WO2017188199A1 - Film for forming protective coating and composite sheet for forming protective coating - Google Patents

Abstract

Provided are a film for forming a protective coating and a composite sheet for forming a protective coating, both of which can prevent curing defects even in the presence of oxygen. Said film for forming a protective coating can be cured by energy rays, and a photoradical initiator having a 365-nm light absorption coefficient is added in the amount of at least 4.0×10¹ ml/(g·cm) to said film for forming a protective coating. The photoradical initiator is preferably a hydrogen-abstraction photoradical initiator having at least three aromatic rings in one molecule, and preferably a photoradical initiator having at least two photodegradable groups in one molecule.

Description

Protective film forming film and protective film forming composite sheet

The present invention relates to a protective film-forming film and a protective film-forming composite sheet.
This application claims priority based on Japanese Patent Application No. 2016-092011 filed in Japan on April 28, 2016, the contents of which are incorporated herein by reference.

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

A resin film containing an organic material is formed as a protective film on the exposed back surface of the semiconductor chip and may be taken into the semiconductor device as a semiconductor chip with a protective film. The protective film is used to prevent cracks from occurring in the semiconductor chip after the dicing process or packaging.

In order to form such a protective film, for example, a protective film-forming composite sheet comprising a protective film-forming film for forming a protective film on a support sheet is used. In the protective film-forming composite sheet, the protective film-forming film can form a protective film by curing. Further, the support sheet can be used as a dicing sheet, and the protective film-forming film and the dicing sheet can be integrated.

As such a composite sheet for forming a protective film, for example, a sheet provided with a thermosetting protective film forming film that forms a protective film by being cured by heating has been mainly used so far. In this case, for example, the protective film-forming composite sheet is attached to the back surface (the surface opposite to the electrode-forming surface) of the semiconductor wafer with a thermosetting protective film-forming film. Thereafter, the protective film-forming film is cured by heating to form a protective film, and the semiconductor wafer is divided together with the protective film by dicing to form semiconductor chips. Curing and dicing of the protective film-forming film may be performed in the reverse order.

However, since the heat curing of the thermosetting protective film-forming film usually takes a long time of about several hours, shortening of the curing time is desired. On the other hand, use of a protective film-forming film that can be cured by irradiation with energy rays such as ultraviolet rays has been studied. For example, an energy beam curable protective film (see Patent Document 1) formed on a release film, or an energy beam curable chip protective film that can form a protective film having high hardness and excellent adhesion to a semiconductor chip. Reference 2) is disclosed.

Japanese Patent No. 5144433 JP 2010-031183 A

7A to 7C are schematic cross-sectional views schematically showing a conventional process from dicing a semiconductor wafer to curing and picking up. The semiconductor wafer 18 has a protective film forming composite sheet 10 affixed to the back surface thereof, and then there are two types: a type in which the protective film forming film 13 'is cured after a dicing step and a type in which dicing is performed after curing. is there. Among these, in the type that is cured after dicing, the semiconductor wafer 18 is cut into a plurality of semiconductor chips 181, 181,... By the dicing blade 20 by dicing (FIG. 17A). At this time, the side surface of the cut semiconductor chip 181 is exposed, and the protective film forming film 13 attached to the back surface of the semiconductor chip 181 is also cut to expose the cross section.

Thus, when the cross section of the protective film-forming film 13 is exposed and exposed to oxygen, oxygen has a property of inhibiting curing. For this reason, in the curing step after dicing (FIG. 17B), the protective film-forming film due to the irradiation of energy rays may not be sufficiently cured, and curing failure may occur. If it is used in the next pick-up process (FIG. 17C) in such a state where the curing is insufficient, there may be a pick-up failure that causes the semiconductor chip 181 to crack or chip at the time of pick-up, resulting in an increase in product yield. There is a problem of lowering.
In FIG. 7, reference numerals 11, 12, 16, 17, 19 and 21 denote a base material, an adhesive layer, a jig adhesive layer, a ring frame, a divided silicon wafer, and an energy beam irradiation device, respectively. Show.

The present invention has been made to solve the above problems. That is, an object of the present invention is to provide an energy ray-curable protective film-forming film and a protective film-forming composite sheet that does not cause poor curing even when cured in the presence of oxygen and does not cause pickup failure. .

The inventors of the present invention have made extensive studies to solve the above problems. As a result, the above-mentioned problem can be obtained by blending a protective film-forming film or a protective-film-forming composite sheet with a photoradical initiator having an absorption coefficient of 4.0 × 10 ¹ ml / (g · cm) or more at a wavelength of 365 nm. As a result, the present invention has been completed.

That is, the present invention is an energy ray-curable film for forming a protective film, and in the protective film-forming film, light having an extinction coefficient at a wavelength of 365 nm of 4.0 × 10 ¹ ml / (g · cm) or more. It is a film for protective film formation containing a radical initiator.
In the protective film-forming film of the present invention, the photo radical initiator is preferably a hydrogen abstraction type photo radical initiator having three or more aromatic rings in one molecule.
In the protective film-forming film of the present invention, the photoradical initiator is preferably a photoradical initiator having two or more photodegradable groups in one molecule.
The present invention may also be a protective film-forming composite sheet comprising the protective film-forming film described above on a support sheet.

According to the present invention, there are provided an energy ray-curable protective film-forming film and a protective film-forming composite sheet that do not cause curing failure even when cured in the presence of oxygen and do not cause pickup failure. .

It is sectional drawing which shows typically one Embodiment of the composite sheet for protective film formation of this invention. It is sectional drawing which shows typically other embodiment of the composite sheet for protective film formation of this invention. It is sectional drawing which shows typically other embodiment of the composite sheet for protective film formation of this invention. It is sectional drawing which shows typically other embodiment of the composite sheet for protective film formation of this invention. It is sectional drawing which shows typically other embodiment of the composite sheet for protective film formation of this invention. It is sectional drawing which shows typically one Embodiment of the sheet | seat for protective film formation of this invention. It is the schematic sectional drawing which showed the conventional process until it hardens | cures and picks up after dicing the semiconductor wafer.

◇ protective film forming film for the protective film forming film present invention relates to a protective film formation film of an energy ray-curable, in the protective film forming film, the absorption coefficient of the wavelength 365nm is 4.0 × 10 ¹ It contains a photoradical initiator of ml / (g · cm) or more.
The photo radical initiator according to the present invention may be a hydrogen abstraction type photo radical initiator having three or more aromatic rings in one molecule.
The photoradical initiator according to the present invention may be a photoradical initiator having two or more photodegradable groups in one molecule.
The photoradical initiator according to the present invention preferably has an extinction coefficient at a wavelength of 365 nm of 1.0 × 10 ⁴ ml / (g · cm) or less.
When the extinction coefficient at a wavelength of 365 nm of the photoradical initiator is not more than the above value, it is possible to suppress unintentional reaction when used under a fluorescent lamp or natural light, and the composite sheet can be used stably. There is.
The protective film-forming film of the invention may have a first release film on at least one surface, and may further have a second release film on the other surface. The film for forming a protective film of the present invention can be provided as a long film wound in a roll shape. FIG. 6 is a cross-sectional view schematically showing one embodiment of the protective film-forming film of the present invention. In FIG. 6, the 1st peeling film 15b, the protective film formation film 13 (23), and the 2nd peeling film 15a are laminated | stacked in this order.

◇ Composite sheet for protective film formation The composite sheet for protective film formation of the present invention is provided with an energy ray-curable protective film-forming film on a support sheet, and in the protective film-forming film, the absorption wavelength is 365 nm. A photo radical initiator having a coefficient of 4.0 × 10 ¹ ml / (g · cm) or more is blended.
In the present specification, the “protective film-forming film” means a film before curing, and the “protective film” means a film obtained by curing the protective film-forming film.

The protective film-forming film is cured by irradiation with energy rays and becomes a protective film. This protective film is for protecting the back surface (surface opposite to the electrode forming surface) of the semiconductor wafer or semiconductor chip. The protective film-forming film is soft and can be easily attached to an object to be attached.
And the composite sheet for protective film formation of this invention has antistatic property by making the surface resistance value rate of the film for protective film formation into 10 < ¹² > ohm * cm or less. For example, the semiconductor chip can be prevented from being charged even after the dicing process. As a result, the semiconductor chips are prevented from adhering to the cover tape when shipped in reels and peeled off in the next step.
Further, since the semiconductor chip itself is prevented from being charged, it is possible to prevent dust or dirt from adhering to the semiconductor chip due to static electricity.

In the present invention, “energy beam” means an electromagnetic wave or charged particle beam having energy quanta, and examples thereof include ultraviolet rays, radiation, and electron beams.
Ultraviolet rays can be irradiated by using, for example, a high-pressure mercury lamp, a fusion H lamp, a xenon lamp, a black light, an LED lamp or the like as an ultraviolet ray source. The electron beam can be emitted by an electron beam accelerator or the like.
In the present invention, “energy beam curability” means a property of being cured by irradiation with energy rays. “Non-energy radiation curable” means a property that does not cure even when irradiated with energy rays.

The thickness of the semiconductor wafer or the semiconductor chip that is the target of use of the composite sheet for forming a protective film of the present invention is not particularly limited. In order to obtain the effects of the present invention more remarkably, the thickness is preferably 30 to 1000 μm, more preferably 100 to 300 μm.
Hereinafter, the configuration of the present invention will be described in detail.

Support sheet The support sheet may be composed of one layer (single layer) or may be composed of two or more layers. When the support sheet is composed of a plurality of layers, the 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.
In the present specification, not limited to the case of the support sheet, “the plurality of layers may be the same or different from each other” means “all the layers may be the same or all the layers are different. It means that only some of the layers may be the same. " Further, “a plurality of layers are different from each other” means “at least one of the constituent material and thickness of each layer is different from each other”.

Preferred support sheets include, for example, those in which the pressure-sensitive adhesive layer is directly contacted and laminated on the substrate, those in which the pressure-sensitive adhesive layer is laminated on the substrate via an intermediate layer, and only the substrate. And the like.

Examples of the composite sheet for forming a protective film of the present invention will be described below for each kind of support sheet with reference to the drawings. In addition, in order to make the features of the present invention easier to understand, the drawings used in the following description may show the main portions in an enlarged manner for convenience, and the dimensional ratios of the respective components are the same as the actual ones. Not necessarily.

FIG. 1 is a cross-sectional view schematically showing one embodiment of a composite sheet for forming a protective film of the present invention. The protective film-forming composite sheet 1 </ b> A shown here comprises a pressure-sensitive adhesive layer 12 on a base material 11, and a protective film-forming film 13 on the pressure-sensitive adhesive layer 12. The support sheet 10 is a laminate of the base material 11 and the pressure-sensitive adhesive layer 12. In other words, the protective film-forming composite sheet 1 </ b> A has a protective film-forming film 13 laminated on one surface 10 a of the support sheet 10. Have a configuration. The protective film-forming composite sheet 1 </ b> A further includes a release film 15 on the protective film-forming film 13.

In the protective film forming composite sheet 1 </ b> A, the pressure-sensitive adhesive layer 12 is laminated on one surface 11 a of the substrate 11. A protective film forming film 13 is laminated on the entire surface 12 a of the pressure-sensitive adhesive layer 12. A jig adhesive layer 16 is laminated on a part of the surface 13a of the protective film-forming film 13, that is, in the vicinity of the peripheral edge. Of the surface 13a of the protective film forming film 13, the release film 15 is laminated on the surface on which the jig adhesive layer 16 is not laminated and on the surface 16a (upper surface and side face) of the jig adhesive layer 16. ing.

In the protective film-forming composite sheet 1A, the protective film-forming film 13 contains a photoradical initiator having an absorption coefficient of 4.0 × 10 ¹ ml / (g · cm) or more at a wavelength of 365 nm.
Further, the adhesive force between the cured protective film-forming film 13 (that is, the protective film) and the support sheet 10, in other words, the adhesive force between the protective film and the adhesive layer 12 is 50 to 1500 mN / 25 mm. Preferably there is.

The adhesive layer 16 for jigs may have, for example, a single-layer structure containing an adhesive component, or a plurality of layers in which layers containing an adhesive component are laminated on both surfaces of a core sheet. It may be of a structure.

In the composite sheet 1A for forming a protective film shown in FIG. 1, the back surface of a semiconductor wafer (not shown) is attached to the front surface 13a of the film 13 for forming a protective film with the release film 15 removed. Further, the upper surface of the surface 16a of the jig adhesive layer 16 is used by being attached to a jig such as a ring frame.

FIG. 2 is a sectional view schematically showing another embodiment of the composite sheet for forming a protective film of the present invention. In FIG. 2 and subsequent figures, the same components as those shown in the already explained figures are given the same reference numerals as those in the already explained figures, and their detailed explanations are omitted.

The protective film-forming composite sheet 1B shown here is the same as the protective film-forming composite sheet 1A shown in FIG. 1 except that it does not include the jig adhesive layer 16. That is, in the protective film-forming composite sheet 1 </ b> B, the pressure-sensitive adhesive layer 12 is laminated on one surface 11 a of the substrate 11. A protective film-forming film 13 is laminated on the entire surface 12 a of the pressure-sensitive adhesive layer 12, and a release film 15 is laminated on the entire surface 13 a of the protective film-forming film 13.

The composite sheet 1B for forming a protective film shown in FIG. 2 has a semiconductor wafer (not shown) formed in a partial region on the center side of the surface 13a of the protective film-forming film 13 with the release film 15 removed. The back side is affixed. Furthermore, the area | region of the peripheral part vicinity of the film 13 for protective film formation is affixed and used for jigs, such as a ring frame.

FIG. 3 is a cross-sectional view schematically showing still another embodiment of the protective sheet-forming composite sheet of the present invention.
The protective sheet-forming composite sheet 1 </ b> C shown here is the same as the protective film-forming composite sheet 1 </ b> A shown in FIG. 1, except that the adhesive layer 12 is not provided. That is, in the protective film-forming composite sheet 1 </ b> C, the support sheet 10 is made of only the base material 11. Then, the protective film-forming film 13 is laminated on one surface 11a of the substrate 11 (one surface 10a of the support sheet 10). Next, the jig adhesive layer 16 is laminated on a part of the surface 13 a of the protective film forming film 13, that is, in the vicinity of the peripheral edge. Of the surface 13a of the protective film forming film 13, the release film 15 is laminated on the surface on which the jig adhesive layer 16 is not laminated and on the surface 16a (upper surface and side face) of the jig adhesive layer 16. ing.

In the protective film-forming composite sheet 1 </ b> C, the protective film-forming film 13 includes a photoradical initiator having an absorption coefficient of wavelength of 365 nm of 4.0 × 10 ¹ ml / (g · cm) or more.
Further, the adhesive force between the cured protective film-forming film 13 (that is, the protective film) and the support sheet 10, in other words, the adhesive force between the protective film and the substrate 11 is 50 to 1500 mN / 25 mm. It is preferable.

As in the protective film forming composite sheet 1A shown in FIG. 1, the protective film forming composite sheet 1C is formed on the surface 13a of the protective film forming film 13 with the release film 15 removed. The back side of (not shown) is attached. Further, the upper surface of the surface 16a of the jig adhesive layer 16 is used by being attached to a jig such as a ring frame.

FIG. 4 is a sectional view schematically showing still another embodiment of the composite sheet for forming a protective film of the present invention.
The protective sheet-forming composite sheet 1D shown here is the same as the protective film-forming composite sheet 1C shown in FIG. 3 except that it does not include the jig adhesive layer 16. That is, in the protective film forming composite sheet 1 </ b> D, the protective film forming film 13 is laminated on one surface 11 a of the substrate 11. And the peeling film 15 is laminated | stacked on the whole surface 13a of the film 13 for protective film formation.

