easy peeling layer, and then laminating it on the surface of the pressure-sensitive adhesive layer A (for example, on the pressure-sensitive adhesive layer containing the gas generating agent). can be done.
• the pressure-sensitive adhesive layer A has a gas barrier layer
• a gas barrier layer is laminated on an adhesive layer containing a gas generating agent.
• a solution for the easy peeling layer is applied and dried to form the easy peeling layer, which is then laminated on the gas barrier layer.
• Such a semiconductor protective tape made of the protective tape of the present invention that is, A protective tape having a substrate, an adhesive layer A having an adhesive layer containing a gas generating agent on one surface of the substrate, and an adhesive layer B on the other surface of the substrate, wherein the gas generating agent
• the pressure-sensitive adhesive layer containing The present invention also provides a semiconductor protective tape having the above and having a 5% weight loss temperature (T d5 ) of 200° C. or more measured at a temperature increase rate of 5° C./min using a simultaneous differential thermal thermogravimetric measurement device. is one of
• the semiconductor protective tape of the present invention is used to facilitate handling of semiconductor devices and prevent breakage during processing of semiconductor devices.
• a conventional semiconductor protective tape containing a gas generating agent has been subjected to various treatments by bonding an adhesive layer containing a gas generating agent to a support and bonding the other adhesive layer to a semiconductor device.
• a gas is generated from the pressure-sensitive adhesive layer containing the gas generating agent to peel off the support and the semiconductor protective tape, and then the semiconductor device is peeled off. is required.
• the method of pasting the conventional semiconductor protective tape is reversed so that the peeling process is performed only once, the irradiated light is sufficiently absorbed while passing through the support, the pressure-sensitive adhesive layer on the opposite side, and the base material. It was not possible to generate a sufficient amount of gas.
• the semiconductor protective tape of the present invention exhibits sufficient performance as a semiconductor protective tape even when the conventional semiconductor protective tape is applied. Even when the side A is attached to the semiconductor device and the pressure-sensitive adhesive layer B side is attached to the support, a sufficient amount of gas can be generated from the gas generating agent. Therefore, the number of peeling steps can be reduced as compared with the conventional manufacturing process using a semiconductor protective tape.
• the semiconductor protective tape of the present invention since the semiconductor protective tape of the present invention has excellent heat resistance, unintended generation of gas is less likely to occur even when the semiconductor device is subjected to heat treatment.
• the semiconductor protective tape of the present invention is preferably used by attaching the pressure-sensitive adhesive layer A containing the gas generating agent to the semiconductor device and the pressure-sensitive adhesive layer B to the support.
• a semiconductor protective tape attaching step of attaching the adhesive layer B side of the semiconductor protective tape of the present invention to a support and attaching the adhesive layer A side to a semiconductor device, a semiconductor device processing step, and light from the support side and generating a gas from the gas generating agent, and peeling the semiconductor device from the laminate of the support and the semiconductor protective tape. is.
• the method for manufacturing a semiconductor device of the present invention comprises, first, a semiconductor protective tape applying step of applying the pressure-sensitive adhesive layer B side of the semiconductor protective tape of the present invention to a support and then applying the pressure-sensitive adhesive layer A side to the semiconductor device.
• Examples of the semiconductor devices include wafers and semiconductor chips.
• the support is not particularly limited as long as it has sufficient strength, is excellent in heat resistance and chemical resistance, and transmits light. Commercially available products such as AF32 (manufactured by Schott) and borofloat 33 (manufactured by Schott) can also be used as the support plate.
• the method for manufacturing a semiconductor device of the present invention includes the step of applying light to the adhesive layer A to cure it, before the step of attaching the adhesive layer B side to a support and the semiconductor device processing step described later. is preferred.
• the pressure-sensitive adhesive layer A before processing the semiconductor device, it is possible to suppress enhancement of adhesion due to high-temperature processing.
• the said adhesive layer B contains a photocurable adhesive, and when a semiconductor protective tape has said easily peelable layer, these are also hardened by this process.
• the wavelength of 365 nm or more can be crosslinked and cured by irradiating with the light of .
• a photocurable adhesive component for example, it is preferable to irradiate light having a wavelength of 365 nm at an illuminance of 5 mW/cm 2 or more, more preferably 10 mW/cm 2 or more.
• Irradiation with an illuminance of 20 mW/cm 2 or more is more preferable, and irradiation with an illuminance of 50 mW/cm 2 or more is particularly preferable.
• irradiation with light having a wavelength of 365 nm is preferably performed at an integrated illuminance of 300 mJ/cm 2 or more, more preferably at an integrated illuminance of 500 mJ/cm 2 or more and 10000 mJ/cm 2 or less, 500 mJ/cm 2 or more, Irradiation with an integrated illuminance of 7500 mJ/cm 2 or less is more preferable, and irradiation with an integrated illuminance of 1000 mJ/cm 2 or more and 5000 mJ/cm 2 or less is particularly preferable.
