TWI722178B - Method of manufacturing semiconductor chip having protective film and method of manufacturing semiconductor device - Google Patents

Abstract

The present invention relates to a method of manufacturing a semiconductor chip (19) having a protective film in which a energy beam-curable film for forming a protective film (13) is adhered to a semicfonductor wafer (18), the film for forming the protective film (13) is irradiated with an energy beam and thereby cured, and the semicfonductor wafer (18) is diced. When the film for forming the protective film (13) is irradiated with the energy beam and thereby a protective film (13’) is formed, the tensile modulus of elasticity is 500MPa or more. Also, the present invention relates to a method of manufacturing the semiconductor device in which the semiconductor chip (19) having the protective film is picked up and the semiconductor chip (19) is connected to a substrate.

Description

Method for manufacturing semiconductor wafer with protective film and method for manufacturing semiconductor device

The present invention relates to a method for manufacturing a semiconductor wafer with a protective film and a method for manufacturing a semiconductor device.

This application claims priority based on Japanese Patent Application No. 2016-92010 filed in Japan on April 28, 2016, and the content of the application is cited herein.

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

There may be cases where a resin film containing an organic material is formed as a protective film on the back surface of the exposed semiconductor chip, and the protective film is incorporated into a semiconductor device in the form of a semiconductor chip with a protective film.

The protective film is used to prevent the semiconductor chip from cracking after the dicing step or packaging.

In order to form such a protective film, for example, a composite sheet for protective film formation provided with a protective film formation film for forming a protective film on a support sheet is used. In the composite sheet for forming a protective film, the protective film forming film can be cured to form a protective film, and a support sheet can be used as a dicing sheet to form a protective film forming film and a dicing sheet. A composite sheet for forming a one-piece protective film.

As such a composite sheet for forming a protective film, for example, a composite sheet for forming a protective film has been mainly used so far with a thermally curable protective film forming film. The thermally curable protective film forming film is cured by heating , Thereby forming a protective film. In this case, for example, after attaching the protective film forming composite sheet with the thermosetting protective film forming film on the back surface of the semiconductor wafer (the surface opposite to the electrode forming surface), the protective film is formed by heating The film is cured to become a protective film, and the semiconductor wafer is divided together with the protective film by dicing to form a semiconductor wafer. Then, the semiconductor wafer is directly pulled away from the support sheet and picked up while keeping the protective film attached. Furthermore, there are cases where the curing and cutting of the protective film forming film are performed in the reverse order.

However, the heat curing of the thermally curable protective film forming film usually takes a long time of about several hours, and therefore it is desired to shorten the curing time. In response to the above situation, the industry is studying the use of a protective film forming film that can be cured by irradiating energy rays such as ultraviolet rays for forming a protective film. For example, there are disclosed: an energy ray hardening type protective film formed on a release film (refer to Patent Document 1); an energy ray hardening type wafer protective film that can form a protective film with high hardness and excellent adhesion to semiconductor wafers (refer to patent Literature 2).

[Prior Technical Literature]

[Patent Literature]

Patent Document 1: Japanese Patent No. 5144433.

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

However, in the process of manufacturing semiconductor wafers and semiconductor devices using the energy-beam-curable wafer protection film disclosed in Patent Document 1 and Patent Document 2, when the semiconductor wafer is diced, there is a problem of blade clogging, or small generation in the protective layer. Defects, that is, the risk of fragmentation.

In addition, for the semiconductor chip with protective film after pickup, in order to be used in the next step, it will be packaged in an emboss carrier tape 102 as shown in FIG. 8, and the emboss carrier tape 102 When it is wound on a reel for storage, transportation, or commercial transactions. When stored in the embossed carrier tape 102, the semiconductor wafer 101 with a protective film after pickup is usually set with the circuit surface side of the semiconductor chip facing the bottom of the pocket 102a of the embossed carrier tape 102, and the protective film side It is stored toward the opening of the aforementioned pocket 102a. The cover tape 103 constituting the cover of the embossed carrier tape 102 is attached, thereby closing the aforementioned opening and packaging. When using the protective film-attached semiconductor wafer 101 in the next step, for example, set the embossed carrier tape 102 with the protective film-attached semiconductor wafer 101 together with the reel on a mounter. The semiconductor wafer 101 with a protective film is mounted on the substrate. At this time, the cover tape 103 is peeled off, and the protective film-attached semiconductor wafer 101 is taken out from the pocket 102a of the embossed carrier tape 102. However, the protective film-attached semiconductor wafer 101 may be formed by attaching the protective film to the cover tape 103. A situation of obstacles in the mounting process of mounting the semiconductor chip 101 with a protective film on the substrate.

Therefore, the object of the present invention is to provide a method for manufacturing a semiconductor wafer with a protective film and a method for manufacturing a semiconductor device. The method for manufacturing a semiconductor wafer with a protective film has the following characteristics: when cutting the semiconductor wafer, it is not easy to produce blades Clogging or fragmentation, when storing the protective film-attached semiconductor wafer in the pocket of the embossed carrier tape, it is possible to prevent the protective film-attached semiconductor wafer from adhering to the cover tape.

In order to solve the above-mentioned problems, the method for manufacturing a semiconductor wafer with a protective film of the present invention involves attaching an energy-ray curable protective film forming film to the semiconductor wafer, and then irradiating the protective film forming film with energy rays to cause the The protective film formation film is cured, and then the semiconductor wafer is diced; and when the protective film formation film is irradiated with energy rays to become a protective film, the tensile modulus of the protective film is 500 MPa or more.

In the method of manufacturing a semiconductor wafer with a protective film of the present invention, the protective film forming film may be irradiated with energy rays to form a protective film, then the protective film may be attached to a support sheet, and then the semiconductor wafer may be diced .

In the method of manufacturing a semiconductor wafer with a protective film of the present invention, the protective film formation film side of the protective film formation composite sheet formed by the protective film formation film provided on the support sheet can be attached to the semiconductor crystal. round.

The manufacturing method of the semiconductor device of this invention picks up the semiconductor wafer with a protective film obtained by the manufacturing method described in any one of the above, and connects the said semiconductor wafer to a board|substrate.

According to the present invention, there is provided a method for manufacturing a semiconductor wafer with a protective film and a method for manufacturing a semiconductor device. In the method for manufacturing a semiconductor wafer with a protective film, the cutting of the semiconductor wafer is unlikely to cause blade clogging or chipping, and will attach When the semiconductor wafer with the protective film is stored in the pocket of the embossed carrier tape, it is possible to prevent the semiconductor wafer with the protective film from adhering to the cover tape.

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

2F‧‧‧Protection film forming sheet

10‧‧‧Support film

10a‧‧‧(supporting film) surface

11‧‧‧Substrate

11a‧‧‧(of the substrate) surface

12‧‧‧Adhesive layer

12a‧‧‧(adhesive layer) surface

13, 23‧‧‧Film for forming protective film

13'‧‧‧Protective film

13a, 23a‧‧‧(One side of the protective film forming film) surface

13b‧‧‧(The other side of the protective film forming film) surface

15‧‧‧Peeling film

15'‧‧‧The first peeling film

15"‧‧‧Second peeling film

16‧‧‧Adhesive layer for fixture

16a‧‧‧(Adhesive layer for jig) surface

17‧‧‧Ring frame

18‧‧‧Semiconductor Wafer

19‧‧‧Semiconductor chip

20‧‧‧Cutting blade

21‧‧‧Energy ray irradiation device

101‧‧‧Semiconductor chip with protective film

102‧‧‧Embossed Carrier Tape

102a‧‧‧(embossed carrier tape) pocket

103‧‧‧Cover tape

FIG. 1 is a schematic diagram showing a method of manufacturing a semiconductor wafer with a protective film according to the present invention.

Fig. 2 is a cross-sectional view schematically showing an embodiment of a composite sheet for forming a protective film that can be used in the present invention.

Fig. 3 is a cross-sectional view schematically showing another embodiment of a composite sheet for forming a protective film that can be used in the present invention.

Fig. 4 is a cross-sectional view schematically showing another embodiment of the composite sheet for forming a protective film that can be used in the present invention.

Fig. 5 is a cross-sectional view schematically showing another embodiment of the composite sheet for forming a protective film that can be used in the present invention.

Fig. 6 is a cross-sectional view schematically showing another embodiment of a composite sheet for forming a protective film that can be used in the present invention.

Fig. 7 is a cross-sectional view schematically showing an embodiment of a sheet for forming a protective film that can be used in the present invention.

8 is a cross-sectional view schematically showing a state in which a semiconductor wafer with a protective film is stored in a pocket of an embossed carrier tape, and a cover tape is attached and sealed, and the state after the cover tape is peeled off.

◇Method for manufacturing semiconductor wafer with protective film and semiconductor device

FIG. 1 is a schematic diagram showing a method of manufacturing a semiconductor wafer with a protective film according to the present invention.

The manufacturing method of the protective film-attached semiconductor wafer 19 of the present invention is that after the energy ray curable protective film formation film 13 is attached to the semiconductor wafer 18, the protective film formation film 13 is irradiated with energy rays to form the protective film The film 13 is cured, and then the semiconductor wafer 18 is diced.

The protective film forming film 13 is irradiated with energy rays to harden the protective film forming film 13 and then diced. The protective film 13' during dicing is harder. Therefore, blade clogging or chipping is less likely to occur when the semiconductor wafer 18 is diced. In addition, since the tensile modulus of the protective film 13' is hard to be 500 MPa or more, it is possible to prevent the semiconductor wafer with the protective film from adhering to the cover tape.

In the method of manufacturing a semiconductor wafer with a protective film of the present invention, the protective film forming film may be irradiated with energy rays to form a protective film, then the protective film may be attached to a support sheet, and then the semiconductor wafer may be diced . In this case, the protective film formation film and the support sheet suitable for the product and manufacture of the semiconductor wafer can be appropriately selected and used.

In this case, the method for manufacturing a semiconductor wafer with a protective film of the present invention is as follows: After attaching an energy-ray curable protective film forming film to the back surface of the semiconductor wafer (the surface opposite to the electrode forming surface), The protective film formation film is irradiated with energy rays to harden the protective film formation film to become a protective film, then the protective film is attached to a support sheet, and then the semiconductor wafer is diced.

In the method of manufacturing a semiconductor wafer with a protective film of the present invention, the protective film formation film side of the protective film formation composite sheet formed by the protective film formation film provided on the support sheet can be attached to the semiconductor crystal. Round, which can simplify the attaching step.

In this case, the manufacturing method of the semiconductor wafer with a protective film of the present invention can be shown below.

The method for manufacturing a semiconductor wafer with a protective film of the present invention is as follows: A composite sheet for forming a protective film formed by providing the aforementioned protective film forming film on a support sheet is used for forming a protective film by the composite sheet for forming a protective film The film is attached to the back surface of the semiconductor wafer (the surface opposite to the electrode formation surface). Next, the film for forming a protective film is irradiated with energy rays to harden the film for forming a protective film, and then the semiconductor wafer is diced.

Hereinafter, using the same method as the previous method, the semiconductor wafer with the protective film is directly pulled away from the supporting sheet while the protective film is still attached to pick up the obtained semiconductor wafer with the protective film After the flip chip of the semiconductor chip is connected to the circuit surface of the substrate, a semiconductor package is made. Then, the semiconductor package can be used to manufacture the target semiconductor device.

◇Composite sheet for forming protective film

The composite sheet for forming a protective film that can be used in the present invention is a film for forming a protective film having energy ray curability on a support sheet.

In this specification, the "protective film formation film" means the protective film formation film before curing, and the "protective film" means the protective film formation film after curing.

In the present invention, the term "energy rays" means electromagnetic waves or charged particle beams having energy quantum, and examples of the aforementioned energy rays include ultraviolet rays, radiation rays, electron beams, and the like.

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

In the present invention, the "energy ray curability" refers to the property of curing by irradiation of energy rays, and the term "non-energy ray curability" refers to the property of not curing even if energy rays are irradiated.

In this specification, the dicing object including the support sheet, the protective film forming film with energy ray curability, and the semiconductor wafer in this order is referred to as a "layered body".

The adhesive force between the support sheet in the laminate and the film for forming the protective film is not particularly limited. For example, it may be 80mN/25mm or more, preferably 100mN/25mm or more, more preferably 150mN/25mm or more, especially It is 200mN/25mm or more. In addition, the upper limit is not particularly limited. For example, it may be 10000 mN/25mm or less, 8000 mN/25mm or less, or 7000 mN/25mm or less. By adjusting to the above-mentioned lower limit or more, peeling of the protective film forming film and the support sheet during dicing can be suppressed, for example, scattering of silicon wafers during dicing can be suppressed. In addition, by adjusting to the upper limit or less, when the protective film is hardened by irradiating energy rays later, the adhesive force between the protective film and the supporting sheet can be easily adjusted appropriately.

In this specification, the adhesive force between the said support sheet and the said film for protective film formation can be measured by the measurement method mentioned later.

The aforementioned film for forming a protective film is cured by irradiation with energy rays to become a protective film. This protective film protects the semiconductor wafer or the back surface (the surface opposite to the electrode formation surface) of the semiconductor wafer. The protective film forming film is soft and can be easily attached to an object to be attached. When the protective film forming film is irradiated with energy rays to form a protective film, the adhesive force between the protective film and the support sheet is preferably 50 mN/25mm to 1500 mN/25mm, more preferably 52 mN/25mm to 1450 mN/25mm, Particularly preferably, it is 53mN/25mm to 1430mN/25mm.

Since the aforementioned adhesion force is above the aforementioned lower limit, when picking up semiconductor chips with protective films, the pick-up of semiconductor chips with protective films outside the target is suppressed, so that the targets with protective films can be picked up with high selectivity Semiconductor wafers. Since the aforementioned adhesive force is below the aforementioned upper limit value, cracks and defects of the semiconductor chip are suppressed when picking up the semiconductor chip with the protective film. In this way, the composite sheet for forming a protective film has good pick-up suitability due to the aforementioned adhesive force being within a specific range.

In this specification, the adhesive force between the protective film and the support sheet can be measured by the measurement method described later.

As an aspect of the present invention, the tensile modulus of the aforementioned protective film is preferably 500 MPa to 10000 MPa, more preferably 600 MPa to 8000 MPa, and particularly preferably 700 MPa to 5000 MPa.

With the aforementioned tensile elastic modulus in this range, when dicing the semiconductor wafer using the aforementioned protective film, blade clogging or chipping is not easy to occur, and when storing the protective film-attached semiconductor wafer in the pocket of the embossed carrier tape, The semiconductor wafer with the protective film can be prevented from adhering to the cover tape.

In this specification, the aforementioned tensile modulus can be measured by the measuring method described in the examples described later.

In the composite sheet for forming a protective film that can be used in the present invention, the aforementioned film for forming a protective film is energy ray curable, which is compared with the conventional composite sheet for forming a protective film, which is thermally curable. In case, the protective film can be formed by curing in a short time.

In the present invention, instead of using the protective film forming composite sheet, the protective film forming film may be attached to the back surface of the semiconductor wafer, and then the support sheet may be attached to the protective film forming film. In this case, the protective film forming film and The support sheet can suitably use the protective film formation film and the support sheet described in the description of the above-mentioned protective film formation composite sheet.

In the present invention, the thickness of the semiconductor wafer or the semiconductor wafer used as the object of the composite sheet for forming a protective film is not particularly limited. In terms of obtaining more significant effects of the present invention, it is preferably 30 μm to 1000 μm, and more preferably 100μm to 300μm.

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

◎Support film

The aforementioned support sheet may be composed of one layer (single layer), or may be composed of multiple layers of two or more layers. When the support sheet is composed of multiple layers, the constituent materials and thicknesses of these multiple layers may be the same or different from each other. As long as the effect of the present invention is not impaired, the combination of these multiple layers is not particularly limited.

