WO2017169958A1 - 半導体ウェハ加工用粘着性フィルム - Google Patents
半導体ウェハ加工用粘着性フィルム Download PDFInfo
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- WO2017169958A1 WO2017169958A1 PCT/JP2017/011134 JP2017011134W WO2017169958A1 WO 2017169958 A1 WO2017169958 A1 WO 2017169958A1 JP 2017011134 W JP2017011134 W JP 2017011134W WO 2017169958 A1 WO2017169958 A1 WO 2017169958A1
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- WIPO (PCT)
- Prior art keywords
- semiconductor wafer
- adhesive
- resin layer
- adhesive film
- layer
- Prior art date
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Images
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
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- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
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- C—CHEMISTRY; METALLURGY
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
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- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/185—Joining of semiconductor bodies for junction formation
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
- H01L21/683—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
- H01L21/683—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping
- H01L21/6835—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
- H01L21/6836—Wafer tapes, e.g. grinding or dicing support tapes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- 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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2433/00—Presence of (meth)acrylic polymer
Definitions
- the present invention relates to an adhesive film for processing semiconductor wafers.
- an adhesive film is attached to the semiconductor wafer in order to fix the semiconductor wafer or prevent damage to the semiconductor wafer.
- an adhesive film a film in which an ultraviolet curable adhesive resin layer is laminated on a base film is generally used.
- this adhesive film is irradiated with ultraviolet rays, the adhesive resin layer is cross-linked and the adhesive force of the adhesive resin layer is reduced, so that the adhesive film can be easily peeled from the semiconductor wafer.
- Patent Document 1 Japanese Patent Application Laid-Open No. 2011-210944.
- Patent Document 1 discloses a pressure-sensitive adhesive tape composed of a base film and a photocurable pressure-sensitive adhesive layer, the antistatic layer containing a conductive polymer on at least one side of the base film, and the antistatic layer.
- An adhesive layer containing a photocurable unsaturated carbon bond in the molecule of the base polymer is provided, and the surface resistivity on the side of the adhesive layer before and after UV curing is 1 ⁇ 10 6 to 5 ⁇ 10 12 ⁇ / ⁇ , the thickness of the pressure-sensitive adhesive layer is 20 to 250 ⁇ m, and when the pressure-sensitive adhesive tape is bonded to a silicon mirror wafer, the pressure-sensitive adhesive layer is peeled off by 90 degrees after UV curing (according to JIS Z 0237; peeling)
- An antistatic semiconductor processing pressure-sensitive adhesive tape characterized in that the speed is 50 mm / min) is 0.15 to 0.25 N / 25 mm is described.
- the present inventors have found the following problems with respect to a conventional adhesive film for processing a semiconductor wafer as described in Patent Document 1.
- the adhesive film described in Patent Document 1 when the adhesive film is peeled from the semiconductor wafer, the adhesive component of the adhesive film tends to remain on the circuit forming surface of the semiconductor wafer, That is, it has been found that adhesive residue is likely to be generated and the contamination resistance to the surface of the semiconductor wafer is poor.
- the present invention has been made in view of the above circumstances, and is excellent in the balance between the adhesion to the surface of the semiconductor wafer and the contamination resistance, and can suppress the amount of static electricity generated when peeling from the semiconductor wafer. It is an object of the present invention to provide an adhesive film for processing semiconductor wafers capable of stably obtaining excellent semiconductor components.
- the inventors of the present invention have made extensive studies in order to achieve the above problems.
- the adhesive resin layer photocured with a high ultraviolet light amount
- the measure of saturation voltage is effective as a design guideline for achieving both contamination resistance and antistatic properties on the semiconductor wafer surface.
- the present inventors have improved the trade-off relationship by setting the saturation voltage of the adhesive resin layer photocured with a high ultraviolet light amount to a specific value or less.
- the present invention has been completed by finding that the contamination resistance and antistatic property to the surface of the semiconductor wafer can be improved in a balanced manner.
- the following adhesive film for semiconductor wafer processing is provided.
- An adhesive film comprising a base material layer and an ultraviolet curable adhesive resin layer provided on one surface side of the base material layer, and used for protecting the surface of the semiconductor wafer or fixing the semiconductor wafer Because
- the adhesive resin layer includes an ultraviolet curable adhesive resin, The following are measured by the method, adhesive film for processing semiconductor wafers is saturated charging voltage V 1 of the said adhesive resin layer surface after UV curing 2.0kV or less.
- the adhesive resin layer is photocured by irradiating ultraviolet light having a dominant wavelength of 365 nm with an irradiation intensity of 100 mW / cm 2 and an ultraviolet light amount of 1080 mJ / cm 2 using a high-pressure mercury lamp in an environment of 25 ° C.
- the adhesive film for semiconductor wafer processing whose tack force of the surface of the said adhesive resin layer after ultraviolet curing measured by the following method is 0.1 N / cm ⁇ 2 > or less.
- the adhesive resin layer is photocured by irradiating ultraviolet light having a dominant wavelength of 365 nm with an irradiation intensity of 100 mW / cm 2 and an ultraviolet light amount of 1080 mJ / cm 2 using a high-pressure mercury lamp in an environment of 25 ° C.
- the probe having a diameter of 5 mm and the surface of the adhesive resin layer were brought into contact with each other at a speed of 10 mm / second, and contacted at a contact load of 0.98 N / cm 2 for 10 seconds. Thereafter, the tack force on the surface of the adhesive resin layer is measured by a method in which the probe is peeled off from the surface of the adhesive resin layer in the vertical direction at a speed of 10 mm / second.
- the adhesive film for semiconductor wafer processing according to any one of [1] to [4] above, Measured by the following method, when the saturation zone voltage of the surface of the adhesive resin layer after ultraviolet curing was V 2, the semiconductor wafer processing adhesive property V 1 / V 2 is 5.0 or less film.
- the adhesive resin layer is photocured by irradiating UV light having a main wavelength of 365 nm with an irradiation intensity of 100 mW / cm 2 and an UV light amount of 200 mJ / cm 2 using a high-pressure mercury lamp in an environment of 25 ° C.
- the adhesive resin layer is an adhesive film for processing a semiconductor wafer having an antistatic layer and an adhesive layer in this order from the base material layer side.
- the antistatic layer is an adhesive film for processing semiconductor wafers containing a conductive polymer.
- the adhesive layer is an adhesive film for processing semiconductor wafers containing an ultraviolet curable adhesive resin and an ionic additive.
- the pressure-sensitive adhesive resin layer is a pressure-sensitive adhesive film for processing a semiconductor wafer, further comprising a concavo-convex absorbent resin layer between the base material layer and the antistatic layer.
- the adhesive film for semiconductor wafer processing whose thickness of the said adhesive layer is less than 30 micrometers.
- the adhesive resin layer further has an uneven absorbent resin layer between the base material layer and the antistatic layer, and the adhesive layer has an adhesive layer thickness of less than 30 ⁇ m for processing semiconductor wafers .
- the UV curable adhesive resin comprises a (meth) acrylic adhesive resin having a photopolymerizable carbon-carbon double bond in the molecule, for processing semiconductor wafers.
- the balance between the adhesion to the surface of the semiconductor wafer and the contamination resistance is excellent, the amount of static electricity generated when peeling from the semiconductor wafer can be suppressed, and the semiconductor component having excellent quality can be stably produced.
- the adhesive film for semiconductor wafer processing which can be obtained can be provided.
- an adhesive film 100 for processing a semiconductor wafer according to the present embodiment (hereinafter also referred to as “adhesive film 100”) is a base layer 10 and one surface side of the base layer 10.
- an ultraviolet curable adhesive resin layer 20 provided on the semiconductor wafer, and is used for protecting the surface of the semiconductor wafer or fixing the semiconductor wafer.
- the adhesive film 100, the adhesive resin layer 20 comprises a UV-curable adhesive resin is measured by the following method, saturated charging voltage V 1 of the adhesive resin layer 20 after ultraviolet curing 2.0kV It is as follows.
- the adhesive resin layer 20 is photocured by irradiating ultraviolet light having a main wavelength of 365 nm with an irradiation intensity of 100 mW / cm 2 and an ultraviolet light amount of 1080 mJ / cm 2 in an environment of 25 ° C. in an environment of 25 ° C.
- voltage was applied to the surface of the adhesive resin layer 20 for 30 seconds under the conditions of an applied voltage of 10 kV, a distance between the sample and the electrode of 20 mm, 25 ° C., and 50% RH, and the adhesive resin layer 20 according to JIS L1094.
- the saturation voltage (V 1 ) of the surface of is calculated.
- the present inventors have found the following problems with respect to a conventional adhesive film for processing a semiconductor wafer as described in Patent Document 1.
- the adhesive film described in Patent Document 1 when the adhesive film is peeled from the semiconductor wafer, the adhesive component of the adhesive film tends to remain on the circuit forming surface of the semiconductor wafer, That is, it has been found that adhesive residue is likely to be generated and the contamination resistance to the surface of the semiconductor wafer is poor.
- the amount of UV irradiation is increased to increase the degree of crosslinking of the adhesive layer.
- a conventional adhesive film for processing a semiconductor wafer has a trade-off relationship between contamination resistance and antistatic property to the surface of the semiconductor wafer. Became clear. That is, the present inventors have found that there is room for improvement in the conventional adhesive film for processing a semiconductor wafer in terms of improving the contamination resistance and antistatic property to the semiconductor wafer surface in a balanced manner. .
- the adhesive film 100 for processing a semiconductor wafer according to the present embodiment has an excellent balance between the adhesiveness to the surface of the semiconductor wafer and the contamination resistance by adopting the above layer structure, and when peeling from the semiconductor wafer. The amount of static electricity generated can be suppressed, and semiconductor components with excellent quality can be obtained stably.
- the saturation voltage V 1 of the adhesive resin layer 20 after UV curing is 2.0 kV or less, preferably 1.5 kV or less, more preferably 1.0 kV. Or less, particularly preferably 0.5 kV or less.
- the lower limit value of the saturation voltage V 1 of the adhesive resin layer 20 after UV curing is, for example, 0.01 kV or more, and preferably 0 kV.
- the adhesive resin layer 20 after UV curing is adjusted.
- saturated band voltages V 1 can be controlled to below the upper limit.
- the saturation voltage V 1 of the adhesive resin layer 20 after UV curing can be cited as an element for setting the desired numerical range. For example, increasing the amount of ionic additive in adhesive resin layer 20, when or providing an antistatic layer 20b, it is possible to reduce the saturated charging voltage V 1.
- the adhesive resin layer 20 with the uneven absorbent resin layer 20c and reducing the thickness of the adhesive layer 20a, the adhesive surface with the semiconductor wafer (that is, the surface of the adhesive resin layer) and the antistatic layer 20b it is possible to reduce the distance, as a result, it is possible to reduce the saturated charging voltages V 1 effectively.
- V 1 / V 2 is preferably 5 when the saturation voltage of the surface of the pressure-sensitive adhesive resin layer 20 after ultraviolet curing, measured by the following method, is V 2. 0.0 or less, more preferably 3.0 or less, and even more preferably 2.5 or less.
- V 1 / V 2 is equal to or less than the above upper limit value, the amount of static electricity generated when peeling from the semiconductor wafer can be more stably suppressed, and a semiconductor component with excellent quality can be obtained more stably.
- the adhesive resin layer 20 is photocured by irradiating ultraviolet light having a main wavelength of 365 nm with an irradiation intensity of 100 mW / cm 2 and an ultraviolet light amount of 200 mJ / cm 2 in an environment of 25 ° C. in an environment of 25 ° C.
