WO2018179475A1 - Protection film-forming composite sheet - Google Patents

Protection film-forming composite sheet Download PDF

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Publication number
WO2018179475A1
WO2018179475A1 PCT/JP2017/027447 JP2017027447W WO2018179475A1 WO 2018179475 A1 WO2018179475 A1 WO 2018179475A1 JP 2017027447 W JP2017027447 W JP 2017027447W WO 2018179475 A1 WO2018179475 A1 WO 2018179475A1
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WO
WIPO (PCT)
Prior art keywords
protective film
forming
film
meth
mass
Prior art date
Application number
PCT/JP2017/027447
Other languages
French (fr)
Japanese (ja)
Inventor
裕之 米山
山本　大輔
健太 古野
Original Assignee
リンテック株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by リンテック株式会社 filed Critical リンテック株式会社
Priority to KR1020197005681A priority Critical patent/KR102445532B1/en
Priority to CN201780056701.9A priority patent/CN109789666B/en
Priority to JP2017561778A priority patent/JP6298226B1/en
Publication of WO2018179475A1 publication Critical patent/WO2018179475A1/en

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L24/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
    • H01L27/02—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers

Definitions

  • the present invention relates to a composite sheet for forming a protective film.
  • semiconductor devices have been manufactured using a mounting method called a so-called face down method.
  • 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 made of an organic material is formed as a protective film on the exposed back surface of the semiconductor chip, and the semiconductor chip with the protective film obtained by forming the protective film in this way is taken into the semiconductor device. There is.
  • the protective film is used to prevent so-called chipping in which cracks and chips are generated in the semiconductor chip in the steps after the dicing step.
  • a protective film-forming composite sheet comprising a protective film-forming film on a support sheet.
  • the support sheet for example, a laminated sheet in which an adhesive layer or the like is laminated on a resin base material is used.
  • the protective film-forming composite sheet in addition to the protective film-forming film having a protective film-forming ability, the support sheet can function as a dicing sheet, and the protective film-forming film and the dicing sheet are integrated. It can be made.
  • laser printing is performed on the surface of the protective film attached to the semiconductor wafer or the semiconductor chip on the support sheet side by irradiation with laser light (referred to as “laser printing” in this specification). May be performed). At this time, the laser light is irradiated through the support sheet from the side opposite to the side where the protective film of the support sheet (base material) is formed. The printing is observed through the support sheet. Further, in the manufacturing process of the semiconductor device, the state of the semiconductor wafer or the semiconductor chip provided with the protective film forming film or the protective film is inspected by an infrared camera or the like through the support sheet and the protective film forming film or the protective film. There are things to do.
  • a composite sheet for forming a protective film having high light transmittance and excellent visibility of an image of a semiconductor chip has been disclosed so far (see Patent Document 1).
  • the base material constituting the support sheet in the composite sheet for forming a protective film at least one surface is usually uneven in order to prevent sticking between the base materials when being rolled up, so-called blocking. It is a surface. Then, due to the presence of the uneven surface, the support sheet becomes clouded, and the semiconductor chip including the protective film cannot be clearly observed, and there is a problem that the visibility of the semiconductor chip is poor.
  • a substrate is provided, and an adhesive layer and a protective film-forming film are laminated on the base material in this order, and are excellent in laser printability on a protective film formed from the protective film-forming film.
  • a composite sheet for forming a protective film that is excellent in the visibility of printing of the protective film is provided.
  • the composite sheet for forming a protective film according to the first aspect of the present invention includes a base material, and an adhesive layer and a film for forming a protective film are laminated on the base material in this order. And the haze of the support sheet which is a laminated body of the said adhesive layer is higher than 45%, and the permeation
  • the surface of the pressure-sensitive adhesive layer on the side provided with the film for forming a protective film is formed in a region where the film for forming the protective film is not laminated.
  • An adhesive layer may be provided.
  • the protective film-forming film may be energy ray curable.
  • the protective film-forming film may be thermosetting.
  • the protective film-forming film may be non-curable.
  • the pressure-sensitive adhesive layer may be energy ray curable or non-energy ray curable.
  • the pressure-sensitive adhesive layer may have a thickness of 3 to 20 ⁇ m.
  • the surface roughness (Ra) of one surface of the base material may be 0.11 ⁇ m or more, and the pressure-sensitive adhesive layer may be laminated in direct contact with the surface having the surface roughness.
  • a base material is provided, and a pressure-sensitive adhesive layer and a protective film-forming film are laminated on the base material in this order.
  • the composite sheet for forming a protective film which is higher than% and the transmission sheet has a transmission clarity of 100 or more.
  • a jig adhesive layer is provided in a region of the pressure-sensitive adhesive layer on the side provided with the protective film-forming film, in a region where the protective film-forming film is not laminated, (1) A composite sheet for forming a protective film as described in 1.
  • the surface roughness (Ra) of one surface of the substrate is 0.11 ⁇ m or more, and the pressure-sensitive adhesive layer is laminated in direct contact with the surface of the surface roughness, (1) The composite sheet for forming a protective film according to any one of (7) to (7).
  • the said aspect it is equipped with a base material, the adhesive layer and the film for protective film formation are laminated
  • a composite sheet for forming a protective film that has excellent printability and excellent visibility of printed protective film.
  • FIG. 2 is a cross-sectional view schematically showing a protective film-forming composite sheet according to the first embodiment of the present invention. It is sectional drawing which shows typically the composite sheet for protective film formation which concerns on 2nd Embodiment of this invention. It is sectional drawing which shows typically the composite sheet for protective film formation which concerns on 3rd Embodiment of this invention. It is sectional drawing which shows typically the composite sheet for protective film formation which concerns on 4th Embodiment of this invention. It is sectional drawing which shows typically the composite sheet for protective film formation which concerns on 5th Embodiment of this invention.
  • the composite sheet for protective film formation of this embodiment is provided with a base material, and an adhesive layer and a film for protective film formation are laminated on the base material in this order. That is, the protective film-forming composite sheet of this embodiment is formed by laminating a base material, an adhesive layer, and a protective film-forming film in this order. Moreover, in the composite sheet for protective film formation of this embodiment, the haze of the support sheet which is a laminate of the base material and the pressure-sensitive adhesive layer is higher than 45%, and the transparent clarity of the support sheet is 100 or more.
  • the “protective film forming film” means a film before being attached to the back surface of a semiconductor wafer or semiconductor chip
  • the “protective film” means a protective film forming film that is a semiconductor wafer or semiconductor. It means the one attached to the back of the chip.
  • a film obtained by curing the protective film-forming film is referred to as a “protective film”.
  • this laminated structure Is referred to as “composite sheet for forming a protective film”.
  • the protective film-forming film is used as a protective film for protecting the back surface of the semiconductor wafer or semiconductor chip (the surface opposite to the electrode forming surface). And since the haze of the support sheet is higher than 45% and the transmission sharpness is 100 or more, the protective film-forming film of this embodiment has good laser printability, and printing of the protective film. Visibility can be improved. More specifically, after the protective film-forming composite sheet is attached to the back surface of the semiconductor wafer or semiconductor chip, laser printing is performed on the support sheet side surface of the protective film attached to the semiconductor wafer or semiconductor chip. At this time, the laser light is irradiated through the support sheet from the side opposite to the side on which the protective film of the support sheet (base material) is formed. The printing is observed through the support sheet. At this time, when the transparency of the support sheet is 100 or more, light scattering on the outer surface of the support sheet is suppressed, and the visibility of laser printing can be improved.
  • the laser printing can be effectively thickened, and the visibility of the laser printing can be improved. Further, since there is no need to increase the laser output, it is possible to suppress the generation of gas accumulation, and it is possible to perform laser printing with the support sheet and the protective film adhered. In addition, since the adhesive strength of the support sheet is appropriate, the pickup suitability is also good.
  • the adhesive layer for jigs is a colorless and transparent protective film-forming composite sheet, or a protective film-forming composite sheet having no jig adhesive layer, a semiconductor wafer or semiconductor
  • the support sheet has a low haze such as 45% or less, and alignment using an optical sensor mounted on the mounter (hereinafter referred to as “position adjustment of the tape tip” ”) was not possible.
  • the haze is higher than 45%, so that the position of the tip of the tape can be adjusted by being detected by an optical sensor mounted on the mounter.
  • the thickness of the semiconductor wafer or semiconductor chip that is the target of use of the composite sheet for forming a protective film of the present embodiment is not particularly limited, but is 30 ⁇ m or more and 1000 ⁇ m or less because the effect of the present embodiment can be obtained more significantly. It is preferably 100 ⁇ m or more and 300 ⁇ m or less.
  • the configuration of the present embodiment will be described in detail.
  • the support sheet includes a base material, and includes a pressure-sensitive adhesive layer on the base material, and is composed of two or more layers.
  • the constituent materials and thicknesses of these multiple layers may be the same or different from each other, and the combination of these multiple layers is not particularly limited as long as the effects in the present embodiment 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 that“ at least one of the constituent materials and thickness of each layer is different from each other ”. Means.
  • the support sheet include those in which a pressure-sensitive adhesive layer is directly contacted and laminated on a substrate, and those in which a pressure-sensitive adhesive layer is laminated on a substrate via an intermediate layer. More preferable support sheets include those in which an adhesive layer is laminated in direct contact with a substrate.
  • FIG. 1 is a cross-sectional view schematically showing a protective film-forming composite sheet according to the first embodiment of 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 configuration in which the protective film forming film 13 is laminated on one surface 10 a of the support sheet 10.
  • a release film 15 is further laminated on the entire surface (upper surface and side surface) of the surface 13a of the protective film-forming film 13 and the surface 12a (upper surface) of the pressure-sensitive adhesive layer.
  • the “peeling film” is a film having a peeling function, and specifically, a protective film forming film for protecting the protective film forming film before being attached to a semiconductor wafer. The film is affixed to the surface of the film and is used by peeling it off during work.
  • the haze of the support sheet 10 that is a laminate of the base material 11 and the pressure-sensitive adhesive layer 12 is higher than 45%, and the transmission clarity of the support sheet 10 is 100 or more.
  • the protective film-forming composite sheet 1A shown in FIG. 1 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 side is affixed.
  • region of the peripheral part vicinity of the film 13 for protective film formation is affixed and used for jigs, such as a ring frame.
  • FIG. 2 is a cross-sectional view schematically showing a composite sheet for forming a protective film according to a second embodiment of 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. 1 except that it is provided with a jig adhesive layer 16. That is, in the protective film-forming composite sheet 1 ⁇ / b> B, the pressure-sensitive adhesive layer 12 is laminated on one surface 11 a of the substrate 11.
  • the protective film-forming film 13 is laminated on a partial region on the center side of the surface 12a of the pressure-sensitive adhesive layer 12, that is, a semiconductor wafer pasting region.
  • a jig adhesive layer 16 is laminated on a part of the surface 12a of the pressure-sensitive adhesive layer 12, that is, in a region near the peripheral edge.
  • a release film 15 is laminated on the surface 13 a (upper surface) of the protective film forming film 13 and the surface 16 a (upper surface) of the jig adhesive layer 16.
  • the haze of the support sheet 10 which is a laminate of the base material 11 and the pressure-sensitive adhesive layer 12, is higher than 45%, and the transmission clarity of the support sheet 10 is 100 or more.
  • 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 back surface of the semiconductor wafer (not shown) is attached to the front surface 13a of the protective film forming film 13 in a state where the release film 15 is removed. Further, the upper surface of the surface 16a of the jig 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 a protective film-forming composite sheet according to the third embodiment of the present invention.
  • the protective sheet-forming composite sheet 1C shown here is the same as the protective film-forming composite sheet 1A shown in FIG. The same thing.
  • the support sheet 10 is a laminate of the base material 11, the pressure-sensitive adhesive layer 12, and the intermediate layer 17.
  • the protective film-forming composite sheet 1 ⁇ / b> C has a configuration in which the protective film-forming film 13 is laminated on one surface 10 a (17 a) of the support sheet 10.
  • the protective film forming composite sheet 1C further includes the entire surface 13a of the protective film forming film 13 (upper surface and side surface), the surface of the intermediate layer 17a (side surface), and the surface 12a (upper surface) of the adhesive layer. Further, a release film 15 is laminated.
  • the haze of the support sheet 10 that is a laminate of the base material 11, the pressure-sensitive adhesive layer 12, and the intermediate layer 17 is higher than 45%, and the transparent clarity of the support sheet 10 is 100 or more. It is.
  • the protective sheet-forming composite sheet 1C 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 side is affixed.
  • region of the peripheral part vicinity of the film 13 for protective film formation is affixed and used for jigs, such as a ring frame.
  • FIG. 4 is a cross-sectional view schematically showing a protective film-forming composite sheet according to the fourth embodiment of the present invention.
  • the protective sheet-forming composite sheet 1D shown here is the same as the protective film-forming composite sheet 1A shown in FIG. 1 except that the intermediate layer 17 is provided between the base material 11 and the adhesive layer 12. is there.
  • the support sheet 10 is a laminate of the base material 11, the intermediate layer 17, and the pressure-sensitive adhesive layer 12.
  • the protective film-forming composite sheet 1 ⁇ / b> D has a configuration in which the protective film-forming film 13 is laminated on one surface 10 a (12 a) of the support sheet 10.
  • a release film 15 is laminated on the entire surface (upper surface and side surface) of the surface 13a of the protective film forming film 13 and the surface 12a (upper surface) of the pressure-sensitive adhesive layer. .
  • the haze of the support sheet 10 which is a laminate of the base material 11, the intermediate layer 17, and the pressure-sensitive adhesive layer 12 is higher than 45%, and the transparent clarity of the support sheet 10 is 100 or more. It is.
  • the protective film-forming composite sheet 1D shown in FIG. 4 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 side is affixed.
  • region of the peripheral part vicinity of the film 13 for protective film formation is affixed and used for jigs, such as a ring frame.
  • FIG. 5 is a cross-sectional view schematically showing a protective film-forming composite sheet according to the fifth embodiment of 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. 2 except that the protective film-forming film is laminated on the entire surface of the pressure-sensitive adhesive layer. . That is, in the protective film forming composite sheet 1 ⁇ / b> E, the pressure-sensitive adhesive layer 12 is laminated on one surface 11 a of the substrate 11.
  • a protective film forming film 13 is laminated on the entire surface 12 a of the pressure-sensitive adhesive layer 12.
  • a jig adhesive layer 16 is laminated on a part of the surface 13a of the protective film-forming film 13, that is, in the vicinity of the peripheral edge.
  • a release film 15 is laminated on the surface 13a (upper surface) of the protective film forming film 13 and the surface 16a (upper surface and side surfaces) of the jig adhesive layer 16.
  • the haze of the support sheet 10 which is a laminate of the base material 11 and the pressure-sensitive adhesive layer 12 is higher than 45%, and the transmission clearness of the support sheet 10 is 100 or more.
  • the back surface of the semiconductor wafer (not shown) is attached to the front surface 13a of the protective film-forming film 13 with the release film 15 removed. Further, the upper surface of the surface 16a of the jig adhesive layer 16 is used by being attached to a jig such as a ring frame.
  • the protective sheet-forming composite sheet of the present embodiment may have any form of the support sheet and the protective film-forming film, or may be provided with an adhesive layer for jigs.
  • the jig is placed on the support sheet 10 or the protective film forming film 13. What provided the adhesive layer 16 for use is preferable.
  • the composite sheet for forming a protective film of the present embodiment is not limited to the one shown in FIGS. 1 to 5, and a part of the configuration shown in FIGS. 1 to 5 is changed or changed within a range not impairing the effect of the present embodiment. What has been deleted, or what has been added so far, may be added.
  • an intermediate layer 17 may be provided between the pressure-sensitive adhesive layer 12 and the protective film-forming film 13. That is, in the composite sheet for forming a protective film of the present embodiment, the support sheet 10 may be formed by laminating the base material 11, the adhesive layer 12, and the intermediate layer 17 in this order.
  • the intermediate layer 17 is the same as the intermediate layer 17 that may be provided in the protective film-forming composite sheet shown in FIGS. Any layer can be selected as the intermediate layer 17 according to the purpose.
  • an intermediate layer 17 may be provided between the base material 11 and the pressure-sensitive adhesive layer 12.
  • the support sheet 10 may be formed by laminating the base material 11, the intermediate layer 17, and the pressure-sensitive adhesive layer 12 in this order.
  • the intermediate layer 17 is the same as the intermediate layer 17 that may be provided in the protective film-forming composite sheet shown in FIGS. Any layer can be selected as the intermediate layer 17 according to the purpose.
  • the intermediate layer 17 may be provided in other places other than the places shown in FIGS.
  • layers other than the intermediate layer 17 may be provided at an arbitrary position.
  • tools may be provided. Further, in the protective film-forming composite sheet of the present embodiment, a part of the gap may be formed between the release film 15 and the layer in direct contact with the release film 15. Moreover, in the composite sheet for protective film formation of this embodiment, the magnitude
  • the support sheet may be opaque or colored according to the purpose.
  • the transparent transparency of the support sheet is 100 or more, preferably 150 or more, more preferably 200 or more and 450 or less, and further preferably 300 or more and 430 or less.
  • the transparency of the support sheet can be measured in accordance with JIS K 7374-2007 using an image clarity measuring device “ICM-10P” manufactured by Suga Test Instruments Co., Ltd.
  • ICM-10P image clarity measuring device manufactured by Suga Test Instruments Co., Ltd.
  • what is necessary is just to adjust the surface roughness of the outer surface of a support sheet, for example, in order to make the transmission clarity of a support sheet into the said range.
  • the haze of the support sheet is higher than 45%, preferably 46% or more, more preferably 47% or more and 90% or less, and further preferably 50% or more and 85% or less.
  • the laser output is appropriately scattered inside the support sheet because the haze of the support sheet is in the above range. Therefore, the laser printing can be effectively thickened, and the visibility of the laser printing can be improved. Further, it is not necessary to increase the laser output. Therefore, generation of gas pools can be suppressed, and laser printing can be performed with the support sheet and the protective film adhered.
  • the adhesive layer for jigs is a colorless and transparent protective film-forming composite sheet, or a protective film-forming composite sheet having no jig adhesive layer, a semiconductor wafer or semiconductor
  • the support sheet has a low haze such as 45% or less, and alignment using an optical sensor mounted on the mounter (hereinafter referred to as “position adjustment of the tape tip”). ”) was not possible.
  • the haze of the support sheet is in the above range, so that it can be detected by the optical sensor mounted on the mounter and the position of the tip of the tape can be adjusted.
  • the haze of the support sheet can be measured using NDH-5000 manufactured by Nippon Denshoku Industries Co., Ltd. according to JIS K 7136-2000.
  • NDH-5000 manufactured by Nippon Denshoku Industries Co., Ltd. according to JIS K 7136-2000.
  • middle layer contain a filler or a coloring agent in order to make the haze of a support sheet into the said range, for example.
  • it may be adjusted by changing the hardness of the pressure-sensitive adhesive layer to form a gap between the base material or the intermediate layer and the pressure-sensitive adhesive layer.
  • the transmittance measured using an integrating sphere 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 light transmittance is in such a range
  • the protective film forming film is irradiated with energy rays (ultraviolet rays) through the support sheet, 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.
  • energy beam curability means a property of being cured by irradiation with energy rays.
  • Non-energy radiation curable means a property that does not cure even when irradiated with energy rays, and includes thermosetting and non-curing properties.
  • Thermosetting means a property of being cured by heating.
  • Non-curing means the property of not being cured by heating or irradiation with energy rays.
  • 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.
  • 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; modification of an ionomer or the like using one or more of the resins exemplified so far. Resins can also be mentioned.
  • (meth) acrylic acid is a concept including both “acrylic acid” and “methacrylic acid”.
  • (meth) acryloyl group is a concept including both “acryloyl group” and “methacryloyl group”
  • (meth) acrylate” is a concept including both” acrylate "and” methacrylate ".
  • 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 40 ⁇ m or more and 300 ⁇ m or less, and more preferably 60 ⁇ m or more and 150 ⁇ m or less.
  • 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 method of measuring thickness using a contact-type thickness meter in arbitrary five places, and calculating the average of a measured value etc. are mentioned, for example.
  • 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.
  • a filler a colorant
  • an antistatic agent an antioxidant
  • an organic lubricant a catalyst
  • a softener plasticizer
  • the haze of the support sheet can be within the above range, so that the visibility of laser printing can be improved.
  • the substrate may be transparent or opaque, may be colorless or colored depending on the purpose, and other layers are processed (for example, vapor deposition). May be.
  • the film for protective film formation has energy-beam sclerosis
  • 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 base material may have a surface subjected to primer treatment.
  • the base material 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 protective film-forming composite sheet are stored in an overlapping manner. It may have a layer or the like.
  • 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 upper limit value of the surface roughness (Ra) of the surface exposed as the outer surface of the support sheet is 0.60 ⁇ m or less, preferably 0.50 ⁇ m or less, more preferably 0. .40 ⁇ m or less, more preferably 0.30 ⁇ m or less. Since the surface roughness of the substrate is less than or equal to the above upper limit value, light scattering on the outer surface of the substrate can be reduced, and the transmission clarity of the support sheet can be within the above range. Can be good.
  • the lower limit of the surface roughness (Ra) is not particularly limited, and may be, for example, 0.005 ⁇ m or more, 0.01 ⁇ m or more, or 0.03 ⁇ m or more, It may be 0.05 ⁇ m or more.
  • an adhesive layer or the like on the surface whose surface roughness is 0.11 ⁇ m or more It is preferable to laminate other layers.
  • the surface roughness exposed as the outer surface of the support sheet in the substrate becomes a surface having the upper limit value or less, the light scattering on the outer surface of the substrate is reduced, and the transmission clarity of the support sheet is within the above range. Therefore, the visibility of laser printing can be improved.
  • the surface roughness of the substrate is less than or equal to the above upper limit value, another layer such as an adhesive layer is laminated on the surface having a larger surface roughness, and the surface having a smaller surface roughness is the outer surface. As long as it is exposed.
  • “surface roughness” means a so-called arithmetic average roughness obtained in accordance with JIS B0601: 2001, and is abbreviated as “Ra” unless otherwise specified. .
  • 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, and ester resins, and acrylic resins are preferable. .
  • the “adhesive resin” is a concept including both an adhesive resin and an adhesive resin.
  • the resin itself has not only an adhesive property.
  • a resin exhibiting tackiness by using in combination with other components such as additives, a resin exhibiting adhesiveness due to the presence of a trigger such as heat or water, and the like 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 3 ⁇ m or more and 20 ⁇ m or less, more preferably 5 ⁇ m or more and 20 ⁇ m or less, and particularly preferably 5 ⁇ m or more and 17 ⁇ m or less.
  • Adhesive strength can be improved when the thickness of the pressure-sensitive adhesive layer is not less than the above lower limit.
  • it when it is a base material whose surface roughness is 0.11 micrometer or more, it can be set as the laminated body which embeds the surface of a base material and has a smooth surface where the light scattering of the base-material outer surface was reduced.
  • blade dicing suitability and pickup suitability can be improved.
  • 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 method of measuring thickness using a contact-type thickness meter in arbitrary five places, and calculating the average of a measured value etc. are mentioned, for example.
  • a gap can be formed between the pressure-sensitive adhesive layer and the base material or the intermediate layer, and the haze of the support sheet can be adjusted within the above range.
  • 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 opaque or colored according to the purpose. And when the film for protective film formation has energy-beam sclerosis
  • 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 non-energy ray curable adhesive includes a thermosetting adhesive and a non-curable 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, for example, a temperature of 15 ° C. or more and 25 ° C. or less.
  • 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 the pressure-sensitive adhesive composition is preferably heated and dried when it contains a solvent described later.
  • the pressure-sensitive adhesive composition is 10 to 70 ° C to 130 ° C. It is preferable to dry under conditions of not less than 2 seconds and not more than 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, or 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 2 or more carbon atoms. And from the point which the adhesive force of an adhesive layer improves more, it is preferable that carbon number of the said alkyl group is 2-12, and it is more preferable that it is 4-8.
  • 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 further has a structural unit derived from a functional group-containing monomer.
  • 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% by mass or more and 29% by mass or less, and preferably 2% by mass or more and 25% by mass or less with respect to the total amount of the structural unit. It is more preferable that it is 3 mass% or more and 23 mass% or less.
  • 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 when there are two or more types, the combination and ratio thereof 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) with respect to the total content of all components other than the solvent is preferably 5% by mass to 99% by mass. More preferably, it is more than 95 mass%, and it is especially preferable that it is 15 mass% or more and 90 mass% or less.
  • 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 with respect to the total content of all components other than the solvent is preferably 1% by mass or more and 95% by mass or less. % To 90% by mass, more preferably 3% to 85% by mass. For example, any of 3 mass% or more and 80 mass% or less, 3 mass% or more and 65 mass% or less, 3 mass% or more and 50 mass% or less, 3 mass% or more and 35 mass% or less, etc. may be sufficient.
  • 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 (cross-linking agent having an aziridinyl group) such as hexa [1- (2-methyl) -aziridinyl] triphosphatriazine; Metal chelate-based cross-linking agent such as aluminum chelate (metal) Cross-linking agent having a chelate structure); isocyanurate-based cross-linking agent (cross-linking agent (
  • 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 0.01 parts by weight or more and 50 parts by weight or less with respect to 100 parts by weight of the pressure-sensitive adhesive resin (I-1a).
  • 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 Acylphosphine oxide compounds such as oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide; Sulfidation of benzylphenyl sulfide, tetramethylthiuram monosulfide, etc.
  • benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethy
  • An ⁇ -ketol compound such as 1-hydroxycyclohexyl phenyl ketone; an azo compound such as azobisisobutyronitrile; a titanocene compound such as titanocene; a thioxanthone compound such as thioxanthone; a peroxide compound; a diketone compound such as diacetyl; Benzophenone; 2,4-diethylthioxanthone; 1,2-diphenylmethane; 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone; 2-chloroanthraquinone and the like.
  • a quinone compound such as 1-chloroanthraquinone
  • a photosensitizer such as amine
  • 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 0.01 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the energy ray curable compound.
  • it is 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 that does not impair the effects of the present embodiment.
  • 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 retarding agent means, for example, an undesired crosslinking reaction in the pressure-sensitive adhesive composition (I-1) during storage by the action of the catalyst mixed in the pressure-sensitive adhesive composition (I-1). It suppresses progress.
  • 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, 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-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.
  • a compound having a group examples include (meth) acryloyl group, vinyl group (ethenyl group), allyl group (2-propenyl group) and the like, 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) with respect to the total content of all components other than the solvent is preferably 5% by mass or more and 99% by mass or less.
  • the content is more preferably no less than 95% and no more than 95%, and particularly preferably no less than 10% and no more than 90%.
  • 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 0.01 parts by weight or more and 25 parts by weight or less with respect to 100 parts by weight of the pressure-sensitive adhesive resin (I-2a). Is more preferably 0.05 parts by mass or more and 20 parts by mass or less, and particularly preferably 0.1 parts by mass or more and 15 parts by mass or less.
  • 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 0.01 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the content of the adhesive resin (I-2a). It is preferably 0.03 to 10 parts by mass, more preferably 0.05 to 5 parts by mass.
  • the pressure-sensitive adhesive composition (I-2) may contain other additives that do not fall under any of the above-described components within a range that does not impair the effects of the present embodiment.
  • 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 resin (I-2a) with respect to the total content of all components other than the solvent is preferably 5% by mass or more and 99% by mass or less. More preferably, it is more than 95 mass%, and it is especially preferable that it is 15 mass% or more and 90 mass% or less.
  • 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 parts by mass or more and 300 parts by mass with respect to 100 parts by mass of the adhesive resin (I-2a). Is preferably 0.03 parts by mass or more and 200 parts by mass or less, and particularly preferably 0.05 parts by mass or more and 100 parts by mass or less.
  • 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 mass with respect to 100 mass parts of the total content of the pressure-sensitive adhesive resin (I-2a) and the energy ray curable compound. It is preferably no less than 20 parts by mass and no greater than 20 parts by mass, more preferably no less than 0.03 parts by mass and no greater than 10 parts by mass, and particularly preferably no less than 0.05 parts by mass and no greater than 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 that does not impair the effects of the present embodiment.
  • 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.
  • the pressure-sensitive adhesive composition (I-4) containing an adhesive resin (I-1a) is preferred, and those containing an acrylic resin are 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) with respect to the total content of all components other than the solvent is preferably 5% by mass or more and 99% by mass or less. More preferably, it is more than 95 mass%, and it is especially preferable that it is 15 mass% or more and 90 mass% or less. For example, any of 3 mass% or more and 85 mass% or less, 40 mass% or more and 85 mass% or less, 50 mass% or more and 85 mass% or less, etc. may be sufficient.
  • 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 0.01 parts by weight or more and 50 parts by weight or less with respect to 100 parts by weight of the pressure-sensitive adhesive resin (I-1a).
  • 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 that does not impair the effects of the present embodiment.
  • 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 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 intermediate layer is in the form of a sheet or film, and its constituent material may be appropriately selected according to the purpose, and is not particularly limited. Moreover, the haze of the composite sheet for protective film formation can be adjusted to the said range by adjusting the haze of an intermediate
  • the intermediate layer may be curable or non-curable. Moreover, when an intermediate
  • the intermediate layer 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. It is not limited.
  • the thickness of the intermediate layer may be, for example, 0.1 ⁇ m or more and 200 ⁇ m or less, may be 1 ⁇ m or more and 150 ⁇ m or less, and may be 3 ⁇ m or more and 120 ⁇ m or less.
  • the thickness of the intermediate layer means the thickness of the entire intermediate layer, and means the total thickness of all the layers constituting the intermediate layer.
  • the method of measuring thickness using a contact-type thickness meter in arbitrary five places, and calculating the average of a measured value etc. are mentioned, for example.
  • middle layer can be formed using the composition for intermediate
  • the intermediate layer can be formed at a target site by applying the intermediate layer-forming composition to the surface on which the intermediate layer is to be formed and drying it as necessary or curing it by irradiation with energy rays.
  • the intermediate layer-forming composition may be applied by a known method, for example, by the same method as that for the above-mentioned pressure-sensitive adhesive composition.
  • the drying conditions of the intermediate layer forming composition are not particularly limited.
  • the intermediate layer-forming composition containing a solvent is preferably dried by heating. In this case, for example, it is preferably dried at 70 to 130 ° C. for 10 seconds to 5 minutes.
  • the composition for forming an intermediate layer has energy ray curability, it is preferably cured by irradiation with energy rays after drying.
  • the intermediate layer forming composition is not particularly limited, and examples thereof include those similar to those exemplified in the above-mentioned pressure-sensitive adhesive composition.
  • the composition for forming an intermediate layer may contain other additives that do not correspond to any of the above-described components within a range not impairing the effects of the invention.
  • the other additives include the same additives as the other additives in the pressure-sensitive adhesive composition (I-1).
  • the composition for forming an intermediate layer contains a filler or a colorant, the haze of the composite sheet for forming a protective film can be adjusted to the above range.
  • the protective film-forming film may be curable or non-curable. Moreover, when the film for protective film formation has sclerosis
  • hardenability may be sufficient.
  • thermosetting protective film examples include those containing a polymer component (A) and a thermosetting component (B).
  • the polymer component (A) is a component that can be regarded as formed by polymerization reaction of the polymerizable compound.
  • the thermosetting component (B) is a component that can undergo a curing (polymerization) reaction using heat as a reaction trigger.
  • the polymerization reaction includes a polycondensation reaction.
  • thermosetting protective film-forming film may be composed of one layer (single layer), or may be composed of two or more layers.
  • the thermosetting protective film-forming film is composed of a plurality of layers, the plurality of layers may be the same as or different from each other.
  • “the plurality of layers may be the same as or different from each other” means the same as in the case of the above-described base material. And when several layers differ from each other, the combination of these several layers is not specifically limited.
  • the thickness of the thermosetting protective film-forming film is preferably 1 ⁇ m or more and 100 ⁇ m or less, more preferably 5 ⁇ m or more and 75 ⁇ m or less, and particularly preferably 5 ⁇ m or more and 50 ⁇ m or less.
  • the thickness of the thermosetting protective film-forming film is equal to or more than the lower limit value, a protective film with higher protective ability can be formed.
  • the thickness of the thermosetting protective film-forming film is equal to or less than the upper limit value, an excessive thickness is suppressed.
  • the “thickness of the thermosetting protective film forming film” means the thickness of the entire thermosetting protective film forming film, for example, a thermosetting protective film forming film composed of a plurality of layers.
  • the thickness means the total thickness of all the layers constituting the thermosetting protective film forming film.
  • the method for measuring the thickness of the thermosetting protective film-forming film includes, for example, a method of measuring the thickness using a contact-type thickness meter at any five locations and calculating the average of the measured values. Can be mentioned.
  • the curing conditions for applying and curing the thermosetting protective film-forming film on the back surface of the semiconductor wafer are not particularly limited as long as the degree of curing is such that the protective film exhibits its function sufficiently. What is necessary is just to select suitably according to the kind of film for protective film formation.
  • the heating temperature during curing of the thermosetting protective film-forming film is preferably 100 ° C. or higher and 200 ° C. or lower, more preferably 110 ° C. or higher and 180 ° C. or lower, and 120 ° C. or higher and 170 ° C. or lower. It is particularly preferred.
  • the heating time during the curing is preferably 0.5 hours or more and 5 hours or less, more preferably 0.5 hours or more and 3 hours or less, and particularly preferably 1 hour or more and 2 hours or less. preferable.
  • the composition for forming a thermosetting protective film can be formed using a composition for forming a thermosetting protective film containing the constituent materials.
  • the composition for forming a thermosetting protective film is applied to the surface to be formed of the film for forming a thermosetting protective film, and dried as necessary to form a thermosetting protective film on the target site.
  • a film can be formed.
  • the ratio of the content of components that do not vaporize at room temperature in the thermosetting protective film-forming composition is usually the same as the content ratio of the components of the thermosetting protective film-forming film.
  • “normal temperature” is as described above.
  • thermosetting protective film-forming composition can be performed, for example, in the same manner as in the case of application of the above-described pressure-sensitive adhesive composition.
  • the drying conditions of the composition for forming a thermosetting protective film are not particularly limited, but when the composition for forming a thermosetting protective film contains a solvent to be described later, it is preferably dried by heating. For example, the drying is preferably performed at 70 ° C. to 130 ° C. for 10 seconds to 5 minutes.
  • composition (III-1) a composition (III-1) for forming a thermosetting protective film containing a polymer component (A) and a thermosetting component (B) (in this specification) May be simply abbreviated as “composition (III-1)”).
  • the polymer component (A) is a polymer compound for imparting film-forming properties, flexibility and the like to the thermosetting protective film-forming film.
  • the polymer component (A) contained in the composition (III-1) and the thermosetting 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.
  • Examples of the polymer component (A) include an acrylic resin (a resin having a (meth) acryloyl group), a polyester, a urethane resin (a resin having a urethane bond), an acrylic urethane resin, and a silicone resin (having a siloxane bond). Resin), rubber resin (resin having a rubber structure), phenoxy resin, thermosetting polyimide and the like, and acrylic resin is preferable.
  • the weight average molecular weight (Mw) of the acrylic resin is preferably from 10,000 to 2,000,000, and more preferably from 100,000 to 1,500,000.
  • Mw weight average molecular weight
  • the weight average molecular weight of the acrylic resin is equal to or more than the lower limit, the shape stability (time stability during storage) of the thermosetting protective film-forming film is improved.
  • the weight average molecular weight of the acrylic resin is not more than the above upper limit value, the thermosetting protective film forming film easily follows the uneven surface of the adherend, and the adherend and the thermosetting protective film are formed. Occurrence of voids and the like with the film is further suppressed.
  • the weight average molecular weight is a polystyrene conversion value measured by a gel permeation chromatography (GPC) method unless otherwise specified.
  • the glass transition temperature (Tg) of the acrylic resin is preferably ⁇ 60 ° C. or higher and 70 ° C. or lower, and more preferably ⁇ 30 ° C. or higher and 50 ° C. or lower.
  • Tg of the acrylic resin is equal to or higher than the lower limit, the adhesive force between the protective film and the support sheet (adhesive layer) is suppressed, and the peelability of the support sheet is improved.
  • adhesive force with the adherend of a protective film improves because Tg of acrylic resin is below the said upper limit.
  • “glass transition temperature (Tg)” is represented by a value measured with a “differential scanning calorimetry (DSC) measuring device” in accordance with JIS K7121.
  • the acrylic resin is selected from, for example, a polymer of one or more (meth) acrylic acid esters; (meth) acrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene, N-methylolacrylamide, and the like. Examples include copolymers of two or more monomers.
  • Examples of the (meth) acrylic acid ester constituting the acrylic resin include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, (meth ) N-butyl acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, (meth) acrylic Heptyl acid, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, n-octyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate , Undecyl (me
  • the acrylic resin is, for example, one or more monomers selected from (meth) acrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene, N-methylolacrylamide and the like in addition to the (meth) acrylic ester. May be obtained by copolymerization.
  • Only one type of monomer constituting the acrylic resin may be used, or two or more types may be used, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected.
  • the acrylic resin may have a functional group that can be bonded to other compounds such as a vinyl group, a (meth) acryloyl group, an amino group, a hydroxyl group, a carboxy group, and an isocyanate group.
  • the functional group of the acrylic resin may be bonded to another compound via a cross-linking agent (F) described later, or may be directly bonded to another compound not via the cross-linking agent (F). .
  • F cross-linking agent
  • thermoplastic resin other than an acrylic resin (hereinafter sometimes simply referred to as “thermoplastic resin”) is used alone without using an acrylic resin. It may be used in combination with an acrylic resin.
  • thermoplastic resin By using the thermoplastic resin, the peelability of the protective film from the support sheet is improved, and the thermosetting protective film-forming film easily follows the uneven surface of the adherend. The generation of voids and the like may be further suppressed between the protective protective film-forming film.
  • the weight average molecular weight of the thermoplastic resin is preferably 1000 or more and 100,000 or less, and more preferably 3000 or more and 80,000 or less.
  • the “weight average molecular weight” is as described above.
  • the glass transition temperature (Tg) of the thermoplastic resin is preferably ⁇ 30 to 150 ° C., more preferably ⁇ 20 to 120 ° C.
  • thermoplastic resin examples include polyester, polyurethane, phenoxy resin, polybutene, polybutadiene, and polystyrene.
  • thermoplastic resin contained in the composition (III-1) and the thermosetting protective film-forming film may be only one kind, two kinds or more, and in the case of two kinds or more, combinations and ratios thereof. Can be chosen arbitrarily.
  • the content is preferably 5% by mass or more and 85% by mass or less, more preferably 5% by mass or more and 80% by mass or less, regardless of the type of the polymer component (A). For example, any of 5 mass% or more and 65 mass% or less, 5 mass% or more and 50 mass% or less, 10 mass% or more and 35 mass% or less, etc. may be sufficient.
  • the polymer component (A) may also correspond to the thermosetting component (B).
  • the composition (III-1) when the composition (III-1) contains components corresponding to both the polymer component (A) and the thermosetting component (B), the composition (III-1) Is considered to contain a polymer component (A) and a thermosetting component (B).
  • thermosetting component (B) is a component for curing a thermosetting protective film-forming film to form a hard protective film.
  • the thermosetting component (B) contained in the composition (III-1) and the thermosetting 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.
  • thermosetting component (B) 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 (B1) and a thermosetting agent (B2).
  • the epoxy thermosetting resin contained in the composition (III-1) and the thermosetting 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.
  • Epoxy resin (B1) 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 (B1).
  • 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, by using an epoxy resin having an unsaturated hydrocarbon group, the reliability of the semiconductor chip with a protective film obtained using the composite sheet for forming a protective film is improved.
  • 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. Moreover, as 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 ethenyl group (vinyl group), 2-propenyl group (allyl group), (meth) acryloyl group, (meth) An acrylamide group etc. are mentioned, An acryloyl group is preferable.
  • the number average molecular weight of an epoxy resin (B1) is not specifically limited, From the point of sclerosis
  • 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 (B1) is preferably 100 g / eq or more and 1000 g / eq or less, and more preferably 150 g / eq or more and 950 g / eq or less.
  • 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.
  • the epoxy resin (B1) may be used alone or in combination of two or more, and when two or more are used in combination, their combination and ratio can be arbitrarily selected.
  • thermosetting agent (B2) functions as a curing agent for the epoxy resin (B1).
  • a thermosetting agent (B2) 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 (B2) examples of the phenolic curing agent having a phenolic hydroxyl group include polyfunctional phenol resins, biphenols, novolac type phenol resins, dicyclopentadiene type phenol resins, and aralkyl type phenol resins. .
  • examples of the amine-based curing agent having an amino group include dicyandiamide (hereinafter sometimes abbreviated as “DICY”).
  • the thermosetting agent (B2) may have an unsaturated hydrocarbon group.
  • examples of the thermosetting agent (B2) having an unsaturated hydrocarbon group include compounds 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 (B2) is the same as the unsaturated hydrocarbon group in the epoxy resin having an unsaturated hydrocarbon group described above.
  • thermosetting agent (B2) When using a phenolic curing agent as the thermosetting agent (B2), it is preferable that the thermosetting agent (B2) has a high softening point or glass transition temperature in terms of improving the peelability of the protective film from the support sheet. .
  • the number average molecular weight of a resin component such as a polyfunctional phenol resin, a novolac-type phenol resin, a dicyclopentadiene-type phenol resin, or an aralkyl-type phenol resin may be 300 or more and 30000 or less. Preferably, it is 400 or more and 10,000 or less, and particularly preferably 500 or more and 3000 or less.
  • the molecular weight of non-resin components such as biphenol and dicyandiamide is not particularly limited, but is preferably 60 or more and 500 or less, for example.
  • thermosetting agent (B2) 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 (B2) is 0.1 parts by mass or more with respect to 100 parts by mass of the epoxy resin (B1).
  • the amount is preferably 500 parts by mass or less, and more preferably 1 part by mass or more and 200 parts by mass or less.
  • any of 1 part by mass or more and 100 parts by mass or less, 1 part by mass or more and 50 parts by mass or less, and 1 part by mass or more and 10 parts by mass or less may be used.
  • the content of the thermosetting agent (B2) is equal to or more than the lower limit value, curing of the thermosetting protective film-forming film is more likely to proceed.
  • the moisture absorption rate of the film for thermosetting protective film formation was reduced because the said content of the thermosetting agent (B2) was below the said upper limit, and it was obtained using the composite sheet for protective film formation Improved package reliability.
  • the content of the thermosetting component (B) (for example, the total content of the epoxy resin (B1) and the thermosetting agent (B2)) is:
  • the content of the polymer component (A) is preferably 20 parts by mass or more and 500 parts by mass or less, more preferably 30 parts by mass or more and 300 parts by mass or less, and more preferably 40 parts by mass or more and 150 parts by mass with respect to 100 parts by mass of the polymer component (A). It is particularly preferable that the amount is not more than part by mass.
  • the composition (III-1) and the thermosetting protective film-forming film may contain a curing accelerator (C).
  • the curing accelerator (C) is a component for adjusting the curing rate of the composition (III-1).
  • Preferred curing accelerators (C) include, for example, tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol; 2-methylimidazole, 2-phenylimidazole Imidazoles such as 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole (one or more hydrogen atoms are other than hydrogen atoms)
  • the curing accelerator (C) contained in the composition (III-1) and the film for forming a thermosetting protective 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 curing accelerator (C) is 100% of the thermosetting component (B). It is preferable that it is 0.01 mass part or more and 10 mass parts or less with respect to a mass part, and it is more preferable that it is 0.1 mass part or more and 7 mass parts or less.
  • the effect by using a hardening accelerator (C) is acquired more notably because the said content of a hardening accelerator (C) is more than the said lower limit.
  • a hardening accelerator (C) is below the said upper limit, for example, a highly polar hardening accelerator (C) is in a film for thermosetting protective film formation under high temperature and high humidity conditions.
  • the effect of suppressing segregation by moving to the adhesion interface side with the adherend is increased, and the reliability of the semiconductor chip with a protective film obtained using the protective film-forming composite sheet is further improved.
  • the composition (III-1) and the thermosetting protective film-forming film may contain a filler (D).
  • the thermosetting protective film-forming film contains the filler (D)
  • the protective film obtained by curing the thermosetting protective film-forming film can easily adjust the thermal expansion coefficient.
  • the reliability of the semiconductor chip with the protective film obtained using the composite sheet for forming the protective film is further improved.
  • the moisture absorption rate of a protective film can be reduced or heat dissipation can be improved because the film for thermosetting protective film formation contains a filler (D).
  • 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 such as silica, alumina, talc, calcium carbonate, titanium white, bengara, silicon carbide, boron nitride; 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 filler (D) contained in the composition (III-1) and the thermosetting protective film-forming film may be only one type, two or more types, and when two or more types are combined, 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 in the composition (III-1) that is, a film for forming a thermosetting protective film
  • the content of the filler (D) is preferably 5% by mass or more and 80% by mass or less, and more preferably 7% by mass or more and 60% by mass or less. Adjustment of said thermal expansion coefficient becomes easier because content of a filler (D) is such a range.
  • the composition (III-1) and the thermosetting protective film-forming film may contain a coupling agent (E).
  • a coupling agent (E) having a functional group capable of reacting with an inorganic compound or an organic compound 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 thermosetting protective film-forming film to the adherend can be improved. it can. Moreover, the water resistance improves the film
  • the coupling agent (E) is preferably a compound having a functional group capable of reacting with the functional group of the polymer component (A), the thermosetting component (B), etc., and is preferably a silane coupling agent. More preferred. Preferred examples of the silane coupling agent 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- (phenyla
  • the coupling agent (E) contained in the composition (III-1) and the thermosetting protective film-forming film may be only one type, two or more types, or a combination thereof when two or more types are used.
  • the ratio can be arbitrarily selected.
  • the content of the coupling agent (E) is the polymer component (A) and the thermosetting component. It is preferable that it is 0.03 mass part or more and 20 mass parts or less with respect to 100 mass parts of total content of (B), It is more preferable that it is 0.05 mass part or more and 10 mass parts or less, 0.1 It is particularly preferable that the amount is not less than 5 parts by mass.
  • the content of the coupling agent (E) is equal to or more than the lower limit, the dispersibility of the filler (D) in the resin is improved, and the thermosetting protective film-forming film is adhered to the adherend.
  • the effect by using a coupling agent (E), such as a property improvement, is acquired more notably. Moreover, generation
  • Crosslinking agent (F) As the polymer component (A), those having functional groups such as vinyl group, (meth) acryloyl group, amino group, hydroxyl group, carboxy group, isocyanate group and the like that can be bonded to other compounds such as the above-mentioned acrylic resin.
  • the composition (III-1) and the thermosetting protective film-forming film may contain a crosslinking agent (F) for bonding the functional group with another compound to crosslink. By crosslinking using the crosslinking agent (F), the initial adhesive force and cohesive force of the thermosetting protective film-forming film can be adjusted.
  • 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 polyisocyanate compound, the aliphatic polyisocyanate compound or the alicyclic polyisocyanate compound, and a low amount such as ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane or castor oil. 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” is as described above.
  • 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.
  • 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 polymer component (A).
  • a reaction between the crosslinking agent (F) and the polymer component (A) results in a thermosetting protective film forming film.
  • a crosslinked structure can be easily introduced.
  • the crosslinking agent (F) contained in the composition (III-1) and the film for forming a thermosetting protective film may be only one type, two or more types, and when two or more types are used, a combination thereof and The ratio can be arbitrarily selected.
  • the content of the crosslinking agent (F) is 0.01 parts by mass or more with respect to 100 parts by mass of the polymer component (A). It is preferably 20 parts by mass or less, more preferably 0.1 parts by mass or more and 10 parts by mass or less, and particularly preferably 0.5 parts by mass or more and 5 parts by mass or less.
  • the effect by using a crosslinking agent (F) is acquired more notably because the said content of a crosslinking agent (F) is more than the said lower limit.
  • 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.
  • the composition (III-1) may contain an energy ray curable resin (G). Since the thermosetting protective film-forming film contains the energy ray-curable resin (G), the characteristics can be changed by irradiation with energy rays.
  • the energy beam curable resin (G) is obtained by polymerizing (curing) an energy beam curable compound.
  • the energy ray curable compound include compounds having at least one polymerizable double bond in the molecule, and acrylate compounds having a (meth) acryloyl group are preferable.
  • acrylate compound examples include trimethylolpropane tri (meth) acrylate, tetramethylolmethanetetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol monohydroxypenta ( Chain aliphatic skeleton-containing (meth) acrylates such as (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,4-butylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate; Cyclic aliphatic skeleton-containing (meth) acrylates such as cyclopentanyl di (meth) acrylate; polyalkylene glycol (meth) acrylates such as polyethylene glycol di (meth) acrylate Oligoester (meth)
  • the weight average molecular weight of the energy ray curable compound is preferably 100 or more and 30000 or less, and more preferably 300 or more and 10,000 or less.
  • the “weight average molecular weight” is as described above.
  • the energy ray-curable compound used for the polymerization 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 energy ray curable resin (G) contained in the composition (III-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 resin (G) is preferably 1% by mass or more and 95% by mass or less, and more preferably 5% by mass or more and 90% by mass or less. It is particularly preferably 10% by mass or more and 85% by mass or less.
  • the composition (III-1) contains the energy ray curable resin (G)
  • the composition (III-1) contains a photopolymerization initiator (H) in order to efficiently advance the polymerization reaction of the energy ray curable resin (G). It may be.
  • Examples of the photopolymerization initiator (H) in the composition (III-1) include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, benzoin methyl benzoate, and benzoin dimethyl ketal.
  • Benzoin compounds such as acetophenone, acetophenone compounds such as acetophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one; Acylphosphine oxide compounds such as 4,6-trimethylbenzoyl) phenylphosphine oxide and 2,4,6-trimethylbenzoyldiphenylphosphine oxide; benzylphenyl sulfide, tetramethylthiuram Sulfide compounds such as nosulfides; ⁇ -ketol compounds such as 1-hydroxycyclohexyl phenyl ketone; azo compounds such as azobisisobutyronitrile; titanocene compounds such as titanocene; thioxanthone compounds such as thioxanthone; peroxide compounds; Diketone compound; benzyl; dibenzyl; benzophenone; 2,4-diethylthio
  • the photopolymerization initiator (H) contained in the composition (III-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 (H) is 0.1 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the energy beam curable resin (G). It is preferably 1 to 10 parts by mass, more preferably 2 to 5 parts by mass.
  • the composition (III-1) and the thermosetting protective film-forming film may contain a colorant (I).
  • a colorant (I) 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 colorant (I) contained in the composition (III-1) and the thermosetting protective film-forming film may be only one type, two or more types, and in the case of two or more types, combinations thereof and The ratio can be arbitrarily selected.
  • the content of the colorant (I) in the thermosetting protective film-forming film may be appropriately adjusted according to the purpose. For example, by adjusting the content of the colorant (I) in the thermosetting protective film-forming film and adjusting the light transmittance of the protective film, the print visibility when laser printing is performed on the protective film Can be adjusted. Further, by adjusting the content of the colorant (I) in the thermosetting protective film-forming film, it is possible to improve the design of the protective film or make it difficult to see the grinding marks on the back surface of the semiconductor wafer.
  • the content of the agent (I) is preferably 0.1% by mass or more and 10% by mass or less, more preferably 0.1% by mass or more and 7.5% by mass or less, and 0.1% by mass. It is particularly preferably 5% by mass or less.
  • the composition (III-1) and the thermosetting protective film-forming film may contain a general-purpose additive (J) as long as the effects of the present embodiment are not impaired.
  • the general-purpose additive (J) may be a known one and can be arbitrarily selected according to the purpose, and is not particularly limited. Is mentioned.
  • the general-purpose additive (J) contained in the composition (III-1) and the thermosetting protective film-forming film may be only one type, two or more types, or a combination thereof when two or more types are used. The ratio can be arbitrarily selected.
  • the content of the general-purpose additive (J) in the composition (III-1) and the thermosetting protective film-forming film is not particularly limited, and may be appropriately selected depending on the purpose.
  • the composition (III-1) preferably further contains a solvent.
  • the composition (III-1) containing a solvent has good handleability.
  • the solvent is not particularly limited. Preferred examples include hydrocarbons such as toluene and xylene; alcohols such as methanol, ethanol, 2-propanol, isobutyl alcohol (2-methylpropan-1-ol), and 1-butanol. 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 composition (III-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 composition (III-1) is preferably methyl ethyl ketone or the like from the viewpoint that the components contained in the composition (III-1) can be mixed more uniformly.
  • the composition for forming a thermosetting protective film such as the composition (III-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 at the time of 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 ° C. or higher and 30 ° C. or lower.
  • the film for forming an energy beam curable protective film contains an energy beam curable component (a).
  • the energy ray curable component (a) is preferably uncured, preferably tacky, and more preferably uncured and tacky.
  • “energy beam” and “energy beam curability” are as described above.
  • the energy ray-curable protective film-forming film may be only one layer (single layer), or may be two or more layers, and when it is a plurality of layers, these layers may be the same or different from each other, The combination of these multiple layers is not particularly limited.
  • the thickness of the energy ray-curable protective film-forming film is preferably 1 ⁇ m or more and 100 ⁇ m or less, more preferably 5 ⁇ m or more and 75 ⁇ m or less, and particularly preferably 5 ⁇ m or more and 50 ⁇ m or less.
  • the thickness of the energy ray-curable protective film-forming film is equal to or more than the lower limit value, a protective film with higher protective ability can be formed.
  • the thickness of the energy ray-curable protective film-forming film is equal to or less than the upper limit, an excessive thickness is suppressed.
  • the thickness of the energy ray curable protective film forming film means the thickness of the entire energy ray curable protective film forming film, for example, the formation of an energy ray curable protective film composed of a plurality of layers.
  • the film thickness means the total thickness of all layers constituting the energy ray-curable protective film-forming film.
  • a method for measuring the thickness of the energy ray-curable protective film-forming film for example, a method of measuring the thickness using a contact-type thickness meter at any five locations and calculating an average of the measured values, etc. Is mentioned.
  • the curing conditions for forming the protective film by applying the energy ray-curable protective film-forming film to the back surface of the semiconductor wafer and curing it are as long as the degree of curing is such that the protective film can fully perform its function. It does not specifically limit and it should just select suitably according to the kind of film for energy-beam curable protective film formation.
  • the illuminance of the energy ray is preferably 120 mW / cm 2 or more 280 mW / cm 2 or less.
  • the amount of the energy ray is preferably 200 mJ / cm 2 or more 1000 mJ / cm 2 or less.
  • the film for forming an energy ray curable protective film can be formed using the composition for forming an energy ray curable protective film containing the constituent material.
  • the energy ray curable protective film is applied to the target surface of the film for forming the energy ray curable protective film, and the energy ray curable protection is applied to the target site by applying the composition for forming the energy ray curable protective film and drying it as necessary.
  • a film-forming film can be formed.
  • the ratio of the contents of components that do not vaporize at room temperature is usually the same as the ratio of the contents of the components of the film for forming an energy ray-curable protective film.
  • “normal temperature” is as described above.
  • the drying conditions of the energy ray-curable protective film-forming composition are not particularly limited, but the energy ray-curable protective film-forming composition preferably comprises heat drying when it contains a solvent described later. In this case, for example, drying is preferably performed at 70 ° C. to 130 ° C. for 10 seconds to 5 minutes.
  • composition (IV-1) ⁇ Composition for forming an energy ray-curable protective film (IV-1)>
  • composition for forming an energy beam curable protective film for example, the composition for forming an energy beam curable protective film (IV-1) containing the energy beam curable component (a) (in this specification, simply And the like (may be abbreviated as “composition (IV-1)”).
  • the energy ray curable component (a) is a component that is cured by irradiation with energy rays, and imparts film forming property, flexibility, etc. to the film for forming an energy ray curable protective film, and is hard protected after curing. It is also a component for forming a film.
  • 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 a molecular weight having an energy ray curable group of 100 to 80000.
  • the following compounds (a2) are mentioned.
  • the polymer (a1) may be crosslinked at least partly with a crosslinking agent or may not be crosslinked.
  • 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 reacting the functional group-reactive group and an energy ray-curable compound (a12) having an energy ray-curable group such as an energy ray-curable double bond. It is done.
  • 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, and a known method can be adopted as a polymerization method.
  • 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.
  • 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, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and (meth) acrylic.
  • N-butyl acid isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, n-octyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, ( Undecyl (meth) acrylate, dodecyl (meth) acrylate (lauric (meth) acrylate ), Tridecyl (meth) acrylate, tetradecyl (meth) acrylate (myristyl (meth) acrylate), pent
  • acrylic monomer having no functional group examples include alkoxy such as methoxymethyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxymethyl (meth) acrylate, and ethoxyethyl (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 amount of the structural unit constituting the polymer is 0.1% by mass or more. It is preferably 50% by mass or less, more preferably 1% by mass or more and 40% by mass or less, and particularly preferably 3% by mass or more and 30% by mass or less.
  • 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 can be easily adjusted within a preferable range of the degree of curing of the protective film.
  • 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 -1) is preferably 1% by mass or more and 70% by mass or less, more preferably 5% by mass or more and 60% by mass or less, and more preferably 10% by mass or more and 50% by mass or less. Particularly preferred.
  • 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). What has a seed
  • the energy beam curable compound (a12) preferably has 1 or more and 5 or less of the energy beam curable groups in one molecule, and more preferably 1 or more and 3 or less.
  • 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 mol% or more and 120 mol% or less, more preferably 35 mol% or more and 100 mol% or less, and particularly preferably 50 mol% or more and 100 mol% or less.
  • the ratio of the content is within such a range, the adhesive force of the protective film after 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 or more and 2,000,000 or less, and more preferably 300,000 or more and 1500,000 or less.
  • the “weight average molecular weight” is as described above.
  • the polymer (a1) is at least partially crosslinked by a crosslinking agent
  • the polymer (a1) has been described as constituting the acrylic polymer (a11).
  • a monomer that does not correspond to any of the monomers and has a group that reacts with the crosslinking agent is polymerized to be crosslinked at the group that reacts with the crosslinking agent, or the energy ray-curable compound ( In the group which reacts with the functional group derived from a12), it may be crosslinked.
  • the polymer (a1) contained in the composition (IV-1) and the energy ray-curable 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 of the energy ray-curable group having the energy ray-curable group and the compound (a2) having a molecular weight of 100 to 80,000 include a group containing an energy ray-curable double bond. ) 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 a thermosetting component described later, but is handled as the compound (a2) in the present embodiment.
  • the compound (a2) preferably has a weight average molecular weight of 100 or more and 30000 or less, and more preferably 300 or more and 10,000 or less.
  • the “weight average molecular weight” is as described above.
  • the compound (a2) contained in the composition (IV-1) and the energy ray-curable 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.
  • composition (IV-1) and the film for forming an energy ray curable protective 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 a crosslinking agent, or may not be crosslinked.
  • polymer (b) having no energy ray curable group examples include acrylic polymers, phenoxy resins, urethane resins, polyesters, rubber resins, and acrylic urethane 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.
  • Examples of the polymer (b) that is at least partially crosslinked by a crosslinking agent and does not have an energy ray-curable group include those in which a reactive functional group in the polymer (b) has reacted with a crosslinking agent. Can be mentioned.
  • the reactive functional group may be appropriately selected according to the type of the crosslinking agent and the like, and is not particularly limited.
  • examples of the reactive functional group include a hydroxyl group, a carboxy group, and an amino group, and among these, a hydroxyl group having high reactivity with an isocyanate group is preferable.
  • the crosslinking agent is an epoxy compound
  • examples of the reactive functional group include a carboxy group, an amino group, an amide group, and the like. Among these, a carboxy group having high reactivity with an epoxy group is preferable.
  • 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 to the total amount of the structural unit constituting the polymer (b) is 1% by mass. It is preferably 20% by mass or less and more preferably 2% by mass or more and 10% by mass or less. When the ratio is within such a range, 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 preferably 10,000 or more and 2,000,000 or less from the viewpoint that the film-forming property of the composition (IV-1) becomes better. More preferably, it is 100,000 or more and 1500,000 or less.
  • the “weight average molecular weight” is as described above.
  • the polymer (b) having no energy ray-curable group contained in the composition (IV-1) and the energy ray-curable protective film-forming film may be only one type or two or more types. In the case of more than species, their combination and ratio can be arbitrarily selected.
  • compositions (IV-1) include those containing one or both of the polymer (a1) and the compound (a2).
  • the composition (IV-1) preferably further contains a polymer (b) having no energy ray-curable group.
  • the composition (IV-1) It is also preferable to contain. Further, the composition (IV-1) does not contain the compound (a2), and may contain both the polymer (a1) and the polymer (b) having no energy ray curable group. .
  • composition (IV-1) contains the polymer (a1), the compound (a2), and the polymer (b) having no energy ray-curable group
  • Content of the said compound (a2) is 10 mass parts or more and 400 mass parts or less with respect to 100 mass parts of total contents of the said polymer (a1) and the polymer (b) which does not have an energy-beam curable group. It is preferable that it is 30 parts by mass or more and 350 parts by mass or less.
  • the total content of the energy ray-curable component (a) and the polymer (b) having no energy ray-curable group) of the energy ray-curable protective film-forming film is 5% by mass or more and 90% by mass or less. It is preferably 10% by mass to 80% by mass, more preferably 20% by mass to 70% by mass.
  • the ratio of the content of the energy ray curable component is within such a range, the energy ray curable film of the energy ray curable protective film forming film becomes more favorable.
  • the composition (IV-1) includes a thermosetting component, a filler, a coupling agent, a crosslinking agent, a photopolymerization initiator, a colorant, and a general-purpose additive depending on the purpose. You may contain 1 type, or 2 or more types selected from the group which consists of.
  • the composition (IV-1) containing the energy ray curable component and the thermosetting component the formed energy ray curable protective film-forming film can be adhered to an adherend by heating. And the strength of the protective film formed from the energy ray-curable protective film-forming film is also improved.
  • thermosetting component examples of the thermosetting component, filler, coupling agent, crosslinking agent, photopolymerization initiator, colorant, and general-purpose additive in the composition (IV-1) are the heat in the composition (III-1).
  • each of the thermosetting component, the filler, the coupling agent, the crosslinking agent, the photopolymerization initiator, the colorant, and the general-purpose additive may be used alone. And when 2 or more types may be used together, and when using 2 or more types together, those combinations and ratios can be selected arbitrarily.
  • the contents of the thermosetting component, filler, coupling agent, crosslinking agent, photopolymerization initiator, colorant, and general-purpose additive in the composition (IV-1) may be appropriately adjusted according to the purpose. There is no particular limitation.
  • the composition (IV-1) preferably further contains a solvent since its handleability is improved by dilution.
  • the solvent contained in the composition (IV-1) include the same solvents as those in the composition (III-1).
  • the solvent contained in the composition (IV-1) may be only one kind or two or more kinds.
  • composition for forming an energy ray-curable protective film such as the composition (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 ° C. or higher and 30 ° C.
  • Non-curable protective film-forming film for example, a non-curable component (c) is contained.
  • the non-curable component (c) does not have curability, has adhesiveness to the support sheet, and has an appropriate hardness to protect the semiconductor wafer or chip. preferable.
  • “non-curable” is as described above.
  • the non-curable protective film-forming film may be only one layer (single layer), or may be two or more layers, and when it is 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 non-curable protective film-forming film is preferably 1 ⁇ m or more and 100 ⁇ m or less, more preferably 5 ⁇ m or more and 75 ⁇ m or less, and particularly preferably 5 ⁇ m or more and 50 ⁇ m or less.
  • the thickness of the non-curable protective film-forming film is equal to or more than the lower limit value, a protective film with higher protective ability can be formed.
  • the thickness of the film for forming a non-curable protective film is equal to or less than the upper limit, an excessive thickness is suppressed.
  • the “thickness of the non-curable protective film-forming film” means the total thickness of the non-curable protective film-forming film, for example, a non-curable protective film-forming film composed of a plurality of layers.
  • the thickness means the total thickness of all the layers constituting the non-curable protective film-forming film.
  • the method for measuring the thickness of the non-curable protective film-forming film includes, for example, a method of measuring the thickness using a contact-type thickness meter at any five locations and calculating the average of the measured values. Can be mentioned.
  • Non-curable protective film forming composition can be formed using a non-curable protective film-forming composition containing the constituent materials.
  • the composition for forming a non-curable protective film is applied to the surface to be formed of the film for forming a non-curable protective film, and is dried as necessary to form a non-curable protective film on the target site.
  • a film can be formed.
  • the ratio of the content of components that do not vaporize at room temperature is usually the same as the ratio of the content of the components in the film for forming a non-curable protective film.
  • “normal temperature” is as described above.
  • the coating of the non-curable protective film-forming composition can be performed, for example, by the same method as in the case of the above-described pressure-sensitive adhesive composition.
  • the drying conditions for the non-curable protective film-forming composition are not particularly limited, but the non-curable protective film-forming composition preferably contains heat-dried when it contains a solvent to be described later.
  • the drying is preferably performed at 70 ° C. to 130 ° C. for 10 seconds to 5 minutes.
  • Non-curable protective film-forming composition (V-1) examples include, for example, a non-curable protective film-forming composition (V-1) containing a non-curable component (c) (in this specification, simply “composition ( V-1) ”) and the like.
  • the non-curable component (c) is a thermoplastic resin, and examples thereof include, but are not limited to, acrylic polymers.
  • acrylic polymers include those exemplified as the acrylic polymer (b-1).
  • composition (V-1) is selected from the group consisting of a filler, a coupling agent, a crosslinking agent, a colorant, and a general-purpose additive in addition to the non-curable component (c). You may contain the seed or two or more sorts.
  • Examples of the filler, coupling agent, crosslinking agent, colorant, and general-purpose additive in the composition (V-1) include the filler (D) and the coupling agent (E in the composition (III-1), respectively. ), Crosslinker (F), colorant (I), and general-purpose additive (J).
  • the filler, coupling agent, crosslinking agent, colorant, and general-purpose additive may be used alone or in combination of two or more. Well, when using 2 or more types together, those combinations and ratios can be arbitrarily selected.
  • the contents of the filler, coupling agent, crosslinking agent, colorant, and general-purpose additive in the composition (V-1) may be appropriately adjusted according to the purpose, and are not particularly limited.
  • the composition (V-1) preferably further contains a solvent since its handleability is improved by dilution.
  • Examples of the solvent contained in the composition (V-1) include the same solvents as those in the composition (III-1).
  • the solvent contained in the composition (V-1) may be only one type or two or more types.
  • composition for forming a non-curable protective film such as the composition (V-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 ° C. or higher and 30 ° C.
  • the composite sheet for forming a protective film includes a protective film-forming film containing the following components, an adhesive layer containing the following components, and a substrate having the following configuration: They are stacked in this order.
  • the protective film-forming film is As the polymer component (A) -1, an acrylic polymer obtained by copolymerizing 85 parts by mass of methyl acrylate and 15 parts by mass of 2-hydroxyethyl acrylate (weight average molecular weight: 350 to 400,000, preferably 370,000) Glass transition temperature: 3 to 9 ° C., preferably 6 ° C.) of 100 to 200 parts by weight, preferably 150 parts by weight;
  • As epoxy resin (B1) -1 bisphenol A type epoxy resin (epoxy equivalent: 180 to 200 g / eq, preferably 184 to 194 g / eq) is 50 to 70 parts by mass, preferably 60 parts by mass;
  • As epoxy resin (B1) -2, bisphenol A type epoxy resin (epoxy equivalent: 750 to 950 g / eq, preferably 800 to 900 g / eq) is 5 to 15 parts by mass, preferably 10 parts by mass;
  • As epoxy resin (B1) -3 dicyclopentadiene type epoxy
  • the adhesive layer is A pre-copolymer having a weight average molecular weight of 800,000 obtained by copolymerizing 2-ethylhexyl acrylate (2EHA) (80 parts by mass) and 2-hydroxylethyl acrylate (HEA) (20 parts by mass) as an acrylic polymer.
  • EHA 2-ethylhexyl acrylate
  • HOA 2-hydroxylethyl acrylate
  • the substrate is a polypropylene film having a thickness of 70 to 90 ⁇ m, preferably 80 ⁇ m.
  • the base includes a matte surface (surface roughness (Ra): 0.20 to 1.30 ⁇ m, preferably 0.20 to 1.20 ⁇ m), and a glossy surface or a fine matte surface (surface roughness (Ra)). : 0.05 to 0.15 ⁇ m, preferably 0.10 to 0.15 ⁇ m).
  • the said adhesive layer is laminated
  • the base material has a mat surface roughness (Ra) (surface roughness (Ra): 0.30 ⁇ m or less, preferably 0.20 ⁇ m) and a glossy surface or a fine mat surface (surface roughness (Ra ): 0.05 to 0.15 ⁇ m, preferably 0.10 to 0.15 ⁇ m), the pressure-sensitive adhesive layer is laminated on the glossy surface or fine mat surface of the substrate.
  • the protective film-forming composite sheet has a protective film-forming film containing the above components, a pressure-sensitive adhesive layer containing the following components, and a substrate having the above-described configuration.
  • the adhesive layer is A pre-copolymer having a weight average molecular weight of 800,000 obtained by copolymerizing 2-ethylhexyl acrylate (2EHA) (80 parts by mass) and 2-hydroxylethyl acrylate (HEA) (20 parts by mass) as an acrylic polymer.
  • EHA 2-ethylhexyl acrylate
  • HOA 2-hydroxylethyl acrylate
  • 90-110 parts by weight preferably 100 parts by weight; 15 to 25 parts by mass, preferably 20 parts by mass of a trifunctional xylylene diisocyanate crosslinking agent; 5 to 15 parts by mass, preferably 10 parts by mass of silicone resin fine particles are contained.
  • the protective film-forming composite sheet has a protective film-forming film containing the above components, a pressure-sensitive adhesive layer containing the following components, and a substrate having the above-described configuration.
  • the adhesive layer is A pre-copolymer having a weight average molecular weight of 800,000 obtained by copolymerizing 2-ethylhexyl acrylate (2EHA) (80 parts by mass) and 2-hydroxylethyl acrylate (HEA) (20 parts by mass) as an acrylic polymer.
  • EHA 2-ethylhexyl acrylate
  • HOA 2-hydroxylethyl acrylate
  • 90-110 parts by weight preferably 100 parts by weight; 15 to 25 parts by mass, preferably 20 parts by mass of a trifunctional xylylene diisocyanate crosslinking agent; It contains 3 to 30 parts by mass, preferably 5 to 25 parts by mass of an epoxy resin.
  • the protective film-forming composite sheet has a protective film-forming film containing the above components, a pressure-sensitive adhesive layer containing the following components, and a substrate having the above-described configuration.
  • the adhesive layer is A pre-copolymer having a weight average molecular weight of 800,000 obtained by copolymerizing 2-ethylhexyl acrylate (2EHA) (80 parts by mass) and 2-hydroxylethyl acrylate (HEA) (20 parts by mass) as an acrylic polymer.
  • EHA 2-ethylhexyl acrylate
  • HOA 2-hydroxylethyl acrylate
  • 90-110 parts by weight preferably 100 parts by weight; 15 to 25 parts by mass, preferably 20 parts by mass of a trifunctional xylylene diisocyanate crosslinking agent; It contains 3 to 7 parts by mass, preferably 5 parts by mass of a titanium oxide-based white pigment.
  • the protective film-forming composite sheet has a protective film-forming film containing the above components, a pressure-sensitive adhesive layer containing the following components, and a substrate having the above-described configuration.
  • the adhesive layer is A pre-copolymer having a weight average molecular weight of 800,000 obtained by copolymerizing 2-ethylhexyl acrylate (2EHA) (80 parts by mass) and 2-hydroxylethyl acrylate (HEA) (20 parts by mass) as an acrylic polymer.
  • EHA 2-ethylhexyl acrylate
  • HOA 2-hydroxylethyl acrylate
  • 90-110 parts by weight preferably 100 parts by weight; 15 to 25 parts by mass, preferably 20 parts by mass of a trifunctional xylylene diisocyanate crosslinking agent; 5 to 15 parts by mass, preferably 10 parts by mass of acrylic polymer fine particles are contained.
  • the protective film forming composite sheet can be produced 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.
  • thermosetting property is applied on the adhesive layer.
  • a protective film-forming film can be directly formed by applying a protective film-forming composition, an energy ray-curable protective film-forming composition, or a non-curable protective film-forming composition.
  • 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 pressure-sensitive adhesive composition is coated on a base material, and dried as necessary, thereby laminating a pressure-sensitive adhesive layer on the base material,
  • a thermosetting protective film-forming composition, an energy ray-curable protective film-forming composition, or a non-curable protective film-forming composition is coated on the release film and dried as necessary.
  • the protective film-forming film is formed on the release film, and the exposed surface of the protective film-forming film is bonded to the exposed surface of the pressure-sensitive adhesive layer laminated on the base material. Is laminated on the adhesive layer to obtain a composite sheet for forming a protective film.
  • the pressure-sensitive adhesive composition is applied on the release film.
  • the pressure-sensitive adhesive layer is formed on the release film by drying as required, and the exposed surface of the pressure-sensitive adhesive layer is bonded to one surface of the base material so that the pressure-sensitive adhesive layer is bonded to the base material. It may be laminated on top. In any method, the release film may be removed at an arbitrary timing after the target laminated structure is formed.
  • all layers (adhesive layer, protective film-forming film) other than the base material constituting the protective film-forming composite sheet are formed in advance on the release film, and on the surface of the target layer. Since lamination can be performed by a method of bonding, a composite film for forming a protective film may be manufactured by appropriately selecting a layer that employs such a process as necessary.
  • the composite sheet for forming a protective film is usually stored in a state in which a release film is bonded to the surface of the outermost layer (for example, a film for forming a protective film) opposite to the support sheet. Therefore, on this release film (preferably its release-treated surface), such as a thermosetting protective film-forming composition, an energy ray-curable protective film-forming composition, or a non-curable protective film-forming composition,
  • a release film preferably its release-treated surface
  • a thermosetting protective film-forming composition such as a thermosetting protective film-forming composition, an energy ray-curable protective film-forming composition, or a non-curable protective film-forming composition
  • the composition for forming the layer constituting the outermost layer is applied and dried as necessary, so that the layer constituting the outermost layer is formed on the release film, and this layer is in contact with the release film.
  • a composite sheet for forming a protective film can be obtained by laminating the remaining layers on the exposed surface on the side opposite to the side to be coated
  • peeling film is a film having a function of peeling, and specifically, a protective film for protecting the protective film-forming film before being attached to a semiconductor wafer or a support sheet. It refers to a film that is affixed to both surfaces of a forming film, and is used by peeling it off during work.
  • release film for example, polyethylene film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film, vinyl chloride copolymer film, polyethylene terephthalate film, polyethylene naphthalate film, polybutylene terephthalate film, Polyurethane film, ethylene vinyl acetate copolymer film, ionomer resin film, ethylene / (meth) acrylic acid copolymer film, ethylene / (meth) acrylic acid ester copolymer film, polystyrene film, polycarbonate film, polyimide film, fluorine A transparent film such as a resin film is used. These crosslinked films are also used.
  • the film which colored these, an opaque film, etc. can be used.
  • the release agent include release agents such as silicone-based, fluorine-based, and long-chain alkyl group-containing carbamates.
  • the thickness of the release film is usually from 10 ⁇ m to 500 ⁇ m, preferably from 15 ⁇ m to 300 ⁇ m, and particularly preferably from 20 ⁇ m to 250 ⁇ m.
  • the “thickness of the release film” means the thickness of the entire release film.
  • the thickness of the release film composed of a plurality of layers means the total thickness of all the layers constituting the release film. means.
  • the method etc. which measure thickness using a contact-type thickness meter in arbitrary five places, and calculate the average of a measured value, etc. are mentioned, for example.
  • the protective film forming composite sheet of the present embodiment 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 heated or irradiated with energy rays as necessary to cure the protective film-forming film to form a protective film. Or when it is the composition for non-curable protective film formation contained in the film for protective film formation, you may use it as a protective film with uncured. Next, the semiconductor wafer is divided together with the protective film by dicing to form semiconductor chips.
  • 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). Thereafter, the semiconductor chip of the obtained semiconductor chip with a protective film is flip-chip connected to the circuit surface of the substrate in the same manner as the conventional method, and then the semiconductor package is obtained. Then, a target semiconductor device may be manufactured using this semiconductor package.
  • the timing when hardening the film for protective film formation by heating or irradiating an energy ray, the timing may be before dicing as mentioned above, and may be after dicing. Especially, it is preferable that the timing which cures the film for protective film formation by heating or irradiating an energy ray is before dicing.
  • the timing of laser printing may be before curing or after curing.
  • the timing of laser printing is preferably after curing.
  • Polymer component (A) -1 Acrylic polymer obtained by copolymerizing 85 parts by mass of methyl acrylate and 15 parts by mass of 2-hydroxyethyl acrylate (weight average molecular weight: 370,000, glass transition temperature: 6 ° C.)
  • Thermosetting component (B1) -1 bisphenol A type epoxy resin (Mitsubishi Chemical jER828, epoxy equivalent 184 to 194 g / eq)
  • B1) -2 Bisphenol A type epoxy resin (Mitsubishi Chemical Corporation jER1055, epoxy equivalent 800-900 g / eq)
  • B1) -3 Dicyclopentadiene type epoxy resin (Dainippon Ink & Chemicals, Inc.
  • Epiklon HP-7200HH, epoxy equivalent 255-260 g / eq) (B2) -1: Thermally active latent epoxy resin curing agent (dicyandiamide (ADEKA HARDNER EH-3636AS manufactured by ADEKA, active hydrogen amount 21 g / eq)) Curing accelerator (C) -1: 2-phenyl-4,5-dihydroxymethylimidazole (Curesol 2PHZ manufactured by Shikoku Kasei Kogyo Co., Ltd.) Filler (D) -1: Silica filler (SC2050MA manufactured by Admatechs, average particle size 0.5 ⁇ m) Coupling agent (E) -1: Silane coupling agent (A-1110 manufactured by Nihon Unicar) Colorant (I) -1: Black pigment (manufactured by Dainichi Seika)
  • pressure-sensitive adhesive composition (I-4) -1) Contains an acrylic polymer (100 parts by mass, solid content) and a trifunctional xylylene diisocyanate-based crosslinking agent (“Takenate D110N” manufactured by Mitsui Takeda Chemical Co., Ltd.) (40 parts by mass (solid content)), and methyl ethyl ketone as a solvent
  • a non-energy ray-curable pressure-sensitive adhesive composition (I-4) -1 containing a mixed solvent of toluene and ethyl acetate and having a solid content concentration of 30% by mass was prepared.
  • the acrylic polymer is a pre-copolymer having a weight average molecular weight of 800,000 obtained by copolymerizing 2-ethylhexyl acrylate (2EHA) (80 parts by mass) and 2-hydroxylethyl acrylate (HEA) (20 parts by mass). is there.
  • the pressure-sensitive adhesive composition (I-4) -1 obtained above was applied to the release-treated surface of a release film obtained by releasing one side of a polyethylene terephthalate film by silicone treatment, and the film was heated at 120 ° C. for 2 A non-energy ray-curable pressure-sensitive adhesive layer having a thickness of 15 ⁇ m was formed by heat drying for a few minutes. Next, an 80 ⁇ m-thick polypropylene film (Mitsubishi Resin, mat surface (surface roughness (Ra): 1.20 ⁇ m) / shiny surface (surface roughness (Ra): 0) is formed on the exposed surface of the pressure-sensitive adhesive layer. .10 ⁇ m) Substrate) was bonded together to produce a support sheet (10) -1.
  • a protective film-forming composition (III) 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. -1) was coated with a knife coater and dried at 100 ° C. for 2 minutes to produce a thermosetting protective film-forming film (13) -1 having a thickness of 25 ⁇ m.
  • SP-PET 381031 manufactured by Lintec Co., Ltd., thickness 38 ⁇ m
  • the exposed surface of the protective film-forming film (13) -1 obtained above is bonded to the pressure-sensitive adhesive layer of the support sheet (10) -1 obtained above to obtain a substrate, a pressure-sensitive adhesive layer, And a protective film-forming composite sheet (13) -1 was laminated in the thickness direction in this order.
  • the width of the support sheet was 270 mm
  • the outer diameter of the protective film-forming film was 210 mm.
  • the protective film-forming film affixed to an 8-inch semiconductor wafer is printed on the protective film layer over the support sheet using the laser printing apparatus CSM300M manufactured by EO Technics, and characters can be visually recognized when visually observed. It was determined whether or not. Printing was performed on the uncured protective film layer. The character size was 0.3 mm ⁇ 0.2 mm. The results are shown in Table 1.
  • the evaluation criteria for laser printing visibility were set as follows. A ... Visible B ... Slightly blurred but visible C ... Not visible
  • Example 2 ⁇ Manufacture of composite sheet for forming protective film> (Production of protective film-forming composition (III-1)) Using the same method as in Example 1, a thermosetting protective film-forming composition (III-1) was obtained.
  • (Production of pressure-sensitive adhesive composition (I-4) -2) Contains an acrylic polymer (100 parts by mass, solid content) and a trifunctional xylylene diisocyanate-based crosslinking agent (“Takenate D110N” manufactured by Takeda Chemicals, Ltd.) (50 parts by mass (solid content)), and methyl ethyl ketone as a solvent And a non-energy ray-curable pressure-sensitive adhesive composition (I-4) -2 having a solid content concentration of 30% by mass was prepared.
  • the acrylic polymer is a pre-copolymer having a weight average molecular weight of 800,000 obtained by copolymerizing 2EHA (80 parts by mass) and HEA (20 parts by mass).
  • a composite sheet for forming a protective film was produced in the same manner as in Example 1 except that (10) -2 was used instead of the support sheet (10) -1.
  • Example 3 ⁇ Manufacture of composite sheet for forming protective film> (Production of protective film-forming composition (III-1)) Using the same method as in Example 1, a thermosetting protective film-forming composition (III-1) was obtained.
  • a polypropylene film having a thickness of 80 ⁇ m (Mitsubishi Resin, mat surface (surface roughness (Ra): 1.20 ⁇ m) / shiny surface (surface roughness (Ra): 0.10 ⁇ m))
  • a polypropylene film having a thickness of 80 ⁇ m (manufactured by Gunze Co., Ltd., mat surface (surface roughness (Ra): 0.20 ⁇ m) / fine mat surface (surface roughness (Ra): 0. 0). 15 ⁇ m)
  • a support sheet (10) -3 was produced in the same manner as in Example 1 except that the mat surface of the base material) was bonded.
  • a composite sheet for forming a protective film was produced in the same manner as in Example 1 except that (10) -3 was used instead of the support sheet (10) -1.
  • Example 4 (Production of protective film-forming composition (III-1)) Using the same method as in Example 1, a thermosetting protective film-forming composition (III-1) was obtained.
  • a composite sheet for forming a protective film was produced in the same manner as in Example 1 except that (10) -4 was used instead of the support sheet (10) -1.
  • Example 5 (Production of protective film-forming composition (III-1)) Using the same method as in Example 1, a thermosetting protective film-forming composition (III-1) was obtained.
  • (Production of pressure-sensitive adhesive composition (I-1) -1) Acrylic polymer (100 parts by mass, solid content), trifunctional xylylene diisocyanate-based crosslinking agent (“Takenate D110N” manufactured by Takeda Chemicals, Ltd.) (20 parts by mass (solid content)), and epoxy resin (manufactured by Mitsubishi Chemical Corporation) “JER834”) (25 parts by mass (solid content)) and further containing methyl ethyl ketone as a solvent, and an energy ray-curable pressure-sensitive adhesive composition (I-1) -1 having a solid content concentration of 30% by mass Prepared.
  • the acrylic polymer is a pre-copolymer having a weight average molecular weight of 800,000 obtained by copolymerizing 2EHA (80 parts by mass) and HEA (20 parts by mass).
  • a composite sheet for forming a protective film was produced in the same manner as in Example 1 except that (10) -5 was used instead of the support sheet (10) -1.
  • Example 6 (Production of protective film-forming composition (III-1)) Using the same method as in Example 1, a thermosetting protective film-forming composition (III-1) was obtained.
  • a composite sheet for forming a protective film was produced in the same manner as in Example 1 except that (10) -6 was used instead of the support sheet (10) -1.
  • Example 7 (Production of protective film-forming composition (III-1)) Using the same method as in Example 1, a thermosetting protective film-forming composition (III-1) was obtained.
  • (Production of pressure-sensitive adhesive composition (I-4) -4) Acrylic polymer (100 parts by mass, solid content), trifunctional xylylene diisocyanate-based crosslinking agent (“Takenate D110N” manufactured by Mitsui Takeda Chemical Co., Ltd.) (20 parts by mass (solid content)), and titanium oxide white pigment (large Nissei Kasei Co., Ltd. “N-DYM8054”) (5 parts by mass (solid content)), further containing methyl ethyl ketone as a solvent, and a solid content concentration of 30% by mass, a non-energy ray curable adhesive composition ( I-4) -4 was prepared.
  • the acrylic polymer is a pre-copolymer having a weight average molecular weight of 800,000 obtained by copolymerizing 2EHA (80 parts by mass) and HEA (20 parts by mass).
  • a composite sheet for forming a protective film was produced in the same manner as in Example 1 except that (10) -7 was used instead of the support sheet (10) -1.
  • Example 8 (Production of protective film-forming composition (III-1)) Using the same method as in Example 1, a thermosetting protective film-forming composition (III-1) was obtained.
  • a composite sheet for forming a protective film was produced in the same manner as in Example 1 except that (10) -8 was used instead of the support sheet (10) -1.
  • Example 9 (Production of protective film-forming composition (III-1)) Using the same method as in Example 1, a thermosetting protective film-forming composition (III-1) was obtained.
  • An adhesive composition (I-4) -2 was used instead of the adhesive composition (I-4) -1, and an 80 ⁇ m thick polypropylene film (manufactured by Mitsubishi Plastics, Inc. Instead of the matte surface of mat surface (surface roughness (Ra): 1.20 ⁇ m) / gloss surface (surface roughness (Ra): 0.10 ⁇ m)), a 80 ⁇ m thick polypropylene film (manufactured by Gunze)
  • the mat surface surface roughness (Ra): 0.20 ⁇ m) / fine mat surface (surface roughness (Ra): 0.15 ⁇ m)
  • a support sheet (10) -9 was obtained.
  • a composite sheet for forming a protective film was produced in the same manner as in Example 1 except that (10) -9 was used instead of the support sheet (10) -1.
  • Example 10 (Production of protective film-forming composition (III-1)) Using the same method as in Example 1, a thermosetting protective film-forming composition (III-1) was obtained.
  • An adhesive composition (I-4) -2 was used instead of the adhesive composition (I-4) -1, and an 80 ⁇ m thick polypropylene film (manufactured by Mitsubishi Plastics, Inc. Instead of the matte surface of mat surface (surface roughness (Ra): 1.20 ⁇ m) / gloss surface (surface roughness (Ra): 0.10 ⁇ m)), a 80 ⁇ m thick polypropylene film (manufactured by Gunze) The same as in Example 1 except that the mat surface (surface roughness (Ra): 0.20 ⁇ m) / fine mat surface (surface roughness (Ra): 0.15 ⁇ m) substrate) was bonded together. Using the method, a support sheet (10) -10 was obtained.
  • a composite sheet for forming a protective film was produced in the same manner as in Example 1 except that (10) -10 was used instead of the support sheet (10) -1.
  • thermosetting protective film-forming composition (III-1) was obtained.
  • a support sheet (10) -9 was produced in the same manner as in Example 1 except that a non-energy ray-curable pressure-sensitive adhesive layer having a thickness of 10 ⁇ m was formed instead of the thickness of 15 ⁇ m.
  • a composite sheet for forming a protective film was produced in the same manner as in Example 1 except that (10) -9 was used instead of the support sheet (10) -1.
  • thermosetting protective film-forming composition (III-1) was obtained.
  • (Production of pressure-sensitive adhesive composition (I-4) -6) Contains acrylic polymer (100 parts by mass, solid content) and trifunctional xylylene diisocyanate crosslinking agent (“Takenate D110N” manufactured by Mitsui Takeda Chemical Co., Ltd.) (30 parts by mass (solid content)), and methyl ethyl ketone as a solvent And a non-energy ray-curable pressure-sensitive adhesive composition (I-4) -6 having a solid content concentration of 30% by mass was prepared.
  • the acrylic polymer is a pre-copolymer having a weight average molecular weight of 800,000 obtained by copolymerizing 2EHA (80 parts by mass) and HEA (20 parts by mass).
  • a composite sheet for forming a protective film was produced in the same manner as in Example 1 except that (10) -10 was used instead of the support sheet (10) -1.
  • thermosetting protective film-forming composition (III-1) was obtained.
  • (Production of pressure-sensitive adhesive composition (I-4) -7) Contains acrylic polymer (100 parts by mass, solid content) and trifunctional xylylene diisocyanate-based cross-linking agent (“Takenate D110N” manufactured by Mitsui Takeda Chemical Co., Ltd.) (5 parts by mass (solid content)), and methyl ethyl ketone as a solvent And a non-energy ray-curable pressure-sensitive adhesive composition (I-4) -7 having a solid content concentration of 30% by mass was prepared.
  • the acrylic polymer is a pre-copolymer having a weight average molecular weight of 800,000 obtained by copolymerizing 2EHA (80 parts by mass) and HEA (20 parts by mass).
  • the pressure-sensitive adhesive composition (I-4) -7 obtained above was applied to the release-treated surface of a release film obtained by releasing one side of a polyethylene terephthalate film by silicone treatment, and the film was coated at 120 ° C.
  • a non-energy ray-curable pressure-sensitive adhesive layer having a thickness of 5 ⁇ m was formed by heat-drying for 5 minutes.
  • an 80 ⁇ m-thick polypropylene film Mitsubishi Resin, mat surface (surface roughness (Ra): 0.50 ⁇ m) / shiny surface (surface roughness (Ra): 0) is formed on the exposed surface of the adhesive layer. .10 ⁇ m
  • the support sheet (10) -11 was produced by bonding the glossy surfaces of the base material).
  • a composite sheet for forming a protective film was produced in the same manner as in Example 1 except that (10) -11 was used instead of the support sheet (10) -1.
  • thermosetting protective film-forming composition (III-1) was obtained.
  • a composite sheet for forming a protective film was produced in the same manner as in Example 1 except that (10) -12 was used instead of the support sheet (10) -1.
  • thermosetting protective film-forming composition (III-1) was obtained.
  • the pressure-sensitive adhesive composition (I-4) -7 obtained above was applied to the release-treated surface of a release film obtained by releasing one side of a polyethylene terephthalate film by silicone treatment, and the film was coated at 120 ° C.
  • a non-energy ray-curable pressure-sensitive adhesive layer having a thickness of 5 ⁇ m was formed by heat-drying for 5 minutes.
  • a 60 ⁇ m-thick polypropylene film manufactured by Riken Technos Co., Ltd., mat surface (surface roughness (Ra): 0.50 ⁇ m) / shiny surface (surface roughness (Ra): 0.
  • a support sheet (10) -13 was produced by laminating the glossy surface of the substrate (10 ⁇ m).
  • a composite sheet for forming a protective film was produced in the same manner as in Example 1 except that (10) -13 was used instead of the support sheet (10) -1.
  • the mounter suitability was A evaluation, the laser print visibility was A or B evaluation, and “other” was “No”. From Table 1, the mounter suitability was A evaluation when the haze of the support sheet was 46% or more. This is because the haze of the support sheet has a certain degree of turbidity (cloudiness) of 46% or more, so that the tip position of the support sheet can be detected by laser irradiation in an optical sensor that adjusts the position of the tip of the tape. It was guessed that this was because it was made.
  • the laser printing visibility is A evaluation. It was. It was speculated that this was because the visibility of laser printing was improved by suppressing light scattering on the outer surface of the substrate located on the bottom surface of the support sheet. Furthermore, since the haze of the support sheet is 46% or more and has a certain degree of turbidity (cloudiness), the laser light can be appropriately scattered inside the support sheet to increase the thickness of the printed characters. It was assumed that it was because it contributed to the improvement of the visibility of printing.
  • the composite sheet for forming a protective film has excellent laser printability on the protective film and excellent visibility of the printed protective film by adjusting the haze and transmission clarity of the support sheet to an appropriate range. It became clear that
  • the present invention can be used for manufacturing semiconductor devices.
  • 1A, 1B, 1C, 1D, 1E Composite sheet for protective film formation, 10 ... Support sheet, 10a ... Surface of support sheet, 11 ... Base material, 11a ... Surface of base material , 12 ... adhesive layer, 12a ... surface of the adhesive layer, 13 ... protective film forming film, 13a ... surface of protective film forming film, 15 ... release film, 16. ..Jig adhesive layer, 16a ... surface of jig adhesive layer, 17 ... intermediate layer, 17a ... surface of intermediate layer

