TWI733870B - Composite sheet for forming protective film - Google Patents

Abstract

Provided is a sheet (1A) for forming protective film, including: a base material (11), an adhesive layer (12) and a protective film-forming film (13), wherein formed by laminating the adhesive layer (12) and the protective film-forming film (13) in this order on the base material (11), wherein the haze of a support sheet which is the laminate of the base material and the adhesive layer (12) is higher than 45%, wherein the permeation clarity of the support sheet is 100 or more. According to this sheet (1A) for forming a protective film, it is possible to form a protective film that allows for the laser printability and visibility of printing on the protective film.

Description

Composite sheet for forming protective film

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

This application claims priority based on Japanese Patent Application No. 2017-068187 filed in Japan on March 30, 2017, and the content of this application is cited herein.

In recent years, the industry has used a so-called face down mounting 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 in which a resin film made of an organic material is formed as a protective film on the back of the exposed semiconductor chip, and the protective film-attached semiconductor chip obtained by forming the protective film in this way is incorporated into a semiconductor device. The protective film is used to prevent the semiconductor wafer from cracking or chipping in the steps after the dicing step, that is, to prevent the so-called chipping.

When forming such a protective film, use a composite sheet for protective film formation provided with a film for protective film formation on a support sheet. As the aforementioned support sheet, for example, a laminated sheet obtained by laminating an adhesive layer or the like on a resin base material is used. In the aforementioned composite sheet for forming a protective film, the film for forming a protective film has the function of forming a protective film, and the support sheet can function as a dicing sheet, which can be said to be a combination of the film for forming a protective film and the dicing sheet. Composite sheet for protective film formation.

On the other hand, during the manufacturing process of semiconductor devices, the surface of the support sheet attached to the semiconductor wafer or the protective film of the semiconductor chip is printed by irradiating laser light (in this manual, sometimes referred to as "ray "Shooting printing"). At this time, the laser beam is irradiated through the support sheet from the side opposite to the side on which the protective film is formed in the support sheet (base material). And, the printing system is observed through the supporting sheet.

In addition, during the manufacturing process of the semiconductor device, the state of the semiconductor wafer or semiconductor wafer equipped with the protective film formation film or protective film may be detected by an infrared camera or the like through the aforementioned support sheet and the protective film formation film or protective film. The situation.

In this way, during the manufacturing process of the semiconductor device, there may be cases in which laser printing is performed through the support sheet, or the protective film forming film, protective film, semiconductor wafer, or semiconductor wafer may be observed. In addition, the composition of the supporting film has a greater impact on the accuracy of these printing or observations.

For example, previously disclosed a composite sheet for forming a protective film, In the inspection of the semiconductor wafer after the step, the light transmittance is high, and the image visibility of the semiconductor wafer is excellent (refer to Patent Document 1). In the base material constituting the support sheet in the protective film forming composite sheet, in order to prevent the base materials from adhering to each other when rolled into a roll shape, that is, so-called blocking, at least one surface is usually uneven. In addition, the presence of the uneven surface has the following problem: the support sheet is cloudy, the semiconductor wafer including the protective film cannot be clearly observed, and the visibility of the semiconductor wafer is poor. In this regard, in the composite sheet for forming a resin film disclosed in Patent Document 1, an adhesive layer is laminated on the uneven surface of the base material, and the haze of the support sheet is set to 45% or less, thereby improving the performance of the support sheet. The visibility of semiconductor wafers.

[Prior Technical Literature] [Patent Literature]

Patent Document 1: Japanese Patent No. 5432853.

However, even if the visibility of the semiconductor chip through the support sheet is high, the laser printability through the protective film of the support sheet is not necessarily excellent. The reason is that even if the supporting sheet can improve the visibility of the semiconductor chip, the laser printing and printing visibility via the protective film of the supporting sheet may not be performed well. In addition, regarding the composite sheet for forming a protective film disclosed in Patent Document 1, it is not yet clear whether or not the laser printability is excellent.

Therefore, the present invention provides a composite sheet for forming a protective film. The protective film has excellent laser printability, and the protective film has excellent print visibility.

That is, the composite sheet for forming a protective film of the first aspect of the present invention includes a substrate, and an adhesive layer and a film for forming a protective film are sequentially laminated on the substrate as the substrate and the adhesive The haze of the support sheet of the laminate of the agent layer is higher than 45%, and the transmission clarity of the aforementioned support sheet is more than 100.

The composite sheet for forming a protective film of the above aspect may be provided with an adhesive for jigs in the area where the film for forming the protective film is not laminated on the surface of the adhesive layer on the side where the film for forming the protective film is provided Floor.

The film for forming a protective film may be energy ray curable.

The film for forming a protective film may be thermosetting.

The film for forming a protective film may be non-curable.

The aforementioned adhesive layer may also be energy ray curable or non-energy ray curable.

The thickness of the aforementioned adhesive layer may also be 3 μm to 20 μm.

It is also possible that the surface roughness (Ra) of one surface of the substrate is 0.11 μm or more, and the adhesive layer is laminated on the surface of the surface roughness in direct contact.

(1) A composite sheet for forming a protective film, comprising a substrate, and an adhesive layer and a protective film forming film are sequentially laminated on the substrate, as a laminate of the substrate and the adhesive layer The haze of the support sheet is higher than 45%, and the transmission clarity of the aforementioned support sheet is more than 100.

(2) The composite sheet for forming a protective film as described in (1), wherein the surface of the adhesive layer on the side where the film for forming the protective film is not laminated with the film for forming the protective film is provided with a treatment With adhesive layer.

(3) The composite sheet for forming a protective film as described in (1) or (2), wherein the film for forming a protective film is energy ray curable.

(4) The composite sheet for forming a protective film as described in (1) or (2), wherein the film for forming a protective film is thermosetting.

(5) The composite sheet for forming a protective film as described in (1) or (2), wherein the film for forming a protective film is non-curable.

(6) The composite sheet for forming a protective film as described in any one of (1) to (5), wherein the adhesive layer is energy ray curable or non-energy curable.

(7) The composite sheet for forming a protective film as described in any one of (1) to (6), wherein the thickness of the adhesive layer is 3 μm to 20 μm.

(8) The composite sheet for forming a protective film as described in any one of (1) to (7), wherein the surface roughness (Ra) of one surface of the substrate is 0.11 μm or more, and the surface roughness On the surface, the aforementioned adhesive layer is laminated in direct contact.

According to the above aspect, a composite sheet for forming a protective film is provided, which has The substrate is prepared, and the adhesive layer and the protective film forming film are sequentially laminated on the substrate. The protective film formed by the protective film forming film has excellent laser printability and the printing of the protective film The visibility is also excellent.

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

10: Support film

10a: The surface of the support sheet

11: Substrate

11a: The surface of the substrate

12: Adhesive layer

12a: The surface of the adhesive layer

13: Film for forming protective film

13a: Surface of protective film formation film

15: Peel off the film

16: Adhesive layer for jigs

16a: Surface of adhesive layer for jig

17: Middle layer

17a: Surface of the middle layer

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

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

Fig. 3 is a cross-sectional view schematically showing a composite sheet for forming a protective film according to a third embodiment of the present invention.

Fig. 4 is a cross-sectional view schematically showing a composite sheet for forming a protective film according to a fourth embodiment of the present invention.

Fig. 5 is a cross-sectional view schematically showing a composite sheet for forming a protective film according to a fifth embodiment of the present invention.

◇Composite sheet for forming protective film

The composite sheet for forming a protective film of the present embodiment includes a base material, and an adhesive layer and a film for forming a protective film are sequentially laminated on the base material. That is, the composite sheet for forming a protective film of this embodiment is formed by laminating a base material, an adhesive layer, and a film for forming a protective film in this order. In addition, in the composite sheet for forming a protective film of this embodiment, the haze of the support sheet, which is a laminate of the substrate and the adhesive layer, is higher than 45%, and the transparency of the support sheet is Above 100.

In addition, in this specification, the "protective film forming film" means a film for forming a protective film before being attached to a semiconductor wafer or the back surface of a semiconductor chip, and the so-called "protective film" means attaching to a semiconductor wafer or A film for forming a protective film behind the back surface of a semiconductor wafer. In addition, when the film for forming a protective film has curability, the cured film of the film for forming a protective film is referred to as a "protective film".

In addition, in this specification, even after the protective film forming film is attached to the semiconductor wafer or semiconductor wafer, as long as the laminated structure of the support sheet and the protective film forming film is maintained, the laminated structure is also referred to as "protective film". Composite sheet for forming".

The aforementioned protective film formation film can be used as a protective film for protecting the semiconductor wafer or the back surface of the semiconductor wafer (the surface opposite to the electrode formation surface). In addition, since the haze of the support sheet is higher than 45% and the transmission clarity is 100 or higher, the film for forming a protective film of the present embodiment has good laser printability, and the printing visibility of the protective film can be improved. More specifically, after attaching the aforementioned composite sheet for forming a protective film to the back surface of the semiconductor wafer or semiconductor chip, laser printing is performed on the surface of the support sheet of the protective film attached to the semiconductor wafer or semiconductor chip. At this time, the laser beam is irradiated through the support sheet from the side opposite to the side on which the protective film is formed in the support sheet (base material). And, the printing system is observed through the supporting sheet. At this time, since the transmission resolution of the support sheet is 100 or more, the light scattering on the outer surface of the support sheet is suppressed, so that the visibility of laser printing can be improved.

In addition, in the past, there has been a problem that in order to make laser printing thicker, laser printing must be performed with high output, and the manufacturing cost increases. In addition, in the case of printing with high output, if irradiation is performed through the support sheet, there is a risk that air may be accumulated between the protective film and the support sheet. In addition, by increasing the adhesive force of the support sheet, gas accumulation can be avoided, but on the other hand, there is a problem of impaired pickup suitability. Therefore, it is necessary to directly perform laser printing on the protective film after peeling off the support sheet. In contrast, in the composite sheet for forming a protective film of the present embodiment, since the haze is higher than 45%, the laser light is appropriately scattered inside the support sheet. Therefore, the laser printing can be thickened effectively, and the visibility of the laser printing can be improved. In addition, since there is no need to increase the laser output, the generation of air can be suppressed, so that laser printing can be performed in a state where the support sheet and the protective film are bonded. In addition, since the adhesive force of the support sheet is also moderate, the pick-up suitability is also good.

In addition, in the past, when the adhesive layer for jigs is a colorless and transparent composite sheet for forming a protective film, or a composite sheet for forming a protective film that does not have the structure of the adhesive layer for jigs, a chip mounter ( mounter) When attaching the aforementioned composite sheet for forming a protective film to the back surface of a semiconductor wafer or semiconductor wafer, the support sheet has a low haze of 45% or less and cannot be aligned with the optical sensor mounted on the mounter ( alignment) (hereinafter referred to as "position adjustment with front end"). In contrast, in the composite sheet for forming a protective film of the present embodiment, since the haze is higher than 45%, the optical sensor mounted on the mounter can detect and adjust the position of the tape tip.

The object of use of the composite sheet for forming a protective film of this embodiment, that is, the thickness of the semiconductor wafer or the semiconductor wafer is not particularly limited, but in terms of obtaining more significant effects in this embodiment, it is preferably 30 μm or more and 1000 μm Hereinafter, it is more preferably 100 μm or more and 300 μm or less.

Hereinafter, the configuration of this embodiment will be described in detail.

◎Support film

The support sheet includes a base material and an adhesive layer on the base material, and is composed of a plurality of layers of two or more layers. The constituent materials and thicknesses of these plural layers may be the same or different from each other, and the combination of these plural layers is not particularly limited as long as the effect in this embodiment is not impaired.

Furthermore, this specification is not limited to the case of the support sheet. The so-called "a plurality of layers may be the same or different from each other" means "all the layers may be the same, or all the layers may be different, and only a part of the layers may be the same"; In addition, "a plurality of 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 obtained by laminating an adhesive layer on a substrate in direct contact, a support sheet obtained by laminating an adhesive layer on a substrate via an intermediate layer, and the like. As a more preferable support sheet, a support sheet formed by laminating an adhesive layer on a substrate in direct contact can be cited.

Hereinafter, with reference to the drawings, examples of the composite sheet for forming a protective film of the present embodiment will be described for each type of such a support sheet. In addition, in the figures used in the following description, in order to make it easier to understand the characteristics of this embodiment, for convenience, the main parts may be enlarged and shown, and they are not limited to the size ratio of each component. Same as reality.

Fig. 1 is a cross-sectional view schematically showing a composite sheet for forming a protective film according to the first embodiment of 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 composite sheet 1A for forming a protective film has a structure in which the film 13 for forming a protective film is laminated on one surface 10a of the support sheet 10. In addition, the protective film forming composite sheet 1A further has a release film 15 laminated on the entire surface (upper surface and side surface) of the surface 13a of the protective film forming film 13 and the surface 12a (upper surface) of the adhesive layer.

In addition, in this specification, the "release film" is a film having a release function, and specifically refers to a film that is attached to the surface of the protective film forming film in order to protect the film for forming the protective film before being attached to the semiconductor wafer A film, and the release film is peeled off at the time of work and used.

In the composite sheet 1A for forming a protective film, the support sheet 10, which is a laminate of the base material 11 and the adhesive layer 12, has a haze of more than 45%, and the transparency of the support sheet 10 is 100 or more.

The protective film forming composite sheet 1A shown in FIG. 1 is in a state where the release film 15 is removed, and a semiconductor wafer (not shown in the figure) is attached to a partial area on the central side of the surface 13a of the protective film forming film 13 )in the back. In addition, the area near the peripheral edge of the protective film forming film 13 is attached to a jig such as a ring frame and used.

Fig. 2 is a cross-sectional view schematically showing a composite sheet for forming a protective film according to a second embodiment of the present invention. In addition, in the figures following FIG. 2, for the same constituent elements as those shown in the previously described figures, the same symbols as in the previously described figures are attached, 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. 1 except that it is provided with 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 11 a of the base material 11. The protective film forming film 13 is laminated on a part of the area on the central side of the surface 12a of the adhesive layer 12, that is, the semiconductor wafer attaching area. An adhesive layer 16 for jigs is laminated on a part of the surface 12a of the adhesive layer 12, that is, a region near the peripheral edge. The release film 15 is laminated|stacked on the surface 13a (upper surface) of the film 13 for protective film formation, and the surface 16a (upper surface) of the adhesive layer 16 for jigs.

In the composite sheet 1B for forming a protective film, the haze of the support sheet 10, which is a laminate of the base material 11 and the adhesive layer 12, is higher than 45%. The transparency of 10 is above 100.

The adhesive layer 16 for a jig may have, for example, a single-layer structure containing adhesive components, or a multiple-layer structure in which layers containing adhesive components are layered on both areas of the core sheet.

The protective film forming composite sheet 1B shown in FIG. 2 has the back surface of a semiconductor wafer (not shown) attached to the surface 13a of the protective film forming film 13 with the release film 15 removed. In addition, the upper surface of the surface 16a of the adhesive layer 16 for jigs is attached to jigs, such as a ring frame, for use.

Fig. 3 is a cross-sectional view schematically showing a composite sheet for forming a protective film according to a third embodiment of 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. 1 except that an intermediate layer 17 is provided between the adhesive layer 12 and the film 13 for forming a protective film same. In the composite sheet 1C for forming a protective film, the support sheet 10 is a laminate of the base material 11, the adhesive layer 12, and the intermediate layer 17. In other words, the composite sheet 1C for forming a protective film has a structure in which the film 13 for forming a protective film is laminated on one surface 10a (17a) of the support sheet 10. In addition, the protective film forming composite sheet 1C is further laminated on the entire surface (upper surface and side surface) of the surface 13a of the protective film forming film 13, the surface (side surface) of the intermediate layer 17a, and the surface 12a (upper surface) of the adhesive layer There is a release film 15.

In the composite sheet 1C for forming a protective film, the support sheet 10 that is a laminate of the base material 11, the adhesive layer 12, and the intermediate layer 17 has a haze of more than 45%, and the transmission clarity of the support sheet 10 is 100 or more.

The protective film forming composite sheet 1C shown in FIG. 3 is in a state where the release film 15 is removed, and a semiconductor wafer (not shown) is attached to a part of the central side of the surface 13a of the protective film forming film 13 )in the back. In addition, the area near the peripheral edge of the protective film forming film 13 is attached to a jig such as a ring frame and used.

Fig. 4 is a cross-sectional view schematically showing a composite sheet for forming a protective film according to a fourth embodiment of the present invention.

The composite sheet 1D for forming a protective film shown here is the same as the composite sheet 1A for forming a protective film shown in FIG. 1 except that the intermediate layer 17 is provided between the base material 11 and the adhesive layer 12. In the composite sheet 1D for forming a protective film, the support sheet 10 is a laminate of the base material 11, the intermediate layer 17, and the adhesive layer 12. In other words, the composite sheet 1D for forming a protective film has a structure in which the film 13 for forming a protective film is laminated on one surface 10a (12a) of the support sheet 10. Moreover, the composite sheet 1D for protective film formation further has the release film 15 laminated|stacked on the whole surface (upper surface and side surface) of the surface 13a of the film 13 for protective film formation, and the surface 12a (upper surface) of an adhesive layer.