- voltage was applied to the surface of the adhesive resin layer 20 for 30 seconds under the conditions of an applied voltage of 10 kV, a distance between the sample and the electrode of 20 mm, 25 ° C., and 50% RH, and the adhesive resin layer 20 according to JIS L1094.
- the saturation voltage (V 2 ) of the surface of is calculated.
- the half-life of the saturation voltage V 1 of the adhesive resin layer 20 after UV curing is preferably 100 seconds or less, more preferably 50 seconds or less, and even more preferably. Is 30 seconds or less, more preferably 10 seconds or less, and particularly preferably 1 second or less.
- the half-life is saturated charging voltage V 1, in the measurement of the saturated charging voltage V 1, until the value of the exit and charged voltage from the voltage application to the surface of the adhesive resin layer 20 is reduced by half Of time.
- Adhesive film 100 according to this embodiment since the saturation zone voltage V 1 of the adhesive resin layer 20 after ultraviolet curing is not more than the above upper limit, it is possible to realize such a short half-life, excellent antistatic properties The adhesive film 100 can be obtained.
- the tack force of the surface of the adhesive resin layer 20 after UV curing is preferably 0.1 N / cm 2 or less, and 0.05 N / Cm 2 or less is more preferable, and 0.01 N / cm 2 or less is more preferable.
- the tack force on the surface of the adhesive resin layer 20 after UV curing is not more than the above upper limit value, it becomes easier to peel the adhesive film 100 from the surface of the semiconductor wafer, and the adhesive resin layer is applied to the surface of the semiconductor wafer. It is possible to further suppress the remaining of a part of 20 and the occurrence of a defect in the semiconductor wafer due to the peeling of the adhesive film 100.
- the adhesive resin layer 20 is photocured by irradiating ultraviolet light having a main wavelength of 365 nm with an irradiation intensity of 100 mW / cm 2 and an ultraviolet light amount of 1080 mJ / cm 2 in an environment of 25 ° C. in an environment of 25 ° C.
- a probe tack tester for example, “TEST TACK MACHINES Inc.
- probe tack tester Model 80-02-01
- a probe having a diameter of 5 mm and the surface of the adhesive resin layer 20 are 10 mm /
- the probe is peeled off from the surface of the adhesive resin layer 20 in the vertical direction at a speed of 10 mm / second.
- the tack force on the surface of the resin layer 20 is measured.
- the total thickness of the adhesive film 100 according to this embodiment is preferably 20 ⁇ m or more and 1000 ⁇ m or less, more preferably 50 ⁇ m or more and 500 ⁇ m or less, from the balance between mechanical properties and handleability.
- the adhesive film 100 is used for protecting the surface of a semiconductor wafer or fixing the semiconductor wafer in a manufacturing process of a semiconductor device, and more specifically, in the manufacturing process of a semiconductor device. It is suitably used as a back grind tape used for protecting a circuit forming surface (that is, a circuit surface including a circuit pattern) of a semiconductor wafer in one back grind process.
- the semiconductor wafer to be attached is a semiconductor wafer having a bump electrode such as a solder bump or a copper pillar bump formed on the surface, the semiconductor wafer is caused by static electricity generated when the adhesive film is peeled off from the semiconductor wafer.
- electrostatic discharge is also applied to a semiconductor wafer having bump electrodes formed on such a surface. It becomes possible to suppress destruction and the like more reliably.
- the semiconductor wafer to which the adhesive film 100 according to the present embodiment can be applied is not particularly limited, and examples thereof include a silicon wafer.
- the base material layer 10 is a layer provided for the purpose of improving the handling properties, mechanical properties, heat resistance, and other properties of the adhesive film 100.
- the base material layer 10 is not particularly limited as long as it has a mechanical strength capable of withstanding an external force applied when processing a semiconductor wafer, and examples thereof include a resin film.
- a known thermoplastic resin can be used as the resin constituting the resin film.
- polyolefins such as polyethylene, polypropylene, poly (4-methyl-1-pentene), poly (1-butene); polyesters such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate; nylon-6, nylon-66, poly Polyamide; Polymethacrylate; Polymethacrylate; Polyvinyl Chloride; Polyimide; Polyetherimide; Ethylene / Vinyl Acetate Copolymer; Polyacrylonitrile; Polycarbonate; Polystyrene; Ionomer; Polysulfone; Polyethersulfone; Polyphenylene One type or two or more types selected from ethers and the like can be mentioned.
- polypropylene polyethylene terephthalate, polyethylene naphthalate, polyamide, polyimide, and ethylene / vinyl acetate copolymer are preferable, and polyethylene terephthalate and polyethylene naphthalate are preferable.
- polypropylene polyethylene terephthalate, polyethylene naphthalate, polyamide, polyimide, and ethylene / vinyl acetate copolymer are preferable, and polyethylene terephthalate and polyethylene naphthalate are preferable.
- phthalates are more preferred.
- the base material layer 10 may be a single layer or two or more layers.
- the form of the resin film used to form the base material layer 10 may be a stretched film or a film stretched in a uniaxial direction or a biaxial direction. From the viewpoint of improving the mechanical strength of the film, a film stretched in a uniaxial direction or a biaxial direction is preferable.
- the thickness of the base material layer 10 is preferably 10 ⁇ m or more and 500 ⁇ m or less, more preferably 20 ⁇ m or more and 300 ⁇ m or less, and further preferably 25 ⁇ m or more and 150 ⁇ m or less from the viewpoint of obtaining good film properties.
- the base material layer 10 may be subjected to a surface treatment in order to improve adhesion with other layers. Specifically, corona treatment, plasma treatment, undercoat treatment, primer coat treatment, or the like may be performed.
- the total light transmittance of the base material layer 10 is preferably 85% or more, and more preferably 90% or more. By carrying out like this, transparency can be given to substrate layer 10. Then, by setting the total light transmittance of the base material layer 10 to the above lower limit value or more, the adhesive film 100 according to this embodiment is irradiated with ultraviolet rays from the base material layer 10 side, and thereby to the adhesive resin layer 20. Ultraviolet rays can be irradiated more effectively, and the ultraviolet irradiation efficiency can be improved.
- the total light transmittance of the base material layer 10 can be measured according to JIS K7105 (1981).
- the adhesive resin layer 20 is a layer provided on one surface side of the base material layer 10, and contacts and adheres to the surface of the semiconductor wafer when the semiconductor wafer processing adhesive film 100 is attached to the semiconductor wafer. Is a layer.
- the adhesive resin layer 20 includes at least an adhesive layer 20a containing an ultraviolet curable adhesive resin as an essential component.
- the adhesive resin layer 20 preferably further includes one or more layers selected from an antistatic layer 20b and an uneven absorbent resin layer 20c, which will be described later, and includes both the antistatic layer 20b and the uneven absorbent resin layer 20c. It is preferable to further provide.
- the thickness of the adhesive resin layer 20 is usually 5 ⁇ m or more and 550 ⁇ m or less, preferably 10 ⁇ m or more and 400 ⁇ m or less, more preferably 30 ⁇ m or more and 300 ⁇ m or less, and particularly preferably 50 ⁇ m or more and 250 ⁇ m. It is as follows. When the thickness of the adhesive resin layer 20 is within the above range, the balance between the adhesiveness to the semiconductor wafer surface and the handleability is good.
- the adhesive layer 20a is a layer formed of an ultraviolet curable adhesive containing an ultraviolet curable adhesive resin as an essential component.
- the ultraviolet curable pressure sensitive adhesive include (meth) acrylic pressure sensitive adhesive, silicone pressure sensitive adhesive, urethane pressure sensitive adhesive, and the like.
- the (meth) acrylic pressure-sensitive adhesive contains a (meth) acrylic pressure-sensitive adhesive resin as an essential component as an ultraviolet curable pressure-sensitive adhesive resin.
- the silicone-based adhesive contains a silicone-based adhesive resin as an essential component as an ultraviolet curable adhesive resin.
- the urethane-based adhesive contains a urethane-based adhesive resin as an essential component as an ultraviolet curable adhesive resin.
- a (meth) acrylic pressure-sensitive adhesive is preferable from the viewpoint of facilitating adjustment of the adhesive strength.
- the (meth) acrylic adhesive includes (meth) acrylic adhesive resin having a photopolymerizable carbon-carbon double bond in the molecule and two or more photopolymerizable carbon-carbon double bonds in the molecule.
- examples thereof include a pressure-sensitive adhesive obtained by crosslinking the (meth) acrylic pressure-sensitive adhesive resin with a crosslinking agent as necessary, which contains a low molecular weight compound and a photoinitiator.
- the (meth) acrylic adhesive resin having a photopolymerizable carbon-carbon double bond in the molecule is specifically obtained as follows. First, a monomer having an ethylenic double bond and a copolymerizable monomer having a functional group (P) are copolymerized. Next, a functional group (P) contained in the copolymer and a monomer having a functional group (Q) capable of causing an addition reaction, a condensation reaction or the like with the functional group (P) are combined into a double bond in the monomer. Is allowed to react, leaving a photopolymerizable carbon-carbon double bond in the copolymer molecule.
- Examples of the monomer having an ethylenic double bond include alkyl alkyl esters such as methyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, butyl (meth) acrylate, and ethyl (meth) acrylate.
- alkyl alkyl esters such as methyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, butyl (meth) acrylate, and ethyl (meth) acrylate.
- monomers having an ethylenic double bond such as methacrylic acid alkyl ester monomers, vinyl esters such as vinyl acetate, (meth) acrylonitrile, (meth) acrylamide and styrene are used.
- Examples of the copolymerizable monomer having the functional group (P) include (meth) acrylic acid, maleic acid, 2-hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate, N-methylol (meth) acrylamide, (meth) And acryloyloxyethyl isocyanate. These may be used alone or in combination of two or more.
- the proportion of the monomer having an ethylenic double bond and the copolymerizable monomer having a functional group (P) is preferably 30 to 1% by mass with respect to the former 70 to 99% by mass. More preferably, the latter is 20 to 5% by mass with respect to the former 80 to 95% by mass.
- the monomer similar to the copolymerizable monomer which has the said functional group (P) can be mentioned, for example.
- a combination in which an addition reaction easily occurs such as a carboxyl group and an epoxy group, a carboxyl group and an aziridyl group, a hydroxyl group and an isocyanate group is desirable.
- any reaction may be used as long as it is a reaction in which a photopolymerizable carbon-carbon double bond can be easily introduced, such as a condensation reaction between a carboxylic acid group and a hydroxyl group.
- Low molecular weight compounds having two or more photopolymerizable carbon-carbon double bonds in the molecule include tripropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, tetramethylolmethane tetraacrylate, pentaerythritol tetra (Meth) acrylate, dipentaerythritol monohydroxypenta (meth) acrylate, dipentaerythritol hexa (meth) acrylate and the like. These may use 1 type (s) or 2 or more types.
- the addition amount of the low molecular weight compound having two or more photopolymerizable carbon-carbon double bonds in the molecule is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the (meth) acrylic adhesive resin. More preferably, it is 5 to 18 parts by mass.
- Photoinitiators include benzoin, isopropyl benzoin ether, isobutyl benzoin ether, benzophenone, Michler ketone, chlorothioxanthone, dodecylthioxanthone, dimethylthioxanthone, diethylthioxanthone, acetophenone diethyl ketal, benzyl dimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy Examples include -2-methyl-1-phenylpropan-1-one. These may be used alone or in combination of two or more.
