WO2017188203A1 - 保護膜付き半導体チップの製造方法及び半導体装置の製造方法 - Google Patents
保護膜付き半導体チップの製造方法及び半導体装置の製造方法 Download PDFInfo
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- WO2017188203A1 WO2017188203A1 PCT/JP2017/016261 JP2017016261W WO2017188203A1 WO 2017188203 A1 WO2017188203 A1 WO 2017188203A1 JP 2017016261 W JP2017016261 W JP 2017016261W WO 2017188203 A1 WO2017188203 A1 WO 2017188203A1
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- protective film
- forming
- film
- meth
- sensitive adhesive
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Images
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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
- H01L21/50—Assembly of semiconductor devices using processes or apparatus not provided for in a single one of the subgroups H01L21/06 - H01L21/326, e.g. sealing of a cap to a base of a container
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- H—ELECTRICITY
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
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- H01L23/31—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape
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- 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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- H01L21/677—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 conveying, e.g. between different workstations
- H01L21/67703—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 conveying, e.g. between different workstations between different workstations
- H01L21/67712—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 conveying, e.g. between different workstations between different workstations the substrate being handled substantially vertically
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- H01L21/677—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 conveying, e.g. between different workstations
- H01L21/67703—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 conveying, e.g. between different workstations between different workstations
- H01L21/67721—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 conveying, e.g. between different workstations between different workstations the substrates to be conveyed not being semiconductor wafers or large planar substrates, e.g. chips, lead frames
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- H01L21/77—Manufacture or treatment of devices consisting of a plurality of solid state components or integrated circuits formed in, or on, a common substrate
- H01L21/78—Manufacture or treatment of devices consisting of a plurality of solid state components or integrated circuits formed in, or on, a common substrate with subsequent division of the substrate into plural individual devices
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- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
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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
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- 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
- C09J2301/00—Additional features of adhesives in the form of films or foils
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Definitions
- the present invention relates to a method for manufacturing a semiconductor chip with a protective film and a method for manufacturing a semiconductor device.
- a semiconductor device using a mounting method called a so-called face-down method has been manufactured.
- a semiconductor chip having electrodes such as bumps on a circuit surface is used, and the electrodes are bonded to a substrate. For this reason, the back surface opposite to the circuit surface of the semiconductor chip may be exposed.
- a resin film containing an organic material is formed as a protective film on the exposed back surface of the semiconductor chip, and may be taken into the semiconductor device as a semiconductor chip with a protective film.
- the protective film is used to prevent cracks from occurring in the semiconductor chip after the dicing process or packaging.
- a protective film-forming composite sheet comprising a protective film-forming film for forming a protective film on a support sheet is used.
- the protective film forming film can form a protective film by curing, and the support sheet can be used as a dicing sheet, and the protective film forming film and the dicing sheet are integrated. It is possible that
- a protective film-forming composite sheet for example, a sheet provided with a thermosetting protective film-forming film that forms a protective film by being cured by heating is currently mainly used.
- a protective film-forming composite sheet is pasted to the back surface (surface opposite to the electrode-forming surface) of the semiconductor wafer with a thermosetting protective film-forming film, and then the protective film-forming film is heated.
- the semiconductor wafer is divided together with the protective film by dicing to form a semiconductor chip. Then, the semiconductor chip is picked up while being separated from the support sheet while the protective film is stuck.
- hardening and dicing of the film for protective film formation may be performed in the reverse order.
- thermosetting protective film-forming film since the heat curing of the thermosetting protective film-forming film usually takes a long time of about several hours, shortening of the curing time is desired.
- a protective film-forming film that can be cured by irradiation with energy rays such as ultraviolet rays has been studied.
- an energy ray curable protective film (see Patent Document 1) formed on a release film, and an energy ray curable chip protective film that can form a protective film having high hardness and excellent adhesion to a semiconductor chip (Patent Document) 2).
- the present invention provides a good protective film on the back surface of the semiconductor chip without fear of chip jumping or intrusion of cutting water between the protective film-forming film or the protective film and the support sheet. It is an object to provide a method for manufacturing a semiconductor chip with a protective film and a method for manufacturing a semiconductor device.
- the present invention provides a laminate comprising a support sheet, an energy ray-curable protective film-forming film, and a semiconductor wafer in this order, and dicing the semiconductor wafer, and then forming the protective film
- a method for producing a semiconductor chip with a protective film wherein the film is cured by irradiating energy rays.
- the adhesive force of the said laminated body between a support sheet and the said film for protective film formation is 100 mN / 25mm or more.
- the laminate is obtained by pasting the protective film-forming film on the semiconductor wafer and then sticking the support sheet to the protective film-forming film. May be.
- the laminate includes the protective film-forming film side of the protective film-forming composite sheet comprising the protective film-forming film on a support sheet. It may be affixed to a wafer.
- the method for manufacturing a semiconductor device of the present invention picks up a semiconductor chip with a protective film obtained by any of the manufacturing methods described above and connects the semiconductor chip to a substrate.
- a protective film when dicing a semiconductor wafer, a protective film can be formed on a semiconductor chip without fear of chip jumping or intrusion of cutting water between the protective film forming film or the protective film and the support sheet.
- a method of manufacturing a semiconductor chip with a protective film and a method of manufacturing a semiconductor device are provided.
- FIG. 1 is a schematic view showing a method for manufacturing a semiconductor chip with a protective film according to the present invention.
- the manufacturing method of the semiconductor chip 19 with a protective film according to the present invention includes dicing the semiconductor wafer 18 of a laminate including the support sheet 10, the energy ray-curable protective film forming film 13 and the semiconductor wafer 18 in this order, Next, the protective film-forming film 13 is cured by irradiation with energy rays. After the dicing, the protective film forming film 13 is irradiated with energy rays and cured, so that the protective film forming film 13 at the time of dicing is relatively soft. Therefore, when the semiconductor wafer 18 is diced, the protective film forming film 13 is used.
- a good protective film 13 ′ can be formed on the back surface of the semiconductor chip 19 without fear of entering cutting water between the protective film 13 ′ and the support sheet 10.
- “dicing” is exemplified by cutting a semiconductor wafer while rotating a dicing blade in which diamond abrasive grains are embedded at high speed, and cutting a semiconductor wafer by a laser dicing method using laser light.
- the laminated body may be one obtained by attaching the protective film-forming film to a semiconductor wafer and then attaching the protective film to the support sheet. At this time, the protective film-forming film suitable for product / manufacturing of a semiconductor wafer and Support sheets can be appropriately selected and used.
- the manufacturing method of the semiconductor chip with a protective film of this invention in this case can be shown below. That is, after a protective film-forming film is attached to the back surface of the semiconductor wafer (the surface opposite to the electrode-forming surface), the protective film-forming film is attached to a support sheet to obtain a laminate. Next, the semiconductor wafer is divided together with the protective film-forming film by dicing to form semiconductor chips. Next, the divided protective film-forming film is irradiated with energy rays, and the protective film-forming film is cured to obtain a semiconductor chip with a protective film.
- the laminate may be a laminate of the protective film-forming composite sheet comprising the protective film-forming film on a support sheet, and the protective film-forming film side attached to the semiconductor wafer.
- a sticking process can be simplified.
- the manufacturing method of the semiconductor chip with a protective film of this invention in this case can be shown below. That is, the protective film-forming composite sheet is attached to the back surface (surface opposite to the electrode forming surface) of the semiconductor wafer with the protective film-forming film. Next, the semiconductor wafer is divided together with the protective film-forming film by dicing to form semiconductor chips. Next, the divided protective film-forming film is irradiated with energy rays, and the protective film-forming film is cured to obtain a semiconductor chip with a protective film.
- the semiconductor chip with the protective film is picked up by separating the semiconductor chip with the protective film from the support sheet in a state similar to the conventional method, with the protective film attached, and the obtained semiconductor chip with the protective film is a substrate. After the flip chip connection to the circuit surface, a semiconductor package is obtained. Then, a target semiconductor device may be manufactured using this semiconductor package.
- the composite sheet for protective film formation that can be used in the present invention comprises an energy ray-curable protective film-forming film on a support sheet.
- the “protective film-forming film” means a film before curing
- the “protective film” means a film obtained by curing the protective film-forming film.
- “energy beam” means an electromagnetic wave or charged particle beam having energy quanta, and examples thereof include ultraviolet rays, radiation, and electron beams.
- Ultraviolet rays can be irradiated by using, for example, a high pressure mercury lamp, a fusion H lamp, a xenon lamp, a black light, an LED lamp, or the like as an ultraviolet ray source.
- the electron beam can be emitted by an electron beam accelerator or the like.
- “energy ray curable” means the property of being cured by irradiation with energy rays
- “non-energy ray curable” means the property of not being cured even when irradiated with energy rays. .
- the adhesive force between the support sheet and the protective film-forming film of the laminate is not particularly limited, and may be, for example, 80 mN / 25 mm or more, or 100 mN / 25 mm or more, It may be 150 mN / 25 mm or more, may be 200 mN / 25 mm or more, and the upper limit is not particularly limited, but may be 10,000 mN / 25 mm or less, or 8000 mN / 25 mm or less, It may be 7000 mN / 25 mm or less.
- the lower limit value or more scattering of silicon chips is suppressed during dicing, and cutting water can be prevented from entering between the protective film-forming film and the support sheet.
- the adhesive force between the protective film and the support sheet when cured by energy ray irradiation to form a protective film can be easily adjusted appropriately.
- the adhesive force between the support sheet and the protective film-forming film of the laminate is 10 to 30000 mN / 25 mm, preferably 100 to 20000 mN / 25 mm, It is more preferably 150 to 10000 mN / 25 mm, and further preferably 200 to 8000 mN / 25 mm.
- the adhesive force between the said support sheet and the said film for protective film formation can be measured with the measuring method mentioned later.
- the protective film-forming film is cured by irradiation with energy rays and becomes a protective film.
- This protective film protects the back surface (the surface opposite to the electrode forming surface) of the semiconductor wafer or semiconductor chip.
- the protective film-forming film is soft and can be easily attached to an object to be attached.
- the adhesive force between the protective film and the support sheet is preferably 50 to 1500 mN / 25 mm, and preferably 52 to 1450 mN / 25 mm. Is more preferable, and 53 to 1430 mN / 25 mm is particularly preferable.
- the adhesive force When the adhesive force is equal to or higher than the lower limit value, pickup of a semiconductor chip with a protective film other than the target is suppressed during pickup of the semiconductor chip with a protective film, and the target semiconductor chip with a protective film is highly selectively picked up. it can.
- the adhesive force is less than or equal to the upper limit value, cracking and chipping of the semiconductor chip are suppressed when the semiconductor chip with a protective film is picked up.
- the adhesive force is within a specific range, the composite sheet for forming a protective film has good pickup suitability.
- the adhesive force between the said protective film and the said support sheet can be measured with the measuring method mentioned later.
- the protective film-forming film is energy ray curable, a conventional protective film-forming composite having a thermosetting protective film-forming film is provided.
- the protective film can be formed by curing in a shorter time than in the case of the sheet.
- a protective film-forming film can be attached to the back surface of a semiconductor wafer, and then a support sheet can be attached to the protective film-forming film.
- a protective film-forming film and the support sheet the protective film-forming film and the support sheet described in the description of the protective film-forming composite sheet can be used as appropriate.
- the thickness of the semiconductor wafer or semiconductor chip, which is a target for use of the composite sheet for forming a protective film is not particularly limited, but is 30 to 1000 ⁇ m because the effects of the present invention can be obtained more remarkably. Preferably, it is 100 to 300 ⁇ m.
- the configuration of the present invention will be described in detail.
- the support sheet may be composed of one layer (single layer) or may be composed of two or more layers.
- the constituent materials and thicknesses of the plurality of layers may be the same or different from each other, and the combination of the plurality of layers is not particularly limited as long as the effects of the present invention are not impaired.
- “a plurality of layers may be the same or different from each other” means “all layers may be the same or all layers are different. Means that only some of the layers may be the same ”, and“ a plurality of layers are different from each other ”means“ at least one of the constituent materials and thickness of each layer is different from each other ” To do.
- Preferred support sheets include, for example, those in which the pressure-sensitive adhesive layer is directly contacted and laminated on the substrate, those in which the pressure-sensitive adhesive layer is laminated on the substrate via an intermediate layer, and only the substrate. And the like.
- FIG. 2 is a cross-sectional view schematically showing one embodiment of a composite sheet for forming a protective film that can be used in the present invention.
- the protective film-forming composite sheet 1 ⁇ / b> A shown here is provided with a pressure-sensitive adhesive layer 12 on a substrate 11 and a protective film-forming film 13 on the pressure-sensitive adhesive layer 12.
- the support sheet 10 is a laminate of the base material 11 and the pressure-sensitive adhesive layer 12.
- the protective film-forming composite sheet 1 ⁇ / b> A has a protective film-forming film 13 laminated on one surface 10 a of the support sheet 10. Have a configuration.
- the protective film forming composite sheet 1 ⁇ / b> A further includes a release film 15 on the protective film forming film 13.
- the pressure-sensitive adhesive layer 12 is laminated on one surface 11a of the substrate 11, and the protective film-forming film 13 is laminated on the entire surface 12a of the pressure-sensitive adhesive layer 12, thereby forming the protective film.
- the jig adhesive layer 16 is laminated on a part of the surface 13 a of the film 13, that is, in the vicinity of the peripheral edge, and the jig adhesive layer 16 is laminated on the surface 13 a of the protective film forming film 13.
- a release film 15 is laminated on the surface that is not formed and the surface 16 a (upper surface and side surface) of the adhesive layer 16 for jigs.
- the adhesive strength is preferably 50 to 1500 mN / 25 mm.
- the adhesive layer 16 for jigs may have, for example, a single-layer structure containing an adhesive component, or a plurality of layers in which layers containing an adhesive component are laminated on both surfaces of a core sheet. It may be of a structure.
- the composite sheet 1A for forming a protective film shown in FIG. 2 has a back surface of a semiconductor wafer (not shown) attached to the front surface 13a of the protective film forming film 13 with the release film 15 removed.
- the upper surface of the surface 16a of the adhesive layer 16 is used by being attached to a jig such as a ring frame.
- FIG. 3 is a cross-sectional view schematically showing another embodiment of the composite sheet for forming a protective film that can be used in the present invention.
- the same components as those shown in the already explained figures are given the same reference numerals as those in the already explained figures, and their detailed explanations are omitted.
- the protective film-forming composite sheet 1B shown here is the same as the protective film-forming composite sheet 1A shown in FIG. 2 except that the jig adhesive layer 16 is not provided. That is, in the protective sheet-forming composite sheet 1B, the pressure-sensitive adhesive layer 12 is laminated on one surface 11a of the base material 11, and the protective film-forming film 13 is laminated on the entire surface 12a of the pressure-sensitive adhesive layer 12. A release film 15 is laminated on the entire surface 13 a of the film forming film 13.
- the protective sheet-forming composite sheet 1B shown in FIG. 3 has a semiconductor wafer (not shown) in a partial region on the center side of the surface 13a of the protective film-forming film 13 with the release film 15 removed.
- the back surface is affixed, and the region near the periphery of the protective film-forming film 13 is affixed to a jig such as a ring frame and used.
- FIG. 4 is a cross-sectional view schematically showing still another embodiment of a protective film-forming composite sheet that can be used in the present invention.
- the protective sheet-forming composite sheet 1 ⁇ / b> C shown here is the same as the protective film-forming composite sheet 1 ⁇ / b> A shown in FIG. 2, except that the adhesive layer 12 is not provided. That is, in the protective film-forming composite sheet 1 ⁇ / b> C, the support sheet 10 is made of only the base material 11.
- a protective film-forming film 13 is laminated on one surface 11a of the substrate 11 (one surface 10a of the support sheet 10), and a part of the surface 13a of the protective film-forming film 13, that is, in a region near the peripheral portion.
- the jig adhesive layer 16 is laminated, and the surface on which the jig adhesive layer 16 is not laminated and the surface 16a (upper surface) of the jig adhesive layer 16 And the side surface) are laminated with a release film 15.
- the adhesive force between the protective film-forming film 13 after curing (ie, the protective film) and the support sheet 10 is: It is preferably 50 to 1500 mN / 25 mm.
- the protective film forming composite sheet 1C is formed on the surface 13a of the protective film forming film 13 with the release film 15 removed.
- the back surface of (not shown) is attached, and the upper surface of the surface 16a of the jig adhesive layer 16 is attached to a jig such as a ring frame.
- FIG. 5 is a cross-sectional view schematically showing still another embodiment of a protective film-forming composite sheet that can be used in the present invention.
- the protective sheet-forming composite sheet 1D shown here is the same as the protective film-forming composite sheet 1C shown in FIG. 4 except that it does not include the jig adhesive layer 16. That is, in the protective sheet-forming composite sheet 1D, the protective film-forming film 13 is laminated on one surface 11a of the substrate 11, and the release film 15 is laminated on the entire surface 13a of the protective film-forming film 13. Yes.
- the protective film-forming composite sheet 1D shown in FIG. 5 is the same as the protective film-forming composite sheet 1B shown in FIG. 3, with the release film 15 being removed, of the surface 13a of the protective film-forming film 13,
- the back surface of a semiconductor wafer (not shown) is affixed to a partial area on the center side, and the area near the periphery of the protective film forming film 13 is affixed to a jig such as a ring frame. .
- FIG. 6 is a cross-sectional view schematically showing still another embodiment of a protective film-forming composite sheet that can be used in the present invention.
- the protective film-forming composite sheet 1E shown here is the same as the protective film-forming composite sheet 1B shown in FIG. 3 except that the shape of the protective film-forming film is different. That is, the protective film-forming composite sheet 1 ⁇ / b> E includes the pressure-sensitive adhesive layer 12 on the base material 11 and the protective film-forming film 23 on the pressure-sensitive adhesive layer 12.
- the support sheet 10 is a laminate of the base material 11 and the pressure-sensitive adhesive layer 12, and in other words, the protective film-forming composite sheet 1E is formed by laminating the protective film-forming film 23 on one surface 10a of the support sheet 10. Have a configuration.
- the protective film-forming composite sheet 1 ⁇ / b> E further includes a release film 15 on the protective film-forming film 23.
- the pressure-sensitive adhesive layer 12 is laminated on one surface 11a of the substrate 11, and a part of the surface 12a of the pressure-sensitive adhesive layer 12, that is, a protective film-forming film is formed in the central region. 23 are stacked.
- the release film 15 is laminated on the surface 12 a of the pressure-sensitive adhesive layer 12 on which the protective film-forming film 23 is not laminated and on the surface 23 a (upper surface and side surfaces) of the protective film-forming film 23. .
- the protective film-forming film 23 When the protective film-forming composite sheet 1E is viewed from above and viewed in plan, the protective film-forming film 23 has a smaller surface area than the pressure-sensitive adhesive layer 12, and has a circular shape or the like, for example.
- the adhesive force between the cured protective film-forming film 23 (that is, the protective film) and the support sheet 10 is 50 to 1500 mN / 25 mm is preferable.
- the back surface of the semiconductor wafer (not shown) is pasted on the front surface 23a of the protective film-forming film 23 with the release film 15 removed.
- the surface on which the protective film forming film 23 is not laminated is attached to a jig such as a ring frame and used.
- the surface 12a of the pressure-sensitive adhesive layer 12 is cured on the surface on which the protective film-forming film 23 is not laminated in the same manner as shown in FIGS.
- a tool adhesive layer may be laminated (not shown).
- the protective film forming composite sheet 1E provided with such a jig adhesive layer has a ring frame whose surface is similar to the protective film forming composite sheet shown in FIGS. Attached to a jig such as
- the protective film-forming composite sheet that can be used in the present invention is provided with an adhesive layer for jigs regardless of the form of the support sheet and the protective film-forming film. Also good. However, normally, as shown in FIGS. 2 and 4, the protective film forming composite sheet provided with the jig adhesive layer is provided with the jig adhesive layer on the protective film forming film. Is preferred.
- the composite sheet for forming a protective film that can be used in the present invention is not limited to the one shown in FIGS. 2 to 6, and a part of the composite sheet shown in FIGS.
- the configuration may be changed or deleted, or another configuration may be added to what has been described so far.
- an intermediate layer may be provided between the base material 11 and the protective film-forming film 13. Any intermediate layer can be selected according to the purpose.
- an intermediate layer may be provided between the base material 11 and the pressure-sensitive adhesive layer 12.
- the support sheet may be formed by laminating a base material, an intermediate layer, and an adhesive layer in this order.
- the intermediate layer is the same as the intermediate layer that may be provided in the protective film-forming composite sheet shown in FIGS. 4 and 5.
- a layer other than the intermediate layer may be provided at an arbitrary position.
- a gap may be partially formed between the release film and the layer that is in direct contact with the release film.
- the size and shape of each layer can be arbitrarily adjusted according to the purpose.
- a layer that is in direct contact with the protective film-forming film of the support sheet, such as an adhesive layer, is non-energy ray curable.
- a semiconductor chip having a protective film on the back surface can be picked up more easily.
- the support sheet may be transparent, opaque, or colored depending on the purpose. Among them, in the present invention in which the protective film-forming film has energy ray curability, the support sheet is preferably capable of transmitting energy rays.
- the transmittance of light having a wavelength of 375 nm is preferably 30% or more, more preferably 50% or more, and particularly preferably 70% or more.
- the degree of curing of the protective film forming film is further improved.
- the upper limit value of the transmittance of light having a wavelength of 375 nm is not particularly limited, but may be 95%, for example.
- the transmittance of light having a wavelength of 532 nm is preferably 30% or more, more preferably 50% or more, and particularly preferably 70% or more.
- the upper limit value of the transmittance of light having a wavelength of 532 nm is not particularly limited, but can be, for example, 95%.
- the transmittance of light having a wavelength of 1064 nm is preferably 30% or more, more preferably 50% or more, and particularly preferably 70% or more.
- the upper limit value of the transmittance of light having a wavelength of 1064 nm is not particularly limited, but can be, for example, 95%.
- the base material is in the form of a sheet or film, and examples of the constituent material include various resins.
- the resin include polyethylenes such as low density polyethylene (LDPE), linear low density polyethylene (LLDPE), and high density polyethylene (HDPE); other than polyethylene such as polypropylene, polybutene, polybutadiene, polymethylpentene, and norbornene resin.
- Polyolefins such as ethylene-vinyl acetate copolymer, ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic acid ester copolymer, ethylene-norbornene copolymer (ethylene as a monomer)
- a copolymer obtained by using a vinyl chloride resin such as polyvinyl chloride and vinyl chloride copolymer (a resin obtained by using vinyl chloride as a monomer); polystyrene; polycycloolefin; polyethylene terephthalate, polyethylene Naphtha Polyesters such as polyesters, polybutylene terephthalates, polyethylene isophthalates, polyethylene-2,6-naphthalene dicarboxylates, wholly aromatic polyesters in which all the structural units have an aromatic cyclic group; Poly (meth) acrylic acid ester; Polyurethane; Polyurethane acrylate; Polyimide; Polyamide; Polycarbonate; Fluororesin
- the polymer alloy of the polyester and the other resin is preferably one in which the amount of the resin other than the polyester is relatively small.
