WO2017188218A1 - 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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- WO2017188218A1 WO2017188218A1 PCT/JP2017/016287 JP2017016287W WO2017188218A1 WO 2017188218 A1 WO2017188218 A1 WO 2017188218A1 JP 2017016287 W JP2017016287 W JP 2017016287W WO 2017188218 A1 WO2017188218 A1 WO 2017188218A1
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- protective film
- forming
- film
- meth
- sensitive adhesive
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Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/50—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
- H01L21/56—Encapsulations, e.g. encapsulation layers, coatings
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
- H01L21/67005—Apparatus not specifically provided for elsewhere
- H01L21/67011—Apparatus for manufacture or treatment
- H01L21/67092—Apparatus for mechanical treatment
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
- H01L21/683—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping
- H01L21/6835—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
- H01L21/6836—Wafer tapes, e.g. grinding or dicing support tapes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- 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
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 circuit surface side of the semiconductor chip is usually directed to the bottom of the pocket 102a of the embossed carrier tape 102, and the protective film side is directed to the pocket. It is stored toward the opening of 102a.
- the cover tape 103 constituting the lid of the embossed carrier tape 102 By sticking the cover tape 103 constituting the lid of the embossed carrier tape 102, the opening is closed and packed.
- the embossed carrier tape 102 packed with the semiconductor chip 101 with the protective film is set on the mounter together with the reel, and the semiconductor chip 101 with the protective film is mounted on the substrate. To do.
- the cover tape 103 is peeled off, and the semiconductor chip 101 with the protective film is taken out from the pocket 102a of the embossed carrier tape 102.
- the semiconductor chip 101 with the protective film adheres to the cover tape 103 by the protective film, and the protective film
- the process of mounting the attached semiconductor chip 101 on the substrate may be an obstacle.
- the present invention is less likely to cause clogging or chipping of the blade when dicing the semiconductor wafer, and when the semiconductor chip with a protective film is stored in the pocket of the embossed carrier tape, the semiconductor chip with the protective film is formed on the cover tape. It is an object of the present invention to provide a method for manufacturing a semiconductor chip with a protective film and a method for manufacturing a semiconductor device, which have characteristics capable of suppressing adhesion.
- the method for producing a semiconductor chip with a protective film of the present invention comprises irradiating the protective film-forming film with energy rays after affixing an energy-ray-curable protective film-forming film to a semiconductor wafer.
- the protective film-forming film is irradiated with an energy ray to form a protective film, and then the protective film is attached to a support sheet, and then the semiconductor wafer is diced. You may do.
- the protective film-forming film side of the protective film-forming composite sheet comprising the protective film-forming film on a support sheet is attached to the semiconductor wafer. It may be.
- 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.
- the semiconductor chip with a protective film is stored in the pocket of the embossed carrier tape, the semiconductor chip with the protective film is formed on the cover tape.
- a method for manufacturing a semiconductor chip with a protective film and a method for manufacturing a semiconductor device, which can suppress adhesion.
- FIG. 1 is a schematic view showing a method for manufacturing a semiconductor chip with a protective film according to the present invention.
- the protective film forming film 13 is irradiated with energy rays and cured.
- the semiconductor wafer 18 is diced.
- the protective film forming film 13 is cured by irradiating it with energy rays, the protective film 13 ′ at the time of dicing is hard by dicing. Not likely to occur.
- the tensile elasticity modulus of protective film 13 ' is as hard as 500 Mpa or more, it can suppress that the semiconductor chip with a protective film adheres to a cover tape.
- the protective film-forming film is irradiated with an energy ray to form a protective film, and then the protective film is attached to a support sheet, and then the semiconductor wafer is diced. You may do.
- a protective film-forming film and a support sheet suitable for semiconductor wafer products and production can be appropriately selected and used.
- the method for producing a semiconductor chip with a protective film according to the present invention that is, after pasting an energy ray curable protective film-forming film on the back surface (surface opposite to the electrode forming surface) of the semiconductor wafer, The protective film-forming film is irradiated with energy rays and cured to form a protective film, and then the protective film is attached to a support sheet, and then the semiconductor wafer is diced.