The protective film-forming composite sheet 1D shown in FIG. 4 is the same as the protective film-forming composite sheet 1B shown in FIG. 2, with the release film 15 removed, of the surface 13a of the protective film-forming film 13, The back surface of a semiconductor wafer (not shown) is attached to a partial area on the center side. Furthermore, the area | region of the peripheral part vicinity of the film 13 for protective film formation is affixed and used for jigs, such as a ring frame.

FIG. 5 is a cross-sectional view schematically showing still another embodiment of the composite sheet for forming a protective film of the present invention.
The protective film-forming composite sheet 1E shown here is the same as the protective film-forming composite sheet 1A shown in FIG. 1 except that the shape of the protective film-forming film is different. That is, the protective film-forming composite sheet 1 </ b> E includes the pressure-sensitive adhesive layer 12 on the base material 11 and the protective film-forming film 23 on the pressure-sensitive adhesive layer 12. The support sheet 10 is a laminate of the base material 11 and the pressure-sensitive adhesive layer 12. In other words, the protective film-forming composite sheet 1 </ b> E has a configuration in which the protective film-forming film 23 is laminated on one surface 10 a of the support sheet 10. The protective film-forming composite sheet 1 </ b> E further includes a release film 15 on the protective film-forming film 23.

In the protective sheet-forming composite sheet 1E, the pressure-sensitive adhesive layer 12 is laminated on one surface 11a of the substrate 11, and a part of the surface 12a of the pressure-sensitive adhesive layer 12, that is, a protective film-forming film is formed in the central region. 23 are stacked. And the peeling film 15 is laminated | stacked on the surface in which the protective film formation film 23 is not laminated | stacked among the surfaces 12a of the adhesive layer 12, and the surface 23a (upper surface and side surface) of the protective film formation film 23. ing.

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

In the protective film-forming composite sheet 1E, the protective film-forming film 23 includes a photoradical initiator having an absorption coefficient of wavelength of 365 nm of 4.0 × 10 ¹ ml / (g · cm) or more.
Further, the adhesive force between the protective film-forming film 23 after curing (ie, the protective film) and the support sheet 10, in other words, the adhesive force between the protective film and the adhesive layer 12 is 50 to 1500 mN / 25 mm. Preferably there is.

In the protective film-forming composite sheet 1E shown in FIG. 5, the back surface of the semiconductor wafer (not shown) is attached to the front surface 23a of the protective film-forming film 23 with the release film 15 removed. Further, the surface of the pressure-sensitive adhesive layer 12 on which the protective film forming film 23 is not laminated is attached to a jig such as a ring frame and used.

In the protective film-forming composite sheet 1E shown in FIG. 5, the surface 12a of the pressure-sensitive adhesive layer 12 is the same as that shown in FIGS. 1 and 3 on the surface on which the protective film-forming film 13 is not laminated. An adhesive layer for jigs may be laminated (not shown). The protective film forming composite sheet 1E provided with such a jig adhesive layer has a jig frame having a ring frame or the like, similar to the protective film forming composite sheet shown in FIGS. Affixed to the jig and used.

Thus, the protective sheet-forming composite sheet of the present invention may have any form of the support sheet and the protective film-forming film, or may be provided with an adhesive layer for jigs. However, normally, as shown in FIGS. 1 and 3, the protective film-forming composite sheet of the present invention having a jig adhesive layer has a jig adhesive layer on the protective film-forming film. Are preferred.

The composite sheet for forming a protective film of the present invention is not limited to the one shown in FIGS. Within the scope of not impairing the effects of the present invention, a part of the structure shown in FIGS. 1 to 5 is changed or deleted, or another structure is added to what has been described so far. Also good.

For example, in the protective film-forming composite sheet shown in FIGS. 3 and 4, an intermediate layer may be provided between the base material 11 and the protective film-forming film 13. Any intermediate layer can be selected according to the purpose.
In the composite sheet for forming a protective film shown in FIGS. 1, 2, and 5, an intermediate layer may be provided between the base material 11 and the pressure-sensitive adhesive layer 12. That is, in the composite sheet for forming a protective film of the present invention, the support sheet may be formed by laminating a base material, an intermediate layer, and an adhesive layer in this order. Here, the intermediate layer is the same as the intermediate layer that may be provided in the protective film-forming composite sheet shown in FIGS.
Further, in the composite sheet for forming a protective film shown in FIGS. 1 to 5, layers other than the intermediate layer may be provided at an arbitrary location.
In the composite sheet for forming a protective film of the present invention, a gap may be partially formed between the release film and the layer that is in direct contact with the release film.
In the composite sheet for forming a protective film of the present invention, the size and shape of each layer can be arbitrarily adjusted according to the purpose.

In the composite sheet for forming a protective film of the present invention, as described later, a layer such as an adhesive layer that is in direct contact with the protective film-forming film of the support sheet is preferably non-energy ray curable. . Such a composite sheet for forming a protective film can more easily pick up a semiconductor chip having a protective film on the back surface.

The support sheet may be transparent, opaque, or colored depending on the purpose.
Among them, in the present invention in which the protective film-forming film has energy ray curability, the support sheet is preferably capable of transmitting energy rays.

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 light transmittance is within such a range, when the protective film-forming film is irradiated with energy rays (ultraviolet rays) via the support sheet, the degree of curing of the protective film-forming film is further improved.
On the other hand, in the support sheet, the upper limit value of the transmittance of light having a wavelength of 375 nm is not particularly limited, but may be 95%, for example.

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 light transmittance is within such a range, when the protective film-forming film or the protective film is irradiated with laser light through the support sheet and printed on these, printing can be performed more clearly.
On the other hand, in the support sheet, the upper limit value of the transmittance of light having a wavelength of 532 nm is not particularly limited, but can be, for example, 95%.

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 light transmittance is within such a range, when the protective film-forming film or the protective film is irradiated with laser light through the support sheet and printed on these, printing can be performed more clearly.
On the other hand, in the support sheet, the upper limit value of the transmittance of light having a wavelength of 1064 nm is not particularly limited, but can be, for example, 95%.
Next, each layer which comprises a support sheet is demonstrated in detail.

-Base material The base material is in the form of a sheet or film, and examples of the constituent material include various resins.
Examples of the resin include the following. Polyethylene such as low density polyethylene (LDPE), linear low density polyethylene (LLDPE), high density polyethylene (HDPE), etc .; polyolefins other than polyethylene such as polypropylene, polybutene, polybutadiene, polymethylpentene, norbornene resin; ethylene-vinyl acetate Polymers, ethylene- (meth) acrylic acid copolymers, ethylene- (meth) acrylic acid ester copolymers, ethylene-based copolymers such as ethylene-norbornene copolymers (copolymers obtained using ethylene as a monomer) Polymer); vinyl chloride resin such as polyvinyl chloride and vinyl chloride copolymer (resin obtained using vinyl chloride as a monomer); polystyrene; polycycloolefin; polyethylene terephthalate, polyethylene naphthalate, polybutylene terf Polyesters such as rate, polyethylene isophthalate, polyethylene-2,6-naphthalene dicarboxylate, wholly aromatic polyesters in which all the structural units have aromatic cyclic groups; copolymers of two or more of the above polyesters; poly ( Poly), polyurethane acrylate, polyimide, polyamide, polycarbonate, fluororesin, polyacetal, modified polyphenylene oxide, polyphenylene sulfide, polysulfone, polyether ketone, and the like.

Moreover, as said resin, polymer alloys, such as a mixture of the said polyester and other resin, are mentioned, for example. The polymer alloy of the polyester and the other resin is preferably one in which the amount of the resin other than the polyester is relatively small.
Examples of the resin include a crosslinked resin in which one or more of the resins exemplified so far are crosslinked; modification of an ionomer or the like using one or more of the resins exemplified so far. Resins can also be mentioned.

In the present specification, “(meth) acrylic acid” is a concept including both “acrylic acid” and “methacrylic acid”. The same applies to terms similar to (meth) acrylic acid.

The resin constituting the substrate may be only one kind, or two or more kinds, and in the case of two or more kinds, the combination and ratio thereof can be arbitrarily selected.

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

The thickness of the substrate is preferably 50 to 300 μm, more preferably 60 to 100 μm. When the thickness of the substrate is within such a range, the flexibility of the composite sheet for forming a protective film and the adhesiveness to a semiconductor wafer or semiconductor chip are further improved.
Here, “the thickness of the substrate” means the thickness of the entire substrate. For example, the thickness of the substrate composed of a plurality of layers means the total thickness of all the layers constituting the substrate. means.

The base material is preferably one having high thickness accuracy, that is, one in which variation in thickness is suppressed regardless of the part. Among the above-mentioned constituent materials, examples of materials that can be used to construct a base material having such a high thickness accuracy include the following. For example, polyethylene, polyolefins other than polyethylene, polyethylene terephthalate, ethylene-vinyl acetate copolymer, and the like.

The base material contains various known additives such as a filler, a colorant, an antistatic agent, an antioxidant, an organic lubricant, a catalyst, and a softener (plasticizer) in addition to the main constituent material such as the resin. May be.

The optical characteristics of the base material only need to satisfy the optical characteristics of the support sheet described above. That is, the substrate may be transparent or opaque, may be colored according to the purpose, or other layers may be deposited.
And in this invention in which the film for protective film formation has energy-beam sclerosis | hardenability, what a base material permeate | transmits an energy beam is preferable.

In order to improve the adhesion with other layers such as a pressure-sensitive adhesive layer provided on the substrate, the substrate is subjected to a roughening treatment such as sandblast treatment, solvent treatment, corona discharge treatment, electron beam irradiation treatment, plasma treatment. The surface may be subjected to oxidation treatment such as ozone / ultraviolet irradiation treatment, flame treatment, chromic acid treatment, and hot air treatment.
The base material may have a surface subjected to primer treatment.
In addition, the base material prevents the base material from adhering to other sheets or the base material from adhering to the adsorption table when the antistatic coating layer and the protective film-forming composite sheet are stored in an overlapping manner. It may have a layer or the like.
Among these, the substrate preferably has a surface subjected to electron beam irradiation treatment from the viewpoint that generation of fragments of the substrate due to blade friction during dicing is suppressed.

The base material can be manufactured by a known method. For example, a base material containing a resin can be produced by molding a resin composition containing the resin.

-Adhesive layer The said adhesive layer is a sheet form or a film form, and contains an adhesive.
Examples of the pressure-sensitive adhesive include the following. Examples thereof include adhesive resins such as acrylic resins, urethane resins, rubber resins, silicone resins, epoxy resins, polyvinyl ethers, polycarbonates, ester resins, and acrylic resins are preferred.

In the present invention, the “adhesive resin” is a concept including both an adhesive resin and an adhesive resin. For example, not only the resin itself has adhesiveness, but also includes a resin that exhibits adhesiveness in combination with other components such as additives, and a resin that exhibits adhesiveness due to the presence of a trigger such as heat or water.

The pressure-sensitive adhesive layer may be composed of one layer (single layer) or may be composed of two or more layers. In the case of a plurality of layers, these layers may be the same as or different from each other, and the combination of these layers is not particularly limited.

The thickness of the pressure-sensitive adhesive layer is preferably 1 to 100 μm, more preferably 1 to 60 μm, and particularly preferably 1 to 30 μm.
Here, the “thickness of the pressure-sensitive adhesive layer” means the thickness of the entire pressure-sensitive adhesive layer. For example, the thickness of the pressure-sensitive adhesive layer composed of a plurality of layers means the total thickness of all the layers constituting the pressure-sensitive adhesive layer.

The optical properties of the pressure-sensitive adhesive layer only need to satisfy the optical properties of the support sheet described above. That is, the pressure-sensitive adhesive layer may be transparent, opaque, or colored depending on the purpose.
In the present invention in which the protective film-forming film has energy ray curability, the pressure-sensitive adhesive layer is preferably capable of transmitting energy rays.

The pressure-sensitive adhesive layer may be formed using an energy ray-curable pressure-sensitive adhesive, or may be formed using a non-energy ray-curable pressure-sensitive adhesive. The pressure-sensitive adhesive layer formed using the energy ray-curable pressure-sensitive adhesive can easily adjust the physical properties before and after curing.

<< Adhesive composition >>
The pressure-sensitive adhesive layer can be formed using a pressure-sensitive adhesive composition containing a pressure-sensitive adhesive. For example, an adhesive layer can be formed in the target site | part by applying an adhesive composition to the formation object surface of an adhesive layer, and making it dry as needed. A more specific method for forming the pressure-sensitive adhesive layer will be described later in detail, along with methods for forming other layers. The ratio of the content of components that do not vaporize at room temperature in the pressure-sensitive adhesive composition is usually the same as the ratio of the content of the components of the pressure-sensitive adhesive layer. In the present specification, “normal temperature” means a temperature at which cooling or heating is not performed, that is, a normal temperature. For example, a temperature of 15 to 25 ° C. can be mentioned.

Application of the pressure-sensitive adhesive composition may be performed by a known method. Examples thereof include methods using various coaters such as an air knife coater, blade coater, bar coater, gravure coater, roll coater, roll knife coater, curtain coater, die coater, knife coater, screen coater, Meyer bar coater, and kiss coater.

The drying conditions for the pressure-sensitive adhesive composition are not particularly limited. The pressure-sensitive adhesive composition is preferably heat-dried when it contains a solvent described later. In this case, for example, drying is preferably performed at 70 to 130 ° C. for 10 seconds to 5 minutes.

When the pressure-sensitive adhesive layer is energy ray curable, examples of the pressure sensitive adhesive composition containing the energy ray curable pressure sensitive adhesive, that is, the energy ray curable pressure sensitive adhesive composition, include the following. For example, a pressure-sensitive adhesive containing a non-energy ray-curable pressure-sensitive adhesive resin (I-1a) (hereinafter sometimes abbreviated as “pressure-sensitive resin (I-1a)”) and an energy beam-curable compound Composition (I-1); energy ray curable adhesive resin (I-2a) in which an unsaturated group is introduced into the side chain of non-energy ray curable adhesive resin (I-1a) (hereinafter referred to as “ A pressure-sensitive adhesive composition (I-2) containing a pressure-sensitive adhesive resin (I-2a); and the pressure-sensitive adhesive resin (I-2a) and an energy ray-curable compound. Examples thereof include a pressure-sensitive adhesive composition (I-3).

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

[Adhesive resin (I-1a)]
The adhesive resin (I-1a) is preferably an acrylic resin.
As said acrylic resin, the acrylic polymer which has a structural unit derived from the (meth) acrylic-acid alkylester at least is mentioned, for example.
The acrylic resin may have only one type of structural unit, two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected.

Examples of the (meth) acrylic acid alkyl ester include those in which the alkyl group constituting the alkyl ester has 1 to 20 carbon atoms. The alkyl group is preferably linear or branched.
More specifically, as (meth) acrylic acid alkyl ester, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, (meth) acrylic acid n-butyl, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, (Meth) acrylic acid 2-ethylhexyl, (meth) acrylic acid isooctyl, (meth) acrylic acid n-octyl, (meth) acrylic acid n-nonyl, (meth) acrylic acid isononyl, (meth) acrylic acid decyl, (meta) ) Undecyl acrylate, dodecyl (meth) acrylate (lauryl (meth) acrylate), ( T) Decyl acrylate, tetradecyl (meth) acrylate (myristyl (meth) acrylate), pentadecyl (meth) acrylate, hexadecyl (meth) acrylate (palmityl (meth) acrylate), heptadecyl (meth) acrylate, Examples thereof include octadecyl (meth) acrylate (stearyl (meth) acrylate), nonadecyl (meth) acrylate, icosyl (meth) acrylate, and the like.

