WO2017149808A1 - Protective film-forming composite sheet - Google Patents

Protective film-forming composite sheet Download PDF

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Publication number
WO2017149808A1
WO2017149808A1 PCT/JP2016/075831 JP2016075831W WO2017149808A1 WO 2017149808 A1 WO2017149808 A1 WO 2017149808A1 JP 2016075831 W JP2016075831 W JP 2016075831W WO 2017149808 A1 WO2017149808 A1 WO 2017149808A1
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WO
WIPO (PCT)
Prior art keywords
protective film
forming
film
meth
acrylate
Prior art date
Application number
PCT/JP2016/075831
Other languages
French (fr)
Japanese (ja)
Inventor
尚哉 佐伯
遼 佐々木
裕之 米山
山本　大輔
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 CN201680082921.4A priority Critical patent/CN108778721B/en
Priority to SG11201807528RA priority patent/SG11201807528RA/en
Priority to KR1020187025059A priority patent/KR102516392B1/en
Priority to JP2018502507A priority patent/JP6833804B2/en
Publication of WO2017149808A1 publication Critical patent/WO2017149808A1/en

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    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • 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
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
    • 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/26—Polymeric coating
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/748—Releasability

Definitions

  • the present invention relates to a composite sheet for forming a protective film for forming a protective film on the back surface of a semiconductor chip.
  • 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 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 chip and may be taken into the semiconductor device as a semiconductor chip with a protective film.
  • the protective film is used to prevent cracks from occurring in the chip after the dicing process or packaging.
  • a protective film-forming composite sheet comprising a protective film-forming film on a support sheet.
  • the support sheet for example, a resin base material or a laminated structure such as a base material and an adhesive layer is used, and a laminated surface such as a protective film forming film or an adhesive layer of the base material is surface-treated. Sometimes it is done.
  • the support 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.
  • one or both sides thereof usually have an uneven shape. This is because if the substrate does not have such an uneven shape, the contact surface between the substrates adheres and blocks when the substrate is wound up to form a roll, making it difficult to use. . If at least one of the contact surfaces of the substrates has an uneven shape, the area of the contact surface is reduced, so that blocking is suppressed.
  • FIG. 4 is a cross-sectional view schematically showing an example of a conventional composite sheet for forming a protective film. Note that, in the drawings used in the following description, for example, in order to make the characteristics of the protective film-forming composite sheet easier to understand, there are cases where the main part is shown enlarged for convenience. The dimensional ratio and the like are not necessarily the same as actual.
  • the conventional protective film-forming composite sheet 9 shown here comprises a protective film-forming film 13 on a support sheet 90, and the support sheet 90 is made of a laminated structure of a base material 91 and an adhesive layer 12.
  • the protective film forming film 13 is provided on the pressure-sensitive adhesive layer 12.
  • the protective film-forming film 13 becomes a protective film by curing.
  • the protective film-forming composite sheet 9 further includes a release film 15 on the protective film-forming film 13, and the release film 15 is removed when the protective film-forming composite sheet 9 is used.
  • the surface (back surface) 90 b opposite to the surface (front surface) 90 a provided with the protective film forming film 13 of the support sheet 90, that is, the adhesive layer 12 of the substrate 91 is formed.
  • a surface (back surface) 91b opposite to the provided surface (front surface) 91a is an uneven surface.
  • the composite sheet 9 for forming the protective film is thus exposed to the back surface 91b of the base material 91 and the release film 15 when the back surface 91b of the base material 91 has a concavo-convex surface and is taken up into a roll. Sticking with the surface (surface) 15a, that is, blocking is suppressed.
  • the composite sheet for protective film formation is printed on the surface of the protective film formed from the protective film-forming film on the support sheet side by irradiation with laser light (hereinafter sometimes referred to as “laser printing”).
  • Laser printing is applied from the opposite side of the support sheet on which the protective film is formed.
  • the protective film is irradiated with laser light from the back surface 91b side of the base material 91 through the support sheet 90. Since it is an uneven surface, there is a problem that light is irregularly reflected here and laser printing becomes unclear.
  • FIG. 5 is a cross-sectional view schematically showing another example of a conventional composite sheet for forming a protective film.
  • the conventional protective film-forming composite sheet 8 shown here comprises a protective film-forming film 13 on a support sheet 80, like the protective film-forming composite sheet 9, and the support sheet 80 is a base material. 81 and a pressure-sensitive adhesive layer 12, and a protective film-forming film 13 is provided on the pressure-sensitive adhesive layer 12.
  • the arrangement of the uneven surface of the base material 81 is opposite to that of the base material 91 in the support sheet 90. That is, in the composite sheet 8 for forming the protective film, the surface (front surface) 81a of the base material 81 provided with the adhesive layer 12 is an uneven surface, and the surface (back surface) opposite to the surface 81a of the base material 81. ) 81b is a smooth surface.
  • the base material 81, the protective film forming film 13 and the release film 15 in the support sheet 80 are the same as the base material 91, the protective film forming film 13 and the release film 15 in the support sheet 90, respectively.
  • the back surface 81b of the substrate 81 that is, the surface (back surface) 80b opposite to the surface (front surface) 80a provided with the adhesive layer 12 of the support sheet 80.
  • the back surface 81b of the substrate 81 and the exposed surface (front surface) 15a of the release film 15 are attached, that is, blocking occurs. It cannot be suppressed.
  • blocking occurs, wrinkles occur in the protective film-forming composite sheet 8, or the release film 15 peels off from the protective film-forming film 13 when the protective film-forming composite sheet 8 is unwound from the roll.
  • the pressure-sensitive adhesive layer 12 needs to have a sufficient thickness so as to eliminate the uneven shape. If this is insufficient, the surface (back surface) 13b on the support sheet 80 side of the protective film forming film 13 will have an uneven shape reflecting the uneven shape of the base material 81, and such a protective film formation will be performed. There was a problem that the laser printing applied to the surface on the support sheet side of the protective film formed from the protective film 13 became unclear.
  • the present invention has been made in view of the above circumstances, and is a protective film-forming composite sheet used for forming a protective film on the back surface of a semiconductor chip, which can suppress blocking and has a clear laser on the protective film. It is an object to provide a composite sheet for forming a protective film that can be printed.
  • a protective film-forming film is provided on one surface of the support sheet, and the surface of the support sheet is opposite to the side provided with the protective film-forming film.
  • a protective film-forming composite sheet comprising a coating layer thereon, wherein the protective film-forming composite sheet has a measured haze value of 47% or less from the coating layer side of the protective film-forming composite sheet.
  • the release film measured by the following method using the protective film-forming composite sheet provided with a release film on the protective film-forming film.
  • the peel force may be 10 mN / 50 mm or less.
  • the film was allowed to stand at 40 ° C.
  • the support sheet is formed by laminating a base material and an adhesive layer, and the protective film-forming composite sheet is the coating layer.
  • the base material, the pressure-sensitive adhesive layer, and the protective film-forming film may be laminated in this order.
  • the pressure-sensitive adhesive layer may be energy ray curable or non-energy ray curable.
  • the protective film-forming film may be thermosetting or energy ray curable.
  • a protective film-forming composite sheet used for forming a protective film on the back surface of a semiconductor chip, which can suppress blocking and can be clearly laser-printed on the protective film.
  • the composite sheet for protective film formation includes a protective film-forming film on one surface of the support sheet, and includes the protective film-forming film of the support sheet.
  • a protective sheet-forming composite sheet comprising a coating layer on the surface opposite to the surface, wherein the measured haze value from the coating layer side of the protective film-forming composite sheet is 47% or less. is there.
  • the protective film-forming composite sheet has a measured value of haze from the coating layer side within the specific range as described above, and with respect to the protective film after curing the protective film-forming film, When laser light is irradiated from the coating layer side, scattering of the laser light is suppressed, so that clear laser printing can be performed on the protective film.
  • the said composite sheet for protective film formation is equipped with the said coating layer which has slipperiness
  • the protective film-forming film is cured by heating or irradiation with energy rays to form a protective film, but the laminated structure of the support sheet and the protective film is also used. As long as it is maintained, it is referred to as a protective sheet-forming composite sheet.
  • a protective sheet-forming composite sheet when the support sheet is a laminated structure of a base material and an adhesive layer, a cured product of the base material and the adhesive layer, As long as the protective film-forming film or the laminated structure of the protective film is maintained, the protective film-forming composite sheet is referred to.
  • FIG. 1 is a cross-sectional view schematically showing one embodiment of a composite sheet for forming a protective film according to one embodiment of the present invention.
  • the protective film-forming composite sheet 1 shown here includes a protective film-forming film 13 on one surface 10 a of the support sheet 10, and a coating layer 14 on the other surface (back surface) 10 b of the support sheet 10.
  • the support sheet 10 is formed by laminating a base material 11 and a pressure-sensitive adhesive layer 12, and includes a pressure-sensitive adhesive layer 12 on one surface 11 a of the base material 11, and the other surface (back surface) of the base material 11.
  • a coating layer 14 is provided on 11b, and a protective film forming film 13 is provided on the pressure-sensitive adhesive layer 12.
  • the protective film-forming composite sheet 1 further includes a release film 15 on the protective film-forming film 13, and the release film 15 is removed when the protective film-forming composite sheet 1 is used.
  • the protective film-forming film 13 becomes a protective film by curing.
  • the pressure-sensitive adhesive layer 12 is laminated on the surface 11 a of the substrate 11, and the protective film-forming film 13 is laminated on a part of the surface 12 a of the pressure-sensitive adhesive layer 12.
  • the peeling film 15 is laminated
  • a gap may exist between the release film 15 and the surface 12 a of the pressure-sensitive adhesive layer 12 or the surface 13 a of the protective film forming film 13.
  • the voids are likely to occur in the vicinity of the protective film-forming film 13.
  • the haze measured from the direction of the surface (back surface) 14b opposite to the surface (front surface) 14a in contact with the support sheet 10 (base material 11) of the coating layer 14 is 47. % Or less.
  • haze means a value obtained by measurement according to JIS K 7136 unless otherwise specified.
  • the protective film-forming composite sheet 1 includes the coating layer 14, so that the back surface 11 b of the base material 11 and the exposed surface (front surface) of the release film 15, even when wound up to form a roll. Sticking with 15a, that is, blocking is suppressed.
  • the surface (back surface) 11b opposite to the provided surface (front surface) 11a is an uneven surface with low smoothness here, but may be a smooth surface.
  • the coating layer 14 covers this surface, so that the support of the coating layer 14 is supported.
  • the surface (rear surface) 14b opposite to the surface (front surface) 14a in contact with the sheet 10 (base material 11) has a high smoothness and a small surface roughness Ra, so that the laser light in the coating layer 14 is obtained. Is suppressed, and laser printing can be clearly performed on the protective film.
  • surface roughness Ra means a so-called arithmetic average roughness defined by JIS B0601: 2001 unless otherwise specified.
  • the surface 11a of the substrate 11 is a smooth surface here, but may be an uneven surface with low smoothness. However, as will be described later, it is easier to suppress the generation of voids between the surface 11a of the base material 11 and the pressure-sensitive adhesive layer, and to make the composite sheet 1 for forming a protective film have favorable characteristics. Therefore, the surface 11a of the substrate 11 is preferably a smooth surface.
  • the composite sheet 1 for forming a protective film shown in FIG. 1 has a back surface of a semiconductor wafer (not shown) attached to the front surface 13a of the protective film forming film 13 with the release film 15 removed.
  • the exposed surface on which the protective film forming film 13 is not laminated is attached to a jig such as a ring frame and used.
  • FIG. 2 is a cross-sectional view schematically showing another embodiment of the composite sheet for forming a protective film according to one aspect of the present invention.
  • the protective film forming composite sheet 2 shown here has a protective film forming film 23 laminated on the entire surface 12 a of the pressure-sensitive adhesive layer 12, and a jig adhesive on a part of the surface 23 a of the protective film forming film 23.
  • Layer 16 is laminated, of the surface 23a of the protective film forming film 23, the exposed surface on which the jig adhesive layer 16 is not laminated, and the surface 16a (upper surface and side surface) of the jig adhesive layer 16 It is the same as the composite sheet 1 for forming a protective film shown in FIG. 1 except that a release film 15 is laminated thereon.
  • a gap may exist between the release film 15 and the surface 23a of the protective film-forming film 23 or the surface 16a of the jig adhesive layer 16.
  • the gap portion is likely to occur in the vicinity of the jig adhesive layer 16.
  • the haze measured from the direction of the surface (back surface) 14b is 47% or less. Therefore, clear laser printing can be performed on the protective film formed from the protective film-forming film 23.
  • the protective film-forming composite sheet 2 is provided with the coating layer 14, so that blocking is suppressed even when the protective film-forming composite sheet 2 is wound up into a roll.
  • the protective film-forming composite sheet 2 shown in FIG. 2 has a semiconductor wafer (not shown) attached to the front surface 23a of the protective film-forming film 23 with the release film 15 removed.
  • the upper surface of the surface 16a of the adhesive layer 16 is used by being attached to a jig such as a ring frame.
  • the composite sheet for forming a protective film according to the present invention is not limited to the one shown in FIGS. 1 and 2, and a part of the structure shown in FIGS. 1 and 2 is changed or deleted within a range not impairing the effects of the present invention.
  • other configurations may be added to those described above.
  • each structure of the composite sheet for protective film formation which concerns on one embodiment of this invention is demonstrated in detail.
  • the support sheet is not particularly limited as long as it can be provided with the protective film-forming film. For example, peeling to prevent dust and the like from adhering to the surface of the protective film-forming film.
  • Examples of the sheet may include a dicing sheet for protecting the surface of the protective film-forming film in a dicing process.
  • Preferable examples of the support sheet include those composed only of a base material usually used in the field of semiconductor wafer processing sheets, and those obtained by laminating a base material and an adhesive layer.
  • the support sheet may be composed of one layer (single layer) or may be composed of two or more layers.
  • the plurality of layers may be the same as or different from each other. That is, all the layers may be the same, all the layers may be different, or only some of the layers may be the same. And when several layers differ from each other, the combination of these several layers is not specifically limited.
  • the plurality of layers being different from each other means that at least one of the material and the thickness of each layer is different from each other.
  • the thickness of the support sheet may be appropriately selected depending on the purpose, but is preferably 10 from the viewpoint that sufficient flexibility can be imparted to the protective film-forming composite sheet and the adhesiveness to the semiconductor wafer becomes good. It is ⁇ 500 ⁇ m, more preferably 20 to 350 ⁇ m, particularly preferably 30 to 200 ⁇ m.
  • the thickness of the support sheet means the total thickness of each layer constituting the support sheet. For example, in the case of a support sheet in which a base material and an adhesive layer are laminated, the base material And the total thickness of the pressure-sensitive adhesive layer. Note that, at least one surface of the support sheet can be an uneven surface, but the thickness of the support sheet is calculated with the tip of the convex portion as one starting point at a portion including the convex portion on the uneven surface of the support sheet. That's fine.
  • the material of the base material is preferably various resins, and specific examples thereof include polyethylene (low density polyethylene (LDPE), linear low density polyethylene (LLDPE), high density polyethylene (HDPE, etc.). )), Polypropylene, ethylene / propylene copolymer, polybutene, polybutadiene, polymethylpentene, polyvinyl chloride, vinyl chloride copolymer, polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polyurethane, polyurethane acrylate, polyimide, ethylene Vinyl acetate copolymer, ionomer resin, ethylene / (meth) acrylic acid copolymer, ethylene / (meth) acrylic acid ester copolymer, polystyrene, polycarbonate, fluororesin, hydrogenation of any of these resins Additives, modified products, cross-linked products or copolymers may be mentioned. In this specification, “(meth) acrylic acid acrylic acid copo
  • the thickness of the base material can be appropriately selected according to the purpose, but is 15 to 300 ⁇ m. And more preferably 20 to 200 ⁇ m.
  • 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.
  • the substrate may be composed of one layer (single layer) or may be composed of two or more layers. When a base material consists of multiple layers, these multiple 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 support sheet.
  • the total thickness of each layer may be set to the preferable thickness of the substrate.
  • the surface roughness Ra of the surface (surface) provided with the pressure-sensitive adhesive layer of the substrate is preferably 0.001 to 0.1 ⁇ m, more preferably 0.005 to 0.08 ⁇ m, and A thickness of 01 to 0.04 ⁇ m is particularly preferable.
  • the surface roughness Ra of the substrate surface is not more than the upper limit value, laser printing can be performed more clearly on the protective film.
  • the surface roughness Ra of the substrate surface can be adjusted by, for example, molding conditions of the substrate, surface treatment conditions, and the like.
  • a method of dividing the semiconductor wafer into semiconductor chips by dicing for example, blade dicing for cutting the semiconductor wafer using a blade, laser dicing for cutting the semiconductor wafer by laser irradiation, or spraying water containing an abrasive And a method using water dicing or the like for cutting a semiconductor wafer.
  • the laser beam in the infrared region is irradiated so as to be focused on the focal point set inside the semiconductor wafer.
  • the protective sheet-forming composite sheet provided with such a substrate has a modified layer in the semiconductor wafer described above. It is suitable for use when forming a semiconductor wafer into individual pieces.
  • the surface roughness Ra of the surface (back surface) opposite to the surface (front surface) provided with the adhesive layer of the substrate in other words, the surface (surface) provided with the protective film forming film of the support sheet.
  • the surface roughness Ra of the opposite surface (back surface) is preferably 0.001 to 4 ⁇ m, more preferably 0.005 to 3.7 ⁇ m, and 0.01 to 3.4 ⁇ m. More preferably, the thickness is 0.02 to 3.1 ⁇ m.
  • the surface roughness Ra on the back surface of the substrate is less than or equal to the upper limit, the surface roughness Ra on the surface of the coating layer opposite to the side in contact with the support sheet can be more easily reduced, and the protective film In contrast, it becomes easier to perform laser printing clearly.
  • the surface roughness Ra of the back surface of the base material can be adjusted by, for example, molding conditions of the base material, surface treatment conditions, and the like.
  • the resin that is the material of the base material may be cross-linked.
  • the resin that is the material of the base material may be a sheet formed by extrusion molding of a thermoplastic resin, or may be a stretched sheet, and a thin layer formed by a known means of a curable resin. It may be formed into a sheet by forming and curing. Further, the base material may be colored or printed.
  • the base material is preferably one containing polypropylene from the viewpoint that it has excellent heat resistance and has an appropriate flexibility so that it has expandability and pick-up suitability.
  • the base material containing polypropylene may be, for example, a single layer or a plurality of layers made of only polypropylene, or a multiple layer base material in which a polypropylene layer and a resin layer other than polypropylene are laminated. May be.
  • the protective film-forming film is thermosetting, the base material has heat resistance, so that deterioration of the base material due to heat can be suppressed, and occurrence of defects in the manufacturing process of the semiconductor device can be effectively suppressed. .
  • the substrate is subjected to a roughening treatment such as a sandblast treatment, a solvent treatment, a corona discharge treatment, an electron beam irradiation treatment, a plasma.
  • the surface may be subjected to oxidation treatment such as treatment, ozone / ultraviolet irradiation treatment, flame treatment, chromic acid treatment, and hot air treatment.
  • the base material may be one whose surface is primed.
  • the said adhesive layer can use a well-known thing suitably.
  • An adhesive layer can be formed using the adhesive composition containing various components, such as an adhesive, for comprising this.
  • the ratio of the content of components that do not vaporize at room temperature in the pressure-sensitive adhesive composition is usually the same as the ratio of the content of the components of the pressure-sensitive adhesive layer.
  • “normal temperature” means a temperature that is not particularly cooled or heated, that is, a normal temperature, and examples thereof include a temperature of 15 to 25 ° C.
  • the thickness of the pressure-sensitive adhesive layer can be appropriately selected depending on the purpose, but is preferably 1 to 100 ⁇ m, more preferably 2 to 80 ⁇ m, and particularly preferably 3 to 50 ⁇ m.
  • the pressure-sensitive adhesive layer may be composed of one layer (single layer) or may be composed of two or more layers. When an adhesive layer consists of multiple layers, these multiple layers may be the same 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 support sheet.
  • the total thickness of each layer may be set to the thickness of the preferable pressure-sensitive adhesive layer.
  • pressure-sensitive adhesive examples include pressure-sensitive adhesive resins such as acrylic resins, urethane resins, rubber resins, silicone resins, and vinyl ether resins. Examples thereof include a linear curable resin.
  • energy beam means an electromagnetic wave or charged particle beam having energy quanta, and examples thereof include ultraviolet rays and electron beams. Ultraviolet rays can be irradiated by using, for example, a high-pressure mercury lamp, a fusion H lamp, or a xenon lamp as an ultraviolet ray source. The electron beam can be emitted by an electron beam accelerator or the like.
  • the energy ray curable resin examples include those having a polymerizable group such as a (meth) acryloyl group and a vinyl group.
  • the adhesive resin is preferably an acrylic resin, and more preferably a (meth) acrylic acid ester copolymer including a structural unit derived from a (meth) acrylic acid ester.
  • the pressure-sensitive adhesive layer contains a component that is polymerized by irradiation with energy rays, such as an energy ray-curable resin
  • the pressure-sensitive adhesive layer becomes energy-ray curable and decreases its adhesiveness by irradiation with energy rays. By doing so, it becomes easy to pick up a semiconductor chip with a protective film, which will be described later.
  • a pressure-sensitive adhesive layer can be formed using, for example, various pressure-sensitive adhesive compositions containing a component that is polymerized by irradiation with energy rays.
  • Adhesive composition examples include those containing a component that polymerizes upon irradiation with energy rays.
  • Examples of such a pressure-sensitive adhesive composition include an acrylic resin and an energy ray-polymerizable compound. What is contained (hereinafter may be abbreviated as “adhesive composition (i)”), the acrylic resin having a hydroxyl group and having a polymerizable group in the side chain (for example, having a hydroxyl group, And those having a polymerizable group in the side chain via a urethane bond) and an isocyanate-based crosslinking agent (hereinafter sometimes abbreviated as “adhesive composition (ii)”). Can be mentioned.
  • the pressure-sensitive adhesive composition (i) contains the acrylic resin and an energy beam polymerizable compound as essential components.
  • each component will be described.
  • acrylic resin Preferred examples of the acrylic resin in the pressure-sensitive adhesive composition (i) include, for example, polymerization of (meth) acrylic acid ester as a monomer and a monomer other than (meth) acrylic acid ester used as necessary.
  • the (meth) acrylic acid ester copolymer obtained by this is mentioned.
  • Examples of the (meth) acrylic acid ester include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, (meth) Hexyl acrylate, heptyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-nonyl (meth) acrylate, (meth) acrylic acid Isononyl, decyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate (lauryl (meth) acrylate), tridecyl (meth) acrylate, tetradecyl (meth) acrylate ((meth) acrylic acid) Myr
  • (meth) acrylic acid alkyl ester in which the alkyl group constituting the alkyl ester has 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-
  • Examples of the monomer other than the (meth) acrylic acid ester include (meth) acrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene, N-methylolacrylamide and the like.
  • monomers such as said (meth) acrylic acid ester and monomers other than said (meth) acrylic acid ester which comprise acrylic resin, all may be only 1 type, and 2 or more types may be sufficient as them.
  • the acrylic resin contained in the pressure-sensitive adhesive composition (i) may be one kind or two or more kinds.
  • the content of the acrylic resin in the pressure-sensitive adhesive composition (i) is preferably 40 to 99% by mass with respect to the total amount of all the components other than the solvent in the pressure-sensitive adhesive composition (i), More preferably, it is 91% by weight.
  • the energy ray polymerizable compound is a compound that is polymerized and cured by irradiation with energy rays, and examples thereof include those having an energy ray polymerizable group such as an energy ray curable double bond in the molecule. .
  • Examples of the energy ray polymerizable compound include low molecular weight compounds (monofunctional or polyfunctional monomers and oligomers) having an energy ray polymerizable group, and more specifically, trimethylolpropane triacrylate, tetramethylol.
  • Acrylates such as methanetetraacrylate, pentaerythritol triacrylate, dipentaerythritol monohydroxypentaacrylate, dipentaerythritol hexaacrylate, 1,4-butylene glycol diacrylate, 1,6-hexanediol diacrylate; Cyclic aliphatic skeleton-containing acrylates such as dicyclopentadiene dimethoxydiacrylate; Examples include acrylate compounds such as polyethylene glycol diacrylate, oligoester acrylate, urethane acrylate oligomer, epoxy-modified acrylate, polyether acrylate, and itaconic acid oligomer.
  • the molecular weight of the energy beam polymerizable compound is preferably 100 to 30,000, and more preferably 300 to 10,000.
  • the energy ray polymerizable compound contained in the pressure-sensitive adhesive composition (i) may be only one type, or two or more types.
  • the content of the energy ray polymerizable compound in the pressure-sensitive adhesive composition (i) is preferably 1 to 125 parts by mass with respect to 100 parts by mass of the acrylic resin, and 10 to 125 parts by mass. It is more preferable.
  • the pressure-sensitive adhesive composition (i) may contain a photopolymerization initiator in addition to the acrylic resin and the energy beam polymerizable compound.
  • the photopolymerization initiator may be a known one, and specifically, for example, 4- (2-hydroxyethoxy) phenyl (2-hydroxy-2-propyl) ketone, ⁇ -hydroxy- ⁇ , ⁇ ′-dimethyl Acetophenone, 2-methyl-2-hydroxypropiophenone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-1- ⁇ 4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl ⁇ -2 ⁇ -ketol compounds such as methyl-propan-1-one; Acetophenone compounds such as methoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinoprop
  • the photopolymerization initiator contained in the pressure-sensitive adhesive composition (i) may be one kind or two or more kinds.
  • the content of the photopolymerization initiator in the pressure-sensitive adhesive composition (i) is 0.1 to 10 parts by mass with respect to 100 parts by mass of the energy beam polymerizable compound. It is preferably 1 to 5 parts by mass.
  • the effect by using a photoinitiator is fully acquired because the said content of a photoinitiator is more than the said lower limit.
  • production of the by-product from an excess photoinitiator is suppressed because the said content of a photoinitiator is below the said upper limit, and hardening of an adhesive layer advances more favorably.
  • the pressure-sensitive adhesive composition (i) may contain a crosslinking agent in addition to the acrylic resin and the energy beam polymerizable compound.
  • a crosslinking agent examples include organic polyvalent isocyanate compounds and organic polyvalent imine compounds.
  • organic polyvalent isocyanate compound examples include aromatic polyvalent isocyanate compounds, aliphatic polyvalent isocyanate compounds, alicyclic polyvalent isocyanate compounds, trimers of these compounds, isocyanurates, adducts, and the aromatic And a terminal isocyanate urethane prepolymer obtained by reacting an aliphatic polyvalent isocyanate compound, an aliphatic polyvalent isocyanate compound, or an alicyclic polyvalent isocyanate compound and a polyol compound.
  • the adduct is composed of the aromatic polyvalent isocyanate compound, the aliphatic polyvalent isocyanate compound or the alicyclic polyvalent isocyanate compound, and low molecular activity such as ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane or castor oil.
  • a reactant with a hydrogen-containing compound is meant.
  • 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
  • a polyol such as propane. ; Lysine diisocyanate.
  • 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.
  • an isocyanate compound is used as the crosslinking agent
  • the crosslinking agent has an isocyanate group and the acrylic resin has a hydroxyl group, a crosslinked structure can be easily introduced into the pressure-sensitive adhesive layer by a reaction between the isocyanate group and the hydroxyl group.
  • the cross-linking agent contained in the pressure-sensitive adhesive composition (i) may be one type or two or more types.
  • the content of the crosslinking agent in the pressure-sensitive adhesive composition (i) is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the acrylic resin. It is more preferably 1 to 16 parts by mass.
  • the pressure-sensitive adhesive composition (i) preferably further contains a solvent in addition to the acrylic resin and the energy beam polymerizable compound.
  • 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. As for the solvent which adhesive composition (i) contains, only 1 type may be sufficient and 2 or more types may be sufficient.
  • the content of the solvent is preferably 40 to 90% by mass, and more preferably 50 to 80% by mass.
  • the pressure-sensitive adhesive composition (i) contains, in addition to the acrylic resin and the energy beam polymerizable compound, other components not corresponding to the photopolymerization initiator, the crosslinking agent, and the solvent within a range not impairing the effects of the present invention. You may contain.
  • the other components may be known ones and can be arbitrarily selected according to the purpose, and are not particularly limited. Preferred examples include dyes, pigments, deterioration inhibitors, antistatic agents, flame retardants, and silicone compounds. And various additives such as a chain transfer agent.
  • the said other component which an adhesive composition (i) contains may be only 1 type, and 2 or more types may be sufficient as it.
  • the pressure-sensitive adhesive composition (ii) is an acrylic resin having a hydroxyl group and having a polymerizable group in the side chain (for example, having a hydroxyl group and having a polymerizable group in the side chain via a urethane bond). And an isocyanate-based crosslinking agent as essential components.
  • the acrylic resin has a polymerizable group in the side chain, so that the energy ray polymerizable compound is used as in the case of the pressure-sensitive adhesive composition (i).
  • the peelability from the adherend is improved due to the reduced adhesiveness of the pressure-sensitive adhesive layer after the polymerization reaction (curing), and the pick-up property of the semiconductor chip with a protective film is improved.
  • the description of “acrylic resin” in the pressure-sensitive adhesive composition (ii) means “acrylic resin having a polymerizable group in a side chain” unless otherwise specified. To do.
  • acrylic resin having a polymerizable group in the side chain
  • examples of the acrylic resin having a polymerizable group in the side chain include hydroxyl groups such as a hydroxyl group-free (meth) acrylate ester having no hydroxyl group and a hydroxyl group-containing (meth) acrylate ester having a hydroxyl group.
  • Examples of the hydroxyl group-free (meth) acrylic acid ester include those other than the hydroxyl group-containing (meth) acrylic acid ester among the (meth) acrylic acid esters in the pressure-sensitive adhesive composition (i). Moreover, as said hydroxyl-containing compound, the same thing as the hydroxyl-containing (meth) acrylic acid ester in adhesive composition (i) is mentioned.
  • Each of the hydroxyl group-free (meth) acrylic acid ester and the hydroxyl group-containing compound constituting the acrylic resin may be one type or two or more types.
  • Examples of the compound having an isocyanate group and a polymerizable group include isocyanate group-containing (meth) acrylic acid esters such as 2-methacryloyloxyethyl isocyanate.
  • the compound which has the said isocyanate group and polymeric group which comprises the said acrylic resin may be only 1 type, and 2 or more types may be sufficient as it.
  • the acrylic resin contained in the pressure-sensitive adhesive composition (ii) may be one kind or two or more kinds.
  • the content of the acrylic resin in the pressure-sensitive adhesive composition (ii) is preferably 80 to 99% by mass, based on the total amount of all the components other than the solvent in the pressure-sensitive adhesive composition (ii), More preferably, it is 97 mass%.
  • isocyanate-based crosslinking agent As said isocyanate type crosslinking agent, the same thing as the said organic polyvalent isocyanate compound which is a crosslinking agent in adhesive composition (i) is mentioned, for example.
  • the isocyanate-based crosslinking agent contained in the pressure-sensitive adhesive composition (ii) may be only one type, or two or more types.
  • the number of moles of isocyanate groups possessed by the isocyanate-based crosslinking agent in the pressure-sensitive adhesive composition (ii) is 0.2 to 3 times the number of moles of hydroxyl groups possessed by the acrylic resin in the pressure-sensitive adhesive composition (ii). Preferably there is.
  • the number of moles of the isocyanate group is equal to or more than the lower limit, the peelability from the adherend due to the decrease in the tackiness of the pressure-sensitive adhesive layer after curing is improved, and the pick-up property of the semiconductor chip with a protective film is improved.
  • production of the by-product by reaction of isocyanate type crosslinking agents can be suppressed more because the said mole number of an isocyanate group is below the said upper limit.
  • the content of the isocyanate-based crosslinking agent in the pressure-sensitive adhesive composition (ii) may be adjusted as appropriate so that the number of moles of the isocyanate group falls within the above-mentioned range.
  • the content is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 15 parts by mass, and 0.3 to 12 parts by mass with respect to 100 parts by mass of the resin content. Particularly preferred.
  • the pressure-sensitive adhesive composition (ii) may contain a photopolymerization initiator in addition to the acrylic resin and the isocyanate-based crosslinking agent.
  • a photopolymerization initiator the same thing as the case of adhesive composition (i) is mentioned, for example.
  • the photopolymerization initiator contained in the pressure-sensitive adhesive composition (ii) may be only one type or two or more types.
  • the content of the photopolymerization initiator in the pressure-sensitive adhesive composition (ii) is preferably 0.05 to 20 parts by mass with respect to 100 parts by mass of the acrylic resin. .
  • the effect by using a photoinitiator is fully acquired because the said content of a photoinitiator is more than the said lower limit.
  • production of the by-product from an excess photoinitiator is suppressed because the said content of a photoinitiator is below the said upper limit, and hardening of an adhesive layer advances more favorably.
  • the pressure-sensitive adhesive composition (ii) preferably further contains a solvent in addition to the acrylic resin and the isocyanate-based crosslinking agent.
  • a solvent in addition to the acrylic resin and the isocyanate-based crosslinking agent.
  • 1 type may be sufficient and 2 or more types may be sufficient as it.
  • the content of the solvent is preferably 40 to 90% by mass, more preferably 50 to 80% by mass.
  • the pressure-sensitive adhesive composition (ii) contains, in addition to the acrylic resin and the isocyanate-based crosslinking agent, other components that do not correspond to the photopolymerization initiator and the solvent, as long as the effects of the present invention are not impaired. Also good.
  • the same thing as the case of adhesive composition (i) is mentioned, for example.
  • the said other component which an adhesive composition (ii) contains may be only 1 type, and 2 or more types may be sufficient as it.
  • the pressure-sensitive adhesive composition containing a component that is polymerized by irradiation with energy rays has been described.
  • a pressure-sensitive adhesive composition that does not contain a component that is polymerized by irradiation with energy rays is used.
  • the pressure-sensitive adhesive layer may be non-energy ray curable without energy ray curable.
  • Preferred examples of such a non-energy ray-curable pressure-sensitive adhesive composition include an acrylic resin and a crosslinking agent (hereinafter, sometimes abbreviated as “pressure-sensitive adhesive composition (iii)”). And may contain optional components such as a solvent and other components not corresponding to the solvent.
  • ⁇ Adhesive composition (iii)> The acrylic resin, crosslinking agent, solvent and other components contained in the pressure-sensitive adhesive composition (iii) are all the same as those in the pressure-sensitive adhesive composition (i).
  • the content of the acrylic resin in the pressure-sensitive adhesive composition (iii) is preferably 40 to 99% by mass with respect to the total amount of all the components other than the solvent in the pressure-sensitive adhesive composition (iii), and is preferably 50 to It is more preferable that it is 93 mass%.
  • the content of the crosslinking agent in the pressure-sensitive adhesive composition (iii) is preferably 3 to 30 parts by mass and more preferably 5 to 25 parts by mass with respect to 100 parts by mass of the acrylic resin. .
  • the pressure-sensitive adhesive composition (iii) is the same as the pressure-sensitive adhesive composition (i) except for the points described above.
  • the pressure-sensitive adhesive compositions such as pressure-sensitive adhesive compositions (i) to (iii) include the components for constituting each pressure-sensitive adhesive composition, such as the pressure-sensitive adhesive and components other than the pressure-sensitive adhesive as necessary. It is obtained by blending.
  • the order of addition at the time of blending each component is not particularly limited, and two or more components may be added simultaneously.
  • the method of mixing each component at the time of compounding is not particularly limited, from a known method such as a method of mixing by rotating a stirrer or a stirring blade; a method of mixing using a mixer; a method of mixing by applying ultrasonic waves What is necessary is just to select suitably.
  • the temperature and time during the addition and mixing of each component are not particularly limited as long as each compounding component does not deteriorate, and may be adjusted as appropriate, but the temperature is preferably 15 to 30 ° C.
  • the protective film-forming film may be either thermosetting or energy ray-curable.
  • the film for forming a protective film is cured and finally becomes a protective film having high impact resistance.
  • This protective film prevents the occurrence of cracks in the semiconductor chip after the dicing process, for example.
  • the protective film-forming film may be referred to as a thermosetting protective film-forming composition or an energy ray-curable protective film-forming composition (hereinafter referred to as a “protective film-forming composition”). ).
  • the protective film-forming film may be only one layer (single layer), or may be two or more layers. In the case of a plurality of layers, these layers may be the same or different from each other. The combination is not particularly limited.
  • the thickness of the protective film-forming film is not particularly limited, but is preferably 1 to 100 ⁇ m, more preferably 5 to 75 ⁇ m, and particularly preferably 5 to 50 ⁇ m.
  • the thickness of the protective film-forming film is equal to or more than the lower limit value, the adhesive force to the adherend semiconductor wafer and semiconductor chip is further increased.
  • the protective film which is a cured product, can be more easily cut using a shearing force when the semiconductor chip is picked up.
  • 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.
  • 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 may be performed by a known method, for example, air knife coater, blade coater, bar coater, gravure coater, roll coater, roll knife coater, curtain coater, die coater, Examples include a method using various coaters such as a knife coater, a screen coater, a Meyer bar coater, and a kiss coater.
  • 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, drying is preferably performed at 70 to 130 ° C. for 10 seconds to 5 minutes.
  • composition for forming protective film (III-1) 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 abbreviated as “composition for forming protective film (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 protective film-forming composition (III-1) and the thermosetting protective film-forming film may be only one type, two or more types, or two or more types. These combinations and ratios 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 10,000 to 2,000,000, and more preferably 100,000 to 1500,000.
  • Mw weight average molecular weight
  • the shape stability (time stability during storage) of the thermosetting protective film-forming film is improved.
  • 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 glass transition temperature (Tg) of the acrylic resin is preferably ⁇ 60 to 70 ° C., and more preferably ⁇ 30 to 50 ° C.
  • 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 is suppressed, and the peelability of the support sheet is improved.
  • the adhesive force with the to-be-adhered body of the thermosetting protective film formation film and a protective film improves because Tg of acrylic resin is below the said upper limit.
  • 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 the acrylic resin (hereinafter sometimes simply referred to as “thermoplastic resin”) may be used in combination with the 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 to 100,000, more preferably 3000 to 80,000.
  • the glass transition temperature (Tg) of the thermoplastic resin is preferably ⁇ 30 to 150 ° C., and more preferably ⁇ 20 to 120 ° C.
  • thermoplastic resin examples include polyester, polyurethane, phenoxy resin, polybutene, polybutadiene, and polystyrene.
  • thermoplastic resin contained in the protective film-forming composition (III-1) and the thermosetting protective film-forming film may be only one kind, two kinds or more, and when there are two kinds or more, These combinations and ratios can be arbitrarily selected.
  • 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 of the thermosetting protective film forming film
  • the content of (A) is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and 15 to 35% by mass, regardless of the type of the polymer component (A). It is particularly preferred.
  • the polymer component (A) may also correspond to the thermosetting component (B).
  • the protective film-forming composition (III-1) contains components corresponding to both the polymer component (A) and the thermosetting component (B)
  • the protective film-forming composition is used.
  • 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 protective film-forming composition (III-1) and the thermosetting protective film-forming film may be one kind, two kinds or more, and two kinds or more. In this case, the combination and ratio 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 protective film-forming composition (III-1) and the thermosetting protective film-forming film may be only one type, two or more types, or two or more types. These combinations and ratios 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, the reliability of the package obtained using the composite sheet for forming a protective film is improved by using an epoxy resin having an unsaturated hydrocarbon group.
  • Examples of the epoxy resin having an unsaturated hydrocarbon group include compounds obtained by converting a part of the epoxy group of a polyfunctional epoxy resin into a group having an unsaturated hydrocarbon group. Such a compound can be obtained, for example, by addition reaction of (meth) acrylic acid or a derivative thereof to an epoxy group. 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 “derivative” means one obtained by substituting one or more hydrogen atoms of the original compound with a group (substituent) other than a hydrogen atom.
  • the number average molecular weight of the epoxy resin (B1) is not particularly limited, but is 300 to 30000 from the viewpoint of the curability of the thermosetting protective film-forming film and the strength and heat resistance of the cured protective film. Preferably, it is 300 to 10,000, more preferably 300 to 3000.
  • the epoxy equivalent of the epoxy resin (B1) is preferably 100 to 1100 g / eq, and more preferably 150 to 1000 g / eq.
  • 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 phenolic resins, biphenols, novolac-type phenolic resins, dicyclopentadiene-based phenolic resins, and aralkylphenolic 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, and the 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 the 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 thermosetting agent (B2) is a solid that is solid at room temperature and does not exhibit curing activity with respect to the epoxy resin (B1), while being dissolved by heating and exhibits curing activity with respect to the epoxy resin (B1) It is preferably a curing agent (hereinafter sometimes abbreviated as “thermally active latent epoxy resin curing agent”).
  • the thermoactive latent epoxy resin curing agent is stably dispersed in the epoxy resin (B1) in the thermosetting protective film-forming film at room temperature, but is compatible with the epoxy resin (B1) by heating. Reacts with the epoxy resin (B1).
  • the thermally active latent epoxy resin curing agent the storage stability of the protective film-forming composite sheet is significantly improved.
  • thermosetting deterioration of the thermosetting protective film-forming film is effectively suppressed.
  • thermosetting degree by heating of the film for thermosetting protective film formation becomes higher, the pick-up property of the semiconductor chip with a protective film mentioned later improves more.
  • thermally active latent epoxy resin curing agent examples include onium salts, dibasic acid hydrazides, dicyandiamide, and amine adducts of curing agents.
  • thermosetting agents (B2) for example, the number average molecular weight of resin components such as polyfunctional phenolic resin, novolac-type phenolic resin, dicyclopentadiene-based phenolic resin, aralkylphenolic resin, etc. is preferably 300 to 30000, It is more preferably 400 to 10,000, and particularly preferably 500 to 3000.
  • the molecular weight of non-resin components such as biphenol and dicyandiamide is not particularly limited, but is preferably 60 to 500, for example.
  • thermosetting agent (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. 0 parts by mass with respect to 100 parts by mass of the epoxy resin (B1).
  • the amount is preferably 1 to 500 parts by mass, and more preferably 1 to 200 parts by mass.
  • the content of the thermosetting component (B) (for example, the total content of the epoxy resin (B1) and the thermosetting agent (B2)) Is preferably 1 to 100 parts by weight, more preferably 1.5 to 85 parts by weight, with respect to 100 parts by weight of the polymer component (A). It is particularly preferred that 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.
  • the protective film-forming 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 protective film-forming 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 protective film-forming composition (III-1) and the thermosetting protective film-forming film may be only one type, two or more types, or two or more types. These combinations and ratios can be arbitrarily selected.
  • the content of the curing accelerator (C) in the protective film-forming composition (III-1) and the thermosetting protective film-forming film is such that the thermosetting component (B)
  • the content is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass.
  • 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.
  • 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. In this case, the effect of suppressing the segregation by moving toward the adhesion interface with the adherend is increased, and the reliability of the package obtained using the composite sheet for forming a protective film is further improved.
  • the protective film-forming 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 package 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 of silica, alumina, talc, calcium carbonate, titanium white, bengara, silicon carbide, boron nitride, and the like; beads formed by spheroidizing these inorganic fillers; surface modification of these inorganic fillers Products; single crystal fibers of these inorganic fillers; glass fibers and the like.
  • the inorganic filler is preferably silica or alumina.
  • the filler (D) contained in the protective film-forming composition (III-1) and the thermosetting protective film-forming film may be only one type, two or more types, or two or more types. Their combination and 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 protective film forming composition (III-1) (that is, thermosetting protection)
  • the content of the filler (D) in the film-forming film is preferably 5 to 80% by mass, more preferably 7 to 60% by mass. Adjustment of said thermal expansion coefficient becomes easier because content of a filler (D) is such a range.
  • the protective film-forming 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.
  • the coupling agent (E) the protective film obtained by curing the thermosetting protective film-forming film has improved water resistance without impairing heat resistance.
  • 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 protective film-forming composition (III-1) and the thermosetting protective film-forming film may be one kind, two kinds or more, and two kinds or more These combinations and ratios can be arbitrarily selected.
  • the content of the coupling agent (E) in the protective film-forming composition (III-1) and the thermosetting protective film-forming film is such that the polymer component (A) and The amount is preferably 0.03 to 20 parts by weight, more preferably 0.05 to 10 parts by weight, and more preferably 0.1 to 5 parts by weight with respect to 100 parts by weight as the total content of the thermosetting component (B).
  • the part by mass is particularly preferred.
  • 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.
  • production of an outgas is suppressed more because the said content of a coupling agent (E) is below the said upper limit.
  • Crosslinking agent (F) 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 protective film-forming composition (III-1) and the thermosetting protective film-forming film contain a crosslinking agent (F) for bonding the functional group with another compound to crosslink. Also good. 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 protective film-forming composition (III-1) and the thermosetting protective film-forming film may be only one type, two or more types, or two or more types. Their combination and ratio can be arbitrarily selected.
  • the content of the crosslinking agent (F) in the protective film-forming composition (III-1) is 0. 0 parts by mass relative to 100 parts by mass of the polymer component (A).
  • the amount is preferably 01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and particularly preferably 0.5 to 5 parts by mass.
  • 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 content of the crosslinking agent (F) is not more than the upper limit value, the adhesive force with the support sheet of the thermosetting protective film forming film, the semiconductor wafer of the thermosetting protective film forming film, or It is suppressed that the adhesive force with a semiconductor chip falls too much.
  • the effects of the present invention can be sufficiently obtained without using the crosslinking agent (F).
  • the protective film-forming 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 to 30000, and more preferably 300 to 10000.
  • 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 protective film-forming 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 are as follows: Can be arbitrarily selected.
  • the content of the energy ray curable resin (G) is preferably 1 to 95% by mass, more preferably 2 to 90% by mass. It is particularly preferable that the content be ⁇ 85% by mass.
  • Photopolymerization initiator (H) When the protective film-forming composition (III-1) contains the energy beam curable resin (G), the photopolymerization initiator (H) is used to efficiently advance the polymerization reaction of the energy beam curable resin (G). ) May be contained.
  • Examples of the photopolymerization initiator (H) in the protective film-forming composition (III-1) include the same photopolymerization initiator as in the pressure-sensitive adhesive composition (ii).
  • the photopolymerization initiator (H) contained in the protective film-forming composition (III-1) may be only one type, or two or more types, and when there are two or more types, the combination and ratio thereof are arbitrary. Can be selected.
  • the content of the photopolymerization initiator (H) is 0.1 to 20 parts by mass 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 protective film-forming 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 protective film-forming composition (III-1) and the thermosetting protective film-forming film may be only one type, two or more types, or two or more types. Their combination and 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.
  • the protective film may be printed by laser irradiation, adjusting the content of the colorant (I) of the thermosetting protective film-forming film, and adjusting the light transmittance of the protective film, Print visibility 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 ratio of the content of the colorant (I) to the total content of all components other than the solvent is preferably 0.1 to 10% by mass, more preferably 0.1 to 7.5% by mass, and 0.1 to 5% by mass. It is particularly preferred that 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.
  • the protective film-forming composition (III-1) and the thermosetting protective film-forming film may contain a general-purpose additive (J) within a range not impairing the effects of the present invention.
  • 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 (I) contained in the protective film-forming composition (III-1) and the thermosetting protective film-forming film may be only one, two or more, or two or more These combinations and ratios can be arbitrarily selected.
  • the content of the general-purpose additive (I) in the protective film-forming 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 for forming a protective film (III-1) preferably further contains a solvent.
  • the protective film-forming 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 and butyl acetate; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran; amides (compounds having an amide bond) such as dimethylformamide and N-methylpyrrolidone;
  • the solvent contained in the protective film-forming composition (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 protective film-forming composition (III-1) is preferably methyl ethyl ketone or the like from the viewpoint that the components in the protective film-forming composition (III-1) can be more uniformly mixed.
  • thermosetting protective film-forming composition such as the protective film-forming 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 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 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 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 materials.
  • 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.
  • Application of the energy ray curable protective film-forming composition may be performed 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. And a method using various coaters such as a knife coater, a screen coater, a Meyer bar coater, and a kiss coater.
  • 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 to 130 ° C. for 10 seconds to 5 minutes.
  • composition for forming protective film (IV-1) for example, the composition for forming an energy ray-curable protective film (IV-1) containing the energy ray-curable component (a) (in this specification, simply And the like (may be abbreviated as “protective film-forming composition (IV-1)”).
  • the energy ray-curable component (a) is a component that is cured by irradiation with energy rays, and is also a component for imparting film forming property, flexibility, and the like to the energy ray-curable protective film-forming film.
  • Examples of the energy ray-curable component (a) include a polymer (a1) having an energy ray-curable group and a weight average molecular weight of 80000 to 2000000, and an energy ray-curable group and a molecular weight of 100 to 80000.
  • a compound (a2) is mentioned.
  • the polymer (a1) may be 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) formed by addition reaction of a 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.
  • acrylic monomer having a functional group examples include a hydroxyl group-containing monomer, a carboxy group-containing monomer, an amino group-containing monomer, a substituted amino group-containing monomer, and an epoxy group-containing monomer.
  • hydroxyl group-containing monomer examples include hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, (meth) Hydroxyalkyl (meth) acrylates such as 2-hydroxybutyl acrylate, 3-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate; non- (meth) acrylic non-methacrylates such as vinyl alcohol and allyl alcohol Saturated alcohol (unsaturated alcohol which does not have a (meth) acryloyl skeleton) etc. are mentioned.
  • Examples of the carboxy group-containing monomer include ethylenically unsaturated monocarboxylic acids (monocarboxylic acids having an ethylenically unsaturated bond) such as (meth) acrylic acid and crotonic acid; fumaric acid, itaconic acid, maleic acid, citracone Ethylenically unsaturated dicarboxylic acids such as acids (dicarboxylic acids having an ethylenically unsaturated bond); anhydrides of the ethylenically unsaturated dicarboxylic acids; carboxyalkyl esters of (meth) acrylic acid such as 2-carboxyethyl methacrylate, etc. It is done.
