TW201806978A - Film for forming protective film and composite sheet for forming protective film - Google Patents

Abstract

The present invention relates to an energy ray-curable film for forming a protective film, wherein when a protective film is formed by irradiation with an energy ray to the energy ray-curable film for forming a protective film, a surface roughness (Ra) of at least one surface ([beta]) of the protective film is not less than 0.038 [mu]m.

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 present application claims priority to Japanese Patent Application No. 2016-92009, 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 sometimes formed as a protective film on the back surface of the bare semiconductor wafer, and incorporated into the semiconductor device in the form of a semiconductor wafer with a protective film.

The protective film is used to prevent cracking of the semiconductor wafer after the cutting step or packaging.

In order to form such a protective film, for example, a composite sheet for forming a protective film having a film for forming a protective film for forming a protective film on a support sheet is used. In the composite sheet for forming a protective film, the film for forming a protective film can be formed into a protective film by curing, and the support sheet can be used as a dicing sheet, whereby the protective film can be formed into a protective film integrally formed with the dicing sheet. A composite sheet for forming.

In the composite sheet for forming a protective film, for example, a composite sheet for forming a protective film having a film for forming a protective film having thermosetting properties is mainly used, and the film for forming a thermosetting protective film is formed by curing by heating. Protective film. In this case, for example, on the back surface of the semiconductor wafer (the surface opposite to the surface on which the electrode is formed), the film for forming a protective film by thermosetting is attached, and then the composite sheet for forming a protective film is attached, and then heated. The film for forming a protective film is cured to form a protective film, and the semiconductor wafer is divided together with the protective film by dicing to form a semiconductor wafer. Then, the state in which the semiconductor wafer is adhered to the protective film is maintained, and the support sheet is pulled away to be picked up. Further, there is a case where the curing and cutting of the film for forming a protective film are performed in the reverse order.

However, since the heat curing of the film for forming a thermosetting protective film usually takes about several hours, it is desirable to shorten the curing time. In view of the above, the industry is investigating a film for forming a protective film which can be cured by irradiation with an energy ray such as ultraviolet rays for forming a protective film. For example, revealing: forming An energy ray-curable protective film for a protective film having a high hardness and excellent adhesion to a semiconductor wafer (see Patent Document 2).

[Previous Technical Literature]

[Patent Literature]

Patent Document 1: Japanese Patent No. 5144433.

Patent Document 2: Japanese Laid-Open Patent Publication No. 2010-031183.

However, it is not determined whether or not the adhesion of the energy ray-curable protective film disclosed in Patent Document 1 to the support sheet is suitable. Further, the energy ray-curable wafer protective film disclosed in Patent Document 2 also discloses an energy ray-curable wafer protective film formed on a support sheet, but it is not determined whether or not the adhesion to the support sheet is suitable. In the film for forming a protective film disclosed in Patent Document 1 and Patent Document 2, the pick-up property is not clear.

In view of the above, it is an object of the present invention to provide a film for forming a protective film for energy ray-hardening and a film for forming a protective film comprising the film for forming a protective film, which can be used for a semiconductor wafer or a semiconductor wafer. A protective film is formed on the back side and has good pick-up properties.

In order to solve the problem, the present invention provides a film for forming a protective film for an energy ray-curable film. When the film for forming a protective film is irradiated with an energy ray to form a protective film, the surface roughness of at least one surface (β) of the protective film is provided. (Ra) is 0.038 μm or more.

In the film for forming a protective film of the present invention, the surface roughness (Ra) of the surface (β) is preferably 1.5 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, wherein the surface (β) of the film for forming a protective film faces the support sheet.

According to the invention, there is provided a composite sheet for forming a protective film, comprising a film for forming a protective film for energy ray-curable, which can form a protective film on a back surface of a semiconductor wafer or a semiconductor wafer, and has a good pick-up Fitness.

1C, 1D‧‧‧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

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 film for forming a protective film of the present invention.

◇Protective film forming film

When the film for forming a protective film of the present invention is energy ray-curable, and the film for forming a protective film is irradiated with an energy ray to form a protective film, the surface roughness (Ra) of at least one surface (β) of the 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. 3 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. 3, 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 semiconductor wafer is referred to as "surface (β)".

The surface roughness (Ra) of at least one surface (β) of the film for forming a protective film of the present invention is preferably 0.038 μm or more, and preferably 1.5 μm or less.

One aspect of the present invention relates to a film for forming a protective film, which has energy ray curability and is used to form a protective film on a back surface of a semiconductor wafer or a semiconductor wafer, and to protect the film for forming a protective film from energy rays. In the case of the film, the surface roughness (Ra) of the surface (β) on the side opposite to the surface (α) attached to the side of the semiconductor wafer or the semiconductor wafer is 0.038 μm or more. The foregoing and attached to a semiconductor wafer or a semiconductor wafer The surface roughness (Ra) of the surface (β) on the opposite side is preferably 1.5 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; When the film for forming a protective film is irradiated with an energy ray to form a protective film, the surface roughness (Ra) of the surface (β) on the side directly contacting the first release film in the protective film is 0.038 μm or more. The surface roughness (Ra) of the surface (β) attached to the side of the first release film is preferably 1.5 μm or less.

The surface roughness (Ra) of the surface of the first release film which is in direct contact with the surface (β) of the film for forming a protective film is preferably from 0.03 μm to 2.0 μm, more preferably from 0.05 μm to 1.8 μm. When the film for forming a protective film is directly laminated on the surface of the release film having such a surface roughness (Ra), and the protective film forming film is irradiated with an energy ray to form a protective film, at least one of the protective films may be used. The surface roughness (Ra) of (β) is adjusted to be 0.038 μm or more and 1.5 μm or less. In other words, the surface (α) of the film for forming a protective film opposite to the side to which the first release film is attached is attached to the back surface of the semiconductor wafer or the semiconductor wafer, and the film for forming a protective film is irradiated. The energy ray is used as a protective film, and the surface roughness (Ra) of the surface (β) of the protective film can be adjusted to 0.038 μm or more and 1.5 μm or less.