- the addition amount of the photoinitiator is preferably 0.1 to 15 parts by mass, more preferably 5 to 10 parts by mass with respect to 100 parts by mass of the (meth) acrylic adhesive resin.
- a crosslinking agent may be added to the ultraviolet curable pressure-sensitive adhesive.
- crosslinking agents epoxy compounds such as sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, diglycerol polyglycidyl ether, tetramethylolmethane-tri- ⁇ -aziridinylpropionate, trimethylolpropane -Tri- ⁇ -aziridinylpropionate, N, N′-diphenylmethane-4,4′-bis (1-aziridinecarboxamide), N, N′-hexamethylene-1,6-bis (1-aziridine Aziridine compounds such as carboxamide), and isocyanate compounds such as tetramethylene diisocyanate, hexamethylene diisocyanate and polyisocyanate.
- the ultraviolet curable pressure-sensitive adhesive may be any of a solvent type, an emul
- the content of the crosslinking agent is preferably in a range in which the number of functional groups in the crosslinking agent does not exceed the number of functional groups in the (meth) acrylic adhesive resin.
- the content of the cross-linking agent in the (meth) acrylic pressure-sensitive adhesive is based on 100 parts by weight of the (meth) acrylic pressure-sensitive adhesive resin from the viewpoint of improving the balance between the heat resistance and adhesion of the pressure-sensitive adhesive resin layer 20. It is preferable that they are 0.1 mass part or more and 15 mass parts or less.
- the ultraviolet curable adhesive according to this embodiment preferably further includes an ionic additive in addition to the ultraviolet curable adhesive resin.
- an ionic additive include a cationic surfactant, an anionic surfactant, a nonionic surfactant, an amphoteric surfactant, and an ionic liquid. From the viewpoint of further improving the antistatic property of the adhesive resin layer 20, at least one selected from a cationic surfactant and an anionic surfactant is preferable, and a cationic surfactant is more preferable.
- Examples of the cationic surfactant include dodecyltrimethylammonium chloride, tetradecyldimethylbenzylammonium chloride, cetyldimethylbenzylammonium chloride, stearyldimethylbenzylammonium chloride, tetradecyltrimethylammonium chloride, hexadecyltrimethylammonium chloride, octadecyltrimethylammonium chloride.
- Examples of the cationic surfactant include a quaternary ammonium salt or amine salt type, and a quaternary ammonium salt is preferable. Of these, tetradecyldimethylbenzylammonium chloride, cetyldimethylbenzylammonium chloride, and stearyldimethylbenzylammonium chloride are preferable.
- anionic surfactant examples include alkyl diphenyl ether disulfonates such as diammonium dodecyl diphenyl ether disulfonate, sodium dodecyl diphenyl ether disulfonate, calcium dodecyl diphenyl ether disulfonate, sodium alkyl diphenyl ether disulfonate; sodium dodecylbenzene sulfonate, dodecylbenzene Alkyl benzene sulfonates such as ammonium sulfonate; alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate; aliphatic carboxylates such as fatty acid sodium and potassium oleate; sulfate salts containing polyoxyalkylene units (eg, polyoxy Sodium ethylene alkyl ether sulfate, polyoxyethylene alkyl ether Polyoxyethylene alkyl ether sulf
- nonionic surfactant examples include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene tridecyl ether, polyoxyalkylene alkyl ether compounds such as polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, A polyoxyalkylene unit-containing ether compound such as a polyoxyalkylene alkyl phenyl ether compound such as polyoxyethylene nonylphenyl ether, a polyoxyalkylene polycyclic phenyl ether compound such as polyoxyethylene polycyclic phenyl ether; a polyoxyethylene monolaurate; Polyoxyalkylene alkyl ester compounds such as polyoxyethylene monostearate and polyoxyethylene monooleate; Polyoxyalkylene alkylamine compounds such as shea polyoxyethylene alkyl amine; sorbitan monolaurate, sorbitan monostearate, sorbitan trioleate, polyoxyethylene sorbitan monolaurate
- amphoteric surfactants examples include lauryl betaine and lauryl dimethylamine oxide.
- ionic additives may be used individually by 1 type, and may be used in combination of 2 or more type.
- the content of the ionic additive in the ultraviolet curable adhesive resin is preferably 0.01 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the ultraviolet curable adhesive resin. More preferably, it is 5 parts by mass or less.
- the adhesive layer 20a can be formed, for example, by applying an adhesive coating solution on other layers such as the base material layer 10, the antistatic layer 20b, and the uneven absorbent resin layer 20c.
- a conventionally known coating method such as a roll coater method, a reverse roll coater method, a gravure roll method, a bar coat method, a comma coater method, a die coater method, or the like can be employed.
- drying conditions of the applied pressure-sensitive adhesive but in general, drying is preferably performed for 10 seconds to 10 minutes in a temperature range of 80 to 200 ° C. More preferably, it is dried at 80 to 170 ° C. for 15 seconds to 5 minutes.
- the pressure-sensitive adhesive coating liquid after the pressure-sensitive adhesive coating liquid has been dried, it may be heated at 40 to 80 ° C. for about 5 to 300 hours.
- the thickness of the adhesive layer 20a is preferably 100 ⁇ m or less, more preferably 50 ⁇ m or less, further preferably less than 30 ⁇ m, still more preferably 25 ⁇ m or less, and further preferably 20 ⁇ m or less. It is particularly preferred that Thereby, the distance of the surface of the adhesive resin layer 20 and the antistatic layer 20b can be made small, As a result, the antistatic property of the adhesive film 100 can be made more favorable.
- the lower limit of the thickness of the adhesive layer 20a is not particularly limited, but is preferably 0.5 ⁇ m or more, more preferably 1.0 ⁇ m or more, further preferably 3.0 ⁇ m or more, and 5.0 ⁇ m from the viewpoint of improving the adhesive strength. The above is particularly preferable.
- the adhesive resin layer 20 preferably further includes an antistatic layer 20b. Thereby, the antistatic property of the adhesive resin layer 20 can be improved, and the amount of static electricity generated when the adhesive film 100 is peeled from the semiconductor wafer can be further suppressed.
- the adhesive resin layer 20 further includes an antistatic layer 20b, the antistatic layer 20b and the adhesive from the base material layer 10 side as shown in FIG. It is preferable to have the layers 20a in this order. Thereby, the amount of static electricity generated at the time of peeling can be further suppressed while the adhesiveness of the adhesive film 100 is maintained.
- the material for forming the antistatic layer 20b preferably contains a conductive polymer from the viewpoint of reducing the surface resistance value of the antistatic layer 20b and suppressing the generation of static electricity accompanying peeling.
- the conductive polymer include a polythiophene-based conductive polymer, a polypyrrole-based conductive polymer, a polyaniline-based conductive polymer, a poly (p-phenylene vinylene) -based conductive polymer, and a polyquinoxaline-based conductive polymer.
- a polythiophene-based conductive polymer is preferable from the viewpoint of a good balance of optical properties, appearance, antistatic properties, coating properties, stability, and the like.
- the polythiophene conductive polymer include polyethylene dioxythiophene and polythiophene. These conductive polymers may be used individually by 1 type, and may be used in combination of 2 or more type.
- the material forming the antistatic layer 20b can further include, for example, a doping agent, a binder resin, and the like.
- the doping agent functions as a dopant and more reliably imparts (doping) conductivity to the conductive polymer, and examples thereof include sulfonic acid compounds.
- sulfonic acid compounds include p-toluenesulfonic acid, benzenesulfonic acid, ethylbenzenesulfonic acid, octylbenzenesulfonic acid, dodecylbenzenesulfonic acid, mesitylenesulfonic acid, m-xylenesulfonic acid, polystyrenesulfonic acid, polyvinylsulfonic acid, and the like. Is mentioned. From the viewpoint of improving the solubility and water dispersibility of the conductive polymer, polystyrene sulfonic acid and polyvinyl sulfonic acid are preferred.
- a sulfonic acid type compound may be used individually by 1 type, and may be used in combination of 2 or more type.
- the conductive polymer and the sulfonic acid compound partially react to form a sulfonate, and the antistatic function of the antistatic layer 20b is further enhanced by the action of the sulfonate. improves.
- the mixing ratio of the doping agent is, for example, 100 to 300 parts by mass with respect to 100 parts by mass of the conductive polymer.
- a combination of the conductive polymer and the doping agent a combination of polyethylene dioxythiophene (PEDOT) and polystyrene sulfonic acid (PSS) is preferable because of excellent antistatic properties.
- the material for forming the antistatic layer 20b may further contain a binder resin from the viewpoint of improving the film formability and adhesion.
- a binder resin examples include polyurethane resin, polyester resin, (meth) acrylic resin, polyether resin, cellulose resin, polyvinyl alcohol resin, epoxy resin, polyvinyl pyrrolidone, polystyrene resin, polyethylene glycol, penta Examples include erythritol.
- Binder resin may be used individually by 1 type, and may be used in combination of 2 or more type. The content of the binder resin is, for example, 10 to 500 parts by mass with respect to 100 parts by mass of the conductive polymer.
- the thickness of the antistatic layer 20b is preferably 0.01 ⁇ m or more and 10 ⁇ m or less, more preferably 0.01 ⁇ m or more and 5 ⁇ m or less, and 0.01 ⁇ m or more and 1 ⁇ m or less. Further preferred.
- the adhesive resin layer 20 further includes an uneven absorbent resin layer 20c.
- the unevenness absorbability of the entire adhesive film 100 is improved, and the unevenness (including bumps) on the unevenness forming surface (for example, the circuit forming surface (that is, the circuit surface including the circuit pattern)) of the semiconductor wafer is followed.
- the adhesion between the uneven surface and the adhesive film 100 can be improved. Furthermore, it is possible to suppress the electrode formed on the surface of the semiconductor wafer from being broken by an external force applied when processing the semiconductor wafer.
- the adhesive resin layer 20 when the adhesive resin layer 20 further includes an antistatic layer 20b and an uneven absorbent resin layer 20c, as shown in FIG. 3, the adhesive resin layer 20 is a base material layer. 10 and the antistatic layer 20b are preferably provided with a concavo-convex absorbent resin layer 20c.
- the thickness of the adhesive layer 20a can be reduced while improving the unevenness absorbability of the adhesive film 100, the distance between the surface of the adhesive resin layer 20 and the antistatic layer 20b can be reduced. As a result, the antistatic property of the adhesive film 100 can be improved.
- Density of the bumps absorbent resin layer 20c from the viewpoint of the balance between mechanical strength and conformity to irregularity, preferably 800 ⁇ 990kg / m 3, more preferably 830 ⁇ 980kg / m 3, is 850 ⁇ 970kg / m 3 Further preferred.
- the resin constituting the uneven absorbent resin layer 20c is not particularly limited as long as it exhibits uneven absorbency.
- olefin resins and ethylene / polar monomer copolymers are preferable.
- the olefin resin examples include linear low density polyethylene (LLDPE), low density polyethylene, high density polyethylene, polypropylene, ethylene and an ⁇ -olefin copolymer containing ethylene and an ⁇ -olefin having 3 to 12 carbon atoms. And a propylene / ⁇ -olefin copolymer containing propylene and an ⁇ -olefin having 4 to 12 carbon atoms, an ethylene / cyclic olefin copolymer, and an ethylene / ⁇ -olefin / cyclic olefin copolymer.
- LLDPE linear low density polyethylene
- low density polyethylene high density polyethylene
- polypropylene ethylene
- ethylene and an ⁇ -olefin copolymer containing ethylene and an ⁇ -olefin having 3 to 12 carbon atoms ethylene and an ⁇ -olefin having 3 to 12 carbon atoms.
