TW201812879A - Film for forming a protective film and composite sheet for forming a protective film - Google Patents

Abstract

The present invention relates to a film for forming a protective film, which is an energy ray-curable film for forming a protective film, and at least one surface (α) of the film for forming a protective film has a surface roughness (Ra) of 0.038 μm or more. The surface roughness (Ra) of the surface (α) is preferably 2.0 μm or less.

Description

 Film for forming a protective film and composite sheet for forming a protective film  

The present invention relates to a film for forming a protective film and a composite sheet for forming a protective film.

The priority of Japanese Patent Application No. 2016-092097, filed on Jan. 28,,,,,,,,,,

In recent years, the industry has manufactured semiconductor devices using a mounting method called a so-called face down method. In the flip chip method, a semiconductor wafer having electrodes such as bumps on a circuit surface is used, and the electrodes are bonded to the substrate. Therefore, the back surface of the semiconductor wafer opposite to the circuit surface may be exposed.

A resin film containing an organic material is formed as a protective film on the back surface of the bare semiconductor wafer, and the semiconductor wafer as a protective film is incorporated into the semiconductor device. The protective film is used to prevent cracking of the semiconductor wafer after the cutting step or packaging.

As a material for forming such a protective film or an adhesive film, various sheets for forming a resin film have been proposed.

For example, Patent Document 1 discloses a film for protecting a wafer having a polymer component composed of an acrylic copolymer, an energy ray-curing component, a dye or a pigment, an inorganic filler, and a photopolymerization initiator. The energy ray-curable film forming component is sandwiched between two release sheets. According to the patent document 1, the wafer protective film can form a protective film for improving laser mark recognition property, hardness, and adhesion to a wafer by irradiating an energy ray, and is superior to the conventional wafer protective film. The steps can be simplified.

Further, Patent Document 2 discloses a dicing tape-integrated wafer back surface protective film comprising: a dicing tape having a substrate and an adhesive; and a wafer back surface protective film which is colored on the adhesive layer of the dicing tape and Has a predetermined modulus of elasticity.

According to Patent Document 2, in the dicing step of the semiconductor wafer, the wafer back surface protective film can exhibit excellent holding power with the semiconductor wafer.

[Previous Technical Literature]

[Patent Literature]

Patent Document 1: Japanese Laid-Open Patent Publication No. 2009-138026.

Patent Document 2: Japanese Laid-Open Patent Publication No. 2010-199543.

However, in the step of attaching the protective film disclosed in Patent Documents 1 and 2 to the wafer, the offset position of the protective film is generated, or the foreign matter on the wafer is not noticed, and the foreign matter is directly contained. In the case where the protective film is attached, it is difficult to peel off the protective film and rework the wafer.

The protective film disclosed in Patent Document 1 and Patent Document 2 is intended to improve the adhesion to the wafer at the time of attachment or the adhesion to the wafer after attachment, and therefore, if temporarily adhered to the wafer, the crystal is bonded to the wafer. The roundness is high, so there is a problem with secondary workability. If the protective film temporarily attached to the wafer is forcibly peeled off, the wafer may be damaged by the peeling force, or a part of the protective film may remain on the wafer. Therefore, it is difficult to reuse the wafer temporarily attached to the protective film.

In other words, in Patent Document 1 and Patent Document 2, the protective film described above is studied from the viewpoint of adhesion to the wafer at the time of attachment or the holding force to the wafer at the time of attachment, but the protective film is not provided. Secondary processing was studied.

The present invention has been made in view of the above problems, and an object thereof is to provide a film for forming a protective film and a composite sheet for forming a protective film which are excellent in secondary workability.

In order to solve the problem, the present invention provides a film for forming a protective film, which is an energy ray-curable film for forming a protective film, and a surface roughness (Ra) of at least one surface (α) of the film for forming a protective film is 0.038 μm. the above.

In the film for forming a protective film of the present invention, the surface roughness (Ra) of the surface (α) is preferably 2.0 μm or less.

Moreover, the present invention provides a composite sheet for forming a protective film, comprising the film for forming a protective film on the support sheet, a surface (β) opposite to the surface (α) of the film for forming a protective film, and the support sheet. Relative.

According to the present invention, there is provided an energy ray-curable protective film forming film and a protective film forming composite sheet comprising the protective film forming film, wherein the energy ray-curable protective film forming film can be used in a semiconductor wafer or A protective film is formed on the back surface of the semiconductor wafer, and has good secondary workability.

In the present specification, the term "secondary workability" refers to a property in which, after being attached to a semiconductor wafer and peeled off again, the semiconductor wafer can be peeled off without being damaged.

1A, 1B, 1C, 1D, 1E‧‧‧ Composite film for protective film formation

1F‧‧‧Protective film forming sheet

10‧‧‧Support tablets

10a‧‧‧Surface of the support sheet

11‧‧‧Substrate

11a‧‧‧ Surface of the substrate

12‧‧‧Adhesive layer

12a‧‧‧ Surface of the adhesive layer

13, 23‧‧‧film for protective film formation

13a, 23a‧‧‧ Surface of film for protective film formation

15‧‧‧Release film

15a‧‧‧2nd release film

15b‧‧‧1st release film

16‧‧‧Layer layer for fixtures

16a‧‧‧ Surface of the adhesive layer for the fixture

Fig. 1 is a cross-sectional view showing an embodiment of a composite sheet for forming a protective film of the present invention.

Fig. 2 is a cross-sectional view showing another embodiment of the composite sheet for forming a protective film of the present invention.

Fig. 3 is a cross-sectional view showing still another embodiment of the composite sheet for forming a protective film of the present invention.

Fig. 4 is a cross-sectional view showing still another embodiment of the composite sheet for forming a protective film of the present invention.

Fig. 5 is a cross-sectional view showing still another embodiment of the composite sheet for forming a protective film of the present invention.

Fig. 6 is a cross-sectional view showing still another embodiment of the film for forming a protective film of the present invention.

◇Protective film forming film

The film for forming a protective film of the present invention is energy ray-curable, and the surface roughness (Ra) of at least one surface (α) of the film for forming a protective film is 0.038 μm or more.

The film for forming a protective film of the present invention may have a first release film on at least one surface or a second release film on the other surface. The film for forming a protective film of the present invention can be provided in the form of a roll film which is wound into a roll. Fig. 6 is a cross-sectional view showing an embodiment of a film for forming a protective film of the present invention in a schematic manner. In FIG. 6, the first release film 15b, the protective film formation film 13 (23), and the second release film 15a are laminated in this order.

In the film for forming a protective film, the surface to be attached to the back surface of the semiconductor wafer (that is, the surface on the opposite side to the circuit surface) may be referred to as "surface (α)", and attached and attached. The surface on the opposite side of the surface of the back surface of the semiconductor wafer is referred to as "surface (β)".

The surface roughness (Ra) of at least one surface (α) of the film for forming a protective film of the present invention is preferably 0.038 μm or more, and preferably 2.0 μm or less.

In the present specification, the term "surface roughness (Ra)" means a so-called arithmetic mean roughness determined in accordance with JIS B0601:2001 unless otherwise specified.

An aspect of the present invention relates to a film for forming a protective film which has energy ray-hardening property for forming a protective film on a back surface of a semiconductor wafer or a semiconductor wafer, and the film for forming a protective film is attached to the semiconductor crystal. The surface roughness (Ra) of the surface (α) on the side of the circular or semiconductor wafer is 0.038 μm or more.

The surface roughness (Ra) of the surface (α) attached to the side of the semiconductor wafer or the semiconductor wafer is preferably 2.0 μm or less.

According to another aspect of the invention, there is provided a film for forming a protective film, comprising: a first release film and a film for forming a protective film; wherein the film for forming a protective film is in direct contact with the first release film, and has energy ray curability; The surface roughness (Ra) of the surface (α) on the side directly in contact with the first release film is 0.038 μm or more. The surface roughness (Ra) of the surface (α) attached to the side of the first release film is preferably 2.0 μm or less.

In the present specification, the surface roughness (Ra) of the surface (α) of the film for forming a protective film can be measured by the measurement method described in the examples.

复合Protective film forming composite sheet

The composite sheet for forming a protective film of the present invention comprises an energy ray-curable protective film forming film on the support sheet, and a surface (β) opposite to the surface (α) in the protective film forming film and the support described above. The pieces are opposite.

The surface roughness (Ra) of the surface (α) of the film for forming a protective film in the composite sheet for forming a protective film of the present invention is preferably 0.038 μm or more, and preferably 2.0 μm or less.

In the present specification, the "film for forming a protective film" means a film for forming a protective film before curing, and the term "protective film" means a film obtained by curing a film for forming a protective film. In addition, the surface roughness (Ra) of the surface (α) of the film for forming a protective film in the composite sheet for forming a protective film can be measured by the measurement method described in the examples.

The film for forming a protective film is cured by irradiation with an energy ray to form a protective film. The protective film protects the back surface of the semiconductor wafer or the semiconductor wafer (the surface opposite to the electrode forming surface). The film for forming a protective film is soft and can be easily attached to an attached object. In addition, the surface roughness (Ra) of at least one surface (α) in the film for forming a protective film is 0.038 μm or more, and the composite sheet for forming a protective film of the present invention has excellent secondary workability.

For example, when a composite sheet for forming a protective film is attached to a position on the back surface of the semiconductor wafer from the target position, the protective film forming composite sheet is peeled off from the semiconductor wafer, and the semiconductor wafer is not damaged. Further, a new composite film for forming a protective film (secondary processing) is reattached, whereby a product can be manufactured using the semiconductor wafer.

Further, in the composite sheet for forming a protective film of the present invention, the film for forming a protective film is energy ray-curable, and the composite sheet for forming a protective film before the film for forming a film having a thermosetting protective film is used. In other cases, the protective film can be formed by hardening in a short time.

In the present invention, the "energy line" means an electromagnetic wave or a charged particle beam having an energy quantum, and examples of the energy line include ultraviolet rays, electron beams, and the like.

The ultraviolet light can be irradiated as an ultraviolet source by using, for example, a high pressure mercury lamp, a Fusion H-type lamp, a xenon lamp, a black light, or an LED (Light Emitting Diode) lamp. The electron beam can illuminate an electron beam generated by an electron beam accelerator or the like.

In the present invention, the term "energy ray hardenability" means a property of being hardened by irradiation with an energy ray, and "non-energy ray curability" means a property that does not harden even when irradiated with an energy ray.

The thickness of the semiconductor wafer or the semiconductor wafer to be used as the composite sheet for forming a protective film of the present invention is not particularly limited, and from the viewpoint of obtaining a more remarkable effect of the present invention, it is preferably 30 μm to 1000 μm, more preferably 100 μm. Up to 300 μm.

Hereinafter, the configuration of the present invention will be described in detail.

◎Support film

The support sheet may be composed of one layer (single layer) or may be composed of a plurality of layers of two or more layers. In the case where the support sheet is composed of a plurality of layers, the constituent materials and thicknesses of the plurality of layers may be the same or different from each other, and the combination of the plurality of layers is not particularly limited as long as the effects of the present invention are not impaired.

Furthermore, in the present specification, the present invention is not limited to the case of the support sheet. The phrase "the plurality of layers may be the same or different from each other" means that "all layers may be the same, or all layers may be different, and only a part of the layers may be the same". The phrase "the plural layers are different from each other" means that "at least one of the constituent materials and the thickness of each layer is different from each other".

Preferred examples of the support sheet include a support sheet in which an adhesive layer is laminated on a substrate in a direct contact manner, and a support sheet formed by laminating an adhesive layer on the substrate. Support sheets for materials.

Hereinafter, an example of the composite sheet for forming a protective film of the present invention will be described with reference to the drawings in accordance with each of the above-mentioned support sheets. In addition, in the drawings used in the following description, in order to facilitate the understanding of the features of the present invention, it is convenient to show a part that is a main part, and the size ratio of each component is not limited to the actual one. .

Fig. 1 is a cross-sectional view showing an embodiment of a composite sheet for forming a protective film of the present invention. The composite sheet 1A for forming a protective film shown here has an adhesive layer 12 on a substrate 11, and a film 13 for forming a protective film on the adhesive layer 12. The support sheet 10 is a laminate of the substrate 11 and the adhesive layer 12, in other words, the composite sheet 1A for forming a protective film has a structure in which a film 13 for forming a protective film is laminated on one surface 10a of the support sheet 10. In addition, the protective film forming composite sheet 1A and the protective film forming film 13 are provided with a release film 15.

In the composite sheet 1A for forming a protective film, the adhesive layer 12 is laminated on one surface 11a of the substrate 11, and the protective film forming film 13 is formed on the entire surface of the surface 12a of the adhesive layer 12 to form a film for forming a protective film. A part of the surface 13a of the surface 13a, that is, a region in the vicinity of the peripheral portion, is laminated with the adhesive layer 16 for the jig, and the surface of the protective film forming film 13 is not laminated with the surface of the adhesive layer 16 for the jig and the jig. A peeling film 15 is laminated on the surface 16a (upper surface and side surface) of the subsequent agent layer 16.

In the composite sheet 1A for forming a protective film, the adhesion between the cured protective film forming film 13 (i.e., the protective film) and the support sheet 10, in other words, the adhesive force between the protective film and the adhesive layer 12 is preferably 50mN/25mm to 1500mN/25mm.

The adhesive-use adhesive layer 16 may be, for example, a single-layer structure containing an adhesive component, or may have a multi-layer structure in which a double-layered layer of a core material has a layer containing an adhesive component.

The composite sheet 1A for forming a protective film shown in Fig. 1 is used by attaching a semiconductor wafer to the surface 13a of the film 13 for forming a protective film in a state where the release film 15 is removed (illustration omitted) Further, the upper surface of the surface 16a of the adhesive adhesive layer 16 is attached to a jig such as a ring frame.

Fig. 2 is a cross-sectional view showing another embodiment of the composite sheet for forming a protective film of the present invention. In the drawings, the same components as those in the above-described drawings are denoted by the same reference numerals, and the detailed description of the symbols will be omitted.

The composite sheet 1B for forming a protective film shown here is the same as the composite sheet 1A for protective film formation shown in FIG. 1 except that the adhesive layer 16 for a jig is not provided. In the composite sheet 1B for forming a protective film, the adhesive layer 12 is laminated on one surface 11a of the substrate 11, and the protective film forming film 13 is formed on the entire surface of the surface 12a of the adhesive layer 12 in the protective film. The entire surface layer of the surface 13a of the film 13 for formation has a release film 15.

The composite sheet 1B for forming a protective film shown in Fig. 2 is used in such a manner that a part of the central portion of the surface 13a of the film 13 for forming a protective film is attached in a state where the release film 15 is removed. In the back surface of the semiconductor wafer (not shown), a region in the vicinity of the peripheral portion of the film for forming a protective film 13 is attached to a jig such as a ring frame.

Fig. 3 is a cross-sectional view showing still another embodiment of the composite sheet for forming a protective film of the present invention.

The composite sheet 1C for forming a protective film shown here is the same as the composite sheet 1A for protective film formation shown in Fig. 1 except that the adhesive layer 12 is not provided. In other words, in the composite sheet 1C for forming a protective film, the support sheet 10 is composed only of the substrate 11. In addition, a film 13 for forming a protective film is laminated on one surface 11a of the substrate 11 (one surface 10a of the support sheet 10), and a part of the surface 13a of the film 13 for forming a protective film, that is, a region in the vicinity of the peripheral portion is laminated. In the adhesive layer 16 for the jig, the surface of the protective film forming film 13 is laminated with the surface of the adhesive layer 16 for the jig and the surface 16a (upper surface and side surface) of the adhesive layer 16 for the jig. 15.

In the composite sheet 1C for forming a protective film, the adhesion between the film 13 for protective film formation (that is, the protective film) and the support sheet 10 after curing, in other words, the adhesion between the protective film and the substrate 11 is preferably 50 mN. /25mm to 1500mN/25mm.