  • monocarboxylic acids having an ethylenically unsaturated bond such as (meth) acrylic acid and crotonic acid
  • fumaric acid, itaconic acid maleic acid, citracone
  • Ethylenically unsaturated dicarboxylic acids such as acids (dica
  • the acrylic monomer having a functional group is preferably a hydroxyl group-containing monomer or a carboxy group-containing monomer, more preferably a hydroxyl group-containing monomer.
  • the acrylic monomer having the functional group that constitutes the acrylic polymer (a11) may be only one type, or two or more types, and when there are two or more types, the combination and ratio thereof are arbitrary. You can choose.
  • acrylic monomer having no functional group examples include, 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 to 50 mass. %, More preferably 1 to 40% by mass, and particularly preferably 3 to 30% by mass.
  • the acrylic resin (a1-1) obtained by copolymerization of the acrylic polymer (a11) and the energy ray-curable compound (a12) The content of the linear curable group 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 the acrylic resin (a1-1) is preferably 1 to 40% by mass, more preferably 2 to 30% by mass. A content of ⁇ 20% by weight is 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). Those having the above are preferred, and those having an isocyanate group as the group are more preferred. For example, when the energy beam curable compound (a12) has an isocyanate group as the group, the isocyanate group easily reacts with the hydroxyl group of the acrylic polymer (a11) having a hydroxyl group as the functional group.
  • the energy beam curable compound (a12) preferably has 1 to 5 energy beam curable groups in one molecule, and more preferably has 1 to 2 energy beam curable groups.
  • Examples of the energy ray curable compound (a12) include 2-methacryloyloxyethyl isocyanate, meta-isopropenyl- ⁇ , ⁇ -dimethylbenzyl isocyanate, methacryloyl isocyanate, allyl isocyanate, 1,1- (bisacryloyloxymethyl).
  • Ethyl isocyanate An acryloyl monoisocyanate compound obtained by reacting a diisocyanate compound or polyisocyanate compound with hydroxyethyl (meth) acrylate; Examples thereof include an acryloyl monoisocyanate compound obtained by a reaction of a diisocyanate compound or a polyisocyanate compound, a polyol compound, and hydroxyethyl (meth) acrylate.
  • the energy beam curable compound (a12) is preferably 2-methacryloyloxyethyl isocyanate.
  • the energy ray-curable compound (a12) constituting the acrylic resin (a1-1) may be only one type, or two or more types, and when there are two or more types, the combination and ratio thereof are arbitrary. Can be selected.
  • the content of the energy beam curable group derived from the energy beam curable compound (a12) with respect to the content of the functional group derived from the acrylic polymer (a11). is preferably 20 to 120 mol%, more preferably 35 to 100 mol%, and particularly preferably 50 to 100 mol%. When the ratio of the content is within such a range, the adhesive force of the protective film 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 polymer (a1) has a weight average molecular weight (Mw) of preferably 100,000 to 2,000,000, and more preferably 300,000 to 1500,000.
  • Mw weight average molecular weight
  • 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 protective film-forming composition (IV-1) and the energy ray-curable protective film-forming film may be only one kind, two kinds or more, and two kinds or more. In such a case, the combination and ratio thereof can be arbitrarily selected.
  • Compound (a2) having an energy ray curable group and a molecular weight of 100 to 80,000 examples include a group containing an energy ray curable double bond. Preferred examples include (meth) An acryloyl group, a vinyl group, etc. are mentioned.
  • the compound (a2) is not particularly limited as long as it satisfies the above conditions, but has a low molecular weight compound having an energy ray curable group, an epoxy resin having an energy ray curable group, and an energy ray curable group.
  • a phenol resin etc. are mentioned.
  • examples of the low molecular weight compound having an energy ray curable group include polyfunctional monomers or oligomers, and an acrylate compound having a (meth) acryloyl group is preferable.
  • examples of the acrylate compound include 2-hydroxy-3- (meth) acryloyloxypropyl methacrylate, polyethylene glycol di (meth) acrylate, propoxylated ethoxylated bisphenol A di (meth) acrylate, and 2,2-bis [4 -((Meth) acryloxypolyethoxy) phenyl] propane, ethoxylated bisphenol A di (meth) acrylate, 2,2-bis [4-((meth) acryloxydiethoxy) phenyl] propane, 9,9-bis [4- (2- (meth) acryloyloxyethoxy) phenyl] fluorene, 2,2-bis [4-((meth) acryloxypolypropoxy) phenyl] propane,
  • the epoxy resin having an energy ray curable group and the phenol resin having an energy ray curable group are described in, for example, paragraph 0043 of “JP 2013-194102 A”. Things can be used.
  • Such a resin corresponds to a resin constituting a thermosetting component described later, but is treated as the compound (a2) in the present invention.
  • the compound (a2) preferably has a weight average molecular weight of 100 to 30,000, more preferably 300 to 10,000.
  • the compound (a2) contained in the protective film-forming composition (IV-1) and the energy ray-curable protective film-forming film may be one kind, two kinds or more, or two kinds or more These combinations and ratios can be arbitrarily selected.
  • Polymer (b) having no energy ray curable group When the protective film-forming composition (IV-1) and the energy ray-curable protective film-forming film contain the compound (a2) as the energy ray-curable component (a), an energy ray-curable group is further added. It is also preferable to contain the polymer (b) that is not included.
  • the polymer (b) may be crosslinked at least partially 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. 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 1-20.
  • the mass is preferably 2% by mass, and more preferably 2 to 10% by mass. 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 10,000 to 2,000,000 from the viewpoint that the film-forming property of the protective film-forming composition (IV-1) becomes better. It is preferably 100000 to 1500,000.
  • the “weight average molecular weight” is as described above.
  • the polymer (b) having no energy ray-curable group contained in the protective film-forming composition (IV-1) and the energy ray-curable protective film-forming film may be only one kind or two or more kinds. However, when there are two or more kinds, the combination and ratio thereof can be arbitrarily selected.
  • Examples of the protective film-forming composition (IV-1) include those containing one or both of the polymer (a1) and the compound (a2).
  • the protective film-forming composition (IV-1) contains the compound (a2), it preferably contains a polymer (b) that does not have an energy ray-curable group. It is also preferable to contain (a1). Further, the protective film-forming composition (IV-1) does not contain the compound (a2) and contains both the polymer (a1) and the polymer (b) having no energy ray-curable group. It may be.
  • the protective film-forming composition (IV-1) contains the polymer (a1), the compound (a2) and the polymer (b) having no energy ray-curable group
  • the protective film-forming composition In (IV-1) the content of the compound (a2) is 10 to 10 parts per 100 parts by mass of the total content of the polymer (a1) and the polymer (b) having no energy ray-curable group.
  • the amount is preferably 400 parts by mass, and more preferably 30 to 350 parts by mass.
  • the total content of the energy beam curable component (a) and the polymer (b) having no energy beam curable group with respect to the total content of components other than the solvent is 5 to 90% by mass. It is preferably 10 to 80% by mass, more preferably 20 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 protective film-forming composition (IV-1) includes a thermosetting component, a photopolymerization initiator, a filler, a coupling agent, a crosslinking agent, a colorant, You may contain 1 type, or 2 or more types selected from the group which consists of a general purpose additive.
  • the protective film forming composition (IV-1) containing the energy ray curable component and the thermosetting component the formed energy ray curable protective film forming film is deposited by heating. The adhesive force to the body is improved, and the strength of the protective film formed from this energy ray-curable protective film-forming film is also improved.
  • thermosetting component photopolymerization initiator, filler, coupling agent, crosslinking agent, colorant and general-purpose additive in the protective film-forming composition (IV-1), the protective film-forming composition, respectively.
  • Thermosetting component (B), photopolymerization initiator (H), filler (D), coupling agent (E), crosslinking agent (F), colorant (I) and general-purpose additives in (III-1) The same thing as (J) is mentioned.
  • each of the thermosetting component, the photopolymerization initiator, the filler, the coupling agent, the crosslinking agent, the colorant, and the general-purpose additive is used alone.
  • two or more types may be used in combination, and when two or more types are used in combination, their combination and ratio can be arbitrarily selected.
  • the contents of the thermosetting component, photopolymerization initiator, filler, coupling agent, crosslinking agent, colorant and general-purpose additive in the protective film-forming composition (IV-1) are appropriately adjusted according to the purpose. There is no particular limitation.
  • the protective film-forming composition (IV-1) preferably further contains a solvent since its handleability is improved by dilution.
  • the solvent contained in the protective film forming composition (IV-1) include the same solvents as those in the protective film forming composition (III-1).
  • the solvent contained in the protective film-forming 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 protective film-forming 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 to 30 ° C.
  • the coating layer what contains the hardened
  • the said energy-beam polymeric compound is (meth) acrylic acid or its derivative (s).
  • the protective sheet-forming composite sheet has not only a function of forming a protective film for protecting the back surface of the semiconductor chip obtained by dicing, but also a function as a dicing sheet when dicing a semiconductor wafer, for example. It can be combined. When the semiconductor wafer is diced, the semiconductor wafer to which the protective film-forming composite sheet is attached may be expanded. In that case, the protective film-forming composite sheet is required to have appropriate flexibility.
  • a flexible resin such as polypropylene may be selected as a material constituting the support sheet. On the other hand, such a flexible resin may be deformed by heating or may have wrinkles. Therefore, it can be said that the coating layer is preferably one that can be formed by curing the composition as a raw material not by heat curing but by irradiation with energy rays.
  • the thickness of the coating layer is not particularly limited, but is preferably 0.1 to 20 ⁇ m, more preferably 0.4 to 15 ⁇ m, and particularly preferably 0.8 to 10 ⁇ m.
  • the thickness of the coating layer is equal to or more than the lower limit value, it becomes easier to reduce the surface roughness Ra on the surface of the coating layer opposite to the side in contact with the support sheet. The effect of suppressing blocking of the forming composite sheet is further increased.
  • the thickness of the coating layer is equal to or less than the upper limit value, the state of the semiconductor wafer after the protective film-forming composite sheet is pasted is examined by an infrared camera or the like through the sheet. A clearer inspection image can be acquired, and further, dicing of the semiconductor wafer with expansion can be performed more easily.
  • the coating layer covers the uneven surface of the support sheet as described above, so that the contact surface with the support sheet can be an uneven surface, but the thickness of the coating layer is the convex portion on the uneven surface of the coating layer. In a region including, the tip of the convex portion may be calculated as one starting point.
  • the surface roughness Ra on the surface of the coating layer opposite to the side in contact with the support sheet is preferably 0.5 ⁇ m or less, more preferably 0.4 ⁇ m or less, and 0.3 ⁇ m. More preferably, it is more preferably 0.2 ⁇ m or less.
  • the surface roughness Ra of the coating layer is not more than the upper limit value, laser printing can be performed more clearly on the protective film.
  • the lower limit value of the surface roughness Ra on the surface of the coating layer on the side opposite to the side in contact with the support sheet is not particularly limited, but may be 0.005 ⁇ m, for example.
  • the surface roughness Ra of the coating layer is, for example, the surface roughness Ra of the surface of the support sheet provided with the coating layer, the thickness of the coating layer, and the application of a coating composition to be described later for forming the coating layer. It can be adjusted by the construction method.
  • the coating layer has a value of [thickness of coating layer ( ⁇ m)] / [surface roughness Ra ( ⁇ m) of the surface of the support sheet provided with the coating layer] of 0.1 to 30 Is more preferable, 0.3 to 20 is more preferable, and 0.5 to 10 is particularly preferable.
  • the value is equal to or greater than the lower limit value, the surface roughness Ra on the surface of the coating layer opposite to the side in contact with the support sheet becomes smaller, and the laser is more clearly formed on the protective film. Printing can be performed, and the effect of suppressing blocking of the protective film-forming composite sheet is further enhanced. Moreover, it is avoided that the thickness of a coating layer becomes excessive because the said value is below the said upper limit.
  • the gloss value of the surface of the coating layer opposite to the side in contact with the support sheet (the support sheet side) is preferably 32 to 95, more preferably 40 to 90, 45 It is particularly preferred that it is .about.85.
  • the gloss value of the coating layer is in such a range, laser printing can be performed more clearly on the protective film.
  • the gloss value of the coating layer is equal to or more than the lower limit value, the state of the semiconductor wafer after the protective film-forming composite sheet is pasted is inspected with an infrared camera or the like through the sheet. A clearer inspection image can be acquired.
  • the gloss value of the coating layer is less than or equal to the upper limit value, the phenomenon that the coating layer shines is similarly suppressed when inspecting the state of the semiconductor wafer, and the inspection image can be more visually recognized by an infrared camera or the like. It becomes easy.
  • the gloss value is a value obtained by measuring the 20 ° specular gloss of the surface of the coating layer from the side opposite to the support sheet side of the coating layer in accordance with JIS K 7105.
  • the measured value of haze from the coating layer side of the composite sheet for forming a protective film is 47% or less, preferably 1 to 47%, more preferably 2 to 40%, more preferably 3 to 30%. It is particularly preferred that When the haze of the composite sheet for forming a protective film is less than or equal to the upper limit value, light scattering is suppressed, and laser printing can be performed more clearly on the protective film. Further, when the state of the semiconductor wafer after the protective film-forming composite sheet is attached is inspected with an infrared camera or the like through the sheet, a clearer inspection image can be acquired.
  • the gloss value of the coating layer can be adjusted by, for example, the thickness of the coating layer, the components of the coating composition to be described later for forming the coating layer, and the like.
  • the measured value of haze from the coating layer side of the protective film-forming composite sheet is, for example, the thickness of each layer constituting the protective film-forming composite sheet, such as a coating layer or a support sheet, for forming each of these layers. It can be adjusted by the components contained in the composition (for example, a coating composition described later).
  • the coating composition is either one or both of silica sol and silica fine particles to which a radical polymerizable unsaturated group-containing organic compound is bonded ( ⁇ ) (hereinafter sometimes abbreviated as “component ( ⁇ )”). And one or more ( ⁇ ) selected from the group consisting of a polyfunctional acrylate monomer and an acrylate prepolymer (hereinafter sometimes abbreviated as “component ( ⁇ )”) are preferred.
  • Component ( ⁇ ) The component ( ⁇ ) lowers the refractive index of the coating layer and lowers the curing shrinkage and the heat and humidity shrinkage of the protective film-forming composite sheet. This suppresses the occurrence of curling in the sheet.
  • silica sol in the component ( ⁇ ) examples include colloidal silica in which silica fine particles are suspended in a colloidal state in an organic solvent such as alcohol or ether derived from ethylene glycol (cellosolve).
  • the average particle diameter of the silica fine particles is preferably 0.001 to 1 ⁇ m, and more preferably 0.03 to 0.05 ⁇ m.
  • the silica fine particles to which the radical polymerizable unsaturated group-containing organic compound in the component ( ⁇ ) is bonded are cross-linked and cured by irradiation with energy rays.
  • a silanol group present on the surface of the silica fine particles reacts with a functional group in the radical polymerizable unsaturated group-containing organic compound.
  • the average particle diameter of the silica fine particles is preferably 0.005 to 1 ⁇ m.
  • the functional group in the radical polymerizable unsaturated group-containing organic compound is not particularly limited as long as it can react with the silanol group in the silica fine particles.
  • radical polymerizable unsaturated group-containing organic compound having the functional group examples include compounds represented by the following general formula (1).
  • R 1 is a hydrogen atom or a methyl group
  • R 2 is a halogen atom or a group represented by any of the following formulas (2a) to (2f)).
  • halogen atom in R 2 for example, elemental chlorine, bromine atom, and an iodine atom.
  • Preferred examples of the radical polymerizable unsaturated group-containing organic compound include (meth) acrylic acid, (meth) acrylic acid chloride, (meth) acrylic acid 2-isocyanatoethyl, (meth) acrylic acid glycidyl, ( Examples include 2,3-iminopropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, (3- (meth) acryloyloxypropyl) trimethoxysilane, and the like.
  • the radical polymerizable unsaturated group-containing organic compound may be used alone or in combination of two or more.
  • the silica fine particles to which the silica sol and the radical polymerizable unsaturated group-containing organic compound are bonded may be each one kind or two kinds or more.
  • silica sol may be used, or only silica fine particles combined with the radical polymerizable unsaturated group-containing organic compound may be used.
  • the silica sol and the radical polymerizable unsaturated group-containing organic compound may be used. You may use together the silica fine particle which the compound couple
  • the content of the component ( ⁇ ) of the coating composition is preferably selected according to the refractive index of the support sheet, but usually the content of silica derived from the component ( ⁇ ) of the coating layer is 20.
  • the amount is preferably ⁇ 60% by mass.
  • the content of silica is not less than the lower limit, the effect of reducing the refractive index of the coating layer and the effect of suppressing the occurrence of curling in the protective film-forming composite sheet are further enhanced.
  • the said content of a silica is below the said upper limit, while the formation of a coating layer becomes easier, the effect which suppresses the fall of the hardness of a coating layer becomes higher.
  • the content of silica derived from the component ( ⁇ ) of the coating layer because the refractive index of the coating layer, ease of formation and hardness, and curling generation suppression in the composite sheet for forming a protective film become better. Is more preferably 20 to 45% by mass.
  • Component ( ⁇ ) is a main photocurable component that forms the coating layer.
  • the polyfunctional acrylate monomer in the component ( ⁇ ) is not particularly limited as long as it is a (meth) acrylic acid derivative having two or more (meth) acryloyl groups in one molecule.
  • Preferred examples of the polyfunctional acrylate monomer include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di ( (Meth) acrylate, hydroxypivalate neopentyl glycol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, caprolactone modified dicyclopentenyl di (meth) acrylate, ethylene oxide modified di (meth) acrylate phosphoric acid, allylated cyclohexyl Di (meth) acrylate, isocyanurate di (meth) acrylate, trimethylolpropane tri
  • the acrylate prepolymer in the component ( ⁇ ) is not particularly limited as long as it is a polymer or oligomer that is a (meth) acrylic ester and has photocurability.
  • Preferred examples of the acrylate prepolymer include polyester acrylate prepolymer, epoxy acrylate prepolymer, urethane acrylate prepolymer, polyol acrylate prepolymer, and the like.
  • polyester acrylate prepolymer for example, a hydroxyl group of a polyester oligomer having a hydroxyl group at both ends of a molecule obtained by a condensation reaction of a polyvalent carboxylic acid and a polyhydric alcohol is esterified with (meth) acrylic acid. And those obtained by esterifying a hydroxyl group at the terminal of an oligomer obtained by addition reaction of an alkylene oxide with a polyvalent carboxylic acid with (meth) acrylic acid.
  • the epoxy acrylate prepolymer include those obtained by reacting an oxirane ring of a relatively low molecular weight bisphenol type epoxy resin or novolac type epoxy resin with (meth) acrylic acid for esterification. .
  • urethane acrylate type prepolymer what is obtained by esterifying the polyurethane oligomer obtained by reaction of polyether polyol or polyester polyol, and polyisocyanate with (meth) acrylic acid is mentioned, for example.
  • polyol acrylate type prepolymer what is obtained by esterifying the hydroxyl group of polyether polyol with (meth) acrylic acid is mentioned, for example.
  • each of the multifunctional acrylate monomer and acrylate prepolymer may be one kind or two kinds or more.
  • the component ( ⁇ ) only the polyfunctional acrylate monomer may be used, or only the acrylate prepolymer may be used, and the polyfunctional acrylate monomer and acrylate prepolymer are used in combination. Also good.
  • the coating composition preferably further contains a solvent in addition to the component ( ⁇ ) and the component ( ⁇ ).
  • a solvent as will be described later, the coating composition can be applied and dried to form a coating film for forming the coating layer more easily.
  • the said solvent may be used individually by 1 type, and may use 2 or more types together.
  • the solvent examples include aliphatic hydrocarbons such as hexane, heptane, and cyclohexane; aromatic hydrocarbons such as toluene and xylene; halogenated hydrocarbons such as methylene chloride and ethylene chloride; methanol, ethanol, propanol, butanol, 1 Alcohols such as methoxy-2-propanol; ketones such as acetone, methyl ethyl ketone, 2-pentanone, isophorone and cyclohexanone; esters such as ethyl acetate and butyl acetate; cellosolves such as 2-ethoxyethanol (ethyl cellosolve) and the like.
  • aliphatic hydrocarbons such as hexane, heptane, and cyclohexane
  • aromatic hydrocarbons such as toluene and xylene
  • halogenated hydrocarbons such as methylene chloride and
  • the coating composition has a monofunctional acrylate-based monomer, a photopolymerization initiator, a photosensitizer, a polymerization inhibitor, as long as the effects of the present invention are not impaired.
  • Various optional components such as a crosslinking agent, an antioxidant, an ultraviolet absorber, a light stabilizer, a leveling agent, and an antifoaming agent may be contained.
  • the said arbitrary component may be used individually by 1 type, and may use 2 or more types together.
  • the monofunctional acrylate monomer as an optional component is a photocurable component and is not particularly limited as long as it is a (meth) acrylic acid derivative having only one (meth) acryloyl group in one molecule.
  • Preferred examples of the monofunctional acrylate monomer include cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate (lauryl (meth) acrylate), and octadecyl (meth) acrylate.
  • Steparyl (meth) acrylate) isobornyl (meth) acrylate and the like.
  • Photopolymerization initiator As said photoinitiator as an arbitrary component, the well-known thing conventionally used with respect to radical polymerization is mentioned.
  • Preferred examples of the photopolymerization initiator include acetophenone compounds, benzophenone compounds, alkylaminobenzophenone compounds, benzyl compounds, benzoin compounds, benzoin ether compounds, benzyldimethylacetal compounds, benzoylbenzoate compounds, ⁇ -Aryl ketone photopolymerization initiators such as acyloxime ester compounds; sulfur-containing photopolymerization initiators such as sulfide compounds and thioxanthone compounds; acylphosphine oxide compounds such as acyl diarylphosphine oxides; anthraquinone compounds Can be mentioned.
  • acylphosphine oxide compounds such as acyl diarylphosphine oxides
  • anthraquinone compounds Can be mentioned.
  • a photoinitiator is unnecessary.
  • the content of the photopolymerization initiator is preferably 0.2 to 10 parts by mass, and 0.5 to 7 parts by mass with respect to 100 parts by mass of the total content of the photocurable components. It is more preferable that
  • the photosensitizer examples include tertiary amines, p-dimethylaminobenzoate, and thiol sensitizers.
  • the content of the photosensitizer is preferably 1 to 20 parts by mass and preferably 2 to 10 parts by mass with respect to 100 parts by mass of the total content of the photocurable components. More preferred.
  • the antioxidant, the ultraviolet absorber and the light stabilizer may be known ones, but may be a reactive antioxidant having a (meth) acryloyl group in the molecule, an ultraviolet absorber and a light stabilizer. preferable. These antioxidants, UV absorbers and light stabilizers bind to the polymer chain formed by irradiation with energy rays, so that dissipation from the cured layer over time is suppressed, and the functions of these components over a long period of time. Is demonstrated.
  • the coating composition preferably contains a silica sol as the component ( ⁇ ), and more preferably contains a silica sol having an average particle size of silica fine particles suspended in a colloidal state of 0.03 to 0.05 ⁇ m. .
  • a silica sol contains such a silica sol, the effect of suppressing blocking of the protective sheet-forming composite sheet is further enhanced.
  • such a silica sol is present more and more unevenly on the surface on the side opposite to the support sheet side and in the vicinity thereof than in other regions, thereby forming the protective film.
  • the effect of suppressing the blocking of the composite sheet is further increased.
  • the coating conditions of the coating composition may be adjusted.
  • the coating composition is, for example, by blending energy ray polymerizable compounds such as the component ( ⁇ ) and the component ( ⁇ ), and other components for constituting the coating composition, if necessary, other components. can get.
  • a coating composition is obtained by the method similar to the case of the above-mentioned adhesive composition except the point from which a compounding component differs, for example.
  • 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.
  • Components other than the solvent in the coating composition may be dissolved, or may be dispersed without dissolving.
  • the concentration and viscosity of each component of the coating composition are not particularly limited as long as the coating composition can be applied.
  • a protective film-forming composite sheet forms a protective film-forming film using the protective film-forming composition, and is coated with the coating composition.
  • a layer can be formed, and a coating layer, a support sheet, and a protective film-forming film can be laminated in this order.
  • the support sheet may be produced by laminating these layers.
  • a pressure-sensitive adhesive layer may be formed using the pressure-sensitive adhesive composition.
  • each layer (coating layer, support sheet, protective film forming film) constituting the protective film forming composite sheet is not particularly limited. Furthermore, the formation of each of these layers from the composition may be performed directly on the surface of the adjacent layer in the state of the protective sheet-forming composite sheet, or may be performed on this surface using a separate release film (release sheet). The formed layer may be bonded to the surface of the adjacent layer in the state of the protective film-forming composite sheet. However, when the surface (back surface) opposite to the surface (front surface) provided with the protective film-forming film of the support sheet is an uneven surface, it is between the coating layer and the uneven surface (back surface) of the support sheet. Furthermore, in order to suppress the formation of voids, the coating layer is preferably formed by directly applying the coating composition to the uneven surface of the support sheet.
  • an example of the preferable manufacturing method of the composite sheet for protective film formation is demonstrated.
  • the coating layer was formed as necessary by applying the coating composition to the uneven surface of the support sheet (in FIGS. 1 and 2, the back surface 10b of the support sheet 10, that is, the back surface 11b of the base material 11), and drying. It is preferably formed by curing the coating film.
  • Coating of the coating composition on the target surface may be performed 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. And a method using various coaters such as a screen coater, a Meyer bar coater, and a kiss coater.
  • the coating composition When the coating composition is applied to the uneven surface of the support sheet, it is preferable to suppress the generation of voids between the coating layer and the uneven surface of the support sheet. By suppressing the generation of the voids, irregular reflection of light at the boundary between the coating layer and the uneven surface of the support sheet is suppressed, and laser printing can be performed more clearly on the surface of the protective film.
  • a coating composition having a low viscosity In order to suppress the generation of the voids, for example, it is preferable to use a coating composition having a low viscosity.
  • the coating composition containing an energy beam polymerizable compound is usually suitable for suppressing the generation of the voids.
  • the drying conditions of the coating composition are not particularly limited, but the coating composition is preferably dried by heating. In this case, for example, it is preferably dried at 70 to 130 ° C. for 0.5 to 5 minutes.
  • the curing conditions for the coating film formed from the coating composition are not particularly limited, and may be performed by a known method.
  • a high pressure mercury lamp, a fusion H lamp, a xenon lamp or the like is used as the ultraviolet ray source, and the irradiation amount is preferably 100 to 500 mJ / cm. 2 may be irradiated.
  • an electron beam is generated by an electron beam accelerator or the like, and the irradiation amount is preferably set to 150 to 350 kV.
  • the coating layer is preferably formed by ultraviolet irradiation.
  • the pressure-sensitive adhesive layer is the surface of the base material provided with the coating layer (the surface 11a of the base material 11 in FIGS. 1 and 2). It can be formed by directly coating the pressure-sensitive adhesive composition. However, usually, for example, a pressure-sensitive adhesive layer formed by applying a pressure-sensitive adhesive composition to a release-treated surface of a release sheet and drying it is bonded to the surface of a substrate, and the release sheet is removed. It is preferable to adopt a method in which a layer is formed separately and this is bonded to the surface of the substrate.
  • the pressure-sensitive adhesive composition can be applied to the target surface in the same manner as in the case of the coating composition.
  • the applied pressure-sensitive adhesive composition may be crosslinked by heating, and the crosslinking by heating may also be performed for drying.
  • the heating conditions can be, for example, 100 to 130 ° C. for 1 to 5 minutes, but are not limited thereto.
  • the support sheet is composed of one layer (single layer) such as a substrate only, or when the support sheet is composed of a plurality of layers, for example, a substrate and a pressure-sensitive adhesive layer are laminated.
  • the composition for forming a protective film is directly applied to the surface of the support sheet provided with the coating layer (in FIGS. 1 and 2, the surface 10a of the support sheet 10, that is, the surface 12a of the pressure-sensitive adhesive layer 12). It is possible to form a protective film-forming film.
  • the protective film-forming film formed by applying the protective film-forming composition to the release-treated surface of the release sheet and drying it is applied to the surface of the support sheet. It is preferable to adopt a method in which a protective film-forming film is separately formed and bonded to the surface of the support sheet, for example, such that the release sheet is removed if necessary.
  • composition for forming a protective film can be applied to the target surface in the same manner as in the case of the coating composition.
  • drying conditions of the composition for protective film formation are not specifically limited, It can be dried by the method similar to the case of a coating composition.
  • the protective film-forming composite sheet according to the present invention can be produced by methods other than those described above.
  • a pressure-sensitive adhesive layer is formed using the pressure-sensitive adhesive composition
  • a protective film-forming film is formed using the protective film-forming composition
  • the pressure-sensitive adhesive layer and the protective film-forming film are overlapped.
  • the surface of the base material (in FIGS. 1 and 2) provided with a coating layer on the surface of the pressure-sensitive adhesive layer of the laminated body (the surface on which the protective film-forming film of the pressure-sensitive adhesive layer is not provided).
  • a composite sheet for forming a protective film can also be produced by laminating the surface 11a) of the substrate 11.
  • the conditions for forming the pressure-sensitive adhesive layer and the protective film-forming film are the same as in the above-described method.
  • the protective film forming composite sheet according to the present embodiment is It can also be manufactured by methods other than those described above.
  • a coating layer is formed using the coating composition, and this is laminated to a smooth surface of a support sheet to form a laminate, while a protective film-forming film is formed using the protective film-forming composition.
  • the composite sheet for forming a protective film can also be produced by forming and bonding this protective film-forming film to the exposed surface of the support sheet of the laminate (the surface on which the coating layer of the support sheet is not provided). .
  • the order of laminating the coating layer and the protective film forming film separately formed on the support sheet may be opposite to the above, and after supporting the protective film forming film on one surface of the support sheet,
  • the composite sheet for forming a protective film can also be produced by attaching a coating layer to the other surface of the sheet (the surface on which the protective film-forming film of the support sheet is not provided). Further, a protective film-forming film is formed on one surface of the support sheet using the protective film-forming composition, and on the other hand, a coating layer is formed using the coating composition.
  • a composite sheet for forming a protective film can also be produced by adhering to the exposed surface of the support sheet (the surface on which the protective film-forming film is not provided). The formation conditions of the coating layer and the protective film-forming film in these cases are the same as in the above-described method.
  • a protective film-forming film previously cut into a predetermined size and shape may be provided on the pressure-sensitive adhesive layer.
  • a method for using the protective film forming composite sheet according to the present embodiment is, for example, as shown below.
  • the usage method of the composite sheet for protective film formation in case the film for protective film formation is thermosetting is demonstrated.
  • the back surface of the semiconductor wafer is attached to the protective film forming film of the protective film forming composite sheet, and the protective film forming composite sheet is fixed to the dicing apparatus.
  • the protective film-forming film is cured by heating to form a protective film.
  • the protective film is usually formed after removing the back grind tape from the semiconductor wafer.
  • the semiconductor wafer is diced into semiconductor chips.
  • printing can be performed on the surface of the protective film by irradiating the protective film with laser light from the coating layer side of the protective film-forming composite sheet.
  • the measured value of haze from the coating layer side of the composite sheet for forming the protective film is within the specific range as described above, so that the laser printing is clearly performed on the protective film. It can be performed.
  • the condition may be checked. For example, in the case of a semiconductor chip, the presence or absence of breakage such as chipping or cracking may be inspected.
  • the semiconductor chip with a protective film according to the present invention as described above, the measured value of haze from the coating layer side is within the specific range as described above. The generation of voids is suppressed between the back surface. Therefore, when a semiconductor wafer or a semiconductor chip is observed from the coating layer side through the protective film forming composite sheet with an infrared camera or the like, a clear inspection image can be obtained, so that the inspection can be performed with high accuracy. .
  • the semiconductor chip is peeled off from the support sheet together with the protective film affixed to the back surface thereof and picked up to obtain a semiconductor chip with a protective film.
  • the support sheet is formed by laminating a base material and an adhesive layer, and the adhesive layer is energy ray curable, the adhesive layer is cured by irradiation of energy rays, A semiconductor chip with a protective film can be more easily obtained by picking up the semiconductor chip from the adhesive layer together with the protective film attached to the back surface thereof.
  • the back surface of the semiconductor wafer is attached to the protective film forming film 13 of the protective film forming composite sheet 1 and the exposed support sheet 10 is exposed.
  • Adhesive layer 12 is affixed to a dicing jig (not shown) such as a ring frame to fix the protective film-forming composite sheet 1 to the dicing apparatus.
  • a dicing jig such as a ring frame
  • laser printing is performed on the protective film, then dicing is performed, and energy beam irradiation is applied to the jig of the adhesive layer 12 as necessary.
  • a semiconductor chip with a protective film may be picked up.
  • the composite sheet 1 for forming a protective film in which the pressure-sensitive adhesive layer 12 is energy ray curable the pressure-sensitive adhesive layer 12 is specified so that it does not peel off from the jig. It is necessary to adjust so that the region does not cure.
  • the composite sheet 1 for forming a protective film there is no need to separately provide a configuration for attaching the composite sheet 1 to the jig.
  • the back surface of the semiconductor wafer is attached to the protective film forming film 23 of the protective film forming composite sheet 2 and the jig bonding is performed.
  • the agent layer 16 is attached to a dicing jig (not shown) such as a ring frame, and the protective film forming composite sheet 2 is fixed to a dicing apparatus.
  • the protective film-forming film 23 is cured to form a protective film
  • laser printing is performed on the protective film, then dicing is performed, and if necessary, the adhesive layer 12 is cured by irradiation with energy rays, A semiconductor chip with a protective film may be picked up.
  • the adhesive layer 12 is different from the case where the protective film-forming composite sheet 1 is used. It is not necessary to adjust so as not to cure the specific region.
  • the protective film-forming composite sheet 2 is required to have a jig adhesive layer 16. By having the adhesive layer 16 for jig
  • the back surface of the semiconductor wafer is attached to the protective film forming film of the protective film forming composite sheet, and the protective film is formed. Fix the composite sheet to the dicing machine.
  • the protective film-forming film is cured by irradiation with energy rays to form a protective film.
  • the protective film is usually formed after removing the back grind tape from the semiconductor wafer.
  • the semiconductor wafer is diced into semiconductor chips.
  • printing can be performed on the surface of the protective film by irradiating the protective film with laser light from the coating layer side of the protective film-forming composite sheet. From this printing to dicing, it can be carried out in the same manner as the above-mentioned film for forming a protective film is thermosetting, and in that case, laser printing can be clearly performed on the protective film, Inspection can be performed with high accuracy by an infrared camera or the like.
  • the semiconductor chip is peeled off from the support sheet together with the protective film stuck on the back surface thereof and picked up, thereby obtaining a semiconductor chip with a protective film.
  • This method is particularly suitable when, for example, a composite sheet for forming a protective film is used in which a support sheet is formed by laminating a base material and a pressure-sensitive adhesive layer, and the pressure-sensitive adhesive layer is non-energy ray curable. It is.
  • the protective film-forming film is cured by irradiation with energy rays and then the semiconductor wafer is diced and a semiconductor chip with a protective film is picked up is described.
  • the adhesive layer is a non-energy ray.
  • the protective film-forming film can be cured by irradiation with energy rays at any stage until the semiconductor chip is picked up.
  • a method described below is preferable. That is, first, as in the above case, the back surface of the semiconductor wafer is attached to the protective film forming film of the protective film forming composite sheet, and the protective film forming composite sheet is fixed to the dicing apparatus. Next, the protective film is irradiated with laser light from the coating layer side of the protective film-forming composite sheet, printing is performed on the surface of the protective film, and the semiconductor wafer is diced into semiconductor chips.
  • the protective film-forming film is cured to form a protective film, and the adhesive layer is cured, and from this cured adhesive layer, the semiconductor chip is adhered to the back surface thereof By picking up with the film, a semiconductor chip with a protective film is obtained.
  • the protective film when winding up a long protective film-forming composite sheet, the protective film usually has a release film (release film 15 in FIGS. 1 and 2) laminated on the exposed surface of the protective film-forming film.
  • a film-forming composite sheet is used.
  • the protective film-forming composite sheet according to the present invention has any configuration (for example, any of the protective film-forming composite sheet 1 shown in FIG. 1 and the protective film-forming composite sheet 2 shown in FIG. 2). Even if the protective sheet-forming composite sheet is wound into a roll, the lamination unit in which the coating layer, the support sheet, the protective film-forming film, and the release film are laminated in this order is sequentially formed in the radial direction of the roll. It will be stacked.
  • the surface of the release film of one laminated unit (the surface opposite to the side on which the protective film-forming film is provided)
  • the back surface of the coating layer of the other laminated unit (the surface opposite to the side in contact with the base material) is in contact and pressed, and in this state, the roll of the protective film-forming composite sheet is Saved.
  • the provision of the coating layer suppresses the sticking of the release film and the coating layer between the laminated units, so that the protective film-forming composite sheet according to this embodiment suppresses blocking. Is done.
  • the peel strength of the release film measured by the following method is preferably 10 mN / 50 mm or less, more preferably 7. 5 mN / 50 mm or less, particularly preferably 5 mN / 50 mm or less.
  • the composite sheet for protective film formation according to the present invention having a width of 50 mm and a length of 100 mm in a state in which a release film is provided on the protective film forming film, so that the coating layers are all directed in the same direction, and the total of the coating layers
  • a laminated body in which the first outermost layer is a coating layer and the second outermost layer is a release film is formed.
  • the film is left to stand at 40 ° C.
  • the adjacent coating layer (the first outermost coating layer in the stacking direction is Measure the peel force when peeled from a nearby coating layer.
  • all the composite sheets for forming a protective film to be stacked are assumed to have the same configuration.
  • the number of the protective sheet-forming composite sheets to be stacked is ten. From the peeling force of such a peeling film, the height of the blocking suppression effect (blocking resistance) of the composite sheet for protective film formation concerning this embodiment can be confirmed.
  • Example 1 A composite sheet for forming a protective film having the structure shown in FIG. 1 was produced. A plan view of this protective film-forming composite sheet is shown in FIG. More specifically, it is as follows.
  • thermosetting protective film Preparation of composition for forming thermosetting protective film
  • the following components were blended in the following amounts (solid content), and methyl ethyl ketone was blended to obtain a protective film-forming composition (III-1) having a solid content concentration of 51% by mass.
  • the protective film-forming composition (III-1) obtained above was applied onto the release-treated surface of the first release film (“SP-P502010 *” manufactured by Lintec Corporation, thickness 50 ⁇ m). And dried at 120 ° C. for 2 minutes to form a protective film-forming film (thickness: 25 ⁇ m).
  • the release treatment surface of the second release film (“SP-PET381031C” manufactured by Lintec Corporation, thickness 38 ⁇ m) is provided.
  • this laminated body By sticking together, the elongate laminated body by which the 1st peeling film, the film for protective film formation, and the 2nd peeling film were laminated
  • this cut laminated body in the width direction center part, it draws a circle with a diameter of 220 mm in plan view from the second release film side to the second release film and the protective film forming film.
  • a half cut was made to make a cut.
  • the “plan view” of the stacked body means that the stacked body is looked down from above in the stacking direction.
  • the second release film and the protective film-forming film are removed from the laminate so as to leave only the circular portion formed by the half cut, and on the release treatment surface of the first release film, As a result, a first laminated body in which a circular protective film-forming film and a second release film were laminated in this order was obtained.
  • the circular protective film-forming film in the first laminate corresponds to the circular protective film-forming film 13 having a diameter d1 of 220 mm in the protective film-forming composite sheet 1 shown in FIG.
  • Preparation of coating composition 150 parts by mass of a silica sol dispersed in 2-ethoxyethanol (ethyl cellosolve) (catalyst chemical industry “OSCAL 1632”, silica sol particle size 30 to 50 nm, solid content concentration 30% by mass), urethane acrylate and A hard coating agent composed of a polyfunctional acrylate monomer ("Arakawa Chemical Industries” Beam Set 575CB ", solid content concentration 100% by weight, containing a photopolymerization initiator) 100 parts by weight, and coating composition (solid content concentration 30% by mass) was obtained.
  • a silica sol dispersed in 2-ethoxyethanol (ethyl cellosolve) catalyst chemical industry “OSCAL 1632”, silica sol particle size 30 to 50 nm, solid content concentration 30% by mass
  • urethane acrylate and A hard coating agent composed of a polyfunctional acrylate monomer (“Arakawa Chemical Industries” Beam Set 575CB ", solid content concentration 100% by weight,
  • (Preparation of adhesive composition) 100 parts by weight of (meth) acrylic acid alkyl ester copolymer and 10 parts by weight (solid content) of aromatic polyisocyanate compound (crosslinking agent, “Takenate D110N” manufactured by Mitsui Chemicals) are blended, and methyl ethyl ketone is further blended. Thus, a pressure-sensitive adhesive composition (iii) having a solid content concentration of 30% by mass was obtained.
  • the (meth) acrylic acid alkyl ester copolymer is obtained by copolymerizing 40 parts by mass of n-butyl acrylate, 55 parts by mass of 2-ethylhexyl acrylate, and 5 parts by mass of 2-hydroxyethyl acrylate. 600,000 acrylic resin.
  • a knife coater is applied to the release-treated surface of a third release film (“SP-PET381031C” manufactured by Lintec Corporation) made of a polyethylene terephthalate film having a thickness of 38 ⁇ m, one side of which is released by forming a silicone-based release agent layer.
  • SP-PET381031C manufactured by Lintec Corporation
  • the pressure-sensitive adhesive composition (iii) obtained above was applied and dried to form a pressure-sensitive adhesive layer (thickness 5 ⁇ m).
  • the surface of the above-mentioned base material on which the coating layer is formed is subjected to corona treatment on the surface opposite to the concavo-convex surface, and then the above-mentioned pressure-sensitive adhesive layer is bonded to this corona-treated surface to form a coating layer, base material, and adhesive.
  • the agent layer and the third release film were laminated in this order to obtain a long second laminate including a support sheet.
  • the second laminated body is arranged in the width direction (the width direction indicated by reference sign w1 of the protective film-forming composite sheet 1 shown in FIG. 3). Was cut by a size of 300 mm.
  • the 2nd peeling film was removed from the 1st laminated body obtained above, and the circular film for protective film formation was exposed. Moreover, the 3rd peeling film was removed from the 2nd laminated body obtained above, and the adhesive layer was exposed. Then, by bonding the exposed surface of the protective film forming film to the exposed surface of the adhesive layer, the coating layer, the base material, the adhesive layer, the protective film forming film, and the first release film are in this order. A third laminated body corresponding to the composite sheet for forming a protective film was obtained.
  • a half cut is performed on the third laminate obtained above from the coating layer side so as to draw a circle having a diameter of 270 mm in a plan view on all of the coating layer, the base material and the adhesive layer. It was.
  • the coating layer, the base material, and the pressure-sensitive adhesive layer are formed so that the circle having a diameter of 270 mm is concentric with the circle having a diameter of 220 mm formed by the protective film-forming film in plan view. Cut everything into cuts.
  • the width of the third laminate in the protective sheet-forming composite sheet 1 shown in FIG. 3 of the composite sheet 1 shown in FIG. 3 is 20 mm away from the circle having a diameter of 270 mm.
  • the above-described half cut that draws two concentric circles and a pair of arcs is made in the longitudinal direction of the third laminated body (in the width direction indicated by the symbol w1 of the protective film-forming composite sheet 1 shown in FIG. 3).
  • the coating layer, the base material, and the adhesive are formed from the coating layer side so as to draw two straight lines that connect the arcs in the longitudinal direction between adjacent portions in plan view.
  • a half cut was made to cut all the agent layer.
  • the notches corresponding to the two straight lines form a planar peripheral edge of the pressure-sensitive adhesive layer indicated by reference numeral 122 in the protective film-forming composite sheet 1 shown in FIG.
  • the composite sheet for forming a protective film shown in FIGS. 1 and 3 was obtained.
  • the circular pressure-sensitive adhesive layer (support sheet) in this protective film-forming composite sheet corresponds to the circular pressure-sensitive adhesive layer 12 (support sheet 10) having a diameter d2 of 270 mm in FIG.
  • the 1st peeling film in this composite sheet for protective film formation corresponds to the peeling film 15 in FIG.
  • Example 2 As shown in Table 1, a composite sheet for forming a protective film was obtained in the same manner as in Example 1 except that a substrate having a surface roughness Ra of the uneven surface of 1 ⁇ m instead of 0.4 ⁇ m was used.
  • Example 3 As shown in Table 1, the same as Example 1, except that a substrate having a surface roughness Ra of 1 ⁇ m instead of 0.4 ⁇ m was used, and the thickness of the coating layer was changed to 1 ⁇ m instead of 3 ⁇ m. By the method, a composite sheet for forming a protective film was obtained.
  • Example 4 As shown in Table 1, a composite sheet for forming a protective film was obtained in the same manner as in Example 1 except that the thickness of the coating layer was changed to 1 ⁇ m instead of 3 ⁇ m.
  • Example 5 As shown in Table 1, the same as Example 1 except that a substrate having a surface roughness Ra of 1 ⁇ m instead of 0.4 ⁇ m was used and the thickness of the coating layer was changed to 6 ⁇ m instead of 3 ⁇ m. By the method, a composite sheet for forming a protective film was obtained.
  • Example 6 As shown in Table 1, the same as Example 1 except that a substrate having a surface roughness Ra of 3 ⁇ m instead of 0.4 ⁇ m was used, and the thickness of the coating layer was changed to 6 ⁇ m instead of 3 ⁇ m. By the method, a composite sheet for forming a protective film was obtained.
  • Example 1 As shown in Table 1, a protective film was formed in the same manner as in Example 1 except that a substrate having a surface roughness Ra of 1 ⁇ m instead of 0.4 ⁇ m was used and a coating layer was not formed. A composite sheet was obtained.
  • Example 2 As shown in Table 1, the base material was arranged so that the uneven surface faced to the opposite side, that is, the pressure-sensitive adhesive layer side (inner side), and the coating layer was not formed (that is, the conventional configuration shown in FIG. Except for the points, a composite sheet for forming a protective film was obtained in the same manner as in Example 1.
  • Example 3 As shown in Table 1, a substrate having a surface roughness Ra of 1 ⁇ m instead of 0.4 ⁇ m is used, and this substrate is placed so that the surface of the uneven surface faces the opposite side, that is, the pressure-sensitive adhesive layer side (inner side). A composite sheet for forming a protective film was obtained in the same manner as in Example 1 except that the coating layer was not formed (that is, the conventional configuration shown in FIG. 5).
  • Pattern 1 Character size 0.4 mm x 0.5 mm, character spacing 0.3 mm, number of characters
  • Pattern 2 Character size 0.2 mm x 0.5 mm, character spacing 0.3 mm, number of characters 20
  • the test piece is sandwiched between two glass plates (width 75 mm, length 15 mm, thickness 5 mm), and the entire laminate of the glass plate and the test piece is placed at a predetermined position with one glass plate as the lowermost layer.
  • the test piece was pressurized by placing a weight on the other uppermost glass plate.
  • the force applied to the test piece in the laminating direction of the tape was 980.665 mN (that is, 100 gf).
  • the entire laminate of the glass plate and the test piece was stored at 40 ° C. for 3 days in a moist heat accelerator (manufactured by ESPEC), and a heating and pressing acceleration test was performed on the test piece.
  • the test piece was taken out from the moist heat accelerator, and the lowermost first release film (the first release film in contact with the lowermost glass plate) and the protective film forming film adjacent thereto were removed and exposed.
  • the pressure-sensitive adhesive layer By sticking the pressure-sensitive adhesive layer to the support plate via a double-sided pressure-sensitive adhesive tape, only the lowermost first release film and the protective film-forming film adjacent thereto are removed from the test piece after the heat and pressure acceleration test. was fixed to the support plate.
  • the peeling force of the 1st peeling film to be measured is sufficiently small, from the said test piece taken out from the moist heat accelerator, the lowermost 1st peeling film (lowermost glass plate and When trying to remove the protective film-forming film adjacent to the first release film that was in contact with the first release film, the first release film to be measured for the peel force was first removed from the adjacent layer (of Examples 1 to 5).
  • the coating layer may peel off from the coating layer, and in the case of Comparative Examples 1 to 3, the base material may peel off.
  • the surface roughness Ra of the surface on the substrate side is a contact-type surface.
  • the cut-off value ⁇ c was 0.8 mm
  • the evaluation length Ln was 4 mm
  • the measurement was performed according to JIS B0601: 2001.
  • Table 1 for the protective film-forming composite sheets of Comparative Examples 1 to 3, as the surface roughness Ra of the substrate-side outermost surface, the surface roughness of the surface opposite to the pressure-sensitive adhesive layer side of the substrate described above Ra is described.
  • the composite sheet for forming a protective film of Examples 1 to 6 has a coating layer on the outermost layer on the substrate side, and the measured value of haze from the coating layer side is small, so that laser printability and blocking resistance are achieved. Both were good.
  • the protective film-forming composite sheets of Examples 1, 2, 4, and 5 were superior in laser printability to the protective film-forming composite sheets of Examples 3 and 6,
  • the composite sheets for forming a protective film of 4 and 5 it is surmised that the haze is further smaller and within a more suitable range.
  • the protective film-forming composite sheets of Examples 1 to 4 are superior in blocking resistance to the protective film-forming composite sheets of Examples 5 and 6, and this is because the protective film-forming composite sheets of Examples 1 to 4 are formed. It is estimated that the composite sheet for use is because the thickness of the coating layer is thinner. In each of the protective film-forming composite sheets of Examples 1 to 6, no void was observed between the substrate and the pressure-sensitive adhesive layer.
  • the protective film-forming composite sheet of Comparative Example 1 has a surface (back surface) opposite to the surface (front surface) on the side having the adhesive layer of the base material, as shown in FIG. ) Is an uneven surface and does not have a coating layer, it was excellent in blocking resistance but inferior in laser printability.
  • the surface (back surface) opposite to the surface (front surface) provided with the pressure-sensitive adhesive layer of the base material is a smooth surface, as shown in FIG.
  • the protective sheet-forming composite sheet of Comparative Example 3 also had the same configuration as the protective film-forming composite sheet of Comparative Example 2, but was inferior not only in blocking resistance but also in laser printability. This is presumed to be because the surface (surface) on the side having the pressure-sensitive adhesive layer of the base material is an uneven surface and the surface roughness Ra is larger than that of the protective sheet-forming composite sheet of Comparative Example 2. Is done.
  • Comparative Example 3 since the surface roughness Ra of the uneven surface is large, the shape of the uneven surface is reflected also on the surface of the protective film, and the degree of unevenness on the surface of the protective film is higher than in the case of Comparative Example 2. It is presumed that the larger the light, the greater the irregular reflection of light and the lower the laser printability. Furthermore, the protective sheet-forming composite sheets of Comparative Examples 2 and 3 both had voids between the uneven surface of the substrate and the pressure-sensitive adhesive layer, but Comparative Example 3 was more uneven than Comparative Example 2. Since the surface roughness Ra of the surface is large, the gap portion is large. Therefore, it is presumed that the comparative example 3 has a larger light irregular reflection than the comparative example 2 and the laser printability is inferior.
  • the protective film-forming composite sheet of Comparative Example 4 is the same surface as the protective film-forming composite sheet of Example 1 (surface) opposite to the surface (front surface) provided with the pressure-sensitive adhesive layer. ) Is an uneven surface and has a coating layer, which is excellent in blocking resistance but inferior in laser printability. This is presumed to be because, in the protective film-forming composite sheet of Comparative Example 4, the measured value of haze from the coating layer side is large.
  • the present invention can be used for manufacturing a semiconductor chip or the like whose back surface is protected by a protective film.