- the protective film forming film side of the protective film forming composite sheet comprising the protective film forming film on a support sheet is attached to the semiconductor wafer.
- the pasting 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.
- the method for producing a semiconductor chip with a protective film according to the present invention is for forming a protective film comprising the protective film-forming film on a support sheet on the back surface (surface opposite to the electrode forming surface) of the semiconductor wafer.
- the composite sheet is pasted with the protective film-forming film.
- the protective film-forming film is irradiated with energy rays and cured, and then the semiconductor wafer is diced.
- 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 object of dicing provided with a support sheet, an energy ray-curable film for forming a protective film, and a semiconductor wafer in this order is referred to as a “laminate” in this specification.
- 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, 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.
- an upper limit is not specifically limited, For example, 10,000 mN / 25 mm or less may be sufficient, but 8000 mN / 25 mm or less may be sufficient and 7000 mN / 25 mm or less may be sufficient.
- peeling between the protective film-forming film and the support sheet is suppressed during dicing.
- scattering of silicon chips is suppressed during dicing.
- the upper limit value or less it is possible to facilitate the appropriate adjustment of the adhesive force between the protective film and the support sheet when cured by energy ray irradiation to form a protective film. it can.
- 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 tensile elastic modulus of the protective film is preferably 500 to 10,000 MPa, more preferably 600 to 8000 MPa, and particularly preferably 700 to 5000 MPa.
- the tensile elastic modulus is in such a range, when dicing a semiconductor wafer using the protective film, clogging or chipping of the blade is difficult to occur, and the semiconductor chip with the protective film is placed in the pocket of the embossed carrier tape. When stored, it is possible to prevent the semiconductor chip with a protective film from adhering to the cover tape.
- the said tensile elasticity modulus can be measured with the measuring method as described in the Example 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 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.
- the protective film forming sheet 2 ⁇ / b> F is cut into a circular shape and laminated on a support sheet, and is used by being held on a jig such as a ring frame by an adhesive portion of the support sheet.
- 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.
- 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 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 Meyer bar 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). 5-30 mass%, more preferably 8-25 mass%) of the total mass of the polymer; (b) a polymer having no energy ray-curable group (b) as a structural unit derived from methyl acrylate (total of acrylic resin 75 to 95% by mass, more preferably 80 to 90% by mass) and 2-hydroxyethyl acrylate (5 to 25% by mass, more preferably 10 to 10% by mass based on the total mass of the acrylic resin).
- an acrylic resin content: 12 to 32% by mass, more preferably 17 to 27% by mass with respect to the total mass of the solid content of the protective film-forming composition (IV-1)
- Light weight As the initiator (c), 1-hydroxy-cyclohexyl-phenyl-ketone content: 0.1 to 1.1% by mass with respect to the total mass of the solid content of the protective film-forming composition (IV-1)), More preferably 0.3 to 0.9% by mass), or 2- (4-methylbenzyl) -2-dimethylamino-1- (4-morpholin-4-yl-phenyl) -butan-one (content : 0.1 to 1.1% by mass, more preferably 0.3 to 0.9% by mass, based on the total mass of the solid content of the protective film-forming composition (IV-1); A silica filler (content: 46 to 66% by mass, more preferably 51 to 61% by mass with respect to the total mass of the solid content of the protective film-forming composition (IV-1)); coupling agent ( e) 3-
- 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
- the composite sheet for forming protective film can be used, for example, by the following method. 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 protective film-forming film is irradiated with energy rays, and the protective film-forming film is cured to form a protective film. Next, the semiconductor wafer is divided together with the protective film by dicing to form semiconductor chips. Then, the semiconductor chip is picked up while being separated from the support sheet while the protective film is attached (that is, as a semiconductor chip with a protective film).
- the picked-up semiconductor chip 101 with protective film is stored in a pocket 102a of an embossed carrier tape 102 as shown in FIG. 8, and the opening is closed by attaching a cover tape 103 to the opening of the pocket 102a. And packed. Then, the embossed carrier tape 102 is stored, transported, or traded in a state of being wound on a reel, and used in the next step of flip chip connecting the semiconductor chip of the semiconductor chip 101 with protective film to the circuit surface of the substrate.