The composite sheet 1C for forming a protective film shown in Fig. 3 is used in the same manner as in the case of the composite sheet 1A for protective film formation shown in Fig. 1, in the state where the release film 15 is removed, in the protective film. The back surface of the semiconductor wafer (not shown) is attached to the surface 13a of the film 13 for forming, and the upper surface of the surface 16a of the adhesive agent layer 16 is attached to a jig such as a ring frame.

Fig. 4 is a cross-sectional view showing still another embodiment of the composite sheet for forming a protective film of the present invention.

The composite sheet 1D for forming a protective film shown here is the same as the composite sheet 1C for forming a protective film shown in FIG. 3 except that the adhesive layer 16 for a jig is not provided. In the composite sheet 1D for forming a protective film, the protective film forming film 13 is laminated on one surface 11a of the substrate 11, and the peeling film 15 is formed over the entire surface 13a of the protective film forming film 13.

The composite sheet 1D for forming a protective film shown in Fig. 4 is used in the same manner as in the case of the composite sheet 1B for protective film formation shown in Fig. 2, in the state where the release film 15 is removed, in the protective film. The back surface of the semiconductor wafer (not shown) is attached to a part of the surface 13a of the surface 13a of the film 13 to be formed, and the region near the peripheral edge portion of the film 13 for forming a protective film is attached to a ring frame or the like. With.

Fig. 5 is a cross-sectional view showing still another embodiment of the composite sheet for forming a protective film of the present invention.

The composite sheet 1E for forming a protective film shown here is the same as the composite sheet 1B for protective film formation shown in FIG. 2 except that the shape of the film for forming a protective film is different. In other words, the composite sheet 1E for forming a protective film has the adhesive layer 12 on the substrate 11, and the film 23 for forming a protective film on the adhesive layer 12. The support sheet 10 is a laminate of the substrate 11 and the adhesive layer 12, in other words, the composite sheet 1E for forming a protective film has a structure in which a film 23 for forming a protective film is laminated on one surface 10a of the support sheet 10. In addition, the protective film forming composite sheet 1E and the protective film forming film 23 are provided with a release film 15 .

In the composite sheet 1E for forming a protective film, the adhesive layer 12 is laminated on one surface 11a of the substrate 11, and a film 23 for forming a protective film is laminated on a part of the surface 12a of the adhesive layer 12, that is, a region on the center side. Further, a release film 15 is laminated on the surface 23a (upper surface and side surface) of the surface 12a of the adhesive layer 12 on which the protective film forming film 23 is not laminated and the protective film forming film 23.

When the protective film forming composite sheet 1E is viewed from above, the surface area of the protective film forming film 23 is smaller than the adhesive layer 12, and has a circular shape or the like, for example.

In the composite sheet 1E for forming a protective film, the adhesion between the cured protective film forming film 23 (that is, the protective film) and the support sheet 10, in other words, the adhesive force between the protective film and the adhesive layer 12 is preferably 50mN/25mm to 1500mN/25mm.

The composite film 1E for protective film formation shown in FIG. 5 is used by attaching a semiconductor wafer to the surface 23a of the film 23 for protective film formation in the state in which the peeling film 15 is removed (illustration omitted Further, the surface of the surface 12a of the adhesive layer 12 on which the protective film forming film 23 is not laminated is attached to a jig such as a ring frame.

Further, in the composite sheet 1E for forming a protective film shown in FIG. 5, the surface of the protective film forming film 23 may not be laminated on the surface 12a of the adhesive layer 12, as shown in FIGS. 1 and 3, An adhesive layer for the build-up fixture (not shown). In the same manner as the composite sheet for forming a protective film shown in Figs. 1 and 3, the composite sheet for protective film formation 1E having the adhesive layer for the above-mentioned jig is attached to the surface of the adhesive layer for the jig. Frame and other fixtures.

In the composite sheet for forming a protective film of the present invention, the adhesive sheet for a jig can be provided regardless of the form of the support sheet and the film for forming a protective film. In addition, as shown in FIG. 1 and FIG. 3, the composite sheet for forming a protective film of the present invention having the adhesive layer for a jig is preferably provided with a pressure-sensitive adhesive layer for a protective film. A composite sheet for forming a protective film.

The composite sheet for forming a protective film of the present invention is not limited to the composite sheet for forming a protective film shown in Figs. 1 to 5, and may be modified or deleted as shown in Figs. 1 to 5 without departing from the effects of the present invention. The composite sheet for forming a protective film is partially formed, or a composite sheet for forming a protective film as described above is added to another structure.

For example, in the composite sheet for forming a protective film shown in FIG. 3 and FIG. 4, an intermediate layer may be provided between the substrate 11 and the film 13 for forming a protective film. As the intermediate layer, any intermediate layer can be selected depending on the purpose.

Further, in the composite sheet for forming a protective film shown in FIG. 1, FIG. 2 and FIG. 5, an intermediate layer may be provided between the substrate 11 and the adhesive layer 12. In other words, in the composite sheet for forming a protective film of the present invention, the support sheet may be formed by sequentially laminating a substrate, an intermediate layer, and an adhesive layer. Here, the intermediate layer is the same as the intermediate layer which can be provided in the composite sheet for forming a protective film shown in FIGS. 3 and 4 .

Further, in the composite sheet for forming a protective film shown in Fig. 1 to Fig. 5, a layer other than the intermediate layer may be provided at an arbitrary position.

Further, in the composite sheet for forming a protective film of the present invention, a part of the gap may be formed between the release film and the layer directly in contact with the release film.

Further, in the composite sheet for forming a protective film of the present invention, the size or shape of each layer can be arbitrarily adjusted according to the purpose.

In the composite sheet for forming a protective film of the present invention, as described later, the layer directly contacting the film for forming a protective film in the support sheet such as the adhesive layer is preferably non-energy line curable. Such a composite sheet for forming a protective film can more easily pick up a semiconductor wafer having a protective film on its back surface.

The support sheet can be transparent or opaque, and can be colored according to the purpose.

In the invention in which the film for forming a protective film has energy ray curability, the support sheet is preferably a support sheet through which energy rays are transmitted.

For example, in the support sheet, the transmittance of light having a wavelength of 375 nm is preferably 30% or more, more preferably 50% or more, and particularly preferably 70% or more. When the transmittance of the light is in such a range and the energy ray (ultraviolet rays) is applied to the film for forming a protective film via the support sheet, the degree of hardening of the film for forming a protective film is further improved.

On the other hand, in the support sheet, the upper limit of the transmittance of light having a wavelength of 375 nm is not particularly limited, and may be, for example, 95%.

Further, in the support sheet, the transmittance of light having a wavelength of 532 nm is preferably 30% or more, more preferably 50% or more, and still more preferably 70% or more. When the transmittance of the light is in such a range, the protective film forming film or the protective film is irradiated with the laser light through the support sheet, and when printing is performed, the printing can be performed more clearly.

On the other hand, in the support sheet, the upper limit of the transmittance of light having a wavelength of 532 nm is not particularly limited, and may be, for example, 95%.

Further, in the support sheet, the transmittance of light having a wavelength of 1064 nm is preferably 30% or more, more preferably 50% or more, and particularly preferably 70% or more. When the transmittance of the light is in such a range, the protective film forming film or the protective film is irradiated with the laser light through the support sheet, and when printing is performed, the printing can be performed more clearly.

On the other hand, in the support sheet, the upper limit of the transmittance of light having a wavelength of 1064 nm is not particularly limited, and may be, for example, 95%.

Next, each layer constituting the support sheet will be described in more detail.

○Substrate

The base material is in the form of a sheet or a film, and examples of the constituent material of the substrate include various resins.

Examples of the resin include polyethylene such as low density polyethylene (LDPE), linear low density polyethylene (LLDPE), and high density polyethylene (HDPE); Polyolefins other than polyethylene such as polypropylene, polybutene, polybutadiene, polymethylpentene, norbornene resin; ethylene-vinyl acetate copolymer, ethylene-(meth)acrylic acid copolymer, ethylene- (meth)acrylate copolymer, ethylene-based copolymer such as ethylene-norbornene copolymer (copolymer obtained by using ethylene as a monomer); vinyl chloride resin such as polyvinyl chloride or vinyl chloride copolymer (using chlorine) a resin obtained by using ethylene as a monomer); polystyrene; polycycloolefin; polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, poly(ethylene isophthalate) a polyester such as a diester or a polyethylene-2,6-naphthalenedicarboxylate; a wholly aromatic polyester having an aromatic ring group; and a copolymer of two or more of the foregoing polyesters; Acrylate; polyurethane; polypropylene Urethane; polyimide; polyamides; polycarbonates; fluorine resin; polyacetal; modified polyphenylene ether; polyphenylene sulfide; polysulfone; polyether ketone.

In addition, as the resin, for example, a polymer alloy such as a mixture of the polyester and a resin other than the polyester may be used. The polymer alloy of the polyester and the resin other than the polyester is preferably a relatively small amount of the resin other than the polyester.

In addition, as the resin, for example, one or two or more kinds of the above-exemplified resins may be used as a cross-linking resin, and one or two or more kinds of ionic polymerizations of the above-exemplified resins may be used. Remodeling resin such as matter.

Further, in the present specification, the concept of "(meth)acrylic acid" includes both "acrylic acid" and "methacrylic acid". The same is true for terms similar to (meth)acrylic acid.

The resin constituting the substrate may be one type or two or more types. When two or more types of the resin are used, the combination and ratio of these may be arbitrarily selected.

The base material may be composed of one layer (single layer) or a plurality of layers of two or more layers. When the plurality of layers are formed, the plurality of layers may be the same or different from each other, and the combination of the plurality of layers is not particularly limited.

The thickness of the substrate is preferably from 50 μm to 300 μm, more preferably from 60 μm to 100 μm. When the thickness of the substrate is in such a range, the flexibility of the composite sheet for forming a protective film and the adhesion to a semiconductor wafer or a semiconductor wafer are further improved.

Here, the "thickness of the base material" means the thickness of the entire base material. For example, the thickness of the base material composed of a plurality of layers means the total thickness of all the layers constituting the base material.

The substrate preferably has a high thickness precision, that is, any portion can suppress thickness unevenness. Among the above-mentioned constituent materials, examples of the material which can be used to constitute such a substrate having high thickness precision include polyolefin, polyethylene, polyethylene terephthalate, and ethylene-vinyl acetate copolymerization. Things and so on.

The base material may contain various additives such as a filler, a colorant, an antistatic agent, an antioxidant, an organic lubricant, a catalyst, and a softener (plasticizer) in addition to the main constituent materials such as the above resin.

The optical characteristics of the substrate may satisfy the optical characteristics of the support sheet described above. That is, the substrate may be transparent or opaque, and may be colored according to the purpose, or may be vapor-deposited.

Further, in the invention in which the film for forming a protective film has energy ray curability, the substrate is preferably a substrate through which energy rays are transmitted.

The surface of the substrate may be subjected to the following treatment to improve adhesion to other layers such as an adhesive layer provided on the substrate: by embossing treatment such as blasting or solvent treatment; or corona discharge treatment or electron beam treatment Oxidation treatment such as irradiation treatment, plasma treatment, ozone/ultraviolet irradiation treatment, flame treatment, chromic acid treatment, hot air treatment, and the like.

In addition, the surface of the substrate may also be subjected to a primer treatment.

Further, the substrate may have an antistatic coating layer or a layer for the following use. When the composite sheet for forming a protective film is stacked and stored, the substrate is prevented from adhering to the other sheet or substrate to the adsorption stage.

Among these, the substrate is preferably subjected to electron beam irradiation treatment in terms of suppressing the occurrence of fragmentation of the substrate due to blade rubbing during cutting.

The substrate can be produced by a known method. For example, a substrate containing a resin can be produced by molding a resin composition containing the above resin.

○Adhesive layer

The adhesive layer is in the form of a sheet or a film and contains an adhesive.

Examples of the pressure-sensitive adhesive include adhesion of an acrylic resin, an urethane resin, a rubber resin, a polyoxyn resin, an epoxy resin, a polyvinyl ether, a polycarbonate, and an ester resin. The resin is preferably an acrylic resin.

Further, in the present invention, the term "adhesive resin" includes both an adhesive resin and a resin having adhesive properties, for example, not only a resin having adhesiveness but also being used in combination with other components such as additives. The resin exhibiting adhesiveness or a resin exhibiting adhesiveness by the presence of a trigger such as heat or water.

The adhesive layer may be composed of one layer (single layer) or a plurality of layers of two or more layers. When the plurality of layers are formed, the plurality of layers may be the same or different from each other, and the combination of the plurality of layers is not particularly limited. .

The thickness of the adhesive layer is preferably from 1 μm to 100 μm, more preferably from 1 μm to 60 μm, still more preferably from 1 μm to 30 μm.

Here, the "thickness of the adhesive layer" means the thickness of the entire adhesive layer. For example, the thickness of the adhesive layer composed of a plurality of layers means the total thickness of all the layers constituting the adhesive layer.

The optical properties of the adhesive layer can satisfy the optical characteristics of the support sheet described above. That is, the adhesive layer may be transparent or opaque, and may be colored according to the purpose.

Further, in the invention in which the film for forming a protective film has energy ray curability, the pressure-sensitive adhesive layer is preferably an adhesive layer through which energy rays pass.

The adhesive layer can be formed using an energy ray-curable adhesive, or can be formed using a non-energetic curable adhesive. The adhesive layer formed by the energy ray-curable adhesive can easily adjust the physical properties before and after hardening.

<<Adhesive composition>>

The adhesive layer can be formed using an adhesive composition containing an adhesive. For example, an adhesive composition is applied to the surface of the object to be formed of the adhesive layer, and if necessary, it is dried, whereby an adhesive layer can be formed at the target portion. A more specific method of forming the adhesive layer will be described in detail later together with the formation method of the other layers. The content ratio of the components which are not vaporized at normal temperature in the adhesive composition is usually the same as the content ratio of the aforementioned components in the adhesive layer. In the present specification, the term "normal temperature" means a temperature which is not particularly cold or particularly hot, that is, a normal temperature, and examples thereof include a temperature of 15 ° C to 25 ° C.

The adhesive composition may be applied by a known method, and examples thereof include the following various coaters: air knife coater, knife coater, bar coater, gravure coater, and roll coater. Cloth machine, roll coater, curtain coater, die coater, knife coater, screen coater, Meyer bar coater, contact coater Wait.

The drying condition of the adhesive composition is not particularly limited. When the adhesive composition contains a solvent to be described later, it is preferably heated and dried. In this case, it is preferably, for example, 70 ° C to 130 ° C and 10 seconds to 5 seconds. Dry under minute conditions.

In the case where the adhesive layer is an energy ray-curable property, the adhesive composition containing the energy ray-curable adhesive, that is, the energy ray-curable adhesive composition, for example, the following adhesive composition: adhesion The agent composition (I-1) contains a non-energy-curable adhesive resin (I-1a) (hereinafter sometimes referred to simply as "adhesive resin (I-1a)"), and an energy ray-curable compound; The agent composition (I-2) contains an energy ray-curable adhesive resin (I-2a) (hereinafter sometimes referred to simply as "adhesive resin (I-2a)"), and the adhesive resin (I-2a) An unsaturated group is introduced into the side chain of the non-energy ray-curable adhesive resin (I-1a); the adhesive composition (I-3) contains the above-mentioned adhesive resin (I-2a), and energy ray hardenability Compound.

<Adhesive Composition (I-1)>

As described above, the pressure-sensitive adhesive composition (I-1) contains a non-energy-curable adhesive resin (I-1a) and an energy ray-curable compound.

[Adhesive resin (I-1a)]

The adhesive resin (I-1a) is preferably an acrylic resin.

The acrylic resin may, for example, be an acrylic polymer having at least a structural unit derived from an alkyl (meth)acrylate.

The structural unit of the acrylic resin may be one type or two or more types. When two or more types are used, the combination and ratio may be arbitrarily selected.

The alkyl (meth)acrylate may, for example, be an alkyl (meth)acrylate having a carbon number of from 1 to 20 which constitutes an alkyl group of an alkyl ester, and the alkyl group is preferably a linear chain or a branch. Chained.