Abstract

This protective film-forming composite sheet is provided with a protective film-forming film on one surface of a support sheet, and is provided with a coating layer on the surface of the support sheet opposite of where the protective film-forming film is provided, wherein, from the coating layer side, the measured value of haze of the protective film-forming composite sheet is 47% or less.

Description

保護膜形成用複合シートComposite sheet for protective film formation
　本発明は、半導体チップの裏面に保護膜を形成するための保護膜形成用複合シートに関する。
　本願は、２０１６年３月４日に日本に出願された、特願２０１６－０４２６９１号に基づき優先権主張し、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 for forming a protective film on the back surface of a semiconductor chip.
This application claims priority based on Japanese Patent Application No. 2016-042691 filed in Japan on March 4, 2016, 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、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 chip may be exposed.
　この剥き出しとなったチップの裏面には、有機材料からなる樹脂膜が保護膜として形成され、保護膜付き半導体チップとして半導体装置に取り込まれることがある。保護膜は、ダイシング工程やパッケージングの後に、チップにおいてクラックが発生するのを防止するために利用される。 A resin film made of an organic material is formed as a protective film on the exposed back surface of the chip and may be taken into the semiconductor device as a semiconductor chip with a protective film. The protective film is used to prevent cracks from occurring in the chip after the dicing process or packaging.
　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、樹脂製の基材や、基材及び粘着剤層等の積層構造体が用いられ、前記基材の保護膜形成用フィルム又は粘着剤層等の積層面が表面処理されることもある。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 resin base material or a laminated structure such as a base material and an adhesive layer is used, and a laminated surface such as a protective film forming film or an adhesive layer of the base material is surface-treated. Sometimes it is done. 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.
　支持シートに用いられる加工前の前記基材において、通常、その片面又は両面は凹凸形状を有している。これは、このような凹凸形状を有していないと、基材を巻き取ってロールとしたときに、基材同士の接触面が貼り付いてブロッキングしてしまい、使用が困難になるためである。基材同士の接触面のうち、少なくとも一方が凹凸形状を有していれば、接触面の面積が小さくなるために、ブロッキングが抑制される。 In the base material before processing used for the support sheet, one or both sides thereof usually have an uneven shape. This is because if the substrate does not have such an uneven shape, the contact surface between the substrates adheres and blocks when the substrate is wound up to form a roll, making it difficult to use. . If at least one of the contact surfaces of the substrates has an uneven shape, the area of the contact surface is reduced, so that blocking is suppressed.
　このような凹凸面を有する基材を用いた従来の保護膜形成用複合シートは、典型的には、図４に示すような構成を有する。図４は、従来の保護膜形成用複合シートの一例を模式的に示す断面図である。なお、以降の説明で用いる図面においては、例えば、保護膜形成用複合シート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。 A conventional composite sheet for forming a protective film using a substrate having such an uneven surface typically has a structure as shown in FIG. FIG. 4 is a cross-sectional view schematically showing an example of a conventional composite sheet for forming a protective film. Note that, in the drawings used in the following description, for example, in order to make the characteristics of the protective film-forming composite sheet easier to understand, there are cases where the main part is shown enlarged for convenience. The dimensional ratio and the like are not necessarily the same as actual.
　ここに示す従来の保護膜形成用複合シート９は、支持シート９０上に保護膜形成用フィルム１３を備えてなるものであり、支持シート９０は基材９１及び粘着剤層１２の積層構造体からなり、粘着剤層１２上に保護膜形成用フィルム１３を備えている。保護膜形成用フィルム１３は硬化によって保護膜となる。保護膜形成用複合シート９は、さらに保護膜形成用フィルム１３上に剥離フィルム１５を備えており、剥離フィルム１５は、保護膜形成用複合シート９の使用時に取り除かれる。保護膜形成用複合シート９において、支持シート９０の保護膜形成用フィルム１３を備えている面（表面）９０ａとは反対側の面（裏面）９０ｂ、すなわち、基材９１の粘着剤層１２を備えている面（表面）９１ａとは反対側の面（裏面）９１ｂは、凹凸面となっている。保護膜形成用複合シート９は、このように、基材９１の裏面９１ｂが凹凸面となっていることにより、巻き取ってロールとしたときに、基材９１の裏面９１ｂと剥離フィルム１５の露出面（表面）１５ａとの貼り付き、すなわちブロッキングが抑制される。 The conventional protective film-forming composite sheet 9 shown here comprises a protective film-forming film 13 on a support sheet 90, and the support sheet 90 is made of a laminated structure of a base material 91 and an adhesive layer 12. The protective film forming film 13 is provided on the pressure-sensitive adhesive layer 12. The protective film-forming film 13 becomes a protective film by curing. The protective film-forming composite sheet 9 further includes a release film 15 on the protective film-forming film 13, and the release film 15 is removed when the protective film-forming composite sheet 9 is used. In the protective film forming composite sheet 9, the surface (back surface) 90 b opposite to the surface (front surface) 90 a provided with the protective film forming film 13 of the support sheet 90, that is, the adhesive layer 12 of the substrate 91 is formed. A surface (back surface) 91b opposite to the provided surface (front surface) 91a is an uneven surface. The composite sheet 9 for forming the protective film is thus exposed to the back surface 91b of the base material 91 and the release film 15 when the back surface 91b of the base material 91 has a concavo-convex surface and is taken up into a roll. Sticking with the surface (surface) 15a, that is, blocking is suppressed.
　一方で、保護膜形成用複合シートは、保護膜形成用フィルムから形成された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（以下、「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。レーザー印字は、支持シートの保護膜が形成されている側とは反対側から照射される。このとき、例えば、保護膜形成用複合シート９の場合には、基材９１の裏面９１ｂ側から支持シート９０を通して、保護膜にレーザー光を照射することになるが、基材９１の裏面９１ｂが凹凸面であるため、ここで光が乱反射してしまい、レーザー印字が不鮮明になるという問題点があった。 On the other hand, the composite sheet for protective film formation is printed on the surface of the protective film formed from the protective film-forming film on the support sheet side by irradiation with laser light (hereinafter sometimes referred to as “laser printing”). Sometimes done. Laser printing is applied from the opposite side of the support sheet on which the protective film is formed. At this time, for example, in the case of the composite sheet 9 for forming the protective film, the protective film is irradiated with laser light from the back surface 91b side of the base material 91 through the support sheet 90. Since it is an uneven surface, there is a problem that light is irregularly reflected here and laser printing becomes unclear.
　このような光の乱反射を防止できる保護膜形成用複合シートとしては、図５に示すような構成を有する保護膜形成用複合シート８が知られている（例えば、特許文献１参照）。
　図５は、従来の保護膜形成用複合シートの他の例を模式的に示す断面図である。 As a protective sheet-forming composite sheet capable of preventing such irregular reflection of light, a protective film-forming composite sheet 8 having a structure as shown in FIG. 5 is known (see, for example, Patent Document 1).
FIG. 5 is a cross-sectional view schematically showing another example of a conventional composite sheet for forming a protective film.
　ここに示す従来の保護膜形成用複合シート８は、保護膜形成用複合シート９と同様に、支持シート８０上に保護膜形成用フィルム１３を備えてなるものであり、支持シート８０は基材８１及び粘着剤層１２の積層構造体からなり、粘着剤層１２上に保護膜形成用フィルム１３を備えている。ただし、支持シート８０において、基材８１の凹凸面の配置は、支持シート９０における基材９１とは反対となっている。すなわち、保護膜形成用複合シート８において、基材８１の粘着剤層１２を備えている面（表面）８１ａが凹凸面となっており、基材８１の表面８１ａとは反対側の面（裏面）８１ｂが平滑面となっている。支持シート８０における基材８１、保護膜形成用フィルム１３及び剥離フィルム１５は、それぞれ支持シート９０における基材９１、保護膜形成用フィルム１３及び剥離フィルム１５と同様のものである。 The conventional protective film-forming composite sheet 8 shown here comprises a protective film-forming film 13 on a support sheet 80, like the protective film-forming composite sheet 9, and the support sheet 80 is a base material. 81 and a pressure-sensitive adhesive layer 12, and a protective film-forming film 13 is provided on the pressure-sensitive adhesive layer 12. However, in the support sheet 80, the arrangement of the uneven surface of the base material 81 is opposite to that of the base material 91 in the support sheet 90. That is, in the composite sheet 8 for forming the protective film, the surface (front surface) 81a of the base material 81 provided with the adhesive layer 12 is an uneven surface, and the surface (back surface) opposite to the surface 81a of the base material 81. ) 81b is a smooth surface. The base material 81, the protective film forming film 13 and the release film 15 in the support sheet 80 are the same as the base material 91, the protective film forming film 13 and the release film 15 in the support sheet 90, respectively.
　しかし、保護膜形成用複合シート８の場合には、基材８１の裏面８１ｂ、すなわち、支持シート８０の粘着剤層１２を備えている面（表面）８０ａとは反対側の面（裏面）８０ｂが平滑面となっており、保護膜形成用複合シート８を巻き取ってロールとしたときに、基材８１の裏面８１ｂと剥離フィルム１５の露出面（表面）１５ａとの貼り付き、すなわちブロッキングが抑制できない。ブロッキングが生じると、保護膜形成用複合シート８にシワが生じたり、保護膜形成用複合シート８をロールから繰り出すときに、剥離フィルム１５が保護膜形成用フィルム１３から剥離してしまう。さらに、基材８１の表面８１ａ上においては、凹凸の形状を解消するように、粘着剤層１２は十分な厚さを有することが必要となる。これが不十分であると、基材８１の凹凸形状を反映して、保護膜形成用フィルム１３の支持シート８０側の面（裏面）１３ｂが凹凸形状を有するようになり、このような保護膜形成用フィルム１３から形成された保護膜の支持シート側の面に施されたレーザー印字が不鮮明になってしまうという問題点があった。 However, in the case of the composite sheet 8 for forming a protective film, the back surface 81b of the substrate 81, that is, the surface (back surface) 80b opposite to the surface (front surface) 80a provided with the adhesive layer 12 of the support sheet 80. Is a smooth surface, and when the protective film-forming composite sheet 8 is wound up into a roll, the back surface 81b of the substrate 81 and the exposed surface (front surface) 15a of the release film 15 are attached, that is, blocking occurs. It cannot be suppressed. When blocking occurs, wrinkles occur in the protective film-forming composite sheet 8, or the release film 15 peels off from the protective film-forming film 13 when the protective film-forming composite sheet 8 is unwound from the roll. Furthermore, on the surface 81a of the base material 81, the pressure-sensitive adhesive layer 12 needs to have a sufficient thickness so as to eliminate the uneven shape. If this is insufficient, the surface (back surface) 13b on the support sheet 80 side of the protective film forming film 13 will have an uneven shape reflecting the uneven shape of the base material 81, and such a protective film formation will be performed. There was a problem that the laser printing applied to the surface on the support sheet side of the protective film formed from the protective film 13 became unclear.
特許第５４３２８５３号公報Japanese Patent No. 5432553
　このように、従来は、ブロッキングの抑制と、保護膜への鮮明なレーザー印字と、を両立できる保護膜形成用複合シートが無いのが実情であった。
　本発明は、上記事情に鑑みてなされたものであり、半導体チップの裏面に保護膜を形成するために用いる保護膜形成用複合シートであって、ブロッキングを抑制でき、かつ保護膜に鮮明にレーザー印字できる保護膜形成用複合シートを提供することを課題とする。 Thus, conventionally, there has been no actual situation in which there is no composite sheet for forming a protective film that can achieve both blocking suppression and clear laser printing on the protective film.
The present invention has been made in view of the above circumstances, and is a protective film-forming composite sheet used for forming a protective film on the back surface of a semiconductor chip, which can suppress blocking and has a clear laser on the protective film. It is an object to provide a composite sheet for forming a protective film that can be printed.
　本発明の一の態様は、以下の通りである。
（１）本発明の一の実施態様においては、支持シートの一方の表面上に保護膜形成用フィルムを備え、前記支持シートの前記保護膜形成用フィルムを備えている側とは反対側の表面上にコーティング層を備えてなる保護膜形成用複合シートであって、前記保護膜形成用複合シートの前記コーティング層側からのヘイズの測定値が４７％以下である、保護膜形成用複合シートを提供する。 One aspect of the present invention is as follows.
(1) In one embodiment of the present invention, a protective film-forming film is provided on one surface of the support sheet, and the surface of the support sheet is opposite to the side provided with the protective film-forming film. A protective film-forming composite sheet comprising a coating layer thereon, wherein the protective film-forming composite sheet has a measured haze value of 47% or less from the coating layer side of the protective film-forming composite sheet. provide.
（２）前記（１）の保護膜形成用複合シートにおいては、さらに前記保護膜形成用フィルム上に剥離フィルムを備えた前記保護膜形成用複合シートを用いて、下記方法で測定した前記剥離フィルムの剥離力が１０ｍＮ／５０ｍｍ以下であってもよい。
（剥離フィルムの剥離力の測定方法）
　保護膜形成用フィルム上に剥離フィルムを備えた、幅５０ｍｍ、長さ１００ｍｍの前記保護膜形成用複合シートを、前記コーティング層がすべて同じ方向を向くように、かつ前記コーティング層の合計の厚さが１０～６０μｍとなるように複数枚重ねることで、第一の最外層がコーティング層で、第二の最外層が剥離フィルムである積層体とし、前記積層体を、前記保護膜形成用複合シートの積層方向において９８０．６６５ｍＮの力を加えたまま４０℃で３日間静置した後、前記積層方向において前記第一の最外層のコーティング層に最も近い剥離フィルムを剥離速度３００ｍｍ／分、剥離角度１８０°の条件で、隣接するコーティング層から剥離させたときの剥離力を測定する。 (2) In the protective film-forming composite sheet of (1), the release film measured by the following method using the protective film-forming composite sheet provided with a release film on the protective film-forming film. The peel force may be 10 mN / 50 mm or less.
(Measurement method of peel strength of release film)
The composite sheet for forming a protective film having a width of 50 mm and a length of 100 mm provided with a release film on the protective film-forming film, so that the coating layers are all directed in the same direction, and the total thickness of the coating layers Are laminated so that the first outermost layer is a coating layer and the second outermost layer is a release film, and the laminate is used as the protective sheet-forming composite sheet. The film was allowed to stand at 40 ° C. for 3 days while applying a force of 980.665 mN in the laminating direction, and the peeling film closest to the first outermost coating layer in the laminating direction was peeled off at a rate of 300 mm / min, peeling angle. The peeling force when peeled from the adjacent coating layer under the condition of 180 ° is measured.
（３）前記（１）又は（２）の保護膜形成用複合シートにおいては、前記支持シートが、基材及び粘着剤層が積層されてなり、前記保護膜形成用複合シートが、前記コーティング層、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っていてもよい。
（４）前記（３）の保護膜形成用複合シートにおいては、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のものであってもよい。
（５）前記（１）～（４）のいずれか一項の保護膜形成用複合シートにおいては、前記保護膜形成用フィルムが、熱硬化性又はエネルギー線硬化性のものであってもよい。 (3) In the protective film-forming composite sheet of (1) or (2), the support sheet is formed by laminating a base material and an adhesive layer, and the protective film-forming composite sheet is the coating layer. The base material, the pressure-sensitive adhesive layer, and the protective film-forming film may be laminated in this order.
(4) In the protective film-forming composite sheet of (3), the pressure-sensitive adhesive layer may be energy ray curable or non-energy ray curable.
(5) In the protective film-forming composite sheet according to any one of (1) to (4), the protective film-forming film may be thermosetting or energy ray curable.
　本発明によれば、半導体チップの裏面に保護膜を形成するために用いる保護膜形成用複合シートであって、ブロッキングを抑制でき、かつ保護膜に鮮明にレーザー印字できる保護膜形成用複合シートが提供される。 According to the present invention, there is provided a protective film-forming composite sheet used for forming a protective film on the back surface of a semiconductor chip, which can suppress blocking and can be clearly laser-printed on the protective film. Provided.
本発明の一の実施態様に係る保護膜形成用複合シートの一実施形態を模式的に示す断面図である。It is sectional drawing which shows typically one Embodiment of the composite sheet for protective film formation which concerns on one embodiment of this invention. 本発明の一の実施態様に係る保護膜形成用複合シートの他の実施形態を模式的に示す断面図である。It is sectional drawing which shows typically other embodiment of the composite sheet for protective film formation which concerns on one embodiment of this invention. 実施例で製造した保護膜形成用複合シートを示す平面図である。It is a top view which shows the composite sheet for protective film formation manufactured in the Example. 従来の保護膜形成用複合シートの一例を模式的に示す断面図である。It is sectional drawing which shows typically an example of the conventional composite sheet for protective film formation. 従来の保護膜形成用複合シートの他の例を模式的に示す断面図である。It is sectional drawing which shows typically the other example of the conventional composite sheet for protective film formation.
◎保護膜形成用複合シート
　本実施形態に係る保護膜形成用複合シートは、支持シートの一方の表面上に保護膜形成用フィルムを備え、前記支持シートの前記保護膜形成用フィルムを備えている側とは反対側の表面上にコーティング層を備えてなる保護膜形成用複合シートであって、前記保護膜形成用複合シートの前記コーティング層側からのヘイズの測定値が４７％以下のものである。
　前記保護膜形成用複合シートは、前記コーティング層側からのヘイズの測定値が、上記のような特定の範囲内であることで、保護膜形成用フィルムを硬化した後の保護膜に対して、コーティング層側からレーザー光を照射したときに、レーザー光の散乱が抑制されるので、保護膜に鮮明にレーザー印字を行うことができる。
　また、前記保護膜形成用複合シートは、易滑性及び帯電防止性を有する前記コーティング層を備えていることにより、巻き取ってロールとしたときに、ブロッキングが抑制される。 ◎ Composite sheet for protective film formation The composite sheet for protective film formation according to this embodiment includes a protective film-forming film on one surface of the support sheet, and includes the protective film-forming film of the support sheet. A protective sheet-forming composite sheet comprising a coating layer on the surface opposite to the surface, wherein the measured haze value from the coating layer side of the protective film-forming composite sheet is 47% or less. is there.
The protective film-forming composite sheet has a measured value of haze from the coating layer side within the specific range as described above, and with respect to the protective film after curing the protective film-forming film, When laser light is irradiated from the coating layer side, scattering of the laser light is suppressed, so that clear laser printing can be performed on the protective film.
Moreover, when the said composite sheet for protective film formation is equipped with the said coating layer which has slipperiness | lubricity and antistatic property, when winding up and making it a roll, blocking is suppressed.
　なお、本明細書においては、前記保護膜形成用複合シートにおいて、保護膜形成用フィルムを加熱又はエネルギー線の照射によって硬化させて保護膜としたものも、前記支持シート及び保護膜の積層構造が維持されている限り、保護膜形成用複合シートと称する。また、前記保護膜形成用複合シートにおいて、前記支持シートが基材及び粘着剤層の積層構造体である場合、粘着剤層を硬化させたものも、前記基材、粘着剤層の硬化物、及び保護膜形成用フィルム又は保護膜の積層構造が維持されている限り、保護膜形成用複合シートと称する。 In the present specification, in the composite sheet for forming a protective film, the protective film-forming film is cured by heating or irradiation with energy rays to form a protective film, but the laminated structure of the support sheet and the protective film is also used. As long as it is maintained, it is referred to as a protective sheet-forming composite sheet. Moreover, in the composite sheet for forming a protective film, when the support sheet is a laminated structure of a base material and an adhesive layer, a cured product of the base material and the adhesive layer, As long as the protective film-forming film or the laminated structure of the protective film is maintained, the protective film-forming composite sheet is referred to.
　図１は、本発明の一の実施態様に係る保護膜形成用複合シートの一実施形態を模式的に示す断面図である。
　ここに示す保護膜形成用複合シート１は、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を備え、支持シート１０の他方の表面（裏面）１０ｂ上にコーティング層１４を備えてなる。さらに、支持シート１０は、基材１１及び粘着剤層１２が積層されてなるものであり、基材１１の一方の表面１１ａ上に粘着剤層１２を備え、基材１１の他方の表面（裏面）１１ｂ上にコーティング層１４を備えており、粘着剤層１２上に保護膜形成用フィルム１３を備える。また、保護膜形成用複合シート１は、さらに保護膜形成用フィルム１３上に剥離フィルム１５を備えており、剥離フィルム１５は保護膜形成用複合シート１の使用時に取り除かれる。保護膜形成用フィルム１３は硬化によって保護膜となる。 FIG. 1 is a cross-sectional view schematically showing one embodiment of a composite sheet for forming a protective film according to one embodiment of the present invention.
The protective film-forming composite sheet 1 shown here includes a protective film-forming film 13 on one surface 10 a of the support sheet 10, and a coating layer 14 on the other surface (back surface) 10 b of the support sheet 10. Become. Furthermore, the support sheet 10 is formed by laminating a base material 11 and a pressure-sensitive adhesive layer 12, and includes a pressure-sensitive adhesive layer 12 on one surface 11 a of the base material 11, and the other surface (back surface) of the base material 11. ) A coating layer 14 is provided on 11b, and a protective film forming film 13 is provided on the pressure-sensitive adhesive layer 12. The protective film-forming composite sheet 1 further includes a release film 15 on the protective film-forming film 13, and the release film 15 is removed when the protective film-forming composite sheet 1 is used. The protective film-forming film 13 becomes a protective film by curing.
　保護膜形成用複合シート１において、粘着剤層１２は基材１１の前記表面１１ａ上に積層され、保護膜形成用フィルム１３は粘着剤層１２の表面１２ａの一部に積層されている。そして、粘着剤層１２の表面１２ａのうち、保護膜形成用フィルム１３が積層されていない露出面と、保護膜形成用フィルム１３の表面１３ａ（上面及び側面）の上に、剥離フィルム１５が積層されている。
　なお、剥離フィルム１５と、粘着剤層１２の表面１２ａ又は保護膜形成用フィルム１３の表面１３ａと、の間には、空隙部が存在していてもよい。例えば、保護膜形成用フィルム１３の側面や、粘着剤層１２の表面１２ａのうち、保護膜形成用フィルム１３の近傍領域は、前記空隙部が生じ易い。 In the protective film-forming composite sheet 1, the pressure-sensitive adhesive layer 12 is laminated on the surface 11 a of the substrate 11, and the protective film-forming film 13 is laminated on a part of the surface 12 a of the pressure-sensitive adhesive layer 12. And the peeling film 15 is laminated | stacked on the surface 13a (upper surface and side surface) of the film 13 for protective film formation among the exposed surface in which the film 13 for protective film formation is not laminated | stacked among the surfaces 12a of the adhesive layer 12. Has been.
Note that a gap may exist between the release film 15 and the surface 12 a of the pressure-sensitive adhesive layer 12 or the surface 13 a of the protective film forming film 13. For example, in the side surface of the protective film-forming film 13 and the surface 12 a of the pressure-sensitive adhesive layer 12, the voids are likely to occur in the vicinity of the protective film-forming film 13.
　保護膜形成用複合シート１において、コーティング層１４の支持シート１０（基材１１）と接触している面（表面）１４ａとは反対側の面（裏面）１４ｂの方向から測定したヘイズは、４７％以下となっている。これにより、保護膜に対して鮮明にレーザー印字を行うことができる。
　なお、本発明において「ヘイズ」とは、特に断りのない限り、ＪＩＳ　Ｋ　７１３６に従って測定して得られた値を意味する。 In the protective film-forming composite sheet 1, the haze measured from the direction of the surface (back surface) 14b opposite to the surface (front surface) 14a in contact with the support sheet 10 (base material 11) of the coating layer 14 is 47. % Or less. Thereby, clear laser printing can be performed on the protective film.
In the present invention, “haze” means a value obtained by measurement according to JIS K 7136 unless otherwise specified.
　また、保護膜形成用複合シート１は、コーティング層１４を備えていることにより、巻き取ってロールとした場合であっても、基材１１の前記裏面１１ｂと剥離フィルム１５の露出面（表面）１５ａとの貼り付き、すなわちブロッキングが抑制される。 Further, the protective film-forming composite sheet 1 includes the coating layer 14, so that the back surface 11 b of the base material 11 and the exposed surface (front surface) of the release film 15, even when wound up to form a roll. Sticking with 15a, that is, blocking is suppressed.
　保護膜形成用複合シート１において、支持シート１０の保護膜形成用フィルム１３を備えている面（表面）１０ａとは反対側の面（裏面）１０ｂ、すなわち、基材１１の粘着剤層１２を備えている面（表面）１１ａとは反対側の面（裏面）１１ｂは、ここでは、平滑度が低い凹凸面となっているが、平滑面であってもよい。保護膜形成用フィルム１３から形成された保護膜（図示略）にレーザー印字を行う場合には、保護膜の支持シート１０側の面に、コーティング層１４側からレーザー光を照射する。このとき、支持シート１０の前記裏面１０ｂ（基材１１の前記裏面１１ｂ）が凹凸面及び平滑面のいずれであっても、コーティング層１４がこの面を被覆しているため、コーティング層１４の支持シート１０（基材１１）と接触している面（表面）１４ａとは反対側の面（裏面）１４ｂの平滑度が高く、その表面粗さＲａが小さいことにより、コーティング層１４でのレーザー光の乱反射が抑制され、保護膜に対して鮮明にレーザー印字を行うことができる。 In the protective film forming composite sheet 1, the surface (back surface) 10 b opposite to the surface (front surface) 10 a provided with the protective film forming film 13 of the support sheet 10, that is, the pressure-sensitive adhesive layer 12 of the substrate 11. The surface (back surface) 11b opposite to the provided surface (front surface) 11a is an uneven surface with low smoothness here, but may be a smooth surface. When laser printing is performed on a protective film (not shown) formed from the protective film forming film 13, the surface of the protective film on the support sheet 10 side is irradiated with laser light from the coating layer 14 side. At this time, even if the back surface 10b of the support sheet 10 (the back surface 11b of the base material 11) is either an uneven surface or a smooth surface, the coating layer 14 covers this surface, so that the support of the coating layer 14 is supported. The surface (rear surface) 14b opposite to the surface (front surface) 14a in contact with the sheet 10 (base material 11) has a high smoothness and a small surface roughness Ra, so that the laser light in the coating layer 14 is obtained. Is suppressed, and laser printing can be clearly performed on the protective film.
　なお、本明細書において、「表面粗さＲａ」とは、特に断りのない限り、ＪＩＳ　Ｂ０６０１：２００１で規定される、いわゆる算術平均粗さを意味する。 In this specification, “surface roughness Ra” means a so-called arithmetic average roughness defined by JIS B0601: 2001 unless otherwise specified.
　保護膜形成用複合シート１において、基材１１の表面１１ａは、ここでは平滑面となっているが、平滑度が低い凹凸面であってもよい。ただし、後述するように、基材１１の表面１１ａと粘着剤層との間における空隙部の発生を抑制し、保護膜形成用複合シート１を好ましい特性のものとすることがより容易である点から、基材１１の表面１１ａは平滑面であることが好ましい。 In the composite sheet 1 for forming a protective film, the surface 11a of the substrate 11 is a smooth surface here, but may be an uneven surface with low smoothness. However, as will be described later, it is easier to suppress the generation of voids between the surface 11a of the base material 11 and the pressure-sensitive adhesive layer, and to make the composite sheet 1 for forming a protective film have favorable characteristics. Therefore, the surface 11a of the substrate 11 is preferably a smooth surface.
　図１に示す保護膜形成用複合シート１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、さらに、粘着剤層１２の表面１２ａのうち、保護膜形成用フィルム１３が積層されていない露出面が、リングフレーム等の治具に貼付されて、使用される。 The composite sheet 1 for forming a protective film shown in FIG. 1 has a back surface of a semiconductor wafer (not shown) attached to the front surface 13a of the protective film forming film 13 with the release film 15 removed. Among the 12 surfaces 12a, the exposed surface on which the protective film forming film 13 is not laminated is attached to a jig such as a ring frame and used.
　図２は、本発明の一の態様に係る保護膜形成用複合シートの他の実施形態を模式的に示す断面図である。なお、図２において、図１に示すものと同じ要素には、図１の場合と同じ符号を付し、その詳細な説明は省略する。これは図２以降の図においても同様である。
　ここに示す保護膜形成用複合シート２は、粘着剤層１２の表面１２ａの全面に保護膜形成用フィルム２３が積層され、保護膜形成用フィルム２３の表面２３ａの一部に治具用接着剤層１６が積層され、保護膜形成用フィルム２３の表面２３ａのうち、治具用接着剤層１６が積層されていない露出面と、治具用接着剤層１６の表面１６ａ（上面及び側面）の上に、剥離フィルム１５が積層されている点以外は、図１に示す保護膜形成用複合シート１と同じものである。 FIG. 2 is a cross-sectional view schematically showing another embodiment of the composite sheet for forming a protective film according to one aspect of the present invention. 2, the same elements as those shown in FIG. 1 are denoted by the same reference numerals as those in FIG. 1, and detailed description thereof is omitted. This also applies to the drawings after FIG.
The protective film forming composite sheet 2 shown here has a protective film forming film 23 laminated on the entire surface 12 a of the pressure-sensitive adhesive layer 12, and a jig adhesive on a part of the surface 23 a of the protective film forming film 23. Layer 16 is laminated, of the surface 23a of the protective film forming film 23, the exposed surface on which the jig adhesive layer 16 is not laminated, and the surface 16a (upper surface and side surface) of the jig adhesive layer 16 It is the same as the composite sheet 1 for forming a protective film shown in FIG. 1 except that a release film 15 is laminated thereon.
　なお、剥離フィルム１５と、保護膜形成用フィルム２３の表面２３ａ又は治具用接着剤層１６の表面１６ａと、の間には、空隙部が存在していてもよい。例えば、治具用接着剤層１６の側面や、保護膜形成用フィルム２３の表面２３ａのうち、治具用接着剤層１６の近傍領域は、前記空隙部が生じ易い。 Note that a gap may exist between the release film 15 and the surface 23a of the protective film-forming film 23 or the surface 16a of the jig adhesive layer 16. For example, in the side surface of the jig adhesive layer 16 and the surface 23 a of the protective film forming film 23, the gap portion is likely to occur in the vicinity of the jig adhesive layer 16.
　保護膜形成用複合シート２においても、保護膜形成用複合シート１の場合と同様に、コーティング層１４の支持シート１０（基材１１）と接触している面（表面）１４ａとは反対側の面（裏面）１４ｂの方向から測定したヘイズは、４７％以下となっている。したがって、保護膜形成用フィルム２３から形成された保護膜に対して、鮮明にレーザー印字を行うことができる。 Also in the protective film-forming composite sheet 2, as in the case of the protective film-forming composite sheet 1, the surface of the coating layer 14 on the side opposite to the surface (surface) 14 a in contact with the support sheet 10 (base material 11). The haze measured from the direction of the surface (back surface) 14b is 47% or less. Therefore, clear laser printing can be performed on the protective film formed from the protective film-forming film 23.
　また、保護膜形成用複合シート２は、コーティング層１４を備えていることにより、巻き取ってロールとした場合であっても、ブロッキングが抑制される。 In addition, the protective film-forming composite sheet 2 is provided with the coating layer 14, so that blocking is suppressed even when the protective film-forming composite sheet 2 is wound up into a roll.
　図２に示す保護膜形成用複合シート２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２３の表面２３ａに半導体ウエハ（図示略）の裏面が貼付され、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。 The protective film-forming composite sheet 2 shown in FIG. 2 has a semiconductor wafer (not shown) attached to the front surface 23a of the protective film-forming film 23 with the release film 15 removed. The upper surface of the surface 16a of the adhesive layer 16 is used by being attached to a jig such as a ring frame.
　本発明に係る保護膜形成用複合シートは、図１～２に示すものに限定されず、本発明の効果を損なわない範囲内において、図１～２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。
　以下、本発明の一の実施態様に係る保護膜形成用複合シートの各構成について、さらに詳細に説明する。 The composite sheet for forming a protective film according to the present invention is not limited to the one shown in FIGS. 1 and 2, and a part of the structure shown in FIGS. 1 and 2 is changed or deleted within a range not impairing the effects of the present invention. In addition, other configurations may be added to those described above.
Hereinafter, each structure of the composite sheet for protective film formation which concerns on one embodiment of this invention is demonstrated in detail.
○支持シート
　前記支持シートは、前記保護膜形成用フィルムを設けることが可能なものであれば、特に限定されず、例えば、保護膜形成用フィルムの表面にホコリ等の付着を防止するための剥離シート、及びダイシング工程等で保護膜形成用フィルムの表面を保護するためのダイシングシート等の役割を果たすものが挙げられる。
　前記支持シートで好ましいものとしては、半導体ウエハの加工用シートの分野で通常用いられる基材のみからなるもの、並びに基材及び粘着剤層が積層されてなるもの等が挙げられる。 ○ Support sheet The support sheet is not particularly limited as long as it can be provided with the protective film-forming film. For example, peeling to prevent dust and the like from adhering to the surface of the protective film-forming film. Examples of the sheet may include a dicing sheet for protecting the surface of the protective film-forming film in a dicing process.
Preferable examples of the support sheet include those composed only of a base material usually used in the field of semiconductor wafer processing sheets, and those obtained by laminating a base material and an adhesive layer.
　支持シートは、１層（単層）からなるものでもよいし、２層以上の複数層からなるものでもよい。支持シートが複数層からなる場合、これら複数層は、互いに同一でも異なっていてもよい。すなわち、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。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。ここで、複数層が互いに異なるとは、各層の材質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。 The support sheet may be composed of one layer (single layer) or may be composed of two or more layers. When the support sheet is composed of a plurality of layers, the plurality of layers may be the same as or different from each other. That is, all the layers may be the same, all the layers may be different, or only some of the layers may be the same. And when several layers differ from each other, the combination of these several layers is not specifically limited. Here, the plurality of layers being different from each other means that at least one of the material and the thickness of each layer is different from each other.
　支持シートの厚さは、目的に応じて適宜選択すればよいが、前記保護膜形成用複合シートに十分な可撓性を付与でき、半導体ウエハに対する貼付性が良好となる点から、好ましくは１０～５００μｍ、より好ましくは２０～３５０μｍ、特に好ましくは３０～２００μｍである。
　ここで、「支持シートの厚さ」とは、支持シートを構成する各層の合計の厚さを意味し、例えば、基材及び粘着剤層が積層されてなる支持シートの場合には、基材の厚さ及び粘着剤層の厚さの合計値を意味する。
　なお、支持シートは、少なくとも一方の面が凹凸面となり得るが、支持シートの厚さは、支持シートのこの凹凸面における凸部を含む部位では、この凸部の先端を一方の起点として算出すればよい。 The thickness of the support sheet may be appropriately selected depending on the purpose, but is preferably 10 from the viewpoint that sufficient flexibility can be imparted to the protective film-forming composite sheet and the adhesiveness to the semiconductor wafer becomes good. It is ˜500 μm, more preferably 20 to 350 μm, particularly preferably 30 to 200 μm.
Here, “the thickness of the support sheet” means the total thickness of each layer constituting the support sheet. For example, in the case of a support sheet in which a base material and an adhesive layer are laminated, the base material And the total thickness of the pressure-sensitive adhesive layer.
Note that, at least one surface of the support sheet can be an uneven surface, but the thickness of the support sheet is calculated with the tip of the convex portion as one starting point at a portion including the convex portion on the uneven surface of the support sheet. That's fine.
・基材
　前記基材の材質は、各種樹脂であることが好ましく、その具体的な例としては、ポリエチレン（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））、ポリプロピレン、エチレン・プロピレン共重合体、ポリブテン、ポリブタジエン、ポリメチルペンテン、ポリ塩化ビニル、塩化ビニル共重合体、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、ポリウレタン、ポリウレタンアクリレート、ポリイミド、エチレン・酢酸ビニル共重合体、アイオノマー樹脂、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、ポリスチレン、ポリカーボネート、フッ素樹脂、これらのいずれかの樹脂の水添加物、変性物、架橋物又は共重合物等が挙げられる。
　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。 -Base material The material of the base material is preferably various resins, and specific examples thereof include polyethylene (low density polyethylene (LDPE), linear low density polyethylene (LLDPE), high density polyethylene (HDPE, etc.). )), Polypropylene, ethylene / propylene copolymer, polybutene, polybutadiene, polymethylpentene, polyvinyl chloride, vinyl chloride copolymer, polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polyurethane, polyurethane acrylate, polyimide, ethylene Vinyl acetate copolymer, ionomer resin, ethylene / (meth) acrylic acid copolymer, ethylene / (meth) acrylic acid ester copolymer, polystyrene, polycarbonate, fluororesin, hydrogenation of any of these resins Additives, modified products, cross-linked products or copolymers may be mentioned.
In this specification, “(meth) acrylic acid” is a concept including both “acrylic acid” and “methacrylic acid”.
　支持シートが、基材と、粘着剤層等のその他のものと、が積層されてなるものである場合、基材の厚さは、目的に応じて適宜選択できるが、１５～３００μｍであることが好ましく、２０～２００μｍ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。 When the support sheet is formed by laminating a base material and another material such as a pressure-sensitive adhesive layer, the thickness of the base material can be appropriately selected according to the purpose, but is 15 to 300 μm. And more preferably 20 to 200 μm. 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.
　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い。基材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、上述の支持シートの場合と同様のことを意味する。
　基材が複数層からなる場合には、各層の合計の厚さが、上記の好ましい基材の厚さとなるようにするとよい。 The substrate may be composed of one layer (single layer) or may be composed of two or more layers. When a base material consists of multiple layers, these multiple 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 support sheet.
In the case where the substrate is composed of a plurality of layers, the total thickness of each layer may be set to the preferable thickness of the substrate.
　基材の粘着剤層を備えている面（表面）の表面粗さＲａは、０．００１～０．１μｍであることが好ましく、０．００５～０．０８μｍであることがより好ましく、０．０１～０．０４μｍであることが特に好ましい。基材表面の前記表面粗さＲａが前記上限値以下であることで、保護膜に対してより鮮明にレーザー印字を行うことができる。
　基材表面の前記表面粗さＲａは、例えば、基材の成形条件や、表面処理条件等により、調節できる。 The surface roughness Ra of the surface (surface) provided with the pressure-sensitive adhesive layer of the substrate is preferably 0.001 to 0.1 μm, more preferably 0.005 to 0.08 μm, and A thickness of 01 to 0.04 μm is particularly preferable. When the surface roughness Ra of the substrate surface is not more than the upper limit value, laser printing can be performed more clearly on the protective film.
The surface roughness Ra of the substrate surface can be adjusted by, for example, molding conditions of the substrate, surface treatment conditions, and the like.
　なお、半導体ウエハをダイシングによって半導体チップへと個片化する方法としては、例えば、ブレードを用いて半導体ウエハを切り込むブレードダイシング、レーザー照射により半導体ウエハを切り込むレーザーダイシング、又は研磨剤を含む水の吹き付けにより半導体ウエハを切り込むウオーターダイシング等を利用する方法が挙げられる。
　一方、半導体ウエハを半導体チップへと個片化する方法としては、これらダイシングを利用する方法以外にも、半導体ウエハの内部に設定された焦点に集束されるように、赤外域のレーザー光を照射して、半導体ウエハの内部に改質層を形成した後、この半導体ウエハに対して力を加えることで、前記改質層の形成部位において半導体ウエハを分割し、個片化する方法も挙げられる。
　基材表面の前記表面粗さＲａが、例えば、０．０１～０．２μｍである場合、このような基材を備えた保護膜形成用複合シートは、上述の半導体ウエハの内部に改質層を形成して半導体ウエハを個片化する際に用いるのに好適である。 In addition, as a method of dividing the semiconductor wafer into semiconductor chips by dicing, for example, blade dicing for cutting the semiconductor wafer using a blade, laser dicing for cutting the semiconductor wafer by laser irradiation, or spraying water containing an abrasive And a method using water dicing or the like for cutting a semiconductor wafer.
On the other hand, as a method of dividing a semiconductor wafer into semiconductor chips, in addition to the method using these dicing methods, the laser beam in the infrared region is irradiated so as to be focused on the focal point set inside the semiconductor wafer. Then, after forming a modified layer inside the semiconductor wafer, a method of dividing the semiconductor wafer into individual pieces by applying force to the semiconductor wafer to form the modified layer is also mentioned. .
When the surface roughness Ra of the substrate surface is, for example, 0.01 to 0.2 μm, the protective sheet-forming composite sheet provided with such a substrate has a modified layer in the semiconductor wafer described above. It is suitable for use when forming a semiconductor wafer into individual pieces.
　一方、基材の粘着剤層を備えている面（表面）とは反対側の面（裏面）の表面粗さＲａ、換言すると、支持シートの保護膜形成用フィルムを備えている面（表面）とは反対側の面（裏面）の表面粗さＲａは、０．００１～４μｍであることが好ましく、０．００５～３．７μｍであることがより好ましく、０．０１～３．４μｍであることがさらに好ましく、０．０２～３．１μｍであることが特に好ましい。基材裏面の前記表面粗さＲａが前記上限値以下であることで、コーティング層の支持シートと接触している側とは反対側の表面における表面粗さＲａをより容易に小さくでき、保護膜に対して鮮明にレーザー印字を行うことがより容易となる。
　基材裏面の前記表面粗さＲａは、例えば、基材の成形条件や、表面処理条件等により、調節できる。 On the other hand, the surface roughness Ra of the surface (back surface) opposite to the surface (front surface) provided with the adhesive layer of the substrate, in other words, the surface (surface) provided with the protective film forming film of the support sheet. The surface roughness Ra of the opposite surface (back surface) is preferably 0.001 to 4 μm, more preferably 0.005 to 3.7 μm, and 0.01 to 3.4 μm. More preferably, the thickness is 0.02 to 3.1 μm. When the surface roughness Ra on the back surface of the substrate is less than or equal to the upper limit, the surface roughness Ra on the surface of the coating layer opposite to the side in contact with the support sheet can be more easily reduced, and the protective film In contrast, it becomes easier to perform laser printing clearly.
The surface roughness Ra of the back surface of the base material can be adjusted by, for example, molding conditions of the base material, surface treatment conditions, and the like.
　基材の材質である樹脂は、架橋されたものであってもよい。
　また、基材の材質である樹脂は、熱可塑性樹脂の押出形成によりシート化されたものであってもよいし、延伸されたものであってもよく、硬化性樹脂の公知の手段による薄層化及び硬化によって、シート化されたものであってもよい。
　また、基材は、着色されたものであってもよいし、印刷が施されたものであってもよい。 The resin that is the material of the base material may be cross-linked.
In addition, the resin that is the material of the base material may be a sheet formed by extrusion molding of a thermoplastic resin, or may be a stretched sheet, and a thin layer formed by a known means of a curable resin. It may be formed into a sheet by forming and curing.
Further, the base material may be colored or printed.
　基材は、耐熱性に優れ、かつ適度な柔軟性を有することでエキスパンド適性を有し、ピックアップ適性も良好となる点から、ポリプロピレンを含有するものが好ましい。
　ポリプロピレンを含有する基材は、例えば、ポリプロピレンのみからなる単層又は複数層の基材であってもよいし、ポリプロピレン層とポリプロピレン以外の樹脂層とが積層されてなる複数層の基材であってもよい。
　保護膜形成用フィルムが熱硬化性である場合には、基材が耐熱性を有することで、基材の熱による劣化が抑制され、半導体装置の製造プロセスにおける不具合の発生を効果的に抑制できる。 The base material is preferably one containing polypropylene from the viewpoint that it has excellent heat resistance and has an appropriate flexibility so that it has expandability and pick-up suitability.
The base material containing polypropylene may be, for example, a single layer or a plurality of layers made of only polypropylene, or a multiple layer base material in which a polypropylene layer and a resin layer other than polypropylene are laminated. May be.
When the protective film-forming film is thermosetting, the base material has heat resistance, so that deterioration of the base material due to heat can be suppressed, and occurrence of defects in the manufacturing process of the semiconductor device can be effectively suppressed. .
　基材は、その上に設けられる粘着剤層又は保護膜形成用フィルムとの接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されたものであってもよい。 In order to improve the adhesiveness with the adhesive layer or the protective film forming film provided on the substrate, the substrate is subjected to a roughening treatment such as a sandblast treatment, a solvent treatment, a corona discharge treatment, an electron beam irradiation treatment, a plasma. The surface may be subjected to oxidation treatment such as treatment, ozone / ultraviolet irradiation treatment, flame treatment, chromic acid treatment, and hot air treatment. Further, the base material may be one whose surface is primed.