From the viewpoint of improving the adhesive strength of the pressure-sensitive adhesive layer, the acrylic polymer preferably has a structural unit derived from a (meth) acrylic acid alkyl ester in which the alkyl group has 4 or more carbon atoms. In view of further improving the adhesive strength of the pressure-sensitive adhesive layer, the alkyl group preferably has 4 to 12 carbon atoms, more preferably 4 to 8 carbon atoms. In addition, the (meth) acrylic acid alkyl ester having 4 or more carbon atoms in the alkyl group is preferably an acrylic acid alkyl ester.

The acrylic polymer preferably has a structural unit derived from a functional group-containing monomer in addition to the structural unit derived from an alkyl (meth) acrylate.
As the functional group-containing monomer, for example, the functional group reacts with a cross-linking agent described later to become a starting point of cross-linking, or the functional group reacts with an unsaturated group in the unsaturated group-containing compound described later. And those that allow introduction of an unsaturated group into the side chain of the acrylic polymer.

Examples of the functional group in the functional group-containing monomer include a hydroxyl group, a carboxy group, an amino group, and an epoxy group.
That is, examples of the functional group-containing monomer include a hydroxyl group-containing monomer, a carboxy group-containing monomer, an amino group-containing monomer, and an epoxy group-containing monomer.

Examples of the hydroxyl group-containing monomer include the following. For example, hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, Hydroxyalkyl (meth) acrylates such as 3-hydroxybutyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate; non- (meth) acrylic unsaturated alcohols such as vinyl alcohol and allyl alcohol ((meth) acryloyl) And unsaturated alcohol having no skeleton).

Examples of the carboxy group-containing monomer include the following. For example, ethylenically unsaturated monocarboxylic acids such as (meth) acrylic acid and crotonic acid (monocarboxylic acids having an ethylenically unsaturated bond); ethylenically unsaturated dicarboxylic acids such as fumaric acid, itaconic acid, maleic acid and citraconic acid Examples thereof include acids (dicarboxylic acids having an ethylenically unsaturated bond); anhydrides of the ethylenically unsaturated dicarboxylic acids; (meth) acrylic acid carboxyalkyl esters such as 2-carboxyethyl methacrylate and the like.

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

The functional group-containing monomer constituting the acrylic polymer may be only one type or two or more types. In the case of two or more types, the combination and ratio thereof can be arbitrarily selected.

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

In addition to the structural unit derived from the (meth) acrylic acid alkyl ester and the structural unit derived from the functional group-containing monomer, the acrylic polymer may further have a structural unit derived from another monomer.
The other monomer is not particularly limited as long as it is copolymerizable with (meth) acrylic acid alkyl ester or the like.
Examples of the other monomer include styrene, α-methylstyrene, vinyl toluene, vinyl formate, vinyl acetate, acrylonitrile, acrylamide and the like.

The other monomer constituting the acrylic polymer may be one kind or two or more kinds. In the case of two or more types, the combination and ratio thereof can be arbitrarily selected.

The acrylic polymer can be used as the above-mentioned non-energy ray curable adhesive resin (I-1a).
On the other hand, the functional group in the acrylic polymer is reacted with an unsaturated group-containing compound having an energy ray-polymerizable unsaturated group (energy ray-polymerizable group). It can be used as the resin (I-2a).

The pressure-sensitive adhesive composition (I-1) contained in the pressure-sensitive adhesive composition (I-1) may be one type or two or more types. In the case of two or more types, the combination and ratio thereof can be arbitrarily selected.

In the pressure-sensitive adhesive composition (I-1), the content of the pressure-sensitive resin (I-1a) is preferably 5 to 99% by mass, more preferably 10 to 95% by mass, and 15 to 90%. It is particularly preferable that the content is% by mass.

[Energy ray curable compound]
Examples of the energy ray-curable compound contained in the pressure-sensitive adhesive composition (I-1) include monomers or oligomers having an energy ray-polymerizable unsaturated group and curable by irradiation with energy rays.
Among the energy ray curable compounds, examples of the monomer include the following. For example, trimethylolpropane tri (meth) acrylate, pentaerythritol (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,4-butylene glycol di (meth) acrylate, 1,6 -Polyvalent (meth) acrylates such as hexanediol (meth) acrylate; urethane (meth) acrylate; polyester (meth) acrylate; polyether (meth) acrylate; epoxy (meth) acrylate and the like.
Among the energy ray-curable compounds, examples of the oligomer include an oligomer formed by polymerizing the monomers exemplified above.
The energy ray-curable compound is preferably a urethane (meth) acrylate or a urethane (meth) acrylate oligomer from the viewpoint that the molecular weight is relatively large and the storage elastic modulus of the pressure-sensitive adhesive layer is hardly lowered.

The energy ray-curable compound contained in the pressure-sensitive adhesive composition (I-1) may be only one type or two or more types. In the case of two or more types, the combination and ratio thereof can be arbitrarily selected.

In the pressure-sensitive adhesive composition (I-1), the content of the energy ray-curable compound is preferably 1 to 95% by mass, more preferably 5 to 90% by mass, and 10 to 85% by mass. % Is particularly preferred.

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

For example, the cross-linking agent reacts with the functional group to cross-link the adhesive resins (I-1a).
The following are mentioned as a crosslinking agent. For example, tolylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, isocyanate-based cross-linking agents such as adducts of these diisocyanates (cross-linking agents having an isocyanate group); epoxy-based cross-linking agents such as ethylene glycol glycidyl ether (cross-linking having a glycidyl group) Agent); aziridine-based crosslinking agent (cross-linking agent having an aziridinyl group) such as hexa [1- (2-methyl) -aziridinyl] triphosphatriazine; metal chelate-based crosslinking agent such as aluminum chelate (cross-linking having a metal chelate structure) Agent); isocyanurate-based crosslinking agent (crosslinking agent having an isocyanuric acid skeleton) and the like.
The crosslinking agent is preferably an isocyanate-based crosslinking agent from the viewpoints of improving the cohesive strength of the pressure-sensitive adhesive and improving the pressure-sensitive adhesive strength of the pressure-sensitive adhesive layer, and being easily available.

The crosslinking agent contained in the pressure-sensitive adhesive composition (I-1) may be only one kind or two or more kinds. In the case of two or more types, the combination and ratio thereof can be arbitrarily selected.

In the pressure-sensitive adhesive composition (I-1), the content of the crosslinking agent is preferably 0.01 to 50 parts by mass with respect to 100 parts by mass of the pressure-sensitive adhesive resin (I-1a). The amount is more preferably 0.1 to 20 parts by mass, and particularly preferably 0.3 to 15 parts by mass.

[Photopolymerization initiator]
The pressure-sensitive adhesive composition (I-1) may further contain a photopolymerization initiator. The pressure-sensitive adhesive composition (I-1) containing a photopolymerization initiator sufficiently proceeds with a curing reaction even when irradiated with a relatively low energy beam such as ultraviolet rays.

Examples of the photopolymerization initiator include the following. For example, benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, methyl benzoin benzoate, benzoin dimethyl ketal; acetophenone, 2-hydroxy-2-methyl-1-phenyl Acetophenone compounds such as propan-1-one and 2,2-dimethoxy-1,2-diphenylethane-1-one; bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, 2,4,6- Acylphosphine oxide compounds such as trimethylbenzoyldiphenylphosphine oxide; Sulfide compounds such as benzylphenyl sulfide and tetramethylthiuram monosulfide; 1-hydroxycyclo Α-ketol compounds such as xylphenyl ketone; azo compounds such as azobisisobutyronitrile; titanocene compounds such as titanocene; thioxanthone compounds such as thioxanthone; peroxide compounds; diketone compounds such as diacetyl; benzyl; 1,2-diethylthioxanthone; 1,2-diphenylmethane; 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone; 2-chloroanthraquinone and the like.
As the photopolymerization initiator, for example, a quinone compound such as 1-chloroanthraquinone; a photosensitizer such as amine can be used.

The photopolymerization initiator contained in the pressure-sensitive adhesive composition (I-1) may be one kind or two or more kinds. In the case of two or more types, the combination and ratio thereof can be arbitrarily selected.

In the pressure-sensitive adhesive composition (I-1), the content of the photopolymerization initiator is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the energy ray curable compound. The amount is more preferably 0.03 to 10 parts by weight, and particularly preferably 0.05 to 5 parts by weight.

[Other additives]
The pressure-sensitive adhesive composition (I-1) may contain other additives that do not fall under any of the above-mentioned components within a range not impairing the effects of the present invention.
Examples of the other additives include antistatic agents, antioxidants, softeners (plasticizers), fillers (fillers), rust inhibitors, colorants (pigments, dyes), sensitizers, and tackifiers. And known additives such as reaction retarders and crosslinking accelerators (catalysts).
Incidentally, the reaction retarding agent means, for example, an undesired crosslinking reaction in the pressure-sensitive adhesive composition (I-1) during storage by the action of the catalyst mixed in the pressure-sensitive adhesive composition (I-1). It suppresses progress. Examples of the reaction retarder include those that form a chelate complex by chelation against a catalyst. More specifically, one having two or more carbonyl groups (—C (═O) —) in one molecule can be mentioned.

The other additive contained in the pressure-sensitive adhesive composition (I-1) may be one type or two or more types. In the case of two or more types, the combination and ratio thereof can be arbitrarily selected.

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

[solvent]
The pressure-sensitive adhesive composition (I-1) may contain a solvent. Since the pressure-sensitive adhesive composition (I-1) contains a solvent, the suitability for coating on the surface to be coated is improved.

The solvent is preferably an organic solvent. Examples of the organic solvent include ketones such as methyl ethyl ketone and acetone; esters such as ethyl acetate (carboxylic acid esters); ethers such as tetrahydrofuran and dioxane; aliphatic hydrocarbons such as cyclohexane and n-hexane; toluene and xylene. Aromatic hydrocarbons; alcohols such as 1-propanol and 2-propanol.

As the solvent, for example, the solvent used in the production of the adhesive resin (I-1a) may be used as it is in the adhesive composition (I-1) without being removed from the adhesive resin (I-1a). . Further, the same or different type of solvent used in the production of the adhesive resin (I-1a) may be added separately during the production of the adhesive composition (I-1).

The solvent contained in the pressure-sensitive adhesive composition (I-1) may be one kind or two or more kinds. In the case of two or more types, the combination and ratio thereof can be arbitrarily selected.

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

<Adhesive composition (I-2)>
As described above, the pressure-sensitive adhesive composition (I-2) is an energy-ray-curable pressure-sensitive adhesive resin in which an unsaturated group is introduced into the side chain of the non-energy-ray-curable pressure-sensitive adhesive resin (I-1a). (I-2a) is contained.

[Adhesive resin (I-2a)]
The adhesive resin (I-2a) can be obtained, for example, by reacting a functional group in the adhesive resin (I-1a) with an unsaturated group-containing compound having an energy ray polymerizable unsaturated group.

The unsaturated group-containing compound can be bonded to the adhesive resin (I-1a) by reacting with the functional group in the adhesive resin (I-1a) in addition to the energy ray polymerizable unsaturated group. A compound having a group.
Examples of the energy ray-polymerizable unsaturated group include (meth) acryloyl group, vinyl group (ethenyl group), allyl group (2-propenyl group) and the like, and (meth) acryloyl group is preferable.
Examples of the group capable of binding to the functional group in the adhesive resin (I-1a) include, for example, an isocyanate group and a glycidyl group that can be bonded to a hydroxyl group or an amino group, and a hydroxyl group and an amino group that can be bonded to a carboxy group or an epoxy group. Etc.

Examples of the unsaturated group-containing compound include (meth) acryloyloxyethyl isocyanate, (meth) acryloyl isocyanate, glycidyl (meth) acrylate, and the like.

The pressure-sensitive adhesive composition (I-2) contained in the pressure-sensitive adhesive composition (I-2) may be one type or two or more types. In the case of two or more types, the combination and ratio thereof can be arbitrarily selected.

In the pressure-sensitive adhesive composition (I-2), the content of the pressure-sensitive resin (I-2a) is preferably 5 to 99% by mass. The content is more preferably 10 to 95% by mass, and particularly preferably 10 to 90% by mass.

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

Examples of the crosslinking agent in the pressure-sensitive adhesive composition (I-2) include the same crosslinking agents as in the pressure-sensitive adhesive composition (I-1).
The crosslinking agent contained in the pressure-sensitive adhesive composition (I-2) may be only one kind or two or more kinds. In the case of two or more types, the combination and ratio thereof can be arbitrarily selected.

In the pressure-sensitive adhesive composition (I-2), the content of the crosslinking agent is preferably 0.01 to 50 parts by mass with respect to 100 parts by mass of the pressure-sensitive adhesive resin (I-2a). The amount is more preferably 0.1 to 20 parts by weight, and particularly preferably 0.3 to 15 parts by weight.

[Photopolymerization initiator]
The pressure-sensitive adhesive composition (I-2) may further contain a photopolymerization initiator. The pressure-sensitive adhesive composition (I-2) containing the photopolymerization initiator sufficiently proceeds with the curing reaction even when irradiated with a relatively low energy beam such as ultraviolet rays.

Examples of the photopolymerization initiator in the pressure-sensitive adhesive composition (I-2) include the same photopolymerization initiator as in the pressure-sensitive adhesive composition (I-1).
The photopolymerization initiator contained in the pressure-sensitive adhesive composition (I-2) may be only one type, or two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected.

In the pressure-sensitive adhesive composition (I-2), the content of the photopolymerization initiator is preferably 0.01 to 20 parts by weight with respect to 100 parts by weight of the pressure-sensitive adhesive resin (I-2a). . The amount is more preferably 0.03 to 10 parts by mass, and particularly preferably 0.05 to 5 parts by mass.

[Other additives]
The pressure-sensitive adhesive composition (I-2) may contain other additives that do not fall under any of the above-mentioned components within a range not impairing the effects of the present invention.
Examples of the other additive in the pressure-sensitive adhesive composition (I-2) include the same additives as those in the pressure-sensitive adhesive composition (I-1).
The other additive contained in the pressure-sensitive adhesive composition (I-2) may be one kind or two or more kinds. In the case of two or more types, the combination and ratio thereof can be arbitrarily selected.

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

[solvent]
The pressure-sensitive adhesive composition (I-2) may contain a solvent for the same purpose as that of the pressure-sensitive adhesive composition (I-1).
Examples of the solvent in the pressure-sensitive adhesive composition (I-2) include the same solvents as those in the pressure-sensitive adhesive composition (I-1).
The solvent contained in the pressure-sensitive adhesive composition (I-2) may be only one kind or two or more kinds. In the case of two or more types, the combination and ratio thereof can be arbitrarily selected.
In the pressure-sensitive adhesive composition (I-2), the content of the solvent is not particularly limited, and may be adjusted as appropriate.

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

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

[Energy ray curable compound]
Examples of the energy ray-curable compound contained in the pressure-sensitive adhesive composition (I-3) include monomers and oligomers having an energy ray-polymerizable unsaturated group and curable by irradiation with energy rays. Furthermore, the same thing as the energy-beam curable compound which adhesive composition (I-1) contains is mentioned.
The energy ray-curable compound contained in the pressure-sensitive adhesive composition (I-3) may be only one type or two or more types. In the case of two or more types, the combination and ratio thereof can be arbitrarily selected.

In the pressure-sensitive adhesive composition (I-3), the content of the energy ray-curable compound is 0.01 to 300 parts by mass with respect to 100 parts by mass of the adhesive resin (I-2a). It is preferable. The amount is more preferably 0.03 to 200 parts by mass, and particularly preferably 0.05 to 100 parts by mass.

[Photopolymerization initiator]
The pressure-sensitive adhesive composition (I-3) may further contain a photopolymerization initiator. The pressure-sensitive adhesive composition (I-3) containing a photopolymerization initiator sufficiently undergoes a curing reaction even when irradiated with energy rays of relatively low energy such as ultraviolet rays.