In the composite sheet 1D for forming a protective film, the haze of the supporting sheet 10, which is a laminate of the base material 11, the intermediate layer 17, and the adhesive layer 12, is higher than 45%, the transmission clarity of the aforementioned support sheet 10 is 100 or more.

The protective film forming composite sheet 1D shown in FIG. 4 is in a state where the release film 15 is removed, and a semiconductor wafer (not shown in the figure) is attached to a part of the area on the central side of the surface 13a of the protective film forming film 13 )in the back. In addition, the area near the peripheral edge of the protective film forming film 13 is attached to a jig such as a ring frame and used.

Fig. 5 is a cross-sectional view schematically showing a composite sheet for forming a protective film according to a fifth embodiment of 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. 2 except that the film for forming a protective film is layered on the entire surface of the adhesive layer. That is, in the composite sheet 1E for forming a protective film, an adhesive layer 12 is laminated on one surface 11 a of the base material 11. The protective film forming film 13 is layered on the entire surface 12a of the adhesive layer 12. An adhesive layer 16 for jigs is laminated on a part of the surface 13 a of the protective film forming film 13, that is, a region near the peripheral edge portion. The release film 15 is laminated|stacked on the surface 13a (upper surface) of the film 13 for protective film formation, and the surface 16a (upper surface and side surface) of the adhesive layer 16 for jigs.

In the composite sheet 1E for forming a protective film, the haze of the supporting sheet 10 as a laminate of the base material 11 and the adhesive layer 12 is higher than 45%, and the transmission clarity of the supporting sheet 10 is 100 or more.

The protective film forming composite sheet 1E shown in FIG. 5 has the back surface of a semiconductor wafer (not shown) attached to the surface 13a of the protective film forming film 13 with the release film 15 removed. In addition, the upper surface of the surface 16a of the adhesive layer 16 for jigs is attached to jigs, such as a ring frame, for use.

In this way, in the composite sheet for forming a protective film of this embodiment, regardless of the form of the support sheet and the film for forming a protective film, the adhesive layer for jigs can be provided. However, generally, as shown in FIGS. 2 and 5, as the composite sheet for forming a protective film of this embodiment provided with an adhesive layer for a jig, it is preferable to have a jig on the support sheet 10 or the film 13 for forming a protective film A composite sheet of the adhesive layer 16 is used.

The composite sheet for forming a protective film of this embodiment is not limited to the composite sheet for forming a protective film shown in Figs. A part of the configuration of the composite sheet for forming a protective film is changed or deleted, or another configuration is added to the composite sheet for forming a protective film described earlier.

For example, in the composite sheet for forming a protective film shown in FIGS. 2 and 5, an intermediate layer 17 may be provided between the adhesive layer 12 and the film 13 for forming a protective film. That is, in the composite sheet for forming a protective film of the present embodiment, the support sheet 10 may be formed by laminating the base material 11, the adhesive layer 12, and the intermediate layer 17 in this order. Here, the intermediate layer 17 is the same as the intermediate layer 17 that can be provided in the composite sheet for forming a protective film shown in FIGS. 3 and 4. As a middle layer 17. Any intermediate layer can be selected according to the purpose.

In addition, for example, in the composite sheet for forming a protective film shown in FIGS. 2 and 5, an intermediate layer 17 may be provided between the base material 11 and the adhesive layer 12. That is, in the composite sheet for forming a protective film of the present embodiment, the support sheet 10 may be formed by laminating the base material 11, the intermediate layer 17, and the adhesive layer 12 in this order. Here, the intermediate layer 17 is the same as the intermediate layer 17 that can be provided in the composite sheet for forming a protective film shown in FIGS. 3 and 4. As the intermediate layer 17, any intermediate layer can be selected according to the purpose.

In addition, in the composite sheet for forming a protective film shown in FIGS. 1 to 5, the intermediate layer 17 may be provided at a location other than those shown in FIGS. 3 and 4.

In addition, in the composite sheet for forming a protective film shown in FIGS. 1 to 5, layers other than the aforementioned intermediate layer 17 may be provided at arbitrary positions.

In addition, the composite sheet for forming a protective film shown in FIGS. 3 and 4 may be provided with an adhesive layer 16 for jigs.

In addition, in the composite sheet for forming a protective film of the present embodiment, a part of a gap may be formed between the release film 15 and the layer directly in contact with the release film 15.

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

In the composite sheet for forming a protective film of this embodiment, the support sheet may be opaque, or may be colored according to the purpose.

Specifically, the transmission resolution of the support sheet is 100 or more, preferably 150 or more, more preferably 200 or more and 450 or less, still more preferably 300 or more and 430 or less.

When the transparency of the support sheet is in the above range, light scattering on the outer surface of the support sheet is suppressed, and the visibility of laser printing can be improved.

Furthermore, the transmission clarity of the support sheet can be measured using an image clarity measuring device "ICM-10P" manufactured by Suga Test Instruments, etc., in accordance with JIS (Japanese Industrial Standard; Japanese Industrial Standard) K 7374-2007.

In addition, in order to make the transmission clarity of the support sheet into the above-mentioned range, for example, the surface roughness of the outer surface of the support sheet may be adjusted.

In addition, the haze of the support sheet is higher than 45%, preferably 46% or higher, more preferably 47% or higher and 90% or lower, and still more preferably 50% or higher and 85% or lower.

In the past, in order to thicken the laser printing, it was necessary to increase the laser output. If irradiation is performed through the support sheet, gas accumulation is generated between the protective film and the support sheet. Therefore, it is necessary to directly perform laser printing on the protective film after peeling off the support sheet. In contrast, in the composite sheet for forming a protective film of the present embodiment, since the haze of the support sheet is in the above range, the laser light is appropriately scattered inside the support sheet. Therefore, the laser printing can be thickened effectively, and the visibility of the laser printing can be improved. In addition, there is no need to increase the laser output. Therefore, it is possible to suppress the generation of air and accumulate, so that the laser printing can be performed in the state where the support sheet and the protective film are bonded.

Furthermore, in the past, the adhesive layer for jigs was a colorless and transparent protective film In the case of a composite sheet for forming or a composite sheet for forming a protective film that does not have an adhesive layer for jigs, attach the composite sheet for forming a protective film to the back surface of the semiconductor wafer or semiconductor wafer using a mounter When the support sheet has a low haze such as 45% or less, it cannot be aligned with the optical sensor mounted on the placement machine (hereinafter referred to as "adjustment of the position of the belt tip"). In contrast, in the composite sheet for forming a protective film of the present embodiment, since the haze of the support sheet is in the above-mentioned range, the optical sensor mounted on the mounter can detect and adjust the position of the tape tip.

Furthermore, the haze of the support sheet can be measured using NDH-5000 manufactured by Nippon Denshoku Industries Co., Ltd. in accordance with JIS K 7136-2000.

In addition, in order to make the haze of the support sheet into the above-mentioned range, for example, the base material or the intermediate layer may contain a filler or a coloring agent for adjustment. Or, for example, the hardness of the adhesive layer may be changed to form a gap between the base material or the intermediate layer and the adhesive layer, and the adjustment may be performed.

In addition, when 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, for the support sheet, the transmittance measured using an integrating sphere 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, for 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 addition, in this specification, the "energy-ray curability" means the property of curing by irradiation of energy rays. The so-called "non-energy-ray-curable" refers to the property that it does not harden even if it is irradiated with energy rays, and includes thermosetting and non-curing properties. The so-called "thermosetting property" means the property of hardening by heating. The so-called "non-curing property" refers to the property of not being cured by heating or irradiating energy rays.

In this specification, 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.

The ultraviolet light can be irradiated by using, for example, 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 the ultraviolet source. The electron beam can be irradiated with an electron beam generated by an electron beam accelerator or the like.

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

○Substrate

The substrate is in the form of a sheet or a film, 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; Vinyl copolymers such as ethylene-vinyl acetate copolymers, ethylene-(meth)acrylic acid copolymers, ethylene-(meth)acrylate copolymers, ethylene-norbornene copolymers (obtained by using ethylene as a monomer) Copolymers); vinyl chloride resins such as polyvinyl chloride and vinyl chloride copolymers (resins obtained by using vinyl chloride as a monomer); polystyrene; polycyclic olefins; polyethylene terephthalate, polyethylene naphthalate Ethylene formate, polybutylene terephthalate, polyethylene isophthalate, polyethylene 2,6-naphthalene dicarboxylate, all structural units with aromatic cyclic groups are fully aromatic poly Polyesters such as esters; copolymers of two or more of the aforementioned polyesters; poly(meth)acrylates; polyurethanes; polyacrylate urethanes; polyimines; polyamides; polycarbonates Ester; Fluorine resin; Polyacetal; Modified polyphenylene ether; Polyphenylene sulfide; Polysulfide; Polyether ketone, etc.

Moreover, 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 aforementioned polyester and the aforementioned resin other than the polyester preferably has a relatively small amount of the resin other than the polyester.

In addition, as the aforementioned resin, for example, a cross-linked resin obtained by cross-linking one or more of the aforementioned resins as exemplified above; ionic polymerization using one or more of the aforementioned resins exemplified in the foregoing Modified resins such as materials.

Furthermore, in this specification, the concept of "(meth)acrylic acid" includes both "acrylic acid" and "methacrylic acid". The terms similar to (meth)acrylic acid are also the same. For example, the concept of "(meth)acrylic acid group" includes both "acrylic acid group" and "methacrylic acid group", and "(meth)acrylic acid group" The concept of "ester" includes both "acrylate" and "methacrylate".

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

The substrate may be composed of one layer (single layer) or two or more layers; when 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 40 μm or more and 300 μm or less, more preferably 60 μm or more and 150 μm or less. When the thickness of the base material is in this range, the flexibility of the composite sheet for forming the 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 addition, as a method of measuring the thickness of the base material, for example, the following method can be exemplified: the thickness is measured using a contact thickness meter at any 5 locations, and the average of the measured values is calculated.

The base material preferably has high thickness accuracy, that is, thickness unevenness can be suppressed at any part. 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.

For example, when the base material contains a filler or a colorant, the haze of the support sheet can be within the above-mentioned range, so that the visibility of laser printing can be improved.

The optical properties of the substrate may satisfy the optical properties of the support sheet described above. That is, the substrate may be transparent or opaque, and may be colorless or colored according to the purpose, and other layers may be processed (for example, vapor deposition).

In addition, when the film for forming a protective film has energy ray curability, the base material is preferably a base material that can transmit energy rays.

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 radiation treatment, flame treatment, chromic acid treatment, hot air treatment and other oxidation treatments.

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

In addition, 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 prevented from being stacked and stored, the substrate is attached to other sheets or the substrate is attached 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 dicing, it is particularly preferable that the surface of the substrate is subjected to electron beam irradiation treatment.

In addition, regarding the surface-treated substrate, the upper limit value of the surface roughness (Ra) of the surface exposed as the outer surface of the support sheet in the substrate is 0.60 μm or less, preferably 0.50 μm or less, more preferably 0.40 μm or less, more preferably 0.30 μm or less. When the surface roughness of the substrate is less than the above upper limit, light scattering on the outer surface of the substrate can be reduced, and the transmission clarity of the support sheet can be within the above range, so that the visibility of laser printing can be improved.

On the other hand, the lower limit of the surface roughness (Ra) is not particularly limited. For example, it may be 0.005 μm or more, 0.01 μm or more, 0.03 μm or more, or 0.05 μm or more.

In addition, when the substrate has a surface with a surface roughness of not more than the above upper limit and a surface with a surface roughness of 0.11 μm or more, other layers such as an adhesive layer with a surface roughness of 0.11 μm or more are preferable. Thereby, the surface whose surface roughness is below the above upper limit becomes the surface exposed by the outer surface of the support sheet in the base material, which can reduce the light scattering of the outer surface of the base material, and can make the transmission clarity of the support sheet become the above-mentioned Therefore, the visibility of laser printing can be improved.

In addition, when the surface roughness of both surfaces of the substrate is below the above upper limit, the adhesive layer and other layers are layered on the area with larger surface roughness, and the surface with smaller surface roughness is used as the outer surface. Just expose it.

In addition, in this specification, the "surface roughness" means the so-called arithmetic average roughness calculated in accordance with JIS B0601:2001, and may be abbreviated as "Ra" unless otherwise specified.

The base material can be manufactured by a well-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.

Furthermore, in this embodiment, the concept of "adhesive resin" includes both adhesive resins and adhesive resins. For example, it includes not only adhesive resins, but also adhesives and additives. Other components are used in combination to show adhesiveness, or resins that show adhesiveness due to the presence of triggers such as heat or water.

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 3 μm or more and 20 μm or less, more preferably 5 μm or more and 20 μm or less, and particularly preferably 5 μm or more and 17 μm or less.

When the thickness of the adhesive layer is more than the above lower limit, the adhesive force can be improved. In addition, in the case of a substrate with a surface roughness of 0.11 μm or more, a laminate with a smooth surface that embeds the surface of the substrate and reduces light scattering on the outer surface of the substrate can be formed. On the other hand, when the thickness of the adhesive layer is below the above upper limit, the blade can have good cutting suitability and picking suitability.

Here, the "thickness of the adhesive layer" means the thickness of the entire adhesive layer. For example, the thickness of the adhesive layer composed of a plurality of layers means the total thickness of all the layers constituting the adhesive layer. In addition, as a measuring method of the thickness of an adhesive layer, the following method etc. are mentioned, for example, the thickness is measured using a contact type thickness meter at arbitrary 5 places, and the average of a measured value is calculated.

By appropriately adjusting the hardness of the adhesive layer, a gap can be formed between the adhesive layer and the substrate or the intermediate layer, and the haze of the support sheet can be adjusted to the above range.

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 opaque or colored according to the purpose.

In addition, when 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-curable adhesive. Furthermore, the non-energy-ray-curable adhesive includes a thermosetting adhesive and a non-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 coated on the surface to be formed of the adhesive layer, and the adhesive composition is dried if necessary, so that the adhesive layer can be formed 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 addition, in this specification, the "normal temperature" means a temperature that is not particularly cold or particularly hot, that is, a normal temperature, for example, a temperature of 15°C or more and 25°C or less.

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, contact coater Wait.

The drying conditions of the adhesive composition are not particularly limited. When the finished product contains a solvent described later, it is preferable to perform heating and drying. In this case, it is preferable to perform drying under the conditions of, for example, 70°C or more and 130°C or less and 10 seconds or more and 5 minutes or less.

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; adhesive The agent composition (I-2) contains an energy-ray curable adhesive resin (I-2a) (hereinafter, sometimes abbreviated as "adhesive resin (I-2a)"), and the energy-ray curable adhesiveness The resin (I-2a) has an unsaturated group 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 aforementioned acrylic resin may have only one structural unit, or There can be two or more types; in the case of two or more types, the combination and ratio of these 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 (lauryl (meth)acrylate) , Tridecyl (meth)acrylate, tetradecyl (meth)acrylate (myristyl (meth)acrylate), pentadecyl (meth)acrylate, ten (meth)acrylate Hexaalkyl ester (palmityl (meth)acrylate), heptadecyl (meth)acrylate, stearyl (meth)acrylate (stearyl (meth)acrylate), (meth) Nonadecyl acrylate, eicosyl (meth)acrylate, etc.

In terms of improving the adhesive force of the adhesive layer, the acrylic polymer preferably has a structural unit derived from an alkyl (meth)acrylate having a carbon number of 2 or more derived from the alkyl group. And, the adhesive force of the adhesive layer is increased In terms of one step improvement, the carbon number of the aforementioned alkyl group is preferably 2 or more and 12 or less, and more preferably 4 or more and 8 or less. In addition, the alkyl (meth)acrylate whose alkyl group has 4 or more carbon atoms 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 monomers, for example, the following monomers can be exemplified, which can be the starting point of crosslinking by reacting the aforementioned functional group with the crosslinking agent described later, or can be formed by reacting the aforementioned functional group with the aforementioned crosslinking agent. The unsaturated group in the unsaturated group 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.

The aforementioned hydroxyl-containing monomers include, for example, hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxy (meth)acrylate Propyl ester, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate and other hydroxyalkyl (meth)acrylates; vinyl alcohol, alkene Non-(meth)acrylic unsaturated alcohols such as propanol (unsaturated alcohols that do not have a (meth)acryloyl skeleton), etc.

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, 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 methacrylate, etc. (form Group) carboxyalkyl acrylate 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, the combination and ratio of these can be arbitrarily selected.

In the aforementioned acrylic polymer, the content of structural units derived from functional group-containing monomers relative to the total amount of structural units is preferably 1% by mass to 29% by mass, more preferably 2% by mass to 25% by mass Below, 3 mass% or more and 23 mass% or less are especially preferable.

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 can be combined with alkyl (meth)acrylate, etc. Copolymerization is not particularly limited.

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, the combination and ratio of these 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).

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, the combination and ratio of these can be arbitrarily selected .

In the adhesive composition (I-1), the content of the adhesive resin (I-1a) is preferably 5% by mass or more and 99% by mass or less, and more preferably 10% by mass relative to the total content of all components other than the solvent Above 95% by mass or less, more preferably 15% by mass or more and 90% by mass or less.

[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 energy ray irradiation.