・粘着剤層
　前記粘着剤層は、公知のものを適宜使用できる。
　粘着剤層は、これを構成するための、粘着剤等の各種成分を含有する粘着剤組成物を用いて形成できる。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、１５～２５℃の温度等が挙げられる。 -Adhesive layer The said adhesive layer can use a well-known thing suitably.
An adhesive layer can be formed using the adhesive composition containing various components, such as an adhesive, for comprising this. 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, and examples thereof include a temperature of 15 to 25 ° C.
　粘着剤層の厚さは、目的に応じて適宜選択できるが、１～１００μｍであることが好ましく、２～８０μｍであることがより好ましく、３～５０μｍであることが特に好ましい。 The thickness of the pressure-sensitive adhesive layer can be appropriately selected depending on the purpose, but is preferably 1 to 100 μm, more preferably 2 to 80 μm, and particularly preferably 3 to 50 μm.
　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い。粘着剤層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、上述の支持シートの場合と同様のことを意味する。
　粘着剤層が複数層からなる場合には、各層の合計の厚さが、上記の好ましい粘着剤層の厚さとなるようにするとよい。 The pressure-sensitive adhesive layer may be composed of one layer (single layer) or may be composed of two or more layers. When an adhesive layer consists of multiple layers, these multiple layers may be the same 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 support sheet.
In the case where the pressure-sensitive adhesive layer is composed of a plurality of layers, the total thickness of each layer may be set to the thickness of the preferable pressure-sensitive adhesive layer.
　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、ビニルエーテル系樹脂等の粘着性樹脂が挙げられ、その樹脂の機能に着目した場合には、例えば、エネルギー線硬化性樹脂等が挙げられる。
　なお、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、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ランプ又はキセノン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。 Examples of the pressure-sensitive adhesive include pressure-sensitive adhesive resins such as acrylic resins, urethane resins, rubber resins, silicone resins, and vinyl ether resins. Examples thereof include a linear curable resin.
In this specification, “energy beam” means an electromagnetic wave or charged particle beam having energy quanta, and examples thereof include ultraviolet rays and electron beams. Ultraviolet rays can be irradiated by using, for example, a high-pressure mercury lamp, a fusion H lamp, or a xenon lamp as an ultraviolet ray source. The electron beam can be emitted by an electron beam accelerator or the like.
　前記エネルギー線硬化性樹脂としては、例えば、（メタ）アクリロイル基、ビニル基等の重合性基を有するものが挙げられる。
　前記粘着性樹脂は、アクリル系樹脂であることが好ましく、（メタ）アクリル酸エステルに由来する構成単位を含む、（メタ）アクリル酸エステル共重合体であることがより好ましい。 Examples of the energy ray curable resin include those having a polymerizable group such as a (meth) acryloyl group and a vinyl group.
The adhesive resin is preferably an acrylic resin, and more preferably a (meth) acrylic acid ester copolymer including a structural unit derived from a (meth) acrylic acid ester.
　前記粘着剤層は、エネルギー線硬化性樹脂等の、エネルギー線の照射により重合する成分を含有している場合には、エネルギー線硬化性のものとなり、エネルギー線を照射してその粘着性を低下させることで、後述する保護膜付き半導体チップのピックアップが容易となる。このような粘着剤層は、例えば、エネルギー線の照射により重合する成分を含有する各種の粘着剤組成物を用いて形成できる。 When the pressure-sensitive adhesive layer contains a component that is polymerized by irradiation with energy rays, such as an energy ray-curable resin, the pressure-sensitive adhesive layer becomes energy-ray curable and decreases its adhesiveness by irradiation with energy rays. By doing so, it becomes easy to pick up a semiconductor chip with a protective film, which will be described later. Such a pressure-sensitive adhesive layer can be formed using, for example, various pressure-sensitive adhesive compositions containing a component that is polymerized by irradiation with energy rays.
＜＜粘着剤組成物＞＞
　前記粘着剤組成物で好ましいものとしては、エネルギー線の照射により重合する成分を含有するものが挙げられ、このような粘着剤組成物としては、例えば、アクリル系樹脂とエネルギー線重合性化合物とを含有するもの（以下、「粘着剤組成物（ｉ）」と略記することがある。）、水酸基を有し、かつ重合性基を側鎖に有する前記アクリル系樹脂（例えば、水酸基を有し、かつウレタン結合を介して重合性基を側鎖に有するもの）と、イソシアネート系架橋剤と、を含有するもの（以下、「粘着剤組成物（ｉｉ）」と略記することがある。）等が挙げられる。 << Adhesive composition >>
Preferred examples of the pressure-sensitive adhesive composition include those containing a component that polymerizes upon irradiation with energy rays. Examples of such a pressure-sensitive adhesive composition include an acrylic resin and an energy ray-polymerizable compound. What is contained (hereinafter may be abbreviated as “adhesive composition (i)”), the acrylic resin having a hydroxyl group and having a polymerizable group in the side chain (for example, having a hydroxyl group, And those having a polymerizable group in the side chain via a urethane bond) and an isocyanate-based crosslinking agent (hereinafter sometimes abbreviated as “adhesive composition (ii)”). Can be mentioned.
＜粘着剤組成物（ｉ）＞
　粘着剤組成物（ｉ）は、前記アクリル系樹脂とエネルギー線重合性化合物とを必須成分として含有する。
　以下、各成分について説明する。 <Adhesive composition (i)>
The pressure-sensitive adhesive composition (i) contains the acrylic resin and an energy beam polymerizable compound as essential components.
Hereinafter, each component will be described.
［アクリル系樹脂］
　粘着剤組成物（ｉ）における前記アクリル系樹脂で好ましいものとしては、例えば、モノマーとして（メタ）アクリル酸エステルと、必要に応じて用いられる、（メタ）アクリル酸エステル以外のモノマーと、を重合して得られた、（メタ）アクリル酸エステル共重合体が挙げられる。 [Acrylic resin]
Preferred examples of the acrylic resin in the pressure-sensitive adhesive composition (i) include, for example, polymerization of (meth) acrylic acid ester as a monomer and a monomer other than (meth) acrylic acid ester used as necessary. The (meth) acrylic acid ester copolymer obtained by this is mentioned.
　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）アクリル酸プロピル、（メタ）アクリル酸ブチル、（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ｎ－オクチル、（メタ）アクリル酸イソオクチル、（メタ）アクリル酸２－エチルヘキシル、（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基、（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）アクリル酸イソオクタデシル（（メタ）アクリル酸イソステアリル）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等が挙げられる。 Examples of the (meth) acrylic acid ester include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, (meth) Hexyl acrylate, heptyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-nonyl (meth) acrylate, (meth) acrylic acid Isononyl, decyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate (lauryl (meth) acrylate), tridecyl (meth) acrylate, tetradecyl (meth) acrylate ((meth) acrylic acid) Myristyl), pentadecyl (meth) acrylate, hexa (meth) acrylate Sil (palmethyl (meth) acrylate), heptadecyl (meth) acrylate, octadecyl (meth) acrylate (stearyl (meth) acrylate), isooctadecyl (meth) acrylate (isostearyl (meth) acrylate), etc. And (meth) acrylic acid alkyl ester in which the alkyl group constituting the alkyl ester has 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-containing (meth) acrylic acid esters such as 3-hydroxybutyl acrylate and 4-hydroxybutyl (meth) acrylate.
　前記（メタ）アクリル酸エステル以外のモノマーとしては、例えば、（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、Ｎ－メチロールアクリルアミド等が挙げられる。 Examples of the monomer other than the (meth) acrylic acid ester include (meth) acrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene, N-methylolacrylamide and the like.
　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、前記（メタ）アクリル酸エステル以外のモノマー等の各種モノマーは、いずれも１種のみでもよいし、２種以上でもよい。 As for various monomers, such as said (meth) acrylic acid ester and monomers other than said (meth) acrylic acid ester which comprise acrylic resin, all may be only 1 type, and 2 or more types may be sufficient as them.
　粘着剤組成物（ｉ）が含有するアクリル系樹脂は、１種のみでもよいし、２種以上でもよい。 The acrylic resin contained in the pressure-sensitive adhesive composition (i) may be one kind or two or more kinds.
　粘着剤組成物（ｉ）のアクリル系樹脂の含有量は、粘着剤組成物（ｉ）中の溶媒以外の全ての含有成分の総量に対して４０～９９質量％であることが好ましく、５０～９１量％であることがより好ましい。 The content of the acrylic resin in the pressure-sensitive adhesive composition (i) is preferably 40 to 99% by mass with respect to the total amount of all the components other than the solvent in the pressure-sensitive adhesive composition (i), More preferably, it is 91% by weight.
［エネルギー線重合性化合物］
　前記エネルギー線重合性化合物は、エネルギー線の照射により重合して硬化する化合物であり、その例としては、分子内にエネルギー線硬化性二重結合等のエネルギー線重合性基を有するものが挙げられる。 [Energy ray polymerizable compound]
The energy ray polymerizable compound is a compound that is polymerized and cured by irradiation with energy rays, and examples thereof include those having an energy ray polymerizable group such as an energy ray curable double bond in the molecule. .
　前記エネルギー線重合性化合物としては、例えば、エネルギー線重合性基を有する低分子量化合物（単官能又は多官能のモノマー及びオリゴマー）が挙げられ、より具体的には、トリメチロールプロパントリアクリレート、テトラメチロールメタンテトラアクリレート、ペンタエリスリトールトリアクリレート、ジペンタエリスリトールモノヒドロキシペンタアクリレート、ジペンタエリスリトールヘキサアクリレート、１，４－ブチレングリコールジアクリレート、１，６－ヘキサンジオールジアクリレート等のアクリレート；
　ジシクロペンタジエンジメトキシジアクリレート等の環状脂肪族骨格含有アクリレート；
　ポリエチレングリコールジアクリレート、オリゴエステルアクリレート、ウレタンアクリレートオリゴマー、エポキシ変性アクリレート、ポリエーテルアクリレート、イタコン酸オリゴマー等のアクリレート系化合物等が挙げられる。 Examples of the energy ray polymerizable compound include low molecular weight compounds (monofunctional or polyfunctional monomers and oligomers) having an energy ray polymerizable group, and more specifically, trimethylolpropane triacrylate, tetramethylol. Acrylates such as methanetetraacrylate, pentaerythritol triacrylate, dipentaerythritol monohydroxypentaacrylate, dipentaerythritol hexaacrylate, 1,4-butylene glycol diacrylate, 1,6-hexanediol diacrylate;
Cyclic aliphatic skeleton-containing acrylates such as dicyclopentadiene dimethoxydiacrylate;
Examples include acrylate compounds such as polyethylene glycol diacrylate, oligoester acrylate, urethane acrylate oligomer, epoxy-modified acrylate, polyether acrylate, and itaconic acid oligomer.
　前記エネルギー線重合性化合物は、分子量が１００～３００００であることが好ましく、３００～１００００であることがより好ましい。 The molecular weight of the energy beam polymerizable compound is preferably 100 to 30,000, and more preferably 300 to 10,000.
　粘着剤組成物（ｉ）が含有するエネルギー線重合性化合物は、１種のみでもよいし、２種以上でもよい。 The energy ray polymerizable compound contained in the pressure-sensitive adhesive composition (i) may be only one type, or two or more types.
　粘着剤組成物（ｉ）のエネルギー線重合性化合物の含有量は、前記アクリル系樹脂の含有量１００質量部に対して、１～１２５質量部であることが好ましく、１０～１２５質量部であることがより好ましい。 The content of the energy ray polymerizable compound in the pressure-sensitive adhesive composition (i) is preferably 1 to 125 parts by mass with respect to 100 parts by mass of the acrylic resin, and 10 to 125 parts by mass. It is more preferable.
［光重合開始剤］
　粘着剤組成物（ｉ）は、前記アクリル系樹脂及びエネルギー線重合性化合物以外に、光重合開始剤を含有していてもよい。
　前記光重合開始剤は、公知のものでよく、具体的には、例えば、４－（２－ヒドロキシエトキシ）フェニル（２－ヒドロキシ－２－プロピル）ケトン、α－ヒドロキシ－α，α’－ジメチルアセトフェノン、２－メチル－２－ヒドロキシプロピオフェノン、１－ヒドロキシシクロヘキシルフェニルケトン、２－ヒロドキシ－１－｛４－［４－（２－ヒドロキシ－２－メチル－プロピオニル）－ベンジル］フェニル｝－２－メチル－プロパン－１－オン等のα－ケトール系化合物；
　メトキシアセトフェノン、２，２－ジメトキシ－２－フェニルアセトフェノン、２，２－ジエトキシアセトフェノン、２－メチル－１－［４－（メチルチオ）フェニル］－２－モルホリノプロパン－１－オン等のアセトフェノン系化合物；
　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、アニソインメチルエーテル等のベンゾインエーテル系化合物；
　ベンジルジメチルケタール等のケタール系化合物；
　２－ナフタレンスルホニルクロリド等の芳香族スルホニルクロリド系化合物；
　１－フェノン－１，１－プロパンジオン－２－（ｏ－エトキシカルボニル）オキシム等の光活性オキシム系化合物；
　ベンゾフェノン、ベンゾイル安息香酸、３，３’－ジメチル－４－メトキシベンゾフェノン等のベンゾフェノン系化合物；
　チオキサンソン、２－クロロチオキサンソン、２－メチルチオキサンソン、２，４－ジメチルチオキサンソン、イソプロピルチオキサンソン、２，４－ジクロロチオキサンソン、２，４－ジエチルチオキサンソン、２，４－ジイソプロピルチオキサンソン等のチオキサンソン系化合物；
　カンファーキノン；ハロゲン化ケトン；アシルホスフィノキシド；アシルホスフォナート等が挙げられる。 [Photopolymerization initiator]
The pressure-sensitive adhesive composition (i) may contain a photopolymerization initiator in addition to the acrylic resin and the energy beam polymerizable compound.
The photopolymerization initiator may be a known one, and specifically, for example, 4- (2-hydroxyethoxy) phenyl (2-hydroxy-2-propyl) ketone, α-hydroxy-α, α′-dimethyl Acetophenone, 2-methyl-2-hydroxypropiophenone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2 Α-ketol compounds such as methyl-propan-1-one;
Acetophenone compounds such as methoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one ;
Benzoin ether compounds such as benzoin ethyl ether, benzoin isopropyl ether and anisoin methyl ether;
Ketal compounds such as benzyldimethyl ketal;
Aromatic sulfonyl chloride compounds such as 2-naphthalenesulfonyl chloride;
Photoactive oxime compounds such as 1-phenone-1,1-propanedione-2- (o-ethoxycarbonyl) oxime;
Benzophenone compounds such as benzophenone, benzoylbenzoic acid, 3,3′-dimethyl-4-methoxybenzophenone;
Thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-diethylthioxanthone, 2,4 A thioxanthone compound such as diisopropylthioxanthone;
Examples include camphorquinone; halogenated ketone; acyl phosphinoxide; acyl phosphonate.
　粘着剤組成物（ｉ）が含有する光重合開始剤は、１種のみでもよいし、２種以上でもよい。 The photopolymerization initiator contained in the pressure-sensitive adhesive composition (i) may be one kind or two or more kinds.
　光重合開始剤を用いる場合、粘着剤組成物（ｉ）の光重合開始剤の含有量は、前記エネルギー線重合性化合物の含有量１００質量部に対して、０．１～１０質量部であることが好ましく、１～５質量部であることがより好ましい。光重合開始剤の前記含有量が前記下限値以上であることで、光重合開始剤を用いたことによる効果が十分に得られる。また、光重合開始剤の前記含有量が前記上限値以下であることで、過剰な光重合開始剤からの副生成分の発生が抑制されて、粘着剤層の硬化がより良好に進行する。 When a photopolymerization initiator is used, the content of the photopolymerization initiator in the pressure-sensitive adhesive composition (i) is 0.1 to 10 parts by mass with respect to 100 parts by mass of the energy beam polymerizable compound. It is preferably 1 to 5 parts by mass. The effect by using a photoinitiator is fully acquired because the said content of a photoinitiator is more than the said lower limit. Moreover, generation | occurrence | production of the by-product from an excess photoinitiator is suppressed because the said content of a photoinitiator is below the said upper limit, and hardening of an adhesive layer advances more favorably.
［架橋剤］
　粘着剤組成物（ｉ）は、前記アクリル系樹脂及びエネルギー線重合性化合物以外に、架橋剤を含有していてもよい。
　前記架橋剤としては、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等が挙げられる。 [Crosslinking agent]
The pressure-sensitive adhesive composition (i) may contain a crosslinking agent in addition to the acrylic resin and the energy beam polymerizable compound.
Examples of the crosslinking agent include organic polyvalent isocyanate compounds and organic polyvalent imine compounds.
　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、脂環族多価イソシアネート化合物並びにこれら化合物の三量体、イソシアヌレート体及びアダクト体や、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する。 Examples of the organic polyvalent isocyanate compound include aromatic polyvalent isocyanate compounds, aliphatic polyvalent isocyanate compounds, alicyclic polyvalent isocyanate compounds, trimers of these compounds, isocyanurates, adducts, and the aromatic And a terminal isocyanate urethane prepolymer obtained by reacting an aliphatic polyvalent isocyanate compound, an aliphatic polyvalent isocyanate compound, or an alicyclic polyvalent isocyanate compound and a polyol compound. The adduct is composed of the aromatic polyvalent isocyanate compound, the aliphatic polyvalent isocyanate compound or the alicyclic polyvalent isocyanate compound, and low molecular activity such as ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane or castor oil. A reactant with a hydrogen-containing compound is meant.
　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若しくは一部の水酸基に、トリレンジイソシアネート及びヘキサメチレンジイソシアネートのいずれか一方又は両方を付加した化合物；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 A compound in which either one or both of tolylene diisocyanate and hexamethylene diisocyanate are added to all or some of the hydroxyl groups of a polyol such as propane. ; 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.
　架橋剤としてイソシアネート化合物を用いる場合、アクリル系樹脂としては、水酸基含有重合体を用いることが好ましい。架橋剤がイソシアネート基を有し、アクリル系樹脂が水酸基を有する場合、これらイソシアネート基と水酸基との反応によって、粘着剤層に架橋構造を簡便に導入できる。 When an isocyanate compound is used as the crosslinking agent, it is preferable to use a hydroxyl group-containing polymer as the acrylic resin. When the crosslinking agent has an isocyanate group and the acrylic resin has a hydroxyl group, a crosslinked structure can be easily introduced into the pressure-sensitive adhesive layer by a reaction between the isocyanate group and the hydroxyl group.
　粘着剤組成物（ｉ）が含有する架橋剤は、１種のみでもよいし、２種以上でもよい。 The cross-linking agent contained in the pressure-sensitive adhesive composition (i) may be one type or two or more types.
　架橋剤を用いる場合、粘着剤組成物（ｉ）の架橋剤の含有量は、前記アクリル系樹脂の含有量１００質量部に対して、０．０１～２０質量部であることが好ましく、０．１～１６質量部であることがより好ましい。 When a crosslinking agent is used, the content of the crosslinking agent in the pressure-sensitive adhesive composition (i) is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the acrylic resin. It is more preferably 1 to 16 parts by mass.
［溶媒］
　粘着剤組成物（ｉ）は、前記アクリル系樹脂及びエネルギー線重合性化合物以外に、さらに溶媒を含有することが好ましい。
　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。
　粘着剤組成物（ｉ）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。 [solvent]
The pressure-sensitive adhesive composition (i) preferably further contains a solvent in addition to the acrylic resin and the energy beam polymerizable compound.
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.
As for the solvent which adhesive composition (i) contains, only 1 type may be sufficient and 2 or more types may be sufficient.
　粘着剤組成物（ｉ）が溶媒を含有する場合の溶媒の含有量は、４０～９０質量％であることが好ましく、５０～８０質量％であることがより好ましい。 When the pressure-sensitive adhesive composition (i) contains a solvent, the content of the solvent is preferably 40 to 90% by mass, and more preferably 50 to 80% by mass.
［その他の成分］
　粘着剤組成物（ｉ）は、前記アクリル系樹脂及びエネルギー線重合性化合物以外に、本発明の効果を損なわない範囲内において、前記光重合開始剤、架橋剤及び溶媒に該当しないその他の成分を含有していてもよい。
　前記その他の成分は、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、染料、顔料、劣化防止剤、帯電防止剤、難燃剤、シリコーン化合物、連鎖移動剤等の各種添加剤が挙げられる。
　粘着剤組成物（ｉ）が含有する前記その他の成分は、１種のみでもよいし、２種以上でもよい。 [Other ingredients]
The pressure-sensitive adhesive composition (i) contains, in addition to the acrylic resin and the energy beam polymerizable compound, other components not corresponding to the photopolymerization initiator, the crosslinking agent, and the solvent within a range not impairing the effects of the present invention. You may contain.
The other components may be known ones and can be arbitrarily selected according to the purpose, and are not particularly limited. Preferred examples include dyes, pigments, deterioration inhibitors, antistatic agents, flame retardants, and silicone compounds. And various additives such as a chain transfer agent.
The said other component which an adhesive composition (i) contains may be only 1 type, and 2 or more types may be sufficient as it.
＜粘着剤組成物（ｉｉ）＞
　粘着剤組成物（ｉｉ）は、水酸基を有し、かつ重合性基を側鎖に有するアクリル系樹脂（例えば、水酸基を有し、かつウレタン結合を介して重合性基を側鎖に有するもの）と、イソシアネート系架橋剤と、を必須成分として含有する。
　粘着剤組成物（ｉｉ）を用いた場合には、アクリル系樹脂が重合性基を側鎖に有することにより、粘着剤組成物（ｉ）の場合のように、エネルギー線重合性化合物を用いて、エネルギー線の照射により重合反応させた場合よりも、重合反応（硬化）後の粘着剤層の粘着性低下による被着体からの剥離性が向上し、保護膜付き半導体チップのピックアップ性が向上する。
　なお、本明細書においては、粘着剤組成物（ｉｉ）における「アクリル系樹脂」との記載は、特に断りのない限り、「重合性基を側鎖に有するアクリル系樹脂」を意味するものとする。 <Adhesive composition (ii)>
The pressure-sensitive adhesive composition (ii) is an acrylic resin having a hydroxyl group and having a polymerizable group in the side chain (for example, having a hydroxyl group and having a polymerizable group in the side chain via a urethane bond). And an isocyanate-based crosslinking agent as essential components.
When the pressure-sensitive adhesive composition (ii) is used, the acrylic resin has a polymerizable group in the side chain, so that the energy ray polymerizable compound is used as in the case of the pressure-sensitive adhesive composition (i). Compared with the case where the polymerization reaction is performed by irradiation with energy rays, the peelability from the adherend is improved due to the reduced adhesiveness of the pressure-sensitive adhesive layer after the polymerization reaction (curing), and the pick-up property of the semiconductor chip with a protective film is improved. To do.
In the present specification, the description of “acrylic resin” in the pressure-sensitive adhesive composition (ii) means “acrylic resin having a polymerizable group in a side chain” unless otherwise specified. To do.
［アクリル系樹脂］
　上述の重合性基を側鎖に有するアクリル系樹脂としては、例えば、モノマーとして、水酸基を有しない水酸基非含有（メタ）アクリル酸エステルと、水酸基を有する水酸基含有（メタ）アクリル酸エステル等の水酸基含有化合物と、を共重合させ、得られた水酸基含有共重合体の水酸基に、イソシアネート基及び重合性基を有する化合物のイソシアネート基を反応させて、ウレタン結合を形成して得られたものが挙げられる。 [Acrylic resin]
Examples of the acrylic resin having a polymerizable group in the side chain include hydroxyl groups such as a hydroxyl group-free (meth) acrylate ester having no hydroxyl group and a hydroxyl group-containing (meth) acrylate ester having a hydroxyl group. And a compound obtained by reacting the hydroxyl group of the resulting hydroxyl group-containing copolymer with the isocyanate group of a compound having an isocyanate group and a polymerizable group to form a urethane bond. It is done.
　前記水酸基非含有（メタ）アクリル酸エステルとしては、例えば、粘着剤組成物（ｉ）における（メタ）アクリル酸エステルのうち、水酸基含有（メタ）アクリル酸エステル以外のものが挙げられる。
　また、前記水酸基含有化合物としては、粘着剤組成物（ｉ）における水酸基含有（メタ）アクリル酸エステルと同じものが挙げられる。
　前記アクリル系樹脂を構成する、水酸基非含有（メタ）アクリル酸エステル及び水酸基含有化合物は、それぞれ１種のみでもよいし、２種以上でもよい。 Examples of the hydroxyl group-free (meth) acrylic acid ester include those other than the hydroxyl group-containing (meth) acrylic acid ester among the (meth) acrylic acid esters in the pressure-sensitive adhesive composition (i).
Moreover, as said hydroxyl-containing compound, the same thing as the hydroxyl-containing (meth) acrylic acid ester in adhesive composition (i) is mentioned.
Each of the hydroxyl group-free (meth) acrylic acid ester and the hydroxyl group-containing compound constituting the acrylic resin may be one type or two or more types.
　前記イソシアネート基及び重合性基を有する化合物としては、例えば、２－メタクリロイルオキシエチルイソシアネート等のイソシアネート基含有（メタ）アクリル酸エステル等が挙げられる。
　前記アクリル系樹脂を構成する、前記イソシアネート基及び重合性基を有する化合物は、１種のみでもよいし、２種以上でもよい。 Examples of the compound having an isocyanate group and a polymerizable group include isocyanate group-containing (meth) acrylic acid esters such as 2-methacryloyloxyethyl isocyanate.
The compound which has the said isocyanate group and polymeric group which comprises the said acrylic resin may be only 1 type, and 2 or more types may be sufficient as it.
　粘着剤組成物（ｉｉ）が含有するアクリル系樹脂は、１種のみでもよいし、２種以上でもよい。 The acrylic resin contained in the pressure-sensitive adhesive composition (ii) may be one kind or two or more kinds.
　粘着剤組成物（ｉｉ）のアクリル系樹脂の含有量は、粘着剤組成物（ｉｉ）中の溶媒以外の全ての含有成分の総量に対して８０～９９質量％であることが好ましく、９０～９７質量％であることがより好ましい。 The content of the acrylic resin in the pressure-sensitive adhesive composition (ii) is preferably 80 to 99% by mass, based on the total amount of all the components other than the solvent in the pressure-sensitive adhesive composition (ii), More preferably, it is 97 mass%.
［イソシアネート系架橋剤］
　前記イソシアネート系架橋剤としては、例えば、粘着剤組成物（ｉ）における架橋剤である前記有機多価イソシアネート化合物と同じものが挙げられる。 [Isocyanate-based crosslinking agent]
As said isocyanate type crosslinking agent, the same thing as the said organic polyvalent isocyanate compound which is a crosslinking agent in adhesive composition (i) is mentioned, for example.
　粘着剤組成物（ｉｉ）が含有するイソシアネート系架橋剤は、１種のみでもよいし、２種以上でもよい。 The isocyanate-based crosslinking agent contained in the pressure-sensitive adhesive composition (ii) may be only one type, or two or more types.
　粘着剤組成物（ｉｉ）中のイソシアネート系架橋剤が有するイソシアネート基のモル数は、粘着剤組成物（ｉｉ）中のアクリル系樹脂が有する水酸基のモル数に対して０．２～３倍であることが好ましい。イソシアネート基の前記モル数が前記下限値以上であることで、硬化後の粘着剤層の粘着性低下による被着体からの剥離性が向上し、保護膜付き半導体チップのピックアップ性が向上する。また、イソシアネート基の前記モル数が前記上限値以下であることで、イソシアネート系架橋剤同士の反応による副生成物の発生をより抑制できる。 The number of moles of isocyanate groups possessed by the isocyanate-based crosslinking agent in the pressure-sensitive adhesive composition (ii) is 0.2 to 3 times the number of moles of hydroxyl groups possessed by the acrylic resin in the pressure-sensitive adhesive composition (ii). Preferably there is. When the number of moles of the isocyanate group is equal to or more than the lower limit, the peelability from the adherend due to the decrease in the tackiness of the pressure-sensitive adhesive layer after curing is improved, and the pick-up property of the semiconductor chip with a protective film is improved. Moreover, generation | occurrence | production of the by-product by reaction of isocyanate type crosslinking agents can be suppressed more because the said mole number of an isocyanate group is below the said upper limit.
　粘着剤組成物（ｉｉ）のイソシアネート系架橋剤の含有量は、イソシアネート基のモル数が上述のような範囲となるように適宜調節すればよいが、このような条件を満たしたうえで、アクリル系樹脂の含有量１００質量部に対して、０．０１～２０質量部であることが好ましく、０．１～１５質量部であることがより好ましく、０．３～１２質量部であることが特に好ましい。 The content of the isocyanate-based crosslinking agent in the pressure-sensitive adhesive composition (ii) may be adjusted as appropriate so that the number of moles of the isocyanate group falls within the above-mentioned range. The content is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 15 parts by mass, and 0.3 to 12 parts by mass with respect to 100 parts by mass of the resin content. Particularly preferred.
［光重合開始剤］
　粘着剤組成物（ｉｉ）は、前記アクリル系樹脂及びイソシアネート系架橋剤以外に、光重合開始剤を含有していてもよい。
　前記光重合開始剤としては、例えば、粘着剤組成物（ｉ）の場合と同じものが挙げられる。
　粘着剤組成物（ｉｉ）が含有する光重合開始剤は、１種のみでもよいし、２種以上でもよい。 [Photopolymerization initiator]
The pressure-sensitive adhesive composition (ii) may contain a photopolymerization initiator in addition to the acrylic resin and the isocyanate-based crosslinking agent.
As said photoinitiator, the same thing as the case of adhesive composition (i) is mentioned, for example.
The photopolymerization initiator contained in the pressure-sensitive adhesive composition (ii) may be only one type or two or more types.
　光重合開始剤を用いる場合、粘着剤組成物（ｉｉ）の光重合開始剤の含有量は、アクリル系樹脂の含有量１００質量部に対して、０．０５～２０質量部であることが好ましい。
光重合開始剤の前記含有量が前記下限値以上であることで、光重合開始剤を用いたことによる効果が十分に得られる。また、光重合開始剤の前記含有量が前記上限値以下であることで、過剰な光重合開始剤からの副生成分の発生が抑制されて、粘着剤層の硬化がより良好に進行する。 When the photopolymerization initiator is used, the content of the photopolymerization initiator in the pressure-sensitive adhesive composition (ii) is preferably 0.05 to 20 parts by mass with respect to 100 parts by mass of the acrylic resin. .
The effect by using a photoinitiator is fully acquired because the said content of a photoinitiator is more than the said lower limit. Moreover, generation | occurrence | production of the by-product from an excess photoinitiator is suppressed because the said content of a photoinitiator is below the said upper limit, and hardening of an adhesive layer advances more favorably.
［溶媒］
　粘着剤組成物（ｉｉ）は、前記アクリル系樹脂及びイソシアネート系架橋剤以外に、さらに溶媒を含有することが好ましい。
　前記溶媒としては、例えば、粘着剤組成物（ｉ）の場合と同じものが挙げられる。
　粘着剤組成物（ｉｉ）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。 [solvent]
The pressure-sensitive adhesive composition (ii) preferably further contains a solvent in addition to the acrylic resin and the isocyanate-based crosslinking agent.
As said solvent, the same thing as the case of adhesive composition (i) is mentioned, for example.
As for the solvent which adhesive composition (ii) contains, 1 type may be sufficient and 2 or more types may be sufficient as it.
　粘着剤組成物（ｉｉ）が溶媒を含有する場合の溶媒の含有量は、４０～９０質量％であることが好ましく、５０～８０質量％であることがより好ましい。 In the case where the pressure-sensitive adhesive composition (ii) contains a solvent, the content of the solvent is preferably 40 to 90% by mass, more preferably 50 to 80% by mass.
［その他の成分］
　粘着剤組成物（ｉｉ）は、前記アクリル系樹脂及びイソシアネート系架橋剤以外に、本発明の効果を損なわない範囲内において、前記光重合開始剤及び溶媒に該当しないその他の成分を含有していてもよい。
　前記その他の成分としては、例えば、粘着剤組成物（ｉ）の場合と同じものが挙げられる。
　粘着剤組成物（ｉｉ）が含有する前記その他の成分は、１種のみでもよいし、２種以上でもよい。 [Other ingredients]
The pressure-sensitive adhesive composition (ii) contains, in addition to the acrylic resin and the isocyanate-based crosslinking agent, other components that do not correspond to the photopolymerization initiator and the solvent, as long as the effects of the present invention are not impaired. Also good.
As said other component, the same thing as the case of adhesive composition (i) is mentioned, for example.
The said other component which an adhesive composition (ii) contains may be only 1 type, and 2 or more types may be sufficient as it.
　ここまでは、エネルギー線の照射により重合する成分を含有する粘着剤組成物について説明したが、粘着剤層の形成には、エネルギー線の照射により重合する成分を含有しない粘着剤組成物を用いてもよい。すなわち、粘着剤層はエネルギー線硬化性を有しない、非エネルギー線硬化性のものでもよい。
　このような非エネルギー線硬化性粘着剤組成物で好ましいものとしては、例えば、アクリル系樹脂及び架橋剤を含有するもの（以下、「粘着剤組成物（ｉｉｉ）」と略記することがある。）等が挙げられ、溶媒、溶媒に該当しないその他の成分等の任意成分を含有していてもよい。 Up to this point, the pressure-sensitive adhesive composition containing a component that is polymerized by irradiation with energy rays has been described. For the formation of the pressure-sensitive adhesive layer, a pressure-sensitive adhesive composition that does not contain a component that is polymerized by irradiation with energy rays is used. Also good. That is, the pressure-sensitive adhesive layer may be non-energy ray curable without energy ray curable.
Preferred examples of such a non-energy ray-curable pressure-sensitive adhesive composition include an acrylic resin and a crosslinking agent (hereinafter, sometimes abbreviated as “pressure-sensitive adhesive composition (iii)”). And may contain optional components such as a solvent and other components not corresponding to the solvent.
＜粘着剤組成物（ｉｉｉ）＞
　粘着剤組成物（ｉｉｉ）が含有する前記アクリル系樹脂、架橋剤、溶媒及びその他の成分は、いずれも粘着剤組成物（ｉ）におけるものと同様のものである。 <Adhesive composition (iii)>
The acrylic resin, crosslinking agent, solvent and other components contained in the pressure-sensitive adhesive composition (iii) are all the same as those in the pressure-sensitive adhesive composition (i).
　粘着剤組成物（ｉｉｉ）のアクリル系樹脂の含有量は、粘着剤組成物（ｉｉｉ）中の溶媒以外の全ての含有成分の総量に対して４０～９９質量％であることが好ましく、５０～９３質量％であることがより好ましい。 The content of the acrylic resin in the pressure-sensitive adhesive composition (iii) is preferably 40 to 99% by mass with respect to the total amount of all the components other than the solvent in the pressure-sensitive adhesive composition (iii), and is preferably 50 to It is more preferable that it is 93 mass%.
　粘着剤組成物（ｉｉｉ）の架橋剤の含有量は、アクリル系樹脂の含有量１００質量部に対して、３～３０質量部であることが好ましく、５～２５質量部であることがより好ましい。 The content of the crosslinking agent in the pressure-sensitive adhesive composition (iii) is preferably 3 to 30 parts by mass and more preferably 5 to 25 parts by mass with respect to 100 parts by mass of the acrylic resin. .
　粘着剤組成物（ｉｉｉ）は、上述の点以外は、粘着剤組成物（ｉ）と同様のものである。 The pressure-sensitive adhesive composition (iii) is the same as the pressure-sensitive adhesive composition (i) except for the points described above.
＜＜粘着剤組成物の製造方法＞＞
　粘着剤組成物（ｉ）～（ｉｉｉ）等の前記粘着剤組成物は、前記粘着剤と、必要に応じて前記粘着剤以外の成分等の、各粘着剤組成物を構成するための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。
　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 such as pressure-sensitive adhesive compositions (i) to (iii) include the components for constituting each pressure-sensitive adhesive composition, such as the pressure-sensitive adhesive and components other than the pressure-sensitive adhesive as necessary. It is obtained by blending.
The order of addition at the time of blending each component is not particularly limited, and two or more components may be added simultaneously.
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.
○保護膜形成用フィルム
　前記保護膜形成用フィルムは、熱硬化性及びエネルギー線硬化性のいずれでもあってもよい。保護膜形成用フィルムは、硬化を経て最終的には耐衝撃性が高い保護膜となる。この保護膜は、例えば、ダイシング工程以降の半導体チップにおける、クラックの発生を防止する。
　保護膜形成用フィルムは、後述する熱硬化性保護膜形成用組成物又はエネルギー線硬化性保護膜形成用組成物（以下、これらを包括して「保護膜形成用組成物」と称することがある）を用いて形成できる。 ○ Protective film-forming film The protective film-forming film may be either thermosetting or energy ray-curable. The film for forming a protective film is cured and finally becomes a protective film having high impact resistance. This protective film prevents the occurrence of cracks in the semiconductor chip after the dicing process, for example.
The protective film-forming film may be referred to as a thermosetting protective film-forming composition or an energy ray-curable protective film-forming composition (hereinafter referred to as a “protective film-forming composition”). ).
　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 protective film-forming film may be only one layer (single layer), or may be two or more layers. In the case of a plurality of layers, these layers may be the same or different from each other. The combination is not particularly limited.
　保護膜形成用フィルムの厚さは、特に限定されないが、１～１００μｍであることが好ましく、５～７５μｍであることがより好ましく、５～５０μｍであることが特に好ましい。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、被着体である半導体ウエハ及び半導体チップに対する接着力が、より大きくなる。また、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により、半導体チップのピックアップ時に、せん断力を利用して硬化物である保護膜をより容易に切断できる。 The thickness of the protective film-forming film is not particularly limited, but is preferably 1 to 100 μm, more preferably 5 to 75 μm, and particularly preferably 5 to 50 μm. When the thickness of the protective film-forming film is equal to or more than the lower limit value, the adhesive force to the adherend semiconductor wafer and semiconductor chip is further increased. Moreover, when the thickness of the film for forming a protective film is not more than the above upper limit value, the protective film, which is a cured product, can be more easily cut using a shearing force when the semiconductor chip is picked up.
・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、本発明において重合反応には、重縮合反応も含まれる。 -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 invention, the polymerization reaction includes a polycondensation reaction.
＜＜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、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。 Application of the thermosetting protective film forming composition may be performed by a known method, for example, air knife coater, blade coater, bar coater, gravure coater, roll coater, roll knife coater, curtain coater, die coater, Examples include a method using various coaters such as a knife coater, a screen coater, a Meyer bar coater, and a kiss coater.
　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、７０～１３０℃で１０秒～５分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, drying is preferably performed at 70 to 130 ° C. for 10 seconds to 5 minutes.
＜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、「保護膜形成用組成物（ＩＩＩ－１）」と略記することがある）等が挙げられる。 <Composition for forming protective film (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 abbreviated as “composition for forming protective film (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。
　保護膜形成用組成物（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 protective film-forming composition (III-1) and the thermosetting protective film-forming film may be only one type, two or more types, or two or more types. These combinations and ratios 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、１００００～２００００００であることが好ましく、１０００００～１５０００００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。 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 10,000 to 2,000,000, and more preferably 100,000 to 1500,000. 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.
　アクリル系樹脂のガラス転移温度（Ｔｇ）は、－６０～７０℃であることが好ましく、－３０～５０℃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、熱硬化性保護膜形成用フィルム及び保護膜の被着体との接着力が向上する。 The glass transition temperature (Tg) of the acrylic resin is preferably −60 to 70 ° C., and more preferably −30 to 50 ° C. 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 is suppressed, and the peelability of the support sheet is improved. Moreover, the adhesive force with the to-be-adhered body of the thermosetting protective film formation film and a protective film improves because Tg of acrylic resin is below the said upper limit.
　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.
　本実施形態においては、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 embodiment, as the polymer component (A), a thermoplastic resin other than the acrylic resin (hereinafter sometimes simply referred to as “thermoplastic resin”) may be used in combination with the 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１０００～１０００００であることが好ましく、３０００～８００００であることがより好ましい。 The weight average molecular weight of the thermoplastic resin is preferably 1000 to 100,000, more preferably 3000 to 80,000.
　前記熱可塑性樹脂のガラス転移温度（Ｔｇ）は、－３０～１５０℃であることが好ましく、－２０～１２０℃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., and 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.
　保護膜形成用組成物（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 protective film-forming composition (III-1) and the thermosetting protective film-forming film may be only one kind, two kinds or more, and when there are two kinds or more, These combinations and ratios can be arbitrarily selected.
　保護膜形成用組成物（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、５～５０質量％であることが好ましく、１０～４０質量％であることがより好ましく、１５～３５質量％であることが特に好ましい。 In the protective film forming 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 of the thermosetting protective film forming film) The content of (A) is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and 15 to 35% by mass, regardless of the type of the polymer component (A). It is particularly preferred.
　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。本発明においては、保護膜形成用組成物（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、保護膜形成用組成物（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 invention, when the protective film-forming composition (III-1) contains components corresponding to both the polymer component (A) and the thermosetting component (B), the protective film-forming composition is used. 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。
　保護膜形成用組成物（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 protective film-forming composition (III-1) and the thermosetting protective film-forming film may be one kind, two kinds or more, and two kinds or more. In this case, the combination and ratio 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。
　保護膜形成用組成物（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 protective film-forming composition (III-1) and the thermosetting protective film-forming film may be only one type, two or more types, or two or more types. These combinations and ratios 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パッケージ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, the reliability of the package obtained using the composite sheet for forming a protective film is improved by using an epoxy resin having an unsaturated hydrocarbon group.
　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。
　なお、本明細書において「誘導体」とは、元の化合物の１個以上の水素原子が水素原子以外の基（置換基）で置換されてなるものを意味する。 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.
In the present specification, the “derivative” means one obtained by substituting one or more hydrogen atoms of the original compound with a group (substituent) other than a hydrogen atom.
　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、３００～３００００であることが好ましく、３００～１００００であることがより好ましく、３００～３０００であることが特に好ましい。
　エポキシ樹脂（Ｂ１）のエポキシ当量は、１００～１１００ｇ／ｅｑであることが好ましく、１５０～１０００ｇ／ｅｑであることがより好ましい。 The number average molecular weight of the epoxy resin (B1) is not particularly limited, but is 300 to 30000 from the viewpoint of the curability of the thermosetting protective film-forming film and the strength and heat resistance of the cured protective film. Preferably, it is 300 to 10,000, more preferably 300 to 3000.
The epoxy equivalent of the epoxy resin (B1) is preferably 100 to 1100 g / eq, and more preferably 150 to 1000 g / eq.
　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系フェノール樹脂、アラルキル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 phenolic resins, biphenols, novolac-type phenolic resins, dicyclopentadiene-based phenolic resins, and aralkylphenolic 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, and the 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 the 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）は、常温では固形で、かつエポキシ樹脂（Ｂ１）に対して硬化活性を示さず、一方で、加熱によって溶解し、かつエポキシ樹脂（Ｂ１）に対して硬化活性を示す熱硬化剤（以下、「熱活性潜在性エポキシ樹脂硬化剤」と略記することがある）であることが好ましい。
　前記熱活性潜在性エポキシ樹脂硬化剤は、常温では熱硬化性保護膜形成用フィルムにおいて、エポキシ樹脂（Ｂ１）中に安定して分散しているが、加熱によってエポキシ樹脂（Ｂ１）と相溶し、エポキシ樹脂（Ｂ１）と反応する。前記熱活性潜在性エポキシ樹脂硬化剤を用いることで、保護膜形成用複合シートの保存安定性が顕著に向上する。例えば、保護膜形成用フィルムから隣接する支持シートへのこの硬化剤の移動が抑制され、熱硬化性保護膜形成用フィルムの熱硬化性の低下が効果的に抑制される。そして、熱硬化性保護膜形成用フィルムの加熱による熱硬化度がより高くなるため、後述する保護膜付き半導体チップのピックアップ性がより向上する。 The thermosetting agent (B2) is a solid that is solid at room temperature and does not exhibit curing activity with respect to the epoxy resin (B1), while being dissolved by heating and exhibits curing activity with respect to the epoxy resin (B1) It is preferably a curing agent (hereinafter sometimes abbreviated as “thermally active latent epoxy resin curing agent”).