In this specification, it is not limited to the case of supporting films. The so-called "plural layers may be the same or different from each other" means "all layers may be the same, or all layers may be different, and only a part of the layers may be the same." "The layers are different from each other" means that "at least one of the constituent materials and thickness of each layer is different from each other."

As a preferable support sheet, for example, a support sheet formed by laminating an adhesive layer on a substrate in direct contact, a support sheet formed by laminating an adhesive layer on a substrate via an intermediate layer, and a support sheet composed of only the base Supporting pieces of material composition, etc.

Hereinafter, examples of the composite sheet for forming a protective film that can be used in the present invention will be described in accordance with each type of the above-mentioned support sheet with reference to the drawings. For the figures used in the following description, in order to facilitate the understanding of the characteristics of the present invention, and for convenience, the main parts may be enlarged and displayed, and the size ratios of the components are not limited to the same as the actual ones.

Fig. 2 is a cross-sectional view schematically showing an embodiment of a composite sheet for forming a protective film that can be used in the present invention.

The composite sheet 1A for forming a protective film shown here includes an adhesive layer 12 on a base material 11 and a protective film forming film 13 on the adhesive layer 12. The support sheet 10 is a laminate of the base material 11 and the adhesive layer 12. In other words, the protective film formation composite sheet 1A has a configuration in which the protective film formation film 13 is laminated on one surface 10 a of the support sheet 10. The protective film forming composite sheet 1A further includes a release film 15 on the protective film forming film 13.

In the composite sheet 1A for forming a protective film, an adhesive layer 12 is laminated on one surface 11a of the base material 11, and a protective film forming film 13 is layered on the entire surface 12a of the adhesive layer 12, which is used for forming a protective film A part of the surface 13a of the film 13, that is, the area near the peripheral edge, is laminated with an adhesive layer 16 for jigs. On the surface 13a of the film 13 for forming a protective film, the adhesive layer 16 for jigs is not laminated and for jigs. A release film 15 is laminated on the surface 16a (upper surface and side surface) of the adhesive layer 16.

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

The adhesive layer 16 for jigs may have, for example, a single-layer structure containing adhesive components, or may have a multiple-layer structure in which the two-area layer of the core sheet has layers containing adhesive components.

The composite sheet 1A for forming a protective film shown in FIG. 2 is used in the following manner: with the release film 15 removed, the back surface of a semiconductor wafer (not shown) is attached to the surface 13a of the film 13 for forming a protective film , And further attach the upper surface of the surface 16a of the jig adhesive layer 16 to jigs such as a ring frame.

Fig. 3 is a cross-sectional view schematically showing another embodiment of a composite sheet for forming a protective film that can be used in the present invention. In addition, in the figures following FIG. 3, the same constituent elements as shown in the already-explained figures are assigned the same symbols as in the already-explained figures, and detailed descriptions of the symbols are omitted.

The composite sheet 1B for forming a protective film shown here is the same as the composite sheet 1A for forming a protective film shown in FIG. 2 except that it does not include the adhesive layer 16 for jigs. That is, in the composite sheet 1B for forming a protective film, an adhesive layer 12 is laminated on one surface 11a of the base material 11, and a protective film forming film 13 is layered on the entire surface 12a of the adhesive layer 12 to protect The release film 15 is layered over the entire surface 13a of the film 13 for film formation.

The composite sheet 1B for forming a protective film shown in FIG. 3 is used in the following manner: with the release film 15 removed, a semiconductor wafer is attached to a part of the area on the central side of the surface 13a of the film 13 for forming a protective film (Illustration omitted), and the area near the peripheral edge of the protective film forming film 13 is further attached to a jig such as a ring frame.

Fig. 4 is a cross-sectional view schematically showing another embodiment of the composite sheet for forming a protective film that can be used in the present invention.

The composite sheet 1C for forming a protective film shown here is the same as the composite sheet 1A for forming a protective film shown in Fig. 2 except that the adhesive layer 12 is not provided. That is, in the composite sheet 1C for forming a protective film, the support sheet 10 is composed of only the base material 11. A protective film forming film 13 is laminated on one surface 11a of the substrate 11 (one surface 10a of the support sheet 10), and a part of the surface 13a of the protective film forming film 13, that is, the area near the peripheral edge is laminated to treat The adhesive layer 16 for tools is laminated with a release film 15 on the surface 13a of the protective film forming film 13 on which the adhesive layer 16 for jigs and the surface 16a (upper surface and side surfaces) of the adhesive layer 16 for jigs are not laminated .

In the protective film forming composite sheet 1C, the adhesive force between the cured protective film forming film 13 (ie, the protective film) and the support sheet 10, in other words, the adhesive force between the protective film and the base material 11 is preferably 50 mN /25mm to 1500mN/25mm.

The composite sheet 1C for forming a protective film shown in FIG. 4 is used in the following manner: similar to the composite sheet 1A for forming a protective film shown in FIG. The back surface of a semiconductor wafer (not shown) is attached to the surface 13a of 13 and the upper surface of the surface 16a of the adhesive layer 16 for jigs is attached to jigs such as a ring frame.

Fig. 5 is a cross-sectional view schematically showing another embodiment of the composite sheet for forming a protective film that can be used in the present invention.

The composite sheet 1D for forming a protective film shown here is the same as the composite sheet 1C for forming a protective film shown in Fig. 4 except that it does not include the adhesive layer 16 for jigs. That is, in the composite sheet 1D for protective film formation, the protective film formation film 13 is laminated|stacked on one surface 11a of the base material 11, and the release film 15 is laminated|stacked on the whole surface 13a of the protective film formation film 13.

The composite sheet 1D for forming a protective film shown in FIG. 5 is used in the following manner: similar to the composite sheet 1B for forming a protective film shown in FIG. A part of the area on the central side of the surface 13a of 13 is attached to the back surface of a semiconductor wafer (not shown), and the area near the periphery of the protective film forming film 13 is attached to a jig such as a ring frame.

Fig. 6 is a cross-sectional view schematically showing another embodiment of a composite sheet for forming a protective film that can be used in the present invention.

The composite sheet 1E for forming a protective film shown here is the same as the composite sheet 1B for forming a protective film shown in FIG. 3 except that the shape of the film for forming a protective film is different. That is, the composite sheet 1E for forming a protective film includes an adhesive layer 12 on a base material 11 and a protective film forming film 23 on the adhesive layer 12. The support sheet 10 is a laminate of the base material 11 and the adhesive layer 12. In other words, the protective film forming composite sheet 1E has a configuration in which the protective film forming film 23 is laminated on one surface 10 a of the support sheet 10. In the composite sheet 1E for forming a protective film, a release film 15 is further provided on the film 23 for forming a protective film.

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

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

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

The protective film forming composite sheet 1E shown in FIG. 6 is used in the following manner: with the release film 15 removed, the back surface of the semiconductor wafer (not shown) is attached to the surface 23a of the protective film forming film 23 , And further affix the surface 12a of the adhesive layer 12 on the surface 12a of the adhesive layer 12 on which the protective film forming film 23 is not laminated to a jig such as a ring frame.

In the protective film forming composite sheet 1E shown in FIG. 6, the surface 12a of the adhesive layer 12 where the protective film forming film 23 is not laminated may be combined with the protective film forming surface shown in FIGS. 2 and 4 The sheet is the same as the adhesive layer for laminated jigs (not shown). The composite sheet 1E for forming a protective film provided with such an adhesive layer for jigs is the same as the composite sheet for forming a protective film shown in FIGS. 2 and 4, and the surface of the adhesive layer for jigs is attached to the ring Frame and other fixtures.

In this way, the composite sheet for forming a protective film that can be used in the present invention can be provided with an adhesive layer for a jig regardless of the form of the support sheet and the film for forming a protective film. However, generally, as shown in FIGS. 2 and 4, as a composite sheet for forming a protective film provided with an adhesive layer for a jig, it is preferable to provide an adhesive layer for a jig on the film for forming a protective film.

The composite sheet for forming a protective film that can be used in the present invention is not limited to the composite sheet for forming a protective film as shown in FIGS. 2 to 6. As long as the effect of the present invention is not impaired, FIGS. 2 to 6 may be changed or deleted. A part of the structure of the composite sheet for forming a protective film as shown, or another structure may be added to the composite sheet for forming a protective film described above.

For example, in the composite sheet for forming a protective film shown in FIGS. 4 and 5, an intermediate layer may be provided between the base material 11 and the film 13 for forming a protective film. As the intermediate layer, any intermediate layer can be selected according to the purpose.

In the composite sheet for forming a protective film shown in FIGS. 2, 3 and 6, an intermediate layer may be provided between the base material 11 and the adhesive layer 12. That is, it can be used in the composite sheet for forming a protective film of the present invention, and the support sheet may be formed by sequentially layering a base material, an intermediate layer, and an adhesive layer. Here, the so-called intermediate layer is the same as the intermediate layer that can be provided in the composite sheet for forming a protective film shown in FIGS. 4 and 5.

In the composite sheet for forming a protective film shown in FIGS. 2 to 6, a layer other than the aforementioned intermediate layer can be provided at any position.

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

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

In the composite sheet for forming a protective film that can be used in the present invention, as described later, it is preferable that the layer directly in contact with the film for forming a protective film in a support sheet such as an adhesive layer is non-energy ray curable. By using such a composite sheet for forming a protective film, a semiconductor wafer with a protective film on the back surface can be picked up more easily.

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

Among them, in the present invention in which the film for forming a protective film has energy ray curability, the support sheet is preferably a support sheet that allows energy rays to pass through.

For example, in the support sheet, the transmittance of light with a wavelength of 375 nm is preferably 30% or more, more preferably 50% or more, and particularly preferably 70% or more. With the aforementioned light transmittance in this range, when energy rays (ultraviolet rays) are irradiated to the protective film forming film through the support sheet, the degree of curing of the protective film forming film is further improved.

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

In the support sheet, the transmittance of light with a wavelength of 532 nm is preferably 30% or more, more preferably 50% or more, and particularly preferably 70% or more.

With the light transmittance in this range, the protective film forming film or the protective film is irradiated with laser light through the support sheet, and printing can be performed more clearly when these are printed.

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

In the support sheet, the transmittance of light with a wavelength of 1064 nm is preferably 30% or more, more preferably 50% or more, and particularly preferably 70% or more. With the light transmittance in this range, the protective film forming film or the protective film is irradiated with laser light through the support sheet, and printing can be performed more clearly when these are printed.

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

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

○Substrate

The substrate is in a sheet shape or a film shape, and as a constituent material of the substrate, various resins can be cited, for example.

Examples of the aforementioned resin include polyethylenes such as low density polyethylene (LDPE; low density polyethylene), linear low density polyethylene (LLDPE), and high density polyethylene (HDPE; high density polyethylene); Polyolefins other than polyethylene such as polypropylene, polybutene, polybutadiene, polymethylpentene, norbornene resin; ethylene-vinyl acetate copolymer, ethylene-(meth)acrylic acid copolymer, ethylene- (Meth) acrylate copolymers, ethylene-norbornene copolymers and other vinyl copolymers (copolymers obtained by using ethylene as a monomer); vinyl chloride resins such as polyvinyl chloride and vinyl chloride copolymers (using chlorine Resin obtained from ethylene as a monomer); polystyrene; polycyclic olefin; polyethylene terephthalate, polyethylene naphthalate, polyethylene naphthalate, polyethylene isophthalate Polyesters, polyethylene 2,6-naphthalene dicarboxylate, wholly aromatic polyesters with aromatic cyclic groups in all structural units; copolymers of two or more of the aforementioned polyesters; poly(methyl) Acrylate; Polyurethane; Polyacrylic urethane; Polyimide; Polyamide; Polycarbonate; Fluororesin; Polyacetal; Modified polyphenylene ether; Polyphenylene sulfide; Poly碸; Polyetherketone etc.

As said resin, polymer alloys, such as a mixture of the said polyester and resin other than the said polyester, can also be mentioned, for example. The polymer alloy of the polyester and the resin other than the polyester preferably has a relatively small amount of the resin other than the polyester.

As the aforementioned resin, for example, a crosslinked resin obtained by crosslinking one or more of the aforementioned resins exemplified above; an ionic polymer using one or more of the aforementioned resins exemplified above, etc. Modified resin.

In this manual, the concept of "(meth)acrylic acid" includes both "acrylic acid" and "methacrylic acid". The same applies to terms similar to (meth)acrylic acid.

The resin constituting the base material may be only one type or two or more types; in the case of two or more types, these combinations and ratios can be arbitrarily selected.

The substrate may be composed of one layer (single layer) or two or more layers; when it is composed of multiple layers, these multiple layers may be the same or different from each other, and the combination of these multiple layers is not particularly limited.

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

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

In this specification, the "thickness" refers to the value displayed as the average of the measured thickness at any 5 locations of the object measured by a contact thickness meter.

The base material preferably has high thickness accuracy, that is, thickness unevenness at any part is suppressed. Among the above-mentioned constituent materials, examples of materials that can be used to construct such a substrate with high thickness precision include polyethylene, polyolefins other than polyethylene, polyethylene terephthalate, and ethylene-vinyl acetate copolymers. Things and so on.

The base material may contain various known additives such as fillers, colorants, antistatic agents, antioxidants, organic lubricants, catalysts, and softeners (plasticizers) in addition to the aforementioned main constituent materials such as resins.

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

In the present invention in which the film for forming a protective film has energy ray curability, the base material is preferably a base material that allows energy rays to pass through.

The surface of the substrate can also be subjected to the following treatments to improve the adhesion with other layers such as the adhesive layer provided on the substrate: using sandblasting treatment, solvent treatment, etc. concave-convex treatment; or corona discharge treatment, electron beam Irradiation treatment, plasma treatment, ozone/ultraviolet irradiation treatment, flame treatment, chromic acid treatment, hot air treatment and other oxidation treatments.

The surface of the substrate may also be subjected to primer treatment.

The substrate may also have an antistatic coating or a layer for the following purposes: when the composite sheet for forming a protective film is stacked and stored, it prevents the substrate from adhering to other sheets or the substrate from adhering to the suction table.

Among these, in terms of suppressing the occurrence of fragmentation of the substrate due to the friction of the blade during cutting, it is particularly preferable that the surface of the substrate is subjected to electron beam irradiation treatment.

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

○Adhesive layer

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

Examples of the aforementioned adhesive include: acrylic resin, urethane resin, rubber resin, silicone resin, epoxy resin, polyvinyl ether, polycarbonate, ester resin, etc. The resin is preferably an acrylic resin.

In the present invention, the concept of "adhesive resin" includes both adhesive resin and adhesive resin. For example, it includes not only the adhesive resin itself, but also the display by combining with other ingredients such as additives. Adhesive resin, or resin that exhibits adhesiveness due to the presence of heat or water and other triggers.

The adhesive layer can be composed of one layer (single layer), or two or more layers; when it is composed of multiple layers, these multiple layers may be the same or different from each other, and the combination of these multiple layers is not particularly limited .

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

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

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

In the present invention in which the film for forming a protective film has energy ray curability, the adhesive layer is preferably an adhesive layer that allows energy rays to pass through.

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

<<Adhesive composition>>

The adhesive layer can be formed using an adhesive composition containing an adhesive. For example, the adhesive composition is applied to the surface to be formed of the adhesive layer, and the adhesive composition is dried as needed, thereby forming the adhesive layer on the target site. A more specific method of forming the adhesive layer will be described in detail later together with the method of forming other layers. The content ratio of the components that do not vaporize at room temperature in the adhesive composition is usually the same as the content ratio of the aforementioned components in the adhesive layer. In this specification, the term "normal temperature" means a temperature that is not particularly cold or hot, that is, a normal temperature, for example, a temperature of 15°C to 25°C.