- the resin include a crosslinked resin in which one or more of the resins exemplified so far are crosslinked; and a modified resin such as an ionomer using one or more of the resins exemplified so far. Can be mentioned.
- (meth) acrylic acid is a concept including both “acrylic acid” and “methacrylic acid”. The same applies to terms similar to (meth) acrylic acid.
- the resin constituting the substrate may be only one kind, or two or more kinds, and in the case of two or more kinds, the combination and ratio thereof can be arbitrarily selected.
- the substrate may be composed of one layer (single layer) or may be composed of two or more layers. When the substrate is composed of a plurality of layers, these layers may be the same or different from each other.
- the combination of layers is not particularly limited.
- the thickness of the substrate is preferably 50 to 300 ⁇ m, more preferably 60 to 100 ⁇ m.
- the thickness of the substrate means the thickness of the entire substrate.
- the thickness of the substrate composed of a plurality of layers means the total thickness of all the layers constituting the substrate. means.
- the “thickness” is a value represented by an average of five arbitrary points of an object measured with a contact-type thickness meter.
- the base material is preferably one having high thickness accuracy, that is, one in which variation in thickness is suppressed regardless of the part.
- materials that can be used to construct such a substrate with high thickness accuracy include polyethylene, polyolefins other than polyethylene, polyethylene terephthalate, ethylene-vinyl acetate copolymer, and the like. Is mentioned.
- the base material contains various known additives such as a filler, a colorant, an antistatic agent, an antioxidant, an organic lubricant, a catalyst, and a softener (plasticizer) in addition to the main constituent material such as the resin. May be.
- the substrate may be transparent, opaque, colored according to the purpose, or other layers may be deposited.
- the substrate preferably transmits energy rays.
- the substrate is subjected to a roughening treatment such as sandblast treatment, solvent treatment, corona discharge treatment, electron beam irradiation treatment, plasma treatment.
- the surface may be subjected to oxidation treatment such as ozone / ultraviolet irradiation treatment, flame treatment, chromic acid treatment, and hot air treatment.
- the substrate may have a surface that has been primed.
- the base material is a layer that prevents the base material from adhering to other sheets or the base material from adhering to the adsorption table when the antistatic coating layer and the composite sheet for forming the protective film are stored in an overlapping manner. It may have.
- the substrate preferably has a surface subjected to electron beam irradiation treatment from the viewpoint that generation of fragments of the substrate due to blade friction during dicing is suppressed.
- the base material can be manufactured by a known method.
- a base material containing a resin can be produced by molding a resin composition containing the resin.
- the said adhesive layer is a sheet form or a film form, and contains an adhesive.
- the adhesive include adhesive resins such as acrylic resins, urethane resins, rubber resins, silicone resins, epoxy resins, polyvinyl ethers, polycarbonates, ester resins, and acrylic resins are preferable. .
- the “adhesive resin” is a concept including both a resin having adhesiveness and a resin having adhesiveness.
- the resin itself has adhesiveness as well as an additive.
- Resins that exhibit tackiness when used in combination with other components such as those that exhibit adhesiveness due to the presence of a trigger such as heat or water are also included.
- the pressure-sensitive adhesive layer may be composed of one layer (single layer), may be composed of two or more layers, and when composed of a plurality of layers, these layers may be the same or different from each other.
- the combination of the multiple layers is not particularly limited.
- the thickness of the pressure-sensitive adhesive layer is preferably 1 to 100 ⁇ m, more preferably 1 to 60 ⁇ m, and particularly preferably 1 to 30 ⁇ m.
- the “thickness of the pressure-sensitive adhesive layer” means the thickness of the whole pressure-sensitive adhesive layer.
- the thickness of the pressure-sensitive adhesive layer composed of a plurality of layers is the total of all layers constituting the pressure-sensitive adhesive layer. Means the thickness.
- the optical properties of the pressure-sensitive adhesive layer only need to satisfy the optical properties of the support sheet described above. That is, the pressure-sensitive adhesive layer may be transparent, opaque, or colored depending on the purpose. In the present invention in which the protective film-forming film has energy ray curability, the pressure-sensitive adhesive layer is preferably capable of transmitting energy rays.
- the pressure-sensitive adhesive layer may be formed using an energy ray-curable pressure-sensitive adhesive, or may be formed using a non-energy ray-curable pressure-sensitive adhesive.
- the pressure-sensitive adhesive layer formed using the energy ray-curable pressure-sensitive adhesive can easily adjust the physical properties before and after curing.
- the pressure-sensitive adhesive layer can be formed using a pressure-sensitive adhesive composition containing a pressure-sensitive adhesive.
- an adhesive layer can be formed in the target site
- a more specific method for forming the pressure-sensitive adhesive layer will be described later in detail, along with methods for forming other layers.
- the ratio of the content of components that do not vaporize at room temperature in the pressure-sensitive adhesive composition is usually the same as the ratio of the content of the components of the pressure-sensitive adhesive layer.
- “normal temperature” means a temperature that is not particularly cooled or heated, that is, a normal temperature, and examples thereof include a temperature of 15 to 25 ° C.
- the adhesive composition may be applied by a known method, for example, an air knife coater, blade coater, bar coater, gravure coater, roll coater, roll knife coater, curtain coater, die coater, knife coater, screen coater. And a method using various coaters such as a Meyer bar coater, a rod coater, and a kiss coater.
- the drying conditions of the pressure-sensitive adhesive composition are not particularly limited, but when the pressure-sensitive adhesive composition contains a solvent described later, it is preferably heat-dried. In this case, for example, at 70 to 130 ° C. for 10 seconds to It is preferable to dry under conditions of 5 minutes.
- the pressure-sensitive adhesive composition containing the energy ray-curable pressure-sensitive adhesive that is, the energy ray-curable pressure-sensitive adhesive composition, for example, non-energy ray-curable pressure-sensitive adhesive
- Energy-ray-curable adhesive resin (I-2a) in which an unsaturated group is introduced into the side chain of the linear-curable adhesive resin (I-1a) hereinafter referred to as “adhesive resin (I-2a)”
- the pressure-sensitive adhesive composition (I-1) contains a non-energy ray-curable pressure-sensitive adhesive resin (I-1a) and an energy ray-curable compound.
- the adhesive resin (I-1a) is preferably an acrylic resin.
- the acrylic resin the acrylic polymer which has a structural unit derived from the (meth) acrylic-acid alkylester at least is mentioned, for example.
- the acrylic resin may have only one type of structural unit, two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected.
- Examples of the (meth) acrylic acid alkyl ester include those in which the alkyl group constituting the alkyl ester has 1 to 20 carbon atoms, and the alkyl group is linear or branched. Is preferred. More specifically, as (meth) acrylic acid alkyl ester, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, (meth) acrylic acid n-butyl, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, (Meth) acrylic acid 2-ethylhexyl, (meth) acrylic acid isooctyl, (meth) acrylic acid n-
- the acrylic polymer preferably has a structural unit derived from a (meth) acrylic acid alkyl ester in which the alkyl group has 4 or more carbon atoms.
- the alkyl group preferably has 4 to 12 carbon atoms, and more preferably 4 to 8 carbon atoms.
- the (meth) acrylic acid alkyl ester having 4 or more carbon atoms in the alkyl group is preferably an acrylic acid alkyl ester.
- the acrylic polymer preferably has a structural unit derived from a functional group-containing monomer in addition to the structural unit derived from an alkyl (meth) acrylate.
- the functional group-containing monomer for example, the functional group reacts with a cross-linking agent described later to become a starting point of cross-linking, or the functional group reacts with an unsaturated group in the unsaturated group-containing compound described later. And those that allow introduction of an unsaturated group into the side chain of the acrylic polymer.
- Examples of the functional group in the functional group-containing monomer include a hydroxyl group, a carboxy group, an amino group, and an epoxy group. That is, examples of the functional group-containing monomer include a hydroxyl group-containing monomer, a carboxy group-containing monomer, an amino group-containing monomer, and an epoxy group-containing monomer.
- hydroxyl group-containing monomer examples include hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, (meth) Hydroxyalkyl (meth) acrylates such as 2-hydroxybutyl acrylate, 3-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate; non- (meth) acrylic non-methacrylates such as vinyl alcohol and allyl alcohol Saturated alcohol (unsaturated alcohol which does not have a (meth) acryloyl skeleton) etc. are mentioned.
- Examples of the carboxy group-containing monomer include ethylenically unsaturated monocarboxylic acids (monocarboxylic acids having an ethylenically unsaturated bond) such as (meth) acrylic acid and crotonic acid; fumaric acid, itaconic acid, maleic acid, citracone Ethylenically unsaturated dicarboxylic acids such as acids (dicarboxylic acids having an ethylenically unsaturated bond); anhydrides of the ethylenically unsaturated dicarboxylic acids; carboxyalkyl esters of (meth) acrylic acid such as 2-carboxyethyl methacrylate, etc. It is done.
- monocarboxylic acids having an ethylenically unsaturated bond such as (meth) acrylic acid and crotonic acid
- fumaric acid, itaconic acid maleic acid, citracone
- Ethylenically unsaturated dicarboxylic acids such as acids (dica
- the functional group-containing monomer is preferably a hydroxyl group-containing monomer or a carboxy group-containing monomer, more preferably a hydroxyl group-containing monomer.
- the functional group-containing monomer constituting the acrylic polymer may be only one type, or two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected.
- the content of the structural unit derived from the functional group-containing monomer is preferably 1 to 35% by mass, more preferably 2 to 32% by mass with respect to the total mass of the structural unit.
- the content is preferably 3 to 30% by mass.
- the acrylic polymer may further have a structural unit derived from another monomer.
- the other monomer is not particularly limited as long as it is copolymerizable with (meth) acrylic acid alkyl ester or the like.
- Examples of the other monomer include styrene, ⁇ -methylstyrene, vinyl toluene, vinyl formate, vinyl acetate, acrylonitrile, acrylamide and the like.
- the other monomer constituting the acrylic polymer may be only one type, or two or more types, and in the case of two or more types, their combination and ratio can be arbitrarily selected.
- the acrylic polymer can be used as the above-mentioned non-energy ray curable adhesive resin (I-1a).
- the functional group in the acrylic polymer is reacted with an unsaturated group-containing compound having an energy ray-polymerizable unsaturated group (energy ray-polymerizable group). It can be used as the resin (I-2a).
- the pressure-sensitive adhesive composition (I-1) contained in the pressure-sensitive adhesive composition (I-1) may be only one type, or two or more types, and when there are two or more types, the combination and ratio thereof are arbitrary. You can choose.
- the content of the pressure-sensitive adhesive resin (I-1a) is 5 to 99% by mass with respect to the total mass of the pressure-sensitive adhesive composition (I-1). It is preferably 10 to 95% by mass, more preferably 15 to 90% by mass.
- Examples of the energy ray-curable compound contained in the pressure-sensitive adhesive composition (I-1) include monomers or oligomers having an energy ray-polymerizable unsaturated group and curable by irradiation with energy rays.
- examples of the monomer include trimethylolpropane tri (meth) acrylate, pentaerythritol (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and 1,4.
- Polybutyl (meth) acrylates such as butylene glycol di (meth) acrylate and 1,6-hexanediol (meth) acrylate; urethane (meth) acrylate; polyester (meth) acrylate; polyether (meth) acrylate; epoxy ( And (meth) acrylate.
- examples of the oligomer include an oligomer formed by polymerizing the monomers exemplified above.
- the energy ray-curable compound is preferably a urethane (meth) acrylate or a urethane (meth) acrylate oligomer from the viewpoint that the molecular weight is relatively large and the storage elastic modulus of the pressure-sensitive adhesive layer is hardly lowered.
- the energy ray-curable compound contained in the pressure-sensitive adhesive composition (I-1) may be only one type, or two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected. .
- the content of the energy ray-curable compound is preferably 1 to 95% by mass with respect to the total mass of the pressure-sensitive adhesive composition (I-1). It is more preferably 5 to 90% by mass, and particularly preferably 10 to 85% by mass.
- a pressure-sensitive adhesive composition ( I-1) preferably further contains a crosslinking agent.
- the cross-linking agent reacts with the functional group to cross-link the adhesive resins (I-1a).
- a crosslinking agent for example, tolylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, isocyanate-based cross-linking agents such as adducts of these diisocyanates (cross-linking agents having an isocyanate group); epoxy-based cross-linking agents such as ethylene glycol glycidyl ether ( Cross-linking agent having a glycidyl group); Aziridine-based cross-linking agent such as hexa [1- (2-methyl) -aziridinyl] triphosphatriazine (cross-linking agent having an aziridinyl group); Metal chelate-based cross-linking agent such as aluminum chelate (metal chelate) Cross-linking agents having a structure); isocyanurate-based cross-linking agents (cross-linking agents (cross
- the crosslinking agent contained in the pressure-sensitive adhesive composition (I-1) may be only one type, or two or more types, and in the case of two or more types, their combination and ratio can be arbitrarily selected.
- the content of the crosslinking agent is preferably 0.01 to 50 parts by weight with respect to 100 parts by weight of the pressure-sensitive adhesive resin (I-1a).
- the amount is more preferably 0.1 to 20 parts by mass, and particularly preferably 0.3 to 15 parts by mass.
- the pressure-sensitive adhesive composition (I-1) may further contain a photopolymerization initiator.
- the pressure-sensitive adhesive composition (I-1) containing a photopolymerization initiator sufficiently proceeds with a curing reaction even when irradiated with a relatively low energy beam such as ultraviolet rays.
- photopolymerization initiator examples include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, methyl benzoin benzoate, and benzoin dimethyl ketal; acetophenone, 2-hydroxy Acetophenone compounds such as -2-methyl-1-phenyl-propan-1-one and 2,2-dimethoxy-1,2-diphenylethane-1-one; bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide Acylphosphine oxide compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide; sulfide compounds such as benzylphenyl sulfide and tetramethylthiuram monosulfide; ⁇ -ketol compounds such as hydroxycyclohexyl phenyl ketone; azo compounds
- the photopolymerization initiator contained in the pressure-sensitive adhesive composition (I-1) may be only one type, two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected.
- the content of the photopolymerization initiator is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the energy ray curable compound.
- the amount is more preferably 0.03 to 10 parts by mass, and particularly preferably 0.05 to 5 parts by mass.
- the pressure-sensitive adhesive composition (I-1) may contain other additives that do not fall under any of the above-mentioned components within a range not impairing the effects of the present invention.
- the other additives include antistatic agents, antioxidants, softeners (plasticizers), fillers (fillers), rust inhibitors, colorants (pigments, dyes), sensitizers, and tackifiers.
- known additives such as reaction retarders and crosslinking accelerators (catalysts).
- the reaction retarder is, for example, an undesired crosslinking reaction in the preserving adhesive composition (I-1) by the action of the catalyst mixed in the adhesive composition (I-1). To suppress.
- the reaction retarder include those that form a chelate complex by chelation against a catalyst, and more specifically, those having two or more carbonyl groups (—C ( ⁇ O) —) in one molecule. Can be mentioned.
- the other additive contained in the pressure-sensitive adhesive composition (I-1) may be only one type, or two or more types, and in the case of two or more types, their combination and ratio can be arbitrarily selected.
- the content of other additives is not particularly limited, and may be appropriately selected according to the type.
- the pressure-sensitive adhesive composition (I-1) may contain a solvent. Since the pressure-sensitive adhesive composition (I-1) contains a solvent, the suitability for coating on the surface to be coated is improved.
- the solvent is preferably an organic solvent.
- organic solvent include ketones such as methyl ethyl ketone and acetone; esters such as ethyl acetate (carboxylic acid esters); ethers such as tetrahydrofuran and dioxane; cyclohexane and n-hexane and the like.
- ketones such as methyl ethyl ketone and
- the solvent used in the production of the adhesive resin (I-1a) may be used as it is in the adhesive composition (I-1) without being removed from the adhesive resin (I-1a).
- the same or different type of solvent used in the production of the adhesive resin (I-1a) may be added separately during the production of the adhesive composition (I-1).
- the solvent contained in the pressure-sensitive adhesive composition (I-1) may be only one type, two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected.
- the content of the solvent is not particularly limited, and may be adjusted as appropriate.
- the pressure-sensitive adhesive composition (I-2) is an energy-ray-curable pressure-sensitive adhesive resin in which an unsaturated group is introduced into the side chain of the non-energy-ray-curable pressure-sensitive adhesive resin (I-1a). (I-2a) is contained.
- the adhesive resin (I-2a) can be obtained, for example, by reacting a functional group in the adhesive resin (I-1a) with an unsaturated group-containing compound having an energy ray polymerizable unsaturated group.
- the unsaturated group-containing compound can be bonded to the adhesive resin (I-1a) by reacting with the functional group in the adhesive resin (I-1a) in addition to the energy ray polymerizable unsaturated group.
- the energy beam polymerizable unsaturated group include (meth) acryloyl group, vinyl group (also referred to as ethenyl group), allyl group (also referred to as 2-propenyl group), and (meth) acryloyl group is preferable. .
- Examples of the group capable of binding to the functional group in the adhesive resin (I-1a) include, for example, an isocyanate group and a glycidyl group that can be bonded to a hydroxyl group or an amino group, and a hydroxyl group and an amino group that can be bonded to a carboxy group or an epoxy group. Etc.
- Examples of the unsaturated group-containing compound include (meth) acryloyloxyethyl isocyanate, (meth) acryloyl isocyanate, glycidyl (meth) acrylate, and the like.
- the pressure-sensitive adhesive composition (I-2) contained in the pressure-sensitive adhesive composition (I-2) may be only one type, or two or more types, and when there are two or more types, the combination and ratio thereof are arbitrary. You can choose.
- the content of the pressure-sensitive adhesive resin (I-2a) is 5 to 99% by mass with respect to the total mass of the pressure-sensitive adhesive composition (I-2). It is preferably 10 to 95% by mass, more preferably 10 to 90% by mass.
- an adhesive composition ( I-2) may further contain a crosslinking agent.
- Examples of the crosslinking agent in the pressure-sensitive adhesive composition (I-2) include the same crosslinking agents as in the pressure-sensitive adhesive composition (I-1).
- the crosslinking agent contained in the pressure-sensitive adhesive composition (I-2) may be only one type, or two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected.
- the content of the crosslinking agent is preferably 0.01 to 50 parts by weight with respect to 100 parts by weight of the pressure-sensitive adhesive resin (I-2a).
- the amount is more preferably 0.1 to 20 parts by mass, and particularly preferably 0.3 to 15 parts by mass.
- the pressure-sensitive adhesive composition (I-2) may further contain a photopolymerization initiator.
- the pressure-sensitive adhesive composition (I-2) containing the photopolymerization initiator sufficiently proceeds with the curing reaction even when irradiated with a relatively low energy beam such as ultraviolet rays.
- Examples of the photopolymerization initiator in the pressure-sensitive adhesive composition (I-2) include the same photopolymerization initiator as in the pressure-sensitive adhesive composition (I-1).
- the photopolymerization initiator contained in the pressure-sensitive adhesive composition (I-2) may be only one type, or two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected.
- the content of the photopolymerization initiator is preferably 0.01 to 20 parts by weight with respect to 100 parts by weight of the pressure-sensitive adhesive resin (I-2a). 0.03 to 10 parts by mass is more preferable, and 0.05 to 5 parts by mass is particularly preferable.
- the pressure-sensitive adhesive composition (I-2) may contain other additives that do not fall under any of the above-mentioned components within a range not impairing the effects of the present invention.
- Examples of the other additive in the pressure-sensitive adhesive composition (I-2) include the same additives as those in the pressure-sensitive adhesive composition (I-1).
- the other additive contained in the pressure-sensitive adhesive composition (I-2) may be only one type, or two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected.
- the content of other additives is not particularly limited, and may be appropriately selected according to the type.
- the pressure-sensitive adhesive composition (I-2) may contain a solvent for the same purpose as that of the pressure-sensitive adhesive composition (I-1).
- Examples of the solvent in the pressure-sensitive adhesive composition (I-2) include the same solvents as those in the pressure-sensitive adhesive composition (I-1).
- the solvent contained in the pressure-sensitive adhesive composition (I-2) may be only one type, or two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected.
- the content of the solvent is not particularly limited, and may be adjusted as appropriate.
- the pressure-sensitive adhesive composition (I-3) contains the pressure-sensitive adhesive resin (I-2a) and an energy ray-curable compound.
- the content of the pressure-sensitive adhesive resin (I-2a) is 5 to 99% by mass with respect to the total mass of the pressure-sensitive adhesive composition (I-3). It is preferably 10 to 95% by mass, more preferably 15 to 90% by mass.
- Examples of the energy ray-curable compound contained in the pressure-sensitive adhesive composition (I-3) include monomers and oligomers having an energy ray-polymerizable unsaturated group and curable by irradiation with energy rays. Examples thereof include the same energy ray curable compounds contained in the product (I-1).
- the energy ray-curable compound contained in the pressure-sensitive adhesive composition (I-3) may be only one type, two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected. .
- the content of the energy ray-curable compound is 0.01 to 300 parts by mass with respect to 100 parts by mass of the adhesive resin (I-2a). It is preferably 0.03 to 200 parts by mass, more preferably 0.05 to 100 parts by mass.
- the pressure-sensitive adhesive composition (I-3) may further contain a photopolymerization initiator.
- the pressure-sensitive adhesive composition (I-3) containing a photopolymerization initiator sufficiently undergoes a curing reaction even when irradiated with energy rays of relatively low energy such as ultraviolet rays.
- Examples of the photopolymerization initiator in the pressure-sensitive adhesive composition (I-3) include the same photopolymerization initiator as in the pressure-sensitive adhesive composition (I-1).
- the photopolymerization initiator contained in the pressure-sensitive adhesive composition (I-3) may be only one type, or two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected.
- the content of the photopolymerization initiator is 0.01 to about 100 parts by mass of the total content of the pressure-sensitive adhesive resin (I-2a) and the energy ray curable compound.
- the amount is preferably 20 parts by mass, more preferably 0.03 to 10 parts by mass, and particularly preferably 0.05 to 5 parts by mass.
- the pressure-sensitive adhesive composition (I-3) may contain other additives that do not fall under any of the above-mentioned components within a range not impairing the effects of the present invention.
- Examples of the other additive include the same additives as those in the pressure-sensitive adhesive composition (I-1).