Specific examples of the (meth)acrylic acid alkyl ester include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, and isopropyl (meth)acrylate. Ester, n-butyl (meth)acrylate, isobutyl (meth)acrylate, second butyl (meth)acrylate, tert-butyl (meth)acrylate, amyl (meth)acrylate, (A) Ethyl acrylate, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, n-octyl (meth)acrylate, (meth)acrylic acid Anthracene ester, isodecyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate (lauryl (meth)acrylate) , tridecyl (meth) acrylate, tetradecyl (meth) acrylate (myristyl (meth) acrylate), pentadecyl (meth) acrylate, (meth) acrylate Hexadecyl ester (palmityl (meth)acrylate), heptadecyl (meth)acrylate, octadecyl (meth)acrylate (stearyl (meth)acrylate), (methyl) Nineyl acrylate, (meth) acrylate Eicosyl acrylate.

The acrylic polymer is preferably a structural unit having an alkyl (meth)acrylate having a carbon number of 4 or more derived from the alkyl group, in terms of improving the adhesion of the adhesive layer. Further, the alkyl group preferably has a carbon number of 4 to 12, more preferably 4 to 8, in terms of further improving the adhesion of the adhesive layer. Further, the alkyl (meth)acrylate having a carbon number of 4 or more in the alkyl group is preferably an alkyl acrylate.

In the acrylic polymer, a structural unit derived from a functional group-containing monomer is preferably contained in addition to the structural unit derived from the alkyl (meth)acrylate.

Examples of the functional group-containing monomer include a monomer which can be reacted with a crosslinking agent to be described later to form a starting point for crosslinking, or can be contained by the functional group and the latter. The unsaturated group in the unsaturated group is reacted, and an unsaturated group is introduced into the side chain of the acrylic polymer.

Examples of the functional group in the functional group-containing monomer include a hydroxyl group, a carboxyl group, an amine group, and an epoxy group.

That is, examples of the functional group-containing monomer include a hydroxyl group-containing monomer, a carboxyl group-containing monomer, an amine group-containing monomer, and an epoxy group-containing monomer.

Examples of the hydroxyl group-containing monomer include hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and (meth)acrylic acid 3- Hydroxypropyl ester, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, etc.; hydroxyalkyl (meth)acrylate; vinyl alcohol, A non-(meth)acrylic unsaturated alcohol such as allyl alcohol (an unsaturated alcohol having no (meth) acrylonitrile skeleton) or the like.

Examples of the carboxyl group-containing monomer include an ethylenically unsaturated monocarboxylic acid (such as a monocarboxylic acid having an ethylenically unsaturated bond) such as (meth)acrylic acid or crotonic acid; and fumaric acid and itaconol. An ethylenically unsaturated dicarboxylic acid (dicarboxylic acid having an ethylenically unsaturated bond) such as an acid, maleic acid or citraconic acid; an anhydride of the above ethylenically unsaturated dicarboxylic acid; 2-carboxyethylmethyl A carboxyalkyl (meth)acrylate such as acrylate.

The functional group-containing monomer is preferably a hydroxyl group-containing monomer, a carboxyl group-containing monomer, more preferably a hydroxyl group-containing monomer.

The functional group-containing monomer constituting the acrylic polymer may be one type or two or more types. When two or more types are used, the combination and ratio may be arbitrarily selected.

In the above acrylic polymer, the content of the structural unit derived from the functional group-containing monomer is preferably from 1% by mass to 35% by mass, more preferably from 2% by mass to 32% by mass, based on the total amount of the structural unit. It is particularly preferably from 3% by mass to 30% by mass.

The acrylic polymer may have a structural unit derived from another monomer in addition to a structural unit derived from an alkyl (meth)acrylate and a structural unit derived from a functional group-containing monomer.

The other monomer is not particularly limited as long as it can be copolymerized with an alkyl (meth)acrylate or the like.

Examples of the other monomer include styrene, α-methylstyrene, vinyltoluene, vinyl formate, vinyl acetate, acrylonitrile, and acrylamide.

The other monomer constituting the acrylic polymer may be one type or two or more types. When two or more types are used, the combination and ratio may be arbitrarily selected.

The acrylic polymer can be used as the above non-energy-curable adhesive resin (I-1a).

On the other hand, a compound obtained by reacting a functional group in the acrylic polymer with an unsaturated group-containing compound having an energy ray polymerizable unsaturated group (energy ray polymerizable group) can be used as the above-mentioned energy ray hardening. Adhesive resin (I-2a).

The adhesive resin (I-1a) contained in the adhesive composition (I-1) may be one type or two or more types. When two or more types are used, the combinations and ratios may be arbitrarily selected. .

In the adhesive composition (I-1), the content of the adhesive resin (I-1a) is preferably from 5% by mass to 99% by mass, more preferably from 10% by mass to 95% by mass, even more preferably from 15% by mass to 90% by mass.

[Energy curing compound]

The energy ray-curable compound contained in the adhesive composition (I-1) includes a monomer or oligomer which has an energy ray polymerizable unsaturated group and can be cured by irradiation with an energy ray.

In the energy ray-curable compound, examples of the monomer include trimethylolpropane tri(meth)acrylate, pentaerythritol (meth)acrylate, pentaerythritol tetra(meth)acrylate, and dipentaerythritol VI (A). Poly(meth)acrylates such as acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol (meth)acrylate; amine (meth)acrylate Ester; polyester (meth) acrylate; polyether (meth) acrylate; epoxy (meth) acrylate, and the like.

In the energy ray-curable compound, examples of the oligomer include an oligomer obtained by polymerizing the above-exemplified monomers.

The energy ray-curable compound is preferably a (meth)acrylic acid urethane or a (meth)acrylic acid urethane in terms of a relatively large molecular weight and a tendency to lower the storage modulus of the adhesive layer. Oligomer.

The energy ray-curable compound to be contained in the adhesive composition (I-1) may be one type or two or more types. When two or more types are used, the combination and ratio may be arbitrarily selected.

In the above-mentioned adhesive composition (I-1), the content of the energy ray-curable compound is preferably from 1% by mass to 95% by mass, more preferably from 5% by mass to 90% by mass, even more preferably from 10% by mass to 85% by mass. quality%.

[crosslinking agent]

When the acrylic polymer having a structural unit derived from a functional group-containing monomer is used as the adhesive resin (I-1a), in addition to the structural unit derived from the alkyl (meth)acrylate, The adhesive composition (I-1) preferably further contains a crosslinking agent.

The crosslinking agent reacts with the aforementioned functional group to crosslink the adhesive resin (I-1a) with each other.

Examples of the crosslinking agent include isocyanate crosslinking agents (crosslinking agents having an isocyanate group) such as toluene diisocyanate, hexamethylene diisocyanate, benzodimethyl diisocyanate, and an adduct of these diisocyanates; Epoxy crosslinking agent such as ethylene glycol glycidyl ether (crosslinking agent having glycidyl group); aziridine crosslinking such as hexa[1-(2-methyl)-aziridine]triphosphine triazine a crosslinking agent (a crosslinking agent having an aziridine group); a metal chelate crosslinking agent such as an aluminum chelate compound (a crosslinking agent having a metal chelate structure); an isocyanurate crosslinking agent ( A crosslinking agent having an isocyanuric acid skeleton) or the like.

The crosslinking agent is preferably an isocyanate crosslinking agent in terms of improving the cohesive force of the adhesive, improving the adhesion of the adhesive layer, and facilitating the acquisition.

The amount of the crosslinking agent contained in the adhesive composition (I-1) may be one or two or more. When two or more kinds are used, the combination and ratio may be arbitrarily selected.

In the above-mentioned adhesive composition (I-1), the content of the crosslinking agent is preferably from 0.01 part by mass to 50 parts by mass, more preferably from 0.1 part by mass, per 100 parts by mass of the content of the adhesive resin (I-1a). It is especially preferably from 0.3 part by mass to 15 parts by mass to 20 parts by mass.

[Photopolymerization initiator]

The adhesive composition (I-1) may further contain a photopolymerization initiator. The adhesive composition (I-1) containing a photopolymerization initiator is sufficiently subjected to a hardening reaction even when irradiated with a relatively low energy energy line such as ultraviolet rays.

Examples of the photopolymerization initiator include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, benzoin methyl benzoate, and benzoin dimethyl ketal. Acetophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one, etc. a ketone compound; a fluorenylphosphine oxide compound such as bis(2,4,6-trimethylbenzylidene)phenylphosphine oxide or 2,4,6-trimethylbenzimidyldiphenylphosphine oxide; a thiol compound such as a phenyl sulfide or a tetramethyl thiuram monosulfide; an α-keto alcohol compound such as 1-hydroxycyclohexyl phenyl ketone; an azo compound such as azobisisobutyronitrile; Titanocene compound; thioxanthone compound such as thioxanthone; peroxide compound; diketone compound such as diethyl hydrazine; benzoin; diphenyl oxime; benzophenone; 2,4-diethyl thioxanthone ; 1,2-diphenylmethane; 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]acetone; 2-chloroindole and the like.

In addition, as the photopolymerization initiator, for example, a ruthenium compound such as 1-chloroindole or a photo sensitizer such as an amine can be used.

The photopolymerization initiator contained in the adhesive composition (I-1) may be one type or two or more types. When two or more types are used, the combination and ratio of these may be arbitrarily selected.

In the adhesive composition (I-1), the content of the photopolymerization initiator is preferably from 0.01 part by mass to 20 parts by mass, more preferably from 0.03 part by mass, per 100 parts by mass of the content of the energy ray-curable compound. 10 parts by mass, particularly preferably from 0.05 parts by mass to 5 parts by mass.

[Other additives]

In the adhesive composition (I-1), other additives which do not belong to any of the above components may be contained within the range which does not impair the effects of the present invention.

Examples of the other additives include an antistatic agent, an antioxidant, a softener (plasticizer), a filler (filler), a rust preventive, a colorant (pigment, dye), a sensitizer, and an adhesion-imparting agent. A known additive such as a reaction retarder or a crosslinking accelerator (catalyst).

In addition, the reaction retardant, for example, suppresses the cross-linking reaction outside the target in the adhesive composition (I-1) which is preserved by the action of the catalyst mixed in the adhesive composition (I-1). . The reaction retardation agent is, for example, a compound which forms a chelate complex by a chelate compound, and more specifically, has two or more carbonyl groups (-C (in one molecule). Compound of =O)-).

The other additives contained in the adhesive composition (I-1) may be one type or two or more types. When two or more types are used, the combination and ratio of these may be arbitrarily selected.

In the adhesive composition (I-1), the content of the other additives is not particularly limited, and may be appropriately selected depending on the type of the other additives.

[solvent]

The adhesive composition (I-1) may also contain a solvent. The adhesive composition (I-1) has an applicability to the coating target surface by containing a solvent.

The solvent is preferably an organic solvent, and examples of the organic solvent include a ketone such as methyl ethyl ketone or acetone; an ester such as ethyl acetate (carboxylate); an ether such as tetrahydrofuran or dioxane; and cyclohexane. An aliphatic hydrocarbon such as n-hexane; an aromatic hydrocarbon such as toluene or xylene; an alcohol such as 1-propanol or 2-propanol; or the like.

As the solvent, for example, the solvent used in the production of the adhesive resin (I-1a) can be removed from the adhesive composition (I-1a) and used directly in the adhesive composition (I-1). When the adhesive composition (I-1) is produced, a solvent of the same kind or a different type as the solvent used in the production of the adhesive resin (I-1a) is separately added.

The solvent contained in the adhesive composition (I-1) may be one type or two or more types. When two or more types are used, the combination and ratio of these may be arbitrarily selected.

In the adhesive composition (I-1), the content of the solvent is not particularly limited, and may be appropriately adjusted.

<Adhesive Composition (I-2)>

As described above, the adhesive composition (I-2) contains an energy ray-curable adhesive resin (I-2a) which is a non-energy-curable adhesive resin (I). The side chain of -1a) is introduced with an unsaturated group.

[Adhesive resin (I-2a)]

The above-mentioned adhesive resin (I-2a) is obtained, for example, by reacting a functional group in the adhesive resin (I-1a) with an unsaturated group-containing compound having an energy ray polymerizable unsaturated group.

The unsaturated group-containing compound has, in addition to the energy ray polymerizable unsaturated group, a group having a group reactive with a functional group in the adhesive resin (I-1a) and an adhesive resin (I). -1a) Bonding.

Examples of the energy ray polymerizable unsaturated group include a (meth) acryl fluorenyl group, a vinyl group (Ethenyl group), an allyl group (2-propenyl group), and the like, and a (meth) acrylonitrile group is preferred. .

The group which can be bonded to the functional group in the adhesive resin (I-1a) may, for example, be an isocyanate group and a glycidyl group which may be bonded to a hydroxyl group or an amine group, and may be bonded to a carboxyl group or an epoxy group. Hydroxyl groups and amine groups.

Examples of the unsaturated group-containing compound include (meth)acryloxyethyl isocyanate, (meth)acryl decyl isocyanate, and glycidyl (meth)acrylate.

The adhesive resin (I-2a) contained in the adhesive composition (I-2) may be one type or two or more types. When two or more types are used, the combinations and ratios may be arbitrarily selected. .

In the adhesive composition (I-2), the content of the adhesive resin (I-2a) is preferably from 5% by mass to 99% by mass, more preferably from 10% by mass to 95% by mass, even more preferably from 10% by mass to 90% by mass.

[crosslinking agent]

When the acrylic polymer having the structural unit derived from the functional group-containing monomer is used as the adhesive resin (I-2a), for example, in the same manner as in the adhesive resin (I-1a), the adhesive composition is used. (I-2) may further contain a crosslinking agent.

The crosslinking agent in the adhesive composition (I-2) is the same as the crosslinking agent in the adhesive composition (I-1).

The amount of the crosslinking agent contained in the adhesive composition (I-2) may be one or two or more. When two or more types are used, the combination and ratio may be arbitrarily selected.

In the above-mentioned adhesive composition (I-2), the content of the crosslinking agent is preferably 0.01 parts by mass to 50 parts by mass, more preferably 0.1 part by mass, per 100 parts by mass of the content of the adhesive resin (I-2a). It is especially preferably from 0.3 part by mass to 15 parts by mass to 20 parts by mass.

[Photopolymerization initiator]

The adhesive composition (I-2) may further contain a photopolymerization initiator. The adhesive composition (I-2) containing a photopolymerization initiator is sufficiently subjected to a hardening reaction even when irradiated with a relatively low energy energy line such as ultraviolet rays.

The photopolymerization initiator in the adhesive composition (I-2) is the same as the photopolymerization initiator in the adhesive composition (I-1).

The photopolymerization initiator contained in the adhesive composition (I-2) may be one type or two or more types. When two or more types are used, the combination and ratio may be arbitrarily selected.

In the adhesive composition (I-2), the content of the photopolymerization initiator is preferably from 0.01 part by mass to 20 parts by mass, more preferably from 0.03 part by mass, based on 100 parts by mass of the content of the adhesive resin (I-2a). The portion is preferably 10 parts by mass, particularly preferably 0.05 parts by mass to 5 parts by mass.

[Other additives]

In the adhesive composition (I-2), other additives which do not belong to any of the above components may be contained within the range which does not impair the effects of the present invention.

The other additives mentioned above in the adhesive composition (I-2) include the same compounds as the other additives in the adhesive composition (I-1).

The other additives contained in the adhesive composition (I-2) may be one type or two or more types. When two or more types are used, the combination and ratio may be arbitrarily selected.

In the adhesive composition (I-2), the content of the other additives is not particularly limited, and may be appropriately selected depending on the type of the other additives.

[solvent]

The adhesive composition (I-2) may also contain a solvent for the same purpose as in the case of the adhesive composition (I-1).

The solvent mentioned in the adhesive composition (I-2) is the same solvent as the solvent in the adhesive composition (I-1).

The solvent contained in the adhesive composition (I-2) may be one type or two or more types. When two or more types are used, the combination and ratio of these may be arbitrarily selected.

In the adhesive composition (I-2), the content of the solvent is not particularly limited, and may be appropriately adjusted.

<Adhesive Composition (I-3)>

As described above, the pressure-sensitive adhesive composition (I-3) contains the above-mentioned adhesive resin (I-2a) and an energy ray-curable compound.