- the “embossed carrier tape” refers to a plurality of recesses (sometimes referred to as pockets) arranged at regular intervals on a long sheet made of resin such as polystyrene, polyethylene terephthalate, or polypropylene.
- each of the plurality of pockets can accommodate, for example, a semiconductor chip with a protective film according to the present invention.
- Each of the plurality of pockets is normally closed when a cover tape having a long shape is pasted in a state where an object to be stored such as a semiconductor chip with a protective film according to the present invention is stored.
- An embossed carrier tape in which a semiconductor chip with a protective film is packed can be used in a state of being wound around a reel.
- the reel can be set on a mounter, and a semiconductor chip with a protective film can be mounted on the substrate.
- the pocket of the embossed carrier tape can be designed and processed according to the size of the object to be stored.
- each pocket of the embossed carrier tape in the present specification examples include those having a vertical dimension of 0.5 mm to 30 mm, a horizontal dimension of 0.5 mm to 30 mm, and a depth of 0.1 mm to 10 mm.
- the long cover tape has a thickness of 10 to 100 ⁇ m and is made of a material such as PET.
- 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 being flip-chip connected to the circuit surface, a semiconductor package is obtained. Then, a target semiconductor device may be manufactured using this semiconductor package.
- 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.)
- MA Methyl acrylate
- HOA 2-hydroxyethyl acrylate
- Photopolymerization initiator (c) -3 1-hydroxy-cyclohexyl-phenyl-ketone (“Irgacure® 184” manufactured by BASF)
- C) -4 2- (4-methylbenzyl) -2-dimethylamino-1- (4-morpholin-4-yl-phenyl) -butan-1-one (“Irgacure®” manufactured by BASF) 379 ", molecular weight 380).
- Filler (d) -1 Silica filler (fused quartz filler, average particle size 8 ⁇ m)
- Colorant (g) -1: 32 parts by mass of phthalocyanine blue pigment (Pigment Blue 15: 3), 18 parts by mass of isoindolinone yellow pigment (Pigment Yellow 139), and anthraquinone red pigment (Pigment Red 177) A pigment obtained by mixing 50 parts by mass and pigmenting the mixture so that the total amount of the three kinds of dyes / the amount of styrene acrylic resin 1/3 (mass ratio).
- (Production of pressure-sensitive adhesive composition (I-4)) Contains an acrylic polymer (100 parts by mass, solid content) and a trifunctional xylylene diisocyanate-based crosslinking agent (“Takenate D110N” manufactured by Takeda Chemical Co., Ltd.) (10.7 parts by mass, solid content), and further as a solvent
- a non-energy ray-curable pressure-sensitive adhesive composition (I-4) containing methyl ethyl ketone and having a solid content concentration of 30% by mass was prepared.
- the acrylic polymer is obtained by copolymerizing 2-ethylhexyl acrylate (hereinafter abbreviated as “2EHA”) (36 parts by mass), BA (59 parts by mass), and HEA (5 parts by mass).
- the weight average molecular weight is 600,000.
- the pressure-sensitive adhesive composition (I-4) obtained above was applied to the release-treated surface of a release film (“SP-PET 381031” manufactured by Lintec Co., Ltd., thickness 38 ⁇ m) obtained by releasing one side of a polyethylene terephthalate film by silicone treatment. ) And dried by heating at 120 ° C. for 2 minutes to form a non-energy ray-curable pressure-sensitive adhesive layer having a thickness of 10 ⁇ m.
- a support sheet provided with the pressure-sensitive adhesive layer on one surface of the base material by bonding a polypropylene film (Young's modulus 400, thickness 80 ⁇ m) as a base material to the exposed surface of the pressure-sensitive adhesive layer. (10) -1 was obtained.
- 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) -9 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) -1 obtained above, and the protective film-forming film (13) -9 obtained above is exposed on the exposed surface of the pressure-sensitive adhesive layer.
- the surfaces were bonded together to prepare a protective film-forming composite sheet in which the base material, the pressure-sensitive adhesive layer, the protective film-forming film (13) -9 and the release film were laminated in this thickness direction in this order.
- Table 2 shows the structure of the obtained protective sheet-forming composite sheet.