Examples of the photopolymerization initiator in the pressure-sensitive adhesive composition (I-3) include the same photopolymerization initiator as in the pressure-sensitive adhesive composition (I-1).
The photopolymerization initiator contained in the pressure-sensitive adhesive composition (I-3) may be only one kind or two or more kinds. In the case of two or more types, the combination and ratio thereof can be arbitrarily selected.

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

[Other additives]
The pressure-sensitive adhesive composition (I-3) may contain other additives that do not fall under any of the above-mentioned components within a range not impairing the effects of the present invention.
Examples of the other additive include the same additives as those in the pressure-sensitive adhesive composition (I-1).
The other additive contained in the pressure-sensitive adhesive composition (I-3) may be one kind or two or more kinds. In the case of two or more types, the combination and ratio thereof can be arbitrarily selected.

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

[solvent]
The pressure-sensitive adhesive composition (I-3) may contain a solvent for the same purpose as that of the pressure-sensitive adhesive composition (I-1).
Examples of the solvent in the pressure-sensitive adhesive composition (I-3) include the same solvents as those in the pressure-sensitive adhesive composition (I-1).
The solvent contained in the pressure-sensitive adhesive composition (I-3) may be only one type or two or more types. In the case of two or more types, the combination and ratio thereof can be arbitrarily selected.
In the pressure-sensitive adhesive composition (I-3), the content of the solvent is not particularly limited, and may be adjusted as appropriate.

<Adhesive compositions other than adhesive compositions (I-1) to (I-3)>
So far, the pressure-sensitive adhesive composition (I-1), the pressure-sensitive adhesive composition (I-2) and the pressure-sensitive adhesive composition (I-3) have been mainly described. However, what has been described as these containing components is the general pressure-sensitive adhesive composition other than these three types of pressure-sensitive adhesive compositions (in this specification, “pressure-sensitive adhesive compositions (I-1) to (I- It can also be used in the same manner as “adhesive composition other than 3)”.

Examples of the pressure-sensitive adhesive composition other than the pressure-sensitive adhesive compositions (I-1) to (I-3) include non-energy ray-curable pressure-sensitive adhesive compositions in addition to the energy ray-curable pressure-sensitive adhesive composition.
Examples of the non-energy ray curable pressure-sensitive adhesive composition include the following. For example, it contains non-energy ray-curable adhesive resin (I-1a) such as acrylic resin, urethane resin, rubber resin, silicone resin, epoxy resin, polyvinyl ether, polycarbonate, ester resin, etc. An adhesive composition (I-4) can be mentioned. Among these, those containing an acrylic resin are preferable.

The pressure-sensitive adhesive compositions other than the pressure-sensitive adhesive compositions (I-1) to (I-3) preferably contain one or more kinds of crosslinking agents. The content can be the same as in the case of the above-mentioned pressure-sensitive adhesive composition (I-1) and the like.

<Adhesive composition (I-4)>
Preferred examples of the pressure-sensitive adhesive composition (I-4) include those containing the pressure-sensitive adhesive resin (I-1a) and a crosslinking agent.

[Adhesive resin (I-1a)]
Examples of the adhesive resin (I-1a) in the pressure-sensitive adhesive composition (I-4) include the same as the pressure-sensitive adhesive resin (I-1a) in the pressure-sensitive adhesive composition (I-1).
The adhesive resin (I-1a) contained in the adhesive composition (I-4) may be one type or two or more types. In the case of two or more types, the combination and ratio thereof can be arbitrarily selected.

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

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

Examples of the crosslinking agent in the pressure-sensitive adhesive composition (I-4) include the same crosslinking agents as those in the pressure-sensitive adhesive composition (I-1).
The crosslinking agent contained in the pressure-sensitive adhesive composition (I-4) may be only one kind or two or more kinds. In the case of two or more types, the combination and ratio thereof can be arbitrarily selected.

In the pressure-sensitive adhesive composition (I-4), the content of the crosslinking agent is preferably 0.01 to 50 parts by weight with respect to 100 parts by weight of the pressure-sensitive adhesive resin (I-1a). The amount is more preferably 0.1 to 20 parts by mass, and particularly preferably 0.3 to 15 parts by mass.

[Other additives]
The pressure-sensitive adhesive composition (I-4) may contain other additives that do not fall under any of the above-mentioned components within a range not impairing the effects of the present invention.
Examples of the other additive include the same additives as those in the pressure-sensitive adhesive composition (I-1).
The other additive contained in the pressure-sensitive adhesive composition (I-4) may be only one type, or two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected.

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

[solvent]
The pressure-sensitive adhesive composition (I-4) may contain a solvent for the same purpose as that of the pressure-sensitive adhesive composition (I-1).
Examples of the solvent in the pressure-sensitive adhesive composition (I-4) include the same solvents as those in the pressure-sensitive adhesive composition (I-1).
The solvent contained in the pressure-sensitive adhesive composition (I-4) may be one type or two or more types. In the case of two or more types, the combination and ratio thereof can be arbitrarily selected.
In the pressure-sensitive adhesive composition (I-4), the content of the solvent is not particularly limited and may be appropriately adjusted.

In the composite sheet for forming a protective film of the present invention, the pressure-sensitive adhesive layer is preferably non-energy ray curable. This is because when the pressure-sensitive adhesive layer is energy ray curable, it is sometimes impossible to suppress the pressure-sensitive adhesive layer from being simultaneously cured when the protective film-forming film is cured by irradiation with energy rays. If the pressure-sensitive adhesive layer is cured at the same time as the protective film-forming film, the cured protective film-forming film and the pressure-sensitive adhesive layer may stick to the interface so as not to be peeled off. In that case, a cured protective film-forming film, that is, a semiconductor chip provided with a protective film on the back surface (in this specification, sometimes referred to as “semiconductor chip with protective film”) is cured adhesive layer. It becomes difficult to make it peel from the support sheet provided with. As a result, the semiconductor chip with a protective film cannot be picked up normally. By making the pressure-sensitive adhesive layer non-energy ray curable with the support sheet in the present invention, such a problem can be reliably avoided and a semiconductor chip with a protective film can be picked up more easily.

Here, the effect when the pressure-sensitive adhesive layer is non-energy ray curable has been described. However, even if the layer in direct contact with the protective film-forming film of the support sheet is a layer other than the pressure-sensitive adhesive layer, the same effect can be obtained as long as this layer is non-energy ray curable.

<< Method for producing pressure-sensitive adhesive composition >>
The pressure-sensitive adhesive compositions other than the pressure-sensitive adhesive compositions (I-1) to (I-3) such as the pressure-sensitive adhesive compositions (I-1) to (I-3) and the pressure-sensitive adhesive composition (I-4) It is obtained by blending each component for constituting the pressure-sensitive adhesive composition, such as the pressure-sensitive adhesive and components other than the pressure-sensitive adhesive, if necessary.
The order of addition at the time of blending each component is not particularly limited, and two or more components may be added simultaneously.

When using a solvent, it may be used by mixing the solvent with any compounding component other than the solvent and diluting the compounding component in advance. Moreover, you may use by mixing a solvent with these compounding components, without diluting any compounding components other than a solvent previously.
The method of mixing each component at the time of mixing is not particularly limited. For example, the method may be appropriately selected from known methods such as a method of mixing by rotating a stirrer or a stirring blade; a method of mixing using a mixer; a method of mixing by applying ultrasonic waves.
The temperature and time during the addition and mixing of each component are not particularly limited as long as each compounding component does not deteriorate, and may be adjusted as appropriate, but the temperature is preferably 15 to 30 ° C.

◎ Protective film-forming film In the present invention, the adhesive force between the protective film obtained by curing the protective film-forming film and the support sheet is preferably 50 to 1500 mN / 25 mm. More preferably, it is 52 to 1450 mN / 25 mm, and further preferably 53 to 1430 mN / 25 mm. When the adhesive force is greater than or equal to the lower limit, pickup of a semiconductor chip with a protective film that is not the purpose is suppressed during pickup of the semiconductor chip with a protective film. As a result, the target semiconductor chip with a protective film can be picked up with high selectivity. Moreover, when the adhesive force is equal to or less than the upper limit value, cracking and chipping of the semiconductor chip are suppressed when the semiconductor chip with a protective film is picked up. Thus, when the adhesive force is within a specific range, the composite sheet for forming a protective film has good pickup suitability.

In the present invention, even after the protective film-forming film is cured, the laminated structure of the cured product of the support sheet and the protective film-forming film (in other words, the support sheet and the protective film) is maintained. As long as this laminate structure is referred to as a “composite sheet for forming a protective film”.

The adhesive force between the protective film and the support sheet can be measured by the following method.
That is, a protective film-forming composite sheet having a width of 25 mm and an arbitrary length is attached to an adherend by the protective film-forming film.
Next, the protective film-forming film is cured by irradiating energy rays to form a protective film. Thereafter, the support sheet is peeled off at a peeling speed of 300 mm / min from this protective film adhered to the adherend. At this time, the support sheet is peeled in the length direction (the length direction of the composite sheet for forming the protective film) so that the surfaces of the protective film and the support sheet that are in contact with each other form an angle of 180 °. The so-called 180 ° peeling is performed. And the load (peeling force) at the time of this 180 degree | times peeling is measured, and let the measured value be the said adhesive force (mN / 25mm).

The length of the protective film-forming composite sheet used for measurement is not particularly limited as long as the adhesive force can be stably detected. It is preferably 100 to 300 mm. In the measurement, it is preferable that the protective sheet-forming composite sheet is stuck on the adherend and the sticking state of the protective film-forming composite sheet is stabilized.

In the present invention, the adhesive force between the protective film-forming film and the support sheet is not particularly limited. For example, it may be 80 mN / 25 mm or more, but is preferably 100 mN / 25 mm or more. It is more preferably 150 mN / 25 mm or more, and particularly preferably 200 mN / 25 mm or more. When the adhesive force is 100 mN / 25 mm or more, peeling between the protective film-forming film and the support sheet is suppressed during dicing. As a result, for example, scattering from the support sheet of the semiconductor chip provided with the protective film forming film on the back surface is suppressed.
On the other hand, the upper limit of the adhesive force between the protective film-forming film and the support sheet is not particularly limited. For example, it can be any of 4000 mN / 25 mm, 3500 mN / 25 mm, 3000 mN / 25 mm, and the like. However, these are examples.

The adhesive force between the protective film-forming film and the support sheet is between the protective film and the support sheet, except that the protective film-forming film used for measurement is not cured by irradiation with energy rays. It can be measured by the same method as adhesive strength.

The above-mentioned adhesive force between the protective film and the support sheet and the adhesive force between the protective film-forming film and the support sheet can be appropriately adjusted. For example, it can be adjusted by adjusting the type and amount of the components contained in the protective film-forming film, the constituent material of the layer on the support sheet where the protective film-forming film is provided, the surface state of this layer, and the like.

For example, the type and amount of the component contained in the protective film-forming film can be adjusted by the type and amount of the component contained in the protective film-forming composition described below. And among the components of the composition for forming a protective film, for example, the type and content of the polymer (b) having no energy ray curable group, the content of the filler (d), or the crosslinking agent (f) By adjusting the content of, the adhesive force between the protective film or the protective film-forming film and the support sheet can be adjusted more easily.

In addition, for example, when the layer for providing the protective film-forming film in the support sheet is an adhesive layer, the constituent material can be adjusted as appropriate by adjusting the type and amount of components contained in the adhesive layer. . And the kind and quantity of the component of an adhesive layer can be adjusted with the kind and quantity of the component of an above-mentioned adhesive composition.
On the other hand, when the layer for providing the protective film-forming film in the support sheet is a base material, the adhesive force between the protective film or the protective film-forming film and the support sheet is not limited to the constituent material of the base material. The surface condition of the substrate can also be adjusted. And the surface state of a base material can be adjusted by performing the following processes. For example, the surface treatment mentioned above for improving the adhesion to other layers of the substrate, that is, roughening treatment by sandblast treatment, solvent treatment, etc .; corona discharge treatment, electron beam irradiation treatment, plasma treatment, ozone -Oxidation treatment such as ultraviolet irradiation treatment, flame treatment, chromic acid treatment, hot air treatment, etc .;

The protective film-forming film has energy ray curability. For example, what contains an energy-beam curable component (a) and a photoradical initiator (c ') is mentioned.
The energy ray curable component (a) is preferably uncured, preferably tacky, and more preferably uncured and tacky.

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

The thickness of the protective film-forming film is preferably 1 to 100 μm. It is more preferably 5 to 75 μm, and particularly preferably 5 to 50 μm. When the thickness of the protective film-forming film is equal to or more than the lower limit value, a protective film having higher protective ability can be formed. Moreover, when the thickness of the protective film-forming film is equal to or less than the upper limit, an excessive thickness is suppressed.
Here, the “thickness of the protective film-forming film” means the thickness of the entire protective film-forming film. For example, the thickness of the protective film-forming film composed of a plurality of layers means the total thickness of all layers constituting the protective film-forming film.

The curing conditions for forming the protective film by curing the protective film-forming film are not particularly limited as long as the degree of curing is such that the protective film sufficiently exhibits its function. What is necessary is just to select suitably according to the kind of film for protective film formation.
For example, the illuminance of the energy rays when the protective film-forming film is cured is preferably 4 to 280 mW / cm ² . The amount of energy rays during the curing is preferably 3 to 1000 mJ / cm ² .

<< Composition for forming protective film >>
The protective film-forming film can be formed using a protective film-forming composition containing the constituent materials. For example, the protective film-forming film can be formed at the target site by applying the protective film-forming composition to the surface on which the protective film-forming film is to be formed and drying it as necessary. In the composition for forming a protective film, the content ratio of components that do not vaporize at room temperature is usually the same as the content ratio of the components of the film for forming a protective film. Here, “normal temperature” is as described above.

Coating of the protective film forming composition may be performed by a known method. Examples thereof include methods using various coaters such as an air knife coater, blade coater, bar coater, gravure coater, roll coater, roll knife coater, curtain coater, die coater, knife coater, screen coater, Meyer bar coater, and kiss coater.

The drying conditions of the protective film forming composition are not particularly limited. When the composition for forming a protective film contains a solvent described later, it is preferably dried by heating. In this case, for example, it is preferably dried at 70 to 130 ° C. for 10 seconds to 5 minutes.

<Composition for forming protective film (IV-1)>
Examples of the protective film-forming composition include the protective film-forming composition (IV-1) containing the energy ray-curable component (a) and the photo radical initiator (c ′).

[Energy ray curable component (a)]
The energy ray-curable component (a) is a component that is cured by irradiation with energy rays, and is also a component for imparting film-forming property, flexibility, and the like to the protective film-forming film.
Examples of the energy ray-curable component (a) include a polymer (a1) having an energy ray-curable group and a weight average molecular weight of 80000 to 2000000, and an energy ray-curable group and a molecular weight of 100 to 80000. A compound (a2) is mentioned. The polymer (a1) may be at least partially crosslinked by a crosslinking agent (f) described later, or may not be crosslinked.
In the present specification, the weight average molecular weight means a polystyrene equivalent value measured by a gel permeation chromatography (GPC) method unless otherwise specified.

(Polymer (a1) having an energy ray curable group and having a weight average molecular weight of 80,000 to 2,000,000)
Examples of the polymer (a1) having an energy ray curable group and having a weight average molecular weight of 80,000 to 2,000,000 include the following. For example, an acrylic polymer (a11) having a functional group capable of reacting with a group possessed by another compound, a group that reacts with the functional group, and an energy ray curable group such as an energy ray curable double bond An acrylic resin (a1-1) obtained by polymerizing the energy beam curable compound (a12).