The thermoactive latent epoxy resin curing agent is stably dispersed in the epoxy resin (B1) in the thermosetting protective film-forming film at room temperature, but is compatible with the epoxy resin (B1) by heating. Reacts with the epoxy resin (B1). By using the thermally active latent epoxy resin curing agent, the storage stability of the protective film-forming composite sheet is significantly improved. For example, the movement of the curing agent from the protective film-forming film to the adjacent support sheet is suppressed, and the thermosetting deterioration of the thermosetting protective film-forming film is effectively suppressed. And since the thermosetting degree by heating of the film for thermosetting protective film formation becomes higher, the pick-up property of the semiconductor chip with a protective film mentioned later improves more.
　前記熱活性潜在性エポキシ樹脂硬化剤としては、例えば、オニウム塩、二塩基酸ヒドラジド、ジシアンジアミド、硬化剤のアミン付加物等が挙げられる。 Examples of the thermally active latent epoxy resin curing agent include onium salts, dibasic acid hydrazides, dicyandiamide, and amine adducts of curing agents.
　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系フェノール樹脂、アラルキルフェノール樹脂等の樹脂成分の数平均分子量は、３００～３００００であることが好ましく、４００～１００００であることがより好ましく、５００～３０００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、６０～５００であることが好ましい。 Among the thermosetting agents (B2), for example, the number average molecular weight of resin components such as polyfunctional phenolic resin, novolac-type phenolic resin, dicyclopentadiene-based phenolic resin, aralkylphenolic resin, etc. is preferably 300 to 30000, It is more preferably 400 to 10,000, and particularly preferably 500 to 3000.
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 to 500, 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.
　保護膜形成用組成物（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、０．１～５００質量部であることが好ましく、１～２００質量部であることがより好ましい。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 protective film-forming composition (III-1) and the thermosetting protective film-forming film, the content of the thermosetting agent (B2) is 0. 0 parts by mass with respect to 100 parts by mass of the epoxy resin (B1). The amount is preferably 1 to 500 parts by mass, and more preferably 1 to 200 parts by mass. When the content of the thermosetting agent (B2) is equal to or higher than the lower limit value, the curing of the thermosetting protective film forming film more easily proceeds. 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.
　保護膜形成用組成物（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、１～１００質量部であることが好ましく、１．５～８５質量部であることがより好ましく、２～７０質量部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 protective film forming 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 preferably 1 to 100 parts by weight, more preferably 1.5 to 85 parts by weight, with respect to 100 parts by weight of the polymer component (A). It is particularly preferred that 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）］
　保護膜形成用組成物（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、保護膜形成用組成物（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 protective film-forming 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 protective film-forming 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.
　保護膜形成用組成物（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 protective film-forming composition (III-1) and the thermosetting protective film-forming film may be only one type, two or more types, or two or more types. These combinations and ratios can be arbitrarily selected.
　硬化促進剤（Ｃ）を用いる場合、保護膜形成用組成物（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、０．０１～１０質量部であることが好ましく、０．１～５質量部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パッケージの信頼性がより向上する。 When the curing accelerator (C) is used, the content of the curing accelerator (C) in the protective film-forming composition (III-1) and the thermosetting protective film-forming film is such that the thermosetting component (B) The content is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass. 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. In this case, the effect of suppressing the segregation by moving toward the adhesion interface with the adherend is increased, and the reliability of the package obtained using the composite sheet for forming a protective film is further improved.
［充填材（Ｄ）］
　保護膜形成用組成物（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パッケージ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 protective film-forming 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 package 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 of silica, alumina, talc, calcium carbonate, titanium white, bengara, silicon carbide, boron nitride, and the like; beads formed by spheroidizing these inorganic fillers; surface modification of these inorganic fillers Products; single crystal fibers of these inorganic fillers; glass fibers and the like.
Among these, the inorganic filler is preferably silica or alumina.
　保護膜形成用組成物（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 protective film-forming composition (III-1) and the thermosetting protective film-forming film may be only one type, two or more types, or two or more types. Their combination and ratio can be arbitrarily selected.
　充填材（Ｄ）を用いる場合、保護膜形成用組成物（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、５～８０質量％であることが好ましく、７～６０質量％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 protective film forming composition (III-1) (that is, thermosetting protection) The content of the filler (D) in the film-forming film is preferably 5 to 80% by mass, more preferably 7 to 60% by mass. 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）］
　保護膜形成用組成物（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保護膜は、耐熱性を損なうことなく、耐水性が向上する。 [Coupling agent (E)]
The protective film-forming 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, by using the coupling agent (E), the protective film obtained by curing the thermosetting protective film-forming film has improved water resistance 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.
　保護膜形成用組成物（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 protective film-forming composition (III-1) and the thermosetting protective film-forming film may be one kind, two kinds or more, and two kinds or more These combinations and ratios can be arbitrarily selected.
　カップリング剤（Ｅ）を用いる場合、保護膜形成用組成物（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、０．０３～２０質量部であることが好ましく、０．０５～１０質量部であることがより好ましく、０．１～５質量部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, the content of the coupling agent (E) in the protective film-forming composition (III-1) and the thermosetting protective film-forming film is such that the polymer component (A) and The amount is preferably 0.03 to 20 parts by weight, more preferably 0.05 to 10 parts by weight, and more preferably 0.1 to 5 parts by weight with respect to 100 parts by weight as the total content of the thermosetting component (B). The part by mass is particularly preferred. 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、保護膜形成用組成物（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 protective film-forming composition (III-1) and the thermosetting protective film-forming film contain a crosslinking agent (F) for bonding the functional group with another compound to crosslink. Also good. 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.
　保護膜形成用組成物（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 protective film-forming composition (III-1) and the thermosetting protective film-forming film may be only one type, two or more types, or two or more types. Their combination and ratio can be arbitrarily selected.
　架橋剤（Ｆ）を用いる場合、保護膜形成用組成物（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、０．０１～２０質量部であることが好ましく、０．１～１０質量部であることがより好ましく、０．５～５質量部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、熱硬化性保護膜形成用フィルムの支持シートとの接着力や、熱硬化性保護膜形成用フィルムの半導体ウエハ又は半導体チップとの接着力が、過度に低下することが抑制される。
　本発明においては、架橋剤（Ｆ）を用いなくても、本発明の効果が十分に得られる。 When the crosslinking agent (F) is used, the content of the crosslinking agent (F) in the protective film-forming composition (III-1) is 0. 0 parts by mass relative to 100 parts by mass of the polymer component (A). The amount is preferably 01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and particularly preferably 0.5 to 5 parts by mass. 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, because the content of the crosslinking agent (F) is not more than the upper limit value, the adhesive force with the support sheet of the thermosetting protective film forming film, the semiconductor wafer of the thermosetting protective film forming film, or It is suppressed that the adhesive force with a semiconductor chip falls too much.
In the present invention, the effects of the present invention can be sufficiently obtained without using the crosslinking agent (F).
［エネルギー線硬化性樹脂（Ｇ）］
　保護膜形成用組成物（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 protective film-forming 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、１００～３００００であることが好ましく、３００～１００００であることがより好ましい。 The weight average molecular weight of the energy ray curable compound is preferably 100 to 30000, and more preferably 300 to 10000.
　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.
　保護膜形成用組成物（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 protective film-forming 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 are as follows: Can be arbitrarily selected.
　保護膜形成用組成物（ＩＩＩ－１）において、エネルギー線硬化性樹脂（Ｇ）の含有量は、１～９５質量％であることが好ましく、２～９０質量％であることがより好ましく、３～８５質量％であることが特に好ましい。 In the protective film-forming composition (III-1), the content of the energy ray curable resin (G) is preferably 1 to 95% by mass, more preferably 2 to 90% by mass. It is particularly preferable that the content be ˜85% by mass.
［光重合開始剤（Ｈ）］
　保護膜形成用組成物（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 protective film-forming composition (III-1) contains the energy beam curable resin (G), the photopolymerization initiator (H) is used to efficiently advance the polymerization reaction of the energy beam curable resin (G). ) May be contained.
　保護膜形成用組成物（ＩＩＩ－１）における光重合開始剤（Ｈ）としては、粘着剤組成物（ｉｉ）における光重合開始剤と同じものが挙げられる。 Examples of the photopolymerization initiator (H) in the protective film-forming composition (III-1) include the same photopolymerization initiator as in the pressure-sensitive adhesive composition (ii).
　保護膜形成用組成物（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 protective film-forming composition (III-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.
　保護膜形成用組成物（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、０．１～２０質量部であることが好ましく、１～１０質量部であることがより好ましく、２～５質量部であることが特に好ましい。 In the protective film-forming composition (III-1), the content of the photopolymerization initiator (H) is 0.1 to 20 parts by mass 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）］
　保護膜形成用組成物（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 protective film-forming 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、ジオキサジン系色素、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, dioxazine dyes, naphthol dyes, azomethine dyes color , Benzimidazolone pigments, pyranthrone pigments and threne color, and the like.
　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.
　保護膜形成用組成物（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 protective film-forming composition (III-1) and the thermosetting protective film-forming film may be only one type, two or more types, or two or more types. Their combination and 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、保護膜はレーザー照射により印字が施される場合があり、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、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にくくすることもできる。これの点を考慮すると、保護膜形成用組成物（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、０．１～１０質量％であることが好ましく、０．１～７．５質量％であることがより好ましく、０．１～５質量％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, the protective film may be printed by laser irradiation, adjusting the content of the colorant (I) of the thermosetting protective film-forming film, and adjusting the light transmittance of the protective film, Print visibility 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. Considering this point, in the protective film forming 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 thermosetting protective film formation) The content of the colorant (I) in the film for use in the film is preferably 0.1 to 10% by mass, more preferably 0.1 to 7.5% by mass, and 0.1 to 5% by mass. It is particularly preferred that 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）］
　保護膜形成用組成物（ＩＩＩ－１）及び熱硬化性保護膜形成用フィルムは、本発明の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 protective film-forming composition (III-1) and the thermosetting protective film-forming film may contain a general-purpose additive (J) within a range not impairing the effects of the present invention.
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.
　保護膜形成用組成物（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（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。
　保護膜形成用組成物（ＩＩＩ－１）及び熱硬化性保護膜形成用フィルムの汎用添加剤（Ｉ）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 (I) contained in the protective film-forming composition (III-1) and the thermosetting protective film-forming film may be only one, two or more, or two or more These combinations and ratios can be arbitrarily selected.
The content of the general-purpose additive (I) in the protective film-forming 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］
　保護膜形成用組成物（ＩＩＩ－１）は、さらに溶媒を含有することが好ましい。溶媒を含有する保護膜形成用組成物（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、酢酸ブチル等のエステル；アセトン、メチルエチルケトン等のケトン；テトラヒドロフラン等のエーテル；ジメチルホルムアミド、Ｎ－メチルピロリドン等のアミド（アミド結合を有する化合物）等が挙げられる。
　保護膜形成用組成物（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 for forming a protective film (III-1) preferably further contains a solvent. The protective film-forming 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 and butyl acetate; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran; amides (compounds having an amide bond) such as dimethylformamide and N-methylpyrrolidone;
The solvent contained in the protective film-forming composition (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.
　保護膜形成用組成物（ＩＩＩ－１）が含有する溶媒は、保護膜形成用組成物（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 protective film-forming composition (III-1) is preferably methyl ethyl ketone or the like from the viewpoint that the components in the protective film-forming composition (III-1) can be more uniformly mixed.
＜＜熱硬化性保護膜形成用組成物の製造方法＞＞
　保護膜形成用組成物（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１５～３０℃であることが好ましい。 << Method for Producing Thermosetting Protective Film Forming Composition >>
A thermosetting protective film-forming composition such as the protective film-forming 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 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.
・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).
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 materials. 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、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。 Application of the energy ray curable protective film-forming composition may be performed 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. And a method using various coaters such as a knife coater, a screen coater, a Meyer bar coater, and a kiss coater.
　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、７０～１３０℃で１０秒～５分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 to 130 ° C. for 10 seconds to 5 minutes.
＜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「保護膜形成用組成物（ＩＶ－１）」と略記することがある）等が挙げられる。 <Composition for forming protective film (IV-1)>
As the composition for forming an energy ray-curable protective film, for example, the composition for forming an energy ray-curable protective film (IV-1) containing the energy ray-curable component (a) (in this specification, simply And the like (may be abbreviated as “protective film-forming 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ための成分でもある。
　エネルギー線硬化性成分（ａ）としては、例えば、エネルギー線硬化性基を有する、重量平均分子量が８００００～２００００００の重合体（ａ１）、及びエネルギー線硬化性基を有する、分子量が１００～８００００の化合物（ａ２）が挙げられる。前記重合体（ａ１）は、その少なくとも一部が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 is also a component for imparting film forming property, flexibility, and the like to the energy ray-curable protective film-forming film.
Examples of the energy ray-curable component (a) include a polymer (a1) having an energy ray-curable group and a weight average molecular weight of 80000 to 2000000, and an energy ray-curable group and a molecular weight of 100 to 80000. A compound (a2) is mentioned. The polymer (a1) may be 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８００００～２００００００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８００００～２００００００の重合体（ａ１）としては、例えば、他の化合物が有する基と反応可能な官能基を有するアクリル系重合体（ａ１１）と、前記官能基と反応する基、及びエネルギー線硬化性二重結合等のエネルギー線硬化性基を有するエネルギー線硬化性化合物（ａ１２）と、が付加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 to 2,000,000 include an acrylic polymer (a11) having a functional group capable of reacting with a group of another compound, An acrylic resin (a1-1) formed by addition reaction of a 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い。 -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.
　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、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 acrylic monomer having a functional group is preferably a hydroxyl group-containing monomer or a carboxy group-containing monomer, more preferably a hydroxyl group-containing monomer.
　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、０．１～５０質量％であることが好ましく、１～４０質量％であることがより好ましく、３～３０質量％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 to 50 mass. %, More preferably 1 to 40% by mass, and particularly preferably 3 to 30% by mass. 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.
　保護膜形成用組成物（ＩＶ－１）において、アクリル系樹脂（ａ１－１）の含有量は、１～４０質量％であることが好ましく、２～３０質量％であることがより好ましく、３～２０質量％であることが特に好ましい。 In the protective film-forming composition (IV-1), the content of the acrylic resin (a1-1) is preferably 1 to 40% by mass, more preferably 2 to 30% by mass. A content of ˜20% by weight is 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). Those having the above are preferred, and those having an isocyanate group as the group are more preferred. For example, when the energy beam curable compound (a12) has an isocyanate group as the group, the isocyanate group easily reacts with the hydroxyl group of the acrylic polymer (a11) having a hydroxyl group as the functional group.
　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１～５個有することが好ましく、１～２個有することがより好ましい。 The energy beam curable compound (a12) preferably has 1 to 5 energy beam curable groups in one molecule, and more preferably has 1 to 2 energy beam curable groups.
　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 a 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、２０～１２０モル％であることが好ましく、３５～１００モル％であることがより好ましく、５０～１００モル％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 to 120 mol%, more preferably 35 to 100 mol%, and particularly preferably 50 to 100 mol%. When the ratio of the content is within such a range, the adhesive force of the protective film 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、１０００００～２００００００であることが好ましく、３０００００～１５０００００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 polymer (a1) has a weight average molecular weight (Mw) of preferably 100,000 to 2,000,000, and more preferably 300,000 to 1500,000.
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.
　保護膜形成用組成物（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 protective film-forming composition (IV-1) and the energy ray-curable protective film-forming film may be only one kind, two kinds or more, and two kinds or more. In such a case, the combination and ratio thereof can be arbitrarily selected.
（エネルギー線硬化性基を有する、分子量が１００～８００００の化合物（ａ２））
　エネルギー線硬化性基を有する、分子量が１００～８００００の化合物（ａ２）が有するエネルギー線硬化性基としては、エネルギー線硬化性二重結合を含む基が挙げられ、好ましいものとしては、（メタ）アクリロイル基、ビニル基等が挙げられる。 (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. Preferred examples include (meth) 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、本発明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 treated as the compound (a2) in the present invention.
　前記化合物（ａ２）は、重量平均分子量が１００～３００００であることが好ましく、３００～１００００であることがより好ましい。 The compound (a2) preferably has a weight average molecular weight of 100 to 30,000, more preferably 300 to 10,000.
　保護膜形成用組成物（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 protective film-forming composition (IV-1) and the energy ray-curable protective film-forming film may be one kind, two kinds or more, or two kinds or more These combinations and ratios can be arbitrarily selected.
［エネルギー線硬化性基を有しない重合体（ｂ）］
　保護膜形成用組成物（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 protective film-forming composition (IV-1) and the energy ray-curable protective film-forming film contain the compound (a2) as the energy ray-curable component (a), an energy ray-curable group is further added. It is also preferable to contain the polymer (b) that is not included.
The polymer (b) may be crosslinked at least partially 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. 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、１～２０質量％であることが好ましく、２～１０質量％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 1-20. The mass is preferably 2% by mass, and more preferably 2 to 10% by mass. 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、保護膜形成用組成物（ＩＶ－１）の造膜性がより良好となる点から、１００００～２００００００であることが好ましく、１０００００～１５０００００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 10,000 to 2,000,000 from the viewpoint that the film-forming property of the protective film-forming composition (IV-1) becomes better. It is preferably 100000 to 1500,000. Here, the “weight average molecular weight” is as described above.
　保護膜形成用組成物（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 protective film-forming composition (IV-1) and the energy ray-curable protective film-forming film may be only one kind or two or more kinds. However, when there are two or more kinds, the combination and ratio thereof can be arbitrarily selected.
　保護膜形成用組成物（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、保護膜形成用組成物（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、保護膜形成用組成物（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 protective film-forming composition (IV-1) include those containing one or both of the polymer (a1) and the compound (a2). When the protective film-forming composition (IV-1) contains the compound (a2), it preferably contains a polymer (b) that does not have an energy ray-curable group. It is also preferable to contain (a1). Further, the protective film-forming composition (IV-1) does not contain the compound (a2) and contains both the polymer (a1) and the polymer (b) having no energy ray-curable group. It may be.
　保護膜形成用組成物（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、保護膜形成用組成物（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、１０～４００質量部であることが好ましく、３０～３５０質量部であることがより好ましい。 When the protective film-forming composition (IV-1) contains the polymer (a1), the compound (a2) and the polymer (b) having no energy ray-curable group, the protective film-forming composition In (IV-1), the content of the compound (a2) is 10 to 10 parts per 100 parts by mass of the total content of the polymer (a1) and the polymer (b) having no energy ray-curable group. The amount is preferably 400 parts by mass, and more preferably 30 to 350 parts by mass.
　保護膜形成用組成物（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、５～９０質量％であることが好ましく、１０～８０質量％であることがより好ましく、２０～７０質量％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 protective film-forming composition (IV-1), the total content of the energy beam curable component (a) and the polymer (b) having no energy beam curable group with respect to the total content of components other than the solvent (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 to 90% by mass. It is preferably 10 to 80% by mass, more preferably 20 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.
　保護膜形成用組成物（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、光重合開始剤、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。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保護膜形成用組成物（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 protective film-forming composition (IV-1) includes a thermosetting component, a photopolymerization initiator, a filler, a coupling agent, a crosslinking agent, a colorant, You may contain 1 type, or 2 or more types selected from the group which consists of a general purpose additive. For example, by using the protective film forming composition (IV-1) containing the energy ray curable component and the thermosetting component, the formed energy ray curable protective film forming film is deposited by heating. The adhesive force to the body is improved, and the strength of the protective film formed from this energy ray-curable protective film-forming film is also improved.
　保護膜形成用組成物（ＩＶ－１）における前記熱硬化性成分、光重合開始剤、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、保護膜形成用組成物（ＩＩＩ－１）における熱硬化性成分（Ｂ）、光重合開始剤（Ｈ）、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。 As the thermosetting component, photopolymerization initiator, filler, coupling agent, crosslinking agent, colorant and general-purpose additive in the protective film-forming composition (IV-1), the protective film-forming composition, respectively. Thermosetting component (B), photopolymerization initiator (H), filler (D), coupling agent (E), crosslinking agent (F), colorant (I) and general-purpose additives in (III-1) The same thing as (J) is mentioned.
　保護膜形成用組成物（ＩＶ－１）において、前記熱硬化性成分、光重合開始剤、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。
　保護膜形成用組成物（ＩＶ－１）における前記熱硬化性成分、光重合開始剤、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 protective film-forming composition (IV-1), each of the thermosetting component, the photopolymerization initiator, the filler, the coupling agent, the crosslinking agent, the colorant, and the general-purpose additive is used alone. Alternatively, two or more types may be used in combination, and when two or more types are used in combination, their combination and ratio can be arbitrarily selected.
The contents of the thermosetting component, photopolymerization initiator, filler, coupling agent, crosslinking agent, colorant and general-purpose additive in the protective film-forming composition (IV-1) are appropriately adjusted according to the purpose. There is no particular limitation.
　保護膜形成用組成物（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。
　保護膜形成用組成物（ＩＶ－１）が含有する溶媒としては、例えば、保護膜形成用組成物（ＩＩＩ－１）における溶媒と同じものが挙げられる。
　保護膜形成用組成物（ＩＶ－１）が含有する溶媒は、１種のみでもよいし、２種以上でもよい。 The protective film-forming composition (IV-1) preferably further contains a solvent since its handleability is improved by dilution.
Examples of the solvent contained in the protective film forming composition (IV-1) include the same solvents as those in the protective film forming composition (III-1).
The solvent contained in the protective film-forming 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＞＞
　保護膜形成用組成物（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１５～３０℃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 protective film-forming 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 to 30 ° C.
○コーティング層
　前記コーティング層としては、例えば、エネルギー線の照射によって硬化されて得られた硬化物を含有するものが好ましく、エネルギー線の照射により重合する、エネルギー線重合性化合物を含有するコーティング組成物を硬化させて得られたものが好ましい。そして、前記エネルギー線重合性化合物は、（メタ）アクリル酸又はその誘導体であることが好ましい。 -Coating layer As said coating layer, what contains the hardened | cured material obtained by hardening | curing by irradiation of an energy ray is preferable, for example, The coating composition containing the energy ray polymeric compound polymerized by irradiation of an energy ray Those obtained by curing are preferred. And it is preferable that the said energy-beam polymeric compound is (meth) acrylic acid or its derivative (s).
　前記保護膜形成用複合シートは、ダイシングして得られた半導体チップの裏面を保護するための保護膜を形成するという機能だけでなく、例えば、半導体ウエハをダイシングするときのダイシングシートとしての機能も兼ね備えたものとすることができる。そして、半導体ウエハのダイシング時には、保護膜形成用複合シートが貼付された半導体ウエハをエキスパンドすることがあり、その場合、保護膜形成用複合シートは、適度な柔軟性を有することが求められる。保護膜形成用複合シートに適度な柔軟性を付与するためには、例えば、前記支持シートを構成する材質として、ポリプロピレン等の柔軟な樹脂が選択されることがある。一方で、このような柔軟な樹脂等は、加熱によって変形してしまったり、皺が入ってしまうことがある。したがって、コーティング層は、原料となる組成物を熱硬化ではなく、エネルギー線の照射による硬化で形成できるものが望ましいといえる。 The protective sheet-forming composite sheet has not only a function of forming a protective film for protecting the back surface of the semiconductor chip obtained by dicing, but also a function as a dicing sheet when dicing a semiconductor wafer, for example. It can be combined. When the semiconductor wafer is diced, the semiconductor wafer to which the protective film-forming composite sheet is attached may be expanded. In that case, the protective film-forming composite sheet is required to have appropriate flexibility. In order to impart appropriate flexibility to the composite sheet for forming a protective film, for example, a flexible resin such as polypropylene may be selected as a material constituting the support sheet. On the other hand, such a flexible resin may be deformed by heating or may have wrinkles. Therefore, it can be said that the coating layer is preferably one that can be formed by curing the composition as a raw material not by heat curing but by irradiation with energy rays.
　前記コーティング層の厚さは、特に限定されないが、０．１～２０μｍであることが好ましく、０．４～１５μｍであることがより好ましく、０．８～１０μｍであることが特に好ましい。コーティング層の厚さが前記下限値以上であることで、コーティング層の前記支持シートと接触している側とは反対側の表面における表面粗さＲａの低減がより容易となり、さらに、前記保護膜形成用複合シートのブロッキングを抑制する効果がより高くなる。また、コーティング層の厚さが前記上限値以下であることで、前記保護膜形成用複合シートが貼付された後の半導体ウエハの状態を、前記シートを介して赤外線カメラ等によって検査するときに、より鮮明な検査画像を取得でき、さらに、エキスパンドを伴う半導体ウエハのダイシングをより容易に行うことができる。
　なお、コーティング層は、上述のように支持シートの凹凸面を被覆することで、支持シートとの接触面が凹凸面となり得るが、コーティング層の厚さは、コーティング層のこの凹凸面における凸部を含む部位では、この凸部の先端を一方の起点として算出すればよい。 The thickness of the coating layer is not particularly limited, but is preferably 0.1 to 20 μm, more preferably 0.4 to 15 μm, and particularly preferably 0.8 to 10 μm. When the thickness of the coating layer is equal to or more than the lower limit value, it becomes easier to reduce the surface roughness Ra on the surface of the coating layer opposite to the side in contact with the support sheet. The effect of suppressing blocking of the forming composite sheet is further increased. In addition, when the thickness of the coating layer is equal to or less than the upper limit value, the state of the semiconductor wafer after the protective film-forming composite sheet is pasted is examined by an infrared camera or the like through the sheet. A clearer inspection image can be acquired, and further, dicing of the semiconductor wafer with expansion can be performed more easily.
The coating layer covers the uneven surface of the support sheet as described above, so that the contact surface with the support sheet can be an uneven surface, but the thickness of the coating layer is the convex portion on the uneven surface of the coating layer. In a region including, the tip of the convex portion may be calculated as one starting point.
　前記コーティング層の前記支持シートと接触している側とは反対側の表面における表面粗さＲａは、０．５μｍ以下であることが好ましく、０．４μｍ以下であることがより好ましく、０．３μｍ以下であることがさらに好ましく、０．２μｍ以下であることが特に好ましい。コーティング層の前記表面粗さＲａが前記上限値以下であることで、保護膜に対してより鮮明にレーザー印字を行うことができる。
　また、前記コーティング層の前記支持シートと接触している側とは反対側の表面における表面粗さＲａの下限値は、特に限定されないが、例えば、０．００５μｍ等とすることが可能である。
　コーティング層の前記表面粗さＲａは、例えば、支持シートのコーティング層を備えている側の表面の表面粗さＲａ、コーティング層の厚さ、コーティング層を形成するための後述するコーティング組成物の塗工方法等により、調節できる。 The surface roughness Ra on the surface of the coating layer opposite to the side in contact with the support sheet is preferably 0.5 μm or less, more preferably 0.4 μm or less, and 0.3 μm. More preferably, it is more preferably 0.2 μm or less. When the surface roughness Ra of the coating layer is not more than the upper limit value, laser printing can be performed more clearly on the protective film.
Moreover, the lower limit value of the surface roughness Ra on the surface of the coating layer on the side opposite to the side in contact with the support sheet is not particularly limited, but may be 0.005 μm, for example.
The surface roughness Ra of the coating layer is, for example, the surface roughness Ra of the surface of the support sheet provided with the coating layer, the thickness of the coating layer, and the application of a coating composition to be described later for forming the coating layer. It can be adjusted by the construction method.
　前記コーティング層は、［コーティング層の厚さ（μｍ）］／［支持シートのコーティング層を備えている側の表面の表面粗さＲａ（μｍ）］の値が、０．１～３０であることが好ましく、０．３～２０であることがより好ましく、０．５～１０であることが特に好ましい。前記値が前記下限値以上であることで、コーティング層の前記支持シートと接触している側とは反対側の表面における表面粗さＲａがより小さくなって、保護膜に対してより鮮明にレーザー印字を行うことができ、さらに、前記保護膜形成用複合シートのブロッキングを抑制する効果がより高くなる。また、前記値が前記上限値以下であることで、コーティング層の厚さが過剰となることが避けられる。 The coating layer has a value of [thickness of coating layer (μm)] / [surface roughness Ra (μm) of the surface of the support sheet provided with the coating layer] of 0.1 to 30 Is more preferable, 0.3 to 20 is more preferable, and 0.5 to 10 is particularly preferable. When the value is equal to or greater than the lower limit value, the surface roughness Ra on the surface of the coating layer opposite to the side in contact with the support sheet becomes smaller, and the laser is more clearly formed on the protective film. Printing can be performed, and the effect of suppressing blocking of the protective film-forming composite sheet is further enhanced. Moreover, it is avoided that the thickness of a coating layer becomes excessive because the said value is below the said upper limit.
　前記コーティング層の前記支持シートと接触している側（前記支持シート側）とは反対側の表面のグロス値は、３２～９５であることが好ましく、４０～９０であることがより好ましく、４５～８５であることが特に好ましい。コーティング層の前記グロス値がこのような範囲であることで、保護膜に対してより鮮明にレーザー印字を行うことができる。
　さらに、コーティング層の前記グロス値が前記下限値以上であることで、前記保護膜形成用複合シートが貼付された後の半導体ウエハの状態を、前記シートを介して赤外線カメラ等によって検査するときに、より鮮明な検査画像を取得できる。そして、コーティング層の前記グロス値が前記上限値以下であることで、同様に半導体ウエハの状態を検査するときに、コーティング層が光る現象が抑制されて、赤外線カメラ等による検査画像の視認がより容易となる。
　なお、前記グロス値は、ＪＩＳ　Ｋ　７１０５に従って、コーティング層の前記支持シート側とは反対側から、コーティング層の表面の２０°鏡面光沢度を測定して得られた値である。 The gloss value of the surface of the coating layer opposite to the side in contact with the support sheet (the support sheet side) is preferably 32 to 95, more preferably 40 to 90, 45 It is particularly preferred that it is .about.85. When the gloss value of the coating layer is in such a range, laser printing can be performed more clearly on the protective film.
Furthermore, when the gloss value of the coating layer is equal to or more than the lower limit value, the state of the semiconductor wafer after the protective film-forming composite sheet is pasted is inspected with an infrared camera or the like through the sheet. A clearer inspection image can be acquired. And since the gloss value of the coating layer is less than or equal to the upper limit value, the phenomenon that the coating layer shines is similarly suppressed when inspecting the state of the semiconductor wafer, and the inspection image can be more visually recognized by an infrared camera or the like. It becomes easy.
The gloss value is a value obtained by measuring the 20 ° specular gloss of the surface of the coating layer from the side opposite to the support sheet side of the coating layer in accordance with JIS K 7105.
　保護膜形成用複合シートの前記コーティング層側からのヘイズの測定値は、４７％以下であり、１～４７％であることが好ましく、２～４０％であることがより好ましく、３～３０％であることが特に好ましい。保護膜形成用複合シートの前記ヘイズが前記上限値以下であることで、光の散乱が抑制され、保護膜に対してより鮮明にレーザー印字を行うことができる。また、前記保護膜形成用複合シートが貼付された後の半導体ウエハの状態を、前記シートを介して赤外線カメラ等によって検査するときに、より鮮明な検査画像を取得できる。 The measured value of haze from the coating layer side of the composite sheet for forming a protective film is 47% or less, preferably 1 to 47%, more preferably 2 to 40%, more preferably 3 to 30%. It is particularly preferred that When the haze of the composite sheet for forming a protective film is less than or equal to the upper limit value, light scattering is suppressed, and laser printing can be performed more clearly on the protective film. Further, when the state of the semiconductor wafer after the protective film-forming composite sheet is attached is inspected with an infrared camera or the like through the sheet, a clearer inspection image can be acquired.
　前記コーティング層のグロス値等の各種特性は、例えば、コーティング層の厚さ、コーティング層を形成するための後述するコーティング組成物の含有成分等により、調節できる。
　保護膜形成用複合シートの前記コーティング層側からのヘイズの測定値は、例えば、コーティング層や支持シート等の、保護膜形成用複合シートを構成する各層の厚さ、これら各層を形成するための組成物（例えば、後述するコーティング組成物）の含有成分等により、調節できる。 Various characteristics such as the gloss value of the coating layer can be adjusted by, for example, the thickness of the coating layer, the components of the coating composition to be described later for forming the coating layer, and the like.
The measured value of haze from the coating layer side of the protective film-forming composite sheet is, for example, the thickness of each layer constituting the protective film-forming composite sheet, such as a coating layer or a support sheet, for forming each of these layers. It can be adjusted by the components contained in the composition (for example, a coating composition described later).
＜＜コーティング組成物＞＞
　前記コーティング組成物は、シリカゾル、及びラジカル重合性不飽和基含有有機化合物が結合したシリカ微粒子、のいずれか一方又は両方（α）（以下、「成分（α）」と略記することがある）と、多官能性アクリレート系モノマー及びアクリレート系プレポリマーからなる群より選択される１種以上（β）（以下、「成分（β）」と略記することがある）と、を含有するものが好ましい。 << Coating composition >>
The coating composition is either one or both of silica sol and silica fine particles to which a radical polymerizable unsaturated group-containing organic compound is bonded (α) (hereinafter sometimes abbreviated as “component (α)”). And one or more (β) selected from the group consisting of a polyfunctional acrylate monomer and an acrylate prepolymer (hereinafter sometimes abbreviated as “component (β)”) are preferred.
［成分（α）］
　前記成分（α）は、前記コーティング層の屈折率を低下させると共に、前記保護膜形成用複合シートの硬化収縮性及び熱湿収縮性を低下させて、これらの収縮に起因する保護膜形成用複合シートにおけるカールの発生を抑制するものである。 [Component (α)]
The component (α) lowers the refractive index of the coating layer and lowers the curing shrinkage and the heat and humidity shrinkage of the protective film-forming composite sheet. This suppresses the occurrence of curling in the sheet.
　成分（α）におけるシリカゾルとしては、例えば、シリカ微粒子が、アルコール、エチレングリコール由来のエーテル（セロソルブ）等の有機溶媒中に、コロイド状態で懸濁してなるコロイダルシリカが挙げられ、懸濁している前記シリカ微粒子の平均粒径は、０．００１～１μｍであることが好ましく、０．０３～０．０５μｍであることがより好ましい。 Examples of the silica sol in the component (α) include colloidal silica in which silica fine particles are suspended in a colloidal state in an organic solvent such as alcohol or ether derived from ethylene glycol (cellosolve). The average particle diameter of the silica fine particles is preferably 0.001 to 1 μm, and more preferably 0.03 to 0.05 μm.
　成分（α）における、ラジカル重合性不飽和基含有有機化合物が結合したシリカ微粒子は、エネルギー線の照射により架橋及び硬化するものである。
　前記ラジカル重合性不飽和基含有有機化合物が結合したシリカ微粒子としては、例えば、シリカ微粒子の表面に存在するシラノール基と、ラジカル重合性不飽和基含有有機化合物中の官能基と、が反応してなるものが挙げられ、このシリカ微粒子の平均粒径は、０．００５～１μｍであることが好ましい。ラジカル重合性不飽和基含有有機化合物中の前記官能基は、シリカ微粒子中の前記シラノール基と反応し得るものであれば、特に限定されない。 The silica fine particles to which the radical polymerizable unsaturated group-containing organic compound in the component (α) is bonded are cross-linked and cured by irradiation with energy rays.
As the silica fine particles to which the radical polymerizable unsaturated group-containing organic compound is bonded, for example, a silanol group present on the surface of the silica fine particles reacts with a functional group in the radical polymerizable unsaturated group-containing organic compound. The average particle diameter of the silica fine particles is preferably 0.005 to 1 μm. The functional group in the radical polymerizable unsaturated group-containing organic compound is not particularly limited as long as it can react with the silanol group in the silica fine particles.
　前記官能基を有するラジカル重合性不飽和基含有有機化合物としては、例えば、下記一般式（１）で表される化合物等が挙げられる。 Examples of the radical polymerizable unsaturated group-containing organic compound having the functional group include compounds represented by the following general formula (1).
Figure JPOXMLDOC01-appb-C000001
 　　　　　　　　　　　　　　　　　　
（式中、Ｒ１は水素原子又はメチル基であり；Ｒ２はハロゲン原子又は下記式（２ａ）～（２ｆ）のいずれかで表される基である。）
Figure JPOXMLDOC01-appb-C000001
(In the formula, R 1 is a hydrogen atom or a methyl group; R 2 is a halogen atom or a group represented by any of the following formulas (2a) to (2f)).
Figure JPOXMLDOC01-appb-C000002
 　　　　　　　　　　　　　　　　　　
 