In the film for forming a protective film of the present invention, the surface roughness (Ra) of the surface (β) is preferably from 0.038 μm to 1.5 μm, more preferably from 0.04 μm to 1.47 μm, still more preferably from 0.08 μm to 1.47 μm. Preferably 0.8 μm to 1.43 μm.

In the present specification, the surface roughness (Ra) of the surface (β) 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

In the composite film for forming a protective film of the present invention, the film for protective film formation having an energy ray-curable property is provided on the support sheet, and when the film for forming a protective film is irradiated with an energy ray to form a protective film, at least one surface of the protective film (β) The surface roughness (Ra) is 0.038 μm or more.

In the composite sheet for forming a protective film of the present invention, it is preferable that the surface (β) of the film for forming a protective film faces the support sheet.

The surface (β) 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 1.5 μm or less. Further, in the film for forming a protective film in the composite sheet for forming a protective film of the present invention, the surface roughness (Ra) of the surface (β) is preferably from 0.038 μm to 1.5 μm, more preferably from 0.04 μm to 1.47 μm. More preferably, it is 0.08 μm to 1.47 μm, and further preferably 0.8 μm to 1.43 μm.

When the film for forming a protective film is irradiated with an energy ray to form a protective film, the adhesive force between the protective film and the support sheet may be 50 mN/25 mm to 1500 mN/25 mm.

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 (β) of the film for forming a protective film in the composite sheet for forming a protective film can be obtained by the embodiment. The measurement method described is measured.

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, when the film for forming a protective film is irradiated with an energy ray to form a protective film, the surface roughness (Ra) of at least one surface (β) of the protective film is 0.038 μm or more, whereby the protective film of the present invention is formed. The composite sheet has good pick-up suitability, for example, the target semiconductor wafer can be picked up with high selectivity, at which time cracking and defect of the semiconductor wafer are suppressed. Further, the adhesive force between the protective film and the support sheet becomes, for example, 50 mN/25 mm to 1500 mN/25 mm, and has good pick-up property.

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 this case, the protective film can be formed by hardening for 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, radiation, 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. Electron beam can be irradiated 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 more remarkable effects of the present invention, it is preferably from 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, and the phrase "the plural 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", and so-called "Multiple layers are different from each other" means that "at least one of the constituent materials and thickness of each layer is different from each other".

As a preferable support sheet, for example, a support sheet in which an adhesive layer is laminated on a substrate in direct contact is used, and the support sheet is formed on the substrate. A support sheet in which a layer of an adhesive layer is laminated, a support sheet composed only of a substrate, and the like. In the present invention, a support sheet composed only of a substrate is preferred.

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 1C for forming a protective film shown here does not have an adhesive layer. 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. The adhesive agent layer 16 is formed by peeling off the surface of the adhesive film forming film 13 on the surface 13a of the protective film forming film 13 and the surface 16a (upper surface and side surface) of the adhesive layer 16 for the jig. Membrane 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 film 1C for forming a protective film shown in FIG. 1 is used in a state in which a semiconductor wafer is attached 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.

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. 1 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. 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. On the back surface of the semiconductor wafer (not shown), a region in the vicinity of the peripheral edge portion of the film for protective film formation 13 is attached to a jig such as a ring frame.

As described above, the composite sheet for forming a protective film of the present invention may further comprise an adhesive layer for a jig. However, as shown in Fig. 1, the composite sheet for forming a protective film of the present invention having an adhesive layer for a jig is preferably used as a protective film. An adhesive layer for a jig is provided on the film for formation.

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 3, and may be modified or deleted as shown in FIGS. 1 to 3 without departing from the effects of the present invention. The composite film for forming a protective film is partially formed, or another structure is added to the composite sheet for forming a protective film described above.

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.

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

Among the inventions in which the film for forming a protective film has energy ray curability, the support sheet preferably transmits energy rays.

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 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 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 low density polyethylene (LDPE), linear low density polyethylene (LLDPE), and high density polyethylene (HDPE; High density polyethylene); polyolefins other than polyethylene such as polypropylene, polybutene, polybutadiene, polymethylpentene, norbornene resin; ethylene-vinyl acetate copolymer, ethylene-(methyl ) an ethylene-based copolymer such as an acrylic copolymer, an ethylene-(meth)acrylate copolymer or an ethylene-borneene copolymer (a copolymer obtained by using ethylene as a monomer); a chlorine such as a polyvinyl chloride or a vinyl chloride copolymer; Vinyl resin (resin obtained using vinyl chloride as a monomer); polystyrene; polycycloolefin; polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, Polyethylene isophthalate, poly(2,6-naphthalenedicarboxylic acid ethylene glycol), polyesters such as wholly aromatic polyesters having an aromatic ring group in all structural units; copolymerization of two or more kinds of the aforementioned polyesters Poly(meth)acrylate;polyurethane;polyurethane amide;polyimine;polyamine;polycarbonate;fluororesin;polyacetal;modified polyphenylene ether ; polyphenylene sulfide; polyfluorene; 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". About (meth)acrylic acid Similar terms are used.

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.

In the present specification, the term "thickness" means a value obtained by measuring any five parts of an object by a contact thickness meter and expressing the average of the measured thicknesses.

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. Object Wait.

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 preferably transmits energy rays.

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 surface roughness (Ra) of the surface of the substrate is such that when the film for forming a protective film is irradiated with an energy ray to form a protective film, the surface roughness (Ra) of at least one surface (β) of the protective film is 0.038. When it is μm or more, it is not particularly limited.

As one aspect of the present invention, the surface roughness (Ra) of at least one surface of the substrate is preferably from 0.03 μm to 2.0 μm, more preferably from 0.05 μm to 1.8 μm. The exposed surface of the film for forming a protective film (that is, the surface (β)) is bonded to the surface of the substrate having such a surface roughness (Ra), and the film for forming a protective film is coated on the release film and then protected. The film forming composition is formed by drying the film for forming a protective film, and the surface roughness (Ra) of at least one surface (β) of the protective film when the protective film forming film is irradiated with an energy ray to form a protective film. It can be adjusted to 0.038 μm or more and 1.5 μm or less.