Examples of the functional group capable of reacting with a group possessed by another compound include a hydroxyl group, a carboxy group, an amino group, and a substituted amino group (one or two hydrogen atoms of the amino group are substituted with a group other than a hydrogen atom). Group), an epoxy group, and the like. However, the functional group is preferably a group other than a carboxy group from the viewpoint of preventing corrosion of a circuit such as a semiconductor wafer or a semiconductor chip.
Among these, the functional group is preferably a hydroxyl group.

-Acrylic polymer having a functional group (a11)
Examples of the acrylic polymer (a11) having the functional group include those obtained by copolymerizing an acrylic monomer having the functional group and an acrylic monomer having no functional group. In addition to monomers, monomers other than acrylic monomers (non-acrylic monomers) may be copolymerized.
The acrylic polymer (a11) may be a random copolymer or a block copolymer.

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

Examples of the hydroxyl group-containing monomer include the following. For example, hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, Hydroxyalkyl (meth) acrylates such as 3-hydroxybutyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate; non- (meth) acrylic unsaturated alcohols such as vinyl alcohol and allyl alcohol ((meth) acryloyl) And unsaturated alcohol having no skeleton).

Examples of the carboxy group-containing monomer include the following. For example, ethylenically unsaturated monocarboxylic acids such as (meth) acrylic acid and crotonic acid (monocarboxylic acids having an ethylenically unsaturated bond); ethylenically unsaturated dicarboxylic acids such as fumaric acid, itaconic acid, maleic acid and citraconic acid Examples thereof include acids (dicarboxylic acids having an ethylenically unsaturated bond); anhydrides of the ethylenically unsaturated dicarboxylic acids; (meth) acrylic acid carboxyalkyl esters such as 2-carboxyethyl methacrylate and the like.

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

The acrylic monomer having the functional group constituting the acrylic polymer (a11) may be only one kind or two or more kinds. In the case of two or more types, the combination and ratio thereof can be arbitrarily selected.

Examples of the acrylic monomer having no functional group include the following. For example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, (meth ) Sec-butyl acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth) acrylic Isooctyl acid, n-octyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate (( (Meth) acrylic acid lauryl), (meth) acrylic acid tridecyl, (meth) acrylic acid tet Decyl (myristyl (meth) acrylate), pentadecyl (meth) acrylate, hexadecyl (meth) acrylate (palmityl (meth) acrylate), heptadecyl (meth) acrylate, octadecyl (meth) acrylate ((meth) acrylic) (Meth) acrylic acid alkyl ester in which the alkyl group constituting the alkyl ester has a chain structure having 1 to 18 carbon atoms, such as acid stearyl).

Moreover, the following are mentioned as an acryl-type monomer which does not have the said functional group. For example, (meth) acrylic acid ester containing alkoxyalkyl groups such as methoxymethyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxymethyl (meth) acrylate, ethoxyethyl (meth) acrylate; (meth) acrylic (Meth) acrylic acid ester having an aromatic group including (meth) acrylic acid aryl ester such as phenyl acid; non-crosslinkable (meth) acrylamide and derivatives thereof; (meth) acrylic acid N, N-dimethylamino Examples also include (meth) acrylic acid esters having a non-crosslinkable tertiary amino group such as ethyl and N, N-dimethylaminopropyl (meth) acrylate.

The acrylic monomer which does not have the functional group constituting the acrylic polymer (a11) may be only one kind or two or more kinds. In the case of two or more types, the combination and ratio thereof can be arbitrarily selected.

Examples of the non-acrylic monomer include olefins such as ethylene and norbornene; vinyl acetate; styrene.
The said non-acrylic monomer which comprises the said acrylic polymer (a11) may be only 1 type, and 2 or more types may be sufficient as it. In the case of two or more types, the combination and ratio thereof can be arbitrarily selected.

In the acrylic polymer (a11), the ratio (content) of the amount of the structural unit derived from the acrylic monomer having the functional group to the total amount of the structural unit constituting the polymer is 0.1 to 50 mass. % Is preferred. The content is more preferably 1 to 40% by mass, and particularly preferably 3 to 30% by mass. When the ratio is within such a range, the acrylic resin (a1-1) obtained by copolymerization of the acrylic polymer (a11) and the energy ray-curable compound (a12) The content of the linear curable group can easily adjust the degree of curing of the first protective film within a preferable range.

The acrylic polymer (a11) constituting the acrylic resin (a1-1) may be only one type or two or more types. In the case of two or more types, the combination and ratio thereof can be arbitrarily selected.

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

Energy beam curable compound (a12)
The energy ray curable compound (a12) is one or two selected from the group consisting of an isocyanate group, an epoxy group and a carboxy group as a group capable of reacting with the functional group of the acrylic polymer (a11). Those having the above are preferred, and those having an isocyanate group as the group are more preferred. For example, when the energy beam curable compound (a12) has an isocyanate group as the group, the isocyanate group easily reacts with the hydroxyl group of the acrylic polymer (a11) having a hydroxyl group as the functional group.

The energy ray curable compound (a12) preferably has 1 to 5 energy ray curable groups in one molecule, and more preferably 1 to 3 energy ray curable groups.

Examples of the energy ray curable compound (a12) include the following. For example, 2-methacryloyloxyethyl isocyanate, meta-isopropenyl-α, α-dimethylbenzyl isocyanate, methacryloyl isocyanate, allyl isocyanate, 1,1- (bisacryloyloxymethyl) ethyl isocyanate;
An acryloyl monoisocyanate compound obtained by reacting a diisocyanate compound or polyisocyanate compound with hydroxyethyl (meth) acrylate;
Examples thereof include an acryloyl monoisocyanate compound obtained by a reaction of a diisocyanate compound or polyisocyanate compound, a polyol compound, and hydroxyethyl (meth) acrylate.
Among these, the energy beam curable compound (a12) is preferably 2-methacryloyloxyethyl isocyanate.

The energy ray-curable compound (a12) constituting the acrylic resin (a1-1) may be only one type or two or more types. In the case of two or more types, the combination and ratio thereof can be arbitrarily selected.

In the acrylic resin (a1-1), the content of the energy beam curable group derived from the energy beam curable compound (a12) with respect to the content of the functional group derived from the acrylic polymer (a11). The ratio is preferably 20 to 120 mol%. More preferably, it is 35 to 100 mol%, and particularly preferably 50 to 100 mol%. When the ratio of the content is within such a range, the adhesive force of the protective film formed by curing is further increased. In addition, when the said energy-beam curable compound (a12) is a monofunctional (it has 1 said group in 1 molecule) compound, the upper limit of the ratio of the said content will be 100 mol%. However, when the energy ray curable compound (a12) is a polyfunctional compound (having two or more of the groups in one molecule), the upper limit of the content ratio may exceed 100 mol%. is there.

The weight average molecular weight (Mw) of the polymer (a1) is preferably 100,000 to 2,000,000, and more preferably 300,000 to 1500,000.

In the case where the polymer (a1) is at least partly crosslinked by the crosslinking agent (f), the polymer (a1) is described as constituting the acrylic polymer (a11). A monomer that does not correspond to any of the above-described monomers and has a group that reacts with the crosslinking agent (f) is polymerized to be crosslinked at the group that reacts with the crosslinking agent (f). . Moreover, what was bridge | crosslinked in the group which reacts with the said functional group derived from the said energy-beam curable compound (a12) may be used.

The polymer (a1) contained in the protective film-forming composition (IV-1) and the protective film-forming film may be one kind or two or more kinds. In the case of two or more types, the combination and ratio thereof can be arbitrarily selected.

(Compound (a2) having an energy ray curable group and a molecular weight of 100 to 80,000)
Examples of the energy beam curable group having the energy beam curable group and the compound (a2) having a molecular weight of 100 to 80,000 include groups containing an energy beam curable double bond. Preferable examples include (meth) acryloyl group, vinyl group and the like.

The compound (a2) is not particularly limited as long as it satisfies the above conditions. 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.

Among the compounds (a2), examples of the low molecular weight compound having an energy ray curable group include polyfunctional monomers or oligomers, and an acrylate compound having a (meth) acryloyl group is preferable.
Examples of the acrylate compound include the following. For example, 2-hydroxy-3- (meth) acryloyloxypropyl methacrylate, polyethylene glycol di (meth) acrylate, propoxylated ethoxylated bisphenol A di (meth) acrylate, 2,2-bis [4-((meth) acryloxy) Polyethoxy) phenyl] propane, ethoxylated bisphenol A di (meth) acrylate, 2,2-bis [4-((meth) acryloxydiethoxy) phenyl] propane, 9,9-bis [4- (2- ( Meth) acryloyloxyethoxy) phenyl] fluorene, 2,2-bis [4-((meth) acryloxypolypropoxy) phenyl] propane, tricyclodecane dimethanol di (meth) acrylate (tricyclodecane dimethylol di (meth) ) Acrylate), 1,10-decandioe Rudi (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol Di (meth) acrylate, polytetramethylene glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, 2,2-bis [4-(( (Meth) acryloxyethoxy) phenyl] propane, neopentyl glycol di (meth) acrylate, ethoxylated polypropylene glycol di (meth) acrylate, 2-hydroxy-1,3-di (meth) acryloxy Difunctional (meth) acrylates such as propane;
Tris (2- (meth) acryloxyethyl) isocyanurate, ε-caprolactone modified tris- (2- (meth) acryloxyethyl) isocyanurate, ethoxylated glycerin tri (meth) acrylate, pentaerythritol tri (meth) acrylate, Trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol poly (meth) acrylate, dipentaerythritol hexa ( Polyfunctional (meth) acrylates such as (meth) acrylate;
Examples include polyfunctional (meth) acrylate oligomers such as urethane (meth) acrylate oligomers.

Among the compounds (a2), the epoxy resin having an energy ray curable group and the phenol resin having an energy ray curable group are described in, for example, paragraph 0043 of “JP 2013-194102 A”. Things can be used. Such a resin corresponds to a resin constituting the thermosetting component (h) described later, but is treated as the compound (a2) in the present invention.

The compound (a2) preferably has a weight average molecular weight of 100 to 30,000, more preferably 300 to 10,000.

The compound (a2) contained in the protective film-forming composition (IV-1) and the protective film-forming film may be only one kind or two or more kinds. In the case of two or more types, the combination and ratio thereof can be arbitrarily selected.

[Polymer (b) having no energy ray curable group]
When the protective film forming composition (IV-1) and the protective film forming film contain the compound (a2) as the energy ray curable component (a), the polymer further does not have an energy ray curable group. It is also preferable to contain (b).
The polymer (b) may be at least partially crosslinked by the crosslinking agent (f) or may not be crosslinked.

Examples of the polymer (b) having no energy ray curable group include the following. Examples include acrylic polymers, phenoxy resins, urethane resins, polyesters, rubber resins, acrylic urethane resins, polyvinyl alcohol (PVA), butyral resins, and polyester urethane resins.
Among these, the polymer (b) is preferably an acrylic polymer (hereinafter sometimes abbreviated as “acrylic polymer (b-1)”).

The acrylic polymer (b-1) may be a known one and includes the following. For example, a homopolymer of one kind of acrylic monomer may be used, a copolymer of two or more kinds of acrylic monomers may be used, one kind or two or more kinds of acrylic monomers, and 1 It may be a copolymer with a monomer (non-acrylic monomer) other than seeds or two or more acrylic monomers.

Examples of the acrylic monomer constituting the acrylic polymer (b-1) include the following. For example, (meth) acrylic acid alkyl ester, (meth) acrylic acid ester having a cyclic skeleton, glycidyl group-containing (meth) acrylic acid ester, hydroxyl group-containing (meth) acrylic acid ester, substituted amino group-containing (meth) acrylic acid ester Etc. Here, the “substituted amino group” is as described above.

Examples of the (meth) acrylic acid alkyl ester include the following. For example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, (meth ) Sec-butyl acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth) acrylic Isooctyl acid, n-octyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate (( (Meth) acrylic acid lauryl), (meth) acrylic acid tridecyl, (meth) acrylic acid tet Decyl (myristyl (meth) acrylate), pentadecyl (meth) acrylate, hexadecyl (meth) acrylate (palmityl (meth) acrylate), heptadecyl (meth) acrylate, octadecyl (meth) acrylate ((meth) acrylic) (Meth) acrylic acid alkyl ester in which the alkyl group constituting the alkyl ester has a chain structure having 1 to 18 carbon atoms, such as acid stearyl).

Examples of the (meth) acrylic acid ester having a cyclic skeleton include the following. For example, (meth) acrylic acid cycloalkyl esters such as isobornyl (meth) acrylate and dicyclopentanyl (meth) acrylate;
(Meth) acrylic acid aralkyl esters such as (meth) acrylic acid benzyl;
(Meth) acrylic acid cycloalkenyl esters such as (meth) acrylic acid dicyclopentenyl ester;
Examples include (meth) acrylic acid cycloalkenyloxyalkyl esters such as (meth) acrylic acid dicyclopentenyloxyethyl ester.

Examples of the glycidyl group-containing (meth) acrylic ester include glycidyl (meth) acrylate.
Examples of the hydroxyl group-containing (meth) acrylic acid ester include the following. For example, hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, Examples include 3-hydroxybutyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate.
Examples of the substituted amino group-containing (meth) acrylic acid ester include N-methylaminoethyl (meth) acrylate.

Examples of the non-acrylic monomer constituting the acrylic polymer (b-1) include olefins such as ethylene and norbornene; vinyl acetate; styrene.

As the polymer (b) at least partially crosslinked by the crosslinking agent (f) and not having the energy ray curable group, for example, the reactive functional group in the polymer (b) is a crosslinking agent (f ).
The reactive functional group may be appropriately selected according to the type of the crosslinking agent (f) and the like, and is not particularly limited. For example, when the crosslinking agent (f) is a polyisocyanate compound, examples of the reactive functional group include a hydroxyl group, a carboxy group, and an amino group. Among these, a hydroxyl group having high reactivity with an isocyanate group. Is preferred. Further, when the crosslinking agent (f) is an epoxy compound, examples of the reactive functional group include a carboxy group, an amino group, an amide group, etc. Among them, a carboxy group having high reactivity with an epoxy group. Groups are preferred. However, the reactive functional group is preferably a group other than a carboxy group in terms of preventing corrosion of a circuit of a semiconductor wafer or a semiconductor chip.

Examples of the polymer (b) having the reactive functional group and not having the energy ray-curable group include those obtained by polymerizing at least the monomer having the reactive functional group. In the case of the acrylic polymer (b-1), those having the reactive functional group as one or both of the acrylic monomer and the non-acrylic monomer mentioned as the monomers constituting the polymer (b-1). Use it. For example, examples of the polymer (b) having a hydroxyl group as a reactive functional group include those obtained by polymerizing a hydroxyl group-containing (meth) acrylic acid ester. In addition to this, the acrylic monomer or non-acrylic monomer mentioned above was obtained by polymerizing a monomer in which one or two or more hydrogen atoms were substituted with the reactive functional group. Things.

In the polymer (b) having a reactive functional group, the ratio (content) of the amount of the structural unit derived from the monomer having the reactive functional group to the total amount of the structural unit constituting the polymer (b) is 1 to 25. It is preferable that it is mass%. It is more preferably 2 to 20% by mass. When the ratio is within such a range, the degree of cross-linking becomes a more preferable range in the polymer (b).

The weight average molecular weight (Mw) of the polymer (b) having no energy ray-curable group is 10,000 to 2,000,000 from the viewpoint that the film-forming property of the protective film-forming composition (IV-1) becomes better. It is preferable. More preferably, it is 100,000 to 1500,000.

The polymer (b) having no energy ray-curable group contained in the protective film-forming composition (IV-1) and the protective film-forming film may be only one kind or two or more kinds. In the case of two or more types, the combination and ratio thereof can be arbitrarily selected.