• the wavelength of the light irradiated does not overlap with the wavelength of the light for activating the gas generating agent.
• a method for irradiating light having such a wavelength include a method using a light source having a specific wavelength and a method using a cut filter that blocks or absorbs light of a specific wavelength.
• the semiconductor device manufacturing method of the present invention then performs a semiconductor device processing step.
• the processing of the semiconductor device include heat processing and processing involving heat generation.
• the chemical solution treatment include plating treatment such as electrolytic plating and electroless plating, wet etching treatment using hydrofluoric acid, tetramethylammonium hydroxide aqueous solution (TMAH), etc., N-methyl-2-pyrrolidone, monoethanolamine. , a resist stripping process using DMSO or the like, and a cleaning process using concentrated sulfuric acid, ammonia water, hydrogen peroxide water, or the like.
• the heat treatment and heat-generating treatment include sputtering, vapor deposition, etching, chemical vapor deposition (CVD), physical vapor deposition (PVD), resist coating/patterning, and reflow.
• a step of irradiating light from the support side to generate gas from the gas generating agent is performed.
• a gap is formed between the semiconductor device and the semiconductor protective tape, and the semiconductor device can be easily peeled off from the semiconductor protective tape.
• a sufficient amount of gas can be generated by irradiating light through the support, the adhesive layer B and the substrate by using the semiconductor protective tape of the present invention.
• the wavelength of light for generating gas is appropriately selected depending on the type of gas generating agent.
• the illuminance of the light for generating the gas is not particularly limited, but from the viewpoint of generating a more sufficient amount of gas, it is preferable to irradiate with an illuminance of 5 mW/cm 2 or more, and irradiate with an illuminance of 10 mW/cm 2 or more. It is more preferable to irradiate with an illuminance of 20 mW/cm 2 or more, and it is particularly preferable to irradiate with an illuminance of 50 mW/cm 2 or more.
• the semiconductor device manufacturing method of the present invention then performs a step of peeling the semiconductor device from the semiconductor protective tape.
• the semiconductor device can be easily peeled off because the step of generating the gas from the gas generating agent is performed.
• a pressure-sensitive adhesive layer containing a gas-generating agent has been attached to a support since it was not possible to generate gas by irradiating light through the base material. Therefore, in order to peel off the semiconductor device, the peeling process of the support must be performed first, and two peeling processes are required.
• gas can be sufficiently generated even when light is irradiated through the substrate, so that the pressure-sensitive adhesive layer A containing the gas generating agent can be attached to the semiconductor device.
• the semiconductor device can be peeled off from the semiconductor protective tape in one peeling step.
• a protective tape that has excellent heat resistance and can reliably generate gas even when light is irradiated through a substrate to easily peel off an adherend such as a semiconductor device.
• a semiconductor protective tape comprising a protective tape and a method for manufacturing a semiconductor device using the semiconductor protective tape can be provided.
• Example 1 Production of polymerizable polymer A reactor equipped with a thermometer, a stirrer and a cooling tube was prepared, and 94 parts by weight of 2-ethylhexyl acrylate as a (meth)acrylic acid alkyl ester and a functional group-containing monomer were placed in the reactor. After adding 6 parts by weight of hydroxyethyl methacrylate, 0.01 part by weight of lauryl mercaptan, and 80 parts by weight of ethyl acetate, the reactor was heated to initiate reflux.
• an ethyl acetate solution of a (meth)acrylic polymer containing functional groups having a solid content of 55% by weight and a weight average molecular weight of 600,000 was obtained.
• 3.5 parts by weight of 2-isocyanatoethyl methacrylate as a functional group-containing unsaturated compound is added to 100 parts by weight of the resin solid content in the ethyl acetate solution of the obtained functional group-containing (meth)acrylic polymer, and reacted. to obtain a polymerizable polymer.
• an ethyl acetate solution of the adhesive constituting the adhesive layer B was applied with a doctor so that the thickness of the dry film was 10 ⁇ m.
• An adhesive layer B was obtained by coating with a knife and drying by heating at 110° C. for 5 minutes.
• a 25 ⁇ m polyethylene terephthalate (PET) film having both sides subjected to corona treatment was prepared as a substrate, and an adhesive layer A and an adhesive layer B were laminated on both sides of the PET film to obtain an adhesive tape.
• Gas generating agent A 5-(4-nitrophenyl)-1H-tetrazole, manufactured by BLDpharmatech, structure is the following formula (2)
• Filler Rheolosil MT-10, Tokuyama cross-linking agent: isocyanate-based cross-linking agent, Coronate L, Nippon Urethane Industry Co., Ltd.