Figure JPOXMLDOC01-appb-C000002
 　　　　　　　　　　　　　　　　　　
 
　Ｒ２における前記ハロゲン原子としては、例えば、塩素元素、臭素原子、ヨウ素原子等が挙げられる。 Examples of the halogen atom in R 2, for example, elemental chlorine, bromine atom, and an iodine atom.
　前記ラジカル重合性不飽和基含有有機化合物で好ましいものとしては、例えば、（メタ）アクリル酸、（メタ）アクリル酸クロリド、（メタ）アクリル酸２－イソシアナ－トエチル、（メタ）アクリル酸グリシジル、（メタ）アクリル酸２，３－イミノプロピル、（メタ）アクリル酸２－ヒドロキシエチル、（３－（メタ）アクリロイルオキシプロピル）トリメトキシシラン等が挙げられる。 Preferred examples of the radical polymerizable unsaturated group-containing organic compound include (meth) acrylic acid, (meth) acrylic acid chloride, (meth) acrylic acid 2-isocyanatoethyl, (meth) acrylic acid glycidyl, ( Examples include 2,3-iminopropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, (3- (meth) acryloyloxypropyl) trimethoxysilane, and the like.
　本発明において、前記ラジカル重合性不飽和基含有有機化合物は、１種を単独で用いてもよいし、２種以上を併用してもよい。 In the present invention, the radical polymerizable unsaturated group-containing organic compound may be used alone or in combination of two or more.
　成分（α）において、シリカゾル、及びラジカル重合性不飽和基含有有機化合物が結合したシリカ微粒子は、それぞれ１種のみでもよいし、２種以上でもよい。 In the component (α), the silica fine particles to which the silica sol and the radical polymerizable unsaturated group-containing organic compound are bonded may be each one kind or two kinds or more.
　成分（α）としては、シリカゾルのみを用いてもよいし、前記ラジカル重合性不飽和基含有有機化合物が結合したシリカ微粒子のみを用いてもよく、シリカゾル、及び前記ラジカル重合性不飽和基含有有機化合物が結合したシリカ微粒子を併用してもよい。 As the component (α), only silica sol may be used, or only silica fine particles combined with the radical polymerizable unsaturated group-containing organic compound may be used. The silica sol and the radical polymerizable unsaturated group-containing organic compound may be used. You may use together the silica fine particle which the compound couple | bonded.
　前記コーティング組成物の成分（α）の含有量は、前記支持シートの屈折率に応じて選択することが好ましいが、通常は、前記コーティング層の成分（α）に由来するシリカの含有量が２０～６０質量％となる量であることが好ましい。シリカの前記含有量が前記下限値以上であることで、コーティング層の屈折率を低下させる効果と、前記保護膜形成用複合シートにおけるカールの発生を抑制する効果とが、より高くなる。また、シリカの前記含有量が前記上限値以下であることで、コーティング層の形成がより容易となるとともに、コーティング層の硬度の低下を抑制する効果がより高くなる。
　上述のコーティング層の屈折率、形成容易性及び硬度、並びに保護膜形成用複合シートにおけるカールの発生抑制性が、より良好となることから、コーティング層の成分（α）に由来するシリカの含有量は、２０～４５質量％であることがより好ましい。 The content of the component (α) of the coating composition is preferably selected according to the refractive index of the support sheet, but usually the content of silica derived from the component (α) of the coating layer is 20. The amount is preferably ˜60% by mass. When the content of silica is not less than the lower limit, the effect of reducing the refractive index of the coating layer and the effect of suppressing the occurrence of curling in the protective film-forming composite sheet are further enhanced. Moreover, while the said content of a silica is below the said upper limit, while the formation of a coating layer becomes easier, the effect which suppresses the fall of the hardness of a coating layer becomes higher.
The content of silica derived from the component (α) of the coating layer because the refractive index of the coating layer, ease of formation and hardness, and curling generation suppression in the composite sheet for forming a protective film become better. Is more preferably 20 to 45% by mass.
［成分（β）］
　前記成分（β）は、前記コーティング層を形成する主要な光硬化性成分である。 [Component (β)]
The component (β) is a main photocurable component that forms the coating layer.
　前記成分（β）における多官能性アクリレート系モノマーは、（メタ）アクリロイル基を１分子中に２個以上有する（メタ）アクリル酸誘導体であれば、特に限定されない。
　好ましい前記多官能性アクリレート系モノマーとしては、例えば、１，４－ブタンジオールジ（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、ネオペンチルグリコールジ（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、ヒドロキシピバリン酸ネオペンチルグリコールジ（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、カプロラクトン変性ジシクロペンテニルジ（メタ）アクリレート、エチレンオキシド変性リン酸ジ（メタ）アクリレート、アリル化シクロヘキシルジ（メタ）アクリレート、イソシアヌレートジ（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、ジペンタエリスリトールトリ（メタ）アクリレート、プロピオン酸変性ジ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トリ（メタ）アクリレート、プロピレンオキシド変性トリメチロールプロパントリ（メタ）アクリレート、トリス（アクリロキシエチル）イソシアヌレート、ジペンタエリスリトールペンタ（メタ）アクリレート、プロピオン酸変性ジペンタエリスリトールペンタ（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、カプロラクトン変性ジペンタエリスリトールヘキサ（メタ）アクリレート等が挙げられる。 The polyfunctional acrylate monomer in the component (β) is not particularly limited as long as it is a (meth) acrylic acid derivative having two or more (meth) acryloyl groups in one molecule.
Preferred examples of the polyfunctional acrylate monomer include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di ( (Meth) acrylate, hydroxypivalate neopentyl glycol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, caprolactone modified dicyclopentenyl di (meth) acrylate, ethylene oxide modified di (meth) acrylate phosphoric acid, allylated cyclohexyl Di (meth) acrylate, isocyanurate di (meth) acrylate, trimethylolpropane tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, propionic acid modified dipe Taerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, propylene oxide modified trimethylolpropane tri (meth) acrylate, tris (acryloxyethyl) isocyanurate, dipentaerythritol penta (meth) acrylate, propionic acid modified di Examples include pentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and caprolactone-modified dipentaerythritol hexa (meth) acrylate.
　前記成分（β）におけるアクリレート系プレポリマーは、（メタ）アクリル酸エステルで光硬化性を有するポリマー又はオリゴマーであれば、特に限定されない。
　好ましい前記アクリレート系プレポリマーとしては、例えば、ポリエステルアクリレート系プレポリマー、エポキシアクリレート系プレポリマー、ウレタンアクリレート系プレポリマー、ポリオールアクリレート系プレポリマー等が挙げられる。 The acrylate prepolymer in the component (β) is not particularly limited as long as it is a polymer or oligomer that is a (meth) acrylic ester and has photocurability.
Preferred examples of the acrylate prepolymer include polyester acrylate prepolymer, epoxy acrylate prepolymer, urethane acrylate prepolymer, polyol acrylate prepolymer, and the like.
　前記ポリエステルアクリレート系プレポリマーとしては、例えば、多価カルボン酸と多価アルコールとの縮合反応によって得られる、分子の両末端に水酸基を有するポリエステルオリゴマーの水酸基を、（メタ）アクリル酸でエステル化することにより得られるもの；多価カルボン酸にアルキレンオキシドを付加反応させて得られるオリゴマーの末端の水酸基を、（メタ）アクリル酸でエステル化することにより得られるもの等が挙げられる。
　前記エポキシアクリレート系プレポリマーとしては、例えば、比較的低分子量のビスフェノール型エポキシ樹脂又はノボラック型エポキシ樹脂のオキシラン環に、（メタ）アクリル酸を反応させてエステル化することにより得られるものが挙げられる。
　前記ウレタンアクリレート系プレポリマーとしては、例えば、ポリエーテルポリオール又はポリエステルポリオールと、ポリイソシアネートと、の反応によって得られるポリウレタンオリゴマーを、（メタ）アクリル酸でエステル化することにより得られるものが挙げられる。
　前記ポリオールアクリレート系プレポリマーとしては、例えば、ポリエーテルポリオールの水酸基を（メタ）アクリル酸でエステル化することにより得られるものが挙げられる。 As the polyester acrylate prepolymer, for example, a hydroxyl group of a polyester oligomer having a hydroxyl group at both ends of a molecule obtained by a condensation reaction of a polyvalent carboxylic acid and a polyhydric alcohol is esterified with (meth) acrylic acid. And those obtained by esterifying a hydroxyl group at the terminal of an oligomer obtained by addition reaction of an alkylene oxide with a polyvalent carboxylic acid with (meth) acrylic acid.
Examples of the epoxy acrylate prepolymer include those obtained by reacting an oxirane ring of a relatively low molecular weight bisphenol type epoxy resin or novolac type epoxy resin with (meth) acrylic acid for esterification. .
As said urethane acrylate type prepolymer, what is obtained by esterifying the polyurethane oligomer obtained by reaction of polyether polyol or polyester polyol, and polyisocyanate with (meth) acrylic acid is mentioned, for example.
As said polyol acrylate type prepolymer, what is obtained by esterifying the hydroxyl group of polyether polyol with (meth) acrylic acid is mentioned, for example.
　成分（β）において、前記多官能性アクリレート系モノマー及びアクリレート系プレポリマーは、それぞれ１種のみでもよいし、２種以上でもよい。 In the component (β), each of the multifunctional acrylate monomer and acrylate prepolymer may be one kind or two kinds or more.
　成分（β）としては、前記多官能性アクリレート系モノマーのみを用いてもよいし、前記アクリレート系プレポリマーのみを用いてもよく、前記多官能性アクリレート系モノマー及びアクリレート系プレポリマーを併用してもよい。 As the component (β), only the polyfunctional acrylate monomer may be used, or only the acrylate prepolymer may be used, and the polyfunctional acrylate monomer and acrylate prepolymer are used in combination. Also good.
［溶媒］
　前記コーティング組成物は、成分（α）及び成分（β）以外に、さらに溶媒を含有するものが好ましい。コーティング組成物が溶媒を含有することで、後述するように、コーティング組成物を塗工及び乾燥させて、コーティング層を形成するための塗膜をより容易に形成できる。
　前記溶媒は、１種を単独で用いてもよいし、２種以上を併用してもよい。 [solvent]
The coating composition preferably further contains a solvent in addition to the component (α) and the component (β). When the coating composition contains a solvent, as will be described later, the coating composition can be applied and dried to form a coating film for forming the coating layer more easily.
The said solvent may be used individually by 1 type, and may use 2 or more types together.
　前記溶媒としては、例えば、ヘキサン、ヘプタン、シクロ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；塩化メチレン、塩化エチレン等のハロゲン化炭化水素；メタノール、エタノール、プロパノール、ブタノール、１－メトキシ－２－プロパノール等のアルコール；アセトン、メチルエチルケトン、２－ペンタノン、イソホロン、シクロヘキサノン等のケトン；酢酸エチル、酢酸ブチル等のエステル；２－エトキシエタノール（エチルセロソルブ）等のセロソルブ等が挙げられる。 Examples of the solvent include aliphatic hydrocarbons such as hexane, heptane, and cyclohexane; aromatic hydrocarbons such as toluene and xylene; halogenated hydrocarbons such as methylene chloride and ethylene chloride; methanol, ethanol, propanol, butanol, 1 Alcohols such as methoxy-2-propanol; ketones such as acetone, methyl ethyl ketone, 2-pentanone, isophorone and cyclohexanone; esters such as ethyl acetate and butyl acetate; cellosolves such as 2-ethoxyethanol (ethyl cellosolve) and the like.
［任意成分］
　前記コーティング組成物は、成分（α）及び成分（β）以外に、本発明の効果を損なわない範囲内において、単官能性アクリレート系モノマー、光重合開始剤、光増感剤、重合禁止剤、架橋剤、酸化防止剤、紫外線吸収剤、光安定剤、レベリング剤、消泡剤等の各種任意成分を含有していてもよい。
　前記任意成分は、１種を単独で用いてもよいし、２種以上を併用してもよい。 [Optional ingredients]
In addition to the component (α) and the component (β), the coating composition has a monofunctional acrylate-based monomer, a photopolymerization initiator, a photosensitizer, a polymerization inhibitor, as long as the effects of the present invention are not impaired. Various optional components such as a crosslinking agent, an antioxidant, an ultraviolet absorber, a light stabilizer, a leveling agent, and an antifoaming agent may be contained.
The said arbitrary component may be used individually by 1 type, and may use 2 or more types together.
（単官能性アクリレート系モノマー）
　任意成分としての前記単官能性アクリレート系モノマーは、光硬化性成分であり、（メタ）アクリロイル基を１分子中に１個のみ有する（メタ）アクリル酸誘導体であれば、特に限定されない。
　好ましい前記単官能性アクリレート系モノマーとしては、例えば、（メタ）アクリル酸シクロヘキシル、（メタ）アクリル酸２－エチルヘキシル、（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）アクリル酸イソボルニル等が挙げられる。 (Monofunctional acrylate monomer)
The monofunctional acrylate monomer as an optional component is a photocurable component and is not particularly limited as long as it is a (meth) acrylic acid derivative having only one (meth) acryloyl group in one molecule.
Preferred examples of the monofunctional acrylate monomer include cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate (lauryl (meth) acrylate), and octadecyl (meth) acrylate. (Stearyl (meth) acrylate), isobornyl (meth) acrylate and the like.
（光重合開始剤）
　任意成分としての前記光重合開始剤としては、ラジカル重合に対して従来用いられている公知のものが挙げられる。
　好ましい前記光重合開始剤としては、例えば、アセトフェノン系化合物、ベンゾフェノン系化合物、アルキルアミノベンゾフェノン系化合物、ベンジル系化合物、ベンゾイン系化合物、ベンゾインエーテル系化合物、ベンジルジメチルアセタール系化合物、ベンゾイルベンゾエート系化合物、α－アシロキシムエステル系化合物等のアリールケトン系光重合開始剤；スルフィド系化合物、チオキサントン系化合物等の含硫黄系光重合開始剤；アシルジアリールホスフィンオキシド等のアシルホスフィンオキシド系化合物；アントラキノン系化合物等が挙げられる。
　なお、前記コーティング組成物を電子線の照射により硬化させる場合には、光重合開始剤は不要である。 (Photopolymerization initiator)
As said photoinitiator as an arbitrary component, the well-known thing conventionally used with respect to radical polymerization is mentioned.
Preferred examples of the photopolymerization initiator include acetophenone compounds, benzophenone compounds, alkylaminobenzophenone compounds, benzyl compounds, benzoin compounds, benzoin ether compounds, benzyldimethylacetal compounds, benzoylbenzoate compounds, α -Aryl ketone photopolymerization initiators such as acyloxime ester compounds; sulfur-containing photopolymerization initiators such as sulfide compounds and thioxanthone compounds; acylphosphine oxide compounds such as acyl diarylphosphine oxides; anthraquinone compounds Can be mentioned.
In addition, when the said coating composition is hardened by irradiation of an electron beam, a photoinitiator is unnecessary.
　前記コーティング組成物において、光重合開始剤の含有量は、光硬化性成分の総含有量１００質量部に対して、０．２～１０質量部であることが好ましく、０．５～７質量部であることがより好ましい。 In the coating composition, the content of the photopolymerization initiator is preferably 0.2 to 10 parts by mass, and 0.5 to 7 parts by mass with respect to 100 parts by mass of the total content of the photocurable components. It is more preferable that
（光増感剤）
　前記光増感剤としては、例えば、第三級アミン類、ｐ－ジメチルアミノ安息香酸エステル、チオール系増感剤等が挙げられる。
　前記コーティング組成物において、光増感剤の含有量は、光硬化性成分の総含有量１００質量部に対して、１～２０質量部であることが好ましく、２～１０質量部であることがより好ましい。 (Photosensitizer)
Examples of the photosensitizer include tertiary amines, p-dimethylaminobenzoate, and thiol sensitizers.
In the coating composition, the content of the photosensitizer is preferably 1 to 20 parts by mass and preferably 2 to 10 parts by mass with respect to 100 parts by mass of the total content of the photocurable components. More preferred.
（酸化防止剤、紫外線吸収剤、光安定剤）
　前記酸化防止剤、紫外線吸収剤及び光安定剤は、公知のものでよいが、分子内に（メタ）アクリロイル基等を有する反応型の酸化防止剤、紫外線吸収剤及び光安定剤であることが好ましい。これら酸化防止剤、紫外線吸収剤及び光安定剤は、エネルギー線の照射により形成されたポリマー鎖に結合するため、経時による硬化層からの逸散が抑制され、長期間に渡ってこれら成分の機能が発揮される。 (Antioxidant, UV absorber, light stabilizer)
The antioxidant, the ultraviolet absorber and the light stabilizer may be known ones, but may be a reactive antioxidant having a (meth) acryloyl group in the molecule, an ultraviolet absorber and a light stabilizer. preferable. These antioxidants, UV absorbers and light stabilizers bind to the polymer chain formed by irradiation with energy rays, so that dissipation from the cured layer over time is suppressed, and the functions of these components over a long period of time. Is demonstrated.
　前記コーティング組成物は、成分（α）としてシリカゾルを含有するものが好ましく、コロイド状態で懸濁しているシリカ微粒子の平均粒径が０．０３～０．０５μｍであるシリカゾルを含有するものがより好ましい。
　前記コーティング層がこのようなシリカゾルを含有することにより、前記保護膜形成用複合シートのブロッキングを抑制する効果がより高くなる。そして、前記コーティング層において、このようなシリカゾルが、支持シート側とは反対側の表面やその近傍領域に、他の領域よりも多く存在して、偏在していることにより、前記保護膜形成用複合シートのブロッキングを抑制する効果がさらに高くなる。前記コーティング層において、シリカゾル等の含有成分を偏在させるためには、前記コーティング組成物の塗工条件を調節すればよい。 The coating composition preferably contains a silica sol as the component (α), and more preferably contains a silica sol having an average particle size of silica fine particles suspended in a colloidal state of 0.03 to 0.05 μm. .
When the coating layer contains such a silica sol, the effect of suppressing blocking of the protective sheet-forming composite sheet is further enhanced. And, in the coating layer, such a silica sol is present more and more unevenly on the surface on the side opposite to the support sheet side and in the vicinity thereof than in other regions, thereby forming the protective film. The effect of suppressing the blocking of the composite sheet is further increased. In order to make the component components such as silica sol unevenly distributed in the coating layer, the coating conditions of the coating composition may be adjusted.
＜＜コーティング組成物の製造方法＞＞
　コーティング組成物は、例えば、成分（α）及び成分（β）等のエネルギー線重合性化合物と、必要に応じてこれ以外の成分等、コーティング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。コーティング組成物は、例えば、配合成分が異なる点以外は、上述の粘着剤組成物の場合と同様の方法で得られる。
　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。
　コーティング組成物中の溶媒以外の成分は、溶解していてもよいし、溶解せずに分散していてもよい。そして、コーティング組成物の各成分の濃度や粘度は、コーティング組成物が塗工可能である限り、特に限定されない。 << Method for producing coating composition >>
The coating composition is, for example, by blending energy ray polymerizable compounds such as the component (α) and the component (β), and other components for constituting the coating composition, if necessary, other components. can get. A coating composition is obtained by the method similar to the case of the above-mentioned adhesive composition except the point from which a compounding component differs, for example.
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.
Components other than the solvent in the coating composition may be dissolved, or may be dispersed without dissolving. The concentration and viscosity of each component of the coating composition are not particularly limited as long as the coating composition can be applied.
◎保護膜形成用複合シートの製造方法
　本実施形態に係る保護膜形成用複合シートは、前記保護膜形成用組成物を用いて保護膜形成用フィルムを形成し、前記コーティング組成物を用いてコーティング層を形成し、コーティング層、支持シート及び保護膜形成用フィルムをこの順に積層することで製造できる。
　支持シートが複数層からなる場合には、これら複数の層を積層して支持シートを作製すればよい。例えば、支持シートが基材及び粘着剤層が積層されたものである場合には、前記粘着剤組成物を用いて粘着剤層を形成すればよい。 ◎ Method for producing protective sheet-forming composite sheet A protective film-forming composite sheet according to this embodiment forms a protective film-forming film using the protective film-forming composition, and is coated with the coating composition. A layer can be formed, and a coating layer, a support sheet, and a protective film-forming film can be laminated in this order.
When the support sheet is composed of a plurality of layers, the support sheet may be produced by laminating these layers. For example, when the support sheet is a laminate of a substrate and a pressure-sensitive adhesive layer, a pressure-sensitive adhesive layer may be formed using the pressure-sensitive adhesive composition.
　保護膜形成用複合シートを構成する各層（コーティング層、支持シート、保護膜形成用フィルム）の形成順は特に限定されない。さらに、これら各層の組成物からの形成は、保護膜形成用複合シートの状態で隣接する層の表面上で直接行ってもよいし、別途剥離フィルム（剥離シート）を用いてこの表面上で行い、この形成した層を、保護膜形成用複合シートの状態で隣接する層の表面に貼り合わせてもよい。ただし、支持シートの保護膜形成用フィルムを備えている面（表面）とは反対側の面（裏面）が凹凸面である場合には、コーティング層と支持シートの凹凸面（裏面）との間に、空隙部が生じることを抑制するために、コーティング層は、支持シートの凹凸面に直接コーティング組成物を塗工して形成することが好ましい。
　以下、保護膜形成用複合シートの好ましい製造方法の一例について、説明する。 The formation order of each layer (coating layer, support sheet, protective film forming film) constituting the protective film forming composite sheet is not particularly limited. Furthermore, the formation of each of these layers from the composition may be performed directly on the surface of the adjacent layer in the state of the protective sheet-forming composite sheet, or may be performed on this surface using a separate release film (release sheet). The formed layer may be bonded to the surface of the adjacent layer in the state of the protective film-forming composite sheet. However, when the surface (back surface) opposite to the surface (front surface) provided with the protective film-forming film of the support sheet is an uneven surface, it is between the coating layer and the uneven surface (back surface) of the support sheet. Furthermore, in order to suppress the formation of voids, the coating layer is preferably formed by directly applying the coating composition to the uneven surface of the support sheet.
Hereinafter, an example of the preferable manufacturing method of the composite sheet for protective film formation is demonstrated.
　コーティング層は、支持シートの凹凸面（図１及び２においては、支持シート１０の裏面１０ｂ、すなわち基材１１の裏面１１ｂ）にコーティング組成物を塗工し、乾燥させ、必要に応じて形成した塗膜を硬化させることで、形成することが好ましい。 The coating layer was formed as necessary by applying the coating composition to the uneven surface of the support sheet (in FIGS. 1 and 2, the back surface 10b of the support sheet 10, that is, the back surface 11b of the base material 11), and drying. It is preferably formed by curing the coating film.
　コーティング組成物の対象面への塗工は、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。 Coating of the coating composition on the target surface may be performed 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. And a method using various coaters such as a screen coater, a Meyer bar coater, and a kiss coater.
　コーティング組成物を支持シートの凹凸面に塗工する場合には、コーティング層と支持シートの凹凸面との間において、空隙部の発生を抑制することが好ましい。前記空隙部の発生を抑制することで、コーティング層と支持シートの凹凸面との境界における光の乱反射が抑制され、保護膜の表面にレーザー印字をより鮮明に行うことができる。
　前記空隙部の発生を抑制するためには、例えば、粘度が小さいコーティング組成物を用いることが好ましい。また、エネルギー線重合性化合物を含有するコーティング組成物は、通常、前記空隙部の発生を抑制するのに好適である。 When the coating composition is applied to the uneven surface of the support sheet, it is preferable to suppress the generation of voids between the coating layer and the uneven surface of the support sheet. By suppressing the generation of the voids, irregular reflection of light at the boundary between the coating layer and the uneven surface of the support sheet is suppressed, and laser printing can be performed more clearly on the surface of the protective film.
In order to suppress the generation of the voids, for example, it is preferable to use a coating composition having a low viscosity. Moreover, the coating composition containing an energy beam polymerizable compound is usually suitable for suppressing the generation of the voids.
　コーティング組成物の乾燥条件は、特に限定されないが、コーティング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０．５～５分の条件で乾燥させることが好ましい。 The drying conditions of the coating composition are not particularly limited, but the coating composition is preferably dried by heating. In this case, for example, it is preferably dried at 70 to 130 ° C. for 0.5 to 5 minutes.
　コーティング組成物から形成した塗膜の硬化条件は、特に限定されず、公知の方法で行えばよい。
　エネルギー線の照射により硬化を行う場合には、例えば、紫外線を照射する場合であれば、紫外線源として高圧水銀ランプ、ヒュージョンＨランプ又はキセノンランプ等を用い、照射量を好ましくは１００～５００ｍＪ／ｃｍ２として、照射すればよい。一方、電子線を照射する場合であれば、電子線加速器等によって電子線を発生させ、照射量を好ましくは１５０～３５０ｋＶとして、照射すればよい。なかでもコーティング層の形成は、紫外線の照射により行うことが好ましい。 The curing conditions for the coating film formed from the coating composition are not particularly limited, and may be performed by a known method.
In the case of curing by irradiation with energy rays, for example, in the case of irradiation with ultraviolet rays, a high pressure mercury lamp, a fusion H lamp, a xenon lamp or the like is used as the ultraviolet ray source, and the irradiation amount is preferably 100 to 500 mJ / cm. 2 may be irradiated. On the other hand, in the case of irradiation with an electron beam, an electron beam is generated by an electron beam accelerator or the like, and the irradiation amount is preferably set to 150 to 350 kV. In particular, the coating layer is preferably formed by ultraviolet irradiation.
　支持シートが、例えば、基材及び粘着剤層が積層されてなるものである場合、粘着剤層は、コーティング層を備えた基材の表面（図１及び２においては基材１１の表面１１ａ）に粘着剤組成物を直接塗工して形成することが可能である。ただし通常は、例えば、剥離シートの剥離処理面に粘着剤組成物を塗工し、乾燥させることで形成した粘着剤層を、基材の表面に貼り合わせ、前記剥離シートを取り除くなど、粘着剤層を別途形成しておき、これを基材の表面に貼り合わせる方法を採用することが好ましい。 For example, when the support sheet is formed by laminating the base material and the pressure-sensitive adhesive layer, the pressure-sensitive adhesive layer is the surface of the base material provided with the coating layer (the surface 11a of the base material 11 in FIGS. 1 and 2). It can be formed by directly coating the pressure-sensitive adhesive composition. However, usually, for example, a pressure-sensitive adhesive layer formed by applying a pressure-sensitive adhesive composition to a release-treated surface of a release sheet and drying it is bonded to the surface of a substrate, and the release sheet is removed. It is preferable to adopt a method in which a layer is formed separately and this is bonded to the surface of the substrate.
　粘着剤組成物は、コーティング組成物の場合と同様の方法で、対象面へ塗工できる。 The pressure-sensitive adhesive composition can be applied to the target surface in the same manner as in the case of the coating composition.
　塗工した粘着剤組成物は、加熱することで架橋させてもよく、この加熱による架橋は乾燥を兼ねて行ってもよい。加熱条件は、例えば、１００～１３０℃で１～５分間とすることができるが、これに限定されない。 The applied pressure-sensitive adhesive composition may be crosslinked by heating, and the crosslinking by heating may also be performed for drying. The heating conditions can be, for example, 100 to 130 ° C. for 1 to 5 minutes, but are not limited thereto.
　支持シートが、基材のみからなるもの等、１層（単層）からなるものである場合と、例えば、基材及び粘着剤層が積層されてなるもの等、複数層からなる場合と、のいずれにおいても、コーティング層を備えた支持シートの表面（図１及び２においては、支持シート１０の表面１０ａ、すなわち粘着剤層１２の表面１２ａ）に保護膜形成用組成物を直接塗工して、保護膜形成用フィルムを形成することが可能である。ただし通常は、上述の粘着剤層の場合と同様に、剥離シートの剥離処理面に保護膜形成用組成物を塗工し、乾燥させることで形成した保護膜形成用フィルムを、支持シートの表面に貼り合わせ、必要に応じて前記剥離シートを取り除くなど、保護膜形成用フィルムを別途形成しておき、これを支持シートの表面に貼り合わせる方法を採用することが好ましい。 When the support sheet is composed of one layer (single layer) such as a substrate only, or when the support sheet is composed of a plurality of layers, for example, a substrate and a pressure-sensitive adhesive layer are laminated. In any case, the composition for forming a protective film is directly applied to the surface of the support sheet provided with the coating layer (in FIGS. 1 and 2, the surface 10a of the support sheet 10, that is, the surface 12a of the pressure-sensitive adhesive layer 12). It is possible to form a protective film-forming film. However, normally, as in the case of the above-mentioned pressure-sensitive adhesive layer, the protective film-forming film formed by applying the protective film-forming composition to the release-treated surface of the release sheet and drying it is applied to the surface of the support sheet. It is preferable to adopt a method in which a protective film-forming film is separately formed and bonded to the surface of the support sheet, for example, such that the release sheet is removed if necessary.
　保護膜形成用組成物は、コーティング組成物の場合と同様の方法で、対象面へ塗工できる。
　保護膜形成用組成物の乾燥条件は、特に限定されないが、コーティング組成物の場合と同様の方法で乾燥させることができる。 The composition for forming a protective film can be applied to the target surface in the same manner as in the case of the coating composition.
Although the drying conditions of the composition for protective film formation are not specifically limited, It can be dried by the method similar to the case of a coating composition.
　支持シートが基材及び粘着剤層が積層されてなるものである場合には、本発明に係る保護膜形成用複合シートは、上述の方法以外でも製造できる。例えば、前記粘着剤組成物を用いて粘着剤層を形成し、前記保護膜形成用組成物を用いて保護膜形成用フィルムを形成した後、これら粘着剤層及び保護膜形成用フィルムを重ね合わせて積層体とし、この積層体の前記粘着剤層の表面（粘着剤層の保護膜形成用フィルムが設けられていない面）に、コーティング層を備えた基材の表面（図１及び２においては基材１１の表面１１ａ）を貼り合わせることによっても、保護膜形成用複合シートを製造できる。
　この場合の粘着剤層及び保護膜形成用フィルムの形成条件は、上述の方法の場合と同じである。 When the support sheet is formed by laminating the base material and the pressure-sensitive adhesive layer, the protective film-forming composite sheet according to the present invention can be produced by methods other than those described above. For example, a pressure-sensitive adhesive layer is formed using the pressure-sensitive adhesive composition, a protective film-forming film is formed using the protective film-forming composition, and then the pressure-sensitive adhesive layer and the protective film-forming film are overlapped. The surface of the base material (in FIGS. 1 and 2) provided with a coating layer on the surface of the pressure-sensitive adhesive layer of the laminated body (the surface on which the protective film-forming film of the pressure-sensitive adhesive layer is not provided). A composite sheet for forming a protective film can also be produced by laminating the surface 11a) of the substrate 11.
In this case, the conditions for forming the pressure-sensitive adhesive layer and the protective film-forming film are the same as in the above-described method.
　支持シートの保護膜形成用フィルムを備えている面（表面）とは反対側の面（裏面）が凹凸面ではなく平滑面である場合には、本実施形態に係る保護膜形成用複合シートは、上述の方法以外でも製造できる。例えば、前記コーティング組成物を用いてコーティング層を形成し、これを支持シートの平滑面に貼り合わせることによって積層体とし、一方で、前記保護膜形成用組成物を用いて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を前記積層体の支持シートの露出面（支持シートのコーティング層が設けられていない面）に貼り合わせることによっても、保護膜形成用複合シートを製造できる。別途形成しておいたコーティング層及び保護膜形成用フィルムの支持シートへの貼り合わせの順序は、上記と反対でもよく、支持シートの一方の表面に保護膜形成用フィルムを貼り合わせた後、支持シートの他方の表面（支持シートの保護膜形成用フィルムが設けられていない面）にコーティング層を貼り合わせることによっても、保護膜形成用複合シートを製造できる。
　また、支持シートの一方の表面に、前記保護膜形成用組成物を用いて保護膜形成用フィルムを形成し、一方で、前記コーティング組成物を用いてコーティング層を形成しておき、このコーティング層を前記支持シートの露出面（支持シートの保護膜形成用フィルムが設けられていない面）に貼り合わせることによっても、保護膜形成用複合シートを製造できる。
　これらの場合のコーティング層及び保護膜形成用フィルムの形成条件は、上述の方法の場合と同じである。 When the surface (back surface) opposite to the surface (front surface) provided with the protective film forming film of the support sheet is a smooth surface instead of an uneven surface, the protective film forming composite sheet according to the present embodiment is It can also be manufactured by methods other than those described above. For example, a coating layer is formed using the coating composition, and this is laminated to a smooth surface of a support sheet to form a laminate, while a protective film-forming film is formed using the protective film-forming composition. The composite sheet for forming a protective film can also be produced by forming and bonding this protective film-forming film to the exposed surface of the support sheet of the laminate (the surface on which the coating layer of the support sheet is not provided). . The order of laminating the coating layer and the protective film forming film separately formed on the support sheet may be opposite to the above, and after supporting the protective film forming film on one surface of the support sheet, The composite sheet for forming a protective film can also be produced by attaching a coating layer to the other surface of the sheet (the surface on which the protective film-forming film of the support sheet is not provided).
Further, a protective film-forming film is formed on one surface of the support sheet using the protective film-forming composition, and on the other hand, a coating layer is formed using the coating composition. A composite sheet for forming a protective film can also be produced by adhering to the exposed surface of the support sheet (the surface on which the protective film-forming film is not provided).
The formation conditions of the coating layer and the protective film-forming film in these cases are the same as in the above-described method.
　例えば、図１に示すような、保護膜形成用複合シートを上方から見下ろして平面視したときに、保護膜形成用フィルムが粘着剤層よりも表面積が小さい保護膜形成用複合シートを製造する場合には、上述の製造方法において、あらかじめ所定の大きさ及び形状に切り出しておいた保護膜形成用フィルムを粘着剤層上に設けるようにすればよい。 For example, when the protective film-forming composite sheet has a smaller surface area than the pressure-sensitive adhesive layer when the protective film-forming composite sheet is viewed from above and viewed in plan, as shown in FIG. In the manufacturing method described above, a protective film-forming film previously cut into a predetermined size and shape may be provided on the pressure-sensitive adhesive layer.
◎保護膜形成用複合シートの使用方法
　本実施形態に係る保護膜形成用複合シートの使用方法は、例えば、以下に示すとおりである。
　まず、保護膜形成用フィルムが熱硬化性である場合の保護膜形成用複合シートの使用方法について説明する。
　この場合には、まず、保護膜形成用複合シートの保護膜形成用フィルムに半導体ウエハの裏面を貼付するとともに、保護膜形成用複合シートをダイシング装置に固定する。
　次いで、保護膜形成用フィルムを加熱によって硬化させて保護膜とする。半導体ウエハの表面（電極形成面）にバックグラインドテープが貼付されている場合には、通常、このバックグラインドテープを半導体ウエハから取り除いてから、保護膜を形成する。 Method for Using Protective Film Forming Composite Sheet A method for using the protective film forming composite sheet according to the present embodiment is, for example, as shown below.
First, the usage method of the composite sheet for protective film formation in case the film for protective film formation is thermosetting is demonstrated.
In this case, first, the back surface of the semiconductor wafer is attached to the protective film forming film of the protective film forming composite sheet, and the protective film forming composite sheet is fixed to the dicing apparatus.
Next, the protective film-forming film is cured by heating to form a protective film. When a back grind tape is affixed to the surface (electrode formation surface) of the semiconductor wafer, the protective film is usually formed after removing the back grind tape from the semiconductor wafer.
　次いで、半導体ウエハをダイシングして半導体チップとする。保護膜を形成してからダイシングを行うまでの間においては、保護膜形成用複合シートのコーティング層側から保護膜にレーザー光を照射して、保護膜の表面に印字を行うことができる。この場合、先の説明のように、保護膜形成用複合シートのコーティング層側からのヘイズの測定値が、上記のような特定の範囲内であることで、保護膜に対して鮮明にレーザー印字を行うことができる。 Next, the semiconductor wafer is diced into semiconductor chips. From the formation of the protective film to the time of dicing, printing can be performed on the surface of the protective film by irradiating the protective film with laser light from the coating layer side of the protective film-forming composite sheet. In this case, as described above, the measured value of haze from the coating layer side of the composite sheet for forming the protective film is within the specific range as described above, so that the laser printing is clearly performed on the protective film. It can be performed.
　また、ダイシングを行う前の半導体ウエハや、ダイシングを行って得られた半導体チップについては、その裏面（保護膜形成用複合シートが貼付されている面）側から赤外線カメラ等によって観察することで、状態を検査することがある。例えば、半導体チップであれば、その欠けや割れ等の破損の有無を検査することがある。
　一方で、本発明に係る保護膜付き半導体チップにおいては、上述のように、コーティング層側からのヘイズの測定値が、上記のような特定の範囲内であり、さらに、コーティング層と支持シートの前記裏面との間には、空隙部の発生が抑制されている。したがって、半導体ウエハや半導体チップを、コーティング層側から保護膜形成用複合シートを介して、赤外線カメラ等によって観察するときに、鮮明な検査画像を取得できるため、高精度に検査を行うことができる。 In addition, for the semiconductor wafer before dicing and the semiconductor chip obtained by dicing, by observing from the back surface (the surface on which the protective film-forming composite sheet is attached) side with an infrared camera or the like, The condition may be checked. For example, in the case of a semiconductor chip, the presence or absence of breakage such as chipping or cracking may be inspected.
On the other hand, in the semiconductor chip with a protective film according to the present invention, as described above, the measured value of haze from the coating layer side is within the specific range as described above. The generation of voids is suppressed between the back surface. Therefore, when a semiconductor wafer or a semiconductor chip is observed from the coating layer side through the protective film forming composite sheet with an infrared camera or the like, a clear inspection image can be obtained, so that the inspection can be performed with high accuracy. .
　次いで、支持シートから、半導体チップをその裏面に貼付されている保護膜とともに剥離させてピックアップすることにより、保護膜付き半導体チップを得る。例えば、支持シートが基材及び粘着剤層が積層されてなり、前記粘着剤層がエネルギー線硬化性のものである場合には、エネルギー線の照射によって粘着剤層を硬化させ、この硬化後の粘着剤層から、半導体チップをその裏面に貼付されている保護膜とともにピックアップすることにより、より容易に保護膜付き半導体チップが得られる。 Next, the semiconductor chip is peeled off from the support sheet together with the protective film affixed to the back surface thereof and picked up to obtain a semiconductor chip with a protective film. For example, when the support sheet is formed by laminating a base material and an adhesive layer, and the adhesive layer is energy ray curable, the adhesive layer is cured by irradiation of energy rays, A semiconductor chip with a protective film can be more easily obtained by picking up the semiconductor chip from the adhesive layer together with the protective film attached to the back surface thereof.
　例えば、図１に示す保護膜形成用複合シート１を用いる場合には、保護膜形成用複合シート１の保護膜形成用フィルム１３に半導体ウエハの裏面を貼付するとともに、露出されている支持シート１０（粘着剤層１２）をリングフレーム等のダイシング用治具（図示略）に貼付して、保護膜形成用複合シート１をダイシング装置に固定する。次いで、保護膜形成用フィルム１３を硬化させて保護膜とした後、保護膜にレーザー印字を行い、次いでダイシングを行い、必要に応じてエネルギー線の照射によって、粘着剤層１２の前記治具への貼付箇所以外の領域を硬化させてから、保護膜付き半導体チップをピックアップすればよい。このように、粘着剤層１２がエネルギー線硬化性のものである保護膜形成用複合シート１を用いた場合には、これが前記治具から剥離してしまわないように、粘着剤層１２の特定領域を硬化させないように調節することが必要となる。一方で、保護膜形成用複合シート１を用いた場合には、これを前記治具へ貼付するための構成を別途設ける必要がない。 For example, in the case of using the protective film forming composite sheet 1 shown in FIG. 1, the back surface of the semiconductor wafer is attached to the protective film forming film 13 of the protective film forming composite sheet 1 and the exposed support sheet 10 is exposed. (Adhesive layer 12) is affixed to a dicing jig (not shown) such as a ring frame to fix the protective film-forming composite sheet 1 to the dicing apparatus. Next, after the protective film forming film 13 is cured to form a protective film, laser printing is performed on the protective film, then dicing is performed, and energy beam irradiation is applied to the jig of the adhesive layer 12 as necessary. After curing the region other than the pasted portion, a semiconductor chip with a protective film may be picked up. Thus, when using the composite sheet 1 for forming a protective film in which the pressure-sensitive adhesive layer 12 is energy ray curable, the pressure-sensitive adhesive layer 12 is specified so that it does not peel off from the jig. It is necessary to adjust so that the region does not cure. On the other hand, when the composite sheet 1 for forming a protective film is used, there is no need to separately provide a configuration for attaching the composite sheet 1 to the jig.
　これに対して、図２に示す保護膜形成用複合シート２を用いる場合には、保護膜形成用複合シート２の保護膜形成用フィルム２３に半導体ウエハの裏面を貼付するとともに、治具用接着剤層１６をリングフレーム等のダイシング用治具（図示略）に貼付して、保護膜形成用複合シート２をダイシング装置に固定する。次いで、保護膜形成用フィルム２３を硬化させて保護膜とした後、保護膜にレーザー印字を行い、次いでダイシングを行い、必要に応じてエネルギー線の照射によって粘着剤層１２を硬化させてから、保護膜付き半導体チップをピックアップすればよい。このように、粘着剤層１２がエネルギー線硬化性のものである保護膜形成用複合シート２を用いた場合には、保護膜形成用複合シート１を用いた場合とは異なり、粘着剤層１２の特定領域を硬化させないように調節することは不要である。一方で、保護膜形成用複合シート２として、保護膜形成用複合シート１とは異なり、治具用接着剤層１６を備えたものが必要となる。治具用接着剤層１６を備えていることで、粘着剤層１２として、目的に応じて幅広い組成のものを選択できる。 On the other hand, when the protective film forming composite sheet 2 shown in FIG. 2 is used, the back surface of the semiconductor wafer is attached to the protective film forming film 23 of the protective film forming composite sheet 2 and the jig bonding is performed. The agent layer 16 is attached to a dicing jig (not shown) such as a ring frame, and the protective film forming composite sheet 2 is fixed to a dicing apparatus. Next, after the protective film-forming film 23 is cured to form a protective film, laser printing is performed on the protective film, then dicing is performed, and if necessary, the adhesive layer 12 is cured by irradiation with energy rays, A semiconductor chip with a protective film may be picked up. Thus, when the protective film-forming composite sheet 2 in which the adhesive layer 12 is energy ray curable is used, the adhesive layer 12 is different from the case where the protective film-forming composite sheet 1 is used. It is not necessary to adjust so as not to cure the specific region. On the other hand, unlike the protective film-forming composite sheet 1, the protective film-forming composite sheet 2 is required to have a jig adhesive layer 16. By having the adhesive layer 16 for jig | tool, the thing of a wide composition can be selected as the adhesive layer 12 according to the objective.
　次に、保護膜形成用フィルムがエネルギー線硬化性である場合の保護膜形成用複合シートの使用方法について説明する。
　この場合には、まず、上述の保護膜形成用フィルムが熱硬化性である場合と同様に、保護膜形成用複合シートの保護膜形成用フィルムに半導体ウエハの裏面を貼付するとともに、保護膜形成用複合シートをダイシング装置に固定する。
　次いで、保護膜形成用フィルムをエネルギー線の照射によって硬化させて保護膜とする。半導体ウエハの表面（電極形成面）にバックグラインドテープが貼付されている場合には、通常、このバックグラインドテープを半導体ウエハから取り除いてから、保護膜を形成する。 Next, a method for using the composite sheet for forming a protective film when the protective film-forming film is energy ray curable will be described.
In this case, first, as in the case where the above-described protective film forming film is thermosetting, the back surface of the semiconductor wafer is attached to the protective film forming film of the protective film forming composite sheet, and the protective film is formed. Fix the composite sheet to the dicing machine.
Next, the protective film-forming film is cured by irradiation with energy rays to form a protective film. When a back grind tape is affixed to the surface (electrode formation surface) of the semiconductor wafer, the protective film is usually formed after removing the back grind tape from the semiconductor wafer.
　次いで、半導体ウエハをダイシングして半導体チップとする。保護膜を形成してからダイシングを行うまでの間においては、保護膜形成用複合シートのコーティング層側から保護膜にレーザー光を照射して、保護膜の表面に印字を行うことができる。この印字からダイシングまでは、上述の保護膜形成用フィルムが熱硬化性である場合と同様に行うことができ、その場合と同様に、保護膜に対して鮮明にレーザー印字を行うことができ、赤外線カメラ等によって高精度に検査を行うことができる。 Next, the semiconductor wafer is diced into semiconductor chips. From the formation of the protective film to the time of dicing, printing can be performed on the surface of the protective film by irradiating the protective film with laser light from the coating layer side of the protective film-forming composite sheet. From this printing to dicing, it can be carried out in the same manner as the above-mentioned film for forming a protective film is thermosetting, and in that case, laser printing can be clearly performed on the protective film, Inspection can be performed with high accuracy by an infrared camera or the like.
　次いで、支持シートから、半導体チップをその裏面に貼付されている保護膜とともに剥離させてピックアップすることにより、保護膜付き半導体チップを得る。
　この方法は、例えば、保護膜形成用複合シートとして、支持シートが基材及び粘着剤層が積層されてなり、かつ前記粘着剤層が非エネルギー線硬化性であるものを用いる場合に、特に好適である。なお、ここでは、保護膜形成用フィルムをエネルギー線の照射によって硬化させてから、半導体ウエハをダイシングし、保護膜付き半導体チップをピックアップする得る場合について説明したが、前記粘着剤層が非エネルギー線硬化性である場合には、保護膜形成用フィルムのエネルギー線の照射による硬化は、半導体チップをピックアップするまでのいずれの段階でも行うことができる。 Next, the semiconductor chip is peeled off from the support sheet together with the protective film stuck on the back surface thereof and picked up, thereby obtaining a semiconductor chip with a protective film.