- the other additive contained in the pressure-sensitive adhesive composition (I-3) may be only one type, or two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected.
- the content of other additives is not particularly limited, and may be appropriately selected according to the type.
- the pressure-sensitive adhesive composition (I-3) may contain a solvent for the same purpose as that of the pressure-sensitive adhesive composition (I-1).
- Examples of the solvent in the pressure-sensitive adhesive composition (I-3) include the same solvents as those in the pressure-sensitive adhesive composition (I-1).
- the solvent contained in the pressure-sensitive adhesive composition (I-3) may be only one type, or two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected.
- the content of the solvent is not particularly limited, and may be adjusted as appropriate.
- Examples of the pressure-sensitive adhesive composition other than the pressure-sensitive adhesive compositions (I-1) to (I-3) include non-energy ray-curable pressure-sensitive adhesive compositions in addition to the energy ray-curable pressure-sensitive adhesive composition.
- Non-energy ray curable pressure-sensitive adhesive compositions include, for example, acrylic resin, urethane resin, rubber resin, silicone resin, epoxy resin, polyvinyl ether, polycarbonate, ester resin, etc.
- An adhesive composition (I-4) containing an adhesive resin (I-1a) is preferable, and an adhesive composition containing an acrylic resin is preferred.
- the pressure-sensitive adhesive composition other than the pressure-sensitive adhesive compositions (I-1) to (I-3) preferably contains one or more kinds of crosslinking agents, and the content thereof is the above-mentioned pressure-sensitive adhesive composition. It can be the same as in the case of (I-1).
- Adhesive resin (I-1a) examples of the adhesive resin (I-1a) in the pressure-sensitive adhesive composition (I-4) include the same as the pressure-sensitive adhesive resin (I-1a) in the pressure-sensitive adhesive composition (I-1).
- the adhesive resin (I-1a) contained in the adhesive composition (I-4) may be only one type, or two or more types, and when there are two or more types, the combination and ratio thereof are arbitrary. You can choose.
- the content of the pressure-sensitive adhesive resin (I-1a) is 5 to 99% by mass with respect to the total mass of the pressure-sensitive adhesive composition (I-4). It is preferably 10 to 95% by mass, more preferably 15 to 90% by mass.
- a pressure-sensitive adhesive composition ( I-4) preferably further contains a crosslinking agent.
- Examples of the crosslinking agent in the pressure-sensitive adhesive composition (I-4) include the same crosslinking agents as those in the pressure-sensitive adhesive composition (I-1).
- the crosslinking agent contained in the pressure-sensitive adhesive composition (I-4) may be only one type, or two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected.
- the content of the crosslinking agent is preferably 0.01 to 50 parts by weight with respect to 100 parts by weight of the pressure-sensitive adhesive resin (I-1a).
- the amount is more preferably 0.1 to 20 parts by mass, and particularly preferably 0.3 to 15 parts by mass.
- the pressure-sensitive adhesive composition (I-4) may contain other additives that do not fall under any of the above-mentioned components within a range not impairing the effects of the present invention.
- Examples of the other additive include the same additives as those in the pressure-sensitive adhesive composition (I-1).
- the other additive contained in the pressure-sensitive adhesive composition (I-4) may be only one type, or two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected.
- the content of other additives is not particularly limited, and may be appropriately selected according to the type.
- the pressure-sensitive adhesive composition (I-4) may contain a solvent for the same purpose as that of the pressure-sensitive adhesive composition (I-1).
- Examples of the solvent in the pressure-sensitive adhesive composition (I-4) include the same solvents as those in the pressure-sensitive adhesive composition (I-1).
- the solvent contained in the pressure-sensitive adhesive composition (I-4) may be only one type, or two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected.
- the content of the solvent is not particularly limited and may be appropriately adjusted.
- the pressure-sensitive adhesive layer is preferably non-energy ray curable. This is because when the pressure-sensitive adhesive layer is energy ray curable, it is sometimes impossible to suppress the pressure-sensitive adhesive layer from being simultaneously cured when the protective film-forming film is cured by irradiation with energy rays. If the pressure-sensitive adhesive layer is cured at the same time as the protective film-forming film, the cured protective film-forming film and the pressure-sensitive adhesive layer may stick to the interface so as not to be peeled off.
- a cured protective film-forming film that is, a semiconductor chip provided with a protective film on the back surface (in this specification, sometimes referred to as “semiconductor chip with protective film”) is cured adhesive layer. It becomes difficult to peel off from the support sheet provided with, and the semiconductor chip with a protective film cannot be picked up normally.
- the pressure-sensitive adhesive layer of the support sheet of the present invention non-energy ray curable, such a problem can be reliably avoided and the semiconductor chip with a protective film can be picked up more easily.
- the pressure-sensitive adhesive compositions other than the pressure-sensitive adhesive compositions (I-1) to (I-3) such as the pressure-sensitive adhesive compositions (I-1) to (I-3) and the pressure-sensitive adhesive composition (I-4) It is obtained by blending each component for constituting the pressure-sensitive adhesive composition, such as the pressure-sensitive adhesive and components other than the pressure-sensitive adhesive, if necessary.
- the order of addition at the time of blending each component is not particularly limited, and two or more components may be added simultaneously.
- a solvent it may be used by mixing the solvent with any compounding component other than the solvent and diluting the compounding component in advance, or by diluting any compounding component other than the solvent in advance.
- the method of mixing each component at the time of compounding is not particularly limited, from a known method such as a method of mixing by rotating a stirrer or a stirring blade; a method of mixing using a mixer; a method of mixing by applying ultrasonic waves What is necessary is just to select suitably.
- the temperature and time during the addition and mixing of each component are not particularly limited as long as each compounding component does not deteriorate, and may be adjusted as appropriate, but the temperature is preferably 15 to 30 ° C.
- the protective film-forming film is used as the above-mentioned protective film-forming composite sheet, and as the protective film-forming sheet in which the protective film-forming film is provided on the release film, After pasting on the back surface of the semiconductor wafer, a support sheet can be pasted and used.
- the protective film-forming film that can be used here is as described in the section of the protective film-forming composite sheet.
- FIG. 7 is a cross-sectional view schematically showing an embodiment of a protective film-forming sheet 2F that can be used in the present invention.
- the protective film forming sheet 2 ⁇ / b> F shown here includes a protective film forming film 13 on the first release film 15 ′, and a second release film 15 ′′ on the protective film forming film 13.
- the protective film forming sheet 2F shown in FIG. 7 has a semiconductor wafer (in a partial region on the central side of the surface 13a of the protective film forming film 13 with the second release film 15 ′′ on the light release side removed). (Not shown) is attached to the back surface, and further supported on the other surface 13b opposite to the surface 13a of the protective film-forming film 13 with the first release film 15 'on the heavy release side removed.
- a sheet is affixed, and a region near the peripheral edge of the protective film-forming film 13 is affixed to a jig such as a ring frame for use.
- the release film having the smaller release force is referred to as a light release side release film
- the release film having the higher release force is referred to as a heavy release side release film. If there is a difference in the peeling force, when only the release film on the light release side is peeled off, the protective film formation film may float from the release film on the heavy release side, or a protective film is formed to follow both release films. The film can be prevented from being stretched and deformed.
- the adhesive force between the protective film obtained by curing the protective film-forming film and the support sheet is preferably 50 to 1500 mN / 25 mm, and preferably 52 to 1450 mN / 25 mm. More preferably, it is 53 to 1430 mN / 25 mm.
- the adhesive force is equal to or higher than the lower limit value, pickup of a semiconductor chip with a protective film other than the target is suppressed during pickup of the semiconductor chip with a protective film, and the target semiconductor chip with a protective film is highly selectively picked up. it can.
- the adhesive force is less than or equal to the upper limit value, cracking and chipping of the semiconductor chip are suppressed when the semiconductor chip with a protective film is picked up.
- the composite sheet for forming a protective film has good pickup suitability.
- the adhesive force between the protective film and the support sheet can be measured by the following method. That is, a protective film-forming composite sheet having a width of 25 mm and an arbitrary length is attached to an adherend by the protective film-forming film. Next, after irradiating energy rays to cure the protective film-forming film to form a protective film, the support sheet is peeled off at a peeling speed of 300 mm / min from this protective film applied to the adherend. At this time, the support sheet is peeled in the length direction (the length direction of the composite sheet for forming the protective film) so that the surfaces of the protective film and the support sheet that are in contact with each other form an angle of 180 °. The so-called 180 ° peeling is performed. And the load (peeling force) at the time of this 180 degree
- the length of the composite sheet for forming a protective film used for the measurement is not particularly limited as long as the adhesive force can be stably detected, but is preferably 100 to 300 mm. In the measurement, it is preferable that the protective sheet-forming composite sheet is stuck on the adherend and the sticking state of the protective film-forming composite sheet is stabilized.
- the adhesive force between the protective film-forming film and the support sheet is not particularly limited, and may be, for example, 80 mN / 25 mm or more, preferably 100 mN / 25 mm or more, It is more preferably 150 mN / 25 mm or more, and particularly preferably 200 mN / 25 mm or more.
- peeling between the protective film-forming film and the support sheet is suppressed during dicing. For example, from a support sheet for a semiconductor chip having a protective film-forming film on the back surface Is prevented from scattering.
- the upper limit value of the adhesive force between the protective film-forming film and the support sheet is not particularly limited, and can be any of, for example, 4000 mN / 25 mm, 3500 mN / 25 mm, 3000 mN / 25 mm, and the like. However, these are examples.
- the adhesive force between the support sheet and the protective film-forming film of the laminate is 10 to 30000 mN / 25 mm, preferably 100 to 20000 mN / 25 mm, It is more preferably 150 to 10000 mN / 25 mm, and further preferably 200 to 8000 mN / 25 mm.
- the adhesive force between the protective film-forming film and the support sheet is between the protective film and the support sheet, except that the protective film-forming film used for measurement is not cured by irradiation with energy rays. It can be measured by the same method as adhesive strength.
- the above-mentioned adhesive force between the protective film and the support sheet and the adhesive force between the protective film-forming film and the support sheet are, for example, the types and amounts of the components contained in the protective film-forming film, It can adjust suitably by adjusting the constituent material of the layer which provides the film for protective film formation, the surface state of this layer, etc.
- the type and amount of the component contained in the protective film-forming film can be adjusted by the type and amount of the component contained in the protective film-forming composition described below. And among the components of the composition for forming a protective film, for example, the type and content of the polymer (b) having no energy ray curable group, the content of the filler (d), or the crosslinking agent (f) By adjusting the content of, the adhesive force between the protective film or the protective film-forming film and the support sheet can be adjusted more easily.
- the constituent material can be adjusted as appropriate by adjusting the type and amount of components contained in the adhesive layer.
- the kind and quantity of the component of an adhesive layer can be adjusted with the kind and quantity of the component of an above-mentioned adhesive composition.
- the adhesive force between the protective film or the protective film-forming film and the support sheet is not limited to the constituent material of the base material.
- the surface condition of the substrate can also be adjusted.
- the surface state of the base material is, for example, the surface treatment mentioned above as improving the adhesion with the other layers of the base material, that is, the concavo-convex treatment by sandblasting, solvent treatment, etc .; corona discharge treatment, It can be adjusted by performing any one of an electron beam irradiation treatment, a plasma treatment, an ozone / ultraviolet ray irradiation treatment, a flame treatment, a chromic acid treatment, a hot air treatment and the like; and a primer treatment.
- the protective film-forming film has energy beam curability, and examples thereof include those containing an energy beam curative component (a).
- the energy ray curable component (a) is preferably uncured, preferably tacky, and more preferably uncured and tacky.
- the protective film-forming film may be only one layer (single layer), or may be two or more layers. In the case of a plurality of layers, these layers may be the same or different from each other. The combination is not particularly limited.
- the thickness of the protective film-forming film is preferably 1 to 100 ⁇ m, more preferably 5 to 75 ⁇ m, and particularly preferably 5 to 50 ⁇ m.
- a protective film having higher protective ability can be formed.
- an excessive thickness is suppressed.
- the “thickness of the protective film-forming film” means the thickness of the entire protective film-forming film.
- the thickness of the protective film-forming film composed of a plurality of layers means the protective film-forming film. Means the total thickness of all the layers that make up.
- the curing conditions for forming the protective film by curing the protective film-forming film are not particularly limited as long as the protective film has a degree of curing that sufficiently exhibits its function, and the type of the protective film-forming film is not limited. Accordingly, it may be appropriately selected.
- the illuminance of the energy rays when the protective film-forming film is cured is preferably 4 to 280 mW / cm 2 .
- the amount of energy rays during the curing is preferably 3 to 1000 mJ / cm 2 .
- the protective film-forming film can be formed using a protective film-forming composition containing the constituent materials.
- the protective film-forming film can be formed at the target site by applying the protective film-forming composition to the surface on which the protective film-forming film is to be formed and drying it as necessary.
- the content ratio of components that do not vaporize at room temperature is usually the same as the content ratio of the components of the film for forming a protective film.
- “normal temperature” is as described above.
- Coating of the composition for forming a protective film may be performed by a known method, for example, air knife coater, blade coater, bar coater, gravure coater, roll coater, roll knife coater, curtain coater, die coater, knife coater, Examples include a method using various coaters such as a screen coater, a Mayer bar coater, a rod coater, and a kiss coater.
- the drying conditions of the protective film-forming composition are not particularly limited, but the protective film-forming composition is preferably heat-dried when it contains a solvent described later. In this case, for example, 70 to 130 ° C. It is preferable to dry under conditions of 10 seconds to 5 minutes.
- composition for forming protective film (IV-1) examples include a protective film forming composition (IV-1) containing the energy ray curable component (a).
- the energy ray-curable component (a) is a component that is cured by irradiation with energy rays, and is also a component for imparting film-forming property, flexibility, and the like to the protective film-forming film.
- Examples of the energy ray-curable component (a) include a polymer (a1) having an energy ray-curable group and a weight average molecular weight of 80000 to 2000000, and an energy ray-curable group and a molecular weight of 100 to 80000.
- a compound (a2) is mentioned.
- the polymer (a1) may be at least partially crosslinked by a crosslinking agent (f) described later, or may not be crosslinked.
- the weight average molecular weight means a polystyrene equivalent value measured by a gel permeation chromatography (GPC) method unless otherwise specified.
- Polymer (a1) having an energy ray curable group and having a weight average molecular weight of 80,000 to 2,000,000 examples include an acrylic polymer (a11) having a functional group capable of reacting with a group of another compound, An acrylic resin (a1-1) obtained by polymerizing a group that reacts with a functional group and an energy ray curable compound (a12) having an energy ray curable group such as an energy ray curable double bond. .
- Examples of the functional group capable of reacting with a group possessed by another compound include a hydroxyl group, a carboxy group, an amino group, and a substituted amino group (one or two hydrogen atoms of the amino group are substituted with a group other than a hydrogen atom). Group), an epoxy group, and the like.
- the functional group is preferably a group other than a carboxy group from the viewpoint of preventing corrosion of a circuit such as a semiconductor wafer or a semiconductor chip.
- the functional group is preferably a hydroxyl group.
- the acrylic polymer (a11) having the functional group examples include those obtained by copolymerizing an acrylic monomer having the functional group and an acrylic monomer having no functional group. In addition to monomers, monomers other than acrylic monomers (non-acrylic monomers) may be copolymerized.
- the acrylic polymer (a11) may be a random copolymer or a block copolymer.
- acrylic monomer having a functional group examples include a hydroxyl group-containing monomer, a carboxy group-containing monomer, an amino group-containing monomer, a substituted amino group-containing monomer, and an epoxy group-containing monomer.
- hydroxyl group-containing monomer examples include hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, (meth) Hydroxyalkyl (meth) acrylates such as 2-hydroxybutyl acrylate, 3-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate; non- (meth) acrylic non-methacrylates such as vinyl alcohol and allyl alcohol Saturated alcohol (unsaturated alcohol which does not have a (meth) acryloyl skeleton) etc. are mentioned.
- Examples of the carboxy group-containing monomer include ethylenically unsaturated monocarboxylic acids (monocarboxylic acids having an ethylenically unsaturated bond) such as (meth) acrylic acid and crotonic acid; fumaric acid, itaconic acid, maleic acid, citracone Ethylenically unsaturated dicarboxylic acids such as acids (dicarboxylic acids having an ethylenically unsaturated bond); anhydrides of the ethylenically unsaturated dicarboxylic acids; carboxyalkyl esters of (meth) acrylic acid such as 2-carboxyethyl methacrylate, etc. It is done.
- monocarboxylic acids having an ethylenically unsaturated bond such as (meth) acrylic acid and crotonic acid
- fumaric acid, itaconic acid maleic acid, citracone
- Ethylenically unsaturated dicarboxylic acids such as acids (dica
- the acrylic monomer having a functional group is preferably a hydroxyl group-containing monomer or a carboxy group-containing monomer, more preferably a hydroxyl group-containing monomer.
- the acrylic monomer having the functional group that constitutes the acrylic polymer (a11) may be only one type, or two or more types, and when there are two or more types, the combination and ratio thereof are arbitrary. You can choose.
- acrylic monomer having no functional group examples include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and (meth) acrylate n.
- acrylic monomer having no functional group examples include alkoxyalkyl groups such as methoxymethyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxymethyl (meth) acrylate, and ethoxyethyl (meth) acrylate.
- (meth) acrylic acid esters Containing (meth) acrylic acid esters; (meth) acrylic acid aryl esters such as (meth) acrylic acid phenyl esters; (meth) acrylic acid esters having aromatic groups; non-crosslinkable (meth) acrylamides and derivatives thereof And (meth) acrylic acid ester having a non-crosslinking tertiary amino group such as N, N-dimethylaminoethyl (meth) acrylate and N, N-dimethylaminopropyl (meth) acrylate.
- the acrylic monomer which does not have the functional group constituting the acrylic polymer (a11) may be only one type, or two or more types, and when there are two or more types, the combination and ratio thereof are arbitrary. Can be selected.
- non-acrylic monomer examples include olefins such as ethylene and norbornene; vinyl acetate; styrene.
- the said non-acrylic monomer which comprises the said acrylic polymer (a11) may be only 1 type, may be 2 or more types, and when it is 2 or more types, those combinations and ratios can be selected arbitrarily.
- the ratio (content) of the amount of the structural unit derived from the acrylic monomer having the functional group to the total mass of the structural unit constituting the acrylic polymer (a11) is 0.1 to 50.
- the mass is preferably 1% by mass, more preferably 1 to 40% by mass, and particularly preferably 3 to 30% by mass.
- the acrylic resin (a1-1) obtained by copolymerization of the acrylic polymer (a11) and the energy ray-curable compound (a12) The content of the linear curable group makes it possible to easily adjust the degree of curing of the first protective film within a preferable range.
- the acrylic polymer (a11) constituting the acrylic resin (a1-1) may be only one type, or two or more types, and when there are two or more types, the combination and ratio thereof are arbitrary. You can choose.
- the content of the acrylic resin (a1-1) is 1 to 40% by mass with respect to the total mass of the protective film-forming composition (IV-1). It is preferably 2 to 30% by mass, more preferably 3 to 20% by mass.
- the energy ray curable compound (a12) is one or two selected from the group consisting of an isocyanate group, an epoxy group and a carboxy group as a group capable of reacting with the functional group of the acrylic polymer (a11). Those having the above are preferred, and those having an isocyanate group as the group are more preferred. For example, when the energy beam curable compound (a12) has an isocyanate group as the group, the isocyanate group easily reacts with the hydroxyl group of the acrylic polymer (a11) having a hydroxyl group as the functional group.
- the energy ray curable compound (a12) preferably has 1 to 5 energy ray curable groups in one molecule, and more preferably 1 to 3 energy ray curable groups.
- Examples of the energy ray-curable compound (a12) include 2-methacryloyloxyethyl isocyanate, meta-isopropenyl- ⁇ , ⁇ -dimethylbenzyl isocyanate, methacryloyl isocyanate, allyl isocyanate, 1,1- (bisacryloyloxymethyl).
- Ethyl isocyanate An acryloyl monoisocyanate compound obtained by reacting a diisocyanate compound or polyisocyanate compound with hydroxyethyl (meth) acrylate; Examples thereof include an acryloyl monoisocyanate compound obtained by a reaction of a diisocyanate compound or polyisocyanate compound, a polyol compound, and hydroxyethyl (meth) acrylate.
- the energy beam curable compound (a12) is preferably 2-methacryloyloxyethyl isocyanate.
- the energy ray-curable compound (a12) constituting the acrylic resin (a1-1) may be only one type, or two or more types, and when there are two or more types, the combination and ratio thereof are arbitrary. Can be selected.
- the content of the energy beam curable group derived from the energy beam curable compound (a12) with respect to the content of the functional group derived from the acrylic polymer (a11). is preferably 20 to 120 mol%, more preferably 35 to 100 mol%, and particularly preferably 50 to 100 mol%. When the ratio of the content is within such a range, the adhesive force of the protective film formed by curing is further increased.
- the upper limit of the content ratio is 100 mol%
- the energy ray curable compound (a12) is a polyfunctional compound (having two or more of the groups in one molecule)
- the upper limit of the content ratio may exceed 100 mol%.
- the weight average molecular weight (Mw) of the polymer (a1) is preferably 100,000 to 2,000,000, and more preferably 300,000 to 1500,000.
- the polymer (a1) When the polymer (a1) is at least partially crosslinked by the crosslinking agent (f), the polymer (a1) has been described as constituting the acrylic polymer (a11).
- crosslinked may be sufficient.
- the polymer (a1) contained in the protective film-forming composition (IV-1) and the protective film-forming film may be only one type, two or more types, and when there are two or more types, Combinations and ratios can be arbitrarily selected.
- Compound (a2) having an energy ray curable group and a molecular weight of 100 to 80,000 examples include a group containing an energy ray curable double bond. Preferred examples include (meth) An acryloyl group, a vinyl group, etc. are mentioned.
- the compound (a2) is not particularly limited as long as it satisfies the above conditions, but has a low molecular weight compound having an energy ray curable group, an epoxy resin having an energy ray curable group, and an energy ray curable group.
- a phenol resin etc. are mentioned.
- examples of the low molecular weight compound having an energy ray curable group include polyfunctional monomers or oligomers, and an acrylate compound having a (meth) acryloyl group is preferable.
- examples of the acrylate compound include 2-hydroxy-3- (meth) acryloyloxypropyl methacrylate, polyethylene glycol di (meth) acrylate, propoxylated ethoxylated bisphenol A di (meth) acrylate, and 2,2-bis [4 -((Meth) acryloxypolyethoxy) phenyl] propane, ethoxylated bisphenol A di (meth) acrylate, 2,2-bis [4-((meth) acryloxydiethoxy) phenyl] propane, 9,9-bis [4- (2- (meth) acryloyloxyethoxy) phenyl] fluorene, 2,2-bis [4-((meth) acryloxypolypropoxy) phenyl] propane,
- the epoxy resin having an energy ray curable group and the phenol resin having an energy ray curable group are described in, for example, paragraph 0043 of “JP 2013-194102 A”. Things can be used.