As another aspect of the invention, the surface roughness (Ra) of at least one surface of the substrate is preferably from 0.05 μm to 1.3 μm. The exposed surface of the film for forming a protective film (that is, the surface (β)) is bonded to the surface of the substrate having such a surface roughness (Ra), and the film for forming a protective film is coated on the release film and then protected. The film forming composition is formed by drying the film for forming a protective film, and the surface roughness (Ra) of at least one surface (β) of the protective film when the protective film forming film is irradiated with an energy ray to form a protective film. It can be adjusted to 0.038 μm or more and 0.9 μm or less.

As still another aspect of the present invention, the surface roughness (Ra) of at least one surface of the substrate may be less than 0.12 μm, more preferably less than 0.03 μm, still more preferably 0.020 μm to 0.025 μm. The surface roughness of the first release film having a surface roughness (Ra) of at least one surface of 0.03 μm to 2.0 μm On the surface of the protective film, a film for forming a protective film to be described later is applied, and if necessary, a film for forming a protective film is formed, and the second release film is bonded to the exposed surface of the film for forming a protective film. The exposed surface (that is, the surface (β)) of the film for forming a protective film of the first release film is bonded to the surface of the substrate having the surface roughness (Ra), thereby irradiating the film for forming the protective film with energy. When the film is a protective film, the surface roughness (Ra) of at least one surface (β) of the protective film can be adjusted to 0.038 μm or more and 0.9 μm or less.

As still another aspect of the present invention, the surface roughness (Ra) of at least one surface of the substrate may be less than 0.12 μm, more preferably less than 0.03 μm, still more preferably 0.020 μm to 0.025 μm. A coating film forming composition to be described later is applied to the second release film, and if necessary, a film for forming a protective film is formed, and the surface roughness of at least one surface is bonded to the exposed surface of the film for forming a protective film. The surface having the surface roughness of the first release film of 0.03 μm to 2.0 μm is bonded to the exposed surface (that is, the surface (β)) of the film for forming a protective film from which the first release film is peeled off. The surface roughness of at least one surface (β) of the protective film when the protective film forming film is irradiated with an energy ray to form a protective film on the surface of the substrate having the surface roughness (Ra) It can be adjusted to 0.038 μm or more and 0.9 μm or less.

In the present specification, the surface roughness (Ra) of the surface of the substrate can be measured by the measurement method described in the examples.

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

◎ Protective film forming film

In the composite sheet for forming a protective film of the present invention, when the protective film forming film is irradiated with an energy ray to form a protective film, at least one surface (β) of the protective film has a surface roughness (Ra) of 0.038 μm or more. By picking up the semiconductor wafer with the protective film by this, the pickup of the semiconductor wafer with the protective film outside the target is suppressed, and the target semiconductor film with the protective film can be picked up with high selectivity. 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. 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. In this way, the adhesive force is in a specific range, whereby the composite sheet for forming a protective film has better pick-up property.

In the present invention, even if the film for forming a protective film is cured, the laminated structure of the cured product (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 a "composite sheet for forming a protective film".

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

That is, a protective film is formed having a width of 25 mm and a length of any The composite sheet is attached to the adherend by the film for forming a protective film of the composite sheet for forming a protective film.

Then, the film for forming a protective film was cured by irradiation with an energy ray, and after the protective film was formed, the protective film was adhered to the adherend, and the support sheet was peeled off at a peeling speed of 300 mm/min. In this case, the peeling system is a so-called 180° peeling in which the surface of the protective film and the support sheet are in contact with each other at an angle of 180°, and the support sheet is along the longitudinal direction of the support sheet (the composite sheet for forming a protective film) Stripped in the length direction. 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 addition, it is preferable to stabilize the attached state of the composite sheet for forming a protective film by attaching the composite sheet for forming a protective film to the adherend.

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, peeling of the film for forming a protective film and the support sheet during dicing is suppressed, and for example, 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. However, these are examples.

The adhesion 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 protective film formation for measurement is not cured by irradiation of the energy ray. The same method of adhesion is 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.

Providing a layer of a film for forming a protective film in a support sheet as a substrate In the case of the shape, the adhesion between the protective film or the film for forming a protective film and the support sheet can be adjusted by the surface state of the substrate in addition to the constituent material 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 includes a film for forming a protective 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 a protective film shape. The thickness of the entire film for forming a film, for example, the thickness of the film for forming a protective film composed of a plurality of layers means the total thickness of all the layers constituting the film for forming a protective film.

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 is dried, whereby a film for forming a protective film can be formed 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 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 protective film-forming composition may be applied by a known method, and examples thereof include the following various coaters: air knife coater and doctor blade coat. Cloth machine, bar coater, gravure coater, roll coater, roll coater, curtain coater, die coater, knife coater, screen coater, Meyer 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 gel permeation chromatography (GPC; Gel Permeation unless otherwise specified). The polystyrene equivalent value determined by the Chromatography method.

(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. However, in terms of preventing 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, monomers other than acrylic monomers (non-acrylic) A monomer obtained by copolymerization.

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 (monocarboxylic acid having an ethylenically unsaturated bond) such as (meth)acrylic acid or crotonic acid; fumaric acid and itaconic acid; An ethylenically unsaturated dicarboxylic acid such as maleic acid or citraconic acid (dicarboxylic acid having an ethylenically unsaturated bond); an anhydride of the above ethylenically unsaturated dicarboxylic acid; 2-carboxyethyl methacrylate; a carboxyalkyl acrylate or the like.

The aforementioned acrylic monomer having a functional group is preferably a hydroxyl group-containing single The monomer, the 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 (also known as lauryl (meth) acrylate ), tridecyl (meth)acrylate, tetradecyl (meth)acrylate (also known as myristyl (meth)acrylate), pentadecyl (meth)acrylate, (a) Cetyl hexyl acrylate (also known as palmityl (meth) acrylate), heptadecyl (meth) acrylate, octadecyl (meth) acrylate (also known as (methyl) Acetyl acrylate Alkyl esters of a chain structure having a carbon number of 1 to 18 of (meth) acrylate and the like.