In the adhesive composition (I-3), the content of the adhesive resin (I-2a) is preferably from 5% by mass to 99% by mass, more preferably from 10% by mass to 95% by mass, even more preferably from 15% by mass to 90% by mass.

[Energy curing compound]

The energy ray-curable compound to be contained in the adhesive composition (I-3) includes a monomer and an oligomer which have an energy ray polymerizable unsaturated group and can be cured by irradiation with an energy ray, and examples thereof include The same compound as the energy ray-curable compound contained in the adhesive composition (I-1).

The energy ray-curable compound to be contained in the adhesive composition (I-3) may be one type or two or more types. When two or more types are used, the combination and ratio may be arbitrarily selected.

In the above-mentioned adhesive composition (I-3), the content of the energy ray-curable compound is preferably from 0.01 part by mass to 300 parts by mass, more preferably from 0.01 part by mass to 300 parts by mass, based on 100 parts by mass of the content of the adhesive resin (I-2a). From 0.03 parts by mass to 200 parts by mass, particularly preferably from 0.05 parts by mass to 100 parts by mass.

[Photopolymerization initiator]

The adhesive composition (I-3) may further contain a photopolymerization initiator. The adhesive composition (I-3) containing a photopolymerization initiator is sufficiently subjected to a hardening reaction even when irradiated with a relatively low energy energy line such as ultraviolet rays.

The photopolymerization initiator in the adhesive composition (I-3) is the same as the photopolymerization initiator in the adhesive composition (I-1).

The photopolymerization initiator contained in the adhesive composition (I-3) may be one type or two or more types. When two or more types are used, the combination and ratio may be arbitrarily selected.

In the adhesive composition (I-3), the content of the photopolymerization initiator is preferably from 0.01 part by mass to 20 parts by mass based on 100 parts by mass of the total of the adhesive resin (I-2a) and the energy ray-curable compound. The parts by mass are more preferably 0.03 parts by mass to 10 parts by mass, particularly preferably 0.05 parts by mass to 5 parts by mass.

[Other additives]

In the adhesive composition (I-3), other additives which do not belong to any of the above components may be contained within the range which does not impair the effects of the present invention.

Examples of the other additives include the same compounds as the other additives in the adhesive composition (I-1).

The other additives contained in the adhesive composition (I-3) may be one type or two or more types. When two or more types are used, the combination and ratio of these may be arbitrarily selected.

In the adhesive composition (I-3), the content of the other additives is not particularly limited, and may be appropriately selected depending on the type of the other additives.

[solvent]

The adhesive composition (I-3) may also contain a solvent for the same purpose as in the case of the adhesive composition (I-1).

The solvent in the adhesive composition (I-3) is the same solvent as the solvent in the adhesive composition (I-1).

The solvent contained in the adhesive composition (I-3) may be one type or two or more types. When two or more types are used, the combination and ratio may be arbitrarily selected.

In the adhesive composition (I-3), the content of the solvent is not particularly limited, and may be appropriately adjusted.

<Adhesive composition other than the adhesive composition (I-1) to the adhesive composition (I-3)>

The adhesive composition (I-1), the adhesive composition (I-2), and the adhesive composition (I-3) are mainly described above, but all the adhesives other than these three adhesive compositions are described. The composition (in the present specification, the "adhesive composition other than the adhesive composition (I-1) to the adhesive composition (I-3)") can be similarly used as the content of the components. The ingredients.

As the adhesive composition other than the adhesive composition (I-1) to the adhesive composition (I-3), in addition to the energy ray-curable adhesive composition, a non-energy curing adhesive may be cited. Composition.

Examples of the non-energy-curable adhesive composition include an acrylic resin, an urethane resin, a rubber resin, a polyoxyn resin, an epoxy resin, a polyvinyl ether, and a polycarbonate. The adhesive composition (I-4) of the non-energy-curable adhesive resin (I-1a) such as an ester or an ester resin is preferably an adhesive composition containing an acrylic resin.

The adhesive composition other than the adhesive composition (I-1) to the adhesive composition (I-3) preferably contains one or more kinds of crosslinking agents, and the content of the crosslinking agent can be set to The above adhesive composition (I-1) and the like are the same.

<Adhesive Composition (I-4)>

As a preferable adhesive composition (I-4), the adhesive composition containing the said adhesive resin (I-1a) and a crosslinking agent is mentioned, for example.

[Adhesive resin (I-1a)]

The adhesive resin (I-1a) in the adhesive composition (I-4) is the same as the adhesive resin (I-1a) in the adhesive composition (I-1).

The adhesive resin (I-1a) contained in the adhesive composition (I-4) may be one type or two or more types. When two or more types are used, the combinations and ratios may be arbitrarily selected. .

In the adhesive composition (I-4), the content of the adhesive resin (I-1a) is preferably from 5% by mass to 99% by mass, more preferably from 10% by mass to 95% by mass, even more preferably from 15% by mass to 90% by mass.

[crosslinking agent]

When the acrylic polymer having a structural unit derived from a functional group-containing monomer is used as the adhesive resin (I-1a), in addition to the structural unit derived from the alkyl (meth)acrylate, The adhesive composition (I-4) preferably further contains a crosslinking agent.

The crosslinking agent in the adhesive composition (I-4) is the same as the crosslinking agent in the adhesive composition (I-1).

The amount of the crosslinking agent contained in the adhesive composition (I-4) may be one or two or more. When two or more kinds are used, the combination and ratio may be arbitrarily selected.

In the above-mentioned adhesive composition (I-4), the content of the crosslinking agent is preferably from 0.01 part by mass to 50 parts by mass, more preferably from 0.1 part by mass, per 100 parts by mass of the content of the adhesive resin (I-1a). It is especially preferably from 0.3 part by mass to 15 parts by mass to 20 parts by mass.

[Other additives]

In the adhesive composition (I-4), other additives which do not belong to any of the above components may be contained within the range which does not impair the effects of the present invention.

Examples of the other additives include the same compounds as the other additives in the adhesive composition (I-1).

The other additives contained in the adhesive composition (I-4) may be one type or two or more types. When two or more types are used, the combination and ratio may be arbitrarily selected.

In the adhesive composition (I-4), the content of the other additives is not particularly limited, and may be appropriately selected depending on the type of the other additives.

[solvent]

The adhesive composition (I-4) may also contain a solvent for the same purpose as in the case of the adhesive composition (I-1).

The solvent in the adhesive composition (I-4) is the same solvent as the solvent in the adhesive composition (I-1).

The solvent contained in the adhesive composition (I-4) may be one type or two or more types. When two or more types are used, the combination and ratio of these may be arbitrarily selected.

In the adhesive composition (I-4), the content of the solvent is not particularly limited, and may be appropriately adjusted.

In the composite sheet for forming a protective film of the present invention, the adhesive layer is preferably non-energy line curable. The reason is that when the adhesive layer is energy ray-curable, it may not be possible to suppress the adhesive film from being cured at the same time when the film for forming a protective film is cured by irradiation of the energy ray. When the adhesive layer and the film for forming a protective film are simultaneously cured, the film for forming a protective film and the adhesive layer after curing may adhere to the interface to such an extent that they cannot be peeled off. In this case, it is difficult to provide the film for forming a protective film after curing on the back surface, that is, the semiconductor wafer of the protective film (in the present specification, sometimes referred to as "a semiconductor wafer with a protective film"), since the adhesive is cured. The support sheet of the layer is peeled off, and the semiconductor wafer with the protective film cannot be picked up normally. Since the adhesive layer in the support sheet of the present invention is made non-energy line hardenability, such a problem can be surely avoided, and the semiconductor wafer with the protective film can be more easily picked up.

The effect of the case where the adhesive layer is non-energy hardening is described herein, but even if the layer directly contacting the film for forming a protective film in the support sheet is a layer other than the adhesive layer, as long as the layer is a non-energy line The hardening property also exerts the same effect.

<<Manufacturing method of adhesive composition>>

Adhesive composition (I-1) to adhesive composition (I-1), adhesive composition (I-3), or adhesive composition (I-4) to adhesive composition (I-3) The other adhesive composition is obtained by blending the above-mentioned adhesive and components other than the above-mentioned adhesive as needed to form each component of the adhesive composition.

The order of addition of each component is not particularly limited, and two or more components may be added at the same time.

When a solvent is used, it can be used by mixing a solvent with any of the formulation components other than the solvent to preliminarily dilute the formulation component; or by using the following method, that is, not Any of the formulation components other than the solvent is diluted in advance to mix the solvent with these formulation components.

The method of mixing the components at the time of preparation is not particularly limited, and may be appropriately selected from the following known methods: a method of mixing by stirring a stirring blade or a stirring blade, a method of mixing using a mixer, and applying ultrasonic waves. The method of mixing, etc.

The temperature and time when the components are added and mixed are not particularly limited as long as the respective components are not deteriorated, and it is preferably adjusted, and the temperature is preferably from 15 ° C to 30 ° C.

◎ Protective film forming film

In the composite sheet for forming a protective film of the present invention, at least one surface (α) has a surface roughness (Ra) of 0.038 μm or more, whereby appropriate secondary workability is imparted. In other words, when the film for forming a protective film is attached to the semiconductor wafer at a position deviated from the predetermined position, the film for forming a protective film can be smoothly peeled off from the semiconductor wafer, and the film for forming a protective film can be peeled off. In the semiconductor wafer, another new film for forming a protective film is attached to an accurate position, whereby the semiconductor wafer can be supplied to the semiconductor wafer without waste.

Further, the adhesion between the protective film obtained by curing the film for forming a protective film and the support sheet is preferably from 50 mN/25 mm to 1500 mN/25 mm, more preferably from 52 mN/25 mm to 1450 mN/25 mm, and even more preferably 53 mN/25 mm. To 1430mN/25mm. When the semiconductor wafer with the protective film is picked up by the adhesive force being at least the above-described lower limit value, the semiconductor wafer with the protective film outside the target is picked up and suppressed, and the target-attached protective film can be picked up with high selectivity. Semiconductor wafer. In addition, when the semiconductor wafer with the protective film is picked up by the adhesion force being equal to or less than the above upper limit value, cracking and defect of the semiconductor wafer are suppressed. In this way, the composite sheet for forming a protective film has a better pick-up property by the adhesive force being within a specific range.

In the present invention, even if the film for forming a protective film is cured, the laminated structure of the cured film (in other words, the support sheet and the protective film) of the support sheet and the film for forming a protective film is maintained. It is called "composite sheet for forming a protective film".

The adhesion between the protective film and the support sheet can be measured by the following method.

In other words, a composite sheet for forming a protective film having a width of 25 mm and a length is attached to the adherend by the film for forming a protective film of the composite sheet for forming a protective film.

Then, the protective film was formed by curing the energy-shielding film to form a protective film, and the support sheet was peeled off at a peeling speed of 300 mm/min from the protective film attached to the adherend. The peeling system at this time is a so-called 180° peeling, that is, the support sheet is formed along the longitudinal direction of the support sheet so that the surfaces of the protective film and the support sheet are in contact with each other at an angle of 180°. Peel off in the longitudinal direction of the composite sheet. Then, the load (peeling force) at the time of 180° peeling was measured, and the measured value of the load (peeling force) was defined as the above-described adhesive force (mN/25 mm).

The length of the composite sheet for forming a protective film to be measured is not particularly limited as long as it is a range in which the adhesive force can be stably detected, and is preferably 100 mm to 300 mm. In the measurement, it is preferable that the composite sheet for forming a protective film is attached to the adherend, and the attached state of the composite sheet for forming a protective film is stabilized in advance.

In the present invention, the adhesive force between the film for forming a protective film and the support sheet is not particularly limited, and may be, for example, 80 mN/25 mm or more, preferably 100 mN/25 mm or more, more preferably 150 mN/25 mm or more. It is 200mN/25mm or more. When the adhesive force is 100 mN/25 mm or more, the peeling of the film for forming a protective film and the support sheet at the time of dicing is suppressed, and for example, the scattering of the semiconductor wafer having the film for forming a protective film on the back surface from the support sheet is suppressed.

On the other hand, the upper limit of the adhesive force between the film for forming a protective film and the support sheet is not particularly limited, and may be, for example, any of 4000 mN/25 mm, 3500 mN/25 mm, and 3000 mN/25 mm. Among them, these are examples.

The adhesive force between the film for forming a protective film and the support sheet can be utilized between the protective film and the support sheet described above, except that the film for protecting the protective film for measurement is not cured by irradiation of the energy ray. The same method of adhesion was used for the measurement.

The adhesion between the protective film and the support sheet and the adhesive force between the film for forming a protective film and the support sheet can be adjusted, for example, by the type and amount of the component contained in the film for forming a protective film, and in the support sheet. The constituent material of the layer of the film for forming a protective film, the surface state of the layer, and the like are appropriately adjusted.

For example, the type and amount of the component contained in the film for forming a protective film can be adjusted by the type and amount of the component contained in the protective film forming composition to be described later. Further, by adjusting the content of the component of the protective film-forming composition, for example, the type and content of the polymer (b) having no energy ray-curable group, the content of the filler (d), or the crosslinking agent (f) The content of the protective film or the film for forming a protective film and the support sheet can be more easily adjusted.

In the case where the layer of the film for forming a protective film in the support sheet is an adhesive layer, the constituent material of the layer can be appropriately adjusted by adjusting the type and amount of the component contained in the adhesive layer. Further, the type and amount of the component contained in the adhesive layer can be adjusted by the type and amount of the component of the above-mentioned adhesive composition.

On the other hand, when the layer of the film for forming a protective film in the support sheet is a substrate, the adhesion between the film for forming the protective film or the protective film and the support sheet is, in addition to the constituent material of the substrate, It can also be adjusted by the surface state of the substrate. Further, the surface state of the substrate can be adjusted, for example, by performing the surface treatment as described above for improving the adhesion between the substrate and the other layer, that is, by the embossing treatment such as blasting or solvent treatment; Any treatment such as faint treatment, electron beam irradiation treatment, plasma treatment, ozone/ultraviolet irradiation treatment, flame treatment, chromic acid treatment, hot air treatment, etc.;

The film for forming a protective film may, for example, be a film having energy ray-curable properties, for example, an energy ray-curable component (a).

The energy ray-curable component (a) is preferably uncured, preferably adhesive, more preferably uncured and adhesive.

The film for forming a protective film may be only one layer (single layer), or may be a plurality of layers of two or more layers. In the case of a plurality of layers, the plurality of layers may be the same or different from each other, and the combination of the plurality of layers is not Specially limited.

The thickness of the film for forming a protective film is preferably from 1 μm to 100 μm, more preferably from 5 μm to 75 μm, still more preferably from 5 μm to 50 μm. When the thickness of the film for forming a protective film is at least the above lower limit value, a protective film having a higher protective ability can be formed. In addition, when the thickness of the film for forming a protective film is equal to or less than the above upper limit value, the thickness can be suppressed from being too thick.

Here, the "thickness of the film for forming a protective film" means the thickness of the entire film for forming a protective film. For example, the thickness of the film for forming a protective film composed of a plurality of layers means the entire layer of the film for forming a protective film. Total thickness.

The curing condition when the protective film forming film is cured to form a protective film is not particularly limited as long as the protective film has a degree of hardening that sufficiently exhibits the function of the protective film, and is appropriately selected depending on the type of the protective film forming film. Just fine.

For example, when the film for forming a protective film is cured, the illuminance of the energy ray is preferably from 4 mW/cm ² to 280 mW/cm ² . Further, in the hardening, the amount of light of the energy ray is preferably from 3 mJ/cm ² to 1000 mJ/cm ² .

<<Constituent for forming a protective film>>

The film for forming a protective film can be formed using a composition for forming a protective film containing a constituent material of the film for forming a protective film. For example, a protective film forming composition is applied to the surface to be formed of the film for forming a protective film, and if necessary, it can be dried to form a film for forming a protective film at a target portion. The content ratio of the components which are not vaporized at normal temperature in the composition for forming a protective film is usually the same as the content ratio of the components in the film for forming a protective film. Here, the "normal temperature" is as described above.