- Such a resin corresponds to a resin constituting the thermosetting component (h) described later, but is treated as the compound (a2) in the present invention.
- the compound (a2) preferably has a weight average molecular weight of 100 to 30,000, more preferably 300 to 10,000.
- the protective film-forming composition (IV-1) and the compound (a2) contained in the protective film-forming film may be only one kind, two kinds or more, and combinations of two or more kinds.
- the ratio can be arbitrarily selected.
- Polymer (b) having no energy ray curable group When the protective film forming composition (IV-1) and the protective film forming film contain the compound (a2) as the energy ray curable component (a), the polymer further does not have an energy ray curable group. It is also preferable to contain (b).
- the polymer (b) may be at least partially crosslinked by the crosslinking agent (f) or may not be crosslinked.
- polymer (b) having no energy ray curable group examples include acrylic polymers, phenoxy resins, urethane resins, polyesters, rubber resins, acrylic urethane resins, polyvinyl alcohol (PVA), butyral resins, and polyester urethanes. Examples thereof include resins.
- the polymer (b) is preferably an acrylic polymer (hereinafter sometimes abbreviated as “acrylic polymer (b-1)”).
- the acrylic polymer (b-1) may be a known one, for example, a homopolymer of one acrylic monomer or a copolymer of two or more acrylic monomers. Alternatively, it may be a copolymer of one or two or more acrylic monomers and a monomer (non-acrylic monomer) other than one or two or more acrylic monomers.
- acrylic monomer constituting the acrylic polymer (b-1) examples include (meth) acrylic acid alkyl ester, (meth) acrylic acid ester having a cyclic skeleton, glycidyl group-containing (meth) acrylic acid ester, Examples include hydroxyl group-containing (meth) acrylic acid esters and substituted amino group-containing (meth) acrylic acid esters.
- substituted amino group is as described above.
- Examples of the (meth) acrylic acid alkyl ester include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and n- (meth) acrylate.
- Examples of the (meth) acrylic acid ester having a cyclic skeleton include (meth) acrylic acid cycloalkyl esters such as isobornyl (meth) acrylate and dicyclopentanyl (meth) acrylate; (Meth) acrylic acid aralkyl esters such as (meth) acrylic acid benzyl; (Meth) acrylic acid cycloalkenyl esters such as (meth) acrylic acid dicyclopentenyl ester; Examples include (meth) acrylic acid cycloalkenyloxyalkyl esters such as (meth) acrylic acid dicyclopentenyloxyethyl ester.
- Examples of the glycidyl group-containing (meth) acrylic ester include glycidyl (meth) acrylate.
- Examples of the hydroxyl group-containing (meth) acrylic acid ester include hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 3-hydroxy (meth) acrylate. Examples include propyl, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and the like.
- Examples of the substituted amino group-containing (meth) acrylic acid ester include N-methylaminoethyl (meth) acrylate.
- non-acrylic monomer constituting the acrylic polymer (b-1) examples include olefins such as ethylene and norbornene; vinyl acetate; styrene.
- the reactive functional group in the polymer (b) is a crosslinking agent (f ).
- the reactive functional group may be appropriately selected according to the type of the crosslinking agent (f) and the like, and is not particularly limited.
- the crosslinking agent (f) is a polyisocyanate compound
- examples of the reactive functional group include a hydroxyl group, a carboxy group, and an amino group. Among these, a hydroxyl group having high reactivity with an isocyanate group. Is preferred.
- the reactive functional group include a carboxy group, an amino group, and an amide group.
- a carboxy group having high reactivity with an epoxy group is included.
- the reactive functional group is preferably a group other than a carboxy group in terms of preventing corrosion of a circuit of a semiconductor wafer or a semiconductor chip.
- Examples of the polymer (b) having the reactive functional group and not having the energy ray-curable group include those obtained by polymerizing at least the monomer having the reactive functional group.
- examples of the polymer (b) having a hydroxyl group as a reactive functional group include those obtained by polymerizing a hydroxyl group-containing (meth) acrylic acid ester.
- Examples of the acrylic monomer or non-acrylic monomer include those obtained by polymerizing a monomer in which one or two or more hydrogen atoms are substituted with the reactive functional group.
- the ratio (content) of the amount of the structural unit derived from the monomer having the reactive functional group with respect to the total mass of the structural unit constituting the polymer is 1 to
- the content is preferably 25% by mass, and more preferably 2 to 20% by mass.
- the degree of cross-linking becomes a more preferable range in the polymer (b).
- the weight average molecular weight (Mw) of the polymer (b) having no energy ray-curable group is 10,000 to 2,000,000 from the viewpoint that the film-forming property of the protective film-forming composition (IV-1) becomes better. It is preferably 100000 to 1500,000.
- the polymer (b) having no energy ray-curable group contained in the protective film-forming composition (IV-1) and the protective film-forming film may be only one kind or two or more kinds. In the case of more than species, their combination and ratio can be arbitrarily selected.
- Examples of the protective film-forming composition (IV-1) include those containing one or both of the polymer (a1) and the compound (a2).
- the protective film-forming composition (IV-1) contains the compound (a2), it preferably further contains a polymer (b) that does not have an energy ray-curable group. It is also preferable to contain a1).
- the protective film-forming composition (IV-1) does not contain the compound (a2) and contains both the polymer (a1) and the polymer (b) having no energy ray-curable group. Also good.
- the protective film-forming composition (IV-1) contains the polymer (a1), the compound (a2) and the polymer (b) having no energy ray-curable group
- the protective film-forming composition In (IV-1) the content of the compound (a2) is 10 to 10 parts per 100 parts by mass of the total content of the polymer (a1) and the polymer (b) having no energy ray-curable group.
- the amount is preferably 400 parts by mass, and more preferably 30 to 350 parts by mass.
- the total content of the energy beam curable component (a) and the polymer (b) having no energy beam curable group with respect to the total content of components other than the solvent is 5 to 90% by mass.
- it is 10 to 80% by mass, more preferably 15 to 70% by mass.
- the protective film forming composition (IV-1) contains the energy beam curable component (a) and the polymer (b) having no energy beam curable group
- the protective film forming composition (IV-1) ) And the protective film-forming film the content of the polymer (b) is preferably 3 to 160 parts by mass with respect to 100 parts by mass of the energy ray-curable component (a). More preferably, it is ⁇ 130 parts by mass.
- the content of the polymer (b) is in such a range, the energy ray curability of the protective film-forming film becomes better.
- the protective film-forming composition (IV-1) comprises a photopolymerization initiator (c) depending on the purpose.
- the protective film-forming composition (IV-1) containing the energy ray-curable component (a) and the thermosetting component (h) the protective film-forming film formed is heated. Adhesive strength to the adherend is improved, and the strength of the protective film formed from this protective film-forming film is also improved.
- Photopolymerization initiator (c) examples include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, benzoin methyl benzoate, and benzoin dimethyl ketal; acetophenone, 2 Acetophenone compounds such as -hydroxy-2-methyl-1-phenyl-propan-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one; bis (2,4,6-trimethylbenzoyl) phenyl Acylphosphine oxide compounds such as phosphine oxide and 2,4,6-trimethylbenzoyldiphenylphosphine oxide; sulfide compounds such as benzylphenyl sulfide and tetramethylthiuram monosulfide ⁇ -ketol compounds such as 1-hydroxycyclo
- the photopolymerization initiator (c) contained in the protective film-forming composition (IV-1) may be only one type, or two or more types, and when there are two or more types, the combination and ratio thereof are arbitrary. Can be selected.
- the content of the photopolymerization initiator (c) is 100 parts by mass of the energy ray-curable compound (a).
- the amount is preferably 0.01 to 20 parts by mass, more preferably 0.03 to 10 parts by mass, and particularly preferably 0.05 to 5 parts by mass.
- the protective film-forming film contains the filler (d)
- the protective film obtained by curing the protective film-forming film can easily adjust the thermal expansion coefficient. By optimizing the object to be formed, the reliability of the package obtained using the composite sheet for forming a protective film is further improved.
- the protective film-forming film contains the filler (d)
- the moisture absorption rate of the protective film can be reduced or the heat dissipation can be improved.
- the filler (d) include those made of a heat conductive material.
- the filler (d) may be either an organic filler or an inorganic filler, but is preferably an inorganic filler.
- Preferred inorganic fillers include, for example, powders of silica, alumina, talc, calcium carbonate, titanium white, bengara, silicon carbide, boron nitride, and the like; beads formed by spheroidizing these inorganic fillers; surface modification of these inorganic fillers Products; single crystal fibers of these inorganic fillers; glass fibers and the like.
- the inorganic filler is preferably silica or alumina.
- the average particle size of the filler (d) is not particularly limited, but is preferably 0.01 to 20 ⁇ m, more preferably 0.1 to 15 ⁇ m, and particularly preferably 0.3 to 10 ⁇ m. .
- the “average particle size” means the value of the particle size (D 50 ) at an integrated value of 50% in the particle size distribution curve obtained by the laser diffraction scattering method, unless otherwise specified.
- the protective film-forming composition (IV-1) and the filler (d) contained in the protective film-forming film may be only one type, two or more types, and combinations of two or more types.
- the ratio can be arbitrarily selected.
- the ratio of the content of the filler (d) to the total content of all components other than the solvent (that is, for forming the protective film) is preferably 5 to 83% by mass, more preferably 7 to 78% by mass.
- Coupleling agent (e) By using a coupling agent (e) having a functional group capable of reacting with an inorganic compound or an organic compound, the adhesion and adhesion of the protective film-forming film to the adherend can be improved.
- the coupling agent (e) By using the coupling agent (e), the protective film obtained by curing the protective film-forming film has improved water resistance without impairing the heat resistance.
- the coupling agent (e) is preferably a compound having a functional group capable of reacting with the functional group of the energy beam curable component (a), the polymer (b) having no energy beam curable group, and the like. More preferably, it is a silane coupling agent.
- silane coupling agent examples include 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxymethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3- (2-aminoethylamino) propyltrimethoxysilane, 3- (2-amino Ethylamino) propylmethyldiethoxysilane, 3- (phenylamino) propyltrimethoxysilane, 3-anilinopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropi Examples include trimethoxysilane, 3-
- the protective film-forming composition (IV-1) and the coupling agent (e) contained in the protective film-forming film may be only one type, two or more types, and when there are two or more types, Combinations and ratios can be arbitrarily selected.
- the content of the coupling agent (e) in the composition for forming a protective film (IV-1) and the film for forming a protective film includes the energy ray curable component (a) and the energy. It is preferably 0.03 to 20 parts by mass, more preferably 0.05 to 10 parts by mass with respect to 100 parts by mass of the total content of the polymer (b) having no linear curable group, The amount is particularly preferably 0.1 to 5 parts by mass.
- the content of the coupling agent (e) is equal to or higher than the lower limit, the dispersibility of the filler (d) in the resin is improved and the adhesion of the protective film-forming film to the adherend is improved.
- the effect by using a coupling agent (e) etc. is acquired more notably. Generation
- production of an outgas is suppressed more because the said content of a coupling agent (e) is below the said upper limit.
- Crosslinking agent (f) By using the crosslinking agent (f) to crosslink the above-mentioned energy ray-curable component (a) or the polymer (b) having no energy ray-curable group, the initial adhesive force and aggregation of the protective film-forming film. You can adjust the power.
- crosslinking agent (f) examples include organic polyvalent isocyanate compounds, organic polyvalent imine compounds, metal chelate crosslinking agents (crosslinking agents having a metal chelate structure), aziridine crosslinking agents (crosslinking agents having an aziridinyl group), and the like. Is mentioned.
- organic polyvalent isocyanate compound examples include an aromatic polyvalent isocyanate compound, an aliphatic polyvalent isocyanate compound, and an alicyclic polyvalent isocyanate compound (hereinafter, these compounds are collectively referred to as “aromatic polyvalent isocyanate compound and the like”).
- a trimer such as the aromatic polyisocyanate compound, isocyanurate and adduct; a terminal isocyanate urethane prepolymer obtained by reacting the aromatic polyvalent isocyanate compound and the polyol compound. Etc.
- the “adduct body” includes the aromatic polyvalent isocyanate compound, the aliphatic polyvalent isocyanate compound, or the alicyclic polyvalent isocyanate compound, and a low amount of ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane, castor oil, or the like. It means a reaction product with a molecularly active hydrogen-containing compound, and examples thereof include an xylylene diisocyanate adduct of trimethylolpropane as described later.
- the “terminal isocyanate urethane prepolymer” means a prepolymer having a urethane bond and an isocyanate group at the end of the molecule.
- organic polyvalent isocyanate compound for example, 2,4-tolylene diisocyanate; 2,6-tolylene diisocyanate; 1,3-xylylene diisocyanate; 1,4-xylene diisocyanate; diphenylmethane-4 Dimethylmethane-2,4'-diisocyanate; 3-methyldiphenylmethane diisocyanate; hexamethylene diisocyanate; isophorone diisocyanate; dicyclohexylmethane-4,4'-diisocyanate; dicyclohexylmethane-2,4'-diisocyanate; trimethylol Any one of tolylene diisocyanate, hexamethylene diisocyanate and xylylene diisocyanate is added to all or some hydroxyl groups of a polyol such as propane. Or two or more compounds are added; lysine diisocyanate.
- a polyol such as propane.
- organic polyvalent imine compound examples include N, N′-diphenylmethane-4,4′-bis (1-aziridinecarboxamide), trimethylolpropane-tri- ⁇ -aziridinylpropionate, and tetramethylolmethane.
- -Tri- ⁇ -aziridinylpropionate, N, N′-toluene-2,4-bis (1-aziridinecarboxamide) triethylenemelamine and the like.
- the crosslinking agent (f) When an organic polyvalent isocyanate compound is used as the crosslinking agent (f), it is preferable to use a hydroxyl group-containing polymer as the energy ray curable component (a) or the polymer (b) having no energy ray curable group.
- the crosslinking agent (f) has an isocyanate group, and the energy ray-curable component (a) or the polymer (b) having no energy ray-curable group has a hydroxyl group, the crosslinking agent (f) and the energy ray-curable property.
- a cross-linked structure can be easily introduced into the protective film-forming film by reaction with the component (a) or the polymer (b) having no energy ray-curable group.
- the crosslinking agent (f) contained in the protective film-forming composition (IV-1) and the protective film-forming film may be only one type, two or more types, or a combination of two or more types.
- the ratio can be arbitrarily selected.
- the content of the crosslinking agent (f) in the protective film-forming composition (IV-1) is such that the energy ray-curable component (a) and the energy ray-curable group having no energy ray-curable group are contained.
- the total content of the combined (b) is preferably 0.01 to 20 parts by weight, more preferably 0.1 to 10 parts by weight, and 0.5 to 5 parts by weight with respect to 100 parts by weight. It is particularly preferred.
- the content of the cross-linking agent (f) is equal to or higher than the lower limit value, the effect of using the cross-linking agent (f) is more remarkably obtained.
- the excessive use of a crosslinking agent (f) is suppressed because the said content of a crosslinking agent (f) is below the said upper limit.
- Colorant (g) examples include known pigments such as inorganic pigments, organic pigments, and organic dyes.
- organic pigments and organic dyes examples include aminium dyes, cyanine dyes, merocyanine dyes, croconium dyes, squalium dyes, azurenium dyes, polymethine dyes, naphthoquinone dyes, pyrylium dyes, and phthalocyanines.
- the inorganic pigment examples include carbon black, cobalt dye, iron dye, chromium dye, titanium dye, vanadium dye, zirconium dye, molybdenum dye, ruthenium dye, platinum dye, ITO ( Indium tin oxide) dyes, ATO (antimony tin oxide) dyes, and the like.
- the protective film-forming composition (IV-1) and the colorant (g) contained in the protective film-forming film may be only one kind, two kinds or more, and combinations of two or more kinds.
- the ratio can be arbitrarily selected.
- the content of the colorant (g) in the protective film-forming film may be appropriately adjusted according to the purpose.
- the protective film may be printed by laser irradiation, and by adjusting the content of the colorant (g) in the protective film-forming film and adjusting the light transmittance of the protective film, the print visibility is improved. Can be adjusted.
- the ratio of the content of the colorant (g) to the total content of all components other than the solvent (that is, the colorant (g )) Is preferably 0.1 to 10% by mass, more preferably 0.4 to 7.5% by mass, and particularly preferably 0.8 to 5% by mass.
- the effect by using a colorant (g) is acquired more notably because the content of the colorant (g) is not less than the lower limit.
- the excessive use of a coloring agent (g) is suppressed because the said content of a coloring agent (g) is below the said upper limit.
- thermosetting component (h) The thermosetting component (h) contained in the protective film-forming composition (IV-1) and the protective film-forming film may be only one kind, two kinds or more, and if two or more kinds, These combinations and ratios can be arbitrarily selected.
- thermosetting component (h) examples include epoxy thermosetting resins, thermosetting polyimides, polyurethanes, unsaturated polyesters, and silicone resins, and epoxy thermosetting resins are preferable.
- the epoxy thermosetting resin includes an epoxy resin (h1) and a thermosetting agent (h2).
- the epoxy thermosetting resin contained in the protective film-forming composition (IV-1) and the protective film-forming film may be only one type, two or more types, and when there are two or more types, Combinations and ratios can be arbitrarily selected.
- Epoxy resin (h1) examples include known ones such as polyfunctional epoxy resins, biphenyl compounds, bisphenol A diglycidyl ether and hydrogenated products thereof, orthocresol novolac epoxy resins, dicyclopentadiene type epoxy resins, Biphenyl type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, phenylene skeleton type epoxy resins, and the like, and bifunctional or higher functional epoxy compounds are listed.
- an epoxy resin having an unsaturated hydrocarbon group may be used as the epoxy resin (h1).
- An epoxy resin having an unsaturated hydrocarbon group is more compatible with an acrylic resin than an epoxy resin having no unsaturated hydrocarbon group. Therefore, the reliability of the package obtained using the composite sheet for forming a protective film is improved by using an epoxy resin having an unsaturated hydrocarbon group.
- Examples of the epoxy resin having an unsaturated hydrocarbon group include compounds obtained by converting a part of the epoxy group of a polyfunctional epoxy resin into a group having an unsaturated hydrocarbon group. Such a compound can be obtained, for example, by addition reaction of (meth) acrylic acid or a derivative thereof to an epoxy group.
- an epoxy resin which has an unsaturated hydrocarbon group the compound etc. which the group which has an unsaturated hydrocarbon group directly couple
- the unsaturated hydrocarbon group is a polymerizable unsaturated group, and specific examples thereof include an ethenyl group (also referred to as a vinyl group), a 2-propenyl group (also referred to as an allyl group), and a (meth) acryloyl group. , (Meth) acrylamide groups and the like, and an acryloyl group is preferred.
- the number average molecular weight of the epoxy resin (h1) is not particularly limited, but is preferably 300 to 30000 from the viewpoint of curability of the protective film-forming film and strength and heat resistance of the protective film, and is preferably 400 to 10,000. More preferably, it is more preferably 500 to 3000.
- the “number average molecular weight” means a number average molecular weight represented by a standard polystyrene equivalent value measured by a gel permeation chromatography (GPC) method unless otherwise specified.
- the epoxy equivalent of the epoxy resin (h1) is preferably 100 to 1000 g / eq, and more preferably 150 to 800 g / eq.
- the “epoxy equivalent” means the number of grams (g / eq) of an epoxy compound containing 1 gram equivalent of an epoxy group, and can be measured according to the method of JIS K 7236: 2001.
- epoxy resin (h1) one type may be used alone, or two or more types may be used in combination, and when two or more types are used in combination, their combination and ratio can be arbitrarily selected.
- thermosetting agent (h2) functions as a curing agent for the epoxy resin (h1).
- a thermosetting agent (h2) the compound which has 2 or more of functional groups which can react with an epoxy group in 1 molecule is mentioned, for example.
- the functional group include a phenolic hydroxyl group, an alcoholic hydroxyl group, an amino group, a carboxy group, a group in which an acid group has been anhydrideized, and the like, and a phenolic hydroxyl group, an amino group, or an acid group has been anhydrideized. It is preferably a group, more preferably a phenolic hydroxyl group or an amino group.
- thermosetting agents (h2) examples of the phenol-based curing agent having a phenolic hydroxyl group include polyfunctional phenol resins, biphenols, novolac-type phenol resins, dicyclopentadiene-based phenol resins, and aralkyl phenol resins.
- examples of the amine-based curing agent having an amino group include dicyandiamide (hereinafter sometimes abbreviated as “DICY”).
- the thermosetting agent (h2) may have an unsaturated hydrocarbon group.
- the thermosetting agent (h2) having an unsaturated hydrocarbon group for example, a compound in which a part of the hydroxyl group of the phenol resin is substituted with a group having an unsaturated hydrocarbon group, an aromatic ring of the phenol resin, Examples thereof include compounds in which a group having a saturated hydrocarbon group is directly bonded.
- the unsaturated hydrocarbon group in the thermosetting agent (h2) is the same as the unsaturated hydrocarbon group in the epoxy resin having an unsaturated hydrocarbon group described above.
- thermosetting agent (h2) In the case where a phenolic curing agent is used as the thermosetting agent (h2), it is preferable that the thermosetting agent (h2) has a high softening point or glass transition temperature from the viewpoint of improving the peelability of the protective film from the support sheet.
- the “glass transition temperature” is represented by the temperature of the inflection point of the DSC curve obtained by measuring the DSC curve of the sample using a differential scanning calorimeter.
- thermosetting agent (h2) for example, the number average molecular weight of the resin component such as polyfunctional phenolic resin, novolac-type phenolic resin, dicyclopentadiene-based phenolic resin, aralkylphenolic resin, etc. is preferably 300 to 30000, It is more preferably 400 to 10,000, and particularly preferably 500 to 3000.
- the molecular weight of non-resin components such as biphenol and dicyandiamide is not particularly limited, but is preferably 60 to 500, for example.
- thermosetting agent (h2) may be used individually by 1 type, may use 2 or more types together, and when using 2 or more types together, those combinations and ratios can be selected arbitrarily.
- the content of the thermosetting agent (h2) is 100% of the epoxy resin (h1).
- the amount is preferably 0.01 to 20 parts by mass with respect to parts by mass.
- thermosetting component (h) when used, the content of the thermosetting component (h) (for example, the epoxy resin (h1) and the heat in the protective film-forming composition (IV-1) and the protective film-forming film)
- the total content of the curing agent (h2) is preferably 1 to 500 parts by mass with respect to 100 parts by mass of the polymer (b) having no energy ray curable group.