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

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 structural unit derived from the acrylic monomer having the functional group to the total mass of the structural unit constituting the acrylic polymer (a11) is preferred. It is 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 acrylic resin (a1-1) obtained by copolymerization of the acrylic polymer (a11) and the energy ray-curable compound (a12) can be used. The content of the strand curable group 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 based on the total mass of the protective film-forming composition (IV-1). % is more preferably 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-methylpropenyloxyisocyanate, m-isopropenyl-α,α-dimethylbenzyl isocyanate, and methacryl Isocyanate, allyl isocyanate, 1,1-(bispropenyloxymethyl)isocyanate; by reaction of a diisocyanate compound or a polyisocyanate compound with hydroxyethyl (meth)acrylate The obtained acrylonitrile-based monoisocyanate compound; an acrylonitrile-based 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-methylpropenyloxy 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. Furthermore, the energy ray-curable compound (a12) is monofunctional (having one molecule) In the case of the compound of the above-mentioned group), the upper limit of the ratio of the content is 100 mol%, but the energy ray-curable compound (a12) is polyfunctional (having two or more of the above groups in one molecule) In the case of a compound, 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 the above-mentioned 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) Propylene Sulfhydryl, vinyl, etc.

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-((A Alkenyloxyethoxy)phenyl]propane, neopentyl glycol di(meth)acrylate, ethoxylated polypropylene glycol di(meth)acrylate, 2-hydroxy-1,3-di Bifunctional (meth) acrylate such as (meth) propylene decyloxypropane; tris(2-(methyl) propylene oxyethyl) isocyanurate, ε-caprolactone modified isocyanurate Tris-(2-(methyl)propenyloxyethyl) acid, ethoxylated glycerol tri(meth) acrylate, pentaerythritol tri(meth) acrylate, trimethylolpropane tris(methyl) Acrylate, di-trimethylolpropane tetra(meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol poly(meth)acrylate A polyfunctional (meth) acrylate oligomer such as dipentaerythritol hexa(meth) acrylate or a polyfunctional (meth) acrylate oligomer such as a (meth) acrylate urethane oligomer.

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, 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.

The aforementioned acrylic single sheet constituting the acrylic polymer (b-1) Examples of the body include (meth)acrylic acid alkyl ester, (meth)acrylate having a cyclic skeleton, glycidyl group-containing (meth)acrylate, hydroxyl group-containing (meth)acrylate, and Amine (meth) acrylate or 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 (also known as lauryl (meth)acrylate) , tridecyl (meth)acrylate, tetradecyl (meth)acrylate (also known as myristyl (meth)acrylate), pentadecyl (meth)acrylate, (methyl) Cetyl acrylate (also known as palmityl (meth) acrylate), heptadecyl (meth) acrylate, octadecyl (meth) acrylate (also known as (meth) acrylate An alkyl group constituting an alkyl ester such as stearyl ester It is an alkyl (meth)acrylate or the like having a chain structure of 1 to 18 carbon atoms.

Examples of the (meth) acrylate having a cyclic skeleton include (meth)acrylic acid cycloalkyl esters such as isobornyl (meth)acrylate and dicyclopentanyl (meth)acrylate; Benzyl acrylate, etc. Alkyl ester; (meth)acrylic acid cycloalkenyl ester such as dicyclopentenyl (meth)acrylate; (meth)acrylic acid cycloalkoxyalkyl group such as dicyclopentenyloxyethyl (meth)acrylate 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. For example, when the crosslinking agent (f) is a polyisocyanate compound, examples of the reactive functional group include a hydroxyl group and a carboxyl group. Among these, a hydroxyl group having high reactivity with an isocyanate group is preferred among these. 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. However, 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 is polymerized.

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 above polymer (b), the degree of crosslinking becomes a better range. Wai.

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 aforementioned compound (a2) The content is preferably 10 parts by mass to 400 parts by mass, more preferably 30 parts by mass to 350 parts by mass per 100 parts by mass of the total of the polymer (a1) and the polymer (b) having no energy ray-curable group. 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 90% by mass, more preferably It is preferably from 10% by mass to 80% by mass, particularly preferably from 15% by mass to 70% 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.

In one aspect of the invention, 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 is preferably 78. The mass% to 92% by mass, more preferably 82% by mass to 91% by mass, still more preferably 84% by mass to 90% by mass.

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. By the aforementioned content of the aforementioned polymer (b) being such a range, The energy ray hardenability of the film for forming a protective film is further improved.

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 protective film forming film is heated by heating. Then, 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 Ketone, B Ketone, benzophenone compound such as 1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-, 1-(O-ethenylhydrazine) Peroxide compound; diketone compound such as diethyl hydrazine; benzoin; diphenyl oxime; 2,4-diethyl thioxanthone; 1,2-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 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 most suitable for the object to be formed of the protective film, thereby protecting the film. The reliability of the package obtained by the composite sheet for film formation is further improved. In addition, since the film for forming a protective film contains the filler (d), the protection can be reduced. The moisture absorption rate of the film or the heat dissipation.

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 cerium oxide whose surface is modified with an epoxy group.

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 the value of the particle diameter (D ₅₀ ) at an integrated value of 50% in the particle size distribution curve obtained by the laser diffraction scattering method unless otherwise specified. .

The 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 5% by mass to 83% by mass, more preferably from 7% by mass to 78% by mass. By the content of the filler (d) being such a range, it becomes easier to adjust the above thermal expansion coefficient.

As one aspect of the present invention, the content of the filler (d) is preferably from 4% by mass to 15% by mass, and more preferably from 4% by mass to 10% by mass based on the mass of the film for forming a protective film.

In another aspect of the present invention, when the average particle diameter of the filler (d) is from 0.05 μm to 0.1 μm, the content of the filler (d) is preferably from 4% by mass to the mass of the film for forming a protective film. 15% by mass, more preferably 4% by mass to 10% by mass.