• photopolymerization initiator Omnirad 379EG, IGM Resins B.I. V. release agent: silicone diacrylate, EBECRYL 350, manufactured by Daicel Cytec Co., Ltd.
• Example 2 A semiconductor protective tape was produced in the same manner as in Example 1, except that the type and blending amount of the gas generating agent were as shown in Table 1. Details of the gas generating agent are as follows.
• Gas generating agent B 2-(1H-tetrazol-5-yl)pyridine, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., having the following formula (3)
• Gas generating agent C 4-(1H-tetrazol-1-yl)-1,2-benzenediamine, manufactured by Fluorocchem, having the following formula (4)
• Gas generating agent D 5-(3-phenoxyphenyl)-1H-tetrazole, manufactured by Accela, having the following formula (5)
• ADCA Azodicarbonamide, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., structure is the following formula (6)
• BHT-PIPE 5,5'-bi-1H-tetrazole piperazine salt, structure is the following formula (7)
• BHT-2Na 5,5'-bi
• Example 4 3 parts by weight of a filler, 0.2 parts by weight of a cross-linking agent, 1 part by weight of a photopolymerization initiator, and 20 parts by weight of a release agent are mixed with 100 parts by weight of the resin solid content of the obtained ethyl acetate solution of the polymerizable polymer. By doing so, an ethyl acetate solution of the adhesive constituting the easy peeling layer was obtained. Ethyl acetate solution of the adhesive constituting the easy peeling layer was coated with a doctor knife on the release-treated surface of the polyethylene terephthalate film, the surface of which was subjected to release treatment, so that the thickness of the dry film was 10 ⁇ m. C.
• a semiconductor protective tape was obtained in the same manner as in Example 1 except that the easily peelable layer thus obtained was laminated on the pressure-sensitive adhesive layer containing the gas generating agent. That is, a semiconductor protective tape was obtained in which an easily peelable layer, an adhesive layer containing a gas generating agent, a substrate, and an adhesive layer B were laminated in this order. (Examples 5 and 10) A semiconductor protective tape was produced in the same manner as in Example 4 except that the type and blending amount of the gas generating agent were as shown in Table 1.
• Example 11 to 16 A semiconductor protective tape was obtained in the same manner as in Example 10, except that the gas barrier layer shown in Table 2 was laminated between the easily peelable layer and the pressure-sensitive adhesive layer containing the gas generating agent. That is, a semiconductor protective tape was obtained in which an easily peelable layer, a gas barrier layer, an adhesive layer containing a gas generating agent, a substrate, and an adhesive layer B were laminated in this order.
• the details of the transparent deposition PET are as follows.
• Transparent deposition PET1 A base material having an aluminum oxide layer on PET having a thickness of 12 ⁇ m (Fine Barrier A type, manufactured by Reiko Co., Ltd.)
• Transparent deposition PET2 A substrate having an aluminum oxide layer and a top coat on a PET having a thickness of 12 ⁇ m (Fine Barrier AT-G type, manufactured by Reiko Co., Ltd.)
• T d5 Measurement of 5% weight loss temperature 5 to 10 mg of the gas generating agent was weighed into an aluminum pan of a thermobalance (TG/DTA6200 manufactured by SII). Then, in an air flow (flow rate of 200 mL/min), the temperature was raised from room temperature (30° C.) to 400° C. at a temperature increase rate of 5° C./min, and the temperature at which the weight decreased by 5% was the 5% weight loss temperature. (T d5 ).
• the gas generating agent was weighed to 2 ⁇ 10 ⁇ 4 mol/L and dissolved in a solvent (a solvent in which each gas generating agent is soluble: acetonitrile, dimethyl sulfoxide, mixed solvent of methyl alcohol and aqueous sodium hydroxide solution). After that, the absorption spectrum of the obtained solution was measured using U-3000 manufactured by Hitachi. Using the absorbance at each wavelength in the obtained absorption spectrum, the molar extinction coefficient was obtained according to the following formula.
• ⁇ (A ⁇ A 0 )/c ⁇ d
• ⁇ represents the molar extinction coefficient
• A represents the absorbance
• c represents the molar concentration (mol/L)
• d represents the cell thickness (cm)
• a 0 represents the absorbance of the solvent containing no gas generating agent (background ) represents.
• a test piece was prepared by cutting the gas barrier layer into a size of 35 mm ⁇ 5 mm.
• the dynamic viscoelastic spectrum of this test piece was measured using a viscoelastic spectrometer (DVA-200, manufactured by IT Keisoku Kogyo Co., Ltd.) under the conditions of a constant heating tension mode, a heating rate of 10° C./min, and 10 Hz. and the storage modulus at 100°C was measured.