- ethylene / polar monomer copolymer examples include ethylene / (meth) ethyl acrylate copolymer, ethylene / (meth) methyl acrylate copolymer, ethylene / (meth) propyl propyl copolymer, ethylene / (meta ) Ethylene / unsaturated carboxylic acid ester copolymer such as butyl acrylate copolymer; ethylene / vinyl acetate copolymer, ethylene / vinyl propionate copolymer, ethylene / vinyl butyrate copolymer, ethylene / vinyl stearate Examples thereof include ethylene / vinyl ester copolymers such as copolymers.
- the resin constituting the uneven absorbent resin layer 20c may be used alone or in combination of two or more.
- Examples of the ⁇ -olefin having 3 to 12 carbon atoms in the ethylene / ⁇ -olefin copolymer include propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, and 4-methyl-1 -Pentene, 3-methyl-1-pentene, 1-heptene, 1-octene, 1-decene, 1-dodecene and the like are preferable, and propylene, 1-butene and the like are preferable.
- low density polyethylene; polypropylene; ethylene / propylene copolymer, ethylene / 1-butene copolymer, ethylene / propylene / ⁇ having 4 to 12 carbon atoms are excellent in terms of excellent conformity when attaching.
- -Ethylene / ⁇ -olefin copolymers such as olefin terpolymers; Propylene / 1-butene / ⁇ -olefin terpolymers having 5 to 12 carbon atoms; Ethylene / vinyl acetate copolymers, etc.
- ethylene / propylene copolymer and ethylene / vinyl acetate copolymer are more preferable.
- the thickness of the uneven absorbent resin layer 20c is not particularly limited as long as the unevenness on the unevenness forming surface of the semiconductor wafer can be embedded, but is preferably 10 ⁇ m or more and 500 ⁇ m or less, for example, 20 ⁇ m or more and 400 ⁇ m or less. More preferably, it is more preferably 30 ⁇ m or more and 300 ⁇ m or less, and particularly preferably 50 ⁇ m or more and 250 ⁇ m or less.
- the adhesive film 100 which concerns on this embodiment may provide the contact bonding layer (not shown) between each layer. According to this adhesive layer, the adhesion between the layers can be improved. Moreover, the adhesive film 100 which concerns on this embodiment may laminate
- the adhesive film 100 for processing a semiconductor wafer according to the present embodiment is different from the conventional manufacturing method, and the manufacturing conditions need to be highly controlled. That is, for the first time by a manufacturing method that highly controls various factors relating to the following two conditions, the saturation voltage V 1 of the adhesive resin layer 20 after UV curing described above satisfies the above-mentioned specific conditions. 100 can be obtained. (1) Types and blending ratios of components constituting the adhesive resin layer 20 (2) Layer configuration of the adhesive resin layer 20
- Examples of the specific configuration of the adhesive film 100 in which the saturation voltage V 1 of the adhesive resin layer 20 after ultraviolet curing satisfies the above-described specific conditions include, for example, Examples 1 to 3 below. .
- the adhesive film 100 which concerns on this embodiment is not limited to these structures.
- the adhesive resin layer 20 has an adhesive layer 20a containing an ionic additive and an uneven absorbent resin layer 20c, and the antistatic layer 20b. No sticky film.
- the thickness of the adhesive layer 20a is preferably 5.0 ⁇ m or more and 50 ⁇ m or less, and from the viewpoint that the antistatic property of the adhesive film 100 can be improved, the thickness is 5.0 ⁇ m or more and less than 30 ⁇ m. More preferably.
- the content of the ionic additive in the ultraviolet curable adhesive resin is preferably 0.1 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the ultraviolet curable adhesive resin. .
- the adhesive resin layer 20 has an adhesive layer 20a that does not contain an ionic additive, an antistatic layer 20b, and an uneven absorbent resin layer 20c.
- Adhesive film In the case of Example 2, it is preferable that the thickness of the adhesive layer 20a is 5.0 ⁇ m or more and less than 30 ⁇ m. Thereby, the distance of the surface of the adhesive resin layer 20 and the antistatic layer 20b can be made small, As a result, the antistatic property of the adhesive film 100 can be made more favorable.
- the adhesive resin layer 20 has an adhesive layer 20a containing an ionic additive, an antistatic layer 20b, and an uneven absorbent resin layer 20c.
- Adhesive film In the case of Example 3, the thickness of the adhesive layer 20a is preferably 5.0 ⁇ m or more and 50 ⁇ m or less, and from the viewpoint that the antistatic property of the adhesive film 100 can be improved, the thickness is 5.0 ⁇ m or more and less than 30 ⁇ m. More preferably.
- the content of the ionic additive in the ultraviolet curable adhesive resin is preferably 0.1 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the ultraviolet curable adhesive resin. .
- an ionic additive may be added to both the adhesive layer 20a and the uneven absorbent resin layer 20c.
- the adhesive film 100 in the present embodiment is based on the premise that various factors related to the above two conditions are highly controlled. For example, various specific manufacturing conditions such as temperature setting of the manufacturing apparatus are adopted. can do. In other words, the adhesive film 100 in the present embodiment can be manufactured by adopting a publicly known method except for highly controlling various factors related to the above two conditions.
- a method for producing the adhesive film 100 will be described on the assumption that various factors related to the above two conditions are highly controlled.
- the uneven absorbent resin layer 20c is formed on one surface of the base material layer 10 by extrusion lamination.
- a predetermined conductive material is applied on a separately prepared release film and dried to form the antistatic layer 20b, and the antistatic layer 20b is laminated on the uneven absorbent resin layer 20c.
- a pressure-sensitive adhesive layer 20a is formed by applying and drying a pressure-sensitive adhesive coating solution on the antistatic layer 20b, and the pressure-sensitive adhesive film 100 is obtained.
- the base material layer 10 and the uneven absorbent resin layer 20c may be formed by coextrusion, or the film base material layer 10 and the film uneven absorbable resin layer 20c are laminated. May be formed.
- the semiconductor wafer back surface grinding method according to the present embodiment is characterized in that the semiconductor wafer processing adhesive film 100 according to the present embodiment is used as a back grind tape when the back surface of the semiconductor wafer is ground.
- the release film is peeled off from the adhesive resin layer 20 of the adhesive film 100, the surface of the adhesive resin layer 20 is exposed, and the circuit forming surface of the semiconductor wafer is attached onto the adhesive resin layer 20.
- the semiconductor wafer is fixed to the chuck table or the like of the grinding machine via the base material layer 10 of the adhesive film 100, and the back surface (circuit non-formed surface) of the semiconductor wafer is ground.
- the adhesive film 100 is peeled off.
- a chemical etching process may be performed before the adhesive film 100 is peeled off.
- cleaning are given with respect to the semiconductor wafer surface.
- the thickness of the semiconductor wafer before grinding is usually 500 to 1000 ⁇ m, but is usually ground to about 100 to 600 ⁇ m depending on the type of semiconductor chip. If necessary, it may be cut thinner than 100 ⁇ m.
- the thickness of the semiconductor wafer before grinding is appropriately determined depending on the diameter and type of the semiconductor wafer, and the thickness of the wafer after grinding is appropriately determined depending on the size of the chip to be obtained, the type of circuit, and the like.
- the operation of attaching the semiconductor wafer to the adhesive film 100 may be performed manually, but is generally performed by an apparatus called an automatic pasting machine having a roll-shaped adhesive film attached thereto.
- a known grinding method such as a through-feed method or an in-feed method is adopted. Grinding is performed while cooling water over a semiconductor wafer and a grindstone. After the back grinding, chemical etching is performed as necessary. Chemical etching adheres to an etching solution selected from the group consisting of acidic aqueous solutions made of hydrofluoric acid, nitric acid, sulfuric acid, acetic acid and the like alone or in a mixed solution, alkaline aqueous solutions such as potassium hydroxide aqueous solution and sodium hydroxide aqueous solution. It is performed by a method such as immersing a semiconductor wafer with the adhesive film 100 attached.
- the etching is performed for the purpose of removing strain generated on the back surface of the semiconductor wafer, further thinning the wafer, removing an oxide film, etc., pretreatment when forming an electrode on the back surface.
- the etching solution is appropriately selected according to the above purpose.
- the adhesive film 100 is peeled off from the semiconductor wafer surface. This series of operations may be performed manually, but is generally performed by an apparatus called an automatic peeling machine.
- the surface of the semiconductor wafer after peeling off the adhesive film 100 is cleaned as necessary.
- the cleaning method include wet cleaning such as water cleaning and solvent cleaning, and dry cleaning such as plasma cleaning. In the case of wet cleaning, ultrasonic cleaning may be used in combination. These cleaning methods are appropriately selected depending on the contamination state of the semiconductor wafer surface.
- Concavity and convexity absorbent resin 1 Ethylene / vinyl acetate copolymer (density: 960 kg / m 3 , “Evaflex EV150” manufactured by Mitsui DuPont Polychemical Co., Ltd.)
- Antistatic layer forming material 1 Conductive material containing polyethylene dioxythiophene / polystyrene sulfonic acid (PEDOT / PSS) (trade name: Denatron P-504CT, manufactured by Nagase ChemteX)
- Ionic additive 1 tetradecyldimethylbenzylammonium chloride (manufactured by NOF Corporation, trade name: Nissan Cation M 2 -100)
- Photoinitiator 1 Benzyldimethyl ketal (trade name: Irgacure 651, manufactured by BASF)
- ⁇ Coating liquid 1 for adhesive layer > 77 parts by mass of n-butyl acrylate, 16 parts by mass of methyl methacrylate, 16 parts by mass of 2-hydroxyethyl acrylate, and 0.5 parts by mass of benzoyl peroxide as a polymerization initiator were mixed.
- the resultant was dropwise added to a nitrogen-substituted flask containing 20 parts by mass of toluene and 80 parts by mass of ethyl acetate with stirring at 85 ° C. over 5 hours, and further reacted by stirring for 5 hours.
- this solution was cooled, and 10 parts by mass of toluene, 7 parts by mass of methacryloyloxyethyl isocyanate (manufactured by Showa Denko KK, product name: Karenz MOI), and 0.02 parts by mass of dibutyltin dilaurate were added.
- the mixture was reacted at 85 ° C. for 12 hours while blowing air to obtain a pressure-sensitive adhesive polymer 1 solution into which a polymerizable carbon-carbon double bond was introduced.
- this solution was cooled, and 25 parts by mass of xylene, 2.5 parts by mass of acrylic acid, and ionic additive 1: 0.5 parts by mass of tetradecyldimethylbenzylammonium chloride were added thereto, and air was blown into the solution.
- the mixture was reacted at 85 ° C. for 32 hours to obtain a pressure-sensitive adhesive polymer 3 solution into which a polymerizable carbon-carbon double bond was introduced.
- Example 1 On the polyethylene terephthalate film used as the base material layer, the uneven absorbent resin 1 used as the uneven absorbent resin layer was extruded and laminated to a thickness of 195 ⁇ m to obtain a two-layer laminated film. Next, the adhesive layer coating liquid 1 was applied to the uneven absorbent resin layer of the obtained laminated film and then dried to form an adhesive layer having a thickness of 10 ⁇ m to obtain an adhesive film. The following evaluation was performed about the obtained adhesive film. The obtained results are shown in Table 1.