[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 Energy line hardening based polymer (b) The total content 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, more remarkable effects by using the coupling agent (e) can be obtained: 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 polyisocyanate compound, and an alicyclic polyisocyanate compound (hereinafter, these compounds may be collectively referred to simply as "aromatic polyisocyanate compounds"); a trimer, an isocyanurate body, and an adduct of the aromatic polyvalent isocyanate compound; and the aromatic polyisocyanate compound and the like and a polyol compound A terminal isocyanate urethane prepolymer obtained by the reaction or 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 term "terminal isocyanate urethane prepolymer" means a prepolymer having a urethane bond and having an isocyanate group at a terminal portion of the molecule.

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, tetramethylol methane-tri-β-aziridine propionic acid Ester, N, N'-toluene-2,4-bis(1-aziridinecarboxamide), tri-ethyl 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 the transmittance of the protective film may be adjusted by adjusting the content of the coloring agent (g) in the film for forming a protective film, thereby improving the print visibility. 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, and the like. A polyoxyxylene resin or the like is preferably an 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.

As the epoxy resin having an unsaturated hydrocarbon group, for example, a plurality of officials A compound in which a part of the epoxy group of the 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 secondary ethyl group (also referred to as a vinyl group), a 2-propenyl group (also referred to as an allyl group), and (a). The acrylonitrile group, the (meth) acrylamide group, and the like are 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.

In the present specification, the "number average molecular weight" means a number average molecular weight expressed by a value in terms of standard polystyrene measured by a gel permeation chromatography (GPC) method unless otherwise specified.

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.

In the present specification, the term "epoxy equivalent" means the number of grams (g/eq) of an epoxy compound containing 1 gram equivalent of an epoxy group, which can be measured in accordance with the method of JIS K 7236:2001.

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 "DICY; Dicyandiamde").

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 present specification, the "glass transition temperature" is a DSC (Differential Scanning Calorimetry) curve of a sample measured by a differential scanning calorimeter and expressed by the inflection point temperature of the obtained DSC curve.

In the thermosetting agent (h2), for example, 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 Good for 400 to 10,000, especially for 500 to 3000.

In the heat curing agent (h2), for example, 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.

When the thermosetting component (h) is used, the protective film forming group In the film (IV-1) and the film for forming a protective film, the content of the thermosetting agent (h2) is preferably 0.01 parts by mass to 20 parts by mass based on 100 parts by mass of the epoxy resin (h1).

When the thermosetting component (h) is used, 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)) The total content of the thermosetting agent (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. Contain The composition (IV-1) having a protective film for forming 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 and isobutanol (also known as 2-methylpropan-1-ol). An alcohol such as 1-butanol; an ester such as ethyl acetate; a ketone such as acetone or methyl ethyl ketone; an ether such as tetrahydrofuran; an amide such as dimethylformamide or N-methylpyrrolidone (having decylamine) The compound of the bond) and the like.

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.

In one aspect of the invention, the protective film-forming composition (IV-1) comprises tricyclodecane dimethylol diacrylate as the energy ray-curable component (a2) (content: formed with respect to a protective film) The total mass of the solid component in the composition (IV-1) is from 37% by mass to 45% by mass, more preferably from 40% by mass to 43% by mass; and the polymer (b) is derived from butyl acrylate. The structural unit (from 8 mass% to 12 mass%, more preferably 10 mass% based on the mass of the acrylic resin) and the structural unit derived from methyl acrylate (68 mass% based on the mass of the acrylic resin) 72% by mass, more preferably 70% by mass), a structural unit derived from glycidyl methacrylate (from 3% by mass to 7% by mass, more preferably 5% by mass based on the mass of the acrylic resin) Structural unit derived from 2-hydroxyethyl acrylate (relative An acrylic resin (content: relative to the solid content in the protective film forming composition (IV-1)) in an amount of 13% by mass to 17% by mass, more preferably 15% by mass based on the mass of the acrylic resin The total mass is 41% by mass to 50% by mass, more preferably 44 to 47% by mass); 2-(dimethylamino)-1-(4-morpholinyl group as photoinitiator (c) Phenyl)-2-benzyl-1-butanone (content: from 0.2% by mass to 1.1% by mass based on the total mass of the solid content component in the protective film-forming composition (IV-1), more preferably 0.6% by mass to 0.64% by mass) and ethyl ketone, 1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-, 1-(O-B (醯) (content: from 0.2% by mass to 1.1% by mass, more preferably from 0.6% by mass to 0.64% by mass based on the total mass of the solid content component in the protective film forming composition (IV-1); The cerium oxide filler (surface modifying group: epoxy group) as the filler (d) (content: 2.1% by mass based on the total mass of the solid content component in the protective film forming composition (IV-1) 13.5 mass%, more preferably 4.2 mass% to 10 mass%); 3-methylpropenyloxypropyl group as coupling agent (e) Methoxy decane (content: 0.4% by mass to 1.5% by mass, more preferably 0.8% by mass to 0.86% by mass) based on the total mass of the solid content component in the protective film forming composition (IV-1); And a pigment containing a phthalocyanine-based blue dye, an isoindolinone-based yellow dye, an anthraquinone-based red pigment, and a styrene-based acrylic resin as a coloring agent (g) (content: composition for forming a protective film) The total mass of the solid content in IV-1) is from 2.0% by mass to 6.25% by mass, more preferably from 4.0% by mass to 4.3% by mass) (wherein the sum of the contents of the respective components is relative to the composition for forming a protective film) The total mass of the solid content in (IV-1) does not exceed 100% by mass).

<<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.

In the same manner as the composite sheet for forming a protective film of the present invention, a composite sheet which is attached to a semiconductor wafer or a semiconductor wafer on the opposite side to the circuit surface, and which has a layer on the support sheet which exhibits an adhesive layer, is cut. Crystal bonded wafer.