• DVA-200 viscoelastic spectrometer
• the water vapor transmission rate was measured using a water vapor transmission rate measuring device (L80-4000J, manufactured by Lissi, Switzerland) in an atmosphere of 40°C and 90% humidity in accordance with JIS K 7129A method. .
• the semiconductor protective tape according to each example and comparative example was measured using a spectrophotometer (U-3900, manufactured by Hitachi, Ltd.). Specifically, the measurement was performed in the range of 800 to 200 nm at a scan speed of 300 nm/min and a slit interval of 4 nm.
• the adhesive layer A side of the semiconductor protective tape cut into a circle with a diameter of 20 cm was attached to a silicon wafer with a diameter of 20 cm and a thickness of about 750 ⁇ m to obtain a laminate.
• the end of the adhesive tape was turned over, and the adhesive tape before heat treatment was evaluated as " ⁇ ” if it could not be peeled off at all, " ⁇ ” if it could be peeled off relatively easily, and "X” if it could be peeled off with almost no resistance. evaluated.
• the adhesiveness after the heat treatment was evaluated according to the same evaluation criteria except that the adhesiveness before the heat treatment was performed except that the heat treatment was performed at 220° C. for 2 hours after the semiconductor protective tape was attached.
• the peelability before the heat treatment was evaluated as " ⁇ " when the adhesive tape was peeled off, and " ⁇ " when the silicon wafer was peeled off from the adhesive tape in less than 70% of the area.
• the laminate was subjected to a heat treatment at 220° C. for 2 hours and then subjected to the same operation as for the peelability before the heat treatment, except that it was irradiated with ultraviolet rays, and the peelability after the heat treatment was evaluated according to the same evaluation criteria.
• the adhesive layer A side of the semiconductor protective tape cut into a circle with a diameter of 20 cm is attached to a silicon wafer having a diameter of 20 cm and a thickness of about 750 ⁇ m, and the adhesive layer B side is attached to a glass plate having a diameter of 20 cm and a thickness of 1 mm.
• a laminate was obtained.
• the adhesive layers A and B were cured by irradiating ultraviolet rays of 365 nm from the glass plate side using a high-pressure mercury ultraviolet irradiation apparatus so that the cumulative irradiation amount was 3000 mJ/cm 2 . After that, heat treatment was performed at 220° C.
• the layered body was placed on a suction table so that the surface of the layered body on the silicon wafer side faced downward. Subsequently, the illuminance was adjusted to 100 mW/cm 2 with light having a wavelength of 365 nm, and the pressure-sensitive adhesive layer A was irradiated with light from the glass plate side for an irradiation time of 2 minutes to generate gas. After the ultraviolet irradiation, a sucker with a hook was attached to the edge of the glass plate, and the semiconductor protective tape and the silicon wafer were peeled off by hooking a digital spring scale on the hook and lifting it. The peel force was evaluated using the maximum value indicated by the spring scale at this time as the peel force.
• the adhesive layer A side of the semiconductor protective tape cut into a circle with a diameter of 20 cm is attached to a silicon wafer having a diameter of 20 cm and a thickness of about 750 ⁇ m, and the adhesive layer B side is attached to a glass plate having a diameter of 20 cm and a thickness of 1 mm.
• a laminate was obtained.
• the adhesive layers A and B were cured by irradiating ultraviolet rays of 365 nm from the glass plate side using a high-pressure mercury ultraviolet irradiation apparatus so that the cumulative irradiation amount was 3000 mJ/cm 2 . After that, heat treatment was performed at 220° C.
• the layered body was placed on a suction table so that the surface of the layered body on the silicon wafer side faced downward. Subsequently, the illuminance was adjusted to 100 mW/cm 2 with light having a wavelength of 365 nm, and the pressure-sensitive adhesive layer A was irradiated with light from the glass plate side for an irradiation time of 2 minutes to generate gas. The amount of vertical deformation was measured immediately after UV irradiation and after 3 hours and 24 hours.
• the amount of vertical deformation is measured by observing the surface of the semiconductor protective tape with a confocal laser microscope after a certain period of time from ultraviolet irradiation, and measuring the difference between the highest point and the lowest point in an arbitrary range on the surface of the semiconductor protective tape as the amount of vertical deformation. did. If the vertical deformation amount decreased by 30% or more for less than 3 hours, " ⁇ ", if it was less than 24 hours, " ⁇ ", If the vertical deformation amount after 24 hours was less than 30%, " ⁇ ” to evaluate the stability over time.
• a protective tape that has excellent heat resistance and can reliably generate gas even when light is irradiated through a substrate to easily peel off an adherend such as a semiconductor device.
• a semiconductor protective tape comprising a protective tape and a method for manufacturing a semiconductor device using the semiconductor protective tape can be provided.

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• 2022
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