- Example 2 On the polyethylene terephthalate film used as the base material layer, the uneven absorbent resin 1 used as the uneven absorbent resin layer was extruded and laminated to a thickness of 195 ⁇ m to obtain a two-layer laminated film. Next, the antistatic layer-forming material 1 is applied on a separately prepared release film and dried to form an antistatic film, and this antistatic film is laminated on the concavo-convex absorbent resin layer. An antistatic layer having a thickness of 0.1 ⁇ m was formed. Next, the coating liquid 2 for the adhesive layer was applied on the antistatic layer of the obtained laminated film and then dried to form an adhesive layer having a thickness of 10 ⁇ m to obtain an adhesive film. The following evaluation was performed about the obtained adhesive film. The obtained results are shown in Table 1.
- Example 3 On the polyethylene terephthalate film used as the base material layer, the uneven absorbent resin 1 used as the uneven absorbent resin layer was extruded and laminated to a thickness of 195 ⁇ m to obtain a two-layer laminated film. Next, the antistatic layer-forming material 1 is applied on a separately prepared release film and dried to form an antistatic film, and this antistatic film is laminated on the concavo-convex absorbent resin layer. An antistatic layer having a thickness of 0.1 ⁇ m was formed. Next, after the coating liquid 1 for the adhesive layer was applied on the antistatic layer of the obtained laminated film, it was dried to form an adhesive layer having a thickness of 10 ⁇ m to obtain an adhesive film. The following evaluation was performed about the obtained adhesive film. The obtained results are shown in Table 1.
- Example 4 A pressure-sensitive adhesive film was obtained in the same manner as in Example 3 except that the pressure-sensitive adhesive layer coating solution 1 was changed to the pressure-sensitive adhesive layer coating solution 3 and the thickness of the pressure-sensitive adhesive layer was 40 ⁇ m. The following evaluation was performed about the obtained adhesive film. The obtained results are shown in Table 1.
- Example 5 An adhesive film was obtained in the same manner as in Example 4 except that the adhesive layer coating solution 3 was changed to the adhesive layer coating solution 1. The following evaluation was performed about the obtained adhesive film. The obtained results are shown in Table 1.
- the surface of the adhesive resin layer was applied under conditions of an applied voltage of 10 kV, a distance between the sample and the electrode of 20 mm, 25 ° C., and 50% RH. The voltage was applied for 30 seconds, and the saturation voltage (V 1 ) and the half life of the saturation voltage V 1 on the surface of the adhesive resin layer were calculated according to JIS L1094. In addition, the saturation voltage of the surface of the adhesive resin layer and the half-life of the saturation voltage were changed in the same procedure as the measurement of the saturation voltage (V 1 ) except that the amount of ultraviolet rays was changed to 200 to 540 mJ / cm 2. Each was measured.
- the adhesive resin layer in the adhesive film is irradiated with ultraviolet light having a dominant wavelength of 365 nm using a high-pressure mercury lamp in an environment of 25 ° C. with an irradiation intensity of 100 mW / cm 2 and an ultraviolet light amount of 1080 mJ / cm 2.
- the adhesive resin layer was photocured by irradiation.
- a probe tack tester (“TEST TACK MACHINES Inc. probe tack tester: Model 80-02-01”) as a measuring device, a probe having a diameter of 5 mm and the surface of the adhesive resin layer were fed at a speed of 10 mm / second.
- the probe was peeled off from the surface of the adhesive resin layer in the vertical direction at a speed of 10 mm / second.
- the tack force was measured. Further, the tack force on the surface of the adhesive resin layer was measured in the same procedure as the tack force measurement except that the amount of ultraviolet rays was changed to 200 to 360 mJ / cm 2 .
- the adhesiveness to the semiconductor wafer surface was evaluated according to the following criteria.
- ⁇ The tack force of the adhesive resin layer not irradiated with ultraviolet rays (that is, the ultraviolet ray amount of 0 mJ / cm 2 ) is 10 N / cm 2 or more.
- X The tack force of the adhesive resin layer not irradiated with the ultraviolet rays amount Is less than 10 N / cm 2
- the contamination resistance to the semiconductor wafer surface was evaluated according to the following criteria. ⁇ : The tack force of the adhesive resin layer photocured by irradiation with an ultraviolet ray amount of 1080 mJ / cm 2 is 0.1 N / cm 2 or less ⁇ : The tack force of the adhesive resin layer photocured by irradiation with an ultraviolet ray amount of 1080 mJ / cm 2 Exceeds 0.1 N / cm 2
- the adhesive films of Examples 1 to 5 in which the saturation voltage V 1 on the surface of the adhesive resin layer after UV curing is 2.0 kV or less are excellent in the balance between the adhesiveness to the semiconductor wafer surface and the contamination resistance, Excellent antistatic properties. That is, according to the adhesive film 100 for processing a semiconductor wafer according to the present embodiment, the amount of static electricity generated when the semiconductor wafer is peeled from the semiconductor wafer can be suppressed, and a semiconductor component having excellent quality can be stably obtained. Understandable. In contrast, the adhesive films of Comparative Examples 1 and 2 in which the saturation voltage V 1 on the surface of the adhesive resin layer after UV curing exceeds 2.0 kV are in balance between the adhesiveness to the semiconductor wafer surface and the contamination resistance. Was excellent, but the antistatic property was inferior.