Among the energy ray curable compounds, examples of monomers include trimethylolpropane tri(meth)acrylate, pentaerythritol (meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, (Meth)acrylates such as acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol (meth)acrylate, etc.; (meth)acrylic urethane 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.

In terms of relatively large molecular weight and not easy to reduce the storage elastic modulus of the adhesive layer, the energy ray curable compound is preferably (meth)acrylate urethane or (meth)acrylate urethane formic acid Ester oligomers.

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, the combination and ratio of these can be arbitrarily selected.

In the adhesive composition (I-1), the content of the energy ray curable compound is preferably 1 relative to the total content of all components other than the solvent Mass% or more and 95 mass% or less, more preferably 2 mass% or more and 90 mass% or less, and particularly preferably 3 mass% or more and 85% by mass or less. For example, it may be any of 3% by mass or more and 80% by mass or less, 3% by mass or more and 65% by mass or less, 3% by mass or more and 50% by mass or less, and 3% by mass or more and 35% by mass or less.

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

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); hexa[1-(2-methyl)-aziridinyl] triphosphine triazine and other aziridine crosslinking agents Linking agent (crosslinking agent with aziridin group); metal chelate crosslinking agent such as aluminum chelate (crosslinking agent with metal chelate structure); isocyanurate crosslinking agent ( Crosslinking agent with isocyanuric acid skeleton) and so on.

In terms of improving the cohesive force of the adhesive and improving the adhesive force of the adhesive layer, as well as easy availability, the crosslinking agent is preferably an isocyanate-based Crosslinking agent.

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, the combination and ratio of these 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 or more and 50 parts by mass or less, more preferably 0.1 parts by mass Part or more and 30 parts by mass or less, more preferably 0.3 part by mass or more and 23 parts by mass or less.

[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; 1-hydroxycyclohexyl phenyl Α-keto alcohol compounds such as ketones; azo compounds such as azobisisobutyronitrile; titanocene compounds such as titanocene; thioxanthone compounds such as thioxanthone; peroxide compounds; diketone compounds such as diacetyl; Benzol; Diphenylol; Benzophenone; 2,4-Diethylthioxanthone; 1,2-Diphenylmethane; 2-Hydroxy-2-methyl-1-[4-(1 -Methylvinyl)phenyl]acetone; 2-chloroanthraquinone and the like.

In addition, 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, the combination and ratio of these can be arbitrarily selected.

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

[Other additives]

The adhesive composition (I-1) may contain other additives that do not meet any of the above-mentioned components within the range that does not impair the efficacy of this embodiment.

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).

Furthermore, the so-called reaction delay agent, for example, inhibits the off-target cross-linking reaction in the adhesive composition (I-1) during storage due to the action of the catalyst mixed in 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 cited. More specifically, it can include: having two or more carbonyl groups (-C( =O)-) Compounds.

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, the combination and ratio of these 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 adhesive resin (I-1a) used in the production of The solvent used is not removed from the adhesive resin (I-1a) and used directly in the adhesive composition (I-1). It can also be added separately when manufacturing the adhesive composition (I-1) to make adhesive properties. The solvent used in the resin (I-1a) is the same type or different types of solvents.

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, the combination and ratio of these 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 energy-ray-curable adhesive resin (I-2a) is used in a non-energy-ray-curable adhesive resin (I-2a) An unsaturated group is introduced into the side chain of the adhesive resin (I-1a).

[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 has the aforementioned energy ray polymerizability In addition to the unsaturated group, it further has the following group which can bond with the adhesive resin (I-1a) by reacting with the functional group in the adhesive resin (I-1a).

Examples of the energy ray polymerizable unsaturated group include (meth)acrylic acid group, vinyl (ethylene group), allyl group (2-propenyl group), etc., and (meth)acrylic acid group is preferred. base.

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.

Adhesive resin (I-2a) 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, the combination and ratio of these can be arbitrarily selected .

In the adhesive composition (I-2), the content of the adhesive resin (I-2a) is preferably 5% by mass or more and 99% by mass or less, and more preferably 10% by mass relative to the total content of all components other than the solvent Above 95% by mass or less, more preferably 10% by mass or more and 90% by mass or less.

[Crosslinking agent]

For use, for example, the same as in the adhesive resin (I-1a), which is derived from containing When the aforementioned acrylic polymer, which is the structural unit of the functional group monomer, is used as the adhesive resin (I-2a), the adhesive composition (I-2) 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, the combination and ratio of these 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 or more and 25 parts by mass or less, more preferably 0.05 parts by mass Part or more and 20 parts by mass or less, and more preferably 0.1 part by mass or more and 15 parts by mass or less.

[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, a combination of these The combination and ratio can be selected arbitrarily.

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 parts by mass or more and 20 parts by mass or less, more preferably 0.03 Part by mass or more and 10 parts by mass or less, more preferably 0.05 part by mass or more and 5 parts by mass or less.

[Other additives]

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

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, the combination and ratio of these 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, the combination and ratio of these 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 the energy ray curable compound.

In the adhesive composition (I-3), the content of the adhesive resin (I-2a) is preferably 5% by mass or more and 99% by mass or less, more preferably 10% by mass relative to the total content of all components other than the solvent Above 95% by mass or less, more preferably 15% by mass or more and 90% by mass or less.

[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 energy ray polymerizable unsaturated groups and can be cured by energy ray irradiation, 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, the combination and ratio of these can be arbitrarily selected.

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

[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 aforementioned 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, the combination and ratio of these 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 parts by mass or more. 20 Parts by mass or less, more preferably 0.03 parts by mass or more and 10 parts by mass or less, and particularly preferably 0.05 parts by mass or more and 5 parts by mass or less.

[Other additives]

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

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-3) may be only one type or two or more types; in the case of two or more types, the combination and ratio of these 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, the combination and ratio of these 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 previous article mainly explained the adhesive composition (I-1), the adhesive composition (I-2), and the adhesive composition (I-3), but for all adhesives except for 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 the components described above The ingredients.

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

As a non-energy-ray-curable adhesive composition, for example, an adhesive composition (I-4) containing the following non-energy-ray-curable adhesive resin (I-1a): acrylic resin, urethane Ester resins, rubber resins, silicone resins, epoxy resins, polyvinyl ethers, polycarbonates, ester resins, etc., preferably contain acrylic resins.

Adhesive compositions other than the adhesive composition (I-1) to the adhesive composition (I-3) preferably contain 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 adhesive resins as the adhesive resin (I-1a) in the adhesive composition (I-1).

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, the combination and ratio of these can be arbitrarily selected .

In the adhesive composition (I-4), the content of the adhesive resin (I-1a) is preferably 5% by mass or more and 99% by mass or less, more preferably 10% by mass relative to the total content of all components other than the solvent Above 95% by mass or less, more preferably 15% by mass or more and 90% by mass or less. For example, it may be any of 3% by mass or more and 85% by mass or less, 40% by mass or more and 85% by mass or less, and 50% by mass or more and 85% by mass or less.

[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 adhesive composition (I-4) may contain only one type of crosslinking agent, or There are two or more types; in the case of two or more types, the combination and ratio of these 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 parts by mass or more and 50 parts by mass or less, more preferably 0.1 parts by mass Part or more and 50 parts by mass or less, more preferably 1 part by mass or more and 50 parts by mass or less.

[Other additives]

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

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, the combination and ratio of these 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 solvents in the adhesive composition (I-4) include adhesives The solvent in the agent composition (I-1) is the same solvent.

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, the combination and ratio of these can be arbitrarily selected.

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

<<Manufacturing method of 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 blending the adhesive and components other than the adhesive if necessary, etc., to constitute the adhesive composition.

The order of addition when formulating 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 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; mixing by applying ultrasonic waves The method and so on.

Regarding the temperature and time when adding and mixing the ingredients, as long as they don’t There is no particular limitation on the deterioration of the compounding components, as long as they are adjusted appropriately, and the temperature is preferably 15°C to 30°C.

○Middle layer

The intermediate layer has a sheet shape or a film shape, and the constituent material of the aforementioned intermediate layer may be appropriately selected according to the purpose, and is not particularly limited.

In addition, by appropriately adjusting the haze of the intermediate layer, the haze of the composite sheet for forming a protective film can be adjusted to the above-mentioned range.

The intermediate layer may be hardenable or non-hardenable. In addition, when the intermediate layer has curability, it may be either thermosetting or energy ray curability.

The intermediate layer may be only one layer (single layer), or plural layers of two or more layers. In the case of plural layers, these plural layers may be the same or different from each other, and the combination of these plural layers is not particularly limited.

The thickness of the intermediate layer may be, for example, 0.1 μm or more and 200 μm or less, may be 1 μm or more and 150 μm or less, and may be 3 μm or more and 120 μm or less.

Here, the "thickness of the intermediate layer" means the thickness of the entire intermediate layer, and means the total thickness of all the layers constituting the intermediate layer. In addition, as a method of measuring the thickness of the intermediate layer, for example, the following method can be cited: the thickness is measured using a contact-type thickness meter at any 5 locations, and the average of the measured values is calculated.

<<Composition for forming intermediate layer>>

The intermediate layer can be formed using a composition for forming an intermediate layer containing the constituent material of the intermediate layer.

For example, the composition for forming the intermediate layer is applied to the surface to be formed of the intermediate layer, and the composition for forming the intermediate layer is dried as necessary, or the composition for forming the intermediate layer is cured by irradiating energy rays. The target part forms an intermediate layer.

The composition for forming the intermediate layer may be applied by a known method, and for example, it may be carried out by the same method as the application of the adhesive composition described above.

The drying conditions of the composition for forming an intermediate layer are not particularly limited. For example, the composition for forming an intermediate layer containing a solvent is preferably heated and dried. In this case, it is preferably dried under the conditions of, for example, 70° C. to 130° C. and 10 seconds to 5 minutes.

When the composition for forming an intermediate layer has energy ray curability, it is preferable to further cure the composition for forming an intermediate layer by irradiating with energy ray after drying.

The composition for forming an intermediate layer is not particularly limited, and examples thereof include the same compositions as those exemplified in the above-mentioned adhesive composition.

The composition for forming the intermediate layer may contain other additives that do not meet any of the above-mentioned components within the range that does not impair the efficacy of the invention.

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

For example, when the composition for forming an intermediate layer contains a filler or a coloring agent, the haze of the composite sheet for forming a protective film can be adjusted to the above range.

◎Film for forming protective film

The film for forming a protective film may have curability or non-curable properties.

In addition, when the film for forming a protective film has curability, it may be either thermosetting or energy ray curability.

○Film for forming thermosetting protective film

As a preferable film for thermosetting protective film formation, a film containing a polymer component (A) and a thermosetting component (B) is mentioned, for example. The polymer component (A) is regarded as a component formed by the polymerization reaction of a polymerizable compound. In addition, the thermosetting component (B) is a component that can perform a hardening (polymerization) reaction using heat as a trigger of the reaction. Furthermore, in the present invention, a polycondensation reaction is also included in the polymerization reaction.

The film for forming a thermosetting protective film may be composed of one layer (single layer), or may be composed of two or more layers. When the film for forming a thermosetting protective film is composed of a plurality of layers, these plurality of layers may be the same or different from each other. Here, "a plurality of layers may be the same or different from each other" means the same as the case of the above-mentioned base material. In addition, when the plural layers are different from each other, the combination of these plural layers is not particularly limited.

The thickness of the film for forming a thermosetting protective film is preferably 1 μm or more and 100 μm or less, more preferably 5 μm or more and 75 μm or less, and particularly preferably 5 μm or more and 50 μm or less. When the thickness of the film for forming a thermosetting protective film is more than the aforementioned lower limit, a protective film with higher protection ability can be formed. In addition, when the thickness of the film for forming a thermosetting protective film is not more than the aforementioned upper limit, it is possible to suppress excessive thickness.

Here, the "thickness of the film for forming a thermosetting protective film" means the thickness of the entire film for forming a thermosetting protective film. For example, the thickness of the film for forming a thermosetting protective film composed of a plurality of layers means the composition The total thickness of all layers of the thermosetting protective film formation film. In addition, as a method for measuring the thickness of the film for forming a thermosetting protective film, for example, the following method is mentioned: the thickness is measured at any 5 locations using a contact thickness meter, and the average of the measured values is calculated.

Regarding the curing conditions when the film for forming a thermosetting protective film is attached to the back surface of a semiconductor wafer and the film for forming a thermosetting protective film is cured, as long as the protective film has a degree of curing that can fully perform the function of the protective film , It is not particularly limited, and may be appropriately selected according to the type of film for forming a thermosetting protective film.

For example, the heating temperature during curing of the film for forming a thermosetting protective film is preferably 100°C or more and 200°C or less, more preferably 110°C or more and 180°C or less, and particularly preferably 120°C or more and 170°C or less. In addition, the heating time during curing is preferably 0.5 hour or more and 5 hours or less, more preferably 0.5 hour Time is more than 3 hours, more preferably 1 hour to 2 hours.

<<Composition for forming thermosetting protective film>>

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

The coating of the composition for forming a thermosetting protective film can be performed, for example, by the same method as in the case of the above-mentioned adhesive composition.

The drying conditions of the composition for forming a thermosetting protective film are not particularly limited. When the composition for forming a thermosetting protective film contains a solvent described later, it is preferable to heat and dry. In this case, it is preferably Drying is performed under the conditions of 70°C or more and 130°C or less and 10 seconds or more and 5 minutes or less.

<Composition for forming thermosetting protective film (III-1)>

As a composition for forming a thermosetting protective film, for example, it contains polymer The composition (III-1) for forming a thermosetting protective film of the component (A) and the thermosetting component (B) (in this specification, it may only be abbreviated as "composition (III-1)") and the like.

[0001]

[Polymer component (A)]

The polymer component (A) is a polymer compound for imparting film forming properties or flexibility to the film for forming a thermosetting protective film.

The polymer component (A) contained in the composition (III-1) and the film for forming a thermosetting protective film may be only one type or two or more types; in the case of two or more types, a combination of these And the ratio can be chosen arbitrarily.

As the polymer component (A), for example, acrylic resin (resin having a (meth)acrylic acid group), polyester, urethane resin (resin having a urethane bond), Acrylic urethane resin, polysiloxane resin (resin with silicone bond), rubber resin (resin with rubber structure), phenoxy resin, thermosetting polyimide, etc., preferably It is an acrylic resin.

Examples of the acrylic resin in the polymer component (A) include known acrylic polymers.

The weight average molecular weight (Mw) of the acrylic resin is preferably 10,000 or more and 2,000,000 or less, more preferably 100,000 or more and 1,500,000 or less. Since the weight average molecular weight of the acrylic resin is more than the aforementioned lower limit, the shape stability of the film for forming a thermosetting protective film (stability with time during storage) 性) improve. In addition, since the weight average molecular weight of the acrylic resin is less than the aforementioned upper limit, the film for forming a thermosetting protective film becomes easy to follow the uneven surface of the adherend, and the adhesion to the adherend and the thermosetting protective film can be further suppressed. Voids and the like are generated between the forming films.

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

The glass transition temperature (Tg) of the acrylic resin is preferably -60°C or higher and 70°C or lower, more preferably -30°C or higher and 50°C or lower. When the Tg of the acrylic resin is more than the aforementioned lower limit, the adhesion between the protective film and the support sheet (adhesive layer) can be suppressed, and the releasability of the support sheet can be improved. In addition, when the Tg of the acrylic resin is equal to or lower than the aforementioned upper limit, the adhesion between the protective film and the adherend is improved.

In addition, in this specification, "Glass transition temperature (Tg)" is the value measured by "Differential Scanning Calorimetry (DSC; Differential Scanning Calorimetry)" in accordance with JIS K7121.

Examples of acrylic resins include: one or two or more (meth)acrylate polymers; selected from (meth)acrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene, and N- Copolymers of two or more monomers in methylol acrylamide, etc.

As the aforementioned (meth)acrylates constituting acrylic resins, for example Examples include: methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, (meth) Isobutyl acrylate, second butyl (meth)acrylate, third butyl (meth)acrylate, amyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, ( 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, n-octyl (meth)acrylate, n-nonyl (meth)acrylate, isononyl (meth)acrylate, (meth) ) Decyl acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate (lauryl (meth) acrylate), tridecyl (meth) acrylate, (meth) ) Myristyl acrylate (myristyl (meth)acrylate), pentadecyl (meth)acrylate, cetyl (meth)acrylate (palmityl (meth)acrylate), ( Heptadecyl meth)acrylate, stearyl (meth)acrylate (stearyl (meth)acrylate), etc. The alkyl group constituting the alkyl ester is a chain structure with a carbon number of 1 to 18. Alkyl (meth)acrylate; cycloalkyl (meth)acrylate such as isobornyl (meth)acrylate, dicyclopentyl (meth)acrylate, etc.; benzyl (meth)acrylate, etc. (meth) Aralkyl acrylate; (meth)cyclopentenyl (meth)acrylate and other cycloalkenyl (meth)acrylates; (meth)cyclopentenyloxyethyl (meth)acrylate and other cycloalkenyl (meth)acrylates Alkyl esters; (meth)acrylimines; (meth)acrylates containing glycidyl groups such as glycidyl (meth)acrylate; hydroxymethyl (meth)acrylate, (meth)acrylic acid 2- Hydroxyethyl, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, (meth)acrylate (Meth)acrylates containing hydroxyl groups such as 4-hydroxybutyl acrylate; (meth)acrylates containing substituted amino groups such as N-methylaminoethyl (meth)acrylate, etc. this Here, the "substituted amino group" means a group in which one or two hydrogen atoms of the amino group are replaced by groups other than hydrogen atoms.