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Abstract

Provided is a protection film-forming composite sheet comprising a base material on which an adhesive agent layer and a protection film-forming film are laminated in this order, the protection film-forming composite sheet providing excellent laser printability on a protection film formed from the protection film-forming film, and also providing excellent visibility of prints on the protection film. The protection film-forming composite sheet is provided with a base material on which an adhesive agent layer and a protection film-forming film are laminated in this order, wherein a support sheet comprising a laminate of the base material and the adhesive agent layer has a haze of more than 45%, and the support sheet has a transmissive clarity of not less than 100.

Description

保護膜形成用複合シートComposite sheet for protective film formation
　本発明は、保護膜形成用複合シートに関する。
　本願は、２０１７年３月３０日に、日本に出願された特願２０１７－０６８１８７号に基づき優先権を主張し、その内容をここに援用する。 The present invention relates to a composite sheet for forming a protective film.
This application claims priority based on Japanese Patent Application No. 2017-068187 filed in Japan on March 30, 2017, the contents of which are incorporated herein by reference.
　近年、いわゆるフェースダウン（ｆａｃｅ　ｄｏｗｎ）方式と呼ばれる実装法を用いた半導体装置の製造が行われている。フェースダウン方式においては、回路面上にバンプ等の電極を有する半導体チップが用いられ、前記電極が基板と接合される。このため、半導体チップの回路面とは反対側の裏面は剥き出しとなることがある。 In recent years, semiconductor devices have been manufactured using a mounting method called a so-called face down method. In the face-down method, 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.
　この剥き出しとなった半導体チップの裏面には、有機材料からなる樹脂膜が保護膜として形成され、このように保護膜を形成して得られた保護膜付き半導体チップが、半導体装置に取り込まれることがある。保護膜は、ダイシング工程以降の工程において、半導体チップにおいて割れや欠けが発生する、いわゆるチッピングを防止するために利用される。 A resin film made of an organic material is formed as a protective film on the exposed back surface of the semiconductor chip, and the semiconductor chip with the protective film obtained by forming the protective film in this way is taken into the semiconductor device. There is. The protective film is used to prevent so-called chipping in which cracks and chips are generated in the semiconductor chip in the steps after the dicing step.
　このような保護膜の形成には、支持シート上に保護膜形成用フィルムを備えてなる保護膜形成用複合シートが用いられる。前記支持シートとしては、例えば、樹脂製の基材上に粘着剤層等が積層されてなる積層シートが用いられる。前記保護膜形成用複合シートは、保護膜形成用フィルムが保護膜形成能を有しているのに加え、支持シートがダイシングシートとして機能可能であり、保護膜形成用フィルムとダイシングシートとが一体化されたものとすることができる。 For the formation of such a protective film, a protective film-forming composite sheet comprising a protective film-forming film on a support sheet is used. As the support sheet, for example, a laminated sheet in which an adhesive layer or the like is laminated on a resin base material is used. In the protective film-forming composite sheet, in addition to the protective film-forming film having a protective film-forming ability, the support sheet can function as a dicing sheet, and the protective film-forming film and the dicing sheet are integrated. It can be made.
　一方で、半導体装置の製造過程では、半導体ウエハ又は半導体チップに貼付されている保護膜の支持シート側の面に、レーザー光の照射によって印字（本明細書においては、「レーザー印字」と称することがある）が行われることがある。このとき、レーザー光は、支持シート（基材）の保護膜が形成されている側とは反対側から支持シートを介して照射される。そして、印字は、支持シートを介して観測する。
　また、半導体装置の製造過程では、保護膜形成用フィルム若しくは保護膜を備えた半導体ウエハ又は半導体チップの状態を、前記支持シートとこれら保護膜形成用フィルム又は保護膜を介して赤外線カメラ等によって検査することがある。
　このように、半導体装置の製造過程では、支持シートを介して、レーザー印字や、保護膜形成用フィルム、保護膜、半導体ウエハ又は半導体チップの観測が行われることがある。そして、支持シートの構成は、これら印字や観測の精度に大きな影響を与える。 On the other hand, in the manufacturing process of a semiconductor device, printing is performed on the surface of the protective film attached to the semiconductor wafer or the semiconductor chip on the support sheet side by irradiation with laser light (referred to as “laser printing” in this specification). May be performed). At this time, the laser light is irradiated through the support sheet from the side opposite to the side where the protective film of the support sheet (base material) is formed. The printing is observed through the support sheet.
Further, in the manufacturing process of the semiconductor device, the state of the semiconductor wafer or the semiconductor chip provided with the protective film forming film or the protective film is inspected by an infrared camera or the like through the support sheet and the protective film forming film or the protective film. There are things to do.
As described above, in the manufacturing process of a semiconductor device, laser printing or observation of a protective film-forming film, a protective film, a semiconductor wafer, or a semiconductor chip may be performed through a support sheet. And the structure of a support sheet has a big influence on the precision of these printing and observation.
　例えば、これまでに、ダイシング工程後の半導体チップの検査において、光線透過率が高く、半導体チップの画像の視認性に優れた保護膜形成用複合シートが開示されている（特許文献１参照）。保護膜形成用複合シート中の支持シートを構成する基材では、ロール状に巻き取られたときに基材同士の貼り付き、いわゆるブロッキングを防止するために、通常は、少なくとも一方の表面が凹凸面となっている。そして、この凹凸面の存在により、支持シートが白濁して、保護膜を含む半導体チップを鮮明に観測することができず、半導体チップの視認性が悪いという問題点があった。これに対して、特許文献１で開示されている樹脂膜形成用複合シートでは、基材の凹凸面上に粘着剤層を積層して、支持シートのヘーズを４５％以下とすることで、支持シートを介した半導体チップの視認性を向上させている。 For example, a composite sheet for forming a protective film having high light transmittance and excellent visibility of an image of a semiconductor chip has been disclosed so far (see Patent Document 1). In the base material constituting the support sheet in the composite sheet for forming a protective film, at least one surface is usually uneven in order to prevent sticking between the base materials when being rolled up, so-called blocking. It is a surface. Then, due to the presence of the uneven surface, the support sheet becomes clouded, and the semiconductor chip including the protective film cannot be clearly observed, and there is a problem that the visibility of the semiconductor chip is poor. On the other hand, in the composite sheet for resin film formation disclosed in Patent Document 1, an adhesive layer is laminated on the concavo-convex surface of the base material, and the haze of the support sheet is 45% or less, thereby supporting The visibility of the semiconductor chip through the sheet is improved.
日本国特許第５４３２８５３号公報Japanese Patent No. 5432853
　しかし、支持シートを介した半導体チップの視認性が高くても、支持シートを介した、保護膜のレーザー印字性が優れているとは、必ずしもいえない。これは、支持シートが半導体チップの視認性向上を可能としていても、このような支持シートを介した保護膜のレーザー印字と印字の視認が、必ずしも良好に行われるとは限らないからである。そして、特許文献１で開示されている保護膜形成用複合シートも、レーザー印字性に優れているかは、定かではない。 However, even if the visibility of the semiconductor chip through the support sheet is high, it cannot necessarily be said that the laser printability of the protective film through the support sheet is excellent. This is because even if the support sheet enables the visibility of the semiconductor chip to be improved, the laser printing of the protective film and the visual recognition of the print via the support sheet are not always performed satisfactorily. And it is not certain whether the composite sheet for forming a protective film disclosed in Patent Document 1 is also excellent in laser printability.
　そこで、基材を備え、前記基材上に、粘着剤層及び保護膜形成用フィルムがこの順に積層されて構成され、前記保護膜形成用フィルムから形成された保護膜へのレーザー印字性に優れ、かつ保護膜の印字の視認性にも優れた保護膜形成用複合シートを提供する。 Therefore, a substrate is provided, and an adhesive layer and a protective film-forming film are laminated on the base material in this order, and are excellent in laser printability on a protective film formed from the protective film-forming film. In addition, a composite sheet for forming a protective film that is excellent in the visibility of printing of the protective film is provided.
　すなわち、本発明の第１の態様に係る保護膜形成用複合シートは、基材を備え、前記基材上に、粘着剤層及び保護膜形成用フィルムがこの順に積層されてなり、前記基材及び前記粘着剤層の積層物である支持シートのヘーズが４５％よりも高く、前記支持シートの透過鮮明度が１００以上である。
　上記態様に係る保護膜形成用複合シートにおいて、前記粘着剤層の前記保護膜形成用フィルムを備えている側の表面のうち、前記保護膜形成用フィルムが積層されていない領域に、治具用接着剤層を備えてもよい。
　前記保護膜形成用フィルムが、エネルギー線硬化性であってもよい。
　前記保護膜形成用フィルムが、熱硬化性であってもよい。
前記保護膜形成用フィルムが、非硬化性であってもよい。
前記粘着剤層が、エネルギー線硬化性又は非エネルギー線硬化性であってもよい。
　前記粘着剤層の厚さが３～２０μｍであってもよい。
　前記基材の一方の表面の表面粗さ（Ｒａ）が０．１１μｍ以上であり、前記表面粗さの表面に、前記粘着剤層が直接接触して積層されていてもよい。 That is, the composite sheet for forming a protective film according to the first aspect of the present invention includes a base material, and an adhesive layer and a film for forming a protective film are laminated on the base material in this order. And the haze of the support sheet which is a laminated body of the said adhesive layer is higher than 45%, and the permeation | transmission definition of the said support sheet is 100 or more.
In the composite sheet for forming a protective film according to the above aspect, the surface of the pressure-sensitive adhesive layer on the side provided with the film for forming a protective film is formed in a region where the film for forming the protective film is not laminated. An adhesive layer may be provided.
The protective film-forming film may be energy ray curable.
The protective film-forming film may be thermosetting.
The protective film-forming film may be non-curable.
The pressure-sensitive adhesive layer may be energy ray curable or non-energy ray curable.
The pressure-sensitive adhesive layer may have a thickness of 3 to 20 μm.
The surface roughness (Ra) of one surface of the base material may be 0.11 μm or more, and the pressure-sensitive adhesive layer may be laminated in direct contact with the surface having the surface roughness.
（１）基材を備え、前記基材上に、粘着剤層及び保護膜形成用フィルムがこの順に積層されてなり、前記基材及び前記粘着剤層の積層物である支持シートのヘーズが４５％よりも高く、前記支持シートの透過鮮明度が１００以上である、保護膜形成用複合シート。
（２）前記粘着剤層の前記保護膜形成用フィルムを備えている側の表面のうち、前記保護膜形成用フィルムが積層されていない領域に、治具用接着剤層を備える、（１）に記載の保護膜形成用複合シート。
（３）前記保護膜形成用フィルムが、エネルギー線硬化性である、（１）又は（２）に記載の保護膜形成用複合シート。
（４）前記保護膜形成用フィルムが、熱硬化性である、（１）又は（２）に記載の保護膜形成用複合シート。
（５）前記保護膜形成用フィルムが、非硬化性である、（１）又は（２）に記載の保護膜形成用複合シート。
（６）前記粘着剤層が、エネルギー線硬化性又は非エネルギー硬化性である、（１）～（５）のいずれか一つに記載の保護膜形成用複合シート。
（７）前記粘着剤層の厚さが３～２０μｍである、（１）～（６）のいずれか一つに記載の保護膜形成用複合シート。
（８）前記基材の一方の表面の表面粗さ（Ｒａ）が０．１１μｍ以上であり、前記表面粗さの表面に、前記粘着剤層が直接接触して積層されている、（１）～（７）のいずれか一つに記載の保護膜形成用複合シート。 (1) A base material is provided, and a pressure-sensitive adhesive layer and a protective film-forming film are laminated on the base material in this order. The composite sheet for forming a protective film, which is higher than% and the transmission sheet has a transmission clarity of 100 or more.
(2) A jig adhesive layer is provided in a region of the pressure-sensitive adhesive layer on the side provided with the protective film-forming film, in a region where the protective film-forming film is not laminated, (1) A composite sheet for forming a protective film as described in 1.
(3) The protective film-forming composite sheet according to (1) or (2), wherein the protective film-forming film is energy ray curable.
(4) The protective film-forming composite sheet according to (1) or (2), wherein the protective film-forming film is thermosetting.
(5) The protective film-forming composite sheet according to (1) or (2), wherein the protective film-forming film is non-curable.
(6) The composite sheet for forming a protective film according to any one of (1) to (5), wherein the pressure-sensitive adhesive layer is energy ray curable or non-energy curable.
(7) The composite sheet for forming a protective film according to any one of (1) to (6), wherein the pressure-sensitive adhesive layer has a thickness of 3 to 20 μm.
(8) The surface roughness (Ra) of one surface of the substrate is 0.11 μm or more, and the pressure-sensitive adhesive layer is laminated in direct contact with the surface of the surface roughness, (1) The composite sheet for forming a protective film according to any one of (7) to (7).
　上記態様によれば、基材を備え、前記基材上に、粘着剤層及び保護膜形成用フィルムがこの順に積層されて構成され、前記保護膜形成用フィルムから形成された保護膜へのレーザー印字性に優れ、かつ保護膜の印字の視認性にも優れた保護膜形成用複合シートが提供される。 According to the said aspect, it is equipped with a base material, the adhesive layer and the film for protective film formation are laminated | stacked in this order on the said base material, The laser to the protective film formed from the said film for protective film formation There is provided a composite sheet for forming a protective film that has excellent printability and excellent visibility of printed protective film.
本発明の第1実施形態に係る保護膜形成用複合シートを模式的に示す断面図である。FIG. 2 is a cross-sectional view schematically showing a protective film-forming composite sheet according to the first embodiment of the present invention. 本発明の第２実施形態に係る保護膜形成用複合シートを模式的に示す断面図である。It is sectional drawing which shows typically the composite sheet for protective film formation which concerns on 2nd Embodiment of this invention. 本発明の第３実施形態に係る保護膜形成用複合シートを模式的に示す断面図である。It is sectional drawing which shows typically the composite sheet for protective film formation which concerns on 3rd Embodiment of this invention. 本発明の第４実施形態に係る保護膜形成用複合シートを模式的に示す断面図である。It is sectional drawing which shows typically the composite sheet for protective film formation which concerns on 4th Embodiment of this invention. 本発明の第５実施形態に係る保護膜形成用複合シートを模式的に示す断面図である。It is sectional drawing which shows typically the composite sheet for protective film formation which concerns on 5th Embodiment of this invention.
◇保護膜形成用複合シート
　本実施形態の保護膜形成用複合シートは、基材を備え、前記基材上に、粘着剤層及び保護膜形成用フィルムがこの順に積層されてなる。すなわち、本実施形態の保護膜形成用複合シートは、基材、粘着剤層及び保護膜形成用フィルムがこの順に積層されてなる。また、本実施形態の保護膜形成用複合シートにおいて、前記基材及び粘着剤層の積層物である支持シートのヘーズは４５％よりも高く、前記支持シートの透過鮮明度が１００以上である。
　なお、本明細書において、「保護膜形成用フィルム」とは、半導体ウエハ又は半導体チップの裏面に貼付前のものを意味し、「保護膜」とは、保護膜形成用フィルムを半導体ウエハ又は半導体チップの裏面に貼付したものを意味する。また、保護膜形成用フィルムが硬化性を有する場合には、保護膜形成用フィルムを硬化させたものを「保護膜」と称する。
　また、本明細書においては、保護膜形成用フィルムが半導体ウエハ又は半導体チップに貼付した後であっても、支持シート及び保護膜形成用フィルムの積層構造が維持されている限り、この積層構造体を「保護膜形成用複合シート」と称する。 ◇ Composite sheet for protective film formation The composite sheet for protective film formation of this embodiment is provided with a base material, and an adhesive layer and a film for protective film formation are laminated on the base material in this order. That is, the protective film-forming composite sheet of this embodiment is formed by laminating a base material, an adhesive layer, and a protective film-forming film in this order. Moreover, in the composite sheet for protective film formation of this embodiment, the haze of the support sheet which is a laminate of the base material and the pressure-sensitive adhesive layer is higher than 45%, and the transparent clarity of the support sheet is 100 or more.
In this specification, the “protective film forming film” means a film before being attached to the back surface of a semiconductor wafer or semiconductor chip, and the “protective film” means a protective film forming film that is a semiconductor wafer or semiconductor. It means the one attached to the back of the chip. In addition, when the protective film-forming film has curability, a film obtained by curing the protective film-forming film is referred to as a “protective film”.
Further, in the present specification, even if the protective film-forming film is attached to a semiconductor wafer or a semiconductor chip, as long as the laminated structure of the support sheet and the protective film-forming film is maintained, this laminated structure Is referred to as “composite sheet for forming a protective film”.
　前記保護膜形成用フィルムは、半導体ウエハ又は半導体チップの裏面（電極形成面とは反対側の面）を保護するための保護膜として活用される。そして、支持シートのヘーズが４５％よりも高く、且つ透過鮮明度が１００以上であることにより、本実施形態の保護膜形成用フィルムは、レーザー印字性が良好であり、且つ保護膜の印字の視認性を良好にすることができる。より具体的には、半導体ウエハ又は半導体チップの裏面に前記保護膜形成用複合シートを貼付後、半導体ウエハ又は半導体チップに貼付されている保護膜の支持シート側の面に、レーザー印字を行う。この際に、レーザー光は、支持シート（基材）の保護膜が形成されている側とは反対側から支持シートを介して照射される。そして、印字は、支持シートを介して観測する。このとき、支持シートの透過鮮明度が１００以上であることにより、支持シートの外表面における光散乱が抑制され、レーザー印字の視認性を向上させることができる。 The protective film-forming film is used as a protective film for protecting the back surface of the semiconductor wafer or semiconductor chip (the surface opposite to the electrode forming surface). And since the haze of the support sheet is higher than 45% and the transmission sharpness is 100 or more, the protective film-forming film of this embodiment has good laser printability, and printing of the protective film. Visibility can be improved. More specifically, after the protective film-forming composite sheet is attached to the back surface of the semiconductor wafer or semiconductor chip, laser printing is performed on the support sheet side surface of the protective film attached to the semiconductor wafer or semiconductor chip. At this time, the laser light is irradiated through the support sheet from the side opposite to the side on which the protective film of the support sheet (base material) is formed. The printing is observed through the support sheet. At this time, when the transparency of the support sheet is 100 or more, light scattering on the outer surface of the support sheet is suppressed, and the visibility of laser printing can be improved.
また、従来では、レーザー印字を太くするためには、高出力でレーザー印字をする必要があり、製造コストがかかるという課題があった。また、高出力で印字する場合には、支持シートを介して照射すると、保護膜と支持シートとの間にガスだまりが発生する虞があった。また、支持シートの粘着力を高めることで、ガスだまりの発生は回避できるが、一方で、ピックアップ適性が損なわれるという課題があった。そのため、支持シートを剥離後に保護膜に直接レーザー印字する必要があった。これに対し、本実施形態の保護膜形成用複合シートでは、ヘーズが４５％よりも高いことで、支持シート内部においてレーザー光が適度に散乱される。そのため、レーザー印字を効果的に太くすることができ、レーザー印字の視認性を向上させることができる。また、レーザー出力を大きくする必要がないため、ガスだまりの発生を抑制でき、支持シートと保護膜とが接着した状態のままレーザー印字を行うことができる。また、支持シートの粘着力も適度であるため、ピックアップ適性も良好である。 Conventionally, in order to increase the thickness of laser printing, it is necessary to perform laser printing at a high output, resulting in a problem of high manufacturing costs. Further, when printing is performed at a high output, there is a possibility that gas accumulation occurs between the protective film and the support sheet when irradiation is performed through the support sheet. Further, by increasing the adhesive strength of the support sheet, it is possible to avoid the accumulation of gas, but there is a problem that the suitability for pickup is impaired. Therefore, it was necessary to perform laser printing directly on the protective film after peeling off the support sheet. On the other hand, in the composite sheet for forming a protective film according to this embodiment, the haze is higher than 45%, so that the laser light is appropriately scattered inside the support sheet. Therefore, the laser printing can be effectively thickened, and the visibility of the laser printing can be improved. Further, since there is no need to increase the laser output, it is possible to suppress the generation of gas accumulation, and it is possible to perform laser printing with the support sheet and the protective film adhered. In addition, since the adhesive strength of the support sheet is appropriate, the pickup suitability is also good.
さらに、従来では、治具用粘着剤層が無色透明である保護膜形成用複合シート、又は治具用粘着剤層を有さない構成の保護膜形成用複合シートである場合、半導体ウエハ又は半導体チップの裏面に前記保護膜形成用複合シートをマウンタで貼付時に、支持シートが４５％以下等の低ヘーズであり、マウンタに搭載された光学センサーを用いたアライメント（以下、「テープ先端の位置調整」と称する。）ができなかった。これに対し、本実施形態の保護膜形成用複合シートでは、ヘーズが４５％よりも高いことで、マウンタに搭載された光センサーにより検知され、テープ先端の位置調整することができる。 Furthermore, conventionally, when the adhesive layer for jigs is a colorless and transparent protective film-forming composite sheet, or a protective film-forming composite sheet having no jig adhesive layer, a semiconductor wafer or semiconductor When the composite sheet for forming a protective film is attached to the back surface of the chip with a mounter, the support sheet has a low haze such as 45% or less, and alignment using an optical sensor mounted on the mounter (hereinafter referred to as “position adjustment of the tape tip” ") Was not possible. On the other hand, in the composite sheet for forming a protective film of the present embodiment, the haze is higher than 45%, so that the position of the tip of the tape can be adjusted by being detected by an optical sensor mounted on the mounter.
　本実施形態の保護膜形成用複合シートの使用対象である半導体ウエハ又は半導体チップの厚さは、特に限定されないが、本実施形態における効果がより顕著に得られることから、３０μｍ以上１０００μｍ以下であることが好ましく、１００μｍ以上３００μｍ以下であることがより好ましい。
　以下、本実施形態の構成について、詳細に説明する。 The thickness of the semiconductor wafer or semiconductor chip that is the target of use of the composite sheet for forming a protective film of the present embodiment is not particularly limited, but is 30 μm or more and 1000 μm or less because the effect of the present embodiment can be obtained more significantly. It is preferably 100 μm or more and 300 μm or less.
Hereinafter, the configuration of the present embodiment will be described in detail.
◎支持シート
　前記支持シートは、基材を備え、前記基材上に粘着剤層を備えるものであり、２層以上の複数層からなるものである。これら複数層の構成材料及び厚さは、互いに同一でも異なっていてもよく、これら複数層の組み合わせは、本実施形態における効果を損なわない限り、特に限定されない。
　なお、本明細書においては、支持シートの場合に限らず、「複数層が互いに同一でも異なっていてもよい」とは、「すべての層が同一であってもよいし、すべての層が異なっていてもよく、一部の層のみが同一であってもよい」ことを意味し、さらに「複数層が互いに異なる」とは、「各層の構成材料及び厚さの少なくとも一方が互いに異なる」ことを意味する。 Support sheet The support sheet includes a base material, and includes a pressure-sensitive adhesive layer on the base material, and is composed of two or more layers. The constituent materials and thicknesses of these multiple layers may be the same or different from each other, and the combination of these multiple layers is not particularly limited as long as the effects in the present embodiment are not impaired.
In the present specification, not only in the case of a support sheet, “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 that“ at least one of the constituent materials and thickness of each layer is different from each other ”. Means.
　好ましい支持シートとしては、例えば、基材上に粘着剤層が直接接触して積層されてなるもの、基材上に中間層を介して粘着剤層が積層されてなるもの等が挙げられる。より好ましい支持シートとしては、基材上に粘着剤層が直接接触して積層されてなるものが挙げられる。 Preferred examples of the support sheet include those in which a pressure-sensitive adhesive layer is directly contacted and laminated on a substrate, and those in which a pressure-sensitive adhesive layer is laminated on a substrate via an intermediate layer. More preferable support sheets include those in which an adhesive layer is laminated in direct contact with a substrate.
　本実施形態の保護膜形成用複合シートの例を、このような支持シートの種類ごとに、以下、図面を参照しながら説明する。なお、以下の説明で用いる図は、本実施形態の特徴を分かり易くするために、便宜上、要部となる部分を拡大して示している場合があり、各構成要素の寸法比率等が実際と同じであるとは限らない。 An example of the composite sheet for forming a protective film of the present embodiment will be described below for each kind of support sheet with reference to the drawings. Note that the drawings used in the following description may show the main part in an enlarged manner for the sake of convenience in order to make the features of the present embodiment easier to understand. It is not always the same.
　図１は、本発明の第１実施形態に係る保護膜形成用複合シートを模式的に示す断面図である。
　ここに示す保護膜形成用複合シート１Ａは、基材１１上に粘着剤層１２を備え、粘着剤層１２上に保護膜形成用フィルム１３を備えてなるものである。支持シート１０は、基材１１及び粘着剤層１２の積層体である。保護膜形成用複合シート１Ａは、換言すると、支持シート１０の一方の表面１０ａ上に保護膜形成用フィルム１３が積層された構成を有する。また、保護膜形成用複合シート１Ａは、さらに保護膜形成用フィルム１３の表面１３ａの全面（上面及び側面）と、粘着剤層の表面１２ａ（上面）とに、剥離フィルム１５が積層されている。
　なお、本明細書において、「剥離フィルム」は、剥がれる機能を有するフィルムであって、具体的には、半導体ウエハへの貼付前の保護膜形成用フィルムを保護するために、保護膜形成用フィルムの表面に貼り付けてあるフィルムをいい、作業時にはこれを剥がして用いられるものである。 FIG. 1 is a cross-sectional view schematically showing a protective film-forming composite sheet according to the first embodiment of 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. In other words, the protective film forming composite sheet 1 </ b> A has a configuration in which the protective film forming film 13 is laminated on one surface 10 a of the support sheet 10. Further, in the protective film-forming composite sheet 1A, a release film 15 is further laminated on the entire surface (upper surface and side surface) of the surface 13a of the protective film-forming film 13 and the surface 12a (upper surface) of the pressure-sensitive adhesive layer. .
In the present specification, the “peeling film” is a film having a peeling function, and specifically, a protective film forming film for protecting the protective film forming film before being attached to a semiconductor wafer. The film is affixed to the surface of the film and is used by peeling it off during work.
　保護膜形成用複合シート１Ａにおいて、基材１１及び粘着剤層１２の積層物である支持シート１０のヘーズは４５％よりも高く、前記支持シート１０の透過鮮明度が１００以上である。 In the protective film-forming composite sheet 1A, the haze of the support sheet 10 that is a laminate of the base material 11 and the pressure-sensitive adhesive layer 12 is higher than 45%, and the transmission clarity of the support sheet 10 is 100 or more.
　図１に示す保護膜形成用複合シート１Ａは、剥離フィルム１５が取り除かれた状態で、保護膜形成用フィルム１３の表面１３ａのうち、中央側の一部の領域に半導体ウエハ（図示略）の裏面が貼付される。さらに、保護膜形成用フィルム１３の周縁部近傍の領域が、リングフレーム等の治具に貼付されて、使用される。 The protective film-forming composite sheet 1A shown in FIG. 1 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 side is affixed. Furthermore, the area | region of the peripheral part vicinity of the film 13 for protective film formation is affixed and used for jigs, such as a ring frame.
　図２は、本発明の第２実施形態に係る保護膜形成用複合シートを模式的に示す断面図である。なお、図２以降の図において、既に説明済みの図に示すものと同じ構成要素には、その説明済みの図の場合と同じ符号を付し、その詳細な説明は省略する。 FIG. 2 is a cross-sectional view schematically showing a composite sheet for forming a protective film according to a second embodiment of the present invention. In FIG. 2 and subsequent figures, 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.
　ここに示す保護膜形成用複合シート１Ｂは、治具用接着剤層１６を備えている点以外は、図１に示す保護膜形成用複合シート１Ａと同じものである。すなわち、保護膜形成用複合シート１Ｂにおいては、基材１１の一方の表面１１ａに粘着剤層１２が積層されている。粘着剤層１２の表面１２ａの中央側の一部の領域、すなわち、半導体ウエハ貼付領域に保護膜形成用フィルム１３が積層されている。粘着剤層１２の表面１２ａの一部、すなわち、周縁部近傍の領域に治具用接着剤層１６が積層されている。保護膜形成用フィルム１３の表面１３ａ（上面）と、治具用接着剤層１６の表面１６ａ（上面）とに、剥離フィルム１５が積層されている。 The protective film-forming composite sheet 1B shown here is the same as the protective film-forming composite sheet 1A shown in FIG. 1 except that it is provided with a jig adhesive layer 16. That is, in the protective film-forming composite sheet 1 </ b> B, the pressure-sensitive adhesive layer 12 is laminated on one surface 11 a of the substrate 11. The protective film-forming film 13 is laminated on a partial region on the center side of the surface 12a of the pressure-sensitive adhesive layer 12, that is, a semiconductor wafer pasting region. A jig adhesive layer 16 is laminated on a part of the surface 12a of the pressure-sensitive adhesive layer 12, that is, in a region near the peripheral edge. A release film 15 is laminated on the surface 13 a (upper surface) of the protective film forming film 13 and the surface 16 a (upper surface) of the jig adhesive layer 16.
　保護膜形成用複合シート１Ｂにおいて、基材１１及び粘着剤層１２の積層物である支持シート１０のヘーズは４５％よりも高く、前記支持シート１０の透過鮮明度が１００以上である。 In the protective film-forming composite sheet 1B, the haze of the support sheet 10, which is a laminate of the base material 11 and the pressure-sensitive adhesive layer 12, is higher than 45%, and the transmission clarity of the support sheet 10 is 100 or more.
　治具用接着剤層１６は、例えば、接着剤成分を含有する単層構造のものであってもよいし、芯材となるシートの両面に接着剤成分を含有する層が積層された複数層構造のものであってもよい。 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.
　図２に示す保護膜形成用複合シート１Ｂは、剥離フィルム１５が取り除かれた状態で、保護膜形成用フィルム１３の表面１３ａに半導体ウエハ（図示略）の裏面が貼付される。さらに、治具用接着剤層１６の表面１６ａのうち上面が、リングフレーム等の治具に貼付されて、使用される。 2, the back surface of the semiconductor wafer (not shown) is attached to the front surface 13a of the protective film forming film 13 in a state where the release film 15 is removed. Further, the upper surface of the surface 16a of the jig adhesive layer 16 is used by being attached to a jig such as a ring frame.
　図３は、本発明の第３実施形態に係る保護膜形成用複合シートを模式的に示す断面図である。
　ここに示す保護膜形成用複合シート１Ｃは、粘着剤層１２と保護膜形成用フィルム１３との間に中間層１７を備えている点以外は、図１に示す保護膜形成用複合シート１Ａと同じものである。保護膜形成用複合シート１Ｃにおいては、支持シート１０は、基材１１、粘着剤層１２、及び中間層１７の積層体である。保護膜形成用複合シート１Ｃは、換言すると、支持シート１０の一方の表面１０ａ（１７ａ）上に保護膜形成用フィルム１３が積層された構成を有する。また、保護膜形成用複合シート１Ｃは、さらに保護膜形成用フィルム１３の表面１３ａの全面（上面及び側面）と、中間層１７ａの表面（側面）と、粘着剤層の表面１２ａ（上面）とに、剥離フィルム１５が積層されている。 FIG. 3 is a cross-sectional view schematically showing a protective film-forming composite sheet according to the third embodiment of the present invention.
The protective sheet-forming composite sheet 1C shown here is the same as the protective film-forming composite sheet 1A shown in FIG. The same thing. In the protective film-forming composite sheet 1 </ b> C, the support sheet 10 is a laminate of the base material 11, the pressure-sensitive adhesive layer 12, and the intermediate layer 17. In other words, the protective film-forming composite sheet 1 </ b> C has a configuration in which the protective film-forming film 13 is laminated on one surface 10 a (17 a) of the support sheet 10. The protective film forming composite sheet 1C further includes the entire surface 13a of the protective film forming film 13 (upper surface and side surface), the surface of the intermediate layer 17a (side surface), and the surface 12a (upper surface) of the adhesive layer. Further, a release film 15 is laminated.
　保護膜形成用複合シート１Ｃにおいて、基材１１、粘着剤層１２、及び中間層１７の積層物である支持シート１０のヘーズは４５％よりも高く、前記支持シート１０の透過鮮明度が１００以上である。 In the protective film-forming composite sheet 1 </ b> C, the haze of the support sheet 10 that is a laminate of the base material 11, the pressure-sensitive adhesive layer 12, and the intermediate layer 17 is higher than 45%, and the transparent clarity of the support sheet 10 is 100 or more. It is.
　図３に示す保護膜形成用複合シート１Ｃは、剥離フィルム１５が取り除かれた状態で、保護膜形成用フィルム１３の表面１３ａのうち、中央側の一部の領域に半導体ウエハ（図示略）の裏面が貼付される。さらに、保護膜形成用フィルム１３の周縁部近傍の領域が、リングフレーム等の治具に貼付されて、使用される。 The protective sheet-forming composite sheet 1C 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 side is affixed. Furthermore, the area | region of the peripheral part vicinity of the film 13 for protective film formation is affixed and used for jigs, such as a ring frame.
　図４は、本発明の第４実施形態に係る保護膜形成用複合シートを模式的に示す断面図である。
　ここに示す保護膜形成用複合シート１Ｄは、基材１１と粘着剤層１２との間に中間層１７を備えている点以外は、図１に示す保護膜形成用複合シート１Ａと同じものである。保護膜形成用複合シート１Ｄにおいては、支持シート１０は、基材１１、中間層１７、及び粘着剤層１２の積層体である。保護膜形成用複合シート１Ｄは、換言すると、支持シート１０の一方の表面１０ａ（１２ａ）上に保護膜形成用フィルム１３が積層された構成を有する。また、保護膜形成用複合シート１Ｄは、さらに保護膜形成用フィルム１３の表面１３ａの全面（上面及び側面）と、粘着剤層の表面１２ａ（上面）とに、剥離フィルム１５が積層されている。 FIG. 4 is a cross-sectional view schematically showing a protective film-forming composite sheet according to the fourth embodiment of the present invention.
The protective sheet-forming composite sheet 1D shown here is the same as the protective film-forming composite sheet 1A shown in FIG. 1 except that the intermediate layer 17 is provided between the base material 11 and the adhesive layer 12. is there. In the protective film-forming composite sheet 1D, the support sheet 10 is a laminate of the base material 11, the intermediate layer 17, and the pressure-sensitive adhesive layer 12. In other words, the protective film-forming composite sheet 1 </ b> D has a configuration in which the protective film-forming film 13 is laminated on one surface 10 a (12 a) of the support sheet 10. Further, in the composite sheet 1D for forming a protective film, a release film 15 is laminated on the entire surface (upper surface and side surface) of the surface 13a of the protective film forming film 13 and the surface 12a (upper surface) of the pressure-sensitive adhesive layer. .
　保護膜形成用複合シート１Ｄにおいて、基材１１、中間層１７、及び粘着剤層１２の積層物である支持シート１０のヘーズは４５％よりも高く、前記支持シート１０の透過鮮明度が１００以上である。 In the protective film-forming composite sheet 1D, the haze of the support sheet 10 which is a laminate of the base material 11, the intermediate layer 17, and the pressure-sensitive adhesive layer 12 is higher than 45%, and the transparent clarity of the support sheet 10 is 100 or more. It is.
　図４に示す保護膜形成用複合シート１Ｄは、剥離フィルム１５が取り除かれた状態で、保護膜形成用フィルム１３の表面１３ａのうち、中央側の一部の領域に半導体ウエハ（図示略）の裏面が貼付される。さらに、保護膜形成用フィルム１３の周縁部近傍の領域が、リングフレーム等の治具に貼付されて、使用される。 The protective film-forming composite sheet 1D shown in FIG. 4 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 side is affixed. Furthermore, the area | region of the peripheral part vicinity of the film 13 for protective film formation is affixed and used for jigs, such as a ring frame.
　図５は、本発明の第５実施形態に係る保護膜形成用複合シートを模式的に示す断面図である。
　ここに示す保護膜形成用複合シート１Ｅは、粘着剤層の表面の全面に保護膜形成用フィルムが積層されている点以外は、図２に示す保護膜形成用複合シート１Ｂと同じものである。すなわち、保護膜形成用複合シート１Ｅにおいては、基材１１の一方の表面１１ａに粘着剤層１２が積層されている。粘着剤層１２の表面１２ａの全面に保護膜形成用フィルム１３が積層されている。保護膜形成用フィルム１３の表面１３ａの一部、すなわち、周縁部近傍の領域に治具用接着剤層１６が積層されている。保護膜形成用フィルム１３の表面１３ａ（上面）と、治具用接着剤層１６の表面１６ａ（上面及び側面）とに、剥離フィルム１５が積層されている。 FIG. 5 is a cross-sectional view schematically showing a protective film-forming composite sheet according to the fifth embodiment of 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. 2 except that the protective film-forming film is laminated on the entire surface of the pressure-sensitive adhesive layer. . That is, in the protective film forming composite sheet 1 </ b> E, the pressure-sensitive adhesive layer 12 is laminated on one surface 11 a of the substrate 11. A protective film forming film 13 is laminated on the entire surface 12 a of the pressure-sensitive adhesive layer 12. A jig adhesive layer 16 is laminated on a part of the surface 13a of the protective film-forming film 13, that is, in the vicinity of the peripheral edge. A release film 15 is laminated on the surface 13a (upper surface) of the protective film forming film 13 and the surface 16a (upper surface and side surfaces) of the jig adhesive layer 16.
　保護膜形成用複合シート１Ｅにおいて、基材１１及び粘着剤層１２の積層物である支持シート１０のヘーズは４５％よりも高く、前記支持シート１０の透過鮮明度が１００以上である。 In the protective film-forming composite sheet 1E, the haze of the support sheet 10 which is a laminate of the base material 11 and the pressure-sensitive adhesive layer 12 is higher than 45%, and the transmission clearness of the support sheet 10 is 100 or more.
　図５に示す保護膜形成用複合シート１Ｅは、剥離フィルム１５が取り除かれた状態で、保護膜形成用フィルム１３の表面１３ａに半導体ウエハ（図示略）の裏面が貼付される。さらに、治具用接着剤層１６の表面１６ａのうち上面が、リングフレーム等の治具に貼付されて、使用される。 In the protective film-forming composite sheet 1E shown in FIG. 5, the back surface of the semiconductor wafer (not shown) is attached to the front surface 13a of the protective film-forming film 13 with the release film 15 removed. Further, the upper surface of the surface 16a of the jig adhesive layer 16 is used by being attached to a jig such as a ring frame.
　このように、本実施形態の保護膜形成用複合シートは、支持シート及び保護膜形成用フィルムがどのような形態であっても、治具用接着剤層を備えたものであってもよい。ただし、通常は、図２及び５に示すように、治具用接着剤層を備えた本実施形態の保護膜形成用複合シートとしては、支持シート１０又は保護膜形成用フィルム１３上に治具用接着剤層１６を備えたものが好ましい。 Thus, the protective sheet-forming composite sheet of the present embodiment may have any form of the support sheet and the protective film-forming film, or may be provided with an adhesive layer for jigs. However, normally, as shown in FIGS. 2 and 5, as the protective film forming composite sheet of the present embodiment having the jig adhesive layer, the jig is placed on the support sheet 10 or the protective film forming film 13. What provided the adhesive layer 16 for use is preferable.
　本実施形態の保護膜形成用複合シートは、図１～５に示すものに限定されず、本実施形態における効果を損なわない範囲内において、図１～５に示すものの一部の構成が変更又は削除されたものや、これまでに説明したものにさらに他の構成が追加されたものであってもよい。 The composite sheet for forming a protective film of the present embodiment is not limited to the one shown in FIGS. 1 to 5, and a part of the configuration shown in FIGS. 1 to 5 is changed or changed within a range not impairing the effect of the present embodiment. What has been deleted, or what has been added so far, may be added.
　例えば、図２及び図５に示す保護膜形成用複合シートにおいては、粘着剤層１２と保護膜形成用フィルム１３との間に、中間層１７が設けられていてもよい。すなわち、本実施形態の保護膜形成用複合シートにおいて、支持シート１０は、基材１１、粘着剤層１２、及び中間層１７がこの順に積層されてなるものでもよい。ここで中間層１７とは、図３及び４に示す保護膜形成用複合シートにおいて設けられていてもよい中間層１７と同じものである。中間層１７としては、目的に応じて任意のものを選択できる。
　また、例えば、図２及び図５に示す保護膜形成用複合シートにおいては、基材１１と粘着剤層１２との間に中間層１７が設けられていてもよい。すなわち、本実施形態の保護膜形成用複合シートにおいて、支持シート１０は、基材１１、中間層１７、及び粘着剤層１２がこの順に積層されてなるものでもよい。ここで中間層１７とは、図３及び４に示す保護膜形成用複合シートにおいて設けられていてもよい中間層１７と同じものである。中間層１７としては、目的に応じて任意のものを選択できる。
　また、図１～５に示す保護膜形成用複合シートにおいては、中間層１７は図３及び４に示す箇所以外の、他の箇所に設けられていてもよい。
　また、図１～５に示す保護膜形成用複合シートは、前記中間層１７以外の層が、任意の箇所に設けられていてもよい。
　また、図３及び４に示す保護膜形成用複合シートにおいては、治具用接着剤層１６が設けられていてもよい。
　また、本実施形態の保護膜形成用複合シートにおいては、剥離フィルム１５と、この剥離フィルム１５と直接接触している層との間に、一部隙間が生じていてもよい。
　また、本実施形態の保護膜形成用複合シートにおいては、各層の大きさや形状は、目的に応じて任意に調節できる。 For example, in the protective film-forming composite sheet shown in FIGS. 2 and 5, an intermediate layer 17 may be provided between the pressure-sensitive adhesive layer 12 and the protective film-forming film 13. That is, in the composite sheet for forming a protective film of the present embodiment, the support sheet 10 may be formed by laminating the base material 11, the adhesive layer 12, and the intermediate layer 17 in this order. Here, the intermediate layer 17 is the same as the intermediate layer 17 that may be provided in the protective film-forming composite sheet shown in FIGS. Any layer can be selected as the intermediate layer 17 according to the purpose.
For example, in the protective film-forming composite sheet shown in FIGS. 2 and 5, an intermediate layer 17 may be provided between the base material 11 and the pressure-sensitive adhesive layer 12. That is, in the composite sheet for forming a protective film of the present embodiment, the support sheet 10 may be formed by laminating the base material 11, the intermediate layer 17, and the pressure-sensitive adhesive layer 12 in this order. Here, the intermediate layer 17 is the same as the intermediate layer 17 that may be provided in the protective film-forming composite sheet shown in FIGS. Any layer can be selected as the intermediate layer 17 according to the purpose.
Further, in the composite sheet for forming a protective film shown in FIGS. 1 to 5, the intermediate layer 17 may be provided in other places other than the places shown in FIGS.
Further, in the composite sheet for forming a protective film shown in FIGS. 1 to 5, layers other than the intermediate layer 17 may be provided at an arbitrary position.
Moreover, in the composite sheet for protective film formation shown to FIG. 3 and 4, the adhesive layer 16 for jig | tools may be provided.
Further, in the protective film-forming composite sheet of the present embodiment, a part of the gap may be formed between the release film 15 and the layer in direct contact with the release film 15.
Moreover, in the composite sheet for protective film formation of this embodiment, the magnitude | size and shape of each layer can be arbitrarily adjusted according to the objective.
　本実施形態の保護膜形成用複合シートにおいては、支持シートは、不透明であってもよく、目的に応じて着色されていてもよい。
具体的には、支持シートの透過鮮明度は、１００以上、好ましくは１５０以上、より好ましくは２００以上４５０以下、さらに好ましくは３００以上４３０以下である。
　支持シートの透過鮮明度が上記範囲であることにより、支持シートの外表面における光散乱が抑制され、レーザー印字の視認性を向上させることができる。
　なお、支持シートの透過鮮明度は、スガ試験機社製の写像性測定器「ＩＣＭ－１０Ｐ」等を使用し、ＪＩＳ　Ｋ　７３７４－２００７に準拠して測定することができる。
　また、支持シートの透過鮮明度を上記範囲とするために、例えば、支持シートの外表面の表面粗さを調整すればよい。 In the protective sheet-forming composite sheet of the present embodiment, the support sheet may be opaque or colored according to the purpose.
Specifically, the transparent transparency of the support sheet is 100 or more, preferably 150 or more, more preferably 200 or more and 450 or less, and further preferably 300 or more and 430 or less.
When the transparency of the support sheet is in the above range, light scattering on the outer surface of the support sheet is suppressed, and the visibility of laser printing can be improved.
The transparency of the support sheet can be measured in accordance with JIS K 7374-2007 using an image clarity measuring device “ICM-10P” manufactured by Suga Test Instruments Co., Ltd.
Moreover, what is necessary is just to adjust the surface roughness of the outer surface of a support sheet, for example, in order to make the transmission clarity of a support sheet into the said range.
　また、支持シートのヘーズが４５％より高く、好ましくは４６％以上、より好ましくは４７％以上９０％以下、さらに好ましくは５０％以上８５％以下である。
従来では、レーザー印字を太くするためには、レーザー出力を大きくする必要があり、支持シートを介して照射すると、保護膜と支持シートとの間にガスだまりが発生する。そのため、支持シートを剥離後に保護膜に直接レーザー印字する必要があった。これに対し、本実施形態の保護膜形成用複合シートでは、支持シートのヘーズが上記範囲であることにより、支持シート内部においてレーザー光が適度に散乱される。そのため、レーザー印字を効果的に太くすることができ、レーザー印字の視認性を向上させることができる。また、レーザー出力を大きくする必要がない。そのため、ガスだまりの発生を抑制でき、支持シートと保護膜とが接着した状態のままレーザー印字を行うことができる。 Further, the haze of the support sheet is higher than 45%, preferably 46% or more, more preferably 47% or more and 90% or less, and further preferably 50% or more and 85% or less.
Conventionally, in order to make laser printing thick, it is necessary to increase the laser output. When irradiation is performed through a support sheet, a gas pool is generated between the protective film and the support sheet. Therefore, it was necessary to perform laser printing directly on the protective film after peeling off the support sheet. In contrast, in the protective film-forming composite sheet of the present embodiment, the laser light is appropriately scattered inside the support sheet because the haze of the support sheet is in the above range. Therefore, the laser printing can be effectively thickened, and the visibility of the laser printing can be improved. Further, it is not necessary to increase the laser output. Therefore, generation of gas pools can be suppressed, and laser printing can be performed with the support sheet and the protective film adhered.
さらに、従来では、治具用粘着剤層が無色透明である保護膜形成用複合シート、又は治具用粘着剤層を有さない構成の保護膜形成用複合シートである場合、半導体ウエハ又は半導体チップの裏面に前記保護膜形成用複合シートをマウンタで貼付時に、支持シートが４５％以下等の低ヘーズであり、マウンタに搭載された光学センサーを用いたアライメント（以下、「テープ先端の位置調整」と称する。）ができなかった。これに対し、本実施形態の保護膜形成用複合シートでは、支持シートのヘーズが上記範囲であることにより、マウンタに搭載された光センサーにより検知され、テープ先端の位置調整することができる。
なお、支持シートのヘーズは、日本電色工業社製のＮＤＨ－５０００等を使用し、ＪＩＳ　Ｋ　７１３６－２０００に準拠して測定することができる。
また、支持シートのヘーズを上記範囲とするために、例えば、基材又は中間層に充填材又は着色剤を含有させて調整すればよい。或いは、例えば、粘着剤層の硬さを変えて基材又は中間層と粘着剤層との間に隙間を形成させ、調整すればよい。 Furthermore, conventionally, when the adhesive layer for jigs is a colorless and transparent protective film-forming composite sheet, or a protective film-forming composite sheet having no jig adhesive layer, a semiconductor wafer or semiconductor When the composite sheet for forming a protective film is attached to the back surface of the chip with a mounter, the support sheet has a low haze such as 45% or less, and alignment using an optical sensor mounted on the mounter (hereinafter referred to as “position adjustment of the tape tip”). ") Was not possible. On the other hand, in the composite sheet for forming a protective film of the present embodiment, the haze of the support sheet is in the above range, so that it can be detected by the optical sensor mounted on the mounter and the position of the tip of the tape can be adjusted.
The haze of the support sheet can be measured using NDH-5000 manufactured by Nippon Denshoku Industries Co., Ltd. according to JIS K 7136-2000.
Moreover, what is necessary is just to make a base material or an intermediate | middle layer contain a filler or a coloring agent in order to make the haze of a support sheet into the said range, for example. Alternatively, for example, it may be adjusted by changing the hardness of the pressure-sensitive adhesive layer to form a gap between the base material or the intermediate layer and the pressure-sensitive adhesive layer.
また、保護膜形成用フィルムがエネルギー線硬化性を有する場合は、支持シートはエネルギー線を透過させるものが好ましい。
　例えば、支持シートにおいて、波長３７５ｎｍの光の積分球を使用して測定した透過率は３０％以上であることが好ましく、５０％以上であることがより好ましく、７０％以上であることが特に好ましい。前記光の透過率がこのような範囲であることで、支持シートを介して保護膜形成用フィルムにエネルギー線（紫外線）を照射したときに、保護膜形成用フィルムの硬化度がより向上する。
　一方、支持シートにおいて、波長３７５ｎｍの光の透過率の上限値は特に限定されないが、例えば、９５％とすることが可能である。 Moreover, when the film for protective film formation has energy-beam sclerosis | hardenability, what a transmission sheet permeate | transmits an energy beam is preferable.
For example, in the support sheet, the transmittance measured using an integrating sphere of light having a wavelength of 375 nm is preferably 30% or more, more preferably 50% or more, and particularly preferably 70% or more. . When the light transmittance is in such a range, when the protective film forming film is irradiated with energy rays (ultraviolet rays) through the support sheet, the degree of curing of the protective film forming film is further improved.
On the other hand, in the support sheet, 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.
なお、本明細書において、「エネルギー線硬化性」とは、エネルギー線を照射することにより硬化する性質を意味する。「非エネルギー線硬化性」とは、エネルギー線を照射しても硬化しない性質を意味し、熱硬化性及び非硬化性を包含する。「熱硬化性」とは、加熱することにより硬化する性質を意味する。「非硬化性」とは、加熱又はエネルギー線の照射等により硬化しない性質を意味する。
本明細書において、「エネルギー線」とは、電磁波又は荷電粒子線の中でエネルギー量子を有するものを意味し、その例として、紫外線、放射線、電子線等が挙げられる。
紫外線は、例えば、紫外線源として高圧水銀ランプ、ヒュージョンＨランプ、キセノンランプ、ブラックライト又はＬＥＤランプ等を用いることで照射できる。電子線は、電子線加速器等によって発生させたものを照射できる。
　次に、支持シートを構成する各層について、さらに詳細に説明する。 In the present specification, “energy beam curability” means a property of being cured by irradiation with energy rays. “Non-energy radiation curable” means a property that does not cure even when irradiated with energy rays, and includes thermosetting and non-curing properties. “Thermosetting” means a property of being cured by heating. “Non-curing” means the property of not being cured by heating or irradiation with energy rays.
In the present specification, “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.
Next, each layer which comprises a support sheet is demonstrated in detail.
○基材
　前記基材は、シート状又はフィルム状であり、その構成材料としては、例えば、各種樹脂が挙げられる。
　前記樹脂としては、例えば、低密度ポリエチレン（ＬＤＰＥ）、直鎖低密度ポリエチレン（ＬＬＤＰＥ）、高密度ポリエチレン（ＨＤＰＥ）等のポリエチレン；ポリプロピレン、ポリブテン、ポリブタジエン、ポリメチルペンテン、ノルボルネン樹脂等のポリエチレン以外のポリオレフィン；エチレン－酢酸ビニル共重合体、エチレン－（メタ）アクリル酸共重合体、エチレン－（メタ）アクリル酸エステル共重合体、エチレン－ノルボルネン共重合体等のエチレン系共重合体（モノマーとしてエチレンを用いて得られた共重合体）；ポリ塩化ビニル、塩化ビニル共重合体等の塩化ビニル系樹脂（モノマーとして塩化ビニルを用いて得られた樹脂）；ポリスチレン；ポリシクロオレフィン；ポリエチレンテレフタレート、ポリエチレンナフタレート、ポリブチレンテレフタレート、ポリエチレンイソフタレート、ポリエチレン－２，６－ナフタレンジカルボキシレート、すべての構成単位が芳香族環式基を有する全芳香族ポリエステル等のポリエステル；２種以上の前記ポリエステルの共重合体；ポリ（メタ）アクリル酸エステル；ポリウレタン；ポリウレタンアクリレート；ポリイミド；ポリアミド；ポリカーボネート；フッ素樹脂；ポリアセタール；変性ポリフェニレンオキシド；ポリフェニレンスルフィド；ポリスルホン；ポリエーテルケトン等が挙げられる。
　また、前記樹脂としては、例えば、前記ポリエステルとそれ以外の樹脂との混合物等のポリマーアロイも挙げられる。前記ポリエステルとそれ以外の樹脂とのポリマーアロイは、ポリエステル以外の樹脂の量が比較的少量であるものが好ましい。
　また、前記樹脂としては、例えば、ここまでに例示した前記樹脂の１種又は２種以上が架橋した架橋樹脂；ここまでに例示した前記樹脂の１種又は２種以上を用いたアイオノマー等の変性樹脂も挙げられる。 -Base material The base material is in the form of a sheet or film, and examples of the constituent material include various resins.
Examples of 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; ethylene-based copolymers 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; Polyacetal; Modified polyphenylene oxide; Polyphenylene sulfide; Polysulfone;
Moreover, as said resin, polymer alloys, such as a mixture of the said polyester and other resin, are mentioned, for example. 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.
Examples of the resin include a crosslinked resin in which one or more of the resins exemplified so far are crosslinked; modification of an ionomer or the like using one or more of the resins exemplified so far. Resins can also be mentioned.
　なお、本明細書において、「（メタ）アクリル酸」とは、「アクリル酸」及び「メタクリル酸」の両方を包含する概念とする。（メタ）アクリル酸と類似の用語についても同様であり、例えば、「（メタ）アクリロイル基」とは、「アクリロイル基」及び「メタクリロイル基」の両方を包含する概念であり、「（メタ）アクリレート」とは、「アクリレート」及び「メタクリレート」の両方を包含する概念である。 In the present specification, “(meth) acrylic acid” is a concept including both “acrylic acid” and “methacrylic acid”. The same applies to terms similar to (meth) acrylic acid. For example, “(meth) acryloyl group” is a concept including both “acryloyl group” and “methacryloyl group”, and “(meth) acrylate” "Is a concept including both" acrylate "and" methacrylate ".
　基材を構成する樹脂は、１種のみでもよいし、２種以上でもよく、２種以上である場合、それらの組み合わせ及び比率は任意に選択できる。 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.
　基材は１層（単層）からなるものでもよいし、２層以上の複数層からなるものでもよく、複数層からなる場合、これら複数層は、互いに同一でも異なっていてもよく、これら複数層の組み合わせは特に限定されない。 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.
　基材の厚さは、４０μｍ以上３００μｍ以下であることが好ましく、６０μｍ以上１５０μｍ以下であることがより好ましい。基材の厚さがこのような範囲であることで、前記保護膜形成用複合シートの可撓性と、半導体ウエハ又は半導体チップへの貼付性がより向上する。
　ここで、「基材の厚さ」とは、基材全体の厚さを意味し、例えば、複数層からなる基材の厚さとは、基材を構成するすべての層の合計の厚さを意味する。なお、基材の厚さの測定方法としては、例えば、任意の５箇所において、接触式厚み計を用いて厚さを測定し、測定値の平均を算出する方法等が挙げられる。 The thickness of the substrate is preferably 40 μm or more and 300 μm or less, and more preferably 60 μm or more and 150 μm or less. When the thickness of the substrate is within such a range, the flexibility of the composite sheet for forming a protective film and the adhesiveness to a semiconductor wafer or semiconductor chip are further improved.
Here, “the thickness of the substrate” means the thickness of the entire substrate. For example, the thickness of the substrate composed of a plurality of layers means the total thickness of all the layers constituting the substrate. means. In addition, as a measuring method of the thickness of a base material, the method of measuring thickness using a contact-type thickness meter in arbitrary five places, and calculating the average of a measured value etc. are mentioned, for example.
　基材は、厚さの精度が高いもの、すなわち、部位によらず厚さのばらつきが抑制されたものが好ましい。上述の構成材料のうち、このような厚さの精度が高い基材を構成するのに使用可能な材料としては、例えば、ポリエチレン、ポリエチレン以外のポリオレフィン、ポリエチレンテレフタレート、エチレン－酢酸ビニル共重合体等が挙げられる。 The base material is preferably one having high thickness accuracy, that is, one in which variation in thickness is suppressed regardless of the part. Among the above-mentioned constituent materials, examples of 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.
　基材は、前記樹脂等の主たる構成材料以外に、充填材、着色剤、帯電防止剤、酸化防止剤、有機滑剤、触媒、軟化剤（可塑剤）等の公知の各種添加剤を含有していてもよい。
例えば、基材が充填材又は着色剤を含有することで、支持シートのヘーズを上記範囲内とすることができるため、レーザー印字の視認性を良好にすることができる。 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.
For example, since the base material contains a filler or a colorant, the haze of the support sheet can be within the above range, so that the visibility of laser printing can be improved.
　基材の光学特性は、先に説明した支持シートの光学特性を満たすようになっていればよい。すなわち、基材は、透明であってもよいし、不透明であってもよく、目的に応じて無色であってもよいし、着色されていてもよく、他の層が加工（例えば、蒸着）されていてもよい。
　そして、保護膜形成用フィルムがエネルギー線硬化性を有する場合においては、基材はエネルギー線を透過させるものが好ましい。 The optical characteristics of the base material only need to satisfy the optical characteristics of the support sheet described above. That is, the substrate may be transparent or opaque, may be colorless or colored depending on the purpose, and other layers are processed (for example, vapor deposition). May be.
And when the film for protective film formation has energy-beam sclerosis | hardenability, what a base material permeate | transmits an energy beam is preferable.
　基材は、その上に設けられる粘着剤層等の他の層との密着性を向上させるために、サンドブラスト処理、溶剤処理等による凹凸化処理や、コロナ放電処理、電子線照射処理、プラズマ処理、オゾン・紫外線照射処理、火炎処理、クロム酸処理、熱風処理等の酸化処理等が表面に施されたものであってもよい。
　また、基材は、表面がプライマー処理を施されたものであってもよい。
　また、基材は、帯電防止コート層、保護膜形成用複合シートを重ね合わせて保存する際に、基材が他のシートに接着することや、基材が吸着テーブルに接着することを防止する層等を有するものであってもよい。
　これらの中でも基材は、ダイシング時のブレードの摩擦による基材の断片の発生が抑制される点から、特に表面が電子線照射処理を施されたものが好ましい。 In order to improve the adhesion with other layers such as a pressure-sensitive adhesive layer provided on the substrate, 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 base material may have a surface subjected to primer treatment.
In addition, the base material 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 protective film-forming composite sheet are stored in an overlapping manner. It may have a layer or the like.
Among these, 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.
　また、表面処理された基材において、基材のうち支持シートの外面として露出される面の表面粗さ（Ｒａ）の上限値は０．６０μｍ以下、好ましくは０．５０μｍ以下、より好ましくは０．４０μｍ以下、さらに好ましくは０．３０μｍ以下である。基材の表面粗さが上記上限値以下であることにより、基材の外面における光散乱を低減させ、支持シートの透過鮮明度を上記範囲内とすることができるため、レーザー印字の視認性を良好にすることができる。
　一方、表面粗さ（Ｒａ）の下限値は、特別な限定はなく、例えば０．００５μｍ以上であってもよく、０．０１μｍ以上であってもよく、０．０３μｍ以上であってもよく、０．０５μｍ以上であってもよい。
また、基材の表面粗さが上記上限値以下である面と、表面粗さが０．１１μｍ以上である面とを有するとき、表面粗さが０．１１μｍ以上である表面に粘着剤層等の他の層を積層させることが好ましい。これにより、基材のうち支持シートの外面として露出される表面粗さが上記上限値以下の面となり、基材の外面における光散乱を低減させ、支持シートの透過鮮明度を上記範囲内とすることができるため、レーザー印字の視認性を良好にすることができる。
また、基材の表面粗さが両面共に上記上限値以下である場合には、より表面粗さの大きい面に粘着剤層等の他の層を積層させ、より表面粗さの小さい面が外面として露出するようにすればよい。
　なお、本明細書において、「表面粗さ」とは、特に断りのない限り、ＪＩＳ　Ｂ０６０１：２００１に準拠して求められる、いわゆる算術平均粗さを意味し、「Ｒａ」と略記することがある。 In the surface-treated substrate, the upper limit value of the surface roughness (Ra) of the surface exposed as the outer surface of the support sheet is 0.60 μm or less, preferably 0.50 μm or less, more preferably 0. .40 μm or less, more preferably 0.30 μm or less. Since the surface roughness of the substrate is less than or equal to the above upper limit value, light scattering on the outer surface of the substrate can be reduced, and the transmission clarity of the support sheet can be within the above range. Can be good.