The adhesive composition can be applied by a known method. For example, methods using the following various coaters can be cited: air knife coater, knife coater, bar coater, gravure coater, roll coater Cloth machine, roll knife coater, curtain coater, die coater, knife coater, screen coater, Meyer bar coater, bar coater Rod coater, contact coater, etc.

The drying conditions of the adhesive composition are not particularly limited. In the case where the adhesive composition contains the solvent described later, it is preferable to heat and dry. In this case, it is preferably at 70°C to 130°C for 10 seconds to 5 seconds. Dry in minutes.

When the adhesive layer is energy ray curable, as an adhesive composition containing an energy ray curable adhesive, that is, an energy ray curable adhesive composition, for example, the following adhesive composition can be cited: Adhesive The agent composition (I-1) contains a non-energy-ray curable adhesive resin (I-1a) (hereinafter, sometimes abbreviated as "adhesive resin (I-1a)"), and an energy-ray curable compound; The adhesive composition (I-2) contains an energy-ray curable adhesive resin (I-2a) (hereinafter, sometimes abbreviated as "adhesive resin (I-2a)"), and the adhesive resin (I- 2a) Unsaturated groups are introduced into the side chain of the non-energy-ray curable adhesive resin (I-1a); the adhesive composition (I-3) contains the aforementioned adhesive resin (I-2a) and energy ray Hardening compound.

<Adhesive composition (I-1)>

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

[Adhesive resin (I-1a)]

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

As said acrylic resin, the acrylic polymer which has at least the structural unit derived from alkyl (meth)acrylate is mentioned, for example.

The structural unit possessed by the aforementioned acrylic resin may be only one type or two or more types; in the case of two or more types, these combinations and ratios can be arbitrarily selected.

Examples of the aforementioned alkyl (meth)acrylate include alkyl (meth)acrylates having 1 to 20 carbon atoms in the alkyl group constituting the alkyl ester, and the aforementioned alkyl group is preferably linear or branched. shape.

As the alkyl (meth)acrylate, more specifically, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate Ester, n-butyl (meth)acrylate, isobutyl (meth)acrylate, second butyl (meth)acrylate, tertiary butyl (meth)acrylate, amyl (meth)acrylate, (meth)acrylate Base) hexyl acrylate, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, n-octyl (meth)acrylate, n-octyl (meth)acrylate Nonyl ester, isononyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate (also known as (meth)acrylic acid) Lauryl ester), tridecyl (meth)acrylate, tetradecyl (meth)acrylate (also known as myristyl (meth)acrylate), pentadecyl (meth)acrylate, Cetyl (meth)acrylate (also known as palmetyl (meth)acrylate), heptadecyl (meth)acrylate, stearyl (meth)acrylate (also known as (meth)acrylate (Base) stearyl acrylate), nonadecyl (meth)acrylate, eicosyl (meth)acrylate and the like.

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

The aforementioned acrylic polymer preferably has a structural unit derived from a monomer containing a functional group in addition to a structural unit derived from an alkyl (meth)acrylate.

As the aforementioned functional group-containing monomer, for example, the following monomers can be exemplified by the reaction of the aforementioned functional group with the crosslinking agent described later to become the starting point of crosslinking, or the aforementioned functional group can react with the following unsaturated group-containing monomer The unsaturated group in the compound reacts, and the unsaturated group is introduced into the side chain of the acrylic polymer.

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

That is, as a monomer containing a functional group, for example, a monomer containing a hydroxyl group, a monomer containing a carboxyl group, a monomer containing an amine group, a monomer containing an epoxy group, and the like can be cited.

Examples of the hydroxyl-containing monomer include: hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate Hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate and other hydroxyalkyl (meth)acrylates; vinyl alcohol, Non-(meth)acrylic unsaturated alcohols such as allyl alcohol (unsaturated alcohols that do not have a (meth)acryloyl skeleton) and the like.

Examples of the aforementioned carboxyl group-containing monomer include: ethylenically unsaturated monocarboxylic acids (monocarboxylic acids having ethylenically unsaturated bonds) such as (meth)acrylic acid and crotonic acid; fumaric acid, itaconic acid, etc. Acid, maleic acid, citraconic acid and other ethylenically unsaturated dicarboxylic acids (dicarboxylic acids with ethylenically unsaturated bonds); anhydrides of the aforementioned ethylenically unsaturated dicarboxylic acids; 2-carboxyethyl methacrylic acid Esters and the like carboxyalkyl (meth)acrylates and the like.

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

The functional group-containing monomer constituting the aforementioned acrylic polymer may be only one type or two or more types; in the case of two or more types, these combinations and ratios can be arbitrarily selected.

In the aforementioned acrylic polymer, the content of the structural unit derived from the functional group-containing monomer relative to the total mass of the structural unit is preferably 1% to 35% by mass, more preferably 2% to 32% by mass, More preferably, it is 3% by mass to 30% by mass.

In the aforementioned acrylic polymer, in addition to the structural unit derived from the alkyl (meth)acrylate and the structural unit derived from the functional group-containing monomer, it may further have a structural unit derived from another monomer.

The aforementioned other monomers are not particularly limited as long as they can be copolymerized with alkyl (meth)acrylates and the like.

Examples of the aforementioned other monomers include styrene, α-methylstyrene, vinyl toluene, vinyl formate, vinyl acetate, acrylonitrile, acrylamide, and the like.

The aforementioned other monomers constituting the aforementioned acrylic polymer may be only one type or two or more types; in the case of two or more types, these combinations and ratios can be arbitrarily selected.

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

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

The adhesive resin (I-1a) contained in the adhesive composition (I-1) may be only one type or two or more types; in the case of two or more types, these combinations and ratios can be arbitrarily selected.

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

[Energy ray hardening compound]

Examples of the aforementioned energy-ray curable compound contained in the adhesive composition (I-1) include monomers or oligomers that have an energy-ray polymerizable unsaturated group and can be cured by irradiation with energy rays.

Among the energy ray curable compounds, examples of monomers include trimethylolpropane tri(meth)acrylate, pentaerythritol (meth)acrylate, pentaerythritol tetra(meth)acrylate, and dipentaerythritol hexa(meth)acrylate. (Meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol (meth)acrylate and other poly(meth)acrylates; (meth)acrylate aminomethyl Acid ester; polyester (meth)acrylate; polyether (meth)acrylate; epoxy (meth)acrylate, etc.

Among the energy ray curable compounds, examples of the oligomer include oligomers obtained by polymerizing the monomers exemplified above.

The energy ray curable compound is preferably (meth)acrylate urethane or (meth)acrylate urethane in terms of its relatively large molecular weight and it is difficult to reduce the storage elastic modulus of the adhesive layer. Oligomer.

The aforementioned energy ray curable compound contained in the adhesive composition (I-1) may be only one type or two or more types; in the case of two or more types, these combinations and ratios can be arbitrarily selected.

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

[Crosslinking agent]

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

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

Examples of the crosslinking agent include isocyanate-based crosslinking agents (crosslinking agents having isocyanate groups) such as toluene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, and adducts of these diisocyanates; Epoxy crosslinking agent such as ethylene glycol glycidyl ether (crosslinking agent with glycidyl group); aziridine series such as hexa[1-(2-methyl)-aziridinyl] triphosphine triazine Cross-linking agent (cross-linking agent with aziridin group); metal chelate-based cross-linking agent such as aluminum chelate (cross-linking agent with metal chelate structure); isocyanurate-based cross-linking agent (Crosslinking agent with isocyanuric acid skeleton) and so on.

The crosslinking agent is preferably an isocyanate-based crosslinking agent in terms of enhancing the cohesive force of the adhesive and enhancing the adhesive force of the adhesive layer, and easy availability.

The crosslinking agent contained in the adhesive composition (I-1) may be only one type or two or more types; in the case of two or more types, these combinations and ratios can be arbitrarily selected.

In the aforementioned adhesive composition (I-1), the content of the crosslinking agent relative to the content of the adhesive resin (I-1a) is 100 parts by mass, preferably 0.01 parts by mass to 50 parts by mass, more preferably 0.1 parts by mass It is 20 parts by mass, particularly preferably 0.3 parts by mass to 15 parts by mass.

[Photopolymerization initiator]

The adhesive composition (I-1) may further contain a photopolymerization initiator. For the adhesive composition (I-1) containing a photopolymerization initiator, even if it is irradiated with relatively low-energy energy rays such as ultraviolet rays, the curing reaction proceeds sufficiently.

Examples of the aforementioned photopolymerization initiator include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, benzoin methyl benzoate, and benzoin dimethyl ketal. ; Acetophenone, 2-hydroxy-2-methyl-1-phenyl-propane-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one, etc. Ketone compounds; bis(2,4,6-trimethylbenzyl)phenyl phosphine oxide, 2,4,6-trimethylbenzyl diphenyl phosphine oxide and other phosphine oxide compounds; benzyl Sulfide compounds such as phenyl sulfide and tetramethylthiuram monosulfide; α-keto alcohol compounds such as 1-hydroxycyclohexyl phenyl ketone; azo compounds such as azobisisobutyronitrile; Titanocene compounds; thioxanthone compounds such as thioxanthone; peroxide compounds; diketone compounds such as diacetin; benzil; benzil; benzophenone; 2,4-diethyl thioxanthone ; 1,2-Diphenylmethane; 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl] acetone; 2-chloroanthraquinone and the like.

As the aforementioned photopolymerization initiator, for example, quinone compounds such as 1-chloroanthraquinone; photosensitizers such as amines, and the like can also be used.

The photopolymerization initiator contained in the adhesive composition (I-1) may be only one type or two or more types; in the case of two or more types, these combinations and ratios can be arbitrarily selected.

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

[Other additives]

The adhesive composition (I-1) may also contain other additives that do not belong to any of the above-mentioned components within the range that does not impair the efficacy of the present invention.

Examples of the aforementioned other additives include: antistatic agents, antioxidants, softeners (plasticizers), fillers (fillers), rust inhibitors, colorants (pigments, dyes), sensitizers, adhesion-imparting agents, Known additives such as reaction delay agents and crosslinking accelerators (catalysts).

The so-called reaction delay agent, for example, suppresses the off-target crosslinking reaction in the adhesive composition (I-1) during storage due to the effect of the catalyst mixed into the adhesive composition (I-1). As the reaction delay agent, for example, a compound that forms a chelate complex by a chelate against a catalyst can be mentioned. More specifically, it can be exemplified by having two or more carbonyl groups (-C(=O) per molecule). -) The compound.

The other additives contained in the adhesive composition (I-1) may be only one type or two or more types; in the case of two or more types, these combinations and ratios can be arbitrarily selected.

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

[Solvent]

The adhesive composition (I-1) may also contain a solvent. The adhesive composition (I-1) contains a solvent to improve the coating suitability of the coating target surface.

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

As the aforementioned solvent, for example, the solvent used in the production of the adhesive resin (I-1a) can be used directly in the adhesive composition (I-1) without being removed from the adhesive resin (I-1a). The same type of solvent or a different type of solvent can be added when manufacturing the adhesive composition (I-1) as the solvent used when manufacturing the adhesive resin (I-1a).

The solvent contained in the adhesive composition (I-1) may be only one type or two or more types; in the case of two or more types, these combinations and ratios can be arbitrarily selected.

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

<Adhesive composition (I-2)>

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

[Adhesive resin (I-2a)]

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

The aforementioned unsaturated group-containing compound, in addition to the aforementioned energy ray polymerizable unsaturated group, further has a group that can react with the adhesive resin (I-1a) by reacting with the functional group in the adhesive resin ( I-1a) Bonding.

Examples of the energy-beam polymerizable unsaturated group include (meth)acryloyl group, vinyl group (also referred to as ethylene group), allyl group (also referred to as 2-propenyl group), etc., preferably (Meth)acryloyl.

Examples of groups that can be bonded to the functional groups in the adhesive resin (I-1a) include: isocyanate groups and glycidyl groups that can be bonded to hydroxyl groups or amino groups, and carboxyl groups or epoxy groups that can be bonded The hydroxyl and amino groups, etc.

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

The adhesive composition (I-2) contained in the adhesive composition (I-2) may contain only one type of adhesive resin (I-2a), or two or more types; in the case of two or more types, these combinations and ratios can be arbitrarily selected.

In the adhesive composition (I-2), the content of the adhesive resin (I-2a) relative to the total mass of the aforementioned adhesive composition (I-2) is preferably 5% to 99% by mass, more preferably It is 10% by mass to 95% by mass, particularly preferably 10% by mass to 90% by mass.

[Crosslinking agent]

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

Examples of the crosslinking agent in the adhesive composition (I-2) include the same compounds as the crosslinking agent in the adhesive composition (I-1).

The crosslinking agent contained in the adhesive composition (I-2) may be only one type or two or more types; in the case of two or more types, these combinations and ratios can be arbitrarily selected.

In the aforementioned adhesive composition (I-2), the content of the crosslinking agent relative to the content of the adhesive resin (I-2a) is 100 parts by mass, preferably 0.01 parts by mass to 50 parts by mass, more preferably 0.1 parts by mass It is 20 parts by mass, particularly preferably 0.3 parts by mass to 15 parts by mass.

[Photopolymerization initiator]

The adhesive composition (I-2) may further contain a photopolymerization initiator. For the adhesive composition (I-2) containing a photopolymerization initiator, even if it is irradiated with relatively low-energy energy rays such as ultraviolet rays, the curing reaction proceeds sufficiently.

Examples of the photopolymerization initiator in the adhesive composition (I-2) include the same compounds as the photopolymerization initiator in the adhesive composition (I-1).

The photopolymerization initiator contained in the adhesive composition (I-2) may be only one type or two or more types; in the case of two or more types, these combinations and ratios can be arbitrarily selected.

In the adhesive composition (I-2), the content of the photopolymerization initiator relative to 100 parts by mass of the adhesive resin (I-2a) is preferably 0.01 to 20 parts by mass, more preferably 0.03 parts by mass Parts to 10 parts by mass, more preferably 0.05 parts by mass to 5 parts by mass.

[Other additives]

The adhesive composition (I-2) may also contain other additives that do not belong to any of the above-mentioned components within the range that does not impair the efficacy of the present invention.

Examples of the aforementioned other additives in the adhesive composition (I-2) include the same compounds as the other additives in the adhesive composition (I-1).

The other additives contained in the adhesive composition (I-2) may be only one type or two or more types; in the case of two or more types, these combinations and ratios can be arbitrarily selected.

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

[Solvent]

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

Examples of the aforementioned solvent in the adhesive composition (I-2) include the same solvents as the solvent in the adhesive composition (I-1).

The solvent contained in the adhesive composition (I-2) may be only one type or two or more types; in the case of two or more types, these combinations and ratios can be arbitrarily selected.

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

<Adhesive composition (I-3)>

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

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

[Energy ray hardening compound]

Examples of the aforementioned energy-ray curable compound contained in the adhesive composition (I-3) include monomers and oligomers that have an energy-ray polymerizable unsaturated group and can be cured by irradiation with energy rays, including The same compound as the energy ray curable compound contained in the adhesive composition (I-1).

The aforementioned energy ray curable compound contained in the adhesive composition (I-3) may be only one type or two or more types; in the case of two or more types, these combinations and ratios can be arbitrarily selected.

In the aforementioned adhesive composition (I-3), the content of the aforementioned energy ray curable compound relative to the content of the adhesive resin (I-2a) is 100 parts by mass, preferably 0.01 to 300 parts by mass, more preferably 0.03 parts by mass to 200 parts by mass, particularly preferably 0.05 parts by mass to 100 parts by mass.