- the general-purpose additive (z) may be a known one, and can be arbitrarily selected according to the purpose, and is not particularly limited. Preferred examples include a plasticizer, an antistatic agent, an antioxidant, and a gettering agent. Is mentioned.
- the general-purpose additive (z) contained in the protective film-forming composition (IV-1) and the protective film-forming film may be only one kind, two or more kinds, and when there are two or more kinds, Combinations and ratios can be arbitrarily selected.
- the content of the general-purpose additive (z) in the protective film-forming composition (IV-1) and the protective film-forming film is not particularly limited and is appropriately selected according to the purpose. do it.
- the protective film-forming composition (IV-1) preferably further contains a solvent.
- the protective film-forming composition (IV-1) containing a solvent has good handleability.
- the solvent is not particularly limited, but preferred examples include hydrocarbons such as toluene and xylene; methanol, ethanol, 2-propanol, isobutyl alcohol (also referred to as 2-methylpropan-1-ol), 1-butanol and the like. And alcohols; esters such as ethyl acetate; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran; amides (compounds having an amide bond) such as dimethylformamide and N-methylpyrrolidone.
- the solvent contained in the protective film-forming composition (IV-1) may be only one type, or two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected.
- the solvent contained in the protective film-forming composition (IV-1) is methyl ethyl ketone, toluene, ethyl acetate, or the like from the viewpoint that the components contained in the protective film-forming composition (IV-1) can be mixed more uniformly. It is preferable.
- the protective film-forming film has a solid content of tricyclodecane dimethylol diacrylate (content: protective film molding composition (IV-1)) as the energy ray-curable component (a2). 5 to 35% by mass, more preferably 10 to 30% by mass) based on the total mass of butyl acrylate as a polymer (b) having no energy ray curing group (total mass of acrylic resin) 5 to 15% by mass, more preferably 7.5 to 12.5% by mass), and a structural unit derived from methyl acrylate (55 to 85% by mass with respect to the total mass of the acrylic resin, more preferably Is 60 to 80% by mass), a structural unit derived from glycidyl methacrylate (2 to 8% by mass, more preferably 3 to 7% by mass with respect to the total mass of the acrylic resin) and 2-hydroxyacrylate.
- content: protective film molding composition (IV-1) as the energy ray-curable component (a2). 5 to 35% by mass, more preferably 10 to 30% by mass) based
- Acrylic resin (content: solid content of the protective film forming composition (IV-1)) composed of ethyl (5 to 25% by mass, more preferably 10 to 20% by mass with respect to the total mass of the acrylic resin) 2- (dimethylamino) -1- (5-morpholinophenyl) -2 as the photopolymerization initiator (c); 0.5-30% by mass relative to the total mass, more preferably 1-25% by mass) -Benzyl-1-butanone (content: 0.1 to 0.5% by mass, more preferably 0.2 to 0.4% by mass based on the total mass of the solid content of the protective film-forming composition (IV-1)) % By mass) and ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) (content: composition for forming a protective film) 0.1 to 0.5% by mass with respect to the total mass of the solid content of (IV-1) More preferably, 0.2 to
- the composition for forming a protective film such as the composition for forming a protective film (IV-1) can be obtained by blending each component for constituting the composition.
- the order of addition at the time of blending each component is not particularly limited, and two or more components may be added simultaneously.
- a solvent it may be used by mixing the solvent with any compounding component other than the solvent and diluting the compounding component in advance, or by diluting any compounding component other than the solvent in advance. You may use it by mixing a solvent with these compounding ingredients, without leaving.
- the method of mixing each component at the time of compounding is not particularly limited, from a known method such as a method of mixing by rotating a stirrer or a stirring blade; a method of mixing using a mixer; a method of mixing by applying ultrasonic waves What is necessary is just to select suitably.
- the temperature and time during the addition and mixing of each component are not particularly limited as long as each compounding component does not deteriorate, and may be adjusted as appropriate, but the temperature is preferably 15 to 30 ° C.
- the protective film-forming composite sheet that can be used in the present invention is affixed to the back surface opposite to the circuit surface of the semiconductor wafer or semiconductor chip, and has a layer showing adhesiveness on the support sheet.
- the composite sheet there is a dicing die bonding sheet.
- the adhesive layer provided in the dicing die bonding sheet functions as an adhesive when the semiconductor chip is picked up from the support sheet together with the semiconductor chip and then attached to the substrate, the lead frame, or another semiconductor chip.
- the protective film-forming film in the protective film-forming composite sheet that can be used in the present invention is the same as the adhesive layer in that it is picked up from the support sheet together with the semiconductor chip.
- the protective film-forming film in the present invention has a different use from the adhesive layer in the dicing die bonding sheet, and naturally the required performance is also different. Reflecting this difference in use, the protective film-forming film is usually harder and more difficult to pick up than the adhesive layer in the dicing die bonding sheet. Therefore, it is usually difficult to divert the adhesive layer in the dicing die bonding sheet as it is as the protective film-forming film in the protective film-forming composite sheet.
- the composite sheet for forming a protective film that can be used in the present invention is appropriately selected from those having an energy ray-curable protective film-forming film, with respect to the suitability for picking up a semiconductor chip with a protective film. used.
- a protective film forming composite sheet that can be used in the present invention can be manufactured by sequentially laminating the above-described layers so as to have a corresponding positional relationship.
- the method for forming each layer is as described above. For example, when a pressure-sensitive adhesive layer is laminated on a substrate when producing a support sheet, the above-described pressure-sensitive adhesive composition may be applied on the substrate and dried as necessary.
- the protective film-forming composition is applied on the adhesive layer, It is possible to form the forming film directly.
- Layers other than the protective film-forming film can also be laminated on the pressure-sensitive adhesive layer in the same manner using the composition for forming this layer.
- the composition is further applied onto the layer formed from the composition to newly form a layer. Can be formed.
- the layer laminated after these two layers is formed in advance using the composition on another release film, and the side of the formed layer that is in contact with the release film is It is preferable to form a continuous two-layer laminated structure by bonding the opposite exposed surface to the exposed surfaces of the remaining layers already formed.
- the composition is preferably applied to the release-treated surface of the release film.
- the release film may be removed as necessary after forming the laminated structure.
- a protective film-forming composite sheet in which a pressure-sensitive adhesive layer is laminated on a base material and a protective film-forming film is laminated on the pressure-sensitive adhesive layer (the support sheet is a laminate of the base material and the pressure-sensitive adhesive layer)
- a pressure-sensitive adhesive composition is coated on a base material and dried as necessary, whereby a pressure-sensitive adhesive layer is laminated on the base material
- the protective film-forming composition is coated on the release film, and dried as necessary to form the protective film-forming film on the release film.
- the exposed surface of the protective film-forming film is bonded to the exposed surface of the adhesive layer laminated on the substrate, and the protective film-forming film is laminated on the adhesive layer, thereby forming a protective film.
- a composite sheet is obtained.
- the pressure-sensitive adhesive composition is applied on the release film and necessary.
- the pressure-sensitive adhesive layer is formed on the release film, and the pressure-sensitive adhesive layer is laminated on the base material by bonding the exposed surface of this layer to one surface of the base material. May be.
- the release film may be removed at an arbitrary timing after the target laminated structure is formed.
- a layer that employs such a process may be appropriately selected to produce a protective sheet-forming composite sheet.
- the protective film-forming composite sheet is usually stored in a state in which a release film is bonded to the surface of the outermost layer (for example, a protective film-forming film) on the side opposite to the support sheet. Therefore, a composition for forming a layer constituting the outermost layer, such as a protective film-forming composition, is applied on this release film (preferably its release-treated surface) and dried as necessary. Then, a layer constituting the outermost layer is formed on the release film, and the remaining layers are laminated on the exposed surface of the layer opposite to the side in contact with the release film by any of the methods described above. And the composite sheet for protective film formation is obtained also by leaving it in the state bonded together, without removing a peeling film.
- a release film for example, a protective film-forming film
- Energy ray curable component (a2) -1 Tricyclodecane dimethylol diacrylate (“KAYARAD R-684”, bifunctional ultraviolet curable compound, molecular weight 304, manufactured by Nippon Kayaku Co., Ltd.)
- Acrylic resin weight average molecular weight 300000, glass transition temperature ⁇ 1 ° C.
- Photopolymerization initiator (c) -1 2- (dimethylamino) -1- (4-morpholinophenyl) -2-benzyl-1-butanone (“Irgacure (registered trademark) 369” manufactured by BASF)
- C) -2 Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) (Irgacure (registered by BASF)) Trademark) OXE02 ")
- the acrylic polymer is obtained by copolymerizing 2-ethylhexyl acrylate (hereinafter abbreviated as “2EHA”) (70 mol%) and HEA (30 mol%) with 2-methacryloyloxyethyl.
- Isocyanate hereinafter abbreviated as “MOI” (the total number of moles of isocyanate groups in 2-methacryloyloxyethyl isocyanate is 0.8 times the total number of moles of HEA-derived hydroxyl groups in the acrylic polymer)
- the weight-average molecular weight is 600,000, having a methacryloyloxy group in the side chain, obtained by reacting
- the protective film-forming composition (IV) obtained above was applied to the release-treated surface of a release film (“SP-PET 381031” manufactured by Lintec Co., Ltd., thickness 38 ⁇ m) from which one side of a polyethylene terephthalate film was released by silicone treatment. -1) was coated with a knife coater and dried at 100 ° C. for 2 minutes to prepare an energy ray-curable protective film-forming film (13) -1 having a thickness of 25 ⁇ m.
- SP-PET 381031 manufactured by Lintec Co., Ltd., thickness 38 ⁇ m
- the release film is removed from the pressure-sensitive adhesive layer of the support sheet (10) -7 obtained above, and the protective film-forming film (13) -1 obtained above is exposed on the exposed surface of the pressure-sensitive adhesive layer.
- the surfaces were bonded together to prepare a composite sheet for forming a protective film, in which a base material, an adhesive layer, a protective film-forming film (13) -1 and a release film were laminated in this order in the thickness direction.
- Table 2 shows the structure of the obtained protective sheet-forming composite sheet.
- the exposed surface of the protective film-forming film (13) -1 of the pre-curing test piece is attached to the double-sided adhesive tape on the support plate, The test piece before hardening was stuck on the support plate through the double-sided adhesive tape.
- the measured values of the load are measured when the support sheet (10) -7 is peeled off over a length of 100 mm, when it is first peeled off by a length of 10 mm, and finally when the length is 10 mm.
- the value obtained by excluding each measured value from the effective value when peeled by an amount was adopted. The results are shown in Table 2.
- test piece before hardening was produced by the same method as the measurement of the adhesive strength of the test piece before curing described above, and the test piece before hardening was stuck on a support plate made of SUS via a double-sided adhesive tape.
- an ultraviolet irradiation device (“RAD2000m / 8” manufactured by Lintec Corporation)
- the test piece before curing is irradiated with ultraviolet rays under the conditions of an illuminance of 195 mW / cm 2 and an amount of light of 170 mJ / cm 2 .
- Film (13) -1 was cured to obtain a test piece after curing.
- the protective film-forming composite sheet obtained above is attached to the # 2000 polished surface of a 6-inch silicon wafer (thickness: 100 ⁇ m) with the protective film-forming film (13) -1 and this sheet is further attached to the ring frame. Fixed. Next, using a dicing blade, the silicon wafer was diced together with the protective film-forming film (13) -1 into individual pieces to obtain 2 mm ⁇ 2 mm silicon chips. At this time, the presence or absence of scattering from the support sheet of the silicon chip is visually confirmed, the case where there is no scattering of the silicon chip is determined as ⁇ ⁇ '', and the case where the silicon chip is slightly scattered is ⁇ X '' And dicing suitability was evaluated. The results are shown in Table 2. The description in the column “Suppression of chip scattering” in Table 2 is the corresponding result. There was no penetration of cutting water between the protective film and the support sheet during dicing.
- a protective film-forming film (13) is formed from the support sheet (10) -7 side under the conditions of an illuminance of 195 mW / cm 2 and a light amount of 170 mJ / cm 2 using an ultraviolet irradiation device (“RAD2000m / 8” manufactured by Lintec Corporation). ) -1 was irradiated with ultraviolet rays to cure the protective film-forming film (13) -1 to obtain a protective film.
- 20 silicon chips with a protective film were picked up using a die bonder (“BESTEM-D02” manufactured by Canon Machinery Co., Ltd.).
- Example 2 A protective film-forming composition obtained as described above was formed on the release-treated surface of a first release film (“SP-PET382150” manufactured by Lintec Co., Ltd., thickness 38 ⁇ m) obtained by releasing one side of a polyethylene terephthalate film by silicone treatment.
- the product (IV-1) was applied with a knife coater and dried at 100 ° C. for 2 minutes to prepare an energy ray-curable protective film-forming film (13) -1 having a thickness of 25 ⁇ m.
- a second release film (“SP-PET 381031” manufactured by Lintec Co., Ltd.) having a thickness of one side of a polyethylene terephthalate film was peeled off by silicone treatment on the exposed surface of the obtained protective film-forming film (13) -1. 38 ⁇ m) is bonded to obtain a protective film-forming sheet comprising a first release film (first release film 15 ′ in FIG. 7: 25 ⁇ m) and a second release film 15 ′′. It was.
- SP-PET 381031 manufactured by Lintec Co., Ltd.
- the protective film-forming film (13) obtained above was applied to the # 2000 polished surface of a 6-inch silicon wafer (thickness: 100 ⁇ m). -1 was affixed to obtain a laminate composed of a 6-inch silicon wafer, a protective film-forming film (13) -1 and a first release film.
- the first release film was removed from the laminate obtained above, and the release film was removed from the pressure-sensitive adhesive layer of the support sheet (10) -7 obtained in the same manner as in Example 1, and the support sheet (10).
- the protective film-forming film (13) -1 and the first release film are attached to the exposed surface of the adhesive layer of -7, and the protective film-forming film (13) -1 is attached, and further this sheet was fixed to the ring frame and allowed to stand for 30 minutes.
- the silicon wafer was diced together with the protective film-forming film (13) -1 into individual pieces to obtain 2 mm ⁇ 2 mm silicon chips.
- Example 3 ⁇ Manufacture of composite sheet for forming protective film> (Production of protective film-forming composition (IV-1)) As shown in Table 1, the content (blending amount) of the polymer (b) -1 was changed to 2 parts by weight instead of 22 parts by weight, and the content (blending amount) of the filler (d) -1 was 56 parts by weight. A protective film-forming composition (IV-1) was prepared in the same manner as in Example 1, except that 76 parts by mass was used instead of parts.
- Example 4 ⁇ Manufacture and evaluation of composite sheet for protective film formation> A corona discharge treatment was applied to the surface of the same substrate (polypropylene film, thickness 80 ⁇ m) as used in the production of the support sheet (10) -7. As shown in Table 2, the same method as in Example 1 was used except that instead of the support sheet (10) -7, the support sheet (10) -8 consisting only of the surface-treated substrate was used. The composite sheet for protective film formation was manufactured and evaluated. The results are shown in Table 2. In this example, the protective film-forming film (13) -1 was provided on the corona discharge treated surface of the base material corresponding to the support sheet (10) -2. Dicing evaluation and pick-up evaluation were performed by the same method as Example 1 using the composite sheet for protective film formation obtained above. The results are shown in Table 2.
- Example 1 ⁇ Manufacture and evaluation of composite sheet for protective film formation> A composite sheet for forming a protective film obtained by the same method as in Example 1 was attached to a # 2000 polished surface of a 6-inch silicon wafer (thickness: 100 ⁇ m) with the protective film-forming film (13) -1 and this The sheet was fixed to the ring frame and allowed to stand for 30 minutes. Next, a protective film-forming film (13) is formed from the support sheet (10) -7 side under the conditions of an illuminance of 195 mW / cm 2 and a light amount of 170 mJ / cm 2 using an ultraviolet irradiation device (“RAD2000m / 8” manufactured by Lintec Corporation).
- RAD2000m / 8 ultraviolet irradiation device
- Example 2 ⁇ Manufacture and evaluation of protective film-forming sheet>
- a laminate composed of a 6-inch silicon wafer, a protective film-forming film (13) -1 and a first release film was produced.
- the first release film was removed from the obtained laminate, and the release film was removed from the pressure-sensitive adhesive layer of the support sheet (10) -7 obtained in the same manner as in Example 1, and the support sheet (10) -7.
- the protective film-forming film (13) -1 and the first release film are attached to the exposed surface of the adhesive layer, and the protective film-forming film (13) -1 is attached.
- the frame was fixed and allowed to stand for 30 minutes.
- a protective film-forming film (13) is formed from the support sheet (10) -7 side under the conditions of an illuminance of 195 mW / cm 2 and a light amount of 170 mJ / cm 2 using an ultraviolet irradiation device (“RAD2000m / 8” manufactured by Lintec Corporation). ) -1 was irradiated with ultraviolet rays to cure the protective film-forming film (13) -1 to obtain a protective film. Next, using a dicing blade, the silicon wafer was diced together with the protective film-forming film (13) -1 into individual pieces to obtain 2 mm ⁇ 2 mm silicon chips.
- an ultraviolet irradiation device (“RAD2000m / 8” manufactured by Lintec Corporation).
- Example 3 ⁇ Manufacture and evaluation of composite sheet for protective film formation> A composite sheet for forming a protective film was produced in the same manner as in Example 3. Table 2 shows the structure of the obtained protective sheet-forming composite sheet.
- the protective film-forming composite sheet obtained above is attached to the # 2000 polished surface of a 6-inch silicon wafer (thickness: 100 ⁇ m) with the protective film-forming film (13) -2, and this sheet is further attached to the ring frame. Fixed and allowed to stand for 30 minutes.
- a protective film-forming film (13) is formed from the support sheet (10) -7 side under the conditions of an illuminance of 195 mW / cm 2 and a light amount of 170 mJ / cm 2 using an ultraviolet irradiation device (“RAD2000m / 8” manufactured by Lintec Corporation). ) -1 was irradiated with ultraviolet rays to cure the protective film-forming film (13) -1 to obtain a protective film. Next, using a dicing blade, the silicon wafer was diced together with the protective film-forming film (13) -1 into individual pieces to obtain 2 mm ⁇ 2 mm silicon chips.
- an ultraviolet irradiation device (“RAD2000m / 8” manufactured by Lintec Corporation).
- Examples 1 to 4 when the semiconductor wafer is diced and then the protective film forming film is irradiated with energy rays and cured, the scattering of silicon chips during dicing is suppressed. Also, the dicing suitability was excellent, and it was possible to prevent the penetration of cutting water between the protective film-forming film and the support sheet.
- the adhesive force between the protective film-forming film and the support sheet during dicing of the semiconductor wafer is within a relatively high adhesive force range of 250 to 6900 mN / 25 mm. It is presumed that the scattering of silicon chips in the film was suppressed, and the intrusion of cutting water between the protective film-forming film and the support sheet could be prevented.
- the semiconductor film is diced after the protective film forming film is irradiated with energy rays and cured.
- the adhesive force between the protective film and the support sheet is in the range of 55 to 70 mN / 25 mm, the adhesive force is small, and the penetration of cutting water between the protective film and the support sheet can be prevented. It is estimated that there was not.
- the present invention can be used for manufacturing semiconductor devices.