Examples of the protective film-forming composition (IV-1) include those containing one or both of the polymer (a1) and the compound (a2). When the protective film-forming composition (IV-1) contains the compound (a2), it preferably further contains a polymer (b) having no energy ray-curable group. In this case, it is also preferable to further contain (a1). Further, the protective film-forming composition (IV-1) does not contain the compound (a2) and contains both the polymer (a1) and the polymer (b) having no energy ray-curable group. It may be.

When the protective film-forming composition (IV-1) contains the polymer (a1), the compound (a2) and the polymer (b) having no energy ray-curable group, the protective film-forming composition In (IV-1), the content of the compound (a2) is 10 to 10 parts per 100 parts by mass of the total content of the polymer (a1) and the polymer (b) having no energy ray-curable group. The amount is preferably 400 parts by mass, and more preferably 30 to 350 parts by mass.

In the protective film-forming composition (IV-1), the total content of the energy beam curable component (a) and the polymer (b) having no energy beam curable group with respect to the total content of components other than the solvent (That is, the total content of the energy ray-curable component (a) and the polymer (b) having no energy ray-curable group in the protective film-forming film) is 5 to 90% by mass. preferable. It is more preferably 10 to 80% by mass, and particularly preferably 15 to 70% by mass. When the ratio of the total content is within such a range, the energy ray curability of the protective film-forming film becomes better.

When the protective film forming composition (IV-1) contains the energy beam curable component (a) and the polymer (b) having no energy beam curable group, the protective film forming composition (IV-1) ) And the protective film-forming film, the content of the polymer (b) is preferably 3 to 160 parts by mass with respect to 100 parts by mass of the energy ray-curable component (a). It is more preferably 6 to 130 parts by mass. When the content of the polymer (b) is in such a range, the energy ray curability of the protective film-forming film becomes better.

In addition to the energy ray-curable component (a) and the polymer (b) having no energy ray-curable group, the protective film-forming composition (IV-1) comprises a photopolymerization initiator (c) depending on the purpose. , A filler (d), a coupling agent (e), a crosslinking agent (f), a colorant (g), a thermosetting component (h), and a general-purpose additive (z). Or you may contain 2 or more types. For example, by using the protective film-forming composition (IV-1) containing the energy ray-curable component (a) and the thermosetting component (h), the protective film-forming film formed is heated. Adhesive strength to the adherend is improved. Furthermore, the strength of the protective film formed from this protective film-forming film is also improved.

[Photoradical initiator (c ′)]
The photo radical initiator used in the composition for forming a protective film of the present invention has an extinction coefficient at a wavelength of 365 nm of 4.0 × 10 ¹ ml / (g · cm) or more (in this specification, “photo radical initiation” Agent (c ′) ”).
The photo-radical initiator (c ′) is not particularly limited as long as it has an extinction coefficient of 365 nm and a wavelength of 4.0 × 10 ¹ ml / (g · cm) or more.
Examples of the photo radical initiator (c ′) include the following. For example, acetophenone, propiophenone, benzophenone, xanthol, fluorin, benzaldehyde, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4-methylacetophenone, 3-pentylacetophenone, 2,2-diethoxyacetophenone, 4 -Methoxyacetophenone, 3-bromoacetophenone, 4-allylacetophenone, p-diacetylbenzene, 3-methoxybenzophenone, 4-methylbenzophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4-chloro-4'-benzyl Benzophenone, 3-chloroxanthone, 3,9-dichloroxanthone, 3-chloro-8-nonylxanthone, benzoin, benzoin methyl ether, benzoin Butyl ether, bis (4-dimethylaminophenyl) ketone, benzylmethoxyketal, 2-chlorothioxanthone, 2,2-dimethoxy-1,2-diphenylethane-1-one (trade name IRGACURE651, manufactured by BASF Japan), 1 -Hydroxy-cyclohexyl-phenyl-ketone (trade name IRGACURE 184, manufactured by BASF Japan, 2-hydroxy-2-methyl-1-phenyl-propan-1-one (trade name DAROCUR 1173, manufactured by BASF Japan), 1- [4- ( 2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one (trade name IRGACURE 2959, manufactured by BASF Japan), 2-methyl-1- [4- (methylthio) phenyl] -2 -Morpholinopropane-1 ON (trade name IRGACURE907, manufactured by BASF Japan), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (trade name IRGACURE369, 2-morpholinopropan-1-one (trade name) IRGACURE907, manufactured by BASF Japan), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (trade name IRGACURE369, manufactured by BASF Japan), 2- (4-methylbenzyl) -dimethylamino Examples include -1- (4-morpholin-4-yl-phenyl) -butan-1-one (trade name: IRGACURE 379, manufactured by BASF Japan), dibenzoyl, and the like.

Of these, α-hydroxy ketone compounds (for example, benzoin, benzoin methyl ether, benzoin butyl ether, 1-hydroxy-cyclohexyl-phenyl-ketone, etc.), phenyl ketone derivatives (for example, acetophenone, propiophenone, benzophenone, 3-methyl) Acetophenone, 4-methylacetophenone, 3-pentylacetophenone, 2,2-diethoxyacetophenone, 4-methoxyacetophenone, 3-bromoacetophenone, 4-allylacetophenone, 4-allylacetophenone, 3-methoxybenzophenone, 4-methylbenzophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4-chloro-4'-benzylbenzophenone, bis (4-dimethylaminophenyl) ketone ) Is preferable.

The photo radical initiator (c ′) is preferably one having two or more photodegradable groups in one molecule.
Examples of the photoradical initiator (c ′) having two or more photodegradable groups in one molecule include the following. For example, 2-hydroxy-1- [4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl-2-methyl-propan-1-one (trade name: 369IRGACURE127, manufactured by BASF Japan), 1 -[4- (4-Benzoxylphenylsulfanyl) phenyl] -2-methyl-2- (4-methylphenylsulfonyl) propan-1-one (trade name ESURE1001M), methylbenzoyl formate (trade name SPEDCURE MBF) LAMBSON), O-ethoxyimino-1-phenylpropan-1-one (trade name: SPEEDCURE PDO, manufactured by LAMBSON), oligo [2-hydroxy-2-methyl- [4- (1-methylvinyl) phenyl] propanone (product) Name ESCURE KIPI50 LA BERTI, Ltd.), and the like.

The photoradical initiator (c ′) is preferably a hydrogen abstraction type photoradical initiator having three or more aromatic rings in one molecule.
Examples of the hydrogen abstraction type radical initiator having three or more aromatic rings in one molecule include the following. For example, 1- [4- (phenylthio) -2- (O-benzoyloxime)] 1,2-octanedione (trade name IRGACURE OXE 01, manufactured by BASF Japan), 1- [9-ethyl-6- (2- Methylbenzoyl) -9H-carbazol-3-yl] -1- (0-acetyloxime) ethanone (trade name IRGACURE OXE 02, manufactured by BASF Japan), 4-benzoyl-4'methyldiphenyl sulfide, 4-phenylbenzophenone, 4 , 4 ′, 4 ″-(hexamethyltriamino) triphenylmethane and the like. In addition, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (trade name DAROCUR TPO, manufactured by BASF Japan), bis (2,4,6-trimethylbenzoyl) -phenylphosphine, which is characterized by improved deep curability Examples thereof include acyl phosphine oxide photo radical initiators such as oxide (trade name: IRGACURE 819, manufactured by BASF Japan) and bis (2,6-dimethylbenzoyl) -2,4,4-trimethyl-pentylphosphine oxide.

The photo radical initiator (c ′) is more preferably the following from the viewpoint of the balance between curability and storage stability of the protective film-forming composition (IV-1). 1-hydroxy-cyclohexyl-phenyl-ketone (trade name: IRGACURE184, manufactured by BASF Japan), 2-hydroxy-2-methyl-1-phenyl-propan-1-one (trade name: DAROCUR1173, manufactured by BASF Japan), bis (4- Dimethylaminophenyl) ketone, 2-hydroxy-1- [4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl] -2-methyl-propan-1-one (trade names IRGACURE127, BASF Made in Japan), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (trade name IRGACURE369, manufactured by BASF Japan), 2- (4-methylbenzyl) -2-dimethylamino- 1- (4-Morpholin-4-yl- Nyl) -butan-1-one (trade name: IRGACURE 379, manufactured by BASF Japan), 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (trade name: DAROCUR TPO, manufactured by BASF Japan), bis (2, 4, 6 -Trimethylbenzoyl) -phenylphosphine oxide (trade name: IRGACURE 819, manufactured by BASF Japan), bis (2,6-dimethylbenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, and the like.

The extinction coefficient of the photo radical initiator (c ′) at a wavelength of 365 nm is preferably 4.0 × 10 ¹ ml / (g · cm) or more. It is more preferably 1.0 × 10 ² ml / (g · cm) or more, and further preferably 1.0 × 10 ³ ml / (g · cm) or more.

The upper limit value of the extinction coefficient of the photo radical initiator (c ′) at a wavelength of 365 nm is not particularly limited. For example, it can be 1.0 × 10 ⁴ ml / (g · cm).

The photoradical initiator (c ′) contained in the protective film-forming composition (IV-1) and the protective film-forming film may be one kind or two or more kinds. In the case of two or more types, the combination and ratio thereof can be arbitrarily selected.

The photo radical initiator (c ′) may be used in combination with other compounds.
Specific examples of combinations with other compounds include the following. 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, diethanolmethylamine, dimethylethanolamine, triethanolamine, ethyl-4-dimethylaminobenzoate, 2-ethylhexyl-4-dimethyl A combination with an amine such as aminobenzoate, a combination with an iodonium salt such as diphenyliodonium chloride, a combination with a dye such as methylene blue and an amine, and the like can be mentioned.

The photo radical initiator (c ′) may be hydroquinone, hydroquinone monomethyl ether, benzoquinone, paratertiary butylcatechol, 2,2,6,6-tetramethylpiperidine-1-oxyl, N, N-diethylhydroxylamine, if necessary. , N, N-distearylhydroxylamine, N, N-dialkylhydroxylamine and the like may be used in combination with a photopolymerization initiator other than the photoradical initiator (c ′).

The photopolymerization initiator contained in the protective film-forming composition (IV-1) may be one type or two or more types. In the case of two or more types, the combination and ratio thereof can be arbitrarily selected.

In the protective film-forming composition (IV-1), the content of the photoradical initiator (c ′) is 0.01 to 20 masses with respect to 100 mass parts of the energy ray-curable compound (a). Part. The amount is more preferably 0.1 to 10 parts by mass, and particularly preferably 0.5 to 5 parts by mass.
When the content of the photo radical initiator (c ′) is not more than the above upper limit value, it is possible to suppress unintentional reaction when used under a fluorescent lamp or natural light, and the composite sheet can be used stably. The effect that it can be obtained.
When the content of the photo radical initiator (c ′) is equal to or more than the lower limit, an effect that the reaction shortage can be suppressed is obtained.

[Filler (d)]
When the protective film-forming film contains the filler (d), the protective film obtained by curing the protective film-forming film can easily adjust the thermal expansion coefficient. Furthermore, the reliability of the package obtained using the composite sheet for forming the protective film is further improved by optimizing the thermal expansion coefficient for the object to be formed with the protective film. Moreover, the moisture absorption rate of a protective film can be reduced or heat dissipation can be improved because the film for protective film formation contains a filler (d).
Examples of the filler (d) include those made of a heat conductive material.

The filler (d) may be either an organic filler or an inorganic filler, but is preferably an inorganic filler.
Preferred inorganic fillers include, for example, powders of silica, alumina, talc, calcium carbonate, titanium white, bengara, silicon carbide, boron nitride, and the like; beads formed by spheroidizing these inorganic fillers; surface modification of these inorganic fillers Products; single crystal fibers of these inorganic fillers; glass fibers and the like.
Among these, the inorganic filler is preferably silica or alumina.

The average particle size of the filler (d) is not particularly limited, but is preferably 0.01 to 20 μm. The thickness is more preferably 0.1 to 15 μm, and particularly preferably 0.3 to 10 μm. When the average particle diameter of the filler (d) is in such a range, it is possible to suppress a decrease in the light transmittance of the protective film while maintaining the adhesion to the object to be formed of the protective film.
In the present specification, “average particle size” means the value of the particle size (D50) 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) contained in the protective film-forming composition (IV-1) and the protective film-forming film may be one kind or two or more kinds. In the case of two or more types, the combination and ratio thereof can be arbitrarily selected.

When the filler (d) is used, in the protective film forming composition (IV-1), the ratio of the content of the filler (d) to the total content of all components other than the solvent (that is, for forming the protective film) The content of the filler (d) in the film is preferably 5 to 83% by mass. It is more preferably 7 to 78% by mass. When the content of the filler (d) is in such a range, the adjustment of the thermal expansion coefficient becomes easier.

[Coupling agent (e)]
By using a coupling agent (e) having a functional group capable of reacting with an inorganic compound or an organic compound, the adhesion and adhesion of the protective film-forming film to the adherend can be improved. Further, by using the coupling agent (e), the protective film obtained by curing the protective film-forming film has improved water resistance without impairing the heat resistance.

The coupling agent (e) is preferably a compound having a functional group capable of reacting with the functional group of the energy beam curable component (a), the polymer (b) having no energy beam curable group, and the like. More preferably, it is a silane coupling agent.
Preferred examples of the silane coupling agent include the following. For example, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxymethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl Trimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3- (2-aminoethylamino) propyltrimethoxysilane, 3- (2-aminoethylamino) propylmethyldiethoxysilane, 3- (phenylamino) propyltrimethoxysilane, 3-anilinopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropi Dimethoxysilane, bis (3-triethoxysilylpropyl) tetrasulfane, methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriacetoxysilane, imidazole silane, and the like.

The coupling agent (e) contained in the protective film-forming composition (IV-1) and the protective film-forming film may be one kind or two or more kinds. In the case of two or more types, the combination and ratio thereof can be arbitrarily selected.

When the coupling agent (e) is used, the content of the coupling agent (e) in the composition for forming a protective film (IV-1) and the film for forming a protective film includes the energy ray curable component (a) and the energy. The amount is preferably 0.03 to 20 parts by mass with respect to 100 parts by mass of the total content of the polymer (b) having no linear curable group. The amount is more preferably 0.05 to 10 parts by mass, and particularly preferably 0.1 to 5 parts by mass. When the content of the coupling agent (e) is equal to or higher than the lower limit, the dispersibility of the filler (d) in the resin is improved and the adhesion of the protective film-forming film to the adherend is improved. The effect by using a coupling agent (e) etc. is acquired more notably. Moreover, generation | occurrence | production of an outgas is suppressed more because the said content of a coupling agent (e) is below the said upper limit.

[Crosslinking agent (f)]
By using the crosslinking agent (F) and crosslinking the polymer (b) having no energy beam curable component (a) or energy beam curable group, the initial adhesive force and cohesive force of the protective film-forming film. Can be adjusted.

Examples of the crosslinking agent (f) include organic polyvalent isocyanate compounds, organic polyvalent imine compounds, metal chelate crosslinking agents (crosslinking agents having a metal chelate structure), aziridine crosslinking agents (crosslinking agents having an aziridinyl group), and the like. Is mentioned.

Examples of the organic polyvalent isocyanate compound include the following. For example, an aromatic polyvalent isocyanate compound, an aliphatic polyvalent isocyanate compound, and an alicyclic polyvalent isocyanate compound (hereinafter, these compounds may be collectively abbreviated as “aromatic polyvalent isocyanate compound etc.”); Examples include trimers such as aromatic polyisocyanate compounds, isocyanurates and adducts; and terminal isocyanate urethane prepolymers obtained by reacting the aromatic polyvalent isocyanate compounds and the like with polyol compounds. The “adduct body” includes the aromatic polyvalent isocyanate compound, the aliphatic polyvalent isocyanate compound, or the alicyclic polyvalent isocyanate compound, and a low amount of ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane, castor oil, or the like. It means a reaction product with a molecularly active hydrogen-containing compound, and examples thereof include an xylylene diisocyanate adduct of trimethylolpropane as described later. The “terminal isocyanate urethane prepolymer” means a prepolymer having a urethane bond and an isocyanate group at the end of the molecule.