However, the adhesive layer provided in the diced wafer has a function of being attached to a support wafer after being picked up from a support wafer, and then mounting the semiconductor wafer on a substrate, a lead frame, or another semiconductor wafer as an adhesive. The function. On the other hand, the film for forming a protective film in the composite sheet for forming a protective film of the present invention is the same as the above-mentioned adhesive layer in terms of picking up from the support sheet together with the semiconductor wafer, but is finally cured by curing. The protective film has the function of protecting the back side of the attached semiconductor wafer. As described above, the use of the film for forming a protective film in the present invention is different from that of the adhesive layer in the diced bonded wafer, and of course the required performance is also different. Further, in view of the difference in the use, in general, when the adhesive layer is formed in comparison with the adhesive layer in the crystal-cut wafer, the film for forming a protective film tends to be hard and difficult to pick up. Therefore, it is generally difficult to directly convert the adhesive layer in the crystal-cut wafer to the film for forming a protective film in the composite sheet for forming a protective film. The composite sheet for forming a protective film of the present invention is provided with an energy ray-curable film for forming a protective film, and the pick-up property of the semiconductor wafer with the protective film is extremely excellent.

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

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 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)>

The second 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. The surface having the surface roughness described above, which is referred to as a first release film, is coated with a composition for forming a protective film, and is 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 be a surface opposite to the surface on which the first release film is attached (that is, the surface (of the surface). α)) Another peeling film (sometimes referred to as a second peeling 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".

In one aspect of the invention, the film for forming a protective film contains tricyclodecane dimethylol diacrylate as the energy ray-curable component (a2) (content: composition for forming a protective film (IV- The total mass of the solid content in 1) is from 37% by mass to 45% by mass, more preferably from 40% by mass to 43% by mass; as the structure of the polymer (b) derived from butyl acrylate A structural unit derived from methyl acrylate (compared to the mass of the acrylic resin) of 68% by mass to 72% by mass based on the mass of the acrylic resin, more preferably 10% by mass, more preferably 10% by mass. (% by mass, more preferably 70% by mass), a structural unit derived from glycidyl methacrylate (from 3% by mass to 7% by mass, more preferably 5% by mass based on the mass of the acrylic resin) and derived from Acrylic resin composed of a structural unit of 2-hydroxyethyl acrylate (13% by mass to 17% by mass, more preferably 15% by mass based on the mass of the acrylic resin) (content: composition for forming a protective film) The total mass of the solid component in the substance (IV-1) is 41% by mass to 50% by mass, more preferably 44 to 47% by mass); 2-(dimethyl group) as the photopolymerization initiator (c) Amino)-1-(4-morpholinylphenyl)-2-benzyl-1-butanone (content: relative to the total mass of the solid component in the composition for forming a protective film (IV-1), It is 0.2% by mass to 1.1% by mass, more preferably 0.6% by mass to 0.64% by mass) and ethyl ketone, 1-[9-ethyl-6-(2-methylbenzylidene)-9H-carbazole- 3-yl]-, 1-(O-ethylindenyl) (content: relative to insurance The total mass of the solid content component in the film-forming composition (IV-1) is from 0.2% by mass to 1.1% by mass, more preferably from 0.6% by mass to 0.64% by mass); as the filler (d), cerium oxide Filler (surface modifying group: epoxy group) (content: 2.1% by mass to 13.5% by mass, more preferably 4.2% by mass based on the total mass of the solid content component in the protective film forming composition (IV-1) To 10% by mass); 3-methylpropenyloxypropyltrimethoxydecane as a coupling agent (e) (content: total amount of solid components in the composition (IV-1) for protective film formation) The mass is 0.4% by mass to 1.5% by mass, more preferably 0.8% by mass to 0.86% by mass); and the coloring agent (g) contains phthalocyanine blue color Pigment of the pigment, the isomeric ketone ketone yellow pigment, the lanthanide red pigment, and the styrene acrylic resin (content: the total mass of the solid component in the protective film forming composition (IV-1) is 2.0 The mass% to 6.25 mass%, more preferably 4.0 mass% to 4.3 mass%) (wherein the sum of the contents of the respective components does not exceed the total mass of the solid component in the protective film forming composition (IV-1) 100% by mass).

<Method for Producing Composite Sheet for Forming Protective Film (1)>

The first 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 of 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 It is necessary to dry the film to form a film for forming a protective film, and the second release film is bonded to the exposed surface of the film for forming a protective film.

The exposed surface (that is, the surface (β)) of the film for forming a protective film from which the first release film is peeled off can be produced by bonding the surface of the substrate as the support sheet. The surface roughness (Ra) of the surface of the substrate is not particularly limited, and it is preferable that the surface roughness (Ra) is, for example, less than 0.12 μm, more preferably less than 0.03 μm, still more preferably 0.020 μm. Smooth surface to 0.025 μm.

<Method for Producing Composite Sheet for Forming Protective Film (2)>

Next, a second aspect of the method for producing a composite sheet for forming a protective film of the present invention will be described.

Applying a protective film forming composition to the second release film, if necessary The first release film having a surface roughness (Ra) of at least one surface having a surface roughness (Ra) of 0.03 μm to 2.0 μm is bonded to the exposed surface of the film for forming a protective film to have the surface roughness. surface.

The exposed surface (that is, the surface (β)) of the film for forming a protective film from which the first release film is peeled off can be produced by bonding the surface of the substrate as the support sheet. The surface roughness (Ra) of the surface of the substrate is not particularly limited, and it is preferable that the surface roughness (Ra) is, for example, less than 0.12 μm, more preferably less than 0.03 μm, still more preferably 0.020 μm. Smooth surface to 0.025 μm.

<Method for Producing Composite Sheet for Forming Protective Film (3)>

Next, a third aspect of the method for producing a composite sheet for forming a protective film of the present invention will be described.

A film for forming a protective film is applied onto the release film, and if necessary, dried to form a film for forming a protective film.

The surface roughness (Ra) having at least one surface to be bonded to the exposed surface of the film for forming a protective film (that is, the surface (β)) may be from 0.03 μm to 2.0 μm, more preferably from 0.05 μm to 1.8. The surface of the surface roughness (Ra) of the substrate having a surface roughness (Ra) of preferably 0.05 μm to 1.3 μm is preferably produced in the range of μm.

The composite sheet for forming a protective film of the present invention can also be produced by sequentially laminating the above layers in a corresponding positional relationship. The formation method of each layer is as described above.