The acrylic resin may be selected from (meth)acrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene, N-methylolacrylamide, etc., in addition to the aforementioned (meth)acrylate. A resin made by copolymerizing one or more of the monomers.

The monomer constituting the acrylic resin may be only one type or two or more types; in the case of two or more types, the combination and ratio of these can be arbitrarily selected.

The acrylic resin may also have functional groups such as vinyl groups, (meth)acrylic groups, amino groups, hydroxyl groups, carboxyl groups, and isocyanate groups that can be bonded to other compounds. The aforementioned functional group in the acrylic resin may be bonded to other compounds via the crosslinking agent (F) described later, or may be directly bonded to other compounds without the crosslinking agent (F). By bonding the acrylic resin to another compound via the aforementioned functional group, the reliability of the package obtained by using the composite sheet for forming a protective film tends to be improved.

In this specification, as the polymer component (A), instead of using acrylic resin, thermoplastic resins other than acrylic resins (hereinafter, sometimes simply referred to as "thermoplastic resins") may be used alone or in combination with acrylic resins. By using the aforementioned thermoplastic resin, there will be a protective film self-supporting sheet The releasability is improved, or the film for forming a thermosetting protective film becomes easier to follow the uneven surface of the adherend, so that the occurrence of voids between the adherend and the film for forming the thermosetting protective film can be further suppressed.

The weight average molecular weight of the aforementioned thermoplastic resin is preferably 1,000 or more and 100,000 or less, more preferably 3,000 or more and 80,000 or less. Here, the so-called "weight average molecular weight" is as described above.

The glass transition temperature (Tg) of the aforementioned thermoplastic resin is preferably -30°C or higher and 150°C or lower, more preferably -20°C or higher and 120°C or lower.

As said thermoplastic resin, polyester, polyurethane, phenoxy resin, polybutene, polybutadiene, polystyrene, etc. are mentioned, for example.

The aforementioned thermoplastic resin contained in the composition (III-1) and the film for forming a thermosetting protective film may be only one type or two or more types; in the case of two or more types, the combination and ratio of these may be Arbitrary choice.

In the composition (III-1), regardless of the type of the polymer component (A), the ratio of the content of the polymer component (A) to the total content of all components other than the solvent (that is, the thermosetting protective film is formed) The content of the polymer component (A) in the film) is preferably 5 mass% or more and 85% by mass or less, and more preferably 5 mass% or more and 80 mass% or less. For example, it can be 5% by mass or more, 65% by mass or less, 5% by mass or more, 50% by mass or less, and 10% by mass or less Any of the above 35% by mass or less.

The polymer component (A) may also conform to the thermosetting component (B). In this embodiment, when the composition (III-1) contains such components that meet both the polymer component (A) and the thermosetting component (B), the composition (III-1) can be regarded as containing Polymer component (A) and thermosetting component (B).

[Thermosetting component (B)]

The thermosetting component (B) is a component for curing the film for forming a thermosetting protective film to form a hard protective film.

The composition (III-1) and the thermosetting component (B) contained in the film for forming a thermosetting protective 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 chosen arbitrarily.

As the thermosetting component (B), 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 is composed of an epoxy resin (B1) and a thermosetting agent (B2).

The epoxy-based thermosetting resin contained in the composition (III-1) and the film for forming a thermosetting protective 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 chosen arbitrarily.

‧Epoxy resin (B1)

As the epoxy resin (B1), well-known epoxy resins can be cited, for example, polyfunctional epoxy resins, biphenyl compounds, bisphenol A diglycidyl ether and its hydrogenated products, o-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 (B1), 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 a semiconductor wafer with a protective film obtained by using a 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.

In addition, 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 constituting the epoxy resin or the like can be cited.

Unsaturated hydrocarbon group is a polymerizable unsaturated group, as the unsaturated group Specific examples of the hydrocarbyl group include: ethylene (vinyl), 2-propenyl (allyl), (meth)acrylic acid, (meth)acrylic acid amino group, etc., preferably acrylic acid group .

The number average molecular weight of the epoxy resin (B1) is not particularly limited, but in terms of the curability of the thermosetting protective film formation film, and the strength and heat resistance of the protective film after curing, it is preferably 300 or more and 30,000 Below, more preferably 300 or more and 10,000 or less, and particularly preferably 300 or more and 3,000 or less.

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

The epoxy equivalent of the epoxy resin (B1) is preferably 100 g/eq or more and 1000 g/eq or less, more preferably 150 g/eq or more and 950 g/eq or less.

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

The epoxy resin (B1) may be used alone or in combination of two or more; when two or more are used in combination, the combination and ratio of these can be arbitrarily selected.

‧Thermal hardener (B2)

Thermal hardener (B2) exerts the function of hardener for epoxy resin (B1) can.

As a thermosetting agent (B2), 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 (B2), examples of phenolic curing agents having phenolic hydroxyl groups include polyfunctional phenol resins, biphenols, novolac type phenol resins, dicyclopentadiene type phenol resins, and aralkyl type phenol resins. Phenolic resin, etc.

In the thermosetting agent (B2), examples of the amine-based curing agent having an amine group include dicyandiamine (hereinafter, abbreviated as "DICY") and the like.

The thermosetting agent (B2) may have an unsaturated hydrocarbon group.

As the thermosetting agent (B2) 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 directly bonded to the aromatic ring of the phenol resin Compounds and so on.

The aforementioned unsaturated hydrocarbon group in the thermosetting agent (B2) is the same as the unsaturated hydrocarbon group in the aforementioned epoxy resin having an unsaturated hydrocarbon group.

In the case of using a phenolic curing agent as the thermosetting agent (B2), in terms of improving the peelability of the protective film from the supporting sheet, the thermosetting agent (B2) is preferably a phenol with a high softening point or glass transition temperature. Department of hardener.

In the thermosetting agent (B2), for example, the number average molecular weight of resin components such as polyfunctional phenol resin, novolak type phenol resin, dicyclopentadiene type phenol resin, and aralkyl type phenol resin is preferably 300 or more and 30,000 or less , More preferably more than 400 and less than 10,000, more preferably more than 500 and less than 3,000.

In the thermosetting agent (B2), for example, the molecular weight of non-resin components such as biphenol and dicyandiamine is not particularly limited. For example, it is preferably 60 or more and 500 or less.

The thermosetting agent (B2) may be used alone or in combination of two or more; when two or more of them are used in combination, the combination and ratio of these can be arbitrarily selected.

In the composition (III-1) and the film for forming a thermosetting protective film, the content of the thermosetting agent (B2) is 100 parts by mass relative to the content of the epoxy resin (B1), preferably 0.1 parts by mass or more and 500 parts by mass Hereinafter, it is more preferably 1 part by mass or more and 200 parts by mass or less. For example, it may be any of 1 part by mass or more and 100 parts by mass or less, 1 part by mass or more and 50 parts by mass or less, and 1 part by mass or more and 10 parts by mass or less. When the aforementioned content of the thermosetting agent (B2) is equal to or greater than the aforementioned lower limit, the film for forming a thermosetting protective film can be cured more easily. In addition, when the aforementioned content of the thermosetting agent (B2) is below the aforementioned upper limit, the moisture absorption rate of the thermosetting protective film formation film is reduced, and the reliability of the package obtained by using the protective film formation composite sheet is further improved. .

In the composition (III-1) and the film for forming a thermosetting protective film, thermosetting The content of the sexual component (B) (for example, the total content of the epoxy resin (B1) and the thermosetting agent (B2)) relative to the content of the polymer component (A) is 100 parts by mass, preferably 20 parts by mass or more and 500 parts by mass Parts or less, more preferably 30 parts by mass or more and 300 parts by mass or less, and particularly preferably 40 parts by mass or more and 150 parts by mass or less. When the aforementioned content of the thermosetting component (B) is in this range, the adhesion between the protective film and the support sheet is suppressed, and the peelability of the support sheet is improved.

[Hardening accelerator (C)]

The composition (III-1) and the film for forming a thermosetting protective film may contain a curing accelerator (C). The hardening accelerator (C) is a component for adjusting the hardening speed of the composition (III-1).

As a preferable hardening accelerator (C), for example, tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, and tris(dimethylaminomethyl)phenol can be cited; 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5- Imidazoles such as hydroxymethylimidazole (imidazoles in which one or more hydrogen atoms are replaced by groups other than hydrogen atoms); organic phosphines such as tributylphosphine, diphenylphosphine, and triphenylphosphine (more than one Phosphine in which hydrogen atoms are replaced by organic groups); tetraphenyl boron salts such as tetraphenyl phosphonium tetraphenyl borate, triphenyl phosphine tetraphenyl borate, etc.

The curing accelerator (C) contained in the composition (III-1) and the film for forming a thermosetting protective film may be only one type or two or more types; in the case of two or more types, a combination of these And the ratio can be chosen arbitrarily.

In the case of using the curing accelerator (C), the content of the curing accelerator (C) in the composition (III-1) and the film for forming a thermosetting protective film is relative to the content of the thermosetting component (B) 100 The parts by mass are preferably 0.01 parts by mass or more and 10 parts by mass or less, more preferably 0.1 parts by mass or more and 7 parts by mass or less. When the aforementioned content of the hardening accelerator (C) is more than the aforementioned lower limit, a significant effect of using the hardening accelerator (C) can be obtained. In addition, since the content of the hardening accelerator (C) is below the aforementioned upper limit, for example, the hardening accelerator (C) with high polarity is prevented from being in the film for forming a thermosetting protective film under high temperature and high humidity conditions. The effect of the transfer and segregation of the adhering body on the adhering interface side becomes higher, so that the reliability of the semiconductor wafer with the protective film obtained by using the composite sheet for forming the protective film is further improved.

[Filling material (D)]

The composition (III-1) and the film for forming a thermosetting protective film may contain a filler (D). When the thermosetting protective film forming film contains the filler (D), the protective film obtained by curing the thermosetting protective film forming film can easily adjust the thermal expansion coefficient so that the thermal expansion coefficient is relative to the object to be formed of the protective film Most preferably, the reliability of the semiconductor wafer with a protective film obtained by using the composite sheet for forming a protective film is further improved. In addition, when the film for forming a thermosetting protective film contains the filler (D), the moisture absorption rate of the protective film can be reduced or the heat dissipation can be improved.

The filling material (D) can be either organic filling material or inorganic filling material One is preferably an inorganic filler 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 material is preferably silica or alumina.

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

When the filler (D) is used, the content of the filler (D) in the composition (III-1) (that is, the content of the filler (D) in the film for forming a thermosetting protective film) is relative to The ratio of the total content of all components other than the solvent is preferably 5% by mass or more and 80% by mass or less, more preferably 7% by mass or more and 60% by mass or less. When the content of the filler (D) is in this range, it is easier to adjust the thermal expansion coefficient.

[Coupling agent (E)]

The composition (III-1) and the film for forming a thermosetting protective film may contain a coupling agent (E). By using a compound having a functional group that can react with an inorganic compound or an organic compound as the coupling agent (E), the adhesion and adhesion of the film for forming a thermosetting protective film to the adherend can be improved. In addition, by Using the coupling agent (E), the film obtained by curing the film for forming a thermosetting protective 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 polymer component (A) and the thermosetting component (B), and more preferably a 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 Oxyoxysilane, 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 triacetoxysilane, imidazole silane, etc.

The coupling agent (E) contained in the composition (III-1) and the film for forming a thermosetting protective film may be only one type or two or more types; in the case of two or more types, the combination of these and The ratio can be selected arbitrarily.

When coupling agent (E) is used, composition (III-1) and thermosetting In the protective film forming film, the content of the coupling agent (E) relative to 100 parts by mass of the total content of the polymer component (A) and the thermosetting component (B), preferably 0.03 parts by mass or more and 20 parts by mass or less, more It is preferably 0.05 parts by mass or more and 10 parts by mass or less, and particularly preferably 0.1 parts by mass or more and 5 parts by mass or less. 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 film for forming a thermosetting protective film and the adherend is improved. In addition, when the aforementioned content of the coupling agent (E) is not more than the aforementioned upper limit, the generation of outgassing can be further suppressed.

[Crosslinking agent (F)]

When using the above-mentioned acrylic resins with functional groups capable of bonding with other compounds, such as vinyl groups, (meth)acrylic groups, amino groups, hydroxyl groups, carboxyl groups, isocyanate groups, etc., as the polymer component (A) When the composition (III-1) and the film for forming a thermosetting protective film may also contain a crosslinking agent (F), the crosslinking agent (F) is used to bond the aforementioned functional groups with other compounds to perform crosslinking. United. By crosslinking with the crosslinking agent (F), the initial adhesive force and cohesive force of the film for forming a thermosetting protective film can be adjusted.

Examples of the crosslinking agent (F) include: organic polyisocyanate compounds, organic polyimine compounds, metal chelate crosslinking agents (crosslinking agents having a metal chelate structure), 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. The reactant of the low-molecular-weight active hydrogen compound, as an example of the aforementioned adduct, includes the xylylene diisocyanate adduct of trimethylolpropane described below, and the like. In addition, the so-called "terminal isocyanate urethane prepolymer" is as described above.

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, Any one or more of hexamethylene diisocyanate and xylylene diisocyanate The compound; lysine diisocyanate and so on.

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(1-aziridinylmethamine) triethylene Based on melamine and so on.

When an organic polyvalent isocyanate compound is used as the crosslinking agent (F), it is preferable to use a hydroxyl group-containing polymer as the polymer component (A). In the case where the crosslinking agent (F) has an isocyanate group and the polymer component (A) has a hydroxyl group, the crosslinking structure can be easily introduced by the reaction between the crosslinking agent (F) and the polymer component (A) In the film for forming a thermosetting protective film.

The composition (III-1) and the crosslinking agent (F) contained in the film for forming a thermosetting protective film may be only one type or two or more types; in the case of two or more types, a combination of these 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 composition (III-1) relative to the content of the polymer component (A) is 100 parts by mass, preferably 0.01 parts by mass or more 20 parts by mass or less, more preferably 0.1 parts by mass or more and 10 parts by mass or less, and particularly preferably 0.5 parts by mass or more and 5 parts by mass or less. 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. In addition, by cross-linking The aforementioned content of the agent (F) is not more than the aforementioned upper limit, and the use of excessive crosslinking agent (F) can be suppressed.

[Energy ray curable resin (G)]

The composition (III-1) may contain an energy ray curable resin (G). By containing the energy-ray-curable resin (G), the film for forming a thermosetting protective film can change its properties by irradiating energy rays.

The energy ray curable resin (G) is obtained by polymerizing (curing) an energy ray curable compound.

Examples of the aforementioned energy ray curable compound include compounds having at least one polymerizable double bond in the molecule, and acrylate-based compounds having a (meth)acryloyl group are preferred.

Examples of the acrylate-based compound include trimethylolpropane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, and pentaerythritol tetra(meth)acrylate. Base) acrylate, dipentaerythritol monohydroxy penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 1,4-butanediol two(meth)acrylate, 1,6-hexanediol two (Meth)acrylates containing chain aliphatic skeletons such as (meth)acrylates; (meth)acrylates containing cyclic aliphatic skeletons such as dicyclopentyl di(meth)acrylate; polyethylene glycol Di(meth)acrylate and other polyalkylene glycol (meth)acrylate; oligoester (meth)acrylate; (meth)acrylate urethane oligomer; epoxy modified (former Base) acrylate; the aforementioned polyalkylene group Polyether (meth)acrylates other than glycol (meth)acrylates; itaconic acid oligomers, etc.

The weight average molecular weight of the aforementioned energy ray curable compound is preferably 100 or more and 30,000 or less, more preferably 300 or more and 10,000 or less. Here, the so-called "weight average molecular weight" is as described above.

The aforementioned energy ray curable compound used for polymerization may be only one type or two or more types; in the case of two or more types, the combination and ratio of these can be arbitrarily selected.

The energy ray curable resin (G) contained in the composition (III-1) may be only one type or two or more types; in the case of two or more types, the combination and ratio of these can be arbitrarily selected.

In the composition (III-1), the content of the energy ray curable resin (G) is preferably 1% by mass or more and 95% by mass or less, more preferably 5% by mass or more and 90% by mass or less, and particularly preferably 10% by mass or more 85% by mass or less.

[Photopolymerization initiator (H)]

When the composition (III-1) contains the energy ray curable resin (G), in order to efficiently polymerize the energy ray curable resin (G), it may contain a photopolymerization initiator (H).