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Abstract
Description
本願は、2016年4月28日に、日本に出願された特願2016-92033号に基づき優先権を主張し、その内容をここに援用する。
保護膜は、ダイシング工程やパッケージングの後に、半導体チップにおいてクラックが発生するのを防止するために利用される。
本発明の保護膜付き半導体チップの製造方法においては、前記積層体の、支持シートと前記保護膜形成用フィルムとの間の粘着力が100mN/25mm以上であることが好ましい。
本発明の保護膜付き半導体チップの製造方法においては、前記積層体は、前記半導体ウエハに前記保護膜形成用フィルムを貼付した後、前記保護膜形成用フィルムに前記支持シートを貼付したものであってもよい。
本発明の保護膜付き半導体チップの製造方法においては、前記積層体は、支持シート上に前記保護膜形成用フィルムを備えてなる保護膜形成用複合シートの前記保護膜形成用フィルム側を前記半導体ウエハに貼付したものであってもよい。
本発明の半導体装置の製造方法は、上記のいずれかに記載の製造方法により得られた保護膜付き半導体チップをピックアップし、前記半導体チップを基板に接続する。
図1は、本発明の保護膜付き半導体チップの製造方法を示す概略図である。
本発明の保護膜付き半導体チップ19の製造方法は、支持シート10、エネルギー線硬化性の保護膜形成用フィルム13及び半導体ウエハ18をこの順に備えた積層体の、前記半導体ウエハ18をダイシングし、次いで、前記保護膜形成用フィルム13にエネルギー線を照射して硬化させる。
ダイシングした後に保護膜形成用フィルム13にエネルギー線を照射して硬化させることにより、ダイシング時の保護膜形成用フィルム13は比較的柔らかいので、半導体ウエハ18をダイシングする際、保護膜形成用フィルム13又は保護膜13’と支持シート10との間への切削水の浸入のおそれなく、半導体チップ19の裏面に良好な保護膜13’を形成することができる。
本明細書において「ダイシング」とは、ダイヤモンド砥粒を埋め込んだダイシングブレードを高速で回転させながら半導体ウエハを切削すること、レーザー光を用いたレーザーダイシング法によって半導体ウエハを切削することなどが例として挙げられる。
前記積層体は、半導体ウエハに前記保護膜形成用フィルムを貼付した後、前記支持シートに貼付したものであってもよく、このとき、半導体ウエハの製品・製造に適した保護膜形成用フィルム及び支持シートを、それぞれ適宜選択して用いることができる。
この場合の本発明の保護膜付き半導体チップの製造方法は、以下に示すことができる。
すなわち、半導体ウエハの裏面(電極形成面とは反対側の面)に、保護膜形成用フィルムを貼付した後、保護膜形成用フィルムに支持シートに貼付して積層体とする。次いで、ダイシングによって、半導体ウエハを保護膜形成用フィルムごと分割して半導体チップとする。次いで、分割済みの保護膜形成用フィルムにエネルギー線を照射して、保護膜形成用フィルムを硬化させて、保護膜付き半導体チップとする。
この場合の本発明の保護膜付き半導体チップの製造方法は、以下に示すことができる。
すなわち、半導体ウエハの裏面(電極形成面とは反対側の面)に、保護膜形成用複合シートをその保護膜形成用フィルムによって貼付する。次いで、ダイシングによって、半導体ウエハを保護膜形成用フィルムごと分割して半導体チップとする。次いで、分割済みの保護膜形成用フィルムにエネルギー線を照射して、保護膜形成用フィルムを硬化させて、保護膜付き半導体チップとする。
本発明に用いることのできる保護膜形成用複合シートは、支持シート上に、エネルギー線硬化性の保護膜形成用フィルムを備えてなる。
本明細書において、「保護膜形成用フィルム」とは硬化前のものを意味し、「保護膜」とは、保護膜形成用フィルムを硬化させたものを意味する。
紫外線は、例えば、紫外線源として高圧水銀ランプ、フュージョンHランプ、キセノンランプ、ブラックライト又はLEDランプ等を用いることで照射できる。電子線は、電子線加速器等によって発生させたものを照射できる。
本発明において、「エネルギー線硬化性」とは、エネルギー線を照射することにより硬化する性質を意味し、「非エネルギー線硬化性」とは、エネルギー線を照射しても硬化しない性質を意味する。
本発明の別の側面としては、前記積層体の、支持シートと前記保護膜形成用フィルムとの間の粘着力は、10~30000mN/25mmであり、100~20000mN/25mmであることが好ましく、150~10000mN/25mmであることがより好ましく、200~8000mN/25mmであることがさらに好ましい。
本明細書において、前記支持シートと前記保護膜形成用フィルムとの間の粘着力は、後述する測定方法により測定することができる。
本明細書において、前記保護膜と前記支持シートとの間の粘着力は、後述する測定方法により測定することができる。
本発明に用いることのできる保護膜形成用複合シートでは、前記保護膜形成用フィルムがエネルギー線硬化性であることにより、熱硬化性の保護膜形成用フィルムを備えた従来の保護膜形成用複合シートの場合よりも、短時間での硬化によって保護膜を形成できる。
以下、本発明の構成について、詳細に説明する。
前記支持シートは、1層(単層)からなるものでもよいし、2層以上の複数層からなるものでもよい。支持シートが複数層からなる場合、これら複数層の構成材料及び厚さは、互いに同一でも異なっていてもよく、これら複数層の組み合わせは、本発明の効果を損なわない限り、特に限定されない。
本明細書においては、支持シートの場合に限らず、「複数層が互いに同一でも異なっていてもよい」とは、「すべての層が同一であってもよいし、すべての層が異なっていてもよく、一部の層のみが同一であってもよい」ことを意味し、さらに「複数層が互いに異なる」とは、「各層の構成材料及び厚さの少なくとも一方が互いに異なる」ことを意味する。
ここに示す保護膜形成用複合シート1Aは、基材11上に粘着剤層12を備え、粘着剤層12上に保護膜形成用フィルム13を備えてなるものである。支持シート10は、基材11及び粘着剤層12の積層体であり、保護膜形成用複合シート1Aは、換言すると、支持シート10の一方の表面10a上に保護膜形成用フィルム13が積層された構成を有する。保護膜形成用複合シート1Aは、さらに保護膜形成用フィルム13上に剥離フィルム15を備えている。
ここに示す保護膜形成用複合シート1Cは、粘着剤層12を備えていない点以外は、図2に示す保護膜形成用複合シート1Aと同じものである。すなわち、保護膜形成用複合シート1Cにおいては、支持シート10が基材11のみからなる。基材11の一方の表面11a(支持シート10の一方の表面10a)に保護膜形成用フィルム13が積層され、保護膜形成用フィルム13の表面13aの一部、すなわち、周縁部近傍の領域に治具用接着剤層16が積層され、保護膜形成用フィルム13の表面13aのうち、治具用接着剤層16が積層されていない面と、治具用接着剤層16の表面16a(上面及び側面)に、剥離フィルム15が積層されている。
ここに示す保護膜形成用複合シート1Dは、治具用接着剤層16を備えていない点以外は、図4に示す保護膜形成用複合シート1Cと同じものである。すなわち、保護膜形成用複合シート1Dにおいては、基材11の一方の表面11aに保護膜形成用フィルム13が積層され、保護膜形成用フィルム13の表面13aの全面に剥離フィルム15が積層されている。
ここに示す保護膜形成用複合シート1Eは、保護膜形成用フィルムの形状が異なる点以外は、図3に示す保護膜形成用複合シート1Bと同じものである。すなわち、保護膜形成用複合シート1Eは、基材11上に粘着剤層12を備え、粘着剤層12上に保護膜形成用フィルム23を備えてなるものである。支持シート10は、基材11及び粘着剤層12の積層体であり、保護膜形成用複合シート1Eは、換言すると、支持シート10の一方の表面10a上に保護膜形成用フィルム23が積層された構成を有する。保護膜形成用複合シート1Eは、さらに保護膜形成用フィルム23上に剥離フィルム15を備えている。
図2、図3及び図6に示す保護膜形成用複合シートにおいては、基材11と粘着剤層12との間に中間層が設けられていてもよい。すなわち、本発明に用いることのできる保護膜形成用複合シートにおいて、支持シートは、基材、中間層及び粘着剤層がこの順に積層されてなるものでもよい。ここで中間層とは、図4及び図5に示す保護膜形成用複合シートにおいて設けられていてもよい中間層と同じものである。
図2~6に示す保護膜形成用複合シートは、前記中間層以外の層が、任意の箇所に設けられていてもよい。
本発明に用いることのできる保護膜形成用複合シートにおいては、剥離フィルムと、この剥離フィルムと直接接触している層との間に、一部隙間が生じていてもよい。
本発明に用いることのできる保護膜形成用複合シートにおいては、各層の大きさや形状は、目的に応じて任意に調節できる。
なかでも、保護膜形成用フィルムがエネルギー線硬化性を有する本発明においては、支持シートはエネルギー線を透過させるものが好ましい。
一方、支持シートにおいて、波長375nmの光の透過率の上限値は特に限定されないが、例えば、95%とすることが可能である。
前記光の透過率がこのような範囲であることで、支持シートを介して保護膜形成用フィルム又は保護膜にレーザー光を照射して、これらに印字したときに、より明りょうに印字できる。
一方、支持シートにおいて、波長532nmの光の透過率の上限値は特に限定されないが、例えば、95%とすることが可能である。
一方、支持シートにおいて、波長1064nmの光の透過率の上限値は特に限定されないが、例えば、95%とすることが可能である。
次に、支持シートを構成する各層について、さらに詳細に説明する。
前記基材は、シート状又はフィルム状であり、その構成材料としては、例えば、各種樹脂が挙げられる。
前記樹脂としては、例えば、低密度ポリエチレン(LDPE)、直鎖低密度ポリエチレン(LLDPE)、高密度ポリエチレン(HDPE)等のポリエチレン;ポリプロピレン、ポリブテン、ポリブタジエン、ポリメチルペンテン、ノルボルネン樹脂等のポリエチレン以外のポリオレフィン;エチレン-酢酸ビニル共重合体、エチレン-(メタ)アクリル酸共重合体、エチレン-(メタ)アクリル酸エステル共重合体、エチレン-ノルボルネン共重合体等のエチレン系共重合体(モノマーとしてエチレンを用いて得られた共重合体);ポリ塩化ビニル、塩化ビニル共重合体等の塩化ビニル系樹脂(モノマーとして塩化ビニルを用いて得られた樹脂);ポリスチレン;ポリシクロオレフィン;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、ポリブチレンテレフタレート、ポリエチレンイソフタレート、ポリエチレン-2,6-ナフタレンジカルボキシレート、すべての構成単位が芳香族環式基を有する全芳香族ポリエステル等のポリエステル;2種以上の前記ポリエステルの共重合体;ポリ(メタ)アクリル酸エステル;ポリウレタン;ポリウレタンアクリレート;ポリイミド;ポリアミド;ポリカーボネート;フッ素樹脂;ポリアセタール;変性ポリフェニレンオキシド;ポリフェニレンスルフィド;ポリスルホン;ポリエーテルケトン等が挙げられる。
前記樹脂としては、例えば、前記ポリエステルとそれ以外の樹脂との混合物等のポリマーアロイも挙げられる。前記ポリエステルとそれ以外の樹脂とのポリマーアロイは、ポリエステル以外の樹脂の量が比較的少量であるものが好ましい。
前記樹脂としては、例えば、ここまでに例示した前記樹脂の1種又は2種以上が架橋した架橋樹脂;ここまでに例示した前記樹脂の1種又は2種以上を用いたアイオノマー等の変性樹脂も挙げられる。
ここで、「基材の厚さ」とは、基材全体の厚さを意味し、例えば、複数層からなる基材の厚さとは、基材を構成するすべての層の合計の厚さを意味する。
本明細書において、「厚さ」とは、接触式厚み計で、対象物の任意の5箇所を測定し、その平均で表される値である。
保護膜形成用フィルムがエネルギー線硬化性を有する本発明においては、基材はエネルギー線を透過させるものが好ましい。
基材は、表面がプライマー処理を施されたものであってもよい。
基材は、帯電防止コート層、保護膜形成用複合シートを重ね合わせて保存する際に、基材が他のシートに接着することや、基材が吸着テーブルに接着することを防止する層等を有するものであってもよい。
これらの中でも基材は、ダイシング時のブレードの摩擦による基材の断片の発生が抑制される点から、特に表面が電子線照射処理を施されたものが好ましい。
前記粘着剤層は、シート状又はフィルム状であり、粘着剤を含有する。
前記粘着剤としては、例えば、アクリル系樹脂、ウレタン系樹脂、ゴム系樹脂、シリコーン系樹脂、エポキシ系樹脂、ポリビニルエーテル、ポリカーボネート、エステル系樹脂等の粘着性樹脂が挙げられ、アクリル系樹脂が好ましい。
ここで、「粘着剤層の厚さ」とは、粘着剤層全体の厚さを意味し、例えば、複数層からなる粘着剤層の厚さとは、粘着剤層を構成するすべての層の合計の厚さを意味する。
保護膜形成用フィルムがエネルギー線硬化性を有する本発明においては、粘着剤層はエネルギー線を透過させるものが好ましい。
粘着剤層は、粘着剤を含有する粘着剤組成物を用いて形成できる。例えば、粘着剤層の形成対象面に粘着剤組成物を塗工し、必要に応じて乾燥させることで、目的とする部位に粘着剤層を形成できる。粘着剤層のより具体的な形成方法は、他の層の形成方法とともに、後ほど詳細に説明する。粘着剤組成物中の、常温で気化しない成分同士の含有量の比率は、通常、粘着剤層の前記成分同士の含有量の比率と同じとなる。本明細書において、「常温」とは、特に冷やしたり、熱したりしない温度、すなわち平常の温度を意味し、例えば、15~25℃の温度等が挙げられる。
前記粘着剤組成物(I-1)は、上述の様に、非エネルギー線硬化性の粘着性樹脂(I-1a)と、エネルギー線硬化性化合物と、を含有する。
前記粘着性樹脂(I-1a)は、アクリル系樹脂であることが好ましい。
前記アクリル系樹脂としては、例えば、少なくとも(メタ)アクリル酸アルキルエステル由来の構成単位を有するアクリル系重合体が挙げられる。
前記アクリル系樹脂が有する構成単位は、1種のみでもよいし、2種以上でもよく、2種以上である場合、それらの組み合わせ及び比率は任意に選択できる。
(メタ)アクリル酸アルキルエステルとして、より具体的には、(メタ)アクリル酸メチル、(メタ)アクリル酸エチル、(メタ)アクリル酸n-プロピル、(メタ)アクリル酸イソプロピル、(メタ)アクリル酸n-ブチル、(メタ)アクリル酸イソブチル、(メタ)アクリル酸sec-ブチル、(メタ)アクリル酸tert-ブチル、(メタ)アクリル酸ペンチル、(メタ)アクリル酸ヘキシル、(メタ)アクリル酸ヘプチル、(メタ)アクリル酸2-エチルヘキシル、(メタ)アクリル酸イソオクチル、(メタ)アクリル酸n-オクチル、(メタ)アクリル酸n-ノニル、(メタ)アクリル酸イソノニル、(メタ)アクリル酸デシル、(メタ)アクリル酸ウンデシル、(メタ)アクリル酸ドデシル((メタ)アクリル酸ラウリルともいう)、(メタ)アクリル酸トリデシル、(メタ)アクリル酸テトラデシル((メタ)アクリル酸ミリスチルともいう)、(メタ)アクリル酸ペンタデシル、(メタ)アクリル酸ヘキサデシル((メタ)アクリル酸パルミチルともいう)、(メタ)アクリル酸ヘプタデシル、(メタ)アクリル酸オクタデシル((メタ)アクリル酸ステアリルともいう)、(メタ)アクリル酸ノナデシル、(メタ)アクリル酸イコシル等が挙げられる。
前記官能基含有モノマーとしては、例えば、前記官能基が後述する架橋剤と反応することで架橋の起点となったり、前記官能基が後述する不飽和基含有化合物中の不飽和基と反応することで、アクリル系重合体の側鎖に不飽和基の導入を可能とするものが挙げられる。
すなわち、官能基含有モノマーとしては、例えば、水酸基含有モノマー、カルボキシ基含有モノマー、アミノ基含有モノマー、エポキシ基含有モノマー等が挙げられる。
前記他のモノマーは、(メタ)アクリル酸アルキルエステル等と共重合可能なものであれば特に限定されない。
前記他のモノマーとしては、例えば、スチレン、α-メチルスチレン、ビニルトルエン、ギ酸ビニル、酢酸ビニル、アクリロニトリル、アクリルアミド等が挙げられる。
一方、前記アクリル系重合体中の官能基に、エネルギー線重合性不飽和基(エネルギー線重合性基)を有する不飽和基含有化合物を反応させたものは、上述のエネルギー線硬化性の粘着性樹脂(I-2a)として使用できる。
粘着剤組成物(I-1)が含有する前記エネルギー線硬化性化合物としては、エネルギー線重合性不飽和基を有し、エネルギー線の照射により硬化可能なモノマー又はオリゴマーが挙げられる。
エネルギー線硬化性化合物のうち、モノマーとしては、例えば、トリメチロールプロパントリ(メタ)アクリレート、ペンタエリスリトール(メタ)アクリレート、ペンタエリスリトールテトラ(メタ)アクリレート、ジペンタエリスリトールヘキサ(メタ)アクリレート、1,4-ブチレングリコールジ(メタ)アクリレート、1,6-へキサンジオール(メタ)アクリレート等の多価(メタ)アクリレート;ウレタン(メタ)アクリレート;ポリエステル(メタ)アクリレート;ポリエーテル(メタ)アクリレート;エポキシ(メタ)アクリレート等が挙げられる。
エネルギー線硬化性化合物のうち、オリゴマーとしては、例えば、上記で例示したモノマーが重合してなるオリゴマー等が挙げられる。
エネルギー線硬化性化合物は、分子量が比較的大きく、粘着剤層の貯蔵弾性率を低下させにくいという点では、ウレタン(メタ)アクリレート、ウレタン(メタ)アクリレートオリゴマーが好ましい。
粘着性樹脂(I-1a)として、(メタ)アクリル酸アルキルエステル由来の構成単位以外に、さらに、官能基含有モノマー由来の構成単位を有する前記アクリル系重合体を用いる場合、粘着剤組成物(I-1)は、さらに架橋剤を含有することが好ましい。
架橋剤としては、例えば、トリレンジイソシアネート、ヘキサメチレンジイソシアネート、キシリレンジイソシアネート、これらジイソシアネートのアダクト体等のイソシアネート系架橋剤(イソシアネート基を有する架橋剤);エチレングリコールグリシジルエーテル等のエポキシ系架橋剤(グリシジル基を有する架橋剤);ヘキサ[1-(2-メチル)-アジリジニル]トリホスファトリアジン等のアジリジン系架橋剤(アジリジニル基を有する架橋剤);アルミニウムキレート等の金属キレート系架橋剤(金属キレート構造を有する架橋剤);イソシアヌレート系架橋剤(イソシアヌル酸骨格を有する架橋剤)等が挙げられる。
粘着剤の凝集力を向上させて粘着剤層の粘着力を向上させる点、及び入手が容易である等の点から、架橋剤はイソシアネート系架橋剤であることが好ましい。
粘着剤組成物(I-1)は、さらに光重合開始剤を含有していてもよい。光重合開始剤を含有する粘着剤組成物(I-1)は、紫外線等の比較的低エネルギーのエネルギー線を照射しても、十分に硬化反応が進行する。
前記光重合開始剤としては、例えば、1-クロロアントラキノン等のキノン化合物;アミン等の光増感剤等を用いることもできる。
粘着剤組成物(I-1)は、本発明の効果を損なわない範囲内において、上述のいずれの成分にも該当しない、その他の添加剤を含有していてもよい。
前記その他の添加剤としては、例えば、帯電防止剤、酸化防止剤、軟化剤(可塑剤)、充填材(フィラー)、防錆剤、着色剤(顔料、染料)、増感剤、粘着付与剤、反応遅延剤、架橋促進剤(触媒)等の公知の添加剤が挙げられる。
反応遅延剤とは、例えば、粘着剤組成物(I-1)中に混入している触媒の作用によって、保存中の粘着剤組成物(I-1)において、目的としない架橋反応が進行するのを抑制する。反応遅延剤としては、例えば、触媒に対するキレートによってキレート錯体を形成するものが挙げられ、より具体的には、1分子中にカルボニル基(-C(=O)-)を2個以上有するものが挙げられる。
粘着剤組成物(I-1)は、溶媒を含有していてもよい。粘着剤組成物(I-1)は、溶媒を含有していることで、塗工対象面への塗工適性が向上する。
前記粘着剤組成物(I-2)は、上述の様に、非エネルギー線硬化性の粘着性樹脂(I-1a)の側鎖に不飽和基が導入されたエネルギー線硬化性の粘着性樹脂(I-2a)を含有する。
前記粘着性樹脂(I-2a)は、例えば、粘着性樹脂(I-1a)中の官能基に、エネルギー線重合性不飽和基を有する不飽和基含有化合物を反応させることで得られる。
前記エネルギー線重合性不飽和基としては、例えば、(メタ)アクリロイル基、ビニル基(エテニル基ともいう)、アリル基(2-プロペニル基ともいう)等が挙げられ、(メタ)アクリロイル基が好ましい。
粘着性樹脂(I-1a)中の官能基と結合可能な基としては、例えば、水酸基又はアミノ基と結合可能なイソシアネート基及びグリシジル基、並びにカルボキシ基又はエポキシ基と結合可能な水酸基及びアミノ基等が挙げられる。
粘着性樹脂(I-2a)として、例えば、粘着性樹脂(I-1a)におけるものと同様の、官能基含有モノマー由来の構成単位を有する前記アクリル系重合体を用いる場合、粘着剤組成物(I-2)は、さらに架橋剤を含有していてもよい。
粘着剤組成物(I-2)が含有する架橋剤は、1種のみでもよいし、2種以上でもよく、2種以上である場合、それらの組み合わせ及び比率は任意に選択できる。
粘着剤組成物(I-2)は、さらに光重合開始剤を含有していてもよい。光重合開始剤を含有する粘着剤組成物(I-2)は、紫外線等の比較的低エネルギーのエネルギー線を照射しても、十分に硬化反応が進行する。
粘着剤組成物(I-2)が含有する光重合開始剤は、1種のみでもよいし、2種以上でもよく、2種以上である場合、それらの組み合わせ及び比率は任意に選択できる。
粘着剤組成物(I-2)は、本発明の効果を損なわない範囲内において、上述のいずれの成分にも該当しない、その他の添加剤を含有していてもよい。
粘着剤組成物(I-2)における前記その他の添加剤としては、粘着剤組成物(I-1)におけるその他の添加剤と同じものが挙げられる。
粘着剤組成物(I-2)が含有するその他の添加剤は、1種のみでもよいし、2種以上でもよく、2種以上である場合、それらの組み合わせ及び比率は任意に選択できる。
粘着剤組成物(I-2)は、粘着剤組成物(I-1)の場合と同様の目的で、溶媒を含有していてもよい。
粘着剤組成物(I-2)における前記溶媒としては、粘着剤組成物(I-1)における溶媒と同じものが挙げられる。
粘着剤組成物(I-2)が含有する溶媒は、1種のみでもよいし、2種以上でもよく、2種以上である場合、それらの組み合わせ及び比率は任意に選択できる。
粘着剤組成物(I-2)において、溶媒の含有量は特に限定されず、適宜調節すればよい。
前記粘着剤組成物(I-3)は、上述の様に、前記粘着性樹脂(I-2a)と、エネルギー線硬化性化合物と、を含有する。
粘着剤組成物(I-3)が含有する前記エネルギー線硬化性化合物としては、エネルギー線重合性不飽和基を有し、エネルギー線の照射により硬化可能なモノマー及びオリゴマーが挙げられ、粘着剤組成物(I-1)が含有するエネルギー線硬化性化合物と同じものが挙げられる。