In the case of forming a continuous two-layer laminated structure, it can be used by the first On the layer on which the composition is formed, a second composition is further applied to form a layer. However, it is preferable to form a continuous two-layer laminated structure by using the second composition on the other release film, and to form the two layers of the back layer in advance. The exposed surface on the opposite side to the side in contact with the release film in the formed layer is bonded to the exposed surface of the remaining layer formed. In this case, the second composition is preferably applied to the release-treated surface of the release film. After forming the laminate structure, the release film may be removed as needed.

The release film can be removed at any point after the formation of the target laminate structure.

In this manner, the layer other than the base material constituting the composite sheet for forming a protective film can be laminated by being formed in advance on the release film and then bonded to the surface of the target layer. Therefore, such a step is appropriately selected as needed. In the layer, a composite sheet for forming a protective film can be produced.

In addition, the composite sheet for forming a protective film is usually stored in the following state, that is, the surface of the outermost layer (for example, a film for forming a protective film) on the opposite side of the support sheet in the composite sheet for forming a protective film. There is a state of peeling film. Therefore, a composite sheet for forming a protective film can be obtained by applying a protective film forming composition or the like to the release film (preferably, a release-treated surface of the release film). The composition constituting the layer constituting the outermost layer is formed, and if necessary, dried, whereby a layer constituting the outermost layer is formed in advance on the release film, and an exposed surface on the opposite side to the side in contact with the release film in the layer is formed. Stacking the remaining layers using any of the above methods (for example, As the substrate of the support sheet, the release film was not removed and the bonding state was maintained.

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 protective film forming film of the protective film forming sheet is attached to the back surface of the semiconductor wafer by the surface (α) on the side opposite to the surface having the first release film in the protective film forming sheet. a surface opposite to the electrode forming surface). Then, 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. Then, the first release film is peeled off, and the exposed surface (surface (β)) of the protective film is attached to the support sheet, and the semiconductor wafer is divided together with the protective film by dicing to form a semiconductor wafer. 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 is pulled out from the support sheet to be picked up. In the present specification, the support sheet is preferably a support sheet composed only of a base material. Here, as the support sheet, the support sheet used in the composite sheet for forming a protective film of the present invention can be applied.

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. Then, 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. Then, by cutting, the semiconductor wafer is divided together with the protective film to form a semiconductor wafer. 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 is 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, and then the entire surface is sealed by a resin to form 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 diced, the case of performing these steps may be reversed when the composite sheet for forming a protective film of the present invention is used. . 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.

[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), and glycidyl methacrylate ( Hereinafter, an acrylic resin (weight average molecular weight: 300,000, which is simply referred to as "GMA") (5 parts by mass) and 2-hydroxyethyl acrylate (hereinafter abbreviated as "HEA") (15 parts by mass) is copolymerized. Glass transfer 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) (average particle diameter: 0.1 μm).

(d)-2: cerium oxide filler (surface modifying group: epoxy group) (average particle diameter: 0.05 μm).

‧ 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 The agent (c)-2 (0.3 parts by mass) and the 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. (% by mass), coupling agent (e)-1 (0.4 parts by mass), and coloring agent (g)-1 (2 parts by mass) were dissolved or dispersed in methyl ethyl ketone, and stirred at 23 ° C to prepare The composition for forming a protective film (IV-1) having a solid content concentration of 50% by mass.

(Manufacture of composite sheet for forming a protective film)

The release-treated surface of the 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 coated by a knife The protective film-forming composition (IV-1) obtained above was applied to a cloth machine and dried at 100 ° C for 2 minutes to prepare a film (13)-1 for protective film formation having an energy ray curability of 25 μm.

Then, the substrate having a polypropylene film (thickness: 80 μm) having a surface roughness (Ra) of 1.3 μm, that is, the surface of the support sheet (10)-1 having the surface roughness (Ra), was obtained by laminating the above. The exposed surface of the film (13)-1 for forming a protective film, and a composite film for forming a protective film formed by sequentially forming a substrate, a film for forming a protective film (13)-1, and a release film in the thickness direction thereof. .

[Embodiment 2]

<Manufacture of composite sheet for forming a protective film>

The support sheet (10)-1, which is a base material of a polypropylene film (thickness: 80 μm) having a surface roughness (Ra) of 1.3 μm used in Example 1, was replaced by a surface roughness (Ra) of 0.05 μm. The support sheet (10)-2, which is a base material of a polypropylene film (thickness: 80 μm), was formed into a film (13)-1 for forming a protective film and a sheet for forming a protective film in the same manner as in Example 1. .

[Example 3]

<Manufacture of composite sheet for forming a protective film>

The filler (d)-1 (2 parts by mass, that is, with respect to the protective film forming composition (IV-1) in the composition for forming a protective film (IV-1) used in Example 1 The total mass of the solid component is 4.3% by mass), and is replaced by the filler (d)-2 (5 parts by mass, that is, the total amount of the solid component in the protective film forming composition (IV-1). A film (13)-2 for forming a protective film and a sheet for forming a protective film were produced in the same manner as in Example 1 except that the mass was 10% by mass.

[Example 4]

<Manufacture of Sheet for Forming Protective Film>

A film made of polyethylene terephthalate having a surface roughness (Ra) of 1.8 μm (thickness: 80 μm), that is, a surface having the surface roughness (Ra) of the first release film, by a knife coater The protective film-forming composition (IV-1) used in Example 1 was applied and dried at 100 ° C for 2 minutes to prepare an energy ray-curable protective film forming film (13)-1 having a thickness of 25 μm. .

Then, the peeling treatment surface of the second release film ("SP-PET381031" manufactured by Lintec Co., Ltd., thickness: 38 μm) which was subjected to the release treatment on the one side of the polyethylene terephthalate film by the polyoxyethylene treatment was attached. In the exposed surface of the film for protective film formation (13)-1 obtained above, the first release film, the film for protective film formation (13)-1, and the second release film are laminated in this thickness direction. A sheet for forming a protective film.

[Comparative Example 1]

<Manufacture of composite sheet for forming a protective film>

The support sheet (10)-1, which is a substrate of a polypropylene film (thickness: 80 μm) having a surface roughness (Ra) of 1.3 μm used in Example 1, was replaced by a surface roughness (Ra) of 0.025 μm. The support sheet (10)-3, which is a base material of a polypropylene film (thickness: 80 μm), was formed into a film (13)-1 for forming a protective film and a sheet for forming a protective film in the same manner as in Example 1. .