Examples of the photopolymerization initiator (H) in the composition (III-1) include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, and benzoin methyl benzoate. Esters, benzoin dimethyl ketal and other benzoin compounds; acetophenone, 2-hydroxy-2-methyl-1-phenyl-propane-1-one, 2,2-dimethoxy-1,2-di Acetophenone compounds such as phenylethane-1-one; bis(2,4,6-trimethylbenzyl) phenyl phosphine oxide, 2,4,6-trimethylbenzyl diphenyl Phosphine oxide and other sulfide compounds; sulfide compounds such as benzyl phenyl sulfide and tetramethylthiuram monosulfide; α-keto alcohol compounds such as 1-hydroxycyclohexyl phenyl ketone; azobisisobutyl Azo compounds such as nitriles; titanocene compounds such as titanocene; thioxanthone compounds such as thioxanthone; peroxide compounds; diketone compounds such as diacetyl; ; 2,4-Diethylthioxanthone; 1,2-diphenylmethane; 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl] acetone; 2- Chloroanthraquinone and so on.

In addition, examples of the photopolymerization initiator include quinone compounds such as 1-chloroanthraquinone; photosensitizers such as amines.

The photopolymerization initiator (H) contained in the composition (III-1) may be only one type or two or more types; in the case of two or more types, the combination and ratio of these can be arbitrarily selected.

In the composition (III-1), the content of the photopolymerization initiator (H) relative to 100 parts by mass of the energy ray curable resin (G) is preferably 0.1 parts by mass or more and 20 parts by mass or less, more preferably 1 part by mass or more and 10 parts by mass or less, More preferably, it is 2 parts by mass or more and 5 parts by mass or less.

[Colorant (I)]

The composition (III-1) and the film for forming a thermosetting protective film may contain a coloring agent (I).

As a coloring agent (I), 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, thiols Indigo dyes, metal complex dyes (metal complex salt dyes), dithiol metal complex dyes, indoxyphenol dyes, triallylmethane dyes, anthraquinone dyes, naphthol dyes , Methine azo pigments, benzimidazolone pigments, pyranthrone pigments and threne colors, 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 (I) contained in the composition (III-1) and the film for forming a thermosetting protective film may be only one type or two or more types; in the case of two or more types, the combination of these and The ratio can be selected arbitrarily.

When using the coloring agent (I), the content of the coloring agent (I) in the film for forming a thermosetting protective film may be appropriately adjusted according to the purpose. For example, by adjusting the content of the coloring agent (I) in the film for forming a thermosetting protective film to adjust the light transmittance of the protective film, the visibility of printing when laser printing is performed on the protective film can be adjusted. In addition, by adjusting the content of the coloring agent (I) in the film for forming a thermosetting protective film, the design of the protective film can be improved, or the grinding marks on the back surface of the semiconductor wafer can be made difficult to see. Considering this aspect, the ratio of the content of the colorant (I) in the composition (III-1) to the total content of all components other than the solvent (that is, the coloring in the film for forming a thermosetting protective film) The content of the agent (I) is preferably from 0.1% by mass to 10% by mass, more preferably from 0.1% by mass to 7.5% by mass, and particularly preferably from 0.1% by mass to 5% by mass. When the aforementioned content of the colorant (I) is above the aforementioned lower limit, more significant effects brought about by the use of the colorant (I) can be obtained. In addition, when the aforementioned content of the coloring agent (I) is equal to or less than the aforementioned upper limit value, it is possible to suppress an excessive decrease in the light transmittance of the film for forming a thermosetting protective film.

[General additives (J)]

The composition (III-1) and the film for forming a thermosetting protective film may contain general additives (J) within a range that does not impair the effects of the present embodiment.

The general additives (J) can be well-known additives, and can be arbitrarily selected according to the purpose, and are not particularly limited. Preferred general additives (J) include, for example, plasticizers, antistatic agents, antioxidants, and getters. (gettering agent) and so on.

The general additives (J) contained in the composition (III-1) and the film for forming a thermosetting protective film may be only one type or two or more types; in the case of two or more types, the combination of these and The ratio can be selected arbitrarily.

The content of the general additive (J) in the composition (III-1) and the film for forming a thermosetting protective film is not particularly limited, and may be appropriately selected according to the purpose.

[Solvent]

It is preferable that the composition (III-1) further contains a solvent. The solvent-containing composition (III-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, isobutanol (2-methylpropane-1-ol), 1 -Alcohols such as butanol; esters such as ethyl acetate; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran; amides such as dimethylformamide and N-methylpyrrolidone (compounds with amide bonds )Wait.

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

The solvent contained in the composition (III-1) is preferably methyl ethyl ketone or the like in terms of mixing the components contained in the composition (III-1) more uniformly.

<<Manufacturing method of composition for forming thermosetting protective film>>

The composition for forming a thermosetting protective film, such as the composition (III-1), is obtained by blending each component that constitutes the composition.

The order of addition when formulating 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 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; mixing by applying ultrasonic waves The method and so on.

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 may be adjusted appropriately. The temperature is preferably 15°C or higher and 30°C or lower.

○Film for forming energy ray curable protective film

The film for forming an energy ray curable protective film contains an energy ray curable component (a).

In the film for forming an energy ray curable protective film, the energy ray curable component (a) is preferably uncured, preferably has adhesiveness, and more preferably has uncured and adhesiveness. Here, the so-called "energy line" and "energy line hardening" are as described above.

The film for forming energy ray curable protective film may have only one layer (single layer) or plural layers of two or more layers. In the case of plural layers, these plural layers may be the same or different from each other. These plural layers The combination is not particularly limited.

The thickness of the film for forming an energy ray curable protective film is preferably 1 μm or more and 100 μm or less, more preferably 5 μm or more and 75 μm or less, and particularly preferably 5 μm or more and 50 μm or less. When the thickness of the film for forming an energy ray curable protective film is more than the aforementioned lower limit, a protective film with higher protection ability can be formed. In addition, when the thickness of the film for forming an energy ray curable protective film is not more than the aforementioned upper limit, it is possible to suppress excessive thickness.

Here, the "thickness of the film for forming an energy ray curable protective film" means the overall thickness of the film for forming an energy ray curable protective film, for example, the thickness of the film for forming an energy ray curable protective film composed of multiple layers The thickness means the total thickness of all layers constituting the film for forming an energy ray curable protective film. In addition, as a method of measuring the thickness of the film for forming an energy ray curable protective film, for example, the following method can be cited: the thickness is measured at any 5 locations using a contact thickness meter, and the average of the measured values is calculated.

Regarding the curing conditions when the energy ray curable protective film formation film is attached to the back surface of the semiconductor wafer and cured to form the protective film, as long as the protective film has a degree of curing that can fully perform the function of the protective film, there is no It is specifically limited, and what is necessary is just to select suitably according to the kind of film for energy-beam curable protective film formation.

For example, energy ray curable protective film when a cured film is formed, the illumination energy ray is preferably of 120mW / cm ² or more 280mW / cm ² or less. In addition, during the aforementioned curing, the light intensity of the energy ray is preferably 200 mJ/cm ² or more and 1000 mJ/cm ² or less.

<<Energy ray curable protective film formation composition>>

The film for forming an energy ray curable protective film can be formed using a composition for forming an energy ray curable protective film containing the constituent material of the film. For example, a composition for forming an energy ray curable protective film is applied to the surface to be formed of the film for forming an energy ray curable protective film, and the composition for forming an energy ray curable protective film is dried as necessary, thereby achieving a target A film for forming an energy ray curable protective film is formed at the site. The content ratio of the components that do not vaporize at room temperature in the composition for forming an energy ray curable protective film is usually the same as the content ratio of the aforementioned components in the film for forming an energy ray curable protective film. Here, the so-called "normal temperature" is as explained above.

The application of the composition for forming an energy ray curable protective film can be performed by, for example, the same method as the application of the above-mentioned adhesive composition.

The drying conditions of the composition for forming an energy ray curable protective film are not particularly limited, but when the composition for forming an energy ray curable protective film contains a solvent described later, it is preferable to heat and dry. In this case, preferably Drying is performed under conditions of, for example, 70°C or higher and 130°C or lower and 10 seconds or longer and 5 minutes or shorter.

<Composition for forming energy ray curable protective film (IV-1)>

As a composition for forming an energy ray curable protective film, for example, the composition for forming an energy ray curable protective film (IV-1) containing the aforementioned energy ray curable component (a) (in this specification, sometimes only abbreviated "Composition (IV-1)") etc.

[Energy ray curable component (a)]

The energy-ray curable component (a) is a component that is cured by irradiating energy rays. The component is used to impart film-forming properties or flexibility to the energy-ray-curable protective film forming film, and to form a hard protection after curing membrane.

As the energy ray curable component (a), for example, a polymer (a1) having an energy ray curable group and a weight average molecular weight of 80,000 or more and 2,000,000 or less, and a polymer having an energy ray curable group and having a molecular weight of 100 or more and 80,000 or less Compound (a2). The aforementioned polymer (a1) may or may not be crosslinked by crosslinking at least a part of the polymer by a crosslinking agent.

(Polymer (a1) with an energy-ray curable base and a weight average molecular weight of 80,000 or more and 2,000,000 or less)

As the polymer (a1) having an energy-ray curable group and having a weight average molecular weight of 80,000 or more and 2,000,000 or less, for example, acrylic resin (a1-1) can be cited. The acrylic resin (a1-1) is an acrylic polymer (a11) is formed by reacting with an energy ray curable compound (a12), the acrylic polymer (a11) has a functional group that can react with groups possessed by other compounds, and the energy ray curable compound (a12) has Energy-ray-curable groups such as the aforementioned functional group-reactive groups and energy-ray-curable 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 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. Regarding the polymerization method, a known method may also be adopted.

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-hydroxymethyl (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, 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 methacrylate, etc. (form Group) carboxyalkyl acrylate and the like.

The acrylic monomer having the aforementioned functional group is 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 types or more In the above situation, the combination and ratio of these can be selected arbitrarily.

Examples of the aforementioned acrylic monomer having no functional group include: 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 (lauryl (meth)acrylate) , Tridecyl (meth)acrylate, tetradecyl (meth)acrylate (myristyl (meth)acrylate), pentadecyl (meth)acrylate, ten (meth)acrylate Alkyl esters such as hexaalkyl ester (palmityl (meth)acrylate), heptadecyl (meth)acrylate, stearyl (meth)acrylate (stearyl (meth)acrylate), etc. The alkyl group is an alkyl (meth)acrylate with a chain structure of 1 to 18 carbon atoms.

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 alkoxy alkyl groups such as ethoxyethyl (meth)acrylate; those containing aryl (meth)acrylates such as phenyl (meth)acrylate, etc. (Meth)acrylate; non-crosslinkable (meth)acrylamide and its derivatives; (A Non-crosslinkable (meth)acrylates with tertiary amino groups such as N,N-dimethylaminoethyl acrylate and N,N-dimethylaminopropyl (meth)acrylate.

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, the combination and ratio of these 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, the combination and ratio of these can be arbitrarily selected.

In the acrylic polymer (a11), the ratio (content) of the amount of the structural unit derived from the acrylic monomer having the functional group relative to the total amount of the structural unit constituting the acrylic polymer (a11) is preferred It is 0.1% by mass or more and 50% by mass or less, more preferably 1% by mass or more and 40% by mass or less, and particularly preferably 3% by mass or more and 30% by mass or less. 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 better range for the degree of hardening of the protective film.

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

In the composition (IV-1), the ratio of the content of the acrylic resin (a1-1) to the total content of the components other than the solvent (that is, the acrylic resin (a1) in the film for forming an energy ray curable protective film The content of -1)) is preferably 1% by mass to 70% by mass, more preferably 5% by mass to 60% by mass, and particularly preferably 10% by mass to 50% by mass.

‧Energy ray hardening compound (a12)

The aforementioned energy ray-curable compound (a12) preferably has one or two or more selected from the group consisting of isocyanate groups, epoxy groups, and carboxyl groups as those 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 one or more and five or less of the energy ray curable groups in one molecule, and more preferably has one or more and three or less.

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

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, the combination and ratio of these 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) Preferably it is 20 mol% or more and 120 mol% or less, more preferably 35 mol% or more and 100 mol% or less, and particularly preferably 50 mol% or more and 100 mol% or less. When the ratio of the aforementioned content is in this range, the adhesive force of the cured protective film is further increased. 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 The linear curable compound (a12) is polyfunctional (having two or more of the aforementioned groups in one molecule) In the case of a 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 or more and 2,000,000 or less, more preferably 300,000 or more and 1,500,000 or less.

Here, the so-called "weight average molecular weight" is as described above.

In the case where at least a part of the aforementioned polymer (a1) is crosslinked by a crosslinking agent, the aforementioned polymer (a1) can be any monomer constituting the aforementioned acrylic polymer (a11) that does not meet the above description and A monomer having a group that reacts with a crosslinking agent is polymerized and crosslinked in the aforementioned group that reacts with the crosslinking agent. It may also be a group derived from the aforementioned energy ray curable compound (a12) that reacts with the aforementioned functional group. Cross-linking in the middle.

The aforementioned polymer (a1) contained in the composition (IV-1) and the film for forming an energy ray curable protective 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 chosen arbitrarily.

(Compound (a2) having an energy-ray curable group and a molecular weight of 100 or more and 80,000 or less)

Examples of the energy-ray-curable group possessed by the compound (a2) having an energy-ray-curable group and a molecular weight of 100 or more and 80,000 or less include a group containing an energy-ray-curable double bond, and a preferable group includes :(First Base) Acrylic, 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.

[0002]

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)acryloyloxypolypropoxy)phenyl]propane, tricyclodecane dimethanol di(meth)acrylate, 1 , 10-decanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, dipropylene glycol di(meth) )Acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polybutylene glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylenedi Alcohol di(meth)acrylate, triethylene glycol di(meth)acrylate, 2,2-bis[4-((meth)acryloyloxyethoxy)phenyl]propane, neopentadiene Alcohol bis (meth) propylene Acid ester, ethoxylated polypropylene glycol di(meth)acrylate, 2-hydroxy-1,3-di(meth)acryloxypropane and other bifunctional (meth)acrylates; three isocyanuric acid (2-(meth)acryloxyethyl) ester, ε-caprolactone modified tris-(2-(meth)acryloxyethyl) isocyanurate, ethoxylated glycerin Tri(meth)acrylate, pentaerythritol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, di-trimethylolpropane tetra(meth)acrylate, ethoxylated pentaerythritol Multifunctional (meth)acrylates such as tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol poly(meth)acrylate, dipentaerythritol hexa(meth)acrylate, etc.; (meth) Polyfunctional (meth)acrylate oligomers such as acrylic 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 paragraph 0043 in "Japanese Patent Laid-Open No. 2013-194102" can be used. Recorded resin. Such resin also corresponds to the resin constituting the thermosetting component described later, but it is regarded as the aforementioned compound (a2) in this embodiment.

The weight average molecular weight of the aforementioned compound (a2) is preferably 100 or more and 30,000 or less, more preferably 300 or more and 10,000 or less. Here, the so-called "weight average molecular weight" is as described above.

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

[Polymer without energy ray curable base (b)]

When the composition (IV-1) and the film for forming an energy ray curable protective film contain the aforementioned compound (a2) as the aforementioned energy ray curable component (a), it is preferable to further contain a group that does not have energy ray curable The polymer (b).

The aforementioned polymer (b) may be crosslinked at least partially by a crosslinking agent, or may not be crosslinked.

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. Wait.

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 (lauryl (meth)acrylate), (meth)acrylate Base) tridecyl acrylate, tetradecyl (meth)acrylate (myristyl (meth)acrylate), pentadecyl (meth)acrylate, hexadecyl (meth)acrylate Ester (palmityl (meth)acrylate), heptadecyl (meth)acrylate, stearyl (meth)acrylate (stearyl (meth)acrylate), etc. constitute the alkyl group of the alkyl ester It is an alkyl (meth)acrylate with a chain structure of 1 to 18 carbon atoms, etc.

Examples of (meth)acrylates having a cyclic skeleton include cycloalkyl (meth)acrylates such as isobornyl (meth)acrylate and dicyclopentyl (meth)acrylate; (meth) ) Aralkyl (meth)acrylates such as benzyl acrylate; cycloalkenyl (meth)acrylates such as dicyclopentenyl (meth)acrylate; dicyclopentenyloxyethyl (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.

Examples of the hydroxyl-containing (meth)acrylates include: hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, (meth) ) 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 partially cross-linked by a cross-linking agent and does not have the aforementioned energy ray curable group include: polymerization in which the reactive functional group in the aforementioned polymer (b) reacts with the cross-linking agent Things.

The aforementioned reactive functional group may be appropriately selected according to the kind of crosslinking agent, etc., and is not particularly limited. For example, when the crosslinking agent is a polyisocyanate compound, as the aforementioned reactive functional group, a hydroxyl group, a carboxyl group, an amino group, etc. can be mentioned. Among these, a hydroxyl group having high reactivity with an isocyanate group is preferred. In addition, when the crosslinking agent is an epoxy-based compound, the reactive functional group may include a carboxyl group, an amino group, an amide group, etc., among these, Preferably, it is a carboxyl group having high reactivity with an epoxy group. 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), any one 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) Preferably it is 1 mass% or more and 20 mass% or less, More preferably, it is 2 mass% or more and 10 mass% or less. When the aforementioned ratio is in such a range, the degree of crosslinking in the aforementioned polymer (b) becomes a more preferable range.