粘着剤組成物(I-3)が含有する前記エネルギー線硬化性化合物は、1種のみでもよいし、2種以上でもよく、2種以上である場合、それらの組み合わせ及び比率は任意に選択できる。
粘着剤組成物(I-3)は、さらに光重合開始剤を含有していてもよい。光重合開始剤を含有する粘着剤組成物(I-3)は、紫外線等の比較的低エネルギーのエネルギー線を照射しても、十分に硬化反応が進行する。
粘着剤組成物(I-3)が含有する光重合開始剤は、1種のみでもよいし、2種以上でもよく、2種以上である場合、それらの組み合わせ及び比率は任意に選択できる。
粘着剤組成物(I-3)は、本発明の効果を損なわない範囲内において、上述のいずれの成分にも該当しない、その他の添加剤を含有していてもよい。
前記その他の添加剤としては、粘着剤組成物(I-1)におけるその他の添加剤と同じものが挙げられる。
粘着剤組成物(I-3)が含有するその他の添加剤は、1種のみでもよいし、2種以上でもよく、2種以上である場合、それらの組み合わせ及び比率は任意に選択できる。
粘着剤組成物(I-3)は、粘着剤組成物(I-1)の場合と同様の目的で、溶媒を含有していてもよい。
粘着剤組成物(I-3)における前記溶媒としては、粘着剤組成物(I-1)における溶媒と同じものが挙げられる。
粘着剤組成物(I-3)が含有する溶媒は、1種のみでもよいし、2種以上でもよく、2種以上である場合、それらの組み合わせ及び比率は任意に選択できる。
粘着剤組成物(I-3)において、溶媒の含有量は特に限定されず、適宜調節すればよい。
ここまでは、粘着剤組成物(I-1)、粘着剤組成物(I-2)及び粘着剤組成物(I-3)について主に説明したが、これらの含有成分として説明したものは、これら3種の粘着剤組成物以外の全般的な粘着剤組成物(本明細書においては、「粘着剤組成物(I-1)~(I-3)以外の粘着剤組成物」と称する)でも、同様に用いることができる。
非エネルギー線硬化性の粘着剤組成物としては、例えば、アクリル系樹脂、ウレタン系樹脂、ゴム系樹脂、シリコーン系樹脂、エポキシ系樹脂、ポリビニルエーテル、ポリカーボネート、エステル系樹脂等の、非エネルギー線硬化性の粘着性樹脂(I-1a)を含有する粘着剤組成物(I-4)が挙げられ、アクリル系樹脂を含有するものが好ましい。
粘着剤組成物(I-4)で好ましいものとしては、例えば、前記粘着性樹脂(I-1a)と、架橋剤と、を含有するものが挙げられる。
粘着剤組成物(I-4)における粘着性樹脂(I-1a)としては、粘着剤組成物(I-1)における粘着性樹脂(I-1a)と同じものが挙げられる。
粘着剤組成物(I-4)が含有する粘着性樹脂(I-1a)は、1種のみでもよいし、2種以上でもよく、2種以上である場合、それらの組み合わせ及び比率は任意に選択できる。
粘着性樹脂(I-1a)として、(メタ)アクリル酸アルキルエステル由来の構成単位以外に、さらに、官能基含有モノマー由来の構成単位を有する前記アクリル系重合体を用いる場合、粘着剤組成物(I-4)は、さらに架橋剤を含有することが好ましい。
粘着剤組成物(I-4)が含有する架橋剤は、1種のみでもよいし、2種以上でもよく、2種以上である場合、それらの組み合わせ及び比率は任意に選択できる。
粘着剤組成物(I-4)は、本発明の効果を損なわない範囲内において、上述のいずれの成分にも該当しない、その他の添加剤を含有していてもよい。
前記その他の添加剤としては、粘着剤組成物(I-1)におけるその他の添加剤と同じものが挙げられる。
粘着剤組成物(I-4)が含有するその他の添加剤は、1種のみでもよいし、2種以上でもよく、2種以上である場合、それらの組み合わせ及び比率は任意に選択できる。
粘着剤組成物(I-4)は、粘着剤組成物(I-1)の場合と同様の目的で、溶媒を含有していてもよい。
粘着剤組成物(I-4)における前記溶媒としては、粘着剤組成物(I-1)における溶媒と同じものが挙げられる。
粘着剤組成物(I-4)が含有する溶媒は、1種のみでもよいし、2種以上でもよく、2種以上である場合、それらの組み合わせ及び比率は任意に選択できる。
粘着剤組成物(I-4)において、溶媒の含有量は特に限定されず、適宜調節すればよい。
粘着剤組成物(I-1)~(I-3)や、粘着剤組成物(I-4)等の粘着剤組成物(I-1)~(I-3)以外の粘着剤組成物は、前記粘着剤と、必要に応じて前記粘着剤以外の成分等の、粘着剤組成物を構成するための各成分を配合することで得られる。
各成分の配合時における添加順序は特に限定されず、2種以上の成分を同時に添加してもよい。
溶媒を用いる場合には、溶媒を溶媒以外のいずれかの配合成分と混合してこの配合成分を予め希釈しておくことで用いてもよいし、溶媒以外のいずれかの配合成分を予め希釈しておくことなく、溶媒をこれら配合成分と混合することで用いてもよい。
配合時に各成分を混合する方法は特に限定されず、撹拌子又は撹拌翼等を回転させて混合する方法;ミキサーを用いて混合する方法;超音波を加えて混合する方法等、公知の方法から適宜選択すればよい。
各成分の添加及び混合時の温度並びに時間は、各配合成分が劣化しない限り特に限定されず、適宜調節すればよいが、温度は15~30℃であることが好ましい。
本発明において保護膜形成用フィルムは、上述の保護膜形成用複合シートとして用いられるほか、剥離フィルム上に保護膜形成用フィルムが設けられた保護膜形成用シートとして、前記半導体ウエハの裏面に貼付した後、支持シートを貼付して用いることもできる。
ここで用いることのできる保護膜形成用フィルムは、上述の保護膜形成用複合シートの項で説明した通りである。
図7は、本発明に用いることのできる保護膜形成用シート2Fの一実施形態を模式的に示す断面図である。
ここに示す保護膜形成用シート2Fは、第1の剥離フィルム15’上に保護膜形成用フィルム13を備え、保護膜形成用フィルム13上に第2の剥離フィルム15”を備える。
図7に示す保護膜形成用シート2Fは、軽剥離側の第2の剥離フィルム15”が取り除かれた状態で、保護膜形成用フィルム13の表面13a中央側の一部の領域に半導体ウエハ(図示略)の裏面が貼付され、さらに、重剥離側の第1の剥離フィルム15’が取り除かれた状態で、保護膜形成用フィルム13の表面13aとは反対側の他方の表面13b上に支持シートが貼付され、さらに、保護膜形成用フィルム13の周縁部近傍の領域が、リングフレーム等の治具に貼付されて、使用される。
ここで、剥離力の小さいほうの剥離フィルムを軽剥離側の剥離フィルムといい、剥離力の大きいほうの剥離フィルムを重剥離側の剥離フィルムという。剥離力に差をつけておけば、軽剥離側の剥離フィルムのみを剥がす際に、保護膜形成用フィルムが重剥離側の剥離フィルムから浮くおそれや、双方の剥離フィルムに追従しようとして保護膜形成用フィルムが引き伸ばされて変形することを防ぐことができる。
すなわち、幅が25mmで長さが任意の保護膜形成用複合シートをその保護膜形成用フィルムにより被着体へ貼付する。
次いで、エネルギー線を照射して保護膜形成用フィルムを硬化させて、保護膜を形成した後、被着体へ貼付されているこの保護膜から、支持シートを剥離速度300mm/minで剥離させる。このときの剥離は、保護膜及び支持シートの互いに接触していた面同士が180°の角度を為すように、支持シートをその長さ方向(保護膜形成用複合シートの長さ方向)へ剥離させる、いわゆる180°剥離とする。そして、この180°剥離のときの荷重(剥離力)を測定し、その測定値を前記粘着力(mN/25mm)とする。
一方、保護膜形成用フィルムと前記支持シートとの間の粘着力の上限値は、特に限定されず、例えば、4000mN/25mm、3500mN/25mm、3000mN/25mm等のいずれかとすることができる。ただし、これらは一例である。
本発明の別の側面としては、前記積層体の、支持シートと前記保護膜形成用フィルムとの間の粘着力は、10~30000mN/25mmであり、100~20000mN/25mmであることが好ましく、150~10000mN/25mmであることがより好ましく、200~8000mN/25mmであることがさらに好ましい。
一方、支持シートにおける保護膜形成用フィルムを設ける層が、基材である場合には、保護膜又は保護膜形成用フィルムと支持シートとの間の粘着力は、基材の構成材料以外に、基材の表面状態でも調節できる。そして、基材の表面状態は、例えば、基材の他の層との密着性を向上させるものとして先に挙げた表面処理、すなわち、サンドブラスト処理、溶剤処理等による凹凸化処理;コロナ放電処理、電子線照射処理、プラズマ処理、オゾン・紫外線照射処理、火炎処理、クロム酸処理、熱風処理等の酸化処理;プライマー処理等のいずれかを施すことで、調節できる。
エネルギー線硬化性成分(a)は、未硬化であることが好ましく、粘着性を有することが好ましく、未硬化でかつ粘着性を有することがより好ましい。
ここで、「保護膜形成用フィルムの厚さ」とは、保護膜形成用フィルム全体の厚さを意味し、例えば、複数層からなる保護膜形成用フィルムの厚さとは、保護膜形成用フィルムを構成するすべての層の合計の厚さを意味する。
例えば、保護膜形成用フィルムの硬化時における、エネルギー線の照度は、4~280mW/cm2であることが好ましい。前記硬化時における、エネルギー線の光量は、3~1000mJ/cm2であることが好ましい。
保護膜形成用フィルムは、その構成材料を含有する保護膜形成用組成物を用いて形成できる。例えば、保護膜形成用フィルムの形成対象面に保護膜形成用組成物を塗工し、必要に応じて乾燥させることで、目的とする部位に保護膜形成用フィルムを形成できる。保護膜形成用組成物中の、常温で気化しない成分同士の含有量の比率は、通常、保護膜形成用フィルムの前記成分同士の含有量の比率と同じとなる。ここで、「常温」とは、先に説明したとおりである。
保護膜形成用組成物としては、例えば、前記エネルギー線硬化性成分(a)を含有する保護膜形成用組成物(IV-1)等が挙げられる。
エネルギー線硬化性成分(a)は、エネルギー線の照射によって硬化する成分であり、保護膜形成用フィルムに造膜性や、可撓性等を付与するための成分でもある。
エネルギー線硬化性成分(a)としては、例えば、エネルギー線硬化性基を有する、重量平均分子量が80000~2000000の重合体(a1)、及びエネルギー線硬化性基を有する、分子量が100~80000の化合物(a2)が挙げられる。前記重合体(a1)は、その少なくとも一部が、後述する架橋剤(f)によって架橋されたものであってもよいし、架橋されていないものであってもよい。
本明細書において、重量平均分子量とは、特に断りのない限り、ゲル・パーミエーション・クロマトグラフィー(GPC)法により測定されるポリスチレン換算値を意味する。
エネルギー線硬化性基を有する、重量平均分子量が80000~2000000の重合体(a1)としては、例えば、他の化合物が有する基と反応可能な官能基を有するアクリル系重合体(a11)と、前記官能基と反応する基、及びエネルギー線硬化性二重結合等のエネルギー線硬化性基を有するエネルギー線硬化性化合物(a12)と、が重合してなるアクリル系樹脂(a1-1)が挙げられる。
これらの中でも、前記官能基は、水酸基であることが好ましい。
前記官能基を有するアクリル系重合体(a11)としては、例えば、前記官能基を有するアクリル系モノマーと、前記官能基を有しないアクリル系モノマーと、が共重合してなるものが挙げられ、これらモノマー以外に、さらにアクリル系モノマー以外のモノマー(非アクリル系モノマー)が共重合したものであってもよい。
前記アクリル系重合体(a11)は、ランダム共重合体であってもよいし、ブロック共重合体であってもよい。
前記アクリル系重合体(a11)を構成する前記非アクリル系モノマーは、1種のみでもよいし、2種以上でもよく、2種以上である場合、それらの組み合わせ及び比率は任意に選択できる。
前記エネルギー線硬化性化合物(a12)は、前記アクリル系重合体(a11)が有する官能基と反応可能な基として、イソシアネート基、エポキシ基及びカルボキシ基からなる群より選択される1種又は2種以上を有するものが好ましく、前記基としてイソシアネート基を有するものがより好ましい。前記エネルギー線硬化性化合物(a12)は、例えば、前記基としてイソシアネート基を有する場合、このイソシアネート基が、前記官能基として水酸基を有するアクリル系重合体(a11)のこの水酸基と容易に反応する。
ジイソシアネート化合物又はポリイソシアネート化合物と、ヒドロキシエチル(メタ)アクリレートとの反応により得られるアクリロイルモノイソシアネート化合物;
ジイソシアネート化合物又はポリイソシアネート化合物と、ポリオール化合物と、ヒドロキシエチル(メタ)アクリレートとの反応により得られるアクリロイルモノイソシアネート化合物等が挙げられる。
これらの中でも、前記エネルギー線硬化性化合物(a12)は、2-メタクリロイルオキシエチルイソシアネートであることが好ましい。
エネルギー線硬化性基を有する、分子量が100~80000の化合物(a2)が有するエネルギー線硬化性基としては、エネルギー線硬化性二重結合を含む基が挙げられ、好ましいものとしては、(メタ)アクリロイル基、ビニル基等が挙げられる。
前記アクリレート系化合物としては、例えば、2-ヒドロキシ-3-(メタ)アクリロイルオキシプロピルメタクリレート、ポリエチレングリコールジ(メタ)アクリレート、プロポキシ化エトキシ化ビスフェノールAジ(メタ)アクリレート、2,2-ビス[4-((メタ)アクリロキシポリエトキシ)フェニル]プロパン、エトキシ化ビスフェノールAジ(メタ)アクリレート、2,2-ビス[4-((メタ)アクリロキシジエトキシ)フェニル]プロパン、9,9-ビス[4-(2-(メタ)アクリロイルオキシエトキシ)フェニル]フルオレン、2,2-ビス[4-((メタ)アクリロキシポリプロポキシ)フェニル]プロパン、トリシクロデカンジメタノールジ(メタ)アクリレート(トリシクロデカンジメチロールジ(メタ)アクリレート)、1,10-デカンジオールジ(メタ)アクリレート、1,6-ヘキサンジオールジ(メタ)アクリレート、1,9-ノナンジオールジ(メタ)アクリレート、ジプロピレングリコールジ(メタ)アクリレート、トリプロピレングリコールジ(メタ)アクリレート、ポリプロピレングリコールジ(メタ)アクリレート、ポリテトラメチレングリコールジ(メタ)アクリレート、エチレングリコールジ(メタ)アクリレート、ジエチレングリコールジ(メタ)アクリレート、トリエチレングリコールジ(メタ)アクリレート、2,2-ビス[4-((メタ)アクリロキシエトキシ)フェニル]プロパン、ネオペンチルグリコールジ(メタ)アクリレート、エトキシ化ポリプロピレングリコールジ(メタ)アクリレート、2-ヒドロキシ-1,3-ジ(メタ)アクリロキシプロパン等の2官能(メタ)アクリレート;
トリス(2-(メタ)アクリロキシエチル)イソシアヌレート、ε-カプロラクトン変性トリス-(2-(メタ)アクリロキシエチル)イソシアヌレート、エトキシ化グリセリントリ(メタ)アクリレート、ペンタエリスリトールトリ(メタ)アクリレート、トリメチロールプロパントリ(メタ)アクリレート、ジトリメチロールプロパンテトラ(メタ)アクリレート、エトキシ化ペンタエリスリトールテトラ(メタ)アクリレート、ペンタエリスリトールテトラ(メタ)アクリレート、ジペンタエリスリトールポリ(メタ)アクリレート、ジペンタエリスリトールヘキサ(メタ)アクリレート等の多官能(メタ)アクリレート;
ウレタン(メタ)アクリレートオリゴマー等の多官能(メタ)アクリレートオリゴマー等が挙げられる。
保護膜形成用組成物(IV-1)及び保護膜形成用フィルムは、前記エネルギー線硬化性成分(a)として前記化合物(a2)を含有する場合、さらにエネルギー線硬化性基を有しない重合体(b)も含有することが好ましい。
前記重合体(b)は、その少なくとも一部が架橋剤(f)によって架橋されたものであってもよいし、架橋されていないものであってもよい。
これらの中でも、前記重合体(b)は、アクリル系重合体(以下、「アクリル系重合体(b-1)」と略記することがある)であることが好ましい。
(メタ)アクリル酸ベンジル等の(メタ)アクリル酸アラルキルエステル;
(メタ)アクリル酸ジシクロペンテニルエステル等の(メタ)アクリル酸シクロアルケニルエステル;
(メタ)アクリル酸ジシクロペンテニルオキシエチルエステル等の(メタ)アクリル酸シクロアルケニルオキシアルキルエステル等が挙げられる。
前記水酸基含有(メタ)アクリル酸エステルとしては、例えば、(メタ)アクリル酸ヒドロキシメチル、(メタ)アクリル酸2-ヒドロキシエチル、(メタ)アクリル酸2-ヒドロキシプロピル、(メタ)アクリル酸3-ヒドロキシプロピル、(メタ)アクリル酸2-ヒドロキシブチル、(メタ)アクリル酸3-ヒドロキシブチル、(メタ)アクリル酸4-ヒドロキシブチル等が挙げられる。
前記置換アミノ基含有(メタ)アクリル酸エステルとしては、例えば、(メタ)アクリル酸N-メチルアミノエチル等が挙げられる。
前記反応性官能基は、架橋剤(f)の種類等に応じて適宜選択すればよく、特に限定されない。例えば、架橋剤(f)がポリイソシアネート化合物である場合には、前記反応性官能基としては、水酸基、カルボキシ基、アミノ基等が挙げられ、これらの中でも、イソシアネート基との反応性が高い水酸基が好ましい。架橋剤(f)がエポキシ系化合物である場合には、前記反応性官能基としては、カルボキシ基、アミノ基、アミド基等が挙げられ、これらの中でもエポキシ基との反応性が高いカルボキシ基が好ましい。ただし、半導体ウエハや半導体チップの回路の腐食を防止するという点では、前記反応性官能基はカルボキシ基以外の基であることが好ましい。
光重合開始剤(c)としては、例えば、ベンゾイン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル、ベンゾインイソブチルエーテル、ベンゾイン安息香酸、ベンゾイン安息香酸メチル、ベンゾインジメチルケタール等のベンゾイン化合物;アセトフェノン、2-ヒドロキシ-2-メチル-1-フェニル-プロパン-1-オン、2,2-ジメトキシ-1,2-ジフェニルエタン-1-オン等のアセトフェノン化合物;ビス(2,4,6-トリメチルベンゾイル)フェニルホスフィンオキサイド、2,4,6-トリメチルベンゾイルジフェニルホスフィンオキサイド等のアシルホスフィンオキサイド化合物;ベンジルフェニルスルフィド、テトラメチルチウラムモノスルフィド等のスルフィド化合物;1-ヒドロキシシクロヘキシルフェニルケトン等のα-ケトール化合物;アゾビスイソブチロニトリル等のアゾ化合物;チタノセン等のチタノセン化合物;チオキサントン等のチオキサントン化合物;ベンゾフェノン、2-(ジメチルアミノ)-1-(4-モルホリノフェニル)-2-ベンジル-1-ブタノン、エタノン,1-[9-エチル-6-(2-メチルベンゾイル)-9H-カルバゾール-3-イル]-,1-(O-アセチルオキシム)等のベンゾフェノン化合物;パーオキサイド化合物;ジアセチル等のジケトン化合物;ベンジル;ジベンジル;2,4-ジエチルチオキサントン;1,2-ジフェニルメタン;2-ヒドロキシ-2-メチル-1-[4-(1-メチルビニル)フェニル]プロパノン;2-クロロアントラキノン等が挙げられる。
光重合開始剤(c)としては、例えば、1-クロロアントラキノン等のキノン化合物;アミン等の光増感剤等を用いることもできる。
保護膜形成用フィルムが充填材(d)を含有することにより、保護膜形成用フィルムを硬化して得られた保護膜は、熱膨張係数の調整が容易となり、この熱膨張係数を保護膜の形成対象物に対して最適化することで、保護膜形成用複合シートを用いて得られたパッケージの信頼性がより向上する。保護膜形成用フィルムが充填材(d)を含有することにより、保護膜の吸湿率を低減したり、放熱性を向上させたりすることもできる。
充填材(d)としては、例えば、熱伝導性材料からなるものが挙げられる。
好ましい無機充填材としては、例えば、シリカ、アルミナ、タルク、炭酸カルシウム、チタンホワイト、ベンガラ、炭化ケイ素、窒化ホウ素等の粉末;これら無機充填材を球形化したビーズ;これら無機充填材の表面改質品;これら無機充填材の単結晶繊維;ガラス繊維等が挙げられる。
これらの中でも、無機充填材は、シリカ又はアルミナであることが好ましい。
本明細書において「平均粒子径」とは、特に断りのない限り、レーザー回折散乱法によって求められた粒度分布曲線における、積算値50%での粒子径(D50)の値を意味する。
カップリング剤(e)として、無機化合物又は有機化合物と反応可能な官能基を有するものを用いることにより、保護膜形成用フィルムの被着体に対する接着性及び密着性を向上させることができる。カップリング剤(e)を用いることで、保護膜形成用フィルムを硬化して得られた保護膜は、耐熱性を損なうことなく、耐水性が向上する。
好ましい前記シランカップリング剤としては、例えば、3-グリシジルオキシプロピルトリメトキシシラン、3-グリシジルオキシプロピルメチルジエトキシシラン、3-グリシジルオキシプロピルトリエトキシシラン、3-グリシジルオキシメチルジエトキシシラン、2-(3,4-エポキシシクロヘキシル)エチルトリメトキシシラン、3-メタクリロイルオキシプロピルトリメトキシシラン、3-アミノプロピルトリメトキシシラン、3-(2-アミノエチルアミノ)プロピルトリメトキシシラン、3-(2-アミノエチルアミノ)プロピルメチルジエトキシシラン、3-(フェニルアミノ)プロピルトリメトキシシラン、3-アニリノプロピルトリメトキシシラン、3-ウレイドプロピルトリエトキシシラン、3-メルカプトプロピルトリメトキシシラン、3-メルカプトプロピルメチルジメトキシシラン、ビス(3-トリエトキシシリルプロピル)テトラスルファン、メチルトリメトキシシラン、メチルトリエトキシシラン、ビニルトリメトキシシラン、ビニルトリアセトキシシラン、イミダゾールシラン等が挙げられる。
架橋剤(f)を用いて、上述のエネルギー線硬化性成分(a)やエネルギー線硬化性基を有しない重合体(b)を架橋することにより、保護膜形成用フィルムの初期接着力及び凝集力を調節できる。
着色剤(g)としては、例えば、無機系顔料、有機系顔料、有機系染料等、公知のものが挙げられる。
保護膜形成用組成物(IV-1)及び保護膜形成用フィルムが含有する熱硬化性成分(h)は、1種のみでもよいし、2種以上でもよく、2種以上である場合、それらの組み合わせ及び比率は任意に選択できる。
エポキシ系熱硬化性樹脂は、エポキシ樹脂(h1)及び熱硬化剤(h2)からなる。
保護膜形成用組成物(IV-1)及び保護膜形成用フィルムが含有するエポキシ系熱硬化性樹脂は、1種のみでもよいし、2種以上でもよく、2種以上である場合、それらの組み合わせ及び比率は任意に選択できる。
エポキシ樹脂(h1)としては、公知のものが挙げられ、例えば、多官能系エポキシ樹脂、ビフェニル化合物、ビスフェノールAジグリシジルエーテル及びその水添物、オルソクレゾールノボラックエポキシ樹脂、ジシクロペンタジエン型エポキシ樹脂、ビフェニル型エポキシ樹脂、ビスフェノールA型エポキシ樹脂、ビスフェノールF型エポキシ樹脂、フェニレン骨格型エポキシ樹脂等、2官能以上のエポキシ化合物が挙げられる。