[Comparative Example 2]

<Manufacture of composite sheet for forming a protective film>

The support sheet (10)-1, which is a base material of a polypropylene film (thickness: 80 μm) having a surface roughness (Ra) of 1.3 μm used in Example 1, was replaced by a surface roughness (Ra) of 0.020 μm. The support sheet (10)-4, which is a base material of a polypropylene film (thickness: 80 μm), was formed into a film (13)-1 for forming a protective film and a sheet for forming a protective film in the same manner as in Example 1. .

[Comparative Example 3]

<Manufacture of composite sheet for forming a protective film>

The filler (d)-1 (2 parts by mass, that is, in the composition for forming a protective film (IV-1), the composition for forming a protective film (IV-1) used in Example 1 The total mass of the solid content is 4.3% by mass), and is replaced by the filler (d)-2 (5 parts by mass, that is, the total mass of the solid component in the protective film forming composition (IV-1). In addition, the support sheet (10)-1, which is a substrate of a polypropylene film (thickness: 80 μm) having a surface roughness (Ra) of 1.3 μm used in Example 1, was replaced with a surface. A support sheet (10)-3 which is a base material of a polypropylene film (thickness: 80 μm) having a roughness (Ra) of 0.025 μm is produced in the same manner as in the first embodiment. The film for protective film formation (13)-2 and the sheet for forming a protective film.

<Evaluation of Sheet for Forming Protective Film and Composite Sheet for Forming Protective Film>

(Measurement of surface roughness (Ra))

Using the optical interference type surface shape measuring device (manufactured by Veeco Metrology Group, product name "WYKO WT1100"), the surface roughness of the surface to be measured was measured at a magnification of 10 times in a PSI (Phase Shift Interferometry) mode at a magnification of 10 times. (Ra) was measured.

In the composite sheet for forming a protective film of the first embodiment to the third embodiment and the comparative example 1 to the comparative example 3, the surface of the film for forming a protective film to be bonded to the substrate of the support sheet is referred to as a surface (β). After the film for forming a protective film is cured to form a protective film, the protective film is peeled off from the substrate of the support sheet, and the surface roughness (Ra) of the surface (β) of the protective film is measured. Moreover, the surface roughness (Ra) of the base material as a support sheet was measured before bonding the film for protective film formation.

The results are shown in Table 1.

(Suppression of chip breakage and defect after picking up)

(1) The composite sheet for forming a protective film obtained in Examples 1 to 3 and Comparative Examples 1 to 3, and the exposed surface of the film for forming a protective film of the composite sheet for forming a protective film ( That is, the surface (α)) was attached to a #2000 polished surface of an 8-inch wafer (thickness: 100 μm), and the sheet was fixed in a ring frame and allowed to stand for 30 minutes.

Then, using a UV irradiation device ("RAD2000m/8" manufactured by Lintec Co., Ltd.), the composite sheet for forming a protective film is irradiated with ultraviolet rays from the side of the support sheet under the conditions of an illuminance of 195 mW/cm ² and a light amount of 170 mJ/cm ² . The film for forming a protective film is cured to form a protective film.

Then, using a dicing blade, the ruthenium wafer was cut together with the protective film to be singulated, and a 5 mm × 5 mm ruthenium wafer was obtained.

Then, using a die bonder ("BESTEM-D02" manufactured by Canon Machinery Co., Ltd.), 20 wafers with a protective film were picked up. At this time, the presence or absence of cracks and defects of the wafer was visually confirmed, and the case where no cracks and defects were completely eliminated was judged as "○", and the case where only a few cracks or defects were found was judged as "x", and the picking property was evaluated.

The results are shown in Table 1.

(2) The second release film of the film for forming a protective film obtained in Example 4 was peeled off, and the exposed surface (that is, the surface (α)) of the film (13)-1 for protective film formation was attached to 8 The #2000 polished surface of the wafer (thickness: 100 μm) was peeled off, and the first release film of the sheet was peeled off, and the exposed surface of the film for forming a protective film (that is, the surface (β)) was bonded to Comparative Example 2. The support sheet (10)-3 was fixed to the ring frame by the obtained laminate, and allowed to stand for 30 minutes.

The steps after the above steps were carried out in the same manner as the procedure described in the above (1) to pick up 20 wafers with a protective film.

The results are shown in Table 2.

According to the above-mentioned results, in the case of using the composite sheet for forming a protective film of Examples 1 to 3 or the sheet for forming a protective film of Example 4, the film for forming a protective film is irradiated with an energy ray to form a protective film. When the surface roughness (Ra) of the surface (β) of the protective film is 0.038 μm or more, cracking and defects of the tantalum wafer are suppressed at the time of pick-up, and no other defects are observed, and the pick-up property is excellent.

On the other hand, the protective film formation of Comparative Example 1 to Comparative Example 3 was used. In the case of using a composite sheet, when the film for forming a protective film is irradiated with an energy ray to form a protective film, if the surface roughness (Ra) of the surface (β) of the protective film is less than 0.038 μm, the wafer is broken at the time of picking up. And the defect is suppressed, and the picking property is poor.

In the above-described aspect, the film for forming a protective film is directly laminated on the substrate. Therefore, when the film for forming a protective film is cured to form a protective film, the interface between the protective film and the substrate is thick in a specific range. The surface is formed, whereby the adhesion between the protective film and the substrate can be appropriately adjusted, and the pick-up property is improved. In this case, since the support sheet is composed only of the base material, it is easy to exhibit the effect of roughening the protective film, which is preferable.

(industry availability)

The invention can be used to fabricate semiconductor devices.

Claims (3)

A film for forming a protective film which is an energy ray-curable protective film forming film; and when the protective film forming film is irradiated with an energy ray to form a protective film, surface roughness of at least one surface (β) of the protective film (Ra) is 0.038 μm or more. The film for forming a protective film according to claim 1, wherein the surface roughness (Ra) is 1.5 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) of the film for forming a protective film faces the support sheet.