As far as the film forming properties of the composition (IV-1) are better, it does not have The weight average molecular weight (Mw) of the energy-ray curable polymer (b) is preferably 10,000 or more and 2,000,000 or less, more preferably 100,000 or more and 1,500,000 or less. Here, the so-called "weight average molecular weight" is as described above.

The composition (IV-1) and the polymer (b) that does not have an energy ray curable group contained in the film for forming an energy ray curable protective film may be only one type, or two or more types; in two types In the above case, the combination and ratio of these can be arbitrarily selected.

As the composition (IV-1), a composition containing either or both of the aforementioned polymer (a1) and aforementioned compound (a2) can be cited. In addition, when the 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, and in this case, it is also preferable to further contain The foregoing (a1). In addition, the composition (IV-1) may not contain the above-mentioned compound (a2), and may also contain the above-mentioned polymer (a1) and the polymer (b) which does not have an energy-ray curable group.

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

In the composition (IV-1), the total content of the aforementioned energy ray curable component (a) and the polymer (b) that does not have an energy ray curable group (that is, the total content of the energy ray curable protective film forming film 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 is preferably from 5 mass% to 90 mass%, It is more preferably 10% by mass or more and 80% by mass or less, and particularly preferably 20% by mass or more and 70% by mass or less. When the aforementioned ratio of the content of the energy ray curable component is in such a range, the energy ray curability of the film for forming an energy ray curable protective film becomes better.

In the composition (IV-1), in addition to the aforementioned energy ray curable component, it may also contain a thermosetting component, a filler, a coupling agent, a crosslinking agent, a photopolymerization initiator, a coloring agent, and One or more of the group consisting of general additives. For example, by using the composition (IV-1) containing the aforementioned energy ray curable component and thermosetting component, the formed film for forming an energy ray curable protective film improves the adhesion to the adherend by heating , The strength of the protective film formed from the film for forming the energy ray curable protective film is also improved.

As the aforementioned thermosetting component, filler, coupling agent, crosslinking agent, photopolymerization initiator, coloring agent, and general additives in the composition (IV-1), there may be mentioned: respectively and the protective film forming composition ( III-1) Thermosetting component (B), filler (D), coupling agent (E), crosslinking agent (F), photopolymerization initiator (H), coloring agent (I) and general additives (J) The same compound.

In the composition (IV-1), the aforementioned thermosetting components, fillers, coupling agents, crosslinking agents, photopolymerization initiators, colorants, and general additives may be used individually or in combination of two or more; When two or more types are used in combination, the combination and ratio of these can be arbitrarily selected.

The content of the aforementioned thermosetting component, filler, coupling agent, crosslinking agent, photopolymerization initiator, coloring agent, and general additives in the composition (IV-1) may be appropriately adjusted according to the purpose, and is not particularly limited.

In terms of improving the workability of the composition by dilution, the composition (IV-1) preferably further contains a solvent.

Examples of the solvent contained in the composition (IV-1) include the same solvents as the solvent in the composition (III-1).

The solvent contained in the composition (IV-1) may be only one type or two or more types.

<<Method for manufacturing composition for forming energy ray curable protective film>>

A composition for forming an energy ray curable protective film, such as the composition (IV-1), can be obtained by blending each component that constitutes the composition.

The order of addition when formulating 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 Tune The formulation components are diluted in advance and the solvent is mixed with these formulation components.

The method of mixing each component during compounding is not particularly limited, and 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; mixing by applying ultrasonic waves The method and so on.

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 may be adjusted appropriately. The temperature is preferably 15°C or higher and 30°C or lower.

○Film for forming non-curing protective film

As a preferable film for forming a non-curable protective film, for example, it contains a non-curable component (c). In the non-curable protective film formation film, the non-curable component (c) does not have curability. The non-curable protective film formation film preferably has adhesiveness to the support sheet and is used to protect semiconductor wafers or chips. Moderate hardness. Here, the so-called "non-curing property" is as described above.

The film for forming a non-curable protective film may be only one layer (single layer), or plural layers of two or more layers. In the case of plural layers, these plural layers may be the same or different from each other. The combination is not particularly limited.

The thickness of the film for forming a non-curable protective film is preferably 1 μm or more and 100 μm or less, more preferably 5 μm or more and 75 μm or less, and particularly preferably 5 μm or more and 50 μm or less. When the thickness of the film for forming a non-curable protective film is greater than or equal to the aforementioned lower limit, a protective film with higher protective ability can be formed. Other In addition, when the thickness of the film for forming a non-curable protective film is not more than the aforementioned upper limit, it is possible to suppress excessive thickness.

Here, the "thickness of the non-curable protective film formation film" means the thickness of the entire non-curable protective film formation film, for example, the thickness of the non-curable protective film formation film composed of multiple layers means Refers to the total thickness of all layers constituting the film for forming a non-curable protective film. In addition, as a method of measuring the thickness of the film for forming a non-curable protective film, for example, the following method can be cited: the thickness is measured at any 5 locations using a contact thickness meter, and the average of the measured values is calculated.

<<Composition for forming non-curable protective film>>

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

The coating of the composition for forming a non-curable protective film can be performed, for example, by the same method as in the case of coating the adhesive composition described above.

The drying conditions of the composition for forming a non-curable protective film are not particularly limited. When the composition for forming a non-curable protective film contains a solvent described later, it is preferable to heat and dry it. In this case, it is preferably, for example, Drying is performed under the conditions of 70°C or more and 130°C or less and 10 seconds or more and 5 minutes or less.

<Composition for forming non-curable protective film (V-1)>

As a composition for forming a non-curable protective film, for example, a composition for forming a non-curable protective film containing a non-curable component (c) (V-1) (in this specification, sometimes simply referred to as "composition (V-1)”) etc.

The non-curable component (c) is a thermoplastic resin, for example, an acrylic polymer etc. are mentioned, but it is not limited to these. Examples of the aforementioned acrylic polymer include the same polymers as those exemplified as the aforementioned acrylic polymer (b-1).

In the composition (V-1), in addition to the aforementioned non-curing component (c), it may also contain selected from the group consisting of fillers, coupling agents, crosslinking agents, colorants, and general additives according to the purpose. One kind or two or more kinds.

As the aforementioned filler, coupling agent, crosslinking agent, colorant, and general additives in the composition (V-1), the filler (D) and the coupling agent (E) in the composition (III-1) can be used. ), the same compound as the crosslinking agent (F), coloring agent (I) and general additives (J).

In the composition (V-1), the aforementioned fillers, coupling agents, crosslinking agents, colorants, and general additives may be used singly, or two or more of them may be used in combination; when two or more of these are used in combination, The combination and ratio can be chosen arbitrarily.

The content of the aforementioned filler, coupling agent, crosslinking agent, coloring agent, and general additives in the composition (V-1) may be appropriately adjusted according to the purpose, and is not particularly limited.

In terms of improving the workability of the composition by dilution, the composition (V-1) preferably further contains a solvent.

Examples of the solvent contained in the composition (V-1) include the same solvents as the solvent in the composition (III-1).

The solvent contained in the composition (V-1) may be only one type or two or more types.

<<Method for manufacturing composition for forming non-curable protective film>>

The composition for forming a non-curable protective film, such as the composition (V-1), is obtained by blending each component for constituting the 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 Tune The formulation components are diluted in advance and the solvent is mixed with these formulation components.

The method of mixing each component during compounding is not particularly limited, and 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; mixing by applying ultrasonic waves The method and so on.

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 may be adjusted appropriately. The temperature is preferably 15°C or higher and 30°C or lower.

In one aspect of the present invention, a composite sheet for forming a protective film is sequentially laminated with a film for forming a protective film containing the components shown below, an adhesive layer containing the components shown below, and a base material with the configuration shown below .

Specifically, the protective film formation film contains: as the polymer component (A)-1, an acrylic polymer obtained by copolymerizing 85 parts by mass of methyl acrylate and 15 parts by mass of 2-hydroxyethyl acrylate (weight Average molecular weight: 350,000 to 400,000, preferably 370,000, glass transition temperature: 3°C to 9°C, preferably 6°C) 100 parts by mass to 200 parts by mass, preferably 150 parts by mass; as epoxy resin (B1)-1 Bisphenol A epoxy resin (epoxy equivalent: 180g/eq to 200g/eq, preferably 184g/eq to 194g/eq) 50 parts by mass to 70 parts by mass, preferably 60 parts by mass Parts; as epoxy resin (B1)-2 bisphenol A type epoxy resin (epoxy equivalent: 750g/eq to 950g/eq, preferably 800g/eq to 900g/eq) 5 parts by mass to 15 parts by mass , Preferably 10 parts by mass; as epoxy resin (B1)-3 dicyclopentadiene type Epoxy resin (epoxy equivalent: 250g/eq to 270g/eq, preferably 255g/eq to 260g/eq) 20 parts by mass to 40 parts by mass, preferably 30 parts by mass; as a thermosetting agent (B2) Thermally active latent epoxy resin hardener (dicyandiamine, active hydrogen amount: 20g/eq to 25g/eq, preferably 21g/eq) 1 part by mass to 3 parts by mass, preferably 2 parts by mass; Hardening accelerator (C) of 2-phenyl-4,5-dihydroxymethylimidazole is 1 part by mass to 3 parts by mass, preferably 2 parts by mass; as filler (D), silica filler (average particle size) Diameter: 0.1 μm to 1 μm, preferably 0.5 μm) 300 parts by mass to 340 parts by mass, preferably 320 parts by mass; as the coupling agent (E), the silane coupling agent is 1 part by mass to 3 parts by mass, preferably 2 Parts by mass; and 16 parts by mass to 20 parts by mass of the black pigment as the colorant (I), preferably 18 parts by mass.

Specifically, the adhesive layer contains: as an acrylic polymer, 2-ethylhexyl acrylate (2EHA) (80 parts by mass) and 2-hydroxyethyl acrylate (HEA) (20 parts by mass) are copolymerized. A prepolymer with a weight average molecular weight of 800,000 is from 90 parts by mass to 110 parts by mass, preferably 100 parts by mass; and a trifunctional xylylene diisocyanate-based crosslinking agent is 35 parts by mass to 60 parts by mass, preferably 40 parts by mass. Parts by mass to 50 parts by mass.

Specifically, the substrate is a polypropylene film with a thickness of 70 μm to 90 μm, preferably 80 μm. Furthermore, the substrate has a matte surface (surface roughness (Ra): 0.20 μm to 1.30 μm, preferably 0.20 μm to 1.20 μm) and a glossy surface or a slightly matte surface (surface roughness (Ra): 0.05 μm to 0.15 μm, preferably 0.10 μm to 0.15 μm).

Furthermore, the aforementioned adhesive is laminated on the matte surface of the substrate.

Alternatively, the aforementioned substrate has a matte surface (surface roughness (Ra): 0.30 μm or less, preferably 0.20 μm) and a glossy surface or a slightly matte surface (surface roughness (Ra): 0.05 μm to 0.15 μm, preferably In the case of 0.10 μm to 0.15 μm), the aforementioned adhesive is laminated on the glossy surface or slightly matte surface of the substrate.

In addition, in one aspect of the present invention, the composite sheet for forming a protective film has a film for forming a protective film containing the above-mentioned components, an adhesive layer containing the components shown below, and a base material having the above-mentioned structure.

Specifically, the adhesive layer contains: as an acrylic polymer, 2-ethylhexyl acrylate (2EHA) (80 parts by mass) and 2-hydroxyethyl acrylate (HEA) (20 parts by mass) are copolymerized. The prepolymer with a weight average molecular weight of 800,000 is 90 to 110 parts by mass, preferably 100 parts by mass; the trifunctional xylylene diisocyanate crosslinking agent is 15 to 25 parts by mass, preferably 20 parts by mass Parts; and 5 parts by mass to 15 parts by mass of silicone resin fine particles, preferably 10 parts by mass.

In addition, in one aspect of the present invention, the composite sheet for forming a protective film has a film for forming a protective film containing the above-mentioned components, an adhesive layer containing the components shown below, and a base material having the above-mentioned structure.

Specifically, the adhesive layer contains: as an acrylic polymer 2-Ethylhexyl acrylate (2EHA) (80 parts by mass) and 2-hydroxyethyl acrylate (HEA) (20 parts by mass) copolymerized prepolymer with a weight average molecular weight of 800,000 90 parts by mass to 110 parts by mass Parts, preferably 100 parts by mass; 15 parts by mass to 25 parts by mass of trifunctional xylylene diisocyanate crosslinking agent, preferably 20 parts by mass; and 3 parts by mass to 30 parts by mass of epoxy resin, preferably It is 5 parts by mass to 25 parts by mass.

In addition, in one aspect of the present invention, the composite sheet for forming a protective film has a film for forming a protective film containing the above-mentioned components, an adhesive layer containing the components shown below, and a base material having the above-mentioned structure.

Specifically, the adhesive layer contains: as an acrylic polymer, 2-ethylhexyl acrylate (2EHA) (80 parts by mass) and 2-hydroxyethyl acrylate (HEA) (20 parts by mass) are copolymerized. The prepolymer with a weight average molecular weight of 800,000 is 90 to 110 parts by mass, preferably 100 parts by mass; the trifunctional xylylene diisocyanate crosslinking agent is 15 to 25 parts by mass, preferably 20 parts by mass Parts; and titanium oxide-based white pigment 3 parts by mass to 7 parts by mass, preferably 5 parts by mass.

In addition, in one aspect of the present invention, the composite sheet for forming a protective film has a film for forming a protective film containing the above-mentioned components, an adhesive layer containing the components shown below, and a base material having the above-mentioned structure.

Specifically, the adhesive layer contains: as an acrylic polymer 2-Ethylhexyl acrylate (2EHA) (80 parts by mass) and 2-hydroxyethyl acrylate (HEA) (20 parts by mass) copolymerized prepolymer with a weight average molecular weight of 800,000 90 parts by mass to 110 parts by mass Parts, preferably 100 parts by mass; 15 parts by mass to 25 parts by mass of the trifunctional xylylene diisocyanate crosslinking agent, preferably 20 parts by mass; and 5 parts by mass to 15 parts by mass of acrylic polymer fine particles, Preferably it is 10 parts by mass.

◇Method for manufacturing composite sheet for forming protective film

The above-mentioned composite sheet for forming a protective film can be produced by sequentially stacking the above-mentioned layers so as to have a corresponding positional relationship. The formation method of each layer is as described above.

For example, when manufacturing a composite sheet for forming a protective film, in the case where a film for forming a protective film is further laminated on the adhesive layer already laminated on the base material, a thermosetting protective film can be applied to the adhesive layer. The composition, the composition for forming an energy ray curable protective film, or the composition for forming a non-curable protective film, directly form the film for forming a protective film. 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, and forming the latter one of these two layers in advance, and then forming the Among the layers, the exposed surface on the opposite side to the side in contact with the release film is bonded to the exposed surface of the remaining layer that has already been formed. At this time, the aforementioned composition is preferably coated on the release film Peel off the treated surface. After the build-up structure is formed, the release film can be removed as necessary.

That is, in the case of manufacturing a composite sheet for forming a protective film, the adhesive composition is coated on the base material, and the adhesive composition is dried as necessary, thereby laminating the adhesive layer on the base material, separately from the release film Apply the composition for forming a thermosetting protective film, the composition for forming an energy ray curable protective film, or the composition for forming a non-curable protective film, and dry it as necessary to form a protective film on the release film Forming a film by laminating the exposed surface of the protective film forming film with the exposed surface of the adhesive layer laminated on the substrate, thereby laminating the protective film forming film on the adhesive layer to obtain a protective film Composite sheet for formation.

On the other hand, when the adhesive layer is laminated on the substrate, as described above, instead of applying the adhesive composition on the substrate, apply the adhesive composition on the release film and make the adhesive composition if necessary. The object is dried to form an adhesive layer on the release film, and the exposed surface of the adhesive layer is bonded to a surface of the substrate, whereby the adhesive layer can also be laminated on the substrate.

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

In this way, layers other than the base material (adhesive layer, protective film formation film) constituting the protective film forming composite sheet can be laminated by the following method, that is, preliminarily formed on the release film, and then bonded to the target layer Surface, so it is suitable to choose the layer that adopts this kind of step as necessary to make the protective film formation. The composite sheet is fine.

In addition, the composite sheet for forming a protective film is usually stored in a state in which the composite sheet for forming a protective film is bonded to the surface of the outermost layer (for example, the film for forming a protective film) on the side opposite to the supporting sheet in the composite sheet for forming a protective film There is a state of peeling film. Therefore, a composite sheet for forming a protective film can also be obtained by coating the release film (preferably the release-treated surface of the release film) with a composition for forming a thermosetting protective film , The composition for forming an energy-ray curable protective film, or a composition for forming a non-curable protective film, etc., used to form the composition that constitutes the outermost layer, and if necessary, dry it to form a structure on the release film For the outermost layer, on the exposed surface of the layer opposite to the side in contact with the release film, use any of the above methods to laminate the remaining layers without removing the release film and keep the attached state unchanged.

In addition, in this specification, the "release film" is a film with a peeling function, specifically, it refers to a film formed by attaching to a protective film in order to protect a film for forming a protective film before attaching to a semiconductor wafer or a support sheet. With the film on both surfaces of the film, the release film is peeled off during operation and used.