On the other hand, the lower limit of the surface roughness (Ra) is not particularly limited, and may be, for example, 0.005 μm or more, 0.01 μm or more, or 0.03 μm or more, It may be 0.05 μm or more.
Moreover, when it has a surface whose surface roughness is not more than the above upper limit value and a surface whose surface roughness is 0.11 μm or more, an adhesive layer or the like on the surface whose surface roughness is 0.11 μm or more It is preferable to laminate other layers. Thereby, the surface roughness exposed as the outer surface of the support sheet in the substrate becomes a surface having the upper limit value or less, the light scattering on the outer surface of the substrate is reduced, and the transmission clarity of the support sheet is within the above range. Therefore, the visibility of laser printing can be improved.
When the surface roughness of the substrate is less than or equal to the above upper limit value, another layer such as an adhesive layer is laminated on the surface having a larger surface roughness, and the surface having a smaller surface roughness is the outer surface. As long as it is exposed.
In the present specification, “surface roughness” means a so-called arithmetic average roughness obtained in accordance with JIS B0601: 2001, and is abbreviated as “Ra” unless otherwise specified. .
　基材は、公知の方法で製造できる。例えば、樹脂を含有する基材は、前記樹脂を含有する樹脂組成物を成形することで製造できる。 The base material can be manufactured by a known method. For example, a base material containing a resin can be produced by molding a resin composition containing the resin.
○粘着剤層
　前記粘着剤層は、シート状又はフィルム状であり、粘着剤を含有する。
　前記粘着剤としては、例えば、アクリル系樹脂、ウレタン系樹脂、ゴム系樹脂、シリコーン系樹脂、エポキシ系樹脂、ポリビニルエーテル、ポリカーボネート、エステル系樹脂等の粘着性樹脂が挙げられ、アクリル系樹脂が好ましい。 -Adhesive layer The said adhesive layer is a sheet form or a film form, and contains an adhesive.
Examples of the adhesive include adhesive resins such as acrylic resins, urethane resins, rubber resins, silicone resins, epoxy resins, polyvinyl ethers, polycarbonates, and ester resins, and acrylic resins are preferable. .
　なお、本実施形態において、「粘着性樹脂」とは、粘着性を有する樹脂と、接着性を有する樹脂と、の両方を含む概念であり、例えば、樹脂自体が粘着性を有するものだけでなく、添加剤等の他の成分との併用により粘着性を示す樹脂や、熱又は水等のトリガーの存在によって接着性を示す樹脂等も含む。 In the present embodiment, the “adhesive resin” is a concept including both an adhesive resin and an adhesive resin. For example, the resin itself has not only an adhesive property. In addition, a resin exhibiting tackiness by using in combination with other components such as additives, a resin exhibiting adhesiveness due to the presence of a trigger such as heat or water, and the like are also included.
　粘着剤層は１層（単層）からなるものでもよいし、２層以上の複数層からなるものでもよく、複数層からなる場合、これら複数層は、互いに同一でも異なっていてもよく、これら複数層の組み合わせは特に限定されない。 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.
　粘着剤層の厚さは３μｍ以上２０μｍ以下であることが好ましく、５μｍ以上２０μｍ以下であることがより好ましく、５μｍ以上１７μｍ以下であることが特に好ましい。
　粘着剤層の厚さが上記下限値以上であることにより、粘着力を向上させることができる。また、表面粗さが０．１１μｍ以上の基材である場合、基材の表面を埋め込み、基材外面の光散乱が低減された平滑な面を有する積層体とすることができる。一方、粘着剤層の厚さが上記上限値以下であることにより、ブレードダイシング適性及びピックアップ適性を良好にすることができる。
　ここで、「粘着剤層の厚さ」とは、粘着剤層全体の厚さを意味し、例えば、複数層からなる粘着剤層の厚さとは、粘着剤層を構成するすべての層の合計の厚さを意味する。なお、粘着剤層の厚さの測定方法としては、例えば、任意の５箇所において、接触式厚み計を用いて厚さを測定し、測定値の平均を算出する方法等が挙げられる。 The thickness of the pressure-sensitive adhesive layer is preferably 3 μm or more and 20 μm or less, more preferably 5 μm or more and 20 μm or less, and particularly preferably 5 μm or more and 17 μm or less.
Adhesive strength can be improved when the thickness of the pressure-sensitive adhesive layer is not less than the above lower limit. Moreover, when it is a base material whose surface roughness is 0.11 micrometer or more, it can be set as the laminated body which embeds the surface of a base material and has a smooth surface where the light scattering of the base-material outer surface was reduced. On the other hand, when the thickness of the pressure-sensitive adhesive layer is not more than the above upper limit value, blade dicing suitability and pickup suitability can be improved.
Here, the “thickness of the pressure-sensitive adhesive layer” means the thickness of the whole pressure-sensitive adhesive layer. For example, 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. In addition, as a measuring method of the thickness of an adhesive layer, the method of measuring thickness using a contact-type thickness meter in arbitrary five places, and calculating the average of a measured value etc. are mentioned, for example.
　粘着剤層の硬さを適宜調整することで、粘着剤層と基材又は中間層との間に隙間をつくり、支持シートのヘーズが上記範囲内となるように調整することができる。 By adjusting the hardness of the pressure-sensitive adhesive layer as appropriate, a gap can be formed between the pressure-sensitive adhesive layer and the base material or the intermediate layer, and the haze of the support sheet can be adjusted within the above range.
　粘着剤層の光学特性は、先に説明した支持シートの光学特性を満たすようになっていればよい。すなわち、粘着剤層は、不透明であってもよく、目的に応じて着色されていてもよい。
　そして、保護膜形成用フィルムがエネルギー線硬化性を有する場合においては、粘着剤層はエネルギー線を透過させるものが好ましい。 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 opaque or colored according to the purpose.
And when the film for protective film formation has energy-beam sclerosis | hardenability, what the energy layer permeate | transmits an adhesive layer is preferable.
　粘着剤層は、エネルギー線硬化性粘着剤を用いて形成されたものでもよいし、非エネルギー線硬化性粘着剤を用いて形成されたものでもよい。なお、非エネルギー線硬化性粘着剤には、熱硬化性粘着剤及び非硬化性粘着剤が包含される。エネルギー線硬化性の粘着剤を用いて形成された粘着剤層は、硬化前及び硬化後での物性を、容易に調節できる。 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 non-energy ray curable adhesive includes a thermosetting adhesive and a non-curable 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.
＜＜粘着剤組成物＞＞
　粘着剤層は、粘着剤を含有する粘着剤組成物を用いて形成できる。例えば、粘着剤層の形成対象面に粘着剤組成物を塗工し、必要に応じて乾燥させることで、目的とする部位に粘着剤層を形成できる。粘着剤層のより具体的な形成方法は、他の層の形成方法とともに、後ほど詳細に説明する。粘着剤組成物中の、常温で気化しない成分同士の含有量の比率は、通常、粘着剤層の前記成分同士の含有量の比率と同じとなる。なお、本明細書において、「常温」とは、特に冷やしたり、熱したりしない温度、すなわち平常の温度を意味し、例えば、１５℃以上２５℃以下の温度等が挙げられる。 << Adhesive composition >>
The pressure-sensitive adhesive layer can be formed using a pressure-sensitive adhesive composition containing a pressure-sensitive adhesive. For example, an adhesive layer can be formed in the target site | part by applying an adhesive composition to the formation object surface of an adhesive layer, and making it dry as needed. 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. In the present specification, “normal temperature” means a temperature that is not particularly cooled or heated, that is, a normal temperature, for example, a temperature of 15 ° C. or more and 25 ° C. or less.
　粘着剤組成物の塗工は、公知の方法で行えばよく、例えば、エアーナイフコーター、ブレードコーター、バーコーター、グラビアコーター、ロールコーター、ロールナイフコーター、カーテンコーター、ダイコーター、ナイフコーター、スクリーンコーター、マイヤーバーコーター、キスコーター等の各種コーターを用いる方法が挙げられる。 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.
　粘着剤組成物の乾燥条件は、特に限定されないが、粘着剤組成物は、後述する溶媒を含有している場合、加熱乾燥させることが好ましく、この場合、例えば、７０℃以上１３０℃以下で１０秒以上５分以下の条件で乾燥させることが好ましい。 The drying conditions of the pressure-sensitive adhesive composition are not particularly limited, but the pressure-sensitive adhesive composition is preferably heated and dried when it contains a solvent described later. In this case, for example, the pressure-sensitive adhesive composition is 10 to 70 ° C to 130 ° C. It is preferable to dry under conditions of not less than 2 seconds and not more than 5 minutes.
　粘着剤層がエネルギー線硬化性である場合、エネルギー線硬化性粘着剤を含有する粘着剤組成物、すなわち、エネルギー線硬化性の粘着剤組成物としては、例えば、非エネルギー線硬化性の粘着性樹脂（Ｉ－１ａ）（以下、「粘着性樹脂（Ｉ－１ａ）」と略記することがある）と、エネルギー線硬化性化合物と、を含有する粘着剤組成物（Ｉ－１）；非エネルギー線硬化性の粘着性樹脂（Ｉ－１ａ）の側鎖に不飽和基が導入されたエネルギー線硬化性の粘着性樹脂（Ｉ－２ａ）（以下、「粘着性樹脂（Ｉ－２ａ）」と略記することがある）を含有する粘着剤組成物（Ｉ－２）；前記粘着性樹脂（Ｉ－２ａ）と、エネルギー線硬化性化合物と、を含有する粘着剤組成物（Ｉ－３）等が挙げられる。 When the pressure-sensitive adhesive layer is energy ray-curable, 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 A pressure-sensitive adhesive composition (I-1) containing a resin (I-1a) (hereinafter sometimes abbreviated as “adhesive resin (I-1a)”) and an energy ray-curable compound; 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)”) A pressure-sensitive adhesive composition (I-2) containing the pressure-sensitive adhesive resin (I-2a) and an energy ray curable compound, etc. Is mentioned.
＜粘着剤組成物（Ｉ－１）＞
　前記粘着剤組成物（Ｉ－１）は、上述の様に、非エネルギー線硬化性の粘着性樹脂（Ｉ－１ａ）と、エネルギー線硬化性化合物と、を含有する。 <Adhesive composition (I-1)>
As described above, 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.
［粘着性樹脂（Ｉ－１ａ）］
　前記粘着性樹脂（Ｉ－１ａ）は、アクリル系樹脂であることが好ましい。
　前記アクリル系樹脂としては、例えば、少なくとも（メタ）アクリル酸アルキルエステル由来の構成単位を有するアクリル系重合体が挙げられる。
　前記アクリル系樹脂が有する構成単位は、１種のみでもよいし、２種以上でもよく、２種以上である場合、それらの組み合わせ及び比率は任意に選択できる。 [Adhesive resin (I-1a)]
The adhesive resin (I-1a) is preferably an acrylic resin.
As said 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, or two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected.
前記（メタ）アクリル酸アルキルエステルとしては、例えば、アルキルエステルを構成するアルキル基の炭素数が１～２０であるのものが挙げられ、前記アルキル基は、直鎖状又は分岐鎖状であることが好ましい。
　（メタ）アクリル酸アルキルエステルとして、より具体的には、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸ｎ－プロピル、（メタ）アクリル酸イソプロピル、（メタ）アクリル酸ｎ－ブチル、（メタ）アクリル酸イソブチル、（メタ）アクリル酸ｓｅｃ－ブチル、（メタ）アクリル酸ｔｅｒｔ－ブチル、（メタ）アクリル酸ペンチル、（メタ）アクリル酸ヘキシル、（メタ）アクリル酸ヘプチル、（メタ）アクリル酸２－エチルヘキシル、（メタ）アクリル酸イソオクチル、（メタ）アクリル酸ｎ－オクチル、（メタ）アクリル酸ｎ－ノニル、（メタ）アクリル酸イソノニル、（メタ）アクリル酸デシル、（メタ）アクリル酸ウンデシル、（メタ）アクリル酸ドデシル（（メタ）アクリル酸ラウリル）、（メタ）アクリル酸トリデシル、（メタ）アクリル酸テトラデシル（（メタ）アクリル酸ミリスチル）、（メタ）アクリル酸ペンタデシル、（メタ）アクリル酸ヘキサデシル（（メタ）アクリル酸パルミチル）、（メタ）アクリル酸ヘプタデシル、（メタ）アクリル酸オクタデシル（（メタ）アクリル酸ステアリル）、（メタ）アクリル酸ノナデシル、（メタ）アクリル酸イコシル等が挙げられる。 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-octyl, (meth) acrylic acid n-nonyl, (meth) acrylic acid isononyl, (meth) acrylic acid decyl, (meta) ) Undecyl acrylate, dodecyl (meth) acrylate (lauryl (meth) acrylate), ( T) Decyl acrylate, tetradecyl (meth) acrylate (myristyl (meth) acrylate), pentadecyl (meth) acrylate, hexadecyl (meth) acrylate (palmityl (meth) acrylate), heptadecyl (meth) acrylate, Examples thereof include octadecyl (meth) acrylate (stearyl (meth) acrylate), nonadecyl (meth) acrylate, icosyl (meth) acrylate, and the like.
　粘着剤層の粘着力が向上する点から、前記アクリル系重合体は、前記アルキル基の炭素数が２以上である（メタ）アクリル酸アルキルエステル由来の構成単位を有することが好ましい。そして、粘着剤層の粘着力がより向上する点から、前記アルキル基の炭素数は、２以上１２以下であることが好ましく、４以上８以下であることがより好ましい。また、前記アルキル基の炭素数が４以上である（メタ）アクリル酸アルキルエステルは、アクリル酸アルキルエステルであることが好ましい。 From the viewpoint of improving the adhesive strength of the pressure-sensitive adhesive layer, the acrylic polymer preferably has a structural unit derived from a (meth) acrylic acid alkyl ester in which the alkyl group has 2 or more carbon atoms. And from the point which the adhesive force of an adhesive layer improves more, it is preferable that carbon number of the said alkyl group is 2-12, and it is more preferable that it is 4-8. In addition, the (meth) acrylic acid alkyl ester having 4 or more carbon atoms in the alkyl group is preferably an acrylic acid alkyl ester.
前記アクリル系重合体は、（メタ）アクリル酸アルキルエステル由来の構成単位以外に、さらに、官能基含有モノマー由来の構成単位を有することが好ましい。
　前記官能基含有モノマーとしては、例えば、前記官能基が後述する架橋剤と反応することで架橋の起点となったり、前記官能基が後述する不飽和基含有化合物中の不飽和基と反応することで、アクリル系重合体の側鎖に不飽和基の導入を可能とするものが挙げられる。 In addition to the structural unit derived from (meth) acrylic acid alkyl ester, the acrylic polymer preferably further has a structural unit derived from a functional group-containing monomer.
As 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.
官能基含有モノマー中の前記官能基としては、例えば、水酸基、カルボキシ基、アミノ基、エポキシ基等が挙げられる。
　すなわち、官能基含有モノマーとしては、例えば、水酸基含有モノマー、カルボキシ基含有モノマー、アミノ基含有モノマー、エポキシ基含有モノマー等が挙げられる。 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.
　前記水酸基含有モノマーとしては、例えば、（メタ）アクリル酸ヒドロキシメチル、（メタ）アクリル酸２－ヒドロキシエチル、（メタ）アクリル酸２－ヒドロキシプロピル、（メタ）アクリル酸３－ヒドロキシプロピル、（メタ）アクリル酸２－ヒドロキシブチル、（メタ）アクリル酸３－ヒドロキシブチル、（メタ）アクリル酸４－ヒドロキシブチル等の（メタ）アクリル酸ヒドロキシアルキル；ビニルアルコール、アリルアルコール等の非（メタ）アクリル系不飽和アルコール（（メタ）アクリロイル骨格を有しない不飽和アルコール）等が挙げられる。 Examples of the hydroxyl group-containing monomer 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.
　前記カルボキシ基含有モノマーとしては、例えば、（メタ）アクリル酸、クロトン酸等のエチレン性不飽和モノカルボン酸（エチレン性不飽和結合を有するモノカルボン酸）；フマル酸、イタコン酸、マレイン酸、シトラコン酸等のエチレン性不飽和ジカルボン酸（エチレン性不飽和結合を有するジカルボン酸）；前記エチレン性不飽和ジカルボン酸の無水物；２－カルボキシエチルメタクリレート等の（メタ）アクリル酸カルボキシアルキルエステル等が挙げられる。 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.
　官能基含有モノマーは、水酸基含有モノマー又はカルボキシ基含有モノマーが好ましく、水酸基含有モノマーがより好ましい。 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.
　前記アクリル系重合体を構成する官能基含有モノマーは、１種のみでもよいし、２種以上でもよく、２種以上である場合、それらの組み合わせ及び比率は任意に選択できる。 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.
　前記アクリル系重合体において、官能基含有モノマー由来の構成単位の含有量は、構成単位の全量に対して、１質量％以上２９質量％以下であることが好ましく、２質量％以上２５質量％以下であることがより好ましく、３質量％以上２３質量％以下であることが特に好ましい。 In the acrylic polymer, the content of the structural unit derived from the functional group-containing monomer is preferably 1% by mass or more and 29% by mass or less, and preferably 2% by mass or more and 25% by mass or less with respect to the total amount of the structural unit. It is more preferable that it is 3 mass% or more and 23 mass% or less.
前記アクリル系重合体は、（メタ）アクリル酸アルキルエステル由来の構成単位、及び官能基含有モノマー由来の構成単位以外に、さらに、他のモノマー由来の構成単位を有していてもよい。
　前記他のモノマーは、（メタ）アクリル酸アルキルエステル等と共重合可能なものであれば特に限定されない。
　前記他のモノマーとしては、例えば、スチレン、α－メチルスチレン、ビニルトルエン、ギ酸ビニル、酢酸ビニル、アクリロニトリル、アクリルアミド等が挙げられる。 In addition to the structural unit derived from the (meth) acrylic acid alkyl ester and the structural unit derived from the functional group-containing monomer, 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, α-methylstyrene, vinyl toluene, vinyl formate, vinyl acetate, acrylonitrile, acrylamide and the like.
前記アクリル系重合体を構成する前記他のモノマーは、１種のみでもよいし、２種以上でもよく、２種以上である場合、それらの組み合わせ及び比率は任意に選択できる。 The other monomer constituting the acrylic polymer may be only one type, or two or more types, and when there are two or more types, the combination and ratio thereof can be arbitrarily selected.
前記アクリル系重合体は、上述の非エネルギー線硬化性の粘着性樹脂（Ｉ－１ａ）として使用できる。
　一方、前記アクリル系重合体中の官能基に、エネルギー線重合性不飽和基（エネルギー線重合性基）を有する不飽和基含有化合物を反応させたものは、上述のエネルギー線硬化性の粘着性樹脂（Ｉ－２ａ）として使用できる。 The acrylic polymer can be used as the above-mentioned non-energy ray curable adhesive resin (I-1a).
On the other hand, 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).
　粘着剤組成物（Ｉ－１）が含有する粘着性樹脂（Ｉ－１ａ）は、１種のみでもよいし、２種以上でもよく、２種以上である場合、それらの組み合わせ及び比率は任意に選択できる。 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.
　粘着剤組成物（Ｉ－１）において、溶媒以外の全ての成分の総含有量に対する粘着性樹脂（Ｉ－１ａ）の含有量は、５質量％以上９９質量％以下であることが好ましく、１０質量％以上９５質量％以下であることがより好ましく、１５質量％以上９０質量％以下であることが特に好ましい。 In the pressure-sensitive adhesive composition (I-1), the content of the pressure-sensitive adhesive resin (I-1a) with respect to the total content of all components other than the solvent is preferably 5% by mass to 99% by mass. More preferably, it is more than 95 mass%, and it is especially preferable that it is 15 mass% or more and 90 mass% or less.
［エネルギー線硬化性化合物］
　粘着剤組成物（Ｉ－１）が含有する前記エネルギー線硬化性化合物としては、エネルギー線重合性不飽和基を有し、エネルギー線の照射により硬化可能なモノマー又はオリゴマーが挙げられる。
　エネルギー線硬化性化合物のうち、モノマーとしては、例えば、トリメチロールプロパントリ（メタ）アクリレート、ペンタエリスリトール（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、１，４－ブチレングリコールジ（メタ）アクリレート、１，６－へキサンジオール（メタ）アクリレート等の多価（メタ）アクリレート；ウレタン（メタ）アクリレート；ポリエステル（メタ）アクリレート；ポリエーテル（メタ）アクリレート；エポキシ（メタ）アクリレート等が挙げられる。
　エネルギー線硬化性化合物のうち、オリゴマーとしては、例えば、上記で例示したモノマーが重合してなるオリゴマー等が挙げられる。
　エネルギー線硬化性化合物は、分子量が比較的大きく、粘着剤層の貯蔵弾性率を低下させにくいという点では、ウレタン（メタ）アクリレート又はウレタン（メタ）アクリレートオリゴマーが好ましい。 [Energy ray curable compound]
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.
Among the energy ray curable compounds, 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.
Among the energy ray-curable compounds, 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.
　粘着剤組成物（Ｉ－１）が含有する前記エネルギー線硬化性化合物は、１種のみでもよいし、２種以上でもよく、２種以上である場合、それらの組み合わせ及び比率は任意に選択できる。 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. .
　前記粘着剤組成物（Ｉ－１）において、溶媒以外の全ての成分の総含有量に対する前記エネルギー線硬化性化合物の含有量は、１質量％以上９５質量％以下であることが好ましく、２質量％以上９０質量％以下であることがより好ましく、３質量％以上８５質量％以下であることが特に好ましい。例えば、３質量％以上８０質量％以下、３質量％以上６５質量％以下、３質量％以上５０質量％以下、及び３質量％以上３５質量％以下等のいずれかであってもよい。 In the pressure-sensitive adhesive composition (I-1), the content of the energy ray-curable compound with respect to the total content of all components other than the solvent is preferably 1% by mass or more and 95% by mass or less. % To 90% by mass, more preferably 3% to 85% by mass. For example, any of 3 mass% or more and 80 mass% or less, 3 mass% or more and 65 mass% or less, 3 mass% or more and 50 mass% or less, 3 mass% or more and 35 mass% or less, etc. may be sufficient.
［架橋剤］
　粘着性樹脂（Ｉ－１ａ）として、（メタ）アクリル酸アルキルエステル由来の構成単位以外に、さらに、官能基含有モノマー由来の構成単位を有する前記アクリル系重合体を用いる場合、粘着剤組成物（Ｉ－１）は、さらに架橋剤を含有することが好ましい。 [Crosslinking agent]
When the acrylic polymer having a structural unit derived from a functional group-containing monomer in addition to the structural unit derived from (meth) acrylic acid alkyl ester is used as the adhesive resin (I-1a), a pressure-sensitive adhesive composition ( I-1) preferably further contains a crosslinking agent.
前記架橋剤は、例えば、前記官能基と反応して、粘着性樹脂（Ｉ－１ａ）同士を架橋するものである。
　架橋剤としては、例えば、トリレンジイソシアネート、ヘキサメチレンジイソシアネート、キシリレンジイソシアネート、これらジイソシアネートのアダクト体等のイソシアネート系架橋剤（イソシアネート基を有する架橋剤）；エチレングリコールグリシジルエーテル等のエポキシ系架橋剤（グリシジル基を有する架橋剤）；ヘキサ［１－（２－メチル）－アジリジニル］トリフオスファトリアジン等のアジリジン系架橋剤（アジリジニル基を有する架橋剤）；アルミニウムキレート等の金属キレート系架橋剤（金属キレート構造を有する架橋剤）；イソシアヌレート系架橋剤（イソシアヌル酸骨格を有する架橋剤）等が挙げられる。
　粘着剤の凝集力を向上させて粘着剤層の粘着力を向上させる点、及び入手が容易である等の点から、架橋剤はイソシアネート系架橋剤であることが好ましい。 For example, the cross-linking agent reacts with the functional group to cross-link the adhesive resins (I-1a).
As 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 (cross-linking agent having an aziridinyl group) such as hexa [1- (2-methyl) -aziridinyl] triphosphatriazine; Metal chelate-based cross-linking agent such as aluminum chelate (metal) Cross-linking agent having a chelate structure); isocyanurate-based cross-linking agent (cross-linking agent having an isocyanuric acid skeleton) and the like.
The crosslinking agent is preferably an isocyanate-based crosslinking agent from the viewpoints of improving the cohesive strength of the pressure-sensitive adhesive and improving the pressure-sensitive adhesive strength of the pressure-sensitive adhesive layer, and being easily available.
　粘着剤組成物（Ｉ－１）が含有する架橋剤は、１種のみでもよいし、２種以上でもよく、２種以上である場合、それらの組み合わせ及び比率は任意に選択できる。 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.
　前記粘着剤組成物（Ｉ－１）において、架橋剤の含有量は、粘着性樹脂（Ｉ－１ａ）の含有量１００質量部に対して、０．０１質量部以上５０質量部以下であることが好ましく、０．１質量部以上３０質量部以下であることがより好ましく、０．３質量部以上２３質量部以下であることが特に好ましい。 In the pressure-sensitive adhesive composition (I-1), the content of the crosslinking agent is 0.01 parts by weight or more and 50 parts by weight or less with respect to 100 parts by weight of the pressure-sensitive adhesive resin (I-1a). Is preferably 0.1 parts by mass or more and 30 parts by mass or less, and particularly preferably 0.3 parts by mass or more and 23 parts by mass or less.
［光重合開始剤］
　粘着剤組成物（Ｉ－１）は、さらに光重合開始剤を含有していてもよい。光重合開始剤を含有する粘着剤組成物（Ｉ－１）は、紫外線等の比較的低エネルギーのエネルギー線を照射しても、十分に硬化反応が進行する。 [Photopolymerization initiator]
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.
前記光重合開始剤としては、例えば、ベンゾイン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル、ベンゾインイソブチルエーテル、ベンゾイン安息香酸、ベンゾイン安息香酸メチル、ベンゾインジメチルケタール等のベンゾイン化合物；アセトフェノン、２－ヒドロキシ－２－メチル－１－フェニル－プロパン－１－オン、２，２－ジメトキシ－１，２－ジフェニルエタン－１－オン等のアセトフェノン化合物；ビス（２，４，６－トリメチルベンゾイル）フェニルフォスフィンオキサイド、２，４，６－トリメチルベンゾイルジフェニルフォスフィンオキサイド等のアシルフォスフィンオキサイド化合物；ベンジルフェニルスルフィド、テトラメチルチウラムモノスルフィド等のスルフィド化合物；１－ヒドロキシシクロヘキシルフェニルケトン等のα－ケトール化合物；アゾビスイソブチロニトリル等のアゾ化合物；チタノセン等のチタノセン化合物；チオキサントン等のチオキサントン化合物；パーオキサイド化合物；ジアセチル等のジケトン化合物；ベンジル；ジベンジル；ベンゾフェノン；２，４－ジエチルチオキサントン；１，２－ジフェニルメタン；２－ヒドロキシ－２－メチル－１－［４－（１－メチルビニル）フェニル］プロパノン；２－クロロアントラキノン等が挙げられる。
　また、前記光重合開始剤としては、例えば、１－クロロアントラキノン等のキノン化合物；アミン等の光増感剤等を用いることもできる。 Examples of the photopolymerization initiator 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 Acylphosphine oxide compounds such as oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide; Sulfidation of benzylphenyl sulfide, tetramethylthiuram monosulfide, etc. An α-ketol compound such as 1-hydroxycyclohexyl phenyl ketone; an azo compound such as azobisisobutyronitrile; a titanocene compound such as titanocene; a thioxanthone compound such as thioxanthone; a peroxide compound; a diketone compound such as diacetyl; Benzophenone; 2,4-diethylthioxanthone; 1,2-diphenylmethane; 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone; 2-chloroanthraquinone and the like.
As the photopolymerization initiator, for example, a quinone compound such as 1-chloroanthraquinone; a photosensitizer such as amine can be used.
粘着剤組成物（Ｉ－１）が含有する光重合開始剤は、１種のみでもよいし、２種以上でもよく、２種以上である場合、それらの組み合わせ及び比率は任意に選択できる。 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.
粘着剤組成物（Ｉ－１）において、光重合開始剤の含有量は、前記エネルギー線硬化性化合物の含有量１００質量部に対して、０．０１質量部以上２０質量部以下であることが好ましく、０．０３質量部以上１０質量部以下であることがより好ましく、０．０５質量部以上５質量部以下であることが特に好ましい。 In the pressure-sensitive adhesive composition (I-1), the content of the photopolymerization initiator is 0.01 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the energy ray curable compound. Preferably, it is 0.03 to 10 parts by mass, and particularly preferably 0.05 to 5 parts by mass.
［その他の添加剤］
　粘着剤組成物（Ｉ－１）は、本実施形態における効果を損なわない範囲内において、上述のいずれの成分にも該当しない、その他の添加剤を含有していてもよい。
　前記その他の添加剤としては、例えば、帯電防止剤、酸化防止剤、軟化剤（可塑剤）、充填材（フィラー）、防錆剤、着色剤（顔料、染料）、増感剤、粘着付与剤、反応遅延剤、架橋促進剤（触媒）等の公知の添加剤が挙げられる。
　なお、反応遅延剤とは、例えば、粘着剤組成物（Ｉ－１）中に混入している触媒の作用によって、保存中の粘着剤組成物（Ｉ－１）において、目的としない架橋反応が進行するのを抑制するものである。反応遅延剤としては、例えば、触媒に対するキレートによってキレート錯体を形成するものが挙げられ、より具体的には、１分子中にカルボニル基（－Ｃ（＝Ｏ）－）を２個以上有するものが挙げられる。 [Other additives]
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 that does not impair the effects of the present embodiment.
Examples of the other additives include antistatic agents, antioxidants, softeners (plasticizers), fillers (fillers), rust inhibitors, colorants (pigments, dyes), sensitizers, and tackifiers. And known additives such as reaction retarders and crosslinking accelerators (catalysts).
Incidentally, the reaction retarding agent means, for example, an undesired crosslinking reaction in the pressure-sensitive adhesive composition (I-1) during storage by the action of the catalyst mixed in the pressure-sensitive adhesive composition (I-1). It suppresses progress. Examples of 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.
粘着剤組成物（Ｉ－１）が含有するその他の添加剤は、１種のみでもよいし、２種以上でもよく、２種以上である場合、それらの組み合わせ及び比率は任意に選択できる。 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, the combination and ratio thereof can be arbitrarily selected.
　粘着剤組成物（Ｉ－１）において、その他の添加剤の含有量は特に限定されず、その種類に応じて適宜選択すればよい。 In the pressure-sensitive adhesive composition (I-1), the content of other additives is not particularly limited, and may be appropriately selected according to the type.
［溶媒］
　粘着剤組成物（Ｉ－１）は、溶媒を含有していてもよい。粘着剤組成物（Ｉ－１）は、溶媒を含有していることで、塗工対象面への塗工適性が向上する。 [solvent]
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.
　前記溶媒は有機溶媒であることが好ましく、前記有機溶媒としては、例えば、メチルエチルケトン、アセトン等のケトン；酢酸エチル等のエステル（カルボン酸エステル）；テトラヒドロフラン、ジオキサン等のエーテル；シクロヘキサン、ｎ－ヘキサン等の脂肪族炭化水素；トルエン、キシレン等の芳香族炭化水素；１－プロパノール、２－プロパノール等のアルコール等が挙げられる。 The solvent is preferably an organic solvent. Examples of the 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. Aliphatic hydrocarbons; aromatic hydrocarbons such as toluene and xylene; alcohols such as 1-propanol and 2-propanol.
前記溶媒としては、例えば、粘着性樹脂（Ｉ－１ａ）の製造時に用いたものを粘着性樹脂（Ｉ－１ａ）から取り除かずに、そのまま粘着剤組成物（Ｉ－１）において用いてもよいし、粘着性樹脂（Ｉ－１ａ）の製造時に用いたものと同一又は異なる種類の溶媒を、粘着剤組成物（Ｉ－１）の製造時に別途添加してもよい。 As the solvent, for example, 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). In addition, 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).
　粘着剤組成物（Ｉ－１）が含有する溶媒は、１種のみでもよいし、２種以上でもよく、２種以上である場合、それらの組み合わせ及び比率は任意に選択できる。 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.
　粘着剤組成物（Ｉ－１）において、溶媒の含有量は特に限定されず、適宜調節すればよい。 In the pressure-sensitive adhesive composition (I-1), the content of the solvent is not particularly limited, and may be adjusted as appropriate.
＜粘着剤組成物（Ｉ－２）＞
　前記粘着剤組成物（Ｉ－２）は、上述の様に、非エネルギー線硬化性の粘着性樹脂（Ｉ－１ａ）の側鎖に不飽和基が導入されたエネルギー線硬化性の粘着性樹脂（Ｉ－２ａ）を含有する。 <Adhesive composition (I-2)>
As described above, 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.
［粘着性樹脂（Ｉ－２ａ）］
　前記粘着性樹脂（Ｉ－２ａ）は、例えば、粘着性樹脂（Ｉ－１ａ）中の官能基に、エネルギー線重合性不飽和基を有する不飽和基含有化合物を反応させることで得られる。 [Adhesive resin (I-2a)]
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.
　前記不飽和基含有化合物は、前記エネルギー線重合性不飽和基以外に、さらに粘着性樹脂（Ｉ－１ａ）中の官能基と反応することで、粘着性樹脂（Ｉ－１ａ）と結合可能な基を有する化合物である。
　前記エネルギー線重合性不飽和基としては、例えば、（メタ）アクリロイル基、ビニル基（エテニル基）、アリル基（２－プロペニル基）等が挙げられ、（メタ）アクリロイル基が好ましい。
　粘着性樹脂（Ｉ－１ａ）中の官能基と結合可能な基としては、例えば、水酸基又はアミノ基と結合可能なイソシアネート基及びグリシジル基、並びにカルボキシ基又はエポキシ基と結合可能な水酸基及びアミノ基等が挙げられる。 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. A compound having a group.
Examples of the energy ray-polymerizable unsaturated group include (meth) acryloyl group, vinyl group (ethenyl group), allyl group (2-propenyl group) and the like, 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.
　前記不飽和基含有化合物としては、例えば、（メタ）アクリロイルオキシエチルイソシアネート、（メタ）アクリロイルイソシアネート、グリシジル（メタ）アクリレート等が挙げられる。 Examples of the unsaturated group-containing compound include (meth) acryloyloxyethyl isocyanate, (meth) acryloyl isocyanate, glycidyl (meth) acrylate, and the like.
　粘着剤組成物（Ｉ－２）が含有する粘着性樹脂（Ｉ－２ａ）は、１種のみでもよいし、２種以上でもよく、２種以上である場合、それらの組み合わせ及び比率は任意に選択できる。 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.
　粘着剤組成物（Ｉ－２）において、溶媒以外の全ての成分の総含有量に対する粘着性樹脂（Ｉ－２ａ）の含有量は、５質量％以上９９質量％以下であることが好ましく、１０質量％以上９５質量％以下であることがより好ましく、１０質量％以上９０質量％以下であることが特に好ましい。 In the pressure-sensitive adhesive composition (I-2), the content of the pressure-sensitive adhesive resin (I-2a) with respect to the total content of all components other than the solvent is preferably 5% by mass or more and 99% by mass or less. The content is more preferably no less than 95% and no more than 95%, and particularly preferably no less than 10% and no more than 90%.
［架橋剤］
　粘着性樹脂（Ｉ－２ａ）として、例えば、粘着性樹脂（Ｉ－１ａ）におけるものと同様の、官能基含有モノマー由来の構成単位を有する前記アクリル系重合体を用いる場合、粘着剤組成物（Ｉ－２）は、さらに架橋剤を含有していてもよい。 [Crosslinking agent]
When the acrylic polymer having a structural unit derived from a functional group-containing monomer similar to that in the adhesive resin (I-1a) is used as the adhesive resin (I-2a), for example, an adhesive composition ( I-2) may further contain a crosslinking agent.
　粘着剤組成物（Ｉ－２）における前記架橋剤としては、粘着剤組成物（Ｉ－１）における架橋剤と同じものが挙げられる。
　粘着剤組成物（Ｉ－２）が含有する架橋剤は、１種のみでもよいし、２種以上でもよく、２種以上である場合、それらの組み合わせ及び比率は任意に選択できる。 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.
　前記粘着剤組成物（Ｉ－２）において、架橋剤の含有量は、粘着性樹脂（Ｉ－２ａ）の含有量１００質量部に対して、０．０１質量部以上２５質量部以下であることが好ましく、０．０５質量部以上２０質量部以下であることがより好ましく、０．１質量部以上１５質量部以下であることが特に好ましい。 In the pressure-sensitive adhesive composition (I-2), the content of the crosslinking agent is 0.01 parts by weight or more and 25 parts by weight or less with respect to 100 parts by weight of the pressure-sensitive adhesive resin (I-2a). Is more preferably 0.05 parts by mass or more and 20 parts by mass or less, and particularly preferably 0.1 parts by mass or more and 15 parts by mass or less.
［光重合開始剤］
　粘着剤組成物（Ｉ－２）は、さらに光重合開始剤を含有していてもよい。光重合開始剤を含有する粘着剤組成物（Ｉ－２）は、紫外線等の比較的低エネルギーのエネルギー線を照射しても、十分に硬化反応が進行する。 [Photopolymerization initiator]
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.
粘着剤組成物（Ｉ－２）における前記光重合開始剤としては、粘着剤組成物（Ｉ－１）における光重合開始剤と同じものが挙げられる。
　粘着剤組成物（Ｉ－２）が含有する光重合開始剤は、１種のみでもよいし、２種以上でもよく、２種以上である場合、それらの組み合わせ及び比率は任意に選択できる。 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.
　粘着剤組成物（Ｉ－２）において、光重合開始剤の含有量は、粘着性樹脂（Ｉ－２ａ）の含有量１００質量部に対して、０．０１質量部以上２０質量部以下であることが好ましく、０．０３質量部以上１０質量部以下であることがより好ましく、０．０５質量部以上５質量部以下であることが特に好ましい。 In the pressure-sensitive adhesive composition (I-2), the content of the photopolymerization initiator is 0.01 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the content of the adhesive resin (I-2a). It is preferably 0.03 to 10 parts by mass, more preferably 0.05 to 5 parts by mass.
［その他の添加剤］
　粘着剤組成物（Ｉ－２）は、本実施形態における効果を損なわない範囲内において、上述のいずれの成分にも該当しない、その他の添加剤を含有していてもよい。
　粘着剤組成物（Ｉ－２）における前記その他の添加剤としては、粘着剤組成物（Ｉ－１）におけるその他の添加剤と同じものが挙げられる。
　粘着剤組成物（Ｉ－２）が含有するその他の添加剤は、１種のみでもよいし、２種以上でもよく、２種以上である場合、それらの組み合わせ及び比率は任意に選択できる。 [Other additives]
The pressure-sensitive adhesive composition (I-2) may contain other additives that do not fall under any of the above-described components within a range that does not impair the effects of the present embodiment.
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.
　粘着剤組成物（Ｉ－２）において、その他の添加剤の含有量は特に限定されず、その種類に応じて適宜選択すればよい。 In the pressure-sensitive adhesive composition (I-2), the content of other additives is not particularly limited, and may be appropriately selected according to the type.
［溶媒］
　粘着剤組成物（Ｉ－２）は、粘着剤組成物（Ｉ－１）の場合と同様の目的で、溶媒を含有していてもよい。
粘着剤組成物（Ｉ－２）における前記溶媒としては、粘着剤組成物（Ｉ－１）における溶媒と同じものが挙げられる。
　粘着剤組成物（Ｉ－２）が含有する溶媒は、１種のみでもよいし、２種以上でもよく、２種以上である場合、それらの組み合わせ及び比率は任意に選択できる。
　粘着剤組成物（Ｉ－２）において、溶媒の含有量は特に限定されず、適宜調節すればよい。 [solvent]
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.
In the pressure-sensitive adhesive composition (I-2), the content of the solvent is not particularly limited, and may be adjusted as appropriate.
＜粘着剤組成物（Ｉ－３）＞
　前記粘着剤組成物（Ｉ－３）は、上述の様に、前記粘着性樹脂（Ｉ－２ａ）と、エネルギー線硬化性化合物と、を含有する。 <Adhesive composition (I-3)>
As described above, the pressure-sensitive adhesive composition (I-3) contains the pressure-sensitive adhesive resin (I-2a) and an energy ray-curable compound.
　粘着剤組成物（Ｉ－３）において、溶媒以外の全ての成分の総含有量に対する粘着性樹脂（Ｉ－２ａ）の含有量は、５質量％以上９９質量％以下であることが好ましく、１０質量％以上９５質量％以下であることがより好ましく、１５質量％以上９０質量％以下であることが特に好ましい。 In the pressure-sensitive adhesive composition (I-3), the content of the pressure-sensitive resin (I-2a) with respect to the total content of all components other than the solvent is preferably 5% by mass or more and 99% by mass or less. More preferably, it is more than 95 mass%, and it is especially preferable that it is 15 mass% or more and 90 mass% or less.
［エネルギー線硬化性化合物］
　粘着剤組成物（Ｉ－３）が含有する前記エネルギー線硬化性化合物としては、エネルギー線重合性不飽和基を有し、エネルギー線の照射により硬化可能なモノマー及びオリゴマーが挙げられ、粘着剤組成物（Ｉ－１）が含有するエネルギー線硬化性化合物と同じものが挙げられる。
　粘着剤組成物（Ｉ－３）が含有する前記エネルギー線硬化性化合物は、１種のみでもよいし、２種以上でもよく、２種以上である場合、それらの組み合わせ及び比率は任意に選択できる。 [Energy ray curable compound]
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. .
　前記粘着剤組成物（Ｉ－３）において、前記エネルギー線硬化性化合物の含有量は、粘着性樹脂（Ｉ－２ａ）の含有量１００質量部に対して、０．０１質量部以上３００質量部以下であることが好ましく、０．０３質量部以上２００質量部以下であることがより好ましく、０．０５質量部以上１００質量部以下であることが特に好ましい。 In the pressure-sensitive adhesive composition (I-3), the content of the energy ray-curable compound is 0.01 parts by mass or more and 300 parts by mass with respect to 100 parts by mass of the adhesive resin (I-2a). Is preferably 0.03 parts by mass or more and 200 parts by mass or less, and particularly preferably 0.05 parts by mass or more and 100 parts by mass or less.
［光重合開始剤］
　粘着剤組成物（Ｉ－３）は、さらに光重合開始剤を含有していてもよい。光重合開始剤を含有する粘着剤組成物（Ｉ－３）は、紫外線等の比較的低エネルギーのエネルギー線を照射しても、十分に硬化反応が進行する。 [Photopolymerization initiator]
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.
　粘着剤組成物（Ｉ－３）における前記光重合開始剤としては、粘着剤組成物（Ｉ－１）における光重合開始剤と同じものが挙げられる。
　粘着剤組成物（Ｉ－３）が含有する光重合開始剤は、１種のみでもよいし、２種以上でもよく、２種以上である場合、それらの組み合わせ及び比率は任意に選択できる。 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.
　粘着剤組成物（Ｉ－３）において、光重合開始剤の含有量は、粘着性樹脂（Ｉ－２ａ）及び前記エネルギー線硬化性化合物の総含有量１００質量部に対して、０．０１質量部以上２０質量部以下であることが好ましく、０．０３質量部以上１０質量部以下であることがより好ましく、０．０５質量部以上５質量部以下であることが特に好ましい。 In the pressure-sensitive adhesive composition (I-3), the content of the photopolymerization initiator is 0.01 mass with respect to 100 mass parts of the total content of the pressure-sensitive adhesive resin (I-2a) and the energy ray curable compound. It is preferably no less than 20 parts by mass and no greater than 20 parts by mass, more preferably no less than 0.03 parts by mass and no greater than 10 parts by mass, and particularly preferably no less than 0.05 parts by mass and no greater than 5 parts by mass.
［その他の添加剤］
　粘着剤組成物（Ｉ－３）は、本実施形態における効果を損なわない範囲内において、上述のいずれの成分にも該当しない、その他の添加剤を含有していてもよい。
　前記その他の添加剤としては、粘着剤組成物（Ｉ－１）におけるその他の添加剤と同じものが挙げられる。
　粘着剤組成物（Ｉ－３）が含有するその他の添加剤は、１種のみでもよいし、２種以上でもよく、２種以上である場合、それらの組み合わせ及び比率は任意に選択できる。 [Other additives]
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 that does not impair the effects of the present embodiment.
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.
　粘着剤組成物（Ｉ－３）において、その他の添加剤の含有量は特に限定されず、その種類に応じて適宜選択すればよい。 In the pressure-sensitive adhesive composition (I-3), the content of other additives is not particularly limited, and may be appropriately selected according to the type.
［溶媒］
　粘着剤組成物（Ｉ－３）は、粘着剤組成物（Ｉ－１）の場合と同様の目的で、溶媒を含有していてもよい。
　粘着剤組成物（Ｉ－３）における前記溶媒としては、粘着剤組成物（Ｉ－１）における溶媒と同じものが挙げられる。
　粘着剤組成物（Ｉ－３）が含有する溶媒は、１種のみでもよいし、２種以上でもよく、２種以上である場合、それらの組み合わせ及び比率は任意に選択できる。
　粘着剤組成物（Ｉ－３）において、溶媒の含有量は特に限定されず、適宜調節すればよい。 [solvent]
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.
In the pressure-sensitive adhesive composition (I-3), the content of the solvent is not particularly limited, and may be adjusted as appropriate.
＜粘着剤組成物（Ｉ－１）～（Ｉ－３）以外の粘着剤組成物＞
　ここまでは、粘着剤組成物（Ｉ－１）、粘着剤組成物（Ｉ－２）、及び粘着剤組成物（Ｉ－３）について主に説明したが、これらの含有成分として説明したものは、これら３種の粘着剤組成物以外の全般的な粘着剤組成物（本明細書においては、「粘着剤組成物（Ｉ－１）～（Ｉ－３）以外の粘着剤組成物」と称する）でも、同様に用いることができる。 <Adhesive compositions other than adhesive compositions (I-1) to (I-3)>
Up to this point, the pressure-sensitive adhesive composition (I-1), the pressure-sensitive adhesive composition (I-2), and the pressure-sensitive adhesive composition (I-3) have been mainly described. , General pressure-sensitive adhesive compositions other than these three types of pressure-sensitive adhesive compositions (referred to herein as “pressure-sensitive adhesive compositions other than pressure-sensitive adhesive compositions (I-1) to (I-3)”) However, it can be used similarly.
　粘着剤組成物（Ｉ－１）～（Ｉ－３）以外の粘着剤組成物としては、エネルギー線硬化性の粘着剤組成物以外に、非エネルギー線硬化性の粘着剤組成物も挙げられる。
　非エネルギー線硬化性の粘着剤組成物としては、例えば、アクリル系樹脂、ウレタン系樹脂、ゴム系樹脂、シリコーン系樹脂、エポキシ系樹脂、ポリビニルエーテル、ポリカーボネート、エステル系樹脂等の、非エネルギー線硬化性の粘着性樹脂（Ｉ－１ａ）を含有する粘着剤組成物（Ｉ－４）が挙げられ、アクリル系樹脂を含有するものが好ましい。 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. The pressure-sensitive adhesive composition (I-4) containing an adhesive resin (I-1a) is preferred, and those containing an acrylic resin are preferred.
　粘着剤組成物（Ｉ－１）～（Ｉ－３）以外の粘着剤組成物は、１種又は２種以上の架橋剤を含有することが好ましく、その含有量は、上述の粘着剤組成物（Ｉ－１）等の場合と同様とすることができる。 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).
＜粘着剤組成物（Ｉ－４）＞
　粘着剤組成物（Ｉ－４）で好ましいものとしては、例えば、前記粘着性樹脂（Ｉ－１ａ）と、架橋剤と、を含有するものが挙げられる。 <Adhesive composition (I-4)>
Preferred examples of the pressure-sensitive adhesive composition (I-4) include those containing the pressure-sensitive adhesive resin (I-1a) and a crosslinking agent.
［粘着性樹脂（Ｉ－１ａ）］
　粘着剤組成物（Ｉ－４）における粘着性樹脂（Ｉ－１ａ）としては、粘着剤組成物（Ｉ－１）における粘着性樹脂（Ｉ－１ａ）と同じものが挙げられる。
　粘着剤組成物（Ｉ－４）が含有する粘着性樹脂（Ｉ－１ａ）は、１種のみでもよいし、２種以上でもよく、２種以上である場合、それらの組み合わせ及び比率は任意に選択できる。 [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.
　粘着剤組成物（Ｉ－４）において、溶媒以外の全ての成分の総含有量に対する粘着性樹脂（Ｉ－１ａ）の含有量は、５質量％以上９９質量％以下であることが好ましく、１０質量％以上９５質量％以下であることがより好ましく、１５質量％以上９０質量％以下であることが特に好ましい。例えば、３質量％以上８５質量％以下、４０質量％以上８５質量％以下、及び５０質量％以上８５質量％以下等のいずれかであってもよい。 In the pressure-sensitive adhesive composition (I-4), the content of the pressure-sensitive adhesive resin (I-1a) with respect to the total content of all components other than the solvent is preferably 5% by mass or more and 99% by mass or less. More preferably, it is more than 95 mass%, and it is especially preferable that it is 15 mass% or more and 90 mass% or less. For example, any of 3 mass% or more and 85 mass% or less, 40 mass% or more and 85 mass% or less, 50 mass% or more and 85 mass% or less, etc. may be sufficient.
［架橋剤］
　粘着性樹脂（Ｉ－１ａ）として、（メタ）アクリル酸アルキルエステル由来の構成単位以外に、さらに、官能基含有モノマー由来の構成単位を有する前記アクリル系重合体を用いる場合、粘着剤組成物（Ｉ－４）は、さらに架橋剤を含有することが好ましい。 [Crosslinking agent]
When the acrylic polymer having a structural unit derived from a functional group-containing monomer in addition to the structural unit derived from (meth) acrylic acid alkyl ester is used as the adhesive resin (I-1a), a pressure-sensitive adhesive composition ( I-4) preferably further contains a crosslinking agent.
　粘着剤組成物（Ｉ－４）における架橋剤としては、粘着剤組成物（Ｉ－１）における架橋剤と同じものが挙げられる。
　粘着剤組成物（Ｉ－４）が含有する架橋剤は、１種のみでもよいし、２種以上でもよく、２種以上である場合、それらの組み合わせ及び比率は任意に選択できる。 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.
　前記粘着剤組成物（Ｉ－４）において、架橋剤の含有量は、粘着性樹脂（Ｉ－１ａ）の含有量１００質量部に対して、０．０１質量部以上５０質量部以下であることが好ましく、０．１質量部以上５０質量部以下であることがより好ましく、１質量部以上５０質量部以下であることが特に好ましい。 In the pressure-sensitive adhesive composition (I-4), the content of the crosslinking agent is 0.01 parts by weight or more and 50 parts by weight or less with respect to 100 parts by weight of the pressure-sensitive adhesive resin (I-1a). Is preferably 0.1 parts by mass or more and 50 parts by mass or less, and particularly preferably 1 part by mass or more and 50 parts by mass or less.
［その他の添加剤］
　粘着剤組成物（Ｉ－４）は、本実施形態における効果を損なわない範囲内において、上述のいずれの成分にも該当しない、その他の添加剤を含有していてもよい。
　前記その他の添加剤としては、粘着剤組成物（Ｉ－１）におけるその他の添加剤と同じものが挙げられる。
　粘着剤組成物（Ｉ－４）が含有するその他の添加剤は、１種のみでもよいし、２種以上でもよく、２種以上である場合、それらの組み合わせ及び比率は任意に選択できる。 [Other additives]
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 that does not impair the effects of the present embodiment.
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.
　粘着剤組成物（Ｉ－４）において、その他の添加剤の含有量は特に限定されず、その種類に応じて適宜選択すればよい。 In the pressure-sensitive adhesive composition (I-4), the content of other additives is not particularly limited, and may be appropriately selected according to the type.
［溶媒］
　粘着剤組成物（Ｉ－４）は、粘着剤組成物（Ｉ－１）の場合と同様の目的で、溶媒を含有していてもよい。
　粘着剤組成物（Ｉ－４）における前記溶媒としては、粘着剤組成物（Ｉ－１）における溶媒と同じものが挙げられる。
　粘着剤組成物（Ｉ－４）が含有する溶媒は、１種のみでもよいし、２種以上でもよく、２種以上である場合、それらの組み合わせ及び比率は任意に選択できる。
　粘着剤組成物（Ｉ－４）において、溶媒の含有量は特に限定されず、適宜調節すればよい。 [solvent]
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.
In the pressure-sensitive adhesive composition (I-4), the content of the solvent is not particularly limited and may be appropriately adjusted.
＜＜粘着剤組成物の製造方法＞＞
　粘着剤組成物（Ｉ－１）～（Ｉ－３）や、粘着剤組成物（Ｉ－４）等の粘着剤組成物（Ｉ－１）～（Ｉ－３）以外の粘着剤組成物は、前記粘着剤と、必要に応じて前記粘着剤以外の成分等の、粘着剤組成物を構成するための各成分を配合することで得られる。
　各成分の配合時における添加順序は特に限定されず、２種以上の成分を同時に添加してもよい。
　溶媒を用いる場合には、溶媒を溶媒以外のいずれかの配合成分と混合してこの配合成分を予め希釈しておくことで用いてもよいし、溶媒以外のいずれかの配合成分を予め希釈しておくことなく、溶媒をこれら配合成分と混合することで用いてもよい。
　配合時に各成分を混合する方法は特に限定されず、撹拌子又は撹拌翼等を回転させて混合する方法；ミキサーを用いて混合する方法；超音波を加えて混合する方法等、公知の方法から適宜選択すればよい。
　各成分の添加及び混合時の温度並びに時間は、各配合成分が劣化しない限り特に限定されず、適宜調節すればよいが、温度は１５～３０℃であることが好ましい。 << Method for producing pressure-sensitive adhesive composition >>
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.
When a solvent is used, 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.
○中間層
　中間層は、シート状又はフィルム状であり、その構成材料は目的に応じて適宜選択すればよく、特に限定されない。
　また、中間層のヘーズを適宜調整することで、保護膜形成用複合シートのヘーズを上記範囲に調整することができる。
　中間層は、硬化性を有していてよく、非硬化性を有していてもよい。また、中間層が硬化性を有する場合、熱硬化性及びエネルギー線硬化性のいずれでもよい。 ○ Intermediate layer The intermediate layer is in the form of a sheet or film, and its constituent material may be appropriately selected according to the purpose, and is not particularly limited.
Moreover, the haze of the composite sheet for protective film formation can be adjusted to the said range by adjusting the haze of an intermediate | middle layer suitably.
The intermediate layer may be curable or non-curable. Moreover, when an intermediate | middle layer has sclerosis | hardenability, either thermosetting and energy-beam sclerosis | hardenability may be sufficient.
　中間層は１層（単層）のみでもよいし、２層以上の複数層でもよく、複数層である場合、これら複数層は、互いに同一でも異なっていてもよく、これら複数層の組み合わせは特に限定されない。 The intermediate layer 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. It is not limited.
　中間層の厚さは、例えば０．１μｍ以上２００μｍ以下であればよく、１μｍ以上１５０μｍ以下であればよく、３μｍ以上１２０μｍ以下であればよい。
　ここで、「中間層の厚さ」とは、中間層全体の厚さを意味し、中間層を構成するすべての層の合計の厚さを意味する。なお、中間層の厚さの測定方法としては、例えば、任意の５箇所において、接触式厚み計を用いて厚さを測定し、測定値の平均を算出する方法等が挙げられる。 The thickness of the intermediate layer may be, for example, 0.1 μm or more and 200 μm or less, may be 1 μm or more and 150 μm or less, and may be 3 μm or more and 120 μm or less.
Here, “the thickness of the intermediate layer” means the thickness of the entire intermediate layer, and means the total thickness of all the layers constituting the intermediate layer. In addition, as a measuring method of the thickness of an intermediate | middle layer, the method of measuring thickness using a contact-type thickness meter in arbitrary five places, and calculating the average of a measured value etc. are mentioned, for example.
＜＜中間層形成用組成物＞＞
　中間層は、その構成材料を含有する中間層形成用組成物を用いて形成できる。
　例えば、中間層の形成対象面に中間層形成用組成物を塗工し、必要に応じて乾燥させたり、エネルギー線の照射によって硬化させることで、目的とする部位に中間層を形成できる。
　中間層形成用組成物の塗工は、公知の方法で行えばよく、例えば、上述の粘着剤組成物の塗工の場合と同じ方法で行うことができる。 << Intermediate layer forming composition >>
An intermediate | middle layer can be formed using the composition for intermediate | middle layer formation containing the constituent material.
For example, the intermediate layer can be formed at a target site by applying the intermediate layer-forming composition to the surface on which the intermediate layer is to be formed and drying it as necessary or curing it by irradiation with energy rays.
The intermediate layer-forming composition may be applied by a known method, for example, by the same method as that for the above-mentioned pressure-sensitive adhesive composition.
　中間層形成用組成物の乾燥条件は、特に限定されない。例えば、溶媒を含有している中間層形成用組成物は、加熱乾燥させることが好ましく、この場合、例えば、７０～１３０℃で１０秒～５分の条件で乾燥させることが好ましい。
　中間層形成用組成物は、エネルギー線硬化性を有する場合、乾燥後に、さらにエネルギー線の照射により硬化させることが好ましい。 The drying conditions of the intermediate layer forming composition are not particularly limited. For example, the intermediate layer-forming composition containing a solvent is preferably dried by heating. In this case, for example, it is preferably dried at 70 to 130 ° C. for 10 seconds to 5 minutes.
When the composition for forming an intermediate layer has energy ray curability, it is preferably cured by irradiation with energy rays after drying.
　中間層形成用組成物としては、特別な限定はなく、例えば、上述の粘着剤組成物において例示されたものと同様のもの等が挙げられる。 The intermediate layer forming composition is not particularly limited, and examples thereof include those similar to those exemplified in the above-mentioned pressure-sensitive adhesive composition.
　中間層形成用組成物は、発明の効果を損なわない範囲内において、上述のいずれの成分にも該当しない、その他の添加剤を含有していてもよい。
　前記その他の添加剤としては、例えば、粘着剤組成物（Ｉ－１）におけるその他の添加剤と同じものが挙げられる。
　例えば、中間層形成用組成物が充填材又は着色剤を含有することにより、保護膜形成用複合シートのヘーズを上記範囲に調整することができる。 The composition for forming an intermediate layer may contain other additives that do not correspond to any of the above-described components within a range not impairing the effects of the invention.
Examples of the other additives include the same additives as the other additives in the pressure-sensitive adhesive composition (I-1).
For example, when the composition for forming an intermediate layer contains a filler or a colorant, the haze of the composite sheet for forming a protective film can be adjusted to the above range.
◎保護膜形成用フィルム
　保護膜形成用フィルムは、硬化性を有していてよく、非硬化性を有していてもよい。
　また、保護膜形成用フィルムが硬化性を有する場合、熱硬化性及びエネルギー線硬化性のいずれでもよい。 ◎ Protective film-forming film The protective film-forming film may be curable or non-curable.
Moreover, when the film for protective film formation has sclerosis | hardenability, any of thermosetting and energy-beam sclerosis | hardenability may be sufficient.
○熱硬化性保護膜形成用フィルム
　好ましい熱硬化性保護膜形成用フィルムとしては、例えば、重合体成分（Ａ）及び熱硬化性成分（Ｂ）を含有するものが挙げられる。重合体成分（Ａ）は、重合性化合物が重合反応して形成されたとみなせる成分である。また、熱硬化性成分（Ｂ）は、熱を反応のトリガーとして、硬化（重合）反応し得る成分である。なお、本実施形態において重合反応には、重縮合反応も含まれる。 A film for forming a thermosetting protective film Examples of preferable film for forming a thermosetting protective film include those containing a polymer component (A) and a thermosetting component (B). The polymer component (A) is a component that can be regarded as formed by polymerization reaction of the polymerizable compound. The thermosetting component (B) is a component that can undergo a curing (polymerization) reaction using heat as a reaction trigger. In the present embodiment, the polymerization reaction includes a polycondensation reaction.
　熱硬化性保護膜形成用フィルムは、１層（単層）からなるものでもよいし、２層以上の複数層からなるものでもよい。熱硬化性保護膜形成用フィルムが複数層からなる場合、これら複数層は、互いに同一でも異なっていてもよい。ここで、「複数層が互いに同一でも異なっていてもよい」とは、上述の基材の場合と同様のことを意味する。そして、複数層が互いに異なる場合、これら複数層の組み合わせは特に限定されない。 The thermosetting protective film-forming film may be composed of one layer (single layer), or may be composed of two or more layers. When the thermosetting protective film-forming film is composed of a plurality of layers, the plurality of layers may be the same as or different from each other. Here, “the plurality of layers may be the same as or different from each other” means the same as in the case of the above-described base material. And when several layers differ from each other, the combination of these several layers is not specifically limited.
　熱硬化性保護膜形成用フィルムの厚さは、１μｍ以上１００μｍ以下であることが好ましく、５μｍ以上７５μｍ以下であることがより好ましく、５μｍ以上５０μｍ以下であることが特に好ましい。熱硬化性保護膜形成用フィルムの厚さが前記下限値以上であることで、保護能がより高い保護膜を形成できる。また、熱硬化性保護膜形成用フィルムの厚さが前記上限値以下であることで、過剰な厚さとなることが抑制される。
　ここで、「熱硬化性保護膜形成用フィルムの厚さ」とは、熱硬化性保護膜形成用フィルム全体の厚さを意味し、例えば、複数層からなる熱硬化性保護膜形成用フィルムの厚さとは、熱硬化性保護膜形成用フィルムを構成するすべての層の合計の厚さを意味する。なお、熱硬化性保護膜形成用フィルムの厚さの測定方法としては、例えば、任意の５箇所において、接触式厚み計を用いて厚さを測定し、測定値の平均を算出する方法等が挙げられる。 The thickness of the thermosetting protective film-forming film is preferably 1 μm or more and 100 μm or less, more preferably 5 μm or more and 75 μm or less, and particularly preferably 5 μm or more and 50 μm or less. When the thickness of the thermosetting protective film-forming film is equal to or more than the lower limit value, a protective film with higher protective ability can be formed. Moreover, when the thickness of the thermosetting protective film-forming film is equal to or less than the upper limit value, an excessive thickness is suppressed.
Here, the “thickness of the thermosetting protective film forming film” means the thickness of the entire thermosetting protective film forming film, for example, a thermosetting protective film forming film composed of a plurality of layers. The thickness means the total thickness of all the layers constituting the thermosetting protective film forming film. The method for measuring the thickness of the thermosetting protective film-forming film includes, for example, a method of measuring the thickness using a contact-type thickness meter at any five locations and calculating the average of the measured values. Can be mentioned.
　熱硬化性保護膜形成用フィルムを半導体ウエハの裏面に貼付し、硬化させるときの硬化条件は、保護膜が十分にその機能を発揮する程度の硬化度となる限り特に限定されず、熱硬化性保護膜形成用フィルムの種類に応じて、適宜選択すればよい。
　例えば、熱硬化性保護膜形成用フィルムの硬化時の加熱温度は、１００℃以上２００℃以下であることが好ましく、１１０℃以上１８０℃以下であることがより好ましく、１２０℃以上１７０℃以下であることが特に好ましい。そして、前記硬化時の加熱時間は、０．５時間以上５時間以下であることが好ましく、０．５時間以上３時間以下であることがより好ましく、１時間以上２時間以下であることが特に好ましい。 The curing conditions for applying and curing the thermosetting protective film-forming film on the back surface of the semiconductor wafer are not particularly limited as long as the degree of curing is such that the protective film exhibits its function sufficiently. What is necessary is just to select suitably according to the kind of film for protective film formation.
For example, the heating temperature during curing of the thermosetting protective film-forming film is preferably 100 ° C. or higher and 200 ° C. or lower, more preferably 110 ° C. or higher and 180 ° C. or lower, and 120 ° C. or higher and 170 ° C. or lower. It is particularly preferred. The heating time during the curing is preferably 0.5 hours or more and 5 hours or less, more preferably 0.5 hours or more and 3 hours or less, and particularly preferably 1 hour or more and 2 hours or less. preferable.
＜＜熱硬化性保護膜形成用組成物＞＞
　熱硬化性保護膜形成用フィルムは、その構成材料を含有する熱硬化性保護膜形成用組成物を用いて形成できる。例えば、熱硬化性保護膜形成用フィルムの形成対象面に熱硬化性保護膜形成用組成物を塗工し、必要に応じて乾燥させることで、目的とする部位に熱硬化性保護膜形成用フィルムを形成できる。熱硬化性保護膜形成用組成物中の、常温で気化しない成分同士の含有量の比率は、通常、熱硬化性保護膜形成用フィルムの前記成分同士の含有量の比率と同じとなる。ここで、「常温」とは、先に説明したとおりである。 << The composition for thermosetting protective film formation >>
The film for forming a thermosetting protective film can be formed using a composition for forming a thermosetting protective film containing the constituent materials. For example, the composition for forming a thermosetting protective film is applied to the surface to be formed of the film for forming a thermosetting protective film, and dried as necessary to form a thermosetting protective film on the target site. A film can be formed. The ratio of the content of components that do not vaporize at room temperature in the thermosetting protective film-forming composition is usually the same as the content ratio of the components of the thermosetting protective film-forming film. Here, “normal temperature” is as described above.
　熱硬化性保護膜形成用組成物の塗工は、例えば、上述の粘着剤組成物の塗工の場合と同じ方法で行うことができる。 Application of the thermosetting protective film-forming composition can be performed, for example, in the same manner as in the case of application of the above-described pressure-sensitive adhesive composition.
　熱硬化性保護膜形成用組成物の乾燥条件は、特に限定されないが、熱硬化性保護膜形成用組成物は、後述する溶媒を含有している場合、加熱乾燥させることが好ましく、この場合、例えば、７０℃以上１３０℃以下で１０秒以上５分以下の条件で乾燥させることが好ましい。 The drying conditions of the composition for forming a thermosetting protective film are not particularly limited, but when the composition for forming a thermosetting protective film contains a solvent to be described later, it is preferably dried by heating. For example, the drying is preferably performed at 70 ° C. to 130 ° C. for 10 seconds to 5 minutes.
＜熱硬化性保護膜形成用組成物（ＩＩＩ－１）＞
　熱硬化性保護膜形成用組成物としては、例えば、重合体成分（Ａ）及び熱硬化性成分（Ｂ）を含有する熱硬化性保護膜形成用組成物（ＩＩＩ－１）（本明細書においては、単に「組成物（ＩＩＩ－１）」と略記することがある）等が挙げられる。 <Thermosetting protective film forming composition (III-1)>
As the composition for forming a thermosetting protective film, for example, a composition (III-1) for forming a thermosetting protective film containing a polymer component (A) and a thermosetting component (B) (in this specification) May be simply abbreviated as “composition (III-1)”).
［重合体成分（Ａ）］
　重合体成分（Ａ）は、熱硬化性保護膜形成用フィルムに造膜性や可撓性等を付与するための重合体化合物である。
　組成物（ＩＩＩ－１）及び熱硬化性保護膜形成用フィルムが含有する重合体成分（Ａ）は、１種のみでもよいし、２種以上でもよく、２種以上である場合、それらの組み合わせ及び比率は任意に選択できる。 [Polymer component (A)]
The polymer component (A) is a polymer compound for imparting film-forming properties, flexibility and the like to the thermosetting protective film-forming film.
The polymer component (A) contained in the composition (III-1) and the thermosetting 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.
　重合体成分（Ａ）としては、例えば、アクリル系樹脂（（メタ）アクリロイル基を有する樹脂）、ポリエステル、ウレタン系樹脂（ウレタン結合を有する樹脂）、アクリルウレタン樹脂、シリコーン系樹脂（シロキサン結合を有する樹脂）、ゴム系樹脂（ゴム構造を有する樹脂）、フェノキシ樹脂、熱硬化性ポリイミド等が挙げられ、アクリル系樹脂が好ましい。 Examples of the polymer component (A) include an acrylic resin (a resin having a (meth) acryloyl group), a polyester, a urethane resin (a resin having a urethane bond), an acrylic urethane resin, and a silicone resin (having a siloxane bond). Resin), rubber resin (resin having a rubber structure), phenoxy resin, thermosetting polyimide and the like, and acrylic resin is preferable.
重合体成分（Ａ）における前記アクリル系樹脂としては、公知のアクリル重合体が挙げられる。
　アクリル系樹脂の重量平均分子量（Ｍｗ）は、１００００以上２００００００以下であることが好ましく、１０００００以上１５０００００以下であることがより好ましい。アクリル系樹脂の重量平均分子量が前記下限値以上であることで、熱硬化性保護膜形成用フィルムの形状安定性（保管時の経時安定性）が向上する。また、アクリル系樹脂の重量平均分子量が前記上限値以下であることで、被着体の凹凸面へ熱硬化性保護膜形成用フィルムが追従し易くなり、被着体と熱硬化性保護膜形成用フィルムとの間でボイド等の発生がより抑制される。
　なお、本明細書において、重量平均分子量とは、特に断りのない限り、ゲル・パーミエーション・クロマトグラフィー（ＧＰＣ）法により測定されるポリスチレン換算値である。 As said acrylic resin in a polymer component (A), a well-known acrylic polymer is mentioned.
The weight average molecular weight (Mw) of the acrylic resin is preferably from 10,000 to 2,000,000, and more preferably from 100,000 to 1,500,000. When the weight average molecular weight of the acrylic resin is equal to or more than the lower limit, the shape stability (time stability during storage) of the thermosetting protective film-forming film is improved. In addition, when the weight average molecular weight of the acrylic resin is not more than the above upper limit value, the thermosetting protective film forming film easily follows the uneven surface of the adherend, and the adherend and the thermosetting protective film are formed. Occurrence of voids and the like with the film is further suppressed.