[Photopolymerization initiator]

The adhesive composition (I-3) may further contain a photopolymerization initiator. For the adhesive composition (I-3) containing a photopolymerization initiator, even if it is irradiated with relatively low-energy energy rays such as ultraviolet rays, the curing reaction proceeds sufficiently.

Examples of the photopolymerization initiator in the adhesive composition (I-3) include the same compounds as the photopolymerization initiator in the adhesive composition (I-1).

The photopolymerization initiator contained in the adhesive composition (I-3) may be only one type or two or more types; in the case of two or more types, these combinations and ratios can be arbitrarily selected.

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

[Other additives]

The adhesive composition (I-3) may also contain other additives that do not belong to any of the above-mentioned components within the range that does not impair the efficacy of the present invention.

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

The other additives contained in the adhesive composition (I-3) may be only one type or two or more types; in the case of two or more types, these combinations and ratios can be arbitrarily selected.

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

[Solvent]

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

Examples of the aforementioned solvent in the adhesive composition (I-3) include the same solvents as the solvent in the adhesive composition (I-1).

The solvent contained in the adhesive composition (I-3) may be only one type or two or more types; in the case of two or more types, these combinations and ratios can be arbitrarily selected.

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

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

The foregoing mainly describes the adhesive composition (I-1), the adhesive composition (I-2), and the adhesive composition (I-3), but for all adhesives other than these three types of adhesive compositions The composition (referred to as the "adhesive composition (I-1) to the adhesive composition other than the adhesive composition (I-3) in this specification") can also be used in the same manner as those described for the contained components ingredient.

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

Examples of non-energy-ray curable adhesive compositions include acrylic resins, urethane resins, rubber resins, silicone resins, epoxy resins, polyvinyl ethers, and polycarbonates. The adhesive composition (I-4) of the non-energy-ray curable adhesive resin (I-1a) such as ester and ester resin is preferably an adhesive composition containing acrylic resin.

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

<Adhesive composition (I-4)>

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

[Adhesive resin (I-1a)]

Examples of the adhesive resin (I-1a) in the adhesive composition (I-4) include the same resins as the adhesive resin (I-1a) in the adhesive composition (I-1).

The adhesive resin (I-1a) contained in the adhesive composition (I-4) may be only one type or two or more types; in the case of two or more types, these combinations and ratios can be arbitrarily selected.

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

[Crosslinking agent]

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

Examples of the crosslinking agent in the adhesive composition (I-4) include the same compounds as the crosslinking agent in the adhesive composition (I-1).

The crosslinking agent contained in the adhesive composition (I-4) may be only one type or two or more types; in the case of two or more types, these combinations and ratios can be arbitrarily selected.

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

[Other additives]

The adhesive composition (I-4) may also contain other additives that do not belong to any of the above-mentioned components within the range that does not impair the efficacy of the present invention.

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

The other additives contained in the adhesive composition (I-4) may be only one type or two or more types; in the case of two or more types, these combinations and ratios can be arbitrarily selected.

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

[Solvent]

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

Examples of the aforementioned solvent in the adhesive composition (I-4) include the same solvents as the solvent in the adhesive composition (I-1).

The solvent contained in the adhesive composition (I-4) may be only one type or two or more types; in the case of two or more types, these combinations and ratios can be arbitrarily selected.

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

In the composite sheet for forming a protective film that can be used in the present invention, the adhesive layer is preferably non-energy ray curable. The reason is that if the adhesive layer is energy-ray curable, it may not be possible to suppress the curing of the adhesive layer at the same time when the protective film formation film is cured by energy ray irradiation. If the adhesive layer and the protective film forming film are cured at the same time, the cured protective film forming film and the adhesive layer may adhere to the interface of these to the extent that they cannot be peeled off. In this case, it is difficult to provide a hardened protective film forming film on the back side, that is, a semiconductor chip with a protective film (in this specification, sometimes referred to as a "semiconductor chip with protective film"), since it has a hardened adhesive The support sheet of the agent layer was peeled off, and the semiconductor wafer with the protective film could not be picked up normally. By making the adhesive layer in the support sheet of the present invention non-energy-ray curable, such a disadvantage can be reliably avoided, and the semiconductor wafer with the protective film can be picked up more easily.

This article describes the effect of the adhesive layer being non-energy-ray hardening, but even if the layer directly in contact with the protective film formation film in the support sheet is a layer other than the adhesive layer, as long as the layer is non-energy-ray Hardening, it also exerts the same effect.

<<Method for manufacturing adhesive composition>>

Adhesive composition (I-1) to adhesive composition (I-3), or adhesive composition (I-4) and other adhesive composition (I-1) to adhesive composition (I-3) The adhesive composition other than that is obtained by mixing the aforementioned adhesive and, if necessary, components other than the aforementioned adhesive to constitute the adhesive composition.

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

When a solvent is used, it can be used by the following method: mixing the solvent with any compounding component other than the solvent and diluting the compounding component in advance; it can also be used by the following method: not adding any one other than the solvent The compounding components are diluted in advance, and the solvent is mixed with these compounding components.

The method of mixing each component during compounding is not particularly limited, and it can be appropriately selected from the following known methods: a method of mixing by rotating a stirrer or a stirring blade, a method of mixing using a mixer, and a method of applying ultrasonic waves. Methods of mixing, etc.

The temperature and time for adding and mixing each component are not particularly limited as long as they do not deteriorate each compounding component, and they may be adjusted appropriately. The temperature is preferably 15°C to 30°C.

◎Sheet for forming protective film

In the present invention, the protective film forming film can be used in the form of the above-mentioned composite sheet for protective film formation, and it can also be used in the form of a protective film forming sheet formed by providing a protective film forming film on a release film. After the back surface of the aforementioned semiconductor wafer, a support sheet is attached and used.

The film for forming a protective film that can be used here is as described in the section of the above-mentioned composite sheet for forming a protective film.

Fig. 7 is a cross-sectional view schematically showing an embodiment of a protective film forming sheet 2F that can be used in the present invention.

The sheet 2F for protective film formation shown here is provided with the film 13 for protective film formation on the 1st peeling film 15', and the 2nd peeling film 15" is provided on the film 13 for protective film formation.

The protective film forming sheet 2F shown in FIG. 7 is used in the following manner: with the second peeling film 15" on the lightly peeling side removed, it is pasted on a part of the central side of the surface 13a of the protective film forming film 13 Attach the back surface of the semiconductor wafer (not shown), and further, with the first release film 15' on the heavy release side removed, on the other side of the protective film formation film 13 opposite to the surface 13a A support sheet is attached to the surface 13b. And, as shown in, for example, FIG. 4, the area near the peripheral edge of the protective film forming film 13 is attached to a jig such as a ring frame via the jig adhesive layer 16, or, As shown in, for example, FIG. 6, the protective film forming sheet 2F is cut into a circular shape and laminated on a support sheet, and the adhesive part in the support sheet is held by a jig such as a ring frame.

Here, the peeling film with a small peeling force is called a peeling film on the light peeling side, and the peeling film with a large peeling force is called a peeling film on the heavy peeling side. If there is a difference in the peeling force, it is possible to prevent the protective film forming film from lifting the peeling film on the weight peeling side when only the peeling film on the lightly peeling side is peeled off, or the protective film forming film is pulling to follow both of the peeling films. The situation of stretching and deformation.

In the present invention, the adhesive force between the protective film and the support sheet obtained by curing the protective film forming film is preferably 50mN/25mm to 1500mN/25mm, more preferably 52mN/25mm to 1450mN/25mm, and particularly preferably 53mN/ 25mm to 1430mN/25mm. Since the aforementioned adhesion force is above the aforementioned lower limit, when picking up semiconductor chips with protective films, the pick-up of semiconductor chips with protective films outside the target is suppressed, so that the targets with protective films can be picked up with high selectivity Semiconductor wafers. Since the aforementioned adhesive force is below the aforementioned upper limit value, cracks and defects of the semiconductor chip are suppressed when picking up the semiconductor chip with the protective film. In this way, the composite sheet for forming a protective film has good pick-up suitability due to the aforementioned adhesive force being within a specific range.

In the present invention, even after the protective film formation film is cured, as long as the laminated structure of the support sheet and the cured product of the protective film formation film (in other words, the support sheet and the protective film) is maintained, the laminated structure is also referred to as " Composite sheet for forming protective film".

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

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

Then, after energy ray is irradiated to harden the protective film forming film to form a protective film, the support sheet is peeled from the protective film attached to the adherend at a peeling speed of 300 mm/min. The peeling at this time is the following so-called 180° peeling: the support sheet is moved along the length direction of the support sheet so that the contact surfaces of the protective film and the support sheet are at an angle of 180°. The length direction) peel off. Then, the load (peel force) at the time of 180° peeling was measured, and the measured value of the load (peel force) was taken as the aforementioned adhesive force (mN/25mm).

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

In the present invention, the adhesive force between the protective film forming film and the aforementioned support sheet is not particularly limited. For example, it can be 80mN/25mm or more, preferably 100mN/25mm or more, more preferably 150mN/25mm or more, and more preferably It is 200mN/25mm or more. With the aforementioned adhesive force of 100 mN/25 mm or more, peeling of the protective film forming film from the support sheet during dicing is suppressed, for example, the scattering of the self-supporting sheet of a semiconductor wafer with a 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 formation film and the support sheet is not particularly limited, and for example, it can be any of 4000mN/25mm, 3500mN/25mm, 3000mN/25mm, etc. However, these are just an example.

Regarding the adhesive force between the protective film formation film and the support sheet, in addition to the aspect that does not harden the protective film formation film for measurement by irradiating energy rays, it can be used with the above-mentioned protective film and support sheet. The adhesion is measured in the same way.

The above-mentioned adhesive force between the protective film and the support sheet and the adhesive force between the protective film formation film and the support sheet can be adjusted by adjusting the type and amount of the components contained in the protective film formation film, and the setting in the support sheet. The constituent material of the layer of the film for forming a protective film, the surface state of the layer, and the like are appropriately adjusted.

For example, the type and amount of components contained in the film for forming a protective film can be adjusted by the types and amounts of components contained in the composition for forming a protective film described later. In addition, by adjusting the components contained in the composition for forming a protective film, for example, the type and content of the polymer (b) that does not have an energy-ray curable group, the content of the filler (d), or the crosslinking agent (f) The content of, can more easily adjust the adhesion between the protective film or the protective film forming film and the support sheet.

For example, when the layer provided with the protective film forming film in the support sheet is an adhesive layer, the constituent material of the layer can be appropriately adjusted by adjusting the types and amounts of components contained in the adhesive layer. In addition, the types and amounts of components contained in the adhesive layer can be adjusted by the types and amounts of components contained in the above-mentioned adhesive composition.

On the other hand, when the layer provided with the protective film formation film in the support sheet is the base material, the adhesion between the protective film or the protective film formation film and the support sheet is not only the constituent material of the base material, but also It can be adjusted by the surface condition of the substrate. In addition, the surface condition of the substrate can be adjusted by, for example, performing the surface treatment listed above as the treatment to improve the adhesion between the substrate and other layers: roughening treatment by sandblasting, solvent treatment, etc.; corona discharge treatment , Electron beam irradiation treatment, plasma treatment, ozone/ultraviolet irradiation treatment, flame treatment, chromic acid treatment, hot air treatment and other oxidation treatments; any treatment such as primer treatment.

Examples of the film for forming a protective film include a film having energy ray curability, for example, containing an energy ray curable component (a).

The energy ray curable component (a) is preferably uncured, preferably has adhesiveness, and more preferably has adhesiveness and uncured.

The protective film formation film can be only one layer (single layer), or multiple layers of two or more layers; in the case of multiple layers, these multiple layers may be the same or different from each other, and there is no combination of these multiple layers Specially limited.

The thickness of the protective film forming film is preferably 1 m to 100 m, more preferably 5 m to 75 m, and particularly preferably 5 m to 50 m. When the thickness of the protective film forming film is more than the aforementioned lower limit, a protective film with higher protective ability can be formed. When the thickness of the film for forming a protective film is not more than the aforementioned upper limit, excessive thickness can be suppressed.

Here, the "thickness of the protective film formation film" means the thickness of the entire protective film formation film. For example, the thickness of the protective film formation film composed of plural layers means all the layers constituting the protective film formation film The total thickness.

Regarding the curing conditions when the protective film forming film is cured to form the protective film, as long as the protective film has a degree of curing sufficient to fully exhibit the function of the protective film, there are no particular restrictions, and it is appropriately selected according to the type of the protective film forming film That's it.

For example, when the film for forming a protective film is cured, the illuminance of the energy ray is preferably 4 mW/cm ² to 280 ^{mW/cm 2} . During the aforementioned curing, the light amount of the energy rays is preferably 3 mJ/cm ² to 1000 mJ/cm ² .

<<Protective film forming composition>>

The film for protective film formation can be formed using the composition for protective film formation containing the constituent material of the film for protective film formation. For example, by coating the protective film forming composition on the surface to be formed of the protective film forming film, and drying the protective film forming composition as necessary, the protective film forming film can be formed on the target site. The content ratio of the components that do not vaporize at room temperature in the protective film formation composition is usually the same as the content ratio of the aforementioned components in the protective film formation film. Here, the so-called "normal temperature" is as explained above.

The composition for forming a protective film may be applied by a known method, for example, methods using various coating machines such as air knife coater, knife coater, bar coater, gravure coater, roll Type coater, roll knife coater, curtain coater, die coater, knife coater, screen coater, wire-wound bar coater, contact coater, etc.

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

<Composition for Forming Protective Film (IV-1)>

As the protective film forming composition, for example, the protective film forming composition (IV-1) containing the aforementioned energy ray curable component (a) can be cited.

[Energy ray hardening component (a)]

The energy-ray curable component (a) is a component that is cured by irradiation of energy rays, and the component is used to impart film-forming properties, flexibility, etc., to the film for forming a protective film.

Examples of the energy ray curable component (a) include: a polymer (a1) having an energy ray curable group and a weight average molecular weight of 80,000 to 2,000,000, and a compound having an energy ray curable group and a molecular weight of 100 to 80,000 (a2). The aforementioned polymer (a1) may be cross-linked at least partially by the cross-linking agent (f) described later, or may not be cross-linked.

In this specification, the weight average molecular weight, unless otherwise specified, means a polystyrene conversion value measured by a gel permeation chromatography (GPC; Gel Permeation Chromatography) method.

(Polymer (a1) with energy ray curable base and 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 acrylic resin (a1-1), and the acrylic resin (a1-1) is an acrylic polymer (a11). ) Is polymerized with an energy ray curable compound (a12), the aforementioned acrylic polymer (a11) has a functional group capable of reacting with groups possessed by other compounds, and the aforementioned energy ray curable compound (a12) has a functional group Energy ray hardening groups such as reaction bases and energy ray hardening double bonds.

Examples of the functional groups that can react with groups possessed by other compounds include hydroxyl groups, carboxyl groups, amino groups, and substituted amino groups (one or two hydrogen atoms of the amino group are substituted with groups other than hydrogen atoms. Group), epoxy group and the like. However, in terms of preventing corrosion of a semiconductor wafer or a circuit of a semiconductor wafer, the aforementioned functional group is preferably a group other than a carboxyl group.

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

. Acrylic polymer with functional group (a11)

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

In addition, the aforementioned acrylic polymer (a11) may be a random copolymer or a block copolymer.

Examples of the aforementioned acrylic monomer having a functional group include: hydroxyl group-containing monomers, carboxyl group-containing monomers, amine group-containing monomers, substituted amine group-containing monomers, epoxy group-containing monomers, etc. .

Examples of the hydroxyl-containing monomer include: hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate Hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate and other hydroxyalkyl (meth)acrylates; vinyl alcohol, Non-(meth)acrylic unsaturated alcohols such as allyl alcohol (unsaturated alcohols that do not have a (meth)acryloyl skeleton) and the like.