As the release film, for example, polyethylene film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film, vinyl chloride copolymer film, polyethylene terephthalate can be used. Diester film, polyethylene naphthalate film, polybutylene terephthalate film, polyurethane film, ethylene-vinyl acetate copolymer film, ionomer resin film, ethylene-(formaldehyde) Base) acrylic copolymer film, ethylene-(meth)acrylate copolymer film, polystyrene Transparent films such as films, polycarbonate films, polyimide films, and fluororesin films. In addition, these cross-linked films can also be used. Furthermore, it may also be a laminated film of these. In addition, these colored films, opaque films, etc. can be used. Examples of the release agent include release agents such as silicone-based, fluorine-based, and long-chain alkyl group-containing urethane.

The thickness of the release film is usually 10 μm or more and 500 μm or less, preferably 15 μm or more and 300 μm or less, and particularly preferably 20 μm or more and about 250 μm or less.

Here, the "thickness of the release film" means the thickness of the entire release film. For example, the thickness of the release film composed of a plurality of layers means the total thickness of all the layers constituting the release film. In addition, as a method of measuring the thickness of the release film, for example, the following method can be cited: the thickness is measured using a contact-type thickness meter at any 5 locations, and the average of the measured values is calculated.

◇How to use the composite sheet for forming protective film

The composite sheet for forming a protective film of this embodiment 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. Then, the film for forming a protective film is heated or irradiated with energy rays as necessary to harden the film for forming a protective film to become a protective film. Alternatively, in the case of a composition for forming a non-curable protective film contained in a film for forming a protective film, it can be used as a protective film while maintaining an uncured state. Then, by dicing, the semiconductor wafer together with the protective film Divide them together to make semiconductor wafers. Then, the semiconductor chip is kept in the state where the protective film is attached (that is, in the form of a semiconductor chip with a protective film), and is pulled away from the supporting sheet to be picked up.

Hereinafter, using the same method as the conventional method, the obtained semiconductor wafer of the semiconductor wafer with a protective film is flip-chip connected to the circuit surface of the substrate to form a semiconductor package. Then, the semiconductor package can be used to manufacture the target semiconductor device.

Furthermore, when the protective film formation film is heated or irradiated with energy rays to harden the protective film formation film, as described above, the time point of the curing may be before or after cutting. Among them, the time at which the film for forming a protective film is heated or irradiated with energy rays to harden the film for forming a protective film is preferably before cutting.

In addition, when the protective film formation film is heated or irradiated with energy rays to harden the protective film formation film, the time of laser printing may be before or after curing. Among them, when the protective film formation film is heated to harden the protective film formation film, the time point of laser printing is preferably after curing.

[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.

‧Polymer composition

(A)-1: An acrylic polymer obtained by copolymerizing 85 parts by mass of methyl acrylate and 15 parts by mass of 2-hydroxyethyl acrylate (weight average molecular weight: 370,000, glass transition temperature: 6°C).

‧Thermosetting component

(B1)-1: Bisphenol A epoxy resin (jER828 manufactured by Mitsubishi Chemical, epoxy equivalent 184g/eq to 194g/eq).

(B1)-2: Bisphenol A epoxy resin (jER1055 manufactured by Mitsubishi Chemical, epoxy equivalent 800g/eq to 900g/eq).

(B1)-3: Dicyclopentadiene epoxy resin (Epiclon HP-7200HH manufactured by Dainippon Ink Chemical Industry Co., Ltd., epoxy equivalent 255g/eq to 260g/eq).

(B2)-1: Thermally active latent epoxy resin hardener (dicyandiamine (Adeka Hardener EH-3636AS manufactured by ADEKA, active hydrogen amount 21g/eq)).

‧ Hardening accelerator

(C)-1: 2-Phenyl-4,5-dihydroxymethylimidazole (Curezol 2PHZ manufactured by Shikoku Chemical Industry Co., Ltd.).

‧Filling agent

(D)-1: Silica filler (SC2050MA manufactured by Admatechs, average particle size 0.5μm).

‧Coupling agent

(E)-1: Silane coupling agent (A-1110 manufactured by Nippon Unicar).

‧Colorant

(I)-1: Black pigment (manufactured by Dainichi Seika Co., Ltd.).

[Example 1]

<Manufacturing of Composite Sheet for Forming Protective Film>

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

In terms of solid weight ratio, polymer component (A)-1 (150 parts by mass), thermosetting component (B1)-1 (60 parts by mass), (B1)-2 (10 parts by mass), (B1) -3 (30 parts by mass), (B2)-1 (2 parts by mass), hardening accelerator (C)-1 (2 parts by mass), filler (D)-1 (320 parts by mass), coupling agent (E )-1 (2 parts by mass) and coloring agent (I)-1 (18 parts by mass) are dissolved or dispersed in a mixed solvent of methyl ethyl ketone, toluene and ethyl acetate, and stirred at 23°C, thereby A thermosetting protective film forming composition (III-1) was obtained.

(Manufacturing of Adhesive Composition (I-4)-1)

A non-energy-ray curable adhesive composition (I-4)-1 with a solid content concentration of 30% by mass was prepared. The adhesive composition (I-4)-1 contained an acrylic polymer (100 parts by mass, Solid content) and trifunctional xylylene diisocyanate crosslinking agent ("Takenate D110N" manufactured by Mitsui Takeda Chemical Co., Ltd.) (40 parts by mass (solid content)), and further contains methyl ethyl ketone as a solvent , Toluene and ethyl acetate mixed solvent. The aforementioned acrylic polymer is prepolymerized by copolymerizing 2-ethylhexyl acrylate (2EHA) (80 parts by mass) and 2-hydroxyethyl acrylate (HEA) (20 parts by mass) with a weight average molecular weight of 800,000 Things.

(Support film manufacturing)

Apply the adhesive composition (I-4)-1 obtained above to the peeling-off surface of the peeling film that was peeled off by silicone treatment on one side of the polyethylene terephthalate film, and Heat and dry at 120°C for 2 minutes to form a non-energy ray-curable adhesive layer with a thickness of 15 μm.

Then, on the exposed surface of the adhesive layer, a polypropylene film with a thickness of 80 μm (manufactured by Mitsubishi Plastics Co., Ltd., matte surface (surface roughness (Ra): 1.20 μm)/gloss surface (surface roughness (Ra): 0.10 μm) the matte surface of the substrate), thereby manufacturing the support sheet (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, with a thickness of 38μm) that is peeled off by silicone treatment is applied by knife coating. The protective film-forming composition (III-1) obtained above was machine-coated and dried at 100°C for 2 minutes to produce a thermosetting protective film-forming film (13)-1 with a thickness of 25 μm.

Then, the adhesive layer in the support sheet (10)-1 obtained above is bonded to the exposed surface of the protective film forming film (13)-1 obtained above to produce a base material, an adhesive layer, and a protective film The film for formation (13)-1 is a composite sheet for forming a protective film which is sequentially laminated in the thickness direction of these. Furthermore, in the produced composite sheet for forming a protective film, the width of the support sheet was 270 mm, and the outer diameter of the film for forming a protective film was 210 mm.

<Evaluation of Supporting Films>

(Haze evaluation)

Measured using "NDH-5000" manufactured by Nippon Denshoku Industry Co., Ltd. in accordance with JIS K 7136-2000. In addition, the measurement was performed with the configuration of the "base material + adhesive layer" in which the release film was peeled from the support sheet (10)-1. The results are shown in Table 1.

(Through the evaluation of clarity)

The measurement was performed using an image clarity measuring device "ICM-10P" manufactured by Suga Test Instruments (stock) in accordance with JIS K 7374-2007. The total value of 5 kinds of slits (slit width: 0.125mm, 0.25mm, 0.5mm, 1mm, and 2mm) is expressed as the clearness of transmission. In addition, the measurement was performed with the configuration of the "base material + adhesive layer" in which the release film was peeled from the support sheet (10)-1. The results are shown in Table 1.

<Evaluation of Composite Sheet for Forming Protective Film>

(Placement machine suitability (evaluation of alignment (with front-end position adjustment))

For the produced composite sheet and ring frame for forming the protective film, for an 8-inch semiconductor wafer (thickness: 200μm), use the placement machine RAD2700 manufactured by Lintec to confirm whether the tape tip position can be adjusted. The results are shown in Table 1.

In addition, the evaluation criteria for the suitability of the mounter were set as follows.

A‧‧‧Able to aim.

B‧‧‧ failed to align.

(Evaluation of the visibility of laser printing)

For the protective film forming film attached to the 8-inch semiconductor wafer, the laser printing device CSM300M manufactured by EO Technics is used to print on the protective film layer through the support sheet, and when it is observed visually, it is judged whether it is visible or not. Word. Printing is performed on the uncured protective film layer. The character size is set to 0.3mm×0.2mm. The results are shown in Table 1.

Furthermore, the evaluation criteria for the visibility of laser printing are set as follows.

A‧‧‧Able to see.

B‧‧‧Slightly blurred but visible.

C‧‧‧ could not be recognized.

(Evaluation of the thickness of printed text)

For the protective film formation film attached to the 8-inch semiconductor wafer, use an ultraviolet irradiation device (manufactured by Lintec, RAD2000m/8, irradiation conditions: illuminance 195mW/cm ² , light intensity 170mJ/cm ² ), irradiated from the support sheet side Ultraviolet rays. Then, after peeling off the support sheet from the protective film, the printing on the protective film was observed with an optical microscope made by KEYENCE, and the thickness of the characters was measured. The results are shown in Table 1.

[Example 2]

<Manufacturing of Composite Sheet for Forming Protective Film>

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

Use the same method as in Example 1 to obtain a thermosetting protective film Composition for formation (III-1).

(Manufacturing of Adhesive Composition (I-4)-2)

A non-energy-ray-curable adhesive composition (I-4)-2 with a solid content concentration of 30% by mass was prepared. The adhesive composition (I-4)-2 contained an acrylic polymer (100 parts by mass, Solid content) and trifunctional xylylene diisocyanate crosslinking agent ("Takenate D110N" manufactured by Mitsui Takeda Chemical Co., Ltd.) (50 parts by mass (solid content)), and further contains methyl ethyl ketone as a solvent . The aforementioned acrylic polymer is a prepolymer with a weight average molecular weight of 800,000 obtained by copolymerizing 2EHA (80 parts by mass) and HEA (20 parts by mass).

(Support film manufacturing)

Except that the adhesive composition (I-4)-2 was used instead of the adhesive composition (I-4)-1, the same method as in Example 1 was used to obtain a support sheet (10)-2.

(Manufacturing of composite sheet for forming protective film)

The supporting sheet (10)-2 was used instead of the supporting sheet (10)-1, except that the same method as in Example 1 was used to produce a composite sheet for forming a protective film.

<Evaluation of Supporting Films>

The same method as in Example 1 was used to evaluate the haze and clarity of transmission. The results are shown in Table 1.

<Evaluation of Composite Sheet for Forming Protective Film>

Using the same method as in Example 1, the applicability of the mounter, the visibility of laser printing, and the thickness of printed characters were evaluated. The results are shown in Table 1.

[Example 3]

<Manufacturing of Composite Sheet for Forming Protective Film>

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

The same method as in Example 1 was used to obtain a thermosetting protective film forming composition (III-1).

(Manufacturing of Adhesive Composition (I-4)-1)

Using the same method as in Example 1, an adhesive composition (I-4)-1 was obtained.

(Support film manufacturing)

On the exposed surface of the adhesive layer, a polypropylene film with a thickness of 80μm (manufactured by Gunze, matte surface (surface roughness (Ra): 0.20μm)/slightly matte surface (surface roughness (Ra): 0.15μm) was laminated on the exposed surface of the adhesive layer The matte surface of the substrate, instead of a polypropylene film with a thickness of 80μm (manufactured by Mitsubishi Plastics, matte surface (surface roughness (Ra): 1.20 μm)/gloss surface (surface roughness (Ra): 0.10 μm) substrate Except for the matte surface of ), the same method as in Example 1 was used to produce a support sheet (10)-3.

(Manufacturing of composite sheet for forming protective film)

The support sheet (10)-3 was used instead of the support sheet (10)-1, except that the same method as in Example 1 was used to produce a composite sheet for forming a protective film.

<Evaluation of Supporting Films>

The same method as in Example 1 was used to evaluate the haze and clarity of transmission. The results are shown in Table 1.

<Evaluation of Composite Sheet for Forming Protective Film>

Using the same method as in Example 1, the applicability of the mounter, the visibility of laser printing, and the thickness of printed characters were evaluated. The results are shown in Table 1.

[Example 4]

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

The same method as in Example 1 was used to obtain a thermosetting protective film forming composition (III-1).

(Manufacture of adhesive composition (I-4)-3)

A non-energy-ray-curable adhesive composition (I-4)-3 with a solid content concentration of 30% by mass was prepared. The adhesive composition (I-4)-3 contained an acrylic polymer (100 parts by mass, Solid content), trifunctional xylylene diisocyanate crosslinking agent ("Takenate D110N" manufactured by Mitsui Takeda Chemical Co., Ltd.) (20 parts by mass (solid content)), and silicone resin particles (manufactured by Tanac) "Tospearl 145") (10 parts by mass (solid )), further containing methyl ethyl ketone as a solvent. The aforementioned acrylic polymer is a prepolymer with a weight average molecular weight of 800,000 obtained by copolymerizing 2EHA (80 parts by mass) and HEA (20 parts by mass).

(Support film manufacturing)

Except that the adhesive composition (I-4)-3 was used instead of the adhesive composition (I-4)-1, the same method as in Example 1 was used to obtain a support sheet (10)-4.

(Manufacturing of composite sheet for forming protective film)

The support sheet (10)-4 was used instead of the support sheet (10)-1, except that the same method as in Example 1 was used to produce a composite sheet for forming a protective film.

<Evaluation of Supporting Films>

The same method as in Example 1 was used to evaluate the haze and clarity of transmission. The results are shown in Table 1.

<Evaluation of Composite Sheet for Forming Protective Film>

Using the same method as in Example 1, the applicability of the mounter, the visibility of laser printing, and the thickness of printed characters were evaluated. The results are shown in Table 1.

[Example 5]

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

Use the same method as in Example 1 to obtain a thermosetting protective film Composition for formation (III-1).

(Manufacturing of Adhesive Composition (I-1)-1)

Prepare an energy-ray curable adhesive composition (I-1)-1 with a solid content of 30% by mass. The adhesive composition (I-1)-1 contains an acrylic polymer (100 parts by mass, solid Component), trifunctional xylylene diisocyanate-based crosslinking agent ("Takenate D110N" manufactured by Mitsui Takeda Chemical Co., Ltd.) (20 parts by mass (solid content)), and epoxy resin ("JER834 manufactured by Mitsubishi Chemical Co., Ltd." ") (25 parts by mass (solid content)), further containing methyl ethyl ketone as a solvent. The aforementioned acrylic polymer is a prepolymer with a weight average molecular weight of 800,000 obtained by copolymerizing 2EHA (80 parts by mass) and HEA (20 parts by mass).

(Support film manufacturing)

Except that the adhesive composition (I-1)-1 was used instead of the adhesive composition (I-4)-1, the same method as in Example 1 was used to obtain a support sheet (10)-5.

(Manufacturing of composite sheet for forming protective film)

The support sheet (10)-5 was used instead of the support sheet (10)-1, except that the same method as in Example 1 was used to produce a composite sheet for forming a protective film.

<Evaluation of Supporting Films>

Using the same method as in Example 1, evaluate the haze and clarity of transmission Spend. The results are shown in Table 1.

<Evaluation of Composite Sheet for Forming Protective Film>

Using the same method as in Example 1, the applicability of the mounter, the visibility of laser printing, and the thickness of printed characters were evaluated. The results are shown in Table 1.

[Example 6]

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

The same method as in Example 1 was used to obtain a thermosetting protective film forming composition (III-1).

(Manufacturing of Adhesive Composition (I-1)-2)

Prepare an energy-ray curable adhesive composition (I-1)-2 with a solid content of 30% by mass. The adhesive composition (I-1)-2 contains an acrylic polymer (100 parts by mass, solid Component), trifunctional xylylene diisocyanate-based crosslinking agent ("Takenate D110N" manufactured by Mitsui Takeda Chemical Co., Ltd.) (20 parts by mass (solid content)), and epoxy resin ("JER1055 manufactured by Mitsubishi Chemical Co., Ltd." ") (5 parts by mass (solid content)), further containing methyl ethyl ketone as a solvent. The aforementioned acrylic polymer is a prepolymer with a weight average molecular weight of 800,000 obtained by copolymerizing 2EHA (80 parts by mass) and HEA (20 parts by mass).

(Support film manufacturing)

Use adhesive composition (I-1)-2 instead of adhesive composition (I-4)-1, Except for this, the same method as in Example 1 was used to obtain a supporting sheet (10)-6.

(Manufacturing of composite sheet for forming protective film)

The support sheet (10)-6 was used instead of the support sheet (10)-1, except that the same method as in Example 1 was used to produce a composite sheet for forming a protective film.

<Evaluation of Supporting Films>

The same method as in Example 1 was used to evaluate the haze and clarity of transmission. The results are shown in Table 1.

<Evaluation of Composite Sheet for Forming Protective Film>

Using the same method as in Example 1, the applicability of the mounter, the visibility of laser printing, and the thickness of printed characters were evaluated. The results are shown in Table 1.