The protective film-forming composition may be applied by a known method, and examples thereof include the following various coaters: air knife coater, knife coater, bar coater, gravure coater, and roll. Coating machine, roll coater, curtain coater, die coater, knife coater, screen coater, wire bar coater, contact coater, and the like.

The drying condition of the protective film-forming composition is not particularly limited. When the protective film-forming composition contains a solvent to be described later, it is preferably heated and dried. In this case, it is preferably, for example, 70 ° C to 130 ° C. Drying is carried out for 10 seconds to 5 minutes.

<Construction film forming composition (IV-1)>

The protective film-forming composition (IV-1) or the like containing the energy ray-curable component (a) is exemplified as the protective film-forming composition.

[Energy line hardening component (a)]

The energy ray-curable component (a) is a component which is cured by irradiation with an energy ray, and this component is used to impart film-forming property or flexibility to the film for forming a protective film.

Examples of the energy ray-curable component (a) include a polymer (a1) having an energy ray-curable group and having a weight average molecular weight of 80,000 to 2,000,000, and a compound having an energy ray-curable group and having a molecular weight of 100 to 80,000. (a2). At least a part of the polymer (a1) may be crosslinked by a crosslinking agent (f) to be described later, or may not be crosslinked.

In the present specification, the weight average molecular weight means a polystyrene equivalent value measured by a Gel Permeation Chromatography (GPC) method unless otherwise specified.

(Polymer (a1) having an energy ray-hardening 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 resin (a1-1), and the acrylic resin (a1-1) is an acrylic polymer (a11). And an energy ray-curable compound (a12) having a functional group reactive with a group of another compound, wherein the energy ray-curable compound (a12) has a functional group An energy ray-curable group such as a reaction group and an energy ray-hardening double bond.

Examples of the functional group which can react with a group of another compound include a hydroxyl group, a carboxyl group, an amine group, and a substituted amine group (one or two hydrogen atoms of the amine group are substituted by a group other than a hydrogen atom) Base), epoxy group, and the like. Among them, in order to prevent corrosion of a circuit such as a semiconductor wafer or a semiconductor wafer, the functional group is preferably a group other than a carboxyl group.

Among these, the aforementioned functional group is preferably a hydroxyl group.

‧Acrylic polymer with functional group (a11)

The acrylic polymer (a11) having a functional group may, for example, be a polymer obtained by copolymerizing the acrylic monomer having a functional group and the acrylic monomer having no functional group, or may be a polymer. In addition to these monomers, a polymer obtained by copolymerizing a monomer other than the acrylic monomer (non-acrylic monomer) is further used.

Further, the acrylic polymer (a11) may be a random copolymer or a block copolymer.

Examples of the acrylic monomer having a functional group include a hydroxyl group-containing monomer, a carboxyl group-containing monomer, an amine group-containing monomer, a substituted amine group-containing monomer, and an epoxy group-containing monomer. .

Examples of the hydroxyl group-containing monomer include hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and (meth)acrylic acid 3- Hydroxypropyl ester, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, etc.; hydroxyalkyl (meth)acrylate; vinyl alcohol, A non-(meth)acrylic unsaturated alcohol such as allyl alcohol (an unsaturated alcohol having no (meth) acrylonitrile skeleton) or the like.

Examples of the carboxyl group-containing monomer include an ethylenically unsaturated monocarboxylic acid (such as a monocarboxylic acid having an ethylenically unsaturated bond) such as (meth)acrylic acid or crotonic acid; and fumaric acid and itaconol. An ethylenically unsaturated dicarboxylic acid (dicarboxylic acid having an ethylenically unsaturated bond) such as an acid, maleic acid or citraconic acid; an anhydride of the above ethylenically unsaturated dicarboxylic acid; 2-carboxyethylmethyl A carboxyalkyl (meth)acrylate such as acrylate.

The acrylic monomer having a functional group is preferably a hydroxyl group-containing monomer or a carboxyl group-containing monomer, more preferably a hydroxyl group-containing monomer.

The acrylic monomer having the functional group in the acrylic polymer (a11) may be one type or two or more types. When two or more types are used, the combination and ratio may be arbitrarily selected.

Examples of the acrylic monomer having no functional group include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, and isopropyl (meth)acrylate. N-butyl (meth)acrylate, isobutyl (meth)acrylate, second butyl (meth)acrylate, tert-butyl (meth)acrylate, amyl (meth)acrylate, (methyl) Hexyl acrylate, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, n-octyl (meth)acrylate, n-decyl (meth)acrylate , isodecyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, lauryl (meth) acrylate (lauryl (meth) acrylate), ( Tridecyl methyl methacrylate, tetradecyl (meth) acrylate (myristyl (meth) acrylate), pentadecyl (meth) acrylate, hexadecane (meth) acrylate Alkyl ester (alkyl palmitate), heptadecyl (meth)acrylate, octadecyl (meth)acrylate (stearyl (meth)acrylate) Based on a carbon number of 1 to 18 The structure (meth) acrylate and the like.

Further, examples of the acrylic monomer having no functional group include methoxymethyl (meth)acrylate, methoxyethyl (meth)acrylate, and ethoxylated (meth)acrylate. An alkoxyalkyl group-containing (meth) acrylate such as an ester or ethoxyethyl (meth) acrylate; or an aromatic group such as an aryl (meth) acrylate such as phenyl (meth) acrylate (meth) acrylate; non-crosslinkable (meth) acrylamide and its derivatives; N,N-dimethylaminoethyl (meth)acrylate, N,N-(meth)acrylate A non-crosslinkable (meth) acrylate having a tertiary amino group such as dimethylaminopropyl ester.

The acrylic monomer having no functional group in the acrylic polymer (a11) may be one type or two or more types. When two or more types are used, the combination and ratio may be arbitrarily selected. .

Examples of the non-acrylic monomer include olefins such as ethylene and norbornene; vinyl acetate; and styrene.

The non-acrylic monomer constituting the acrylic polymer (a11) may be one type or two or more types. When two or more types are used, the combination and ratio may be arbitrarily selected.

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 mass of the structural unit constituting the acrylic polymer (a11) It is preferably from 0.1% by mass to 50% by mass, more preferably from 1% by mass to 40% by mass, even more preferably from 3% by mass to 30% by mass. When the ratio is in such a range, the energy ray-curable group in the acrylic resin (a1-1) obtained by copolymerization of the acrylic polymer (a11) and the energy ray-curable compound (a12) can be used. The content is easily adjusted to a range in which the degree of hardening of the first protective film is better.

The acrylic polymer (a11) constituting the acrylic resin (a1-1) may be one type or two or more types. When two or more types are used, the combination and ratio may be arbitrarily selected.

In the protective film-forming composition (IV-1), the content of the acrylic resin (a1-1) is preferably from 1% by mass to 40% by mass, more preferably from 2% by mass to 30% by mass, particularly preferably 3% by mass. % to 20% by mass.

‧Energy line hardening compound (a12)

The energy ray-curable compound (a12) preferably has one or more selected from the group consisting of an isocyanate group, an epoxy group, and a carboxyl group, and is compatible with the acrylic polymer (a11). The group of the functional group reaction is more preferably an isocyanate group as the above group. When the energy ray-curable compound (a12) has, for example, an isocyanate group as the above-mentioned group, the isocyanate group is easily reacted with the hydroxyl group of the acrylic polymer (a11) having a hydroxyl group as a functional group.

The energy ray-curable compound (a12) preferably has one to five of the energy ray-curable groups in one molecule, and more preferably has one to three.

Examples of the energy ray-curable compound (a12) include 2-methacryloxyethyl isocyanate, m-isopropenyl-α, α-dimethylbenzyl isocyanate, and methacryl oxime isocyanate. , allyl isocyanate, 1,1-(bispropenyloxymethyl)ethyl isocyanate; obtained by reaction of a diisocyanate compound or a polyisocyanate compound with hydroxyethyl (meth)acrylate An acrylonitrile monoisocyanate compound; an acrylonitrile monoisocyanate compound obtained by a reaction of a diisocyanate compound or a polyisocyanate compound, a polyol compound, and a hydroxyethyl (meth)acrylate.

Among these, the energy ray-curable compound (a12) is preferably 2-methylpropenyloxyethyl isocyanate.

The energy ray-curable compound (a12) constituting the acrylic resin (a1-1) may be one type or two or more types. When two or more types are used, the combinations and ratios may be arbitrarily selected. .

In the acrylic resin (a1-1), the ratio of the content of the energy ray-curable group derived from the energy ray-curable compound (a12) to the content of the aforementioned functional group derived from the acrylic polymer (a11) It is preferably from 20 mol% to 120 mol%, more preferably from 35 mol% to 100 mol%, still more preferably from 50 mol% to 100 mol%. By the above content ratio being such a range, the adhesion force of the protective film formed by hardening becomes larger. In the case where the energy ray-curable compound (a12) is a monofunctional compound (having one of the above-mentioned groups in one molecule), the upper limit of the ratio of the content is 100 mol%, but the energy is When the linear curable compound (a12) is a polyfunctional (having two or more of the above-mentioned groups in one molecule), the upper limit of the ratio of the above content may exceed 100 mol%.

The weight average molecular weight (Mw) of the aforementioned polymer (a1) is preferably from 100,000 to 2,000,000, more preferably from 300,000 to 1,500,000.

When at least a part of the polymer (a1) is crosslinked by a crosslinking agent (f), the polymer (a1) may be any one of the acrylic polymers (a11) which does not conform to the above description. The monomer having a monomer reactive with the crosslinking agent (f) is polymerized, crosslinked in a group reactive with the crosslinking agent (f), or may be derived from the aforementioned energy ray-curable compound (a12) Crosslinking is carried out in the group reactive with the aforementioned functional groups.

The polymer (a1) to be contained in the protective film-forming composition (IV-1) and the film for forming a protective film may be one type or two or more types. When two or more types are used, these are Combinations and ratios can be arbitrarily chosen.

(Compound (a2) having an energy ray-hardening group and having a molecular weight of 100 to 80,000)

Examples of the energy ray-curable group of the compound (a2) having an energy ray-curable group and having a molecular weight of from 100 to 80,000 include a group containing an energy ray-curable double bond, and preferred examples of the group include (A) Base) acrylonitrile, vinyl, and the like.

When the compound (a2) satisfies the above conditions, it is not particularly limited, and examples thereof include a low molecular weight compound having an energy ray-curable group, an epoxy resin having an energy ray-curable group, and a phenol resin having an energy ray-curable group. Wait.

In the compound (a2), the low molecular weight compound having an energy ray-curable group may, for example, be a polyfunctional monomer or oligomer, and is preferably an acrylate-based compound having a (meth) acrylonitrile group.

Examples of the acrylate-based compound include 2-hydroxy-3-(meth)acryloxypropyl methacrylate, polyethylene glycol di(meth)acrylate, and propoxylated ethoxylate. Bisphenol bis(meth)acrylate, 2,2-bis[4-((meth)propenyloxypolyethoxy)phenyl]propane, ethoxylated bisphenol A di(A) Acrylate, 2,2-bis[4-((meth)propenyloxydiethoxy)phenyl]propane, 9,9-bis[4-(2-(methyl)propene oxime) Ethyloxy)phenyl]anthracene, 2,2-bis[4-((meth)propenyloxypolypropoxy)phenyl]propane, tricyclodecane dimethanol di(meth)acrylate ( Also known as tricyclodecane dimethylol di(meth) acrylate), 1,10-nonanediol 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 (Meth) acrylate, ethylene glycol di(meth) acrylate, diethylene glycol di(meth) acrylate, triethylene glycol di(meth) acrylate, 2, 2- bis [ 4-((Meth)acryloxyethoxyethoxy)phenyl]propane, neopentyl glycol di(meth)acrylate, ethoxylated polypropylene glycol di(meth)acrylate, 2-hydroxy- Bifunctional (meth) acrylate such as 1,3-bis(methyl)propenyloxypropane; tris(2-(methyl)propenyloxyethyl) isocyanurate, ε-caprolactone Modified tris-(2-(methyl)propenyloxyethyl) isocyanurate, ethoxylated glycerol tri(meth) acrylate, pentaerythritol tri(meth) acrylate, trimethylol Propane tri(meth)acrylate, di-trimethylolpropane tetra(meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol poly( Polyfunctional (meth) acrylate such as methyl acrylate or dipentaerythritol hexa(meth) acrylate; polyfunctional (meth) acrylate oligomer such as (meth) acrylate urethane oligomer Wait.

In the above-mentioned compound (a2), as the epoxy resin having an energy ray-curable group or a phenol resin having an energy ray-curable group, for example, paragraph 0043 in "Japanese Patent Laid-Open Publication No. 2013-194102", or the like can be used. The resin is described. Such a resin also conforms to the resin constituting the thermosetting component (h) to be described later, but in the present invention, the compound (a2) is regarded.

The weight average molecular weight of the aforementioned compound (a2) is preferably from 100 to 30,000, more preferably from 300 to 10,000.

The compound (a2) to be contained in the protective film-forming composition (IV-1) and the film for forming a protective film may be one type or two or more types. When two or more types are used, the combination thereof may be used. And the ratio can be arbitrarily chosen.

[Polymer without energy line hardening group (b)]

When the protective film-forming composition (IV-1) and the film for forming a protective film contain the compound (a2) as the energy ray-curable component (a), it is preferable to further contain no energy ray curability. Base polymer (b).

The polymer (b) may be crosslinked at least in part by the crosslinking agent (f) or may not be crosslinked.

Examples of the polymer (b) having no energy ray-curable group include an acrylic polymer, a phenoxy resin, a urethane resin, a polyester, a rubber resin, and an urethane urethane resin. Polyvinyl alcohol (PVA), butyral resin, polyester urethane resin, and the like.

Among these, the polymer (b) is preferably an acrylic polymer (hereinafter sometimes simply referred to as "acrylic polymer (b-1)").

The acrylic polymer (b-1) may be a known polymer, and may be, for example, a homopolymer of one type of acrylic monomer, or a copolymer of two or more types of acrylic monomers, or one type or A copolymer of two or more kinds of acrylic monomers and one or more monomers (non-acrylic monomers) other than the acrylic monomers.

Examples of the acrylic monomer constituting the acrylic polymer (b-1) include an alkyl (meth)acrylate, a (meth)acrylate having a cyclic skeleton, and a glycidyl group (A). Acrylate, hydroxyl group-containing (meth) acrylate, substituted amino group-containing (meth) acrylate, and the like. Here, the "substituted amine group" is as described above.

Examples of the alkyl (meth)acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, and isopropyl (meth)acrylate. N-butyl methacrylate, isobutyl (meth)acrylate, second butyl (meth)acrylate, tert-butyl (meth)acrylate, amyl (meth)acrylate, (meth)acrylic acid Hexyl ester, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, n-octyl (meth)acrylate, n-decyl (meth)acrylate, Isodecyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate (lauryl (meth)acrylate), (A) Tridecyl acrylate, tetradecyl (meth) acrylate (myristyl (meth) acrylate), pentadecyl (meth) acrylate, cetyl (meth) acrylate An alkyl group of an alkyl ester such as an ester (palmityl (meth)acrylate), a heptadecyl (meth)acrylate, or an octadecyl (meth)acrylate (stearyl (meth)acrylate) a chain structure with a carbon number of 1 to 18 Alkyl (meth)acrylate or the like.

Examples of the (meth) acrylate having a cyclic skeleton include (meth)acrylic acid cycloalkyl esters such as isobornyl (meth)acrylate and dicyclopentanyl (meth)acrylate; Arylalkyl (meth)acrylate such as benzyl acrylate; cycloalkenyl (meth) acrylate such as dicyclopentenyl (meth)acrylate; dicyclopentenyloxyethyl (meth)acrylate (meth)acrylic cycloalkenyloxyalkyl ester and the like.

Examples of the glycidyl group-containing (meth) acrylate include glycidyl (meth)acrylate and the like.

Examples of the hydroxyl group-containing (meth) acrylate include hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and (methyl). 3 - hydroxypropyl acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and the like.

Examples of the (meth) acrylate containing a substituted amino group include N-methylaminoethyl (meth) acrylate and the like.