In the present specification, the weight average molecular weight is a polystyrene conversion value measured by a gel permeation chromatography (GPC) method unless otherwise specified.
　アクリル系樹脂のガラス転移温度（Ｔｇ）は、－６０℃以上７０℃以下であることが好ましく、－３０℃以上５０℃以下であることがより好ましい。アクリル系樹脂のＴｇが前記下限値以上であることで、保護膜と支持シート（粘着剤層）との接着力が抑制されて、支持シートの剥離性が向上する。また、アクリル系樹脂のＴｇが前記上限値以下であることで、保護膜の被着体との接着力が向上する。
　なお、本明細書において、「ガラス転移温度（Ｔｇ）とは、ＪＩＳ　Ｋ７１２１に準拠して「示差走査熱量測定（ＤＳＣ）測定器」で測定した値で表される。 The glass transition temperature (Tg) of the acrylic resin is preferably −60 ° C. or higher and 70 ° C. or lower, and more preferably −30 ° C. or higher and 50 ° C. or lower. When the Tg of the acrylic resin is equal to or higher than the lower limit, the adhesive force between the protective film and the support sheet (adhesive layer) is suppressed, and the peelability of the support sheet is improved. Moreover, adhesive force with the adherend of a protective film improves because Tg of acrylic resin is below the said upper limit.
In the present specification, “glass transition temperature (Tg)” is represented by a value measured with a “differential scanning calorimetry (DSC) measuring device” in accordance with JIS K7121.
　アクリル系樹脂としては、例えば、１種又は２種以上の（メタ）アクリル酸エステルの重合体；（メタ）アクリル酸、イタコン酸、酢酸ビニル、アクリロニトリル、スチレン及びＮ－メチロールアクリルアミド等から選択される２種以上のモノマーの共重合体等が挙げられる。 The acrylic resin is selected from, for example, a polymer of one or more (meth) acrylic acid esters; (meth) acrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene, N-methylolacrylamide, and the like. Examples include copolymers of two or more monomers.
アクリル系樹脂を構成する前記（メタ）アクリル酸エステルとしては、例えば、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸ｎ－プロピル、（メタ）アクリル酸イソプロピル、（メタ）アクリル酸ｎ－ブチル、（メタ）アクリル酸イソブチル、（メタ）アクリル酸ｓｅｃ－ブチル、（メタ）アクリル酸ｔｅｒｔ－ブチル、（メタ）アクリル酸ペンチル、（メタ）アクリル酸ヘキシル、（メタ）アクリル酸ヘプチル、（メタ）アクリル酸２－エチルヘキシル、（メタ）アクリル酸イソオクチル、（メタ）アクリル酸ｎ－オクチル、（メタ）アクリル酸ｎ－ノニル、（メタ）アクリル酸イソノニル、（メタ）アクリル酸デシル、（メタ）アクリル酸ウンデシル、（メタ）アクリル酸ドデシル（（メタ）アクリル酸ラウリル）、（メタ）アクリル酸トリデシル、（メタ）アクリル酸テトラデシル（（メタ）アクリル酸ミリスチル）、（メタ）アクリル酸ペンタデシル、（メタ）アクリル酸ヘキサデシル（（メタ）アクリル酸パルミチル）、（メタ）アクリル酸ヘプタデシル、（メタ）アクリル酸オクタデシル（（メタ）アクリル酸ステアリル）等の、アルキルエステルを構成するアルキル基が、炭素数が１～１８の鎖状構造である（メタ）アクリル酸アルキルエステル；
　（メタ）アクリル酸イソボルニル、（メタ）アクリル酸ジシクロペンタニル等の（メタ）アクリル酸シクロアルキルエステル；
　（メタ）アクリル酸ベンジル等の（メタ）アクリル酸アラルキルエステル；
　（メタ）アクリル酸ジシクロペンテニルエステル等の（メタ）アクリル酸シクロアルケニルエステル；
　（メタ）アクリル酸ジシクロペンテニルオキシエチルエステル等の（メタ）アクリル酸シクロアルケニルオキシアルキルエステル；
　（メタ）アクリル酸イミド；
　（メタ）アクリル酸グリシジル等のグリシジル基含有（メタ）アクリル酸エステル；
　（メタ）アクリル酸ヒドロキシメチル、（メタ）アクリル酸２－ヒドロキシエチル、（メタ）アクリル酸２－ヒドロキシプロピル、（メタ）アクリル酸３－ヒドロキシプロピル、（メタ）アクリル酸２－ヒドロキシブチル、（メタ）アクリル酸３－ヒドロキシブチル、（メタ）アクリル酸４－ヒドロキシブチル等の水酸基含有（メタ）アクリル酸エステル；
　（メタ）アクリル酸Ｎ－メチルアミノエチル等の置換アミノ基含有（メタ）アクリル酸エステル等が挙げられる。ここで、「置換アミノ基」とは、アミノ基の１個又は２個の水素原子が水素原子以外の基で置換されてなる基を意味する。 Examples of the (meth) acrylic acid ester constituting the acrylic resin include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, (meth ) N-butyl acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, (meth) acrylic Heptyl acid, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, n-octyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate , Undecyl (meth) acrylate, dodecyl (meth) acrylate ((meth) acrylic acid (Uril), tridecyl (meth) acrylate, tetradecyl (meth) acrylate (myristyl (meth) acrylate), pentadecyl (meth) acrylate, hexadecyl (meth) acrylate (palmityl (meth) acrylate), (meth) (Meth) acrylic acid alkyl esters in which the alkyl group constituting the alkyl ester, such as heptadecyl acrylate and octadecyl (meth) acrylate (stearyl (meth) acrylate), is a chain structure having 1 to 18 carbon atoms;
(Meth) acrylic acid cycloalkyl esters such as (meth) acrylic acid isobornyl, (meth) acrylic acid dicyclopentanyl;
(Meth) acrylic acid aralkyl esters such as (meth) acrylic acid benzyl;
(Meth) acrylic acid cycloalkenyl esters such as (meth) acrylic acid dicyclopentenyl ester;
(Meth) acrylic acid cycloalkenyloxyalkyl esters such as (meth) acrylic acid dicyclopentenyloxyethyl ester;
(Meth) acrylic imide;
Glycidyl group-containing (meth) acrylic acid ester such as (meth) acrylic acid glycidyl;
Hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, (meta ) Hydroxyl group-containing (meth) acrylic acid esters such as 3-hydroxybutyl acrylate and 4-hydroxybutyl (meth) acrylate;
Examples thereof include substituted amino group-containing (meth) acrylic acid esters such as N-methylaminoethyl (meth) acrylate. Here, the “substituted amino group” means a group formed by replacing one or two hydrogen atoms of an amino group with a group other than a hydrogen atom.
　アクリル系樹脂は、例えば、前記（メタ）アクリル酸エステル以外に、（メタ）アクリル酸、イタコン酸、酢酸ビニル、アクリロニトリル、スチレン及びＮ－メチロールアクリルアミド等から選択される１種又は２種以上のモノマーが共重合してなるものでもよい。 The acrylic resin is, for example, one or more monomers selected from (meth) acrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene, N-methylolacrylamide and the like in addition to the (meth) acrylic ester. May be obtained by copolymerization.
　アクリル系樹脂を構成するモノマーは、１種のみでもよいし、２種以上でもよく、２種以上である場合、それらの組み合わせ及び比率は任意に選択できる。 Only one type of monomer constituting the acrylic resin may be used, or two or more types may be used, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected.
　アクリル系樹脂は、ビニル基、（メタ）アクリロイル基、アミノ基、水酸基、カルボキシ基、イソシアネート基等の他の化合物と結合可能な官能基を有していてもよい。アクリル系樹脂の前記官能基は、後述する架橋剤（Ｆ）を介して他の化合物と結合してもよいし、架橋剤（Ｆ）を介さずに他の化合物と直接結合していてもよい。アクリル系樹脂が前記官能基により他の化合物と結合することで、保護膜形成用複合シートを用いて得られたパッケージの信頼性が向上する傾向がある。 The acrylic resin may have a functional group that can be bonded to other compounds such as a vinyl group, a (meth) acryloyl group, an amino group, a hydroxyl group, a carboxy group, and an isocyanate group. The functional group of the acrylic resin may be bonded to another compound via a cross-linking agent (F) described later, or may be directly bonded to another compound not via the cross-linking agent (F). . When the acrylic resin is bonded to another compound through the functional group, the reliability of the package obtained using the composite sheet for forming a protective film tends to be improved.
　本明細書においては、重合体成分（Ａ）として、アクリル系樹脂以外の熱可塑性樹脂（以下、単に「熱可塑性樹脂」と略記することがある）を、アクリル系樹脂を用いずに単独で用いてもよいし、アクリル系樹脂と併用してもよい。前記熱可塑性樹脂を用いることで、保護膜の支持シートからの剥離性が向上したり、被着体の凹凸面へ熱硬化性保護膜形成用フィルムが追従し易くなり、被着体と熱硬化性保護膜形成用フィルムとの間でボイド等の発生がより抑制されることがある。 In the present specification, as the polymer component (A), a thermoplastic resin other than an acrylic resin (hereinafter sometimes simply referred to as “thermoplastic resin”) is used alone without using an acrylic resin. It may be used in combination with an acrylic resin. By using the thermoplastic resin, the peelability of the protective film from the support sheet is improved, and the thermosetting protective film-forming film easily follows the uneven surface of the adherend. The generation of voids and the like may be further suppressed between the protective protective film-forming film.
　前記熱可塑性樹脂の重量平均分子量は１０００以上１０００００以下であることが好ましく、３０００以上８００００以下であることがより好ましい。ここで、「重量平均分子量」とは、先に説明したとおりである。 The weight average molecular weight of the thermoplastic resin is preferably 1000 or more and 100,000 or less, and more preferably 3000 or more and 80,000 or less. Here, the “weight average molecular weight” is as described above.
　前記熱可塑性樹脂のガラス転移温度（Ｔｇ）は、－３０以上１５０℃以下であることが好ましく、－２０以上１２０℃以下であることがより好ましい。 The glass transition temperature (Tg) of the thermoplastic resin is preferably −30 to 150 ° C., more preferably −20 to 120 ° C.
　前記熱可塑性樹脂としては、例えば、ポリエステル、ポリウレタン、フェノキシ樹脂、ポリブテン、ポリブタジエン、ポリスチレン等が挙げられる。 Examples of the thermoplastic resin include polyester, polyurethane, phenoxy resin, polybutene, polybutadiene, and polystyrene.
　組成物（ＩＩＩ－１）及び熱硬化性保護膜形成用フィルムが含有する前記熱可塑性樹脂は、１種のみでもよいし、２種以上でもよく、２種以上である場合、それらの組み合わせ及び比率は任意に選択できる。 The thermoplastic resin contained in the composition (III-1) and the thermosetting protective film-forming film may be only one kind, two kinds or more, and in the case of two kinds or more, combinations and ratios thereof. Can be chosen arbitrarily.
　組成物（ＩＩＩ－１）において、溶媒以外の全ての成分の総含有量に対する重合体成分（Ａ）の含有量の割合（すなわち、熱硬化性保護膜形成用フィルムの重合体成分（Ａ）の含有量）は、重合体成分（Ａ）の種類によらず、５質量％以上８５質量％以下であることが好ましく、５質量％以上８０質量％以下であることがより好ましい。例えば、５質量％以上６５質量％以下、５質量％以上５０質量％以下、及び１０質量％以上３５質量％以下等のいずれかであってもよい。 In the composition (III-1), the ratio of the content of the polymer component (A) to the total content of all components other than the solvent (that is, the polymer component (A) of the thermosetting protective film-forming film) The content is preferably 5% by mass or more and 85% by mass or less, more preferably 5% by mass or more and 80% by mass or less, regardless of the type of the polymer component (A). For example, any of 5 mass% or more and 65 mass% or less, 5 mass% or more and 50 mass% or less, 10 mass% or more and 35 mass% or less, etc. may be sufficient.
重合体成分（Ａ）は、熱硬化性成分（Ｂ）にも該当する場合がある。本実施形態においては、組成物（ＩＩＩ－１）が、このような重合体成分（Ａ）及び熱硬化性成分（Ｂ）の両方に該当する成分を含有する場合、組成物（ＩＩＩ－１）は、重合体成分（Ａ）及び熱硬化性成分（Ｂ）を含有するとみなす。 The polymer component (A) may also correspond to the thermosetting component (B). In the present embodiment, when the composition (III-1) contains components corresponding to both the polymer component (A) and the thermosetting component (B), the composition (III-1) Is considered to contain a polymer component (A) and a thermosetting component (B).
［熱硬化性成分（Ｂ）］
　熱硬化性成分（Ｂ）は、熱硬化性保護膜形成用フィルムを硬化させて、硬質の保護膜を形成するための成分である。
　組成物（ＩＩＩ－１）及び熱硬化性保護膜形成用フィルムが含有する熱硬化性成分（Ｂ）は、１種のみでもよいし、２種以上でもよく、２種以上である場合、それらの組み合わせ及び比率は任意に選択できる。 [Thermosetting component (B)]
The thermosetting component (B) is a component for curing a thermosetting protective film-forming film to form a hard protective film.
The thermosetting component (B) contained in the composition (III-1) and the thermosetting 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.
　熱硬化性成分（Ｂ）としては、例えば、エポキシ系熱硬化性樹脂、熱硬化性ポリイミド、ポリウレタン、不飽和ポリエステル、シリコーン樹脂等が挙げられ、エポキシ系熱硬化性樹脂が好ましい。 Examples of the thermosetting component (B) include epoxy thermosetting resins, thermosetting polyimides, polyurethanes, unsaturated polyesters, and silicone resins, and epoxy thermosetting resins are preferable.
（エポキシ系熱硬化性樹脂）
　エポキシ系熱硬化性樹脂は、エポキシ樹脂（Ｂ１）及び熱硬化剤（Ｂ２）からなる。
　組成物（ＩＩＩ－１）及び熱硬化性保護膜形成用フィルムが含有するエポキシ系熱硬化性樹脂は、１種のみでもよいし、２種以上でもよく、２種以上である場合、それらの組み合わせ及び比率は任意に選択できる。 (Epoxy thermosetting resin)
The epoxy thermosetting resin includes an epoxy resin (B1) and a thermosetting agent (B2).
The epoxy thermosetting resin contained in the composition (III-1) and the thermosetting 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.
・エポキシ樹脂（Ｂ１）
　エポキシ樹脂（Ｂ１）としては、公知のものが挙げられ、例えば、多官能系エポキシ樹脂、ビフェニル化合物、ビスフェノールＡジグリシジルエーテル及びその水添物、オルソクレゾールノボラックエポキシ樹脂、ジシクロペンタジエン型エポキシ樹脂、ビフェニル型エポキシ樹脂、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、フェニレン骨格型エポキシ樹脂等、２官能以上のエポキシ化合物が挙げられる。 ・ Epoxy resin (B1)
Examples of the epoxy resin (B1) 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.
　エポキシ樹脂（Ｂ１）としては、不飽和炭化水素基を有するエポキシ樹脂を用いてもよい。不飽和炭化水素基を有するエポキシ樹脂は、不飽和炭化水素基を有しないエポキシ樹脂よりもアクリル系樹脂との相溶性が高い。そのため、不飽和炭化水素基を有するエポキシ樹脂を用いることで、保護膜形成用複合シートを用いて得られた保護膜付き半導体チップの信頼性が向上する。 As the epoxy resin (B1), an epoxy resin having an unsaturated hydrocarbon group may be used. 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, by using an epoxy resin having an unsaturated hydrocarbon group, the reliability of the semiconductor chip with a protective film obtained using the composite sheet for forming a protective film is improved.
　不飽和炭化水素基を有するエポキシ樹脂としては、例えば、多官能系エポキシ樹脂のエポキシ基の一部が不飽和炭化水素基を有する基に変換されてなる化合物が挙げられる。このような化合物は、例えば、エポキシ基へ（メタ）アクリル酸又はその誘導体を付加反応させることにより得られる。
　また、不飽和炭化水素基を有するエポキシ樹脂としては、例えば、エポキシ樹脂を構成する芳香環等に、不飽和炭化水素基を有する基が直接結合した化合物等が挙げられる。
　不飽和炭化水素基は、重合性を有する不飽和基であり、その具体的な例としては、エテニル基（ビニル基）、２－プロペニル基（アリル基）、（メタ）アクリロイル基、（メタ）アクリルアミド基等が挙げられ、アクリロイル基が好ましい。 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.
Moreover, as an epoxy resin which has an unsaturated hydrocarbon group, the compound etc. which the group which has an unsaturated hydrocarbon group directly couple | bonded with the aromatic ring etc. which comprise an epoxy resin are mentioned, for example.
The unsaturated hydrocarbon group is a polymerizable unsaturated group, and specific examples thereof include ethenyl group (vinyl group), 2-propenyl group (allyl group), (meth) acryloyl group, (meth) An acrylamide group etc. are mentioned, An acryloyl group is preferable.
　エポキシ樹脂（Ｂ１）の数平均分子量は、特に限定されないが、熱硬化性保護膜形成用フィルムの硬化性、並びに硬化後の保護膜の強度及び耐熱性の点から、３００以上３００００以下であることが好ましく、３００以上１００００以下であることがより好ましく、３００以上３０００以下であることが特に好ましい。
　本明細書において、「数平均分子量」とは、特に断らない限り、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）法によって測定される標準ポリスチレン換算の値で表される数平均分子量を意味する。 Although the number average molecular weight of an epoxy resin (B1) is not specifically limited, From the point of sclerosis | hardenability of the film for thermosetting protective film formation, and the intensity | strength and heat resistance of the protective film after hardening, it is 300 or more and 30000 or less. Is more preferably 300 or more and 10,000 or less, and particularly preferably 300 or more and 3000 or less.
In the present specification, 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.
　エポキシ樹脂（Ｂ１）のエポキシ当量は、１００ｇ／ｅｑ以上１０００ｇ／ｅｑ以下であることが好ましく、１５０ｇ／ｅｑ以上９５０ｇ／ｅｑ以下であることがより好ましい。
　本明細書において、「エポキシ当量」とは、１グラム当量のエポキシ基を含むエポキシ化合物のグラム数（ｇ／ｅｑ）を意味し、ＪＩＳ　Ｋ　７２３６：２００１の方法に従って測定することができる。 The epoxy equivalent of the epoxy resin (B1) is preferably 100 g / eq or more and 1000 g / eq or less, and more preferably 150 g / eq or more and 950 g / eq or less.
In the present specification, 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.
　エポキシ樹脂（Ｂ１）は、１種を単独で用いてもよいし、２種以上を併用してもよく、２種以上を併用する場合、それらの組み合わせ及び比率は任意に選択できる。 The epoxy resin (B1) may be used alone or in combination of two or more, and when two or more are used in combination, their combination and ratio can be arbitrarily selected.
・熱硬化剤（Ｂ２）
　熱硬化剤（Ｂ２）は、エポキシ樹脂（Ｂ１）に対する硬化剤として機能する。
　熱硬化剤（Ｂ２）としては、例えば、１分子中にエポキシ基と反応し得る官能基を２個以上有する化合物が挙げられる。前記官能基としては、例えば、フェノール性水酸基、アルコール性水酸基、アミノ基、カルボキシ基、酸基が無水物化された基等が挙げられ、フェノール性水酸基、アミノ基、又は酸基が無水物化された基であることが好ましく、フェノール性水酸基又はアミノ基であることがより好ましい。 ・ Thermosetting agent (B2)
The thermosetting agent (B2) functions as a curing agent for the epoxy resin (B1).
As a thermosetting agent (B2), the compound which has 2 or more of functional groups which can react with an epoxy group in 1 molecule is mentioned, for example. Examples of 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.
　熱硬化剤（Ｂ２）のうち、フェノール性水酸基を有するフェノール系硬化剤としては、例えば、多官能フェノール樹脂、ビフェノール、ノボラック型フェノール樹脂、ジシクロペンタジエン型フェノール樹脂、アラルキル型フェノール樹脂等が挙げられる。
　熱硬化剤（Ｂ２）のうち、アミノ基を有するアミン系硬化剤としては、例えば、ジシアンジアミド（以下、「ＤＩＣＹ」と略記することがある）等が挙げられる。 Among the thermosetting agents (B2), examples of the phenolic curing agent having a phenolic hydroxyl group include polyfunctional phenol resins, biphenols, novolac type phenol resins, dicyclopentadiene type phenol resins, and aralkyl type phenol resins. .
Among the thermosetting agents (B2), examples of the amine-based curing agent having an amino group include dicyandiamide (hereinafter sometimes abbreviated as “DICY”).
　熱硬化剤（Ｂ２）は、不飽和炭化水素基を有するものでもよい。
　不飽和炭化水素基を有する熱硬化剤（Ｂ２）としては、例えば、フェノール樹脂の水酸基の一部が、不飽和炭化水素基を有する基で置換されてなる化合物、フェノール樹脂の芳香環に、不飽和炭化水素基を有する基が直接結合してなる化合物等が挙げられる。
　熱硬化剤（Ｂ２）における前記不飽和炭化水素基は、上述の不飽和炭化水素基を有するエポキシ樹脂における不飽和炭化水素基と同様のものである。 The thermosetting agent (B2) may have an unsaturated hydrocarbon group.
Examples of the thermosetting agent (B2) having an unsaturated hydrocarbon group include compounds 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 (B2) is the same as the unsaturated hydrocarbon group in the epoxy resin having an unsaturated hydrocarbon group described above.
　熱硬化剤（Ｂ２）としてフェノール系硬化剤を用いる場合には、保護膜の支持シートからの剥離性が向上する点から、熱硬化剤（Ｂ２）は軟化点又はガラス転移温度が高いものが好ましい。 When using a phenolic curing agent as the thermosetting agent (B2), it is preferable that the thermosetting agent (B2) has a high softening point or glass transition temperature in terms of improving the peelability of the protective film from the support sheet. .
　熱硬化剤（Ｂ２）のうち、例えば、多官能フェノール樹脂、ノボラック型フェノール樹脂、ジシクロペンタジエン型フェノール樹脂、アラルキル型フェノール樹脂等の樹脂成分の数平均分子量は、３００以上３００００以下であることが好ましく、４００以上１００００以下であることがより好ましく、５００以上３０００以下であることが特に好ましい。
　熱硬化剤（Ｂ２）のうち、例えば、ビフェノール、ジシアンジアミド等の非樹脂成分の分子量は、特に限定されないが、例えば、６０以上５００以下であることが好ましい。 Among the thermosetting agents (B2), for example, the number average molecular weight of a resin component such as a polyfunctional phenol resin, a novolac-type phenol resin, a dicyclopentadiene-type phenol resin, or an aralkyl-type phenol resin may be 300 or more and 30000 or less. Preferably, it is 400 or more and 10,000 or less, and particularly preferably 500 or more and 3000 or less.
Among the thermosetting agents (B2), for example, the molecular weight of non-resin components such as biphenol and dicyandiamide is not particularly limited, but is preferably 60 or more and 500 or less, for example.
　熱硬化剤（Ｂ２）は、１種を単独で用いてもよいし、２種以上を併用してもよく、２種以上を併用する場合、それらの組み合わせ及び比率は任意に選択できる。 A thermosetting agent (B2) 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.
　組成物（ＩＩＩ－１）及び熱硬化性保護膜形成用フィルムにおいて、熱硬化剤（Ｂ２）の含有量は、エポキシ樹脂（Ｂ１）の含有量１００質量部に対して、０．１質量部以上５００質量部以下であることが好ましく、１質量部以上２００質量部以下であることがより好ましい。例えば、１質量部以上１００質量部以下、１質量部以上５０質量部以下、及び１質量部以上１０質量部以下等のいずれかであってもよい。熱硬化剤（Ｂ２）の前記含有量が前記下限値以上であることで、熱硬化性保護膜形成用フィルムの硬化がより進行し易くなる。また、熱硬化剤（Ｂ２）の前記含有量が前記上限値以下であることで、熱硬化性保護膜形成用フィルムの吸湿率が低減されて、保護膜形成用複合シートを用いて得られたパッケージの信頼性がより向上する。 In the composition (III-1) and the thermosetting protective film forming film, the content of the thermosetting agent (B2) is 0.1 parts by mass or more with respect to 100 parts by mass of the epoxy resin (B1). The amount is preferably 500 parts by mass or less, and more preferably 1 part by mass or more and 200 parts by mass or less. For example, any of 1 part by mass or more and 100 parts by mass or less, 1 part by mass or more and 50 parts by mass or less, and 1 part by mass or more and 10 parts by mass or less may be used. When the content of the thermosetting agent (B2) is equal to or more than the lower limit value, curing of the thermosetting protective film-forming film is more likely to proceed. Moreover, the moisture absorption rate of the film for thermosetting protective film formation was reduced because the said content of the thermosetting agent (B2) was below the said upper limit, and it was obtained using the composite sheet for protective film formation Improved package reliability.
組成物（ＩＩＩ－１）及び熱硬化性保護膜形成用フィルムにおいて、熱硬化性成分（Ｂ）の含有量（例えば、エポキシ樹脂（Ｂ１）及び熱硬化剤（Ｂ２）の総含有量）は、重合体成分（Ａ）の含有量１００質量部に対して、２０質量部以上５００質量部以下であることが好ましく、３０質量部以上３００質量部以下であることがより好ましく、４０質量部以上１５０質量部以下であることが特に好ましい。熱硬化性成分（Ｂ）の前記含有量がこのような範囲であることで、保護膜と支持シートとの接着力が抑制されて、支持シートの剥離性が向上する。 In the composition (III-1) and the thermosetting protective film-forming film, the content of the thermosetting component (B) (for example, the total content of the epoxy resin (B1) and the thermosetting agent (B2)) is: The content of the polymer component (A) is preferably 20 parts by mass or more and 500 parts by mass or less, more preferably 30 parts by mass or more and 300 parts by mass or less, and more preferably 40 parts by mass or more and 150 parts by mass with respect to 100 parts by mass of the polymer component (A). It is particularly preferable that the amount is not more than part by mass. When the content of the thermosetting component (B) is in such a range, the adhesive force between the protective film and the support sheet is suppressed, and the peelability of the support sheet is improved.
［硬化促進剤（Ｃ）］
　組成物（ＩＩＩ－１）及び熱硬化性保護膜形成用フィルムは、硬化促進剤（Ｃ）を含有していてもよい。硬化促進剤（Ｃ）は、組成物（ＩＩＩ－１）の硬化速度を調整するための成分である。
　好ましい硬化促進剤（Ｃ）としては、例えば、トリエチレンジアミン、ベンジルジメチルアミン、トリエタノールアミン、ジメチルアミノエタノール、トリス（ジメチルアミノメチル）フェノール等の第３級アミン；２－メチルイミダゾール、２－フェニルイミダゾール、２－フェニル－４－メチルイミダゾール、２－フェニル－４，５－ジヒドロキシメチルイミダゾール、２－フェニル－４－メチル－５－ヒドロキシメチルイミダゾール等のイミダゾール類（１個以上の水素原子が水素原子以外の基で置換されたイミダゾール）；トリブチルホスフィン、ジフェニルホスフィン、トリフェニルホスフィン等の有機ホスフィン類（１個以上の水素原子が有機基で置換されたホスフィン）；テトラフェニルホスホニウムテトラフェニルボレート、トリフェニルホスフィンテトラフェニルボレート等のテトラフェニルボロン塩等が挙げられる。 [Curing accelerator (C)]
The composition (III-1) and the thermosetting protective film-forming film may contain a curing accelerator (C). The curing accelerator (C) is a component for adjusting the curing rate of the composition (III-1).
Preferred curing accelerators (C) include, for example, tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol; 2-methylimidazole, 2-phenylimidazole Imidazoles such as 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole (one or more hydrogen atoms are other than hydrogen atoms) An imidazole substituted with a group of; an organic phosphine such as tributylphosphine, diphenylphosphine, triphenylphosphine (a phosphine having one or more hydrogen atoms substituted with an organic group); tetraphenylphosphonium tetraphenylborate Tetraphenyl boron salts such as triphenyl phosphine tetraphenyl borate and the like.
　組成物（ＩＩＩ－１）及び熱硬化性保護膜形成用フィルムが含有する硬化促進剤（Ｃ）は、１種のみでもよいし、２種以上でもよく、２種以上である場合、それらの組み合わせ及び比率は任意に選択できる。 The curing accelerator (C) contained in the composition (III-1) and the film for forming a thermosetting protective film may be only one type, two or more types, or a combination of two or more types. The ratio can be arbitrarily selected.
　硬化促進剤（Ｃ）を用いる場合、組成物（ＩＩＩ－１）及び熱硬化性保護膜形成用フィルムにおいて、硬化促進剤（Ｃ）の含有量は、熱硬化性成分（Ｂ）の含有量１００質量部に対して、０．０１質量部以上１０質量部以下であることが好ましく、０．１質量部以上７質量部以下であることがより好ましい。硬化促進剤（Ｃ）の前記含有量が前記下限値以上であることで、硬化促進剤（Ｃ）を用いたことによる効果がより顕著に得られる。また、硬化促進剤（Ｃ）の含有量が前記上限値以下であることで、例えば、高極性の硬化促進剤（Ｃ）が、高温・高湿度条件下で熱硬化性保護膜形成用フィルム中において被着体との接着界面側に移動して偏析することを抑制する効果が高くなり、保護膜形成用複合シートを用いて得られた保護膜付き半導体チップの信頼性がより向上する。 When the curing accelerator (C) is used, in the composition (III-1) and the thermosetting protective film-forming film, the content of the curing accelerator (C) is 100% of the thermosetting component (B). It is preferable that it is 0.01 mass part or more and 10 mass parts or less with respect to a mass part, and it is more preferable that it is 0.1 mass part or more and 7 mass parts or less. The effect by using a hardening accelerator (C) is acquired more notably because the said content of a hardening accelerator (C) is more than the said lower limit. Moreover, since content of a hardening accelerator (C) is below the said upper limit, for example, a highly polar hardening accelerator (C) is in a film for thermosetting protective film formation under high temperature and high humidity conditions. The effect of suppressing segregation by moving to the adhesion interface side with the adherend is increased, and the reliability of the semiconductor chip with a protective film obtained using the protective film-forming composite sheet is further improved.
［充填材（Ｄ）］
　組成物（ＩＩＩ－１）及び熱硬化性保護膜形成用フィルムは、充填材（Ｄ）を含有していてもよい。熱硬化性保護膜形成用フィルムが充填材（Ｄ）を含有することにより、熱硬化性保護膜形成用フィルムを硬化して得られた保護膜は、熱膨張係数の調整が容易となり、この熱膨張係数を保護膜の形成対象物に対して最適化することで、保護膜形成用複合シートを用いて得られた保護膜付き半導体チップの信頼性がより向上する。また、熱硬化性保護膜形成用フィルムが充填材（Ｄ）を含有することにより、保護膜の吸湿率を低減したり、放熱性を向上させたりすることもできる。 [Filler (D)]
The composition (III-1) and the thermosetting protective film-forming film may contain a filler (D). When the thermosetting protective film-forming film contains the filler (D), the protective film obtained by curing the thermosetting protective film-forming film can easily adjust the thermal expansion coefficient. By optimizing the expansion coefficient with respect to the object for forming the protective film, the reliability of the semiconductor chip with the protective film obtained using the composite sheet for forming the protective film is further improved. Moreover, the moisture absorption rate of a protective film can be reduced or heat dissipation can be improved because the film for thermosetting protective film formation contains a filler (D).
　充填材（Ｄ）は、有機充填材及び無機充填材のいずれでもよいが、無機充填材であることが好ましい。
　好ましい無機充填材としては、例えば、シリカ、アルミナ、タルク、炭酸カルシウム、チタンホワイト、ベンガラ、炭化ケイ素、窒化ホウ素等の粉末；これら無機充填材を球形化したビーズ；これら無機充填材の表面改質品；これら無機充填材の単結晶繊維；ガラス繊維等が挙げられる。
　これらの中でも、無機充填材は、シリカ又はアルミナであることが好ましい。 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 such as silica, alumina, talc, calcium carbonate, titanium white, bengara, silicon carbide, boron nitride; 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.
Among these, the inorganic filler is preferably silica or alumina.
　組成物（ＩＩＩ－１）及び熱硬化性保護膜形成用フィルムが含有する充填材（Ｄ）は、１種のみでもよいし、２種以上でもよく、２種以上である場合、それらの組み合わせ及び比率は任意に選択できる。 The filler (D) contained in the composition (III-1) and the thermosetting protective film-forming film may be only one type, two or more types, and when two or more types are combined, The ratio can be arbitrarily selected.
　充填材（Ｄ）を用いる場合、組成物（ＩＩＩ－１）において、溶媒以外の全ての成分の総含有量に対する充填材（Ｄ）の含有量の割合（すなわち、熱硬化性保護膜形成用フィルムの充填材（Ｄ）の含有量）は、５質量％以上８０質量％以下であることが好ましく、７質量％以上６０質量％以下であることがより好ましい。充填材（Ｄ）の含有量がこのような範囲であることで、上記の熱膨張係数の調整がより容易となる。 When the filler (D) is used, the ratio of the content of the filler (D) to the total content of all components other than the solvent in the composition (III-1) (that is, a film for forming a thermosetting protective film) The content of the filler (D) is preferably 5% by mass or more and 80% by mass or less, and more preferably 7% by mass or more and 60% by mass or less. Adjustment of said thermal expansion coefficient becomes easier because content of a filler (D) is such a range.
［カップリング剤（Ｅ）］
　組成物（ＩＩＩ－１）及び熱硬化性保護膜形成用フィルムは、カップリング剤（Ｅ）を含有していてもよい。カップリング剤（Ｅ）として、無機化合物又は有機化合物と反応可能な官能基を有するものを用いることにより、熱硬化性保護膜形成用フィルムの被着体に対する接着性及び密着性を向上させることができる。また、カップリング剤（Ｅ）を用いることで、熱硬化性保護膜形成用フィルムを硬化して得られた膜は、耐熱性を損なうことなく、耐水性が向上する。 [Coupling agent (E)]
The composition (III-1) and the thermosetting protective film-forming film may contain a coupling 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 thermosetting protective film-forming film to the adherend can be improved. it can. Moreover, the water resistance improves the film | membrane obtained by hardening | curing the film for thermosetting protective film formation by using a coupling agent (E), without impairing heat resistance.
　カップリング剤（Ｅ）は、重合体成分（Ａ）、熱硬化性成分（Ｂ）等が有する官能基と反応可能な官能基を有する化合物であることが好ましく、シランカップリング剤であることがより好ましい。
　好ましい前記シランカップリング剤としては、例えば、３－グリシジルオキシプロピルトリメトキシシラン、３－グリシジルオキシプロピルメチルジエトキシシラン、３－グリシジルオキシプロピルトリエトキシシラン、３－グリシジルオキシメチルジエトキシシラン、２－（３，４－エポキシシクロヘキシル）エチルトリメトキシシラン、３－メタクリロイルオキシプロピルトリメトキシシラン、３－アミノプロピルトリメトキシシラン、３－（２－アミノエチルアミノ）プロピルトリメトキシシラン、３－（２－アミノエチルアミノ）プロピルメチルジエトキシシラン、３－（フェニルアミノ）プロピルトリメトキシシラン、３－アニリノプロピルトリメトキシシラン、３－ウレイドプロピルトリエトキシシラン、３－メルカプトプロピルトリメトキシシラン、３－メルカプトプロピルメチルジメトキシシラン、ビス（３－トリエトキシシリルプロピル）テトラスルファン、メチルトリメトキシシラン、メチルトリエトキシシラン、ビニルトリメトキシシラン、ビニルトリアセトキシシラン、イミダゾールシラン等が挙げられる。 The coupling agent (E) is preferably a compound having a functional group capable of reacting with the functional group of the polymer component (A), the thermosetting component (B), etc., and is preferably a silane coupling agent. More preferred.
Preferred examples of the silane coupling agent 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-mercaptopropylmethyldimethoxysilane, bis (3-triethoxysilylpropyl) tetrasulfane, methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriacetoxysilane, and imidazolesilane. It is done.
　組成物（ＩＩＩ－１）及び熱硬化性保護膜形成用フィルムが含有するカップリング剤（Ｅ）は、１種のみでもよいし、２種以上でもよく、２種以上である場合、それらの組み合わせ及び比率は任意に選択できる。 The coupling agent (E) contained in the composition (III-1) and the thermosetting protective film-forming film may be only one type, two or more types, or a combination thereof when two or more types are used. The ratio can be arbitrarily selected.
　カップリング剤（Ｅ）を用いる場合、組成物（ＩＩＩ－１）及び熱硬化性保護膜形成用フィルムにおいて、カップリング剤（Ｅ）の含有量は、重合体成分（Ａ）及び熱硬化性成分（Ｂ）の総含有量１００質量部に対して、０．０３質量部以上２０質量部以下であることが好ましく、０．０５質量部以上１０質量部以下であることがより好ましく、０．１質量部以上５質量部以下であることが特に好ましい。カップリング剤（Ｅ）の前記含有量が前記下限値以上であることで、充填材（Ｄ）の樹脂への分散性の向上や、熱硬化性保護膜形成用フィルムの被着体との接着性の向上など、カップリング剤（Ｅ）を用いたことによる効果がより顕著に得られる。また、カップリング剤（Ｅ）の前記含有量が前記上限値以下であることで、アウトガスの発生がより抑制される。 When the coupling agent (E) is used, in the composition (III-1) and the thermosetting protective film-forming film, the content of the coupling agent (E) is the polymer component (A) and the thermosetting component. It is preferable that it is 0.03 mass part or more and 20 mass parts or less with respect to 100 mass parts of total content of (B), It is more preferable that it is 0.05 mass part or more and 10 mass parts or less, 0.1 It is particularly preferable that the amount is not less than 5 parts by mass. When the content of the coupling agent (E) is equal to or more than the lower limit, the dispersibility of the filler (D) in the resin is improved, and the thermosetting protective film-forming film is adhered to the adherend. The effect by using a coupling agent (E), such as a property improvement, is acquired more notably. Moreover, generation | occurrence | production of an outgas is suppressed more because the said content of a coupling agent (E) is below the said upper limit.
［架橋剤（Ｆ）］
　重合体成分（Ａ）として、上述のアクリル系樹脂等の、他の化合物と結合可能なビニル基、（メタ）アクリロイル基、アミノ基、水酸基、カルボキシ基、イソシアネート基等の官能基を有するものを用いる場合、組成物（ＩＩＩ－１）及び熱硬化性保護膜形成用フィルムは、前記官能基を他の化合物と結合させて架橋するための架橋剤（Ｆ）を含有していてもよい。架橋剤（Ｆ）を用いて架橋することにより、熱硬化性保護膜形成用フィルムの初期接着力及び凝集力を調節できる。 [Crosslinking agent (F)]
As the polymer component (A), those having functional groups such as vinyl group, (meth) acryloyl group, amino group, hydroxyl group, carboxy group, isocyanate group and the like that can be bonded to other compounds such as the above-mentioned acrylic resin. When used, the composition (III-1) and the thermosetting protective film-forming film may contain a crosslinking agent (F) for bonding the functional group with another compound to crosslink. By crosslinking using the crosslinking agent (F), the initial adhesive force and cohesive force of the thermosetting protective film-forming film can be adjusted.
架橋剤（Ｆ）としては、例えば、有機多価イソシアネート化合物、有機多価イミン化合物、金属キレート系架橋剤（金属キレート構造を有する架橋剤）、アジリジン系架橋剤（アジリジニル基を有する架橋剤）等が挙げられる。 Examples of the crosslinking agent (F) 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.
　前記有機多価イソシアネート化合物としては、例えば、芳香族多価イソシアネート化合物、脂肪族多価イソシアネート化合物及び脂環族多価イソシアネート化合物（以下、これら化合物をまとめて「芳香族多価イソシアネート化合物等」と略記することがある）；前記芳香族多価イソシアネート化合物等の三量体、イソシアヌレート体及びアダクト体；前記芳香族多価イソシアネート化合物等とポリオール化合物とを反応させて得られる末端イソシアネートウレタンプレポリマー等が挙げられる。前記「アダクト体」は、前記芳香族多価イソシアネート化合物、脂肪族多価イソシアネート化合物又は脂環族多価イソシアネート化合物と、エチレングリコール、プロピレングリコール、ネオペンチルグリコール、トリメチロールプロパン又はヒマシ油等の低分子活性水素含有化合物との反応物を意味し、その例としては、後述するようなトリメチロールプロパンのキシリレンジイソシアネート付加物等が挙げられる。また、「末端イソシアネートウレタンプレポリマー」とは、先に説明したとおりである。 Examples of the organic polyvalent isocyanate compound 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 polyisocyanate compound, the aliphatic polyisocyanate compound or the alicyclic polyisocyanate compound, and a low amount such as ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane or castor oil. 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” is as described above.
　前記有機多価イソシアネート化合物として、より具体的には、例えば、２，４－トリレンジイソシアネート；２，６－トリレンジイソシアネート；１，３－キシリレンジイソシアネート；１，４－キシレンジイソシアネート；ジフェニルメタン－４，４’－ジイソシアネート；ジフェニルメタン－２，４’－ジイソシアネート；３－メチルジフェニルメタンジイソシアネート；ヘキサメチレンジイソシアネート；イソホロンジイソシアネート；ジシクロヘキシルメタン－４，４’－ジイソシアネート；ジシクロヘキシルメタン－２，４’－ジイソシアネート；トリメチロールプロパン等のポリオールのすべて又は一部の水酸基に、トリレンジイソシアネート、ヘキサメチレンジイソシアネート及びキシリレンジイソシアネートのいずれか１種又は２種以上が付加した化合物；リジンジイソシアネート等が挙げられる。 More specifically, as the 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.
　前記有機多価イミン化合物としては、例えば、Ｎ，Ｎ’－ジフェニルメタン－４，４’－ビス（１－アジリジンカルボキシアミド）、トリメチロールプロパン－トリ－β－アジリジニルプロピオネート、テトラメチロールメタン－トリ－β－アジリジニルプロピオネート、Ｎ，Ｎ’－トルエン－２，４－ビス（１－アジリジンカルボキシアミド）トリエチレンメラミン等が挙げられる。 Examples of the organic polyvalent imine compound include N, N′-diphenylmethane-4,4′-bis (1-aziridinecarboxamide), trimethylolpropane-tri-β-aziridinylpropionate, and tetramethylolmethane. -Tri-β-aziridinylpropionate, N, N′-toluene-2,4-bis (1-aziridinecarboxamide) triethylenemelamine and the like.
　架橋剤（Ｆ）として有機多価イソシアネート化合物を用いる場合、重合体成分（Ａ）としては、水酸基含有重合体を用いることが好ましい。架橋剤（Ｆ）がイソシアネート基を有し、重合体成分（Ａ）が水酸基を有する場合、架橋剤（Ｆ）と重合体成分（Ａ）との反応によって、熱硬化性保護膜形成用フィルムに架橋構造を簡便に導入できる。 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 polymer component (A). When the crosslinking agent (F) has an isocyanate group and the polymer component (A) has a hydroxyl group, a reaction between the crosslinking agent (F) and the polymer component (A) results in a thermosetting protective film forming film. A crosslinked structure can be easily introduced.
　組成物（ＩＩＩ－１）及び熱硬化性保護膜形成用フィルムが含有する架橋剤（Ｆ）は、１種のみでもよいし、２種以上でもよく、２種以上である場合、それらの組み合わせ及び比率は任意に選択できる。 The crosslinking agent (F) contained in the composition (III-1) and the film for forming a thermosetting protective film may be only one type, two or more types, and when two or more types are used, a combination thereof and The ratio can be arbitrarily selected.
　架橋剤（Ｆ）を用いる場合、組成物（ＩＩＩ－１）において、架橋剤（Ｆ）の含有量は、重合体成分（Ａ）の含有量１００質量部に対して、０．０１質量部以上２０質量部以下であることが好ましく、０．１質量部以上１０質量部以下であることがより好ましく、０．５質量部以上５質量部以下であることが特に好ましい。架橋剤（Ｆ）の前記含有量が前記下限値以上であることで、架橋剤（Ｆ）を用いたことによる効果がより顕著に得られる。また、架橋剤（Ｆ）の前記含有量が前記上限値以下であることで、架橋剤（Ｆ）の過剰使用が抑制される。 When the crosslinking agent (F) is used, in the composition (III-1), the content of the crosslinking agent (F) is 0.01 parts by mass or more with respect to 100 parts by mass of the polymer component (A). It is preferably 20 parts by mass or less, more preferably 0.1 parts by mass or more and 10 parts by mass or less, and particularly preferably 0.5 parts by mass or more and 5 parts by mass or less. The effect by using a crosslinking agent (F) is acquired more notably because the said content of a crosslinking agent (F) is more than the said lower limit. Moreover, 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.
［エネルギー線硬化性樹脂（Ｇ）］
　組成物（ＩＩＩ－１）は、エネルギー線硬化性樹脂（Ｇ）を含有していてもよい。熱硬化性保護膜形成用フィルムは、エネルギー線硬化性樹脂（Ｇ）を含有していることにより、エネルギー線の照射によって特性を変化させることができる。 [Energy ray curable resin (G)]
The composition (III-1) may contain an energy ray curable resin (G). Since the thermosetting protective film-forming film contains the energy ray-curable resin (G), the characteristics can be changed by irradiation with energy rays.
　エネルギー線硬化性樹脂（Ｇ）は、エネルギー線硬化性化合物を重合（硬化）して得られたものである。
　前記エネルギー線硬化性化合物としては、例えば、分子内に少なくとも１個の重合性二重結合を有する化合物が挙げられ、（メタ）アクリロイル基を有するアクリレート系化合物が好ましい。 The energy beam curable resin (G) is obtained by polymerizing (curing) an energy beam curable compound.
Examples of the energy ray curable compound include compounds having at least one polymerizable double bond in the molecule, and acrylate compounds having a (meth) acryloyl group are preferable.
　前記アクリレート系化合物としては、例えば、トリメチロールプロパントリ（メタ）アクリレート、テトラメチロールメタンテトラ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールモノヒドロキシペンタ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、１，４－ブチレングリコールジ（メタ）アクリレート、１，６－ヘキサンジオールジ（メタ）アクリレート等の鎖状脂肪族骨格含有（メタ）アクリレート；ジシクロペンタニルジ（メタ）アクリレート等の環状脂肪族骨格含有（メタ）アクリレート；ポリエチレングリコールジ（メタ）アクリレート等のポリアルキレングリコール（メタ）アクリレート；オリゴエステル（メタ）アクリレート；ウレタン（メタ）アクリレートオリゴマー；エポキシ変性（メタ）アクリレート；前記ポリアルキレングリコール（メタ）アクリレート以外のポリエーテル（メタ）アクリレート；イタコン酸オリゴマー等が挙げられる。 Examples of the acrylate compound include trimethylolpropane tri (meth) acrylate, tetramethylolmethanetetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol monohydroxypenta ( Chain aliphatic skeleton-containing (meth) acrylates such as (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,4-butylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate; Cyclic aliphatic skeleton-containing (meth) acrylates such as cyclopentanyl di (meth) acrylate; polyalkylene glycol (meth) acrylates such as polyethylene glycol di (meth) acrylate Oligoester (meth) acrylate; urethane (meth) acrylate oligomer, epoxy-modified (meth) acrylate; the polyalkylene glycol (meth) Polyether (meth) acrylates other than the acrylates; itaconic acid oligomer, and the like.
　前記エネルギー線硬化性化合物の重量平均分子量は、１００以上３００００以下であることが好ましく、３００以上１００００以下であることがより好ましい。ここで、「重量平均分子量」とは、先に説明したとおりである。 The weight average molecular weight of the energy ray curable compound is preferably 100 or more and 30000 or less, and more preferably 300 or more and 10,000 or less. Here, the “weight average molecular weight” is as described above.
　重合に用いる前記エネルギー線硬化性化合物は、１種のみでもよいし、２種以上でもよく、２種以上である場合、それらの組み合わせ及び比率は任意に選択できる。 The energy ray-curable compound used for the polymerization 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.
　組成物（ＩＩＩ－１）が含有するエネルギー線硬化性樹脂（Ｇ）は、１種のみでもよいし、２種以上でもよく、２種以上である場合、それらの組み合わせ及び比率は任意に選択できる。 The energy ray curable resin (G) contained in the composition (III-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. .
　組成物（ＩＩＩ－１）において、エネルギー線硬化性樹脂（Ｇ）の含有量は、１質量％以上９５質量％以下であることが好ましく、５質量％以上９０質量％以下であることがより好ましく、１０質量％以上８５質量％以下であることが特に好ましい。 In the composition (III-1), the content of the energy ray curable resin (G) is preferably 1% by mass or more and 95% by mass or less, and more preferably 5% by mass or more and 90% by mass or less. It is particularly preferably 10% by mass or more and 85% by mass or less.
［光重合開始剤（Ｈ）］
　組成物（ＩＩＩ－１）は、エネルギー線硬化性樹脂（Ｇ）を含有する場合、エネルギー線硬化性樹脂（Ｇ）の重合反応を効率よく進めるために、光重合開始剤（Ｈ）を含有していてもよい。 [Photopolymerization initiator (H)]
When the composition (III-1) contains the energy ray curable resin (G), the composition (III-1) contains a photopolymerization initiator (H) in order to efficiently advance the polymerization reaction of the energy ray curable resin (G). It may be.
組成物（ＩＩＩ－１）における光重合開始剤（Ｈ）としては、例えば、ベンゾイン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル、ベンゾインイソブチルエーテル、ベンゾイン安息香酸、ベンゾイン安息香酸メチル、ベンゾインジメチルケタール等のベンゾイン化合物；アセトフェノン、２－ヒドロキシ－２－メチル－１－フェニル－プロパン－１－オン、２，２－ジメトキシ－１，２－ジフェニルエタン－１－オン等のアセトフェノン化合物；ビス（２，４，６－トリメチルベンゾイル）フェニルフォスフィンオキサイド、２，４，６－トリメチルベンゾイルジフェニルフォスフィンオキサイド等のアシルフォスフィンオキサイド化合物；ベンジルフェニルスルフィド、テトラメチルチウラムモノスルフィド等のスルフィド化合物；１－ヒドロキシシクロヘキシルフェニルケトン等のα－ケトール化合物；アゾビスイソブチロニトリル等のアゾ化合物；チタノセン等のチタノセン化合物；チオキサントン等のチオキサントン化合物；パーオキサイド化合物；ジアセチル等のジケトン化合物；ベンジル；ジベンジル；ベンゾフェノン；２，４－ジエチルチオキサントン；１，２－ジフェニルメタン；２－ヒドロキシ－２－メチル－１－［４－（１－メチルビニル）フェニル］プロパノン；２－クロロアントラキノン等が挙げられる。
　また、前記光重合開始剤としては、例えば、１－クロロアントラキノン等のキノン化合物；アミン等の光増感剤等も挙げられる。 Examples of the photopolymerization initiator (H) in the composition (III-1) include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, benzoin methyl benzoate, and benzoin dimethyl ketal. Benzoin compounds such as acetophenone, acetophenone compounds such as acetophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one; Acylphosphine oxide compounds such as 4,6-trimethylbenzoyl) phenylphosphine oxide and 2,4,6-trimethylbenzoyldiphenylphosphine oxide; benzylphenyl sulfide, tetramethylthiuram Sulfide compounds such as nosulfides; α-ketol compounds such as 1-hydroxycyclohexyl phenyl ketone; azo compounds such as azobisisobutyronitrile; titanocene compounds such as titanocene; thioxanthone compounds such as thioxanthone; peroxide compounds; Diketone compound; benzyl; dibenzyl; benzophenone; 2,4-diethylthioxanthone; 1,2-diphenylmethane; 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone; 2-chloroanthraquinone, etc. Is mentioned.
Examples of the photopolymerization initiator include quinone compounds such as 1-chloroanthraquinone; photosensitizers such as amine.
　組成物（ＩＩＩ－１）が含有する光重合開始剤（Ｈ）は、１種のみでもよいし、２種以上でもよく、２種以上である場合、それらの組み合わせ及び比率は任意に選択できる。 The photopolymerization initiator (H) contained in the composition (III-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.
　組成物（ＩＩＩ－１）において、光重合開始剤（Ｈ）の含有量は、エネルギー線硬化性樹脂（Ｇ）の含有量１００質量部に対して、０．１質量部以上２０質量部以下であることが好ましく、１質量部以上１０質量部以下であることがより好ましく、２質量部以上５質量部以下であることが特に好ましい。 In the composition (III-1), the content of the photopolymerization initiator (H) is 0.1 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the energy beam curable resin (G). It is preferably 1 to 10 parts by mass, more preferably 2 to 5 parts by mass.
［着色剤（Ｉ）］
　組成物（ＩＩＩ－１）及び熱硬化性保護膜形成用フィルムは、着色剤（Ｉ）を含有していてもよい。
　着色剤（Ｉ）としては、例えば、無機系顔料、有機系顔料、有機系染料等、公知のものが挙げられる。 [Colorant (I)]
The composition (III-1) and the thermosetting protective film-forming film may contain a colorant (I).
Examples of the colorant (I) include known pigments such as inorganic pigments, organic pigments, and organic dyes.
　前記有機系顔料及び有機系染料としては、例えば、アミニウム系色素、シアニン系色素、メロシアニン系色素、クロコニウム系色素、スクアリウム系色素、アズレニウム系色素、ポリメチン系色素、ナフトキノン系色素、ピリリウム系色素、フタロシアニン系色素、ナフタロシアニン系色素、ナフトラクタム系色素、アゾ系色素、縮合アゾ系色素、インジゴ系色素、ペリノン系色素、ペリレン系色素、ジオキサジン系色素、キナクリドン系色素、イソインドリノン系色素、キノフタロン系色素、ピロール系色素、チオインジゴ系色素、金属錯体系色素（金属錯塩染料）、ジチオール金属錯体系色素、インドールフェノール系色素、トリアリルメタン系色素、アントラキノン系色素、ナフトール系色素、アゾメチン系色素、ベンズイミダゾロン系色素、ピランスロン系色素及びスレン系色素等が挙げられる。 Examples of the organic pigments and organic dyes include aminium dyes, cyanine dyes, merocyanine dyes, croconium dyes, squalium dyes, azurenium dyes, polymethine dyes, naphthoquinone dyes, pyrylium dyes, and phthalocyanines. Dyes, naphthalocyanine dyes, naphtholactam dyes, azo dyes, condensed azo dyes, indigo dyes, perinone dyes, perylene dyes, dioxazine dyes, quinacridone dyes, isoindolinone dyes, quinophthalone dyes , Pyrrole dyes, thioindigo dyes, metal complex dyes (metal complex dyes), dithiol metal complex dyes, indolephenol dyes, triallylmethane dyes, anthraquinone dyes, naphthol dyes, azomethine dyes, benzimidazo B Systems dyes, pyranthrone pigments and threne dyes.
　前記無機系顔料としては、例えば、カーボンブラック、コバルト系色素、鉄系色素、クロム系色素、チタン系色素、バナジウム系色素、ジルコニウム系色素、モリブデン系色素、ルテニウム系色素、白金系色素、ＩＴＯ（インジウムスズオキサイド）系色素、ＡＴＯ（アンチモンスズオキサイド）系色素等が挙げられる。 Examples of the inorganic pigment 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.
　組成物（ＩＩＩ－１）及び熱硬化性保護膜形成用フィルムが含有する着色剤（Ｉ）は、１種のみでもよいし、２種以上でもよく、２種以上である場合、それらの組み合わせ及び比率は任意に選択できる。 The colorant (I) contained in the composition (III-1) and the thermosetting protective film-forming film may be only one type, two or more types, and in the case of two or more types, combinations thereof and The ratio can be arbitrarily selected.
　着色剤（Ｉ）を用いる場合、熱硬化性保護膜形成用フィルムの着色剤（Ｉ）の含有量は、目的に応じて適宜調節すればよい。例えば、熱硬化性保護膜形成用フィルムの着色剤（Ｉ）の含有量を調節し、保護膜の光透過性を調節することにより、保護膜に対してレーザー印字を行った場合の印字視認性を調節できる。また、熱硬化性保護膜形成用フィルムの着色剤（Ｉ）の含有量を調節することで、保護膜の意匠性を向上させたり、半導体ウエハの裏面の研削痕を見え難くすることもできる。これの点を考慮すると、組成物（ＩＩＩ－１）において、溶媒以外の全ての成分の総含有量に対する着色剤（Ｉ）の含有量の割合（すなわち、熱硬化性保護膜形成用フィルムの着色剤（Ｉ）の含有量）は、０．１質量％以上１０質量％以下であることが好ましく、０．１質量％以上７．５質量％以下であることがより好ましく、０．１質量％以上５質量％以下であることが特に好ましい。着色剤（Ｉ）の前記含有量が前記下限値以上であることで、着色剤（Ｉ）を用いたことによる効果がより顕著に得られる。また、着色剤（Ｉ）の前記含有量が前記上限値以下であることで、熱硬化性保護膜形成用フィルムの光透過性の過度な低下が抑制される。 When using the colorant (I), the content of the colorant (I) in the thermosetting protective film-forming film may be appropriately adjusted according to the purpose. For example, by adjusting the content of the colorant (I) in the thermosetting protective film-forming film and adjusting the light transmittance of the protective film, the print visibility when laser printing is performed on the protective film Can be adjusted. Further, by adjusting the content of the colorant (I) in the thermosetting protective film-forming film, it is possible to improve the design of the protective film or make it difficult to see the grinding marks on the back surface of the semiconductor wafer. In consideration of this point, in the composition (III-1), the ratio of the content of the colorant (I) to the total content of all components other than the solvent (that is, the coloring of the thermosetting protective film-forming film) The content of the agent (I) is preferably 0.1% by mass or more and 10% by mass or less, more preferably 0.1% by mass or more and 7.5% by mass or less, and 0.1% by mass. It is particularly preferably 5% by mass or less. When the content of the colorant (I) is equal to or more than the lower limit value, the effect of using the colorant (I) is more remarkably obtained. Moreover, the excessive fall of the light transmittance of the film for thermosetting protective film formation is suppressed because the said content of a coloring agent (I) is below the said upper limit.
［汎用添加剤（Ｊ）］
　組成物（ＩＩＩ－１）及び熱硬化性保護膜形成用フィルムは、本実施形態における効果を損なわない範囲内において、汎用添加剤（Ｊ）を含有していてもよい。
　汎用添加剤（Ｊ）は、公知のものでよく、目的に応じて任意に選択でき、特に限定されないが、好ましいものとしては、例えば、可塑剤、帯電防止剤、酸化防止剤、ゲッタリング剤等が挙げられる。 [General-purpose additive (J)]
The composition (III-1) and the thermosetting protective film-forming film may contain a general-purpose additive (J) as long as the effects of the present embodiment are not impaired.
The general-purpose additive (J) may be a known one and can be arbitrarily selected according to the purpose, and is not particularly limited. Is mentioned.
　組成物（ＩＩＩ－１）及び熱硬化性保護膜形成用フィルムが含有する汎用添加剤（Ｊ）は、１種のみでもよいし、２種以上でもよく、２種以上である場合、それらの組み合わせ及び比率は任意に選択できる。
　組成物（ＩＩＩ－１）及び熱硬化性保護膜形成用フィルムの汎用添加剤（Ｊ）の含有量は、特に限定されず、目的に応じて適宜選択すればよい。 The general-purpose additive (J) contained in the composition (III-1) and the thermosetting protective film-forming film may be only one type, two or more types, or a combination thereof when two or more types are used. The ratio can be arbitrarily selected.
The content of the general-purpose additive (J) in the composition (III-1) and the thermosetting protective film-forming film is not particularly limited, and may be appropriately selected depending on the purpose.
［溶媒］
　組成物（ＩＩＩ－１）は、さらに溶媒を含有することが好ましい。溶媒を含有する組成物（ＩＩＩ－１）は、取り扱い性が良好となる。
　前記溶媒は特に限定されないが、好ましいものとしては、例えば、トルエン、キシレン等の炭化水素；メタノール、エタノール、２－プロパノール、イソブチルアルコール（２－メチルプロパン－１－オール）、１－ブタノール等のアルコール；酢酸エチル等のエステル；アセトン、メチルエチルケトン等のケトン；テトラヒドロフラン等のエーテル；ジメチルホルムアミド、Ｎ－メチルピロリドン等のアミド（アミド結合を有する化合物）等が挙げられる。
　組成物（ＩＩＩ－１）が含有する溶媒は、１種のみでもよいし、２種以上でもよく、２種以上である場合、それらの組み合わせ及び比率は任意に選択できる。 [solvent]
The composition (III-1) preferably further contains a solvent. The composition (III-1) containing a solvent has good handleability.
The solvent is not particularly limited. Preferred examples include hydrocarbons such as toluene and xylene; alcohols such as methanol, ethanol, 2-propanol, isobutyl alcohol (2-methylpropan-1-ol), and 1-butanol. 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 composition (III-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.
　組成物（ＩＩＩ－１）が含有する溶媒は、組成物（ＩＩＩ－１）中の含有成分をより均一に混合できる点から、メチルエチルケトン等であることが好ましい。 The solvent contained in the composition (III-1) is preferably methyl ethyl ketone or the like from the viewpoint that the components contained in the composition (III-1) can be mixed more uniformly.
＜＜熱硬化性保護膜形成用組成物の製造方法＞＞
　組成物（ＩＩＩ－１）等の熱硬化性保護膜形成用組成物は、これを構成するための各成分を配合することで得られる。
　各成分の配合時における添加順序は特に限定されず、２種以上の成分を同時に添加してもよい。
　溶媒を用いる場合には、溶媒を溶媒以外のいずれかの配合成分と混合してこの配合成分を予め希釈しておくことで用いてもよいし、溶媒以外のいずれかの配合成分を予め希釈しておくことなく、溶媒をこれら配合成分と混合することで用いてもよい。
　配合時に各成分を混合する方法は特に限定されず、撹拌子又は撹拌翼等を回転させて混合する方法；ミキサーを用いて混合する方法；超音波を加えて混合する方法等、公知の方法から適宜選択すればよい。
　各成分の添加及び混合時の温度並びに時間は、各配合成分が劣化しない限り特に限定されず、適宜調節すればよいが、温度は１５℃以上３０℃以下であることが好ましい。 << Method for Producing Thermosetting Protective Film Forming Composition >>
The composition for forming a thermosetting protective film such as the composition (III-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.
When a solvent is used, 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 at the time of 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 ° C. or higher and 30 ° C. or lower.
○エネルギー線硬化性保護膜形成用フィルム
　エネルギー線硬化性保護膜形成用フィルムは、エネルギー線硬化性成分（ａ）を含有する。
　エネルギー線硬化性保護膜形成用フィルムにおいて、エネルギー線硬化性成分（ａ）は、未硬化であることが好ましく、粘着性を有することが好ましく、未硬化でかつ粘着性を有することがより好ましい。ここで、「エネルギー線」及び「エネルギー線硬化性」とは、先に説明したとおりである。 -Film for forming an energy beam curable protective film The film for forming an energy beam curable protective film contains an energy beam curable component (a).
In the energy ray curable protective film-forming film, the energy ray curable component (a) is preferably uncured, preferably tacky, and more preferably uncured and tacky. Here, “energy beam” and “energy beam curability” are as described above.
　エネルギー線硬化性保護膜形成用フィルムは１層（単層）のみでもよいし、２層以上の複数層でもよく、複数層である場合、これら複数層は、互いに同一でも異なっていてもよく、これら複数層の組み合わせは特に限定されない。 The energy ray-curable protective film-forming film may be only one layer (single layer), or may be two or more layers, and when it is a plurality of layers, these layers may be the same or different from each other, The combination of these multiple layers is not particularly limited.
　エネルギー線硬化性保護膜形成用フィルムの厚さは、１μｍ以上１００μｍ以下であることが好ましく、５μｍ以上７５μｍ以下であることがより好ましく、５μｍ以上５０μｍ以下であることが特に好ましい。エネルギー線硬化性保護膜形成用フィルムの厚さが前記下限値以上であることで、保護能がより高い保護膜を形成できる。また、エネルギー線硬化性保護膜形成用フィルムの厚さが前記上限値以下であることで、過剰な厚さとなることが抑制される。
　ここで、「エネルギー線硬化性保護膜形成用フィルムの厚さ」とは、エネルギー線硬化性保護膜形成用フィルム全体の厚さを意味し、例えば、複数層からなるエネルギー線硬化性保護膜形成用フィルムの厚さとは、エネルギー線硬化性保護膜形成用フィルムを構成するすべての層の合計の厚さを意味する。なお、エネルギー線硬化性保護膜形成用フィルムの厚さの測定方法としては、例えば、任意の５箇所において、接触式厚み計を用いて厚さを測定し、測定値の平均を算出する方法等が挙げられる。 The thickness of the energy ray-curable protective film-forming film is preferably 1 μm or more and 100 μm or less, more preferably 5 μm or more and 75 μm or less, and particularly preferably 5 μm or more and 50 μm or less. When the thickness of the energy ray-curable protective film-forming film is equal to or more than the lower limit value, a protective film with higher protective ability can be formed. Moreover, when the thickness of the energy ray-curable protective film-forming film is equal to or less than the upper limit, an excessive thickness is suppressed.
Here, “the thickness of the energy ray curable protective film forming film” means the thickness of the entire energy ray curable protective film forming film, for example, the formation of an energy ray curable protective film composed of a plurality of layers. The film thickness means the total thickness of all layers constituting the energy ray-curable protective film-forming film. In addition, as a method for measuring the thickness of the energy ray-curable protective film-forming film, for example, a method of measuring the thickness using a contact-type thickness meter at any five locations and calculating an average of the measured values, etc. Is mentioned.
　エネルギー線硬化性保護膜形成用フィルムを半導体ウエハの裏面に貼付し、硬化させて、保護膜を形成するときの硬化条件は、保護膜が十分にその機能を発揮する程度の硬化度となる限り特に限定されず、エネルギー線硬化性保護膜形成用フィルムの種類に応じて、適宜選択すればよい。
　例えば、エネルギー線硬化性保護膜形成用フィルムの硬化時における、エネルギー線の照度は、１２０ｍＷ／ｃｍ２以上２８０ｍＷ／ｃｍ２以下であることが好ましい。そして、前記硬化時における、エネルギー線の光量は、２００ｍＪ／ｃｍ２以上１０００ｍＪ／ｃｍ２以下であることが好ましい。 The curing conditions for forming the protective film by applying the energy ray-curable protective film-forming film to the back surface of the semiconductor wafer and curing it are as long as the degree of curing is such that the protective film can fully perform its function. It does not specifically limit and it should just select suitably according to the kind of film for energy-beam curable protective film formation.
For example, at the time of curing of the energy ray-curable protective film forming film, the illuminance of the energy ray is preferably 120 mW / cm 2 or more 280 mW / cm 2 or less. Then, the during curing, the amount of the energy ray is preferably 200 mJ / cm 2 or more 1000 mJ / cm 2 or less.
＜＜エネルギー線硬化性保護膜形成用組成物＞＞
　エネルギー線硬化性保護膜形成用フィルムは、その構成材料を含有するエネルギー線硬化性保護膜形成用組成物を用いて形成できる。例えば、エネルギー線硬化性保護膜形成用フィルムの形成対象面にエネルギー線硬化性保護膜形成用組成物を塗工し、必要に応じて乾燥させることで、目的とする部位にエネルギー線硬化性保護膜形成用フィルムを形成できる。エネルギー線硬化性保護膜形成用組成物中の、常温で気化しない成分同士の含有量の比率は、通常、エネルギー線硬化性保護膜形成用フィルムの前記成分同士の含有量の比率と同じとなる。ここで、「常温」とは、先に説明したとおりである。 << Energy ray-curable protective film-forming composition >>
The film for forming an energy ray curable protective film can be formed using the composition for forming an energy ray curable protective film containing the constituent material. For example, the energy ray curable protective film is applied to the target surface of the film for forming the energy ray curable protective film, and the energy ray curable protection is applied to the target site by applying the composition for forming the energy ray curable protective film and drying it as necessary. A film-forming film can be formed. In the composition for forming an energy ray-curable protective film, the ratio of the contents of components that do not vaporize at room temperature is usually the same as the ratio of the contents of the components of the film for forming an energy ray-curable protective film. . Here, “normal temperature” is as described above.
　エネルギー線硬化性保護膜形成用組成物の塗工は、例えば、上述の粘着剤組成物の塗工の場合と同じ方法で行うことができる。 Application of the energy ray-curable protective film-forming composition can be performed, for example, in the same manner as in the case of application of the above-described pressure-sensitive adhesive composition.