Examples of the aforementioned carboxyl group-containing monomer include: ethylenically unsaturated monocarboxylic acids (monocarboxylic acids having ethylenically unsaturated bonds) such as (meth)acrylic acid and crotonic acid; fumaric acid, itaconic acid, etc. Acid, maleic acid, citraconic acid and other ethylenically unsaturated dicarboxylic acids (dicarboxylic acids with ethylenically unsaturated bonds); anhydrides of the aforementioned ethylenically unsaturated dicarboxylic acids; 2-carboxyethyl methacrylic acid Esters and the like carboxyalkyl (meth)acrylates and the like.

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

The aforementioned acrylic monomer having a functional group constituting the aforementioned acrylic polymer (a11) may be only one type or two or more types; in the case of two or more types, these combinations and ratios can be arbitrarily selected.

Examples of acrylic monomers that do not have the aforementioned functional group include: methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, N-Butyl (meth)acrylate, isobutyl (meth)acrylate, second butyl (meth)acrylate, tertiary butyl (meth)acrylate, pentyl (meth)acrylate, (meth) Hexyl acrylate, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, n-octyl (meth)acrylate, n-nonyl (meth)acrylate , Isononyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate (also known as lauryl (meth)acrylate ), tridecyl (meth)acrylate, tetradecyl (meth)acrylate (also known as myristyl (meth)acrylate), pentadecyl (meth)acrylate, (meth) Base) hexadecyl acrylate (also known as palmetyl (meth) acrylate), heptadecyl (meth) acrylate, stearyl (meth) acrylate (also known as (meth) acrylate) Stearyl acrylate) and other alkyl (meth)acrylates having a chain structure with a carbon number of 1 to 18 constituting the alkyl group of the alkyl ester.

In addition, as the aforementioned acrylic monomer having no functional group, for example, methoxymethyl (meth)acrylate, methoxyethyl (meth)acrylate, and ethoxymethyl (meth)acrylate can also be cited. (Meth)acrylates containing alkoxyalkyl groups such as ethoxyethyl (meth)acrylate, etc.; those containing aryl (meth)acrylates such as phenyl (meth)acrylate, etc., have aromatic groups (Meth)acrylate; non-crosslinkable (meth)acrylamide and its derivatives; (meth)acrylic acid N,N-dimethylaminoethyl, (meth)acrylic acid N,N- Non-crosslinkable (meth)acrylates with tertiary amino groups such as dimethylaminopropyl.

The aforementioned acrylic monomer having no functional group constituting the aforementioned acrylic polymer (a11) may be only one type or two or more types; in the case of two or more types, these combinations and ratios can be arbitrarily selected.

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

The aforementioned non-acrylic monomer constituting the aforementioned acrylic polymer (a11) may be only one type or two or more types; in the case of two or more types, these combinations and ratios can be arbitrarily selected.

In the aforementioned acrylic polymer (a11), the ratio (content) of the amount of structural units derived from the acrylic monomer having the aforementioned functional group relative to the total mass of the structural units constituting the acrylic polymer (a11) is preferred It is 0.1% by mass to 50% by mass, more preferably 1% by mass to 40% by mass, and particularly preferably 3% by mass to 30% by mass. With the aforementioned ratio in this range, the energy-ray-curable group in the acrylic resin (a1-1) obtained by copolymerization of the aforementioned acrylic polymer (a11) and the aforementioned energy-ray-curable compound (a12) The content of is easily adjusted to a range where the degree of hardening of the first protective film is preferable.

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, these combinations and ratios can be arbitrarily selected.

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

. Energy ray hardening compound (a12)

The aforementioned energy ray curable compound (a12) preferably has one or more selected from the group consisting of an isocyanate group, an epoxy group, and a carboxyl group as the one that can be combined with the aforementioned acrylic polymer (a11). The functional group reaction group more preferably has an isocyanate group as the aforementioned group. When the energy ray curable compound (a12) has, for example, 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 a functional group.

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

Examples of the energy ray curable compound (a12) include 2-methacryloxyethyl isocyanate, m-isopropenyl-α,α-dimethylbenzyl isocyanate, and methacrylic acid. Isocyanate, allyl isocyanate, 1,1-(bisacryloxymethyl) ethyl isocyanate; by the reaction of a diisocyanate compound or a polyisocyanate compound with hydroxyethyl (meth)acrylate Acrylic monoisocyanate compound obtained; Acrylic monoisocyanate compound obtained by reaction of diisocyanate compound or polyisocyanate compound, polyol compound and hydroxyethyl (meth)acrylate, etc.

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

The aforementioned energy ray curable compound (a12) constituting the aforementioned acrylic resin (a1-1) may be only one type or two or more types; in the case of two or more types, these combinations and ratios can be arbitrarily selected.

In the acrylic resin (a1-1), the ratio of the content of the energy ray curable group derived from the energy ray curable compound (a12) to the content of the functional group derived from the acrylic polymer (a11) It is preferably 20 mol% to 120 mol%, more preferably 35 mol% to 100 mol%, and particularly preferably 50 mol% to 100 mol%. When the aforementioned content ratio is in this range, the adhesive force of the protective film formed by curing becomes greater. In addition, when the energy ray curable compound (a12) is a monofunctional (having one group in one molecule) compound, the upper limit of the ratio of the content becomes 100 mol%, but it is less than the energy When the linear curable compound (a12) is a polyfunctional (having two or more of the aforementioned groups in one molecule) compound, the upper limit of the aforementioned content ratio may exceed 100 mol%.

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

When at least a part of the aforementioned polymer (a1) is cross-linked by a cross-linking agent (f), the aforementioned polymer (a1) can be any one of the aforementioned acrylic polymer (a11) that does not belong to the above description. It is a monomer and a monomer having a group reactive with the crosslinking agent (f) is polymerized, and the crosslinking is carried out in the aforementioned group reactive with the crosslinking agent (f). It may also be derived from the aforementioned energy ray curable compound (a12 ) Is cross-linked in the group that reacts with the aforementioned functional group.

The aforementioned polymer (a1) contained in the protective film forming composition (IV-1) and the protective film forming film may be only one type or two or more types; in the case of two or more types, these polymers are combined And the ratio can be chosen arbitrarily.

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

Examples of the energy-ray-curable group possessed by the compound (a2) having an energy-ray-curable group and a molecular weight of 100 to 80,000 include a group containing an energy-ray-curable double bond, and as a preferable group, (former) Base) acryloyl, vinyl and the like.

If the aforementioned compound (a2) satisfies the above conditions, it is not particularly limited. Examples include low molecular weight compounds having energy ray curable groups, epoxy resins having energy ray curable groups, and phenol resins having energy ray curable groups. Wait.

Among the aforementioned compounds (a2), examples of the low-molecular-weight compound having an energy ray-curable group include polyfunctional monomers or oligomers, and preferably acrylate-based compounds having a (meth)acryloyl group.

Examples of the acrylate-based compound include: 2-hydroxy-3-(meth)acryloxypropyl methacrylate, polyethylene glycol di(meth)acrylate, and propoxylated ethoxy Bisphenol A bis(meth)acrylate, 2,2-bis[4-((meth)acryloyloxypolyethoxy)phenyl]propane, ethoxylated bisphenol A bis(methyl) )Acrylate, 2,2-bis[4-((meth)acryloyloxydiethoxy)phenyl]propane, 9,9-bis[4-(2-(meth)acryloyloxy) Ethoxy) phenyl] 茀, 2,2-bis[4-((meth) propylene oxypolypropoxy) phenyl] propane, tricyclodecane dimethanol di(meth)acrylate (three Cyclodecane dimethylol di(meth)acrylate), 1,10-decanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9- Nonanediol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polybutylene glycol di(meth) Acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, 2,2-bis[4-((methyl) ) Allyloxyethoxy) phenyl) propane, neopentyl glycol di(meth)acrylate, ethoxylated polypropylene glycol di(meth)acrylate, 2-hydroxy-1,3-bis( 2-functional (meth)acrylates such as meth)acryloxypropane; tris(2-(meth)acryloxyethyl)isocyanurate, ε-caprolactone modified isocyanuric acid Tris-(2-(meth)acryloyloxyethyl) ester, ethoxylated glycerol tri(meth)acrylate, pentaerythritol tri(meth)acrylate, trimethylolpropane tri(meth) Acrylate, di-trimethylolpropane tetra(meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol poly(meth)acrylate, Multifunctional (meth)acrylates such as dipentaerythritol hexa(meth)acrylate; Multifunctional (meth)acrylate oligomers such as (meth)acrylate urethane oligomers, etc.

Among the aforementioned compounds (a2), as an epoxy resin having an energy ray curable group and a phenol resin having an energy ray curable group, for example, the description in paragraph 0043 in "JP 2013-194102 A" can be used.之resin. Such a resin also corresponds to the resin constituting the thermosetting component (h) described later, but is regarded as the aforementioned compound (a2) in the present invention.

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

The aforementioned compound (a2) contained in the protective film forming composition (IV-1) and the protective film forming film may be only one type or two or more types; in the case of two or more types, these combinations and The ratio can be chosen arbitrarily.

[Polymer without energy ray curable base (b)]

When the protective film forming composition (IV-1) and the protective film forming film contain the aforementioned compound (a2) as the aforementioned energy-ray curable component (a), it is preferable to further contain the non-energy-ray curable component Base polymer (b).

The aforementioned polymer (b) may be cross-linked at least partially by the cross-linking agent (f), or may not be cross-linked.

Examples of the polymer (b) that does not have an energy-ray curable group include acrylic polymers, phenoxy resins, urethane resins, polyesters, rubber resins, and acrylic urethane resins. , Polyvinyl alcohol (PVA), butyraldehyde resin, polyester urethane resin, etc.

Among these, the aforementioned polymer (b) is preferably an acrylic polymer (hereinafter, abbreviated as "acrylic polymer (b-1)" in some cases).

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

Examples of the aforementioned acrylic monomers constituting the acrylic polymer (b-1) include alkyl (meth)acrylates, (meth)acrylates having a cyclic skeleton, and (meth)acrylates containing glycidyl groups. (Methyl)acrylate, hydroxyl-containing (meth)acrylate, substituted amine-containing (meth)acrylate, etc. Here, the so-called "substituted amino group" is as described above.

Examples of the aforementioned alkyl (meth)acrylate include: methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, ( N-Butyl (meth)acrylate, isobutyl (meth)acrylate, second butyl (meth)acrylate, tertiary butyl (meth)acrylate, amyl (meth)acrylate, (meth)acrylic acid Hexyl ester, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, n-octyl (meth)acrylate, n-nonyl (meth)acrylate, Isononyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate (also known as lauryl (meth)acrylate) , Tridecyl (meth)acrylate, tetradecyl (meth)acrylate (also known as myristyl (meth)acrylate), pentadecyl (meth)acrylate, (meth) ) Cetyl acrylate (also known as palm ester (meth)acrylate), heptadecyl (meth)acrylate, stearyl (meth)acrylate (also known as (meth)acrylic acid) Stearyl ester) and other alkyl (meth)acrylates having a chain structure with a carbon number of 1 to 18 constituting the alkyl group of the alkyl ester.

Examples of (meth)acrylates having a cyclic skeleton include cycloalkyl (meth)acrylates such as isobornyl (meth)acrylate and dicyclopentyl (meth)acrylate; (meth) ) Aralkyl (meth)acrylate such as benzyl acrylate; cycloalkenyl (meth)acrylate such as dicyclopentenyl (meth)acrylate; dicyclopentenoxyethyl (meth)acrylate, etc. (Meth) acrylate cycloalkenyloxy alkyl ester and the like.

As said glycidyl group-containing (meth)acrylate, glycidyl (meth)acrylate etc. are mentioned, for example.

As the aforementioned hydroxyl group-containing (meth)acrylates, for example, hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, (methyl) ) 3-hydroxypropyl acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, etc.

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

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

Examples of the polymer (b) that is at least partly cross-linked by the cross-linking agent (f) and does not have the aforementioned energy-ray curable group include: the reactive functional group in the aforementioned polymer (b) and the cross-linking agent (f) Reactive polymer.

The aforementioned reactive functional group may be appropriately selected according to the kind of crosslinking agent (f), etc., and is not particularly limited. For example, when the crosslinking agent (f) is a polyisocyanate compound, the reactive functional group may include a hydroxyl group, a carboxyl group, an amino group, etc. Among these, a hydroxyl group having high reactivity with an isocyanate group is preferred. . When the crosslinking agent (f) is an epoxy-based compound, the reactive functional group may include a carboxyl group, an amino group, an amide group, etc. Among these, it is preferred that the reactivity with an epoxy group is high的carboxyl. However, in terms of preventing corrosion of the semiconductor wafer or the circuit of the semiconductor wafer, the aforementioned reactive functional group is preferably a group other than a carboxyl group.

As a polymer (b) which has the said reactive functional group and does not have an energy-ray curable group, the polymer obtained by polymerizing at least the monomer which has the said reactive functional group is mentioned, for example. In the case of acrylic polymer (b-1), either or both of the aforementioned acrylic monomers and non-acrylic monomers listed as monomers constituting the acrylic polymer (b-1) It is sufficient to use a monomer having the aforementioned reactive functional group. For example, as the aforementioned polymer (b) having a hydroxyl group as a reactive functional group, for example, a polymer obtained by polymerizing a hydroxyl-containing (meth)acrylate may be mentioned. A polymer obtained by polymerizing a monomer in which one or more hydrogen atoms in the aforementioned acrylic monomer or non-acrylic monomer is substituted with the aforementioned reactive functional group.

In the aforementioned 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 relative to the total amount of the structural unit constituting the polymer (b) It is preferably 1% by mass to 25% by mass, more preferably 2% by mass to 20% by mass. When the aforementioned ratio is in such a range, the degree of crosslinking in the aforementioned polymer (b) becomes a more preferable range.

In terms of better film forming properties of the protective film forming composition (IV-1), the weight average molecular weight (Mw) of the polymer (b) that does not have an energy ray curable group is preferably 10,000 to 2,000,000, More preferably, it is 100,000 to 1,500,000.

The composition for forming protective film (IV-1) and the polymer (b) having no energy ray curable group contained in the film for forming protective film may be only one type, or two or more types; in two types In the above case, these combinations and ratios can be arbitrarily selected.

As the composition (IV-1) for forming a protective film, a composition containing either or both of the aforementioned polymer (a1) and aforementioned compound (a2) can be cited. When the protective film forming composition (IV-1) contains the aforementioned compound (a2), it is preferable to further contain a polymer (b) that does not have an energy-ray curable group. In this case, it is also preferable It further contains the aforementioned (a1). The composition (IV-1) for forming a protective film may not contain the compound (a2), and may also contain the polymer (a1) and the polymer (b) that does not have an energy ray curable group.

When the protective film forming composition (IV-1) contains the aforementioned polymer (a1), the aforementioned compound (a2), and the polymer (b) without an energy-ray curable group, the protective film forming composition ( In IV-1), the content of the aforementioned compound (a2) is 100 parts by mass relative to the total content of the aforementioned polymer (a1) and the polymer (b) without an energy-ray curable group, preferably 10 parts by mass to 400 Parts by mass, more preferably 30 parts by mass to 350 parts by mass.

In the protective film forming composition (IV-1), the ratio of the total content of the aforementioned energy-ray curable component (a) and polymer (b) without energy-ray curable group to the total content of components other than the solvent (That is, the total content of the aforementioned energy ray curable component (a) and the polymer (b) having no energy ray curable group in the film for forming a protective film) is preferably 5 to 90% by mass, more preferably It is 10% by mass to 80% by mass, and more preferably 15% by mass to 70% by mass. When the ratio of the aforementioned total content is in such a range, the energy ray curability of the protective film formation film becomes more favorable.