The non-acrylic monomer constituting the acrylic polymer (b-1) may, for example, be an olefin such as ethylene or norbornene; vinyl acetate; styrene or the like.

As the polymer (b) which is crosslinked by at least a part of the crosslinking agent (f) and does not have the aforementioned energy ray-curable group, for example, a reactive functional group and a crosslinking agent in the above polymer (b) (f) a polymer of the reaction.

The reactive functional group is appropriately selected depending on the type of the crosslinking agent (f), and the like, and is not particularly limited. In the case where the crosslinking agent (f) is a polyisocyanate compound, the reactive functional group may, for example, be a hydroxyl group, a carboxyl group or an amine group. Among them, a hydroxyl group having high reactivity with an isocyanate group is preferred. In the case where the crosslinking agent (f) is an epoxy compound, the reactive functional group may, for example, be a carboxyl group, an amine group or a guanamine group, and among these, a reaction with an epoxy group is preferred. High carboxyl group. Among them, in terms of preventing corrosion of a circuit of a semiconductor wafer or a semiconductor wafer, the reactive functional group is preferably a group other than a carboxyl group.

The polymer (b) having the reactive functional group and having no energy ray-curable group may, for example, be a polymer obtained by polymerizing at least a monomer having the reactive functional group. In the case of the acrylic polymer (b-1), either or both of the acrylic monomer and the non-acrylic monomer exemplified as the monomer constituting the acrylic polymer (b-1) A monomer having the aforementioned reactive functional group may be used. For example, the polymer (b) having a hydroxyl group as a reactive functional group may, for example, be a polymer obtained by polymerizing a hydroxyl group-containing (meth) acrylate, and may be exemplified above. A polymer obtained by polymerizing a monomer in which one or two or more hydrogen atoms of the acrylic monomer or non-acrylic monomer are substituted with the reactive functional group.

In the aforementioned polymer (b) having a reactive functional group, the ratio of the amount of the structural unit derived from the monomer having a reactive functional group to the total amount of the structural unit constituting the polymer (b) is higher It is preferably from 1% by mass to 25% by mass, more preferably from 2% by mass to 20% by mass. By the above ratio being such a range, in the polymer (b), the degree of crosslinking is in a more preferable range.

The weight average molecular weight (Mw) of the polymer (b) having no energy ray-curable group is preferably from 10,000 to 2,000,000, in terms of the film forming property of the protective film-forming composition (IV-1) being more excellent. More preferably, it is 100,000 to 1,500,000.

The polymer (b) having no energy ray-curable group contained in the protective film-forming composition (IV-1) and the film for forming a protective film may be used alone or in combination of two or more kinds. In the above cases, the combinations and ratios of these can be arbitrarily selected.

The composition (IV-1) for forming a protective film includes a composition containing either or both of the polymer (a1) and the compound (a2). In the case where the protective film-forming composition (IV-1) contains the compound (a2), it is preferred to further contain the polymer (b) having no energy ray-curable group, and in this case, Further, it further contains the aforementioned (a1). In addition, the protective film-forming composition (IV-1) may not contain the compound (a2), and may contain the polymer (a1) and the polymer (b) having no energy ray-curable group.

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 the above IV-1), the content of the compound (a2) is preferably from 10 parts by mass to 100 parts by mass based on 100 parts by mass of the total of the polymer (a1) and the polymer (b) having no energy ray-curable group. The parts by mass are more preferably from 30 parts by mass to 350 parts by mass.

In the composition for forming a protective film (IV-1), the ratio of the total content of the energy ray-curable component (a) and the polymer (b) having no energy ray-curable group to the total content of components other than the solvent (that is, the total content of the energy ray-curable component (a) and the polymer (b) having no energy ray-curable group in the film for forming a protective film) is preferably from 5% by mass to 95% by mass, more preferably It is preferably from 10% by mass to 93% by mass, particularly preferably from 15% by mass to 91% by mass. When the ratio of the total content is in such a range, the energy ray hardenability of the film for forming a protective film becomes better.

When the protective film-forming composition (IV-1) contains the energy ray-curable component (a) and the polymer (b) having no energy ray-curable group, the protective film-forming composition (IV-1) In the film for forming a protective film, the content of the polymer (b) is preferably from 3 parts by mass to 160 parts by mass, more preferably 6 parts by mass, per 100 parts by mass of the content of the energy ray-curable component (a). Up to 130 parts by mass. When the content of the polymer (b) is in such a range, the energy ray hardenability of the film for forming a protective film becomes better.

In addition to the energy ray-curable component (a) and the polymer (b) having no energy ray-curable group, the protective film-forming composition (IV-1) may be selected from photopolymerization initiators depending on the purpose. (c), a filler (d), a coupling agent (e), a crosslinking agent (f), a coloring agent (g), a thermosetting component (h), and a general additive (z) One or two or more. For example, by using the protective film-forming composition (IV-1) containing the energy ray-curable component (a) and the thermosetting component (h), the formed film for forming a protective film is heated by heating. The adhesion of the body is increased, and the strength of the protective film formed of the film for forming a protective film is also improved.

[Photopolymerization initiator (c)]

Examples of the photopolymerization initiator (c) include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, benzoin benzoic acid methyl ester, benzoin dimethyl ketal, and the like. Benzoin compounds; acetophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one, etc. Acetophenone compound; fluorenylphosphine oxide compound such as bis(2,4,6-trimethylbenzylidene)phenylphosphine oxide or 2,4,6-trimethylbenzimidyldiphenylphosphine oxide a sulfonate compound such as benzyl phenyl sulfide or tetramethyl thiuram monosulfide; an α-keto alcohol compound such as 1-hydroxycyclohexyl phenyl ketone; an azo compound such as azobisisobutyronitrile; Isoferrocene compound; thioxanthone compound such as thioxanthone; benzophenone, 2-(dimethylamino)-1-(4-morpholinylphenyl)-2-benzyl-1-butane Ketones, ethyl ketones, diphenyls such as 1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-, 1-(O-ethenylhydrazine) Ketone compound; peroxide compound; diketone compound such as diethyl hydrazine; benzoin; diphenyl oxime; 2,4-diethyl thioxanthone; , 2-diphenylmethane; 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]acetone; 2-chloroindole and the like.

Further, as the photopolymerization initiator (c), for example, a ruthenium compound such as 1-chloroindole or a photosensitizer such as an amine can be used.

The photopolymerization initiator (c) contained in the protective film-forming composition (IV-1) may be one type or two or more types. When two or more types are used, the combinations and ratios thereof may be Free to choose.

In the case of using the photopolymerization initiator (c), the content of the photopolymerization initiator (c) in the composition for forming a protective film (IV-1) relative to the content of the energy ray-curable compound (a) is 100. The parts by mass are preferably from 0.01 part by mass to 20 parts by mass, more preferably from 0.03 part by mass to 10 parts by mass, still more preferably from 0.05 part by mass to 5 parts by mass.

[filler (d)]

When the film for forming a protective film contains the filler (d), the protective film obtained by curing the film for forming a protective film is easily adjusted in thermal expansion coefficient, and the coefficient of thermal expansion is optimized for the object to be formed of the protective film. The reliability of the package obtained by the composite sheet for forming a protective film is further improved. Further, when the film for forming a protective film contains the filler (d), the moisture absorption rate of the protective film can be lowered or the heat dissipation property can be improved. Further, when the film for forming a protective film contains a filler (d) having an appropriate size, the surface roughness (Ra) of the surface (α) in the film for forming a protective film can be easily adjusted.

As the filler (d), for example, a material composed of a thermally conductive material can be cited.

The filler (d) may be any of an organic filler and an inorganic filler, and is preferably an inorganic filler.

Examples of preferred inorganic fillers include powders of cerium oxide, aluminum oxide, talc, calcium carbonate, titanium white, iron oxide, tantalum carbide, and boron nitride; and these inorganic filler materials are spheroidized. Beads; surface modification of these inorganic fillers; single crystal fibers of these inorganic fillers; glass fibers, and the like.

Among these, the inorganic filler is preferably cerium oxide or aluminum oxide, more preferably epoxy-modified cerium oxide.

The average particle diameter of the filler (d) is not particularly limited, but is preferably from 0.01 μm to 20 μm, more preferably from 0.1 μm to 15 μm, still more preferably from 0.3 μm to 10 μm. Further, in one aspect of the invention, the filler (d) has an average particle diameter of from 0.05 μm to 0.1 μm. When the average particle diameter of the filler (d) is in such a range, the adhesion to the object to be formed of the protective film can be maintained, and the decrease in the transmittance of light of the protective film can be suppressed.

In the present specification, the "average particle diameter" means a particle diameter (D ₅₀ ) at an integrated value of 50% in a particle size distribution curve obtained by a laser diffraction scattering method unless otherwise specified. The value.

The filler (d) which is contained in the protective film-forming composition (IV-1) and the film for forming a protective film may be one type or two or more types. When two or more types are used, the combination of these may be used. And the ratio can be arbitrarily chosen.

In the case of using the filler (d), 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 (IV-1) (that is, the formation of a protective film) The content of the filler (d) in the film is preferably from 2% by mass to 83% by mass, more preferably from 3% by mass to 68% by mass, even more preferably from 4% by mass to 30% by mass. By the content of the filler (d) being such a range, it is easier to adjust the above thermal expansion coefficient.

[coupler (e)]

By using a coupling agent having a functional group reactive with an inorganic compound or an organic compound as the coupling agent (e), the adhesion of the film for forming a protective film to the adherend and the adhesion can be improved. In addition, by using the coupling agent (e), the protective film obtained by curing the film for protective film formation is not resistant to heat resistance and water resistance is improved.

The coupling agent (e) is preferably a compound having a functional group reactive with a functional group having an energy ray-curable component (a) and a polymer (b) having no energy ray-curable group, and more preferably a decane. Coupling agent.

Preferred examples of the decane coupling agent include 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropylmethyldiethoxydecane, and 3-glycidoxypropyl group. Triethoxy decane, 3-glycidoxymethyl diethoxy decane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-methylpropenyloxypropyltrimethyl Oxydecane, 3-aminopropyltrimethoxydecane, 3-(2-aminoethylamino)propyltrimethoxydecane, 3-(2-aminoethylamino)propylmethyl Diethoxydecane, 3-(phenylamino)propyltrimethoxydecane, 3-anilinopropyltrimethoxydecane, 3-ureidopropyltriethoxydecane, 3-mercaptopropyltrimethyl Oxydecane, 3-mercaptopropylmethyldimethoxydecane, bis(3-triethoxydecylpropyl)tetrasulfide, methyltrimethoxydecane, methyltriethoxydecane, ethylene Trimethoxy decane, vinyl triethoxy decane, imidazolium, and the like.

The coupling agent (IV) and the protective film forming film may be used alone or in combination of two or more kinds. In the case of two or more types, these combinations may be used. And the ratio can be arbitrarily chosen.

In the case of using the coupling agent (e), the protective film-forming composition (IV-1) and the film for forming a protective film have a content of the coupling agent (e) with respect to the energy ray-curable component (a) and The total content of the energy ray-curable group-containing polymer (b) is 100 parts by mass, preferably 0.03 parts by mass to 20 parts by mass, more preferably 0.05 parts by mass to 10 parts by mass, still more preferably 0.1 part by mass to 5 parts by mass. . When the content of the coupling agent (e) is at least the above lower limit value, it is possible to obtain a more remarkable effect by using the coupling agent (e): the dispersibility of the filler (d) in the resin is improved, or The adhesion between the film for forming a protective film and the adherend is improved. Further, when the content of the coupling agent (e) is at most the above upper limit value, generation of outgas can be further suppressed.

[crosslinking agent (f)]

By using the crosslinking agent (F), the energy ray-curable component (a) or the polymer (b) having no energy ray-curable group is crosslinked, whereby the initial adhesion of the film for forming a protective film can be adjusted. And cohesion.

Examples of the crosslinking agent (f) include an organic polyvalent isocyanate compound, an organic polyimine compound, a metal chelate crosslinking agent (a crosslinking agent having a metal chelate structure), and an aziridine crosslinking. A reagent (a cross-linking agent having an aziridine group) or the like.

Examples of the organic polyvalent isocyanate compound include an aromatic polyisocyanate compound, an aliphatic polyvalent isocyanate compound, and an alicyclic polyisocyanate compound (hereinafter, these compounds may be collectively referred to simply as "aromatic polyisocyanate compounds"); a trimer such as an aromatic polyvalent isocyanate compound, an isocyanurate body or an adduct, a terminal isocyanate urethane prepolymer obtained by reacting the aromatic polyisocyanate compound or the like with a polyol compound, and the like. The term "adduct" means the aforementioned aromatic polyisocyanate compound, aliphatic polyisocyanate compound or alicyclic polyisocyanate compound, and is contained in ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane or castor oil. The reactant of the compound of the low molecular weight active hydrogen, as an example of the above-mentioned adduct, may be a benzodimethyl diisocyanate adduct of trimethylolpropane mentioned later. Further, the "terminal isocyanate urethane prepolymer" means a prepolymer having a urethane bond and having an isocyanate group at a molecular terminal portion.

As the above-mentioned organic polyvalent isocyanate compound, more specifically, for example, 2,4-toluene diisocyanate; 2,6-toluene diisocyanate; 1,3-benzenedimethyl diisocyanate; 1,4-dimethylbenzene Isocyanate; diphenylmethane-4,4'-diisocyanate; diphenylmethane-2,4'-diisocyanate; 3-methyldiphenylmethane diisocyanate; hexamethylene diisocyanate; isophorone Diisocyanate; dicyclohexylmethane-4,4'-diisocyanate; dicyclohexylmethane-2,4'-diisocyanate; addition of toluene diisocyanate to all or a part of hydroxyl groups of polyhydric alcohols such as trimethylolpropane A compound obtained by using one or more of hexamethylene diisocyanate and benzodimethyl diisocyanate; an isocyanuric acid diisocyanate or the like.

The organic polyimine compound may, for example, be N,N'-diphenylmethane-4,4'-bis(1-aziridinecarboxamide) or trimethylolpropane-tri-beta-nitrogen. Propidyl propionate, tetramethylolmethane-tri-β-aziridine propionate, N,N'-toluene-2,4-bis(1-aziridinecarbamamine) Based on melamine and the like.

When an organic polyvalent isocyanate compound is used as the crosslinking agent (f), it is preferred to use a hydroxyl group-containing polymer as the energy ray-curable component (a) or the polymer (b) having no energy ray-curable group. . When the crosslinking agent (f) has an isocyanate group, and the energy ray-curable component (a) or the polymer (b) having no energy ray-curable group has a hydroxyl group, the crosslinking agent (f) and the energy ray are used. The reaction of the curable component (a) or the polymer (b) having no energy ray-curable group can easily introduce the crosslinked structure into the film for forming a protective film.

The protective film-forming composition (IV-1) and the crosslinking agent (f) contained in the film for forming a protective film may be one type or two or more types. When two or more types are used, these are Combinations and ratios can be arbitrarily chosen.

In the case of using the crosslinking agent (f), in the protective film-forming composition (IV-1), the content of the crosslinking agent (f) is relative to the energy ray-curable component (a) and has no energy ray hardenability. The total content of the polymer (b) based on 100 parts by mass is preferably from 0.01 part by mass to 20 parts by mass, more preferably from 0.1 part by mass to 10 parts by mass, still more preferably from 0.5 part by mass to 5 parts by mass. When the content of the crosslinking agent (f) is at least the above lower limit value, a more remarkable effect by the use of the crosslinking agent (f) can be obtained. Further, when the content of the crosslinking agent (f) is at most the above upper limit value, excessive use of the crosslinking agent (f) can be suppressed.

[coloring agent (g)]

Examples of the colorant (g) include known coloring agents such as inorganic pigments, organic pigments, and organic dyes.