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Abstract
Description
このような粘着性フィルムには、一般的に、基材フィルムに紫外線硬化型の粘着性樹脂層を積層させたフィルムが用いられている。この粘着性フィルムは紫外線を照射することで、粘着性樹脂層が架橋して粘着性樹脂層の粘着力が低下するため、半導体ウェハから粘着性フィルムを容易に剥離することができる。
特に、近年の半導体ウェハの高密度化・配線の狭ピッチ化に伴って、半導体ウェハはこれまで以上に静電気による影響を受けやすくなってきている傾向にある。
こうした事情に鑑みて、近年、半導体装置の製造工程において半導体ウェハの固定や損傷の防止のために使用する粘着性フィルムについても、帯電防止性能をさらに向上させることが要求されている。
本発明者らは、特許文献1に記載されているような従来の半導体ウェハ加工用粘着性フィルムに関し、以下のような課題を見出した。
まず、本発明者らは、特許文献1に記載されている粘着性フィルムは、半導体ウェハから粘着性フィルムを剥離した際に、半導体ウェハの回路形成面に粘着性フィルムの粘着成分が残りやすい、すなわち糊残りが発生しやすく、半導体ウェハ表面への耐汚染性に劣ることを知見した。
さらに、本発明者らの検討によれば、特許文献1に記載されている粘着性フィルムにおいて、糊残りの発生を抑制するために紫外線の照射量を増加させて粘着剤層の架橋度を高めると、糊残りの発生が抑制されて半導体ウェハ表面への耐汚染性が改善される一方で、今度は帯電防止性が悪化することが明らかになった。
つまり、本発明者らの検討によれば、従来の半導体ウェハ加工用粘着性フィルムには、半導体ウェハ表面への耐汚染性と帯電防止性との間には、トレードオフの関係が存在することが明らかになった。すなわち、本発明者らは、従来の半導体ウェハ加工用粘着性フィルムには、半導体ウェハ表面への耐汚染性および帯電防止性をバランスよく向上させるという観点において、改善の余地があることを見出した。
そして、本発明者らは上記知見を元にさらに鋭意検討した結果、高い紫外線量で光硬化させた粘着性樹脂層の飽和帯電圧を特定値以下とすることにより、上記トレードオフの関係を改善でき、半導体ウェハ表面への耐汚染性および帯電防止性をバランスよく向上できることを見出して、本発明を完成させた。
基材層と、上記基材層の一方の面側に設けられた紫外線硬化型の粘着性樹脂層と、を備え、半導体ウェハの表面を保護または半導体ウェハを固定するために用いられる粘着性フィルムであって、
上記粘着性樹脂層は紫外線硬化型粘着性樹脂を含み、
下記の方法で測定される、紫外線硬化後の上記粘着性樹脂層表面の飽和帯電圧V1が2.0kV以下である半導体ウェハ加工用粘着性フィルム。
(方法)
上記粘着性樹脂層に対し、25℃の環境下で高圧水銀ランプを用いて主波長365nmの紫外線を照射強度100mW/cm2で紫外線量1080mJ/cm2照射して上記粘着性樹脂層を光硬化させる。次いで、印加電圧10kV、試料と電極との距離20mm、25℃、50%RHの条件下で上記粘着性樹脂層の表面に電圧の印加を30秒おこない、JIS L1094に準じて上記粘着性樹脂層の表面の飽和帯電圧(V1)を算出する。
[2]
上記[1]に記載の半導体ウェハ加工用粘着性フィルムにおいて、
バックグラインドテープである半導体ウェハ加工用粘着性フィルム。
[3]
上記[1]または[2]に記載の半導体ウェハ加工用粘着性フィルムにおいて、
上記半導体ウェハの表面にはバンプ電極が形成されている半導体ウェハ加工用粘着性フィルム。
[4]
上記[1]乃至[3]いずれか一つに記載の半導体ウェハ加工用粘着性フィルムにおいて、
下記の方法で測定される、紫外線硬化後の上記粘着性樹脂層の表面のタック力が0.1N/cm2以下である半導体ウェハ加工用粘着性フィルム。
(方法)
上記粘着性樹脂層に対し、25℃の環境下で高圧水銀ランプを用いて主波長365nmの紫外線を照射強度100mW/cm2で紫外線量1080mJ/cm2照射して上記粘着性樹脂層を光硬化させる。次いで、測定装置としてプローブタックテスターを用いて、直径5mmのプローブと上記粘着性樹脂層の表面とを10mm/秒の速度で接触させ、0.98N/cm2の接触荷重で10秒間接触させた後、10mm/秒の速度で上記プローブを上記粘着性樹脂層の表面から垂直方向に剥離する方法で上記粘着性樹脂層の表面のタック力を測定する。
[5]
上記[1]乃至[4]いずれか一つに記載の半導体ウェハ加工用粘着性フィルムにおいて、
下記の方法で測定される、紫外線硬化後の上記粘着性樹脂層の表面の飽和帯電圧をV2としたとき、V1/V2が5.0以下である半導体ウェハ加工用粘着性フィルム。
(方法)
上記粘着性樹脂層に対し、25℃の環境下で高圧水銀ランプを用いて主波長365nmの紫外線を照射強度100mW/cm2で紫外線量200mJ/cm2照射して上記粘着性樹脂層を光硬化させる。次いで、印加電圧10kV、試料と電極との距離20mm、25℃、50%RHの条件下で上記粘着性樹脂層の表面に電圧の印加を30秒おこない、JIS L1094に準じて上記粘着性樹脂層の表面の飽和帯電圧(V2)を算出する。
[6]
上記[1]乃至[5]いずれか一つに記載の半導体ウェハ加工用粘着性フィルムにおいて、
上記飽和帯電圧V1の半減期が100秒以下である半導体ウェハ加工用粘着性フィルム。
[7]
上記[1]乃至[6]いずれか一つに記載の半導体ウェハ加工用粘着性フィルムにおいて、
上記粘着性樹脂層の厚みが5μm以上550μm以下である半導体ウェハ加工用粘着性フィルム。
[8]
上記[1]乃至[7]いずれか一つに記載の半導体ウェハ加工用粘着性フィルムにおいて、
上記粘着性樹脂層は、上記基材層側から帯電防止層および粘着性層をこの順番に有する半導体ウェハ加工用粘着性フィルム。
[9]
上記[8]に記載の半導体ウェハ加工用粘着性フィルムにおいて、
上記帯電防止層は導電性高分子を含む半導体ウェハ加工用粘着性フィルム。
[10]
上記[8]または[9]に記載の半導体ウェハ加工用粘着性フィルムにおいて、
上記粘着性層は紫外線硬化型粘着性樹脂およびイオン性添加剤を含む半導体ウェハ加工用粘着性フィルム。
[11]
上記[8]乃至[10]いずれか一つに記載の半導体ウェハ加工用粘着性フィルムにおいて、
上記粘着性樹脂層は、上記基材層と上記帯電防止層との間に凹凸吸収性樹脂層をさらに有する半導体ウェハ加工用粘着性フィルム。
[12]
上記[8]乃至[11]いずれか一つに記載の半導体ウェハ加工用粘着性フィルムにおいて、
上記粘着性層の厚みが30μm未満である半導体ウェハ加工用粘着性フィルム。
[13]
上記[8]乃至[10]いずれか一つに記載の半導体ウェハ加工用粘着性フィルムにおいて、
上記粘着性樹脂層は、上記基材層と上記帯電防止層との間に凹凸吸収性樹脂層をさらに有し、かつ、上記粘着性層の厚みが30μm未満である半導体ウェハ加工用粘着性フィルム。
[14]
上記[8]乃至[13]いずれか一つに記載の半導体ウェハ加工用粘着性フィルムにおいて、
上記帯電防止層の厚みが0.01μm以上10μm以下である半導体ウェハ加工用粘着性フィルム。
[15]
上記[1]乃至[14]いずれか一つに記載の半導体ウェハ加工用粘着性フィルムにおいて、
上記紫外線硬化型粘着性樹脂は分子中に光重合性炭素-炭素二重結合を有する(メタ)アクリル系粘着性樹脂を含む半導体ウェハ加工用粘着性フィルム。
図1に示すように、本実施形態に係る半導体ウェハ加工用粘着性フィルム100(以下、「粘着性フィルム100」とも示す。)は、基材層10と、基材層10の一方の面側に設けられた紫外線硬化型の粘着性樹脂層20と、を備え、半導体ウェハの表面を保護または半導体ウェハを固定するために用いられるものである。そして、粘着性フィルム100において、粘着性樹脂層20は紫外線硬化型粘着性樹脂を含み、下記の方法で測定される、紫外線硬化後の粘着性樹脂層20の飽和帯電圧V1が2.0kV以下である。
(方法)
粘着性樹脂層20に対し、25℃の環境下で高圧水銀ランプを用いて主波長365nmの紫外線を照射強度100mW/cm2で紫外線量1080mJ/cm2照射して粘着性樹脂層20を光硬化させる。次いで、印加電圧10kV、試料と電極との距離20mm、25℃、50%RHの条件下で粘着性樹脂層20の表面に電圧の印加を30秒おこない、JIS L1094に準じて粘着性樹脂層20の表面の飽和帯電圧(V1)を算出する。
このため、帯電防止性により優れた半導体ウェハ加工用粘着性フィルムを実現することが求められていた。
まず、本発明者らは、特許文献1に記載されている粘着性フィルムは、半導体ウェハから粘着性フィルムを剥離した際に、半導体ウェハの回路形成面に粘着性フィルムの粘着成分が残りやすい、すなわち糊残りが発生しやすく、半導体ウェハ表面への耐汚染性に劣ることを知見した。
さらに、本発明者らの検討によれば、特許文献1に記載されている粘着性フィルムにおいて、糊残りの発生を抑制するために紫外線の照射量を増加させて粘着剤層の架橋度を高めると、糊残りの発生が抑制されて半導体ウェハ表面への耐汚染性が改善される一方で、今度は帯電防止性が悪化することが明らかになった。
つまり、本発明者らの検討によれば、従来の半導体ウェハ加工用粘着性フィルムには、半導体ウェハ表面への耐汚染性および帯電防止性との間には、トレードオフの関係が存在することが明らかになった。すなわち、本発明者らは、従来の半導体ウェハ加工用粘着性フィルムには、半導体ウェハ表面への耐汚染性および帯電防止性をバランスよく向上させるという観点において、改善の余地があることを見出した。
そして、本発明者らは上記知見を元にさらに鋭意検討した結果、紫外線硬化後の粘着性樹脂層20の上記飽和帯電圧V1を2.0kV以下とすることにより、上記トレードオフの関係を改善でき、半導体ウェハ表面への耐汚染性および帯電防止性をバランスよく向上できることを初めて見出した。
すなわち、本実施形態に係る半導体ウェハ加工用粘着性フィルム100は、上記層構成とすることで、半導体ウェハ表面への粘着性と耐汚染性とのバランスに優れるとともに、半導体ウェハから剥離する際に発生する静電気の量を抑制でき、品質に優れた半導体部品を安定的に得ることができる。
紫外線硬化後の粘着性樹脂層20の飽和帯電圧V1の下限値は、例えば、0.01kV以上であり、好ましくは0kVである。
これらの中でも、例えば粘着性樹脂層20中のイオン性添加剤の含有量や、粘着性樹脂層20における帯電防止層20bの有無、帯電防止層20bの位置、粘着性層20aの厚み等が、紫外線硬化後の粘着性樹脂層20の飽和帯電圧V1を所望の数値範囲とするための要素として挙げられる。
例えば、粘着性樹脂層20中のイオン性添加剤の含有量を増やしたり、帯電防止層20bを設けたりすると、飽和帯電圧V1を低下させることができる。
また、粘着性樹脂層20に凹凸吸収性樹脂層20cを設け、粘着性層20aの厚みを薄くすることにより、半導体ウェハとの粘着面(すなわち粘着性樹脂層の表面)と帯電防止層20bとの距離を小さくすることができ、その結果、飽和帯電圧V1を効果的に低下させることができる。
(方法)
粘着性樹脂層20に対し、25℃の環境下で高圧水銀ランプを用いて主波長365nmの紫外線を照射強度100mW/cm2で紫外線量200mJ/cm2照射して粘着性樹脂層20を光硬化させる。次いで、印加電圧10kV、試料と電極との距離20mm、25℃、50%RHの条件下で粘着性樹脂層20の表面に電圧の印加を30秒おこない、JIS L1094に準じて粘着性樹脂層20の表面の飽和帯電圧(V2)を算出する。
ここで、飽和帯電圧V1の半減期とは、飽和帯電圧V1の測定において、粘着性樹脂層20の表面への電圧の印加を終了してから帯電圧の値が半分に低下するまでの時間をいう。
本実施形態に係る粘着性フィルム100は、紫外線硬化後の粘着性樹脂層20の飽和帯電圧V1が上記上限値以下であるため、このような短い半減期を実現でき、帯電防止性に優れた粘着性フィルム100とすることができる。
紫外線硬化後の粘着性樹脂層20の表面のタック力が上記上限値以下であることにより、半導体ウェハ表面から粘着性フィルム100を剥離することがより容易になり、半導体ウェハ表面へ粘着性樹脂層20の一部が残ってしまうことや、粘着性フィルム100の剥離により半導体ウェハに不具合が発生してしまうこと等をより一層抑制することができる。