When the protective film forming composition (IV-1) contains the aforementioned energy ray curable component (a) and the polymer (b) without an energy ray curable group, the protective film forming composition (IV-1) ) And the protective film forming film, the content of the aforementioned polymer (b) relative to 100 parts by mass of the energy ray curable component (a), preferably 3 parts by mass to 160 parts by mass, more preferably 6 parts by mass To 130 parts by mass. When the content of the polymer (b) is in this range, the energy ray curability of the protective film formation film becomes more favorable.

The composition (IV-1) for forming a protective film may contain a photopolymerization initiator according to the purpose in addition to the energy-ray curable component (a) and the polymer (b) without an energy-ray curable group (c), filler (d), coupling agent (e), crosslinking agent (f), coloring agent (g), thermosetting component (h) and general additives (z) in the group consisting of 1 One or more than two. For example, by using the protective film forming composition (IV-1) containing the aforementioned energy ray curable component (a) and thermosetting component (h), the formed protective film forming film is heated against the substrate The adhesive force of the adhering body is improved, and the strength of the protective film formed of the protective film forming film is also improved.

[Photopolymerization initiator (c)]

Examples of the photopolymerization initiator (c) include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, benzoin methyl benzoate, benzoin dimethyl ketal, etc. Benzoin compounds; acetophenone, 2-hydroxy-2-methyl-1-phenyl-propane-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one, etc. Acetophenone compounds; bis(2,4,6-trimethylbenzyl)phenyl phosphine oxide, 2,4,6-trimethylbenzyl diphenyl phosphine oxide and other phosphine oxide compounds ; Sulfide compounds such as benzyl phenyl sulfide and tetramethylthiuram monosulfide; α-keto alcohol compounds such as 1-hydroxycyclohexyl phenyl ketone; azo compounds such as azobisisobutyronitrile; Titanocene And other titanocene compounds; thioxanthone and other thioxanthone compounds; benzophenone, 2-(dimethylamino)-1-(4-morpholine (morpholine) phenyl)-2-benzyl- 1-Butanone, ethyl ketone, 1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]-,1-(O-acetyloxime) Benzophenone compounds; peroxide compounds; diketone compounds such as diacetin; benzil; benzil; 2,4-diethylthioxanthone; 1,2-diphenylmethane; 2 -Hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]acetone; 2-chloroanthraquinone and the like.

As the photopolymerization initiator (c), for example, quinone compounds such as 1-chloroanthraquinone; photosensitizers such as amines, and the like can also be used.

The photopolymerization initiator (c) contained in the protective film forming composition (IV-1) may be only one type or two or more types; in the case of two or more types, these combinations and ratios may be arbitrary select.

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

[Filling material (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 and optimize the thermal expansion coefficient for the object to be formed of the protective film. The reliability of the package obtained by the composite sheet for forming a protective film is further improved. When the protective film forming film contains the filler (d), the moisture absorption rate of the protective film can be reduced or the heat dissipation can be improved.

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

The filling material (d) may be any one of an organic filling material and an inorganic filling material, preferably an inorganic filling material.

As preferred inorganic fillers, for example, powders such as silica, alumina, talc, calcium carbonate, titanium dioxide, iron oxide, silicon carbide, boron nitride, etc. can be cited; these inorganic fillers are made by spheroidizing these inorganic fillers. Beads; surface modification products of these inorganic fillers; single crystal fibers of these inorganic fillers; glass fibers, etc.

Among these, the inorganic filler is preferably silica or alumina.

The average particle size of the filler (d) is not particularly limited, and is preferably 0.01 μm to 20 μm, more preferably 0.1 μm to 15 μm, and particularly preferably 0.3 μm to 10 μm. When the average particle size of the filler (d) is in this range, the adhesion to the object to be formed of the protective film can be maintained, and the decrease in the light transmittance of the protective film can be suppressed.

In this specification, the "average particle size", unless otherwise specified, means the value of the particle size (D ₅₀ ) at 50% of the cumulative value in the particle size distribution curve obtained by the laser diffraction scattering method.

The protective film forming composition (IV-1) and the protective film forming film may contain only one type of filler (d), or two or more types; in the case of two or more types, these combinations and The ratio can be chosen arbitrarily.

When the filler (d) is used, the ratio of the content of the filler (d) to the total content of all components other than the solvent in the protective film forming composition (IV-1) (that is, the protective film forming composition) The content of the filler (d) in the film) is preferably 5 to 83% by mass, more preferably 7 to 78% by mass. With the content of the filler (d) in this range, it is easier to adjust the above-mentioned coefficient of thermal expansion.

[Coupling agent (e)]

By using a coupling agent having a functional group capable of reacting with an inorganic compound or an organic compound as the coupling agent (e), the adhesion and adhesion of the protective film forming film to the adherend can be improved. By using the coupling agent (e), the protective film obtained by curing the protective film forming film does not impair heat resistance and improves water resistance.

The coupling agent (e) is preferably a compound having a functional group capable of reacting with the functional group possessed by the energy-ray curable component (a), polymer (b) without an energy-ray curable group, etc., more preferably silane Coupling agent.

As a preferred silane coupling agent, for example, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyl Triethoxysilane, 3-glycidoxymethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-methacryloxypropyltrimethyl Oxysilane, 3-aminopropyltrimethoxysilane, 3-(2-aminoethylamino)propyltrimethoxysilane, 3-(2-aminoethylamino)propylmethyl Diethoxysilane, 3-(phenylamino)propyltrimethoxysilane, 3-anilinopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropyltrimethyl Oxysilane, 3-mercaptopropylmethyldimethoxysilane, bis(3-triethoxysilylpropyl) tetrasulfide, methyltrimethoxysilane, methyltriethoxysilane, ethylene Trimethoxysilane, vinyl triethoxysilane, imidazole silane, etc.

The protective film forming composition (IV-1) and the protective film forming film may contain only one type of coupling agent (e), or two or more types; in the case of two or more types, these combinations and The ratio can be chosen arbitrarily.

When the coupling agent (e) is used, in the protective film forming composition (IV-1) and the protective film forming film, the content of the coupling agent (e) is relative to the energy ray curable component (a) and does not have The total content of the polymer (b) of the energy ray curable base is 100 parts by mass, preferably 0.03 parts by mass to 20 parts by mass, more preferably 0.05 parts by mass to 10 parts by mass, particularly preferably 0.1 parts by mass to 5 parts by mass . With the aforementioned content of the coupling agent (e) above the aforementioned lower limit, the following more significant effects brought about by the use of the coupling agent (e) can be obtained: the dispersibility of the filler (d) in the resin is improved, or The adhesion between the protective film forming film and the adherend is improved. When the aforementioned content of the coupling agent (e) is below the aforementioned upper limit value, the generation of outgassing can be further suppressed.

[Crosslinking agent (f)]

By using a crosslinking agent (f) to crosslink the above-mentioned energy ray curable component (a) or polymer (b) without an energy ray curable group, the initial adhesive force of the protective film formation film can be adjusted And cohesion.

Examples of the crosslinking agent (f) include organic polyisocyanate compounds, organic polyimine compounds, metal chelate crosslinking agents (crosslinking agents having a metal chelate structure), and aziridine crosslinking Agent (crosslinking agent with aziridinyl group) and the like.

Examples of the aforementioned organic polyvalent isocyanate compound include: aromatic polyvalent isocyanate compounds, aliphatic polyvalent isocyanate compounds, and alicyclic polyvalent isocyanate compounds (hereinafter, these compounds may be collectively referred to as "aromatic polyvalent isocyanate compounds, etc."); Trimers, isocyanurate bodies, and adducts of the aforementioned aromatic polyvalent isocyanate compounds, etc.; terminal isocyanate urethane prepolymers obtained by reacting the aforementioned aromatic polyvalent isocyanate compounds, etc. with polyol compounds, etc. . The aforementioned "adduct" means the aforementioned aromatic polyisocyanate compound, aliphatic polyisocyanate compound, or alicyclic polyisocyanate compound, which contains ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane, or castor oil. As an example of the aforementioned adduct, the reactant of the low molecular active hydrogen compound includes the xylylene diisocyanate adduct of trimethylolpropane and the like described later. The term "terminal isocyanate urethane prepolymer" means a prepolymer having a urethane bond and an isocyanate group at the end of the molecule.

As the aforementioned organic polyvalent isocyanate compound, more specifically, for example, 2,4-toluene diisocyanate; 2,6-toluene diisocyanate; 1,3-xylylene diisocyanate; 1,4-xylene diisocyanate Isocyanate; Diphenylmethane-4,4'-Diisocyanate; Diphenylmethane-2,4'-Diisocyanate; 3-Methyldiphenylmethane Diisocyanate; Hexamethylene Diisocyanate; Isophorone Diisocyanate; Dicyclohexylmethane-4,4'-diisocyanate; Dicyclohexylmethane-2,4'-diisocyanate; All or part of the hydroxyl groups of polyols such as trimethylolpropane, added toluene diisocyanate, Compounds of any one or more of hexamethylene diisocyanate and xylylene diisocyanate; lysine diisocyanate, etc.

As the aforementioned organic polyimine compound, for example, N,N'-diphenylmethane-4,4'-bis(1-aziridinemethamide), trimethylolpropane-tri-β-nitrogen Propidinyl propionate, tetramethylolmethane-tris-β-aziridinyl propionate, N,N'-toluene-2,4-bis()-aziridinylmethamine) triethylene Based on melamine and so on.

When an organic polyisocyanate compound is used as the crosslinking agent (f), it is preferable to use a hydroxyl-containing polymer as the energy-ray curable component (a) or polymer (b) that does not have an energy-ray curable group . When the crosslinking agent (f) has an isocyanate group and the energy ray curable component (a) or the polymer (b) without an energy ray curable group has a hydroxyl group, the crosslinking agent (f) and the energy ray The reaction of the curable component (a) or the polymer (b) that does not have an energy-ray curable group can easily introduce a cross-linked structure into the protective film forming film.

The composition for forming a protective film (IV-1) and the crosslinking agent (f) contained in the film for forming a protective film may be only one type or two or more types; in the case of two or more types, these are combined And the ratio can be chosen arbitrarily.

In the case of using the crosslinking agent (f), the content of the crosslinking agent (f) in the protective film forming composition (IV-1) is relative to the energy ray curable component (a) and does not have energy ray curability The total content of the base polymer (b) is 100 parts by mass, preferably 0.01 parts by mass to 20 parts by mass, more preferably 0.1 parts by mass to 10 parts by mass, and particularly preferably 0.5 parts by mass to 5 parts by mass. When the aforementioned content of the cross-linking agent (f) is above the aforementioned lower limit, more significant effects brought about by the use of the cross-linking agent (f) can be obtained. When the aforementioned content of the cross-linking agent (f) is below the aforementioned upper limit, the excessive use of the cross-linking agent (f) can be suppressed.

[Colorant (g)]

As a coloring agent (g), well-known coloring agents, such as an inorganic type pigment, an organic type pigment, an organic type dye, etc. are mentioned, for example.

Examples of the aforementioned organic pigments and organic dyes include: ammonium-based pigments, cyanine-based pigments, merocyanine-based pigments, croconium-based pigments, squalilium-based pigments, and azulenium-based pigments. Pigments, polymethine pigments, naphthoquinone pigments, pyrylium pigments, phthalocyanine pigments, naphthalocyanine pigments, naphthalene lactam pigments, azo pigments, condensed azo pigments, indigo Pigments, perinone pigments, perylene pigments, dioxane pigments, quinacridone pigments, isoindolinone pigments, quinophthalone pigments, pyrrole pigments, Thioindigo dyes, metal complex dyes (metal complex salt dyes), dithiol metal complex dyes, indoxyphenol dyes, triallylmethane dyes, anthraquinone dyes, naphthol Pigments, methine azo pigments, benzimidazolone pigments, pyranthrone pigments, threne pigments, etc.

Examples of the aforementioned inorganic pigments include carbon black, cobalt pigments, iron pigments, chromium pigments, titanium pigments, vanadium pigments, zirconium pigments, molybdenum pigments, ruthenium pigments, platinum pigments, ITO (Indium Tin Oxide; Indium Tin Oxide) based pigments, ATO (Antimony Tin Oxide; Antimony Tin Oxide) based pigments, etc.

The coloring agent (g) contained in the protective film forming composition (IV-1) and the protective film forming film may be only one type or two or more types; in the case of two or more types, these combinations and The ratio can be chosen arbitrarily.

In the case of using a coloring agent (g), the content of the coloring agent (g) in the film for forming a protective film may be appropriately adjusted according to the purpose. For example, there may be cases where printing is performed on the protective film by laser irradiation. By adjusting the content of the coloring agent (g) in the protective film forming film, the light transmittance of the protective film can be adjusted, and the visibility of printing can be adjusted. In this case, in the protective film forming composition (IV-1), the content of the colorant (g) is the ratio of the total content of all components other than the solvent (that is, the coloring agent in the protective film forming film (g) The content of) is preferably 0.1% by mass to 10% by mass, more preferably 0.4% by mass to 7.5% by mass, and particularly preferably 0.8% by mass to 5% by mass. When the aforementioned content of the colorant (g) is more than the aforementioned lower limit, more significant effects brought about by the use of the colorant (g) can be obtained. When the aforementioned content of the colorant (g) is not more than the aforementioned upper limit, the excessive use of the colorant (g) can be suppressed.

[Thermosetting component (h)]

The thermosetting component (h) contained in the protective film forming composition (IV-1) and the protective film forming film may be only one type or two or more types; in the case of two or more types, these The combination and ratio can be selected arbitrarily.

As the thermosetting component (h), for example, epoxy-based thermosetting resins, thermosetting polyimides, polyurethanes, unsaturated polyesters, silicone resins, etc. can be cited, and preferred are Epoxy-based thermosetting resin.

(Epoxy-based thermosetting resin)

The epoxy-based thermosetting resin system is composed of an epoxy resin (h1) and a thermosetting agent (h2).

The epoxy-based thermosetting resin contained in the protective film forming composition (IV-1) and the protective film forming film may be only one type or two or more types; in the case of two or more types, these The combination and ratio can be selected arbitrarily.

. Epoxy resin (h1)

As the epoxy resin (h1), well-known epoxy resins can be cited, for example, polyfunctional epoxy resins, biphenyl compounds, bisphenol A diglycidyl ether and its hydrogenated products, ortho-cresol novolac epoxy Resins, dicyclopentadiene type epoxy resins, biphenyl type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, phenylene skeleton type epoxy resins and other epoxy resins with more than two functions Compound.

As the epoxy resin (h1), an epoxy resin having an unsaturated hydrocarbon group can also be used. Epoxy resins with unsaturated hydrocarbon groups have higher compatibility with acrylic resins than epoxy resins without unsaturated hydrocarbon groups. Therefore, by using an epoxy resin having an unsaturated hydrocarbon group, the reliability of the package obtained by using the composite sheet for forming a protective film is improved.

As an epoxy resin having an unsaturated hydrocarbon group, for example, a compound in which a part of the epoxy group of a polyfunctional epoxy resin is replaced with a group having an unsaturated hydrocarbon group is exemplified. Such a compound is obtained, for example, by performing an addition reaction of (meth)acrylic acid or a derivative thereof with an epoxy group.

As an epoxy resin having an unsaturated hydrocarbon group, for example, a compound in which a group having an unsaturated hydrocarbon group is directly bonded to an aromatic ring or the like constituting the epoxy resin can be cited.

The unsaturated hydrocarbon group is a polymerizable unsaturated group. Specific examples of the unsaturated hydrocarbon group include ethylene (also referred to as vinyl), 2-propenyl (also referred to as allyl), (form The acryloyl group, (meth)acryloylamino group, etc., is preferably an acryloyl group.