More specifically, as the organic polyvalent isocyanate compound, for example, 2,4-tolylene diisocyanate; 2,6-tolylene diisocyanate; 1,3-xylylene diisocyanate; 1,4-xylene diisocyanate; diphenylmethane-4 Dimethylmethane-2,4'-diisocyanate; 3-methyldiphenylmethane diisocyanate; hexamethylene diisocyanate; isophorone diisocyanate; dicyclohexylmethane-4,4'-diisocyanate; dicyclohexylmethane-2,4'-diisocyanate; trimethylol Any one of tolylene diisocyanate, hexamethylene diisocyanate and xylylene diisocyanate is added to all or some hydroxyl groups of a polyol such as propane. Or two or more compounds are added; lysine diisocyanate.

Examples of the organic polyvalent imine compound include N, N′-diphenylmethane-4,4′-bis (1-aziridinecarboxamide), trimethylolpropane-tri-β-aziridinylpropionate, and tetramethylolmethane. -Tri-β-aziridinylpropionate, N, N′-toluene-2,4-bis (1-aziridinecarboxamide) triethylenemelamine and the like.

When an organic polyvalent isocyanate compound is used as the crosslinking agent (f), it is preferable to use a hydroxyl group-containing polymer as the energy ray curable component (a) or the polymer (b) having no energy ray curable group. 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-curable property. A cross-linked structure can be easily introduced into the protective film-forming film by reaction with the component (a) or the polymer (b) having no energy ray-curable group.

The protective film forming composition (IV-1) and the protective film forming film may contain only one type of crosslinking agent (f), or two or more types. In the case of two or more types, the combination and ratio thereof can be arbitrarily selected.

In the case where the crosslinking agent (f) is used, the content of the crosslinking agent (f) in the protective film-forming composition (IV-1) is such that the energy ray-curable component (a) and the energy ray-curable group having no energy ray-curable group are contained. The amount is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass as the total content of the combined (b). The amount is more preferably 0.1 to 10 parts by mass, and particularly preferably 0.5 to 5 parts by mass. When the content of the cross-linking agent (f) is equal to or higher than the lower limit value, the effect of using the cross-linking agent (f) is more remarkably obtained. Moreover, the excessive use of a crosslinking agent (f) is suppressed because the said content of a crosslinking agent (f) is below the said upper limit.

[Colorant (g)]
Examples of the colorant (g) include known pigments such as inorganic pigments, organic pigments, and organic dyes.

Examples of the organic pigment and organic dye include the following. For example, aminium dyes, cyanine dyes, merocyanine dyes, croconium dyes, squalium dyes, azurenium dyes, polymethine dyes, naphthoquinone dyes, pyrylium dyes, phthalocyanine dyes, naphthalocyanine dyes, naphtholactam dyes Azo dyes, condensed azo dyes, indigo dyes, perinone dyes, perylene dyes, dioxazine dyes, quinacridone dyes, isoindolinone dyes, quinophthalone dyes, pyrrole dyes, thioindigo dyes, metal complexes System dyes (metal complex dyes), dithiol metal complex dyes, indolephenol dyes, triallylmethane dyes, anthraquinone dyes, naphthol dyes, azomethine dyes, benzimidazolone dyes, pyranthrone dyes, and selenium dyes Arsenide, and the like.

Examples of the inorganic pigment include carbon black, cobalt dye, iron dye, chromium dye, titanium dye, vanadium dye, zirconium dye, molybdenum dye, ruthenium dye, platinum dye, ITO ( Indium tin oxide) dyes, ATO (antimony tin oxide) dyes, and the like.

The colorant (g) contained in the protective film-forming composition (IV-1) and the protective film-forming film may be one kind or two or more kinds. In the case of two or more types, the combination and ratio thereof can be arbitrarily selected.

When using the colorant (g), the content of the colorant (g) in the protective film-forming film may be appropriately adjusted according to the purpose. For example, the protective film may be printed by laser irradiation, and by adjusting the content of the colorant (g) in the protective film-forming film and adjusting the light transmittance of the protective film, the print visibility is improved. Can be adjusted. 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 components other than the solvent (that is, the colorant (g )) Is preferably 0.1 to 10% by mass. The content is more preferably 0.4 to 7.5% by mass, and particularly preferably 0.8 to 5% by mass. The effect by using a colorant (g) is acquired more notably because the content of the colorant (g) is not less than the lower limit. Moreover, the excessive use of a coloring agent (g) is suppressed because the said content of a coloring agent (g) is below the said upper limit.

[Thermosetting component (h)]
The thermosetting component (h) contained in the protective film-forming composition (IV-1) and the protective film-forming film may be one kind or two or more kinds. In the case of two or more types, the combination and ratio thereof can be arbitrarily selected.

Examples of the thermosetting component (h) include epoxy thermosetting resins, thermosetting polyimides, polyurethanes, unsaturated polyesters, and silicone resins, and epoxy thermosetting resins are preferable.

(Epoxy thermosetting resin)
The epoxy thermosetting resin includes an epoxy resin (h1) and a thermosetting agent (h2). The epoxy thermosetting resin contained in the protective film-forming composition (IV-1) and the protective film-forming film may be only one type, two or more types, and when there are two or more types, Combinations and ratios can be arbitrarily selected.

・ Epoxy resin (h1)
As an epoxy resin (h1), a well-known thing is mentioned. For example, polyfunctional epoxy resin, biphenyl compound, bisphenol A diglycidyl ether and its hydrogenated product, orthocresol novolac epoxy resin, dicyclopentadiene type epoxy resin, biphenyl type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy Bifunctional or higher functional epoxy compounds such as resins and phenylene skeleton type epoxy resins are exemplified.

As the epoxy resin (h1), an epoxy resin having an unsaturated hydrocarbon group may be used. An epoxy resin having an unsaturated hydrocarbon group is more compatible with an acrylic resin than an epoxy resin having no unsaturated hydrocarbon group. Therefore, the reliability of the package obtained using the composite sheet for forming a protective film is improved by using an epoxy resin having an unsaturated hydrocarbon group.

Examples of the epoxy resin having an unsaturated hydrocarbon group include compounds obtained by converting a part of the epoxy group of a polyfunctional epoxy resin into a group having an unsaturated hydrocarbon group. Such a compound can be obtained, for example, by addition reaction of (meth) acrylic acid or a derivative thereof to an epoxy group.
Moreover, as an epoxy resin which has an unsaturated hydrocarbon group, the compound etc. which the group which has an unsaturated hydrocarbon group directly couple | bonded with the aromatic ring etc. which comprise an epoxy resin are mentioned, for example. An unsaturated hydrocarbon group is a polymerizable unsaturated group. Specific examples thereof include ethenyl group (vinyl group), 2-propenyl group (allyl group), (meth) acryloyl group, (meth) acrylamide group and the like, and acryloyl group is preferable.

The number average molecular weight of the epoxy resin (h1) is not particularly limited. However, from the viewpoint of the curability of the protective film-forming film and the strength and heat resistance of the protective film, it is preferably 300 to 30000. It is more preferably 400 to 10,000, and particularly preferably 500 to 3000.
The epoxy equivalent of the epoxy resin (h1) is preferably 100 to 1000 g / eq, and more preferably 150 to 800 g / eq.

As the epoxy resin (h1), one type may be used alone, or two or more types may be used in combination, and when two or more types are used in combination, their combination and ratio can be arbitrarily selected.

・ Thermosetting agent (h2)
The thermosetting agent (h2) functions as a curing agent for the epoxy resin (h1).
As a thermosetting agent (h2), the compound which has 2 or more of functional groups which can react with an epoxy group in 1 molecule is mentioned, for example. Examples of the functional group include phenolic hydroxyl groups, alcoholic hydroxyl groups, amino groups, carboxy groups, and groups in which acid groups have been anhydrideized. A phenolic hydroxyl group, amino group, or acid group is preferably an anhydride group, and more preferably a phenolic hydroxyl group or amino group.

Among the thermosetting agents (h2), examples of the phenol-based curing agent having a phenolic hydroxyl group include polyfunctional phenol resins, biphenols, novolac-type phenol resins, dicyclopentadiene-based phenol resins, and aralkyl phenol resins.
Among the thermosetting agents (h2), examples of the amine-based curing agent having an amino group include dicyandiamide (hereinafter sometimes abbreviated as “DICY”).

The thermosetting agent (h2) may have an unsaturated hydrocarbon group.
As the thermosetting agent (h2) having an unsaturated hydrocarbon group, for example, a compound in which a part of the hydroxyl group of the phenol resin is substituted with a group having an unsaturated hydrocarbon group, an aromatic ring of the phenol resin, Examples thereof include compounds in which a group having a saturated hydrocarbon group is directly bonded.
The unsaturated hydrocarbon group in the thermosetting agent (h2) is the same as the unsaturated hydrocarbon group in the epoxy resin having an unsaturated hydrocarbon group described above.

In the case where a phenolic curing agent is used as the thermosetting agent (h2), it is preferable that the thermosetting agent (h2) has a high softening point or glass transition temperature from the viewpoint of improving the peelability of the protective film from the support sheet. .

The following are mentioned among thermosetting agents (h2). For example, the number average molecular weight of a resin component such as a polyfunctional phenol resin, a novolak-type phenol resin, a dicyclopentadiene phenol resin, or an aralkyl phenol resin is preferably 300 to 30,000, and more preferably 400 to 10,000. 500 to 3000 is particularly preferable.
Among the thermosetting agents (h2), for example, the molecular weight of non-resin components such as biphenol and dicyandiamide is not particularly limited, but is preferably 60 to 500, for example.

A thermosetting agent (h2) may be used individually by 1 type, and may use 2 or more types together. When using 2 or more types together, those combinations and ratios can be arbitrarily selected.

When the thermosetting component (h) is used, in the protective film-forming composition (IV-1) and the protective film-forming film, the content of the thermosetting agent (h2) is 100% of the epoxy resin (h1). The amount is preferably 0.01 to 20 parts by mass with respect to parts by mass.

When the thermosetting component (h) is used, the content of the thermosetting component (h) (for example, the epoxy resin (h1) and the heat in the protective film-forming composition (IV-1) and the protective film-forming film) The total content of the curing agent (h2) is preferably 1 to 500 parts by mass with respect to 100 parts by mass of the polymer (b) having no energy ray curable group.

[General-purpose additive (z)]
The general-purpose additive (z) may be a known one, can be arbitrarily selected according to the purpose, and is not particularly limited. Preferable examples include plasticizers, antistatic agents, antioxidants, gettering agents and the like.

The general-purpose additive (z) contained in the protective film-forming composition (IV-1) and the protective film-forming film may be only one kind or two or more kinds. In the case of two or more types, the combination and ratio thereof can be arbitrarily selected.
When the general-purpose additive (z) is used, the content of the general-purpose additive (z) in the protective film-forming composition (IV-1) and the protective film-forming film is not particularly limited and is appropriately selected according to the purpose. do it.

[solvent]
The protective film-forming composition (IV-1) preferably further contains a solvent. The protective film-forming composition (IV-1) containing a solvent has good handleability.
Although the said solvent is not specifically limited, The following are mentioned as a preferable thing. For example, hydrocarbons such as toluene and xylene; alcohols such as methanol, ethanol, 2-propanol, isobutyl alcohol (2-methylpropan-1-ol) and 1-butanol; esters such as ethyl acetate; ketones such as acetone and methyl ethyl ketone Ethers such as tetrahydrofuran; amides such as dimethylformamide and N-methylpyrrolidone (compounds having an amide bond), and the like.
The solvent contained in the protective film-forming composition (IV-1) may be only one kind or two or more kinds. In the case of two or more types, the combination and ratio thereof can be arbitrarily selected.

The solvent contained in the protective film-forming composition (IV-1) is methyl ethyl ketone, toluene, ethyl acetate, or the like from the viewpoint that the components contained in the protective film-forming composition (IV-1) can be mixed more uniformly. It is preferable.

<< Method for producing protective film-forming composition >>
The composition for forming a protective film such as the composition for forming a protective film (IV-1) can be obtained by blending each component for constituting the composition.
The order of addition at the time of blending each component is not particularly limited, and two or more components may be added simultaneously.
When using a solvent, it may be used by mixing the solvent with any compounding component other than the solvent and diluting the compounding component in advance. Moreover, you may use by mixing a solvent with these compounding components, without diluting any compounding components other than a solvent previously.
The method of mixing each component at the time of mixing is not particularly limited. What is necessary is just to select suitably from well-known methods, such as the method of rotating and stirring a stirring bar or a stirring blade, the method of mixing using a mixer, and the method of mixing by adding an ultrasonic wave.
The temperature and time during addition and mixing of each component are not particularly limited as long as each compounding component does not deteriorate. The temperature may be adjusted as appropriate, but the temperature is preferably 15 to 30 ° C.

Similar to the protective film-forming composite sheet of the present invention, it is affixed to the back surface opposite to the circuit surface of the semiconductor wafer or semiconductor chip, and as a composite sheet provided with a layer showing adhesion on the support sheet. There is a dicing die bonding sheet.
However, the adhesive layer provided in the dicing die bonding sheet functions as an adhesive when the semiconductor chip is picked up from the support sheet together with the semiconductor chip and then attached to the substrate, the lead frame, or another semiconductor chip. On the other hand, the protective film-forming film in the protective film-forming composite sheet of the present invention is the same as the adhesive layer in that it is picked up from the support sheet together with the semiconductor chip, but eventually becomes a protective film by curing, It has a function of protecting the back surface of the semiconductor chip that is affixed. Thus, the protective film-forming film in the present invention has a different use from the adhesive layer in the dicing die bonding sheet, and naturally the required performance is also different. Reflecting this difference in use, the protective film-forming film is usually harder and more difficult to pick up than the adhesive layer in the dicing die bonding sheet. Therefore, it is usually difficult to divert the adhesive layer in the dicing die bonding sheet as it is as the protective film-forming film in the protective film-forming composite sheet. The composite sheet for forming a protective film according to the present invention is extremely excellent as compared with the conventional one with regard to the suitability for picking up a semiconductor chip with a protective film, provided with an energy ray curable protective film-forming film.

◇ Method for Producing Protective Film-Forming Composite Sheet The protective film-forming composite sheet of the present invention can be produced by sequentially laminating the above-mentioned layers so as to have a corresponding positional relationship. The method for forming each layer is as described above.
For example, when a pressure-sensitive adhesive layer is laminated on a substrate when producing a support sheet, the above-described pressure-sensitive adhesive composition may be applied on the substrate and dried as necessary.

On the other hand, for example, when a protective film-forming film is further laminated on the adhesive layer laminated on the substrate, the protective film-forming composition is applied on the adhesive layer, It is possible to form the forming film directly. Layers other than the protective film-forming film can also be laminated on the pressure-sensitive adhesive layer in the same manner using the composition for forming this layer. As described above, when a continuous two-layer laminated structure is formed using any of the compositions, the composition is further applied onto the layer formed from the composition to newly form a layer. Can be formed. However, the layer laminated after these two layers is formed in advance using the composition on another release film, and the side of the formed layer that is in contact with the release film is It is preferable to form a continuous two-layer laminated structure by bonding the opposite exposed surface to the exposed surfaces of the remaining layers already formed. At this time, the composition is preferably applied to the release-treated surface of the release film. The release film may be removed as necessary after forming the laminated structure.