　エネルギー線硬化性保護膜形成用組成物の乾燥条件は、特に限定されないが、エネルギー線硬化性保護膜形成用組成物は、後述する溶媒を含有している場合、加熱乾燥させることが好ましく、この場合、例えば、７０℃以上１３０℃以下で１０秒以上５分以下の条件で乾燥させることが好ましい。 The drying conditions of the energy ray-curable protective film-forming composition are not particularly limited, but the energy ray-curable protective film-forming composition preferably comprises heat drying when it contains a solvent described later. In this case, for example, drying is preferably performed at 70 ° C. to 130 ° C. for 10 seconds to 5 minutes.
＜エネルギー線硬化性保護膜形成用組成物（ＩＶ－１）＞
　エネルギー線硬化性保護膜形成用組成物としては、例えば、前記エネルギー線硬化性成分（ａ）を含有するエネルギー線硬化性保護膜形成用組成物（ＩＶ－１）（本明細書においては、単に「組成物（ＩＶ－１）」と略記することがある）等が挙げられる。 <Composition for forming an energy ray-curable protective film (IV-1)>
As the composition for forming an energy beam curable protective film, for example, the composition for forming an energy beam curable protective film (IV-1) containing the energy beam curable component (a) (in this specification, simply And the like (may be abbreviated as “composition (IV-1)”).
［エネルギー線硬化性成分（ａ）］
　エネルギー線硬化性成分（ａ）は、エネルギー線の照射によって硬化する成分であり、エネルギー線硬化性保護膜形成用フィルムに造膜性や、可撓性等を付与するとともに、硬化後に硬質の保護膜を形成するための成分でもある。
　エネルギー線硬化性成分（ａ）としては、例えば、エネルギー線硬化性基を有する、重量平均分子量が８００００以上２００００００以下の重合体（ａ１）、及びエネルギー線硬化性基を有する、分子量が１００以上８００００以下の化合物（ａ２）が挙げられる。前記重合体（ａ１）は、その少なくとも一部が架橋剤によって架橋されたものであってもよいし、架橋されていないものであってもよい。 [Energy ray curable component (a)]
The energy ray curable component (a) is a component that is cured by irradiation with energy rays, and imparts film forming property, flexibility, etc. to the film for forming an energy ray curable protective film, and is hard protected after curing. It is also a component for forming a 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 a molecular weight having an energy ray curable group of 100 to 80000. The following compounds (a2) are mentioned. The polymer (a1) may be crosslinked at least partly with a crosslinking agent or may not be crosslinked.
（エネルギー線硬化性基を有する、重量平均分子量が８００００以上２００００００以下の重合体（ａ１））
　エネルギー線硬化性基を有する、重量平均分子量が８００００以上２００００００以下の重合体（ａ１）としては、例えば、他の化合物が有する基と反応可能な官能基を有するアクリル系重合体（ａ１１）と、前記官能基と反応する基、及びエネルギー線硬化性二重結合等のエネルギー線硬化性基を有するエネルギー線硬化性化合物（ａ１２）と、が反応してなるアクリル系樹脂（ａ１－１）が挙げられる。 (Polymer (a1) having an energy ray-curable group and having a weight average molecular weight of 80,000 to 2,000,000)
Examples of the polymer (a1) having an energy ray curable group and having a weight average molecular weight of 80,000 or more and 2,000,000 or less 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 reacting the functional group-reactive group and an energy ray-curable compound (a12) having an energy ray-curable group such as an energy ray-curable double bond. It is done.
他の化合物が有する基と反応可能な前記官能基としては、例えば、水酸基、カルボキシ基、アミノ基、置換アミノ基（アミノ基の１個又は２個の水素原子が水素原子以外の基で置換されてなる基）、エポキシ基等が挙げられる。ただし、半導体ウエハや半導体チップ等の回路の腐食を防止するという点では、前記官能基はカルボキシ基以外の基であることが好ましい。
　これらの中でも、前記官能基は、水酸基であることが好ましい。 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. However, 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.
Among these, the functional group is preferably a hydroxyl group.
・官能基を有するアクリル系重合体（ａ１１）
　前記官能基を有するアクリル系重合体（ａ１１）としては、例えば、前記官能基を有するアクリル系モノマーと、前記官能基を有しないアクリル系モノマーと、が共重合してなるものが挙げられ、これらモノマー以外に、さらにアクリル系モノマー以外のモノマー（非アクリル系モノマー）が共重合したものであってもよい。
　また、前記アクリル系重合体（ａ１１）は、ランダム共重合体であってもよいし、ブロック共重合体であってもよく、重合方法についても公知の方法を採用できる。 -Acrylic polymer having a functional group (a11)
Examples of the acrylic polymer (a11) having the functional group 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, and a known method can be adopted as a polymerization method.
　前記官能基を有するアクリル系モノマーとしては、例えば、水酸基含有モノマー、カルボキシ基含有モノマー、アミノ基含有モノマー、置換アミノ基含有モノマー、エポキシ基含有モノマー等が挙げられる。 Examples of the acrylic monomer having a functional group 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.
　前記水酸基含有モノマーとしては、例えば、（メタ）アクリル酸ヒドロキシメチル、（メタ）アクリル酸２－ヒドロキシエチル、（メタ）アクリル酸２－ヒドロキシプロピル、（メタ）アクリル酸３－ヒドロキシプロピル、（メタ）アクリル酸２－ヒドロキシブチル、（メタ）アクリル酸３－ヒドロキシブチル、（メタ）アクリル酸４－ヒドロキシブチル等の（メタ）アクリル酸ヒドロキシアルキル；ビニルアルコール、アリルアルコール等の非（メタ）アクリル系不飽和アルコール（（メタ）アクリロイル骨格を有しない不飽和アルコール）等が挙げられる。 Examples of the hydroxyl group-containing monomer 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.
　前記カルボキシ基含有モノマーとしては、例えば、（メタ）アクリル酸、クロトン酸等のエチレン性不飽和モノカルボン酸（エチレン性不飽和結合を有するモノカルボン酸）；フマル酸、イタコン酸、マレイン酸、シトラコン酸等のエチレン性不飽和ジカルボン酸（エチレン性不飽和結合を有するジカルボン酸）；前記エチレン性不飽和ジカルボン酸の無水物；２－カルボキシエチルメタクリレート等の（メタ）アクリル酸カルボキシアルキルエステル等が挙げられる。 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.
　前記官能基を有するアクリル系モノマーは、水酸基含有モノマーが好ましい。 The acrylic monomer having a functional group is preferably a hydroxyl group-containing monomer.
　前記アクリル系重合体（ａ１１）を構成する、前記官能基を有するアクリル系モノマーは、１種のみでもよいし、２種以上でもよく、２種以上である場合、それらの組み合わせ及び比率は任意に選択できる。 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.
　前記官能基を有しないアクリル系モノマーとしては、例えば、例えば、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸ｎ－プロピル、（メタ）アクリル酸イソプロピル、（メタ）アクリル酸ｎ－ブチル、（メタ）アクリル酸イソブチル、（メタ）アクリル酸ｓｅｃ－ブチル、（メタ）アクリル酸ｔｅｒｔ－ブチル、（メタ）アクリル酸ペンチル、（メタ）アクリル酸ヘキシル、（メタ）アクリル酸ヘプチル、（メタ）アクリル酸２－エチルヘキシル、（メタ）アクリル酸イソオクチル、（メタ）アクリル酸ｎ－オクチル、（メタ）アクリル酸ｎ－ノニル、（メタ）アクリル酸イソノニル、（メタ）アクリル酸デシル、（メタ）アクリル酸ウンデシル、（メタ）アクリル酸ドデシル（（メタ）アクリル酸ラウリル）、（メタ）アクリル酸トリデシル、（メタ）アクリル酸テトラデシル（（メタ）アクリル酸ミリスチル）、（メタ）アクリル酸ペンタデシル、（メタ）アクリル酸ヘキサデシル（（メタ）アクリル酸パルミチル）、（メタ）アクリル酸ヘプタデシル、（メタ）アクリル酸オクタデシル（（メタ）アクリル酸ステアリル）等の、アルキルエステルを構成するアルキル基が、炭素数が１～１８の鎖状構造である（メタ）アクリル酸アルキルエステル等が挙げられる。 Examples of the acrylic monomer having no functional group include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and (meth) acrylic. N-butyl acid, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, n-octyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, ( Undecyl (meth) acrylate, dodecyl (meth) acrylate (lauric (meth) acrylate ), Tridecyl (meth) acrylate, tetradecyl (meth) acrylate (myristyl (meth) acrylate), pentadecyl (meth) acrylate, hexadecyl (meth) acrylate (palmityl (meth) acrylate), (meth) acrylic (Meth) acrylic acid alkyl esters and the like, in which the alkyl group constituting the alkyl ester, such as heptadecyl acid and octadecyl (meth) acrylate (stearyl (meth) acrylate), has a chain structure of 1 to 18 carbon atoms, etc. Can be mentioned.
　また、前記官能基を有しないアクリル系モノマーとしては、例えば、（メタ）アクリル酸メトキシメチル、（メタ）アクリル酸メトキシエチル、（メタ）アクリル酸エトキシメチル、（メタ）アクリル酸エトキシエチル等のアルコキシアルキル基含有（メタ）アクリル酸エステル；（メタ）アクリル酸フェニル等の（メタ）アクリル酸アリールエステル等を含む、芳香族基を有する（メタ）アクリル酸エステル；非架橋性の（メタ）アクリルアミド及びその誘導体；（メタ）アクリル酸Ｎ，Ｎ－ジメチルアミノエチル、（メタ）アクリル酸Ｎ，Ｎ－ジメチルアミノプロピル等の非架橋性の３級アミノ基を有する（メタ）アクリル酸エステル等も挙げられる。 Examples of the acrylic monomer having no functional group include alkoxy such as methoxymethyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxymethyl (meth) acrylate, and ethoxyethyl (meth) acrylate. Alkyl group-containing (meth) acrylic acid ester; (meth) acrylic acid aryl ester such as (meth) acrylic acid phenyl ester, etc .; (meth) acrylic acid ester having an aromatic group; non-crosslinkable (meth) acrylamide and Derivatives thereof: (meth) acrylic acid esters having a non-crosslinking tertiary amino group such as N, N-dimethylaminoethyl (meth) acrylate and N, N-dimethylaminopropyl (meth) acrylate .
　前記アクリル系重合体（ａ１１）を構成する、前記官能基を有しないアクリル系モノマーは、１種のみでもよいし、２種以上でもよく、２種以上である場合、それらの組み合わせ及び比率は任意に選択できる。 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.
　前記非アクリル系モノマーとしては、例えば、エチレン、ノルボルネン等のオレフィン；酢酸ビニル；スチレン等が挙げられる。
　前記アクリル系重合体（ａ１１）を構成する前記非アクリル系モノマーは、１種のみでもよいし、２種以上でもよく、２種以上である場合、それらの組み合わせ及び比率は任意に選択できる。 Examples of the non-acrylic monomer 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.
　前記アクリル系重合体（ａ１１）において、これを構成する構成単位の全量に対する、前記官能基を有するアクリル系モノマーから誘導された構成単位の量の割合（含有量）は、０．１質量％以上５０質量％以下であることが好ましく、１質量％以上４０質量％以下であることがより好ましく、３質量％以上３０質量％以下であることが特に好ましい。前記割合がこのような範囲であることで、前記アクリル系重合体（ａ１１）と前記エネルギー線硬化性化合物（ａ１２）との共重合によって得られた前記アクリル系樹脂（ａ１－１）において、エネルギー線硬化性基の含有量は、保護膜の硬化の程度を好ましい範囲に容易に調節可能となる。 In the acrylic polymer (a11), the ratio (content) of the amount of the structural unit derived from the acrylic monomer having the functional group to the total amount of the structural unit constituting the polymer is 0.1% by mass or more. It is preferably 50% by mass or less, more preferably 1% by mass or more and 40% by mass or less, and particularly preferably 3% by mass or more and 30% by mass or less. When the ratio is within such a range, 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 can be easily adjusted within a preferable range of the degree of curing of the protective film.
　前記アクリル系樹脂（ａ１－１）を構成する前記アクリル系重合体（ａ１１）は、１種のみでもよいし、２種以上でもよく、２種以上である場合、それらの組み合わせ及び比率は任意に選択できる。 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.
　組成物（ＩＶ－１）において、溶媒以外の成分の総含有量に対する、アクリル系樹脂（ａ１－１）の含有量の割合（すなわち、エネルギー線硬化性保護膜形成用フィルムのアクリル系樹脂（ａ１－１）の含有量）は、１質量％以上７０質量％以下であることが好ましく、５質量％以上６０質量％以下であることがより好ましく、１０質量％以上５０質量％以下であることが特に好ましい。 In the composition (IV-1), the ratio of the content of the acrylic resin (a1-1) to the total content of components other than the solvent (that is, the acrylic resin (a1) of the film for forming an energy ray-curable protective film) The content of -1) is preferably 1% by mass or more and 70% by mass or less, more preferably 5% by mass or more and 60% by mass or less, and more preferably 10% by mass or more and 50% by mass or less. Particularly preferred.
・エネルギー線硬化性化合物（ａ１２）
　前記エネルギー線硬化性化合物（ａ１２）は、前記アクリル系重合体（ａ１１）が有する官能基と反応可能な基として、イソシアネート基、エポキシ基、及びカルボキシ基からなる群より選択される１種又は２種以上を有するものが好ましく、前記基としてイソシアネート基を有するものがより好ましい。前記エネルギー線硬化性化合物（ａ１２）は、例えば、前記基としてイソシアネート基を有する場合、このイソシアネート基が、前記官能基として水酸基を有するアクリル系重合体（ａ１１）のこの水酸基と容易に反応する。 Energy beam curable compound (a12)
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). What has a seed | species or more is preferable, and what has an isocyanate group as said group is more preferable. 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.
　前記エネルギー線硬化性化合物（ａ１２）は、１分子中に前記エネルギー線硬化性基を１個以上５個以下有することが好ましく、１個以上３個以下有することがより好ましい。 The energy beam curable compound (a12) preferably has 1 or more and 5 or less of the energy beam curable groups in one molecule, and more preferably 1 or more and 3 or less.
　前記エネルギー線硬化性化合物（ａ１２）としては、例えば、２－メタクリロイルオキシエチルイソシアネート、メタ－イソプロペニル－α，α－ジメチルベンジルイソシアネート、メタクリロイルイソシアネート、アリルイソシアネート、１，１－（ビスアクリロイルオキシメチル）エチルイソシアネート；
　ジイソシアネート化合物又はポリイソシアネート化合物と、ヒドロキシエチル（メタ）アクリレートとの反応により得られるアクリロイルモノイソシアネート化合物；
　ジイソシアネート化合物又はポリイソシアネート化合物と、ポリオール化合物と、ヒドロキシエチル（メタ）アクリレートとの反応により得られるアクリロイルモノイソシアネート化合物等が挙げられる。
　これらの中でも、前記エネルギー線硬化性化合物（ａ１２）は、２－メタクリロイルオキシエチルイソシアネートであることが好ましい。 Examples of the energy ray curable compound (a12) include 2-methacryloyloxyethyl isocyanate, meta-isopropenyl-α, α-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.
Among these, the energy beam curable compound (a12) is preferably 2-methacryloyloxyethyl isocyanate.
　前記アクリル系樹脂（ａ１－１）を構成する前記エネルギー線硬化性化合物（ａ１２）は、１種のみでもよいし、２種以上でもよく、２種以上である場合、それらの組み合わせ及び比率は任意に選択できる。 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.
　前記アクリル系樹脂（ａ１－１）において、前記アクリル系重合体（ａ１１）に由来する前記官能基の含有量に対する、前記エネルギー線硬化性化合物（ａ１２）に由来するエネルギー線硬化性基の含有量の割合は、２０モル％以上１２０モル％以下であることが好ましく、３５モル％以上１００モル％以下であることがより好ましく、５０モル％以上１００モル％以下であることが特に好ましい。前記含有量の割合がこのような範囲であることで、硬化後の保護膜の接着力がより大きくなる。なお、前記エネルギー線硬化性化合物（ａ１２）が一官能（前記基を１分子中に１個有する）化合物である場合には、前記含有量の割合の上限値は１００モル％となるが、前記エネルギー線硬化性化合物（ａ１２）が多官能（前記基を１分子中に２個以上有する）化合物である場合には、前記含有量の割合の上限値は１００モル％を超えることがある。 In the acrylic resin (a1-1), 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 mol% or more and 120 mol% or less, more preferably 35 mol% or more and 100 mol% or less, and particularly preferably 50 mol% or more and 100 mol% or less. When the ratio of the content is within such a range, the adhesive force of the protective film after curing is further increased. In addition, when the energy ray curable compound (a12) is a monofunctional compound (having one of the groups per molecule), the upper limit of the content ratio is 100 mol%, When 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%.
　前記重合体（ａ１）の重量平均分子量（Ｍｗ）は、１０００００以上２００００００以下であることが好ましく、３０００００以上１５０００００以下であることがより好ましい。
　ここで、「重量平均分子量」とは、先に説明したとおりである。 The weight average molecular weight (Mw) of the polymer (a1) is preferably 100,000 or more and 2,000,000 or less, and more preferably 300,000 or more and 1500,000 or less.
Here, the “weight average molecular weight” is as described above.
　前記重合体（ａ１）が、その少なくとも一部が架橋剤によって架橋されたものである場合、前記重合体（ａ１）は、前記アクリル系重合体（ａ１１）を構成するものとして説明した、上述のモノマーのいずれにも該当せず、かつ架橋剤と反応する基を有するモノマーが重合して、前記架橋剤と反応する基において架橋されたものであってもよいし、前記エネルギー線硬化性化合物（ａ１２）に由来する、前記官能基と反応する基において、架橋されたものであってもよい。 In the case where the polymer (a1) is at least partially crosslinked by a crosslinking agent, the polymer (a1) has been described as constituting the acrylic polymer (a11). A monomer that does not correspond to any of the monomers and has a group that reacts with the crosslinking agent is polymerized to be crosslinked at the group that reacts with the crosslinking agent, or the energy ray-curable compound ( In the group which reacts with the functional group derived from a12), it may be crosslinked.
　組成物（ＩＶ－１）及びエネルギー線硬化性保護膜形成用フィルムが含有する前記重合体（ａ１）は、１種のみでもよいし、２種以上でもよく、２種以上である場合、それらの組み合わせ及び比率は任意に選択できる。 The polymer (a1) contained in the composition (IV-1) and the energy ray-curable 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.
（エネルギー線硬化性基を有する、分子量が１００以上８００００以下の化合物（ａ２））
　エネルギー線硬化性基を有する、分子量が１００以上８００００以下の化合物（ａ２）が有するエネルギー線硬化性基としては、エネルギー線硬化性二重結合を含む基が挙げられ、好ましいものとしては、（メタ）アクリロイル基、ビニル基等が挙げられる。 (Compound (a2) having an energy ray-curable group and a molecular weight of 100 to 80,000)
Examples of the energy ray-curable group having the energy ray-curable group and the compound (a2) having a molecular weight of 100 to 80,000 include a group containing an energy ray-curable double bond. ) An acryloyl group, a vinyl group, etc. are mentioned.
　前記化合物（ａ２）は、上記の条件を満たすものであれば、特に限定されないが、エネルギー線硬化性基を有する低分子量化合物、エネルギー線硬化性基を有するエポキシ樹脂、エネルギー線硬化性基を有するフェノール樹脂等が挙げられる。 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.
　前記化合物（ａ２）のうち、エネルギー線硬化性基を有する低分子量化合物としては、例えば、多官能のモノマー又はオリゴマー等が挙げられ、（メタ）アクリロイル基を有するアクリレート系化合物が好ましい。
　前記アクリレート系化合物としては、例えば、２－ヒドロキシ－３－（メタ）アクリロイルオキシプロピルメタクリレート、ポリエチレングリコールジ（メタ）アクリレート、プロポキシ化エトキシ化ビスフェノールＡジ（メタ）アクリレート、２，２－ビス［４－（（メタ）アクリロキシポリエトキシ）フェニル］プロパン、エトキシ化ビスフェノールAジ（メタ）アクリレート、２，２－ビス［４－（（メタ）アクリロキシジエトキシ）フェニル］プロパン、９，９－ビス［４－（２－（メタ）アクリロイルオキシエトキシ）フェニル］フルオレン、２，２－ビス［４－（（メタ）アクリロキシポリプロポキシ）フェニル］プロパン、トリシクロデカンジメタノールジ（メタ）アクリレート、１，１０－デカンジオールジ（メタ）アクリレート、１，６－ヘキサンジオールジ（メタ）アクリレート、１，９－ノナンジオールジ（メタ）アクリレート、ジプロピレングリコールジ（メタ）アクリレート、トリプロピレングリコールジ（メタ）アクリレート、ポリプロピレングリコールジ（メタ）アクリレート、ポリテトラメチレングリコールジ（メタ）アクリレート、エチレングリコールジ（メタ）アクリレート、ジエチレングリコールジ（メタ）アクリレート、トリエチレングリコールジ（メタ）アクリレート、２，２－ビス［４－（（メタ）アクリロキシエトキシ）フェニル］プロパン、ネオペンチルグリコールジ（メタ）アクリレート、エトキシ化ポリプロピレングリコールジ（メタ）アクリレート、２－ヒドロキシ－１，３－ジ（メタ）アクリロキシプロパン等の２官能（メタ）アクリレート；
　トリス（２－（メタ）アクリロキシエチル）イソシアヌレート、ε－カプロラクトン変性トリス－（２－（メタ）アクリロキシエチル）イソシアヌレート、エトキシ化グリセリントリ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、ジトリメチロールプロパンテトラ（メタ）アクリレート、エトキシ化ペンタエリスリトールテトラ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールポリ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート等の多官能（メタ）アクリレート；
　ウレタン（メタ）アクリレートオリゴマー等の多官能（メタ）アクリレートオリゴマー等が挙げられる。 Among the compounds (a2), 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, tricyclodecane dimethanol di (meth) acrylate, 1 , 10-decanediol di (meth) acrylate 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) ) Acrylate, polytetramethylene glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, 2,2-bis [4-((meth) acrylic) Bifunctional (such as loxyethoxy) phenyl] propane, neopentyl glycol di (meth) acrylate, ethoxylated polypropylene glycol di (meth) acrylate, 2-hydroxy-1,3-di (meth) acryloxypropane Data) acrylate;
Tris (2- (meth) acryloxyethyl) isocyanurate, ε-caprolactone modified tris- (2- (meth) acryloxyethyl) isocyanurate, ethoxylated glycerin tri (meth) acrylate, pentaerythritol tri (meth) acrylate, Trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol poly (meth) acrylate, dipentaerythritol hexa ( Polyfunctional (meth) acrylates such as (meth) acrylate;
Examples include polyfunctional (meth) acrylate oligomers such as urethane (meth) acrylate oligomers.
　前記化合物（ａ２）のうち、エネルギー線硬化性基を有するエポキシ樹脂、エネルギー線硬化性基を有するフェノール樹脂としては、例えば、「特開２０１３－１９４１０２号公報」の段落００４３等に記載されているものを用いることができる。このような樹脂は、後述する熱硬化性成分を構成する樹脂にも該当するが、本実施形態においては前記化合物（ａ２）として取り扱う。 Among the compounds (a2), 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 a thermosetting component described later, but is handled as the compound (a2) in the present embodiment.
　前記化合物（ａ２）は、重量平均分子量が１００以上３００００以下であることが好ましく、３００以上１００００以下であることがより好ましい。ここで、「重量平均分子量」とは、先に説明したとおりである。 The compound (a2) preferably has a weight average molecular weight of 100 or more and 30000 or less, and more preferably 300 or more and 10,000 or less. Here, the “weight average molecular weight” is as described above.
　組成物（ＩＶ－１）及びエネルギー線硬化性保護膜形成用フィルムが含有する前記化合物（ａ２）は、１種のみでもよいし、２種以上でもよく、２種以上である場合、それらの組み合わせ及び比率は任意に選択できる。 The compound (a2) contained in the composition (IV-1) and the energy ray-curable 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.
［エネルギー線硬化性基を有しない重合体（ｂ）］
　組成物（ＩＶ－１）及びエネルギー線硬化性保護膜形成用フィルムは、前記エネルギー線硬化性成分（ａ）として前記化合物（ａ２）を含有する場合、さらにエネルギー線硬化性基を有しない重合体（ｂ）も含有することが好ましい。
　前記重合体（ｂ）は、その少なくとも一部が架橋剤によって架橋されたものであってもよいし、架橋されていないものであってもよい。 [Polymer (b) having no energy ray curable group]
When the composition (IV-1) and the film for forming an energy ray curable protective 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 a crosslinking agent, or may not be crosslinked.
　エネルギー線硬化性基を有しない重合体（ｂ）としては、例えば、アクリル系重合体、フェノキシ樹脂、ウレタン樹脂、ポリエステル、ゴム系樹脂、アクリルウレタン樹脂等が挙げられる。
　これらの中でも、前記重合体（ｂ）は、アクリル系重合体（以下、「アクリル系重合体（ｂ－１）」と略記することがある）であることが好ましい。 Examples of the polymer (b) having no energy ray curable group include acrylic polymers, phenoxy resins, urethane resins, polyesters, rubber resins, and acrylic urethane resins.
Among these, the polymer (b) is preferably an acrylic polymer (hereinafter sometimes abbreviated as “acrylic polymer (b-1)”).
　アクリル系重合体（ｂ－１）は、公知のものでよく、例えば、１種のアクリル系モノマーの単独重合体であってもよいし、２種以上のアクリル系モノマーの共重合体であってもよいし、１種又は２種以上のアクリル系モノマーと、１種又は２種以上のアクリル系モノマー以外のモノマー（非アクリル系モノマー）と、の共重合体であってもよい。 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.
　アクリル系重合体（ｂ－１）を構成する前記アクリル系モノマーとしては、例えば、（メタ）アクリル酸アルキルエステル、環状骨格を有する（メタ）アクリル酸エステル、グリシジル基含有（メタ）アクリル酸エステル、水酸基含有（メタ）アクリル酸エステル、置換アミノ基含有（メタ）アクリル酸エステル等が挙げられる。ここで、「置換アミノ基」とは、先に説明したとおりである。 Examples of the acrylic monomer constituting the acrylic polymer (b-1) 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. Here, the “substituted amino group” is as described above.
　前記（メタ）アクリル酸アルキルエステルとしては、例えば、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸ｎ－プロピル、（メタ）アクリル酸イソプロピル、（メタ）アクリル酸ｎ－ブチル、（メタ）アクリル酸イソブチル、（メタ）アクリル酸ｓｅｃ－ブチル、（メタ）アクリル酸ｔｅｒｔ－ブチル、（メタ）アクリル酸ペンチル、（メタ）アクリル酸ヘキシル、（メタ）アクリル酸ヘプチル、（メタ）アクリル酸２－エチルヘキシル、（メタ）アクリル酸イソオクチル、（メタ）アクリル酸ｎ－オクチル、（メタ）アクリル酸ｎ－ノニル、（メタ）アクリル酸イソノニル、（メタ）アクリル酸デシル、（メタ）アクリル酸ウンデシル、（メタ）アクリル酸ドデシル（（メタ）アクリル酸ラウリル）、（メタ）アクリル酸トリデシル、（メタ）アクリル酸テトラデシル（（メタ）アクリル酸ミリスチル）、（メタ）アクリル酸ペンタデシル、（メタ）アクリル酸ヘキサデシル（（メタ）アクリル酸パルミチル）、（メタ）アクリル酸ヘプタデシル、（メタ）アクリル酸オクタデシル（（メタ）アクリル酸ステアリル）等の、アルキルエステルを構成するアルキル基が、炭素数が１～１８の鎖状構造である（メタ）アクリル酸アルキルエステル等が挙げられる。 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. Butyl, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, (meth ) 2-ethylhexyl acrylate, isooctyl (meth) acrylate, n-octyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, (meth) acrylic Undecyl acid, dodecyl (meth) acrylate (lauryl (meth) acrylate), ( T) Decyl acrylate, tetradecyl (meth) acrylate (myristyl (meth) acrylate), pentadecyl (meth) acrylate, hexadecyl (meth) acrylate (palmityl (meth) acrylate), heptadecyl (meth) acrylate, Examples include (meth) acrylic acid alkyl esters in which the alkyl group constituting the alkyl ester such as octadecyl (meth) acrylate (stearyl (meth) acrylate) has a chain structure having 1 to 18 carbon atoms.
　前記環状骨格を有する（メタ）アクリル酸エステルとしては、例えば、（メタ）アクリル酸イソボルニル、（メタ）アクリル酸ジシクロペンタニル等の（メタ）アクリル酸シクロアルキルエステル；
　（メタ）アクリル酸ベンジル等の（メタ）アクリル酸アラルキルエステル；
　（メタ）アクリル酸ジシクロペンテニルエステル等の（メタ）アクリル酸シクロアルケニルエステル；
　（メタ）アクリル酸ジシクロペンテニルオキシエチルエステル等の（メタ）アクリル酸シクロアルケニルオキシアルキルエステル等が挙げられる。 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.
　前記グリシジル基含有（メタ）アクリル酸エステルとしては、例えば、（メタ）アクリル酸グリシジル等が挙げられる。
　前記水酸基含有（メタ）アクリル酸エステルとしては、例えば、（メタ）アクリル酸ヒドロキシメチル、（メタ）アクリル酸２－ヒドロキシエチル、（メタ）アクリル酸２－ヒドロキシプロピル、（メタ）アクリル酸３－ヒドロキシプロピル、（メタ）アクリル酸２－ヒドロキシブチル、（メタ）アクリル酸３－ヒドロキシブチル、（メタ）アクリル酸４－ヒドロキシブチル等が挙げられる。
　前記置換アミノ基含有（メタ）アクリル酸エステルとしては、例えば、（メタ）アクリル酸Ｎ－メチルアミノエチル等が挙げられる。 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.
　アクリル系重合体（ｂ－１）を構成する前記非アクリル系モノマーとしては、例えば、エチレン、ノルボルネン等のオレフィン；酢酸ビニル；スチレン等が挙げられる。 Examples of the non-acrylic monomer constituting the acrylic polymer (b-1) include olefins such as ethylene and norbornene; vinyl acetate; styrene.
　少なくとも一部が架橋剤によって架橋された、前記エネルギー線硬化性基を有しない重合体（ｂ）としては、例えば、前記重合体（ｂ）中の反応性官能基が架橋剤と反応したものが挙げられる。
　前記反応性官能基は、架橋剤の種類等に応じて適宜選択すればよく、特に限定されない。例えば、架橋剤がポリイソシアネート化合物である場合には、前記反応性官能基としては、水酸基、カルボキシ基、アミノ基等が挙げられ、これらの中でも、イソシアネート基との反応性が高い水酸基が好ましい。また、架橋剤がエポキシ系化合物である場合には、前記反応性官能基としては、カルボキシ基、アミノ基、アミド基等が挙げられ、これらの中でもエポキシ基との反応性が高いカルボキシ基が好ましい。ただし、半導体ウエハや半導体チップの回路の腐食を防止するという点では、前記反応性官能基はカルボキシ基以外の基であることが好ましい。 Examples of the polymer (b) that is at least partially crosslinked by a crosslinking agent and does not have an energy ray-curable group include those in which a reactive functional group in the polymer (b) has reacted with a crosslinking agent. Can be mentioned.
The reactive functional group may be appropriately selected according to the type of the crosslinking agent and the like, and is not particularly limited. For example, when the crosslinking agent is a polyisocyanate compound, examples of the reactive functional group include a hydroxyl group, a carboxy group, and an amino group, and among these, a hydroxyl group having high reactivity with an isocyanate group is preferable. In addition, when the crosslinking agent is an epoxy compound, examples of the reactive functional group include a carboxy group, an amino group, an amide group, and the like. Among these, a carboxy group having high reactivity with an epoxy group is preferable. . However, 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.
　前記反応性官能基を有する、エネルギー線硬化性基を有しない重合体（ｂ）としては、例えば、少なくとも前記反応性官能基を有するモノマーを重合させて得られたものが挙げられる。アクリル系重合体（ｂ－１）の場合であれば、これを構成するモノマーとして挙げた、前記アクリル系モノマー及び非アクリル系モノマーのいずれか一方又は両方として、前記反応性官能基を有するものを用いればよい。例えば、反応性官能基として水酸基を有する前記重合体（ｂ）としては、例えば、水酸基含有（メタ）アクリル酸エステルを重合して得られたものが挙げられ、これ以外にも、先に挙げた前記アクリル系モノマー又は非アクリル系モノマーにおいて、１個又は２個以上の水素原子が前記反応性官能基で置換されてなるモノマーを重合して得られたものが挙げられる。 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. In the case of the acrylic polymer (b-1), those having the reactive functional group as one or both of the acrylic monomer and the non-acrylic monomer mentioned as the monomers constituting the polymer (b-1). Use it. For example, 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.
　反応性官能基を有する前記重合体（ｂ）において、これを構成する構成単位の全量に対する、反応性官能基を有するモノマーから誘導された構成単位の量の割合（含有量）は、１質量％以上２０質量％以下であることが好ましく、２質量％以上１０質量％以下であることがより好ましい。前記割合がこのような範囲であることで、前記重合体（ｂ）において、架橋の程度がより好ましい範囲となる。 In the polymer (b) having a reactive functional group, the ratio (content) of the amount of the structural unit derived from the monomer having the reactive functional group to the total amount of the structural unit constituting the polymer (b) is 1% by mass. It is preferably 20% by mass or less and more preferably 2% by mass or more and 10% by mass or less. When the ratio is within such a range, the degree of cross-linking becomes a more preferable range in the polymer (b).
　エネルギー線硬化性基を有しない重合体（ｂ）の重量平均分子量（Ｍｗ）は、組成物（ＩＶ－１）の造膜性がより良好となる点から、１００００以上２００００００以下であることが好ましく、１０００００以上１５０００００以下であることがより好ましい。ここで、「重量平均分子量」とは、先に説明したとおりである。 The weight average molecular weight (Mw) of the polymer (b) having no energy ray-curable group is preferably 10,000 or more and 2,000,000 or less from the viewpoint that the film-forming property of the composition (IV-1) becomes better. More preferably, it is 100,000 or more and 1500,000 or less. Here, the “weight average molecular weight” is as described above.
　組成物（ＩＶ－１）及びエネルギー線硬化性保護膜形成用フィルムが含有する、エネルギー線硬化性基を有しない重合体（ｂ）は、１種のみでもよいし、２種以上でもよく、２種以上である場合、それらの組み合わせ及び比率は任意に選択できる。 The polymer (b) having no energy ray-curable group contained in the composition (IV-1) and the energy ray-curable protective film-forming film may be only one type or two or more types. In the case of more than species, their combination and ratio can be arbitrarily selected.
　組成物（ＩＶ－１）としては、前記重合体（ａ１）及び前記化合物（ａ２）のいずれか一方又は両方を含有するものが挙げられる。そして、組成物（ＩＶ－１）は、前記化合物（ａ２）を含有する場合、さらにエネルギー線硬化性基を有しない重合体（ｂ）も含有することが好ましく、この場合、さらに前記（ａ１）を含有することも好ましい。また、組成物（ＩＶ－１）は、前記化合物（ａ２）を含有せず、前記重合体（ａ１）、及びエネルギー線硬化性基を有しない重合体（ｂ）をともに含有していてもよい。 Examples of the composition (IV-1) include those containing one or both of the polymer (a1) and the compound (a2). When the composition (IV-1) contains the compound (a2), the composition (IV-1) preferably further contains a polymer (b) having no energy ray-curable group. In this case, the composition (IV-1) It is also preferable to contain. Further, the composition (IV-1) does not contain the compound (a2), and may contain both the polymer (a1) and the polymer (b) having no energy ray curable group. .
　組成物（ＩＶ－１）が、前記重合体（ａ１）、前記化合物（ａ２）、及びエネルギー線硬化性基を有しない重合体（ｂ）を含有する場合、組成物（ＩＶ－１）において、前記化合物（ａ２）の含有量は、前記重合体（ａ１）及びエネルギー線硬化性基を有しない重合体（ｂ）の総含有量１００質量部に対して、１０質量部以上４００質量部以下であることが好ましく、３０質量部以上３５０質量部以下であることがより好ましい。 When the composition (IV-1) contains the polymer (a1), the compound (a2), and the polymer (b) having no energy ray-curable group, in the composition (IV-1): Content of the said compound (a2) is 10 mass parts or more and 400 mass parts or less with respect to 100 mass parts of total contents of the said polymer (a1) and the polymer (b) which does not have an energy-beam curable group. It is preferable that it is 30 parts by mass or more and 350 parts by mass or less.
　組成物（ＩＶ－１）において、溶媒以外の成分の総含有量に対する、前記エネルギー線硬化性成分（ａ）及びエネルギー線硬化性基を有しない重合体（ｂ）の合計含有量の割合（すなわち、エネルギー線硬化性保護膜形成用フィルムの前記エネルギー線硬化性成分（ａ）及びエネルギー線硬化性基を有しない重合体（ｂ）の合計含有量）は、５質量％以上９０質量％以下であることが好ましく、１０質量％以上８０質量％以下であることがより好ましく、２０質量％以上７０質量％以下であることが特に好ましい。エネルギー線硬化性成分の含有量の前記割合がこのような範囲であることで、エネルギー線硬化性保護膜形成用フィルムのエネルギー線硬化性がより良好となる。 In the composition (IV-1), the ratio of the total content of the energy beam curable component (a) and the polymer (b) having no energy beam curable group to the total content of components other than the solvent (that is, The total content of the energy ray-curable component (a) and the polymer (b) having no energy ray-curable group) of the energy ray-curable protective film-forming film is 5% by mass or more and 90% by mass or less. It is preferably 10% by mass to 80% by mass, more preferably 20% by mass to 70% by mass. When the ratio of the content of the energy ray curable component is within such a range, the energy ray curable film of the energy ray curable protective film forming film becomes more favorable.
　組成物（ＩＶ－１）は、前記エネルギー線硬化性成分以外に、目的に応じて、熱硬化性成分、充填材、カップリング剤、架橋剤、光重合開始剤、着色剤、及び汎用添加剤からなる群より選択される１種又は２種以上を含有していてもよい。例えば、前記エネルギー線硬化性成分及び熱硬化性成分を含有する組成物（ＩＶ－１）を用いることにより、形成されるエネルギー線硬化性保護膜形成用フィルムは、加熱によって被着体に対する接着力が向上し、このエネルギー線硬化性保護膜形成用フィルムから形成された保護膜の強度も向上する。 In addition to the energy ray curable component, the composition (IV-1) includes a thermosetting component, a filler, a coupling agent, a crosslinking agent, a photopolymerization initiator, a colorant, and a general-purpose additive depending on the purpose. You may contain 1 type, or 2 or more types selected from the group which consists of. For example, by using the composition (IV-1) containing the energy ray curable component and the thermosetting component, the formed energy ray curable protective film-forming film can be adhered to an adherend by heating. And the strength of the protective film formed from the energy ray-curable protective film-forming film is also improved.
　組成物（ＩＶ－１）における前記熱硬化性成分、充填材、カップリング剤、架橋剤、光重合開始剤、着色剤、及び汎用添加剤としては、それぞれ、組成物（ＩＩＩ－１）における熱硬化性成分（Ｂ）、充填材（Ｄ）、カップリング剤（Ｅ）、架橋剤（Ｆ）、光重合開始剤（Ｈ）、着色剤（Ｉ）及び汎用添加剤（Ｊ）と同じものが挙げられる。 Examples of the thermosetting component, filler, coupling agent, crosslinking agent, photopolymerization initiator, colorant, and general-purpose additive in the composition (IV-1) are the heat in the composition (III-1). The same as the curable component (B), filler (D), coupling agent (E), crosslinking agent (F), photopolymerization initiator (H), colorant (I), and general-purpose additive (J). Can be mentioned.
　組成物（ＩＶ－１）において、前記熱硬化性成分、充填材、カップリング剤、架橋剤、光重合開始剤、着色剤、及び汎用添加剤は、それぞれ、１種を単独で用いてもよいし、２種以上を併用してもよく、２種以上を併用する場合、それらの組み合わせ及び比率は任意に選択できる。
　組成物（ＩＶ－１）における前記熱硬化性成分、充填材、カップリング剤、架橋剤、光重合開始剤、着色剤、及び汎用添加剤の含有量は、目的に応じて適宜調節すればよく、特に限定されない。 In the composition (IV-1), each of the thermosetting component, the filler, the coupling agent, the crosslinking agent, the photopolymerization initiator, the colorant, and the general-purpose additive may be used alone. And when 2 or more types may be used together, and when using 2 or more types together, those combinations and ratios can be selected arbitrarily.
The contents of the thermosetting component, filler, coupling agent, crosslinking agent, photopolymerization initiator, colorant, and general-purpose additive in the composition (IV-1) may be appropriately adjusted according to the purpose. There is no particular limitation.
　組成物（ＩＶ－１）は、希釈によってその取り扱い性が向上することから、さらに溶媒を含有するものが好ましい。
　組成物（ＩＶ－１）が含有する溶媒としては、例えば、組成物（ＩＩＩ－１）における溶媒と同じものが挙げられる。
　組成物（ＩＶ－１）が含有する溶媒は、１種のみでもよいし、２種以上でもよい。 The composition (IV-1) preferably further contains a solvent since its handleability is improved by dilution.
Examples of the solvent contained in the composition (IV-1) include the same solvents as those in the composition (III-1).
The solvent contained in the composition (IV-1) may be only one kind or two or more kinds.
＜＜エネルギー線硬化性保護膜形成用組成物の製造方法＞＞
　組成物（ＩＶ－１）等のエネルギー線硬化性保護膜形成用組成物は、これを構成するための各成分を配合することで得られる。
　各成分の配合時における添加順序は特に限定されず、２種以上の成分を同時に添加してもよい。
　溶媒を用いる場合には、溶媒を溶媒以外のいずれかの配合成分と混合してこの配合成分を予め希釈しておくことで用いてもよいし、溶媒以外のいずれかの配合成分を予め希釈しておくことなく、溶媒をこれら配合成分と混合することで用いてもよい。
　配合時に各成分を混合する方法は特に限定されず、撹拌子又は撹拌翼等を回転させて混合する方法；ミキサーを用いて混合する方法；超音波を加えて混合する方法等、公知の方法から適宜選択すればよい。
　各成分の添加及び混合時の温度並びに時間は、各配合成分が劣化しない限り特に限定されず、適宜調節すればよいが、温度は１５℃以上３０℃であることが好ましい。 << Method for producing composition for forming energy ray-curable protective film >>
The composition for forming an energy ray-curable protective film such as the composition (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.
When a solvent is used, 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 ° C. or higher and 30 ° C.
○非硬化性保護膜形成用フィルム
　好ましい非硬化性保護膜形成用フィルムとしては、例えば、非硬化性成分（ｃ）を含有する。非硬化性保護膜形成用フィルムにおいて、非硬化性成分（ｃ）は、硬化性を有さず、支持シートへの粘着性、及び半導体ウエハ又はチップを保護するために適度な硬度を有することが好ましい。ここで、「非硬化性」とは、先に説明したとおりである。 ○ Non-curable protective film-forming film As a preferable non-curable protective film-forming film, for example, a non-curable component (c) is contained. In the film for forming a non-curable protective film, the non-curable component (c) does not have curability, has adhesiveness to the support sheet, and has an appropriate hardness to protect the semiconductor wafer or chip. preferable. Here, “non-curable” is as described above.
　非硬化性保護膜形成用フィルムは１層（単層）のみでもよいし、２層以上の複数層でもよく、複数層である場合、これら複数層は、互いに同一でも異なっていてもよく、これら複数層の組み合わせは特に限定されない。 The non-curable protective film-forming film may be only one layer (single layer), or may be two or more layers, and when it is 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.
　非硬化性保護膜形成用フィルムの厚さは、１μｍ以上１００μｍ以下であることが好ましく、５μｍ以上７５μｍ以下であることがより好ましく、５μｍ以上５０μｍ以下であることが特に好ましい。非硬化性保護膜形成用フィルムの厚さが前記下限値以上であることで、保護能がより高い保護膜を形成できる。また、非硬化性保護膜形成用フィルムの厚さが前記上限値以下であることで、過剰な厚さとなることが抑制される。
　ここで、「非硬化性保護膜形成用フィルムの厚さ」とは、非硬化性保護膜形成用フィルム全体の厚さを意味し、例えば、複数層からなる非硬化性保護膜形成用フィルムの厚さとは、非硬化性保護膜形成用フィルムを構成するすべての層の合計の厚さを意味する。なお、非硬化性保護膜形成用フィルムの厚さの測定方法としては、例えば、任意の５箇所において、接触式厚み計を用いて厚さを測定し、測定値の平均を算出する方法等が挙げられる。 The thickness of the non-curable protective film-forming film is preferably 1 μm or more and 100 μm or less, more preferably 5 μm or more and 75 μm or less, and particularly preferably 5 μm or more and 50 μm or less. When the thickness of the non-curable protective film-forming film is equal to or more than the lower limit value, a protective film with higher protective ability can be formed. Moreover, when the thickness of the film for forming a non-curable protective film is equal to or less than the upper limit, an excessive thickness is suppressed.
Here, the “thickness of the non-curable protective film-forming film” means the total thickness of the non-curable protective film-forming film, for example, a non-curable protective film-forming film composed of a plurality of layers. The thickness means the total thickness of all the layers constituting the non-curable protective film-forming film. The method for measuring the thickness of the non-curable protective film-forming film includes, for example, a method of measuring the thickness using a contact-type thickness meter at any five locations and calculating the average of the measured values. Can be mentioned.
＜＜非硬化性保護膜形成用組成物＞＞
　非硬化性保護膜形成用フィルムは、その構成材料を含有する非硬化性保護膜形成用組成物を用いて形成できる。例えば、非硬化性保護膜形成用フィルムの形成対象面に非硬化性保護膜形成用組成物を塗工し、必要に応じて乾燥させることで、目的とする部位に非硬化性保護膜形成用フィルムを形成できる。非硬化性保護膜形成用組成物中の、常温で気化しない成分同士の含有量の比率は、通常、非硬化性保護膜形成用フィルムの前記成分同士の含有量の比率と同じとなる。ここで、「常温」とは、先に説明したとおりである。 << Non-curable protective film forming composition >>
The non-curable protective film-forming film can be formed using a non-curable protective film-forming composition containing the constituent materials. For example, the composition for forming a non-curable protective film is applied to the surface to be formed of the film for forming a non-curable protective film, and is dried as necessary to form a non-curable protective film on the target site. A film can be formed. In the composition for forming a non-curable protective film, the ratio of the content of components that do not vaporize at room temperature is usually the same as the ratio of the content of the components in the film for forming a non-curable protective film. Here, “normal temperature” is as described above.
　非硬化性保護膜形成用組成物の塗工は、例えば、上述の粘着剤組成物の塗工の場合と同じ方法で行うことができる。 The coating of the non-curable protective film-forming composition can be performed, for example, by the same method as in the case of the above-described pressure-sensitive adhesive composition.
　非硬化性保護膜形成用組成物の乾燥条件は、特に限定されないが、非硬化性保護膜形成用組成物は、後述する溶媒を含有している場合、加熱乾燥させることが好ましく、この場合、例えば、７０℃以上１３０℃以下で１０秒以上５分以下の条件で乾燥させることが好ましい。 The drying conditions for the non-curable protective film-forming composition are not particularly limited, but the non-curable protective film-forming composition preferably contains heat-dried when it contains a solvent to be described later. For example, the drying is preferably performed at 70 ° C. to 130 ° C. for 10 seconds to 5 minutes.
＜非硬化性保護膜形成用組成物（Ｖ－１）＞
　非硬化性保護膜形成用組成物としては、例えば、非硬化性成分（ｃ）を含有する非硬化性保護膜形成用組成物（Ｖ－１）（本明細書においては、単に「組成物（Ｖ－１）」と略記することがある）等が挙げられる。 <Non-curable protective film-forming composition (V-1)>
Examples of the non-curable protective film-forming composition include, for example, a non-curable protective film-forming composition (V-1) containing a non-curable component (c) (in this specification, simply “composition ( V-1) ”) and the like.
　非硬化性成分（ｃ）は、熱可塑性樹脂であり、例えば、アクリル系重合体等が挙げられ、これらに限定されない。前記アクリル系重合体としては、上記アクリル系重合体（ｂ－１）として例示されたものと同様のものが挙げられる。 The non-curable component (c) is a thermoplastic resin, and examples thereof include, but are not limited to, acrylic polymers. Examples of the acrylic polymer include those exemplified as the acrylic polymer (b-1).
　組成物（Ｖ－１）は、前記非硬化性成分（ｃ）以外に、目的に応じて、充填材、カップリング剤、架橋剤、着色剤、及び汎用添加剤からなる群より選択される１種又は２種以上を含有していてもよい。 The composition (V-1) is selected from the group consisting of a filler, a coupling agent, a crosslinking agent, a colorant, and a general-purpose additive in addition to the non-curable component (c). You may contain the seed or two or more sorts.
　組成物（Ｖ－１）における前記充填材、カップリング剤、架橋剤、着色剤、及び汎用添加剤としては、それぞれ、組成物（ＩＩＩ－１）における充填材（Ｄ）、カップリング剤（Ｅ）、架橋剤（Ｆ）、着色剤（Ｉ）及び汎用添加剤（Ｊ）と同じものが挙げられる。 Examples of the filler, coupling agent, crosslinking agent, colorant, and general-purpose additive in the composition (V-1) include the filler (D) and the coupling agent (E in the composition (III-1), respectively. ), Crosslinker (F), colorant (I), and general-purpose additive (J).
　組成物（Ｖ－１）において、前記充填材、カップリング剤、架橋剤、着色剤、及び汎用添加剤は、それぞれ、１種を単独で用いてもよいし、２種以上を併用してもよく、２種以上を併用する場合、それらの組み合わせ及び比率は任意に選択できる。
　組成物（Ｖ－１）における前記充填材、カップリング剤、架橋剤、着色剤、及び汎用添加剤の含有量は、目的に応じて適宜調節すればよく、特に限定されない。 In the composition (V-1), the filler, coupling agent, crosslinking agent, colorant, and general-purpose additive may be used alone or in combination of two or more. Well, when using 2 or more types together, those combinations and ratios can be arbitrarily selected.
The contents of the filler, coupling agent, crosslinking agent, colorant, and general-purpose additive in the composition (V-1) may be appropriately adjusted according to the purpose, and are not particularly limited.
　組成物（Ｖ－１）は、希釈によってその取り扱い性が向上することから、さらに溶媒を含有するものが好ましい。
　組成物（Ｖ－１）が含有する溶媒としては、例えば、組成物（ＩＩＩ－１）における溶媒と同じものが挙げられる。
　組成物（Ｖ－１）が含有する溶媒は、１種のみでもよいし、２種以上でもよい。 The composition (V-1) preferably further contains a solvent since its handleability is improved by dilution.
Examples of the solvent contained in the composition (V-1) include the same solvents as those in the composition (III-1).
The solvent contained in the composition (V-1) may be only one type or two or more types.
＜＜非硬化性保護膜形成用組成物の製造方法＞＞
　組成物（Ｖ－１）等の非硬化性保護膜形成用組成物は、これを構成するための各成分を配合することで得られる。
　各成分の配合時における添加順序は特に限定されず、２種以上の成分を同時に添加してもよい。
　溶媒を用いる場合には、溶媒を溶媒以外のいずれかの配合成分と混合してこの配合成分を予め希釈しておくことで用いてもよいし、溶媒以外のいずれかの配合成分を予め希釈しておくことなく、溶媒をこれら配合成分と混合することで用いてもよい。
　配合時に各成分を混合する方法は特に限定されず、撹拌子又は撹拌翼等を回転させて混合する方法；ミキサーを用いて混合する方法；超音波を加えて混合する方法等、公知の方法から適宜選択すればよい。
　各成分の添加及び混合時の温度並びに時間は、各配合成分が劣化しない限り特に限定されず、適宜調節すればよいが、温度は１５℃以上３０℃であることが好ましい。 << Method for producing composition for forming non-curable protective film >>
The composition for forming a non-curable protective film such as the composition (V-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.
When a solvent is used, 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 ° C. or higher and 30 ° C.
　本発明の１つの側面において、保護膜形成用複合シートは、以下に示す成分を含有する保護膜形成用フィルム、以下に示す成分を含有する粘着剤層、及び、以下に示す構成の基材がこの順に積層している。 In one aspect of the present invention, the composite sheet for forming a protective film includes a protective film-forming film containing the following components, an adhesive layer containing the following components, and a substrate having the following configuration: They are stacked in this order.
　保護膜形成用フィルムは、具体的には、
重合体成分（Ａ）－１として、メチルアクリレート８５質量部、及び、２－ヒドロキシエチルアクリレート１５質量部を共重合してなるアクリル系重合体（重量平均分子量：３５～４０万、好ましくは３７万、ガラス転移温度：３～９℃、好ましくは６℃）を１００～２００質量部、好ましくは１５０質量部と；
　エポキシ樹脂（Ｂ１）－１として、ビスフェノールＡ型エポキシ樹脂（エポキシ当量：１８０～２００ｇ／ｅｑ、好ましくは１８４～１９４ｇ／ｅｑ）を５０～７０質量部、好ましくは６０質量部と；
　エポキシ樹脂（Ｂ１）－２として、ビスフェノールＡ型エポキシ樹脂（エポキシ当量：７５０～９５０ｇ／ｅｑ、好ましくは８００～９００ｇ／ｅｑ）を５～１５質量部、好ましくは１０質量部と；
エポキシ樹脂（Ｂ１）－３として、ジシクロペンタジエン型エポキシ樹脂（エポキシ当量：２５０～２７０ｇ／ｅｑ、好ましくは２５５～２６０ｇ／ｅｑ）を２０～４０質量部、好ましくは３０質量部と；
熱硬化剤（Ｂ２）として、熱活性潜在性エポキシ樹脂硬化剤（ジシアンジアミド、活性水素量：２０～２５ｇ／ｅｑ、好ましくは２１ｇ／ｅｑ）を１～３質量部、好ましくは２質量部と；
硬化促進剤（Ｃ）として、２－フェニル－４，５－ジヒドロキシメチルイミダゾールを１～３質量部、好ましくは２質量部と；
充填剤（Ｄ）として、シリカフィラー（平均粒子径：０．１～１μｍ、好ましくは０．５μｍ）を３００～３４０質量部、好ましくは３２０質量部と；
カップリング剤（Ｅ）として、シランカップリング剤を１～３質量部、好ましくは２質量部と；
着色剤（Ｉ）として、黒色顔料を１６～２０質量部、好ましくは１８質量部と、を含有する。 Specifically, the protective film-forming film is
As the polymer component (A) -1, an acrylic polymer obtained by copolymerizing 85 parts by mass of methyl acrylate and 15 parts by mass of 2-hydroxyethyl acrylate (weight average molecular weight: 350 to 400,000, preferably 370,000) Glass transition temperature: 3 to 9 ° C., preferably 6 ° C.) of 100 to 200 parts by weight, preferably 150 parts by weight;
As epoxy resin (B1) -1, bisphenol A type epoxy resin (epoxy equivalent: 180 to 200 g / eq, preferably 184 to 194 g / eq) is 50 to 70 parts by mass, preferably 60 parts by mass;
As epoxy resin (B1) -2, bisphenol A type epoxy resin (epoxy equivalent: 750 to 950 g / eq, preferably 800 to 900 g / eq) is 5 to 15 parts by mass, preferably 10 parts by mass;
As epoxy resin (B1) -3, dicyclopentadiene type epoxy resin (epoxy equivalent: 250 to 270 g / eq, preferably 255 to 260 g / eq) is 20 to 40 parts by mass, preferably 30 parts by mass;
As the thermosetting agent (B2), 1 to 3 parts by mass, preferably 2 parts by mass of a thermoactive latent epoxy resin curing agent (dicyandiamide, active hydrogen amount: 20 to 25 g / eq, preferably 21 g / eq);
1-3 parts by weight, preferably 2 parts by weight, of 2-phenyl-4,5-dihydroxymethylimidazole as the curing accelerator (C);
As filler (D), silica filler (average particle size: 0.1 to 1 μm, preferably 0.5 μm) is 300 to 340 parts by mass, preferably 320 parts by mass;
As a coupling agent (E), 1 to 3 parts by mass, preferably 2 parts by mass of a silane coupling agent;
The colorant (I) contains 16 to 20 parts by mass, preferably 18 parts by mass of a black pigment.
　粘着剤層は、具体的には、
アクリル系重合体として、２－エチルヘキシルアクリレート（２ＥＨＡ）（８０質量部）、及び、２－ヒドロキシルエチルアクリレート（ＨＥＡ）（２０質量部）を共重合してなる重量平均分子量８０００００のプレ共重合体を９０～１１０質量部、好ましくは１００質量部と；
３官能キシリレンジイソシアネート系架橋剤を３５～６０質量部、好ましくは４０～５０質量部と、を含有する。 Specifically, the adhesive layer is
A pre-copolymer having a weight average molecular weight of 800,000 obtained by copolymerizing 2-ethylhexyl acrylate (2EHA) (80 parts by mass) and 2-hydroxylethyl acrylate (HEA) (20 parts by mass) as an acrylic polymer. 90-110 parts by weight, preferably 100 parts by weight;
35 to 60 parts by mass, preferably 40 to 50 parts by mass of a trifunctional xylylene diisocyanate crosslinking agent is contained.
　基材は、具体的には、厚さが７０～９０μｍ、好ましくは８０μｍのポリプロピレン製フィルムである。さらに、基剤は、マット面（表面粗さ（Ｒａ）：０．２０～１．３０μｍ、好ましくは０．２０～１．２０μｍ）、及び、ツヤ面又は微マット面（表面粗さ（Ｒａ）：０．０５～０．１５μｍ、好ましくは０．１０～０．１５μｍ）を有する。
　なお、前記粘着剤層は、基材のマット面上に積層されている。
或いは、前記基材が、マット面の表面粗さ（Ｒａ）（表面粗さ（Ｒａ）：０．３０μｍ以下、好ましくは０．２０μｍ）、及び、ツヤ面又は微マット面（表面粗さ（Ｒａ）：０．０５～０．１５μｍ、好ましくは０．１０～０．１５μｍ）を有する場合、前記粘着剤層は、基材のツヤ面又は微マット面上に積層されている。 Specifically, the substrate is a polypropylene film having a thickness of 70 to 90 μm, preferably 80 μm. Further, the base includes a matte surface (surface roughness (Ra): 0.20 to 1.30 μm, preferably 0.20 to 1.20 μm), and a glossy surface or a fine matte surface (surface roughness (Ra)). : 0.05 to 0.15 μm, preferably 0.10 to 0.15 μm).
In addition, the said adhesive layer is laminated | stacked on the mat | matte surface of a base material.
Alternatively, the base material has a mat surface roughness (Ra) (surface roughness (Ra): 0.30 μm or less, preferably 0.20 μm) and a glossy surface or a fine mat surface (surface roughness (Ra ): 0.05 to 0.15 μm, preferably 0.10 to 0.15 μm), the pressure-sensitive adhesive layer is laminated on the glossy surface or fine mat surface of the substrate.
　また、本発明の１つの側面において、保護膜形成用複合シートは、上記成分を含有する保護膜形成用フィルム、以下に示す成分を含有する粘着剤層、及び、上記構成の基材を有する。 Also, in one aspect of the present invention, the protective film-forming composite sheet has a protective film-forming film containing the above components, a pressure-sensitive adhesive layer containing the following components, and a substrate having the above-described configuration.
　粘着剤層は、具体的には、
アクリル系重合体として、２－エチルヘキシルアクリレート（２ＥＨＡ）（８０質量部）、及び、２－ヒドロキシルエチルアクリレート（ＨＥＡ）（２０質量部）を共重合してなる重量平均分子量８０００００のプレ共重合体を９０～１１０質量部、好ましくは１００質量部と；
３官能キシリレンジイソシアネート系架橋剤を１５～２５質量部、好ましくは２０質量部と；
シリコーン樹脂微粒子を５～１５質量部、好ましくは１０質量部と、を含有する。 Specifically, the adhesive layer is
A pre-copolymer having a weight average molecular weight of 800,000 obtained by copolymerizing 2-ethylhexyl acrylate (2EHA) (80 parts by mass) and 2-hydroxylethyl acrylate (HEA) (20 parts by mass) as an acrylic polymer. 90-110 parts by weight, preferably 100 parts by weight;
15 to 25 parts by mass, preferably 20 parts by mass of a trifunctional xylylene diisocyanate crosslinking agent;
5 to 15 parts by mass, preferably 10 parts by mass of silicone resin fine particles are contained.
　また、本発明の１つの側面において、保護膜形成用複合シートは、上記成分を含有する保護膜形成用フィルム、以下に示す成分を含有する粘着剤層、及び、上記構成の基材を有する。 Also, in one aspect of the present invention, the protective film-forming composite sheet has a protective film-forming film containing the above components, a pressure-sensitive adhesive layer containing the following components, and a substrate having the above-described configuration.
　粘着剤層は、具体的には、
アクリル系重合体として、２－エチルヘキシルアクリレート（２ＥＨＡ）（８０質量部）、及び、２－ヒドロキシルエチルアクリレート（ＨＥＡ）（２０質量部）を共重合してなる重量平均分子量８０００００のプレ共重合体を９０～１１０質量部、好ましくは１００質量部と；
３官能キシリレンジイソシアネート系架橋剤を１５～２５質量部、好ましくは２０質量部と；
エポキシ樹脂を３～３０質量部、好ましくは５～２５質量部と、を含有する。 Specifically, the adhesive layer is
A pre-copolymer having a weight average molecular weight of 800,000 obtained by copolymerizing 2-ethylhexyl acrylate (2EHA) (80 parts by mass) and 2-hydroxylethyl acrylate (HEA) (20 parts by mass) as an acrylic polymer. 90-110 parts by weight, preferably 100 parts by weight;
15 to 25 parts by mass, preferably 20 parts by mass of a trifunctional xylylene diisocyanate crosslinking agent;
It contains 3 to 30 parts by mass, preferably 5 to 25 parts by mass of an epoxy resin.
　また、本発明の１つの側面において、保護膜形成用複合シートは、上記成分を含有する保護膜形成用フィルム、以下に示す成分を含有する粘着剤層、及び、上記構成の基材を有する。 Also, in one aspect of the present invention, the protective film-forming composite sheet has a protective film-forming film containing the above components, a pressure-sensitive adhesive layer containing the following components, and a substrate having the above-described configuration.
　粘着剤層は、具体的には、
アクリル系重合体として、２－エチルヘキシルアクリレート（２ＥＨＡ）（８０質量部）、及び、２－ヒドロキシルエチルアクリレート（ＨＥＡ）（２０質量部）を共重合してなる重量平均分子量８０００００のプレ共重合体を９０～１１０質量部、好ましくは１００質量部と；
３官能キシリレンジイソシアネート系架橋剤を１５～２５質量部、好ましくは２０質量部と；
酸化チタン系白色顔料を３～７質量部、好ましくは５質量部と、を含有する。 Specifically, the adhesive layer is
A pre-copolymer having a weight average molecular weight of 800,000 obtained by copolymerizing 2-ethylhexyl acrylate (2EHA) (80 parts by mass) and 2-hydroxylethyl acrylate (HEA) (20 parts by mass) as an acrylic polymer. 90-110 parts by weight, preferably 100 parts by weight;
15 to 25 parts by mass, preferably 20 parts by mass of a trifunctional xylylene diisocyanate crosslinking agent;
It contains 3 to 7 parts by mass, preferably 5 parts by mass of a titanium oxide-based white pigment.
　また、本発明の１つの側面において、保護膜形成用複合シートは、上記成分を含有する保護膜形成用フィルム、以下に示す成分を含有する粘着剤層、及び、上記構成の基材を有する。 Also, in one aspect of the present invention, the protective film-forming composite sheet has a protective film-forming film containing the above components, a pressure-sensitive adhesive layer containing the following components, and a substrate having the above-described configuration.
　粘着剤層は、具体的には、
アクリル系重合体として、２－エチルヘキシルアクリレート（２ＥＨＡ）（８０質量部）、及び、２－ヒドロキシルエチルアクリレート（ＨＥＡ）（２０質量部）を共重合してなる重量平均分子量８０００００のプレ共重合体を９０～１１０質量部、好ましくは１００質量部と；
３官能キシリレンジイソシアネート系架橋剤を１５～２５質量部、好ましくは２０質量部と；
アクリル系ポリマー微粒子を５～１５質量部、好ましくは１０質量部と、を含有する。 Specifically, the adhesive layer is
A pre-copolymer having a weight average molecular weight of 800,000 obtained by copolymerizing 2-ethylhexyl acrylate (2EHA) (80 parts by mass) and 2-hydroxylethyl acrylate (HEA) (20 parts by mass) as an acrylic polymer. 90-110 parts by weight, preferably 100 parts by weight;
15 to 25 parts by mass, preferably 20 parts by mass of a trifunctional xylylene diisocyanate crosslinking agent;
5 to 15 parts by mass, preferably 10 parts by mass of acrylic polymer fine particles are contained.
◇保護膜形成用複合シートの製造方法
　前記保護膜形成用複合シートは、上述の各層を対応する位置関係となるように順次積層することで製造できる。各層の形成方法は、先に説明したとおりである。 ◇ Method for Producing Protective Film Forming Composite Sheet The protective film forming composite sheet can be produced 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.
　例えば、保護膜形成用複合シートを製造するときに、基材上に積層済みの粘着剤層の上に、さらに保護膜形成用フィルムを積層する場合には、粘着剤層上に、熱硬化性保護膜形成用組成物、エネルギー線硬化性保護膜形成用組成物、又は非硬化性保護膜形成用組成物を塗工して、保護膜形成用フィルムを直接形成することが可能である。このように、いずれかの組成物を用いて、連続する２層の積層構造を形成する場合には、前記組成物から形成された層の上に、さらに組成物を塗工して新たに層を形成することが可能である。ただし、これら２層のうちの後から積層する層は、別の剥離フィルム上に前記組成物を用いてあらかじめ形成しておき、この形成済みの層の前記剥離フィルムと接触している側とは反対側の露出面を、既に形成済みの残りの層の露出面と貼り合わせることで、連続する２層の積層構造を形成することが好ましい。このとき、前記組成物は、剥離フィルムの剥離処理面に塗工することが好ましい。剥離フィルムは、積層構造の形成後、必要に応じて取り除けばよい。 For example, when producing a protective sheet-forming composite sheet, if a protective film-forming film is further laminated on the adhesive layer already laminated on the substrate, the thermosetting property is applied on the adhesive layer. A protective film-forming film can be directly formed by applying a protective film-forming composition, an energy ray-curable protective film-forming composition, or a non-curable protective film-forming composition. As described above, when a continuous two-layer laminated structure is formed using any of the compositions, the composition is further applied onto the layer formed from the composition to newly form a layer. Can be formed. However, 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. At this time, 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.
　すなわち、保護膜形成用複合シートを製造する場合には、基材上に粘着剤組成物を塗工し、必要に応じて乾燥させることで、基材上に粘着剤層を積層しておき、別途、剥離フィルム上に熱硬化性保護膜形成用組成物、エネルギー線硬化性保護膜形成用組成物、又は非硬化性保護膜形成用組成物を塗工し、必要に応じて乾燥させることで、剥離フィルム上に保護膜形成用フィルムを形成しておき、この保護膜形成用フィルムの露出面を、基材上に積層済みの粘着剤層の露出面と貼り合わせて、保護膜形成用フィルムを粘着剤層上に積層することで、保護膜形成用複合シートが得られる。 That is, when producing a composite sheet for forming a protective film, a pressure-sensitive adhesive composition is coated on a base material, and dried as necessary, thereby laminating a pressure-sensitive adhesive layer on the base material, Separately, a thermosetting protective film-forming composition, an energy ray-curable protective film-forming composition, or a non-curable protective film-forming composition is coated on the release film and dried as necessary. The protective film-forming film is formed on the release film, and the exposed surface of the protective film-forming film is bonded to the exposed surface of the pressure-sensitive adhesive layer laminated on the base material. Is laminated on the adhesive layer to obtain a composite sheet for forming a protective film.
　一方、基材上に粘着剤層を積層する場合には、上述の様に、基材上に粘着剤組成物を塗工する方法に代えて、剥離フィルム上に粘着剤組成物を塗工し、必要に応じて乾燥させることで、剥離フィルム上に粘着剤層を形成しておき、この粘着剤層の露出面を、基材の一方の表面と貼り合わせることで、粘着剤層を基材上に積層してもよい。
　いずれの方法においても、剥離フィルムは目的とする積層構造を形成後の任意のタイミングで取り除けばよい。 On the other hand, when laminating the pressure-sensitive adhesive layer on the substrate, as described above, instead of the method of coating the pressure-sensitive adhesive composition on the substrate, the pressure-sensitive adhesive composition is applied on the release film. The pressure-sensitive adhesive layer is formed on the release film by drying as required, and the exposed surface of the pressure-sensitive adhesive layer is bonded to one surface of the base material so that the pressure-sensitive adhesive layer is bonded to the base material. It may be laminated on top.
In any method, the release film may be removed at an arbitrary timing after the target laminated structure is formed.
　このように、保護膜形成用複合シートを構成する基材以外の層（粘着剤層、保護膜形成用フィルム）はいずれも、剥離フィルム上にあらかじめ形成しておき、目的とする層の表面に貼り合わせる方法で積層できるため、必要に応じてこのような工程を採用する層を適宜選択して、保護膜形成用複合シートを製造すればよい。 Thus, all layers (adhesive layer, protective film-forming film) other than the base material constituting the protective film-forming composite sheet are formed in advance on the release film, and on the surface of the target layer. Since lamination can be performed by a method of bonding, a composite film for forming a protective film may be manufactured by appropriately selecting a layer that employs such a process as necessary.