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

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

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

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

The epoxy resin (h1) may be used individually by 1 type, and may use 2 or more types together. When using 2 or more types together, these combinations and ratios can be selected arbitrarily.

. Thermal hardener (h2)

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

As a thermosetting agent (h2), the compound which has 2 or more functional groups which can react with an epoxy group in 1 molecule is mentioned, for example. As the aforementioned functional group, for example, a phenolic hydroxyl group, an alcoholic hydroxyl group, an amino group, a carboxyl group, a group formed by an anhydride of an acid group, etc. are mentioned, preferably a phenolic hydroxyl group, an amino group, or an acid group formed by an anhydride The formed group is more preferably a phenolic hydroxyl group or an amino group.

Among the thermosetting agents (h2), as phenolic curing agents having phenolic hydroxyl groups, for example, polyfunctional phenol resins, biphenols, novolak type phenol resins, dicyclopentadiene phenol resins, and aralkylphenols can be cited Resin etc.

In the thermosetting agent (h2), examples of the amine-based curing agent having an amine group include dicyandiamine (hereinafter, abbreviated as "DICY") and the like.

The thermal hardener (h2) may also 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 a phenol resin is substituted with a group having an unsaturated hydrocarbon group, and a group having an unsaturated hydrocarbon group is directly bonded to the aromatic ring of the phenol resin Compounds and so on.

The aforementioned unsaturated hydrocarbon group in the thermosetting agent (h2) is the same as the unsaturated hydrocarbon group in the aforementioned epoxy resin having an unsaturated hydrocarbon group.

When a phenolic hardener is used as the thermosetting agent (h2), in terms of improving the peelability of the protective film from the supporting sheet, the thermosetting agent (h2) is preferably a phenol with a high softening point or glass transition temperature. Department of hardener.

In this specification, the so-called "glass transition temperature" is to measure the DSC (Differential Scanning Calorimetry; Differential Scanning Calorimetry) curve of the sample using a differential scanning calorimeter and display it as the inflection point temperature of the obtained DSC curve.

In the thermosetting agent (h2), for example, the number average molecular weight of resin components such as polyfunctional phenol resin, novolak type phenol resin, dicyclopentadiene phenol resin, and aralkylphenol resin is preferably 300 to 30,000, and more It is preferably 400 to 10,000, particularly preferably 500 to 3,000.

In the thermosetting agent (h2), for example, the molecular weight of non-resin components such as biphenol and dicyandiamine is not particularly limited. For example, it is preferably 60 to 500.

The thermosetting agent (h2) may be used alone or in combination of two or more types. When two or more types are used in combination, these combinations and ratios can be arbitrarily selected.

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

In the case of using the thermosetting component (h), the content of the thermosetting component (h) in the protective film forming composition (IV-1) and the protective film forming film (for example, epoxy resin (h1) And the total content of the thermosetting agent (h2)) relative to 100 parts by mass of the polymer (b) that does not have an energy ray curable group, preferably 1 part by mass to 500 parts by mass.

[General additives (z)]

The general-purpose additives (z) can be known general-purpose additives, and can be arbitrarily selected according to the purpose, and are not particularly limited. Preferred general-purpose additives include, for example, plasticizers, antistatic agents, antioxidants, getters, etc. .

The protective film forming composition (IV-1) and the general additive (z) contained in the protective film forming film may be only one type or two or more types; in the case of two or more types, these combinations and The ratio can be chosen arbitrarily.

When a 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 may be appropriately selected according to the purpose.

[Solvent]

The composition (IV-1) for forming a protective film preferably further contains a solvent. The solvent-containing protective film forming composition (IV-1) has good operability.

The aforementioned solvent is not particularly limited. Preferred examples of the aforementioned solvent include hydrocarbons such as toluene and xylene; methanol, ethanol, 2-propanol, and isobutanol (also known as 2-methylpropane-1-ol). ), 1-butanol and other alcohols; ethyl acetate and other esters; acetone, methyl ethyl ketone and other ketones; tetrahydrofuran and other ethers; dimethylformamide, N-methylpyrrolidone and other amides (with amide Bond compound) and so on.

The solvent contained in the composition (IV-1) for forming a protective film may be only one type or two or more types; in the case of two or more types, these combinations and ratios can be arbitrarily selected.

The solvent contained in the protective film forming composition (IV-1) is preferably methyl ethyl ketone in terms of allowing the components contained in the protective film forming composition (IV-1) to be more uniformly mixed. , Toluene or ethyl acetate, etc.

In one aspect of the present invention, the protective film forming film contains tricyclodecane dimethylol diacrylate as an energy ray curable component (a2) (content: relative to the protective film forming composition (IV- 1) The total mass of the solid content is 5 mass% to 30 mass%, more preferably 8 mass% to 25 mass%); as the polymer (b) that does not have an energy ray curable group is derived from The structural unit of methyl acrylate (relative to the total mass of the acrylic resin, 75% to 95% by mass, more preferably 80% to 90% by mass), and 2-hydroxyethyl acrylate (relative to the acrylic resin The total mass of the resin is 5 mass% to 25 mass%, more preferably 10 mass% to 20 mass%) composed of acrylic resin (content: relative to the solid content in the protective film forming composition (IV-1) The total mass of the components is 12% to 32% by mass, more preferably 17% to 27% by mass); 1-hydroxy-cyclohexyl-phenyl-ketone as the photopolymerization initiator (c) (content: 0.1% to 1.1% by mass, more preferably 0.3% to 0.9% by mass) or 2-(4-methyl) relative to the total mass of the solid components in the protective film forming composition (IV-1) Benzyl)-2-dimethylamino-1-(4-morpholin-4-yl-phenyl)-butan-one (content: relative to that in the protective film forming composition (IV-1) The total mass of solid components is 0.1% to 1.1% by mass, more preferably 0.3% to 0.9% by mass); silica filler as filler (d) (content: relative to the protective film forming composition (IV-1) The total mass of the solid content is 46% to 66% by mass, more preferably 51% to 61% by mass); 3-methacryloyloxy group as the coupling agent (e) Propyl trimethoxysilane (content: 0.1% to 0.7% by mass, more preferably 0.3% to 0.5% by mass relative to the total mass of the solid components in the protective film forming composition (IV-1) ); and as a coloring agent (g) containing phthalocyanine-based blue pigments, isoindolinone-based yellow pigments and anthraquinone-based red pigments, and styrene acrylic resin (content: relative to the protective film formation composition The total mass of the solid components in the substance (IV-1) is 0.5% to 3.5% by mass, more preferably 1.0% to 3.0% by mass) (wherein, the sum of the contents of each component is relative to the protective film formation The total mass of the solid components in the composition (IV-1) does not exceed 100% by mass).

<<Production method of protective film forming composition>>

The protective film forming composition (IV-1), such as the protective film forming composition, is obtained by blending each component for constituting the protective film forming composition.

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

When a solvent is used, it can be used by the following method: mixing the solvent with any compounding component other than the solvent and diluting the compounding component in advance; it can also be used by the following method: not adding any one other than the solvent The compounding components are diluted in advance, and the solvent is mixed with these compounding components.

The method of mixing each component during compounding is not particularly limited, and it can be appropriately selected from the following known methods: a method of mixing by rotating a stirrer or a stirring blade, a method of mixing using a mixer, and a method of applying ultrasonic waves. Methods of mixing, etc.

The temperature and time when adding and mixing each component are not particularly limited as long as they do not deteriorate each compounding component, and they may be adjusted appropriately, and the temperature is preferably 15°C to 30°C.

Like the composite sheet for forming a protective film that can be used in the present invention, it is a composite sheet that is attached to a semiconductor wafer or a semiconductor wafer on the back side opposite to the circuit surface, and is provided with a layer showing adhesiveness on a support sheet, There is a dicing die bonding sheet.

However, the adhesive layer of the dicing die bonding sheet has the following functions: after picking up the semiconductor wafer from the support sheet, it functions as an adhesive when the semiconductor wafer is mounted on a substrate, lead frame, or other semiconductor wafers, etc. . On the other hand, the protective film forming film that can be used in the protective film forming composite sheet of the present invention is the same as the aforementioned adhesive layer in terms of picking up from the support sheet together with the semiconductor wafer, but is finally cured by curing It becomes a protective film, which has the function of protecting the back surface of the attached semiconductor chip. In this way, the application of the protective film forming film in the present invention is different from that of the adhesive layer in the dicing die bonding sheet, and of course the required performance is also different. Reflecting the difference in use, generally, when compared with the adhesive layer in the dicing die bonding sheet, the protective film formation film tends to be harder and difficult to pick up. Therefore, it is generally difficult to directly transfer the adhesive layer in the dicing die bonding sheet to the protective film formation film in the protective film formation composite sheet. As a composite sheet for forming a protective film that can be used for the film for forming a protective film having energy ray curability in the present invention, a composite sheet for forming a protective film using a semiconductor wafer with a protective film and having excellent pick-up suitability can be appropriately selected.

◇Method for manufacturing composite sheet for protective film formation

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

For example, in the case of laminating an adhesive layer on a substrate when manufacturing a support sheet, the above-mentioned adhesive composition may be applied on the substrate, and the adhesive composition may be dried if necessary.

On the other hand, for example, when the protective film forming film is laminated on the adhesive layer already laminated on the base material, the protective film forming composition can be coated on the adhesive layer to directly form the protective film forming film . The layer other than the film for forming a protective film can also use the composition for forming the layer, and the layer is laminated on the adhesive layer by the same method. In this way, when any composition is used to form a continuous two-layer laminated structure, the composition can be further coated on the layer formed of the aforementioned composition to form a new layer.

However, it is preferable to form a continuous two-layer laminated structure by using the aforementioned composition on another release film to pre-form the post-laminated layer of these two layers, and to form the layer in the already formed layer. The exposed surface on the opposite side to the side that is in contact with the release film is bonded to the exposed surface of the remaining layer that has already been formed. In this case, the aforementioned composition is preferably applied to the release-treated surface of the release film. After the build-up structure is formed, the release film can be removed as necessary.

For example, in the manufacture of a composite sheet for forming a protective film formed by laminating an adhesive layer on a base material and laminating a protective film forming film on the aforementioned adhesive layer (the support sheet is a protective film for the laminate of the base material and the adhesive layer In the case of forming a composite sheet), apply the adhesive composition on the substrate, and dry the adhesive composition as necessary, thereby pre-laminating the adhesive layer on the substrate, and separately coating the protective film formation on the release film As for the composition, the protective film forming composition is dried as necessary to form a protective film forming film on the release film in advance. 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 obtaining a composite sheet for forming a protective film .

When the adhesive layer is laminated on the substrate, as described above, instead of applying the adhesive composition on the substrate, the adhesive composition is applied on the release film, and the adhesive composition is applied as needed. By drying, an adhesive layer is formed in advance on the release film, and the exposed surface of the layer is bonded to one surface of the base material, thereby depositing the adhesive layer on the base material.

In either method, it is sufficient to remove the release film at any time point after the target build-up structure is formed.

In this way, all layers other than the base material constituting the protective film forming composite sheet can be laminated by the following method: preliminarily formed on the release film, and then bonded to the surface of the target layer. Therefore, the layer that adopts such a step can be appropriately selected as needed. What is necessary is just to manufacture the composite sheet for protective film formation.

In addition, the composite sheet for forming a protective film is usually stored in a state in which a release film is attached to the surface of the outermost layer (for example, the film for forming a protective film) on the opposite side of the supporting sheet in the composite sheet for forming a protective film The state. Therefore, a composite sheet for forming a protective film can also be obtained by coating the release film (preferably the release-treated surface of the release film) with a composition for forming a protective film, etc., to form the most For the composition of the surface layer layer, if necessary, the composition is dried to form a layer constituting the outermost layer on the release film in advance, and the exposed surface of the layer opposite to the side contacting the release film is used. Either way, the remaining layers are laminated without removing the release film and maintaining the attached state.

◇How to use the composite sheet for protective film formation

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

That is, the composite sheet for protective film formation is attached to the back surface of the semiconductor wafer (the surface opposite to the electrode formation surface) through the protective film formation film of the composite sheet for protective film formation. Next, the protective film formation film is irradiated with energy rays to harden the protective film formation film to become a protective film. Then, by dicing, the semiconductor wafer and the protective film are divided together to form a semiconductor wafer. Then, the semiconductor wafer is directly (that is, in the form of a semiconductor wafer with a protective film) pulled away from the support sheet and picked up while keeping the protective film attached.

The semiconductor chip 101 with the protective film picked up is stored in the pocket 102a of the embossed carrier tape 102 as shown in FIG. 8, and the cover tape 103 is attached to the opening of the pocket 102a to close the opening. package. Then, the embossed carrier tape 102 is wound on a reel for storage, transportation, or commercial transactions. In the next step, the semiconductor chip of the semiconductor chip 101 with a protective film is flip-chip connected to the circuit surface of the substrate Used in the steps.

In this manual, the so-called "embossed carrier tape" is formed on a long strip of resin made of polystyrene, polyethylene terephthalate, or polypropylene. The packaging material is sometimes referred to as a pocket). In each of the aforementioned plural pockets, for example, the semiconductor chip with the protective film of the present invention can be stored. The aforementioned plural pockets are usually closed and covered by the following method: in a state where the semiconductor chip with a protective film of the present invention is stored, a long cover tape is attached to the opening. The embossed carrier tape packaged with a semiconductor wafer with a protective film can be used in the state of being wound on a reel. For example, the aforementioned reel can be set in a placement machine, and a semiconductor wafer with a protective film can be mounted on the substrate. The embossed carrier tape pocket can be designed and processed according to the size of the contents. The pockets of the embossed carrier tape in this specification include, for example, pockets with a longitudinal dimension of 0.5 mm to 30 mm, a lateral dimension of 0.5 mm to 30 mm, and a depth of 0.1 mm to 10 mm. The aforementioned strip-shaped cover tape has a thickness of 10 μm to 100 μm, and is formed of materials such as PET (polyethylene terephthalate; polyethylene terephthalate).

Hereinafter, using the same method as the previous method, the semiconductor wafer with the protective film is directly pulled away from the supporting sheet while the protective film is still attached to pick up the obtained semiconductor wafer with the protective film After the flip chip of the semiconductor chip is connected to the circuit surface of the substrate, a semiconductor package is made. Then, the semiconductor package can be used to manufacture the target semiconductor device.

[Example]

Hereinafter, the present invention will be described in more detail through specific embodiments. However, the present invention is not limited at all by the examples shown below.

The components used to manufacture the protective film forming composition are shown below.

. Energy ray hardening component

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

. Polymer without energy ray hardening base

(b)-2: Copolymerizing methyl acrylate (hereinafter, abbreviated as "MA") (85 parts by mass) and 2-hydroxyethyl acrylate (hereinafter, abbreviated as "HEA") (15 parts by mass) Acrylic resin (weight average molecular weight 300,000).

. Photopolymerization initiator

(c)-3: 1-hydroxy-cyclohexyl-phenyl-ketone ("Irgacure (registered trademark) 184" manufactured by BASF Corporation).

(c)-4: 2-(4-Methylbenzyl)-2-dimethylamino-1-(4-morpholin-4-yl-phenyl)-butan-1-one (BASF Manufactured "Irgacure (registered trademark) 379", molecular weight 380).

. Filler

(d)-1: Silica filler (fused silica filler, average particle size 8μm).

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

[Example 1]

<Manufacturing of Composite Sheet for Forming Protective Film>

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

Make energy ray curable component (a2)-1, polymer (b)-2, photopolymerization initiator (c)-3, photopolymerization initiator (c)-4, filler (d)-1, Coupling agent (e)-1 and coloring agent (g)-1 are dissolved or dispersed in methyl ethyl ketone so that their content (amount of solid content, parts by mass) becomes the value shown in Table 1 By stirring at 23° C., a protective film forming composition (IV-1) having a solid content concentration of 50% by mass was prepared. In addition, when the column of the contained component in Table 1 is described as "-", it means that the protective film forming composition (IV-1) does not contain the component.