For example, a protective film-forming composite sheet in which a pressure-sensitive adhesive layer is laminated on a base material and a protective film-forming film is laminated on the pressure-sensitive adhesive layer (the support sheet is a laminate of the base material and the pressure-sensitive adhesive layer) In the case of producing a protective sheet-forming composite sheet), a pressure-sensitive adhesive composition is coated on a base material and dried as necessary, whereby a pressure-sensitive adhesive layer is laminated on the base material, The protective film-forming composition is coated on the release film, and dried as necessary to form the protective film-forming film on the release film. Then, the exposed surface of the protective film-forming film is bonded to the exposed surface of the adhesive layer laminated on the substrate, and the protective film-forming film is laminated on the adhesive layer, thereby forming a protective film. A composite sheet is obtained.

In addition, when laminating the pressure-sensitive adhesive layer on the substrate, as described above, instead of the method of coating the pressure-sensitive adhesive composition on the substrate, the pressure-sensitive adhesive composition is applied on the release film. The pressure-sensitive adhesive layer is formed on the release film by drying as necessary, and the exposed surface of this layer is bonded to one surface of the base material so that the pressure-sensitive adhesive layer is placed on the base material. You may laminate.
In any method, the release film may be removed at an arbitrary timing after the target laminated structure is formed.

Thus, any layer other than the base material constituting the composite sheet for forming a protective film can be laminated by a method in which the layer is formed in advance on the release film and bonded to the surface of the target layer. Therefore, a protective film-forming composite sheet may be produced by appropriately selecting a layer that employs such a process as necessary.

In addition, the composite sheet for forming a protective film is usually stored in a state in which a release film is bonded to the surface of the outermost layer (for example, a film for forming a protective film) opposite to the support sheet. Therefore, a composition for forming a layer constituting the outermost layer, such as a protective film-forming composition, is applied on this release film (preferably its release-treated surface) and dried as necessary. Then, a layer constituting the outermost layer is formed on the release film, and the remaining layers are laminated on the exposed surface of the layer opposite to the side in contact with the release film by any of the methods described above. And the composite sheet for protective film formation is obtained also by leaving it in the state bonded together, without removing a peeling film.

◇ Method of using protective sheet-forming composite sheet The protective film-forming composite sheet of the present invention can be used, for example, by the method described below.
That is, the protective film-forming composite sheet is attached to the back surface (surface opposite to the electrode forming surface) of the semiconductor wafer with the protective film-forming film. Next, the semiconductor wafer is divided together with the protective film forming film by dicing to form a semiconductor chip with the protective film forming film. Next, the protective film forming film of the semiconductor chip with the protective film forming film is irradiated with energy rays to cure the protective film forming film to form a protective film. Then, the semiconductor chip is picked up while being separated from the support sheet while the protective film is attached (that is, as a semiconductor chip with a protective film).
Thereafter, the semiconductor chip of the obtained semiconductor chip with a protective film is flip-chip connected to the circuit surface of the substrate in the same manner as the conventional method, and then the semiconductor package is obtained. Then, a target semiconductor device may be manufactured using this semiconductor package.

◇ Protective Film Forming Sheet FIG. 6 is a cross-sectional view schematically showing a protective film forming film according to an embodiment of the protective film forming sheet of the present invention.
As shown in FIG. 6, the protective film forming sheet 1 </ b> F according to the present embodiment is suitable for a “roll type”. The protective film-forming sheet 1F is provided between the release film 15a (hereinafter sometimes referred to as “first release film”) and the release film 15b (hereinafter also referred to as “second release film”). It has a structure in which the protective film-forming composition is applied in layers so that the protective film-forming film 13 is disposed.
The protective film forming composition used for the protective film forming sheet 1F is in accordance with the above-described protective film forming composition.
The protective film forming sheet 1F is formed by, for example, coating the protective film forming composition on the release surface of the first release film 15a and drying to form the protective film forming film 13, and then It can form by sticking the peeling surface of the 2nd peeling film 15b to an exposed surface. The method for applying the protective film forming composition is in accordance with the method for applying the protective film forming composition.

◇ Method of using protective film-forming film The protective film-forming film of the present invention can be used, for example, by the method described below.
That is, a protective film-forming film is attached to the back surface of the semiconductor wafer (the surface opposite to the electrode forming surface). Next, the semiconductor wafer is divided together with the protective film forming film by dicing to form a semiconductor chip with the protective film forming film. Next, the protective film forming film of the semiconductor chip with the protective film forming film is irradiated with energy rays to cure the protective film forming film to form a protective film. Then, the semiconductor chip is picked up while being separated from the support sheet while the protective film is attached (that is, as a semiconductor chip with a protective film).
Thereafter, the semiconductor chip of the obtained semiconductor chip with a protective film is flip-chip connected to the circuit surface of the substrate in the same manner as the conventional method, and then the semiconductor package is obtained. Then, a target semiconductor device may be manufactured using this semiconductor package.

Hereinafter, the present invention will be described in more detail with reference to specific examples. However, the present invention is not limited to the following examples.

The components used for the production of the protective film-forming composition are shown below.
Energy ray curable component (a2) -1: Tricyclodecane dimethylol diacrylate (“KAYARAD R-684”, bifunctional ultraviolet curable compound, molecular weight 304, manufactured by Nippon Kayaku Co., Ltd.)
Polymer having no energy ray-curable group (b) -1: butyl acrylate (hereinafter abbreviated as “BA”) (10 parts by mass), methyl acrylate (hereinafter abbreviated as “MA”) ( 70 parts by mass), glycidyl methacrylate (hereinafter abbreviated as “GMA”) (5 parts by mass) and 2-hydroxyethyl acrylate (hereinafter abbreviated as “HEA”) (15 parts by mass) Acrylic resin (weight average molecular weight 300000, glass transition temperature −1 ° C.).

Photoradical initiator (c ′)-1: 2- (dimethylamino) -1- (4-morpholinophenyl) -2-benzyl-1-butanone (“Irgacure® 369” manufactured by BASF, wavelength 365 nm) Extinction coefficient of 7.9 × 10 ³ )
(C ′)-2: Etanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) (“Irgacure ( (Registered trademark) OXE02 ", extinction coefficient of wavelength 365 nm: 7.7 × 10 ³ )
(C ′)-3: 1- [4- (phenylthio)-, 2- (O-benzoyloxime)] 1,2-octanedione) (“Irgacure® OXE01” manufactured by BASF, light absorption at 365 nm wavelength) Coefficient: 7.0 × 10 ³ )
(C ′)-4: 2-Hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propan-1-one (manufactured by BASF “ Irgacure (registered trademark) 127 ", extinction coefficient at a wavelength of 365 nm: 1.1 × 10 ² )
(C) -1: Phenylglyoxylic acid methyl ester (“Irgacure (registered trademark) MBF” manufactured by BASF, absorption coefficient at wavelength 365 nm: 3.8 × 101)

Filler (d) -1: Silica filler (fused quartz filler, average particle size 8 μm)
Coupling agent (e) -1: 3-methacryloxypropyltrimethoxysilane (“KBM-503” manufactured by Shin-Etsu Chemical Co., Ltd., silane coupling agent)

Colorant (g) -1: 32 parts by mass of phthalocyanine blue pigment (Pigment Blue 15: 3), 18 parts by mass of isoindolinone yellow pigment (Pigment Yellow 139), and anthraquinone red pigment (Pigment Red 177) A pigment obtained by mixing 50 parts by mass and pigmenting the mixture so that the total amount of the three kinds of dyes / the amount of styrene acrylic resin = 1/3 (mass ratio).

[Example 1]
<Manufacture of composite sheet for forming protective film>
(Production of protective film-forming composition (IV-1))
Energy ray curable component (a2) -1, polymer (b) -1, photo radical initiator (c ')-1, photo radical initiator (c')-2, filler (d) -1, cup The ring agent (e) -1 and the colorant (g) -1 were dissolved or dispersed in methyl ethyl ketone so that their contents (solid content, parts by mass) were as shown in Table 1, and stirred at 23 ° C. Thus, a protective film-forming composition (IV-1) having a solid content concentration of 50% by mass was prepared. In addition, the description of “-” in the column of the contained component in Table 1 means that the protective film-forming composition (IV-1) does not contain the component.

(Production of pressure-sensitive adhesive composition (I-4))
Contains an acrylic polymer (100 parts by mass, solid content) and a trifunctional xylylene diisocyanate-based crosslinking agent (“Takenate D110N” manufactured by Takeda Chemical Co., Ltd.) (10.7 parts by mass, solid content), and further as a solvent A non-energy ray-curable pressure-sensitive adhesive composition (I-4) containing methyl ethyl ketone and having a solid content concentration of 30% by mass was prepared. The acrylic polymer is obtained by copolymerizing 2-ethylhexyl acrylate (hereinafter abbreviated as “2EHA”) (36 parts by mass), BA (59 parts by mass), and HEA (5 parts by mass). The weight average molecular weight is 600,000.

(Manufacture of support sheet)
On the release-treated surface of a release film (“SP-PET 381031” manufactured by Lintec Corporation, thickness 38 μm, hereinafter sometimes referred to as “P1”) obtained by releasing one side of a polyethylene terephthalate film by silicone treatment, The pressure-sensitive adhesive composition (I-4) obtained in (1) was applied and dried by heating at 120 ° C. for 2 minutes to form a non-energy ray-curable pressure-sensitive adhesive layer having a thickness of 10 μm.
Subsequently, a polypropylene film (Young's modulus: 400 MPa, thickness: 80 μm, hereinafter sometimes referred to as “S1”) is bonded to the exposed surface of the pressure-sensitive adhesive layer as a base material, thereby one surface of the base material. A support sheet (10) -1 having the pressure-sensitive adhesive layer thereon was obtained.

(Manufacture of composite sheet for protective film formation)
A protective film-forming composition obtained as described above is formed on the release-treated surface of a release film (“SP-PET 381031” manufactured by Lintec Corporation, thickness 38 μm, P1) obtained by releasing one side of a polyethylene terephthalate film by silicone treatment. (IV-1) was applied with a knife coater and dried at 100 ° C. for 2 minutes to prepare an energy ray-curable protective film-forming film (13) -1 having a thickness of 25 μm.

Next, the release film is removed from the pressure-sensitive adhesive layer of the support sheet (10) -1 obtained above, and the protective film-forming film (13) -1 obtained above is exposed on the exposed surface of the pressure-sensitive adhesive layer. The surfaces were bonded together to prepare a composite sheet for forming a protective film, in which a base material, an adhesive layer, a protective film-forming film (13) -1 and a release film were laminated in this order in the thickness direction. Table 2 shows the structure of the obtained protective sheet-forming composite sheet.

(Evaluation of dicing suitability)
The protective film-forming composite sheet obtained above is attached to the # 2000 polished surface of a 6-inch silicon wafer (thickness 350 μm) with the protective film-forming film (13) -1 and this sheet is further attached to the ring frame. Fixed.
Next, using a dicing blade, the silicon wafer was diced together with the protective film-forming film (13) -1 and separated into individual pieces to obtain silicon chips of 5 mm × 5 mm.

(Evaluation of pickup suitability)
Next, a protective film-forming film (13) is formed from the support sheet (10) -1 side under the conditions of an illuminance of 195 mW / cm ² and a light amount of 170 mJ / cm ² using an ultraviolet irradiation device (“RAD2000m / 8” manufactured by Lintec Corporation). ) -1 was irradiated with ultraviolet rays to cure the protective film-forming film (13) -1 to obtain a protective film.
Next, using a die bonder (“BESTEM-D02” manufactured by Canon Machinery Co., Ltd.), any 15 silicon chips with a protective film were picked up with one pin and picked up. At this time, the presence or absence of cracks and chips of the silicon chip is visually confirmed, the case where there are no cracks and chips is determined as “A”, and the case where there are slight cracks or chips is determined as “B”. Pickup suitability was evaluated. The results are shown in Table 2. The description in the column of “Suppression of chip cracks / chips” in Table 2 is the corresponding result.

<Manufacture and evaluation of composite sheet for protective film formation>
[Example 2]
A protective film-forming film (13) -2 was produced in the same manner as in Example 1 except that (c ′)-1 was used as a photoradical initiator and the addition amount was 0.6 parts by mass. Furthermore, the composite sheet for protective film formation was manufactured using this, and the characteristic was evaluated. The results are shown in Table 2.

<Manufacture and evaluation of composite sheet for protective film formation>
[Example 3]
A protective film-forming film (13) -3 was produced in the same manner as in Example 1 except that (c ′)-2 was used as a photoradical initiator and the addition amount was 0.6 parts by mass. Furthermore, the composite sheet for protective film formation was manufactured using this, and the characteristic was evaluated. The results are shown in Table 2.

<Manufacture and evaluation of composite sheet for protective film formation>
[Example 4]
A protective film-forming film (13) -4 was produced in the same manner as in Example 1 except that (c ′)-3 was used as a photoradical initiator and the addition amount was 0.6 parts by mass. Furthermore, the composite sheet for protective film formation was manufactured using this, and the characteristic was evaluated. The results are shown in Table 2.

<Manufacture and evaluation of composite sheet for protective film formation>
[Example 5]
A protective film-forming film (13) -5 was produced in the same manner as in Example 1 except that (c ′)-4 was used as a photoradical initiator and the addition amount was 0.6 parts by mass. Furthermore, the composite sheet for protective film formation was manufactured using this, and the characteristic was evaluated. The results are shown in Table 2.

<Manufacture and evaluation of composite sheet for protective film formation>
[Comparative Example 1]
A protective film-forming film (13) -6 was produced in the same manner as in Example 1 except that (c) -1 was used as a photoradical initiator and the addition amount was 0.6 parts by mass. Furthermore, the composite sheet for protective film formation was manufactured using this, and the characteristic was evaluated. The results are shown in Table 2.

As is clear from the above results, when the protective film-forming films (13) -1 to (13) -5 of Examples 1 to 4 were used, no chip cracking or chipping during pickup was observed. On the other hand, when the protective film-forming protective film (13) -6 of Comparative Example 1 was used, chip cracking and chipping during pickup were observed.

From the above results, when the photo radical initiators (c ′)-1 to (c ′)-4 were used, no curing failure of the protective film-forming film due to oxygen inhibition occurred, and the light of (c) -1 When a polymerization initiator is used, it is considered that defective curing of the protective film-forming film due to oxygen inhibition occurred. From this, it is considered effective to use a photoradical initiator having an extinction coefficient at a wavelength of 365 nm of 4 × 10 ¹ ml / (g · cm) or more.

The present invention can be used for manufacturing semiconductor devices.

1A, 1B, 1C, 1D, 1E ... Composite sheet for forming a protective film,
1F ... protective film forming sheet,
10 ... support sheet,
10a ... the surface of the support sheet,
11 ... base material,
11a ... surface of the substrate,
12 ... adhesive layer,
12a: the surface of the pressure-sensitive adhesive layer,
13, 23 ... protective film-forming film,
13a, 23a ... surface of the protective film-forming film,
15 ... release film,
16 ... Adhesive layer for jigs,
16a: adhesive layer for jig

Claims (4)

1. An energy ray-curable protective film-forming film,
   In the protective film forming film, the absorption coefficient of wavelength 365nm comprises ^{4.0 × 10 1 ml / (g} · cm) or more photoradical initiators, protective film formation film.
2. The film for protective film formation according to claim 1, wherein the photo radical initiator is a hydrogen abstraction type photo radical initiator having three or more aromatic rings in one molecule.
3. The protective film-forming film according to claim 1 or 2, wherein the photoradical initiator is a photoradical initiator having two or more photodegradable groups in one molecule.
4. A composite sheet for forming a protective film, comprising the protective film-forming film according to any one of claims 1 to 3 on a support sheet.

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