　なお、保護膜形成用複合シートは、通常、その支持シートとは反対側の最表層（例えば、保護膜形成用フィルム）の表面に剥離フィルムが貼り合わされた状態で保管される。したがって、この剥離フィルム（好ましくはその剥離処理面）上に、熱硬化性保護膜形成用組成物、エネルギー線硬化性保護膜形成用組成物、又は非硬化性保護膜形成用組成物等の、最表層を構成する層を形成するための組成物を塗工し、必要に応じて乾燥させることで、剥離フィルム上に最表層を構成する層を形成しておき、この層の剥離フィルムと接触している側とは反対側の露出面上に残りの各層を上述のいずれかの方法で積層し、剥離フィルムを取り除かずに貼り合わせた状態のままとすることでも、保護膜形成用複合シートが得られる。 In addition, the composite sheet for forming a protective film is usually stored in a state in which a release film is bonded to the surface of the outermost layer (for example, a film for forming a protective film) opposite to the support sheet. Therefore, on this release film (preferably its release-treated surface), such as a thermosetting protective film-forming composition, an energy ray-curable protective film-forming composition, or a non-curable protective film-forming composition, The composition for forming the layer constituting the outermost layer is applied and dried as necessary, so that the layer constituting the outermost layer is formed on the release film, and this layer is in contact with the release film. A composite sheet for forming a protective film can be obtained by laminating the remaining layers on the exposed surface on the side opposite to the side to be coated by any one of the methods described above and leaving the laminated film bonded without removing the release film. Is obtained.
　なお、本明細書において、「剥離フィルム」は、剥がれる機能を有するフィルムであって、具体的には、半導体ウエハ又は支持シートへの貼付前の保護膜形成用フィルムを保護するために、保護膜形成用フィルムの両方の表面に貼り付けてあるフィルムをいい、作業時にはこれを剥がして用いられるものである。
　剥離フィルムとしては、例えば、ポリエチレンフィルム、ポリプロピレンフィルム、ポリブテンフィルム、ポリブタジエンフィルム、ポリメチルペンテンフィルム、ポリ塩化ビニルフィルム、塩化ビニル共重合体フィルム、ポリエチレンテレフタレートフィルム、ポリエチレンナフタレートフィルム、ポリブチレンテレフタレートフィルム、ポリウレタンフィルム、エチレン酢酸ビニル共重合体フィルム、アイオノマー樹脂フィルム、エチレン・（メタ）アクリル酸共重合体フィルム、エチレン・（メタ）アクリル酸エステル共重合体フィルム、ポリスチレンフィルム、ポリカーボネートフィルム、ポリイミドフィルム、フッ素樹脂フィルム等の透明フィルムが用いられる。またこれらの架橋フィルムも用いられる。さらにこれらの積層フィルムであってもよい。また、これらを着色したフィルム、不透明フィルムなどを用いることができる。剥離剤としては、例えば、シリコーン系、フッ素系、長鎖アルキル基含有カルバメート等の剥離剤が挙げられる。
　剥離フィルムの厚さは、通常は１０μｍ以上５００μｍ以下、好ましくは１５μｍ以上３００μｍ以下、特に好ましくは２０μｍ以上２５０μｍ以下程度である。
ここで、「剥離フィルムの厚さ」とは、剥離フィルム全体の厚さを意味し、例えば、複数層からなる剥離フィルムの厚さとは、剥離フィルムを構成するすべての層の合計の厚さを意味する。なお、剥離フィルムの厚さの測定方法としては、例えば、任意の５箇所において、接触式厚み計を用いて厚さを測定し、測定値の平均を算出する方法等が挙げられる。 In the present specification, the “peeling film” is a film having a function of peeling, and specifically, a protective film for protecting the protective film-forming film before being attached to a semiconductor wafer or a support sheet. It refers to a film that is affixed to both surfaces of a forming film, and is used by peeling it off during work.
As the release film, for example, polyethylene film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film, vinyl chloride copolymer film, polyethylene terephthalate film, polyethylene naphthalate film, polybutylene terephthalate film, Polyurethane film, ethylene vinyl acetate copolymer film, ionomer resin film, ethylene / (meth) acrylic acid copolymer film, ethylene / (meth) acrylic acid ester copolymer film, polystyrene film, polycarbonate film, polyimide film, fluorine A transparent film such as a resin film is used. These crosslinked films are also used. Furthermore, these laminated films may be sufficient. Moreover, the film which colored these, an opaque film, etc. can be used. Examples of the release agent include release agents such as silicone-based, fluorine-based, and long-chain alkyl group-containing carbamates.
The thickness of the release film is usually from 10 μm to 500 μm, preferably from 15 μm to 300 μm, and particularly preferably from 20 μm to 250 μm.
Here, the “thickness of the release film” means the thickness of the entire release film. For example, the thickness of the release film composed of a plurality of layers means the total thickness of all the layers constituting the release film. means. In addition, as a measuring method of the thickness of a peeling film, the method etc. which measure thickness using a contact-type thickness meter in arbitrary five places, and calculate the average of a measured value, etc. are mentioned, for example.
◇保護膜形成用複合シートの使用方法
　本実施形態の保護膜形成用複合シートは、例えば、以下に示す方法で使用できる。
　すなわち、半導体ウエハの裏面（電極形成面とは反対側の面）に、保護膜形成用複合シートをその保護膜形成用フィルムによって貼付する。次いで、保護膜形成用フィルムに必要に応じて加熱又はエネルギー線を照射して、保護膜形成用フィルムを硬化させて、保護膜とする。或いは、保護膜形成用フィルムに含まれる非硬化性保護膜形成用組成物である場合には、未硬化のまま保護膜として用いてもよい。次いで、ダイシングによって、半導体ウエハを保護膜ごと分割して半導体チップとする。そして、半導体チップを、この保護膜が貼付された状態のまま（すなわち、保護膜付き半導体チップとして）、支持シートから引き離してピックアップする。
　以降は従来法と同様の方法で、得られた保護膜付き半導体チップの半導体チップを基板の回路面にフリップチップ接続した後、半導体パッケージとする。そして、この半導体パッケージを用いて、目的とする半導体装置を作製すればよい。
　なお、保護膜形成用フィルムを加熱又はエネルギー線を照射して硬化させる場合、そのタイミングは、上述のとおり、ダイシングの前であってもよく、ダイシングの後であってもよい。中でも、保護膜形成用フィルムを加熱又はエネルギー線を照射して硬化させるタイミングは、ダイシングの前であることが好ましい。
　また、保護膜形成用フィルムを加熱又はエネルギー線を照射して硬化させる場合、レーザー印字のタイミングは、硬化前であってもよく、硬化後であってもよい。中でも、保護膜形成用フィルムを加熱して硬化させる場合、レーザー印字のタイミングは、硬化後であることが好ましい。 ◇ Method for Using Protective Film Forming Composite Sheet The protective film forming composite sheet of the present embodiment 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 heated or irradiated with energy rays as necessary to cure the protective film-forming film to form a protective film. Or when it is the composition for non-curable protective film formation contained in the film for protective film formation, you may use it as a protective film with uncured. 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).
Thereafter, the semiconductor chip of the obtained semiconductor chip with a protective film is flip-chip connected to the circuit surface of the substrate in the same manner as the conventional method, and then the semiconductor package is obtained. Then, a target semiconductor device may be manufactured using this semiconductor package.
In addition, when hardening the film for protective film formation by heating or irradiating an energy ray, the timing may be before dicing as mentioned above, and may be after dicing. Especially, it is preferable that the timing which cures the film for protective film formation by heating or irradiating an energy ray is before dicing.
When the protective film-forming film is cured by heating or irradiation with energy rays, the timing of laser printing may be before curing or after curing. In particular, when the protective film-forming film is heated and cured, the timing of laser printing is preferably after curing.
　以下、具体的実施例により、本発明についてより詳細に説明する。ただし、本発明は、以下に示す実施例に、何ら限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to specific examples. However, the present invention is not limited to the following examples.
　保護膜形成用組成物の製造に用いた成分を以下に示す。
・重合体成分
　（Ａ）－１：メチルアクリレート８５質量部、及び２－ヒドロキシエチルアクリレート１５質量部を共重合してなるアクリル系重合体（重量平均分子量：３７万、ガラス転移温度：６℃）
・熱硬化性成分
　（Ｂ１）－１：ビスフェノールＡ型エポキシ樹脂（三菱化学製ｊＥＲ８２８、エポキシ当量１８４～１９４ｇ／ｅｑ）
　（Ｂ１）－２：ビスフェノールＡ型エポキシ樹脂（三菱化学製ｊＥＲ１０５５、エポキシ当量８００～９００ｇ／ｅｑ）
　（Ｂ１）－３：ジシクロペンタジエン型エポキシ樹脂（大日本インキ化学工業（株）製エピクロンＨＰ－７２００ＨＨ、エポキシ当量２５５～２６０ｇ／ｅｑ）
　（Ｂ２）－１：熱活性潜在性エポキシ樹脂硬化剤（ジシアンジアミド（ＡＤＥＫＡ製アデカハードナーＥＨ－３６３６ＡＳ、活性水素量２１ｇ／ｅｑ））
・硬化促進剤
　（Ｃ）－１：２－フェニル－４，５－ジヒドロキシメチルイミダゾール（四国化成工業社製キュアゾール２ＰＨＺ）
・充填剤
　（Ｄ）－１：シリカフィラー（アドマテックス製ＳＣ２０５０ＭＡ、平均粒子径０．５μｍ）
・カップリング剤
　（Ｅ）－１：シランカップリング剤（日本ユニカー製Ａ－１１１０）
・着色剤
　（Ｉ）－１：黒色顔料（大日精化社製） The components used for the production of the protective film-forming composition are shown below.
Polymer component (A) -1: Acrylic polymer obtained by copolymerizing 85 parts by mass of methyl acrylate and 15 parts by mass of 2-hydroxyethyl acrylate (weight average molecular weight: 370,000, glass transition temperature: 6 ° C.)
Thermosetting component (B1) -1: bisphenol A type epoxy resin (Mitsubishi Chemical jER828, epoxy equivalent 184 to 194 g / eq)
(B1) -2: Bisphenol A type epoxy resin (Mitsubishi Chemical Corporation jER1055, epoxy equivalent 800-900 g / eq)
(B1) -3: Dicyclopentadiene type epoxy resin (Dainippon Ink & Chemicals, Inc. Epiklon HP-7200HH, epoxy equivalent 255-260 g / eq)
(B2) -1: Thermally active latent epoxy resin curing agent (dicyandiamide (ADEKA HARDNER EH-3636AS manufactured by ADEKA, active hydrogen amount 21 g / eq))
Curing accelerator (C) -1: 2-phenyl-4,5-dihydroxymethylimidazole (Curesol 2PHZ manufactured by Shikoku Kasei Kogyo Co., Ltd.)
Filler (D) -1: Silica filler (SC2050MA manufactured by Admatechs, average particle size 0.5 μm)
Coupling agent (E) -1: Silane coupling agent (A-1110 manufactured by Nihon Unicar)
Colorant (I) -1: Black pigment (manufactured by Dainichi Seika)
［実施例１］
＜保護膜形成用複合シートの製造＞
（保護膜形成用組成物（ＩＩＩ－１）の製造）
　固形重量比で、重合体成分（Ａ）－１（１５０質量部）、熱硬化性成分（Ｂ１）－１（６０質量部）、（Ｂ１）－２（１０質量部）、（Ｂ１）－３（３０質量部）、（Ｂ２）－１（２質量部）、硬化促進剤　（Ｃ）－１（２質量部）、充填剤（Ｄ）－１（３２０質量部）、カップリング剤（Ｅ）－１（２質量部）、及び着色剤（Ｉ）－１（１８質量部）をメチルエチルケトン、トルエン及び酢酸エチルの混合溶媒に溶解又は分散させて、２３℃で撹拌することで、熱硬化性の保護膜形成用組成物（ＩＩＩ－１）を得た。 [Example 1]
<Manufacture of composite sheet for forming protective film>
(Production of protective film-forming composition (III-1))
In terms of solid weight ratio, polymer component (A) -1 (150 parts by mass), thermosetting component (B1) -1 (60 parts by mass), (B1) -2 (10 parts by mass), (B1) -3 (30 parts by mass), (B2) -1 (2 parts by mass), curing accelerator (C) -1 (2 parts by mass), filler (D) -1 (320 parts by mass), coupling agent (E) -1 (2 parts by mass) and colorant (I) -1 (18 parts by mass) are dissolved or dispersed in a mixed solvent of methyl ethyl ketone, toluene and ethyl acetate, and stirred at 23 ° C. A protective film-forming composition (III-1) was obtained.
（粘着剤組成物（Ｉ－４）－１の製造）
　アクリル系重合体（１００質量部、固形分）、及び３官能キシリレンジイソシアネート系架橋剤（三井武田ケミカル社製「タケネートＤ１１０Ｎ」）（４０質量部（固形分））を含有し、さらに溶媒としてメチルエチルケトン、トルエン及び酢酸エチルの混合溶媒を含有する、固形分濃度が３０質量％の非エネルギー線硬化性の粘着剤組成物（Ｉ－４）－１を調製した。前記アクリル系重合体は、２－エチルヘキシルアクリレート（２ＥＨＡ）（８０質量部）、及び２－ヒドロキシルエチルアクリレート（ＨＥＡ）（２０質量部）を共重合してなる重量平均分子量８０００００のプレ共重合体である。 (Production of pressure-sensitive adhesive composition (I-4) -1)
Contains an acrylic polymer (100 parts by mass, solid content) and a trifunctional xylylene diisocyanate-based crosslinking agent (“Takenate D110N” manufactured by Mitsui Takeda Chemical Co., Ltd.) (40 parts by mass (solid content)), and methyl ethyl ketone as a solvent A non-energy ray-curable pressure-sensitive adhesive composition (I-4) -1 containing a mixed solvent of toluene and ethyl acetate and having a solid content concentration of 30% by mass was prepared. The acrylic polymer is a pre-copolymer having a weight average molecular weight of 800,000 obtained by copolymerizing 2-ethylhexyl acrylate (2EHA) (80 parts by mass) and 2-hydroxylethyl acrylate (HEA) (20 parts by mass). is there.
（支持シートの製造）
　ポリエチレンテレフタレート製フィルムの片面がシリコーン処理により剥離処理されてなる剥離フィルムの、前記剥離処理面に、上記で得られた粘着剤組成物（Ｉ－４）－１を塗工し、１２０℃で２分加熱乾燥させることにより、厚さ１５μｍの非エネルギー線硬化性の粘着剤層を形成した。
　次いで、この粘着剤層の露出面に、厚さ８０μｍのポリプロピレン製フィルム（三菱樹脂社製、マット面（表面粗さ（Ｒａ）：１．２０μｍ）／ツヤ面（表面粗さ（Ｒａ）：０．１０μｍ）基材）のマット面を貼り合わせることで、支持シート（１０）－１を製造した。 (Manufacture of support sheet)
The pressure-sensitive adhesive composition (I-4) -1 obtained above was applied to the release-treated surface of a release film obtained by releasing one side of a polyethylene terephthalate film by silicone treatment, and the film was heated at 120 ° C. for 2 A non-energy ray-curable pressure-sensitive adhesive layer having a thickness of 15 μm was formed by heat drying for a few minutes.
Next, an 80 μm-thick polypropylene film (Mitsubishi Resin, mat surface (surface roughness (Ra): 1.20 μm) / shiny surface (surface roughness (Ra): 0) is formed on the exposed surface of the pressure-sensitive adhesive layer. .10 μm) Substrate) was bonded together to produce a support sheet (10) -1.
（保護膜形成用複合シートの製造）
　ポリエチレンテレフタレート製フィルムの片面がシリコーン処理により剥離処理された剥離フィルム（リンテック社製「ＳＰ－ＰＥＴ３８１０３１」、厚さ３８μｍ）の前記剥離処理面に、上記で得られた保護膜形成用組成物（ＩＩＩ－１）をナイフコーターにより塗工し、１００℃で２分乾燥させることにより、厚さ２５μｍの熱硬化性の保護膜形成用フィルム（１３）－１を作製した。 (Manufacture of composite sheet for protective film formation)
A protective film-forming composition (III) obtained above was applied to the release-treated surface of a release film (“SP-PET 381031” manufactured by Lintec Co., Ltd., thickness 38 μm) obtained by releasing one side of a polyethylene terephthalate film by silicone treatment. -1) was coated with a knife coater and dried at 100 ° C. for 2 minutes to produce a thermosetting protective film-forming film (13) -1 having a thickness of 25 μm.
　次いで、上記で得られた支持シート（１０）－１の粘着剤層に、上記で得られた保護膜形成用フィルム（１３）－１の露出面を貼り合わせて、基材、粘着剤層、及び保護膜形成用フィルム（１３）－１が、これらの厚さ方向においてこの順に積層されてなる保護膜形成用複合シートを作製した。なお、作製した保護膜形成用複合シートにおいて、支持シートの幅は２７０ｍｍであり、保護膜形成用フィルムの外径は２１０ｍｍであった。 Next, the exposed surface of the protective film-forming film (13) -1 obtained above is bonded to the pressure-sensitive adhesive layer of the support sheet (10) -1 obtained above to obtain a substrate, a pressure-sensitive adhesive layer, And a protective film-forming composite sheet (13) -1 was laminated in the thickness direction in this order. In the produced protective film-forming composite sheet, the width of the support sheet was 270 mm, and the outer diameter of the protective film-forming film was 210 mm.
＜支持シートの評価＞
（ヘーズ評価）
　日本電色工業製「ＮＤＨ‐５０００」を使用し、ＪＩＳ　Ｋ　７１３６－２０００に準拠して測定した。なお、支持シート（１０）－１から剥離フィルムを剥がした「基材＋粘着剤層」という構成で測定した。結果を表１に示す。 <Evaluation of support sheet>
(Haze evaluation)
Measurement was performed according to JIS K 7136-2000 using “NDH-5000” manufactured by Nippon Denshoku Industries Co., Ltd. The measurement was made with a configuration of “base material + adhesive layer” in which the release film was peeled off from the support sheet (10) -1. The results are shown in Table 1.
（透過鮮明度の評価）
　スガ試験機(株)製写像性測定器「ＩＣＭ－１０Ｐ」を使用し、ＪＩＳ　Ｋ　７３７４－２００７に準拠して測定した。５種類のスリット（スリット幅：０．１２５ｍｍ、０．２５ｍｍ、０．５ｍｍ、１ｍｍ、及び２ｍｍ）の合計値を透過鮮明度と表した。なお、支持シート（１０）－１から剥離フィルムを剥がした「基材＋粘着剤層」という構成で測定した。結果を表１に示す。 (Evaluation of transmission clarity)
The measurement was performed in accordance with JIS K 7374-2007 using an image clarity measuring device “ICM-10P” manufactured by Suga Test Instruments Co., Ltd. The total value of five types of slits (slit widths: 0.125 mm, 0.25 mm, 0.5 mm, 1 mm, and 2 mm) was expressed as transmission sharpness. The measurement was made with a configuration of “base material + adhesive layer” in which the release film was peeled off from the support sheet (10) -1. The results are shown in Table 1.
＜保護膜形成用複合シートの評価＞
（マウンタ適性（アライメント（テープ先端位置調整）の評価）
　作製した保護膜形成用複合シート及びリングフレームについて、８インチの半導体ウエハ（厚み：２００μｍ）に対し、リンテック製テープマウンタＲＡＤ２７００を用いて、テープ先端位置調整が可能かを確認した。結果を表１に示す。
　なお、マウンタ適性の評価基準は以下のように設定した。
　Ａ・・・アライメント可能
Ｂ・・・アライメント不可能 <Evaluation of composite sheet for forming protective film>
(Mounter suitability (evaluation of alignment (adjustment of tape tip position))
With respect to the produced protective film-forming composite sheet and ring frame, it was confirmed that the tape tip position could be adjusted using a Lintec tape mounter RAD2700 on an 8-inch semiconductor wafer (thickness: 200 μm). The results are shown in Table 1.
The evaluation criteria for mounter suitability were set as follows.
A ... Alignable B ... Unalignable
（レーザー印字視認性の評価）
　８インチの半導体ウエハに貼付された保護膜形成用フィルムについて、ＥＯテクニクス製レーザー印字装置ＣＳＭ３００Ｍを用いて、支持シート越しに保護膜層に印字を行い、目視で観察した際に、文字が視認できるか否かを判定した。印字は未硬化の保護膜層に対して行った。文字サイズは０．３ｍｍ×０．２ｍｍとした。結果を表１に示す。
　なお、レーザー印字視認性の評価基準は以下のように設定した。
Ａ・・・視認可能
Ｂ・・・若干ぼけているが視認可能
Ｃ・・・視認不可能 (Evaluation of laser printing visibility)
The protective film-forming film affixed to an 8-inch semiconductor wafer is printed on the protective film layer over the support sheet using the laser printing apparatus CSM300M manufactured by EO Technics, and characters can be visually recognized when visually observed. It was determined whether or not. Printing was performed on the uncured protective film layer. The character size was 0.3 mm × 0.2 mm. The results are shown in Table 1.
The evaluation criteria for laser printing visibility were set as follows.
A ... Visible B ... Slightly blurred but visible C ... Not visible
（印字文字太さの評価）
　８インチの半導体ウエハに貼付された保護膜形成用フィルムについて、紫外線照射装置（リンテック社製、ＲＡＤ２０００ｍ／８、照射条件：照度１９５ｍＷ／ｃｍ２、光量１７０ｍＪ／ｃｍ２）を用いて、支持シート側から紫外線を照射した。次いで、保護膜から支持シートを剥がした後、保護膜上の印字をキーエンス製光学顕微鏡で観察して、文字の太さを測定した。結果を表１に示す。 (Evaluation of print character thickness)
For the protective film-forming film affixed to an 8-inch semiconductor wafer, using a UV irradiation device (Rintec Corporation, RAD 2000 m / 8, irradiation conditions: illuminance 195 mW / cm 2 , light quantity 170 mJ / cm 2 ) Were irradiated with ultraviolet rays. Subsequently, after peeling off the support sheet from the protective film, the print on the protective film was observed with an optical microscope manufactured by Keyence, and the thickness of the characters was measured. The results are shown in Table 1.
［実施例２］
＜保護膜形成用複合シートの製造＞
（保護膜形成用組成物（ＩＩＩ－１）の製造）
　実施例１と同様の方法を用いて、熱硬化性の保護膜形成用組成物（ＩＩＩ－１）を得た。 [Example 2]
<Manufacture of composite sheet for forming protective film>
(Production of protective film-forming composition (III-1))
Using the same method as in Example 1, a thermosetting protective film-forming composition (III-1) was obtained.
（粘着剤組成物（Ｉ－４）－２の製造）
　アクリル系重合体（１００質量部、固形分）、及び３官能キシリレンジイソシアネート系架橋剤（三井武田ケミカル社製「タケネートＤ１１０Ｎ」）（５０質量部（固形分））を含有し、さらに溶媒としてメチルエチルケトンを含有する、固形分濃度が３０質量％の非エネルギー線硬化性の粘着剤組成物（Ｉ－４）－２を調製した。前記アクリル系重合体は、２ＥＨＡ（８０質量部）、及びＨＥＡ（２０質量部）を共重合してなる重量平均分子量８０００００のプレ共重合体である。 (Production of pressure-sensitive adhesive composition (I-4) -2)
Contains an acrylic polymer (100 parts by mass, solid content) and a trifunctional xylylene diisocyanate-based crosslinking agent (“Takenate D110N” manufactured by Takeda Chemicals, Ltd.) (50 parts by mass (solid content)), and methyl ethyl ketone as a solvent And a non-energy ray-curable pressure-sensitive adhesive composition (I-4) -2 having a solid content concentration of 30% by mass was prepared. The acrylic polymer is a pre-copolymer having a weight average molecular weight of 800,000 obtained by copolymerizing 2EHA (80 parts by mass) and HEA (20 parts by mass).
（支持シートの製造）
　粘着剤組成物（Ｉ－４）－１の代わりに粘着剤組成物（Ｉ－４）－２を使用した以外は、実施例１と同様の方法を用いて、支持シート（１０）－２を得た。 (Manufacture of support sheet)
Using the same method as in Example 1, except that the pressure-sensitive adhesive composition (I-4) -2 was used instead of the pressure-sensitive adhesive composition (I-4) -1, the support sheet (10) -2 was Obtained.
（保護膜形成用複合シートの製造）
　支持シート（１０）－１の代わりに（１０）－２を使用した以外は、実施例１と同様の方法を用いて、保護膜形成用複合シートを作製した。 (Manufacture of composite sheet for protective film formation)
A composite sheet for forming a protective film was produced in the same manner as in Example 1 except that (10) -2 was used instead of the support sheet (10) -1.
＜支持シートの評価＞
　実施例１と同様の方法を用いて、ヘーズ及び透過鮮明度を評価した。結果を表１に示す。 <Evaluation of support sheet>
Using the same method as in Example 1, haze and transmission sharpness were evaluated. The results are shown in Table 1.
＜保護膜形成用複合シートの評価＞
　実施例１と同様の方法を用いて、マウンタ適性、レーザー印字視認性及び印字文字太さを評価した。結果を表１に示す。 <Evaluation of composite sheet for forming protective film>
Using the same method as in Example 1, mounter suitability, laser printing visibility, and printed character thickness were evaluated. The results are shown in Table 1.
［実施例３］
＜保護膜形成用複合シートの製造＞
（保護膜形成用組成物（ＩＩＩ－１）の製造）
　実施例１と同様の方法を用いて、熱硬化性の保護膜形成用組成物（ＩＩＩ－１）を得た。 [Example 3]
<Manufacture of composite sheet for forming protective film>
(Production of protective film-forming composition (III-1))
Using the same method as in Example 1, a thermosetting protective film-forming composition (III-1) was obtained.
（粘着剤組成物（Ｉ－４）－１の製造）
　実施例１と同様の方法を用いて、粘着剤組成物（Ｉ－４）－１を得た。 (Production of pressure-sensitive adhesive composition (I-4) -1)
Using the same method as in Example 1, pressure-sensitive adhesive composition (I-4) -1 was obtained.
（支持シートの製造）
　粘着剤層の露出面に、厚さ８０μｍのポリプロピレン製フィルム（三菱樹脂社製、マット面（表面粗さ（Ｒａ）：１．２０μｍ）／ツヤ面（表面粗さ（Ｒａ）：０．１０μｍ）基材）のマット面の代わりに、厚さ８０μｍのポリプロピレン製フィルム（グンゼ社製、マット面（表面粗さ（Ｒａ）：０．２０μｍ）／微マット面（表面粗さ（Ｒａ）：０．１５μｍ）基材）のマット面を貼り合わせた以外は、実施例１と同様の方法を用いて、支持シート（１０）－３を製造した。 (Manufacture of support sheet)
On the exposed surface of the pressure-sensitive adhesive layer, a polypropylene film having a thickness of 80 μm (Mitsubishi Resin, mat surface (surface roughness (Ra): 1.20 μm) / shiny surface (surface roughness (Ra): 0.10 μm)) Instead of the mat surface of the base material, a polypropylene film having a thickness of 80 μm (manufactured by Gunze Co., Ltd., mat surface (surface roughness (Ra): 0.20 μm) / fine mat surface (surface roughness (Ra): 0. 0). 15 μm) A support sheet (10) -3 was produced in the same manner as in Example 1 except that the mat surface of the base material) was bonded.
（保護膜形成用複合シートの製造）
　支持シート（１０）－１の代わりに（１０）－３を使用した以外は、実施例１と同様の方法を用いて、保護膜形成用複合シートを作製した。 (Manufacture of composite sheet for protective film formation)
A composite sheet for forming a protective film was produced in the same manner as in Example 1 except that (10) -3 was used instead of the support sheet (10) -1.
＜支持シートの評価＞
　実施例１と同様の方法を用いて、ヘーズ及び透過鮮明度を評価した。結果を表１に示す。 <Evaluation of support sheet>
Using the same method as in Example 1, haze and transmission sharpness were evaluated. The results are shown in Table 1.
＜保護膜形成用複合シートの評価＞
　実施例１と同様の方法を用いて、マウンタ適性、レーザー印字視認性及び印字文字太さを評価した。結果を表１に示す。 <Evaluation of composite sheet for forming protective film>
Using the same method as in Example 1, mounter suitability, laser printing visibility, and printed character thickness were evaluated. The results are shown in Table 1.
［実施例４］
（保護膜形成用組成物（ＩＩＩ－１）の製造）
　実施例１と同様の方法を用いて、熱硬化性の保護膜形成用組成物（ＩＩＩ－１）を得た。 [Example 4]
(Production of protective film-forming composition (III-1))
Using the same method as in Example 1, a thermosetting protective film-forming composition (III-1) was obtained.
（粘着剤組成物（Ｉ－４）－３の製造）
　アクリル系重合体（１００質量部、固形分）、３官能キシリレンジイソシアネート系架橋剤（三井武田ケミカル社製「タケネートＤ１１０Ｎ」）（２０質量部（固形分））、及びシリコーン樹脂微粒子（タナック社製「トスパール１４５」）（１０質量部（固形分））を含有し、さらに溶媒としてメチルエチルケトンを含有する、固形分濃度が３０質量％の非エネルギー線硬化性の粘着剤組成物（Ｉ－４）－３を調製した。前記アクリル系重合体は、２ＥＨＡ（８０質量部）、及びＨＥＡ（２０質量部）を共重合してなる重量平均分子量８０００００のプレ共重合体である。 (Production of pressure-sensitive adhesive composition (I-4) -3)
Acrylic polymer (100 parts by mass, solid content), trifunctional xylylene diisocyanate-based crosslinking agent (“Takenate D110N” manufactured by Takeda Chemicals, Ltd.) (20 parts by mass (solid content)), and silicone resin fine particles (manufactured by Tanac Co., Ltd.) “Tospearl 145”) (10 parts by mass (solid content)) and further containing methyl ethyl ketone as a solvent, a solid content concentration of 30% by mass, a non-energy ray-curable pressure-sensitive adhesive composition (I-4) — 3 was prepared. The acrylic polymer is a pre-copolymer having a weight average molecular weight of 800,000 obtained by copolymerizing 2EHA (80 parts by mass) and HEA (20 parts by mass).
（支持シートの製造）
　粘着剤組成物（Ｉ－４）－１の代わりに粘着剤組成物（Ｉ－４）－３を使用した以外は、実施例１と同様の方法を用いて、支持シート（１０）－４を得た。 (Manufacture of support sheet)
Using the same method as in Example 1, except that the pressure-sensitive adhesive composition (I-4) -3 was used instead of the pressure-sensitive adhesive composition (I-4) -1, the support sheet (10) -4 was prepared. Obtained.
（保護膜形成用複合シートの製造）
　支持シート（１０）－１の代わりに（１０）－４を使用した以外は、実施例１と同様の方法を用いて、保護膜形成用複合シートを作製した。 (Manufacture of composite sheet for protective film formation)
A composite sheet for forming a protective film was produced in the same manner as in Example 1 except that (10) -4 was used instead of the support sheet (10) -1.
＜支持シートの評価＞
　実施例１と同様の方法を用いて、ヘーズ及び透過鮮明度を評価した。結果を表１に示す。 <Evaluation of support sheet>
Using the same method as in Example 1, haze and transmission sharpness were evaluated. The results are shown in Table 1.
＜保護膜形成用複合シートの評価＞
　実施例１と同様の方法を用いて、マウンタ適性、レーザー印字視認性及び印字文字太さを評価した。結果を表１に示す。 <Evaluation of composite sheet for forming protective film>
Using the same method as in Example 1, mounter suitability, laser printing visibility, and printed character thickness were evaluated. The results are shown in Table 1.
［実施例５］
（保護膜形成用組成物（ＩＩＩ－１）の製造）
　実施例１と同様の方法を用いて、熱硬化性の保護膜形成用組成物（ＩＩＩ－１）を得た。 [Example 5]
(Production of protective film-forming composition (III-1))
Using the same method as in Example 1, a thermosetting protective film-forming composition (III-1) was obtained.
（粘着剤組成物（Ｉ－１）－１の製造）
　アクリル系重合体（１００質量部、固形分）、３官能キシリレンジイソシアネート系架橋剤（三井武田ケミカル社製「タケネートＤ１１０Ｎ」）（２０質量部（固形分））、及びエポキシ樹脂（三菱化学社製「ＪＥＲ８３４」）（２５質量部（固形分））を含有し、さらに溶媒としてメチルエチルケトンを含有する、固形分濃度が３０質量％のエネルギー線硬化性の粘着剤組成物（Ｉ－１）－１を調製した。前記アクリル系重合体は、２ＥＨＡ（８０質量部）、及びＨＥＡ（２０質量部）を共重合してなる重量平均分子量８０００００のプレ共重合体である。 (Production of pressure-sensitive adhesive composition (I-1) -1)
Acrylic polymer (100 parts by mass, solid content), trifunctional xylylene diisocyanate-based crosslinking agent (“Takenate D110N” manufactured by Takeda Chemicals, Ltd.) (20 parts by mass (solid content)), and epoxy resin (manufactured by Mitsubishi Chemical Corporation) “JER834”) (25 parts by mass (solid content)) and further containing methyl ethyl ketone as a solvent, and an energy ray-curable pressure-sensitive adhesive composition (I-1) -1 having a solid content concentration of 30% by mass Prepared. The acrylic polymer is a pre-copolymer having a weight average molecular weight of 800,000 obtained by copolymerizing 2EHA (80 parts by mass) and HEA (20 parts by mass).
（支持シートの製造）
　粘着剤組成物（Ｉ－４）－１の代わりに粘着剤組成物（Ｉ－１）－１を使用した以外は、実施例１と同様の方法を用いて、支持シート（１０）－５を得た。 (Manufacture of support sheet)
Using the same method as in Example 1, except that the adhesive composition (I-1) -1 was used instead of the adhesive composition (I-4) -1, the support sheet (10) -5 was Obtained.
（保護膜形成用複合シートの製造）
　支持シート（１０）－１の代わりに（１０）－５を使用した以外は、実施例１と同様の方法を用いて、保護膜形成用複合シートを作製した。 (Manufacture of composite sheet for protective film formation)
A composite sheet for forming a protective film was produced in the same manner as in Example 1 except that (10) -5 was used instead of the support sheet (10) -1.
＜支持シートの評価＞
　実施例１と同様の方法を用いて、ヘーズ及び透過鮮明度を評価した。結果を表１に示す。 <Evaluation of support sheet>
Using the same method as in Example 1, haze and transmission sharpness were evaluated. The results are shown in Table 1.
＜保護膜形成用複合シートの評価＞
　実施例１と同様の方法を用いて、マウンタ適性、レーザー印字視認性及び印字文字太さを評価した。結果を表１に示す。 <Evaluation of composite sheet for forming protective film>
Using the same method as in Example 1, mounter suitability, laser printing visibility, and printed character thickness were evaluated. The results are shown in Table 1.
［実施例６］
（保護膜形成用組成物（ＩＩＩ－１）の製造）
　実施例１と同様の方法を用いて、熱硬化性の保護膜形成用組成物（ＩＩＩ－１）を得た。 [Example 6]
(Production of protective film-forming composition (III-1))
Using the same method as in Example 1, a thermosetting protective film-forming composition (III-1) was obtained.
（粘着剤組成物（Ｉ－１）－２の製造）
　アクリル系重合体（１００質量部、固形分）、３官能キシリレンジイソシアネート系架橋剤（三井武田ケミカル社製「タケネートＤ１１０Ｎ」）（２０質量部（固形分））、及びエポキシ樹脂（三菱化学社製「ＪＥＲ１０５５」）（５質量部（固形分））を含有し、さらに溶媒としてメチルエチルケトンを含有する、固形分濃度が３０質量％のエネルギー線硬化性の粘着剤組成物（Ｉ－１）－２を調製した。前記アクリル系重合体は、２ＥＨＡ（８０質量部）、及びＨＥＡ（２０質量部）を共重合してなる重量平均分子量８０００００のプレ共重合体である。 (Production of pressure-sensitive adhesive composition (I-1) -2)
Acrylic polymer (100 parts by mass, solid content), trifunctional xylylene diisocyanate-based crosslinking agent (“Takenate D110N” manufactured by Takeda Chemicals, Ltd.) (20 parts by mass (solid content)), and epoxy resin (manufactured by Mitsubishi Chemical Corporation) “JER1055”) (5 parts by mass (solid content)) and further containing methyl ethyl ketone as a solvent, and an energy ray-curable pressure-sensitive adhesive composition (I-1) -2 having a solid content concentration of 30% by mass Prepared. The acrylic polymer is a pre-copolymer having a weight average molecular weight of 800,000 obtained by copolymerizing 2EHA (80 parts by mass) and HEA (20 parts by mass).
（支持シートの製造）
　粘着剤組成物（Ｉ－４）－１の代わりに粘着剤組成物（Ｉ－１）－２を使用した以外は、実施例１と同様の方法を用いて、支持シート（１０）－６を得た。 (Manufacture of support sheet)
Using the same method as in Example 1, except that the adhesive composition (I-1) -2 was used instead of the adhesive composition (I-4) -1, the support sheet (10) -6 was Obtained.
（保護膜形成用複合シートの製造）
　支持シート（１０）－１の代わりに（１０）－６を使用した以外は、実施例１と同様の方法を用いて、保護膜形成用複合シートを作製した。 (Manufacture of composite sheet for protective film formation)
A composite sheet for forming a protective film was produced in the same manner as in Example 1 except that (10) -6 was used instead of the support sheet (10) -1.
＜支持シートの評価＞
　実施例１と同様の方法を用いて、ヘーズ及び透過鮮明度を評価した。結果を表１に示す。 <Evaluation of support sheet>
Using the same method as in Example 1, haze and transmission sharpness were evaluated. The results are shown in Table 1.
＜保護膜形成用複合シートの評価＞
　実施例１と同様の方法を用いて、マウンタ適性、レーザー印字視認性及び印字文字太さを評価した。結果を表１に示す。 <Evaluation of composite sheet for forming protective film>
Using the same method as in Example 1, mounter suitability, laser printing visibility, and printed character thickness were evaluated. The results are shown in Table 1.
［実施例７］
（保護膜形成用組成物（ＩＩＩ－１）の製造）
　実施例１と同様の方法を用いて、熱硬化性の保護膜形成用組成物（ＩＩＩ－１）を得た。 [Example 7]
(Production of protective film-forming composition (III-1))
Using the same method as in Example 1, a thermosetting protective film-forming composition (III-1) was obtained.
（粘着剤組成物（Ｉ－４）－４の製造）
　アクリル系重合体（１００質量部、固形分）、３官能キシリレンジイソシアネート系架橋剤（三井武田ケミカル社製「タケネートＤ１１０Ｎ」）（２０質量部（固形分））、及び酸化チタン系白色顔料（大日精化社製「Ｎ－ＤＹＭ８０５４」）（５質量部（固形分））を含有し、さらに溶媒としてメチルエチルケトンを含有する、固形分濃度が３０質量％の非エネルギー線硬化性の粘着剤組成物（Ｉ－４）－４を調製した。前記アクリル系重合体は、２ＥＨＡ（８０質量部）、及びＨＥＡ（２０質量部）を共重合してなる重量平均分子量８０００００のプレ共重合体である。 (Production of pressure-sensitive adhesive composition (I-4) -4)
Acrylic polymer (100 parts by mass, solid content), trifunctional xylylene diisocyanate-based crosslinking agent (“Takenate D110N” manufactured by Mitsui Takeda Chemical Co., Ltd.) (20 parts by mass (solid content)), and titanium oxide white pigment (large Nissei Kasei Co., Ltd. “N-DYM8054”) (5 parts by mass (solid content)), further containing methyl ethyl ketone as a solvent, and a solid content concentration of 30% by mass, a non-energy ray curable adhesive composition ( I-4) -4 was prepared. The acrylic polymer is a pre-copolymer having a weight average molecular weight of 800,000 obtained by copolymerizing 2EHA (80 parts by mass) and HEA (20 parts by mass).
（支持シートの製造）
　粘着剤組成物（Ｉ－４）－１の代わりに粘着剤組成物（Ｉ－４）－４を使用した以外は、実施例１と同様の方法を用いて、支持シート（１０）－７を得た。 (Manufacture of support sheet)
Using the same method as in Example 1, except that the pressure-sensitive adhesive composition (I-4) -4 was used instead of the pressure-sensitive adhesive composition (I-4) -1, the support sheet (10) -7 was Obtained.
（保護膜形成用複合シートの製造）
　支持シート（１０）－１の代わりに（１０）－７を使用した以外は、実施例１と同様の方法を用いて、保護膜形成用複合シートを作製した。 (Manufacture of composite sheet for protective film formation)
A composite sheet for forming a protective film was produced in the same manner as in Example 1 except that (10) -7 was used instead of the support sheet (10) -1.
＜支持シートの評価＞
　実施例１と同様の方法を用いて、ヘーズ及び透過鮮明度を評価した。結果を表１に示す。 <Evaluation of support sheet>
Using the same method as in Example 1, haze and transmission sharpness were evaluated. The results are shown in Table 1.
＜保護膜形成用複合シートの評価＞
　実施例１と同様の方法を用いて、マウンタ適性、レーザー印字視認性及び印字文字太さを評価した。結果を表１に示す。 <Evaluation of composite sheet for forming protective film>
Using the same method as in Example 1, mounter suitability, laser printing visibility, and printed character thickness were evaluated. The results are shown in Table 1.
［実施例８］
（保護膜形成用組成物（ＩＩＩ－１）の製造）
　実施例１と同様の方法を用いて、熱硬化性の保護膜形成用組成物（ＩＩＩ－１）を得た。 [Example 8]
(Production of protective film-forming composition (III-1))
Using the same method as in Example 1, a thermosetting protective film-forming composition (III-1) was obtained.
（粘着剤組成物（Ｉ－４）－５の製造）
　アクリル系重合体（１００質量部、固形分）、３官能キシリレンジイソシアネート系架橋剤（三井武田ケミカル社製「タケネートＤ１１０Ｎ」）（２０質量部（固形分））、及びアクリル系ポリマー微粒子（大日精化社製「２１５（ＭＤ）ホワイト」）（１０質量部（固形分））を含有し、さらに溶媒としてメチルエチルケトンを含有する、固形分濃度が３０質量％の非エネルギー線硬化性の粘着剤組成物（Ｉ－４）－５を調製した。前記アクリル系重合体は、２ＥＨＡ（８０質量部）、及びＨＥＡ（２０質量部）を共重合してなる重量平均分子量８０００００のプレ共重合体である。 (Production of pressure-sensitive adhesive composition (I-4) -5)
Acrylic polymer (100 parts by mass, solid content), trifunctional xylylene diisocyanate-based cross-linking agent (“Takenate D110N” manufactured by Mitsui Takeda Chemical Co., Ltd.) (20 parts by mass (solid content)), and acrylic polymer fine particles (Daisensei) Non-energy ray-curable pressure-sensitive adhesive composition having a solid content concentration of 30% by mass, containing “215 (MD) white” (10 parts by mass (solid content)) and further containing methyl ethyl ketone as a solvent. (I-4) -5 was prepared. The acrylic polymer is a pre-copolymer having a weight average molecular weight of 800,000 obtained by copolymerizing 2EHA (80 parts by mass) and HEA (20 parts by mass).
（支持シートの製造）
　粘着剤組成物（Ｉ－４）－１の代わりに粘着剤組成物（Ｉ－４）－５を使用した以外は、実施例１と同様の方法を用いて、支持シート（１０）－８を得た。 (Manufacture of support sheet)
Using the same method as in Example 1, except that the pressure-sensitive adhesive composition (I-4) -5 was used instead of the pressure-sensitive adhesive composition (I-4) -1, the support sheet (10) -8 was Obtained.
（保護膜形成用複合シートの製造）
　支持シート（１０）－１の代わりに（１０）－８を使用した以外は、実施例１と同様の方法を用いて、保護膜形成用複合シートを作製した。 (Manufacture of composite sheet for protective film formation)
A composite sheet for forming a protective film was produced in the same manner as in Example 1 except that (10) -8 was used instead of the support sheet (10) -1.
＜支持シートの評価＞
　実施例１と同様の方法を用いて、ヘーズ及び透過鮮明度を評価した。結果を表１に示す。 <Evaluation of support sheet>
Using the same method as in Example 1, haze and transmission sharpness were evaluated. The results are shown in Table 1.
＜保護膜形成用複合シートの評価＞
　実施例１と同様の方法を用いて、マウンタ適性、レーザー印字視認性及び印字文字太さを評価した。結果を表１に示す。 <Evaluation of composite sheet for forming protective film>
Using the same method as in Example 1, mounter suitability, laser printing visibility, and printed character thickness were evaluated. The results are shown in Table 1.
［実施例９］
（保護膜形成用組成物（ＩＩＩ－１）の製造）
　実施例１と同様の方法を用いて、熱硬化性の保護膜形成用組成物（ＩＩＩ－１）を得た。 [Example 9]
(Production of protective film-forming composition (III-1))
Using the same method as in Example 1, a thermosetting protective film-forming composition (III-1) was obtained.
（粘着剤組成物（Ｉ－４）－２の製造）
　実施例２と同様の方法を用いて、固形分濃度が３０質量％の非エネルギー線硬化性の粘着剤組成物（Ｉ－４）－２を調製した。 (Production of pressure-sensitive adhesive composition (I-4) -2)
Using the same method as in Example 2, a non-energy ray-curable pressure-sensitive adhesive composition (I-4) -2 having a solid content concentration of 30% by mass was prepared.
（支持シートの製造）
　粘着剤組成物（Ｉ－４）－１の代わりに粘着剤組成物（Ｉ－４）－２を使用し、粘着剤層の露出面に、厚さ８０μｍのポリプロピレン製フィルム（三菱樹脂社製、マット面（表面粗さ（Ｒａ）：１．２０μｍ）／ツヤ面（表面粗さ（Ｒａ）：０．１０μｍ）基材）のマット面の代わりに、厚さ８０μｍのポリプロピレン製フィルム（グンゼ社製、マット面（表面粗さ（Ｒａ）：０．２０μｍ）／微マット面（表面粗さ（Ｒａ）：０．１５μｍ）基材）のマット面を貼り合わせた以外は、実施例１と同様の方法を用いて、支持シート（１０）－９を得た。 (Manufacture of support sheet)
An adhesive composition (I-4) -2 was used instead of the adhesive composition (I-4) -1, and an 80 μm thick polypropylene film (manufactured by Mitsubishi Plastics, Inc. Instead of the matte surface of mat surface (surface roughness (Ra): 1.20 μm) / gloss surface (surface roughness (Ra): 0.10 μm)), a 80 μm thick polypropylene film (manufactured by Gunze) The mat surface (surface roughness (Ra): 0.20 μm) / fine mat surface (surface roughness (Ra): 0.15 μm)) is the same as in Example 1 except that the mat surface is bonded. Using the method, a support sheet (10) -9 was obtained.
（保護膜形成用複合シートの製造）
　支持シート（１０）－１の代わりに（１０）－９を使用した以外は、実施例１と同様の方法を用いて、保護膜形成用複合シートを作製した。 (Manufacture of composite sheet for protective film formation)
A composite sheet for forming a protective film was produced in the same manner as in Example 1 except that (10) -9 was used instead of the support sheet (10) -1.
＜支持シートの評価＞
　実施例１と同様の方法を用いて、ヘーズ及び透過鮮明度を評価した。結果を表１に示す。 <Evaluation of support sheet>
Using the same method as in Example 1, haze and transmission sharpness were evaluated. The results are shown in Table 1.
＜保護膜形成用複合シートの評価＞
　実施例１と同様の方法を用いて、マウンタ適性、レーザー印字視認性及び印字文字太さを評価した。結果を表１に示す。 <Evaluation of composite sheet for forming protective film>
Using the same method as in Example 1, mounter suitability, laser printing visibility, and printed character thickness were evaluated. The results are shown in Table 1.
［実施例１０］
（保護膜形成用組成物（ＩＩＩ－１）の製造）
　実施例１と同様の方法を用いて、熱硬化性の保護膜形成用組成物（ＩＩＩ－１）を得た。 [Example 10]
(Production of protective film-forming composition (III-1))
Using the same method as in Example 1, a thermosetting protective film-forming composition (III-1) was obtained.
（粘着剤組成物（Ｉ－４）－２の製造）
　実施例２と同様の方法を用いて、固形分濃度が３０質量％の非エネルギー線硬化性の粘着剤組成物（Ｉ－４）－２を調製した。 (Production of pressure-sensitive adhesive composition (I-4) -2)
Using the same method as in Example 2, a non-energy ray-curable pressure-sensitive adhesive composition (I-4) -2 having a solid content concentration of 30% by mass was prepared.
（支持シートの製造）
　粘着剤組成物（Ｉ－４）－１の代わりに粘着剤組成物（Ｉ－４）－２を使用し、粘着剤層の露出面に、厚さ８０μｍのポリプロピレン製フィルム（三菱樹脂社製、マット面（表面粗さ（Ｒａ）：１．２０μｍ）／ツヤ面（表面粗さ（Ｒａ）：０．１０μｍ）基材）のマット面の代わりに、厚さ８０μｍのポリプロピレン製フィルム（グンゼ社製、マット面（表面粗さ（Ｒａ）：０．２０μｍ）／微マット面（表面粗さ（Ｒａ）：０．１５μｍ）基材）の微マット面を貼り合わせた以外は、実施例１と同様の方法を用いて、支持シート（１０）－１０を得た。 (Manufacture of support sheet)
An adhesive composition (I-4) -2 was used instead of the adhesive composition (I-4) -1, and an 80 μm thick polypropylene film (manufactured by Mitsubishi Plastics, Inc. Instead of the matte surface of mat surface (surface roughness (Ra): 1.20 μm) / gloss surface (surface roughness (Ra): 0.10 μm)), a 80 μm thick polypropylene film (manufactured by Gunze) The same as in Example 1 except that the mat surface (surface roughness (Ra): 0.20 μm) / fine mat surface (surface roughness (Ra): 0.15 μm) substrate) was bonded together. Using the method, a support sheet (10) -10 was obtained.
（保護膜形成用複合シートの製造）
　支持シート（１０）－１の代わりに（１０）－１０を使用した以外は、実施例１と同様の方法を用いて、保護膜形成用複合シートを作製した。 (Manufacture of composite sheet for protective film formation)
A composite sheet for forming a protective film was produced in the same manner as in Example 1 except that (10) -10 was used instead of the support sheet (10) -1.
＜支持シートの評価＞
　実施例１と同様の方法を用いて、ヘーズ及び透過鮮明度を評価した。結果を表１に示す。 <Evaluation of support sheet>
Using the same method as in Example 1, haze and transmission sharpness were evaluated. The results are shown in Table 1.
＜保護膜形成用複合シートの評価＞
　実施例１と同様の方法を用いて、マウンタ適性、レーザー印字視認性及び印字文字太さを評価した。結果を表１に示す。 <Evaluation of composite sheet for forming protective film>
Using the same method as in Example 1, mounter suitability, laser printing visibility, and printed character thickness were evaluated. The results are shown in Table 1.
［比較例１］
（保護膜形成用組成物（ＩＩＩ－１）の製造）
　実施例１と同様の方法を用いて、熱硬化性の保護膜形成用組成物（ＩＩＩ－１）を得た。 [Comparative Example 1]
(Production of protective film-forming composition (III-1))
Using the same method as in Example 1, a thermosetting protective film-forming composition (III-1) was obtained.
（粘着剤組成物（Ｉ－４）－１の製造）
　実施例１と同様の方法を用いて、粘着剤組成物（Ｉ－４）－１を得た。 (Production of pressure-sensitive adhesive composition (I-4) -1)
Using the same method as in Example 1, pressure-sensitive adhesive composition (I-4) -1 was obtained.
（支持シートの製造）
　厚さ１５μｍの代わりに、厚さ１０μｍの非エネルギー線硬化性の粘着剤層を形成した以外は、実施例１と同様の方法を用いて、支持シート（１０）－９を製造した。 (Manufacture of support sheet)
A support sheet (10) -9 was produced in the same manner as in Example 1 except that a non-energy ray-curable pressure-sensitive adhesive layer having a thickness of 10 μm was formed instead of the thickness of 15 μm.
（保護膜形成用複合シートの製造）
　支持シート（１０）－１の代わりに（１０）－９を使用した以外は、実施例１と同様の方法を用いて、保護膜形成用複合シートを作製した。 (Manufacture of composite sheet for protective film formation)
A composite sheet for forming a protective film was produced in the same manner as in Example 1 except that (10) -9 was used instead of the support sheet (10) -1.
＜支持シートの評価＞
　実施例１と同様の方法を用いて、ヘーズ及び透過鮮明度を評価した。結果を表１に示す。 <Evaluation of support sheet>
Using the same method as in Example 1, haze and transmission sharpness were evaluated. The results are shown in Table 1.
＜保護膜形成用複合シートの評価＞
　実施例１と同様の方法を用いて、マウンタ適性、レーザー印字視認性及び印字文字太さを評価した。結果を表１に示す。 <Evaluation of composite sheet for forming protective film>
Using the same method as in Example 1, mounter suitability, laser printing visibility, and printed character thickness were evaluated. The results are shown in Table 1.
［比較例２］
（保護膜形成用組成物（ＩＩＩ－１）の製造）
　実施例１と同様の方法を用いて、熱硬化性の保護膜形成用組成物（ＩＩＩ－１）を得た。 [Comparative Example 2]
(Production of protective film-forming composition (III-1))
Using the same method as in Example 1, a thermosetting protective film-forming composition (III-1) was obtained.
（粘着剤組成物（Ｉ－４）－６の製造）
　アクリル系重合体（１００質量部、固形分）、及び３官能キシリレンジイソシアネート系架橋剤（三井武田ケミカル社製「タケネートＤ１１０Ｎ」）（３０質量部（固形分））を含有し、さらに溶媒としてメチルエチルケトンを含有する、固形分濃度が３０質量％の非エネルギー線硬化性の粘着剤組成物（Ｉ－４）－６を調製した。前記アクリル系重合体は、２ＥＨＡ（８０質量部）、及びＨＥＡ（２０質量部）を共重合してなる重量平均分子量８０００００のプレ共重合体である。 (Production of pressure-sensitive adhesive composition (I-4) -6)
Contains acrylic polymer (100 parts by mass, solid content) and trifunctional xylylene diisocyanate crosslinking agent (“Takenate D110N” manufactured by Mitsui Takeda Chemical Co., Ltd.) (30 parts by mass (solid content)), and methyl ethyl ketone as a solvent And a non-energy ray-curable pressure-sensitive adhesive composition (I-4) -6 having a solid content concentration of 30% by mass was prepared. The acrylic polymer is a pre-copolymer having a weight average molecular weight of 800,000 obtained by copolymerizing 2EHA (80 parts by mass) and HEA (20 parts by mass).
（支持シートの製造）
　粘着剤組成物（Ｉ－４）－１の代わりに粘着剤組成物（Ｉ－４）－６を使用した以外は、実施例１と同様の方法を用いて、支持シート（１０）－１０を得た。 (Manufacture of support sheet)
Using the same method as in Example 1, except that the adhesive composition (I-4) -6 was used instead of the adhesive composition (I-4) -1, the support sheet (10) -10 was Obtained.
（保護膜形成用複合シートの製造）
　支持シート（１０）－１の代わりに（１０）－１０を使用した以外は、実施例１と同様の方法を用いて、保護膜形成用複合シートを作製した。 (Manufacture of composite sheet for protective film formation)
A composite sheet for forming a protective film was produced in the same manner as in Example 1 except that (10) -10 was used instead of the support sheet (10) -1.
＜支持シートの評価＞
　実施例１と同様の方法を用いて、ヘーズ及び透過鮮明度を評価した。結果を表１に示す。 <Evaluation of support sheet>
Using the same method as in Example 1, haze and transmission sharpness were evaluated. The results are shown in Table 1.
＜保護膜形成用複合シートの評価＞
　実施例１と同様の方法を用いて、マウンタ適性、レーザー印字視認性及び印字文字太さを評価した。結果を表１に示す。 <Evaluation of composite sheet for forming protective film>
Using the same method as in Example 1, mounter suitability, laser printing visibility, and printed character thickness were evaluated. The results are shown in Table 1.
［比較例３］
（保護膜形成用組成物（ＩＩＩ－１）の製造）
　実施例１と同様の方法を用いて、熱硬化性の保護膜形成用組成物（ＩＩＩ－１）を得た。 [Comparative Example 3]
(Production of protective film-forming composition (III-1))
Using the same method as in Example 1, a thermosetting protective film-forming composition (III-1) was obtained.
（粘着剤組成物（Ｉ－４）－７の製造）
　アクリル系重合体（１００質量部、固形分）、及び３官能キシリレンジイソシアネート系架橋剤（三井武田ケミカル社製「タケネートＤ１１０Ｎ」）（５質量部（固形分））を含有し、さらに溶媒としてメチルエチルケトンを含有する、固形分濃度が３０質量％の非エネルギー線硬化性の粘着剤組成物（Ｉ－４）－７を調製した。前記アクリル系重合体は、２ＥＨＡ（８０質量部）、及びＨＥＡ（２０質量部）を共重合してなる重量平均分子量８０００００のプレ共重合体である。 (Production of pressure-sensitive adhesive composition (I-4) -7)
Contains acrylic polymer (100 parts by mass, solid content) and trifunctional xylylene diisocyanate-based cross-linking agent (“Takenate D110N” manufactured by Mitsui Takeda Chemical Co., Ltd.) (5 parts by mass (solid content)), and methyl ethyl ketone as a solvent And a non-energy ray-curable pressure-sensitive adhesive composition (I-4) -7 having a solid content concentration of 30% by mass was prepared. The acrylic polymer is a pre-copolymer having a weight average molecular weight of 800,000 obtained by copolymerizing 2EHA (80 parts by mass) and HEA (20 parts by mass).
（支持シートの製造）
　ポリエチレンテレフタレート製フィルムの片面がシリコーン処理により剥離処理されてなる剥離フィルムの、前記剥離処理面に、上記で得られた粘着剤組成物（Ｉ－４）－７を塗工し、１２０℃で２分加熱乾燥させることにより、厚さ５μｍの非エネルギー線硬化性の粘着剤層を形成した。
　次いで、この粘着剤層の露出面に、厚さ８０μｍのポリプロピレン製フィルム（三菱樹脂社製、マット面（表面粗さ（Ｒａ）：０．５０μｍ）／ツヤ面（表面粗さ（Ｒａ）：０．１０μｍ）基材）のツヤ面を貼り合わせることで、支持シート（１０）－１１を製造した。 (Manufacture of support sheet)
The pressure-sensitive adhesive composition (I-4) -7 obtained above was applied to the release-treated surface of a release film obtained by releasing one side of a polyethylene terephthalate film by silicone treatment, and the film was coated at 120 ° C. A non-energy ray-curable pressure-sensitive adhesive layer having a thickness of 5 μm was formed by heat-drying for 5 minutes.
Next, an 80 μm-thick polypropylene film (Mitsubishi Resin, mat surface (surface roughness (Ra): 0.50 μm) / shiny surface (surface roughness (Ra): 0) is formed on the exposed surface of the adhesive layer. .10 μm) The support sheet (10) -11 was produced by bonding the glossy surfaces of the base material).
（保護膜形成用複合シートの製造）
　支持シート（１０）－１の代わりに（１０）－１１を使用した以外は、実施例１と同様の方法を用いて、保護膜形成用複合シートを作製した。 (Manufacture of composite sheet for protective film formation)
A composite sheet for forming a protective film was produced in the same manner as in Example 1 except that (10) -11 was used instead of the support sheet (10) -1.
＜支持シートの評価＞
　実施例１と同様の方法を用いて、ヘーズ及び透過鮮明度を評価した。結果を表１に示す。 <Evaluation of support sheet>
Using the same method as in Example 1, haze and transmission sharpness were evaluated. The results are shown in Table 1.
＜保護膜形成用複合シートの評価＞
　実施例１と同様の方法を用いて、マウンタ適性、レーザー印字視認性及び印字文字太さを評価した。結果を表１に示す。 <Evaluation of composite sheet for forming protective film>
Using the same method as in Example 1, mounter suitability, laser printing visibility, and printed character thickness were evaluated. The results are shown in Table 1.
［比較例４］
（保護膜形成用組成物（ＩＩＩ－１）の製造）
　実施例１と同様の方法を用いて、熱硬化性の保護膜形成用組成物（ＩＩＩ－１）を得た。 [Comparative Example 4]
(Production of protective film-forming composition (III-1))
Using the same method as in Example 1, a thermosetting protective film-forming composition (III-1) was obtained.
（粘着剤組成物（Ｉ－４）－７の製造）
　比較例３と同様の方法を用いて、非エネルギー線硬化性の粘着剤組成物（Ｉ－４）－７を調製した。 (Production of pressure-sensitive adhesive composition (I-4) -7)
Using the same method as in Comparative Example 3, a non-energy ray curable pressure-sensitive adhesive composition (I-4) -7 was prepared.
（支持シートの製造）
　粘着剤組成物（Ｉ－４）－１の代わりに粘着剤組成物（Ｉ－４）－７を使用した以外は、実施例１と同様の方法を用いて、支持シート（１０）－１２を得た。 (Manufacture of support sheet)
Using the same method as in Example 1, except that the adhesive composition (I-4) -7 was used instead of the adhesive composition (I-4) -1, the support sheet (10) -12 was Obtained.
（保護膜形成用複合シートの製造）
　支持シート（１０）－１の代わりに（１０）－１２を使用した以外は、実施例１と同様の方法を用いて、保護膜形成用複合シートを作製した。 (Manufacture of composite sheet for protective film formation)
A composite sheet for forming a protective film was produced in the same manner as in Example 1 except that (10) -12 was used instead of the support sheet (10) -1.
＜支持シートの評価＞
　実施例１と同様の方法を用いて、ヘーズ及び透過鮮明度を評価した。結果を表１に示す。 <Evaluation of support sheet>
Using the same method as in Example 1, haze and transmission sharpness were evaluated. The results are shown in Table 1.
＜保護膜形成用複合シートの評価＞
　実施例１と同様の方法を用いて、マウンタ適性、レーザー印字視認性及び印字文字太さを評価した。結果を表１に示す。 <Evaluation of composite sheet for forming protective film>
Using the same method as in Example 1, mounter suitability, laser printing visibility, and printed character thickness were evaluated. The results are shown in Table 1.
［比較例５］
（保護膜形成用組成物（ＩＩＩ－１）の製造）
　実施例１と同様の方法を用いて、熱硬化性の保護膜形成用組成物（ＩＩＩ－１）を得た。 [Comparative Example 5]
(Production of protective film-forming composition (III-1))
Using the same method as in Example 1, a thermosetting protective film-forming composition (III-1) was obtained.
（粘着剤組成物（Ｉ－４）－７の製造）
　比較例３と同様の方法を用いて、非エネルギー線硬化性の粘着剤組成物（Ｉ－４）－７を調製した。 (Production of pressure-sensitive adhesive composition (I-4) -7)
Using the same method as in Comparative Example 3, a non-energy ray curable pressure-sensitive adhesive composition (I-4) -7 was prepared.
（支持シートの製造）
　ポリエチレンテレフタレート製フィルムの片面がシリコーン処理により剥離処理されてなる剥離フィルムの、前記剥離処理面に、上記で得られた粘着剤組成物（Ｉ－４）－７を塗工し、１２０℃で２分加熱乾燥させることにより、厚さ５μｍの非エネルギー線硬化性の粘着剤層を形成した。
　次いで、この粘着剤層の露出面に、厚さ６０μｍのポリプロピレン製フィルム（リケンテクノス社製、マット面（表面粗さ（Ｒａ）：０．５０μｍ）／ツヤ面（表面粗さ（Ｒａ）：０．１０μｍ）基材）のツヤ面を貼り合わせることで、支持シート（１０）－１３を製造した。 (Manufacture of support sheet)
The pressure-sensitive adhesive composition (I-4) -7 obtained above was applied to the release-treated surface of a release film obtained by releasing one side of a polyethylene terephthalate film by silicone treatment, and the film was coated at 120 ° C. A non-energy ray-curable pressure-sensitive adhesive layer having a thickness of 5 μm was formed by heat-drying for 5 minutes.
Next, a 60 μm-thick polypropylene film (manufactured by Riken Technos Co., Ltd., mat surface (surface roughness (Ra): 0.50 μm) / shiny surface (surface roughness (Ra): 0. A support sheet (10) -13 was produced by laminating the glossy surface of the substrate (10 μm).
（保護膜形成用複合シートの製造）
　支持シート（１０）－１の代わりに（１０）－１３を使用した以外は、実施例１と同様の方法を用いて、保護膜形成用複合シートを作製した。 (Manufacture of composite sheet for protective film formation)
A composite sheet for forming a protective film was produced in the same manner as in Example 1 except that (10) -13 was used instead of the support sheet (10) -1.
＜支持シートの評価＞
　実施例１と同様の方法を用いて、ヘーズ及び透過鮮明度を評価した。結果を表１に示す。 <Evaluation of support sheet>
Using the same method as in Example 1, haze and transmission sharpness were evaluated. The results are shown in Table 1.
＜保護膜形成用複合シートの評価＞
　実施例１と同様の方法を用いて、マウンタ適性、レーザー印字視認性及び印字文字太さを評価した。結果を表１に示す。 <Evaluation of composite sheet for forming protective film>
Using the same method as in Example 1, mounter suitability, laser printing visibility, and printed character thickness were evaluated. The results are shown in Table 1.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　表１において、合否判定については、マウンタ適性がＡ評価であり、レーザー印字視認性がＡ又はＢ評価のものを「合」とし、それ以外を「否」とした。
　表１から、支持シートのヘーズが４６％以上であるとき、マウンタ適性がＡ評価となっていた。これは、支持シートのヘーズが４６％以上と、ある程度の濁度（曇度）を有することにより、テープ先端の位置調整を行う光センサーにおいて、レーザー照射により支持シートの先端位置を検知することができたためであると推察された。 In Table 1, regarding the pass / fail judgment, the mounter suitability was A evaluation, the laser print visibility was A or B evaluation, and “other” was “No”.
From Table 1, the mounter suitability was A evaluation when the haze of the support sheet was 46% or more. This is because the haze of the support sheet has a certain degree of turbidity (cloudiness) of 46% or more, so that the tip position of the support sheet can be detected by laser irradiation in an optical sensor that adjusts the position of the tip of the tape. It was guessed that this was because it was made.
　また、表１から、支持シートのヘーズが４６％以上であり、且つ透過鮮明度が１００以上であるとき、レーザー印字視認性がＢ評価以上、２００以上であるとき、レーザー印字視認性がＡ評価となっていた。これは、支持シートの底面に位置する基材の外表面における光散乱が抑制されていることで、レーザー印字の視認性が向上したためであると推察された。さらに、支持シートのヘーズが４６％以上と、ある程度の濁度（曇度）を有することにより、支持シート内部においてレーザー光を適度に散乱させて、印字文字太さを太くすることができ、レーザー印字の視認性の向上に寄与したためであると推察された。 Also, from Table 1, when the haze of the support sheet is 46% or more and the transmission sharpness is 100 or more, when the laser printing visibility is B evaluation or more and 200 or more, the laser printing visibility is A evaluation. It was. It was speculated that this was because the visibility of laser printing was improved by suppressing light scattering on the outer surface of the substrate located on the bottom surface of the support sheet. Furthermore, since the haze of the support sheet is 46% or more and has a certain degree of turbidity (cloudiness), the laser light can be appropriately scattered inside the support sheet to increase the thickness of the printed characters. It was assumed that it was because it contributed to the improvement of the visibility of printing.
　以上のことから、支持シートのヘーズ及び透過鮮明度を適当な範囲とすることで、保護膜へのレーザー印字性に優れ、かつ保護膜の印字の視認性にも優れた保護膜形成用複合シートが得られることが明らかとなった。 From the above, the composite sheet for forming a protective film has excellent laser printability on the protective film and excellent visibility of the printed protective film by adjusting the haze and transmission clarity of the support sheet to an appropriate range. It became clear that
本発明は、半導体装置の製造に利用可能である。 The present invention can be used for manufacturing semiconductor devices.
１Ａ，１Ｂ，１Ｃ，１Ｄ，１Ｅ・・・保護膜形成用複合シート、１０・・・支持シート、１０ａ・・・支持シートの表面、１１・・・基材、１１ａ・・・基材の表面、１２・・・粘着剤層、１２ａ・・・粘着剤層の表面、１３・・・保護膜形成用フィルム、１３ａ・・・保護膜形成用フィルムの表面、１５・・・剥離フィルム、１６・・・治具用接着剤層、１６ａ・・・治具用接着剤層の表面、１７・・・中間層、１７ａ・・・中間層の表面 1A, 1B, 1C, 1D, 1E ... Composite sheet for protective film formation, 10 ... Support sheet, 10a ... Surface of support sheet, 11 ... Base material, 11a ... Surface of base material , 12 ... adhesive layer, 12a ... surface of the adhesive layer, 13 ... protective film forming film, 13a ... surface of protective film forming film, 15 ... release film, 16. ..Jig adhesive layer, 16a ... surface of jig adhesive layer, 17 ... intermediate layer, 17a ... surface of intermediate layer