(Manufacturing of Adhesive Composition (I-4))

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

(Support film manufacturing)

On one side of the polyethylene terephthalate film, the peeling film ("SP-PET381031" made by Lintec, thickness 38μm) that was peeled off by silicone treatment was applied to the peeling treated surface, and the above-obtained surface was coated The adhesive composition (I-4) was heated and dried at 120°C for 2 minutes to form a non-energy-ray-curable adhesive layer with a thickness of 10 μm.

Next, a polypropylene film (Young's ratio 400, thickness 80μm) as a base material was pasted on the exposed surface of the adhesive layer, thereby obtaining a support sheet with the adhesive layer on one surface of the base material (10)-1.

(Manufacturing of composite sheet for forming protective film)

On one side of the polyethylene terephthalate film, the peeling film ("SP-PET381031" made by Lintec, thickness 38μm) that is peeled off by silicone treatment is applied to the aforementioned peeling surface by knife coating. The protective film forming composition (IV-1) obtained above was coated with a cloth machine and dried at 100° C. for 2 minutes to produce an energy ray curable protective film forming film (13)-9 with a thickness of 25 μm.

Next, the release film is removed from the adhesive layer in the support sheet (10)-1 obtained above, and the exposed surface of the adhesive layer is attached to the exposed surface of the protective film forming film (13)-9 obtained above On the other hand, a composite sheet for forming a protective film was prepared. The composite sheet-based substrate for forming a protective film, an adhesive layer, a film (13)-9 for forming a protective film, and a release film were laminated in this order in the thickness direction. The composition of the obtained composite sheet for forming a protective film is shown in Table 2.

<Evaluation of protective film formation film>

The tensile modulus (Young's ratio) of the film (13)-9 for forming a protective film was evaluated in the following manner.

That is, two layers of protective film forming sheets (thickness: 25μm) were laminated to obtain a thickness of 50μm, and the sample was subjected to a tensile test (tensile speed: 50mm/min) with a size of 15mm×100mm. The slope of the initial stress-strain line was calculated, and the tensile modulus of the protective film forming film (13)-9 was calculated.

The evaluation results are shown in Table 2.

<Evaluation of Protective Film>

The tensile modulus (Young's ratio) of the film (13)-9 for forming a protective film after curing was evaluated in the following manner.

That is, two layers of protective film formation film (13)-9 (thickness: 25μm) were laminated to have a thickness of 50μm, and UV was irradiated once from both sides (illuminance: 230mW/cm ² , light intensity: 170mJ/cm ² ) Harden the film (13)-9 for forming a protective film.

Then, the sample was subjected to a tensile test (tensile speed: 50 mm/min) with a size of 15 mm×100 mm, and the tensile modulus of the protective film was calculated from the slope of the stress-strain line at the initial stage of stretching.

The evaluation results are shown in Table 2.

(Cutting evaluation)

The composite sheet for forming a protective film obtained above is attached to the #2000 polished surface of a 6-inch silicon wafer (thickness 100μm) by using the protective film forming film (13)-9 of the composite sheet for forming a protective film , And then fix the piece to the ring frame and let it stand for 30 minutes.

Subsequently, the ultraviolet irradiation device (manufactured by the Lintec Company "RAD2000m / 8") at an illuminance 195mW / cm ^2, light quantity of 170mJ / cm condition ^2, the film from the support sheet (10) -1-side forming a protective film ( 13)-9 is irradiated with ultraviolet rays to harden the protective film forming film (13)-9 to become a protective film.

Then, using a dicing blade, the silicon wafer together with the protective film are cut and singulated to obtain a 2mm×2mm silicon wafer.

Next, use a die bonder ("BESTEM-D02" manufactured by Canon Machinery) to pick up 20 silicon wafers with protective films. At this time, a digital microscope (manufactured by Keyence, VHX-100, magnification: 100 times) was used to observe the cut surface of the cut silicon wafer. When cracks or defects with a width or depth of 20 µm or more are confirmed, fragments are generated and judged as bad (B), and if such defects are not confirmed, it is judged as good (A). The results are shown in Table 2. The corresponding results are recorded in the column of "chip cracking and defect suppression" in Table 2.

(Blade clogging evaluation)

Use a digital microscope (manufactured by Keyence, VHX-100, magnification: 100 times) to observe the tip of the blade after cutting, and set the blade without the protective film as "A" and the blade with the protective film as "B".

(Evaluation of cover tape adhesion)

The composite sheet for forming a protective film obtained above is attached to the #2000 polished surface of a 6-inch silicon wafer (thickness 100μm) by using the protective film forming film (13)-9 of the composite sheet for forming a protective film , And then fix the piece to the ring frame and let it stand for 30 minutes.

Subsequently, the ultraviolet irradiation device (manufactured by the Lintec Company "RAD2000m / 8") at an illuminance 195mW / cm ^2, light quantity of 170mJ / cm condition ^2, the self-supporting sheet (10) -1-side protective film of the composite sheet is formed By irradiating ultraviolet rays, the film (13)-9 for forming a protective film is cured to become a protective film.

Next, using a dicing blade, the silicon wafer together with the protective film is cut and singulated to obtain a silicon wafer with a length of 3 mm × a width of 3 mm, a protective layer thickness of 25 μm and a Si (silicon) layer thickness of 350 μm.

Next, use a die bonder ("BESTEM-D02" manufactured by Canon Machinery) to pick up 20 silicon wafers with protective films.

On an iron plate of length 12cm×width 12cm and thickness 5mm, the 16 silicon wafers with protective film obtained above are placed in a square grid at equal intervals The above silicon wafer is covered with a 12cm x 3.8cm cover tape (manufactured by Sumitomo Bakelite, CSL-Z7302), placed on a hot plate heated to 40°C, and a metal plate is placed on the hot plate, And set it in such a way that the pressure applied to the silicon chip with the protective film becomes 350gf, and overheat for one minute. Then, the metal plate is removed, the aforementioned cover tape is peeled off, and whether the silicon wafer with the protective film is attached to the cover tape is checked. The results are shown in Table 2.

As a judgment method, it is judged as "B" when at least one of the 16 silicon wafers with protective film is attached to the cover tape, and when none of the 16 silicon wafers with protective film is attached to the cover tape It is judged as "A".

<Production and Evaluation of Sheets for Forming Protective Films>

[Example 2]

The first peeling film ("SP-PET382150" manufactured by Lintec, thickness 38μm) of the first peeling film ("SP-PET382150" made by Lintec, thickness 38μm) that was peeled off on one side of the polyethylene terephthalate film was treated with a knife. The protective film formation composition (IV-1) obtained above was applied by a type coater, and dried at 100°C for 2 minutes to produce an energy ray curable protective film formation film with a thickness of 25 μm (13)- 9.

Next, on the exposed surface of the obtained protective film formation film (13)-9, a second release film (Lintec The release surface of "SP-PET381031" manufactured by the company, thickness 38μm), is used to form a protective film composed of the first release film (the first release film 15' in FIG. 7: 25μm) and the second release film 15" Slices.

After peeling off the second release film of the protective film forming sheet obtained above, the protective film forming film (13)-9 obtained above was attached to the #2000 polished surface of a 6-inch silicon wafer (thickness 100μm) , To obtain a laminate composed of a 6-inch silicon wafer, a protective film forming film (13)-9, and a first release film.

The first release film was removed from the laminate obtained above. In addition, the release film was removed from the adhesive layer of the support sheet (10)-1 obtained in the same manner as in Example 1, on the support sheet (10)- On the exposed surface of the adhesive layer of 1, the protective film forming film (13)-9 and the first release film are attached, and the protective film forming film (13)-9 is attached to fix the sheet Ring frame, let stand for 30 minutes.

Subsequently, the ultraviolet irradiation device (manufactured by the Lintec Company "RAD2000m / 8") at an illuminance 195mW / cm ^2, light quantity of 170mJ / cm condition ^2, the self-supporting sheet (10) -1-side protective film of the composite sheet is formed By irradiating ultraviolet rays, the film (13)-9 for forming a protective film is cured to become a protective film.

Next, using a dicing blade, the silicon wafer and the protective film forming film (13)-9 are diced and singulated to obtain a 2mm×2mm silicon wafer.

In the same manner as in Example 1, evaluation of suppression of chip cracking and chipping caused by dicing, evaluation of suppression of blade clogging, and evaluation of adhesion to cover tape were performed. The tensile modulus is the same as in Example 1. The evaluation results are shown in Table 2.

[Example 3]

<Manufacturing of Composite Sheet for Forming Protective Film>

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

As shown in Table 1, the content (mixed amount) of the energy ray curable component (a2)-1 is set to 10 parts by mass instead of 20 parts by mass, and the photopolymerization initiator (c)-4 is used instead of the photopolymerization initiator (c)-3, except that the content (mixed amount) of the photopolymerization initiator (c)-4 was 0.6 parts by mass, the same method as in Example 1 was used to prepare a protective film forming composition ( IV-1).

(Manufacturing of composite sheet for forming protective film)

Using the protective film forming composition (IV-1) obtained above, except for this point, the same method as in Example 1 was used to produce an energy ray curable protective film forming film (13)-10 with a thickness of 25 μm.

In addition, the protective film formation film (13)-10 was used instead of the protective film formation film (13)-9, and except for this point, the same method as in Example 1 was used to produce a composite sheet for protective film formation. The composition of the obtained composite sheet for forming a protective film is shown in Table 2.

<Manufacturing and Evaluation of Composite Sheets for Forming Protective Films>

Using the composite sheet for protective film formation obtained above, the same method as in Example 1 was used to measure the tensile modulus, evaluate the suppression of chip breakage and chipping caused by dicing, and evaluate the suppression of blade clogging. And the evaluation of the adhesion of the cover tape. The evaluation results are shown in Table 2.

[Comparative Example 1]

<Manufacturing and Evaluation of Composite Sheets for Forming Protective Films>

The composite sheet for forming a protective film obtained by the same method as in Example 1 was attached to a 6-inch silicon wafer (thickness) by using the protective film forming film (13)-9 of the composite sheet for forming a protective film 100μm) #2000 polished surface, and then fixed the sheet to the ring frame, and let it stand for 30 minutes.

Next, using a dicing blade, the silicon wafer and the protective film forming film (13)-9 are diced and singulated to obtain a 2mm×2mm silicon wafer.

Using the same method as in Example 1, the evaluation of the suppression of chip cracking and chipping caused by dicing, the evaluation of the suppression of blade clogging, and the evaluation of the adhesion to the cover tape were performed. The tensile elastic modulus of the protective film forming film at the time of cutting is the same as the tensile modulus of the protective film forming film of Example 1. The evaluation results are shown in Table 2.

[Comparative Example 2]

<Production and Evaluation of Sheets for Forming Protective Films>

A laminate composed of a 6-inch silicon wafer, a protective film forming film (13)-9, and a first release film was produced by the same method as in Example 2.

The first release film was removed from the obtained laminate. In addition, the release film was removed from the adhesive layer of the support sheet (10)-1 obtained in the same manner as in Example 1, on the support sheet (10)- On the exposed surface of the adhesive layer of 1, the protective film forming film (13)-9 and the first release film are attached, and the protective film forming film (13)-9 is attached to fix the sheet Ring frame, let stand for 30 minutes.

Next, using a dicing blade, the silicon wafer and the protective film forming film (13)-9 are diced and singulated to obtain a 2mm×2mm silicon wafer.

Using the same method as in Example 2, the evaluation of the suppression of chip cracking and chipping caused by dicing, the evaluation of the suppression of blade clogging, and the evaluation of the adhesion to the cover tape were performed. The tensile elastic modulus of the protective film forming film at the time of cutting is the same as the tensile modulus of the protective film forming film of Example 2. The evaluation results are shown in Table 2.

[Comparative Example 3]

<Manufacturing and Evaluation of Composite Sheets for Forming Protective Films>

The composite sheet for forming a protective film was manufactured by the same method as in Example 3. The composition of the obtained composite sheet for forming a protective film is shown in Table 2.

The composite sheet for forming a protective film obtained above is attached to the #2000 polished surface of a 6-inch silicon wafer (thickness 100μm) by using the protective film forming film (13)-10 of the composite sheet for forming a protective film , And then fix the piece to the ring frame and let it stand for 30 minutes.

Next, using a dicing blade, the silicon wafer and the protective film forming film (13)-10 are diced and singulated to obtain a 2mm×2mm silicon wafer.

Using the same method as in Example 1, the evaluation of the suppression of chip cracking and chipping caused by dicing, the evaluation of the suppression of blade clogging, and the evaluation of the adhesion to the cover tape were performed. The tensile modulus of the protective film formation film at the time of cutting is the same as the tensile modulus of the protective film formation film of Example 3. The evaluation results are shown in Table 2.

According to the results of Examples 1 to 3, it is clear that when the protective film forming film is cured by irradiating energy rays to the protective film forming film, when the semiconductor wafer is diced, clogging of the dicing blade during dicing is suppressed. The cutting suitability is also excellent. It is estimated that in Examples 1 to 3, the tensile elastic modulus of the protective film during dicing of the semiconductor wafer is relatively high, which is 500 MPa or more, thereby suppressing fragmentation of the protective film during dicing and preventing clogging of the blade.

In contrast, in Comparative Examples 1 to 3, the protective film formation film was not irradiated with energy rays to harden the protective film formation film, but the semiconductor wafer was cut. In this case, the tensile elastic modulus (Young's modulus) of the protective film forming film at the time of dicing is relatively small, 50 MPa to 90 MPa, so chip cracks and chipping caused by dicing occur, and blade clogging is likely to occur. In addition, Adhere to the cover tape.

(Industrial availability)

The present invention can be used to manufacture semiconductor devices.

10‧‧‧Support film

11‧‧‧Substrate

12‧‧‧Adhesive layer

13‧‧‧Film for forming protective film

13'‧‧‧Protective film

16‧‧‧Adhesive layer for fixture

17‧‧‧Ring frame

18‧‧‧Semiconductor Wafer

19‧‧‧Semiconductor chip

20‧‧‧Cutting blade

21‧‧‧Energy ray irradiation device

Claims (4)

A method for manufacturing a semiconductor wafer with a protective film. After attaching an energy-ray curable protective film forming film to the semiconductor wafer, the protective film forming film is irradiated with energy rays to harden the protective film forming film Next, the semiconductor wafer is cut; the protective film forming film has the following characteristics: the protective film forming film with a thickness of 50μm is irradiated from both sides of the protective film forming film once. Illuminance: 230mW/cm ² and Light quantity: When the ^{protective film is made of ultraviolet rays of 170mJ/cm 2} , the tensile modulus of the protective film obtained by the following measurement method is 500 MPa or more; the measurement method: the tensile rate of the protective film of 15mm×100mm : In a tensile test of 50mm/min, calculate the tensile elastic modulus based on the slope of the stress-strain line at the initial stage of stretching. The method for manufacturing a semiconductor wafer with a protective film as described in claim 1, wherein after the protective film is irradiated with energy rays to form a protective film, the protective film is attached to a support sheet, and then the semiconductor crystal Round to cut. The method of manufacturing a semiconductor wafer with a protective film as described in claim 1, wherein the protective film formation film side of the protective film formation composite sheet provided with the protective film formation film on the support sheet The aforementioned semiconductor wafer. A method of manufacturing a semiconductor device by picking up a semiconductor chip with a protective film as described in any one of claims 1 to 3 The semiconductor wafer with the protective film obtained by the manufacturing method is connected to the substrate.

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