- the tensile elastic modulus (Young's modulus) of the protective film-forming film (13) -9 was evaluated as follows. That is, two layers of protective film-forming sheets (thickness: 25 ⁇ m) are laminated to a thickness of 50 ⁇ m, the sample is subjected to a tensile test (tensile speed: 50 mm / min) with a size of 15 mm ⁇ 100 mm, and initial tensile stress The tensile elastic modulus of the protective film-forming film (13) -9 was calculated from the slope of the strain curve. The evaluation results are shown in Table 2.
- the tensile modulus (Young's modulus) after curing of the protective film-forming film (13) -9 was evaluated as follows. That is, two layers of protective film-forming film (13) -9 (thickness: 25 ⁇ m) are laminated to a thickness of 50 ⁇ m, and UV (illuminance: 230 mW / cm 2 , light amount: 170 mJ / cm 2 ) is applied once from both sides. Irradiated one by one and cured.
- 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) -9, 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) -1 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). ) -9 was irradiated with ultraviolet rays to cure the protective film-forming film (13) -9 to obtain a protective film.
- the silicon wafer was diced together with the protective film to obtain individual silicon chips of 2 mm ⁇ 2 mm.
- the protective film-forming composite sheet obtained above was attached to the # 2000 polished surface of a 6-inch silicon wafer (thickness: 100 ⁇ m) with the protective film-forming film (13) -9, Furthermore, this sheet
- the protective sheet-forming composite sheet is formed from the support sheet (10) -1 side under the conditions of an illuminance of 195 mW / cm 2 and a light amount of 170 mJ / cm 2. By irradiating with ultraviolet rays, the protective film-forming film (13) -9 was cured to form a protective film.
- the silicon wafer was diced together with the protective film using a dicing blade, and a silicon chip having a length of 3 mm ⁇ width of 3 mm, a protective layer thickness of 25 ⁇ m, and a Si layer thickness of 350 ⁇ m was obtained.
- 20 silicon chips with a protective film were picked up using a die bonder (“BESTEM-D02” manufactured by Canon Machinery Co., Ltd.). Square grid-like positions of 4 x 4 x silicon chips with a protective film obtained on a 12 mm long x 12 cm wide, 5 mm thick iron chip so that the distance between them is uniform.
- a cover tape (CSL-Z7302 manufactured by Sumitomo Bakelite Co., Ltd., 12 cm long and 3.8 cm wide) is placed on the plate, placed on a hot plate heated to 40 ° C., and a metal plate is placed thereon. It was set so that the pressure applied to the silicon chip with the protective film applied was 350 gf and heated for one minute. Thereafter, the metal plate was removed, the cover tape was peeled off, and it was tested whether or not the silicon chip with a protective film adhered to the cover tape. The results are shown in Table 2. As a determination method, if any one of the 16 silicon chips with protective film adheres to the cover tape, it is determined as “B”, and one of the 16 silicon chips with protective film is also applied to the cover tape. When it did not adhere, it was determined to be “A”.
- 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) -9 having a thickness of 25 ⁇ m.
- a second release film (“SP-PET 381031” manufactured by Lintec Co., Ltd., with a thickness of one side of a polyethylene terephthalate film was removed by silicone treatment on the exposed surface of the obtained protective film-forming film (13) -9, 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.
- the protective film-forming film (13) obtained above was applied to the # 2000 polished surface of a 6-inch silicon wafer (thickness: 100 ⁇ m). -9 was affixed to obtain a laminate composed of a 6-inch silicon wafer, a protective film-forming film (13) -9, 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) -1 obtained in the same manner as in Example 1, and the support sheet (10)
- the protective film-forming film (13) -9 and the first release film are attached to the exposed surface of the adhesive layer of -1, and the protective film-forming film (13) -9 is attached.
- the protective sheet-forming composite sheet is formed from the support sheet (10) -1 side under the conditions of an illuminance of 195 mW / cm 2 and a light amount of 170 mJ / cm 2.
- the protective film-forming film (13) -9 was cured to form a protective film.
- the silicon wafer was diced together with the protective film-forming film (13) -9 to obtain individual silicon chips of 2 mm ⁇ 2 mm.