Claims (8)

  1. 　基材を備え、前記基材上に、粘着剤層及び保護膜形成用フィルムがこの順に積層されてなり、
    　前記基材及び前記粘着剤層の積層物である支持シートのヘーズが４５％よりも高く、
    　前記支持シートの透過鮮明度が１００以上である、保護膜形成用複合シート。     Provided with a base material, on the base material, a pressure-sensitive adhesive layer and a protective film-forming film are laminated in this order,
    The haze of the support sheet which is a laminate of the base material and the pressure-sensitive adhesive layer is higher than 45%,
    A composite sheet for forming a protective film, wherein the support sheet has a transmission clarity of 100 or more.
  2. 　前記粘着剤層の前記保護膜形成用フィルムを備えている側の表面のうち、前記保護膜形成用フィルムが積層されていない領域に、治具用接着剤層を備える、請求項１に記載の保護膜形成用複合シート。 The jig | tool adhesive layer is provided in the area | region where the said film for protective film formation is not laminated | stacked among the surfaces of the side provided with the said film for protective film formation of the said adhesive layer. Composite sheet for protective film formation.
  3. 　前記保護膜形成用フィルムが、エネルギー線硬化性である、請求項１又は２に記載の保護膜形成用複合シート。 The protective film-forming composite sheet according to claim 1 or 2, wherein the protective film-forming film is energy ray curable.
  4. 　前記保護膜形成用フィルムが、熱硬化性である、請求項１又は２に記載の保護膜形成用複合シート。 The protective film-forming composite sheet according to claim 1 or 2, wherein the protective film-forming film is thermosetting.
  5. 　前記保護膜形成用フィルムが、非硬化性である、請求項１又は２に記載の保護膜形成用複合シート。 The protective film-forming composite sheet according to claim 1, wherein the protective film-forming film is non-curable.
  6. 　前記粘着剤層が、エネルギー線硬化性又は非エネルギー硬化性である、請求項１～５のいずれか一項に記載の保護膜形成用複合シート。 The composite sheet for forming a protective film according to any one of claims 1 to 5, wherein the pressure-sensitive adhesive layer is energy ray curable or non-energy curable.
  7. 　前記粘着剤層の厚さが３～２０μｍである、請求項１～６のいずれか一項に記載の保護膜形成用複合シート。 The composite sheet for forming a protective film according to any one of claims 1 to 6, wherein the pressure-sensitive adhesive layer has a thickness of 3 to 20 µm.
  8. 　前記基材の一方の表面の表面粗さ（Ｒａ）が０．１１μｍ以上であり、前記表面粗さの表面に、前記粘着剤層が直接接触して積層されている、請求項１～７のいずれか一項に記載の保護膜形成用複合シート。 The surface roughness (Ra) of one surface of the substrate is 0.11 μm or more, and the pressure-sensitive adhesive layer is laminated in direct contact with the surface of the surface roughness. The composite sheet for forming a protective film according to any one of the above.
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CN111154419A (en) * 2020-03-03 2020-05-15 江西科为薄膜新型材料有限公司 Matte white board film