Examples of the organic pigment and the organic dye include an ammonium dye, a cyanine dye, a merocyanine dye, a croconium dye, a squalilium dye, and an anthraquinone. Pigment, polymethine dye, naphthoquinone dye, pyryl quinone dye, phthalocyanine dye, naphthalocyanine dye, naphthalene amide dye, azo dye, condensed azo dye, indigo a pigment, a perinone dye, an anthraquinone dye, a dioxane dye, a quinacridone dye, an isoindolinone dye, a quinophthalone pigment, a pyrrole dye, A thioindigo dye, a metal complex dye (metal stear salt dye), a dithiol metal complex dye, a nonylphenol dye, a triallylmethane dye, an anthraquinone dye, a naphthol A coloring matter, a methine azo dye, a benzimidazolone dye, a swainone pigment, and a threne pigment.

Examples of the inorganic pigment include carbon black, a cobalt dye, an iron dye, a chromium dye, a titanium dye, a vanadium dye, a zirconium dye, a molybdenum dye, an anthraquinone dye, a platinum dye, and ITO. (Indium Tin Oxide; indium tin oxide) dye, ATO (Antimony Tin Oxide) pigment, and the like.

The coloring agent (g) to be contained in the protective film-forming composition (IV-1) and the film for forming a protective film may be one type or two or more types. When two or more types are used, these combinations may be used. And the ratio can be arbitrarily chosen.

In the case of using the coloring agent (g), the content of the coloring agent (g) in the film for forming a protective film may be appropriately adjusted depending on the purpose. For example, printing may be performed on the protective film by laser irradiation, and by adjusting the content of the coloring agent (g) in the film for forming a protective film, the light transmittance of the protective film can be adjusted, and the print visibility can be adjusted. In this case, in the protective film-forming composition (IV-1), the ratio of the content of the colorant (g) to the total content of all the components other than the solvent (that is, the coloring agent in the film for forming a protective film ( The content of g) is preferably from 0.1% by mass to 10% by mass, more preferably from 0.4% by mass to 7.5% by mass, even more preferably from 0.8% by mass to 5% by mass. When the content of the coloring agent (g) is at least the above lower limit value, a more remarkable effect by the use of the coloring agent (g) can be obtained. In addition, when the content of the coloring agent (g) is at most the above upper limit value, excessive use of the coloring agent (g) can be suppressed.

[thermosetting component (h)]

The thermosetting component (h) contained in the protective film-forming composition (IV-1) and the film for forming a protective film may be one type or two or more types. When two or more types are used, these are The combination and ratio can be arbitrarily selected.

Examples of the thermosetting component (h) include an epoxy thermosetting resin, a thermosetting polyimide, a polyurethane, an unsaturated polyester, a polyoxyl resin, and the like. Epoxy thermosetting resin.

(epoxy thermosetting resin)

The epoxy thermosetting resin is composed of an epoxy resin (h1) and a thermosetting agent (h2). The epoxy-based thermosetting resin contained in the protective film-forming composition (IV-1) and the film for forming a protective film may be one type or two or more types. When two or more types are used, these are The combination and ratio can be arbitrarily selected.

‧Epoxy resin (h1)

Examples of the epoxy resin (h1) include known epoxy resins, and examples thereof include polyfunctional epoxy resins, biphenyl compounds, bisphenol A diglycidyl ether and hydrogenated products thereof, and o-cresol novolac epoxy. Two or more epoxy resins such as resin, dicyclopentadiene type epoxy resin, biphenyl type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, and phenyl skeleton type epoxy resin Compound.

As the epoxy resin (h1), an epoxy resin having an unsaturated hydrocarbon group can also be used. The epoxy resin having an unsaturated hydrocarbon group has higher compatibility with the acrylic resin than the epoxy resin having no unsaturated hydrocarbon group. Therefore, the reliability of the package obtained by 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 a compound in which a part of the epoxy group of the polyfunctional epoxy resin is replaced with a group having an unsaturated hydrocarbon group. Such a compound is obtained, for example, by subjecting (meth)acrylic acid or a derivative thereof to an addition reaction with an epoxy group.

In addition, examples of the epoxy resin having an unsaturated hydrocarbon group include a compound in which a group having an unsaturated hydrocarbon group is directly bonded to an aromatic ring or the like constituting the epoxy resin. The unsaturated hydrocarbon group is a polymerizable unsaturated group, and specific examples of the unsaturated hydrocarbon group include a vinyl group (Ethenyl group), a 2-propenyl group (allyl), and a (meth) acrylonitrile group. Methyl) acrylamide or the like is preferably an acrylonitrile group.

The number average molecular weight of the epoxy resin (h1) is not particularly limited, and is preferably from 300 to 30,000, more preferably from 400 to 3, in terms of the curability of the film for forming a protective film and the strength and heat resistance of the protective film. 10,000, especially 500 to 3000.

The epoxy equivalent of the epoxy resin (h1) is preferably from 100 g/eq to 1000 g/eq, more preferably from 150 g/eq to 800 g/eq.

The epoxy resin (h1) may be used singly or in combination of two or more. When two or more kinds are used in combination, the combination and ratio may be arbitrarily selected.

‧Heat hardener (h2)

The heat hardener (h2) functions as a hardener for the epoxy resin (h1).

The thermosetting agent (h2) is, for example, a compound having two or more functional groups reactive with an epoxy group in one molecule. Examples of the functional group include a phenolic hydroxyl group, an alcoholic hydroxyl group, an amine group, a carboxyl group, and a group in which an acid group is anhydride-formed. Preferably, the phenolic hydroxyl group, the amine group, or the acid group is anhydride-treated. More preferably, it is a phenolic hydroxyl group or an amine group.

In the thermosetting agent (h2), examples of the phenolic curing agent having a phenolic hydroxyl group include a polyfunctional phenol resin, a biphenol, a novolak type phenol resin, a dicyclopentadiene type phenol resin, and an aralkylphenol. Resin, etc.

In the thermosetting agent (h2), examples of the amine-based curing agent having an amine group include dicyandiamide (hereinafter sometimes abbreviated as "Dicyanodiamide; DICY").

The heat hardener (h2) may also have an unsaturated hydrocarbon group.

Examples of the thermosetting agent (h2) having an unsaturated hydrocarbon group include a compound in which a part of the hydroxyl group of the phenol resin is substituted with a group having an unsaturated hydrocarbon group, and a group in which an aromatic ring of the phenol resin is directly bonded to have an unsaturated hydrocarbon group. Compounds and the like.

The aforementioned unsaturated hydrocarbon group in the heat hardener (h2) is the same as the unsaturated hydrocarbon group in the above epoxy resin having an unsaturated hydrocarbon group.

When a phenolic curing agent is used as the thermosetting agent (h2), the thermosetting agent (h2) is preferably a phenol having a softening point or a high glass transition temperature in terms of improving the peeling property of the protective film from the support sheet. A hardener.

In the thermal curing agent (h2), the resin component such as a polyfunctional phenol resin, a novolac type phenol resin, a dicyclopentadiene phenol resin, or an aralkyl phenol resin preferably has a number average molecular weight of 300 to 30,000, more preferably It is 400 to 10,000, and particularly preferably 500 to 3,000.

In the thermal curing agent (h2), the molecular weight of the non-resin component such as biphenol or dicyandiamide is not particularly limited, and is, for example, preferably 60 to 500.

The heat-hardening agent (h2) can be used singly or in combination of two or more. When two or more types are used in combination, the combination and ratio can be arbitrarily selected.

In the case of using the thermosetting component (h), the content of the thermosetting agent (h2) relative to the content of the epoxy resin (h1) in the protective film-forming composition (IV-1) and the film for forming a protective film. 100 parts by mass, preferably 0.01 parts by mass to 20 parts by mass.

In the case of using the thermosetting component (h), the content of the thermosetting component (h) in the protective film-forming composition (IV-1) and the film for forming a protective film (for example, epoxy resin (h1) and The total content of the heat hardener (h2) is preferably from 1 part by mass to 500 parts by mass based on 100 parts by mass of the polymer (b) having no energy ray-curable group.

[General Additives (z)]

The general-purpose additive (z) can be a known general-purpose additive, and can be arbitrarily selected according to the purpose, and is not particularly limited. Examples of preferred general-purpose additives include plasticizers, antistatic agents, antioxidants, getters, and the like. .

The protective film forming composition (IV-1) and the protective film forming film may be used alone or in combination of two or more kinds. And the ratio can be arbitrarily chosen.

In the case of using the general-purpose additive (z), the content of the general-purpose additive (z) in the protective film-forming composition (IV-1) and the film for forming a protective film is not particularly limited, and may be appropriately selected according to the purpose.

[solvent]

The protective film-forming composition (IV-1) preferably further contains a solvent. The handling property (IV-1) for forming a protective film containing a solvent is excellent in handleability.

The solvent is not particularly limited, and examples of preferred solvents include hydrocarbons such as toluene and xylene; methanol, ethanol, 2-propanol, isobutanol (2-methylpropan-1-ol), and 1 - an alcohol such as butanol; an ester such as ethyl acetate; a ketone such as acetone or methyl ethyl ketone; an ether such as tetrahydrofuran; a decylamine such as dimethylformamide or N-methylpyrrolidone (a compound having a guanamine bond) )Wait.

The solvent contained in the protective film-forming composition (IV-1) may be one type or two or more types. When two or more types are used, the combination and ratio may be arbitrarily selected.

The solvent contained in the protective film-forming composition (IV-1) is preferably methyl ethyl ketone, in that the component contained in the protective film-forming composition (IV-1) is more uniformly mixed. , toluene or ethyl acetate.

<<Method for Producing Composition for Protective Film Formation>>

The protective film forming composition such as the protective film-forming composition (IV-1) is obtained by blending the components constituting the protective film-forming composition.

The order of addition of each component is not particularly limited, and two or more components may be added at the same time.

When a solvent is used, it can be used by mixing a solvent with any of the formulation components other than the solvent to preliminarily dilute the formulation component; or by using the following method, that is, not Any of the formulation components other than the solvent is diluted in advance to mix the solvent with these formulation components.

The method of mixing the components at the time of preparation is not particularly limited, and may be appropriately selected from the following known methods: a method of mixing by stirring a stirring blade or a stirring blade, a method of mixing using a mixer, and applying ultrasonic waves for mixing. Method and so on.

The temperature and time when the components are added and mixed are not particularly limited as long as the respective components are not deteriorated, and it is preferably adjusted, and the temperature is preferably from 15 ° C to 30 ° C.

◇Protective film forming film and method for producing protective film forming composite sheet

<Method for Producing Film for Protective Film Formation (1)>

The first aspect of the method for producing a film for forming a protective film of the present invention can be produced by, for example, a release film having a surface roughness (Ra) of at least one surface of from 0.03 μm to 2.0 μm (sometimes On the surface having the surface roughness described above, which is referred to as a first release film, a protective film-forming composition is applied and dried as necessary. In this case, the surface roughness (Ra) of the surface of the first release film is preferably from 0.03 μm to 1.8 μm. In addition, the film for forming a protective film of the present invention may have a surface opposite to the surface on which the first release film is attached (that is, the surface (β) in the film for forming a protective film produced as described above. Another adhesive film (sometimes referred to as a second release film) is attached.

In the present specification, a film for forming a protective film having a release film may be referred to as a "sheet for forming a protective film".

<Method for Producing Film for Protective Film Formation (2)>

In the second aspect of the method for producing a film for forming a protective film of the present invention, the filler having a predetermined average particle diameter is blended in the protective film-forming composition to expose the surface of the film for forming a protective film (surface). α) forms a face having a predetermined surface roughness (Ra). In this case, a surface having a surface roughness (Ra) of 0.03 μm to 2.0 μm can be formed by blending a filler having an average particle diameter of 0.01 μm to 20 μm.

<Method for Producing Composite Sheet for Forming Protective Film>

One aspect of the method for producing a composite sheet for forming a protective film of the present invention will be described below.

Applying a protective film forming composition to a surface having the surface roughness in a release film (sometimes referred to as a first release film) having a surface roughness (Ra) of at least one surface of 0.03 μm to 2.0 μm The film for forming a protective film is formed by drying it as needed, and the second release film is bonded to the exposed surface of the film for forming a protective film.

The composite sheet for forming a protective film of the present invention can be produced by bonding the exposed surface (that is, the surface (β)) of the film for forming a protective film from which the second release film has been removed to the surface of the support sheet.

Method for using ruthenium film for protective film formation and composite sheet for forming protective film

The film for forming a protective film or the sheet for forming a protective film of the present invention can be used, for example, by the method described below.

In other words, the surface (α) having the side of the first release film in the sheet for forming a protective film is attached to the back surface of the semiconductor wafer (the electrode) by the film for forming a protective film for forming the protective film. Form the face on the opposite side).

At this time, when the film for forming a protective film is attached to a position on the back surface of the semiconductor wafer which is deviated from the position to be attached, the film for forming a protective film attached to the back surface of the semiconductor wafer is peeled off. Specifically, the surface of the damaged protective film forming film opposite to the surface to be attached to the semiconductor wafer, that is, the surface (β), is attached at an appropriate position, and the so-called secondary processing adhesive sheet is attached to the peeling. The adhesive sheet for secondary processing is peeled off from the semiconductor wafer integrally with the film for forming a protective film which is damaged by the coating.

In this case, the surface (α) of the film for forming a protective film is formed with a surface roughness (Ra) of a predetermined thickness of 0.038 μm or more. Therefore, the film for forming a protective film to be attached can be used together with the adhesive sheet for secondary processing. Smoothly stripped. In other words, the semiconductor wafer can be prevented from being damaged by the force at the time of peeling or a part of the film for forming a protective film remains on the back surface of the semiconductor wafer. Therefore, a new sheet for forming a protective film (film for forming a protective film) is prepared directly or after the minimum cleaning of the semiconductor wafer, and the first release film is peeled off and attached again. The appropriate position of the back surface of the aforementioned semiconductor wafer.

In the same manner as in the prior art, the film for forming a protective film is irradiated with an energy ray, and the film for forming a protective film is cured to form a protective film, and the second release film is peeled off, and the exposed surface of the protective film is exposed. (β)) is attached to a support sheet, and by cutting, the semiconductor wafer is divided together with the protective film to form a semiconductor wafer.

Hereinafter, the semiconductor wafer of the obtained semiconductor wafer with the protective film obtained is flip-chip bonded to the circuit surface of the substrate by the same method as the prior art, and then a semiconductor package is produced. Then, the target semiconductor device can be fabricated using the semiconductor package.

The composite sheet for forming a protective film of the present invention can be used, for example, by the method shown below.

In other words, the composite film for forming a protective film is attached to the back surface of the semiconductor wafer (the surface opposite to the electrode forming surface) by the protective film forming film of the protective film forming composite sheet.

In this case, when the composite sheet for forming a protective film is attached to a position on the back surface of the semiconductor wafer that is away from the position to be attached, the composite sheet for forming a protective film attached to the back surface of the semiconductor wafer is attached. Stripped. Specifically, the composite sheet for forming a protective film which is damaged and attached at an appropriate position is integrally peeled off from the semiconductor wafer.

In this case, the surface (α) of the composite sheet for forming a protective film is formed with a surface roughness (Ra) of a predetermined thickness of 0.038 μm or more. Therefore, the composite sheet for forming a protective film to be attached can be smoothly peeled off. In other words, the semiconductor wafer can be prevented from being damaged by the force at the time of peeling or a part of the composite sheet for forming a protective film remains on the back surface of the semiconductor wafer. Therefore, after the minimum surface cleaning of the back surface of the semiconductor wafer is performed, a new composite film for forming a protective film is prepared, and the first release film is peeled off and attached to the back surface of the semiconductor wafer. The proper location.

Hereinafter, the semiconductor wafer is formed by the same method as the prior art, that is, by irradiating the energy ray to be hardened, and by dividing the semiconductor wafer together with the protective film.

Then, the semiconductor wafer is held in a state in which the protective film is attached (that is, in the form of a semiconductor wafer with a protective film attached thereto) and pulled out from the support sheet to be picked up.

Hereinafter, the semiconductor wafer of the obtained semiconductor wafer with the protective film obtained is flip-chip bonded to the circuit surface of the substrate by the same method as the prior art, thereby fabricating a semiconductor package. Then, the target semiconductor device can be fabricated using the semiconductor package.