This method is particularly suitable when, for example, a composite sheet for forming a protective film is used in which a support sheet is formed by laminating a base material and a pressure-sensitive adhesive layer, and the pressure-sensitive adhesive layer is non-energy ray curable. It is. Here, the case where the protective film-forming film is cured by irradiation with energy rays and then the semiconductor wafer is diced and a semiconductor chip with a protective film is picked up is described. However, the adhesive layer is a non-energy ray. When it is curable, the protective film-forming film can be cured by irradiation with energy rays at any stage until the semiconductor chip is picked up.
　例えば、支持シートが基材及び粘着剤層が積層されてなり、かつ前記粘着剤層がエネルギー線硬化性のものである保護膜形成用複合シートを用いる場合には、以下に説明する方法が好ましい。
　すなわち、まず、上記の場合と同様に、保護膜形成用複合シートの保護膜形成用フィルムに半導体ウエハの裏面を貼付するとともに、保護膜形成用複合シートをダイシング装置に固定する。
　次いで、保護膜形成用複合シートのコーティング層側から保護膜にレーザー光を照射して、保護膜の表面に印字を行い、さらに半導体ウエハをダイシングして半導体チップとする。この印字からダイシングまでは、上述の保護膜形成用フィルムが熱硬化性である場合と同様に行うことができ、その場合と同様に、保護膜に対して鮮明にレーザー印字を行うことができ、赤外線カメラ等によって高精度に検査を行うことができる。 For example, when a support sheet is formed by laminating a base material and a pressure-sensitive adhesive layer and the pressure-sensitive adhesive layer is an energy ray-curable composite sheet, a method described below is preferable. .
That is, first, as in the above case, the back surface of the semiconductor wafer is attached to the protective film forming film of the protective film forming composite sheet, and the protective film forming composite sheet is fixed to the dicing apparatus.
Next, the protective film is irradiated with laser light from the coating layer side of the protective film-forming composite sheet, printing is performed on the surface of the protective film, and the semiconductor wafer is diced into semiconductor chips. From this printing to dicing, it can be carried out in the same manner as the above-mentioned film for forming a protective film is thermosetting, and in that case, laser printing can be clearly performed on the protective film, Inspection can be performed with high accuracy by an infrared camera or the like.
　次いで、エネルギー線の照射によって、保護膜形成用フィルムを硬化させて保護膜とすると共に、粘着剤層を硬化させ、この硬化後の粘着剤層から、半導体チップをその裏面に貼付されている保護膜とともにピックアップすることにより、保護膜付き半導体チップが得られる。 Next, by irradiating energy rays, the protective film-forming film is cured to form a protective film, and the adhesive layer is cured, and from this cured adhesive layer, the semiconductor chip is adhered to the back surface thereof By picking up with the film, a semiconductor chip with a protective film is obtained.
　一方、長尺の保護膜形成用複合シートを巻き取る場合には、通常、保護膜形成用フィルムの露出面上に剥離フィルム（図１及び２においては剥離フィルム１５）が積層された状態の保護膜形成用複合シートが使用される。そして、本発明に係る保護膜形成用複合シートは、如何なる構成であっても（例えば、図１に示す保護膜形成用複合シート１、及び図２に示す保護膜形成用複合シート２のいずれであっても）、保護膜形成用複合シートをロール状に巻き取るに従って、コーティング層、支持シート、保護膜形成用フィルム及び剥離フィルムがこの順に積層されている積層単位が、ロールの径方向に順次積み重ねられていく。その結果、ロールの径方向において互いに接触している積層単位同士の間では、一方の積層単位の剥離フィルムの表面（保護膜形成用フィルムが設けられている側とは反対側の面）と、他方の積層単位のコーティング層の裏面（基材と接触している側とは反対側の面）とが接触し、押圧された状態となり、この状態のまま、保護膜形成用複合シートのロールは保存される。しかし、コーティング層が設けられていることにより、積層単位同士の間では、これら剥離フィルム及びコーティング層の貼り付きが抑制されるため、本実施形態に係る保護膜形成用複合シートは、ブロッキングが抑制される。 On the other hand, when winding up a long protective film-forming composite sheet, the protective film usually has a release film (release film 15 in FIGS. 1 and 2) laminated on the exposed surface of the protective film-forming film. A film-forming composite sheet is used. The protective film-forming composite sheet according to the present invention has any configuration (for example, any of the protective film-forming composite sheet 1 shown in FIG. 1 and the protective film-forming composite sheet 2 shown in FIG. 2). Even if the protective sheet-forming composite sheet is wound into a roll, the lamination unit in which the coating layer, the support sheet, the protective film-forming film, and the release film are laminated in this order is sequentially formed in the radial direction of the roll. It will be stacked. As a result, between the laminated units that are in contact with each other in the radial direction of the roll, the surface of the release film of one laminated unit (the surface opposite to the side on which the protective film-forming film is provided), The back surface of the coating layer of the other laminated unit (the surface opposite to the side in contact with the base material) is in contact and pressed, and in this state, the roll of the protective film-forming composite sheet is Saved. However, the provision of the coating layer suppresses the sticking of the release film and the coating layer between the laminated units, so that the protective film-forming composite sheet according to this embodiment suppresses blocking. Is done.
　前記保護膜形成用フィルム上に剥離フィルムを備えた前記保護膜形成用複合シートを用いて、下記方法で測定した前記剥離フィルムの剥離力が、好ましくは、１０ｍＮ／５０ｍｍ以下、より好ましくは７．５ｍＮ／５０ｍｍ以下、特に好ましくは５ｍＮ／５０ｍｍ以下である。
（剥離フィルムの剥離力の測定方法）
　保護膜形成用フィルム上に剥離フィルムを備えた状態の、幅５０ｍｍ、長さ１００ｍｍの本発明に係る保護膜形成用複合シートを、コーティング層がすべて同じ方向を向くように、かつコーティング層の合計の厚さが１０～６０μｍとなるように複数枚重ねることで、第一の最外層がコーティング層で、第二の最外層が剥離フィルムである積層体とし、この積層体を、保護膜形成用複合シートの積層方向において９８０．６６５ｍＮ（すなわち１００ｇｆ）の力（外力）を加えたまま４０℃で３日間静置した後、前記積層方向において前記第一の最外層のコーティング層に最も近い剥離フィルムを剥離速度３００ｍｍ／分、剥離角度１８０°の条件で、隣接するコーティング層（前記積層方向において前記第一の最外層のコーティング層に最も近いコーティング層）から剥離させたときの剥離力を測定する。
　なお、ここで複数枚重ねる保護膜形成用複合シートは、すべて同じ構成のものとする。また、重ねる保護膜形成用複合シートの枚数は、１０枚であることが好ましい。このような剥離フィルムの剥離力から、本実施形態に係る保護膜形成用複合シートのブロッキング抑制効果（耐ブロッキング性）の高さを確認できる。 Using the protective film-forming composite sheet provided with a release film on the protective film-forming film, the peel strength of the release film measured by the following method is preferably 10 mN / 50 mm or less, more preferably 7. 5 mN / 50 mm or less, particularly preferably 5 mN / 50 mm or less.
(Measurement method of peel strength of release film)
The composite sheet for protective film formation according to the present invention having a width of 50 mm and a length of 100 mm in a state in which a release film is provided on the protective film forming film, so that the coating layers are all directed in the same direction, and the total of the coating layers By stacking a plurality of layers so as to have a thickness of 10 to 60 μm, a laminated body in which the first outermost layer is a coating layer and the second outermost layer is a release film is formed. The film is left to stand at 40 ° C. for 3 days with a force (external force) of 980.665 mN (ie, 100 gf) in the laminating direction of the composite sheet, and then the release film closest to the first outermost coating layer in the laminating direction On the condition that the peeling speed is 300 mm / min and the peeling angle is 180 °, the adjacent coating layer (the first outermost coating layer in the stacking direction is Measure the peel force when peeled from a nearby coating layer.
Here, all the composite sheets for forming a protective film to be stacked are assumed to have the same configuration. Moreover, it is preferable that the number of the protective sheet-forming composite sheets to be stacked is ten. From the peeling force of such a peeling film, the height of the blocking suppression effect (blocking resistance) of the composite sheet for protective film formation concerning this embodiment can be confirmed.
　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.
＜保護膜形成用複合シートの製造＞
［実施例１］
　図１に示す構成の保護膜形成用複合シートを製造した。この保護膜形成用複合シートの平面図を図３に示す。より具体的には、以下のとおりである。 <Manufacture of composite sheet for forming protective film>
[Example 1]
A composite sheet for forming a protective film having the structure shown in FIG. 1 was produced. A plan view of this protective film-forming composite sheet is shown in FIG. More specifically, it is as follows.
［第１積層体の製造］
（熱硬化性保護膜形成用組成物の調製）
　下記成分を下記量（固形分）で配合し、さらにメチルエチルケトンを配合して、固形分濃度が５１質量％の保護膜形成用組成物（ＩＩＩ－１）を得た。 [Production of first laminate]
(Preparation of composition for forming thermosetting protective film)
The following components were blended in the following amounts (solid content), and methyl ethyl ketone was blended to obtain a protective film-forming composition (III-1) having a solid content concentration of 51% by mass.
（重合体成分（Ａ））
　（Ａ）－１：アクリル酸ｎ－ブチル１０質量部、アクリル酸メチル７０質量部、メタクリル酸グリシジル５質量部及びアクリル酸２－ヒドロキシエチル１５質量部を共重合してなるアクリル系樹脂（重量平均分子量４０００００、ガラス転移温度－１℃）１５０質量部
（熱硬化性成分（Ｂ））
・エポキシ樹脂（Ｂ１）
　（Ｂ１）－１：ビスフェノールＡ型エポキシ樹脂（三菱化学社製「ＪＥＲ８２８」、エポキシ当量１８３～１９４ｇ／ｅｑ、分子量３７０）６０質量部
　（Ｂ１）－２：ビスフェノールＡ型エポキシ樹脂（三菱化学社製「ＪＥＲ１０５５」、エポキシ当量８００～９００ｇ／ｅｑ、分子量１６００）１０質量部
　（Ｂ１）－３：ジシクロペンタジエン型エポキシ樹脂（ＤＩＣ社製「エピクロンＨＰ－７２００ＨＨ」、エポキシ当量２７４～２８６ｇ／ｅｑ）３０質量部
・熱硬化剤（Ｂ２）
　（Ｂ２）－１：ジシアンジアミド（固体分散型潜在性硬化剤、ＡＤＥＫＡ社製「アデカハードナーＥＨ－３６３６ＡＳ」、活性水素量２１ｇ／ｅｑ）２質量部
（硬化促進剤（Ｃ））
　（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」）２質量部
（充填材（Ｄ））
　（Ｄ）－１：シリカフィラー（アドマテックス社「ＳＣ２０５０ＭＡ」、エポキシ系化合物で表面修飾されたもの、平均粒子径０．５μｍ）３２０質量部
（カップリング剤（Ｅ））
　（Ｅ）－１：γ－グリシドキシプロピルトリメトキシシラン（シランカップリング剤、信越化学工業社製「ＫＢＭ４０３」、メトキシ当量１２．７ｍｍｏｌ／ｇ、分子量２３６．３）０．４質量部
（着色剤（Ｉ））
　（Ｉ）－１：カーボンブラック（顔料、三菱化学社製「ＭＡ６００Ｂ」、平均粒径２８ｎｍ）１．２質量部 (Polymer component (A))
(A) -1: an acrylic resin (weight average) obtained by copolymerizing 10 parts by mass of n-butyl acrylate, 70 parts by mass of methyl acrylate, 5 parts by mass of glycidyl methacrylate and 15 parts by mass of 2-hydroxyethyl acrylate 150 parts by mass (thermosetting component (B))
・ Epoxy resin (B1)
(B1) -1: Bisphenol A type epoxy resin (“JER828” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 183 to 194 g / eq, molecular weight 370) 60 parts by mass (B1) -2: Bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Corporation) “JER1055”, epoxy equivalent 800-900 g / eq, molecular weight 1600) 10 parts by mass (B1) -3: dicyclopentadiene type epoxy resin (“Epiclon HP-7200HH” manufactured by DIC, epoxy equivalent 274-286 g / eq) 30 Part by mass / thermosetting agent (B2)
(B2) -1: Dicyandiamide (solid dispersion type latent curing agent, “ADEKA HARDNER EH-3636AS” manufactured by ADEKA, 21 g / eq of active hydrogen) 2 parts by mass (curing accelerator (C))
(C) -1: 2 parts by mass (filler (D)) of 2-phenyl-4,5-dihydroxymethylimidazole (“Curesol 2PHZ” manufactured by Shikoku Kasei Kogyo Co., Ltd.)
(D) -1: Silica filler (Admatex “SC2050MA”, surface-modified with an epoxy compound, average particle size 0.5 μm) 320 parts by mass (coupling agent (E))
(E) -1: 0.4 part by mass of γ-glycidoxypropyltrimethoxysilane (silane coupling agent, “KBM403” manufactured by Shin-Etsu Chemical Co., Ltd., methoxy equivalent 12.7 mmol / g, molecular weight 236.3) Agent (I))
(I) -1: Carbon black (pigment, “MA600B” manufactured by Mitsubishi Chemical Corporation, average particle size 28 nm) 1.2 parts by mass
（保護膜形成用フィルムの形成、第１積層体の製造）
　第１剥離フィルム（リンテック社製「ＳＰ－Ｐ５０２０１０＊」、厚さ５０μｍ）の剥離処理面上に、ナイフコーターを用いて、上記で得られた保護膜形成用組成物（ＩＩＩ－１）を塗布し、１２０℃で２分間乾燥させて、保護膜形成用フィルム（厚さ２５μｍ）を形成した。
　次いで、この保護膜形成用フィルムの第１剥離フィルムが設けられている面とは反対側の面に、第２剥離フィルム（リンテック社製「ＳＰ－ＰＥＴ３８１０３１Ｃ」、厚さ３８μｍ）の剥離処理面を貼り合わせて、第１剥離フィルム、保護膜形成用フィルム及び第２剥離フィルムがこの順に積層されてなる、長尺の積層体を得た。次いで、この長尺の積層体を巻き取ってロールとした後、この積層体を、その幅方向（図３に示す保護膜形成用複合シート１の符号ｗ１で示す幅の方向）において３００ｍｍの大きさの分だけ裁断した。 (Formation of protective film-forming film, production of first laminate)
Using the knife coater, the protective film-forming composition (III-1) obtained above was applied onto the release-treated surface of the first release film (“SP-P502010 *” manufactured by Lintec Corporation, thickness 50 μm). And dried at 120 ° C. for 2 minutes to form a protective film-forming film (thickness: 25 μm).
Next, on the surface of the protective film-forming film opposite to the surface on which the first release film is provided, the release treatment surface of the second release film (“SP-PET381031C” manufactured by Lintec Corporation, thickness 38 μm) is provided. By sticking together, the elongate laminated body by which the 1st peeling film, the film for protective film formation, and the 2nd peeling film were laminated | stacked in this order was obtained. Subsequently, after winding this elongate laminated body into a roll, this laminated body is 300 mm in the width direction (the width direction indicated by reference sign w1 of the protective film-forming composite sheet 1 shown in FIG. 3). I cut only that much.
　そして、この裁断した積層体に対して、その幅方向中央部において、第２剥離フィルム側から、第２剥離フィルム及び保護膜形成用フィルムにともに、平面視にて直径２２０ｍｍの円形を描くように切れ込みを入れるハーフカットを行った。なお、本明細書において積層体の「平面視」とは、積層体をその積層方向上方から見下ろすことを意味する。そして、このハーフカットで形成した円形の部分のみを残すようにして、第２剥離フィルム及び保護膜形成用フィルムを前記積層体から除去することにより、第１剥離フィルムの剥離処理面上に、平面視にて円形の保護膜形成用フィルム及び第２剥離フィルムがこの順に積層されてなる第１積層体を得た。この第１積層体における円形の保護膜形成用フィルムは、図３に示す保護膜形成用複合シート１における、直径ｄ１が２２０ｍｍの円形の保護膜形成用フィルム１３に相当する。 And with respect to this cut laminated body, in the width direction center part, it draws a circle with a diameter of 220 mm in plan view from the second release film side to the second release film and the protective film forming film. A half cut was made to make a cut. In the present specification, the “plan view” of the stacked body means that the stacked body is looked down from above in the stacking direction. Then, the second release film and the protective film-forming film are removed from the laminate so as to leave only the circular portion formed by the half cut, and on the release treatment surface of the first release film, As a result, a first laminated body in which a circular protective film-forming film and a second release film were laminated in this order was obtained. The circular protective film-forming film in the first laminate corresponds to the circular protective film-forming film 13 having a diameter d1 of 220 mm in the protective film-forming composite sheet 1 shown in FIG.
（コーティング組成物の調製）
　シリカゾルが２－エトキシエタノール（エチルセロソルブ）中に分散された分散液（触媒化成工業社製「ＯＳＣＡＬ１６３２」、シリカゾルの粒径３０～５０ｎｍ、固形分濃度３０質量％）１５０質量部に、ウレタンアクリレート及び多官能性アクリレートモノマーからなるハードコート剤（荒川化学工業社製「ビームセット５７５ＣＢ」、固形分濃度１００質量％、光重合開始剤含有）１００質量部を配合して、コーティング組成物（固形分濃度３０質量％）を得た。 (Preparation of coating composition)
150 parts by mass of a silica sol dispersed in 2-ethoxyethanol (ethyl cellosolve) (catalyst chemical industry “OSCAL 1632”, silica sol particle size 30 to 50 nm, solid content concentration 30% by mass), urethane acrylate and A hard coating agent composed of a polyfunctional acrylate monomer ("Arakawa Chemical Industries" Beam Set 575CB ", solid content concentration 100% by weight, containing a photopolymerization initiator) 100 parts by weight, and coating composition (solid content concentration 30% by mass) was obtained.
（コーティング層の形成）
　次いで、凹凸面の表面粗さＲａが０．４μｍで、この凹凸面とは反対側の面の表面粗さＲａが０．０２μｍであるポリプロピレン製基材（厚さ１００μｍ、融点１４０～１６０℃）の前記凹凸面に、マイヤーバーコーターを用いて、上記で得られたコーティング組成物を塗布し、８０℃で１分乾燥させた後、約２３０ｍＪ／ｃｍ２の光量で紫外線を照射して乾燥後の塗膜を硬化させ、コーティング層（厚さ３μｍ）を形成した。 (Formation of coating layer)
Next, a polypropylene substrate (thickness 100 μm, melting point 140 to 160 ° C.) having a surface roughness Ra of 0.4 μm on the uneven surface and a surface roughness Ra of 0.02 μm on the surface opposite to the uneven surface After applying the coating composition obtained above to the uneven surface of the film using a Mayer bar coater, drying at 80 ° C. for 1 minute, and then irradiating with ultraviolet light at a light intensity of about 230 mJ / cm 2 The coating film was cured to form a coating layer (thickness 3 μm).
（粘着剤組成物の調製）
　（メタ）アクリル酸アルキルエステル共重合体１００質量部、及び芳香族系ポリイソシアネート化合物（架橋剤、三井化学社製「タケネートＤ１１０Ｎ」）１０質量部（固形分）を配合し、さらにメチルエチルケトンを配合して、固形分濃度が３０質量％の粘着剤組成物（ｉｉｉ）を得た。
　前記（メタ）アクリル酸アルキルエステル共重合体は、アクリル酸ｎ－ブチル４０質量部、アクリル酸２－エチルヘキシル５５質量部及びアクリル酸２－ヒドロキシエチル５質量部を共重合してなる、重量平均分子量６０００００のアクリル系樹脂である。 (Preparation of adhesive composition)
100 parts by weight of (meth) acrylic acid alkyl ester copolymer and 10 parts by weight (solid content) of aromatic polyisocyanate compound (crosslinking agent, “Takenate D110N” manufactured by Mitsui Chemicals) are blended, and methyl ethyl ketone is further blended. Thus, a pressure-sensitive adhesive composition (iii) having a solid content concentration of 30% by mass was obtained.
The (meth) acrylic acid alkyl ester copolymer is obtained by copolymerizing 40 parts by mass of n-butyl acrylate, 55 parts by mass of 2-ethylhexyl acrylate, and 5 parts by mass of 2-hydroxyethyl acrylate. 600,000 acrylic resin.
（粘着剤層（支持シート）の形成、第２積層体の製造）
　片面がシリコーン系の剥離剤層の形成によって剥離処理されてなる、厚さ３８μｍのポリエチレンテレフタレート製フィルムからなる第３剥離フィルム（リンテック社製「ＳＰ－ＰＥＴ３８１０３１Ｃ」）の前記剥離処理面に、ナイフコーターを用いて、上記で得られた粘着剤組成物（ｉｉｉ）を塗布し、乾燥させて、粘着剤層（厚さ５μｍ）を形成した。
　次いで、コーティング層が形成された上述の基材の、凹凸面とは反対側の面をコロナ処理した後、このコロナ処理面に、上記の粘着剤層を貼り合わせ、コーティング層、基材、粘着剤層及び第３剥離フィルムがこの順に積層されてなり、支持シートを含む、長尺の第２積層体を得た。
　次いで、この長尺の第２積層体を巻き取ってロールとした後、この第２積層体を、その幅方向（図３に示す保護膜形成用複合シート１の符号ｗ１で示す幅の方向）において３００ｍｍの大きさの分だけ裁断した。 (Formation of pressure-sensitive adhesive layer (support sheet), production of second laminate)
A knife coater is applied to the release-treated surface of a third release film (“SP-PET381031C” manufactured by Lintec Corporation) made of a polyethylene terephthalate film having a thickness of 38 μm, one side of which is released by forming a silicone-based release agent layer. The pressure-sensitive adhesive composition (iii) obtained above was applied and dried to form a pressure-sensitive adhesive layer (thickness 5 μm).
Next, the surface of the above-mentioned base material on which the coating layer is formed is subjected to corona treatment on the surface opposite to the concavo-convex surface, and then the above-mentioned pressure-sensitive adhesive layer is bonded to this corona-treated surface to form a coating layer, base material, and adhesive. The agent layer and the third release film were laminated in this order to obtain a long second laminate including a support sheet.
Next, after winding the long second laminated body into a roll, the second laminated body is arranged in the width direction (the width direction indicated by reference sign w1 of the protective film-forming composite sheet 1 shown in FIG. 3). Was cut by a size of 300 mm.
（保護膜形成用複合シートの製造）
　上記で得られた第１積層体から第２剥離フィルムを取り除き、円形の保護膜形成用フィルムを露出させた。また、上記で得られた第２積層体から第３剥離フィルムを取り除き、粘着剤層を露出させた。そして、この粘着剤層の露出面に、上記の保護膜形成用フィルムの露出面を貼り合わせることで、コーティング層、基材、粘着剤層、保護膜形成用フィルム及び第１剥離フィルムがこの順に積層されてなる、保護膜形成用複合シートに相当する第３積層体を得た。 (Manufacture of composite sheet for protective film formation)
The 2nd peeling film was removed from the 1st laminated body obtained above, and the circular film for protective film formation was exposed. Moreover, the 3rd peeling film was removed from the 2nd laminated body obtained above, and the adhesive layer was exposed. Then, by bonding the exposed surface of the protective film forming film to the exposed surface of the adhesive layer, the coating layer, the base material, the adhesive layer, the protective film forming film, and the first release film are in this order. A third laminated body corresponding to the composite sheet for forming a protective film was obtained.
　上記で得られた第３積層体に対して、コーティング層側から、コーティング層、基材及び粘着剤層のすべてに、平面視にて直径２７０ｍｍの円形を描くように切れ込みを入れるハーフカットを行った。このハーフカットでは、平面視にて、直径２７０ｍｍの前記円が、保護膜形成用フィルムが形成している直径２２０ｍｍの円に対して同心円となるように、コーティング層、基材及び粘着剤層のすべてに切れ込みを入れた。
　次いで、平面視にて、上記の直径２７０ｍｍの円に対して、この円の径方向外側に２０ｍｍ離れた位置に、第３積層体の幅方向（図３に示す保護膜形成用複合シート１の符号ｗ１で示す幅の方向）において対向する一対の円弧を描くように、コーティング層側から、コーティング層、基材及び粘着剤層のすべてに切れ込みを入れるハーフカットを行った。
この一対の円弧に相当する切れ込みは、図３に示す保護膜形成用複合シート１における、符号１２１で示す粘着剤層の曲面状の周縁部を形成する。そして、直径２７０ｍｍの円と、前記円弧との間の距離（２０ｍｍ）は、図３に示す保護膜形成用複合シート１における、符号ｗ２に相当する。 A half cut is performed on the third laminate obtained above from the coating layer side so as to draw a circle having a diameter of 270 mm in a plan view on all of the coating layer, the base material and the adhesive layer. It was. In this half-cut, the coating layer, the base material, and the pressure-sensitive adhesive layer are formed so that the circle having a diameter of 270 mm is concentric with the circle having a diameter of 220 mm formed by the protective film-forming film in plan view. Cut everything into cuts.
Next, in a plan view, the width of the third laminate (in the protective sheet-forming composite sheet 1 shown in FIG. 3 of the composite sheet 1 shown in FIG. 3) is 20 mm away from the circle having a diameter of 270 mm. From the coating layer side, a half cut was made to cut all of the coating layer, the base material, and the pressure-sensitive adhesive layer so as to draw a pair of arcs facing each other in the width direction indicated by the symbol w1.
The notches corresponding to the pair of arcs form a curved peripheral portion of the pressure-sensitive adhesive layer denoted by reference numeral 121 in the protective film-forming composite sheet 1 shown in FIG. And the distance (20 mm) between the circle | round | yen with a diameter of 270 mm and the said circular arc is equivalent to the code | symbol w2 in the composite sheet 1 for protective film formation shown in FIG.
　このような、２個の同心円と一対の円弧を描く上述のハーフカットを、第３積層体の長手方向（図３に示す保護膜形成用複合シート１の符号ｗ１で示す幅の方向に対して直交する方向）における複数箇所で行い、平面視にて、隣り合う箇所の間で円弧同士を前記長手方向で連結する直線を２本描くように、コーティング層側から、コーティング層、基材及び粘着剤層のすべてに切れ込みを入れるハーフカットを行った。この２本の直線に相当する切れ込みは、図３に示す保護膜形成用複合シート１における、符号１２２で示す粘着剤層の平面状の周縁部を形成する。
　次いで、平面視にて、上記の直径２７０ｍｍの円と一対の円弧との間の部分、及び上記の円弧同士を連結する２本の直線で挟まれた部分における、コーティング層、基材及び粘着剤層を取り除くことで、図１及び３に示す保護膜形成用複合シートを得た。この保護膜形成用複合シートにおける円形の粘着剤層（支持シート）は、図３における、直径ｄ２が２７０ｍｍの円形の粘着剤層１２（支持シート１０）に相当する。また、この保護膜形成用複合シートにおける第１剥離フィルムは、図３における剥離フィルム１５に相当する。 The above-described half cut that draws two concentric circles and a pair of arcs is made in the longitudinal direction of the third laminated body (in the width direction indicated by the symbol w1 of the protective film-forming composite sheet 1 shown in FIG. 3). The coating layer, the base material, and the adhesive are formed from the coating layer side so as to draw two straight lines that connect the arcs in the longitudinal direction between adjacent portions in plan view. A half cut was made to cut all the agent layer. The notches corresponding to the two straight lines form a planar peripheral edge of the pressure-sensitive adhesive layer indicated by reference numeral 122 in the protective film-forming composite sheet 1 shown in FIG.
Next, in a plan view, a coating layer, a base material, and an adhesive in a portion between the circle having a diameter of 270 mm and a pair of arcs, and a portion sandwiched by two straight lines connecting the arcs By removing the layer, the composite sheet for forming a protective film shown in FIGS. 1 and 3 was obtained. The circular pressure-sensitive adhesive layer (support sheet) in this protective film-forming composite sheet corresponds to the circular pressure-sensitive adhesive layer 12 (support sheet 10) having a diameter d2 of 270 mm in FIG. Moreover, the 1st peeling film in this composite sheet for protective film formation corresponds to the peeling film 15 in FIG.
［実施例２］
　表１に示すように、凹凸面の表面粗さＲａが０．４μｍではなく１μｍである基材を用いた点以外は、実施例１と同じ方法で、保護膜形成用複合シートを得た。 [Example 2]
As shown in Table 1, a composite sheet for forming a protective film was obtained in the same manner as in Example 1 except that a substrate having a surface roughness Ra of the uneven surface of 1 μm instead of 0.4 μm was used.
［実施例３］
　表１に示すように、凹凸面の表面粗さＲａが０．４μｍではなく１μｍである基材を用い、コーティング層の厚さを３μｍに代えて１μｍとした点以外は、実施例１と同じ方法で、保護膜形成用複合シートを得た。 [Example 3]
As shown in Table 1, the same as Example 1, except that a substrate having a surface roughness Ra of 1 μm instead of 0.4 μm was used, and the thickness of the coating layer was changed to 1 μm instead of 3 μm. By the method, a composite sheet for forming a protective film was obtained.
［実施例４］
　表１に示すように、コーティング層の厚さを３μｍに代えて１μｍとした点以外は、実施例１と同じ方法で、保護膜形成用複合シートを得た。 [Example 4]
As shown in Table 1, a composite sheet for forming a protective film was obtained in the same manner as in Example 1 except that the thickness of the coating layer was changed to 1 μm instead of 3 μm.
［実施例５］
　表１に示すように、凹凸面の表面粗さＲａが０．４μｍではなく１μｍである基材を用い、コーティング層の厚さを３μｍに代えて６μｍとした点以外は、実施例１と同じ方法で、保護膜形成用複合シートを得た。 [Example 5]
As shown in Table 1, the same as Example 1 except that a substrate having a surface roughness Ra of 1 μm instead of 0.4 μm was used and the thickness of the coating layer was changed to 6 μm instead of 3 μm. By the method, a composite sheet for forming a protective film was obtained.
［実施例６］
　表１に示すように、凹凸面の表面粗さＲａが０．４μｍではなく３μｍである基材を用い、コーティング層の厚さを３μｍに代えて６μｍとした点以外は、実施例１と同じ方法で、保護膜形成用複合シートを得た。 [Example 6]
As shown in Table 1, the same as Example 1 except that a substrate having a surface roughness Ra of 3 μm instead of 0.4 μm was used, and the thickness of the coating layer was changed to 6 μm instead of 3 μm. By the method, a composite sheet for forming a protective film was obtained.
［比較例１］
　表１に示すように、凹凸面の表面粗さＲａが０．４μｍではなく１μｍである基材を用い、コーティング層を形成しなかった点以外は、実施例１と同じ方法で、保護膜形成用複合シートを得た。 [Comparative Example 1]
As shown in Table 1, a protective film was formed in the same manner as in Example 1 except that a substrate having a surface roughness Ra of 1 μm instead of 0.4 μm was used and a coating layer was not formed. A composite sheet was obtained.
［比較例２］
　表１に示すように、凹凸面が反対側、すなわち粘着剤層側（内側）に向くように基材を配置して、コーティング層を形成しなかった（すなわち、図５に示す従来の構成とした）点以外は、実施例１と同じ方法で、保護膜形成用複合シートを得た。 [Comparative Example 2]
As shown in Table 1, the base material was arranged so that the uneven surface faced to the opposite side, that is, the pressure-sensitive adhesive layer side (inner side), and the coating layer was not formed (that is, the conventional configuration shown in FIG. Except for the points, a composite sheet for forming a protective film was obtained in the same manner as in Example 1.
［比較例３］
　表１に示すように、凹凸面の表面粗さＲａが０．４μｍではなく１μｍである基材を用い、凹凸面が反対側、すなわち粘着剤層側（内側）に向くようにこの基材を配置して、コーティング層を形成しなかった（すなわち、図５に示す従来の構成とした）点以外は、実施例１と同じ方法で、保護膜形成用複合シートを得た。 [Comparative Example 3]
As shown in Table 1, a substrate having a surface roughness Ra of 1 μm instead of 0.4 μm is used, and this substrate is placed so that the surface of the uneven surface faces the opposite side, that is, the pressure-sensitive adhesive layer side (inner side). A composite sheet for forming a protective film was obtained in the same manner as in Example 1 except that the coating layer was not formed (that is, the conventional configuration shown in FIG. 5).
［比較例４］
　シリカゾルが２－エトキシエタノール中に分散された分散液に代えて、固形分として同じ量の、エポキシ基で表面修飾された球状シリカ（アドマテックス社製「ＳＣ２０５０ＭＡ」、平均粒子径０．５μｍ）を用いた点以外は、実施例１と同じ方法でコーティング組成物を調製した。
　そして、このコーティング組成物を用いた点以外は、実施例１と同じ方法で、保護膜形成用複合シートを得た。
　得られた保護膜形成用複合シートにおいて、基材側最表面の表面粗さＲａは、表１に示すように、０．８μｍであった。 [Comparative Example 4]
Instead of a dispersion in which silica sol is dispersed in 2-ethoxyethanol, the same amount of spherical silica surface-modified with an epoxy group (“Advertex“ SC2050MA ”, average particle size 0.5 μm) as a solid content is used. A coating composition was prepared in the same manner as in Example 1 except for the points used.
And the composite sheet for protective film formation was obtained by the same method as Example 1 except the point which used this coating composition.
In the obtained composite sheet for forming a protective film, the surface roughness Ra of the outermost surface on the substrate side was 0.8 μm as shown in Table 1.
＜保護膜形成用複合シートの評価＞
［レーザー印字性］
　上記で得られた各実施例及び比較例の保護膜形成用複合シートにおいて、第１剥離フィルムを取り除き、貼付装置（リンテック社製「ＲＡＤ－２７００Ｆ／１２」）を用いて、ステンレス製リングフレームに粘着剤層を貼付するとともに、７０℃に加熱したシリコンウエハ（外径８インチ、厚さ１００μｍ）の裏面に保護膜形成用フィルムを貼付した。
　次いで、保護膜形成用フィルムを１３０℃で２時間加熱処理することで、保護膜形成用フィルムを熱硬化させて保護膜を形成した。
　次いで、印字装置（ＫＥＹＥＮＣＥ社製「ＶＫ９７００」）を用いて、出力０．６Ｗ、周波数４０ｋＨｚ、走査速度１００ｍｍ／秒の条件で、基材側から保護膜に対して波長５３２ｎｍのレーザー光を照射して、下記の２つのパターン（パターン１、パターン２）で保護膜にレーザー印字を行った。
（パターン）
　パターン１：文字サイズ０．４ｍｍ×０．５ｍｍ、文字間隔０．３ｍｍ、文字数２０
　パターン２：文字サイズ０．２ｍｍ×０．５ｍｍ、文字間隔０．３ｍｍ、文字数２０ <Evaluation of composite sheet for forming protective film>
[Laser printability]
In the composite sheet for protective film formation of each Example and Comparative Example obtained above, the first release film was removed, and a stainless steel ring frame was applied using a sticking device (“RAD-2700F / 12” manufactured by Lintec). While sticking an adhesive layer, the protective film formation film was stuck on the back surface of the silicon wafer (outer diameter 8 inches, thickness 100 micrometers) heated at 70 degreeC.
Next, the protective film-forming film was heat-treated at 130 ° C. for 2 hours, whereby the protective film-forming film was thermally cured to form a protective film.
Next, using a printing device (“VK9700” manufactured by KEYENCE, Inc.), a laser beam having a wavelength of 532 nm was irradiated from the substrate side to the protective film under the conditions of an output of 0.6 W, a frequency of 40 kHz, and a scanning speed of 100 mm / second. Then, laser printing was performed on the protective film with the following two patterns (pattern 1 and pattern 2).
(pattern)
Pattern 1: Character size 0.4 mm x 0.5 mm, character spacing 0.3 mm, number of characters 20
Pattern 2: Character size 0.2 mm x 0.5 mm, character spacing 0.3 mm, number of characters 20
　次いで、上記のレーザー印字で保護膜に形成された文字について、基材側からの視認性（レーザー印字性）を下記基準に従って評価した。結果を表１に示す。
（評価基準）
　Ａ：パターン１及び２の全ての文字が鮮明であり、パターン１及び２の文字を問題なく読むことができた。
　Ｂ：パターン２では少なくとも一部の文字が不鮮明であるが、パターン１では全ての文字が鮮明であり、パターン１の文字を問題なく読むことができた。
　Ｃ：パターン１及び２のいずれにおいても、少なくとも一部の文字が不鮮明であった。 Next, the visibility (laser printability) from the base material side of the characters formed on the protective film by the laser printing was evaluated according to the following criteria. The results are shown in Table 1.
(Evaluation criteria)
A: All characters of patterns 1 and 2 were clear, and the characters of patterns 1 and 2 could be read without problems.
B: At least some characters were unclear in pattern 2, but all characters were clear in pattern 1, and the characters in pattern 1 could be read without problems.
C: In both patterns 1 and 2, at least some characters were unclear.
［耐ブロッキング性（１）］
　上記で得られた各実施例及び比較例の保護膜形成用複合シートを、３インチ径のＡＢＳ樹脂製コアに１０ｍの長さで巻き取り、この状態のまま室温で３日間静置した。
　次いで、実施例１～５の保護膜形成用複合シートについては、コーティング層、基材、粘着剤層、保護膜形成用フィルム及び第１剥離フィルムがこの順に積層されている積層単位１０個分を、比較例１～３の保護膜形成用複合シートについては、コーティング層が存在しないため、基材、粘着剤層、保護膜形成用フィルム及び第１剥離フィルムがこの順に積層されている積層単位１０個分を、それぞれ繰り出すことを試み、このとき、巻き取り時に互いに接触していた保護膜形成用複合シートの接触部同士の貼り付きの有無と、貼り付きがあった場合にはその程度について、下記基準に従って評価した。結果を表１に示す。
（評価基準）
　Ａ：前記接触部同士の貼り付きが全く認められなかった。
　Ｂ：前記接触部同士の軽度の貼り付きが認められたが、問題なく保護膜形成用複合シートを繰り出すことができた。
　Ｃ：前記接触部同士が一部で完全に貼り付いており、保護膜形成用複合シートを繰り出すときに、第１剥離フィルムが粘着剤層から剥離してしまった。 [Blocking resistance (1)]
The composite sheet for protective film formation of each Example and Comparative Example obtained above was wound around a 3-inch diameter ABS resin core with a length of 10 m, and left in this state at room temperature for 3 days.
Next, for the protective film-forming composite sheets of Examples 1 to 5, the coating layer, the base material, the pressure-sensitive adhesive layer, the protective film-forming film, and the first release film were laminated in this order for 10 lamination units. In the protective film-forming composite sheets of Comparative Examples 1 to 3, since there is no coating layer, the base unit, the pressure-sensitive adhesive layer, the protective film-forming film, and the first release film are laminated in this order. Attempts to feed out the individual pieces, at this time, the presence or absence of sticking between the contact parts of the protective film-forming composite sheet that were in contact with each other at the time of winding, and if there was sticking, about the extent, Evaluation was made according to the following criteria. The results are shown in Table 1.
(Evaluation criteria)
A: No sticking between the contact portions was observed.
B: Although slight sticking between the contact portions was recognized, the composite sheet for forming a protective film could be fed out without any problem.
C: The contact portions were partly adhered to each other, and the first release film was peeled off from the pressure-sensitive adhesive layer when the protective film-forming composite sheet was fed out.
［耐ブロッキング性（２）］
　上記で得られた各実施例及び比較例の保護膜形成用複合シートを、幅５０ｍｍ、長さ１００ｍｍの大きさのテープとなるように切り出した。なお、切り出しに際しては、このテープの長さ方向が粘着剤組成物の塗布方向と一致するようにした。
　このようにして得られたテープを１０枚用意し、これらテープを積層して試験片とした。このとき、実施例１～５の場合には、いずれもコーティング層が上向きとなるように前記テープを積層した。そして、比較例１～３の場合には、コーティング層が存在しないため、いずれも基材が上向きとなるように前記テープを積層した。次いで、この試験片を２枚のガラス板（幅７５ｍｍ、長さ１５ｍｍ、厚さ５ｍｍ）で挟み込み、これらガラス板と試験片との積層物全体を、一方のガラス板を最下層として所定の箇所に載置し、他方の最上層のガラス板上に錘を載せて、前記試験片を加圧した。このときの、前記テープの積層方向において、前記試験片に加えられた力は９８０．６６５ｍＮ（すなわち１００ｇｆ）であった。この状態でこれらガラス板と試験片との積層物全体を、湿熱促進器（ＥＳＰＥＣ社製）内で、４０℃で３日間保管し、前記試験片に対して加熱加圧促進試験を行った。 [Blocking resistance (2)]
The protective film-forming composite sheets obtained in the above examples and comparative examples were cut out to form a tape having a width of 50 mm and a length of 100 mm. When cutting out, the length direction of the tape was made to coincide with the application direction of the pressure-sensitive adhesive composition.
Ten tapes thus obtained were prepared, and these tapes were laminated to obtain test pieces. At this time, in each of Examples 1 to 5, the tape was laminated so that the coating layer faced upward. In Comparative Examples 1 to 3, since no coating layer was present, the tapes were laminated so that the base material faced upward. Next, the test piece is sandwiched between two glass plates (width 75 mm, length 15 mm, thickness 5 mm), and the entire laminate of the glass plate and the test piece is placed at a predetermined position with one glass plate as the lowermost layer. The test piece was pressurized by placing a weight on the other uppermost glass plate. At this time, the force applied to the test piece in the laminating direction of the tape was 980.665 mN (that is, 100 gf). In this state, the entire laminate of the glass plate and the test piece was stored at 40 ° C. for 3 days in a moist heat accelerator (manufactured by ESPEC), and a heating and pressing acceleration test was performed on the test piece.
　次いで、湿熱促進器から前記試験片を取り出し、最下層の第１剥離フィルム（最下層のガラス板と接触していた第１剥離フィルム）及びこれに隣接する保護膜形成用フィルムを取り除き、露出した粘着剤層を、両面粘着テープを介して支持板に貼り合わせることで、加熱加圧促進試験後の前記試験片から最下層の第１剥離フィルム及びこれに隣接する保護膜形成用フィルムのみ取り除かれたものを前記支持板に固定した。
　次いで、実施例１～５の場合には、上記の固定したもののうち、前記支持板から最も遠い最上層のコーティング層、基材、粘着剤層及び保護膜形成用フィルムからなる積層物を取り除き、露出した第１剥離フィルムを、引張試験機を用いて、剥離速度３００ｍｍ／分、剥離角度１８０°の条件で、隣接するコーティング層から剥離させたときの剥離力を測定した。比較例１～３の場合には、上記の固定したもののうち、前記支持板から最も遠い最上層の基材、粘着剤層及び保護膜形成用フィルムからなる積層物を取り除き、露出した第１剥離フィルムを、引張試験機を用いて、剥離速度３００ｍｍ／分、剥離角度１８０°の条件で、隣接する基材から剥離させたときの剥離力を測定した。このようにして得られた、第１剥離フィルムの剥離力の測定値を、保護膜形成用複合シートの耐ブロッキング性の指標とした。
　なお、測定しようとする第１剥離フィルムの剥離力が十分に小さい場合には、湿熱促進器から取り出した前記試験片から、上述の様に最下層の第１剥離フィルム（最下層のガラス板と接触していた第１剥離フィルム）に隣接する保護膜形成用フィルムを取り除こうとするときに、剥離力の測定対象である第１剥離フィルムが先に、その隣接する層（実施例１～５の場合にはコーティング層、比較例１～３の場合には基材）から剥離してしまうことがある。その場合には、湿熱促進器から取り出した前記試験片から、最下層の第１剥離フィルムを取り除いた後、これに隣接する保護膜形成用フィルムは取り除かずに、この保護膜形成用フィルムを、両面粘着テープを介して支持板に貼り合わせることで、前記試験片から最下層の第１剥離フィルムのみが取り除かれたものを前記支持板に固定して、この固定したものについて、上記と同様に第１剥離フィルムの剥離力を測定した。
　結果を表１に示す。 Next, the test piece was taken out from the moist heat accelerator, and the lowermost first release film (the first release film in contact with the lowermost glass plate) and the protective film forming film adjacent thereto were removed and exposed. By sticking the pressure-sensitive adhesive layer to the support plate via a double-sided pressure-sensitive adhesive tape, only the lowermost first release film and the protective film-forming film adjacent thereto are removed from the test piece after the heat and pressure acceleration test. Was fixed to the support plate.
Next, in the case of Examples 1 to 5, among the above fixed ones, the laminate composed of the uppermost coating layer, the base material, the pressure-sensitive adhesive layer and the protective film-forming film farthest from the support plate is removed, The peel force when the exposed first release film was peeled from the adjacent coating layer was measured using a tensile tester under the conditions of a peel speed of 300 mm / min and a peel angle of 180 °. In the case of Comparative Examples 1 to 3, among the above fixed ones, the uppermost base material farthest from the support plate, the adhesive layer, and the laminate composed of the protective film-forming film were removed, and the exposed first release The peeling force when the film was peeled off from an adjacent substrate under the conditions of a peeling speed of 300 mm / min and a peeling angle of 180 ° was measured using a tensile tester. The measured value of the peeling force of the first release film thus obtained was used as an index of blocking resistance of the protective film-forming composite sheet.
In addition, when the peeling force of the 1st peeling film to be measured is sufficiently small, from the said test piece taken out from the moist heat accelerator, the lowermost 1st peeling film (lowermost glass plate and When trying to remove the protective film-forming film adjacent to the first release film that was in contact with the first release film, the first release film to be measured for the peel force was first removed from the adjacent layer (of Examples 1 to 5). In some cases, the coating layer may peel off from the coating layer, and in the case of Comparative Examples 1 to 3, the base material may peel off. In that case, after removing the first release film of the lowermost layer from the test piece taken out from the wet heat accelerator, without removing the protective film forming film adjacent thereto, this protective film forming film, By sticking to a support plate via a double-sided adhesive tape, the one from which only the first release film of the lowermost layer is removed from the test piece is fixed to the support plate. The peel strength of the first release film was measured.
The results are shown in Table 1.
［基材側最表面の表面粗さＲａ］
　上記で得られた各実施例及び比較例の保護膜形成用複合シートについて、基材側最表面、すなわち、コーティング層の基材側とは反対側の面の表面粗さＲａを、接触式表面粗さ計（ミツトヨ社製「ＳＵＲＦＴＥＳＴ　ＳＶ－３０００」）を用いて、カットオフ値λｃを０．８ｍｍ、評価長さＬｎを４ｍｍとし、ＪＩＳ　Ｂ０６０１：２００１に従って測定した。結果を表１に示す。表１において、比較例１～３の保護膜形成用複合シートについては、基材側最表面の表面粗さＲａとして、上述の基材の粘着剤層側とは反対側の面の表面粗さＲａを記載した。 [Surface roughness Ra on the outermost surface of the substrate]
About the composite film for protective film formation of each Example and Comparative Example obtained above, the surface roughness Ra of the surface on the substrate side, that is, the surface opposite to the substrate side of the coating layer, is a contact-type surface. Using a roughness meter (“SURFTEST SV-3000” manufactured by Mitutoyo Corporation), the cut-off value λc was 0.8 mm, the evaluation length Ln was 4 mm, and the measurement was performed according to JIS B0601: 2001. The results are shown in Table 1. In Table 1, for the protective film-forming composite sheets of Comparative Examples 1 to 3, as the surface roughness Ra of the substrate-side outermost surface, the surface roughness of the surface opposite to the pressure-sensitive adhesive layer side of the substrate described above Ra is described.
［コーティング層の表面のグロス値］
　上記で得られた各実施例及び比較例の保護膜形成用複合シートについて、光沢計（日本電色社製グロスメーター「ＶＧ　２０００」）を用いて、ＪＩＳ　Ｋ　７１０５に従って、コーティング層の基材側とは反対側から、コーティング層の表面の２０°鏡面光沢度を測定し、その測定値をコーティング層の表面のグロス値とした。結果を表１に示す。 [Gloss value of coating layer surface]
About the composite sheet for protective film formation of each Example and comparative example obtained above, according to JIS K 7105, using the gloss meter (Nippon Denshoku Co., Ltd. gloss meter "VG2000"), the base material side of a coating layer From the opposite side, the 20 ° specular glossiness of the surface of the coating layer was measured, and the measured value was taken as the gloss value of the surface of the coating layer. The results are shown in Table 1.
［コーティング層側からのヘイズの測定値］
　上記で得られた各実施例及び比較例の保護膜形成用複合シートについて、ヘイズメーター（日本電色工業社製「ＮＤＨ－２０００」）を用いて、ＪＩＳ　Ｋ　７１３６に従って、コーティング層側からヘイズを測定した。結果を表１に示す。 [Measured value of haze from the coating layer side]
Using the haze meter (“NDH-2000” manufactured by Nippon Denshoku Industries Co., Ltd.), the haze was applied from the coating layer side to the composite sheet for protective film formation of each Example and Comparative Example obtained above according to JIS K 7136. It was measured. The results are shown in Table 1.
Figure JPOXMLDOC01-appb-T000003
 　　　　　　　　　　　　　　　　　　
 