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010073897A (en) * 2008-09-18 2010-04-02 Lintec Corp Laser dicing sheet, and manufacturing method of semiconductor chip
WO2012077471A1 (en) * 2010-12-06 2012-06-14 株式会社きもと Auxiliary sheet for laser dicing
WO2015178346A1 (en) * 2014-05-23 2015-11-26 リンテック株式会社 Composite sheet for forming protective film
JP2016225342A (en) * 2015-05-27 2016-12-28 日東電工株式会社 Dicing die bonding film, method of manufacturing semiconductor device, and semiconductor device

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5432853B2 (en) 1971-10-11 1979-10-17
JP5452353B2 (en) * 2010-05-14 2014-03-26 三井化学東セロ株式会社 Adhesive film for protecting semiconductor wafer and adhesive film roll for protecting semiconductor wafer
JP5432853B2 (en) * 2010-07-30 2014-03-05 日東電工株式会社 Dicing tape-integrated film for semiconductor back surface, manufacturing method thereof, and manufacturing method of semiconductor device
JP2012212122A (en) * 2011-03-18 2012-11-01 Sumitomo Chemical Co Ltd Polarizer protective film
JP6058905B2 (en) * 2011-03-31 2017-01-11 住友化学株式会社 Manufacturing method of light diffusion film and manufacturing method of polarizing plate
JP5821309B2 (en) * 2011-06-14 2015-11-24 住友化学株式会社 Light diffusing adhesive sheet, polarizing plate and liquid crystal display panel
WO2014155756A1 (en) * 2013-03-26 2014-10-02 リンテック株式会社 Adhesive sheet, composite sheet for forming protective film, and method for manufacturing chip with protective film
KR102053703B1 (en) * 2014-03-28 2019-12-09 동우 화인켐 주식회사 Composition for Light Diffused Anti-Glare Film and Light Diffused Anti-Glare Film Using the Same
CN106463370B (en) * 2014-07-04 2019-06-21 琳得科株式会社 Film is used in protective film formation
SG11201709978PA (en) * 2015-06-05 2017-12-28 Lintec Corp Composite sheet for forming protective film

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010073897A (en) * 2008-09-18 2010-04-02 Lintec Corp Laser dicing sheet, and manufacturing method of semiconductor chip
WO2012077471A1 (en) * 2010-12-06 2012-06-14 株式会社きもと Auxiliary sheet for laser dicing
WO2015178346A1 (en) * 2014-05-23 2015-11-26 リンテック株式会社 Composite sheet for forming protective film
JP2016225342A (en) * 2015-05-27 2016-12-28 日東電工株式会社 Dicing die bonding film, method of manufacturing semiconductor device, and semiconductor device

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI783131B (en) * 2018-03-30 2022-11-11 日商琳得科股份有限公司 Composite sheet for forming protective film
CN111793452A (en) * 2019-04-03 2020-10-20 琳得科株式会社 Adhesive sheet and display
CN111793452B (en) * 2019-04-03 2023-08-25 琳得科株式会社 Adhesive sheet and display
JP2021002599A (en) * 2019-06-21 2021-01-07 リンテック株式会社 Composite sheet for protection film formation and manufacturing method of semiconductor chip with protection film
JP7333211B2 (en) 2019-06-21 2023-08-24 リンテック株式会社 Composite sheet for forming protective film and method for manufacturing semiconductor chip with protective film
TWI833953B (en) * 2019-06-21 2024-03-01 日商琳得科股份有限公司 Composite sheet for protective film formation and method for manufacturing semiconductor wafer with protective film
WO2021193923A1 (en) * 2020-03-27 2021-09-30 リンテック株式会社 Sheet used for manufacturing semiconductor device, method for producing sheet used for manufacturing semiconductor device, and method for manufacturing semiconductor chip equipped with film-like adhesive agent
KR20220082726A (en) 2020-12-10 2022-06-17 린텍 가부시키가이샤 Manufacturing method of workpiece with protective film and workpiece with protective film forming film

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CN109789666B (en) 2024-06-04
KR20190134992A (en) 2019-12-05

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