In the case where the film for forming a protective film is cured to form a protective film and then dicing, the film is formed by using the film for forming a protective film or the composite sheet for forming a protective film of the present invention. The order can be reversed. In other words, after the composite sheet for forming a protective film is attached to the back surface of the semiconductor wafer, the semiconductor wafer is divided together with the film for forming a protective film by dicing to form a semiconductor wafer. Then, the film for forming a protective film to be divided is irradiated with an energy ray to cure the film for forming a protective film to form a protective film. In the same manner as described above, the semiconductor wafer with the protective film is pulled away from the support sheet and picked up to produce a target semiconductor device.

(矽 wafer regeneration method)

The film for forming a film for protective film of the present invention is obtained by laminating a film formed of a film (α) on a ruthenium wafer, and peeling off the film for forming a protective film to regenerate the ruthenium wafer, for example, The method of regenerating the wafer after step (1) to step (2).

Step (1): the adhesive layer of the secondary processing adhesive sheet having the substrate and the adhesive layer is attached to the surface of the protective film for forming the laminate and attached to the surface of the germanium wafer (α) ) is the step of the opposite side of the surface (β).

Step (2): The step of peeling off the secondary processing adhesive sheet attached in the step (1), and peeling off the film for forming a protective film attached to the silicon wafer.

The above-described method for regenerating the tantalum wafer utilizes the properties of the film for forming a protective film of the present invention having excellent secondary workability, that is, when the film is to be attached after being attached to the tantalum wafer, the wafer may not be used. It is broken and peeled off without causing any residue.

Further, the method for regenerating the tantalum wafer can be applied not only to the laminate in which the tantalum wafer is attached to the surface (α) of the film for forming a protective film of the present invention, but also to the application after 24 hours of attachment. In the left and right, the laminate of the state in which the adhesion between the wafer and the film for forming a protective film is improved.

<Step (1)>

The step (1) is a step of attaching the adhesive layer having the adhesive sheet of the substrate and the adhesive layer to the surface of the protective film for forming the laminate and attaching to the surface of the germanium wafer ( α) is the surface (β) on the opposite side.

The adhesive sheet for secondary processing used in this step has a base material and an adhesive layer. In the case where the composite sheet having the support composed of the adhesive sheet is attached to the tantalum wafer, the support may be used as the "adhesive sheet for secondary processing" in this step.

As the substrate, a resin film is preferred.

The adhesive for forming the pressure-sensitive adhesive layer is not particularly limited as long as it has adhesion to the extent that the protective film-forming sheet can be peeled off from the tantalum wafer in the step (2).

Specific examples of the pressure-sensitive adhesive include an acrylic pressure-sensitive adhesive, a urethane-based pressure-sensitive adhesive, and a polyoxynoxy-based pressure-sensitive adhesive.

The shape of the secondary processing adhesive sheet is not particularly limited, and is preferably the same as the protective film forming sheet or the protective film forming composite sheet from the viewpoint of workability in the following step (2). The shape of the protective sheet or the adhesive sheet having a larger shape than the protective film forming sheet or the protective film forming composite sheet.

As the adhesive sheet for secondary processing, a support sheet in a composite sheet for forming a protective film of the present invention or a cut sheet of a commercially available product can be used.

As a method of attaching the surface (β) to the adhesive layer of the adhesive sheet in this step, it can be attached by using a device or by manual work.

<Step (2)>

In the step (2), the secondary processing adhesive sheet attached in the step (1) is peeled off, and the film for forming a protective film attached to the silicon wafer is peeled off.

In this step, since the surface roughness (Ra) of the surface (α) attached to the tantalum wafer in the film for forming a protective film of the present invention is adjusted to the above range, the step (1) is attached. The adhesive sheet for secondary processing on the surface (β) is peeled off, and the film for forming a protective film is also peeled off together, whereby the film for forming a protective film can be peeled off from the wafer.

The peeling speed and the peeling angle of the adhesive sheet are not particularly limited and can be appropriately set.

Further, in this step, the adhesive tape may be peeled off by using a device. However, from the viewpoint of workability, it is preferable to peel off the adhesive sheet by hand, and to peel off the film for forming a protective film from the wafer.

In this step, after peeling off the film for forming a protective film, the surface of the ruthenium wafer may be washed with an organic solvent such as ethanol as necessary.

By the above steps, the wafer in which the film for forming a protective film is temporarily attached can be regenerated.

[Examples]

Hereinafter, the present invention will be described in more detail by way of specific examples. However, the present invention is not limited by the examples shown below.

The components for producing a composition for forming a protective film are shown below.

‧ energy line hardening ingredients

(a2)-1: tricyclodecane dimethylol diacrylate ("KAYARAD R-684" manufactured by Nippon Kayaku Co., Ltd., bifunctional ultraviolet curable compound, molecular weight 304).

‧ polymer without energy line hardening

(b)-1: butyl acrylate (hereinafter abbreviated as "BA") (10 parts by mass), methyl acrylate (hereinafter abbreviated as "MA") (70 parts by mass), glycidyl methacrylate (hereinafter referred to as glycerol methacrylate) Acrylic resin obtained by copolymerizing "GMA" (5 parts by mass) and 2-hydroxyethyl acrylate (hereinafter referred to as "HEA") (15 parts by mass) (weight average molecular weight: 300,000, glass transition temperature - 1 ° C).

‧Photopolymerization initiator

(c)-1: 2-(Dimethylamino)-1-(4-morpholinylphenyl)-2-benzyl-1-butanone (Irgacure (registered trademark) 369, manufactured by BASF Corporation) ).

(c)-2: Ethylketone, 1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-, 1-(O-ethylindenyl) (Irgacure (registered trademark) OXE02" manufactured by BASF Corporation).

‧Filler

(d)-1: cerium oxide filler (surface modifying group: epoxy group) having an average particle diameter of 100 nm.

(d)-2: cerium oxide filler (surface modifying group: epoxy group) having an average particle diameter of 50 nm.

‧ coupling agent

(e)-1: 3-methacryloxypropyltrimethoxydecane ("KBM-503" manufactured by Shin-Etsu Chemical Co., Ltd., decane coupling agent).

‧Colorant

(g)-1: 32 parts by mass of a phthalocyanine-based blue pigment (Pigment Blue 15:3), 18 parts by mass of an isoindolinone-based yellow pigment (Pigment Yellow 139), and a lanthanide red pigment (Pigment Red) 177) A pigment obtained by pigmenting at a mass ratio of 50 mass parts of the above three types of dyes/the amount of styrene acrylic resin = 1/3 (mass ratio).

[Example 1]

<Manufacture of composite sheet for forming a protective film>

(Manufacture of protective film forming composition (IV-1))

Energy ray curable component (a2)-1 (20 parts by mass), polymer (b)-1 (22 parts by mass), photopolymerization initiator (c)-1 (0.3 parts by mass), photopolymerization initiation (c)-2 (0.3 parts by mass), filler (d)-1 (2 parts by mass, that is, the total mass of the solid component in the protective film forming composition (IV-1) is 4.3 mass %), coupling agent (e)-1 (0.4 parts by mass), and coloring agent (g)-1 (2 parts by mass), dissolved or dispersed in methyl ethyl ketone, stirred at 23 ° C, thereby preparing The composition for forming a protective film (IV-1) having a solid content concentration of 50% by mass. Further, the amount of each component shown here is the amount of the solid component. In addition, when the column containing the component in Table 1 is "-", it means that the protective film-forming composition (IV-1) does not contain the component.

<Manufacture of Sheet for Forming Protective Film>

The first release film having a polyethylene terephthalate film having a surface roughness (Ra) of 1.8 μm (having a thickness of 80 μm or less, sometimes referred to as "P3") has the surface roughness (Ra). On the surface, the protective film-forming composition (IV-1) was applied by a knife coater, and dried at 100 ° C for 2 minutes to prepare an energy-curable protective film forming film (13) having a thickness of 25 μm. -1.

Then, the second release film (SP-PET382150) manufactured by Lintec Co., Ltd., which has been subjected to a release treatment on a single side of a polyethylene terephthalate film, has a thickness of 38 μm. Hereinafter, it may be expressed as " The peeling-treated surface of P2") is bonded to the exposed surface of the film for protective film formation (13)-1 obtained above, and the sheet for forming a protective film is formed, and the sheet for forming a protective film is a first peeling film or a protective film. The film for formation (13)-1 and the second release film are sequentially laminated in the thickness direction of these.

(Example 2)

A release film (hereinafter sometimes referred to as "P4") using polyethylene terephthalate having a surface roughness (Ra) of 0.040 μm was used in the same manner as in Example 1 except that P3 was used as the first release film. In the manner of making a film for forming a protective film.

(Example 3)

A release film (hereinafter sometimes referred to as "P4") using polyethylene terephthalate having a surface roughness (Ra) of 0.040 μm is used instead of P3 as a second release film, and a film for forming a protective film (13) is used. In the same manner as in Example 1, except that the film for protective film formation (13)-1 was used, a sheet for forming a protective film was produced. The film for protective film formation (13)-2 is formed by using the protective film of Example 1 except that 5 parts by mass of the filler (d)-2 is used instead of 2 parts by mass of the filler (d)-1. It was produced in the same manner as the film (13)-1.

(Example 4)

(Manufacture of adhesive composition (I-4))

A non-energy-curable adhesive composition (I-4) having a solid content concentration of 30% by mass, wherein the adhesive composition (I-4) contains an acrylic polymer (100 parts by mass, a solid content) And a trifunctional phthalic diisocyanate-based crosslinking agent ("Takenate D110N" manufactured by Mitsui Takeda Chemical Co., Ltd.) (10.7 parts by mass, a solid component), and further contains methyl ethyl ketone as a solvent. The acrylic polymer is obtained by copolymerizing 2-ethylhexyl acrylate (hereinafter abbreviated as "2EHA") (36 parts by mass), BA (59 parts by mass), and HEA (5 parts by mass), and The weight average molecular weight is 600,000.

(Support for the manufacture of tablets)

The above-mentioned peeling-treated surface of a release film ("SP-PET381031" manufactured by Lintec Co., Ltd., thickness: 38 μm) which was subjected to a release treatment on a single side of a polyethylene terephthalate film by a polyphthalic acid treatment was applied as described above. The adhesive composition (I-4) was dried by heating at 120 ° C for 2 minutes to form a non-energy-curable adhesive layer having a thickness of 10 μm.

Then, on the exposed surface of the adhesive layer, a polypropylene-based film (Young's ratio: 400 MPa, thickness: 80 μm, hereinafter, referred to as "S1") may be adhered to the exposed surface of the adhesive layer, thereby obtaining one of the substrates. The support sheet (10)-1 having the aforementioned adhesive layer on the surface.

(Manufacture of composite sheet for forming a protective film)

A film (13)-1 for forming a protective film for energy ray curability having a thickness of 25 μm was produced in the same manner as in Example 1.

Then, the release film is removed from the adhesive layer in the support sheet (10)-1 obtained above, and the film for protective film formation (13)-1 obtained as described above is bonded to the exposed surface of the adhesive layer. The composite sheet for forming a protective film is formed on the exposed surface, and the composite sheet-based substrate for forming a protective film, the adhesive layer, and the protective film forming film (13)-1 and the film (P3) are sequentially laminated in the thickness direction. Made. The composition of the obtained composite sheet for forming a protective film is shown in Table 2.

(Comparative Example 1)

A film of polyethylene terephthalate having a surface roughness (Ra) of 0.026 μm (hereinafter sometimes referred to as "P5") was used as the first release film, and was produced in the same manner as in Example 1. A sheet for forming a protective film.

(Comparative Example 2)

A film of polyethylene terephthalate (hereinafter sometimes referred to as "P6") having a surface roughness (Ra) of 0.020 μm was used as the first release film, and was produced in the same manner as in Example 1. A sheet for forming a protective film.

(Comparative Example 3)

A film (P6) using a polyethylene terephthalate having a surface roughness (Ra) of 0.020 μm is used as the first release film, and a film for forming a protective film (13)-2 is used instead of the film for forming a protective film (13). A sheet for forming a protective film was produced in the same manner as in Example 1 except for the above. In the film for protective film formation (13)-2, 5 parts by mass of the filler (d)-2 is used instead of the filler (d)-1 of 2 parts by mass, and the protective film of the first embodiment is used. The film was formed in the same manner as the film (13)-1.

(Comparative Example 4)

A polyethylene terephthalate film (P5) was used instead of the polyethylene terephthalate film (P3) as a release film using a surface roughness (Ra) of 0.026 μm, and other examples were used. 4 A sheet for forming a protective film was produced in the same manner. The protective film forming composition (IV-1) is applied to the surface of the film (P5) having the surface roughness (Ra).

(Measurement of surface roughness (Ra))

The optical interference type surface shape measuring device (manufactured by Veeco Metrology Group, product name "WYKO WT1100") was used in the PSI (Phase Shift Interferometry) mode at a magnification of 10 times, and the measurement target was measured in accordance with JIS B0601:2001. The surface roughness (Ra) of the surface was measured.

(Evaluation of secondary workability of film for forming a protective film)

The first release film of the protective film formation sheet or the protective film formation composite sheet produced in the examples and the comparative examples is removed, and the surface (α) of the exposed protective film formation film is laminated on the surface. 2000 grinding enamel wafer (diameter: 8 吋, thickness: 280 μm) on the grinding surface, using a placement machine (Lintec Co., Ltd., product name "Adwill RAD-3600 F/12"), one side heated to 70 ° C Attached on one side.

When a sheet for forming a protective film is used after the attachment, a commercially available general-purpose dicing tape (Lintec) is adhered to the surface of the film for forming a protective film which is removed by removing the second release film at room temperature (25 ° C). The adhesive layer in the company's trade name "Adwill D-510T" is used as a secondary processing adhesive sheet.

Then, when the protective film forming sheet is used, the general dicing tape is peeled off by hand work, and when the protective film forming composite sheet is used, the support sheet is peeled off, thereby observing whether or not the protective film can be formed together. The film was peeled off from the wafer, and the presence or absence of the residue on the surface of the germanium wafer after the peeling was performed, and the secondary workability of the sheet for forming a protective film was evaluated by the following criteria.

○: The film for forming a protective film can be completely peeled off from the wafer. The residue of the film for forming a protective film which was visually confirmed was not observed on the wafer after the peeling. Alternatively, the film for forming a protective film can be peeled off from the tantalum wafer. However, a small amount of the remaining film of the protective film forming film can be seen on the wafer after peeling, and the film can be completely removed by wiping with ethanol.

×: The wafer was damaged during the peeling. Alternatively, the film for forming a protective film is not peeled off, and the remaining film of the film for forming a protective film which is difficult to be rubbed with ethanol is confirmed on the wafer after the peeling.

Alternatively, it is known that the time when the wafer is not peeled off to the extent that it cannot be peeled off is set to be defective (×).

[Table 2]  

According to the above results, in the case of using the protective film forming sheet of Examples 1 to 3 or the protective film forming composite sheet of Example 4, the surface (α) of the protective film is 0.038 μm or more. A good secondary processability is obtained.

On the other hand, in the case of using the protective film forming sheet of Comparative Example 1 to Comparative Example 3 or the composite sheet for forming a protective film of Comparative Example 4, the surface roughness of the surface (α) of the protective film forming film ( Ra) is less than 0.038 μm. Therefore, when the film for forming a protective film is peeled off from the back surface of the semiconductor wafer, the semiconductor wafer is broken, or a part of the film for forming a protective film remains on the back surface of the semiconductor wafer, and the secondary workability is poor. .

(industry availability)

The invention can be used to fabricate semiconductor devices.

Claims (3)

 A film for forming a protective film is a film for forming an energy ray-curable protective film; and at least one surface (α) of the film for forming a protective film has a surface roughness (Ra) of 0.038 μm or more.    The film for forming a protective film according to claim 1, wherein the surface roughness (Ra) of the surface (α) is 2.0 μm or less.    A composite sheet for forming a protective film, comprising the film for forming a protective film according to claim 1 or 2, wherein the surface (β) opposite to the surface (α) of the film for forming a protective film is The aforementioned support sheets are opposed to each other.