[Example 7]

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

The same method as in Example 1 was used to obtain a thermosetting protective film forming composition (III-1).

(Manufacturing of Adhesive Composition (I-4)-4)

A non-energy-ray-curable adhesive composition (I-4)-4 with a solid content concentration of 30% by mass was prepared. The adhesive composition (I-4)-4 contained an acrylic polymer (100 parts by mass, Solid content), trifunctional xylylene Diisocyanate-based crosslinking agent ("Takenate D110N" manufactured by Mitsui Takeda Chemical Co., Ltd.) (20 parts by mass (solid content)) and titanium oxide-based white pigment ("N-DYM8054" manufactured by Dainichi Seika Co., Ltd.) (5 mass parts) Parts (solid content)), further containing methyl ethyl ketone as a solvent. The aforementioned acrylic polymer is a prepolymer with a weight average molecular weight of 800,000 obtained by copolymerizing 2EHA (80 parts by mass) and HEA (20 parts by mass).

(Support film manufacturing)

Except that the adhesive composition (I-4)-4 was used instead of the adhesive composition (I-4)-1, the same method as in Example 1 was used to obtain a support sheet (10)-7.

(Manufacturing of composite sheet for forming protective film)

The support sheet (10)-7 was used instead of the support sheet (10)-1, except that the same method as in Example 1 was used to produce a composite sheet for forming a protective film.

<Evaluation of Supporting Films>

The same method as in Example 1 was used to evaluate the haze and clarity of transmission. The results are shown in Table 1.

<Evaluation of Composite Sheet for Forming Protective Film>

Using the same method as in Example 1, the applicability of the mounter, the visibility of laser printing, and the thickness of printed characters were evaluated. The results are shown in Table 1.

[Example 8]

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

The same method as in Example 1 was used to obtain a thermosetting protective film forming composition (III-1).

(Manufacturing of Adhesive Composition (I-4)-5)

A non-energy-ray-curable adhesive composition (I-4)-5 with a solid content concentration of 30% by mass was prepared, and the adhesive composition (I-4)-5 contained an acrylic polymer (100 parts by mass, Solid content), trifunctional xylylene diisocyanate-based crosslinking agent ("Takenate D110N" manufactured by Mitsui Takeda Chemical Co., Ltd.) (20 parts by mass (solid content)), and acrylic polymer particles (Dainichi Seika Co., Ltd.) The manufactured "215 (MD) White") (10 parts by mass (solid content)) further contains methyl ethyl ketone as a solvent. The aforementioned acrylic polymer is a prepolymer with a weight average molecular weight of 800,000 obtained by copolymerizing 2EHA (80 parts by mass) and HEA (20 parts by mass).

(Support film manufacturing)

Except that the adhesive composition (I-4)-5 was used instead of the adhesive composition (I-4)-1, the same method as in Example 1 was used to obtain a support sheet (10)-8.

(Manufacturing of composite sheet for forming protective film)

The support sheet (10)-8 was used instead of the support sheet (10)-1, except that the same method as in Example 1 was used to produce a composite sheet for forming a protective film.

<Evaluation of Supporting Films>

The same method as in Example 1 was used to evaluate the haze and clarity of transmission. The results are shown in Table 1.

<Evaluation of Composite Sheet for Forming Protective Film>

Using the same method as in Example 1, the applicability of the mounter, the visibility of laser printing, and the thickness of printed characters were evaluated. The results are shown in Table 1.

[Example 9]

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

The same method as in Example 1 was used to obtain a thermosetting protective film forming composition (III-1).

(Manufacturing of Adhesive Composition (I-4)-2)

Using the same method as in Example 2, a non-energy ray-curable adhesive composition (I-4)-2 with a solid content concentration of 30% by mass was prepared.

(Support film manufacturing)

Using adhesive composition (I-4)-2 instead of adhesive composition (I-4)-1, on the exposed surface of the adhesive layer, a polypropylene film with a thickness of 80μm (manufactured by Gunze Co., matte surface ( Surface roughness (Ra): 0.20μm)/slight matte surface (surface roughness (Ra): 0.15μm) matte surface, instead of 80μm thick polypropylene film (manufactured by Mitsubishi Plastics, matte surface (table) Surface roughness (Ra): 1.20 μm)/glossy surface (surface roughness (Ra): 0.10 μm) matte surface, except that the same method as in Example 1 was used to obtain a support sheet (10) -9.

(Manufacturing of composite sheet for forming protective film)

The support sheet (10)-9 was used instead of the support sheet (10)-1, except that the same method as in Example 1 was used to produce a composite sheet for forming a protective film.

<Evaluation of Supporting Films>

The same method as in Example 1 was used to evaluate the haze and clarity of transmission. The results are shown in Table 1.

<Evaluation of Composite Sheet for Forming Protective Film>

Using the same method as in Example 1, the applicability of the mounter, the visibility of laser printing, and the thickness of printed characters were evaluated. The results are shown in Table 1.

[Example 10]

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

The same method as in Example 1 was used to obtain a thermosetting protective film forming composition (III-1).

(Manufacturing of Adhesive Composition (I-4)-2)

Using the same method as in Example 2, a non-energy ray-curable adhesive composition (I-4)-2 with a solid content concentration of 30% by mass was prepared.

(Support film manufacturing)

Using adhesive composition (I-4)-2 instead of adhesive composition (I-4)-1, on the exposed surface of the adhesive layer, a polypropylene film with a thickness of 80μm (manufactured by Gunze Co., matte surface ( Surface roughness (Ra): 0.20μm)/Micro matte surface (surface roughness (Ra): 0.15μm) substrate), instead of a polypropylene film with a thickness of 80μm (made by Mitsubishi Plastics, matte surface ( Except for the matte surface of the surface roughness (Ra): 1.20 μm)/glossy surface (surface roughness (Ra): 0.10 μm) substrate), the same method as in Example 1 was used to obtain a support sheet (10) -10.

(Manufacturing of composite sheet for forming protective film)

The support sheet (10)-10 was used instead of the support sheet (10)-1, except that the same method as in Example 1 was used to produce a composite sheet for forming a protective film.

<Evaluation of Supporting Films>

The same method as in Example 1 was used to evaluate the haze and clarity of transmission. The results are shown in Table 1.

<Evaluation of Composite Sheet for Forming Protective Film>

Using the same method as in Example 1, the applicability of the mounter, the visibility of laser printing, and the thickness of printed characters were evaluated. The results are shown in Table 1.

[Comparative Example 1]

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

The same method as in Example 1 was used to obtain a thermosetting protective film forming composition (III-1).

(Manufacturing of Adhesive Composition (I-4)-1)

Using the same method as in Example 1, an adhesive composition (I-4)-1 was obtained.

(Support film manufacturing)

Except that a non-energy-ray-curable adhesive layer with a thickness of 10 μm was formed instead of the layer with a thickness of 15 μm, the same method as in Example 1 was used to manufacture the support sheet (10)-11.

(Manufacturing of composite sheet for forming protective film)

The support sheet (10)-11 was used instead of the support sheet (10)-1, except that the same method as in Example 1 was used to produce a composite sheet for forming a protective film.

<Evaluation of Supporting Films>

The same method as in Example 1 was used to evaluate the haze and clarity of transmission. The results are shown in Table 1.

<Evaluation of Composite Sheet for Forming Protective Film>

Using the same method as in Example 1, the applicability of the mounter, the visibility of laser printing, and the thickness of printed characters were evaluated. The results are shown in Table 1.

[Comparative Example 2]

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

The same method as in Example 1 was used to obtain a thermosetting protective film forming composition (III-1).

(Manufacture of adhesive composition (I-4)-6)

Prepare a non-energy-ray-curable adhesive composition (I-4)-6 with a solid content concentration of 30% by mass. The non-energy-ray-curable adhesive composition (I-4)-6 contains an acrylic polymer (100 parts by mass, solid content) and trifunctional xylylene diisocyanate-based crosslinking agent ("Takenate D110N" manufactured by Mitsui Takeda Chemical Co., Ltd.) (30 parts by mass (solid content)), and further contains as a solvent Methyl ethyl ketone. The aforementioned acrylic polymer is a prepolymer with a weight average molecular weight of 800,000 obtained by copolymerizing 2EHA (80 parts by mass) and HEA (20 parts by mass).

(Support film manufacturing)

Except for using adhesive composition (I-4)-6 instead of adhesive composition (I-4)-1, the same method as in Example 1 was used to obtain a support sheet (10)-12.

(Manufacturing of composite sheet for forming protective film)

The support sheet (10)-12 was used instead of the support sheet (10)-1, except that the same method as in Example 1 was used to produce a composite sheet for forming a protective film.

<Evaluation of Supporting Films>

The same method as in Example 1 was used to evaluate the haze and clarity of transmission. The results are shown in Table 1.

<Evaluation of Composite Sheet for Forming Protective Film>

Using the same method as in Example 1, the applicability of the mounter, the visibility of laser printing, and the thickness of printed characters were evaluated. The results are shown in Table 1.

[Comparative Example 3]

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

The same method as in Example 1 was used to obtain a thermosetting protective film forming composition (III-1).

(Manufacture of adhesive composition (I-4)-7)

A non-energy-ray-curable adhesive composition (I-4)-7 with a solid content concentration of 30% by mass was prepared. The adhesive composition (I-4)-7 contained an acrylic polymer (100 parts by mass, Solid content) and trifunctional xylylene diisocyanate crosslinking agent ("Takenate D110N" manufactured by Mitsui Takeda Chemical Co., Ltd.) (5 parts by mass (solid content)), and further contains methyl ethyl ketone as a solvent . The aforementioned acrylic polymer is a prepolymer with a weight average molecular weight of 800,000 obtained by copolymerizing 2EHA (80 parts by mass) and HEA (20 parts by mass).

(Support film manufacturing)

The adhesive composition (I-4)-7 obtained above was applied to the peeling treatment surface of the peeling film on one side of the polyethylene terephthalate film that was peeled off by the silicone treatment. Heat and dry at 120°C for 2 minutes to form a non-energy ray-curable adhesive layer with a thickness of 5 μm.

Then, on the exposed surface of the adhesive layer, a polypropylene film with a thickness of 80 μm (manufactured by Mitsubishi Plastics Co., Ltd., matte surface (surface roughness (Ra): 0.50 μm)/gloss surface (surface roughness (Ra): 0.10 μm) the glossy surface of the substrate), thereby manufacturing the support sheet (10)-13.

(Manufacturing of composite sheet for forming protective film)

The support sheet (10)-13 was used instead of the support sheet (10)-1, except that the same method as in Example 1 was used to produce a composite sheet for forming a protective film.

<Evaluation of Supporting Films>

The same method as in Example 1 was used to evaluate the haze and clarity of transmission. The results are shown in Table 1.

<Evaluation of Composite Sheet for Forming Protective Film>

Using the same method as in Example 1, the applicability of the mounter, the visibility of laser printing, and the thickness of printed characters were evaluated. The results are shown in Table 1.

[Comparative Example 4]

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

The same method as in Example 1 was used to obtain a thermosetting protective film forming composition (III-1).

(Manufacture of adhesive composition (I-4)-7)

Using the same method as in Comparative Example 3, a non-energy-ray-curable adhesive composition (I-4)-7 was prepared.

(Support film manufacturing)

Except that the adhesive composition (I-4)-7 was used instead of the adhesive composition (I-4)-1, the same method as in Example 1 was used to obtain a support sheet (10)-14.

(Manufacturing of composite sheet for forming protective film)

The supporting sheet (10)-14 was used instead of the supporting sheet (10)-1, except that the same method as in Example 1 was used to produce a composite sheet for forming a protective film.

<Evaluation of Supporting Films>

The same method as in Example 1 was used to evaluate the haze and clarity of transmission. The results are shown in Table 1.

<Evaluation of Composite Sheet for Forming Protective Film>

Using the same method as in Example 1, the applicability of the mounter, the visibility of laser printing, and the thickness of printed characters were evaluated. The results are shown in Table 1.

[Comparative Example 5]

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

The same method as in Example 1 was used to obtain a thermosetting protective film forming composition (III-1).

(Manufacture of adhesive composition (I-4)-7)

Using the same method as in Comparative Example 3, a non-energy-ray-curable adhesive composition (I-4)-7 was prepared.

(Support film manufacturing)

The adhesive composition (I-4)-7 obtained above was applied to the peeling treatment surface of the peeling film on one side of the polyethylene terephthalate film that was peeled off by the silicone treatment. Heat and dry at 120°C for 2 minutes to form a non-energy ray-curable adhesive layer with a thickness of 5 μm.

Then, on the exposed surface of the adhesive layer, a polypropylene film with a thickness of 60 μm (manufactured by Riken Technos Co., Ltd., matte surface (surface roughness (Ra): 0.50 μm)/gloss surface (surface roughness (Ra): 0.10 μm) the glossy surface of the substrate), thereby manufacturing the support sheet (10)-15.

(Manufacturing of composite sheet for forming protective film)

The support sheet (10)-15 was used instead of the support sheet (10)-1, except that the same method as in Example 1 was used to produce a composite sheet for forming a protective film.

<Evaluation of Supporting Films>

The same method as in Example 1 was used to evaluate the haze and clarity of transmission. The results are shown in Table 1.

<Evaluation of Composite Sheet for Forming Protective Film>

Using the same method as in Example 1, the applicability of the mounter, the visibility of laser printing, and the thickness of printed characters were evaluated. The results are shown in Table 1.

In Table 1, the applicability of the mounter is evaluated as A, the recognizability of laser printing is evaluated as A or B as "pass", and the cases other than the above are regarded as "unqualified".

According to Table 1, when the haze of the support sheet is 46% or more, the mounter suitability is evaluated as A. Presumably, the reason is that when the haze of the support sheet is 46% or more, it has a certain degree of turbidity (haze), which can be used to position the front end of the belt. In the adjusted optical sensor, the position of the front end of the support sheet can be detected by laser irradiation.

In addition, according to Table 1, when the haze of the support sheet is 46% or more, and the transmission resolution is 100 or more, the laser printing visibility is rated B or higher, and when the transmission resolution is 200 or more, the laser printing visibility is A Evaluation. Presumably, the reason is that the visibility of laser printing is improved by suppressing light scattering on the outer surface of the substrate located on the bottom surface of the support sheet. In addition, when the haze of the support sheet is 46% or more, it has a certain degree of turbidity (haze), by which the laser light is properly scattered inside the support sheet, which can widen the thickness of the printed text, thereby helping to improve The visibility of laser printing.

Based on the above, it is clear that by setting the haze and transparency of the support sheet to an appropriate range, it is possible to obtain a composite for forming a protective film with excellent laser printability on the protective film and excellent visibility of the printing on the protective film. piece.

(Industrial availability)

The present invention can be used to manufacture semiconductor devices.

1A‧‧‧Composite sheet for forming protective film

10‧‧‧Support film

10a‧‧‧Support the surface of the film

11‧‧‧Substrate

11a‧‧‧The surface of the substrate

12‧‧‧Adhesive layer

12a‧‧‧The surface of the adhesive layer

13‧‧‧Film for forming protective film

13a‧‧‧The surface of the protective film forming film

15‧‧‧Peeling film

Claims (8)

A composite sheet for forming a protective film, comprising a base material and sequentially laminating an adhesive layer and a protective film forming film on the base material; as a support sheet for the laminate of the base material and the adhesive layer The haze is higher than 45% to 90% or less; the transparency of the support sheet is from 100 to 450; the constituent materials of the substrate are polyethylene, polyolefins other than polyethylene, ethylene-based copolymers, and chlorine Vinyl resins, polystyrene, polycyclic olefins, polyesters, copolymers of two or more of the aforementioned polyesters, poly(meth)acrylates, polyurethanes, polyacrylate urethanes, poly Imide, polyamide, polycarbonate, fluororesin, polyacetal, modified polyphenylene ether, polyphenylene sulfide, polysulfide, or polyetherketone; the adhesive contained in the aforementioned adhesive layer is acrylic Resin, urethane-based resin, rubber-based resin, silicone-based resin, epoxy-based resin, polyvinyl ether, polycarbonate, or ester-based resin. The composite sheet for forming a protective film according to claim 1, wherein the area on the surface of the adhesive layer on the side where the film for forming the protective film is not laminated with the film for forming the protective film is provided with an adhesive for jig Agent layer. The composite sheet for forming a protective film according to claim 1 or 2, wherein the film for forming a protective film is energy ray curable. The composite sheet for forming a protective film according to claim 1 or 2, wherein the film for forming a protective film is thermosetting. The composite sheet for forming a protective film according to claim 1 or 2, wherein the film for forming a protective film is non-curable. The composite sheet for forming a protective film according to claim 1 or 2, wherein the adhesive layer is energy ray curable or non-energy curable. The composite sheet for forming a protective film according to claim 1 or 2, wherein the thickness of the adhesive layer is 3 μm to 20 μm. The composite sheet for forming a protective film as described in claim 1 or 2, wherein the surface roughness of one surface of the aforementioned base material is 0.11 μm or more and 1.30 μm or less, and is laminated on the surface of the aforementioned surface roughness in direct contact There is the aforementioned adhesive layer.

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