(方法)
粘着性樹脂層20に対し、25℃の環境下で高圧水銀ランプを用いて主波長365nmの紫外線を照射強度100mW/cm2で紫外線量1080mJ/cm2照射して粘着性樹脂層20を光硬化させる。次いで、測定装置としてプローブタックテスター(例えば、「TESTING MACHINES Inc.社製プローブタックテスター:モデル80-02-01」)を用いて、直径5mmのプローブと粘着性樹脂層20の表面とを10mm/秒の速度で接触させ、0.98N/cm2の接触荷重で10秒間接触させた後、10mm/秒の速度で上記プローブを粘着性樹脂層20の表面から垂直方向に剥離する方法で粘着性樹脂層20の表面のタック力を測定する。
ここで、貼り付ける対象の半導体ウェハが表面にはんだバンプや銅ピラーバンプ等のバンプ電極が形成された半導体ウェハの場合、半導体ウェハから粘着性フィルムを剥離する際に発生する静電気が原因で半導体ウェハに形成した回路が破壊されるという静電破壊等が起きやすいが、本実施形態に係る粘着性フィルム100を用いることによって、このような表面にバンプ電極が形成された半導体ウェハに対しても静電破壊等をより確実に抑制することが可能となる。
基材層10は、粘着性フィルム100の取り扱い性や機械的特性、耐熱性等の特性をより良好にすることを目的として設けられる層である。
基材層10は、半導体ウェハを加工する際に加わる外力に耐えうる機械的強度があれば特に限定されないが、例えば、樹脂フィルムが挙げられる。
上記樹脂フィルムを構成する樹脂としては、公知の熱可塑性樹脂を用いることができる。例えば、ポリエチレン、ポリプロピレン、ポリ(4-メチル-1-ペンテン)、ポリ(1-ブテン)等のポリオレフィン;ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリエチレンナフタレート等のポリエステル;ナイロン-6、ナイロン-66、ポリメタキシレンアジパミド等のポリアミド;ポリアクリレート;ポリメタアクリレート;ポリ塩化ビニル;ポリイミド;ポリエーテルイミド;エチレン・酢酸ビニル共重合体;ポリアクリロニトリル;ポリカーボネート;ポリスチレン;アイオノマー;ポリスルホン;ポリエーテルスルホン;ポリフェニレンエーテル等から選択される一種または二種以上を挙げることができる。
これらの中でも、透明性を良好にする観点から、ポリプロピレン、ポリエチレンテレフタレート、ポリエチレンナフタレート、ポリアミド、ポリイミド、エチレン・酢酸ビニル共重合体から選択される一種または二種以上が好ましく、ポリエチレンテレフタレート、ポリエチレンナフタレートから選択される一種または二種以上がより好ましい。
また、基材層10を形成するために使用する樹脂フィルムの形態としては、延伸フィルムであってもよいし、一軸方向または二軸方向に延伸したフィルムであってもよいが、基材層10の機械的強度を向上させる観点から、一軸方向または二軸方向に延伸したフィルムであることが好ましい。
基材層10は他の層との接着性を改良するために、表面処理を行ってもよい。具体的には、コロナ処理、プラズマ処理、アンダーコート処理、プライマーコート処理等を行ってもよい。
粘着性樹脂層20は、基材層10の一方の面側に設けられる層であり、半導体ウェハ加工用粘着性フィルム100を半導体ウェハに貼り付ける際に、半導体ウェハの表面に接触して粘着する層である。
また、粘着性樹脂層20は、後述する帯電防止層20bおよび凹凸吸収性樹脂層20cから選択される1層以上をさらに備えることが好ましく、帯電防止層20bおよび凹凸吸収性樹脂層20cの両方をさらに備えることが好ましい。
粘着性層20aは、紫外線硬化型粘着性樹脂を必須成分として含む紫外線硬化型粘着剤により形成された層である。
紫外線硬化型粘着剤としては、例えば、(メタ)アクリル系粘着剤、シリコーン系粘着剤、ウレタン系粘着剤等が挙げられる。
(メタ)アクリル系粘着剤は、紫外線硬化型粘着性樹脂として(メタ)アクリル系粘着性樹脂を必須成分として含んでいる。シリコーン系粘着剤は、紫外線硬化型粘着性樹脂としてシリコーン系粘着性樹脂を必須成分として含んでいる。ウレタン系粘着剤は、紫外線硬化型粘着性樹脂としてウレタン系粘着性樹脂を必須成分として含んでいる。
これらの中でも粘着力の調整を容易にする観点等から、(メタ)アクリル系粘着剤が好ましい。
上記官能基(Q)を有するモノマーとしては、例えば、上記官能基(P)を有する共重合性モノマーと同様のモノマーを挙げることができる。
(メタ)アクリル系粘着剤中の架橋剤の含有量は、粘着性樹脂層20の耐熱性や密着力とのバランスを向上させる観点から、(メタ)アクリル系粘着性樹脂100質量部に対し、0.1質量部以上15質量部以下であることが好ましい。
イオン性添加剤としては、例えば、カチオン性界面活性剤、アニオン性界面活性剤、ノニオン性界面活性剤、両性界面活性剤、イオン液体等が挙げられる。粘着性樹脂層20の帯電防止性をより向上できる観点からカチオン性界面活性剤およびアニオン性界面活性剤から選択される少なくとも一種が好ましく、カチオン性界面活性剤がより好ましい。
カチオン性界面活性剤としては第4級アンモニウム塩またはアミン塩型を挙げることができ、第4級アンモニウム塩が好ましい。
中でも、テトラデシルジメチルベンジルアンモニウムクロライド、セチルジメチルベンジルアンモニウムクロライド、ステアリルジメチルベンジルアンモニウムクロライドが好ましい。
紫外線硬化型粘着性樹脂中のイオン性添加剤の含有量は、紫外線硬化型粘着性樹脂100質量部に対し、0.01質量部以上10質量部以下であることが好ましく、0.1質量部以上5質量部以下であることがより好ましい。
粘着剤塗布液を塗布する方法としては、従来公知の塗布方法、例えば、ロールコーター法、リバースロールコーター法、グラビアロール法、バーコート法、コンマコーター法、ダイコーター法等が採用できる。塗布された粘着剤の乾燥条件には特に制限はないが、一般的には、80~200℃の温度範囲において、10秒~10分間乾燥することが好ましい。更に好ましくは、80~170℃において、15秒~5分間乾燥する。架橋剤と(メタ)アクリル系粘着性樹脂との架橋反応を十分に促進させるために、粘着剤塗布液の乾燥が終了した後、40~80℃において5~300時間程度加熱してもよい。
粘着性層20aの厚みの下限値は特に限定されないが、粘着力を良好にする観点から、0.5μm以上が好ましく、1.0μm以上がより好ましく、3.0μm以上がさらに好ましく、5.0μm以上が特に好ましい。
粘着性樹脂層20は、帯電防止層20bをさらに備えることが好ましい。これにより、粘着性樹脂層20の帯電防止性を向上させ、半導体ウェハから粘着性フィルム100を剥離する際に発生する静電気の量をより抑制することができる。
導電性高分子としては、例えば、ポリチオフェン系導電性高分子、ポリピロール系導電性高分子、ポリアニリン系導電性高分子、ポリ(p-フェニレンビニレン)系導電性高分子、ポリキノキサリン系導電性高分子等が挙げられる。
光学特性や外観、帯電防止性、塗工性、安定性等のバランスが良好であるという観点からポリチオフェン系導電性高分子が好ましい。ポリチオフェン系導電性高分子としては、例えば、ポリエチレンジオキシチオフェン、ポリチオフェンが挙げられる。
これらの導電性高分子は1種単独で使用してもよいし、2種以上を組み合わせて使用してもよい。
ドーピング剤は、ドーパントとして機能して、導電性高分子に導電性をより確実に付与(ドーピング)するものであって、例えば、スルホン酸系化合物が挙げられる。
スルホン酸系化合物は1種単独で使用してもよいし、2種以上を組み合わせて使用してもよい。
ドーピング剤の配合割合は、導電性高分子100質量部に対して、例えば、100~300質量部である。
導電性高分子とドーピング剤との組み合わせとしては、ポリエチレンジオキシチオフェン(PEDOT)とポリスチレンスルホン酸(PSS)との組み合わせが帯電防止性により優れるため好ましい。
バインダー樹脂としては、例えば、ポリウレタン系樹脂、ポリエステル系樹脂、(メタ)アクリル系樹脂、ポリエーテル系樹脂、セルロース系樹脂、ポリビニルアルコール系樹脂、エポキシ樹脂、ポリビニルピロリドン、ポリスチレン系樹脂、ポリエチレングリコール、ペンタエリスリトール等が挙げられる。
バインダー樹脂は1種単独で使用してもよいし、2種以上を組み合わせて使用してもよい。バインダー樹脂の含有量は、例えば、導電性高分子100質量部に対して10~500質量部である。
粘着性樹脂層20は、凹凸吸収性樹脂層20cをさらに備えることが好ましい。
これにより粘着性フィルム100全体の凹凸吸収性が向上し、半導体ウェハの凹凸形成面(例えば、回路形成面(すなわち回路パターンを含む回路面))の凹凸(バンプを含む)に追従し、半導体ウェハの凹凸形成面と粘着性フィルム100との密着性を向上させることができる。さらに半導体ウェハを加工する際に加わる外力等によって半導体ウェハの表面に形成された電極が割れることを抑制することができる。
これにより、粘着性フィルム100の凹凸吸収性を良好にしつつ粘着性層20aの厚みを薄くすることができるため、粘着性樹脂層20の表面と帯電防止層20bとの距離を小さくすることができ、その結果、粘着性フィルム100の帯電防止性をより良好にすることができる。
これらの中でも、オレフィン系樹脂、エチレン・極性モノマー共重合体が好ましい。
エチレン・極性モノマー共重合体としては、エチレン・(メタ)アクリル酸エチル共重合体、エチレン・(メタ)アクリル酸メチル共重合体、エチレン・(メタ)アクリル酸プロピル共重合体、エチレン・(メタ)アクリル酸ブチル共重合体等のエチレン・不飽和カルボン酸エステル共重合体;エチレン・酢酸ビニル共重合体、エチレン・プロピオン酸ビニル共重合体、エチレン・酪酸ビニル共重合体、エチレン・ステアリン酸ビニル共重合体等のエチレン・ビニルエステル共重合体等が挙げられる。
凹凸吸収性樹脂層20cを構成する樹脂は単独で用いてもよいし、二種以上をブレンドして用いてもよい。
また、本実施形態に係る粘着性フィルム100は、離型フィルムをさらに積層させてもよい。
(1)粘着性樹脂層20を構成する各成分の種類や配合割合
(2)粘着性樹脂層20の層構成
例1の場合、粘着性層20aの厚みが5.0μm以上50μm以下であることが好ましく、粘着性フィルム100の帯電防止性をより良好にすることができる観点から、5.0μm以上30μm未満であることがより好ましい。また、例1の場合、紫外線硬化型粘着性樹脂中のイオン性添加剤の含有量が紫外線硬化型粘着性樹脂100質量部に対し、0.1質量部以上5質量部以下であることが好ましい。
例2の場合、粘着性層20aの厚みが5.0μm以上30μm未満であることが好ましい。これにより粘着性樹脂層20の表面と帯電防止層20bとの距離を小さくすることができ、その結果、粘着性フィルム100の帯電防止性をより良好にすることができる。
例3の場合、粘着性層20aの厚みが5.0μm以上50μm以下であることが好ましく、粘着性フィルム100の帯電防止性をより良好にすることができる観点から、5.0μm以上30μm未満であることがより好ましい。また、例3の場合、紫外線硬化型粘着性樹脂中のイオン性添加剤の含有量が紫外線硬化型粘着性樹脂100質量部に対し、0.1質量部以上5質量部以下であることが好ましい。
また、粘着性樹脂層20の表面と帯電防止層20bとの距離が比較的大きい場合、粘着性層20aおよび凹凸吸収性樹脂層20cの両方にイオン性添加剤を配合することが好ましい。なお、粘着性層20aの厚みが30μm未満と薄い場合でも、粘着性層20aおよび凹凸吸収性樹脂層20cの両方にイオン性添加剤を配合してもよい。
また、基材層10と凹凸吸収性樹脂層20cとは共押出成形によって形成してもよいし、フィルム状の基材層10とフィルム状の凹凸吸収性樹脂層20cとをラミネート(積層)して形成してもよい。
ポリエチレンテレフタレートフィルム(厚さ50μm)
凹凸吸収性樹脂1:エチレン・酢酸ビニル共重合体(密度:960kg/m3、三井デュポンポリケミカル社製「エバフレックスEV150」)
帯電防止層形成用材料1:ポリエチレンジオキシチオフェン/ポリスチレンスルホン酸(PEDOT/PSS)を含む導電性材料(ナガセケムテックス社製、商品名:デナトロンP-504CT)
イオン性添加剤1:テトラデシルジメチルベンジルアンモニウムクロライド(日油社製、商品名:ニッサンカチオンM2-100)
光開始剤1:ベンジルジメチルケタール(BASF社製、商品名:イルガキュア651)