不飽和炭化水素基を有するエポキシ樹脂としては、例えば、エポキシ樹脂を構成する芳香環等に、不飽和炭化水素基を有する基が直接結合した化合物等が挙げられる。
不飽和炭化水素基は、重合性を有する不飽和基であり、その具体的な例としては、エテニル基(ビニル基ともいう)、2-プロペニル基(アリル基ともいう)、(メタ)アクリロイル基、(メタ)アクリルアミド基等が挙げられ、アクリロイル基が好ましい。
本明細書において、「数平均分子量」は、特に断らない限り、ゲルパーミエーションクロマトグラフィー(GPC)法によって測定される標準ポリスチレン換算の値で表される数平均分子量を意味する。
エポキシ樹脂(h1)のエポキシ当量は、100~1000g/eqであることが好ましく、150~800g/eqであることがより好ましい。
本明細書において、「エポキシ当量」とは1グラム当量のエポキシ基を含むエポキシ化合物のグラム数(g/eq)を意味し、JIS K 7236:2001の方法に従って測定することができる。
熱硬化剤(h2)は、エポキシ樹脂(h1)に対する硬化剤として機能する。
熱硬化剤(h2)としては、例えば、1分子中にエポキシ基と反応し得る官能基を2個以上有する化合物が挙げられる。前記官能基としては、例えば、フェノール性水酸基、アルコール性水酸基、アミノ基、カルボキシ基、酸基が無水物化された基等が挙げられ、フェノール性水酸基、アミノ基、又は酸基が無水物化された基であることが好ましく、フェノール性水酸基又はアミノ基であることがより好ましい。
熱硬化剤(h2)のうち、アミノ基を有するアミン系硬化剤としては、例えば、ジシアンジアミド(以下、「DICY」と略記することがある)等が挙げられる。
不飽和炭化水素基を有する熱硬化剤(h2)としては、例えば、フェノール樹脂の水酸基の一部が、不飽和炭化水素基を有する基で置換されてなる化合物、フェノール樹脂の芳香環に、不飽和炭化水素基を有する基が直接結合してなる化合物等が挙げられる。
熱硬化剤(h2)における前記不飽和炭化水素基は、上述の不飽和炭化水素基を有するエポキシ樹脂における不飽和炭化水素基と同様である。
本明細書において「ガラス転移温度」とは、示差走査熱量計を用いて、試料のDSC曲線を測定し、得られたDSC曲線の変曲点の温度で表される。
熱硬化剤(h2)のうち、例えば、ビフェノール、ジシアンジアミド等の非樹脂成分の分子量は、特に限定されないが、例えば、60~500であることが好ましい。
汎用添加剤(z)は、公知のものでよく、目的に応じて任意に選択でき、特に限定されないが、好ましいものとしては、例えば、可塑剤、帯電防止剤、酸化防止剤、ゲッタリング剤等が挙げられる。
汎用添加剤(z)を用いる場合、保護膜形成用組成物(IV-1)及び保護膜形成用フィルムの汎用添加剤(z)の含有量は、特に限定されず、目的に応じて適宜選択すればよい。
保護膜形成用組成物(IV-1)は、さらに溶媒を含有することが好ましい。溶媒を含有する保護膜形成用組成物(IV-1)は、取り扱い性が良好となる。
前記溶媒は特に限定されないが、好ましいものとしては、例えば、トルエン、キシレン等の炭化水素;メタノール、エタノール、2-プロパノール、イソブチルアルコール(2-メチルプロパン-1-オールともいう)、1-ブタノール等のアルコール;酢酸エチル等のエステル;アセトン、メチルエチルケトン等のケトン;テトラヒドロフラン等のエーテル;ジメチルホルムアミド、N-メチルピロリドン等のアミド(アミド結合を有する化合物)等が挙げられる。
保護膜形成用組成物(IV-1)が含有する溶媒は、1種のみでもよいし、2種以上でもよく、2種以上である場合、それらの組み合わせ及び比率は任意に選択できる。
保護膜形成用組成物(IV-1)等の保護膜形成用組成物は、これを構成するための各成分を配合することで得られる。
各成分の配合時における添加順序は特に限定されず、2種以上の成分を同時に添加してもよい。
溶媒を用いる場合には、溶媒を溶媒以外のいずれかの配合成分と混合してこの配合成分を予め希釈しておくことで用いてもよいし、溶媒以外のいずれかの配合成分を予め希釈しておくことなく、溶媒をこれら配合成分と混合することで用いてもよい。
配合時に各成分を混合する方法は特に限定されず、撹拌子又は撹拌翼等を回転させて混合する方法;ミキサーを用いて混合する方法;超音波を加えて混合する方法等、公知の方法から適宜選択すればよい。
各成分の添加及び混合時の温度並びに時間は、各配合成分が劣化しない限り特に限定されず、適宜調節すればよいが、温度は15~30℃であることが好ましい。
しかし、ダイシングダイボンディングシートが備える接着剤層は、半導体チップとともに支持シートからピックアップされた後、この半導体チップを基板、リードフレーム、又は他の半導体チップ等に取り付ける際の接着剤として機能する。一方、本発明に用いることのできる保護膜形成用複合シートにおける保護膜形成用フィルムは、半導体チップとともに支持シートからピックアップされる点では前記接着剤層と同じであるが、最終的には硬化によって保護膜となり、貼付されている半導体チップの裏面を保護するという機能を有する。このように、本発明における保護膜形成用フィルムは、ダイシングダイボンディングシートにおける接着剤層とは、用途が異なり、求められる性能も当然に異なる。この用途の違いを反映して、保護膜形成用フィルムは、通常、ダイシングダイボンディングシートにおける接着剤層と比較すると、硬めで、ピックアップが難しい傾向にある。したがって、ダイシングダイボンディングシートにおける接着剤層を、そのまま保護膜形成用複合シートにおける保護膜形成用フィルムとして転用することは、通常、困難である。本発明に用いることのできる保護膜形成用複合シートは、エネルギー線硬化性の保護膜形成用フィルムを備えたものとしては、保護膜付き半導体チップのピックアップ適性に関して、優れたものを適宜選択して使用される。
本発明に用いることのできる保護膜形成用複合シートは、上述の各層を対応する位置関係となるように順次積層することで製造できる。各層の形成方法は、先に説明したとおりである。
例えば、支持シートを製造するときに、基材上に粘着剤層を積層する場合には、基材上に上述の粘着剤組成物を塗工し、必要に応じて乾燥させればよい。
ただし、これら2層のうちの後から積層する層は、別の剥離フィルム上に前記組成物を用いてあらかじめ形成しておき、この形成済みの層の前記剥離フィルムと接触している側とは反対側の露出面を、既に形成済みの残りの層の露出面と貼り合わせることで、連続する2層の積層構造を形成することが好ましい。このとき、前記組成物は、剥離フィルムの剥離処理面に塗工することが好ましい。剥離フィルムは、積層構造の形成後、必要に応じて取り除けばよい。
いずれの方法においても、剥離フィルムは目的とする積層構造を形成後の任意のタイミングで取り除けばよい。
・エネルギー線硬化性成分
(a2)-1:トリシクロデカンジメチロールジアクリレート(日本化薬社製「KAYARAD R-684」、2官能紫外線硬化性化合物、分子量304)
・エネルギー線硬化性基を有しない重合体
(b)-1:アクリル酸ブチル(以下、「BA」と略記する)(10質量部)、アクリル酸メチル(以下、「MA」と略記する)(70質量部)、メタクリル酸グリシジル(以下、「GMA」と略記する)(5質量部)及びアクリル酸-2-ヒドロキシエチル(以下、「HEA」と略記する)(15質量部)を共重合してなるアクリル系樹脂(重量平均分子量300000、ガラス転移温度-1℃)。
・光重合開始剤
(c)-1:2-(ジメチルアミノ)-1-(4-モルホリノフェニル)-2-ベンジル-1-ブタノン(BASF社製「Irgacure(登録商標)369」)
(c)-2:エタノン,1-[9-エチル-6-(2-メチルベンゾイル)-9H-カルバゾール-3-イル]-,1-(O-アセチルオキシム)(BASF社製「Irgacure(登録商標)OXE02」)
・充填材
(d)-1:シリカフィラー(溶融石英フィラー、平均粒子径8μm)
・カップリング剤
(e)-1:3-メタクリロキシプロピルトリメトキシシラン(信越化学工業社製「KBM-503」、シランカップリング剤)
・着色剤
(g)-1:フタロシアニン系青色色素(Pigment Blue 15:3)32質量部と、イソインドリノン系黄色色素(Pigment Yellow 139)18質量部と、アントラキノン系赤色色素(Pigment Red 177)50質量部とを混合し、前記3種の色素の合計量/スチレンアクリル樹脂量=1/3(質量比)となるように顔料化して得られた顔料。
<保護膜形成用複合シートの製造>
(保護膜形成用組成物(IV-1)の製造)
エネルギー線硬化性成分(a2)-1、重合体(b)-1、光重合開始剤(c)-1、光重合開始剤(c)-2、充填材(d)-1、カップリング剤(e)-1及び着色剤(g)-1を、これらの含有量(固形分量、質量部)が表1に示す値となるようにメチルエチルケトンに溶解又は分散させて、23℃で撹拌することで、固形分濃度が50質量%である保護膜形成用組成物(IV-1)を調製した。
アクリル系重合体(100質量部、固形分)、ヘキサメチレンジイソシアネート系架橋剤(日本ポリウレタン社製「コロネートHL」、9質量部)、及びオリゴ[2-ヒドロキシ-2-メチル-1-(4-(1-メチルビニル)フェニル)プロパノン] (DKSH社製「KIP-150」、3質量部)を含有し、さらに溶媒としてメチルエチルケトンを含有する、固形分濃度が30質量%の紫外線硬化性の粘着剤組成物(I-2)を調製した。前記アクリル系重合体は、アクリル酸-2-エチルヘキシル(以下、「2EHA」と略記する)(70mol%)及びHEA(30mol%)を共重合してなるアクリル系重合体に、2-メタクリロイルオキシエチルイソシアネート(以下、「MOI」と略記する)(前記アクリル系重合体中のHEA由来の水酸基の総モル数に対して、2-メタクリロイルオキシエチルイソシアネート中のイソシアネート基の総モル数が0.8倍となる量)を反応させて得られた、側鎖にメタクリロイルオキシ基を有する、重量平均分子量が600000である。
ポリエチレンテレフタレート製フィルムの片面がシリコーン処理により剥離処理された剥離フィルム(リンテック社製「SP-PET381031」、厚さ38μm)の前記剥離処理面に、上記で得られた粘着剤組成物(I-3)を塗工し、120℃で2分加熱乾燥させることにより、厚さ10μmの非エネルギー線硬化性の粘着剤層を形成した。
次いで、この粘着剤層の露出面に、基材としてポリプロピレン系フィルム(厚さ80μm)を貼り合せることにより、前記基材の一方の表面上に前記粘着剤層を備えた支持シート(10)-7を得た。
ポリエチレンテレフタレート製フィルムの片面がシリコーン処理により剥離処理された剥離フィルム(リンテック社製「SP-PET381031」、厚さ38μm)の前記剥離処理面に、上記で得られた保護膜形成用組成物(IV-1)をナイフコーターにより塗工し、100℃で2分乾燥させることにより、厚さ25μmのエネルギー線硬化性の保護膜形成用フィルム(13)-1を作製した。
(保護膜形成用フィルムと支持シートとの間の粘着力)
上記で得られた保護膜形成用複合シートを25mm×140mmの大きさに裁断し、保護膜形成用複合シートから剥離フィルムを取り除いて、保護膜形成用フィルム(13)-1の一方の表面を露出させ、硬化前試験片とした。一方、SUS製の支持板(70mm×150mm)の表面に両面粘着テープを貼り合わせたものを用意した。そして、ラミネーター(Fuji社製「LAMIPACKER LPD3214」)を用いて、硬化前試験片の保護膜形成用フィルム(13)-1の露出面を、支持板上の前記両面粘着テープに貼付することで、支持板に両面粘着テープを介して硬化前試験片を貼付した。
上述の、硬化前試験片の粘着力の測定時と同じ方法で、硬化前試験片を作製し、SUS製の支持板に両面粘着テープを介してこの硬化前試験片を貼付した。
次いで、紫外線照射装置(リンテック社製「RAD2000m/8」)を用いて、照度195mW/cm2、光量170mJ/cm2の条件で、硬化前試験片に紫外線を照射することで、保護膜形成用フィルム(13)-1を硬化させ、硬化後試験片を得た。
次いで、この硬化後試験片について、上述の硬化前試験片の場合と同じ方法で、保護膜形成用フィルム(13)-1を硬化させた保護膜と、支持シート(10)-7との間の粘着力を測定した。結果を表2に示す。
6インチシリコンウエハ(厚さ100μm)の#2000研磨面に、上記で得られた保護膜形成用複合シートをその保護膜形成用フィルム(13)-1によって貼付し、さらにこのシートをリングフレームに固定した。
次いで、ダイシングブレードを用いて、シリコンウエハを保護膜形成用フィルム(13)-1ごとダイシングして個片化し、2mm×2mmのシリコンチップを得た。このとき、シリコンチップの支持シートからの飛散の有無を目視で確認し、シリコンチップの飛散が全くなかった場合を「○」と判定し、シリコンチップの飛散が僅かでもあった場合を「×」と判定し、ダイシング適性を評価した。結果を表2に示す。表2中の「チップの飛散の抑制」の欄の記載が該当する結果である。
ダイシング時において保護膜と支持シートとの間への切削水の浸入もなかった。
次いで、紫外線照射装置(リンテック社製「RAD2000m/8」)を用いて、照度195mW/cm2、光量170mJ/cm2の条件で、支持シート(10)-7側から保護膜形成用フィルム(13)-1に紫外線を照射することで、保護膜形成用フィルム(13)-1を硬化させ、保護膜とした。
次いで、ダイボンダー(キャノンマシナリー社製「BESTEM-D02」)を用いて、20個の保護膜付きシリコンチップをピックアップした。このとき、ダイシングしたシリコンチップの切断面をデジタル顕微鏡(キーエンス社製,VHX-100,倍率:100倍)を用いて観察した。20μm以上の幅又は深さの割れ・欠けが認められた場合には、チッピングが発生したものとして不良(×)と判定し、このような欠けが認められない場合には良好(○)と判定した。結果を表2に示す。表2中の「チップの割れ・欠けの抑制」の欄の記載が該当する結果である。
[実施例2]
ポリエチレンテレフタレート製フィルムの片面がシリコーン処理により剥離処理された第1の剥離フィルム(リンテック社製「SP-PET382150」、厚さ38μm)の前記剥離処理面に、上記で得られた保護膜形成用組成物(IV-1)をナイフコーターにより塗工し、100℃で2分乾燥させることにより、厚さ25μmのエネルギー線硬化性の保護膜形成用フィルム(13)-1を作製した。
次いで、得られた保護膜形成用フィルム(13)-1の露出面に、ポリエチレンテレフタレート製フィルムの片面がシリコーン処理により剥離処理された第2の剥離フィルム(リンテック社製「SP-PET381031」、厚さ38μm)の剥離面を貼合して、第1の剥離フィルム(図7における第1の剥離フィルム15’:25μm)と、第2の剥離フィルム15”とからなる保護膜形成用シートを得た。
次いで、ダイシングブレードを用いて、シリコンウエハを保護膜形成用フィルム(13)-1ごとダイシングして個片化し、2mm×2mmのシリコンチップを得た。このとき、シリコンチップの支持シートからの飛散の有無を目視で確認し、シリコンチップの飛散が全くなかった場合を「○」と判定し、シリコンチップの飛散が僅かでもあった場合を「×」と判定し、ダイシング適性を評価した。結果を表2に示す。表2中の「チップの飛散の抑制」の欄の記載が該当する結果である。
<保護膜形成用複合シートの製造>
(保護膜形成用組成物(IV-1)の製造)
表1に示すように、重合体(b)-1の含有量(配合量)を22質量部に代えて2質量部とし、充填材(d)-1の含有量(配合量)を56質量部に代えて76質量部とした点以外は、実施例1と同じ方法で、保護膜形成用組成物(IV-1)を調製した。
上記で得られた保護膜形成用組成物(IV-1)を用いた点以外は、実施例1と同じ方法で、厚さ25μmのエネルギー線硬化性の保護膜形成用フィルム(13)-2を作製した。
保護膜形成用フィルム(13)-1に代えて、この保護膜形成用フィルム(13)-2を用いた点以外は、実施例1と同じ方法で保護膜形成用複合シートを製造した。
得られた保護膜形成用複合シートの構成を表2に示す。
上記で得られた保護膜形成用複合シートを用いて、実施例1と同じ方法でダイシング評価及びピックアップ評価をした。結果を表2に示す。
<保護膜形成用複合シートの製造及び評価>
支持シート(10)-7の製造時に用いたものと同じ基材(ポリプロピレン系フィルム、厚さ80μm)の表面に、コロナ放電処理を施した。表2に示すように、支持シート(10)-7に代えて、この表面処理を行った基材のみからなる支持シート(10)-8を用いた点以外は、実施例1と同じ方法で、保護膜形成用複合シートを製造及び評価した。結果を表2に示す。なお、本実施例においては、支持シート(10)-2に相当する前記基材のコロナ放電処理面に、保護膜形成用フィルム(13)-1を設けた。
上記で得られた保護膜形成用複合シートを用いて、実施例1と同じ方法でダイシング評価及びピックアップ評価をした。結果を表2に示す。
<保護膜形成用複合シートの製造及び評価>
6インチシリコンウエハ(厚さ100μm)の#2000研磨面に、実施例1と同じ方法で得られた保護膜形成用複合シートをその保護膜形成用フィルム(13)-1によって貼付し、さらにこのシートをリングフレームに固定して、30分静置した。
次いで、紫外線照射装置(リンテック社製「RAD2000m/8」)を用いて、照度195mW/cm2、光量170mJ/cm2の条件で、支持シート(10)-7側から保護膜形成用フィルム(13)-1に紫外線を照射することで、保護膜形成用フィルム(13)-1を硬化させ、保護膜とした。
次いで、ダイシングブレードを用いて、シリコンウエハを保護膜形成用フィルム(13)-1ごとダイシングして個片化し、2mm×2mmのシリコンチップを得た。このとき、シリコンチップの支持シートからの飛散の有無を目視で確認し、シリコンチップの飛散が全くなかった場合を「○」と判定し、シリコンチップの飛散が僅かでもあった場合を「×」と判定し、ダイシング適性を評価した。結果を表2に示す。表2中の「チップの飛散の抑制」の欄の記載が該当する結果である。
ダイシング時において保護膜と支持シートとの間への切削水の浸入があった。
<保護膜形成用シートの製造及び評価>
実施例2と同じ方法で、6インチシリコンウエハと、保護膜形成用フィルム(13)-1と、第1の剥離フィルムとからなる積層体を作製した。
得られた積層体から第1の剥離フィルムを取り除き、また、実施例1と同様にして得られた支持シート(10)-7の粘着剤層から剥離フィルムを取り除き、支持シート(10)-7の粘着剤層の露出面に、保護膜形成用フィルム(13)-1及び第1の剥離フィルムを貼付して、その保護膜形成用フィルム(13)-1によって貼付し、さらにこのシートをリングフレームに固定して、30分静置した。
次いで、紫外線照射装置(リンテック社製「RAD2000m/8」)を用いて、照度195mW/cm2、光量170mJ/cm2の条件で、支持シート(10)-7側から保護膜形成用フィルム(13)-1に紫外線を照射することで、保護膜形成用フィルム(13)-1を硬化させ、保護膜とした。
次いで、ダイシングブレードを用いて、シリコンウエハを保護膜形成用フィルム(13)-1ごとダイシングして個片化し、2mm×2mmのシリコンチップを得た。このとき、シリコンチップの支持シートからの飛散の有無を目視で確認し、シリコンチップの飛散が全くなかった場合を「○」と判定し、シリコンチップの飛散が僅かでもあった場合を「×」と判定し、ダイシング適性を評価した。結果を表2に示す。表2中の「チップの飛散の抑制」の欄の記載が該当する結果である。
ダイシング時において保護膜と支持シートとの間への切削水の浸入があった。
<保護膜形成用複合シートの製造及び評価>
実施例3と同じ方法で保護膜形成用複合シートを製造した。得られた保護膜形成用複合シートの構成を表2に示す。
6インチシリコンウエハ(厚さ100μm)の#2000研磨面に、上記で得られた保護膜形成用複合シートをその保護膜形成用フィルム(13)-2によって貼付し、さらにこのシートをリングフレームに固定して、30分静置した。
次いで、紫外線照射装置(リンテック社製「RAD2000m/8」)を用いて、照度195mW/cm2、光量170mJ/cm2の条件で、支持シート(10)-7側から保護膜形成用フィルム(13)-1に紫外線を照射することで、保護膜形成用フィルム(13)-1を硬化させ、保護膜とした。
次いで、ダイシングブレードを用いて、シリコンウエハを保護膜形成用フィルム(13)-1ごとダイシングして個片化し、2mm×2mmのシリコンチップを得た。このとき、シリコンチップの支持シートからの飛散の有無を目視で確認し、シリコンチップの飛散が全くなかった場合を「○」と判定し、シリコンチップの飛散が僅かでもあった場合を「×」と判定し、ダイシング適性を評価した。結果を表2に示す。表2中の「チップの飛散の抑制」の欄の記載が該当する結果である。
ダイシング時において保護膜と支持シートとの間への切削水の浸入があった。
2F・・・保護膜形成用シート
10・・・支持シート
10a・・・支持シートの表面
11・・・基材
11a・・・基材の表面
12・・・粘着剤層
12a・・・粘着剤層の表面
13,23・・・保護膜形成用フィルム
13’,23’・・・保護膜
13a,23a・・・保護膜形成用フィルムの表面(一方の面)
13b・・・保護膜形成用フィルムの表面(他方の面)
15・・・剥離フィルム
15’・・・第1の剥離フィルム
15”・・・第2の剥離フィルム
16・・・治具用接着剤層
16a・・・治具用接着剤層の表面
17・・・リングフレーム
18・・・半導体ウエハ
19・・・半導体チップ
20・・・ダイシングブレード
21・・・エネルギー線照射装置
Claims (5)
- 支持シート、エネルギー線硬化性の保護膜形成用フィルム及び半導体ウエハをこの順に備えた積層体の、前記半導体ウエハをダイシングし、次いで、前記保護膜形成用フィルムにエネルギー線を照射して硬化させる、保護膜付き半導体チップの製造方法。
- 前記積層体の、支持シートと前記保護膜形成用フィルムとの間の粘着力が80mN/25mm以上である、請求項1に記載の保護膜付き半導体チップの製造方法。
- 前記積層体は、前記半導体ウエハに前記保護膜形成用フィルムを貼付した後、前記保護膜形成用フィルムに支持シートを貼付したものである、請求項1又は2に記載の保護膜付き半導体チップの製造方法。
- 前記積層体は、支持シート上に前記保護膜形成用フィルムを備えてなる保護膜形成用複合シートの前記保護膜形成用フィルム側を前記半導体ウエハに貼付したものである、請求項1又は2に記載の保護膜付き半導体チップの製造方法。
- 請求項1~4のいずれかに記載の製造方法により得られた保護膜付き半導体チップをピックアップし、前記半導体チップを基板に接続する、半導体装置の製造方法。
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