- evaluation of suppression of chip cracking and chipping by dicing, evaluation of suppression of blade clogging, and evaluation of adhesion to the cover tape were performed.
- the tensile modulus is the same as in Example 1. The evaluation results are shown in Table 2.
- Example 3 ⁇ Manufacture of composite sheet for forming protective film> (Production of protective film-forming composition (IV-1))
- the content (blending amount) of the energy ray curable component (a2) -1 is changed to 10 parts by mass instead of 20 parts by mass, and photopolymerization is performed instead of the photopolymerization initiator (c) -3.
- a protective film was formed in the same manner as in Example 1 except that the initiator (c) -4 was used and the content (blending amount) of the photopolymerization initiator (c) -4 was 0.6 parts by mass.
- Composition (IV-1) was prepared.
- 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) -9. The sheet was fixed to the ring frame and allowed to stand for 30 minutes. Next, using a dicing blade, the silicon wafer was diced together with the protective film-forming film (13) -9 to obtain individual silicon chips of 2 mm ⁇ 2 mm. In the same manner as in Example 1, evaluation of suppression of chip cracking and chipping by dicing, evaluation of suppression of blade clogging, and evaluation of adhesion to the cover tape were performed. The tensile elastic modulus of the protective film-forming film during dicing is the same as the tensile elastic modulus of the protective film-forming film of Example 1. The evaluation results are shown in Table 2.
- the silicon wafer was diced together with the protective film-forming film (13) -9 to obtain individual silicon chips of 2 mm ⁇ 2 mm.
- evaluation of suppression of chip cracking / chip due to dicing, evaluation of suppression of blade clogging, and evaluation of adhesion to the cover tape were performed.
- the tensile elastic modulus of the protective film-forming film during dicing is the same as the tensile elastic modulus of the protective film-forming film of Example 2.
- the evaluation results are shown in Table 2.
- 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) -10, and this sheet is further attached to the ring frame. Fixed and allowed to stand for 30 minutes. Next, using a dicing blade, the silicon wafer was diced together with the protective film-forming film (13) -10 to obtain individual silicon chips of 2 mm ⁇ 2 mm.
- Example 2 In the same manner as in Example 1, evaluation of suppression of chip cracking and chipping by dicing, evaluation of suppression of blade clogging, and evaluation of adhesion to the cover tape were performed.
- the tensile elastic modulus of the protective film-forming film during dicing is the same as the tensile elastic modulus of the protective film-forming film of Example 3.
- the evaluation results are shown in Table 2.
- the tensile elastic modulus of the protective film during dicing of the semiconductor wafer is a relatively high elastic modulus of 500 MPa or more, thereby suppressing chipping of the protective film during dicing and suppressing blade clogging. I guess it was possible.
- Comparative Examples 1 to 3 the semiconductor wafer is diced without being cured by irradiating the protective film-forming film with energy rays.
- the tensile elastic modulus (Young's modulus) of the protective film-forming film during dicing is relatively small, 50 to 90 MPa, chip breakage or chipping occurs due to dicing, and blade clogging is likely to occur. It is presumed that adhesion to the tape has occurred.
- the present invention can be used for manufacturing semiconductor devices.
- Semiconductor wafer 19 Semiconductor chip 20 . Dicing blade 21 ... Energy beam irradiation device 101 .
- Semiconductor chip with protective film 102 ...
- Embossed carrier tape 102a ...
- Embossed carrier tape pocket 103 ... Cover tape
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US11133219B2 (en) | 2018-01-16 | 2021-09-28 | Disco Corporation | Method of processing a wafer |
US11626324B2 (en) | 2018-01-16 | 2023-04-11 | Disco Corporation | Method of processing a wafer |
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CN109075046B (zh) | 2023-07-18 |
TW201812878A (zh) | 2018-04-01 |
KR20190003943A (ko) | 2019-01-10 |
TWI722178B (zh) | 2021-03-21 |
KR102410096B1 (ko) | 2022-06-17 |
JPWO2017188218A1 (ja) | 2019-03-07 |
JP6837057B2 (ja) | 2021-03-03 |
CN109075046A (zh) | 2018-12-21 |
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