アクリル酸n-ブチル77質量部、メタクリル酸メチル16質量部、アクリル酸2-ヒドロキシエチル16質量部、および重合開始剤としてベンゾイルパーオキサイド0.5質量部を混合した。これを、トルエン20質量部、酢酸エチル80質量部が入った窒素置換フラスコ中に、撹拌しながら85℃で5時間かけて滴下し、さらに5時間撹拌して反応させた。反応終了後、この溶液を冷却し、これにトルエン10質量部、メタクリロイルオキシエチルイソシアネート(昭和電工(株)製、製品名:カレンズMOI)7質量部、およびジラウリル酸ジブチル錫0.02質量部を加え、空気を吹き込みながら85℃で12時間反応させ、重合性炭素-炭素二重結合が導入された粘着剤ポリマー1溶液を得た。
この溶液に、共重合体(固形分)100質量部に対して光開始剤としてベンジルジメチルケタール(BASF(株)製、イルガキュア651)7質量部、イソシアネート系架橋剤(三井化学(株)製、商品名:オレスターP49-75S)2質量部、1分子内に重合性炭素-炭素二重結合を2個以上有する低分子量化合物としてジペンタエリスリトールヘキサアクリレート(東亞合成(株)製、商品名:アロニックスM-400)12質量部、イオン性添加剤1:テトラデシルジメチルベンジルアンモニウムクロライド(日油(株)製、カチオンM2-100)0.5質量部を添加し、粘着層用塗布液1を得た。
イオン性添加剤1を添加しない以外は粘着層用塗布液1と同様にして粘着層用塗布液2を得た。
アクリル酸エチル48質量部、アクリル酸-2-エチルヘキシル27質量部、アクリル酸メチル20質量部、メタクリル酸グリシジル5質量部、および重合開始剤としてベンゾイルパーオキサイド0.5質量部を混合した。これを、トルエン65質量部、酢酸エチル50質量部が入った窒素置換フラスコ中に、撹拌しながら80℃で5時間かけて滴下し、さらに5時間撹拌して反応させた。反応終了後、この溶液を冷却し、これにキシレン25質量部、アクリル酸2.5質量部、およびイオン性添加剤1:テトラデシルジメチルベンジルアンモニウムクロライド0.5質量部を加え、空気を吹き込みながら85℃で32時間反応させ、重合性炭素-炭素二重結合が導入された粘着剤ポリマー3溶液を得た。
この溶液に、共重合体(固形分)100質量部に対して光開始剤としてベンジルジメチルケタール(BASF(株)製、イルガキュア651)7質量部、イソシアネート系架橋剤(三井化学(株)製、商品名:オレスターP49-75S)2質量部、1分子内に重合性炭素-炭素二重結合を2個以上有する低分子量化合物としてジペンタエリスリトールヘキサアクリレート(東亞合成(株)製、商品名:アロニックスM-400)12質量部を添加し、粘着層用塗布液3を得た。
基材層となるポリエチレンテレフタレートフィルム上に、凹凸吸収性樹脂層となる凹凸吸収性樹脂1を厚さ195μmで押出しラミネートして2層の積層フィルムを得た。
次いで、得られた積層フィルムの凹凸吸収性樹脂層に、粘着層用塗布液1を塗布した後、乾燥させて、厚み10μmの粘着性層を形成し、粘着性フィルムを得た。
得られた粘着性フィルムについて以下の評価をおこなった。得られた結果を表1に示す。
基材層となるポリエチレンテレフタレートフィルム上に、凹凸吸収性樹脂層となる凹凸吸収性樹脂1を厚さ195μmで押出しラミネートして2層の積層フィルムを得た。
次いで、別途用意した離型フィルム上に帯電防止層形成用材料1を塗布し乾燥させることによって、帯電防止膜を形成し、この帯電防止膜を凹凸吸収性樹脂層上に積層することにより、厚さ0.1μmの帯電防止層を形成した。
次いで、得られた積層フィルムの帯電防止層上に、粘着層用塗布液2を塗布した後、乾燥させて、厚み10μmの粘着性層を形成し、粘着性フィルムを得た。
得られた粘着性フィルムについて以下の評価をおこなった。得られた結果を表1に示す。
基材層となるポリエチレンテレフタレートフィルム上に、凹凸吸収性樹脂層となる凹凸吸収性樹脂1を厚さ195μmで押出しラミネートして2層の積層フィルムを得た。
次いで、別途用意した離型フィルム上に帯電防止層形成用材料1を塗布し乾燥させることによって、帯電防止膜を形成し、この帯電防止膜を凹凸吸収性樹脂層上に積層することにより、厚さ0.1μmの帯電防止層を形成した。
次いで、得られた積層フィルムの帯電防止層上に、粘着層用塗布液1を塗布した後、乾燥させて、厚み10μmの粘着性層を形成し、粘着性フィルムを得た。
得られた粘着性フィルムについて以下の評価をおこなった。得られた結果を表1に示す。
粘着層用塗布液1を粘着層用塗布液3に変更し、かつ、粘着性層の厚みを40μmにした以外は実施例3と同様にして粘着性フィルムを得た。
得られた粘着性フィルムについて以下の評価をおこなった。得られた結果を表1に示す。
粘着層用塗布液3を粘着層用塗布液1に変更した以外は実施例4と同様にして粘着性フィルムを得た。
得られた粘着性フィルムについて以下の評価をおこなった。得られた結果を表1に示す。
粘着層用塗布液1を粘着層用塗布液2にした以外は実施例1と同様にして粘着性フィルムを得た。
得られた粘着性フィルムについて以下の評価をおこなった。得られた結果を表1に示す。
帯電防止層を形成しない以外は実施例4と同様にして粘着性フィルムを得た。
得られた粘着性フィルムについて以下の評価をおこなった。得られた結果を表1に示す。
(1)飽和帯電圧の測定
粘着性フィルム中の粘着性樹脂層に対し、25℃の環境下で高圧水銀ランプ(ウシオ電機社製UVX-02528S1AJA02)を用いて主波長365nmの紫外線を照射強度100mW/cm2で紫外線量1080mJ/cm2照射して粘着性樹脂層を光硬化させた。次いで、測定装置としてシシド静電気社製スタティックオネストメーターH-0110-S4を用いて、印加電圧10kV、試料と電極との距離20mm、25℃、50%RHの条件下で粘着性樹脂層の表面に電圧の印加を30秒おこない、JIS L1094に準じて粘着性樹脂層の表面の飽和帯電圧(V1)および飽和帯電圧V1の半減期をそれぞれ算出した。
また、紫外線量を200~540mJ/cm2に変更する以外は、上記飽和帯電圧(V1)の測定と同じ手順で、粘着性樹脂層の表面の飽和帯電圧および飽和帯電圧の半減期をそれぞれ測定した。
粘着性フィルム中の粘着性樹脂層に対し、25℃の環境下で高圧水銀ランプを用いて主波長365nmの紫外線を照射強度100mW/cm2で紫外線量1080mJ/cm2照射して粘着性樹脂層を光硬化させた。次いで、測定装置としてプローブタックテスター(「TESTING MACHINES Inc.社製プローブタックテスター:モデル80-02-01」)を用いて、直径5mmのプローブと粘着性樹脂層の表面とを10mm/秒の速度で接触させ、0.98N/cm2の接触荷重で10秒間接触させた後、10mm/秒の速度でプローブを粘着性樹脂層の表面から垂直方向に剥離する方法で粘着性樹脂層の表面のタック力を測定した。
また、紫外線量を200~360mJ/cm2に変更する以外は、上記タック力の測定と同じ手順で、粘着性樹脂層の表面のタック力をそれぞれ測定した。
粘着性フィルムの帯電防止性は以下の基準で評価した。
〇:飽和帯電圧V1が2.0kV以下で、かつ、飽和帯電圧V1の半減期が100秒以下であるもの
×:飽和帯電圧V1が2.0kVを超えるか、あるいは飽和帯電圧V1の半減期が100秒を超えるもの
半導体ウェハ表面への粘着性は以下の基準で評価した。
〇:紫外線を照射しなかった粘着性樹脂層(すなわち、紫外線量が0mJ/cm2のもの)のタック力が10N/cm2以上
×:紫外線量を照射しなかった粘着性樹脂層のタック力が10N/cm2未満
半導体ウェハ表面への耐汚染性は以下の基準で評価した。
〇:紫外線量1080mJ/cm2照射で光硬化させた粘着性樹脂層のタック力が0.1N/cm2以下
×:紫外線量1080mJ/cm2照射で光硬化させた粘着性樹脂層のタック力が0.1N/cm2を超える
これに対し、紫外線硬化後の粘着性樹脂層表面の飽和帯電圧V1が2.0kVを超える比較例1~2の粘着性フィルムは半導体ウェハ表面への粘着性と耐汚染性とのバランスには優れていたが、帯電防止性が劣っていた。
Claims (15)
- 基材層と、前記基材層の一方の面側に設けられた紫外線硬化型の粘着性樹脂層と、を備え、半導体ウェハの表面を保護または半導体ウェハを固定するために用いられる粘着性フィルムであって、
前記粘着性樹脂層は紫外線硬化型粘着性樹脂を含み、
下記の方法で測定される、紫外線硬化後の前記粘着性樹脂層表面の飽和帯電圧V1が2.0kV以下である半導体ウェハ加工用粘着性フィルム。
(方法)
前記粘着性樹脂層に対し、25℃の環境下で高圧水銀ランプを用いて主波長365nmの紫外線を照射強度100mW/cm2で紫外線量1080mJ/cm2照射して前記粘着性樹脂層を光硬化させる。次いで、印加電圧10kV、試料と電極との距離20mm、25℃、50%RHの条件下で前記粘着性樹脂層の表面に電圧の印加を30秒おこない、JIS L1094に準じて前記粘着性樹脂層の表面の飽和帯電圧(V1)を算出する。 - 請求項1に記載の半導体ウェハ加工用粘着性フィルムにおいて、
バックグラインドテープである半導体ウェハ加工用粘着性フィルム。 - 請求項1または2に記載の半導体ウェハ加工用粘着性フィルムにおいて、
前記半導体ウェハの表面にはバンプ電極が形成されている半導体ウェハ加工用粘着性フィルム。 - 請求項1乃至3いずれか一項に記載の半導体ウェハ加工用粘着性フィルムにおいて、
下記の方法で測定される、紫外線硬化後の前記粘着性樹脂層の表面のタック力が0.1N/cm2以下である半導体ウェハ加工用粘着性フィルム。
(方法)
前記粘着性樹脂層に対し、25℃の環境下で高圧水銀ランプを用いて主波長365nmの紫外線を照射強度100mW/cm2で紫外線量1080mJ/cm2照射して前記粘着性樹脂層を光硬化させる。次いで、測定装置としてプローブタックテスターを用いて、直径5mmのプローブと前記粘着性樹脂層の表面とを10mm/秒の速度で接触させ、0.98N/cm2の接触荷重で10秒間接触させた後、10mm/秒の速度で前記プローブを前記粘着性樹脂層の表面から垂直方向に剥離する方法で前記粘着性樹脂層の表面のタック力を測定する。 - 請求項1乃至4いずれか一項に記載の半導体ウェハ加工用粘着性フィルムにおいて、
下記の方法で測定される、紫外線硬化後の前記粘着性樹脂層の表面の飽和帯電圧をV2としたとき、V1/V2が5.0以下である半導体ウェハ加工用粘着性フィルム。
(方法)
前記粘着性樹脂層に対し、25℃の環境下で高圧水銀ランプを用いて主波長365nmの紫外線を照射強度100mW/cm2で紫外線量200mJ/cm2照射して前記粘着性樹脂層を光硬化させる。次いで、印加電圧10kV、試料と電極との距離20mm、25℃、50%RHの条件下で前記粘着性樹脂層の表面に電圧の印加を30秒おこない、JIS L1094に準じて前記粘着性樹脂層の表面の飽和帯電圧(V2)を算出する。 - 請求項1乃至5いずれか一項に記載の半導体ウェハ加工用粘着性フィルムにおいて、
前記飽和帯電圧V1の半減期が100秒以下である半導体ウェハ加工用粘着性フィルム。 - 請求項1乃至6いずれか一項に記載の半導体ウェハ加工用粘着性フィルムにおいて、
前記粘着性樹脂層の厚みが5μm以上550μm以下である半導体ウェハ加工用粘着性フィルム。 - 請求項1乃至7いずれか一項に記載の半導体ウェハ加工用粘着性フィルムにおいて、
前記粘着性樹脂層は、前記基材層側から帯電防止層および粘着性層をこの順番に有する半導体ウェハ加工用粘着性フィルム。 - 請求項8に記載の半導体ウェハ加工用粘着性フィルムにおいて、
前記帯電防止層は導電性高分子を含む半導体ウェハ加工用粘着性フィルム。 - 請求項8または9に記載の半導体ウェハ加工用粘着性フィルムにおいて、
前記粘着性層は紫外線硬化型粘着性樹脂およびイオン性添加剤を含む半導体ウェハ加工用粘着性フィルム。 - 請求項8乃至10いずれか一項に記載の半導体ウェハ加工用粘着性フィルムにおいて、
前記粘着性樹脂層は、前記基材層と前記帯電防止層との間に凹凸吸収性樹脂層をさらに有する半導体ウェハ加工用粘着性フィルム。 - 請求項8乃至11いずれか一項に記載の半導体ウェハ加工用粘着性フィルムにおいて、
前記粘着性層の厚みが30μm未満である半導体ウェハ加工用粘着性フィルム。 - 請求項8乃至10いずれか一項に記載の半導体ウェハ加工用粘着性フィルムにおいて、
前記粘着性樹脂層は、前記基材層と前記帯電防止層との間に凹凸吸収性樹脂層をさらに有し、かつ、前記粘着性層の厚みが30μm未満である半導体ウェハ加工用粘着性フィルム。 - 請求項8乃至13いずれか一項に記載の半導体ウェハ加工用粘着性フィルムにおいて、
前記帯電防止層の厚みが0.01μm以上10μm以下である半導体ウェハ加工用粘着性フィルム。 - 請求項1乃至14いずれか一項に記載の半導体ウェハ加工用粘着性フィルムにおいて、
前記紫外線硬化型粘着性樹脂は分子中に光重合性炭素-炭素二重結合を有する(メタ)アクリル系粘着性樹脂を含む半導体ウェハ加工用粘着性フィルム。
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