Figure JPOXMLDOC01-appb-T000003
 　　　　　　　　　　　　　　　　　　
 
　実施例１～６の保護膜形成用複合シートは、基材側の最外層にコーティング層を備えており、このコーティング層側からのヘイズの測定値が小さいことで、レーザー印字性及び耐ブロッキング性がいずれも良好であった。
　特に、実施例１、２、４及び５の保護膜形成用複合シートは、実施例３及び６の保護膜形成用複合シートよりもレーザー印字性に優れており、これは、実施例１、２、４及び５の保護膜形成用複合シートでは、前記ヘイズがさらに小さく、より適した範囲内となっているためであると推測される。
　また、実施例１～４の保護膜形成用複合シートは、実施例５及び６の保護膜形成用複合シートよりも耐ブロッキング性に優れており、これは、実施例１～４の保護膜形成用複合シートの方が、コーティング層の厚さが薄いためであると推測される。
　なお、実施例１～６の保護膜形成用複合シートは、いずれも基材と粘着剤層との間に空隙部が認められなかった。 The composite sheet for forming a protective film of Examples 1 to 6 has a coating layer on the outermost layer on the substrate side, and the measured value of haze from the coating layer side is small, so that laser printability and blocking resistance are achieved. Both were good.
In particular, the protective film-forming composite sheets of Examples 1, 2, 4, and 5 were superior in laser printability to the protective film-forming composite sheets of Examples 3 and 6, In the composite sheets for forming a protective film of 4 and 5, it is surmised that the haze is further smaller and within a more suitable range.
The protective film-forming composite sheets of Examples 1 to 4 are superior in blocking resistance to the protective film-forming composite sheets of Examples 5 and 6, and this is because the protective film-forming composite sheets of Examples 1 to 4 are formed. It is estimated that the composite sheet for use is because the thickness of the coating layer is thinner.
In each of the protective film-forming composite sheets of Examples 1 to 6, no void was observed between the substrate and the pressure-sensitive adhesive layer.
　これに対して、比較例１の保護膜形成用複合シートは、図４に示すものと同様に、基材の粘着剤層を備えている側の面（表面）とは反対側の面（裏面）が凹凸面であり、かつコーティング層も備えていないことにより、耐ブロッキング性には優れていたものの、レーザー印字性に劣っていた。 On the other hand, the protective film-forming composite sheet of Comparative Example 1 has a surface (back surface) opposite to the surface (front surface) on the side having the adhesive layer of the base material, as shown in FIG. ) Is an uneven surface and does not have a coating layer, it was excellent in blocking resistance but inferior in laser printability.
　比較例２の保護膜形成用複合シートは、図５に示すものと同様に、基材の粘着剤層を備えている側の面（表面）とは反対側の面（裏面）が平滑面であり、かつコーティング層も備えていないことにより、レーザー印字性は良好であったものの、耐ブロッキング性に劣っていた。比較例３の保護膜形成用複合シートも、比較例２の保護膜形成用複合シートと同様の構成を有しているものの、耐ブロッキング性だけでなく、レーザー印字性にも劣っていた。これは、基材の粘着剤層を備えている側の面（表面）が凹凸面であり、かつその表面粗さＲａが比較例２の保護膜形成用複合シートよりも大きいためであると推測される。比較例３では、前記凹凸面の表面粗さＲａが大きいために、凹凸面の形状が保護膜の表面にも反映されてしまい、保護膜の表面における凹凸の度合いが比較例２の場合よりも大きくなってしまったことで、光の乱反射がより大きく、レーザー印字性がより劣っていたと推測される。さらに、比較例２及び３の保護膜形成用複合シートは、いずれも基材の凹凸面と粘着剤層との間に空隙部があったが、比較例３の方が比較例２よりも凹凸面の表面粗さＲａが大きいために空隙部が大きくなっており、そのため、比較例３の方が比較例２よりも光の乱反射がより大きく、レーザー印字性がより劣っていたと推測される。 In the composite sheet for forming a protective film of Comparative Example 2, the surface (back surface) opposite to the surface (front surface) provided with the pressure-sensitive adhesive layer of the base material is a smooth surface, as shown in FIG. Although the laser printability was good because it was present and the coating layer was not provided, the blocking resistance was poor. The protective sheet-forming composite sheet of Comparative Example 3 also had the same configuration as the protective film-forming composite sheet of Comparative Example 2, but was inferior not only in blocking resistance but also in laser printability. This is presumed to be because the surface (surface) on the side having the pressure-sensitive adhesive layer of the base material is an uneven surface and the surface roughness Ra is larger than that of the protective sheet-forming composite sheet of Comparative Example 2. Is done. In Comparative Example 3, since the surface roughness Ra of the uneven surface is large, the shape of the uneven surface is reflected also on the surface of the protective film, and the degree of unevenness on the surface of the protective film is higher than in the case of Comparative Example 2. It is presumed that the larger the light, the greater the irregular reflection of light and the lower the laser printability. Furthermore, the protective sheet-forming composite sheets of Comparative Examples 2 and 3 both had voids between the uneven surface of the substrate and the pressure-sensitive adhesive layer, but Comparative Example 3 was more uneven than Comparative Example 2. Since the surface roughness Ra of the surface is large, the gap portion is large. Therefore, it is presumed that the comparative example 3 has a larger light irregular reflection than the comparative example 2 and the laser printability is inferior.
　比較例４の保護膜形成用複合シートは、実施例１の保護膜形成用複合シートと同様に、基材の粘着剤層を備えている側の面（表面）とは反対側の面（裏面）が凹凸面であり、かつコーティング層も備えており、耐ブロッキング性には優れていたものの、レーザー印字性に劣っていた。これは、比較例４の保護膜形成用複合シートでは、コーティング層側からのヘイズの測定値が大きいためであると推測される。 The protective film-forming composite sheet of Comparative Example 4 is the same surface as the protective film-forming composite sheet of Example 1 (surface) opposite to the surface (front surface) provided with the pressure-sensitive adhesive layer. ) Is an uneven surface and has a coating layer, which is excellent in blocking resistance but inferior in laser printability. This is presumed to be because, in the protective film-forming composite sheet of Comparative Example 4, the measured value of haze from the coating layer side is large.
　本発明は、裏面が保護膜で保護された半導体チップ等の製造に利用可能である。 The present invention can be used for manufacturing a semiconductor chip or the like whose back surface is protected by a protective film.
　１，２・・・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、１０ｂ・・・支持シートの裏面、１１・・・基材、１１ａ・・・基材の表面、１１ｂ・・・基材の裏面、１２・・・粘着剤層、１２ａ・・・粘着剤層の表面、１３，２３・・・保護膜形成用フィルム、１３ａ，２３ａ・・・保護膜形成用フィルムの表面、１４・・・コーティング層、１４ａ・・・コーティング層の表面、１４ｂ・・・コーティング層の裏面、１５・・・剥離フィルム、１５ａ・・・剥離フィルムの表面、１６・・・治具用接着剤層、１６ａ・・・治具用接着剤層の表面 DESCRIPTION OF SYMBOLS 1,2 ... Composite sheet for protective film formation, 10 ... Support sheet, 10a ... The surface of a support sheet, 10b ... The back surface of a support sheet, 11 ... Base material, 11a ... Base Material surface, 11b ... Back surface of substrate, 12 ... Adhesive layer, 12a ... Surface of adhesive layer, 13, 23 ... Protective film forming film, 13a, 23a ... Protection Surface of film forming film, 14 ... coating layer, 14a ... surface of coating layer, 14b ... back surface of coating layer, 15 ... release film, 15a ... surface of release film, 16. ..Jig adhesive layer, 16a ... Surface of jig adhesive layer

Claims (5)

  1. 　支持シートの一方の表面上に保護膜形成用フィルムを備え、前記支持シートの前記保護膜形成用フィルムを備えている側とは反対側の表面上にコーティング層を備えてなる保護膜形成用複合シートであって、
    　前記保護膜形成用複合シートの前記コーティング層側からのヘイズの測定値が４７％以下である、保護膜形成用複合シート。     A protective film-forming composite comprising a protective film-forming film on one surface of the support sheet, and a coating layer on the surface of the support sheet opposite to the side having the protective film-forming film A sheet,
    The composite sheet for protective film formation whose haze measured value from the said coating layer side of the said composite sheet for protective film formation is 47% or less.
  2. 　さらに前記保護膜形成用フィルム上に剥離フィルムを備えた前記保護膜形成用複合シートを用いて、下記方法で測定した前記剥離フィルムの剥離力が１０ｍＮ／５０ｍｍ以下である、請求項１に記載の保護膜形成用複合シート。
    （剥離フィルムの剥離力の測定方法）
    　保護膜形成用フィルム上に剥離フィルムを備えた、幅５０ｍｍ、長さ１００ｍｍの前記保護膜形成用複合シートを、前記コーティング層がすべて同じ方向を向くように、かつ前記コーティング層の合計の厚さが１０～６０μｍとなるように複数枚重ねることで、第一の最外層がコーティング層で、第二の最外層が剥離フィルムである積層体とし、前記積層体を、前記保護膜形成用複合シートの積層方向において９８０．６６５ｍＮの力を加えたまま４０℃で３日間静置した後、前記積層方向において前記第一の最外層のコーティング層に最も近い剥離フィルムを剥離速度３００ｍｍ／分、剥離角度１８０°の条件で、隣接するコーティング層から剥離させたときの剥離力を測定する。     Furthermore, the peeling force of the said peeling film measured by the following method using the said composite film for protective film formation provided with the peeling film on the said film for protective film formation is 10 mN / 50mm or less, The Claim 1 Composite sheet for protective film formation.
    (Measurement method of peel strength of release film)
    The composite sheet for forming a protective film having a width of 50 mm and a length of 100 mm provided with a release film on the protective film-forming film, so that the coating layers are all directed in the same direction, and the total thickness of the coating layers Are laminated so that the first outermost layer is a coating layer and the second outermost layer is a release film, and the laminate is used as the protective sheet-forming composite sheet. The film was allowed to stand at 40 ° C. for 3 days while applying a force of 980.665 mN in the laminating direction, and the peeling film closest to the first outermost coating layer in the laminating direction was peeled off at a rate of 300 mm / min, peeling angle. The peeling force when peeled from the adjacent coating layer under the condition of 180 ° is measured.
  3. 　前記支持シートが、基材及び粘着剤層が積層されてなり、
    　前記保護膜形成用複合シートが、前記コーティング層、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、請求項１又は２に記載の保護膜形成用複合シート。     The support sheet is formed by laminating a base material and an adhesive layer,
    The composite sheet for protective film formation according to claim 1 or 2, wherein the composite sheet for protective film formation is formed by laminating the coating layer, the substrate, the pressure-sensitive adhesive layer, and the film for protective film formation in this order.
  4. 　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のものである、請求項３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 claim 3, wherein the pressure-sensitive adhesive layer is energy ray curable or non-energy ray curable.
  5. 　前記保護膜形成用フィルムが、熱硬化性又はエネルギー線硬化性のものである、請求項１～４のいずれか一項に記載の保護膜形成用複合シート。 The protective film-forming composite sheet according to any one of claims 1 to 4, wherein the protective film-forming film is thermosetting or energy ray-curable.
PCT/JP2016/075831 2016-03-04 2016-09-02 Protective film-forming composite sheet WO2017149808A1 (en)

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KR1020187025059A KR102516392B1 (en) 2016-03-04 2016-09-02 Composite sheet for forming protective film
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